Although lithium–sulfur batteries (LSBs) are promising next‐generation secondary batteries, their mass commercialization has not yet been achieved primarily owing to critical issues such as the “shuttle effect” of soluble lithium polysulfides (LiPSs) and uncontrollable Li dendrite growth. Thus, most reviews on LSBs are focused on strategies for inhibiting shuttle behavior and achieving dendrite‐free LSBs to improve the cycle life and Coulombic efficiency of LSBs. However, LSBs have various promising advantages, including an ultrahigh energy density (2600 Wh kg⁻¹), cost‐effectiveness, environmental friendliness, low weight, and flexible attributes, which suggest the feasibility of their current and near‐future practical applications in fields that require these characteristics, irrespective of their moderate lifespan. Here, for the first time, challenges impeding the current and near‐future applications of LSBs are comprehensively addressed. In particular, the latest progress and novel materials based on their electrochemical characteristics are summarized, with a focus on the gravimetric/volumetric energy density (capacity), loading mass and sulfur content in cathodes, electrolyte‐to‐sulfur ratios, rate capability, and maximization of these advantageous characteristics for applications in specific areas. Additionally, potential areas for practical applications of LSBs are suggested, with insights for improving LSB performances from a different standpoint and facilitating their integration into various application domains.

The phosphate lithium-ion conductor Li_1.5Al_0.5Ti_1.5(PO₄)₃ (LATP) is an economically attractive solid electrolyte for the fabrication of safe and robust solid-state batteries, but high sintering temperatures pose a material engineering challenge for the fabrication of cell components. In particular, the high surface roughness of composite cathodes resulting from enhanced crystal growth is detrimental to their integration into cells with practical energy density. In this work, we demonstrate that efficient free-standing ceramic cathodes of LATP and LiFePO₄ (LFP) can be produced by using a scalable tape casting process. This is achieved by adding 5 wt % of Li₂WO₄ (LWO) to the casting slurry and optimizing the fabrication process. LWO lowers the sintering temperature without affecting the phase composition of the materials, resulting in mechanically stable, electronically conductive, and free-standing cathodes with a smooth, homogeneous surface. The optimized cathode microstructure enables the deposition of a thin polymer separator attached to the Li metal anode to produce a cell with good volumetric and gravimetric energy densities of 289 Wh dm^-3 and 180 Wh kg^-1, respectively, on the cell level and Coulombic efficiency above 99% after 30 cycles at 30 °C.