The Versatile Establishment of Charge Storage in Polymer Solid Electrolyte with Enhanced Charge Transfer for LiF‐Rich SEI Generation in Lithium Metal Batteries

Abstract The solid‐state electrolyte interface (SEI) between the solid‐state polymer electrolyte and the lithium metal anode dramatically affects the overall battery performance. Increasing the content of lithium fluoride (LiF) in SEI can help the uniform deposition of lithium and inhibit the growth of lithium dendrites, thus improving the cycle stability performance of lithium batteries. Currently, most methods of constructing LiF SEI involve decomposing the lithium salt by the polar groups of the filler. However, there is a lack of research reports on how to affect the SEI layer of Li‐ion batteries by increasing the charge transfer number. In this study, a porous organic polymer with “charge storage” properties was prepared and doped into a polymer composite solid electrolyte to study the effect of sufficient charge transfer on the decomposition of lithium salts. The results show in contrast to porphyrins, the unique structure of POF allows for charge transfer between each individual porphyrin. Therefore, during TFSI − decomposition to the formation of LiF, TFSI − can obtain sufficient charge, thereby promoting the break of C−F and forming the LiF‐rich SEI. Compared with single porphyrin (0.423 e − ), POF provides 2.7 times more charge transfer to LiTFSI (1.147 e − ). The experimental results show that Li//Li symmetric batteries equipped with PEO‐POF can be operated stably for more than 2700 h at 60 °C. Even the Li//Li (45 μm) symmetric cells are stable for more than 1100 h at 0.1 mA cm −1 . In addition, LiFePO 4 //PEO‐POF//Li batteries have excellent cycling performance at 2 C (80 % capacity retention after 750 cycles). Even LiFePO 4 //PEO‐POF//Li (45 μm) cells have excellent cycling performance at 1 C (96 % capacity retention after 300 cycles). Even when the PEO‐base is replaced with a PEG‐base and a PVDF‐base, the performance of the cell is still significantly improved. Therefore, we believe that the concept of charge transfer offers a novel perspective for the preparation of high‐performance assemblies.