Severe interfacial side reactions of polymer electrolyte with LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) cathode and Li metal anode restrict the cycling performance of solid-state NCM811/ Li batteries.H erein, we propose ac hemically stable ceramicpolymer-anchored solvent composite electrolyte with high ionic conductivity of 6.0 10 À4 Scm À1 ,w hiche nables the solid-state NCM811/Li batteries to cycle 1500 times.T he Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 nanowires (LNs) can tightly anchor the essential N, N-dimethylformamide (DMF) in poly(vinylidene fluoride) (PVDF), greatly enhancing its electrochemical stability and suppressing the side reactions.W ei dentify the ceramic-polymer-liquid multiple ion transport mechanism of the LNs-PVDF-DMF composite electrolyte by tracking the 6 Li and 7 Li substitution behavior via solid-state NMR. The stable interface chemistry and efficient ion transport of LNs-PVDF-DMF contribute to superior performances of the solid-state batteries at wide temperature range of À20-60 8 8C.

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Figure 6. Illustration of the mass transfer mechanisms in LAO-LLZOF and LLZO. a) LAO-LLZOF structure illustrating multiple Li ion transport paths without electron-conducting capabilities in the biphasic grains. b,c) Operating mechanisms of ASLMBs. b) LAO-LLZOF illustrating the electronic blocking effect and ion-conducting capacity that results in uniform Li plating/stripping during cycling. c) LLZO with deposited Li dendrites penetrating the grain and Li filaments growing along the electron-conducting GBs. d) Energy bandgap and DOS calculation for LAO.