Tuning the Li⁺ Solvation Structure by a “Bulky Coordinating” Strategy Enables Nonflammable Electrolyte for Ultrahigh Voltage Lithium Metal Batteries

In battery electrolyte design principles, tuning Li + solvation structure is an effective way to connect electrolyte chemistry with interfacial chemistry. Although recent proposed solvation tuning strategies are able to improve battery cyclability, a comprehensive strategy for electrolyte design remains imperative. Here, we report a solvation tuning strategy by utilizing molecular steric effect to create a “bulky coordinating” structure. Based on this strategy, the designed electrolyte generates an inorganic-rich solid electrolyte interphase (SEI) and cathode–electrolyte interphase (CEI), leading to excellent compatibility with both Li metal anodes and high-voltage cathodes. Under an ultrahigh voltage of 4.6 V, Li/NMC811 full-cells ( N / P = 2.0) hold an 84.1% capacity retention over 150 cycles and industrial Li/NMC811 pouch cells realize an energy density of 495 Wh kg –1 . This study provides innovative insights into Li + solvation tuning for electrolyte engineering and offers a promising path toward developing high-energy Li metal batteries.