A self-healing polymerized-ionic-liquid-based polymer electrolyte enables a long lifespan and dendrite-free solid-state Li metal batteries at room temperature.

The implementation of high-safety Li metal batteries (LMBs) needs more stable and safer electrolytes. The solid-state electrolytes (SSEs) with their advantageous properties stand out for this purpose. However, low Li/electrolyte interfacial instability and uncontrolled Li dendrites growth trigger unceasing breakage of the solid electrolyte interphase (SEI), leading to fast capacity degradation. In response to these shortcomings, a new type of polymer electrolyte with self-healing capacity is introduced by grafting ionic liquid chain units into the backbones of polymers, which inherits the chemical inertness against the Li anode, allowing high Li transport, wide electrochemical window, and self-healing traits. Benefiting from the strong external H-bonding interactions, the obtained polymer electrolyte can spontaneously reconstruct dendrite-induced defects and fatigue crack growth at the Li/electrolyte interface, and, in turn, help tailor Li deposition. Owing to the resilient Li/electrolyte interface and dendrite-free Li plating, the equipped Li|LFP batteries display a high initial specific capacity of 134.7 mA h g, rendering a capacity retention of 91.2% after 206 cycles at room temperature. The new polymer electrolyte will undoubtedly bring inspiration for developing practical LMBs with highly improved safety and interfacial stability.