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Vacancy diffusion and its consequences for void growth at the interface of a stripping metal electrode and solid electrolyte

Published version
Peer-reviewed

Repository DOI


Type

Article

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Authors

Fleck, NA 
McMeeking, RM 

Abstract

It is commonly observed that voids can nucleate and grow in the lithium anode of a solid state Li-ion battery at a location adjacent to the solid electrolyte during the stripping (discharge) phase of the battery; a similar phenomenon is observed in sodium-based batteries. It is hypothesised in the current literature that the formation of these voids is due to the coalescence of vacancies that have been generated at the electrode/electrolyte interface when metal atoms are oxidized and transported into the electrolyte: the slow diffusion of the vacancies away from the electrolyte interface into the adjacent electrode results in their coalescence and the consequent growth of voids. These hypotheses are challenged in the current study by using the Onsager formalism to generate a variational principle for vacancy diffusion. Our analysis reveals that no driving force exists for the diffusion of vacancies into a homogeneous metal electrode that thins by stripping. This finding is contrary to models in the literature which have mistakenly assumed that the vanishing flux at the current collector prevents rigid body motion (drift) of the electrode which in turn prevents thinning of the electrode during stripping. Based on our analysis, we conclude that vacancy diffusion within a homogeneous electrode is not responsible for the nucleation and growth of voids at the interface between a stripping metal electrode and a solid electrolyte.

Description

Keywords

Solid-state battery, Ceramic electrolyte, Butler-volmer kinetics, Void growth

Journal Title

Electrochimica Acta

Conference Name

Journal ISSN

0013-4686
1873-3859

Volume Title

467

Publisher

Elsevier BV