In Situ Observation of the Electrochemical Lithiation of a Single SnO2 Nanowire Electrode
Fragile Tin Oxide Electrodes
While tin oxide has a high energy density, and would thus make an attractive anode material for a Li-ion battery, it undergoes significant volume changes when Li is intercalated. The large strains cause cracking, pulverization, and a resultant loss of electrical conduction. Huang et al. (p. 1515; see the Perspective by Chiang) used in situ transmission electron microscopy on a single tin oxide nanowire to identify the physical changes that occur during intercalation and observed a moving cloud of dislocations that separated the reacted and unreacted sections. Upon completion of the electrochemical charging, the nanowire showed up to 90% elongation and a 35% increase in diameter.
Abstract
We report the creation of a nanoscale electrochemical device inside a transmission electron microscope—consisting of a single tin dioxide (SnO2) nanowire anode, an ionic liquid electrolyte, and a bulk lithium cobalt dioxide (LiCoO2) cathode—and the in situ observation of the lithiation of the SnO2 nanowire during electrochemical charging. Upon charging, a reaction front propagated progressively along the nanowire, causing the nanowire to swell, elongate, and spiral. The reaction front is a “Medusa zone” containing a high density of mobile dislocations, which are continuously nucleated and absorbed at the moving front. This dislocation cloud indicates large in-plane misfit stresses and is a structural precursor to electrochemically driven solid-state amorphization. Because lithiation-induced volume expansion, plasticity, and pulverization of electrode materials are the major mechanical effects that plague the performance and lifetime of high-capacity anodes in lithium-ion batteries, our observations provide important mechanistic insight for the design of advanced batteries.
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References and Notes
1
Limthongkul P., Jang Y. I., Dudney N. J., Chiang Y. M., Electrochemically-driven solid-state amorphization in lithium-silicon alloys and implications for lithium storage. Acta Mater. 51, 1103 (2003).
2
Padhi A. K., Nanjundaswamy K. S., Goodenough J. B., Phospho-olivines as positive-electrode materials for rechargeable lithium batteries. J. Electrochem. Soc. 144, 1188 (1997).
3
Tarascon J. M., Armand M., Issues and challenges facing rechargeable lithium batteries. Nature 414, 359 (2001).
4
Shao-Horn Y., Croguennec L., Delmas C., Nelson E. C., O’Keefe M. A., Atomic resolution of lithium ions in LiCoO2. Nat. Mater. 2, 464 (2003).
5
Kang B., Ceder G., Battery materials for ultrafast charging and discharging. Nature 458, 190 (2009).
6
Lai W., et al., Ultrahigh-energy-density microbatteries enabled by new electrode architecture and micropackaging design. Adv. Mater. 22, E139 (2010).
7
Nam K. T., et al., Virus-enabled synthesis and assembly of nanowires for lithium ion battery electrodes. Science 312, 885 (2006); 10.1126/science.1122716.
8
Park M. S., et al., Preparation and electrochemical properties of SnO2 nanowires for application in lithium-ion batteries. Angew. Chem. Int. Ed. 46, 750 (2007).
9
Chan C. K., et al., High-performance lithium battery anodes using silicon nanowires. Nat. Nanotechnol. 3, 31 (2008).
10
Kim H., Cho J., Superior lithium electroactive mesoporous Si@carbon core-shell nanowires for lithium battery anode material. Nano Lett. 8, 3688 (2008).
11
Ko Y. D., Kang J. G., Park J. G., Lee S., Kim D. W., Self-supported SnO2 nanowire electrodes for high-power lithium-ion batteries. Nanotechnology 20, 455701 (2009).
12
Magasinski A., et al., High-performance lithium-ion anodes using a hierarchical bottom-up approach. Nat. Mater. 9, 353 (2010).
13
Bhandakkar T. K., Gao H. J., Cohesive modeling of crack nucleation under diffusion induced stresses in a thin strip: Implications on the critical size for flaw tolerant battery electrodes. Int. J. Solids Struct. 47, 1424 (2010).
14
Zhu T., Li J., Ultra-strength materials. Prog. Mater. Sci. 55, 710 (2010).
15
Liu D. R., Williams D. B., Philos. Mag. B 53, L123 (1986).
16
Courtney I. A., Dahn J. R., Electrochemical and in situ x-ray diffraction studies of the reaction of lithium with tin oxide composites. J. Electrochem. Soc. 144, 2045 (1997).
17
Gabrisch H., Yazami R., Fultz B., The character of dislocations in LiCoO2. Electrochem. Solid State Lett. 5, A111 (2002).
18
Wang Y. M., Li J., Hamza A. V., Barbee T. W., Ductile crystalline-amorphous nanolaminates. Proc. Natl. Acad. Sci. U.S.A. 104, 11155 (2007).
19
Shan Z. W., et al., Plastic flow and failure resistance of metallic glass: Insight from in situ compression of nanopillars. Phys. Rev. B 77, 155419 (2008).
20
Legros M., Dehm G., Arzt E., Balk T. J., Observation of giant diffusivity along dislocation cores. Science 319, 1646 (2008).
21
Wolf D., Okamoto P. R., Yip S., Lutsko J. F., Kluge M., Thermodynamic parallels between solid-state amorphization and melting. J. Mater. Res. 5, 286 (1990).
22
Fecht H. J., Defect-induced melting and solid-state amorphization. Nature 356, 133 (1992).
23
Bakker H., Zhou G. F., Yang H., Mechanically driven disorder and phase transformations in alloys. Prog. Mater. Sci. 39, 159 (1995).
24
Suryanarayana C., Mechanical alloying and milling. Prog. Mater. Sci. 46, 1 (2001).
25
Huang J. Y., Yasuda H., Mori H., Deformation-induced amorphization in ball-milled silicon. Philos. Mag. Lett. 79, 305 (1999).
26
Huang J. Y., Zhu Y. T., Liao X. Z., Valiev R. Z., Amorphization of TiNi induced by high-pressure torsion. Philos. Mag. Lett. 84, 183 (2004).
27
Mughrabi H., Deformation-induced long-range internal stresses and lattice plane misorientations and the role of geometrically necessary dislocations. Philos. Mag. 86, 4037 (2006).
28
A. G. Khachaturyan, Theory of Structural Transformations in Solids (Wiley, New York, 1983).
29
Ohno H., et al., Conductivities of a sintered pellet and a single crystal of Li2O. J. Nucl. Mater. 118, 242 (1983).
30
Oda T., Tanaka S., Modeling of Li diffusivity in Li2O by molecular dynamics simulation. J. Nucl. Mater. 386–388, 1087 (2009).
31
Habasaki J., Hiwatari Y., Molecular dynamics study of the mechanism of ion transport in lithium silicate glasses: Characteristics of the potential energy surface and structures. Phys. Rev. B 69, 144207 (2004).
32
Brazier A., et al., First cross-section observation of an all solid-state lithium-ion “nanobattery” by transmission electron microscopy. Chem. Mater. 20, 2352 (2008).
33
Kostarelos K., Nanorobots for medicine: How close are we? Nanomedicine 5, 341 (2010).
34
Curtright A. E., Bouwman P. J., Wartena R. C., Swider-Lyons K. E., Int. J. Nanotechnol. 1, 226 (2004).
35
Wang Z. L., Song J., Piezoelectric nanogenerators based on zinc oxide nanowire arrays. Science 312, 242 (2006).
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Published In
Science
Volume 330 | Issue 6010
10 December 2010
10 December 2010
Copyright
Copyright © 2010, American Association for the Advancement of Science.
Submission history
Received: 26 July 2010
Accepted: 26 October 2010
Published in print: 10 December 2010
Acknowledgments
J.Y.H. thanks K. Xu for valuable discussions. Supported by a Laboratory Directed Research and Development (LDRD) project at Sandia National Laboratories (SNL) and by the Science of Precision Multifunctional Nanostructures for Electrical Energy Storage (NEES), an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES) under award DESC0001160. This work was performed in part at the Sandia-Los Alamos Center for Integrated Nanotechnologies (CINT), a U.S. DOE, Office of BES user facility. The LDRD supported the development and fabrication of platforms and the development of TEM techniques. The NEES center supported some of the additional platform development and fabrication and materials characterization. CINT supported the TEM capability and the fabrication capabilities that were used for the TEM characterization, and this work represents the efforts of several CINT users, primarily those with affiliation external to SNL. SNL is a multiprogram laboratory operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin company, for the DOE’s National Nuclear Security Administration under contract DE-AC04-94AL85000. The work of C.M.W. and W.X. was supported by the DOE Office of Science, Offices of Biological and Environmental Research, and was conducted in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory, which is operated by Battelle for the DOE under contract DE-AC05-76RLO1830. L.Q., A.K., and J.L. were supported by Honda Research Institute USA, Xi’an Jiaotong University, NSF grants CMMI-0728069, DMR-1008104, and DMR-0520020, and Air Force Office of Scientific Research grant FA9550-08-1-0325. S.X.M., L.Z., and L.Q.Z. were supported by NSF grants CMMI0825842 and CMMI0928517 through the University of Pittsburgh and SNL. L.Q.Z. thanks the Chinese Scholarship Council for financial support and Z. Ye’s encouragement from Zhejiang University.
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