Exploration of cobalt selenite-carbon composite porous nanofibers as anode for sodium-ion batteries and unveiling their conversion reaction mechanism

摘要

Efforts have been made to develop a promising anode material with a novel composition for sodiumion batteries(SIBs).In this study,the sodium-ion storage mechanism of transition metal selenite that comprises transition metal cation coupled with two anions is studied.Amorphous cobalt selenite(CoSeO_(3))-carbon composite nanofibers containing numerous pores are synthesized via electrospinning process.Upon heat treatment of the electrospun nanofibers containing selenium,CoSe_(2)nanoclusters are formed.During the subsequent oxidation,CoSe_(2)transformed into amorphous CoSeO_(3)and some part of carbon was oxidized into CO_(2),leaving the pores inside the nanofiber.To unveil the electrochemical reaction mechanism,analytical methods including cyclic voltammetry,ex-situ X-ray photoelectron spectroscopy,ex-situ transmission electron microscopy,and in-situ electrochemical impedance spectroscopy techniques were adopted.Based on the analyses,the following conversion reaction from the second cycle onward is suggested:CoO+xSeO_(2)+(1-x)Se+4(x+1)Na^(+)+4(x+1)e~-?Co+(2x+1)Na_(2)O+Na_(2)Se.Furthermore,the electrochemical properties of porous CoSeO_(3)-carbon composite nanofibers are analyzed in detail.The anode material exhibited stable cycle stability up to 200 cycles at 0.5 A g^(-1)and high rate performance up to 5 A g^(-1).