Controlling the Potential of Affordable Quasi‐Solid Composite Gel Polymer Electrolytes for High‐Voltage Lithium‐Ion Batteries

Abstract This study focuses on the development of a composite gel polymer electrolyte membrane (CGPEM) as a solution to address safety concerns arising from the reactivity of lithium metal and the formation of dendrites. The CGPEM integrates a solid polymer matrix, solid‐electrolyte LSiPS (Li₁₀SiP₂S₁₂), with a plasticizer that countering the performance decline caused by sulfide solid electrolyte (SSE) interactions with the cathode. Poly ethylene oxide (PEO) emerges as a promising polymer matrix due to its flexibility, cost‐effectiveness, eco‐friendliness, solvability for Li‐salt, mechanical processing adaptability, adhesive strength, and ionic conductivity. Conductivity and processability of CGPEM were optimized through meticulous adjustment of liquid plasticizer concentration. The CGPEM′s chemical and electrochemical stability were systematically investigated using in‐situ electrochemical impedance spectroscopy (EIS) and distribution of relaxation times (DRTs). A lithium metal battery is constructed against a high voltage cathode and newly developed CGPEM. Impressively, the cell exhibited outstanding performance, maintaining a discharge capacity of around 146.22 mAh/g after 200 cycles, retaining 86.38 % of its initial capacity. The formation of a LiF‐rich interface layer near the lithium surface, a vital element in curbing CGPE degradation and dendritic growth, resulted in enhanced overall cell performance.