- Geng, Lin;
- Xue, Dingchuan;
- Yao, Jingming;
- Dai, Qiushi;
- Sun, Haiming;
- Zhu, Dingding;
- Rong, Zhaoyu;
- Fang, Ruyue;
- Zhang, Xuedong;
- Su, Yong;
- Yan, Jitong;
- Harris, Stephen J;
- Ichikawa, Satoshi;
- Zhang, Liqiang;
- Tang, Yongfu;
- Zhang, Sulin;
- Huang, Jianyu
All solid-state batteries (ASSBs) with ceramic electrolytes and alkali metal anodes are a potential future energy storage technology for vehicle electrification and smart grids. However, uncontrollable dendrite growth toward ultimate short circuiting in solid electrolytes (SEs) has become a serious concern in the design of long-cycle, safe ASSBs, and the underlying mechanism has remained unclear. Here through multiscale imaging and morphodynamic tracking we show that Na dendrites grow in β′′-Al2O3 SEs through an alternating sequence of Na deposition and crack propagation. Atomic-scale imaging evidenced that electrochemical cycling causes massive delamination cracking along the Na+ conduction planes, accompanied by the closure of neighboring conduction channels. In situ SEM observations revealed a dynamic interplay between Na deposition and crack propagation: Na deposition accumulates mechanical stress that induces cracking; cracking releases the local stress, which promotes further Na deposition. Thus, Na deposition and cracking alternatingly proceed until short circuits take place. A multiscale phase-field model is developed to recapitulate the morphodynamics of Na dendrite growth, predicting the tree-like fractal morphology of the growing dendrites. Our findings suggest that decoupling between Na deposition and cracking represents an important route to mitigate uncontrollable dendrite growth in ASSBs.