Tunable Crosslinked Ether Polymer Network Electrolytes for High‐Performance All‐Solid‐State Sodium Batteries

Abstract All‐solid‐state batteries (ASSBs) are critical for achieving high energy density and enhanced safety. Solid polymer electrolytes (SPEs) offer key advantages over other electrolytes, including improved safety, flexibility, and interfacial contact. Among the SPEs, ether‐based polymers are widely studied due to their ease of processing and high ionic conductivity (σ i ) in the amorphous state. In this work, the introduction of poly(ethylene glycol) methyl ether methacrylate (PEGMEMA) into an SPE matrix composed of poly(ethylene glycol) diacrylate (PEGDA), poly(ethylene glycol) (PEG2k), and sodium bis(fluorosulfonyl)imide (NaFSI) salt is investigated to facilitate the formation of amorphous, high σ i SPEs through end‐group engineering and polymer ratio optimization. PEGMEMA enhances structural integrity via crosslinking with PEGDA through its methacrylate group, while its methyl end group aids ion conduction. A 2:1:7 ratio of PEGDA:PEGMEMA:PEG2k exhibits a σ i of 1.16 x 10 −4 S cm −1 and oxidative stability up to 4.4 V at 60 °C. A solid‐state cell incorporating this SPE, a Na 2/3 Ni 1/3 Mn 2/3 O 2 (NM12) cathode, and a sodium‐metal anode demonstrates excellent cycling stability, retaining over 80 % of its initial capacity for 150 cycles at 60 °C. The findings highlight the potential of end‐group engineering in improving the electrochemical performance of SPEs.