Sn-based anode materials such as Sn, SnO2, Sn4P3, and SnS2 that exhibit large theoretical capacities are promising alternatives to traditional... Show moreSn-based anode materials such as Sn, SnO2, Sn4P3, and SnS2 that exhibit large theoretical capacities are promising alternatives to traditional graphite anodes for Li-ion batteries. However, their capacities fade drastically in a few cycles due to substantial volume changes during the lithiation/delithiation process resulting in cracking and pulverization of the electrode. A graphite matrix is introduced by high-energy ball milling to obtain a graphite composite and enhance the electrochemical performance. Indeed, Sn4P3/graphite composite exhibits a reversible capacity of 651 mA h g-1 in the 100th cycle, and SnS2/graphite composite shows 591 mA h g-1 in the 50th cycle.To obtain a better understanding of the improved performance of the composite materials and the reason for the more gradual capacity fading, in situ EXAFS is used to investigate these mechanisms using in situ coin cells and in situ vacuum-sealed pouch cells. The collected EXAFS data were analyzed by modeling to extract detailed local environment changes during the lithiation/delithiation process.In the crystalline phases of Sn-based materials, the conversion reaction forming metallic Sn is partially reversible and partially irreversible, and the subsequent alloying/dealloying reaction forming LiSn alloys is reversible. Introducing the graphite matrix increases electrical conductivity and prevents aggregation of intermediate Sn clusters. The graphite matrix also plays a significant role in transforming composites into highly dispersed amorphous phases. These amorphous phases, formed in the first few cycles of Sn4P3/graphite and SnS2/graphite composites, exhibit excellent reversibility in both conversion and alloying/dealloying reactions, which is the main reason for the significant improvements in electrochemical performance. The slow growth of metallic Sn clusters and the slight reduction in amorphous phases result in gradual capacity loss over long-term cycling. Introducing the graphite matrix and creating highly dispersed composite samples are the successful strategies that can be scaled up to develop new battery materials in the future. Show less
