Thermal Warning and Shut‐down of Lithium Metal Batteries Based on Thermoresponsive Electrolytes

Abstract The thermal runaway issue represents a long‐standing obstacle that retards large‐scale applications of lithium metal batteries. Various approaches to inhibit thermal runaway suffer from some intrinsic drawbacks, either being irreversible or delayed thermal protection. Herein, this work has explored thermo‐responsive lower critical solution temperature (LCST) ionic liquid‐based electrolytes, which provides reversible overheating protection for batteries with warning and shut‐down stages, well corresponding to an initial stage of thermal runaway process. The batteries could function stably below 70 °C as a working mode, while demonstrating a warning mode above 80 °C with a noticeable reduction in specific capacitance to delay temperature increase of batteries. In terms of 110 °C as a critically dangerous temperature, a shut‐down mode is designed to minimize the thermal energy releasing as the batteries are barely chargeable and dischargeable. Dynamically growing polymeric particles above LCST contributed to such an intelligent and mild control on specific capacitance. Larger size will occupy larger surfaces of electrodes and close more pores of separators, enabling a gradual suppressing of Li + transfer and reactions. The present work demonstrated a scientific design of thermoresponsive LCST electrolytes with a superiorly precise and intelligent control of electrochemical performances to achieve self‐adapted overheating protections.