Post‐lithium‐ion battery technology is considered a key element of future energy storage and management. Apart from high gravimetric and volumetric energy densities, economic, ecologic and safety issues become increasingly important. In that regards, both the anode and cathode materials must be easily available, recyclable, non‐toxic and safe, which renders magnesium‐sulfur (Mg−S) batteries a promising choice. Herein, we present Mg−S cells based on a sulfurated poly(acrylonitrile) composite cathode (SPAN), together with a halogen‐free electrolyte containing both Mg[BH4]2 and Li[BH4] in diglyme and a high‐specific surface area magnesium anode based on Rieke magnesium powder. These cells deliver discharge capacities of 1400 and 800 mAh/gsulfur with >99 % Coulombic efficiency at 0.1 C and 0.5 C, respectively, and are stable over at least 300 cycles. Energy densities are 470 and 400 Wh/kgsulfur at 0.1 C and 0.5 C, respectively. Rate tests carried out between 0.1 C and 2 C demonstrate good rate capability of the cells. Detailed mechanistic studies based on X‐ray photoelectron spectroscopy and electric impedance spectroscopy are presented.
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