Elucidating Gas Reduction Effects of Organosilicon Additives in Lithium-Ion Batteries

Wang, Jingyang; Guillot, Sarah L.; Usrey, Monica L.; Hou, Tingzheng; Persson, Kristin A.

doi:10.1021/jacs.5c00402

Title: Elucidating Gas Reduction Effects of Organosilicon Additives in Lithium-Ion Batteries

Journal Article · 26 February 2025 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.5c00402 · OSTI ID:2524612

^[1]; Guillot, Sarah L. ^[2]; Usrey, Monica L. ^[2];

^[3]; Persson, Kristin A. ^[4]

Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Silatronix, Inc., Madison, WI (United States)
University of California, Berkeley, CA (United States); Tsinghua University, Shenzhen, Guangdong (China)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of California, Berkeley, CA (United States)

Lithium-ion batteries (LIBs) with nonaqueous liquid electrolytes are prone to gas generation at elevated voltages and temperatures, degrading battery performance and posing serious safety risks. Organosilicon (OS) additives are an emerging candidate solution for gassing problems in LIBs, but a detailed understanding of their functional mechanisms remains elusive. In this work, we present a combined computational and experimental study to elucidate the gasreducing effects of OS additives. Cell volume measurements and gas chromatography–mass spectrometry reveal that OS additives can substantially reduce gas evolution in LIBs, particularly CO₂ regardless of source. Through density functional theory calculations, we identify multiple plausible pathways for CO₂ evolution, including (1) nucleophile-induced ring-opening of ethylene carbonate (EC) and the subsequent electro-oxidation and (2) direct electro-oxidation of lithium carbonate (Li₂CO₃). Correspondingly, we find that OS additives function via two primary mechanisms: (1) scavenging of nucleophiles such as superoxide (O₂^•–), peroxide (O₂ ^2–), and carbonate ion (CO₃ ^2–); (2) oligomerization with ethylene carbonate oxide ion and ethylene dicarbonate ion. Moreover, we discover that OS additives possess strong lithium coordination affinity, which helps further reduce the nucleophilic reaction energies and hence increases their nucleophile-scavenging efficiency. Finally, we provide a mechanistic interpretation for the enhanced gasreduction effects observed with fluorinated OS compounds, corroborated by surface analysis results from X-ray photoelectron spectroscopy. Our study offers the first molecular-level insights into how OS additives contribute to reduced gas formation in LIBs, paving the way for improved safety and performance of LIBs.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of California, Berkeley, CA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2524612

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 10 Vol. 147; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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