Wide Temperature Electrolytes for Lithium Batteries: Solvation Chemistry and Interfacial Reactions

Abstract Improving the wide‐temperature operation of rechargeable batteries is crucial for boosting the adoption of electric vehicles and further advancing their application scope in harsh environments like deep ocean and space probes. Herein, recent advances in electrolyte solvation chemistry are critically summarized, aiming to address the long‐standing challenge of notable energy diminution at sub‐zero temperatures and rapid capacity degradation at elevated temperatures (>45°C). This review provides an in‐depth analysis of the fundamental mechanisms governing the Li‐ion transport process, illustrating how these insights have been effectively harnessed to synergize with high‐capacity, high‐rate electrodes. Another critical part highlights the interplay between solvation chemistry and interfacial reactions, as well as the stability of the resultant interphases, particularly in batteries employing ultrahigh‐nickel layered oxides as cathodes and high‐capacity Li/Si materials as anodes. The detailed examination reveals how these factors are pivotal in mitigating the rapid capacity fade, thereby ensuring a long cycle life, superior rate capability, and consistent high‐/low‐temperature performance. In the latter part, a comprehensive summary of in situ/operational analysis is presented. This holistic approach, encompassing innovative electrolyte design, interphase regulation, and advanced characterization, offers a comprehensive roadmap for advancing battery technology in extreme environmental conditions.