Surprising Relationship between Silicon Anode Calendar Aging and Electrolyte Components in a Localized High-Concentration Electrolyte System

Steven Lam; Ankit Verma; Maxwell C. Schulze; Robert L. Sacci; Harry M. Meyer; Michael J. Lance; Khryslyn G. Araño; Amanda L. Musgrove; Marco Tulio Fonseca Rodrigues; Stephen E. Trask; Andrew Colclasure; Gabriel M. Veith

doi:10.1021/acsami.5c07869

Surprising Relationship between Silicon Anode Calendar Aging and Electrolyte Components in a Localized High-Concentration Electrolyte System

Steven Lam
, Ankit Verma
, Maxwell C. Schulze
, Robert L. Sacci
, Harry M. Meyer
, Michael J. Lance
, Khryslyn G. Araño
, Amanda L. Musgrove
, Marco Tulio Fonseca Rodrigues
, Stephen E. Trask
, Andrew Colclasure
, Gabriel M. Veith

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

Abstract

Although localized high-concentration electrolytes (LHCEs) have been shown to improve the calendar lifetime of silicon anodes, the roles of the electrolyte constituents in calendar aging are not well understood. Here, we utilize a voltage hold protocol and an LHCE with varying molar ratios of lithium bis(fluorosulfonyl)imide (LiFSI), tetramethylene sulfone (TMS), and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) to probe the component roles during aging. Interestingly, the estimated calendar lifetime and irreversible lithium losses from the V-hold experiments are independent of the electrolyte formulations. Contrarily, the solid electrolyte interphase (SEI) composition depends on the electrolyte formulation. X-ray photoelectron spectroscopy shows that TMS-coordinated species decompose to form insoluble alkanes and lithium hydroxide (LiOH), while lithium fluoride (LiF) originates from the anion-coordination complex. The SEI composition does not appear to play a significant role in the silicon anode passivity, as measured by parasitic current, suggesting that the SEI-electrolyte interactions dictate the calendar aging mechanisms.

Original language	English
Pages (from-to)	43020-43033
Number of pages	14
Journal	ACS Applied Materials and Interfaces
Volume	17
Issue number	30
DOIs	https://doi.org/10.1021/acsami.5c07869
State	Published - Jul 30 2025

Funding

This research was supported by the U.S. Department of Energy, Vehicle Technologies Office (DOE-VTO) under the Silicon Consortium Project, directed by Nicolas Eidson, Carine Steinway, Thomas Do, and Brian Cunningham, and managed by Anthony Burrell. This manuscript has been authored in part by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the U.S. Department of Energy (DOE). The publisher, by accepting the article for publication, acknowledges that the U.S. government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for U.S. government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doepublic-accessplan). Argonne National Laboratory (“Argonne”) is operated by UChicago Argonne LLC and is a U.S. Department of Energy Office of Science laboratory, operated under Contract No. DE-AC02-06CH11357. The National Renewable Energy Laboratory is operated by Alliance for Sustainable Energy, LLC, for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-08GO28308.

Keywords

Calendar Aging
Si Anode
localized high concentration electrolytes
parasitic reactions
solid electrolyte Interphase

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10.1021/acsami.5c07869

Cite this

Lam, S., Verma, A., Schulze, M. C., Sacci, R. L., Meyer, H. M., Lance, M. J., Araño, K. G., Musgrove, A. L., Fonseca Rodrigues, M. T., Trask, S. E., Colclasure, A., & Veith, G. M. (2025). Surprising Relationship between Silicon Anode Calendar Aging and Electrolyte Components in a Localized High-Concentration Electrolyte System. ACS Applied Materials and Interfaces, 17(30), 43020-43033. https://doi.org/10.1021/acsami.5c07869

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title = "Surprising Relationship between Silicon Anode Calendar Aging and Electrolyte Components in a Localized High-Concentration Electrolyte System",

abstract = "Although localized high-concentration electrolytes (LHCEs) have been shown to improve the calendar lifetime of silicon anodes, the roles of the electrolyte constituents in calendar aging are not well understood. Here, we utilize a voltage hold protocol and an LHCE with varying molar ratios of lithium bis(fluorosulfonyl)imide (LiFSI), tetramethylene sulfone (TMS), and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) to probe the component roles during aging. Interestingly, the estimated calendar lifetime and irreversible lithium losses from the V-hold experiments are independent of the electrolyte formulations. Contrarily, the solid electrolyte interphase (SEI) composition depends on the electrolyte formulation. X-ray photoelectron spectroscopy shows that TMS-coordinated species decompose to form insoluble alkanes and lithium hydroxide (LiOH), while lithium fluoride (LiF) originates from the anion-coordination complex. The SEI composition does not appear to play a significant role in the silicon anode passivity, as measured by parasitic current, suggesting that the SEI-electrolyte interactions dictate the calendar aging mechanisms.",

keywords = "Calendar Aging, Si Anode, localized high concentration electrolytes, parasitic reactions, solid electrolyte Interphase",

author = "Steven Lam and Ankit Verma and Schulze, \{Maxwell C.\} and Sacci, \{Robert L.\} and Meyer, \{Harry M.\} and Lance, \{Michael J.\} and Ara{\~n}o, \{Khryslyn G.\} and Musgrove, \{Amanda L.\} and \{Fonseca Rodrigues\}, \{Marco Tulio\} and Trask, \{Stephen E.\} and Andrew Colclasure and Veith, \{Gabriel M.\}",

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doi = "10.1021/acsami.5c07869",

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Lam, S, Verma, A, Schulze, MC, Sacci, RL , Meyer, HM , Lance, MJ, Araño, KG, Musgrove, AL, Fonseca Rodrigues, MT, Trask, SE, Colclasure, A & Veith, GM 2025, 'Surprising Relationship between Silicon Anode Calendar Aging and Electrolyte Components in a Localized High-Concentration Electrolyte System', ACS Applied Materials and Interfaces, vol. 17, no. 30, pp. 43020-43033. https://doi.org/10.1021/acsami.5c07869

TY - JOUR

T1 - Surprising Relationship between Silicon Anode Calendar Aging and Electrolyte Components in a Localized High-Concentration Electrolyte System

AU - Lam, Steven

AU - Verma, Ankit

AU - Schulze, Maxwell C.

AU - Sacci, Robert L.

AU - Meyer, Harry M.

AU - Lance, Michael J.

AU - Araño, Khryslyn G.

AU - Musgrove, Amanda L.

AU - Fonseca Rodrigues, Marco Tulio

AU - Trask, Stephen E.

AU - Colclasure, Andrew

AU - Veith, Gabriel M.

PY - 2025/7/30

Y1 - 2025/7/30

N2 - Although localized high-concentration electrolytes (LHCEs) have been shown to improve the calendar lifetime of silicon anodes, the roles of the electrolyte constituents in calendar aging are not well understood. Here, we utilize a voltage hold protocol and an LHCE with varying molar ratios of lithium bis(fluorosulfonyl)imide (LiFSI), tetramethylene sulfone (TMS), and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) to probe the component roles during aging. Interestingly, the estimated calendar lifetime and irreversible lithium losses from the V-hold experiments are independent of the electrolyte formulations. Contrarily, the solid electrolyte interphase (SEI) composition depends on the electrolyte formulation. X-ray photoelectron spectroscopy shows that TMS-coordinated species decompose to form insoluble alkanes and lithium hydroxide (LiOH), while lithium fluoride (LiF) originates from the anion-coordination complex. The SEI composition does not appear to play a significant role in the silicon anode passivity, as measured by parasitic current, suggesting that the SEI-electrolyte interactions dictate the calendar aging mechanisms.

AB - Although localized high-concentration electrolytes (LHCEs) have been shown to improve the calendar lifetime of silicon anodes, the roles of the electrolyte constituents in calendar aging are not well understood. Here, we utilize a voltage hold protocol and an LHCE with varying molar ratios of lithium bis(fluorosulfonyl)imide (LiFSI), tetramethylene sulfone (TMS), and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) to probe the component roles during aging. Interestingly, the estimated calendar lifetime and irreversible lithium losses from the V-hold experiments are independent of the electrolyte formulations. Contrarily, the solid electrolyte interphase (SEI) composition depends on the electrolyte formulation. X-ray photoelectron spectroscopy shows that TMS-coordinated species decompose to form insoluble alkanes and lithium hydroxide (LiOH), while lithium fluoride (LiF) originates from the anion-coordination complex. The SEI composition does not appear to play a significant role in the silicon anode passivity, as measured by parasitic current, suggesting that the SEI-electrolyte interactions dictate the calendar aging mechanisms.

KW - Calendar Aging

KW - Si Anode

KW - localized high concentration electrolytes

KW - parasitic reactions

KW - solid electrolyte Interphase

UR - https://www.scopus.com/pages/publications/105012784396

U2 - 10.1021/acsami.5c07869

DO - 10.1021/acsami.5c07869

M3 - Article

C2 - 40673890

AN - SCOPUS:105012784396

SN - 1944-8244

VL - 17

SP - 43020

EP - 43033

JO - ACS Applied Materials and Interfaces

JF - ACS Applied Materials and Interfaces

IS - 30

ER -

Surprising Relationship between Silicon Anode Calendar Aging and Electrolyte Components in a Localized High-Concentration Electrolyte System

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