High-Performance All-Solid-State Na-S Battery Enabled by Casting-Annealing Technology.

Room-temperature all-solid-state Na-S batteries (ASNSBs) using sulfide solid electrolytes are a promising next-generation battery technology due to the high energy, enhanced safety, and earth abundant resources of both sodium and sulfur. Currently, the sulfide electrolyte ASNSBs are fabricated by a simple cold-pressing process leaving with high residential stress. Even worse, the large volume change of S/Na2S during charge/discharge cycles induces additional stress, seriously weakening the less-contacted interfaces among the solid electrolyte, active materials, and the electron conductive agent that are formed in the cold-pressing process. The high and continuous increase of the interface resistance hindered its practical application. Herein, we significantly reduce the interface resistance and eliminate the residential stress in Na2S cathodes by fabricating Na2S-Na3PS4-CMK-3 nanocomposites using melting-casting followed by stress-release annealing-precipitation process. The casting-annealing process guarantees the close contact between the Na3PS4 solid electrolyte and the CMK-3 mesoporous carbon in mixed ionic/electronic conductive matrix, while the in situ precipitated Na2S active species from the solid electrolyte during the annealing process guarantees the interfacial contact among these three subcomponents without residential stress, which greatly reduces the interfacial resistance and enhances the electrochemical performance. The in situ synthesized Na2S-Na3PS4-CMK-3 composite cathode delivers a stable and highly reversible capacity of 810 mAh/g at 50 mA/g for 50 cycles at 60 °C. The present casting-annealing strategy should provide opportunities for the advancement of mechanically robust and high-performance next-generation ASNSBs.