Operando characterization and theoretical modeling of Metal|Electrolyte interphase growth kinetics in solid-state batteries. Part I: experiments
File(s)
Published version
Author(s)
Quérel, Edouard
Williams, Nicholas J
Seymour, Ieuan D
Skinner, Stephen J
Aguadero, Ainara
Type
Journal Article
Abstract
To harness all of the benefits of solid-state battery (SSB) architectures in terms of energy density, their negative electrode should be an alkali metal. However, the high chemical potential of alkali metals makes them prone to reduce most solid electrolytes (SE), resulting in a decomposition layer called an interphase at the metal|SE interface. Quantitative information about the interphase chemical composition and rate of formation is challenging to obtain because the reaction occurs at a buried interface. In this study, a thin layer of Na metal (Na0) is plated on the surface of an SE of the NaSICON family (Na3.4Zr2Si2.4P0.6O12 or NZSP) inside a commercial X-ray photoelectron spectroscopy (XPS) system while continuously analyzing the composition of the interphase operando. We identify the existence of a solid electrolyte interphase at the Na0|NZSP interface, and more importantly, we demonstrate for the first time that this protocol can be used to study the kinetics of interphase formation. A second important outcome of this article is that the surface chemistry of NZSP samples can be tuned to improve their stability against Na0. It is demonstrated by XPS and time-resolved electrochemical impedance spectroscopy (EIS) that a native NaxPOy layer present on the surface of as-sintered NZSP samples protects their surface against decomposition.
Date Issued
2023-01-20
Date Acceptance
2023-01-06
Citation
Chemistry of Materials, 2023, 35 (3), pp.853-862
ISSN
0897-4756
Publisher
American Chemical Society (ACS)
Start Page
853
End Page
862
Journal / Book Title
Chemistry of Materials
Volume
35
Issue
3
Copyright Statement
Copyright © 2023 The Authors. Published by American Chemical Society. This work is published under a CC BY licence.
License URL
Sponsor
Engineering & Physical Science Research Council (EPSRC)
Identifier
https://pubs.acs.org/doi/10.1021/acs.chemmater.2c03130
Grant Number
EP/R002010/1
Subjects
Materials
03 Chemical Sciences
09 Engineering
Publication Status
Published
Date Publish Online
2023-01-20