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PreprintCC BYChemRxiv

Site-Selective Fluorination for Decoupling Oxidative Stability and Ionic Transport of Oxychloride Solid Electrolytes

  • Jae-Seung Kim1,2,3,4
  • Jinyeong Choe3,4
  • Hae-Yong Kim5,6
  • Jiwon Seo3,4
  • Jemin Yeon5,6
  • Sungsoo Kim7,2
  • Beom Jin Park7,2
  • Youngkyung Kim7,2
  • Jiwon Kim7,2
  • Heeju Park3,4
  • Hyeon-Jong Lee3,4
  • Hojoon Kim3,4
3 more authors
  • Kyung-Wan Nam5,6
  • Sung-Kyun Jung1,2,7,3,8,9
  • Dong-Hwa Seo3,4
9 affiliations
  1. 1Institute for Battery Research Innovation
  2. 2Seoul National University (SNU
  3. 3Department of Materials Science and Engineering
  4. 4Korea Advanced Institute of Science and Technology (KAIST
  5. 5Department of Energy and Materials Engineering
  6. 6Dongguk University
  7. 7Research Institute of Advanced Materials (RIAM
  8. 8Seoul National University
  9. 9School of Transdisciplinary Innovations
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Abstract

Fluorination in solid electrolytes is widely used to enhance oxidative stability owing to fluorine's high electronegativity, yet strong Li–F interactions hinder Li-ion transport. Here we show that this anodic stability–ionic conductivity trade-off can be largely decoupled through lattice-level anion design in the highly Li-ion-conductive LiTaOCl4. By distinguishing oxygen's framework-linking role from chloride's transport-defining role, we targeted fluorination at framework-linking O-sites to minimize perturbation of the Li-ion conduction network. The fluorinated oxychlorides retain ~10 mS cm–1-class ionic conductivity while raising the oxidation onset from 4.08 to 4.27 V versus Li+/Li, improving capacity retention as catholytes cycled to 4.5 V. First-principles calculations reveal that fluorination stabilizes oxidation-prone O- and Cl-derived electronic states through an inductive effect, while transport-network topology and correlated lattice dynamics preserve fast Li-ion transport. These results establish site-selective anion occupation as a design principle for decoupling oxidative stabilization from fast ion transport in mixed-anion solid electrolytes.

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Cite

BibTeXRIS
BibTeX
@misc{kim2026siteselective,
  title = {{Site-Selective Fluorination for Decoupling Oxidative Stability and Ionic Transport of Oxychloride Solid Electrolytes}},
  author = {Jae-Seung Kim and Jinyeong Choe and Hae-Yong Kim and Jiwon Seo and Jemin Yeon and Sungsoo Kim and Beom Jin Park and Youngkyung Kim and Jiwon Kim and Heeju Park and Hyeon-Jong Lee and Hojoon Kim and Kyung-Wan Nam and Sung-Kyun Jung and Dong-Hwa Seo},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15011034/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011034/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Site-Selective Fluorination for Decoupling Oxidative Stability and Ionic Transport of Oxychloride Solid Electrolytes
AU  - Jae-Seung Kim
AU  - Jinyeong Choe
AU  - Hae-Yong Kim
AU  - Jiwon Seo
AU  - Jemin Yeon
AU  - Sungsoo Kim
AU  - Beom Jin Park
AU  - Youngkyung Kim
AU  - Jiwon Kim
AU  - Heeju Park
AU  - Hyeon-Jong Lee
AU  - Hojoon Kim
AU  - Kyung-Wan Nam
AU  - Sung-Kyun Jung
AU  - Dong-Hwa Seo
PY  - 2026
DA  - 2026/10/26
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15011034/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011034/v1
AB  - Fluorination in solid electrolytes is widely used to enhance oxidative stability owing to fluorine's high electronegativity, yet strong Li–F interactions hinder Li-ion transport. Here we show that this anodic stability–ionic conductivity trade-off can be largely decoupled through lattice-level anion design in the highly Li-ion-conductive LiTaOCl4. By distinguishing oxygen's framework-linking role from chloride's transport-defining role, we targeted fluorination at framework-linking O-sites to minimize perturbation of the Li-ion conduction network. The fluorinated oxychlorides retain ~10 mS cm–1-class ionic conductivity while raising the oxidation onset from 4.08 to 4.27 V versus Li+/Li, improving capacity retention as catholytes cycled to 4.5 V. First-principles calculations reveal that fluorination stabilizes oxidation-prone O- and Cl-derived electronic states through an inductive effect, while transport-network topology and correlated lattice dynamics preserve fast Li-ion transport. These results establish site-selective anion occupation as a design principle for decoupling oxidative stabilization from fast ion transport in mixed-anion solid electrolytes.
ER  -