Weak Electrostatic Force on K⁺ in Gel Polymer Electrolyte Realizes High Ion Transference Number for Quasi Solid‐State Potassium Ion Batteries

Abstract Quasi‐solid‐state potassium‐ion batteries (SSPIBs) are of great potential for commercial use due to the abundant reserves and cost‐effectiveness of resources, as well as high safety. Gel polymer electrolytes (GPEs) with high ionic conductivity and fast interfacial charge transport are necessary for SSPIBs. Here, the weak electrostatic force between K⁺ and electronegative functional groups in the ethoxylated trimethylolpropane triacrylate (ETPTA) polymer chains, which can promote fast migration of free K⁺, is revealed. To further enhance the interfacial reaction kinetics, a multilayered GPE by in situ growth of poly(vinylidenefluoride‐co‐hexafluoropropylene) (PVDF‐HFP) on ETPTA (PVDF‐HFP|ETPTA|PVDF‐HFP) is constructed to improve the interface contact and provide sufficient K⁺ concentration in PVDF‐HFP. A high ion transference number (0.92) and a superior ionic conductivity (5.15 × 10⁻³ S cm⁻¹) are achieved. Consequently, the SSPIBs with both intercalation‐type (PB) and conversion‐type (PTCDA) cathodes show the best battery performance among all reported SSPIBs of the same cathode. These findings demonstrate that potassium‐ion batteries have the potential to surpass Li/Na ion batteries in solid‐state systems.