| Summary: | The increased demand for energy has prompted users to seek alternative energy storage devices. Post‐Li‐ion battery chemistries have been considered potential contenders for the development of next‐generation battery technologies. The high specific capacity (≈1675 mAh g−1) and high natural abundance (≈953 ppm) of sulfur provide opportunities to meet the rigorous requirements of the market's demands, such as high energy density and low cost. When combined with a high capacity metal anode (e.g., Na ≈ 1165 mAh g−1, Mg ≈ 2205 mAh g−1, and Al ≈2980 mAh g−1), it leads to high energy density that can outperform the existing battery technologies, including high‐energy Li‐ion batteries. Despite the unique attributes of the sulfur‐based battery system, it remains in infancy owing to the complex reaction chemistry of sulfur cathode, and the level of complexity increases with an increase in valency of metal ions. This review summarizes the unique aspects of a sulfur cathode essential to stabilizing sulfur cathode‐based high‐energy rechargeable batteries. Furthermore, deeper insight into the electrochemical performance of various metal–sulfur‐based systems has been provided. This review may pave the path for the researchers to accelerate the development of sulfur cathode for post‐Li‐ion batteries.
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