Advanced Nonflammable Organic Electrolyte Promises Safer Li‐Metal Batteries: From Solvation Structure Perspectives

Abstract Batteries with a Li‐metal anode have recently attracted extensive attention from the battery communities owing to their high energy density. However, severe dendrite growth hinders their practical applications. More seriously, when Li dendrites pierce the separators and trigger short circuit in a highly flammable organic electrolyte, the results would be catastrophic. Although the issues of growth of Li dendrites have been almost addressed by various methods, the highly flammable nature of conventional organic liquid electrolytes is still a lingering fear facing high‐energy‐density Li‐metal batteries given the possibility of thermal runaway of the high‐voltage cathode. Recently, various kinds of nonflammable liquid‐ or solid‐state electrolytes have shown great potential toward safer Li‐metal batteries with minimal detrimental effect on the battery performance or even enhanced electrochemical performance. In this review, recent advances in developing nonflammable electrolyte for high‐energy‐density Li‐metal batteries including high‐concentration electrolyte, localized high‐concentration electrolyte, fluorinated electrolyte, ionic liquid electrolyte, and polymer electrolyte are summarized. Then, the solvation structure of different kinds of nonflammable liquid and polymer electrolytes are analyzed to provide insight into the mechanism for dendrite suppression and fire extinguishing. Finally, guidelines for future design of nonflammable electrolyte for safer Li‐metal batteries are provided.