Lithium–sulfur (Li–S) batteries are one of the most promising next‐generation energy storage systems due to their ultrahigh theoretical specific capacity. However, their practical applications are seriously hindered by some inevitable disadvantages such as the insulative nature of sulfur and Li2S, volume expansion of the cathode, the shuttle effect of polysulfides, and the growth of lithium dendrites on the anode. Of these, the polysulfide shuttle effect is one of the most critical issues causing the irreversible loss of active materials and rapid capacity degradation of batteries. Herein, modified separators with functional coatings inhibiting the migration of polysulfides are enumerated based on three effects toward polysulfides: the adsorption effect, separation effect, and catalytic effect. To solve the shuttle effect problem, researchers have replaced liquid electrolytes with solid‐state electrolytes. In this review, solid‐state electrolytes for lithium–sulfur batteries are grouped into three categories: inorganic solid electrolytes, solid polymer electrolytes, and composite solid electrolytes. Challenges and perspectives regarding the development of an optimized strategy to inhibit the polysulfide shuttle for enhancing cycle stability in lithium–sulfur batteries are also proposed.

Lithium–sulfur batteries (LSBs) are considered one of the most promising candidates for next-generation energy storage owing to their large energy capacity. Tremendous effort has been devoted to overcoming the inherent problems of LSBs to facilitate their commercialization, such as polysulfide shuttling and dendritic lithium growth. Pouch cells present additional challenges for LSBs as they require greater electrode active material utilization, a lower electrolyte–sulfur ratio, and more mechanically robust electrode architectures to ensure long-term cycling stability. In this review, the critical challenges facing practical Li–S pouch cells that dictate their energy density and long-term cyclability are summarized. Strategies and perspectives for every major pouch cell component—cathode/anode active materials and electrode construction, separator design, and electrolyte—are discussed with emphasis placed on approaches aimed at improving the reversible electrochemical conversion of sulfur and lithium anode protection for high-energy Li–S pouch cells.

Lithium metal batteries with polyethylene oxide (PEO) electrolytes are considered as one of the ideal candidates for next generation power sources. However, the low ambient operation capability and conventional solvent‐based fabrication process of PEO limit their large‐scale application. In this work, a comb‐like quasi‐solid polymer electrolyte (QPE) reinforced with polyethylene glycol terephthalate nonwoven is fabricated. Combining the density functional theory calculation analysis and polymer structure design, optimized and synergized ion conductive channels are established by copolymerization of tetrahydrofurfuryl acrylate and introduction of plasticizer tetramethyl urea. Additionally, a unique two‐stage solventless UV polymerization strategy is utilized for rheology tuning and electrolyte fabrication. Compared with the conventional one‐step UV process, this strategy is ideally suited for the roll‐to‐roll continuous coating fabrication process with environmental friendliness. The fabricated QPE exhibits high ionic conductivity of 0.40 mS cm−1 and Li+ transference number (t = 0.77) at room temperature. LiFePO4//Li batteries are assembled to evaluate battery performance, which deliver excellent discharge capacity (144.9 mAh g−1 at 0.5 C) and cycling stability (with the retention rate 94.5% at 0.5 C after 200 cycles) at room temperature. The results demonstrate that it has high potential for solid‐state lithium metal batteries.