Differentiated Lithium Salt Design for Multilayered PEO Electrolyte Enables a High‐Voltage Solid‐State Lithium Metal Battery

Low ionic conductivity at room temperature and limited electrochemical window of poly(ethylene oxide) (PEO) are the bottlenecks restricting its further application in high-energy density lithium metal battery. Herein, a differentiated salt designed multilayered PEO-based solid polymer electrolyte (DSM-SPE) is exploited to achieve excellent electrochemical performance toward both the high-voltage LiCoO₂ cathode and the lithium metal anode. The LiCoO₂/Li metal battery with DSM-SPE displays a capacity retention of 83.3% after 100 cycles at 60 °C with challenging voltage range of 2.5 to 4.3 V, which is the best cycling performance for high-voltage (≥4.3 V) LiCoO₂/Li metal battery with PEO-based electrolytes up to now. Moreover, the Li/Li symmetrical cells present stable and low polarization plating/stripping behavior (less than 80 mV over 600 h) at current density of 0.25 mA cm⁻² (0.25 mAh cm⁻²). Even under a high-area capacity of 2 mAh cm⁻², the profiles still maintain stable. The pouch cell with DSM-SPE exhibits no volume expansion, voltage decline, ignition or explosion after being impaled and cut at a fully charged state, proving the excellent safety characteristic of the DSM-SPE-based lithium metal battery.