- Access by Xinjiang University
Three-Phase Model for the Reversible Lithiation-Delithiation of SnO Anodes in Li-Ion Batteries
Phys. Rev. Applied 4, 034005 – Published 16 September, 2015
DOI: https://doi.org/10.1103/PhysRevApplied.4.034005
Abstract
A high reversible capacity is a key feature for any rechargeable battery. In lithium-ion battery technology, tin-oxide anodes do fulfill this requirement, but a fast loss of capacity hinders a full commercialization. Using first-principles calculations, we propose a microscopic model that sheds light on the reversible lithiation-delithiation of SnO and reveals that a sintering of Sn causes a strong degradation of SnO-based anodes. When the initial irreversible transformation ends, active anode grains consist of Li-oxide layers separated by Sn bilayers. During the following reversible lithiation, the Li oxide undergoes two phase transformations that give rise to a Li enrichment of the oxide and the formation of a layered SnLi composite. We find that the model-predicted anode volume expansion and voltage profile agree well with experiments, and a layered anode grain is highly conductive and has a theoretical reversible capacity of 4.5 Li atoms per a SnO host unit. The model suggests that the grain structure has to remain layered to sustain its reversible capacity and a thin-film design of battery anodes could be a remedy for the capacity loss.
Article Text
References (29)
- M. N. Obrovac, L. Christensen, D. B. Le, and J. R. Dahn, Alloy design for lithium-ion battery anodes, J. Electrochem. Soc. 154, A849 (2007).
- B. A. Boukamp, G. C. Lesh, and R. A. Huggins, All-solid lithium electrodes with mixed-conductor matrix, J. Electrochem. Soc. 128, 725 (1981).
- C.-M. Park, J.-H. Kim, H. Kim, and H.-J. Sohn, Li-alloy-based anode materials for Li secondary batteries, Chem. Soc. Rev. 39, 3115 (2010).
- Y. Idota, Tin-based amorphous oxide: A high-capacity lithium-ion-storage material, Science 276, 1395 (1997).
- I. A. Courtney and J. R. Dahn, Electrochemical and in situ x-ray diffraction studies of the reaction of lithium with tin oxide composites, J. Electrochem. Soc. 144, 2045 (1997).
- J. Chouvin, J. Olivier-Fourcade, J. C. Jumas, B. Simon, P. H. Biensan, F. Madrigal, J. L. Tirado, and C. P. Vicente, SnO reduction in lithium cells: Study by x-ray absorption, Sn-119 Mössbauer spectroscopy and x-ray diffraction, J. Electroanal. Chem. 494, 136 (2000).
- Y. Wang, J. Sakamoto, S. Kostov, A. N. Mansour, M. L. denBoer, S. G. Greenbaum, C. K. Huang, and S. Surampudi, Structural aspects of electrochemically lithiated SnO: Nuclear magnetic resonance and x-ray absorption studies, J. Power Sources 89, 232 (2000).
- I. Sandu, T. Brousse, D. M. Schleich, and M. Danot, negative electrode for lithium ion cell: In situ Mössbauer investigation of chemical changes upon discharge, J. Solid State Chem. 177, 4332 (2004).
- L. Q. Zhang, X. H. Liu, Y.-C. Perng, J. Cho, J. P. Chang, S. X. Mao, Z. Z. Ye, and J. Y. Huang, Direct observation of Sn crystal growth during the lithiation and delithiation processes of nanowires, Micron 43, 1127 (2012).
- G. Jeong, C. Shin, Y.-J. Kim, H. Lee, and H.-J. Sohn, Aggregation behavior of tin in tin oxides reacted with lithium, Electrochim. Acta 92, 291 (2013).
- I. A. Courtney, R. A. Dunlap, and J. R. Dahn, In-situ Mössbauer effect studies of the reaction of lithium with SnO and glass, Electrochim. Acta 45, 51 (1999).
- I. Sandu, T. Brousse, D. M. Schleich, and M. Danot, The chemical changes occurring upon cycling of a negative electrode for lithium ion cell: In situ Mössbauer investigation, J. Solid State Chem. 179, 476 (2006).
- I. A. Courtney and J. R. Dahn, Key factors controlling the reversibility of the reaction of lithium with and glass, J. Electrochem. Soc. 144, 2943 (1997).
- M. Behm and J. Irvine, Influence of structure and composition upon performance of tin-phosphate-based negative electrodes for lithium batteries, Electrochim. Acta 47, 1727 (2002).
- H. Tavassol, M. W. Cason, R. G. Nuzzo, and A. A. Gewirth, Influence of oxides on the stress evolution and reversibility during conversion and Li-Sn alloying reactions, Adv. Energy Mater. 5, 1400317 (2014).
- M. Ebner, F. Marone, M. Stampanoni, and V. Wood, Visualization and quantification of electrochemical and mechanical degradation in Li ion batteries, Science 342, 716 (2013).
- A. Pedersen and M. Luisier, Lithiation of tin oxide: A computational study, ACS Appl. Mater. Interfaces 6, 22257 (2014).
- W.-J. Zhang, A review of the electrochemical performance of alloy anodes for lithium-ion batteries, J. Power Sources 196, 13 (2011).
- S.-W. Kim, D.-H. Seo, X. Ma, G. Ceder, and K. Kang, Electrode materials for rechargeable sodium-ion batteries: Potential alternatives to current lithium-ion batteries, Adv. Energy Mater. 2, 710 (2012).
- J. P. Perdew, K. Burke, and M. Ernzerhof, Generalized Gradient Approximation Made Simple, Phys. Rev. Lett. 77, 3865 (1996).
- P. E. Blöchl, Projector augmented-wave method, Phys. Rev. B 50, 17953 (1994).
- G. Kresse and J. Furthmuller, Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set, Phys. Rev. B 54, 11169 (1996).
- G. Kresse and J. Furthmuller, Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set, Comput. Mater. Sci. 6, 15 (1996).
- I. A. Courtney, J. S. Tse, O. Mao, J. Hafner, and J. R. Dahn, Ab initio calculation of the lithium-tin voltage profile, Phys. Rev. B 58, 15583 (1998).
- P. A. Khomyakov, A. Pedersen, and M. Luisier (unpublished).
- P. Poizot, S. Laruelle, S. Grugeon, and L. Dupont, Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries, Nature (London) 407, 496 (2000).
- P. Poizot, S. Laruelle, S. Grugeon, and J. M. Tarascon, Rationalization of the low-potential reactivity of 3D-metal-based inorganic compounds toward Li, J. Electrochem. Soc. 149, A1212 (2002).
- D. Su, C. Wang, H. Ahn, and G. Wang, Octahedral tin dioxide nanocrystals as high capacity anode materials for Na-ion batteries, Phys. Chem. Chem. Phys. 15, 12543 (2013).
- M. H. Han, E. Gonzalo, G. Singh, and T. Rojo, A comprehensive review of sodium layered oxides: Powerful cathodes for Na-ion batteries, Energy Environ. Sci. 8, 81 (2015).