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Lithium-sulfur (Li–S) battery is one of the most promising candidates for the next generation energy storage systems. However, several barriers, including polysulfide shuttle effect, the slow solid-solid surface reaction pathway in the lower discharge plateau, and corrosion of Li anode still limit its practical applications, especially under the lean electrolyte condition required for high energy density. Here, we propose a solution-mediated sulfur reduction pathway to improve the capacity and reversibility of the sulfur cathode. With this method, a high coulombic efficiency (99%) and stable cycle life over 100 cycles were achieved under application-relevant conditions (S loading: 6.2 mg cm−2; electrolyte to sulfur ratio: 3 mLE gs−1; sulfur weight ratio: 72 wt%). This result is enabled by a specially designed Li2S4-rich electrolyte, in which Li2S is formed through a chemical disproportionation reaction instead of electrochemical routes. A single diglyme solvent was used to obtain electrolytes with the optimum range of Li2S4 concentration. Operando X-ray absorption spectroscopy confirms the solution pathway in a practical Li–S cell. This solution pathway not only introduces a new electrolyte regime for practical Li–S batteries, but also provides a new perspective for bypassing the inefficient surface pathway for other electrochemical processes.

Conventional electrolytes made by mixing simple Mg2+ salts and aprotic solvents, analogous to those in Li-ion batteries, are incompatible with Mg anodes because Mg metal readily reacts with such electrolytes, producing a passivation layer that blocks Mg2+ transport. Here, we report that, through tuning a conventional electrolyte - Mg(TFSI)2 (TFSI- is N(SO2CF3)2-) - with an Mg(BH4)2 cosalt, highly reversible Mg plating/stripping with a high Coulombic efficiency is achieved by neutralizing the first solvation shell of Mg cationic clusters between Mg2+ and TFSI- and enhanced reductive stability of free TFSI-. A critical adsorption step between Mg0 atoms and active Mg cation clusters involving BH4- anions is identified to be the key enabler for reversible Mg plating/stripping through analysis of the distribution of relaxation times (DRT) from operando electrochemical impedance spectroscopy (EIS), operando electrochemical X-ray absorption spectroscopy (XAS), nuclear magnetic resonance (NMR), and density functional theory (DFT) calculations.

To enable next-generation high-energy-density lithium (Li)-metal batteries (LMBs), an electrolyte that has simultaneous high Li-metal Coulombic efficiency (CE) and high anodic stability on cathodes is of significant importance. Sulfones are known for strong resistance against oxidation, yet their application in LMBs is restricted because of their poor compatibility with Li-metal anodes, high viscosity, and poor wettability. Here, we demonstrate that a high Li CE over 98% can be achieved in concentrated sulfone-based electrolytes. Furthermore, the viscosity and wettability issues of sulfones are resolved by the addition of a fluorinated ether, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, to form a localized high-concentration electrolyte (LHCE), which not only provides further improvement in Li CE (98.8%) but also remains anodically stable with high-voltage cathodes, suppresses Al corrosion, and enables LMBs to operate in a wide temperature range. As a result, significantly improved cycling performance of LMBs has been realized with sulfone-based LHCE. For high-voltage rechargeable lithium (Li)-metal batteries (LMBs), electrolytes with good stabilities on both the highly oxidative cathodes and the highly reductive Li-metal anodes are urgently desired. Sulfones have excellent oxidative stability, yet their high viscosity, poor wettability, and, in particular, incompatibility with Li anodes greatly hinder their applications in LMBs. Here, we demonstrate that a high Li Coulombic efficiency (CE) of 98.2% during repeated Li plating and stripping cycles can be realized in concentrated lithium bis(fluorosulfonyl)imide (LiFSI)-tetramethylene sulfone electrolyte. More importantly, the localized high-concentration electrolyte, formed by the dilution of the high-concentration electrolyte with a non-solvating fluorinated ether, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, solves the viscosity and wettability issues, further improves Li CE (98.8%), and improves the high-voltage (4.9 V) performance of LMBs with effective Al protection. High-voltage batteries with Li-metal anodes can offer desirable high energy densities. Despite their excellent oxidative stability, sulfones have various limitations to be useful in Li-metal batteries, in particular their instability with Li metal. Here, we achieved a high Li Coulombic efficiency of nearly 99% in a sulfone-based localized high-concentration electrolyte (LHCE) with the addition of a non-solvating co-solvent. In addition, this co-solvent is highly beneficial for realizing stable battery cycling up to 4.9 V.