Lithium Metal Batteries for High Temperature Environments

Abstract The escalating global demand for high‐energy‐density electrochemical storage in challenging thermal environments necessitates a comprehensive reevaluation of battery technologies. While conventional lithium‐ion batteries are constrained by narrow operating temperature windows (below 60 °C) along with modest energy density, lithium metal batteries (LMBs) offer exceptional theoretical energy density and versatile cathode chemistries, presenting a compelling alternative for applications such as desert grid storage, electric aviation, and subsurface oil ang gas exploration. Despite their cutting‐edge potential, commercializing LMBs, particularly for HT applications, faces significant hurdles. This review critically analyzes the state‐of‐the‐art advancements and persistent challenges in high‐temperature lithium metal batteries (HT‐LMBs). It delineates the fundamental thermodynamic, electrochemical, and electro‐chemo‐mechanical factors that govern their performance and degradation at elevated temperatures. The design principles, limitations, and innovative strategies across core components, including high‐voltage and sulfur‐based cathodes, lithium metal anodes, liquid and solid‐state electrolytes, and crucial auxiliary components like separators, binders, and current collectors are examined. Finally, this review summarizes promising approaches to develop reliable HT‐LMBs, and calls for concerted efforts in real‐world performance benchmarking to accelerate cooling‐free battery designs.