A Rational Reconfiguration of Electrolyte for High‐Energy and Long‐Life Lithium–Chalcogen Batteries

Lithium-chalcogen batteries are an appealing choice for high-energy-storage technology. However, the traditional battery that employs liquid electrolytes suffers irreversible loss and shuttle of the soluble intermediates. New batteries that adopt Li⁺ -conductive polymer electrolytes to mitigate the shuttle problem are hindered by incomplete discharge of sulfur/selenium. To address the trade-off between energy and cycle life, a new electrolyte is proposed that reconciles the merits of liquid and polymer electrolytes while resolving each of their inferiorities. An in situ interfacial polymerization strategy is developed to create a liquid/polymer hybrid electrolyte between a LiPF₆ -coated separator and the cathode. A polymer-gel electrolyte in situ formed on the separator shows high Li⁺ transfer number to serve as a chemical barrier against the shuttle effect. Between the gel electrolyte and the cathode surface is a thin gradient solidification layer that enables transformation from gel to liquid so that the liquid electrolyte is maintained inside the cathode for rapid Li⁺ transport and high utilization of active materials. By addressing the dilemma between the shuttle chemistry and incomplete discharge of S/Se, the new electrolyte configuration demonstrates its feasibility to trigger higher capacity retention of the cathodes. As a result, Li-S and Li-Se cells with high energy and long cycle lives are realized, showing promise for practical use.