Enhancing the Areal Capacity and Stability of Cu₂ZnSnS₄Anode Materials by Carbon Coating: Mechanistic and Structural Studies during Lithiation and Delithiation

The widespread use of energy storage technologies has created a high demand for the development of novel anode materials in Li-ion batteries (LIBs) with high areal capacity and faster electron-transfer kinetics. In this work, carbon-coated Cu2ZnSnS4 with a hierarchical 3D structure (CZTS@C) is used as an anode material for LIBs. The CZTS@C microstructures with enhanced electrical conductivity and improved Li-ion diffusivity exhibit high areal and gravimetric capacities of 2.45 mA h/cm2 and 1366 mA h/g, respectively. The areal capacity achieved in the present study is higher than that of previously reported CZTS-based materials. Moreover, in situ X-ray diffraction results show that lithium ions are stored in CZTS through the insertion reaction, followed by the alloying and conversion reactions at ∼1 V. The structural evolution of Li2S and Cu-Sn/Cu-Zn alloy phases occurs during the conversion and alloying reactions. The present work provides a cost-effective and simple method to prepare bulk CZTS and highlights the conformal carbon coating over CZTS, which can enhance the electrical and ionic conductivities of CZTS materials and increase the mass loading (1-2.3 mg/cm2). The improved stability and rate capability of CZTS@C anode materials can therefore be achieved.