Insights into Reactivity of Silicon Negative Electrodes: Analysis Using Isothermal Microcalorimetry

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.

doi:10.1021/acsami.9b10772

Title: Insights into Reactivity of Silicon Negative Electrodes: Analysis Using Isothermal Microcalorimetry

Journal Article · Tue Sep 24 00:00:00 EDT 2019 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.9b10772· OSTI ID:1580221

Housel, Lisa M. ^[1]; Li, Wenzao ^[1]; Quilty, Calvin D. ^[1]; Vila, Mallory N. ^[1];

^[2]; Tang, Christopher R. ^[1]; Bock, David C. ^[2]; Wu, Qiyuan ^[2]; Tong, Xiao ^[2];

^[2];

^[1];

^[3];

^[3]

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)

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.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2mt); Brookhaven National Lab. (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704; SC0012673

OSTI ID:: 1580221

Report Number(s):: BNL-212444-2019-JAAM

Journal Information:: ACS Applied Materials and Interfaces, Vol. 11, Issue 41; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 21 works

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25 ENERGY STORAGE
isothermal microcalorimetry
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heat flow
entropy
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Title: Insights into Reactivity of Silicon Negative Electrodes: Analysis Using Isothermal Microcalorimetry

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