Hyperconjugation-controlled molecular conformation weakens lithium-ion solvation and stabilizes lithium metal anodes

Tuning the solvation structure of lithium ions via electrolyte engineering has proven effective for lithium metal (Li) anodes. Further advancement that bypasses the trial-and-error practice relies on the establishment of molecular design principles. Expanding the scope of our previous work on solvent fluorination, we report here an alternative design principle for non-fluorinated solvents, which potentially have reduced cost, environmental impact, and toxicity. By studying non-fluorinated ethers systematically, we found that the short-chain acetals favor the [gauche, gauche] molecular conformation due to hyperconjugation, which leads to weakened monodentate coordination with Li⁺. The dimethoxymethane electrolyte showed fast activation to >99% coulombic efficiency (CE) and high ionic conductivity of 8.03 mS cm⁻¹. The electrolyte performance was demonstrated in anode-free Cu‖LFP pouch cells at current densities up to 4 mA cm⁻² (70 to 100 cycles) and thin-Li‖high-loading-LFP coin cells (200–300 cycles). Overall, we demonstrated and rationalized the improvement in Li metal cyclability by the acetal structure compared to ethylene glycol ethers. We expect further improvement in performance by tuning the acetal structure.