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Inorganic Solid Electrolyte Interphase Engineering Rationales Inspired by Hexafluorophosphate Decomposition Mechanisms

  • Dacheng Kuai
    Dacheng Kuai
    Department of Chemical Engineering, Texas A&M University, College Station, Texas 77843, United States
    Department of Chemistry, Texas A&M University, College Station, Texas 77843, United States
    More by Dacheng Kuai
    Orcidhttps://orcid.org/0000-0002-4787-7331
  •  and 
  • Perla B. Balbuena*
    Perla B. Balbuena
    Department of Chemical Engineering, Texas A&M University, College Station, Texas 77843, United States
    Department of Chemistry, Texas A&M University, College Station, Texas 77843, United States
    Department of Materials Science and Engineering, Texas A&M University, College Station, Texas 77843, United States
    *Email: [email protected]
    More by Perla B. Balbuena
    Orcidhttps://orcid.org/0000-0002-2358-3910
Cite this: J. Phys. Chem. C 2023, 127, 4, 1744–1751
Publication Date (Web):January 23, 2023
https://doi.org/10.1021/acs.jpcc.2c07838

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Abstract

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Solid electrolyte interphase (SEI) engineering is an efficient approach to enhancing the cycling performance of lithium metal batteries. Lithium hexafluorophosphate (LiPF6) is a popular electrolyte salt. Mechanistic insights into its degradation pathways near the lithium metal anode are critical in modifying the battery electrolyte and SEI. In this work, we elucidate plausible reaction pathways in multiple representative electrolyte systems. Through ab initio molecular dynamics simulations, lithiation and electron transfer are identified as the triggering factors for LiPF6 degradation. Meanwhile, we find that lithium morphology and charge distribution substantially impact the interfacial dissociation pathways. Thermodynamic evaluation of the solvation effects shows that higher electrolyte dielectric constant and lithiation extent profoundly assist the LiPF6 decomposition. These findings offer quantitative thermodynamic and electronic structure information, which promotes rational SEI engineering and electrolyte tuning for lithium metal anode performance enhancement.

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Introduction

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Current commercially available lithium-ion batteries are approaching their theoretical limits, while the electronics market still urges further energy capacity extension. (1) The lithium metal battery (LMB) is a promising technical route for next-generation energy storage devices. (2) The cycling efficiency and safety risk control on the battery anode are the primary technical obstacles that hinder LMB commercialization. (3) Solid electrolyte interphase (SEI) formed on the anode surface regulates Li+ ion migration and deposition, which is critical in minimizing lithium dendrite and whisker formation. (4) Therefore, the battery’s electrochemical performance is tightly bonded with SEI morphology and composition. (5)
Fluorination has been suggested as an efficient strategy in battery electrolytes and SEI engineering. (6) The fluorine-containing electrolyte components, such as LiPF6, lithium bis(fluorosulfonyl)imide (LiFSI), and fluoroethylene carbonate (FEC), experience decomposition and yield lithium fluoride nanoparticles in SEI. However, the SEI internal structures are notoriously complex to resolve due to their fragility and chemical reactiveness. (2) So far, only limited while expensive techniques such as cryo-electron microscopy are able to precisely probe the spatial distributions of SEI nanostructures, where battery disassembly is mandatory. (7) In addition, the electrolyte species also alter the solvation environment, which profoundly impacts the thermochemistry and kinetics of SEI formation reactions. (8,9) Aside from the designing principles based on empirical concepts, theoretical approaches are expected to envision the electrolyte–electrode interfacial chemistry and ion transport mechanisms. (3,10−12) Hereby, we study the reactions resulting in prevalent inorganic components in SEI from LiPF6-based electrolytes. The quantitative understanding of the reaction thermodynamics may enable future multiscale simulations of the SEI formation processes.
It is inherently challenging to characterize the electrode–electrolyte interfacial chemistry at the nanoscale. (13) The SEI grows in such a highly reductive and salty environment. Despite limited experimental data available to precisely elucidate the SEI composition and formation mechanisms, many proposals depict plausible scenarios in generating SEI of LMB. (2,13) Hexafluorophosphate degradation is recognized as the primary contributor to the LiF in SEI based on this electrolyte chemistry, while few reports denote the destination of phosphorus. A trace amount of moisture in battery electrolyte can cause hydrolysis of PF6–, yielding POF3 and its derivatives as detected in spectroscopic analysis. (14,15) Further information regarding the direct PF6– decomposition and reduction without water participation is less reported in the experimental work. The characterization of interfacial chemistry is particularly challenging in accessing delicate nanoscale surfaces. (13,16) First principles simulation is compelling in predicting the molecular behavior at the metal–liquid interface, which is fragile to atmospheric interruptions. (17) Ab initio molecular dynamics (AIMD) successfully predicts the stabilities and reductive dissociation of electrolyte solvents near metallic surfaces. (18,19)
The LiPF6 degradation chemistry near the anode shows unique features. The phosphorous element usually demonstrates a singlet electronic state in stable compounds. However, some reported atomic charge analysis on the AIMD simulation shows that this rule may not apply to all cases in the LiPF6 decomposition near lithium battery anode surfaces. Martinez de la Hoz et al. identified the plausible oxidation state pathway on the silicone anode surface, where the equilibrium charge state of phosphorous was identified to be −1. (20) A fully reduced phosphorous reduction product was found in the lithium metal case. (21) Both these scenarios require continuous electron uptake.
Ether-based electrolytes are mainly composed of dimethoxyethane (DME) and 1,3-dioxolane (DOL), with moderate dielectric constants (ε) varying from 4 to 10. (22) High salt concentration is mandatory in maintaining the integrity of ether solvents in high voltages, despite their compatibility with lithium metal. (23,24) The commonly used carbonate solvents, including ethylene carbonate (EC), propylene carbonate (PC), and vinylene carbonate (VC), create a solvation environment with much higher dielectric constants and unique solvation structures. (22) In the electrolyte environment with a positive dielectric constant, the direct electron tunneling probability decays exponentially with respect to particle–metal-surface distance. Consequently, electron-induced reactions usually occur via complex charge transport mechanisms that manipulate the corresponding redox reaction rate. (25) The ion–solvent interactions are one of the most important factors in bottom-up LMB development. (26) The beginning stages of phase separation and ionic nucleation in forming SEI have been reported in previous molecular dynamics (MD) and AIMD studies. (27−29) A longer simulation time scale may compensate for this issue by implementing high-quality ab initio thermodynamic information in kinetic Monte Carlo (kMC) simulations. (30) Beyond elucidating the underlying chemical processes, we aim to contribute toward data-driven LMB electrolyte and SEI engineering from the electrolyte solvation and anode morphology perspectives.

Computational Methods

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After creating a vacuum slab on top of the Li metal crystal surface structure, the initial configurations for AIMD were obtained by packing the geometry-optimized structures of electrolyte species in the vacuum space based on the Amorphous Cell Packing module in Materials Studio v8. In the selected configuration, relative positions of hexafluorophosphate particles were verified to include both the following conditions: (1) close contact to the Li metal surface and (2) dissolved in electrolyte while the mass center is at least 5 Å away from the lithium surface. The molar ratios of each species and the system density were further assessed to be consistent with the experimental macroscopic properties. The AIMD simulations were performed via VASP 5.4.4. (31) The Perdew–Burke–Ernzerhof (PBE) functional was used to describe the electron exchange and correlation energies within the generalized gradient approximation (GGA). (32) Electron–ion interactions were considered within the projector augmented wave (PAW) pseudopotentials. (33,34) The plane waves were extended to a cutoff energy of 520 eV. The simulations were based on an NVT ensemble at 300 K with 1-fs time step. DFT-D3 method of Grimme with the zero-damping function was implemented to correct van der Waals interaction terms. (35) The atomic Bader charges were analyzed based on the grid-based method developed by Henkelman et al. (36)
Molecular modeling was primarily conducted on the Gaussian16 package. All intermediate structures were optimized to their local minimum without imaginary vibration mode, and the corresponding free energy values were converted to the standard state of 1 M. M06-2X/aug-cc-pVDZ level of theory was employed based on the benchmark results previously reported by Han et al. (37−39) Solvation effects were evaluated based on the implicit solvation model based on density (SMD). (40) Empirical dispersion interactions were introduced in calculations. (41)

Results and Discussion

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We initially estimate the degradation energetics of LiPF6 with different spin states at the molecular level, as shown in Table S1 in SI. The only free energy barrier exists at the first P–F cleavage process. However, the real SEI formation environment is much more complex than this simple model. As an example of the complexity of interfacial reactions, it has been reported that the solvent–reactant interactions at the air–liquid interface can profoundly alter the reaction thermodynamic profile, and such impact varies under different dielectric environments. (16) Similarly, many factors, including metal–electrolyte interfacial effects, solvation effects, charge transport, and lithium coordination, contribute to the LiPF6 degradation reactions. Here, we apply AIMD simulations to elucidate the interfacial decomposition reactions and further quantitatively evaluate the key conditions at the molecular level.

Lithiation and Electron-Tunneling-Induced Salt Degradation

We perform AIMD simulations to reveal the ultrafast decomposition of LiPF6 in different electrolyte systems. The initial configuration contained PF6– structures with different lithium coordination degrees and distances to the lithium metal surface. The time scale required for salt degradation varies in different solvation environments. In the cyclic carbonate-solvated system (Figure 1), the PF6– structures close to the lithium metal surface easily decompose within 2 ps of simulation time. Following such an event, the EC and VC structures disintegrate into carbonyl/carbon monoxide and ethylene di-carbonate (EDC). The solvent degradation pathways have been investigated in many systematic works. (42−45) In addition to the complete degradation at the electrolyte–metal interface, we also observe the partial dissociation phenomenon of [Li2PF6]+ complex, which is located 15 Å from the lithium metal surface and 8 Å from the top periodic boundary of the x–y plane in Figure 1 (blue-circled). Such a process is reproducible in other solvent systems, such as DME-DOL. The rearranged structure resembles a seesaw-shaped PF4 coordinated with a rhombic Li2F2 complex. Throughout the P–F cleavage and rearrangement processes, chronological Bader charge analysis (see Figure S1 for details) indicates no charge variation occurring on neighbor electrolyte species or He; only Li and PF6 clusters are involved in the charge transport without direct contact. Therefore, we suggest that such charge transfer-driven partial decomposition may be caused by electron tunneling from lithium metal to the dual-lithiated cation.

Figure 1

Figure 1. AIMD simulation of LiPF6 decomposition on and near lithium metal surface. The initial electrolyte configuration is composed of 3 Li+, 3 PF6–, 18 EC, and 1 VC structures, with a density of 1.3 g/mL. The coordinates of the top-layer He atoms (dark gray) are fixed to refrain electrolyte molecular movement from contacting the lithium layer repeated in the z-direction due to periodic boundary conditions. Some cluster structures are rotated for a clear perspective. Color scheme: He (gray ball); C (gray dash); H (white dash); O (red dash); Li (purple ball); P (tan ball); F (cyan ball).

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Moreover, such partial dissociation highly depends on the dual-lithium coordination to hexafluorophosphate and on the cluster charge state. Specifically, in the comparable configuration without extra “free” Li+ available in the neighboring region of LiPF6 or PF6–, the partial dissociation does not occur in the corresponding AIMD simulations. With dual lithiation, the P–F cleavage ceases after the [Li2PF6]+ cluster receives an electron from Li metal and becomes negatively charged. We also compute Li+ affinity energetics of different electrolyte species (Figure S2) and find that the lithiation free energies for the formation of [Li2PF6]+ and [solvent-Li]+ adduct are close to each other. Therefore, the population ratio of [Li2PF6]+ cluster is equivalent to that of the solvated Li+ in concentrated electrolytes. The [Li2PF6]+ partial decomposition depicted above should be a non-negligible event during LMB fabrication.
We further analyze the Li-coordination’s impacts on the electronic structure of [PF6]x species. Previous studies have shown that lithiation reconstructs common electrolyte solvent molecules’ HOMO and LUMO structures. (46,47) As suggested in Figure 2a,b, P–F bonding has strong covalency in PF6– anion and neutral LiPF6 molecule, while the bond length is slightly extended due to the lithium coordination. When two lithium atoms are coordinated, some particular P–F bonds demonstrate ionic properties, as the electronic Laplacian planar plot indicates. The P–F distance (dashed bonds in 2d and 2e) also extends from 1.7 to 2.0 Å. Meanwhile, it is interesting to notice that the Li–P interaction shows positive Laplacian in the anionic cluster, suggesting covalent interactions between Li and P atoms, unlike the ionic Li–F cases. Therefore, high-level lithiation destabilizes the electronic configuration in [PF6]x structure.

Figure 2

Figure 2. Geometry (left), electron density (middle), and electronic Laplacian (right) analysis of Li2PF6 clusters, including the optimized geometries of [PF6]− (a) LiPF6 (b), [Li2PF6]+ (c), as well as the [Li2PF6]− structures (d, e) retrieved from AIMD simulations. (49) All of the electronic structure figures are plotted based on the planes determined by labeled atoms. Atomic color coding in structural geometries is identical to Figure 1. The rainbow color scale is labeled on the left (electron density) and right (Laplacian) sides of each diagram, where red indicates positive, and blue indicates zero/negative values.

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The semi-equilibrium geometry of [Li2PF6]x cluster, as described in Figures 1 and 2, is reproducible in AIMD simulations of both electrolyte systems of cyclic carbonate and ether solvents and is able to maintain its integrity within the feasible simulation time range (see Figures S1 and S3 for additional details). Based on Mulliken charge analysis of the two anionic [Li2PF6]− structures, the partial charges of Li2F2 moieties are generally neutral while the rest of the PF4 substructures occupy most of the negative charge density (−0.83 and −0.87, respectively). Current computing power limits AIMD from probing the final chemical forms of the partially dissociated [Li2PF6]x cluster. Over a longer time scale, such species may either (a) join undissociated PF6– anions and serve as ionic carriers in liquid electrolyte or (b) further decompose and become part of SEI. The close–shell [PF4]− anion generated from Li1-F3 cleavage has a smaller diameter than the unreacted [PF6]− and is thus expected to have a higher diffusion coefficient. From the battery electrolyte and SEI engineering perspective, the PF6– partial degradation near the anode material can lead to electrolyte ionic conductivity properties that differentiate from the direct measurement of pure LiPF6 solution. Meanwhile, the electrolyte dielectric constant not only impacts the solvation of ionic species but also influences the electron transport rate from the metallic surface, determining the quantities of corresponding products. (25,48) For instance, it requires less than 1 ps in ether electrolytes (lower ε) to obtain the metastable [Li2PF6]− structure, while the equivalent process takes more than 2 ps in the carbonate system (higher ε). The Bader charge analysis of both systems (Figure S5) further confirms that such reductive dissociation results in significant charge variations on the lithium metal surface. Therefore, future LMB development could also benefit from the real-time analysis of electrolyte composition in working conditions.

Lithium Metal Surface Morphology

The lithium surface facet was found to be contributive to the electrolyte carbonate solvent defluorination thermodynamic pathways. (8) The surface Li–Li distances vary from 3.51 Å (100), 3.04 Å (110), to 4.96 Å (111), depending on the facets. The degradation energy profile of LiPF6 also shows a significant mechanistic correlation with the regional metal surface structure.
We perform AIMD simulations on hexafluorophosphate species with different initial lithiation statuses. Background charge of opposite sign is applied to PF6–-containing slabs (a) and (b) as no counter ion is included. Bader charge analysis of the initial configurations shows that the PF6 clusters in both cases have −1.1 e equivalent charges, while lithium atoms representing bulk structures are generally neutral. Comparing Figure 3a–c,b–d, charge-neutral LiPF6 demonstrates faster interfacial adsorption and dissociation than PF6– anion in equivalent Li facets. Mulliken charge analysis shows that lithium coordination “pushes” electron density to the fluorine atoms on the opposite side. In other words, the bare fluorine atoms are more electronegative than the Li-coordinated ones in a hexafluorophosphate cluster. The uneven internal charge distribution of LiPF6 is mainly responsible for the increased degradation rate.

Figure 3

Figure 3. Energy profile of the hexafluorophosphate dissociation on different lithium metal facets retrieved from AIMD simulations. Important events are labeled with (a), (b), (c), and (d). The background charge of configurations (a) and (b) are both −1 e, while panels (c) and (d) are neutral. Atomic color coding is consistent with Figure 1.

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Based on the time required to reach comparable equilibrium, the hexafluorophosphate dissociation on Li(110) is slightly faster than that on Li(100), which has longer Li–Li distances. The first significant energy relaxation is a consequence of the hexafluorophosphate adsorption to the metal interface. Anionic hexafluorophosphate species can form more than four binding sites with the lithium metal surfaces before dissociation. When PF6– approaches the Li(100) surface, five F atoms simultaneously coordinate with neighboring Li atoms in 1 ps. PF6– maintains its geometric integrity longer until adsorbing to the Li(110) facet after approximately 3.5 ps. Comparatively, the charge-neutral LiPF6 allows three fluorine atoms to bind with interfacial Li atoms upon adsorption. Thus, given the impact of salt concentration and solvent chemistry on the electrolyte structure at the Li metal/electrolyte interface, we expect that the observed significant chemical difference in the interactions of the anion with the surface highlighted here would influence the SEI properties derived from each electrolyte.
The differences in adsorption patterns result in the facet-dependency of fluorophosphate decomposition pathways. In Li(100) configurations, anionic PF6– experiences one-by-one sequential P–F bond cleavages (Figure 3a), while two fluorine atoms simultaneously cleave from the LiPF6 structure (Figure 3c). A similar two-atom dissociation happens to PF6– on Li(110) (Figure 3b), while three fluoride anions leave the phosphorous center of LiPF6 (Figure 3d). It is worth noting that at least two Li atoms are coordinated with the dissociated F atom in all of the dissociation events.
Based on our findings, anode metal surface modifications could be a rational strategy in SEI engineering. The Li–Li distances and surface charge distributions profoundly influence the SEI growing rate. Therefore, delicate modifications, including doping and chemical pretreatment, may tune the SEI to ideal structures and functional performance. (50)
Combined with the electronic structure evidence in the Introduction section, we can conclude that hexafluorophosphate degradation requires multiple (at least three) lithium coordinations to fluorine atoms. The semi-covalent Li–P interaction destabilizes P–F bonds and induces further charge transfer from nearby electron-rich lithium atoms. The accumulated negative charges further result in P–F bond cleavages. We compute the energy profile at the molecular level to quantitatively evaluate the impacts of lithiation and solvation in the decomposition pathway.

Hexafluorophosphate Degradation Pathway and Solvation’s Role in Thermodynamic Profiles

To further understand the LiPF6 decomposition reaction mechanism in the electrolyte, we investigate the energy profiles in different solvation systems. The Bader charge analysis of key time points in hexafluorophosphate degradation AIMD (Figures S3–S4 in the Supporting Information) demonstrates two necessary steps for P–F bond cleavages: (1) lithium coordination; (2) [PFx]y− cluster receives external electron(s). Based on these criteria, we propose a plausible reaction mechanism that includes electron uptake followed by P–F bond cleavage. We also investigate the lithium bonding’s thermodynamic role in such processes. In addition to the implicit SMD model, which mimics the DME-DOL electrolyte (Figure 4), we also obtain the free energy surface of the identical reaction pathway in higher dielectric constant and in gas-phase conditions shown in Figures S3 in the SI. Such a thermodynamic analysis of the primary SEI fluorination reaction in different solvation environments benefits a quantitative understanding of the reaction pathway and promotes rational electrolyte tuning in future work.

Figure 4

Figure 4. Free energy profile of LiPF6 degradation computed in SMD (ε = 7.4). The red, purple, blue, and gray curves stand for nonlithiated, mono-lithiated, bi-lithiated, and tri-lithiated species, respectively. The relative free energies are labeled in kcal/mol, so are the enthalpy values in parenthesis.

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To model the complex solution–metal interfacial reactions, the relative energetics of each species are calculated with respect to LiPF6, Li+, Li(0), and F– (Figure 4). This method provides rich information in understanding the stepwise energy barriers while being conservative in evaluating the exergonicity and exothermicity, especially when the generated particles embed into the solid surface. The largest free energy uphill is found at the electron-receiving step in forming the closed-shell PF4 structures. Lithiation does not show any thermodynamic assistance in this step, while the thermochemistry is particularly favorable in the later reaction stages when more lithium cations bind with the intermediates. This is consistent with the AIMD finding that the dissociation progress is significantly faster after two P–F bonds are cleaved. Figure 4 shows that the nonlithiated pathway is unfeasible in the medium-dielectric environment, and the singly lithiated one is reluctant to proceed. The thermochemistry is generally favorable when at least two lithium atoms are coordinated. Therefore, the lithiation of [PFx]y− intermediate induces charge transfer and plays an assistive role in P–F bond breaking.
We find that the transition states for P–F cleavages do not form significant thermodynamic obstacles; the electron uptake steps hinder the degradation instead. Note that compared with free energy, the enthalpy change in each stage is generally more positive/less negative, indicating that the dissociation progress is primarily entropy-driven. When the decomposition finishes and the initial SEI layer forms, the entropy reaches a local maximum. Besides the energy increase in generating the corresponding open-shell [PFx]y− structures, charge transfer would be more sophisticated after the metallic surface is passivated.
We also assess solvation effects’ role in hexafluorophosphate degradation. In the gas phase, where the dielectric constant is zero, the reaction shows a clear increasing trend in the free energy surface (Figure S6a). Such a pattern is completely inverted in high-dielectric-constant solvation conditions. As shown in Figure S6c, with a solvation environment comparable to the EC–VC electrolyte, the energy barrier for generating PF4 is significantly lower than that in DME-DOL. In addition, the following P–F dissociation steps are thermodynamically favorable in all of the lithiation conditions. The free energy uphill of all steps after generating the low-spin PF4 species is significantly lower than the corresponding medium-dielectric scenario.
The solvation effects play two significant roles in the initial layer formation reactions of SEI. One is hindering direct electron tunneling between lithiated hexafluorophosphate species and lithium metal, and the other is creating a stabilizing solvation shell for intermediates in salt degradation. Thus, both the ionic conductivities and viscosity are altered together with the SEI formation kinetics and morphology when tuning the LMB liquid electrolyte. In the meantime, because the dissociation reaction rates are strongly correlated with the dielectric environment, people may rationally design the reagents for artificial SEI construction to control the ratios and distributions of different SEI components based on the criteria we present in this work.

Conclusions

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This work showcases the complex chemical interactions among LiPF6, electrolyte solvent, and lithium metal. The hexafluorophosphate structures that directly contact the Li metal surface easily experience further lithiation at the electrolyte–lithium–metal interface, where electrons are available for further reduction. The early-stage pathways and reaction rates of such interfacial dissociations are dependent on the regional lithium metal morphology. According to the continuum modeling, strong solvation effects and high lithiation degrees are assistive toward the decomposition thermochemistry. Energy barriers are flatter in a higher dielectric environment. In the solution phase, the electrolyte-dissolved hexafluorophosphate species is partially protected from complete degradation by limited lithiation and charge-transfer rates. Nonetheless, the dual-lithiated species [Li2PF6]+ can still be incompletely reduced via electron tunneling without being adsorbed to the lithium surface. This partial decomposition is caused by elevated ionicity and destabilized electronic configurations of P–F bonding properties in the reduced and multilithiated structures.
The interfacial LiPF6 degradation rate is associated with the porosity and density of the SEI initial layer. Techniques, including the surface modification for Li(110) facet exposure and pretreatments using high-dielectric LiPF6-containing solutions, would benefit the formation of a dense LiF layer on lithium metal. The detailed mechanistic and thermodynamic information can be incorporated into coarse-grained kMC simulations for the understanding of SEI evolution processes on a larger time and length scale.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpcc.2c07838.

  • Details of charge distribution, atomic coordinates, energetics, etc. are available in the docx file. This information includes a stepwise free energy table for LiPF6 dissociation; chronological Bader charge analysis of the electron-tunneling-induced [Li2PF6]+ partial dissociation; lithium cation affinity energetics; Bader charge analysis of key AIMD frames of DME-DOL-solvated system; chronological Bader charge analysis of [LiPF6] and [PF6]− interfacial degradations; significant events in forming metastable [Li2PF6]− structures in EC–VC and DME-DOL electrolytes; free energy profiles of LiPF6 decomposition in different implicit solvation environments; detailed energetics of species involved in LiPF6 decomposition pathways; and Cartesian coordinates of important structures (PDF)

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Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Author Information

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  • Corresponding Author
    • Perla B. Balbuena - Department of Chemical Engineering, Texas A&M University, College Station, Texas 77843, United States;  Department of Chemistry, Texas A&M University, College Station, Texas 77843, United States;  Department of Materials Science and Engineering, Texas A&M University, College Station, Texas 77843, United States;  Orcidhttps://orcid.org/0000-0002-2358-3910;  Email: [email protected]
  • Author
    • Dacheng Kuai - Department of Chemical Engineering, Texas A&M University, College Station, Texas 77843, United States;  Department of Chemistry, Texas A&M University, College Station, Texas 77843, United States;  Orcidhttps://orcid.org/0000-0002-4787-7331
  • Author Contributions

    The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

  • Funding

    US Department of Energy Contract DE-AC02-05CH11357.

  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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The authors acknowledge the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy, through the US-Germany Cooperation on Energy Storage under Contract DE-AC02-05CH11357. Computational resources from the Texas A&M University High Performance Research Computing are gratefully acknowledged. The valuable discussions with Dr. Ulrike Krewer and Janika Wagner are appreciated.

Abbreviations

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SEI

solid electrolyte interphase
LiPF6

lithium hexafluorophosphate
LMB

lithium metal battery
LiFSI

bis(fluorosulfonyl)imide
FEC

fluoroethylene carbonate
AIMD

ab initio molecular dynamics
DME

dimethoxyethane
DOL

1,3-dioxolane
ε

dielectric constants
EC

ethylene carbonate
PC

propylene carbonate
VC

vinylene carbonate
MD

molecular dynamics
kMC

kinetic Monte Carlo
EDC

ethylene di-carbonate
SMD

solvation model based on density
PBE

Perdew–Burke–Ernzerhof
GGA

generalized gradient approximation
PAW

projector augmented wave

References

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    The passivity of lithium electrodes in liquid electrolytes for secondary batteries
    He, Xin; Bresser, Dominic; Passerini, Stefano; Baakes, Florian; Krewer, Ulrike; Lopez, Jeffrey; Mallia, Christopher Thomas; Shao-Horn, Yang; Cekic-Laskovic, Isidora; Wiemers-Meyer, Simon; Soto, Fernando A.; Ponce, Victor; Seminario, Jorge M.; Balbuena, Perla B.; Jia, Hao; Xu, Wu; Xu, Yaobin; Wang, Chongmin; Horstmann, Birger; Amine, Rachid; Su, Chi-Cheung; Shi, Jiayan; Amine, Khalil; Winter, Martin; Latz, Arnulf; Kostecki, Robert
    Nature Reviews Materials (2021), 6 (11), 1036-1052CODEN: NRMADL; ISSN:2058-8437. (Nature Portfolio)
    Abstr.: Rechargeable Li metal batteries are currently limited by safety concerns, continuous electrolyte decompn. and rapid consumption of Li. These issues are mainly related to reactions occurring at the Li metal-liq. electrolyte interface. The formation of a passivation film (i.e., a solid electrolyte interphase) dets. ionic diffusion and the structural and morphol. evolution of the Li metal electrode upon cycling. In this Review, we discuss spontaneous and operation-induced reactions at the Li metal-electrolyte interface from a corrosion science perspective. We highlight that the instantaneous formation of a thin protective film of corrosion products at the Li surface, which acts as a barrier to further chem. reactions with the electrolyte, precedes film reformation, which occurs during subsequent electrochem. stripping and plating of Li during battery operation. Finally, we discuss solns. to overcoming remaining challenges of Li metal batteries related to Li surface science, electrolyte chem., cell engineering and the intrinsic instability of the Li metal-electrolyte interface.
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  4. 4
    Jang, E. K.; Ahn, J.; Yoon, S.; Cho, K. Y. High Dielectric, Robust Composite Protective Layer for Dendrite-Free and Lipf6 Degradation-Free Lithium Metal Anode. Adv. Funct. Mater. 2019, 29, 1905078  DOI: 10.1002/adfm.201905078
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    4
    High Dielectric, Robust Composite Protective Layer for Dendrite-Free and LiPF6 Degradation-Free Lithium Metal Anode
    Jang, Eun Kwang; Ahn, Jinhyeok; Yoon, Sukeun; Cho, Kuk Young
    Advanced Functional Materials (2019), 29 (48), 1905078CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The development of lithium metal anodes for next generation batteries remains a challenge. Uncontrolled Li dendrite growth not only induces severe safety issues but also leads to capacity fading by continuously consuming the electrolyte. This study demonstrates the design and fabrication of a composite protective layer composed of a high dielec. polymer, inorg. particles, and an electrolyte to overcome these obstacles. This layer not only suppresses dendrite growth, but also prevents LiPF6 degrdn. The electrolyte introduced in the protective layer remains within the coating layer after solvent removal and acts as an ion transport channel at the interface. This enables the protective layer to exhibit high ionic cond. and mech. strength. The composite protective layer, which exhibits synergistic soft-rigid characteristics, is placed on the Li metal anode and facilitates superior interfacial stability during long-term cycles. LiMn2O4/coated lithium full cells using the composite protective layer show a superior rate capability and enhanced capacity retention compared to the cells using a bare lithium anode. The proposed strategy opens new avenues to fabricate a sustainable composite protective layer that affords superior performance in lithium metal batteries.
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  5. 5
    Peled, E.; Menkin, S. Review─SEI: Past, Present and Future. J. Electrochem. Soc. 2017, 164, A1703– A1719,  DOI: 10.1149/2.1441707jes
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    5
    Review-SEI: Past, Present and Future
    Peled, E.; Menkin, S.
    Journal of the Electrochemical Society (2017), 164 (7), A1703-A1719CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)
    The Solid-Electrolyte-Interphase (SEI) model for non-aq. alkali-metal batteries constitutes a paradigm change in the understanding of lithium batteries and has thus enabled the development of safer, durable, higher-power and lower-cost lithium batteries for portable and EV applications. Prior to the publication of the SEI model (1979), researchers used the Butler-Volmer equation, in which a direct electron transfer from the electrode to lithium cations in the soln. is assumed. The SEI model proved that this is a mistaken concept and that, in practice, the transfer of electrons from the electrode to the soln. in a lithium battery, must be prevented, since it will result in fast self-discharge of the active materials and poor battery performance. This model provides [E. Peled, in "Lithium Batteries," J.P. Gabano (ed), Academic Press, (1983), E. Peled, J. Electrochem. Soc., 126, 2047 (1979).] new equations for: electrode kinetics (io and b), anode corrosion, SEI resistivity and growth rate and irreversible capacity loss of lithium-ion batteries. This model became a cornerstone in the science and technol. of lithium batteries. This paper reviews the past, present and the future of SEI batteries.
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  6. 6
    Yu, Z.; Rudnicki, P. E.; Zhang, Z. Rational Solvent Molecule Tuning for High-Performance Lithium Metal Battery Electrolytes. Nat. Energy 2022, 7, 94– 106,  DOI: 10.1038/s41560-021-00962-y
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    6
    Rational solvent molecule tuning for high-performance lithium metal battery electrolytes
    Yu, Zhiao; Rudnicki, Paul E.; Zhang, Zewen; Huang, Zhuojun; Celik, Hasan; Oyakhire, Solomon T.; Chen, Yuelang; Kong, Xian; Kim, Sang Cheol; Xiao, Xin; Wang, Hansen; Zheng, Yu; Kamat, Gaurav A.; Kim, Mun Sek; Bent, Stacey F.; Qin, Jian; Cui, Yi; Bao, Zhenan
    Nature Energy (2022), 7 (1), 94-106CODEN: NEANFD; ISSN:2058-7546. (Nature Portfolio)
    Electrolyte engineering improved cycling of Li metal batteries and anode-free cells at low current densities; however, high-rate capability and tuning of ionic conduction in electrolytes are desirable yet less-studied. Here, we design and synthesize a family of fluorinated-1,2-diethoxyethanes as electrolyte solvents. The position and amt. of F atoms functionalized on 1,2-diethoxyethane were found to greatly affect electrolyte performance. Partially fluorinated, locally polar -CHF2 is identified as the optimal group rather than fully fluorinated -CF3 in common designs. Paired with 1.2 M lithium bis(fluorosulfonyl)imide, these developed single-salt-single-solvent electrolytes simultaneously enable high cond., low and stable overpotential, >99.5% Li||Cu half-cell efficiency (up to 99.9%, ±0.1% fluctuation) and fast activation (Li efficiency >99.3% within two cycles). Combined with high-voltage stability, these electrolytes achieve roughly 270 cycles in 50-μm-thin Li||high-loading-NMC811 full batteries and >140 cycles in fast-cycling Cu||microparticle-LiFePO4 industrial pouch cells under realistic testing conditions. The correlation of Li+-solvent coordination, solvation environments and battery performance is investigated to understand structure-property relationships.
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  7. 7
    Li, Y.; Li, Y.; Pei, A. Atomic Structure of Sensitive Battery Materials and Interfaces Revealed by Cryo-Electron Microscopy. Science 2017, 358, 506– 510,  DOI: 10.1126/science.aam6014
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    7
    Atomic structure of sensitive battery materials and interfaces revealed by cryo-electron microscopy
    Li, Yuzhang; Li, Yanbin; Pei, Allen; Yan, Kai; Sun, Yongming; Wu, Chun-Lan; Joubert, Lydia-Marie; Chin, Richard; Koh, Ai Leen; Yu, Yi; Perrino, John; Butz, Benjamin; Chu, Steven; Cui, Yi
    Science (Washington, DC, United States) (2017), 358 (6362), 506-510CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
    Whereas std. transmission electron microscopy studies are unable to preserve the native state of chem. reactive and beam-sensitive battery materials after operation, such materials remain pristine at cryogenic conditions. It is then possible to atomically resolve individual Li metal atoms and their interface with the solid electrolyte interphase (SEI). We observe that dendrites in carbonate-based electrolytes grow along the <111> (preferred), <110>, or <211> directions as faceted, single-cryst. nanowires. These growth directions can change at kinks with no observable crystallog. defect. We reveal distinct SEI nanostructures formed in different electrolytes.
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  8. 8
    Zhang, Y.; Viswanathan, V. Not All Fluorination Is the Same: Unique Effects of Fluorine Functionalization of Ethylene Carbonate for Tuning Solid-Electrolyte Interphase in Li Metal Batteries. Langmuir 2020, 36, 11450– 11466,  DOI: 10.1021/acs.langmuir.0c01652
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    8
    Not All Fluorination Is the Same: Unique Effects of Fluorine Functionalization of Ethylene Carbonate for Tuning Solid-Electrolyte Interphase in Li Metal Batteries
    Zhang, Yumin; Viswanathan, Venkatasubramanian
    Langmuir (2020), 36 (39), 11450-11466CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
    Li metal batteries (LMBs) are crucial for electrifying transportation and aviation. Engineering electrolytes to form desired solid-electrolyte interphase (SEI) is one of the most promising approaches to enable stable long-lasting LMBs. Among the liq. electrolytes explored, fluoroethylene carbonate (FEC) has seen great success in leading to desirable SEI properties for enabling stable cycling of LMBs. Given the many facets to desirable SEI properties, numerous descriptors and mechanisms have been proposed. To build a detailed mechanistic understanding, we analyze varying degrees of fluorination of the same prototype mol., chosen to be ethylene carbonate (EC) to tease out the interfacial reactivity at the Li metal/electrolyte. Using d. functional theory (DFT) calcns., we study the effect of mono-, di-, tri-, and tetra-fluorine substitutions of EC on its reactivity with Li surface facets in the presence and absence of Li salt. We find that the formation of LiF at the early stage of SEI formation, posited as a desirable SEI component, depends on the F-abstraction mechanism rather than the no. of fluorine substitution. The best illustrations of this are cis- and trans-difluoro ECs, where F-abstraction is spontaneous with the trans case, while the cis case needs to overcome a nonzero energy barrier. Using a Pearson correlation map, we find that the extent of initial chem. decompn. quantified by the assocd. reaction free energy is linearly correlated with the charge transferred from the Li surface and the no. of covalent-like bonds formed at the surface. The effect of salt and the surface facet have a much weaker role in detg. the decompns. at the immediate electrolyte/electrode interfaces. Putting all of this together, we find that tetra-FEC could act as a high-performing SEI modifier as it leads to a more homogeneous, denser LiF-contg. SEI. Using this methodol., future investigations will explore -CF3 functionalization and other backbone mols. (linear carbonates).
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  9. 9
    Hobold, G. M.; Lopez, J.; Guo, R.; Minafra, N.; Banerjee, A.; Shirley Meng, Y.; Shao-Horn, Y.; Gallant, B. M. Moving Beyond 99.9% Coulombic Efficiency for Lithium Anodes in Liquid Electrolytes. Nat. Energy 2021, 6, 951– 960,  DOI: 10.1038/s41560-021-00910-w
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    9
    Moving beyond 99.9% Coulombic efficiency for lithium anodes in liquid electrolytes
    Hobold, Gustavo M.; Lopez, Jeffrey; Guo, Rui; Minafra, Nicolo; Banerjee, Abhik; Shirley Meng, Y.; Shao-Horn, Yang; Gallant, Betar M.
    Nature Energy (2021), 6 (10), 951-960CODEN: NEANFD; ISSN:2058-7546. (Nature Portfolio)
    A review. As Li-ion battery costs decrease, energy d. and thus driving range remains a roadblock for mass-market vehicle electrification. While Li-metal anodes help achieve Department of Energy targets of 500 Wh kg-1 (750 Wh l-1), Li Coulombic efficiencies fall below the 99.95+% required for 1,000+ cycles. Here we examine historical electrolyte developments underlying increased Coulombic efficiency and discuss emerging frameworks that support rational strategies to move beyond 99.9%. While multiple electrolytes reach 98-99% Coulombic efficiency over subsets of cycles, achieving >99.9% Coulombic efficiency consistently throughout cycling is an as yet unmet challenge. We analyze important interplays between electrolyte, solid electrolyte interphase compn., plating-stripping kinetics and Li morphol., many of which are only recently being quantified exptl. at the Li interface, and which collectively det. Coulombic efficiency. We also discuss forward-looking strategies that, if mastered, represent new opportunities to refine understanding and support new record values of Coulombic efficiency in the coming years.
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  10. 10
    Tarascon, J. M.; Armand, M. Issues and Challenges Facing Rechargeable Lithium Batteries. Nature 2001, 414, 359– 367,  DOI: 10.1038/35104644
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    10
    Issues and challenges facing rechargeable lithium batteries
    Tarascon, J.-M.; Armand, M.
    Nature (London, United Kingdom) (2001), 414 (6861), 359-367CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)
    A review of the development of lithium-based rechargeable batteries. Ongoing research strategies are highlighted, and the challenges that remain regarding the synthesis, characterization, electrochem. performance, and safety of these systems are discussed.
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  11. 11
    Kuai, D.; Balbuena, P. B. Solvent Degradation and Polymerization in the Li-Metal Battery: Organic-Phase Formation in Solid-Electrolyte Interphases. ACS Appl. Mater. Interfaces 2022, 14, 2817– 2824,  DOI: 10.1021/acsami.1c20487
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    11
    Solvent Degradation and Polymerization in the Li-Metal Battery: Organic-Phase Formation in Solid-Electrolyte Interphases
    Kuai, Dacheng; Balbuena, Perla B.
    ACS Applied Materials & Interfaces (2022), 14 (2), 2817-2824CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    The products of solvent polymn. and degrdn. are crucial components of the Li-metal battery solid-electrolyte interphase. However, in-depth mechanistic studies of these reactions are still scarce. Here, we model the polymn. of common lithium battery electrolyte solvents-ethylene carbonate (EC) and vinylene carbonate (VC)-near the anode surface. Being consistent with the mol. calcn., ab initio mol. dynamic (AIMD) simulations reveal fast solvent decompns. upon contact with the Li anode. Addnl., we assessed the thermochem. impacts of decarboxylation reactions as well as the lithium bonding with reaction intermediates. In both EC and VC polymn. pathways, lithium bonding demonstrated profound catalytic effects while different degrees of decarboxylation were obsd. The VC polymn. pathways with and without ring-opening events were evaluated systematically, and the latter one which leads to poly(VC) formation was proven to dominate the oligomerization process. Both the decompn. and polymn. reactivities of VC are found to be higher than EC, while the cross-coupling between EC and VC has an even lower-energy barrier. These findings are in good agreement with exptl. evidence and explanatory toward the enhanced performance of VC-added lithium-metal batteries.
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  12. 12
    Shi, S.; Lu, P.; Liu, Z.; Qi, Y.; Hector, L. G., Jr.; Li, H.; Harris, S. J. Direct Calculation of Li-Ion Transport in the Solid Electrolyte Interphase. J. Am. Chem. Soc. 2012, 134, 15476– 15487,  DOI: 10.1021/ja305366r
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    12
    Direct Calculation of Li-Ion Transport in the Solid Electrolyte Interphase
    Shi, Siqi; Lu, Peng; Liu, Zhongyi; Qi, Yue; Hector, Louis G.; Li, Hong; Harris, Stephen J.
    Journal of the American Chemical Society (2012), 134 (37), 15476-15487CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    The mechanism of Li+ transport through the solid electrolyte interphase (SEI), a passivating film on electrode surfaces, has never been clearly elucidated despite its overwhelming importance to Li-ion battery operation and lifetime. The present paper develops a multiscale theor. methodol. to reveal the mechanism of Li+ transport in a SEI film. The methodol. incorporates the boundary conditions of the first direct diffusion measurements on a model SEI consisting of porous (outer) org. and dense (inner) inorg. layers (similar to typical SEI films). New exptl. evidence confirms that the inner layer in the ∼20 nm thick model SEI is primarily cryst. Li2CO3. Using d. functional theory, we first detd. that the dominant diffusion carrier in Li2CO3 below the voltage range of SEI formation is excess interstitial Li+. This diffuses via a knock-off mechanism to maintain higher O-coordination, rather than direct-hopping through empty spaces in the Li2CO3 lattice. Mesoscale diffusion equations were then formulated upon a new two-layer/two-mechanism model: pore diffusion in the outer layer and knock-off diffusion in the inner layer. This diffusion model predicted the unusual isotope ratio 6Li+/7Li+ profile measured by TOF-SIMS, which increases from the SEI/electrolyte surface and peaks at a depth of 5 nm, and then gradually decreases within the dense layer. With no fitting parameters, our approach is applicable to model general transport properties, such as ionic cond., for SEI films on the surface of other electrodes, from the at. scale to the mesoscale, as well as aging phenomenon.
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  13. 13
    Zhang, Z.; Li, Y.; Xu, R. Capturing the Swelling of Solid-Electrolyte Interphase in Lithium Metal Batteries. Science 2022, 375, 66– 70,  DOI: 10.1126/science.abi8703
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    13
    Capturing the swelling of solid-electrolyte interphase in lithium metal batteries
    Zhang, Zewen; Li, Yuzhang; Xu, Rong; Zhou, Weijiang; Li, Yanbin; Oyakhire, Solomon T.; Wu, Yecun; Xu, Jinwei; Wang, Hansen; Yu, Zhiao; Boyle, David T.; Huang, William; Ye, Yusheng; Chen, Hao; Wan, Jiayu; Bao, Zhenan; Chiu, Wah; Cui, Yi
    Science (Washington, DC, United States) (2022), 375 (6576), 66-70CODEN: SCIEAS; ISSN:1095-9203. (American Association for the Advancement of Science)
    Although liq.-solid interfaces are foundational in broad areas of science, characterizing this delicate interface remains inherently difficult because of shortcomings in existing tools to access liq. and solid phases simultaneously at the nanoscale. This leads to substantial gaps in our understanding of the structure and chem. of key interfaces in battery systems. We adopt and modify a thin film vitrification method to preserve the sensitive yet crit. interfaces in batteries at native liq. electrolyte environments to enable cryo-electron microscopy and spectroscopy. We report substantial swelling of the solid-electrolyte interphase (SEI) on lithium metal anode in various electrolytes. The swelling behavior is dependent on electrolyte chem. and is highly correlated to battery performance. Higher degrees of SEI swelling tend to exhibit poor electrochem. cycling.
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  14. 14
    Qian, Y.; Hu, S.; Zou, X. How Electrolyte Additives Work in Li-Ion Batteries. Energy Storage Mater. 2019, 20, 208– 215,  DOI: 10.1016/j.ensm.2018.11.015
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    Yu, Y.; Karayaylali, P.; Katayama, Y.; Giordano, L.; Gauthier, M.; Maglia, F.; Jung, R.; Lund, I.; Shao-Horn, Y. Coupled Lipf6 Decomposition and Carbonate Dehydrogenation Enhanced by Highly Covalent Metal Oxides in High-Energy Li-Ion Batteries. J. Phys. Chem. C. 2018, 122, 27368– 27382,  DOI: 10.1021/acs.jpcc.8b07848
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    15
    Coupled LiPF6 Decomposition and Carbonate Dehydrogenation Enhanced by Highly Covalent Metal Oxides in High-Energy Li-Ion Batteries
    Yu, Yang; Karayaylali, Pinar; Katayama, Yu; Giordano, Livia; Gauthier, Magali; Maglia, Filippo; Jung, Roland; Lund, Isaac; Shao-Horn, Yang
    Journal of Physical Chemistry C (2018), 122 (48), 27368-27382CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
    The (electro)chem. reactions between pos. electrodes and electrolytes are not well understood. The oxidn. is examd. of a LiPF6-based electrolyte with ethylene carbonate (EC) with layered lithium nickel, manganese, and cobalt oxides (NMC). D. functional theory calcns. showed that the driving force for EC dehydrogenation on oxides, yielding surface protic species, increased with greater Ni content in NMC. Ex situ IR and Raman spectroscopy revealed exptl. evidence for EC dehydrogenation on charged NMC surfaces. Protic species on charged NMC surfaces from EC dehydrogenation could further react with LiPF6 to generate less-coordinated F species such as PF3O-like and lithium nickel oxyfluoride species on charged NMC particles and HF and PF2O2- in the electrolyte. Larger degree of salt decompn. was coupled with increasing EC dehydrogenation on charged NMC with increasing Ni or lithium deintercalation. An oxide-mediated chem. oxidn. of electrolytes was proposed, providing new insights in stabilizing high-energy pos. electrodes and improving Li-ion battery cycle life.
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  16. 16
    Kuai, D.; Cheng, H.; Kuan, K.-Y.; Yan, X. Accelerated Five-Component Spiro-Pyrrolidine Construction at the Air–Liquid Interface. Chem. Commun. 2021, 57, 3757– 3760,  DOI: 10.1039/D1CC00574J
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    16
    Accelerated five-component spiro-pyrrolidine construction at the air-liquid interface
    Kuai, Dacheng; Cheng, Heyong; Kuan, Kai-Yuan; Yan, Xin
    Chemical Communications (Cambridge, United Kingdom) (2021), 57 (31), 3757-3760CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
    Multi-component reactions assemble complex mols. in a highly effective way, however, they often suffer from long reaction times. We demonstrate that acceleration of a five-component spiro-pyrrolidine construction can be achieved in microdroplets and thin films. The deposition method and mild heating are crucial factors for product formation. Three key intermediates were captured by mass spectrometry to elucidate the tandem reaction mechanism. We also found that hydrogen bonding can significantly flatten the energy barrier at the air-liq. interface.
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  17. 17
    Yao, N.; Chen, X.; Fu, Z.-H.; Zhang, Q. Applying Classical, Ab Initio, and Machine-Learning Molecular Dynamics Simulations to the Liquid Electrolyte for Rechargeable Batteries. Chem. Rev. 2022, 122, 10970– 11021,  DOI: 10.1021/acs.chemrev.1c00904
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    17
    Applying Classical, Ab Initio, and Machine-Learning Molecular Dynamics Simulations to the Liquid Electrolyte for Rechargeable Batteries
    Yao, Nan; Chen, Xiang; Fu, Zhong-Heng; Zhang, Qiang
    Chemical Reviews (Washington, DC, United States) (2022), 122 (12), 10970-11021CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    A review. Rechargeable batteries have become indispensable implements in our daily life and are considered a promising technol. to construct sustainable energy systems in the future. The liq. electrolyte is one of the most important parts of a battery and is extremely crit. in stabilizing the electrode-electrolyte interfaces and constructing safe and long-life-span batteries. Tremendous efforts have been devoted to developing new electrolyte solvents, salts, additives, and recipes, where mol. dynamics (MD) simulations play an increasingly important role in exploring electrolyte structures, physicochem. properties such as ionic cond., and interfacial reaction mechanisms. This review affords an overview of applying MD simulations in the study of liq. electrolytes for rechargeable batteries. First, the fundamentals and recent theor. progress in three-class MD simulations are summarized, including classical, ab initio, and machine-learning MD simulations (section 2). Next, the application of MD simulations to the exploration of liq. electrolytes, including probing bulk and interfacial structures (section 3), deriving macroscopic properties such as ionic cond. and dielec. const. of electrolytes (section 4), and revealing the electrode-electrolyte interfacial reaction mechanisms (section 5), are sequentially presented. Finally, a general conclusion and an insightful perspective on current challenges and future directions in applying MD simulations to liq. electrolytes are provided. Machine-learning technologies are highlighted to figure out these challenging issues facing MD simulations and electrolyte research and promote the rational design of advanced electrolytes for next-generation rechargeable batteries.
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  18. 18
    Dhattarwal, H. S.; Kuo, J.-L.; Kashyap, H. K. Mechanistic Insight on the Stability of Ether and Fluorinated Ether Solvent-Based Lithium Bis(Fluoromethanesulfonyl) Electrolytes near Li Metal Surface. J. Phys. Chem. C. 2022, 126, 8953– 8963,  DOI: 10.1021/acs.jpcc.2c02323
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    18
    Mechanistic Insight on the Stability of Ether and Fluorinated Ether Solvent-Based Lithium Bis(fluoromethanesulfonyl) Electrolytes near Li Metal Surface
    Dhattarwal, Harender S.; Kuo, Jer-Lai; Kashyap, Hemant K.
    Journal of Physical Chemistry C (2022), 126 (20), 8953-8963CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
    Recently, ether-based solvents and their fluorinated derivs. have shown extraordinary ability to facilitate the formation of a highly stable ultrathin solid-electrolyte interphase (SEI) layer in lithium metal batteries (LMBs). Herein, d. functional theory based mol. dynamics (DFT-MD) simulations have been performed to provide a mechanistic insight on the stability of Li-bis(fluoromethanesulfonyl)imide ([Li][FSI]) salt dissolved in dimethoxybutane (DMB) and fluorinated dimethoxybutane (FDMB) solvents near the surface of lithium metal which is employed as anode in LMBs. It is obsd. that because of the strong reducing nature of Li, the FSI anions in both of the electrolytes readily dissoc. to form LiF, Li2O, and other species. Our anal. reveals that while the DMB mols. in the [Li][FSI]-DMB system are relatively stable against reductive dissocn., the FDMB mols. in the [Li][FSI]-FDMB system easily undergo reductive dissocn. upon charge transfer from the Li surface. It is shown that the SF bonds of the FSI anions and CF bonds of FDMB mols. are the first ones to break upon their exposure to the Li metal surface. It is obsd. that the dissocd. species of [Li][FSI]-FDMB electrolyte cover the Li surface completely, preventing further dissocn. of other FSI anions and solvent mols. It is found that the FDMB dissocn. majorly contributes F atoms forming addnl. LiF which is an essential component for the formation of a uniform and robust SEI.
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  19. 19
    Yamijala, S. S. R. K. C.; Kwon, H.; Guo, J.; Wong, B. M. Stability of Calcium Ion Battery Electrolytes: Predictions from Ab Initio Molecular Dynamics Simulations. ACS Appl. Mater. Interfaces 2021, 13, 13114– 13122,  DOI: 10.1021/acsami.0c21716
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    19
    Stability of Calcium Ion Battery Electrolytes: Predictions from Ab Initio Molecular Dynamics Simulations
    Yamijala, Sharma S. R. K. C.; Kwon, Hyuna; Guo, Juchen; Wong, Bryan M.
    ACS Applied Materials & Interfaces (2021), 13 (11), 13114-13122CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    Multivalent batteries, such as magnesium-ion, calcium-ion, and zinc-ion batteries, have attracted significant attention as next-generation electrochem. energy storage devices to complement conventional lithium-ion batteries (LIBs). Among them, calcium-ion batteries (CIBs) are the least explored due to difficult reversible Ca deposition-dissoln. In this work, we examd. the stability of four different Ca salts with weakly coordinating anions and three different solvents commonly employed in existing battery technologies to identify suitable candidates for CIBs. By employing Born-Oppenheimer mol. dynamics (BOMD) simulations on salt-Ca and solvent-Ca interfaces, we find that the tetraglyme solvent and carborane salt are promising candidates for CIBs. Due to the strong reducing nature of the calcium surface, the other salts and solvents readily decomp. We explain the microscopic mechanisms of salt/solvent decompn. on the Ca surface using time-dependent projected d. of states, time-dependent charge-transfer plots, and climbing-image nudged elastic band calcns. Collectively, this work presents the first mechanistic assessment of the dynamical stability of candidate salts and solvents on a Ca surface using BOMD simulations, and provides a predictive path toward designing stable electrolytes for CIBs.
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  20. 20
    Martinez de la Hoz, J. M.; Soto, F. A.; Balbuena, P. B. Effect of the Electrolyte Composition on Sei Reactions at Si Anodes of Li-Ion Batteries. J. Phys. Chem. C. 2015, 119, 7060– 7068,  DOI: 10.1021/acs.jpcc.5b01228
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    20
    Effect of the Electrolyte Composition on SEI Reactions at Si Anodes of Li-Ion Batteries
    Martinez de la Hoz, Julibeth M.; Soto, Fernando A.; Balbuena, Perla B.
    Journal of Physical Chemistry C (2015), 119 (13), 7060-7068CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
    Solid-electrolyte interphase (SEI) layers formed at the surface of Si anodes due to reductive decompn. of the electrolyte components are partially responsible of the irreversible capacity loss that neg. affects battery performance. The authors use ab initio mol. dynamics simulations to study how the electrolyte compn. including org. carbonates and LiPF6 affects such reactions. Solvent polarity defines salt dissocn., and there is a competition between salt and solvent/additive dissocn. The salt anion decomps., yielding a PF3 group and 3 F- anions. The PF3 group is relatively stable, but after some time, it decomps. nucleating on the anode surface as LiF. During anion decompn. the P atom progressively reduces finally becoming coupled to a surface atom or to fragments of the solvent/additive decompn. that takes place prior or simultaneously with the salt decompn. New pathways are found for formation of CO2 from vinylene carbonate reaction with the surface and for nucleation of Li oxide precursors.
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  21. 21
    Galvez-Aranda, D. E.; Seminario, J. M. Li-Metal Anode in a Conventional Li-Ion Battery Electrolyte: Solid Electrolyte Interphase Formation Using Ab Initio Molecular Dynamics. J. Electrochem. Soc. 2022, 169, 030502  DOI: 10.1149/1945-7111/ac55c8
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    21
    Li-metal anode in a conventional Li-ion battery electrolyte: solid electrolyte interphase formation using ab initio molecular dynamics
    Galvez-Aranda, Diego E.; Seminario, Jorge M.
    Journal of the Electrochemical Society (2022), 169 (3), 030502CODEN: JESOAN; ISSN:1945-7111. (IOP Publishing Ltd.)
    Ab initio mol. dynamics simulations were performed for Li+ conducting electrolytes based on 1M lithium hexafluorophosphate (Li+PF-6) in ethylene carbonate (EC)-ethylmethyl carbonate (EMC) (3:7wt) with 5 wt% vinylene carbonate (VC) in contact with Li-metal (electrode), finding a variety of products due to dissocns. of all electrolyte components. The formed solid electrolyte interphase from electrolyte degrdn. arranges in an outer layer composed of denser materials (sitting over the anode surface) such as Li2(CH2O)2 from EC, Li2CO3, Li2C2H2 and Li2CO2 from VC, and Li2C3H5O2 and LiCH3O from EMC dissocns. Then follows an inner layer made of Li-binary compds., Li3CO, Li2O and Li3C from EC, Li2O, Li2C2 and LiH from VC, and LiF and Li3P from PF-6 dissocns. We calcd. electron affinities of electrolyte mols. during their decompn. using a polarizable continuum model to consider solvent effects mols. degrdn. PF-6 has the highest first and second electron affinities, despite explicit Coulomb repulsion, which eventually dissocs. the mol. right after capturing an electron from the metal-anode; therefore, PF-6 is also the fastest to dissoc. EMC has the lowest first and second electron affinities, thus it is the least prone to accept electrons and the least likely to dissoc. at the Li-metal interface.
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  22. 22
    Yao, N.; Chen, X.; Shen, X.; Zhang, R.; Fu, Z.-H.; Ma, X.-X.; Zhang, X.-Q.; Li, B.-Q.; Zhang, Q. An Atomic Insight into the Chemical Origin and Variation of Dielectric Constant in Liquid Electrolytes. Angew. Chem., Int. Ed. 2021, 60, 21473– 21478,  DOI: 10.1002/anie.202107657
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    22
    An Atomic Insight into the Chemical Origin and Variation of the Dielectric Constant in Liquid Electrolytes
    Yao, Nan; Chen, Xiang; Shen, Xin; Zhang, Rui; Fu, Zhong-Heng; Ma, Xia-Xia; Zhang, Xue-Qiang; Li, Bo-Quan; Zhang, Qiang
    Angewandte Chemie, International Edition (2021), 60 (39), 21473-21478CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The dielec. const. is a crucial physicochem. property of liqs. in tuning solute-solvent interactions and solvation microstructures. Herein the dielec. const. variation of liq. electrolytes regarding to temps. and electrolyte compns. is probed by mol. dynamics simulations. Dielec. consts. of solvents reduce as temps. increase due to accelerated mobility of mols. For solvent mixts. with different mixing ratios, their dielec. consts. either follow a linear superposition rule or satisfy a polynomial function, depending on weak or strong intermol. interactions. Dielec. consts. of electrolytes exhibit a volcano trend with increasing salt concns., which can be attributed to dielec. contributions from salts and formation of solvation structures. This work affords an at. insight into the dielec. const. variation and its chem. origin, which can deepen the fundamental understanding of soln. chem.
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  23. 23
    Ren, X.; Zou, L.; Jiao, S. High-Concentration Ether Electrolytes for Stable High-Voltage Lithium Metal Batteries. ACS Energy Lett. 2019, 4, 896– 902,  DOI: 10.1021/acsenergylett.9b00381
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    High-Concentration Ether Electrolytes for Stable High-Voltage Lithium Metal Batteries
    Ren, Xiaodi; Zou, Lianfeng; Jiao, Shuhong; Mei, Donghai; Engelhard, Mark H.; Li, Qiuyan; Lee, Hongkyung; Niu, Chaojiang; Adams, Brian D.; Wang, Chongmin; Liu, Jun; Zhang, Ji-Guang; Xu, Wu
    ACS Energy Letters (2019), 4 (4), 896-902CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)
    High-voltage (>4.3 V) rechargeable lithium (Li) metal batteries (LMBs) face huge obstacles due to the high reactivity of Li metal with traditional electrolytes. Despite their good stability with Li metal, conventional ether-based electrolytes are typically used only in <4.0 V LMBs because of their limited oxidn. stability. Here we report high-concn. ether electrolytes that can induce the formation of a unique cathode electrolyte interphase via the synergy between the salt and the ether solvent, which effectively stabilizes the catalytically active cathodes and preserves their structural integrity under high voltages. Eventually, LMBs can retain 92% capacity after 500 cycles at 4.3 V with limited Li consumption. More importantly, such ether electrolytes enable stable battery cycling not only under voltages as high as 4.5 V but also on highly demanding Ni-rich layered cathodes. These findings significantly expand knowledge of ether electrolytes and provide new perspectives of electrolyte design for high-energy-d. LMBs.
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    Jiao, S.; Ren, X.; Cao, R. Stable Cycling of High-Voltage Lithium Metal Batteries in Ether Electrolytes. Nat. Energy 2018, 3, 739– 746,  DOI: 10.1038/s41560-018-0199-8
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    Stable cycling of high-voltage lithium metal batteries in ether electrolytes
    Jiao, Shuhong; Ren, Xiaodi; Cao, Ruiguo; Engelhard, Mark H.; Liu, Yuzi; Hu, Dehong; Mei, Donghai; Zheng, Jianming; Zhao, Wengao; Li, Qiuyan; Liu, Ning; Adams, Brian D.; Ma, Cheng; Liu, Jun; Zhang, Ji-Guang; Xu, Wu
    Nature Energy (2018), 3 (9), 739-746CODEN: NEANFD; ISSN:2058-7546. (Nature Research)
    The key to enabling long-term cycling stability of high-voltage lithium (Li) metal batteries is the development of functional electrolytes that are stable against both Li anodes and high-voltage (above 4 V vs. Li/Li+) cathodes. Due to their limited oxidative stability ( <4 V), ethers have so far been excluded from being used in high-voltage batteries, in spite of their superior reductive stability against Li metal compared to conventional carbonate electrolytes. Here, we design a concd. dual-salt/ether electrolyte that induces the formation of stable interfacial layers on both a high-voltage LiNi1/3Mn1/3Co1/3O2 cathode and the Li metal anode, thus realizing a capacity retention of >90% over 300 cycles and ∼80% over 500 cycles with a charge cut-off voltage of 4.3 V. This study offers a promising approach to enable ether-based electrolytes for high-voltage Li metal battery applications.
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    Rostkier-Edelstein, D.; Urbakh, M.; Nitzan, A. Electron Tunneling through a Dielectric Barrier. J. Chem. Phys. 1994, 101, 8224– 8237,  DOI: 10.1063/1.468207
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    Electron tunneling through a dielectric barrier
    Rostkier-Edelstein, Dorita; Urbakh, Michael; Nitzan, Abraham
    Journal of Chemical Physics (1994), 101 (9), 8224-37CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
    Electron tunneling through a dielec. barrier is considered with special attention given to questions relevant for STM expts. in dielec. liqs. The effect of the barrier dielec. response on the tunneling probability is studied using the effective Hamiltonian formalism for the polarization dynamics in the barrier, and two different theor. approaches for the calcn. of the tunneling probability: a generalization of Bardeen's formalism to inelastic tunneling and the quasi-classical of Brink, Nemes, and Vautherin as expanded by Sumetskii. Although based on different approxns., both approaches yield similar results in the slow barrier limit, where their ranges of validity coincide. The approach based on the Bardeen's formalism relies on the adiabatic approxn. and fails for fast barrier dynamics. The overall effect of the barrier dielec. response is to enhance the tunneling probability relative to the rigid barrier case. The enhancement factor is larger for thicker barrier, higher temp., and faster barrier dynamics. Both the elastic and inelastic components of the tunneling current show these trends in the relevant range of parameters.
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    Chen, X.; Zhang, Q. Atomic Insights into the Fundamental Interactions in Lithium Battery Electrolytes. Acc. Chem. Res. 2020, 53, 1992– 2002,  DOI: 10.1021/acs.accounts.0c00412
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    Atomic Insights into the Fundamental Interactions in Lithium Battery Electrolytes
    Chen, Xiang; Zhang, Qiang
    Accounts of Chemical Research (2020), 53 (9), 1992-2002CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
    A review. Building high-energy-d. batteries is urgently demanded in contemporary society because of the continuous increase in global energy consumption and the quick upgrade of electronic devices, which promotes the use of high-capacity lithium metal anodes and high-voltage cathodes. Achieving a stable interface between electrolytes and highly reactive electrodes is a prerequisite to constructing a safe and powerful battery, in which electrolyte regulation plays a decisive role and largely dets. the long-term and rate performances. The bulk and interfacial properties of electrolytes are directly detd. by the fundamental interactions and the as-derived microstructures in electrolytes. Different from exptl. trial-and-error approaches, the rational bottom-up design of electrolytes based on a comprehensive and deep understanding of the fundamental interactions between electrolyte compns. and the structure-function relationship is highly expected to accelerate breaking through the bottleneck in current technol. and realizing next-generation Li batteries. An overview is presented of the authors recent attempts toward rational electrolyte design for safe Li batteries based on a comprehensive understanding of the cation-solvent, cation-anion, and anion-solvent interactions in electrolytes. The formation of cation-solvent complexes decreases the reductive stability but increases the oxidative stability of solvent mols. according to frontier MO theory, whereas the introduction of anions into the Li+ solvation shell has the opposite function in regulating solvent stability compared with cations. The competitive coordination of anions and solvent mols. with cations directly dets. the salt soly. in electrolytes and the formation of ion pairs and aggregates, which widely exist in high-concn. electrolytes and stabilize Li metal anodes. An easy and effective route to dissolve lithium nitrate in ester electrolytes is accordingly proposed. Although anions are hardly solvated in routine solvents, solvents with a high acceptor no. or an exposed pos. charge site are highly expected to enhance the anion-solvent interaction. The solvation of anions will have a strong effect on electrolytes, including regulating the electrolyte solvation structure and stability, increasing the cation transference no., and promoting salt dissocn. The emerging Li bond theory and big-data approaches, combined with first-principles calcns. and exptl. characterizations, are also expected to promote rational electrolyte design with much reduced time and expense. Collectively, with a comprehensive and deep understanding of the fundamental interactions in electrolytes and the structure-function relationship, bottom-up engineering of Li battery electrolytes is expected to be achieved, accelerating the applications of safe high-energy-d. Li batteries. The general principles demonstrated in Li batteries are also supposed to be applicable to other battery systems and even universal electrochem. in solns., including fuel cells and various electrocatalyzers.
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    Lu, D.; Shao, Y.; Lozano, T. Failure Mechanism for Fast-Charged Lithium Metal Batteries with Liquid Electrolytes. Adv. Energy Mater. 2015, 5, 1400993  DOI: 10.1002/aenm.201400993
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    Ospina-Acevedo, F.; Guo, N.; Balbuena, P. B. Lithium Oxidation and Electrolyte Decomposition at Li-Metal/Liquid Electrolyte Interfaces. J. Mater. Chem. A 2020, 8, 17036– 17055,  DOI: 10.1039/D0TA05132B
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    Lithium oxidation and electrolyte decomposition at Li-metal/liquid electrolyte interfaces
    Ospina-Acevedo, Francisco; Guo, Ningxuan; Balbuena, Perla B.
    Journal of Materials Chemistry A: Materials for Energy and Sustainability (2020), 8 (33), 17036-17055CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
    We examine the evolution of events occurring when a Li metal surface is in contact with a 2 M soln. of a Li salt in a solvent or mixt. of solvents, via classical mol. dynamics simulations with a reactive force field allowing bond breaking and bond forming. The main events include Li oxidn. and electrolyte redn. along with expansion of the Li surface layers forming a porous phase that is the basis for the formation of the solid-electrolyte interphase (SEI) components. Nucleation of the main SEI components (LiF, Li oxides, and some orgs.) is characterized. The anal. clearly reveals the details of these phys.-chem. events as a function of time, during 20 ns. The effects of the chem. of the electrolyte on Li oxidn. and dissoln. in the liq. electrolyte, and SEI nucleation and structure are identified by testing two salts: LiPF6 and LiCF3SO3, and various solvents including ethers and carbonates and mixts. of them. The kinetics and thermodn. of Li6F, the core nuclei in the LiF crystal, are studied by anal. of the MD trajectories, and via d. functional theory calcns. resp. The SEI formed in this computational expt. is the "native" film that would form upon contact of the Li foil with the liq. electrolyte. As such, this work is the first in a series of computational expts. that will help elucidate the intricate interphase layer formed during battery cycling using metal anodes.
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    Perez Beltran, S.; Balbuena, P. B. Sei Formation Mechanisms and Li+ Dissolution in Lithium Metal Anodes: Impact of the Electrolyte Composition and the Electrolyte-to-Anode Ratio. J. Power Sources 2022, 551, 232203– 232210,  DOI: 10.1016/j.jpowsour.2022.232203
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    29
    SEI formation mechanisms and Li+ dissolution in lithium metal anode and impact of electrolyte composition and electrolyte-anode ratio
    Perez Beltran, Saul; Balbuena, Perla B.
    Journal of Power Sources (2022), 551 (), 232203CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
    A review. The lithium metal battery is one of today's most promising high-energy-d. storage devices. Its full-scale implementation depends on solving operational and safety issues intrinsic to the Li metal high reactivity leading to uncontrolled electrolyte decompn. and uneven Li deposition. In this work, we study the spontaneous formation of the solid electrolyte interphase (SEI) upon contact of Li metal with the electrolyte and describe the heterogeneous SEI morphol. features. Multiple electrolyte formulations based on lithium bis(fluorosulfonyl)imide (LiFSI), dimethoxyethane (DME), di-Me carbonate (DMC), 1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) and bis(2,2,2-trifluoroethyl) ether (BTFE) are used. Findings include the description of the SEI evolution from dispersed LiO, LiS, LiN, and LiF clusters to a continuous and compact inorg. phase in which the LiO and LiF content depend on the presence of fluorine diluents. The role of the DME ether solvent helping the growth of a "wet-SEI" is compared to that of the highly unstable carbonate DMC, which decompg. into complex radical oligomers that might contribute to further electrolyte decompn. The impact of the electrolyte-anode ratio on LiFSI decompn. is highlighted. Finally, we suggest the existence of a crit. LiFSI concn. and electrolyte-anode ratio that could potentially balance the rate of electrolyte depletion and lithium consumption.
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    Spotte-Smith, E. W. C.; Kam, R. L.; Barter, D.; Xie, X.; Hou, T.; Dwaraknath, S.; Blau, S. M.; Persson, K. A. Toward a Mechanistic Model of Solid–Electrolyte Interphase Formation and Evolution in Lithium-Ion Batteries. ACS Energy Lett. 2022, 7, 1446– 1453,  DOI: 10.1021/acsenergylett.2c00517
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    Toward a Mechanistic Model of Solid-Electrolyte Interphase Formation and Evolution in Lithium-Ion Batteries
    Spotte-Smith, Evan Walter Clark; Kam, Ronald L.; Barter, Daniel; Xie, Xiaowei; Hou, Tingzheng; Dwaraknath, Shyam; Blau, Samuel M.; Persson, Kristin A.
    ACS Energy Letters (2022), 7 (4), 1446-1453CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)
    The formation of passivation films by interfacial reactions, though crit. for applications ranging from advanced alloys to electrochem. energy storage, is often poorly understood. In this work, we explore the formation of an exemplar passivation film, the solid-electrolyte interphase (SEI), which is responsible for stabilizing lithium-ion batteries. Using stochastic simulations based on quantum chem. calcns. and data-driven chem. reaction networks, we directly model competition between SEI products at a mechanistic level for the first time. Our results recover the Peled-like sepn. of the SEI into inorg. and org. domains resulting from rich reactive competition without fitting parameters to exptl. inputs. By conducting accelerated simulations at elevated temp., we track SEI evolution, confirming the postulated redn. of lithium ethylene monocarbonate to dilithium ethylene monocarbonate and H2. These findings furnish fundamental insights into the dynamics of SEI formation and illustrate a path forward toward a predictive understanding of electrochem. passivation.
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    Ab initio molecular dynamics of liquid metals
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    Physical Review B: Condensed Matter and Materials Physics (1993), 47 (1), 558-61CODEN: PRBMDO; ISSN:0163-1829.
    The authors present ab initio quantum-mech. mol.-dynamics calcns. based on the calcn. of the electronic ground state and of the Hellmann-Feynman forces in the local-d. approxn. at each mol.-dynamics step. This is possible using conjugate-gradient techniques for energy minimization, and predicting the wave functions for new ionic positions using sub-space alignment. This approach avoids the instabilities inherent in quantum-mech. mol.-dynamics calcns. for metals based on the use of a factitious Newtonian dynamics for the electronic degrees of freedom. This method gives perfect control of the adiabaticity and allows one to perform simulations over several picoseconds.
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    Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized Gradient Approximation Made Simple. Phys. Rev. Lett. 1996, 77, 3865– 3868,  DOI: 10.1103/PhysRevLett.77.3865
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    Physical Review Letters (1996), 77 (18), 3865-3868CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)
    Generalized gradient approxns. (GGA's) for the exchange-correlation energy improve upon the local spin d. (LSD) description of atoms, mols., and solids. We present a simple derivation of a simple GGA, in which all parameters (other than those in LSD) are fundamental consts. Only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked. Improvements over PW91 include an accurate description of the linear response of the uniform electron gas, correct behavior under uniform scaling, and a smoother potential.
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    There is no expanded citation for this reference.
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    Kresse, G.; Joubert, D. From Ultrasoft Pseudopotentials to the Projector Augmented-Wave Method. Phys. Rev. B 1999, 59, 1758– 1775,  DOI: 10.1103/PhysRevB.59.1758
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    From ultrasoft pseudopotentials to the projector augmented-wave method
    Kresse, G.; Joubert, D.
    Physical Review B: Condensed Matter and Materials Physics (1999), 59 (3), 1758-1775CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
    The formal relationship between ultrasoft (US) Vanderbilt-type pseudopotentials and Blochl's projector augmented wave (PAW) method is derived. The total energy functional for US pseudopotentials can be obtained by linearization of two terms in a slightly modified PAW total energy functional. The Hamilton operator, the forces, and the stress tensor are derived for this modified PAW functional. A simple way to implement the PAW method in existing plane-wave codes supporting US pseudopotentials is pointed out. In addn., crit. tests are presented to compare the accuracy and efficiency of the PAW and the US pseudopotential method with relaxed-core all-electron methods. These tests include small mols. (H2, H2O, Li2, N2, F2, BF3, SiF4) and several bulk systems (diamond, Si, V, Li, Ca, CaF2, Fe, Co, Ni). Particular attention is paid to the bulk properties and magnetic energies of Fe, Co, and Ni.
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    Ehrlich, S.; Moellmann, J.; Reckien, W.; Bredow, T.; Grimme, S. System-Dependent Dispersion Coefficients for the Dft-D3 Treatment of Adsorption Processes on Ionic Surfaces. ChemPhysChem 2011, 12, 3414– 3420,  DOI: 10.1002/cphc.201100521
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    System-Dependent Dispersion Coefficients for the DFT-D3 Treatment of Adsorption Processes on Ionic Surfaces
    Ehrlich, Stephan; Moellmann, Jonas; Reckien, Werner; Bredow, Thomas; Grimme, Stefan
    ChemPhysChem (2011), 12 (17), 3414-3420CODEN: CPCHFT; ISSN:1439-4235. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Dispersion-cor. d. functional theory calcns. (DFT-D3) were performed for the adsorption of CO on MgO and C2H2 on NaCl surfaces. An extension of our non-empirical scheme for the computation of atom-in-mols. dispersion coeffs. is proposed. It is based on electrostatically embedded M4X4 (M = Na, Mg) clusters that are used in TDDFT calcns. of dynamic dipole polarizabilities. We find that the C6MM dispersion coeffs. for bulk NaCl and MgO are reduced by factors of about 100 and 35 for Na and Mg, resp., compared to the values of the free atoms. These are used in periodic DFT calcns. with the revPBE semi-local d. functional. As demonstrated by calcns. of adsorption potential energy curves, the new C6 coeffs. lead to much more accurate energies (Eads) and mol.-surface distances than with previous DFT-D schemes. For NaCl/C2H2 we obtained at the revPBE-D3(BJ) level a value of Eads = -7.4 kcal mol-1 in good agreement with exptl. data (-5.7 to -7.1 kcal mol-1). Dispersion-uncorrected DFT yields an unbound surface state. For the MgO/CO system, the computed revPBE-D3(BJ) value of Eads = -4.1 kcal mol-1 is also in reasonable agreement with exptl. results (-3.0 kcal mol-1) when thermal corrections are taken into account. Our new dispersion correction also improves computed lattice consts. of the bulk systems significantly compared to plain DFT or previous DFT-D results. The extended DFT-D3 scheme also provides accurate non-covalent interactions for ionic systems without empirical adjustments and is suggested as a general tool in surface science.
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    Tang, W.; Sanville, E.; Henkelman, G. A Grid-Based Bader Analysis Algorithm without Lattice Bias. J. Phys.: Condens. Matter 2009, 21, 084204  DOI: 10.1088/0953-8984/21/8/084204
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    A grid-based Bader analysis algorithm without lattice bias
    Tang, W.; Sanville, E.; Henkelman, G.
    Journal of Physics: Condensed Matter (2009), 21 (8), 084204/1-084204/7CODEN: JCOMEL; ISSN:0953-8984. (Institute of Physics Publishing)
    A computational method for partitioning a charge d. grid into Bader vols. is presented which is efficient, robust, and scales linearly with the no. of grid points. The partitioning algorithm follows the steepest ascent paths along the charge d. gradient from grid point to grid point until a charge d. max. is reached. In this paper, we describe how accurate off-lattice ascent paths can be represented with respect to the grid points. This improvement maintains the efficient linear scaling of an earlier version of the algorithm, and eliminates a tendency for the Bader surfaces to be aligned along the grid directions. As the algorithm assigns grid points to charge d. maxima, subsequent paths are terminated when they reach previously assigned grid points. It is this grid-based approach which gives the algorithm its efficiency, and allows for the anal. of the large grids generated from plane-wave-based d. functional theory calcns.
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    Dunning, T. H., Jr. Gaussian Basis Sets for Use in Correlated Molecular Calculations. I. The Atoms Boron through Neon and Hydrogen. J. Chem. Phys. 1989, 90, 1007– 1023,  DOI: 10.1063/1.456153
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    Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
    Dunning, Thom H., Jr.
    Journal of Chemical Physics (1989), 90 (2), 1007-23CODEN: JCPSA6; ISSN:0021-9606.
    Guided by the calcns. on oxygen in the literature, basis sets for use in correlated at. and mol. calcns. were developed for all of the first row atoms from boron through neon, and for hydrogen. As in the oxygen atom calcns., the incremental energy lowerings, due to the addn. of correlating functions, fall into distinct groups. This leads to the concept of correlation-consistent basis sets, i.e., sets which include all functions in a given group as well as all functions in any higher groups. Correlation-consistent sets are given for all of the atoms considered. The most accurate sets detd. in this way, [5s4p3d2f1g], consistently yield 99% of the correlation energy obtained with the corresponding at.-natural-orbital sets, even though the latter contains 50% more primitive functions and twice as many primitive polarization functions. It is estd. that this set yields 94-97% of the total (HF + 1 + 2) correlation energy for the atoms neon through boron.
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    Woon, D. E.; T, H. D., Jr. Gaussian Basis Sets for Use in Correlated Molecular Calculations. Iii. The Atoms Aluminum through Argon. J. Chem. Phys. 1993, 98, 1358– 1371,  DOI: 10.1063/1.464303
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    Gaussian basis sets for use in correlated molecular calculations. III. The atoms aluminum through argon
    Woon, David E.; Dunning, Thom H., Jr.
    Journal of Chemical Physics (1993), 98 (2), 1358-71CODEN: JCPSA6; ISSN:0021-9606.
    Correlation consistent and augmented correlation consistent basis sets were detd. for the second row atoms. The methodol., originally developed for the first row atoms (T. H. D., Jr., 1989) is first applied to S. The exponents for the polarization functions (dfgh) are systematically optimized for a correlated wave function (HF+1+2). The (sp) correlation functions are taken from the appropriate HF primitive sets; these functions differ little from the optimum functions. Basis sets of double zeta [4s3p1d], triple zeta [5s4p2d1f], and quadruple zeta [6s5p3d2f1g] quality are defined. Each of these sets is then augmented with diffuse functions to better describe electron affinities and other mol. properties: s and p functions were obtained by optimization for the anion HF energy, while an addnl. polarization function for each symmetry present in the std. set was optimized for the anion HF+1+2 energy. The results for S are then used to assist in detg. double zeta, triple zeta, and quadruple zeta basis sets for the remainder of the second row of the p block.
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    Han, J.; Zheng, Y.; Guo, N.; Balbuena, P. B. Calculated Reduction Potentials of Electrolyte Species in Lithium–Sulfur Batteries. J. Phys. Chem. C 2020, 124, 20654– 20670,  DOI: 10.1021/acs.jpcc.0c04173
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    Calculated Reduction Potentials of Electrolyte Species in Lithium-Sulfur Batteries
    Han, Jaebeom; Zheng, Yu; Guo, Ningxuan; Balbuena, Perla B.
    Journal of Physical Chemistry C (2020), 124 (38), 20654-20670CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
    Redn. potentials of electrolyte mols. in the lithium-sulfur (Li/S) battery and their variations in several solvent environments are studied using the d. functional theory method with Dunning's triple-ζ correlation consistent basis set. Reliable redn. potential values are key for electrolyte additive design needed for suppressing polysulfide dissoln. shuttle mechanism, resulting in poor cycle performance and severe self-discharge of the Li/S battery. Although isolated electrolyte mols. have redn. potentials outside the operating voltage range of the Li/S battery, complexation with other electrolyte species enables the electrolyte mols. to be reduced within the operating voltage range. Among the electrolyte species considered in this study, bis(fluorosulfonyl)imide (FSI-) and fluoroethylene carbonate (FEC) yield redn. potentials within the expected range, suggesting the development of fluorine-contg. additives as a promising line of research.
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    Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions. J. Phys. Chem. B 2009, 113, 6378– 6396,  DOI: 10.1021/jp810292n
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    Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
    Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
    Journal of Physical Chemistry B (2009), 113 (18), 6378-6396CODEN: JPCBFK; ISSN:1520-6106. (American Chemical Society)
    We present a new continuum solvation model based on the quantum mech. charge d. of a solute mol. interacting with a continuum description of the solvent. The model is called SMD, where the "D" stands for "d." to denote that the full solute electron d. is used without defining partial at. charges. "Continuum" denotes that the solvent is not represented explicitly but rather as a dielec. medium with surface tension at the solute-solvent boundary. SMD is a universal solvation model, where "universal" denotes its applicability to any charged or uncharged solute in any solvent or liq. medium for which a few key descriptors are known (in particular, dielec. const., refractive index, bulk surface tension, and acidity and basicity parameters). The model separates the observable solvation free energy into two main components. The first component is the bulk electrostatic contribution arising from a self-consistent reaction field treatment that involves the soln. of the nonhomogeneous Poisson equation for electrostatics in terms of the integral-equation-formalism polarizable continuum model (IEF-PCM). The cavities for the bulk electrostatic calcn. are defined by superpositions of nuclear-centered spheres. The second component is called the cavity-dispersion-solvent-structure term and is the contribution arising from short-range interactions between the solute and solvent mols. in the first solvation shell. This contribution is a sum of terms that are proportional (with geometry-dependent proportionality consts. called at. surface tensions) to the solvent-accessible surface areas of the individual atoms of the solute. The SMD model has been parametrized with a training set of 2821 solvation data including 112 aq. ionic solvation free energies, 220 solvation free energies for 166 ions in acetonitrile, methanol, and DMSO, 2346 solvation free energies for 318 neutral solutes in 91 solvents (90 nonaq. org. solvents and water), and 143 transfer free energies for 93 neutral solutes between water and 15 org. solvents. The elements present in the solutes are H, C, N, O, F, Si, P, S, Cl, and Br. The SMD model employs a single set of parameters (intrinsic at. Coulomb radii and at. surface tension coeffs.) optimized over six electronic structure methods: M05-2X/MIDI!6D, M05-2X/6-31G*, M05-2X/6-31+G**, M05-2X/cc-pVTZ, B3LYP/6-31G*, and HF/6-31G*. Although the SMD model has been parametrized using the IEF-PCM protocol for bulk electrostatics, it may also be employed with other algorithms for solving the nonhomogeneous Poisson equation for continuum solvation calcns. in which the solute is represented by its electron d. in real space. This includes, for example, the conductor-like screening algorithm. With the 6-31G* basis set, the SMD model achieves mean unsigned errors of 0.6-1.0 kcal/mol in the solvation free energies of tested neutrals and mean unsigned errors of 4 kcal/mol on av. for ions with either Gaussian03 or GAMESS.
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    Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. A Consistent and Accurate Ab Initio Parametrization of Density Functional Dispersion Correction (Dft-D) for the 94 Elements H-Pu. J. Chem. Phys. 2010, 132, 154104  DOI: 10.1063/1.3382344
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    A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
    Grimme, Stefan; Antony, Jens; Ehrlich, Stephan; Krieg, Helge
    Journal of Chemical Physics (2010), 132 (15), 154104/1-154104/19CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
    The method of dispersion correction as an add-on to std. Kohn-Sham d. functional theory (DFT-D) has been refined regarding higher accuracy, broader range of applicability, and less empiricism. The main new ingredients are atom-pairwise specific dispersion coeffs. and cutoff radii that are both computed from first principles. The coeffs. for new eighth-order dispersion terms are computed using established recursion relations. System (geometry) dependent information is used for the first time in a DFT-D type approach by employing the new concept of fractional coordination nos. (CN). They are used to interpolate between dispersion coeffs. of atoms in different chem. environments. The method only requires adjustment of two global parameters for each d. functional, is asymptotically exact for a gas of weakly interacting neutral atoms, and easily allows the computation of at. forces. Three-body nonadditivity terms are considered. The method has been assessed on std. benchmark sets for inter- and intramol. noncovalent interactions with a particular emphasis on a consistent description of light and heavy element systems. The mean abs. deviations for the S22 benchmark set of noncovalent interactions for 11 std. d. functionals decrease by 15%-40% compared to the previous (already accurate) DFT-D version. Spectacular improvements are found for a tripeptide-folding model and all tested metallic systems. The rectification of the long-range behavior and the use of more accurate C6 coeffs. also lead to a much better description of large (infinite) systems as shown for graphene sheets and the adsorption of benzene on an Ag(111) surface. For graphene it is found that the inclusion of three-body terms substantially (by about 10%) weakens the interlayer binding. We propose the revised DFT-D method as a general tool for the computation of the dispersion energy in mols. and solids of any kind with DFT and related (low-cost) electronic structure methods for large systems. (c) 2010 American Institute of Physics.
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    Wang, Y.; Nakamura, S.; Ue, M.; Balbuena, P. B. Theoretical Studies to Understand Surface Chemistry on Carbon Anodes for Lithium-Ion Batteries: Reduction Mechanisms of Ethylene Carbonate. J. Am. Chem. Soc. 2001, 123, 11708– 11718,  DOI: 10.1021/ja0164529
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    Theoretical studies to understand surface chemistry on carbon anodes for lithium-ion batteries: Reduction mechanisms of ethylene carbonate
    Wang, Yixuan; Nakamura, Shinichiro; Ue, Makoto; Balbuena, Perla B.
    Journal of the American Chemical Society (2001), 123 (47), 11708-11718CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    Reductive decompn. mechanisms for ethylene carbonate (EC) mol. in electrolyte solns. for lithium-ion batteries are comprehensively investigated by using d. functional theory. In gas phase the redn. of EC is thermodynamically forbidden, whereas in bulk solvent it is likely to undergo one- as well as two-electron redn. processes. The presence of Li cation considerably stabilizes the EC redn. intermediates. The adiabatic electron affinities of the supermol. Li+(EC)n (n = 1-4) successively decrease with the no. of EC mols., independently of EC or Li+ being reduced. Regarding the reductive decompn. mechanism, Li+(EC)n is initially reduced to an ion-pair intermediate that will undergo homolytic C-O bond cleavage via an approx. 11.0 kcal/mol barrier, bringing up a radical anion coordinated with Li+. Among the possible termination pathways of the radical anion, thermodynamically the most favorable is the formation of lithium butylene bicarbonate, (CH2CH2OCO2Li)2, followed by the formation of one O-Li bond compd. contg. an ester group, LiO(CH2)2CO2(CH2)2OCO2Li, then two very competitive reactions of the further redn. of the radical anion and the formation of lithium ethylene bicarbonate, (CH2OCO2Li)2, and the least favorable is the formation of a C-Li bond compd. (Li carbides), Li(CH2)2OCO2Li. The products show a weak EC concn. dependence as has also been revealed for the reactions of LiCO3- with Li+(EC)n; i.e., the formation of Li2CO3 is slightly more favorable at low EC concns., whereas (CH2OCO2Li)2 is favored at high EC concns. A two-electron redn. indeed takes place by a stepwise path. Regarding the compn. of the surface films resulting from solvent redn., for which expts. usually indicate that (CH2OCO2Li)2 is a dominant component, we conclude that they comprise two leading lithium alkyl bicarbonates, (CH2CH2OCO2Li)2 and (CH2OCO2Li)2, together with LiO(CH2)2CO2(CH2)2OCO2Li, Li(CH2)2OCO2Li and Li2CO3.
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    Wang, Y.; Nakamura, S.; Tasaki, K.; Balbuena, P. B. Theoretical Studies to Understand Surface Chemistry on Carbon Anodes for Lithium-Ion Batteries: How Does Vinylene Carbonate Play Its Role as an Electrolyte Additive?. J. Am. Chem. Soc. 2002, 124, 4408– 4421,  DOI: 10.1021/ja017073i
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    Theoretical Studies To Understand Surface Chemistry on Carbon Anodes for Lithium-Ion Batteries: How Does Vinylene Carbonate Play Its Role as an Electrolyte Additive?
    Wang, Yixuan; Nakamura, Shinichiro; Tasaki, Ken; Balbuena, Perla B.
    Journal of the American Chemical Society (2002), 124 (16), 4408-4421CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    To elucidate the role of vinylene carbonate (VC) as a solvent additive in org. polar solns. for lithium-ion batteries, reductive decompns. for VC and ethylene carbonate (EC) mols. have been comprehensively investigated both in the gas phase and in soln. by means of d. functional theory calcns. The salt and solvent effects are incorporated with the clusters (EC)nLi+(VC) (n = 0 - 3), and further corrections that account for bulk solvent effects are added using the polarized continuum model. The electron affinities of (EC)nLi+(VC) (n = 0 - 3) monotonically decrease when the no. of EC mols. increases; a sharp decrease of about 20.0 kcal/mol is found from n = 0 to 1 and a more gentle variation for n > 1. For (EC)nLi+(VC) (n = 1 - 3), the redn. of VC brings about more stable ion-pair intermediates than those due to redn. of the EC mol. by 3.1, 6.1, and 5.3 kcal/mol, resp. This finding qual. agrees with the exptl. fact that the redn. potential of VC in the presence of Li salt is more neg. than that of EC. The calcd. redn. potentials corresponding to radical anion formation are close to the exptl. potentials detd. with cyclic voltammetry on a gold electrode surface (-2.67 and -3.19 eV on the phys. scale for VC and EC, resp., vs. exptl. values -2.96 and -2.94 eV). Regarding the decompn. mechanisms, the VC and EC moieties undergo homolytic ring opening from their resp. redn. intermediates, and the energy barrier of VC is about one time higher than that of EC (e.g., 20.1 vs. 8.8 kcal/mol for (EC)2Li+(VC)); both are weakly affected by the explicit solvent mols. and by a bulk solvent represented by a continuum model. Alternatively, starting from the VC redn. intermediate, the ring opening of the EC moiety via an intramol. electron-transfer transition state has also been located; its barrier lies between those of EC and VC (e.g., 17.2 kcal/mol for (EC)2Li+(VC)). On the basis of these results, we suggest the following explanation about the role that VC may play as additive in EC-based lithium-ion battery electrolytes; VC is initially reduced to a more stable intermediate than that from EC redn. One possibility then is that the reduced VC decomps. to form a radical anion via a barrier of about 20 kcal/mol, which undergoes a series of reactions to give rise to more active film-forming products than those resulting from EC redn., such as lithium divinylene dicarbonate, Li-C carbides, lithium vinylene dicarbonate, R-O-Li compd., and even oligomers with repeated vinylene and carbonate-vinylene units. Another possibility starting from the VC redn. intermediate is that the ring opening occurs on the non-reduced EC moiety instead of being on the reduced VC, via an intramol. electron transfer transition state, the energy barrier of which is lower than that of the former, in which VC just helps the intermediate formation and is not consumed. The factors that det. the additive functioning mechanism are briefly discussed, and consequently a general rule for the selection of electrolyte additive is proposed.
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    Leung, K.; Budzien, J. L. Ab Initio Molecular Dynamics Simulations of the Initial Stages of Solid–Electrolyte Interphase Formation on Lithium Ion Battery Graphitic Anodes. Phys. Chem. Chem. Phys. 2010, 12, 6583– 6586,  DOI: 10.1039/b925853a
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    Ab initio molecular dynamics simulations of the initial stages of solid-electrolyte interphase formation on lithium ion battery graphitic anodes
    Leung, Kevin; Budzien, Joanne L.
    Physical Chemistry Chemical Physics (2010), 12 (25), 6583-6586CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
    The decompn. of ethylene carbonate (EC) during the initial growth of solid-electrolyte interphase films at the solvent-graphitic anode interface is crit. to lithium-ion battery operations. Ab initio mol. dynamics simulations of explicit liq. EC/graphite interfaces are conducted to study these electrochem. reactions. We show that carbon edge terminations are crucial at this stage, and that achievable exptl. conditions can lead to surprisingly fast EC breakdown mechanisms, yielding decompn. products seen in expts. but not previously predicted.
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    Borodin, O.; Olguin, M.; Spear, C. E.; Leiter, K. W.; Knap, J. Towards High Throughput Screening of Electrochemical Stability of Battery Electrolytes. Nanotechnology 2015, 26, 354003  DOI: 10.1088/0957-4484/26/35/354003
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    Towards high throughput screening of electrochemical stability of battery electrolytes
    Borodin, Oleg; Olguin, Marco; Spear, Carrie E.; Leiter, Kenneth W.; Knap, Jaroslaw
    Nanotechnology (2015), 26 (35), 354003/1-354003/15CODEN: NNOTER; ISSN:1361-6528. (IOP Publishing Ltd.)
    High throughput screening of solvents and additives with potential applications in lithium batteries is reported. The initial test set is limited to carbonate and phosphate-based compds. and focused on their electrochem. properties. Solvent stability towards first and second redn. and oxidn. is reported from d. functional theory (DFT) calcns. performed on isolated solvents surrounded by implicit solvent. The reorganization energy is estd. from the difference between vertical and adiabatic redox energies and found to be esp. important for the accurate prediction of redn. stability. A majority of tested compds. had the second redn. potential higher than the first redn. potential indicating that the second redn. reaction might play an important role in the passivation layer formation. Similarly, the second oxidn. potential was smaller for a significant subset of tested mols. than the first oxidn. potential. A no. of potential sources of errors introduced during screening of the electrolyte electrochem. properties were examd. The formation of lithium fluoride during redn. of semifluorinated solvents such as fluoroethylene carbonate and the H-transfer during oxidn. of solvents were found to shift the electrochem. potential by 1.5-2 V and could shrink the electrochem. stability window by as much as 3.5 V when such reactions are included in the screening procedure. The initial oxidn. reaction of ethylene carbonate and di-Me carbonate at the surface of the completely de-lithiated LiNi0.5Mn1.5O4 high voltage spinel cathode was examd. using DFT. Depending on the mol. orientation at the cathode surface, a carbonate mol. either exhibited deprotonation or was found bound to the transition metal via its carbonyl oxygen.
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    Chen, X.; Li, H.-R.; Shen, X.; Zhang, Q. The Origin of the Reduced Reductive Stability of Ion–Solvent Complexes on Alkali and Alkaline Earth Metal Anodes. Angew. Chem., Int. Ed. 2018, 57, 16643– 16647,  DOI: 10.1002/anie.201809203
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    The Origin of the Reduced Reductive Stability of Ion-Solvent Complexes on Alkali and Alkaline Earth Metal Anodes
    Chen, Xiang; Li, Hao-Ran; Shen, Xin; Zhang, Qiang
    Angewandte Chemie, International Edition (2018), 57 (51), 16643-16647CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The intrinsic instability of org. electrolytes seriously impedes practical applications of high-capacity metal (Li, Na) anodes. Ion-solvent complexes can even promote the decompn. of electrolytes on metal anodes. Herein, first-principles calcns. were performed to investigate the origin of the reduced reductive stability of ion-solvent complexes. Both ester and ether electrolyte solvents are selected to interact with Li+, Na+, K+, Mg2+, and Ca2+. The LUMO energy levels of ion-ester complexes exhibit a linear relationship with the binding energy, regulated by the ratio of carbon AO in the LUMO, while LUMOs of ion-ether complexes are composed by the metal AOs. This work shows why ion-solvent complexes can reduce the reductive stability of electrolytes, reveals different mechanisms for ester and ether electrolytes, and provides a theor. understanding of the electrolyte-anode interfacial reactions and guidance to electrolyte and metal anode design.
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    Unveiling the Role of Li+ Solvation Structures with Commercial Carbonates in the Formation of Solid Electrolyte Interphase for Lithium Metal Batteries
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This article is cited by 5 publications.

  1. Andrew Dopilka, Jonathan M. Larson, Hyungyeon Cha, Robert Kostecki. Synchrotron Near-Field Infrared Nanospectroscopy and Nanoimaging of Lithium Fluoride in Solid Electrolyte Interphases in Li-Ion Battery Anodes. ACS Nano 2024, Article ASAP.
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  3. Dacheng Kuai, Shen Wang, Saul Perez-Beltran, Sicen Yu, Gerard A. Real, Ping Liu, Perla B. Balbuena. Interfacial Electrochemical Lithiation and Dissolution Mechanisms at a Sulfurized Polyacrylonitrile Cathode Surface. ACS Energy Letters 2024, 9 (3) , 810-818. https://doi.org/10.1021/acsenergylett.3c02757
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  • Abstract

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    Figure 1

    Figure 1. AIMD simulation of LiPF6 decomposition on and near lithium metal surface. The initial electrolyte configuration is composed of 3 Li+, 3 PF6–, 18 EC, and 1 VC structures, with a density of 1.3 g/mL. The coordinates of the top-layer He atoms (dark gray) are fixed to refrain electrolyte molecular movement from contacting the lithium layer repeated in the z-direction due to periodic boundary conditions. Some cluster structures are rotated for a clear perspective. Color scheme: He (gray ball); C (gray dash); H (white dash); O (red dash); Li (purple ball); P (tan ball); F (cyan ball).

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    Figure 2

    Figure 2. Geometry (left), electron density (middle), and electronic Laplacian (right) analysis of Li2PF6 clusters, including the optimized geometries of [PF6]− (a) LiPF6 (b), [Li2PF6]+ (c), as well as the [Li2PF6]− structures (d, e) retrieved from AIMD simulations. (49) All of the electronic structure figures are plotted based on the planes determined by labeled atoms. Atomic color coding in structural geometries is identical to Figure 1. The rainbow color scale is labeled on the left (electron density) and right (Laplacian) sides of each diagram, where red indicates positive, and blue indicates zero/negative values.

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    Figure 3

    Figure 3. Energy profile of the hexafluorophosphate dissociation on different lithium metal facets retrieved from AIMD simulations. Important events are labeled with (a), (b), (c), and (d). The background charge of configurations (a) and (b) are both −1 e, while panels (c) and (d) are neutral. Atomic color coding is consistent with Figure 1.

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    Figure 4

    Figure 4. Free energy profile of LiPF6 degradation computed in SMD (ε = 7.4). The red, purple, blue, and gray curves stand for nonlithiated, mono-lithiated, bi-lithiated, and tri-lithiated species, respectively. The relative free energies are labeled in kcal/mol, so are the enthalpy values in parenthesis.

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  • References

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    This article references 50 other publications.

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      Choi, J. W.; Aurbach, D. Promise and Reality of Post-Lithium-Ion Batteries with High Energy Densities. Nat. Rev. Mater. 2016, 1, 16013  DOI: 10.1038/natrevmats.2016.13
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      Energy d. is the main property of rechargeable batteries that has driven the entire technol. forward in past decades. Lithium-ion batteries (LIBs) now surpass other, previously competitive battery types (for example, lead-acid and nickel metal hydride) but still require extensive further improvement to, in particular, extend the operation hours of mobile IT devices and the driving mileages of all-elec. vehicles. In this Review, we present a crit. overview of a wide range of post-LIB materials and systems that could have a pivotal role in meeting such demands. We divide battery systems into two categories: near-term and long-term technologies. To provide a realistic and balanced perspective, we describe the operating principles and remaining issues of each post-LIB technol., and also evaluate these materials under com. cell configurations.
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      Wang, H.; Yu, Z.; Kong, X.; Kim, S. C.; Boyle, D. T.; Qin, J.; Bao, Z.; Cui, Y. Liquid Electrolyte: The Nexus of Practical Lithium Metal Batteries. Joule 2022, 6, 588– 616,  DOI: 10.1016/j.joule.2021.12.018
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      Liquid electrolyte: The nexus of practical lithium metal batteries
      Wang, Hansen; Yu, Zhiao; Kong, Xian; Kim, Sang Cheol; Boyle, David T.; Qin, Jian; Bao, Zhenan; Cui, Yi
      Joule (2022), 6 (3), 588-616CODEN: JOULBR; ISSN:2542-4351. (Cell Press)
      A review. The specific energy of com. lithium (Li)-ion batteries is reaching the theor. limit. Future consumer electronics and elec. vehicle markets call for the development of high energy d. Li metal batteries, which have been plagued by poor cyclability. Electrolyte engineering can afford a promising approach to address the issues assocd. with Li metal batteries and has recently resulted in much improved cycle life under practical conditions. However, gaps still exist between the performance of current Li metal batteries and those required for com. applications. Further improvements will require systematic anal. of existing electrolyte design methodologies. In this review, we first summarize recent approaches of advanced electrolytes for Li metal batteries paired with high-voltage cathodes. We then ext. common features among these advanced electrolytes and finally discuss the future rational design directions and strategies.
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      He, X.; Bresser, D.; Passerini, S. The Passivity of Lithium Electrodes in Liquid Electrolytes for Secondary Batteries. Nat. Rev. Mater. 2021, 6, 1036– 1052,  DOI: 10.1038/s41578-021-00345-5
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      The passivity of lithium electrodes in liquid electrolytes for secondary batteries
      He, Xin; Bresser, Dominic; Passerini, Stefano; Baakes, Florian; Krewer, Ulrike; Lopez, Jeffrey; Mallia, Christopher Thomas; Shao-Horn, Yang; Cekic-Laskovic, Isidora; Wiemers-Meyer, Simon; Soto, Fernando A.; Ponce, Victor; Seminario, Jorge M.; Balbuena, Perla B.; Jia, Hao; Xu, Wu; Xu, Yaobin; Wang, Chongmin; Horstmann, Birger; Amine, Rachid; Su, Chi-Cheung; Shi, Jiayan; Amine, Khalil; Winter, Martin; Latz, Arnulf; Kostecki, Robert
      Nature Reviews Materials (2021), 6 (11), 1036-1052CODEN: NRMADL; ISSN:2058-8437. (Nature Portfolio)
      Abstr.: Rechargeable Li metal batteries are currently limited by safety concerns, continuous electrolyte decompn. and rapid consumption of Li. These issues are mainly related to reactions occurring at the Li metal-liq. electrolyte interface. The formation of a passivation film (i.e., a solid electrolyte interphase) dets. ionic diffusion and the structural and morphol. evolution of the Li metal electrode upon cycling. In this Review, we discuss spontaneous and operation-induced reactions at the Li metal-electrolyte interface from a corrosion science perspective. We highlight that the instantaneous formation of a thin protective film of corrosion products at the Li surface, which acts as a barrier to further chem. reactions with the electrolyte, precedes film reformation, which occurs during subsequent electrochem. stripping and plating of Li during battery operation. Finally, we discuss solns. to overcoming remaining challenges of Li metal batteries related to Li surface science, electrolyte chem., cell engineering and the intrinsic instability of the Li metal-electrolyte interface.
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      Jang, E. K.; Ahn, J.; Yoon, S.; Cho, K. Y. High Dielectric, Robust Composite Protective Layer for Dendrite-Free and Lipf6 Degradation-Free Lithium Metal Anode. Adv. Funct. Mater. 2019, 29, 1905078  DOI: 10.1002/adfm.201905078
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      High Dielectric, Robust Composite Protective Layer for Dendrite-Free and LiPF6 Degradation-Free Lithium Metal Anode
      Jang, Eun Kwang; Ahn, Jinhyeok; Yoon, Sukeun; Cho, Kuk Young
      Advanced Functional Materials (2019), 29 (48), 1905078CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The development of lithium metal anodes for next generation batteries remains a challenge. Uncontrolled Li dendrite growth not only induces severe safety issues but also leads to capacity fading by continuously consuming the electrolyte. This study demonstrates the design and fabrication of a composite protective layer composed of a high dielec. polymer, inorg. particles, and an electrolyte to overcome these obstacles. This layer not only suppresses dendrite growth, but also prevents LiPF6 degrdn. The electrolyte introduced in the protective layer remains within the coating layer after solvent removal and acts as an ion transport channel at the interface. This enables the protective layer to exhibit high ionic cond. and mech. strength. The composite protective layer, which exhibits synergistic soft-rigid characteristics, is placed on the Li metal anode and facilitates superior interfacial stability during long-term cycles. LiMn2O4/coated lithium full cells using the composite protective layer show a superior rate capability and enhanced capacity retention compared to the cells using a bare lithium anode. The proposed strategy opens new avenues to fabricate a sustainable composite protective layer that affords superior performance in lithium metal batteries.
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      Peled, E.; Menkin, S. Review─SEI: Past, Present and Future. J. Electrochem. Soc. 2017, 164, A1703– A1719,  DOI: 10.1149/2.1441707jes
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      Review-SEI: Past, Present and Future
      Peled, E.; Menkin, S.
      Journal of the Electrochemical Society (2017), 164 (7), A1703-A1719CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)
      The Solid-Electrolyte-Interphase (SEI) model for non-aq. alkali-metal batteries constitutes a paradigm change in the understanding of lithium batteries and has thus enabled the development of safer, durable, higher-power and lower-cost lithium batteries for portable and EV applications. Prior to the publication of the SEI model (1979), researchers used the Butler-Volmer equation, in which a direct electron transfer from the electrode to lithium cations in the soln. is assumed. The SEI model proved that this is a mistaken concept and that, in practice, the transfer of electrons from the electrode to the soln. in a lithium battery, must be prevented, since it will result in fast self-discharge of the active materials and poor battery performance. This model provides [E. Peled, in "Lithium Batteries," J.P. Gabano (ed), Academic Press, (1983), E. Peled, J. Electrochem. Soc., 126, 2047 (1979).] new equations for: electrode kinetics (io and b), anode corrosion, SEI resistivity and growth rate and irreversible capacity loss of lithium-ion batteries. This model became a cornerstone in the science and technol. of lithium batteries. This paper reviews the past, present and the future of SEI batteries.
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      Yu, Z.; Rudnicki, P. E.; Zhang, Z. Rational Solvent Molecule Tuning for High-Performance Lithium Metal Battery Electrolytes. Nat. Energy 2022, 7, 94– 106,  DOI: 10.1038/s41560-021-00962-y
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      Rational solvent molecule tuning for high-performance lithium metal battery electrolytes
      Yu, Zhiao; Rudnicki, Paul E.; Zhang, Zewen; Huang, Zhuojun; Celik, Hasan; Oyakhire, Solomon T.; Chen, Yuelang; Kong, Xian; Kim, Sang Cheol; Xiao, Xin; Wang, Hansen; Zheng, Yu; Kamat, Gaurav A.; Kim, Mun Sek; Bent, Stacey F.; Qin, Jian; Cui, Yi; Bao, Zhenan
      Nature Energy (2022), 7 (1), 94-106CODEN: NEANFD; ISSN:2058-7546. (Nature Portfolio)
      Electrolyte engineering improved cycling of Li metal batteries and anode-free cells at low current densities; however, high-rate capability and tuning of ionic conduction in electrolytes are desirable yet less-studied. Here, we design and synthesize a family of fluorinated-1,2-diethoxyethanes as electrolyte solvents. The position and amt. of F atoms functionalized on 1,2-diethoxyethane were found to greatly affect electrolyte performance. Partially fluorinated, locally polar -CHF2 is identified as the optimal group rather than fully fluorinated -CF3 in common designs. Paired with 1.2 M lithium bis(fluorosulfonyl)imide, these developed single-salt-single-solvent electrolytes simultaneously enable high cond., low and stable overpotential, >99.5% Li||Cu half-cell efficiency (up to 99.9%, ±0.1% fluctuation) and fast activation (Li efficiency >99.3% within two cycles). Combined with high-voltage stability, these electrolytes achieve roughly 270 cycles in 50-μm-thin Li||high-loading-NMC811 full batteries and >140 cycles in fast-cycling Cu||microparticle-LiFePO4 industrial pouch cells under realistic testing conditions. The correlation of Li+-solvent coordination, solvation environments and battery performance is investigated to understand structure-property relationships.
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      Li, Y.; Li, Y.; Pei, A. Atomic Structure of Sensitive Battery Materials and Interfaces Revealed by Cryo-Electron Microscopy. Science 2017, 358, 506– 510,  DOI: 10.1126/science.aam6014
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      Atomic structure of sensitive battery materials and interfaces revealed by cryo-electron microscopy
      Li, Yuzhang; Li, Yanbin; Pei, Allen; Yan, Kai; Sun, Yongming; Wu, Chun-Lan; Joubert, Lydia-Marie; Chin, Richard; Koh, Ai Leen; Yu, Yi; Perrino, John; Butz, Benjamin; Chu, Steven; Cui, Yi
      Science (Washington, DC, United States) (2017), 358 (6362), 506-510CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
      Whereas std. transmission electron microscopy studies are unable to preserve the native state of chem. reactive and beam-sensitive battery materials after operation, such materials remain pristine at cryogenic conditions. It is then possible to atomically resolve individual Li metal atoms and their interface with the solid electrolyte interphase (SEI). We observe that dendrites in carbonate-based electrolytes grow along the <111> (preferred), <110>, or <211> directions as faceted, single-cryst. nanowires. These growth directions can change at kinks with no observable crystallog. defect. We reveal distinct SEI nanostructures formed in different electrolytes.
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      Zhang, Y.; Viswanathan, V. Not All Fluorination Is the Same: Unique Effects of Fluorine Functionalization of Ethylene Carbonate for Tuning Solid-Electrolyte Interphase in Li Metal Batteries. Langmuir 2020, 36, 11450– 11466,  DOI: 10.1021/acs.langmuir.0c01652
      8
      Not All Fluorination Is the Same: Unique Effects of Fluorine Functionalization of Ethylene Carbonate for Tuning Solid-Electrolyte Interphase in Li Metal Batteries
      Zhang, Yumin; Viswanathan, Venkatasubramanian
      Langmuir (2020), 36 (39), 11450-11466CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
      Li metal batteries (LMBs) are crucial for electrifying transportation and aviation. Engineering electrolytes to form desired solid-electrolyte interphase (SEI) is one of the most promising approaches to enable stable long-lasting LMBs. Among the liq. electrolytes explored, fluoroethylene carbonate (FEC) has seen great success in leading to desirable SEI properties for enabling stable cycling of LMBs. Given the many facets to desirable SEI properties, numerous descriptors and mechanisms have been proposed. To build a detailed mechanistic understanding, we analyze varying degrees of fluorination of the same prototype mol., chosen to be ethylene carbonate (EC) to tease out the interfacial reactivity at the Li metal/electrolyte. Using d. functional theory (DFT) calcns., we study the effect of mono-, di-, tri-, and tetra-fluorine substitutions of EC on its reactivity with Li surface facets in the presence and absence of Li salt. We find that the formation of LiF at the early stage of SEI formation, posited as a desirable SEI component, depends on the F-abstraction mechanism rather than the no. of fluorine substitution. The best illustrations of this are cis- and trans-difluoro ECs, where F-abstraction is spontaneous with the trans case, while the cis case needs to overcome a nonzero energy barrier. Using a Pearson correlation map, we find that the extent of initial chem. decompn. quantified by the assocd. reaction free energy is linearly correlated with the charge transferred from the Li surface and the no. of covalent-like bonds formed at the surface. The effect of salt and the surface facet have a much weaker role in detg. the decompns. at the immediate electrolyte/electrode interfaces. Putting all of this together, we find that tetra-FEC could act as a high-performing SEI modifier as it leads to a more homogeneous, denser LiF-contg. SEI. Using this methodol., future investigations will explore -CF3 functionalization and other backbone mols. (linear carbonates).
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    9. 9
      Hobold, G. M.; Lopez, J.; Guo, R.; Minafra, N.; Banerjee, A.; Shirley Meng, Y.; Shao-Horn, Y.; Gallant, B. M. Moving Beyond 99.9% Coulombic Efficiency for Lithium Anodes in Liquid Electrolytes. Nat. Energy 2021, 6, 951– 960,  DOI: 10.1038/s41560-021-00910-w
      9
      Moving beyond 99.9% Coulombic efficiency for lithium anodes in liquid electrolytes
      Hobold, Gustavo M.; Lopez, Jeffrey; Guo, Rui; Minafra, Nicolo; Banerjee, Abhik; Shirley Meng, Y.; Shao-Horn, Yang; Gallant, Betar M.
      Nature Energy (2021), 6 (10), 951-960CODEN: NEANFD; ISSN:2058-7546. (Nature Portfolio)
      A review. As Li-ion battery costs decrease, energy d. and thus driving range remains a roadblock for mass-market vehicle electrification. While Li-metal anodes help achieve Department of Energy targets of 500 Wh kg-1 (750 Wh l-1), Li Coulombic efficiencies fall below the 99.95+% required for 1,000+ cycles. Here we examine historical electrolyte developments underlying increased Coulombic efficiency and discuss emerging frameworks that support rational strategies to move beyond 99.9%. While multiple electrolytes reach 98-99% Coulombic efficiency over subsets of cycles, achieving >99.9% Coulombic efficiency consistently throughout cycling is an as yet unmet challenge. We analyze important interplays between electrolyte, solid electrolyte interphase compn., plating-stripping kinetics and Li morphol., many of which are only recently being quantified exptl. at the Li interface, and which collectively det. Coulombic efficiency. We also discuss forward-looking strategies that, if mastered, represent new opportunities to refine understanding and support new record values of Coulombic efficiency in the coming years.
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      Tarascon, J. M.; Armand, M. Issues and Challenges Facing Rechargeable Lithium Batteries. Nature 2001, 414, 359– 367,  DOI: 10.1038/35104644
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      Issues and challenges facing rechargeable lithium batteries
      Tarascon, J.-M.; Armand, M.
      Nature (London, United Kingdom) (2001), 414 (6861), 359-367CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)
      A review of the development of lithium-based rechargeable batteries. Ongoing research strategies are highlighted, and the challenges that remain regarding the synthesis, characterization, electrochem. performance, and safety of these systems are discussed.
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    11. 11
      Kuai, D.; Balbuena, P. B. Solvent Degradation and Polymerization in the Li-Metal Battery: Organic-Phase Formation in Solid-Electrolyte Interphases. ACS Appl. Mater. Interfaces 2022, 14, 2817– 2824,  DOI: 10.1021/acsami.1c20487
      11
      Solvent Degradation and Polymerization in the Li-Metal Battery: Organic-Phase Formation in Solid-Electrolyte Interphases
      Kuai, Dacheng; Balbuena, Perla B.
      ACS Applied Materials & Interfaces (2022), 14 (2), 2817-2824CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      The products of solvent polymn. and degrdn. are crucial components of the Li-metal battery solid-electrolyte interphase. However, in-depth mechanistic studies of these reactions are still scarce. Here, we model the polymn. of common lithium battery electrolyte solvents-ethylene carbonate (EC) and vinylene carbonate (VC)-near the anode surface. Being consistent with the mol. calcn., ab initio mol. dynamic (AIMD) simulations reveal fast solvent decompns. upon contact with the Li anode. Addnl., we assessed the thermochem. impacts of decarboxylation reactions as well as the lithium bonding with reaction intermediates. In both EC and VC polymn. pathways, lithium bonding demonstrated profound catalytic effects while different degrees of decarboxylation were obsd. The VC polymn. pathways with and without ring-opening events were evaluated systematically, and the latter one which leads to poly(VC) formation was proven to dominate the oligomerization process. Both the decompn. and polymn. reactivities of VC are found to be higher than EC, while the cross-coupling between EC and VC has an even lower-energy barrier. These findings are in good agreement with exptl. evidence and explanatory toward the enhanced performance of VC-added lithium-metal batteries.
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    12. 12
      Shi, S.; Lu, P.; Liu, Z.; Qi, Y.; Hector, L. G., Jr.; Li, H.; Harris, S. J. Direct Calculation of Li-Ion Transport in the Solid Electrolyte Interphase. J. Am. Chem. Soc. 2012, 134, 15476– 15487,  DOI: 10.1021/ja305366r
      12
      Direct Calculation of Li-Ion Transport in the Solid Electrolyte Interphase
      Shi, Siqi; Lu, Peng; Liu, Zhongyi; Qi, Yue; Hector, Louis G.; Li, Hong; Harris, Stephen J.
      Journal of the American Chemical Society (2012), 134 (37), 15476-15487CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      The mechanism of Li+ transport through the solid electrolyte interphase (SEI), a passivating film on electrode surfaces, has never been clearly elucidated despite its overwhelming importance to Li-ion battery operation and lifetime. The present paper develops a multiscale theor. methodol. to reveal the mechanism of Li+ transport in a SEI film. The methodol. incorporates the boundary conditions of the first direct diffusion measurements on a model SEI consisting of porous (outer) org. and dense (inner) inorg. layers (similar to typical SEI films). New exptl. evidence confirms that the inner layer in the ∼20 nm thick model SEI is primarily cryst. Li2CO3. Using d. functional theory, we first detd. that the dominant diffusion carrier in Li2CO3 below the voltage range of SEI formation is excess interstitial Li+. This diffuses via a knock-off mechanism to maintain higher O-coordination, rather than direct-hopping through empty spaces in the Li2CO3 lattice. Mesoscale diffusion equations were then formulated upon a new two-layer/two-mechanism model: pore diffusion in the outer layer and knock-off diffusion in the inner layer. This diffusion model predicted the unusual isotope ratio 6Li+/7Li+ profile measured by TOF-SIMS, which increases from the SEI/electrolyte surface and peaks at a depth of 5 nm, and then gradually decreases within the dense layer. With no fitting parameters, our approach is applicable to model general transport properties, such as ionic cond., for SEI films on the surface of other electrodes, from the at. scale to the mesoscale, as well as aging phenomenon.
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    13. 13
      Zhang, Z.; Li, Y.; Xu, R. Capturing the Swelling of Solid-Electrolyte Interphase in Lithium Metal Batteries. Science 2022, 375, 66– 70,  DOI: 10.1126/science.abi8703
      13
      Capturing the swelling of solid-electrolyte interphase in lithium metal batteries
      Zhang, Zewen; Li, Yuzhang; Xu, Rong; Zhou, Weijiang; Li, Yanbin; Oyakhire, Solomon T.; Wu, Yecun; Xu, Jinwei; Wang, Hansen; Yu, Zhiao; Boyle, David T.; Huang, William; Ye, Yusheng; Chen, Hao; Wan, Jiayu; Bao, Zhenan; Chiu, Wah; Cui, Yi
      Science (Washington, DC, United States) (2022), 375 (6576), 66-70CODEN: SCIEAS; ISSN:1095-9203. (American Association for the Advancement of Science)
      Although liq.-solid interfaces are foundational in broad areas of science, characterizing this delicate interface remains inherently difficult because of shortcomings in existing tools to access liq. and solid phases simultaneously at the nanoscale. This leads to substantial gaps in our understanding of the structure and chem. of key interfaces in battery systems. We adopt and modify a thin film vitrification method to preserve the sensitive yet crit. interfaces in batteries at native liq. electrolyte environments to enable cryo-electron microscopy and spectroscopy. We report substantial swelling of the solid-electrolyte interphase (SEI) on lithium metal anode in various electrolytes. The swelling behavior is dependent on electrolyte chem. and is highly correlated to battery performance. Higher degrees of SEI swelling tend to exhibit poor electrochem. cycling.
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    14. 14
      Qian, Y.; Hu, S.; Zou, X. How Electrolyte Additives Work in Li-Ion Batteries. Energy Storage Mater. 2019, 20, 208– 215,  DOI: 10.1016/j.ensm.2018.11.015
      There is no corresponding record for this reference.
    15. 15
      Yu, Y.; Karayaylali, P.; Katayama, Y.; Giordano, L.; Gauthier, M.; Maglia, F.; Jung, R.; Lund, I.; Shao-Horn, Y. Coupled Lipf6 Decomposition and Carbonate Dehydrogenation Enhanced by Highly Covalent Metal Oxides in High-Energy Li-Ion Batteries. J. Phys. Chem. C. 2018, 122, 27368– 27382,  DOI: 10.1021/acs.jpcc.8b07848
      15
      Coupled LiPF6 Decomposition and Carbonate Dehydrogenation Enhanced by Highly Covalent Metal Oxides in High-Energy Li-Ion Batteries
      Yu, Yang; Karayaylali, Pinar; Katayama, Yu; Giordano, Livia; Gauthier, Magali; Maglia, Filippo; Jung, Roland; Lund, Isaac; Shao-Horn, Yang
      Journal of Physical Chemistry C (2018), 122 (48), 27368-27382CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
      The (electro)chem. reactions between pos. electrodes and electrolytes are not well understood. The oxidn. is examd. of a LiPF6-based electrolyte with ethylene carbonate (EC) with layered lithium nickel, manganese, and cobalt oxides (NMC). D. functional theory calcns. showed that the driving force for EC dehydrogenation on oxides, yielding surface protic species, increased with greater Ni content in NMC. Ex situ IR and Raman spectroscopy revealed exptl. evidence for EC dehydrogenation on charged NMC surfaces. Protic species on charged NMC surfaces from EC dehydrogenation could further react with LiPF6 to generate less-coordinated F species such as PF3O-like and lithium nickel oxyfluoride species on charged NMC particles and HF and PF2O2- in the electrolyte. Larger degree of salt decompn. was coupled with increasing EC dehydrogenation on charged NMC with increasing Ni or lithium deintercalation. An oxide-mediated chem. oxidn. of electrolytes was proposed, providing new insights in stabilizing high-energy pos. electrodes and improving Li-ion battery cycle life.
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    16. 16
      Kuai, D.; Cheng, H.; Kuan, K.-Y.; Yan, X. Accelerated Five-Component Spiro-Pyrrolidine Construction at the Air–Liquid Interface. Chem. Commun. 2021, 57, 3757– 3760,  DOI: 10.1039/D1CC00574J
      16
      Accelerated five-component spiro-pyrrolidine construction at the air-liquid interface
      Kuai, Dacheng; Cheng, Heyong; Kuan, Kai-Yuan; Yan, Xin
      Chemical Communications (Cambridge, United Kingdom) (2021), 57 (31), 3757-3760CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
      Multi-component reactions assemble complex mols. in a highly effective way, however, they often suffer from long reaction times. We demonstrate that acceleration of a five-component spiro-pyrrolidine construction can be achieved in microdroplets and thin films. The deposition method and mild heating are crucial factors for product formation. Three key intermediates were captured by mass spectrometry to elucidate the tandem reaction mechanism. We also found that hydrogen bonding can significantly flatten the energy barrier at the air-liq. interface.
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    17. 17
      Yao, N.; Chen, X.; Fu, Z.-H.; Zhang, Q. Applying Classical, Ab Initio, and Machine-Learning Molecular Dynamics Simulations to the Liquid Electrolyte for Rechargeable Batteries. Chem. Rev. 2022, 122, 10970– 11021,  DOI: 10.1021/acs.chemrev.1c00904
      17
      Applying Classical, Ab Initio, and Machine-Learning Molecular Dynamics Simulations to the Liquid Electrolyte for Rechargeable Batteries
      Yao, Nan; Chen, Xiang; Fu, Zhong-Heng; Zhang, Qiang
      Chemical Reviews (Washington, DC, United States) (2022), 122 (12), 10970-11021CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review. Rechargeable batteries have become indispensable implements in our daily life and are considered a promising technol. to construct sustainable energy systems in the future. The liq. electrolyte is one of the most important parts of a battery and is extremely crit. in stabilizing the electrode-electrolyte interfaces and constructing safe and long-life-span batteries. Tremendous efforts have been devoted to developing new electrolyte solvents, salts, additives, and recipes, where mol. dynamics (MD) simulations play an increasingly important role in exploring electrolyte structures, physicochem. properties such as ionic cond., and interfacial reaction mechanisms. This review affords an overview of applying MD simulations in the study of liq. electrolytes for rechargeable batteries. First, the fundamentals and recent theor. progress in three-class MD simulations are summarized, including classical, ab initio, and machine-learning MD simulations (section 2). Next, the application of MD simulations to the exploration of liq. electrolytes, including probing bulk and interfacial structures (section 3), deriving macroscopic properties such as ionic cond. and dielec. const. of electrolytes (section 4), and revealing the electrode-electrolyte interfacial reaction mechanisms (section 5), are sequentially presented. Finally, a general conclusion and an insightful perspective on current challenges and future directions in applying MD simulations to liq. electrolytes are provided. Machine-learning technologies are highlighted to figure out these challenging issues facing MD simulations and electrolyte research and promote the rational design of advanced electrolytes for next-generation rechargeable batteries.
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    18. 18
      Dhattarwal, H. S.; Kuo, J.-L.; Kashyap, H. K. Mechanistic Insight on the Stability of Ether and Fluorinated Ether Solvent-Based Lithium Bis(Fluoromethanesulfonyl) Electrolytes near Li Metal Surface. J. Phys. Chem. C. 2022, 126, 8953– 8963,  DOI: 10.1021/acs.jpcc.2c02323
      18
      Mechanistic Insight on the Stability of Ether and Fluorinated Ether Solvent-Based Lithium Bis(fluoromethanesulfonyl) Electrolytes near Li Metal Surface
      Dhattarwal, Harender S.; Kuo, Jer-Lai; Kashyap, Hemant K.
      Journal of Physical Chemistry C (2022), 126 (20), 8953-8963CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
      Recently, ether-based solvents and their fluorinated derivs. have shown extraordinary ability to facilitate the formation of a highly stable ultrathin solid-electrolyte interphase (SEI) layer in lithium metal batteries (LMBs). Herein, d. functional theory based mol. dynamics (DFT-MD) simulations have been performed to provide a mechanistic insight on the stability of Li-bis(fluoromethanesulfonyl)imide ([Li][FSI]) salt dissolved in dimethoxybutane (DMB) and fluorinated dimethoxybutane (FDMB) solvents near the surface of lithium metal which is employed as anode in LMBs. It is obsd. that because of the strong reducing nature of Li, the FSI anions in both of the electrolytes readily dissoc. to form LiF, Li2O, and other species. Our anal. reveals that while the DMB mols. in the [Li][FSI]-DMB system are relatively stable against reductive dissocn., the FDMB mols. in the [Li][FSI]-FDMB system easily undergo reductive dissocn. upon charge transfer from the Li surface. It is shown that the SF bonds of the FSI anions and CF bonds of FDMB mols. are the first ones to break upon their exposure to the Li metal surface. It is obsd. that the dissocd. species of [Li][FSI]-FDMB electrolyte cover the Li surface completely, preventing further dissocn. of other FSI anions and solvent mols. It is found that the FDMB dissocn. majorly contributes F atoms forming addnl. LiF which is an essential component for the formation of a uniform and robust SEI.
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    19. 19
      Yamijala, S. S. R. K. C.; Kwon, H.; Guo, J.; Wong, B. M. Stability of Calcium Ion Battery Electrolytes: Predictions from Ab Initio Molecular Dynamics Simulations. ACS Appl. Mater. Interfaces 2021, 13, 13114– 13122,  DOI: 10.1021/acsami.0c21716
      19
      Stability of Calcium Ion Battery Electrolytes: Predictions from Ab Initio Molecular Dynamics Simulations
      Yamijala, Sharma S. R. K. C.; Kwon, Hyuna; Guo, Juchen; Wong, Bryan M.
      ACS Applied Materials & Interfaces (2021), 13 (11), 13114-13122CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      Multivalent batteries, such as magnesium-ion, calcium-ion, and zinc-ion batteries, have attracted significant attention as next-generation electrochem. energy storage devices to complement conventional lithium-ion batteries (LIBs). Among them, calcium-ion batteries (CIBs) are the least explored due to difficult reversible Ca deposition-dissoln. In this work, we examd. the stability of four different Ca salts with weakly coordinating anions and three different solvents commonly employed in existing battery technologies to identify suitable candidates for CIBs. By employing Born-Oppenheimer mol. dynamics (BOMD) simulations on salt-Ca and solvent-Ca interfaces, we find that the tetraglyme solvent and carborane salt are promising candidates for CIBs. Due to the strong reducing nature of the calcium surface, the other salts and solvents readily decomp. We explain the microscopic mechanisms of salt/solvent decompn. on the Ca surface using time-dependent projected d. of states, time-dependent charge-transfer plots, and climbing-image nudged elastic band calcns. Collectively, this work presents the first mechanistic assessment of the dynamical stability of candidate salts and solvents on a Ca surface using BOMD simulations, and provides a predictive path toward designing stable electrolytes for CIBs.
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    20. 20
      Martinez de la Hoz, J. M.; Soto, F. A.; Balbuena, P. B. Effect of the Electrolyte Composition on Sei Reactions at Si Anodes of Li-Ion Batteries. J. Phys. Chem. C. 2015, 119, 7060– 7068,  DOI: 10.1021/acs.jpcc.5b01228
      20
      Effect of the Electrolyte Composition on SEI Reactions at Si Anodes of Li-Ion Batteries
      Martinez de la Hoz, Julibeth M.; Soto, Fernando A.; Balbuena, Perla B.
      Journal of Physical Chemistry C (2015), 119 (13), 7060-7068CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
      Solid-electrolyte interphase (SEI) layers formed at the surface of Si anodes due to reductive decompn. of the electrolyte components are partially responsible of the irreversible capacity loss that neg. affects battery performance. The authors use ab initio mol. dynamics simulations to study how the electrolyte compn. including org. carbonates and LiPF6 affects such reactions. Solvent polarity defines salt dissocn., and there is a competition between salt and solvent/additive dissocn. The salt anion decomps., yielding a PF3 group and 3 F- anions. The PF3 group is relatively stable, but after some time, it decomps. nucleating on the anode surface as LiF. During anion decompn. the P atom progressively reduces finally becoming coupled to a surface atom or to fragments of the solvent/additive decompn. that takes place prior or simultaneously with the salt decompn. New pathways are found for formation of CO2 from vinylene carbonate reaction with the surface and for nucleation of Li oxide precursors.
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    21. 21
      Galvez-Aranda, D. E.; Seminario, J. M. Li-Metal Anode in a Conventional Li-Ion Battery Electrolyte: Solid Electrolyte Interphase Formation Using Ab Initio Molecular Dynamics. J. Electrochem. Soc. 2022, 169, 030502  DOI: 10.1149/1945-7111/ac55c8
      21
      Li-metal anode in a conventional Li-ion battery electrolyte: solid electrolyte interphase formation using ab initio molecular dynamics
      Galvez-Aranda, Diego E.; Seminario, Jorge M.
      Journal of the Electrochemical Society (2022), 169 (3), 030502CODEN: JESOAN; ISSN:1945-7111. (IOP Publishing Ltd.)
      Ab initio mol. dynamics simulations were performed for Li+ conducting electrolytes based on 1M lithium hexafluorophosphate (Li+PF-6) in ethylene carbonate (EC)-ethylmethyl carbonate (EMC) (3:7wt) with 5 wt% vinylene carbonate (VC) in contact with Li-metal (electrode), finding a variety of products due to dissocns. of all electrolyte components. The formed solid electrolyte interphase from electrolyte degrdn. arranges in an outer layer composed of denser materials (sitting over the anode surface) such as Li2(CH2O)2 from EC, Li2CO3, Li2C2H2 and Li2CO2 from VC, and Li2C3H5O2 and LiCH3O from EMC dissocns. Then follows an inner layer made of Li-binary compds., Li3CO, Li2O and Li3C from EC, Li2O, Li2C2 and LiH from VC, and LiF and Li3P from PF-6 dissocns. We calcd. electron affinities of electrolyte mols. during their decompn. using a polarizable continuum model to consider solvent effects mols. degrdn. PF-6 has the highest first and second electron affinities, despite explicit Coulomb repulsion, which eventually dissocs. the mol. right after capturing an electron from the metal-anode; therefore, PF-6 is also the fastest to dissoc. EMC has the lowest first and second electron affinities, thus it is the least prone to accept electrons and the least likely to dissoc. at the Li-metal interface.
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    22. 22
      Yao, N.; Chen, X.; Shen, X.; Zhang, R.; Fu, Z.-H.; Ma, X.-X.; Zhang, X.-Q.; Li, B.-Q.; Zhang, Q. An Atomic Insight into the Chemical Origin and Variation of Dielectric Constant in Liquid Electrolytes. Angew. Chem., Int. Ed. 2021, 60, 21473– 21478,  DOI: 10.1002/anie.202107657
      22
      An Atomic Insight into the Chemical Origin and Variation of the Dielectric Constant in Liquid Electrolytes
      Yao, Nan; Chen, Xiang; Shen, Xin; Zhang, Rui; Fu, Zhong-Heng; Ma, Xia-Xia; Zhang, Xue-Qiang; Li, Bo-Quan; Zhang, Qiang
      Angewandte Chemie, International Edition (2021), 60 (39), 21473-21478CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The dielec. const. is a crucial physicochem. property of liqs. in tuning solute-solvent interactions and solvation microstructures. Herein the dielec. const. variation of liq. electrolytes regarding to temps. and electrolyte compns. is probed by mol. dynamics simulations. Dielec. consts. of solvents reduce as temps. increase due to accelerated mobility of mols. For solvent mixts. with different mixing ratios, their dielec. consts. either follow a linear superposition rule or satisfy a polynomial function, depending on weak or strong intermol. interactions. Dielec. consts. of electrolytes exhibit a volcano trend with increasing salt concns., which can be attributed to dielec. contributions from salts and formation of solvation structures. This work affords an at. insight into the dielec. const. variation and its chem. origin, which can deepen the fundamental understanding of soln. chem.
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    23. 23
      Ren, X.; Zou, L.; Jiao, S. High-Concentration Ether Electrolytes for Stable High-Voltage Lithium Metal Batteries. ACS Energy Lett. 2019, 4, 896– 902,  DOI: 10.1021/acsenergylett.9b00381
      23
      High-Concentration Ether Electrolytes for Stable High-Voltage Lithium Metal Batteries
      Ren, Xiaodi; Zou, Lianfeng; Jiao, Shuhong; Mei, Donghai; Engelhard, Mark H.; Li, Qiuyan; Lee, Hongkyung; Niu, Chaojiang; Adams, Brian D.; Wang, Chongmin; Liu, Jun; Zhang, Ji-Guang; Xu, Wu
      ACS Energy Letters (2019), 4 (4), 896-902CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)
      High-voltage (>4.3 V) rechargeable lithium (Li) metal batteries (LMBs) face huge obstacles due to the high reactivity of Li metal with traditional electrolytes. Despite their good stability with Li metal, conventional ether-based electrolytes are typically used only in <4.0 V LMBs because of their limited oxidn. stability. Here we report high-concn. ether electrolytes that can induce the formation of a unique cathode electrolyte interphase via the synergy between the salt and the ether solvent, which effectively stabilizes the catalytically active cathodes and preserves their structural integrity under high voltages. Eventually, LMBs can retain 92% capacity after 500 cycles at 4.3 V with limited Li consumption. More importantly, such ether electrolytes enable stable battery cycling not only under voltages as high as 4.5 V but also on highly demanding Ni-rich layered cathodes. These findings significantly expand knowledge of ether electrolytes and provide new perspectives of electrolyte design for high-energy-d. LMBs.
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    24. 24
      Jiao, S.; Ren, X.; Cao, R. Stable Cycling of High-Voltage Lithium Metal Batteries in Ether Electrolytes. Nat. Energy 2018, 3, 739– 746,  DOI: 10.1038/s41560-018-0199-8
      24
      Stable cycling of high-voltage lithium metal batteries in ether electrolytes
      Jiao, Shuhong; Ren, Xiaodi; Cao, Ruiguo; Engelhard, Mark H.; Liu, Yuzi; Hu, Dehong; Mei, Donghai; Zheng, Jianming; Zhao, Wengao; Li, Qiuyan; Liu, Ning; Adams, Brian D.; Ma, Cheng; Liu, Jun; Zhang, Ji-Guang; Xu, Wu
      Nature Energy (2018), 3 (9), 739-746CODEN: NEANFD; ISSN:2058-7546. (Nature Research)
      The key to enabling long-term cycling stability of high-voltage lithium (Li) metal batteries is the development of functional electrolytes that are stable against both Li anodes and high-voltage (above 4 V vs. Li/Li+) cathodes. Due to their limited oxidative stability ( <4 V), ethers have so far been excluded from being used in high-voltage batteries, in spite of their superior reductive stability against Li metal compared to conventional carbonate electrolytes. Here, we design a concd. dual-salt/ether electrolyte that induces the formation of stable interfacial layers on both a high-voltage LiNi1/3Mn1/3Co1/3O2 cathode and the Li metal anode, thus realizing a capacity retention of >90% over 300 cycles and ∼80% over 500 cycles with a charge cut-off voltage of 4.3 V. This study offers a promising approach to enable ether-based electrolytes for high-voltage Li metal battery applications.
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    25. 25
      Rostkier-Edelstein, D.; Urbakh, M.; Nitzan, A. Electron Tunneling through a Dielectric Barrier. J. Chem. Phys. 1994, 101, 8224– 8237,  DOI: 10.1063/1.468207
      25
      Electron tunneling through a dielectric barrier
      Rostkier-Edelstein, Dorita; Urbakh, Michael; Nitzan, Abraham
      Journal of Chemical Physics (1994), 101 (9), 8224-37CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
      Electron tunneling through a dielec. barrier is considered with special attention given to questions relevant for STM expts. in dielec. liqs. The effect of the barrier dielec. response on the tunneling probability is studied using the effective Hamiltonian formalism for the polarization dynamics in the barrier, and two different theor. approaches for the calcn. of the tunneling probability: a generalization of Bardeen's formalism to inelastic tunneling and the quasi-classical of Brink, Nemes, and Vautherin as expanded by Sumetskii. Although based on different approxns., both approaches yield similar results in the slow barrier limit, where their ranges of validity coincide. The approach based on the Bardeen's formalism relies on the adiabatic approxn. and fails for fast barrier dynamics. The overall effect of the barrier dielec. response is to enhance the tunneling probability relative to the rigid barrier case. The enhancement factor is larger for thicker barrier, higher temp., and faster barrier dynamics. Both the elastic and inelastic components of the tunneling current show these trends in the relevant range of parameters.
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    26. 26
      Chen, X.; Zhang, Q. Atomic Insights into the Fundamental Interactions in Lithium Battery Electrolytes. Acc. Chem. Res. 2020, 53, 1992– 2002,  DOI: 10.1021/acs.accounts.0c00412
      26
      Atomic Insights into the Fundamental Interactions in Lithium Battery Electrolytes
      Chen, Xiang; Zhang, Qiang
      Accounts of Chemical Research (2020), 53 (9), 1992-2002CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
      A review. Building high-energy-d. batteries is urgently demanded in contemporary society because of the continuous increase in global energy consumption and the quick upgrade of electronic devices, which promotes the use of high-capacity lithium metal anodes and high-voltage cathodes. Achieving a stable interface between electrolytes and highly reactive electrodes is a prerequisite to constructing a safe and powerful battery, in which electrolyte regulation plays a decisive role and largely dets. the long-term and rate performances. The bulk and interfacial properties of electrolytes are directly detd. by the fundamental interactions and the as-derived microstructures in electrolytes. Different from exptl. trial-and-error approaches, the rational bottom-up design of electrolytes based on a comprehensive and deep understanding of the fundamental interactions between electrolyte compns. and the structure-function relationship is highly expected to accelerate breaking through the bottleneck in current technol. and realizing next-generation Li batteries. An overview is presented of the authors recent attempts toward rational electrolyte design for safe Li batteries based on a comprehensive understanding of the cation-solvent, cation-anion, and anion-solvent interactions in electrolytes. The formation of cation-solvent complexes decreases the reductive stability but increases the oxidative stability of solvent mols. according to frontier MO theory, whereas the introduction of anions into the Li+ solvation shell has the opposite function in regulating solvent stability compared with cations. The competitive coordination of anions and solvent mols. with cations directly dets. the salt soly. in electrolytes and the formation of ion pairs and aggregates, which widely exist in high-concn. electrolytes and stabilize Li metal anodes. An easy and effective route to dissolve lithium nitrate in ester electrolytes is accordingly proposed. Although anions are hardly solvated in routine solvents, solvents with a high acceptor no. or an exposed pos. charge site are highly expected to enhance the anion-solvent interaction. The solvation of anions will have a strong effect on electrolytes, including regulating the electrolyte solvation structure and stability, increasing the cation transference no., and promoting salt dissocn. The emerging Li bond theory and big-data approaches, combined with first-principles calcns. and exptl. characterizations, are also expected to promote rational electrolyte design with much reduced time and expense. Collectively, with a comprehensive and deep understanding of the fundamental interactions in electrolytes and the structure-function relationship, bottom-up engineering of Li battery electrolytes is expected to be achieved, accelerating the applications of safe high-energy-d. Li batteries. The general principles demonstrated in Li batteries are also supposed to be applicable to other battery systems and even universal electrochem. in solns., including fuel cells and various electrocatalyzers.
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    27. 27
      Lu, D.; Shao, Y.; Lozano, T. Failure Mechanism for Fast-Charged Lithium Metal Batteries with Liquid Electrolytes. Adv. Energy Mater. 2015, 5, 1400993  DOI: 10.1002/aenm.201400993
      There is no corresponding record for this reference.
    28. 28
      Ospina-Acevedo, F.; Guo, N.; Balbuena, P. B. Lithium Oxidation and Electrolyte Decomposition at Li-Metal/Liquid Electrolyte Interfaces. J. Mater. Chem. A 2020, 8, 17036– 17055,  DOI: 10.1039/D0TA05132B
      28
      Lithium oxidation and electrolyte decomposition at Li-metal/liquid electrolyte interfaces
      Ospina-Acevedo, Francisco; Guo, Ningxuan; Balbuena, Perla B.
      Journal of Materials Chemistry A: Materials for Energy and Sustainability (2020), 8 (33), 17036-17055CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
      We examine the evolution of events occurring when a Li metal surface is in contact with a 2 M soln. of a Li salt in a solvent or mixt. of solvents, via classical mol. dynamics simulations with a reactive force field allowing bond breaking and bond forming. The main events include Li oxidn. and electrolyte redn. along with expansion of the Li surface layers forming a porous phase that is the basis for the formation of the solid-electrolyte interphase (SEI) components. Nucleation of the main SEI components (LiF, Li oxides, and some orgs.) is characterized. The anal. clearly reveals the details of these phys.-chem. events as a function of time, during 20 ns. The effects of the chem. of the electrolyte on Li oxidn. and dissoln. in the liq. electrolyte, and SEI nucleation and structure are identified by testing two salts: LiPF6 and LiCF3SO3, and various solvents including ethers and carbonates and mixts. of them. The kinetics and thermodn. of Li6F, the core nuclei in the LiF crystal, are studied by anal. of the MD trajectories, and via d. functional theory calcns. resp. The SEI formed in this computational expt. is the "native" film that would form upon contact of the Li foil with the liq. electrolyte. As such, this work is the first in a series of computational expts. that will help elucidate the intricate interphase layer formed during battery cycling using metal anodes.
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    29. 29
      Perez Beltran, S.; Balbuena, P. B. Sei Formation Mechanisms and Li+ Dissolution in Lithium Metal Anodes: Impact of the Electrolyte Composition and the Electrolyte-to-Anode Ratio. J. Power Sources 2022, 551, 232203– 232210,  DOI: 10.1016/j.jpowsour.2022.232203
      29
      SEI formation mechanisms and Li+ dissolution in lithium metal anode and impact of electrolyte composition and electrolyte-anode ratio
      Perez Beltran, Saul; Balbuena, Perla B.
      Journal of Power Sources (2022), 551 (), 232203CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      A review. The lithium metal battery is one of today's most promising high-energy-d. storage devices. Its full-scale implementation depends on solving operational and safety issues intrinsic to the Li metal high reactivity leading to uncontrolled electrolyte decompn. and uneven Li deposition. In this work, we study the spontaneous formation of the solid electrolyte interphase (SEI) upon contact of Li metal with the electrolyte and describe the heterogeneous SEI morphol. features. Multiple electrolyte formulations based on lithium bis(fluorosulfonyl)imide (LiFSI), dimethoxyethane (DME), di-Me carbonate (DMC), 1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) and bis(2,2,2-trifluoroethyl) ether (BTFE) are used. Findings include the description of the SEI evolution from dispersed LiO, LiS, LiN, and LiF clusters to a continuous and compact inorg. phase in which the LiO and LiF content depend on the presence of fluorine diluents. The role of the DME ether solvent helping the growth of a "wet-SEI" is compared to that of the highly unstable carbonate DMC, which decompg. into complex radical oligomers that might contribute to further electrolyte decompn. The impact of the electrolyte-anode ratio on LiFSI decompn. is highlighted. Finally, we suggest the existence of a crit. LiFSI concn. and electrolyte-anode ratio that could potentially balance the rate of electrolyte depletion and lithium consumption.
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    30. 30
      Spotte-Smith, E. W. C.; Kam, R. L.; Barter, D.; Xie, X.; Hou, T.; Dwaraknath, S.; Blau, S. M.; Persson, K. A. Toward a Mechanistic Model of Solid–Electrolyte Interphase Formation and Evolution in Lithium-Ion Batteries. ACS Energy Lett. 2022, 7, 1446– 1453,  DOI: 10.1021/acsenergylett.2c00517
      30
      Toward a Mechanistic Model of Solid-Electrolyte Interphase Formation and Evolution in Lithium-Ion Batteries
      Spotte-Smith, Evan Walter Clark; Kam, Ronald L.; Barter, Daniel; Xie, Xiaowei; Hou, Tingzheng; Dwaraknath, Shyam; Blau, Samuel M.; Persson, Kristin A.
      ACS Energy Letters (2022), 7 (4), 1446-1453CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)
      The formation of passivation films by interfacial reactions, though crit. for applications ranging from advanced alloys to electrochem. energy storage, is often poorly understood. In this work, we explore the formation of an exemplar passivation film, the solid-electrolyte interphase (SEI), which is responsible for stabilizing lithium-ion batteries. Using stochastic simulations based on quantum chem. calcns. and data-driven chem. reaction networks, we directly model competition between SEI products at a mechanistic level for the first time. Our results recover the Peled-like sepn. of the SEI into inorg. and org. domains resulting from rich reactive competition without fitting parameters to exptl. inputs. By conducting accelerated simulations at elevated temp., we track SEI evolution, confirming the postulated redn. of lithium ethylene monocarbonate to dilithium ethylene monocarbonate and H2. These findings furnish fundamental insights into the dynamics of SEI formation and illustrate a path forward toward a predictive understanding of electrochem. passivation.
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    31. 31
      Kresse, G.; Hafner, J. Ab Initio Molecular Dynamics for Liquid Metals. Phys. Rev. B 1993, 47, 558– 561,  DOI: 10.1103/PhysRevB.47.558
      31
      Ab initio molecular dynamics of liquid metals
      Kresse, G.; Hafner, J.
      Physical Review B: Condensed Matter and Materials Physics (1993), 47 (1), 558-61CODEN: PRBMDO; ISSN:0163-1829.
      The authors present ab initio quantum-mech. mol.-dynamics calcns. based on the calcn. of the electronic ground state and of the Hellmann-Feynman forces in the local-d. approxn. at each mol.-dynamics step. This is possible using conjugate-gradient techniques for energy minimization, and predicting the wave functions for new ionic positions using sub-space alignment. This approach avoids the instabilities inherent in quantum-mech. mol.-dynamics calcns. for metals based on the use of a factitious Newtonian dynamics for the electronic degrees of freedom. This method gives perfect control of the adiabaticity and allows one to perform simulations over several picoseconds.
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    32. 32
      Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized Gradient Approximation Made Simple. Phys. Rev. Lett. 1996, 77, 3865– 3868,  DOI: 10.1103/PhysRevLett.77.3865
      32
      Generalized gradient approximation made simple
      Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
      Physical Review Letters (1996), 77 (18), 3865-3868CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)
      Generalized gradient approxns. (GGA's) for the exchange-correlation energy improve upon the local spin d. (LSD) description of atoms, mols., and solids. We present a simple derivation of a simple GGA, in which all parameters (other than those in LSD) are fundamental consts. Only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked. Improvements over PW91 include an accurate description of the linear response of the uniform electron gas, correct behavior under uniform scaling, and a smoother potential.
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    33. 33
      Blöchl, P. E. Projector Augmented-Wave Method. Phys. Rev. B 1994, 50, 17953– 17979,  DOI: 10.1103/PhysRevB.50.17953
      33
      Projector augmented-wave method
      Blochl
      Physical review. B, Condensed matter (1994), 50 (24), 17953-17979 ISSN:0163-1829.
      There is no expanded citation for this reference.
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    34. 34
      Kresse, G.; Joubert, D. From Ultrasoft Pseudopotentials to the Projector Augmented-Wave Method. Phys. Rev. B 1999, 59, 1758– 1775,  DOI: 10.1103/PhysRevB.59.1758
      34
      From ultrasoft pseudopotentials to the projector augmented-wave method
      Kresse, G.; Joubert, D.
      Physical Review B: Condensed Matter and Materials Physics (1999), 59 (3), 1758-1775CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
      The formal relationship between ultrasoft (US) Vanderbilt-type pseudopotentials and Blochl's projector augmented wave (PAW) method is derived. The total energy functional for US pseudopotentials can be obtained by linearization of two terms in a slightly modified PAW total energy functional. The Hamilton operator, the forces, and the stress tensor are derived for this modified PAW functional. A simple way to implement the PAW method in existing plane-wave codes supporting US pseudopotentials is pointed out. In addn., crit. tests are presented to compare the accuracy and efficiency of the PAW and the US pseudopotential method with relaxed-core all-electron methods. These tests include small mols. (H2, H2O, Li2, N2, F2, BF3, SiF4) and several bulk systems (diamond, Si, V, Li, Ca, CaF2, Fe, Co, Ni). Particular attention is paid to the bulk properties and magnetic energies of Fe, Co, and Ni.
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    35. 35
      Ehrlich, S.; Moellmann, J.; Reckien, W.; Bredow, T.; Grimme, S. System-Dependent Dispersion Coefficients for the Dft-D3 Treatment of Adsorption Processes on Ionic Surfaces. ChemPhysChem 2011, 12, 3414– 3420,  DOI: 10.1002/cphc.201100521
      35
      System-Dependent Dispersion Coefficients for the DFT-D3 Treatment of Adsorption Processes on Ionic Surfaces
      Ehrlich, Stephan; Moellmann, Jonas; Reckien, Werner; Bredow, Thomas; Grimme, Stefan
      ChemPhysChem (2011), 12 (17), 3414-3420CODEN: CPCHFT; ISSN:1439-4235. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Dispersion-cor. d. functional theory calcns. (DFT-D3) were performed for the adsorption of CO on MgO and C2H2 on NaCl surfaces. An extension of our non-empirical scheme for the computation of atom-in-mols. dispersion coeffs. is proposed. It is based on electrostatically embedded M4X4 (M = Na, Mg) clusters that are used in TDDFT calcns. of dynamic dipole polarizabilities. We find that the C6MM dispersion coeffs. for bulk NaCl and MgO are reduced by factors of about 100 and 35 for Na and Mg, resp., compared to the values of the free atoms. These are used in periodic DFT calcns. with the revPBE semi-local d. functional. As demonstrated by calcns. of adsorption potential energy curves, the new C6 coeffs. lead to much more accurate energies (Eads) and mol.-surface distances than with previous DFT-D schemes. For NaCl/C2H2 we obtained at the revPBE-D3(BJ) level a value of Eads = -7.4 kcal mol-1 in good agreement with exptl. data (-5.7 to -7.1 kcal mol-1). Dispersion-uncorrected DFT yields an unbound surface state. For the MgO/CO system, the computed revPBE-D3(BJ) value of Eads = -4.1 kcal mol-1 is also in reasonable agreement with exptl. results (-3.0 kcal mol-1) when thermal corrections are taken into account. Our new dispersion correction also improves computed lattice consts. of the bulk systems significantly compared to plain DFT or previous DFT-D results. The extended DFT-D3 scheme also provides accurate non-covalent interactions for ionic systems without empirical adjustments and is suggested as a general tool in surface science.
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    36. 36
      Tang, W.; Sanville, E.; Henkelman, G. A Grid-Based Bader Analysis Algorithm without Lattice Bias. J. Phys.: Condens. Matter 2009, 21, 084204  DOI: 10.1088/0953-8984/21/8/084204
      36
      A grid-based Bader analysis algorithm without lattice bias
      Tang, W.; Sanville, E.; Henkelman, G.
      Journal of Physics: Condensed Matter (2009), 21 (8), 084204/1-084204/7CODEN: JCOMEL; ISSN:0953-8984. (Institute of Physics Publishing)
      A computational method for partitioning a charge d. grid into Bader vols. is presented which is efficient, robust, and scales linearly with the no. of grid points. The partitioning algorithm follows the steepest ascent paths along the charge d. gradient from grid point to grid point until a charge d. max. is reached. In this paper, we describe how accurate off-lattice ascent paths can be represented with respect to the grid points. This improvement maintains the efficient linear scaling of an earlier version of the algorithm, and eliminates a tendency for the Bader surfaces to be aligned along the grid directions. As the algorithm assigns grid points to charge d. maxima, subsequent paths are terminated when they reach previously assigned grid points. It is this grid-based approach which gives the algorithm its efficiency, and allows for the anal. of the large grids generated from plane-wave-based d. functional theory calcns.
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    37. 37
      Dunning, T. H., Jr. Gaussian Basis Sets for Use in Correlated Molecular Calculations. I. The Atoms Boron through Neon and Hydrogen. J. Chem. Phys. 1989, 90, 1007– 1023,  DOI: 10.1063/1.456153
      37
      Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
      Dunning, Thom H., Jr.
      Journal of Chemical Physics (1989), 90 (2), 1007-23CODEN: JCPSA6; ISSN:0021-9606.
      Guided by the calcns. on oxygen in the literature, basis sets for use in correlated at. and mol. calcns. were developed for all of the first row atoms from boron through neon, and for hydrogen. As in the oxygen atom calcns., the incremental energy lowerings, due to the addn. of correlating functions, fall into distinct groups. This leads to the concept of correlation-consistent basis sets, i.e., sets which include all functions in a given group as well as all functions in any higher groups. Correlation-consistent sets are given for all of the atoms considered. The most accurate sets detd. in this way, [5s4p3d2f1g], consistently yield 99% of the correlation energy obtained with the corresponding at.-natural-orbital sets, even though the latter contains 50% more primitive functions and twice as many primitive polarization functions. It is estd. that this set yields 94-97% of the total (HF + 1 + 2) correlation energy for the atoms neon through boron.
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    38. 38
      Woon, D. E.; T, H. D., Jr. Gaussian Basis Sets for Use in Correlated Molecular Calculations. Iii. The Atoms Aluminum through Argon. J. Chem. Phys. 1993, 98, 1358– 1371,  DOI: 10.1063/1.464303
      38
      Gaussian basis sets for use in correlated molecular calculations. III. The atoms aluminum through argon
      Woon, David E.; Dunning, Thom H., Jr.
      Journal of Chemical Physics (1993), 98 (2), 1358-71CODEN: JCPSA6; ISSN:0021-9606.
      Correlation consistent and augmented correlation consistent basis sets were detd. for the second row atoms. The methodol., originally developed for the first row atoms (T. H. D., Jr., 1989) is first applied to S. The exponents for the polarization functions (dfgh) are systematically optimized for a correlated wave function (HF+1+2). The (sp) correlation functions are taken from the appropriate HF primitive sets; these functions differ little from the optimum functions. Basis sets of double zeta [4s3p1d], triple zeta [5s4p2d1f], and quadruple zeta [6s5p3d2f1g] quality are defined. Each of these sets is then augmented with diffuse functions to better describe electron affinities and other mol. properties: s and p functions were obtained by optimization for the anion HF energy, while an addnl. polarization function for each symmetry present in the std. set was optimized for the anion HF+1+2 energy. The results for S are then used to assist in detg. double zeta, triple zeta, and quadruple zeta basis sets for the remainder of the second row of the p block.
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    39. 39
      Han, J.; Zheng, Y.; Guo, N.; Balbuena, P. B. Calculated Reduction Potentials of Electrolyte Species in Lithium–Sulfur Batteries. J. Phys. Chem. C 2020, 124, 20654– 20670,  DOI: 10.1021/acs.jpcc.0c04173
      39
      Calculated Reduction Potentials of Electrolyte Species in Lithium-Sulfur Batteries
      Han, Jaebeom; Zheng, Yu; Guo, Ningxuan; Balbuena, Perla B.
      Journal of Physical Chemistry C (2020), 124 (38), 20654-20670CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
      Redn. potentials of electrolyte mols. in the lithium-sulfur (Li/S) battery and their variations in several solvent environments are studied using the d. functional theory method with Dunning's triple-ζ correlation consistent basis set. Reliable redn. potential values are key for electrolyte additive design needed for suppressing polysulfide dissoln. shuttle mechanism, resulting in poor cycle performance and severe self-discharge of the Li/S battery. Although isolated electrolyte mols. have redn. potentials outside the operating voltage range of the Li/S battery, complexation with other electrolyte species enables the electrolyte mols. to be reduced within the operating voltage range. Among the electrolyte species considered in this study, bis(fluorosulfonyl)imide (FSI-) and fluoroethylene carbonate (FEC) yield redn. potentials within the expected range, suggesting the development of fluorine-contg. additives as a promising line of research.
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    40. 40
      Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions. J. Phys. Chem. B 2009, 113, 6378– 6396,  DOI: 10.1021/jp810292n
      40
      Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
      Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
      Journal of Physical Chemistry B (2009), 113 (18), 6378-6396CODEN: JPCBFK; ISSN:1520-6106. (American Chemical Society)
      We present a new continuum solvation model based on the quantum mech. charge d. of a solute mol. interacting with a continuum description of the solvent. The model is called SMD, where the "D" stands for "d." to denote that the full solute electron d. is used without defining partial at. charges. "Continuum" denotes that the solvent is not represented explicitly but rather as a dielec. medium with surface tension at the solute-solvent boundary. SMD is a universal solvation model, where "universal" denotes its applicability to any charged or uncharged solute in any solvent or liq. medium for which a few key descriptors are known (in particular, dielec. const., refractive index, bulk surface tension, and acidity and basicity parameters). The model separates the observable solvation free energy into two main components. The first component is the bulk electrostatic contribution arising from a self-consistent reaction field treatment that involves the soln. of the nonhomogeneous Poisson equation for electrostatics in terms of the integral-equation-formalism polarizable continuum model (IEF-PCM). The cavities for the bulk electrostatic calcn. are defined by superpositions of nuclear-centered spheres. The second component is called the cavity-dispersion-solvent-structure term and is the contribution arising from short-range interactions between the solute and solvent mols. in the first solvation shell. This contribution is a sum of terms that are proportional (with geometry-dependent proportionality consts. called at. surface tensions) to the solvent-accessible surface areas of the individual atoms of the solute. The SMD model has been parametrized with a training set of 2821 solvation data including 112 aq. ionic solvation free energies, 220 solvation free energies for 166 ions in acetonitrile, methanol, and DMSO, 2346 solvation free energies for 318 neutral solutes in 91 solvents (90 nonaq. org. solvents and water), and 143 transfer free energies for 93 neutral solutes between water and 15 org. solvents. The elements present in the solutes are H, C, N, O, F, Si, P, S, Cl, and Br. The SMD model employs a single set of parameters (intrinsic at. Coulomb radii and at. surface tension coeffs.) optimized over six electronic structure methods: M05-2X/MIDI!6D, M05-2X/6-31G*, M05-2X/6-31+G**, M05-2X/cc-pVTZ, B3LYP/6-31G*, and HF/6-31G*. Although the SMD model has been parametrized using the IEF-PCM protocol for bulk electrostatics, it may also be employed with other algorithms for solving the nonhomogeneous Poisson equation for continuum solvation calcns. in which the solute is represented by its electron d. in real space. This includes, for example, the conductor-like screening algorithm. With the 6-31G* basis set, the SMD model achieves mean unsigned errors of 0.6-1.0 kcal/mol in the solvation free energies of tested neutrals and mean unsigned errors of 4 kcal/mol on av. for ions with either Gaussian03 or GAMESS.
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    41. 41
      Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. A Consistent and Accurate Ab Initio Parametrization of Density Functional Dispersion Correction (Dft-D) for the 94 Elements H-Pu. J. Chem. Phys. 2010, 132, 154104  DOI: 10.1063/1.3382344
      41
      A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
      Grimme, Stefan; Antony, Jens; Ehrlich, Stephan; Krieg, Helge
      Journal of Chemical Physics (2010), 132 (15), 154104/1-154104/19CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)
      The method of dispersion correction as an add-on to std. Kohn-Sham d. functional theory (DFT-D) has been refined regarding higher accuracy, broader range of applicability, and less empiricism. The main new ingredients are atom-pairwise specific dispersion coeffs. and cutoff radii that are both computed from first principles. The coeffs. for new eighth-order dispersion terms are computed using established recursion relations. System (geometry) dependent information is used for the first time in a DFT-D type approach by employing the new concept of fractional coordination nos. (CN). They are used to interpolate between dispersion coeffs. of atoms in different chem. environments. The method only requires adjustment of two global parameters for each d. functional, is asymptotically exact for a gas of weakly interacting neutral atoms, and easily allows the computation of at. forces. Three-body nonadditivity terms are considered. The method has been assessed on std. benchmark sets for inter- and intramol. noncovalent interactions with a particular emphasis on a consistent description of light and heavy element systems. The mean abs. deviations for the S22 benchmark set of noncovalent interactions for 11 std. d. functionals decrease by 15%-40% compared to the previous (already accurate) DFT-D version. Spectacular improvements are found for a tripeptide-folding model and all tested metallic systems. The rectification of the long-range behavior and the use of more accurate C6 coeffs. also lead to a much better description of large (infinite) systems as shown for graphene sheets and the adsorption of benzene on an Ag(111) surface. For graphene it is found that the inclusion of three-body terms substantially (by about 10%) weakens the interlayer binding. We propose the revised DFT-D method as a general tool for the computation of the dispersion energy in mols. and solids of any kind with DFT and related (low-cost) electronic structure methods for large systems. (c) 2010 American Institute of Physics.
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    42. 42
      Wang, Y.; Nakamura, S.; Ue, M.; Balbuena, P. B. Theoretical Studies to Understand Surface Chemistry on Carbon Anodes for Lithium-Ion Batteries: Reduction Mechanisms of Ethylene Carbonate. J. Am. Chem. Soc. 2001, 123, 11708– 11718,  DOI: 10.1021/ja0164529
      42
      Theoretical studies to understand surface chemistry on carbon anodes for lithium-ion batteries: Reduction mechanisms of ethylene carbonate
      Wang, Yixuan; Nakamura, Shinichiro; Ue, Makoto; Balbuena, Perla B.
      Journal of the American Chemical Society (2001), 123 (47), 11708-11718CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Reductive decompn. mechanisms for ethylene carbonate (EC) mol. in electrolyte solns. for lithium-ion batteries are comprehensively investigated by using d. functional theory. In gas phase the redn. of EC is thermodynamically forbidden, whereas in bulk solvent it is likely to undergo one- as well as two-electron redn. processes. The presence of Li cation considerably stabilizes the EC redn. intermediates. The adiabatic electron affinities of the supermol. Li+(EC)n (n = 1-4) successively decrease with the no. of EC mols., independently of EC or Li+ being reduced. Regarding the reductive decompn. mechanism, Li+(EC)n is initially reduced to an ion-pair intermediate that will undergo homolytic C-O bond cleavage via an approx. 11.0 kcal/mol barrier, bringing up a radical anion coordinated with Li+. Among the possible termination pathways of the radical anion, thermodynamically the most favorable is the formation of lithium butylene bicarbonate, (CH2CH2OCO2Li)2, followed by the formation of one O-Li bond compd. contg. an ester group, LiO(CH2)2CO2(CH2)2OCO2Li, then two very competitive reactions of the further redn. of the radical anion and the formation of lithium ethylene bicarbonate, (CH2OCO2Li)2, and the least favorable is the formation of a C-Li bond compd. (Li carbides), Li(CH2)2OCO2Li. The products show a weak EC concn. dependence as has also been revealed for the reactions of LiCO3- with Li+(EC)n; i.e., the formation of Li2CO3 is slightly more favorable at low EC concns., whereas (CH2OCO2Li)2 is favored at high EC concns. A two-electron redn. indeed takes place by a stepwise path. Regarding the compn. of the surface films resulting from solvent redn., for which expts. usually indicate that (CH2OCO2Li)2 is a dominant component, we conclude that they comprise two leading lithium alkyl bicarbonates, (CH2CH2OCO2Li)2 and (CH2OCO2Li)2, together with LiO(CH2)2CO2(CH2)2OCO2Li, Li(CH2)2OCO2Li and Li2CO3.
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    43. 43
      Wang, Y.; Nakamura, S.; Tasaki, K.; Balbuena, P. B. Theoretical Studies to Understand Surface Chemistry on Carbon Anodes for Lithium-Ion Batteries: How Does Vinylene Carbonate Play Its Role as an Electrolyte Additive?. J. Am. Chem. Soc. 2002, 124, 4408– 4421,  DOI: 10.1021/ja017073i
      43
      Theoretical Studies To Understand Surface Chemistry on Carbon Anodes for Lithium-Ion Batteries: How Does Vinylene Carbonate Play Its Role as an Electrolyte Additive?
      Wang, Yixuan; Nakamura, Shinichiro; Tasaki, Ken; Balbuena, Perla B.
      Journal of the American Chemical Society (2002), 124 (16), 4408-4421CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      To elucidate the role of vinylene carbonate (VC) as a solvent additive in org. polar solns. for lithium-ion batteries, reductive decompns. for VC and ethylene carbonate (EC) mols. have been comprehensively investigated both in the gas phase and in soln. by means of d. functional theory calcns. The salt and solvent effects are incorporated with the clusters (EC)nLi+(VC) (n = 0 - 3), and further corrections that account for bulk solvent effects are added using the polarized continuum model. The electron affinities of (EC)nLi+(VC) (n = 0 - 3) monotonically decrease when the no. of EC mols. increases; a sharp decrease of about 20.0 kcal/mol is found from n = 0 to 1 and a more gentle variation for n > 1. For (EC)nLi+(VC) (n = 1 - 3), the redn. of VC brings about more stable ion-pair intermediates than those due to redn. of the EC mol. by 3.1, 6.1, and 5.3 kcal/mol, resp. This finding qual. agrees with the exptl. fact that the redn. potential of VC in the presence of Li salt is more neg. than that of EC. The calcd. redn. potentials corresponding to radical anion formation are close to the exptl. potentials detd. with cyclic voltammetry on a gold electrode surface (-2.67 and -3.19 eV on the phys. scale for VC and EC, resp., vs. exptl. values -2.96 and -2.94 eV). Regarding the decompn. mechanisms, the VC and EC moieties undergo homolytic ring opening from their resp. redn. intermediates, and the energy barrier of VC is about one time higher than that of EC (e.g., 20.1 vs. 8.8 kcal/mol for (EC)2Li+(VC)); both are weakly affected by the explicit solvent mols. and by a bulk solvent represented by a continuum model. Alternatively, starting from the VC redn. intermediate, the ring opening of the EC moiety via an intramol. electron-transfer transition state has also been located; its barrier lies between those of EC and VC (e.g., 17.2 kcal/mol for (EC)2Li+(VC)). On the basis of these results, we suggest the following explanation about the role that VC may play as additive in EC-based lithium-ion battery electrolytes; VC is initially reduced to a more stable intermediate than that from EC redn. One possibility then is that the reduced VC decomps. to form a radical anion via a barrier of about 20 kcal/mol, which undergoes a series of reactions to give rise to more active film-forming products than those resulting from EC redn., such as lithium divinylene dicarbonate, Li-C carbides, lithium vinylene dicarbonate, R-O-Li compd., and even oligomers with repeated vinylene and carbonate-vinylene units. Another possibility starting from the VC redn. intermediate is that the ring opening occurs on the non-reduced EC moiety instead of being on the reduced VC, via an intramol. electron transfer transition state, the energy barrier of which is lower than that of the former, in which VC just helps the intermediate formation and is not consumed. The factors that det. the additive functioning mechanism are briefly discussed, and consequently a general rule for the selection of electrolyte additive is proposed.
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    44. 44
      Leung, K.; Budzien, J. L. Ab Initio Molecular Dynamics Simulations of the Initial Stages of Solid–Electrolyte Interphase Formation on Lithium Ion Battery Graphitic Anodes. Phys. Chem. Chem. Phys. 2010, 12, 6583– 6586,  DOI: 10.1039/b925853a
      44
      Ab initio molecular dynamics simulations of the initial stages of solid-electrolyte interphase formation on lithium ion battery graphitic anodes
      Leung, Kevin; Budzien, Joanne L.
      Physical Chemistry Chemical Physics (2010), 12 (25), 6583-6586CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
      The decompn. of ethylene carbonate (EC) during the initial growth of solid-electrolyte interphase films at the solvent-graphitic anode interface is crit. to lithium-ion battery operations. Ab initio mol. dynamics simulations of explicit liq. EC/graphite interfaces are conducted to study these electrochem. reactions. We show that carbon edge terminations are crucial at this stage, and that achievable exptl. conditions can lead to surprisingly fast EC breakdown mechanisms, yielding decompn. products seen in expts. but not previously predicted.
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    45. 45
      Borodin, O.; Olguin, M.; Spear, C. E.; Leiter, K. W.; Knap, J. Towards High Throughput Screening of Electrochemical Stability of Battery Electrolytes. Nanotechnology 2015, 26, 354003  DOI: 10.1088/0957-4484/26/35/354003
      45
      Towards high throughput screening of electrochemical stability of battery electrolytes
      Borodin, Oleg; Olguin, Marco; Spear, Carrie E.; Leiter, Kenneth W.; Knap, Jaroslaw
      Nanotechnology (2015), 26 (35), 354003/1-354003/15CODEN: NNOTER; ISSN:1361-6528. (IOP Publishing Ltd.)
      High throughput screening of solvents and additives with potential applications in lithium batteries is reported. The initial test set is limited to carbonate and phosphate-based compds. and focused on their electrochem. properties. Solvent stability towards first and second redn. and oxidn. is reported from d. functional theory (DFT) calcns. performed on isolated solvents surrounded by implicit solvent. The reorganization energy is estd. from the difference between vertical and adiabatic redox energies and found to be esp. important for the accurate prediction of redn. stability. A majority of tested compds. had the second redn. potential higher than the first redn. potential indicating that the second redn. reaction might play an important role in the passivation layer formation. Similarly, the second oxidn. potential was smaller for a significant subset of tested mols. than the first oxidn. potential. A no. of potential sources of errors introduced during screening of the electrolyte electrochem. properties were examd. The formation of lithium fluoride during redn. of semifluorinated solvents such as fluoroethylene carbonate and the H-transfer during oxidn. of solvents were found to shift the electrochem. potential by 1.5-2 V and could shrink the electrochem. stability window by as much as 3.5 V when such reactions are included in the screening procedure. The initial oxidn. reaction of ethylene carbonate and di-Me carbonate at the surface of the completely de-lithiated LiNi0.5Mn1.5O4 high voltage spinel cathode was examd. using DFT. Depending on the mol. orientation at the cathode surface, a carbonate mol. either exhibited deprotonation or was found bound to the transition metal via its carbonyl oxygen.
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    46. 46
      Chen, X.; Li, H.-R.; Shen, X.; Zhang, Q. The Origin of the Reduced Reductive Stability of Ion–Solvent Complexes on Alkali and Alkaline Earth Metal Anodes. Angew. Chem., Int. Ed. 2018, 57, 16643– 16647,  DOI: 10.1002/anie.201809203
      46
      The Origin of the Reduced Reductive Stability of Ion-Solvent Complexes on Alkali and Alkaline Earth Metal Anodes
      Chen, Xiang; Li, Hao-Ran; Shen, Xin; Zhang, Qiang
      Angewandte Chemie, International Edition (2018), 57 (51), 16643-16647CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The intrinsic instability of org. electrolytes seriously impedes practical applications of high-capacity metal (Li, Na) anodes. Ion-solvent complexes can even promote the decompn. of electrolytes on metal anodes. Herein, first-principles calcns. were performed to investigate the origin of the reduced reductive stability of ion-solvent complexes. Both ester and ether electrolyte solvents are selected to interact with Li+, Na+, K+, Mg2+, and Ca2+. The LUMO energy levels of ion-ester complexes exhibit a linear relationship with the binding energy, regulated by the ratio of carbon AO in the LUMO, while LUMOs of ion-ether complexes are composed by the metal AOs. This work shows why ion-solvent complexes can reduce the reductive stability of electrolytes, reveals different mechanisms for ester and ether electrolytes, and provides a theor. understanding of the electrolyte-anode interfacial reactions and guidance to electrolyte and metal anode design.
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    47. 47
      He, J.; Wang, H.; Zhou, Q.; Qi, S.; Wu, M.; Li, F.; Hu, W.; Ma, J. Unveiling the Role of Li+ Solvation Structures with Commercial Carbonates in the Formation of Solid Electrolyte Interphase for Lithium Metal Batteries. Small Methods 2021, 5, 2100441  DOI: 10.1002/smtd.202100441
      47
      Unveiling the Role of Li+ Solvation Structures with Commercial Carbonates in the Formation of Solid Electrolyte Interphase for Lithium Metal Batteries
      He, Jian; Wang, Huaping; Zhou, Qing; Qi, Shihan; Wu, Mingguang; Li, Fang; Hu, Wei; Ma, Jianmin
      Small Methods (2021), 5 (8), 2100441CODEN: SMMECI; ISSN:2366-9608. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Solid electrolyte interphase (SEI), detd. by the components of electrolytes, can endow batteries with the ability to repress the growth of Li dendrites. Nevertheless, the mechanism of com. carbonates on in situ-generated SEI and the consequential effect on cycling performance is not well understood yet, although some carbonates are well used in electrolytes. In this work, quantum chem. calcns. and mol. dynamics are used to reveal the formation mechanisms of SEI with carbonate-based electrolyte additives on the at. level. It is confirmed that the Li-coordinated carbonate species are the leading participant of SEI formation and their impact on battery performance is clarified. Fluoroethylene carbonate (FEC) exhibits a completely different behavior from vinyl ethylene carbonate (VEC), ethylene carbonate (EC), and vinylene carbonate (VC). High redn. potential Li+-coordinated additives, e.g. FEC and VEC can dominate the formation of SEI by excluding propylene carbonate (PC) and LiPF6 from the decompn., and the corresponding Li||Li sym. cells show enhanced long-term performance compared with those with pure PC electrolyte, while the low redn. priority additives (e.g., EC and VC) cannot form a uniform SEI by winning the competitive reaction.
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    48. 48
      Winkler, J. R.; Gray, H. B. Long-Range Electron Tunneling. J. Am. Chem. Soc. 2014, 136, 2930– 2939,  DOI: 10.1021/ja500215j
      48
      Long-Range Electron Tunneling
      Winkler, Jay R.; Gray, Harry B.
      Journal of the American Chemical Society (2014), 136 (8), 2930-2939CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      A review. Electrons have so little mass that in less than a second they can tunnel through potential energy barriers that are several electron-volts high and several nanometers wide. Electron tunneling is a crit. functional element in a broad spectrum of applications, ranging from semiconductor diodes to the photosynthetic and respiratory charge transport chains. Prior to the 1970s, chemists generally believed that reactants had to collide in order to effect a transformation. Exptl. demonstrations that electrons can transfer between reactants sepd. by several nanometers led to a revision of the chem. reaction paradigm. Exptl. investigations of electron exchange between redox partners sepd. by mol. bridges have elucidated many fundamental properties of these reactions, particularly the variation of rate consts. with distance. Theor. work has provided crit. insights into the superexchange mechanism of electronic coupling between distant redox centers. Kinetics measurements have shown that electrons can tunnel about 2.5 nm through proteins on biol. relevant time scales. Longer-distance biol. charge flow requires multiple electron tunneling steps through chains of redox cofactors. The range of phenomena that depends on long-range electron tunneling continues to expand, providing new challenges for both theory and expt.
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    49. 49
      Lu, T.; Chen, F. Multiwfn: A Multifunctional Wavefunction Analyzer. J. Comput. Chem. 2012, 33, 580– 592,  DOI: 10.1002/jcc.22885
      49
      Multiwfn: A multifunctional wavefunction analyzer
      Lu, Tian; Chen, Feiwu
      Journal of Computational Chemistry (2012), 33 (5), 580-592CODEN: JCCHDD; ISSN:0192-8651. (John Wiley & Sons, Inc.)
      Multiwfn is a multifunctional program for wavefunction anal. Its main functions are: (1) Calcg. and visualizing real space function, such as electrostatic potential and electron localization function at point, in a line, in a plane or in a spatial scope. (2) Population anal. (3) Bond order anal. (4) Orbital compn. anal. (5) Plot d.-of-states and spectrum. (6) Topol. anal. for electron d. Some other useful utilities involved in quantum chem. studies are also provided. The built-in graph module enables the results of wavefunction anal. to be plotted directly or exported to high-quality graphic file. The program interface is very user-friendly and suitable for both research and teaching purpose. The code of Multiwfn is substantially optimized and parallelized. Its efficiency is demonstrated to be significantly higher than related programs with the same functions. Five practical examples involving a wide variety of systems and anal. methods are given to illustrate the usefulness of Multiwfn. The program is free of charge and open-source. Its precompiled file and source codes are available from http://multiwfn.codeplex.com. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011.
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    50. 50
      Fu, L. J.; Liu, H.; Li, C.; Wu, Y. P.; Rahm, E.; Holze, R.; Wu, H. Q. Surface Modifications of Electrode Materials for Lithium Ion Batteries. Solid State Sci. 2006, 8, 113– 128,  DOI: 10.1016/j.solidstatesciences.2005.10.019
      50
      Surface modifications of electrode materials for lithium ion batteries
      Fu, L. J.; Liu, H.; Li, C.; Wu, Y. P.; Rahm, E.; Holze, R.; Wu, H. Q.
      Solid State Sciences (2006), 8 (2), 113-128CODEN: SSSCFJ; ISSN:1293-2558. (Elsevier B.V.)
      Review of surface modification of both anode and cathode materials for lithium ion batteries, with 131 refs.
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    • Details of charge distribution, atomic coordinates, energetics, etc. are available in the docx file. This information includes a stepwise free energy table for LiPF6 dissociation; chronological Bader charge analysis of the electron-tunneling-induced [Li2PF6]+ partial dissociation; lithium cation affinity energetics; Bader charge analysis of key AIMD frames of DME-DOL-solvated system; chronological Bader charge analysis of [LiPF6] and [PF6]− interfacial degradations; significant events in forming metastable [Li2PF6]− structures in EC–VC and DME-DOL electrolytes; free energy profiles of LiPF6 decomposition in different implicit solvation environments; detailed energetics of species involved in LiPF6 decomposition pathways; and Cartesian coordinates of important structures (PDF)


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