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Small congeneric solvents for practical sodium metal batteries

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Na-FSA_plus_manuscript-17.pdf

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Author(s)
Chen, Weiyin
•
Hsu, Chia-Wei
•
James Kilgallon, Landon
•
Kim, So
•
Lim, Hyojun
•
Niu, Yaoshen
•
Phong, Jason
•
Ko, Kwangwook
•
Kwon, Choah
•
Lancaster, Tom
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Date Issued
August 3, 2026
Journal
Joule
Publisher
Cell Press
Version
Author's final manuscript
Abstract
Recent advances in electrolyte engineering have boosted the cycling stability of rechargeable metal batteries by weakening cation solvation, thereby compromising their kinetic properties and high-rate capability. Here, we report an electrolyte design with small congeneric solvents exhibiting up to ~20× higher ionic conductivity than larger counterparts, ~0.4 V higher electrode potential and balanced redox kinetics relative to diffusion, contributing to superior high-rate plating/stripping reversibility. Solvents with similar structures as N,N-dimethyltrifluoromethane sulfonamide were generated and screened using molecular design and three-dimensional Zernike model respectively, revealing the essential contributions to electrochemical performance from solvent geometry, affinity and reactivity. A model small solvent N,Ndimethylsulfamoyl fluoride demonstrates extraordinarily stable cycling performance against high-voltage NaNi0.33Mn0.33Fe0.33O2 cathode and Na-metal anode. Spectroscopic analysis and molecular dynamics simulations reflect the corresponding changes in ion-dipole interaction and solvation structures. The small congeneric solvent principle for electrolyte design enables other practical alkali-metal batteries and electrolyte systems.
Subjects
Sodium metal batteries
small congeneric solvents
electrochemical stability
kinetic properties
conditional molecular design
three-dimensional Zernike model
electrochemical "leveling effect"
Terms of Use
Creative Commons Attribution-NonCommercial-NoDerivatives
https://creativecommons.org/licenses/by-nc-nd/4.0/
Persistent DSpace Link
https://dspace.mit.edu/handle/1721.1/169891
DOI of Published Version
https://doi.org/10.1016/j.joule.2026.102585
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