Solid Electrolyte–Cathode Interface Dictates Reaction Heterogeneity and Anode Stability

Solid-state batteries (SSBs) employing a lithium metal anode are a promising candidate for next-generation energy storage systems, delivering higher power and energy densities. Interfacial instabilities due to non-uniform electrodeposition at the anode-solid electrolyte (SE) interface pose major constraints on the safety and endurance of SSBs. In this regard, non-uniform kinetic interactions at the anode-SE interface which are derived from cathode microstructural heterogeneity can have significant impact on anode stability. In this work, we present a comprehensive insight into microstructural heterogeneity-driven cathode-anode cross-talk and delineate the role of cathode architecture and SE separator design in dictating reaction heterogeneity at the anode-SE interface. We show that intrinsic and extrinsic parameters, such as cathode loading, separator thickness, particle morphologies of active material and SE, and temperature can have significant impact on reaction heterogeneity at the anode-SE interface and thus govern anode stability. Tradeoff between energy density and anode stability while achieving higher cathode loading and thinner SE separators is highlighted, and potential strategies to mitigate this problem are discussed. This work provides fundamental insights into cathode-anode cross-talk involving interfacial heterogeneities and enhancement in energy densities of SSBs via electrode engineering.