Inside or Outside: Origin of Lithium Dendrite Formation of All Solid‐State Electrolytes

Abstract All‐solid‐state lithium metal batteries (ASSLMBs) stand out for the next generation of energy storage system. However, the further realization is severely hampered by the lithium dendrite formation in solid state electrolytes (SSEs), by mechanisms that remain controversial. Herein, with the aid of experimental and theoretical approaches, the origin of dendrite formation in representative LiBH 4 SSE, which is thermodynamically stable with the Li metal, suppressing the side reaction between Li and SSE is elucidated. It is demonstrated that upon diffusion, Li + encounters an electron, and is subsequently reduced to Li 0 within the grain boundary/pore of SSE, eventually leading to short circuit. Thus, introducing LiF with the ability of interstitial filling and low electronic conductivity into SSE is the effective countermeasure, and as expected, with the addition of LiF, the critical current density (CCD) increases by 235% compared to the value of pure LiBH 4 . The TiS 2 |LiBH 4 –LiF|Li ASSLMBs manifest a reversible capacity of 137 mAh g −1 at 0.4 C upon 60 cycles. These findings not only unravel critical issues in Li dendrite formation in SSE, but also propose the countermeasure.