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

Journal Article · · ACS Applied Materials and Interfaces
 [1];  [2];  [2];  [2];  [2];  [3];  [3];  [2];  [4];  [4];  [4];  [4];  [4];  [4]
  1. Stony Brook Univ., NY (United States); Northwestern University, Evanston, IL, United States
  2. Stony Brook Univ., NY (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  4. Stony Brook Univ., NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
+ Show Author Affiliations
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.
Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M/t); Northwestern Univ., Evanston, IL (United States)
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:
SC0012673; SC0012704; SC0021314
OSTI ID:
1865649
Alternate ID(s):
OSTI ID: 1963195
Report Number(s):
BNL-224162-2023-JAAM
Journal Information:
ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 18 Vol. 14; ISSN 1944-8244
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

25 ENERGY STORAGE
battery
carbon
heat dissipation
isothermal microcalorimetry
particle size
silicon