Journal
NANO LETTERS
Volume 12, Issue 11, Pages 5897-5902Publisher
AMER CHEMICAL SOC
DOI: 10.1021/nl303305c
Keywords
Tin nanoparticles; sodiation; amorphous NaxSn alloy; Na15Sn4; sodium ion battery; in situ transmission electron microscopy
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Funding
- Laboratory Directed Research and Development (LDRD) project at Sandia National Laboratories (SNL)
- Nanostructures for Electrical Energy Storage (NEES), an Energy Frontier Research Center (EFRC)
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DESC0001160]
- U.S. Department of Energy's National Nuclear Security Administration [DE-AC04-94AL85000]
- NSF CMMI through University of Pittsburgh [08 010934]
- Directorate For Engineering
- Div Of Civil, Mechanical, & Manufact Inn [0928517] Funding Source: National Science Foundation
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The microstructural changes and phase transformations of tin nanoparticles during electrochemical sodiation were studied with a nanosized sodium ion battery using in situ transmission electron microscopy. It was found that the first sodiation process occurred in two steps; that is, the crystalline Sn nanoparticles were initially sodiated via a two-phase mechanism with a migrating phase boundary to form a Na-poor, amorphous NaxSn alloy (x similar to 0.5), which was further sodiated to several Na-rich amorphous phases and finally to the crystallized Na15Sn4 (x = 3.75) via a single-phase mechanism. The volumetric expansion was about 60% in the first step and 420% after the second step. However, despite the huge expansion, cracking or fracture was not observed, which is attributed to the second step of the single-phase sodiation that accommodates large portion of the sodiation-induced stress over the entire particle. Excellent cyclability was also observed during the reversible sodiation/desodiation cycles, showing great potential of Sn nanoparticles as a robust electrode material for rechargeable batteries.
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