Interfacial catalysis in lithium salt decomposition: Impacts on lithium metal battery performance

Lithium metal batteries (LMBs) have emerged as the focal point of next-generation energy storage systems due to their high energy density and low electrochemical potential of the lithium metal anode. However, their practical application is hindered by intrinsic interfacial instabilities, including uncontrolled dendrite growth, continuous electrolyte depletion, and the formation of fragile interphases. Substantial efforts have been made to stabilize electrode–electrolyte interfaces through artificial interlayers and electrolyte design. Recently, there has been a growing focus on the interfacial catalysis of lithium salt decomposition, signifying a shift from passive protection to active kinetic regulation. This emerging approach is expected to play an important role in controlling lithium salt decomposition and forming robust inorganic-rich solid electrolyte interphases (SEI). Nevertheless, despite several pioneering studies demonstrating the effectiveness of specific catalytic materials, a systematic review dedicated to this topic is still lacking. In this context, the present review aims to provide a comprehensive summary of recent advances in interfacial catalysis strategies for lithium salt decomposition. It begins with a brief introduction, followed by an in-depth examination of catalytic mechanisms, including orbital modulation, solvation kinetics regulation, and local electric field engineering. The review then summarizes representative applications in liquid/solid-state lithium metal batteries, anode-free architectures, and post-lithium systems (including sodium and lithium–sulfur batteries). Finally, it addresses existing challenges and future research directions to bridge the gap between fundamental catalytic principles and practical battery applications. Graphical abstract of interface catalysis for lithium salt decomposition.