Insights into Reactivity of Silicon Negative Electrodes: Analysis Using Isothermal Microcalorimetry
Abstract
Silicon offers high theoretical capacity as a negative electrode material for lithium-ion batteries; however, high irreversible capacity upon initial cycling and poor cycle life have limited commercial adoption. Herein, we report an operando isothermal microcalorimetry (IMC) study of a model system containing lithium metal and silicon composite film electrodes during the first two cycles of (de)lithiation. The total heat flow data are analyzed in terms of polarization, entropic, and parasitic heat flow contributions to quantify and determine the onset of parasitic reactions. These parasitic reactions, which include solid–electrolyte interphase formation, contribute to electrochemical irreversibility. Cycle 1 lithiation demonstrates the highest thermal energy output at 1509 mWh/g, compared to cycle 1 delithiation and cycle 2. To complement the calorimetry, operando X-ray diffraction is used to track the phase evolution of silicon. During cycle 1 lithiation, crystalline Si undergoes transformation to amorphous lithiated silicon and ultimately to crystalline Li15Si4. The solid-state amorphization process is correlated to a decrease in entropic heat flow, suggesting that heat associated with the amorphization contributes significantly to the entropic heat flow term. In conclusion, this study effectively uses IMC to probe the parasitic reactions that occur during lithiation of a silicon electrode, demonstrating an approach that canmore »
- Authors:
-
- Stony Brook Univ., Stony Brook, NY (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Stony Brook Univ., Stony Brook, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2mt); Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1580221
- Report Number(s):
- BNL-212444-2019-JAAM
Journal ID: ISSN 1944-8244
- Grant/Contract Number:
- SC0012704; SC0012673
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Applied Materials and Interfaces
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 41; Journal ID: ISSN 1944-8244
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; isothermal microcalorimetry; silicon; lithiation; heat flow; entropy; polarization
Citation Formats
Housel, Lisa M., Li, Wenzao, Quilty, Calvin D., Vila, Mallory N., Wang, Lei, Tang, Christopher R., Bock, David C., Wu, Qiyuan, Tong, Xiao, Head, Ashley R., Takeuchi, Kenneth J., Marschilok, Amy C., and Takeuchi, Esther S. Insights into Reactivity of Silicon Negative Electrodes: Analysis Using Isothermal Microcalorimetry. United States: N. p., 2019.
Web. doi:10.1021/acsami.9b10772.
Housel, Lisa M., Li, Wenzao, Quilty, Calvin D., Vila, Mallory N., Wang, Lei, Tang, Christopher R., Bock, David C., Wu, Qiyuan, Tong, Xiao, Head, Ashley R., Takeuchi, Kenneth J., Marschilok, Amy C., & Takeuchi, Esther S. Insights into Reactivity of Silicon Negative Electrodes: Analysis Using Isothermal Microcalorimetry. United States. https://doi.org/10.1021/acsami.9b10772
Housel, Lisa M., Li, Wenzao, Quilty, Calvin D., Vila, Mallory N., Wang, Lei, Tang, Christopher R., Bock, David C., Wu, Qiyuan, Tong, Xiao, Head, Ashley R., Takeuchi, Kenneth J., Marschilok, Amy C., and Takeuchi, Esther S. Tue .
"Insights into Reactivity of Silicon Negative Electrodes: Analysis Using Isothermal Microcalorimetry". United States. https://doi.org/10.1021/acsami.9b10772. https://www.osti.gov/servlets/purl/1580221.
@article{osti_1580221,
title = {Insights into Reactivity of Silicon Negative Electrodes: Analysis Using Isothermal Microcalorimetry},
author = {Housel, Lisa M. and Li, Wenzao and Quilty, Calvin D. and Vila, Mallory N. and Wang, Lei and Tang, Christopher R. and Bock, David C. and Wu, Qiyuan and Tong, Xiao and Head, Ashley R. and Takeuchi, Kenneth J. and Marschilok, Amy C. and Takeuchi, Esther S.},
abstractNote = {Silicon offers high theoretical capacity as a negative electrode material for lithium-ion batteries; however, high irreversible capacity upon initial cycling and poor cycle life have limited commercial adoption. Herein, we report an operando isothermal microcalorimetry (IMC) study of a model system containing lithium metal and silicon composite film electrodes during the first two cycles of (de)lithiation. The total heat flow data are analyzed in terms of polarization, entropic, and parasitic heat flow contributions to quantify and determine the onset of parasitic reactions. These parasitic reactions, which include solid–electrolyte interphase formation, contribute to electrochemical irreversibility. Cycle 1 lithiation demonstrates the highest thermal energy output at 1509 mWh/g, compared to cycle 1 delithiation and cycle 2. To complement the calorimetry, operando X-ray diffraction is used to track the phase evolution of silicon. During cycle 1 lithiation, crystalline Si undergoes transformation to amorphous lithiated silicon and ultimately to crystalline Li15Si4. The solid-state amorphization process is correlated to a decrease in entropic heat flow, suggesting that heat associated with the amorphization contributes significantly to the entropic heat flow term. In conclusion, this study effectively uses IMC to probe the parasitic reactions that occur during lithiation of a silicon electrode, demonstrating an approach that can be broadly applied to quantify parasitic reactions in other complex systems.},
doi = {10.1021/acsami.9b10772},
journal = {ACS Applied Materials and Interfaces},
number = 41,
volume = 11,
place = {United States},
year = {Tue Sep 24 00:00:00 EDT 2019},
month = {Tue Sep 24 00:00:00 EDT 2019}
}
Web of Science
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