A Star‐Structured Polymer Electrolyte for Low‐Temperature Solid‐State Lithium Batteries

Abstract Solid‐state polymer lithium metal batteries (SSLMBs) have attracted considerable attention because of their excellent safety and high energy density. However, the application of SSLMBs is significantly impeded by uneven Li deposition at the interface between solid‐state electrolytes and lithium metal anode, especially at a low temperature. Herein, this issue is addressed by designing an agarose‐based solid polymer electrolyte containing branched structure. The star‐structured polymer is synthesized by grafting poly (ethylene glycol) monomethyl‐ether methacrylate and lithium 2‐acrylamido‐2‐methylpropanesulfonate onto tannic acid. The star structure regulates Li‐ion flux in the bulk of the electrolyte and at the electrolyte/electrode interfaces. This unique omnidirectional Li‐ion transportation effectively improves ionic conductivity, facilitates a uniform Li‐ion flux, inhibits Li dendrite growth, and alleviates polarization. As a result, a solid‐state LiFePO 4 ||Li battery with the electrolyte exhibits outstanding cyclability with a specific capacity of 134 mAh g −1 at 0.5C after 800 cycles. The battery shows a high discharge capacity of 145 mAh g −1 at 0.1 C after 200 cycles, even at 0 °C. The study offers a promising strategy to address the uneven Li deposition at the solid‐state electrolyte/electrode interface, which has potential applications in long‐life solid‐state lithium metal batteries at a low temperature.