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  • Review

From Single-Site Regulation to Multi-Site Synergy: Recent Advances in Substitution Engineering of Na3V2(PO4)3 Cathodes for Sodium-Ion Batteries

  • Xia Liu †,   
  • Baolin Xie †,   
  • Zhenchao Bai,   
  • Rui Wang,   
  • Da Chen,   
  • Quan Zong,   
  • Qiaoling Kang  *,   
  • Lijing Yan *

Received: 27 Jun 2026 | Revised: 04 Aug 2026 | Accepted: 06 Aug 2026 | Published: 19 Aug 2026

Abstract

Sodium-ion batteries (SIBs) have emerged as one of the most promising alternatives to lithium-ion batteries for large-scale energy-storage applications owing to the natural abundance, low cost, and wide geographical distribution of sodium resources. Among various cathode candidates, Na3V2(PO4)3 (NVP) has attracted considerable attention because of its robust NASICON framework, high operating voltage, and excellent structural stability. Nevertheless, its intrinsically low electronic conductivity, limited reaction kinetics, and the high cost associated with vanadium resources continue to hinder practical applications. To address these challenges, extensive efforts have been devoted to site-specific substitution engineering of NVP-based cathodes. This review systematically summarizes recent advances in Na-site, V-site, and PO4-site substitution strategies, as well as multi-site synergistic regulation approaches. The effects of different substitution mechanisms on crystal structure evolution, electronic configuration, Na+ diffusion behavior, redox activity, and electrochemical performance are comprehensively discussed. Furthermore, the structure-property relationships governing various substitution strategies are critically analyzed and compared. Finally, the remaining challenges and future perspectives for rational compositional design, mechanistic understanding, and practical commercialization of NVP-based cathodes are highlighted. This review aims to provide valuable insights and design principles for the development of high-performance NASICON-type cathode materials for next-generation sodium-ion batteries.

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DOI
10.53941/echem.2026.100009
Issue
Volume 2, Issue 2
How to Cite
Liu, X.; Xie, B.; Bai, Z.; Wang, R.; Chen, D.; Zong, Q.; Kang , Q.; Yan, L. From Single-Site Regulation to Multi-Site Synergy: Recent Advances in Substitution Engineering of Na3V2(PO4)3 Cathodes for Sodium-Ion Batteries. eChem 2026, 2 (2), 9. https://doi.org/10.53941/echem.2026.100009.
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