Fluorine-Doped NaTi₂(PO₄)₃ Via Electronic Orbital Modulation and Bandgap Engineering for Aqueous Li/Na/K-Ion Batteries

Abstract

Sodium titanium phosphate (NaTi₂(PO₄)₃, NTP) has emerged as a promising electrode material due to its three-dimensional open framework. This study investigates the use of NTP in aqueous dilute Li⁺/Na⁺ electrolytes and extends its application to high-concentration K⁺ electrolytes. X-ray photoelectron spectroscopy, X-ray absorption near-edge structure analysis, and density functional theory calculations revealed that highly electronegative fluorine partially substitutes for oxygen in the NTP lattice, resulting in the formation of Ti-F bonds. The substitution effectively modulates the electronic structure of Ti⁴⁺, alters the local coordination environment, and influences the redox dynamics. Enhanced long-term cycling stability and rate performance were demonstrated across aqueous sodium-ion, lithium-ion, and potassium-ion half-cells. Among the investigated systems, the aqueous sodium-ion system exhibited the best electrochemical performance, characterized by a single, well-defined charge–discharge plateau, stable cycling behavior with 88.7% capacity retention after 500 cycles at 1 A g^–1, and an initial specific discharge capacity of 121.7 mAh g^–1 at 0.2 A g^–1. The results establish F-doped NTP as a promising candidate for advanced energy storage applications in aqueous alkali metal-ion batteries.

Keywords

aqueous Li/Na/K-ion batteries / electronic structure / ionic conductivity / NASICON-type NaTi₂(PO₄)₃ electrode

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2025 The Author(s). Energy & Environmental Materials published by John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.