Traditional lithium-ion batteries employing carbonate-based liquid electrolytes might suffer from safety hazards such as leakage, combustion and explosion under abused conditions. In comparison, poly(ethylene oxide) (PEO) based solid-state polymer electrolytes can significantly enhance the safety performance of lithium batteries owing to their intrinsic safety. In addition, PEO can also be made into specific shapes to meet the harsh requirements of special fields owing of their excellent plasticity. More importantly, PEO-based solid-state polymer electrolytes possess superior interfacial compatibility with lithium metal anodes, endowing PEO a very promising solid polymer electrolyte (SPE) for solid-state lithium metal batteries. However, the low electrochemical oxidation potential of PEO-based solid polymer electrolytes makes them chal-