High Chaos Induced Multiple-Anion-Rich Solvation Structure Enabling Ultrahigh Voltage and Wide Temperature Lithium-Metal Batteries

The optimal electrolyte for ultrahigh energy density (>400 Wh/kg) lithium-metal batteries with a LiNi_0.8Co_0.1Mn_0.1O₂ cathode is required to withstand high voltage (≥4.7 V) and be adaptable over a wide temperature range. However, the battery performance is degraded by aggressive electrode–electrolyte reactions at high temperature and high voltage, while excessive growth of lithium dendrites usually occurs due to poor kinetics at low temperature. Accordingly, the development of electrolytes has encountered challenges in that there is almost no electrolyte simultaneously meeting the above requirements. Herein, a high chaos electrolyte design strategy is proposed, which promotes the formation of weak solvation structures involving multiple anions. By tailoring a Li⁺-EMC-DMC-DFOB^–-PO₂F₂^–-PF₆^– multiple-anion-rich solvation sheath, a robust inorganic-rich interphase is obtained for the electrode–electrolyte interphase (EEI), which is resistant to the intense interfacial reactions at high voltage (4.7 V) and high temperature (45 °C). In addition, the Li⁺ solvation is weakened by the multiple-anion solvation structure, which is a benefit to Li⁺ desolventization at low temperature (−30 °C), greatly improving the charge transfer kinetics and inhibiting the lithium dendrite growth. This work provides an innovative strategy to manipulate the high chaos electrolyte to further optimize solvation chemistry for high voltage and wide temperature applications.