Operando Characterization and Theoretical Modeling of Metal|Electrolyte Interphase Growth Kinetics in Solid-State Batteries. Part II: Modeling

Nicholas J. Williams; Edouard Quérel; Ieuan D. Seymour; Stephen J. Skinner; Ainara Aguadero

doi:10.1021/acs.chemmater.2c03131

Operando Characterization and Theoretical Modeling of Metal|Electrolyte Interphase Growth Kinetics in Solid-State Batteries. Part II: Modeling

Nicholas J. Williams^*, Edouard Quérel, Ieuan D. Seymour, Stephen J. Skinner, Ainara Aguadero

^*Corresponding author for this work

Chemistry

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

3 Citations (Scopus)

Abstract

Understanding the interfacial dynamics of batteries is crucial to control degradation and increase electrochemical performance and cycling life. If the chemical potential of a negative electrode material lies outside of the stability window of an electrolyte (either solid or liquid), a decomposition layer (interphase) will form at the interface. To better understand and control degradation at interfaces in batteries, theoretical models describing the rate of formation of these interphases are required. This study focuses on the growth kinetics of the interphase forming between solid electrolytes and metallic negative electrodes in solid-state batteries. More specifically, we demonstrate that the rate of interphase formation and metal plating during charge can be accurately described by adapting the theory of coupled ion-electron transfer (CIET). The model is validated by fitting experimental data presented in the first part of this study. The data was collected operando as a Na metal layer was plated on top of a NaSICON solid electrolyte (Na_3.4Zr₂Si_2.4P_0.6O₁₂ or NZSP) inside an XPS chamber. This study highlights the depth of information which can be extracted from this single operando experiment and is widely applicable to other solid-state electrolyte systems.

Original language	English
Pages (from-to)	863-869
Number of pages	7
Journal	Chemistry of Materials
Volume	35
Issue number	3
Early online date	28 Jan 2023
DOIs	https://doi.org/10.1021/acs.chemmater.2c03131
Publication status	Published - 14 Feb 2023

Bibliographical note

Funding Information:
E.Q., I.D.S., and S.J.S. acknowledge the EPSRC for funding through the award of grant EP/R002010/1. This work was supported by Ceres Power Ltd and Shell Global Solutions International B.V. The authors would like to thank Professor Martin Bazant and Alexander Cohen for fruitful discussions of this work throughout the project.

Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society.

Data Availability Statement

The XPS data and fitting models used in this work are accessible on the following GitHub repository: https://github.com/nw7g14/Modelling-XPS-ODE-constrained-opt.

Keywords

electrodes
interfaces
metals
surface chemistry
charge transfer

Access to Document

10.1021/acs.chemmater.2c03131

Williams_etal_CM_Operando_Characterization_and_VOR
https://creativecommons.org/licenses/by/4.0/
Final published version, 2.56 MBLicence: CC BY

Cite this

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title = "Operando Characterization and Theoretical Modeling of Metal|Electrolyte Interphase Growth Kinetics in Solid-State Batteries. Part II: Modeling",

abstract = "Understanding the interfacial dynamics of batteries is crucial to control degradation and increase electrochemical performance and cycling life. If the chemical potential of a negative electrode material lies outside of the stability window of an electrolyte (either solid or liquid), a decomposition layer (interphase) will form at the interface. To better understand and control degradation at interfaces in batteries, theoretical models describing the rate of formation of these interphases are required. This study focuses on the growth kinetics of the interphase forming between solid electrolytes and metallic negative electrodes in solid-state batteries. More specifically, we demonstrate that the rate of interphase formation and metal plating during charge can be accurately described by adapting the theory of coupled ion-electron transfer (CIET). The model is validated by fitting experimental data presented in the first part of this study. The data was collected operando as a Na metal layer was plated on top of a NaSICON solid electrolyte (Na3.4Zr2Si2.4P0.6O12 or NZSP) inside an XPS chamber. This study highlights the depth of information which can be extracted from this single operando experiment and is widely applicable to other solid-state electrolyte systems.",

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author = "Williams, {Nicholas J.} and Edouard Qu{\'e}rel and Seymour, {Ieuan D.} and Skinner, {Stephen J.} and Ainara Aguadero",

note = "Funding Information: E.Q., I.D.S., and S.J.S. acknowledge the EPSRC for funding through the award of grant EP/R002010/1. This work was supported by Ceres Power Ltd and Shell Global Solutions International B.V. The authors would like to thank Professor Martin Bazant and Alexander Cohen for fruitful discussions of this work throughout the project. Publisher Copyright: {\textcopyright} 2023 The Authors. Published by American Chemical Society.",

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AU - Seymour, Ieuan D.

AU - Skinner, Stephen J.

AU - Aguadero, Ainara

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N2 - Understanding the interfacial dynamics of batteries is crucial to control degradation and increase electrochemical performance and cycling life. If the chemical potential of a negative electrode material lies outside of the stability window of an electrolyte (either solid or liquid), a decomposition layer (interphase) will form at the interface. To better understand and control degradation at interfaces in batteries, theoretical models describing the rate of formation of these interphases are required. This study focuses on the growth kinetics of the interphase forming between solid electrolytes and metallic negative electrodes in solid-state batteries. More specifically, we demonstrate that the rate of interphase formation and metal plating during charge can be accurately described by adapting the theory of coupled ion-electron transfer (CIET). The model is validated by fitting experimental data presented in the first part of this study. The data was collected operando as a Na metal layer was plated on top of a NaSICON solid electrolyte (Na3.4Zr2Si2.4P0.6O12 or NZSP) inside an XPS chamber. This study highlights the depth of information which can be extracted from this single operando experiment and is widely applicable to other solid-state electrolyte systems.

AB - Understanding the interfacial dynamics of batteries is crucial to control degradation and increase electrochemical performance and cycling life. If the chemical potential of a negative electrode material lies outside of the stability window of an electrolyte (either solid or liquid), a decomposition layer (interphase) will form at the interface. To better understand and control degradation at interfaces in batteries, theoretical models describing the rate of formation of these interphases are required. This study focuses on the growth kinetics of the interphase forming between solid electrolytes and metallic negative electrodes in solid-state batteries. More specifically, we demonstrate that the rate of interphase formation and metal plating during charge can be accurately described by adapting the theory of coupled ion-electron transfer (CIET). The model is validated by fitting experimental data presented in the first part of this study. The data was collected operando as a Na metal layer was plated on top of a NaSICON solid electrolyte (Na3.4Zr2Si2.4P0.6O12 or NZSP) inside an XPS chamber. This study highlights the depth of information which can be extracted from this single operando experiment and is widely applicable to other solid-state electrolyte systems.

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KW - interfaces

KW - metals

KW - surface chemistry

KW - charge transfer

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Operando Characterization and Theoretical Modeling of Metal|Electrolyte Interphase Growth Kinetics in Solid-State Batteries. Part II: Modeling

Abstract

Bibliographical note

Data Availability Statement

Keywords

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