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PreprintCC BYChemRxiv

Chemical tuning of framework libration as a design principle for Na-oxide superionic conductors

  • Hyeon-Jong Lee1,2
  • Jae-Seung Kim3,4
  • You-Yeob Song1,2
  • Minjun Kwon1,2
  • Seungyong Shin1,2
  • Jiwon Seo1,2
  • Heeju Park1,2
  • KyuJung Jun5,6,7
  • Dong-Hwa Seo1,2
7 affiliations
  1. 1Department of Materials Science and Engineering
  2. 2Korea Advanced Institute of Science and Technology (KAIST)
  3. 3Institute for Battery Research Innovation
  4. 4Seoul National University (SNU)
  5. 5School of Mechanical Engineering
  6. 6Korea University
  7. 7School of Smart Mobility
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Abstract

Most design principles for superionic conductors (SICs) are derived from known SICs and evaluated on static structures, which can miss transport enabled by finite-temperature framework motion. Both limitations are particularly severe for Na-oxides, a low-cost, stable chemistry with only a few known SIC frameworks. Here we establish a Na-oxide design principle that links local Na-site geometry to framework dynamics using chemical substitution and compositional modification strategies. Using molecular dynamics simulations with a Na-oxide-specialized machine-learning interatomic potential, we screen all 8,504 Na-oxides in the Materials Project and identify six superionic frameworks, four of them previously unreported. The highest extrapolated room-temperature conductivity reaches 29 mS cm -1 . We identify a finite-temperature Na-site size window of 1.2–1.5 Å that favors Na hopping and show that the framework motion required to access this window depends on the initial geometry: larger-amplitude libration opens initially small sites, whereas smaller-amplitude libration preserves initially larger sites. Thus, stronger framework motion is not universally favorable for ion transport. Furthermore, we show that libration is governed by polyhedral connectivity and can be tuned through Na content and cation substitution within a fixed framework. Our findings extend Na-oxide design principles from static structure to framework dynamics and indicate that frameworks overlooked at their default compositions can become conductive once the framework dynamics are tuned.

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Cite

BibTeXRIS
BibTeX
@misc{lee2026chemical,
  title = {{Chemical tuning of framework libration as a design principle for Na-oxide superionic conductors}},
  author = {Hyeon-Jong Lee and Jae-Seung Kim and You-Yeob Song and Minjun Kwon and Seungyong Shin and Jiwon Seo and Heeju Park and KyuJung Jun and Dong-Hwa Seo},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15009573/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009573/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Chemical tuning of framework libration as a design principle for Na-oxide superionic conductors
AU  - Hyeon-Jong Lee
AU  - Jae-Seung Kim
AU  - You-Yeob Song
AU  - Minjun Kwon
AU  - Seungyong Shin
AU  - Jiwon Seo
AU  - Heeju Park
AU  - KyuJung Jun
AU  - Dong-Hwa Seo
PY  - 2026
DA  - 2026/09/28
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15009573/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009573/v1
AB  - Most design principles for superionic conductors (SICs) are derived from known SICs and evaluated on static structures, which can miss transport enabled by finite-temperature framework motion. Both limitations are particularly severe for Na-oxides, a low-cost, stable chemistry with only a few known SIC frameworks. Here we establish a Na-oxide design principle that links local Na-site geometry to framework dynamics using chemical substitution and compositional modification strategies. Using molecular dynamics simulations with a Na-oxide-specialized machine-learning interatomic potential, we screen all 8,504 Na-oxides in the Materials Project and identify six superionic frameworks, four of them previously unreported. The highest extrapolated room-temperature conductivity reaches 29 mS cm -1 . We identify a finite-temperature Na-site size window of 1.2–1.5 Å that favors Na hopping and show that the framework motion required to access this window depends on the initial geometry: larger-amplitude libration opens initially small sites, whereas smaller-amplitude libration preserves initially larger sites. Thus, stronger framework motion is not universally favorable for ion transport. Furthermore, we show that libration is governed by polyhedral connectivity and can be tuned through Na content and cation substitution within a fixed framework. Our findings extend Na-oxide design principles from static structure to framework dynamics and indicate that frameworks overlooked at their default compositions can become conductive once the framework dynamics are tuned.
ER  -