Polymer electrolytes have attracted great interest for next-generation lithium (Li)-based batteries in terms of high energy density and safety. In this review, we summarize the ion-transport mechanisms, fundamental properties, and preparation techniques of various classes of polymer electrolytes, such as solvent-free polymer electrolytes (SPEs), gel polymer electrolytes (GPEs), and composite polymer electrolytes (CPEs). We also introduce the recent advances of non-aqueous Li-based battery systems, in which their performances can be intrinsically enhanced by polymer electrolytes. Those include high-voltage Liion batteries, flexible Li-ion batteries, Li-metal batteries, lithium-sulfur (Li-S) batteries, lithium-oxygen (Li-O 2 ) batteries, and smart Li-ion batteries. Especially, the advantages of polymer electrolytes beyond safety improvement are highlighted. Finally, the remaining challenges and future perspectives are outlined to provide strategies to develop novel polymer electrolytes for high-performance Li-based batteries.

High-temperature sodium–sulfur batteries operating at 300–350 °C have been commercially applied for large-scale energy storage and conversion. However, the safety concerns greatly inhibit their widespread adoption. Herein, we report a room-temperature sodium–sulfur battery with high electrochemical performances and enhanced safety by employing a “cocktail optimized” electrolyte system, containing propylene carbonate and fluoroethylene carbonate as co-solvents, highly concentrated sodium salt, and indium triiodide as an additive. As verified by first-principle calculation and experimental characterization, the fluoroethylene carbonate solvent and high salt concentration not only dramatically reduce the solubility of sodium polysulfides, but also construct a robust solid-electrolyte interface on the sodium anode upon cycling. Indium triiodide as redox mediator simultaneously increases the kinetic transformation of sodium sulfide on the cathode and forms a passivating indium layer on the anode to prevent it from polysulfide corrosion. The as-developed sodium–sulfur batteries deliver high capacity and long cycling stability.

Rechargeable sodium-sulfur (Na-S) batteries are regarded as a promising energy storage technology due to their high energy density and low cost. High-temperature sodium-sulfur (HT Na-S) batteries with molten sodium and...