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

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 () and Dong-Hwa Seo ()
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Jae-Seung Kim: Korea Advanced Institute of Science and Technology (KAIST), Department of Materials Science and Engineering
Daseul Han: Dongguk University, Department of Energy and Materials Engineering
Jinyeong Choe: Korea Advanced Institute of Science and Technology (KAIST), Department of Materials Science and Engineering
Youngkyung Kim: Seoul National University (SNU), Department of Materials Science and Engineering
Hae-Yong Kim: Dongguk University, Department of Energy and Materials Engineering
Soeul Lee: Dongguk University, Department of Energy and Materials Engineering
Jiwon Seo: Korea Advanced Institute of Science and Technology (KAIST), Department of Materials Science and Engineering
Seung-Hui Ham: Korea Advanced Institute of Science and Technology (KAIST), Department of Materials Science and Engineering
You-Yeob Song: Korea Advanced Institute of Science and Technology (KAIST), Department of Materials Science and Engineering
Chang-Dae Lee: Korea Advanced Institute of Science and Technology (KAIST), Department of Materials Science and Engineering
Juho Lee: Daegu Gyeongbuk Institute of Science and Technology (DGIST), Department of Energy Science and Engineering
Hiram Kwak: Yonsei University, Department of Chemical and Biomolecular Engineering
Jinsoo Kim: Daegu Gyeongbuk Institute of Science and Technology (DGIST), Department of Energy Science and Engineering
Yoon-Seok Jung: Yonsei University, Department of Chemical and Biomolecular Engineering
Sung-Kyun Jung: Seoul National University (SNU), Department of Materials Science and Engineering
Kyung-Wan Nam: Dongguk University, Department of Energy and Materials Engineering
Dong-Hwa Seo: Korea Advanced Institute of Science and Technology (KAIST), Department of Materials Science and Engineering

Nature Communications, 2025, vol. 16, issue 1, 1-14

Abstract: Abstract 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.

Date: 2025
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DOI: 10.1038/s41467-025-65702-2

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