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Title: Toward quantifying capacity losses due to solid electrolyte interphase evolution in silicon thin film batteries

Abstract

To understand the origins of failure and limited cycle life in lithium-ion batteries (LIBs), it is imperative to quantitatively link capacity-fading mechanisms to electrochemical and chemical processes. This is extremely challenging in real systems where capacity is lost during each cycle to both active material loss and solid electrolyte interphase (SEI) evolution, two indistinguishable contributions in traditional electrochemical measurements. Here, we have used a model system in combination with (1) precision measurements of the overall Coulombic efficiency via electrochemical experiments and (2) x-ray reflectivity measurements of the active material losses. The model system consisted of a 515 Å thick amorphous silicon (a-Si) thin film on silicon carbide in half-cell geometry using a carbonate electrolyte with LiPF6 salt. This approach allowed us to quantify the capacity lost during each cycle due to SEI evolution. Combined with electrochemical analysis, we identify SEI growth as the major contribution to capacity fading. Specifically, the continued SEI growth results in increasing overpotentials due to increased SEI resistance, and this leads to lower extent of lithiation when the cutoff voltage is reached during lithiation. Our results suggest that SEI grows more with increased time spent at low voltages where electrolyte decomposition is favored. Finally, we extractedmore » a proportionality constant for SEI growth following a parabolic growth law. Our methodology allows for the quantitative determination of lithium-ion loss mechanisms in LIBs by separately tracking lithium ions within the active materials and the SEI and offers a powerful method of quantitatively understanding LIB loss mechanisms.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1606741
Alternate Identifier(s):
OSTI ID: 1634117
Grant/Contract Number:  
AC05-00OR22725; AC02-76SF00515
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 152; Journal Issue: 8; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Chemical processes; Half-cell; X-ray reflectivity; Interphases; Batteries; Thin films; Electrochemical analysis; Power electronics; Electrolytes

Citation Formats

Steinrück, Hans-Georg, Cao, Chuntian, Veith, Gabriel M., and Toney, Michael F. Toward quantifying capacity losses due to solid electrolyte interphase evolution in silicon thin film batteries. United States: N. p., 2020. Web. doi:10.1063/1.5142643.
Steinrück, Hans-Georg, Cao, Chuntian, Veith, Gabriel M., & Toney, Michael F. Toward quantifying capacity losses due to solid electrolyte interphase evolution in silicon thin film batteries. United States. https://doi.org/10.1063/1.5142643
Steinrück, Hans-Georg, Cao, Chuntian, Veith, Gabriel M., and Toney, Michael F. Fri . "Toward quantifying capacity losses due to solid electrolyte interphase evolution in silicon thin film batteries". United States. https://doi.org/10.1063/1.5142643.
@article{osti_1606741,
title = {Toward quantifying capacity losses due to solid electrolyte interphase evolution in silicon thin film batteries},
author = {Steinrück, Hans-Georg and Cao, Chuntian and Veith, Gabriel M. and Toney, Michael F.},
abstractNote = {To understand the origins of failure and limited cycle life in lithium-ion batteries (LIBs), it is imperative to quantitatively link capacity-fading mechanisms to electrochemical and chemical processes. This is extremely challenging in real systems where capacity is lost during each cycle to both active material loss and solid electrolyte interphase (SEI) evolution, two indistinguishable contributions in traditional electrochemical measurements. Here, we have used a model system in combination with (1) precision measurements of the overall Coulombic efficiency via electrochemical experiments and (2) x-ray reflectivity measurements of the active material losses. The model system consisted of a 515 Å thick amorphous silicon (a-Si) thin film on silicon carbide in half-cell geometry using a carbonate electrolyte with LiPF6 salt. This approach allowed us to quantify the capacity lost during each cycle due to SEI evolution. Combined with electrochemical analysis, we identify SEI growth as the major contribution to capacity fading. Specifically, the continued SEI growth results in increasing overpotentials due to increased SEI resistance, and this leads to lower extent of lithiation when the cutoff voltage is reached during lithiation. Our results suggest that SEI grows more with increased time spent at low voltages where electrolyte decomposition is favored. Finally, we extracted a proportionality constant for SEI growth following a parabolic growth law. Our methodology allows for the quantitative determination of lithium-ion loss mechanisms in LIBs by separately tracking lithium ions within the active materials and the SEI and offers a powerful method of quantitatively understanding LIB loss mechanisms.},
doi = {10.1063/1.5142643},
url = {https://www.osti.gov/biblio/1606741}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 8,
volume = 152,
place = {United States},
year = {2020},
month = {2}
}

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