This article presents a study on the structural regulation of halide superionic conductors for all-solid-state lithium batteries. The researchers propose a new concept called the "cationic polarization factor" (τ) to predict the stacking structure of halide electrolytes. By analyzing the ionic potential and radius ratio of cations and anions, they establish a framework for designing halide electrolytes with high ionic conductivity. The study shows that the cationic polarization factor can effectively distinguish between different halide structures, such as hcp-T, hcp-O, and ccp-M, and predict their ionic conductivity. The researchers also demonstrate that by adjusting the composition of halide electrolytes, such as substituting Ho³+ with In³+ or Br⁻ for Cl⁻, they can control the structure and enhance the ionic conductivity. The study highlights the importance of cation-anion interactions in determining the structure and performance of halide electrolytes. The proposed methodology enables the systematic screening of potential halide electrolytes and provides a guide for designing superionic conductors with high performance. The study also discusses the limitations of the cationic polarization factor in cases with large cation radius differences and suggests modifications to improve its accuracy. Overall, the research provides a comprehensive understanding of the structural and compositional factors that influence the performance of halide superionic conductors for all-solid-state lithium batteries.This article presents a study on the structural regulation of halide superionic conductors for all-solid-state lithium batteries. The researchers propose a new concept called the "cationic polarization factor" (τ) to predict the stacking structure of halide electrolytes. By analyzing the ionic potential and radius ratio of cations and anions, they establish a framework for designing halide electrolytes with high ionic conductivity. The study shows that the cationic polarization factor can effectively distinguish between different halide structures, such as hcp-T, hcp-O, and ccp-M, and predict their ionic conductivity. The researchers also demonstrate that by adjusting the composition of halide electrolytes, such as substituting Ho³+ with In³+ or Br⁻ for Cl⁻, they can control the structure and enhance the ionic conductivity. The study highlights the importance of cation-anion interactions in determining the structure and performance of halide electrolytes. The proposed methodology enables the systematic screening of potential halide electrolytes and provides a guide for designing superionic conductors with high performance. The study also discusses the limitations of the cationic polarization factor in cases with large cation radius differences and suggests modifications to improve its accuracy. Overall, the research provides a comprehensive understanding of the structural and compositional factors that influence the performance of halide superionic conductors for all-solid-state lithium batteries.