The electrolytes in lithium metal batteries have to be compatible with both lithium metal anodes and high voltage cathodes,a nd can be regulated by manipulating the solvation structure.H erein, to enhance the electrolyte stability,l ithium nitrate (LiNO 3)a nd 1,1,2,2-tetrafuoroethyl-2',2',2'trifuoroethyl(HFE) are introduced into the high-concentration sulfolane electrolyte to suppress Li dendrite growth and achieve ah igh Coulombic efficiency of > 99 %f or both the Li anode and LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathodes.M olecular dynamics simulations showt hat NO 3 À participates in the solvation sheath of lithium ions enabling more bis(trifluoromethanesulfonyl)imide anion (TFSI À)t oc oordinate with Li + ions.T herefore,ar obust LiN x O y À LiF-richs olid electrolyte interface (SEI) is formed on the Li surface, suppressing Li dendrite growth. The LiNO 3-containing sulfolane electrolyte can also support the highly aggressive Li-Ni 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathode,d elivering ad ischarge capacity of 190.4 mAh g À1 at 0.5 Cfor 200 cycles with acapacity retention rate of 99.5 %.

An LLTO/PAN/SNE hybrid solid electrolyte membrane with high ionic conductivity and excellent compatibility with both LiFePO4 cathode and metallic lithium anode.

The electrolytes in lithium metal batteries have to be compatible with both lithium metal anodes and high voltage cathodes,a nd can be regulated by manipulating the solvation structure.H erein, to enhance the electrolyte stability,l ithium nitrate (LiNO 3)a nd 1,1,2,2-tetrafuoroethyl-2',2',2'trifuoroethyl(HFE) are introduced into the high-concentration sulfolane electrolyte to suppress Li dendrite growth and achieve ah igh Coulombic efficiency of > 99 %f or both the Li anode and LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathodes.M olecular dynamics simulations show that NO 3 À participates in the solvation sheath of lithium ions enabling more bis(trifluoromethanesulfonyl)imide anion (TFSI À)t oc oordinate with Li + ions.T herefore,arobust LiN x O y À LiF-richs olid electrolyte interface (SEI) is formed on the Li surface,s uppressing Li dendrite growth. The LiNO 3-containing sulfolane electrolyte can also support the highly aggressive Li-Ni 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathode,d elivering ad ischarge capacity of 190.4 mAh g À1 at 0.5 Cf or 200 cycles with ac apacity retention rate of 99.5 %.