Interpreting Abnormal Charge–Discharge Plateau Migration in Cu_xS during Long-Term Cycling

Voltage polarization during cycling, the charge potential increase of anode or discharge plateau decrease of cathode, is widely observed and would lower the output voltage. Conversely, an anomalous potential plateau negative migration phenomenon was observed in CuxS anode of sodium-ion battery. In this study, the background mechanism was clarified from the switch of intercalation–conversion reactions and structure evolution. The dynamic cooperation between intercalation and conversion reactions may root the potential plateau negative migration during cycling. In the initial stage, the intercalation-type reaction with Na3Cu4S4 and Na4Cu2S3 products at 2.13 and 1.92 V would dominate the early migration process of potential plateaus. In the second stage, the conversion-type reaction dominated by Na2S and metallic copper formed at 1.85 and 1.53 V in the later period. The aforementioned results would provide new perspective on the electrochemical behavior of transition-metal sulfide anode and provide a clue for reducing voltage polarization.