Abstract

AbstractAll‐solid‐state sodium batteries (ASSSBs) with nonflammable electrolytes and ubiquitous sodium resource are a promising solution to the safety and cost concerns for lithium‐ion batteries. However, the intrinsic mismatch between low anodic decomposition potential of superionic sulfide electrolytes and high operating potentials of sodium‐ion cathodes leads to a volatile cathode–electrolyte interface and undesirable cell performance. Here we report a high‐capacity organic cathode, Na4C6O6, that is chemically and electrochemically compatible with sulfide electrolytes. A bulk‐type ASSSB shows high specific capacity (184 mAh g−1) and one of the highest specific energies (395 Wh kg−1) among intercalation compound‐based ASSSBs. The capacity retentions of 76 % after 100 cycles at 0.1 C and 70 % after 400 cycles at 0.2 C represent the record stability for ASSSBs. Additionally, Na4C6O6 functions as a capable anode material, enabling a symmetric all‐organic ASSSB with Na4C6O6 as both cathode and anode materials.

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