Interfacial Mechanical Strength Enhancement for High-Performance ZnS Thin-Film Anodes

Thin-film lithium-ion microbatteries with a high energy density and long lifespan are exceedingly desired for developing self-powered integrated micro-nano devices and systems. However, exploring high-performance thin-film anodes still remains a challenge. Herein, a double-layer-structure diamond-like carbon-ZnS (DLC-ZnS) thin-film anode fabricated by radio frequency magnetron sputtering exhibits high specific capacity and good cycling stability up to 1000 cycles, superior to the pure ZnS thin-film anode. To understand the mechanism, the bimodal amplitude modulated-frequency modulated atomic force microscopy was used to explore the mechanical properties of the thin films, and the DLC layer shows significantly higher Young's modulus than the ZnS thin film. The DLC interface with a high Young's modulus can effectively buffer the mechanical stress originating from the huge volume changes of the ZnS layer during lithiation/delithiation processes; therefore, the DLC interface maintains the higher mechanical integrity of the DLC-ZnS thin film and improves the utilization of ZnS. In addition, the electrochemical kinetics of the DLC-ZnS and ZnS thin films were also investigated by electrochemical methods. Electrochemical impedance spectroscopy tests indicate the obstacle of the DLC interface to Li⁺ ion diffusion in the initial charge/discharge processes; however, the DLC-ZnS thin film exhibits lower total resistance than the ZnS thin film afterward. In particular, galvanostatic intermittent titration technique tests were performed to find out the differences between the two thin films during the galvanostatical charge/discharge processes. The results demonstrate the obviously enhanced conversion reaction reversibility and decreased alloy reaction polarization of the DLC-ZnS thin film; therefore, it delivers higher reversible capacity.