| Abstract: | Metal–metal batteries such as the 3 V Cu‐Al system are highly desirable for large‐scale energy storage owing to their low cost and excellent scalability of Cu and Al foils. However, the dissolved Cu cations will crossover from the cathode to the anode leading to poor electrochemical performance. In this work, it is demonstrated that the reversibility of the Cu‐Al battery depends strongly on the interaction of the Cu ions with the electrolyte solvent and subsequently the affinity of the solvated Cu ion with the membrane separator. Specifically, a series of common carbonate‐based electrolyte solvents are investigated via molecular dynamics and contact angle measurements to understand the interaction between the solvents and a polypropylene (PP) membrane, as well as that between cations and solvent. Among different solvents, fluoroethylene carbonate (FEC) is shown to drastically enhance the coulombic efficiency to 97%, compared to that of 27% with dimethyl carbonate. Remarkable cyclability of a 3 V Cu‐Al battery with 3 m LiTFSI FEC and PP membrane up to 1000 cycles is further demonstrated. This finding opens new opportunities for the development of low‐cost, high performance Cu‐Al systems for stationary applications. |
