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<p>Research into solid electrolytes for all-solid-state batteries has intensified due to demand for safer and higher-energy-density batteries. Halide solid electrolytes are valued for their high ionic conductivity, oxidative stability, and ductility. Among them, Li<sub>2</sub>ZrCl<sub>6</sub> is cost-effective but has a relatively lower Li⁺ ionic conductivity (0.4 mS cm<sup>−1</sup> at 25 °C) compared to other halides, such as Li<sub>3</sub>InCl<sub>6</sub> (&gt; 1 mS cm<sup>−1</sup> at 25 °C). Here, we elucidate a fundamental mechanism of divalent-anion-driven framework modification that enables enhanced ionic conduction in Zr-based halides. Specifically, we demonstrate enhanced Li<sup>+</sup> conductivities for oxygen- (0.8Li<sub>2</sub>O–ZrCl<sub>4</sub>: 1.78 mS cm<sup>−1</sup> at 25 °C) and sulfur- (0.8Li<sub>2</sub>S–ZrCl<sub>4</sub>: 1.01 mS cm<sup>−1</sup> at 25 °C) substituted lattices. Synchrotron-based X-ray analyses identify distinct anionic sublattices and first-principles calculations reveal that divalent anions locally cluster within the lattice, inducing structural distortion and Li-site destabilization. These changes widen lithium conduction channels and alter the bonding environment, weakening and diversifying Li–Cl interactions. As a result, the energy landscape for lithium migration is flattened, leading to improved ionic conduction. These findings highlight design strategies for divalent-anion-driven framework regulation in halide solid electrolytes.</p>

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Divalent anion-driven framework regulation in Zr-based halide solid electrolytes for all-solid-state batteries

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年11月27日

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  • Jae-Seung Kim,
  • Daseul Han,
  • Jinyeong Choe,
  • Youngkyung Kim,
  • Hae-Yong Kim,
  • Soeul Lee,
  • Jiwon Seo,
  • Seung-Hui Ham,
  • You-Yeob Song,
  • Chang-Dae Lee,
  • Juho Lee,
  • Hiram Kwak,
  • Jinsoo Kim,
  • Yoon Seok Jung,
  • Sung-Kyun Jung,
  • Kyung-Wan Nam,
  • Dong-Hwa Seo

摘要

Research into solid electrolytes for all-solid-state batteries has intensified due to demand for safer and higher-energy-density batteries. Halide solid electrolytes are valued for their high ionic conductivity, oxidative stability, and ductility. Among them, Li2ZrCl6 is cost-effective but has a relatively lower Li⁺ ionic conductivity (0.4 mS cm−1 at 25 °C) compared to other halides, such as Li3InCl6 (> 1 mS cm−1 at 25 °C). Here, we elucidate a fundamental mechanism of divalent-anion-driven framework modification that enables enhanced ionic conduction in Zr-based halides. Specifically, we demonstrate enhanced Li+ conductivities for oxygen- (0.8Li2O–ZrCl4: 1.78 mS cm−1 at 25 °C) and sulfur- (0.8Li2S–ZrCl4: 1.01 mS cm−1 at 25 °C) substituted lattices. Synchrotron-based X-ray analyses identify distinct anionic sublattices and first-principles calculations reveal that divalent anions locally cluster within the lattice, inducing structural distortion and Li-site destabilization. These changes widen lithium conduction channels and alter the bonding environment, weakening and diversifying Li–Cl interactions. As a result, the energy landscape for lithium migration is flattened, leading to improved ionic conduction. These findings highlight design strategies for divalent-anion-driven framework regulation in halide solid electrolytes.