Revealing Capacity Degradation of Ge Anodes in Lithium‐Ion Batteries Triggered by Interfacial LiH

Abstract The Germanium (Ge), as a fast‐charging and high specific capacity (1568 mAh g −1 ) alloy anode, is greatly hampered in practical application by poor cyclability. To date, the understanding of cycling performance degradation remains elusive. This study illustrates that, contrary to conventional beliefs, most of the Ge material in failed anodes still retains good integrity and does not undergo severe pulverization. It is revealed that capacity degradation is clearly correlated to the interfacial evolution of lithium hydride (LiH). Tetralithium germanium hydride (Li 4 Ge 2 H), as a new species derived from LiH, is identified as the culprit of Ge anode degradation, which is the dominant crystalized component in an ever‐growing and ever‐insulating interphase. The significantly increased thickness of the solid electrolyte interface (SEI) is accompanied by the accumulation of insulating Li 4 Ge 2 H upon cycling, which severely retards the charge transport process and ultimately triggers the anode failure. We believe that the comprehensive understanding of the failure mechanism presented in this study is of great significance to promoting the design and development of alloy anode for the next generation of lithium‐ion batteries.