Issue

Vol. 18 (2026)

Anion Chemistry: Structure, Electrochemistry and Stability of NASICON Cathodes

https://doi.org/10.1007/s40820-026-02241-5
Tingting Cai
Institute of Zhejiang University-Quzhou, Zheda Road 99, Quzhou 324000, People’s Republic of China
Dongxu Yu
Institute of Zhejiang University-Quzhou, Zheda Road 99, Quzhou 324000, People’s Republic of China
Xueyan Zhang
Institute of Zhejiang University-Quzhou, Zheda Road 99, Quzhou 324000, People’s Republic of China
Shuangshuang Zhao
School of Materials and New Energy, South China Normal University, Shanwei 516600, People’s Republic of China
Liguang Wang
College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310058, People’s Republic of China

Corresponding Author: Liguang Wang

wanglg@zju.edu.cn

Nano-Micro Letters, Vol. 18 (2026), Article Number: 395

Abstract

The development of high‐energy‐density sodium‐ion batteries places stringent requirements on cathode materials to simultaneously achieve high operating voltages, rapid Na+ ions transport, and long‐term structural and interfacial stability. Polyanionic NASICON‐type frameworks have emerged as a compelling cathode platform due to their robust three‐dimensional Na+ ions diffusion networks, strong inductive effects, and excellent thermal stability. Within this materials family, fluorophosphate NASICON cathodes offer elevated redox potentials, while targeted anion chemistry modulation provides an effective strategy to tune electronic structure, ion migration, and interfacial reactivity. Representative vanadium‐based fluorophosphate cathodes, Na3V2(PO4)2F3 (NVPF) and Na3V2O2(PO4)2F (NVOPF), exhibit closely related crystal frameworks yet display distinct sodium storage behavior and degradation characteristics under high‐voltage operation. In NVOPF, partial substitution of F− by O2− enhances electronic conductivity and Na+ ions transport kinetics, while NVPF maintains a higher redox potential associated with the V3+/V4+ couple. This review critically compares NVPF‐ and NVOPF‐based cathodes in terms of crystal structure, sodium storage mechanism, synthesis and modification strategies, and high‐voltage cathode/electrolyte interfacial stability. By correlating structural chemistry with electrochemical and interfacial evolution, this work provides general insights and design guidelines for high‐voltage NASICON‐type cathodes in sodium‐ion batteries.


Highlights:
1 Na3V2(PO4)2F3 and Na3V2O2(PO4)2F are systematically compared to elucidate the influence of subtle anion chemistry differences on crystal structure and Na+ ions diffusion pathways.
2 Synthesis and modification strategies are critically evaluated to clarify the relationships among structure, properties, and performance in fluorophosphate NASICON cathodes.
3 Voltage-driven interfacial degradation mechanisms are analyzed, providing transferable insights for designing durable high-voltage sodium-ion battery cathodes.

Keywords

Sodium‐ion batteries Interfacial stability Crystal structure Sodium storage mechanism Synthesis and modification strategies
Cai, Tingting, Dongxu Yu, Xueyan Zhang, Shuangshuang Zhao, and Liguang Wang. 2026. “Anion Chemistry: Structure, Electrochemistry and Stability of NASICON Cathodes”. Nano-Micro Letters 18 (June):395. https://doi.org/10.1007/s40820-026-02241-5.
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