NASICON型Na4MV（PO4）3（M = Mn，Fe）钠离子电池正极的局域结构畸变与调控研究进展

李艳艳; 樊博; 李成贵; 金贤锐; 陈亮; 阮殿波; 林良栋; 李高锋

doi:10.19799/j.cnki.2095-4239.2026.0615

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NASICON型Na₄MV（PO₄）₃（M = Mn，Fe）钠离子电池正极的局域结构畸变与调控研究进展

储能材料与器件 | 更新时间：2026-09-04

- NASICON型Na₄MV（PO₄）₃（M = Mn，Fe）钠离子电池正极的局域结构畸变与调控研究进展
- Research Progress on Local Structural Distortions and Their Regulation in NASICON-Type Na₄MV(PO₄)₃ (M = Mn, Fe) Cathodes for Sodium-Ion Batteries
- 储能科学与技术 2026年页码：1-15
- 作者机构：
  
  1.宁波大学先进储能技术与装备研究院，浙江宁波 315211
  2.宁波大学机械工程与智能制造学院，浙江宁波 315211
  3.全省特种电化学储能电源重点实验室，浙江宁波 315211
- 作者简介：
  
  李艳艳（1991—），女，研究生，实验师，电池材料的制备与改性，E-mail：liyanyan@nbu.edu.cn；
  李高锋，助理研究员，钠离子电池，E-mail：ligaofeng@nbu.edu.cn。
- 基金信息：
  
  浙江省自然科学基金(LY24B030001);宁波市重大科技专项(2022Z022)
- DOI：10.19799/j.cnki.2095-4239.2026.0615
  中图分类号： TM 912
- 收稿：2026-07-15，
  
  修回：2026-08-31，
  
  网络首发：2026-09-03，
- 稿件说明：
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李艳艳, 樊博, 李成贵, 等. NASICON型Na₄MV(PO₄)₃(M = Mn,Fe)钠离子电池正极的局域结构畸变与调控研究进展[J]. 储能科学与技术, XXXX, XX(XX): 1-15. DOI: 10.19799/j.cnki.2095-4239.2026.0615.

LI Yanyan, FAN Bo, LI Chenggui, et al. Research Progress on Local Structural Distortions and Their Regulation in NASICON-Type Na₄MV(PO₄)₃ (M = Mn, Fe) Cathodes for Sodium-Ion Batteries[J]. Energy Storage Science and Technology, XXXX, XX(XX): 1-15. DOI: 10.19799/j.cnki.2095-4239.2026.0615.
李艳艳, 樊博, 李成贵, 等. NASICON型Na₄MV(PO₄)₃(M = Mn,Fe)钠离子电池正极的局域结构畸变与调控研究进展[J]. 储能科学与技术, XXXX, XX(XX): 1-15. DOI: 10.19799/j.cnki.2095-4239.2026.0615. DOI：

LI Yanyan, FAN Bo, LI Chenggui, et al. Research Progress on Local Structural Distortions and Their Regulation in NASICON-Type Na₄MV(PO₄)₃ (M = Mn, Fe) Cathodes for Sodium-Ion Batteries[J]. Energy Storage Science and Technology, XXXX, XX(XX): 1-15. DOI: 10.19799/j.cnki.2095-4239.2026.0615. DOI：

摘要

在钠离子电池中，NASICON型Na

MV(PO

)

（M = Mn，Fe）正极兼具高工作电压与三电子反应潜力，但深度脱钠诱发的局域结构畸变既是其高压失效的根源，也是构效关系解析与改性设计的关键所在。本文回顾了Na

MV(PO

)

的晶体结构特征与多电子储钠机制，梳理了脱/嵌钠过程中固溶体与两相反应的相变行为及其与结构稳定性的关联，围绕Mn

的Jahn-Teller畸变、高价V诱导的 vanadyl (V=O)与Na位占据无序三种局域结构畸变，从晶体结构、电子结构与离子输运三个层面剖析其起源，阐明三者如何共同导致电压滞后、首周不可逆容量损失与循环衰减；介绍了原位XRD、原位XAS等表征手段捕捉三种畸变结构特征的具体途径，以及第一性原理计算在解析畸变起源、预测Na

迁移势垒方面的作用；并分类评述阳离子取代、阴离子取代、熵工程与碳复合/界面工程四类基础策略及多策略组合的复合协同改性，比较了各类策略在缓解畸变、提升容量与倍率循环性能方面的优势与局限，指出单一策略难以同时兼顾多个调控目的。针对高压区

氧化还原归属、Mn溶解定量分歧与构型熵真实作用等争议，本文指出，以原位表征追踪畸变演化、第一性原理计算佐证其起源，并发展兼顾 Mn、V与Na子晶格的协同设计，是实现三电子反应可逆的关键路径。

Abstract

NASICON-type Na

MV(PO

)

(M = Mn

Fe) cathodes offer both a high operating voltage and three-electron reaction capability for sodium-ion batteries. Deep desodiation

however

triggers local structural distortions

which cause high-voltage failure and hold the key to structure-property analysis and modification design. This review summarizes the crystal structure and the multi-electron sodium storage mechanism of Na

MV(PO

)

and outlines the solid-solution and two-phase transitions upon sodium extraction/insertion together with their link to structural stability. Three local distortions receive particular attention: the Jahn-Teller distortion of Mn

vanadyl (V=O) formation induced by high-valent V

and Na-site occupancy disorder. Analysis of their origins at the crystal structure

electronic structure and ionic transport levels clarifies how the three distortions jointly produce voltage hysteresis

initial irreversible capacity loss and capacity fading. The review further describes how operando XRD and operando XAS capture the structural features of each distortion

and how first-principles calculations resolve distortion origins and predict Na

migration barriers. Four basic strategies

namely cation substitution

anion substitution

entropy engineering and carbon compositing/interface engineering

as well as synergistic multi-strategy modifications

are evaluated

and their merits and limitations in mitigating distortions and improving capacity

rate capability and cycling stability are compared. No single strategy meets all regulation targets simultaneously. Debates remain over high-voltage redox attribution

the quantification of Mn dissolution and the true role of configurational entropy. Tracking distortion evolution by operando characterization

corro

borating distortion origins by first-principles calculations

and developing synergistic designs that stabilize the Mn

V and Na sublattices define the key pathway toward reversible three-electron reactions.

关键词

Keywords

references

GUO Y J, JIN R X, FAN M, et al. Sodium layered oxide cathodes: properties, practicality and prospects[J]. Chemical Society Reviews, 2024, 53(15): 7828-7874.

PENG J, ZHANG W, LIU Q, et al. Prussian blue analogues for sodium-ion batteries: past, present, and future[J]. Advanced Materials, 2022, 34(15): 2108384.

JIN T, LI H, ZHU K, et al. Polyanion-type cathode materials for sodium-ion batteries[J]. Chemical Society Reviews, 2020, 49(8): 2342-2377.

金宇玄, 周权, 周琳, 等. 钠离子电池 NASICON 型磷酸盐正极材料研究进展[J]. 储能科学与技术, 2025, 14(11): 4184-4198.

JIN Y X, ZHOU Q, ZHOU L, et al. Research progress of NASICON-type phosphate cathode materials for sodium-ion batteries[J]. Energy Storage Science and Technology, 2025, 14(11): 4184-4198.

LIU Y, SUN C, LI Y, et al. Recent progress of Mn-based NASICON-type sodium ion cathodes[J]. Energy Storage Materials, 2023, 57: 69-80.

CHEN S, WU C, SHEN L, et al. Challenges and perspectives for NASICON-type electrode materials for advanced sodium-ion batteries[J]. Advanced Materials, 2017, 29(48): 1700431.

ZHOU W, XUE L, LÜ X, et al. Na x MV(PO 4 ) 3 (M = Mn, Fe, Ni) structure and properties for sodium extraction[J ] . Nano Letters, 2016, 16(12): 7836-7841.

LI H, JIN T, CHEN X, et al. Rational architecture design enables superior Na storage in greener NASICON-Na 4 MnV(PO 4 ) 3 cathode[J ] . Advanced Energy Materials, 2018, 8(24): 1801418.

PARK S, CHOTARD J N, CARLIER D, et al. Crystal structures and local environments of NASICON-type Na 3 FeV(PO 4 ) 3 and Na 4 FeV(PO 4 ) 3 positive electrode materials for Na-ion batteries[J ] . Chemistry of Materials, 2021, 33(13): 5355-5367.

HU J, LI X, LIANG Q, et al. Optimization strategies of Na 3 V 2 (PO 4 ) 3 cathode materials for sodium-ion batteries[J ] . Nano-Micro Letters, 2025, 17(1): 33.

BANERJEE S, CHOUDHARY R B, ANSARI S. Na 3 V 2 (PO 4 ) 3 derived cathode materials for sodium-ion batteries (SIBs): a review[J ] . Future Batteries, 2024, 4: 100010.

RAJAGOPALAN R, ZHANG Z, TANG Y, et al. Understanding crystal structures, ion diffusion mechanisms and sodium storage behaviors of NASICON materials[J]. Energy Storage Materials, 2021, 34: 171-193.

JOY A, KUMARI K, PARWEEN F, et al. A comprehensive review on strategies for enhancing the performance of polyanionic-based sodium-ion battery cathodes[J]. ACS Omega, 2024, 9(21): 22509-22531.

PANDIT B, JOHANSEN M, MARTINEZ-CISNEROS C S, et al. Na 3 V 2 (PO 4 ) 3 cathode for room-temperature solid-state sodium-ion batteries: advanced in situ synchrotron X-ray studies to understand intermediate phase evolution[J ] . Chemistry of Materials, 2024, 36(5): 2314-2324.

JIAN Z, HAN W, LU X, et al. Superior electrochemical performance and storage mechanism of Na 3 V 2 (PO 4 ) 3 cathode for room-temperature sodium-ion batteries[J ] . Advanced Energy Materials, 2013, 3(2): 156-160.

PARK S, WANG Z, DENG Z, et al. Crystal structure of Na 2 V 2 (PO 4 ) 3 , an intriguing phase spotted in the Na 3 V 2 (PO 4 ) 3 –Na 1 V 2 (PO 4 ) 3 system[J ] . Chemistry of Materials, 2022, 34(1): 451-462.

WANG Q, GAO H, LI J, et al. Importance of crystallographic sites on sodium-ion extraction from NASICON-structured cathodes for sodium-ion batteries[J]. ACS Applied Materials & Interfaces, 2021, 13(12): 14312-14320.

XU C, ZHAO J, WANG Y A, et al. Reversible activation of V 4+ /V 5+ redox couples in NASICON phosphate cathodes[J ] . Advanced Energy Materials, 2022, 12(25): 2200966.

CHEN F, KOVRUGIN V M, DAVID R, et al. A NASICON-type positive electrode for Na batteries with high energy density: Na 4 MnV(PO 4 ) 3 [J ] . Small Methods, 2019, 3(4): 1800218.

ZAKHARKIN M V, DROZHZHIN O A, TERESHCHENKO I V, et al. Enhancing Na + extraction limit through high-voltage activation of the NASICON-type Na 4 MnV(PO 4 ) 3 cathode[J ] . ACS Applied Energy Materials, 2018, 1(11): 5842-5846.

GAO X, LIAN R, HE L, et al. Phase transformation, charge transfer, and ionic diffusion of Na 4 MnV(PO 4 ) 3 in sodium-ion batteries: a combined first-principles and experimental study[J ] . Journal of Materials Chemistry A, 2020, 8(34): 17477-17486.

LU F, WANG J, CHANG S, et al. New-type NASICON-Na 4 FeV(PO 4 ) 3 cathode with high retention and durability for sodium ion batteries[J ] . Carbon, 2022, 196: 562-572.

PARK S, CHOTARD J N, CARLIER D, et al. An asymmetric sodium extraction/insertion mechanism for the Fe/V-mixed NASICON Na 4 FeV(PO 4 ) 3 [J ] . Chemistry of Materials, 2022, 34(9): 4142-4152.

WANG S, ZHENG J, HE L, et al. Carbon-modified NASICON Na 4 FeV(PO 4 ) 3 cathode with enhanced kinetics for high-performance sodium-ion batteries[J ] . ACS Applied Energy Materials, 2022, 5(8): 9616-9624.

PARK S, CHOTARD J N, CARLIER D, et al. Irreversible electrochemical reaction at high voltage induced by distortion of Mn and V structural environments in Na 4 MnV(PO 4 ) 3 [J ] . Chemistry of Materials, 2023, 35(8): 3181-3195.

JAHN H A, TELLER E. Stability of polyatomic molecules in degenerate electronic states-I — Orbital degeneracy[J]. Proceedings of the Royal Society of London A, 1937, 161(905): 220-235.

CHEN C, WANG L, DENG Z, et al. Enabling one-step de-sodiation of Na 4 MnV(PO 4 ) 3 cathode via regulating coordination environment for high-power and long-lasting sodium-ion batteries[J ] . Adva nced Functional Materials, 2025, 35(14): 2418642.

HUNTER J C. Preparation of a new crystal form of manganese dioxide: λ-MnO 2 [J ] . Journal of Solid State Chemistry, 1981, 39(2): 142-147.

LIU T, DAI A, LU J, et al. Correlation between manganese dissolution and dynamic phase stability in spinel-based lithium-ion battery[J]. Nature Communications, 2019, 10: 4721.

GUMMOW R J, DE KOCK A, THACKERAY M M. Improved capacity retention in rechargeable 4 V lithium/lithium-manganese oxide (spinel) cells[J]. Solid State Ionics, 1994, 69(1): 59-67.

HWANG J, MATSUMOTO K, HAGIWARA R. Electrolytes toward high-voltage Na 3 V 2 (PO 4 ) 2 F 3 positive electrode durable against temperature variation[J ] . Advanced Energy Materials, 2020, 10(34): 2001880.

WONG J, LYTLE F W, MESSMER R P, et al. K-edge absorption spectra of selected vanadium compounds[J]. Physical Review B, 1984, 30(10): 5596-5610.

DENG S, YANG M, WANG Y C, et al. Regulating Na/Mn antisite defects and revitalizing reversible redox reactions in phosphate cathodes[J]. ACS Nano, 2025, 19(33): 30010-30020.

GHOSH S, BARMAN N, SENGUTTUVAN P. Impact of Mg 2+ and Al 3+ substitutions on the structural and electrochemical properties of NASICON-NaxVMn 0.75 M 0.25 (PO 4 ) 3 (M = Mg and Al) cathodes for sodium-ion batteries[J ] . Small, 2020, 16(45): 2003973.

MUKKATTU KUNIYIL N C, ROBIN R, GOKULNATH S, et al. Nanoarchitectonic approach to zinc-substituted NASICON Na 4 VMn 1-x Zn x (PO 4 ) 3 /C as high-rate cathodes for sodium-ion batteries[J ] . Energy & Fuels, 2024, 38(17): 17026-17037.

XU C, ZHAO J, WANG E, et al. A novel NASICON-typed Na 4 VMn 0.5 Fe 0.5 (PO 4 ) 3 cathode for high-performance Na-ion batteries[J ] . Advanced Energy Materials, 2021, 11(22): 2100729.

ZHANG J, SHI L, ZHAO S F, et al. Lattice strengthening of Na 4 MnV(PO 4 ) 3 by dual doping as advanced cathode materials for sodium-ion batteries[J ] . Journal of Energy Storage, 2025, 134: 118175.

MUKKATTU KUNIYIL N C, ROBIN R, KUMARASAMY R K, et al. Tailoring of high-valent Sn-doped porous Na 3 V 2 (PO 4 ) 3 /C nanoarchitechtonics: An ultra high-rate cathode for sodium-ion batteries [J ] . ACS Applied Materials & Interfaces, 2024, 16(22): 28599-28612.

MA X, YU X, LI X, et al. Modulating Na vacancies of Na 4 FeV(PO 4 ) 3 via Zr-substitution: toward a superior rate and ultrastable cathode for sodium-ion batteries[J ] . Journal of Power Sources, 2022, 541: 231727.

ZHENG L, TANG A, GONG X, et al. Na 3.8 MnV 0.8 Zr 0.2 (PO 4 ) 3 /C/rGO composite cathode for sodium-ion battery with enhanced cycling stability and rate capability[J ] . Carbon Letters, 2024, 34(7): 1961-1969.

YU H, RUAN X, WANG J, et al. From solid-solution MXene to Cr-substituted Na 3 V 2 (PO 4 ) 3 : breaking the symmetry of sodium ions for high-voltage and ultrahigh-rate cathode performance[J ] . ACS Nano, 2022, 16(12): 21174-21185.

ZHANG W, XU Z, LI H, et al. All-climate and air-stable NASICON-Na 2 TiV(PO 4 ) 3 cathode with three-electron reaction toward high-performance sodium-ion batteries[J ] . Chemical Engineering Journal, 2022, 433: 133542.

HOU J, HADOUCHI M, SUI L, et al. Unlocking fast and reversible sodium intercalation in NASICON Na 4 MnV(PO 4 ) 3 by fluorine substitution[J ] . Energy Storage Materials, 2021, 42: 307-316.

YUAN Y, WANG J, YANG A, et al. Polyanion lattice engineering of Na 4 MnV(PO 4 ) 3 cathode for high-perfor mance sodium-ion batteries[J ] . Advanced Functional Materials, 2026, 36(16): e19233.

WU C Y, HUANG C E, LUO A C, et al. Enabling high-performance and high-rate-capability Na 4 MnV(PO 4 ) 3 sodium-ion battery cathodes through tuning the NASICON framework[J ] . Journal of Materials Chemistry A, 2025, 13(4): 2716-2729.

ZHU Q, WU J, LI W, et al. Boosting sodium-ion battery performance by anion doping in NASICON Na 4 MnCr(PO 4 ) 3 cathode[J ] . Journal of Colloid and Interface Science, 2024, 663: 191-202.

HU P, WANG X, WANG T, et al. Boron substituted Na 3 V 2 (P 1-x B x O 4 ) 3 cathode materials with enhanced performance for sodium-ion batteries[J ] . Advanced Science, 2016, 3(12): 1600112.

OKITA N, MATSUMURA K, HARADA Y, et al. Sulfate-substituted Na 3 V 2 (PO 4 ) 3 nanodots embedded in carbon nanotubes for ultrafast sodium-ion storage[J ] . Nano Letters, 2025, 25(41): 14872-14879.

DU M, LI K, YU N, et al. Ultrafast preparation of high-entropy NASICON cathode enables stabilized multielectron redox and wide-temperature (-50–60°C) workability in sodium-ion batteries[J]. Advanced Materials, 2025, 37(9): 2418219.

FAN D, WANG Y, ZHAO X, et al. A novel NASICON-Na 3.4 MnV 0.2 Cr 0.2 Ti 0.6 (PO 4 ) 3 cathode with ultrahigh energy density and remarkable cycling stability toward practical Na-ion batteries[J ] . Materials Today, 2025, 86: 63-73.

ZHANG W, HE L, LI J, et al. Configurational entropy-tailored NASICON cathode redox chemistry for capacity-dense and ultralong cyclability[J]. Energy & Environmental Science, 2025, 18(14): 7278-7290.

WU X H, JIANG W J, DAI C, et al. A phase-transition-free sodium vanadium phosphate cathode via medium-entropy engineering for superior sodium ion batteries[J]. Advanced Materials, 2025, 37(8): 2414358.

WANG K, HUA W B, HUANG X H, et al. Synergy of cations in high entropy oxide lithium ion battery anode[J]. Nature Communications, 2023, 14: 1487.

FRACCHIA M, CODURI M, GHIGNA P, et al. Phase stability of high entropy oxides: a critical review[J]. Journal of the European Ceramic Society, 2024, 44(2): 585-594.

ZHU Y, XU H, MA J, et al. The recent advances of NASICON-Na 3 V 2 (PO 4 ) 3 cathode materials for sodium-ion batteries[J ] . Journal of Solid State Chemistry, 2023, 317: 123669.

DING X, YANG X, LI J, et al. High-entropy and Na-rich-designed high-energy-density Na 3 V 2 (PO 4 ) 3 /C cathode[J ] . ACS Nano, 2024, 18(52): 35632-35643.

FAN H H, CHEN X M, LI F M, et al. Structure design and electrochemical performance regulation of Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 cathode materials for sodium-ion batteries[J ] . Acta Physico-Chimica Sinica, 2026: 100247.

CHEN X M, CHEN K, JI F J, et al. Achieving fast ion/electron transportation and smooth phase transition in polyanion cathode by the high entropy strategy[J]. Advanced Energy Materials, 2025, 15(26): 2500502.

CHEN X M, HAN L X, ZHAO Y N, et al. Insights in iron-based polyanion electrode materials for advanced sodium-ion batteries[J]. Chemical Engineering Journal, 2024, 501: 157600.

HU P, ZHU T, CAI C, et al. Sodium ion storage in Na 4 MnV(PO 4 ) 3 @C free-standing electrode[J ] . Advanced Functional Materials, 2022, 32(52): 2208051.

WANG Y, WANG Q, DING X, et al. The nitrogen-doped carbon coated Na 4 MnV(PO 4 ) 3 as a high electrochemical performance cathode material for sodium-ion batteries[J ] . Applied Surface Science, 2022, 601: 154218.

CUI G, DONG Q, WANG Z, et al. Achieving highly reversible and fast sodium storage of Na 4 VMn(PO 4 ) 3 /C-rGO composite with low-fraction rGO via spray-drying technique[J ] . Nano Energy, 2021, 89: 106462.

WANG Z, WANG H, WU Y, et al. Novel design and fabrication of CNT-decorated Na 4 FeV(PO 4 ) 3 @C microspheres as novel cathode materials for sodium energy storage[J ] . Ceramics International, 2025, 51(20): 31713-31718.

SONG C, LI S, BAI Y. High-lattice-adapted surface modifying Na 4 MnV(PO 4 ) 3 for better sodium storage[J ] . Nano Research, 2024, 17(4): 2728-2735.

WANG S, BAI J, WANG P, et al. Boosting long-life sodium storage of Na 4 MnV(PO 4 ) 3 via synergistic bond structure regulation and interfacial modification[J ] . Advanced Functional Materials, 2026, 36(31): e23851.

WANG L, WANG J, WANG L, et al. Synergistic strain suppressing and interface engineering in Na 4 MnV(PO 4 ) 3 /C for wide-temperature and long-calendar-life sodium-ion storage[J ] . ACS Nano, 2024, 18(16): 10863-10873.

WANG X, CHEN J, HUANG Y, et al. Cation/anion doping strategy for Na 4 MnV(PO 4 ) 3 with high energy density and long c ycling life through construction by Aspergillus niger[J ] . ACS Applied Materials & Interfaces, 2024, 16(41): 55771-55782.

BLACK A P, SORRENTINO A, FAUTH F, et al. Synchrotron radiation based operando characterization of battery materials[J]. Chemical Science, 2023, 14(7): 1641-1665.

FAN D, SHEN Q, LI H, et al. Redox couple modulation in NASICON phosphates toward high-performance cathodes for Na-ion batteries[J]. Energy Material Advances, 2024, 5: 0073.

CHEN B, PENG Z, YUAN Z. Constructing sandwich structure of Nb-substituted Na 3 V 2 (PO 4 ) 3 /C nanoparticles enwrapped on three-dimensional graphene with superior sodium storage property[J ] . Ceramics International, 2022, 48(22): 33957-33966.

ZHOU T, CHEN Y. Constructing heterostructure by co-doping of Ta 5+ and F - with carbon nanotubes to improve kinetic properties of Na 3 V 2 (PO 4 ) 3 [J ] . Journal of Energy Storage, 2024, 85: 111139.

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