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Title: Probing the Failure Mechanism of SnO{sub 2} Nanowires for Sodium-Ion Batteries

Nonlithium metals such as sodium have attracted wide attention as a potential charge carrying ion for rechargeable batteries. Using in situ transmission electron microscopy in combination with density functional theory calculations, we probed the structural and chemical evolution of SnO{sub 2} nanowire anodes in Na-ion batteries and compared them quantitatively with results from Li-ion batteries (Huang, J. Y.; et al. Science 2010, 330, 1515-1520). Upon Na insertion into SnO{sub 2}, a displacement reaction occurs, leading to the formation of amorphous Na{sub x}Sn nanoparticles dispersed in Na{sub 2}O matrix. With further Na insertion, the Na{sub x}Sn crystallized into Na{sub 15}Sn{sub 4} (x = 3.75). Upon extraction of Na (desodiation), the Na{sub x}Sn transforms to Sn nanoparticles. Associated with the dealloying, pores are found to form, leading to a structure of Sn particles confined in a hollow matrix of Na{sub 2}O. These pores greatly increase electrical impedance, therefore accounting for the poor cyclability of SnO{sub 2}. DFT calculations indicate that Na{sup +} diffuses 30 times slower than Li{sup +} in SnO{sub 2}, in agreement with in situ TEM measurement. Insertion of Na can chemomechanically soften the reaction product to a greater extent than in lithiation. Therefore, in contrast to the lithiation ofmore » SnO{sub 2} significantly less dislocation plasticity was seen ahead of the sodiation front. This direct comparison of the results from Na and Li highlights the critical role of ionic size and electronic structure of different ionic species on the charge/discharge rate and failure mechanisms in these batteries.« less
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Publication Date:
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Resource Type:
Journal Article
Resource Relation:
Journal Name: Nano Letters; Journal Volume: 13
Research Org:
Joint Center for Energy Storage Research (JCESR)
Sponsoring Org:
USDOE SC Office of Basic Energy Sciences (SC-22)
Country of Publication:
United States
25 ENERGY STORAGE; 77 NANOSCIENCE AND NANOTECHNOLOGY Na-ion battery; SnO2 anode; in situ TEM; Na diffusion; DFT calculation; failure mechanism