Solid-state lithium batteries with solid polymer electrolytes have recently attracted extensive attention due to their promising potential in high energy density and safety. However, the principal issues plaguing the solid polymer electrolytes are their restricted ionic conductivities at ambient temperature and the limited tolerance to the widely used high-voltage cathodes (such as LiNi0.8Mn0.1Co0.1O2, NCM811), thus limiting their practical applications seriously. In this regard, a superior polymer-in-salt solid electrolyte from poly(caprolactone)-graft-polyrotaxane (PGPE) is developed for high-voltage lithium batteries operated at room temperature. The PGPE displays remarkable electrochemical properties at room temperature, with an exceptional ionic conductivity of 4.89 × 10-4 S cm-1 and a lithium-ion transference number of approximately 0.64, stemming from the rapid segmental motions of PCL sidechains by the enhanced dynamics of the cyclic molecules along the axial polymer chain of polyrotaxane. More importantly, the PGPE demonstrates a high electrochemical oxidation voltage of ∼4.7 V, suggesting the excellent electrochemical stability of PGPE against the NCM811-based cathode. Owing to the dense LiF-rich CEI self-generated on the NCM811 particles in the cathode, the transition metal ion diffusion is successfully constrained and the PGPE is well protected from continuous decomposition. The PGPE also shows superior interfacial stability between the metallic Li and the electrolyte. As a result, the all-solid-state NCM811|PGPE|Li cell exhibits superior discharge capacity (196 mAh g-1) and extraordinary long-term cycling stability (74% capacity retention at 150 cycles) at 30 °C.
Keywords: NCM811; high-voltage lithium metal battery; poly(caprolactone); poly(rotaxane); polymer-in-salt electrolyte.