Conventional carbonate solvents with lowH OMO levels are theoretically compatible with the low-cost, highvoltage chemistry of Zn/graphite batteries.H owever,t he nucleophilic attacko ft he anion on carbonates induces an oxidative breakdown at high potentials.H ere,w er estore the inherent anodic stability of carbonate electrolytes by designing amicro-heterogeneous anion solvation network. Based on the addition of as trongly electron-donating solvent, trimethyl phosphate (TMP), the oxidation-vulnerable anion-carbonate affinities are decoupled because of the preferential sequestration of anions into solvating TMP domains around the metal cations.The hybridized electrolytes elevate the electrochemical window of carbonate electrolytes by 0.45 Va nd enable the operation of Zn/graphite dual-ion cells at 2.80 Vw ith al ong cycle life (92 %c apacity retention after 1000 cycles). By inheriting the non-flammability from TMP and the high iontransport kinetics from the carbonate systems,t his facile strategy provides cells with the additional benefits of fire retardancy and high-power capability.

Solid-state zinc (Zn) batteries offer anew candidate for emerging applications sensitive to volume,safety and cost. However,c urrent solid polymeric or ceramic electrolyte structures remain poorly conductive for the divalent Zn 2+ , especially at room temperature.C onstructing aheterogeneous interface whichallows Zn 2+ percolation is aviable option, but this is rarely involved in multivalent systems.H erein, we construct as olid Zn 2+ -ion conductor by inducing crystallization of tailored eutectic liquids formed by organic Zn salts and bipolar ligands.H igh-entropye utectic-networks weaken the ion-association and form interfacial Zn 2+ -percolated channels on the nucleator surfaces,r esulting in as olid crystal with exceptional selectivity for Zn 2+ transport (t Zn 2þ = 0.64) and appreciable Zn 2+ conductivity (s Zn 2þ = 3.78 10 À5 Scm À1 at 30 8 8C, over 2o rders of magnitude higher than conventional polymers), and finally enabling practical ambient-temperature Zn/V 2 O 5 metal solid cells.T his design principle leveraged by the eutectic solidification affords new insights on the multivalent solid electrochemistry suffering from slow ion migration.

Solid-state zinc (Zn) batteries offer anew candidate for emerging applications sensitive to volume,safety and cost. However,c urrent solid polymeric or ceramic electrolyte structures remain poorly conductive for the divalent Zn 2+ , especially at room temperature.C onstructing aheterogeneous interface whichallows Zn 2+ percolation is aviable option, but this is rarely involved in multivalent systems.H erein, we construct as olid Zn 2+ -ion conductor by inducing crystallization of tailored eutectic liquids formed by organic Zn salts and bipolar ligands.H igh-entropye utectic-networks weaken the ion-association and form interfacial Zn 2+ -percolated channels on the nucleator surfaces,r esulting in as olid crystal with exceptional selectivity for Zn 2+ transport (t Zn 2þ = 0.64) and appreciable Zn 2+ conductivity (s Zn 2þ = 3.78 10 À5 Scm À1 at 30 8 8C, over 2o rders of magnitude higher than conventional polymers), and finally enabling practical ambient-temperature Zn/V 2 O 5 metal solid cells.T his design principle leveraged by the eutectic solidification affords new insights on the multivalent solid electrochemistry suffering from slow ion migration.

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