Unlocking Mechanism of Anion and Cation Interaction on Ion Conduction of Polymer Based Electrolyte in Metal Batteries

Abstract Polymer based electrolyte shows advantages in compatibly improving safety and interface stability of batteries, while its limited ion conductivity and transfer number make it difficult to apply in batteries with high energy density. Herein, by designing four crosslinking polyesters with different electron withdrawing group (EWG), it is found that strengthening the binding of EWG to anion for weakening the binding of anion to Li + is critical for high Li + transfer number ( ) and ionic conductivity of electrolyte. As a result, poly (2,2,3,3‐tetrafluoropropyl methacrylate) (PTFM) based gel polymer electrolyte (GPE) shows an ionic conductivity of 0.78 mS cm −1 and a of 0.85, much higher than those of poly (methyl methacrylate) (PMMA) without EWG. Moreover, PTFM based GPE shows excellent flame retardancy property. Li||PTFM||NCM811 batteries with an ultrahigh capacity of 5.5 mAh cm −2 show stable cycles of 5 times to that of Li||PMMA||NCM811. Moreover, the assembled graphite||PTFM||NCM811 pouch cell shows a capacity retention rate of 92 % after 500 cycles. This work clarifies the mechanism of cation/anion interaction on ionic conductivity of GPE, which is important to develop high‐performance devices with good safety and flexibility.