LAUSR

Abstract The widespread implementation of lithium‐metal batteries (LMBs) with Li metal anodes of high energy density has long been prevented due to the safety concern of dendrite‐related failure. Here a solid–liquid hybrid electrolyte consisting of composite polymer electrolyte (CPE) soaked with liquid electrolyte is reported. The CPE membrane composes of self‐healing polymer and Li+‐conducting nanoparticles. The electrodeposited lithium metal in a uniform, smooth, and dense behavior is achieved using a hybrid electrolyte, rather than dendritic and pulverized structure for a conventional separator. The Li foil symmetric cells can deliver remarkable cycling performance at ultrahigh current density up to 20 mA cm−2 with an extremely low voltage hysteresis over 1500 cycles. A large areal capacity of 10 mAh cm−2 at 10 mA cm−2 could also be obtained. Furthermore, the Li|Li4Ti5O12 cells based on the hybrid electrolyte achieve a higher specific capacity and longer cycling life than those using conventional separators. The superior performances are mainly attributed to strong adhesion, volume conformity, and self‐healing functionality of CPE, providing a novel approach and a significant step toward cost‐effective and large‐scalable LMBs.