Interfacial Reactivity of Silicon Electrodes: Impact of Electrolyte Solvent and Presence of Conductive Carbon
Abstract
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% increasemore »
- Authors:
-
[1];
[2];
[3];
[3];
[3];
[3];
[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)
- Publication Date:
- Research Org.:
- 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 Org.:
- Mercedes-Benz Research and Development North America, Inc.; US Army Research Laboratory (USARL); USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1865649
- Alternate Identifier(s):
- OSTI ID: 1963195
- Report Number(s):
- BNL-224162-2023-JAAM
Journal ID: ISSN 1944-8244
- Grant/Contract Number:
- SC0021314; SC0012673; SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Applied Materials and Interfaces
- Additional Journal Information:
- Journal Volume: 14; Journal Issue: 18; Journal ID: ISSN 1944-8244
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; isothermal microcalorimetry; silicon; particle size; carbon; heat dissipation; battery
Citation Formats
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., and Takeuchi, Esther S. Interfacial Reactivity of Silicon Electrodes: Impact of Electrolyte Solvent and Presence of Conductive Carbon. United States: N. p., 2022.
Web. doi:10.1021/acsami.1c22044.
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. Interfacial Reactivity of Silicon Electrodes: Impact of Electrolyte Solvent and Presence of Conductive Carbon. United States. https://doi.org/10.1021/acsami.1c22044
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., and Takeuchi, Esther S. Thu .
"Interfacial Reactivity of Silicon Electrodes: Impact of Electrolyte Solvent and Presence of Conductive Carbon". United States. https://doi.org/10.1021/acsami.1c22044. https://www.osti.gov/servlets/purl/1865649.
@article{osti_1865649,
title = {Interfacial Reactivity of Silicon Electrodes: Impact of Electrolyte Solvent and Presence of Conductive Carbon},
author = {Vila, Mallory N. and Bernardez, Edelmy Marin and Li, Wenzao and Stackhouse, Chavis A. and Kern, Christopher J. and Head, Ashley R. and Tong, Xiao and Yan, Shan and Wang, Lei and Bock, David C. and Takeuchi, Kenneth J. and Housel, Lisa M. and Marschilok, Amy C. and Takeuchi, Esther S.},
abstractNote = {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.},
doi = {10.1021/acsami.1c22044},
journal = {ACS Applied Materials and Interfaces},
number = 18,
volume = 14,
place = {United States},
year = {Thu Mar 31 00:00:00 EDT 2022},
month = {Thu Mar 31 00:00:00 EDT 2022}
}
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