The integration of solid-polymer electrolytes into all-solid-state lithium batteries is highly desirable to overcome the limitations of current battery configurations that have a low energy density and severe safety concerns. Polyacrylonitrile is an appealing matrix for solid-polymer electrolytes; however, the practical utilization of such polymer electrolytes in all-solid-state cells is impeded by inferior ionic conductivity and instability against a lithium-metal anode. In this work, we show that a polymer-in-salt electrolyte based on polyacrylonitrile with a lithium salt as the major component exhibits a wide electrochemically stable window, a high ionic conductivity, and an increased lithium-ion transference number. The growth of dendrites from the lithium-metal anode was suppressed effectively by the polymer-in-salt electrolyte to increase the safety features of the batteries. In addition, we found that a stable interphase was formed between the lithium-metal anode and the polymer-in-salt electrolyte to restrain the uncontrolled parasitic reactions, and we demonstrated an all-solid-state battery configuration with a LiFePO4 cathode and the polymer-in-salt electrolyte, which exhibited a superior cycling stability and rate capability.
