Starving Free Solvents: Toward Immiscible Binary Liquid Electrolytes for Li‐Metal Full Cells

Abstract Current state‐of‐the‐art Li batteries use single‐phase electrolytes; however, these electrolytes often encounter difficulty in simultaneously fulfilling the nonidentical electrochemical requirements of cathodes and anodes. Here, a class of immiscible binary liquid electrolyte (BLE) is designed by starving free solvent molecules. Based on their electrochemical stability window, 1,2‐dimethoxyethane (DME) and succinonitrile (SN) are selected as model solvents for Li‐metal anodes and LiNi 0.8 Co 0.1 Mn 0.1 (NCM811) cathodes, respectively. Li bis(fluorosulfonyl)imide (LiFSI), which promotes Li + solvation (i.e., reduces free solvents), enables the phase separation of the miscible solvent mixture (SN−DME), and an increase in its concentration strengthens the coordination of Li + −FSI − in the solvation sheath, thus yielding (anion‐derived) fluorine‐rich electrode–electrolyte interphases. The resulting BLE allows 4.4 V Li‐metal full cells to exhibit a stable capacity retention under a constrained cell condition (Li (20 µm, 4.1 mAh cm −2 )||NCM811 (3.8 mAh cm −2 ), N (negative)/P (positive) capacity ratio = 1.08), which exceed those of previously reported binary liquid electrolytes.