Interfacial Reactivity of Silicon Electrodes: Impact of Electrolyte Solvent and Presence of Conductive Carbon

Vila, Mallory N.; Bernardez, Edelmy Marin; Li, Wenzao; Stackhouse, Chavis A.; Kern, Christopher J.; Head, Ashley R.; Tong, Xiao; Yan, Shan; Wang, Lei; Bock, David C.; Takeuchi, Kenneth J.; Housel, Lisa M.; Marschilok, Amy C.; Takeuchi, Esther S.

doi:10.1021/acsami.1c22044

Title: Interfacial Reactivity of Silicon Electrodes: Impact of Electrolyte Solvent and Presence of Conductive Carbon

Journal Article · Thu Mar 31 00:00:00 EDT 2022 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.1c22044· OSTI ID:1865649

Vila, Mallory N. ^[1]; Bernardez, Edelmy Marin ^[1];

^[1]; Stackhouse, Chavis A. ^[1]; Kern, Christopher J. ^[1];

^[2]; Tong, Xiao ^[2]; Yan, Shan ^[1];

^[3];

^[3]

Stony Brook Univ., NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Stony Brook Univ., NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)

Silicon (Si) is a promising high-capacity material for lithium-ion batteries; however, its limited reversibility hinders commercial adoption. Approaches such as particle and crystallite size reduction, introduction of conductive carbon, and use of different electrolyte solvents have been explored to overcome these electrochemical limitations. Herein, operando isothermal microcalorimetry (IMC) is used to probe the influence of silicon particle size, electrode composition, and electrolyte additives fluoroethylene carbonate and vinylene carbonate on the heat flow during silicon lithiation. In this work, the IMC data are complemented by X-ray photoelectron and Raman spectroscopies to elucidate differences in solid electrolyte interphase (SEI) composition. Nanosized (~50 nm, n-Si) and micrometer-sized (~4 μm, μ-Si) silicon electrodes are formulated with and without amorphous carbon and electrochemically lithiated in ethylene carbonate (EC), fluoroethylene carbonate (FEC), or vinylene carbonate (VC) based electrolytes. Notably, n-Si electrodes generate 53–61% more normalized heat relative to their μ-Si counterparts, consistent with increased surface area and electrode/electrolyte reactivity. Introduction of amorphous carbon significantly alters the heat flow profile where multiple exothermic peaks and increased normalized heat dissipation are observed for all electrolyte types. Notably, the VC-containing electrolyte demonstrates the greatest normalized heat dissipation of the electrode compositions tested showing as much as a 50% increase compared to the EC or FEC counterparts. The results are relevant to the understanding of silicon negative electrode function in the presence of electrolyte additives and provide insight relative to silicon containing cell reactivity and safety.

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Research Organization:: Northwestern Univ., Evanston, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M/t); Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)

Sponsoring Organization:: Mercedes-Benz Research and Development North America, Inc.; US Army Research Laboratory (USARL); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0021314; SC0012673; SC0012704

OSTI ID:: 1865649

Alternate ID(s):: OSTI ID: 1963195

Report Number(s):: BNL-224162-2023-JAAM

Journal Information:: ACS Applied Materials and Interfaces, Vol. 14, Issue 18; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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25 ENERGY STORAGE
isothermal microcalorimetry
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particle size
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heat dissipation
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Title: Interfacial Reactivity of Silicon Electrodes: Impact of Electrolyte Solvent and Presence of Conductive Carbon

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