How Does Stacking Pressure Affect the Performance of Solid Electrolytes and All‐Solid‐State Lithium Metal Batteries?

All‐solid‐state lithium metal batteries (ASSLMBs) with solid electrolytes (SEs) have emerged as a promising alternative to liquid electrolyte‐based Li‐ion batteries due to their higher energy density and safety. However, since ASSLMBs lack the wetting properties of liquid electrolytes, they require stacking pressure to prevent contact loss between electrodes and SEs. Though previous studies showed that stacking pressure could impact certain performance aspects, a comprehensive investigation into the effects of stacking pressure has not been conducted. To address this gap, we utilized the Li 6 PS 5 Cl solid electrolyte as a reference and investigated the effects of stacking pressures on the performance of SEs and ASSLMBs. We also developed models to explain the underlying origin of these effects and predict battery performance, such as ionic conductivity and critical current density. Our results demonstrated that an appropriate stacking pressure is necessary to achieve optimal performance, and each step of applying pressure requires a specific pressure value. These findings can help explain discrepancies in the literature and provide guidance to establish standardized testing conditions and reporting benchmarks for ASSLMBs. Overall, this study contributes to the understanding of the impact of stacking pressure on the performance of ASSLMBs and highlights the importance of careful pressure optimization for optimal battery performance.