PEO‐LITFSI‐SiO(2)‐SN System Promotes the Application of Polymer Electrolytes in All‐Solid‐State Lithium‐ion Batteries

All‐solid‐state polymer lithium‐ion batteries are ideal choice for the next generation of rechargeable lithium‐ion batteries due to their high energy, safety and flexibility. Among all polymer electrolytes, PEO‐based polymer electrolytes have attracted extensive attention because they can dissolve various lithium salts. However, the ionic conductivity of pure PEO‐based polymer electrolytes is limited due to high crystallinity and poor segment motion. An inorganic filler SiO(2) nanospheres and a plasticizer Succinonitrile (SN) are introduced into the PEO matrix to improve the crystallization of PEO, promote the formation of amorphous region, and thus improve the movement of PEO chain segment. Herein, a PEO(18)−LiTFSI−5 %SiO(2)−5 %SN composite solid polymer electrolyte (CSPE) was prepared by solution‐casting. The high ionic conductivity of the electrolyte was demonstrated at 60 °C up to 3.3×10(−4) S cm(−1). Meanwhile, the electrochemical performance of LiFePO(4)/CSPE/Li all‐solid‐state battery was tested, with discharge capacity of 157.5 mAh g(−1) at 0.5 C, and capacity retention rate of 99 % after 100 cycles at 60 °C. This system provides a feasible strategy for the development of efficient all‐solid‐state lithium‐ion batteries.