Enhanced Cycle Stability of Zinc Sulfide Anode for High-Performance Lithium-Ion Storage: Effect of Conductive Hybrid Matrix on Active ZnS

Abstract

Zinc sulfide (ZnS) nanocrystallites embedded in a conductive hybrid matrix of titanium carbide and carbon, are successfully fabricated via a facile high-energy ball-milling (HEBM) process. The structural and morphological analyses of the ZnS-TiC-C nanocomposites reveal that ZnS and TiC nanocrystallites are homogeneously distributed in an amorphous carbon matrix. Compared with ZnS-C and ZnS composites, the ZnS-TiC-C nanocomposite exhibits significantly improved electrochemical performance, delivering a highly reversible specific capacity (613 mA h g(-1) over 600 cycles at 0.1 A g(-1), i.e., similar to 85% capacity retention), excellent long-term cyclic performance (545 mA h g(-1) and 467 mA h g(-1) at 0.5 A g(-1) and 1 A g(-1), respectively, after 600 cycles), and good rate capability at 10 A g(-1) (69% capacity retention at 0.1 A g(-1)). The electrochemical performance is significantly improved, primarily owing to the presence of conductive hybrid matrix of titanium carbide and amorphous carbon in the ZnS-TiC-C nanocomposites. The matrix not only provides high conductivity but also acts as a mechanical buffering matrix preventing huge volume changes during prolonged cycling. The lithiation/delithiation mechanisms of the ZnS-TiC-C electrodes are examined via ex situ X-ray diffraction (XRD) analysis. Furthermore, to investigate the practical application of the ZnS-TiC-C nanocomposite, a coin-type full cell consisting of a ZnS-TiC-C anode and a LiFePO4-graphite cathode is assembled and characterized. The cell exhibits excellent cyclic stability up to 200 cycles and a good rate performance. This study clearly demonstrates that the ZnS-TiC-C nanocomposite can be a promising negative electrode material for the next-generation lithium-ion batteries.