Element Screening of High-Entropy Silicon Anodes for Superior Li-Storage Performance of Li-Ion Batteries

The high-entropy silicon anodes are attractive for enhancing electronic and Li-ionic conductivity while mitigating volume effects for advanced Li-ion batteries (LIBs), but are plagued by the complicated elements screening process. Inspired by the resemblances in the structure between sphalerite and diamond, we have selected sphalerite-structured SiP with metallic conductivity as the parent phase for exploring the element screening of high-entropy silicon-based anodes. The inclusion of the Zn in the sphalerite structure is crucial for improving the structural stability and Li-storage capacity. Within the same group, Li-storage performance is significantly improved with increasing atomic number in the order of BZnSiP₃ < AlZnSiP₃ < GaZnSiP₃ < InZnSiP₃. Thus, InZnSiP₃-based electrodes achieved a high capacity of 719 mA h g^-1 even after 1,500 cycles at 2,000 mA g^-1, and a high-rate capacity of 725 mA h g^-1 at 10,000 mA g^-1, owing to its superior lithium-ion affinity, faster electronic conduction and lithium-ion diffusion, higher Li-storage capacity and reversibility, and mechanical integrity than others. Additionally, the incorporation of elements with larger atomic sizes leads to greater lattice distortion and more defects, further facilitating mass and charge transport. Following these screening rules, high-entropy disordered-cation silicon-based compounds such as GaCuSnInZnSiP₆, GaCu(or Sn)InZnSiP₅, and CuSnInZnSiP₅, as well as high-entropy compounds with mixed-cation and -anion compositions, such as InZnSiPSeTe and InZnSiP₂Se(or Te), are synthesized, demonstrating improved Li-storage performance with metallic conductivity. The phase formation mechanism of these compounds is attributed to the negative formation energies arising from elevated entropy.