Overcoming the Obstacle of Polymer–Polymer Resistances in Double Layer Solid Polymer Electrolytes

[Image: see text] Double-layer solid polymer electrolytes (DLSPEs) comprising one layer that is stable toward lithium metal and one which is stable against a high-voltage cathode are commonly suggested as a promising strategy to achieve high-energy-density lithium batteries. Through in-depth EIS analysis, it is here concluded that the polymer–polymer interface is the primary contributor to electrolyte resistance in such DLSPEs consisting of polyether-, polyester-, or polycarbonate-bad SPEs. In comparison to the bulk ionic resistance, the polymer–polymer interface resistance is approximately 10-fold higher. Nevertheless, the interfacial resistance was successfully lowered by doubling the salt concentration from 25 to 50 wt % LiTFSI owing to improved miscibility at the interface of the two polymer layers.