<p>Alloying-type anodes hold promise for sodium-ion batteries (SIBs) due to their high theoretical capacities, yet they suffer from severe capacity fading caused by large volume expansion during sodiation. Identifying a universal structural descriptor that links lattice chemistry with stress resistance and ion transport is therefore critical. Here, we introduce the crystal packing factor (PF) as a predictive metric and validate its effectiveness in layered bismuth compounds (BiOCl, Bi<sub>2</sub>O<sub>2</sub>S, and Bi<sub>2</sub>O<sub>2</sub>NCN) spanning a broad PF range. Bi<sub>2</sub>O<sub>2</sub>NCN, characterized by an atomically sparse and electronically conjugated [Bi<sub>2</sub>O<sub>2</sub>]<sup>2+</sup>-NCN<sup>2−</sup> layered framework with the lowest PF (0.613), markedly outperforms Bi<sub>2</sub>O<sub>2</sub>S (0.694) and BiOCl (0.763). Its open framework provides abundant interlayer free volume and weak steric constraints, thereby buffering mechanical strain and accelerating Na<sup>+</sup> diffusion. First-principles calculations corroborate that Bi<sub>2</sub>O<sub>2</sub>NCN shows suppressed stress accumulation and a lower migration barrier of 0.18 eV compared to Bi<sub>2</sub>O<sub>2</sub>S and BiOCl. Experimentally, Bi<sub>2</sub>O<sub>2</sub>NCN delivers a high capacity of 486 mA·h·g<sup>−1</sup> at 0.3 C (1 C=656 mA·g<sup>−1</sup>) and maintains 230 mA·h·g<sup>−1</sup> after 6600 cycles at 15 C with 93% capacity retention. Multimodal structural characterizations further confirm a reversible conversion-alloying mechanism. These findings establish the crystal PF as a generalizable guideline for designing stress-resistant alloying-type anodes, offering a powerful pathway toward durable, high-performance SIBs.</p>

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Crystal Packing Factor-guided Design of Stress-resistant Alloying-type Anodes for Durable Sodium-ion Storage

  • Zhuoran Lv,
  • Ximeng Lv,
  • Wujie Dong,
  • Fuqiang Huang

摘要

Alloying-type anodes hold promise for sodium-ion batteries (SIBs) due to their high theoretical capacities, yet they suffer from severe capacity fading caused by large volume expansion during sodiation. Identifying a universal structural descriptor that links lattice chemistry with stress resistance and ion transport is therefore critical. Here, we introduce the crystal packing factor (PF) as a predictive metric and validate its effectiveness in layered bismuth compounds (BiOCl, Bi2O2S, and Bi2O2NCN) spanning a broad PF range. Bi2O2NCN, characterized by an atomically sparse and electronically conjugated [Bi2O2]2+-NCN2− layered framework with the lowest PF (0.613), markedly outperforms Bi2O2S (0.694) and BiOCl (0.763). Its open framework provides abundant interlayer free volume and weak steric constraints, thereby buffering mechanical strain and accelerating Na+ diffusion. First-principles calculations corroborate that Bi2O2NCN shows suppressed stress accumulation and a lower migration barrier of 0.18 eV compared to Bi2O2S and BiOCl. Experimentally, Bi2O2NCN delivers a high capacity of 486 mA·h·g−1 at 0.3 C (1 C=656 mA·g−1) and maintains 230 mA·h·g−1 after 6600 cycles at 15 C with 93% capacity retention. Multimodal structural characterizations further confirm a reversible conversion-alloying mechanism. These findings establish the crystal PF as a generalizable guideline for designing stress-resistant alloying-type anodes, offering a powerful pathway toward durable, high-performance SIBs.