Dendrite initiation and propagation in lithium metal solid-state batteries

Ziyang Ning, Guanchen Li, Dominic L.R. Melvin, Yang Chen, Junfu Bu, Dominic Spencer Jolly, Junliang Liu, Bingkun Hu, Xiangwen Gao, Johann Perera, Chen Gong, Shengda D. Pu, Shengming Zhang, Boyang Liu, Gareth O. Hartley, Andew J. Bodey, Richard I. Todd, Patrick S. Grant, David E. J. Amstrong, James MarrowCharles W. Monroe, Peter G Bruce

Research output: Contribution to journalArticlepeer-review

109 Citations (SciVal)

Abstract

All-solid-state batteries with a Li anode and ceramic electrolyte have the potential to deliver a step change in performance compared with today’s Li-ion batteries 1,2. However, Li dendrites (filaments) form on charging at practical rates and penetrate the ceramic electrolyte, leading to short circuit and cell failure 3,4. Previous models of dendrite penetration have generally focused on a single process for dendrite initiation and propagation, with Li driving the crack at its tip 5–9. Here we show that initiation and propagation are separate processes. Initiation arises from Li deposition into subsurface pores, by means of microcracks that connect the pores to the surface. Once filled, further charging builds pressure in the pores owing to the slow extrusion of Li (viscoplastic flow) back to the surface, leading to cracking. By contrast, dendrite propagation occurs by wedge opening, with Li driving the dry crack from the rear, not the tip. Whereas initiation is determined by the local (microscopic) fracture strength at the grain boundaries, the pore size, pore population density and current density, propagation depends on the (macroscopic) fracture toughness of the ceramic, the length of the Li dendrite (filament) that partially occupies the dry crack, current density, stack pressure and the charge capacity accessed during each cycle. Lower stack pressures suppress propagation, markedly extending the number of cycles before short circuit in cells in which dendrites have initiated.

Original languageEnglish
Pages (from-to)287-293
Number of pages7
JournalNature
Volume618
Issue number7964
Early online date7 Jun 2023
DOIs
Publication statusPublished - 8 Jun 2023

Bibliographical note

Funding Information:
P.G.B. is indebted to the Faraday Institution SOLBAT (FIRG007, FIRG008, FIRG026), as well as the Engineering and Physical Sciences Research Council, Enabling Next Generation Lithium Batteries (EP/M009521/1), the University of Oxford experimental equipment upgrade (EP/M02833X/1) and the Henry Royce Institute for Advanced Materials (EP/R0066X/1, EP/S019367/1, EP/R010145/1) for financial support. We thank the Diamond Light Source for the provision of synchrotron radiation beam time (experiment no. MG23980-1) at the I13-2 beamline at the Diamond Light Source. We acknowledge technical and experimental support at the I13-2 beamline by A. J. Bodey.

Data availability
The datasets generated and/or analysed during this study are available from the corresponding author on reasonable request

Fingerprint

Dive into the research topics of 'Dendrite initiation and propagation in lithium metal solid-state batteries'. Together they form a unique fingerprint.

Cite this