A high-performance solid-state electrolyte Na4ZrF8 with exceptional ionic conductivity and electrochemical and interfacial stability

Abstract

We propose a promising sodium fluoride solid-state electrolyte (SSE), Na4ZrF8 (NZF), by using density functional theory combined with ab initio molecular dynamics simulations and grand potential phase diagram analysis. NZF exhibits excellent dynamic, thermal, and mechanical stability, along with a wide band gap of 8.18 eV. It delivers a high ionic conductivity of 3.5 mS cm−1 at 300 K, with a low activation energy of 0.22 eV and migration energy barriers of 0.23 eV in 2D channels and 0.36 eV in 3D channels. NZF also shows a broad electrochemical stability window (0.62–5.89) V, and an oxidation potential exceeding 5 V. Furthermore, it exhibits exceptionally lower interfacial reaction energies (<20 meV per atom) with polyanion cathodes, thus ensuring superior compatibility with high-voltage cathodes. These attributes highlight NZF's potential as a high-performance SSE for sodium-ion batteries and complement recent experimental advances in zirconium-based halide metal-ion conductors such as: Li4ZrCl4O2 [Nature Commun. 2023, 14, 3807], Li4ZrF8 [Adv. Energy Mater. 2022, 12, 2201808], NaxZrCl4+x and Na0.5ZrCl4F0.5 [Nature Commun. 2025, 16, 2808].

Graphical abstract: A high-performance solid-state electrolyte Na4ZrF8 with exceptional ionic conductivity and electrochemical and interfacial stability

Supplementary files

Article information

Article type
Paper
Submitted
27 May 2025
Accepted
15 Jul 2025
First published
29 Jul 2025

J. Mater. Chem. A, 2025, Advance Article

A high-performance solid-state electrolyte Na4ZrF8 with exceptional ionic conductivity and electrochemical and interfacial stability

S. J. Hussain, S. N. Khan, R. Raza and Q. Sun, J. Mater. Chem. A, 2025, Advance Article , DOI: 10.1039/D5TA04261E

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