The void formation behaviors in working solid-state Li metal batteries

Abstract

The fundamental understanding of the elusive evolution behavior of the buried solid-solid interfaces is the major barrier to exploring solid-state electrochemical devices. Here, we uncover the interfacial void evolution principles in solid-state batteries, build a solid-state void nucleation and growth model, and make an analogy with the bubble formation in liquid phases. In solid-state lithium metal batteries, the lithium stripping–induced interfacial void formation determines the morphological instabilities that result in battery failure. The void-induced contact loss processes are quantified in a phase diagram under wide current densities ranging from 1.0 to 10.0 milliamperes per square centimeter by rational electrochemistry calculations. The in situ–visualized morphological evolutions reveal the microscopic features of void defects under different stripping circumstances. The electrochemical-morphological relationship helps to elucidate the current density– and areal capacity–dependent void nucleation and growth mechanisms, which affords fresh insights on understanding and designing solid-solid interfaces for advanced solid-state batteries.