钠离子电池因钠资源丰富与低成本优势,在大规模储能领域备受关注。锰基聚阴离子钠超离子导体(NASICON)正极材料凭借高工作电压、多电子反应与结构稳定性成为研究重点。综述了该类材料在应对Jahn-Teller畸变与锰溶出等挑战方面的进展,系统阐述了阳离子/阴离子掺杂、熵工程、纳米结构与碳复合等多尺度改性策略,以提升材料结构稳定性与电化学性能。同时探讨了多电子反应调控与全电池优化等能量密度提升路径,并总结了先进原位表征技术在揭示材料动态演变机制中的作用。最后对高熵设计、界面调控及实用化挑战等未来方向进行了展望。
Sodium-ion batteries (SIBs) have garnered significant interest for large-scale energy storage applications due to the abundance of sodium resources and low cost.Manganese-based polyanionic sodium superionic conductors (NASICON) cathode materials have emerged as a key research focus,owing to their high operating voltage,multi-electron reactions,and structural stability.This review summarized recent progress in addressing challenges such as Jahn-Teller distortion and manganese dissolution in these materials.It systematically elaborated on multi-scale modification strategies,including cation/anion doping,entropy engineering,nanostructuring,and carbon compositing,aimed at enhancing the structural stability and electrochemical performance of these materials.Furthermore,pathways for increasing energy density,such as the regulation of multi-electron reactions and optimization of full-cell configurations,were discussed.The crucial role of advanced in situ characterization techniques in elucidating the dynamic evolution mechanisms of materials was also highlighted.Finally,future research directions,including high-entropy design,interface engineering,and practical challenges,were prospected.
[1] Xia J,Gao L,Cao M L,et al.Mn incorporated BiOCl anode for high performance sodium ion batteries[J].Applied Surface Science,2025,695:162888.
[2] Wu F,Wu S Y,Ye X,et al.Research progress of high-entropy cathode materials for sodium-ion batteries[J].Chinese Chemical Letters,2025,36(4):109851.
[3] Chayal L,El Arni S,Saadi M,et al.Insights into structure,morphology and conductivity of the earth-abundant NASICON phosphate,Na4MnFe(PO4)3[J].RSC Advances,2024,14(31):22159-22168.
[4] Wu C Y,Huang C E,Luo A C,et al.Enabling high-performance and high-rate-capability Na4MnV(PO4)3 sodium-ion battery cathodes through tuning the NASICON framework[J].Journal of Materials Chemistry A,2025,13(4):2716-2729.
[5] Chen Y,Peng P,Sun K Y,et al.Stabilizing NASICON-type Na4MnCr(PO4)3 by Ti-substitution toward a high-voltage cathode material for sodium ion batteries[J].Journal of Colloid and Interface Science,2024,671:385-393.
[6] Lu S T,Cai Y X,Li Y Y,et al.Anion substitution to suppress the voltage hysteresis of Na3MnTi(PO4)3 as a cathode material for sodium-ion batteries[J].ACS Applied Materials & Interfaces,2024,16(29):38092-38100.
[7] Li S Y,Yin Q M,Gu Z Y,et al.Cation/anion-dual regulation in Na3MnTi(PO4)3 cathode achieves enhanced electrochemical properties of sodium-ion batteries[J].Journal of Colloid and Interface Science,2024,664:381-388.
[8] Ahsan M T,Ali Z,Qiu D P,et al.A strategy to mitigate Jahn Teller effect of Mn-rich NASICON framework for sodium-ion batteries[J].Small,2024,20(43):2402275.
[9] Zeng J Y,Gao J Q,Jian W S,et al.Multivalent cation incorporated into manganese-iron based NASICON cathodes for high voltage sodium-ion batteries[J].Advanced Functional Materials,2024,34(52):2410992.
[10] Zikri A T,Alfaruqi M H,Zulkifli,et al.An Na3VMn0.5Ti0.5(PO4)3 NASICON cathode with multielectron reactions for sustainable energy storage[J].Journal of Materials Chemistry A,2025,13(30):24889-24902.
[11] Xie M,Li X Y,Chen Y F,et al.Multiple redox Centers and defect engineering in Fe/Mo dual-doped Na3V2(PO4)3 cathodes for high-performance sodium-ion batteries[J].Journal of Colloid and Interface Science,2025,700:138461.
[12] Liu X X,Pan Z T,Xu Y,et al.W doping enhances rate and cycle performance of Na4VMn(PO4)3 in Sodium-Ion Batteries[J].Journal of Energy Storage,2025,120:116429.
[13] Liao X Y,Wu X,Xie M,et al.Leveraging high-entropy substitution to achieve V4+/V5+ redox couple and superior Na+ storage in Na3V2(PO4)3-based cathodes for sodium-ion battery[J].Energy Storage Materials,2025,77:104166.
[14] Long T,Li R T,Kong X L,et al.Synergistically boosted Na+ migration and deep desodiation stability of NASICON cathode via high entropy regulation[J].Small,2025,21(7):2410456.
[15] Zhou Y F,Xu G F,Lin J D,et al.A multicationic-substituted configurational entropy-enabled NASICON cathode for high-power sodium-ion batteries[J].Nano Energy,2024,128:109812.
[16] Zhu P,Wang Y P,Li J,et al.A strategy of high entropy enabling advanced NASICON sodium-ion cathodes with high stabilization and multicationic redox[J].Energy Storage Materials,2024,71:103650.
[17] Lu F Q,Lu Y D,Zhao L Z.Dual carbon decorated Na3.5Mn0.5V1.5(PO4)3 cathode with high-density and long-cycling span-life for sodium-ion batteries[J].Journal of Power Sources,2025,645:237194.
[18] Li B,Xiao D D,Shang C Q,et al.Superior reversibility of NASICON-Na3.5Mn0.5V1.5(PO4)3 cathode enabled by dual-carbon conductive network[J].Journal of Alloys and Compounds,2024,977:173259.
[19] Zhu Y Q,Xu H,Bao Y H,et al.Ternary NASICON-type Na3.25VMn0.25Fe0.75(PO4)3/NC@CNTs cathode with reversible multielectron reaction and long life for Na-ion batteries[J].ACS Applied Materials & Interfaces,2025,17(5):7581-7594.
[20] Chen H J,Su Y X,Chen Y C,et al.Unlocking Na-storage potential:hierarchical NASICON Na4MnV(PO4)3 cathode with precise V(Ⅲ)/Mn(Ⅱ) integration through the citric acid-derived carbon Layer[J].ACS Applied Energy Materials,2025,8(4):2647-2659.
[21] Deng S P,Song C R,Cheng S S,et al.Coordination chemistry regulation suppressing voltage hysteresis for Na3MnTi(PO4)3 in high-rate sodium-ion batteries[J].ACS Nano,2025,19(10):10381-10391.
[22] Gokulnath S,Krishnan S,Yadav V,et al.Insights and nanoarchitectonics in Fe-substituted newer NaSICON Na4MnxFeyCr2(PO4)3 cathodes for sodium-ion batteries[J].Energy & Fuels,2024,38(14):13407-13415.
[23] Zheng Y R,Yang J,Chen H D,et al.Mitigating Jahn-Teller effects:first-principles and experimental study of aluminium-doped manganese-based NASICON cathodes for sodium-ion batteries[J].Journal of Colloid and Interface Science,2025,686:367-378.
[24] Chen S,Hou J,He X,et al.Enhancing the sodium storage performance of Na4MnCr(PO4)3 through the manipulation of intrinsic site occupation defects[J].ACS Applied Materials & Interfaces,2024,16(39):52653-52662.
[25] Qi Q,Zhang W,Zhang Y J,et al.Enhancing the electrochemical performance of Na4MnV(PO4)3 cathode material by Zr substitution[J].Electrochimica Acta,2025,531:146456.
[26] Wang X D,Chen J P,Huang Y,et al.Cation/anion doping strategy for Na4MnV(PO4)3 with high energy density and long cycling life through construction by aspergillus niger[J].ACS Applied Materials & Interfaces,2024,16(41):55771-55782.
[27] Liao X Y,Li Y J,Xie B,et al.Unlocking advanced sodium storage performance:high-entropy modulates crystallographic sites with reversible multi-electron reaction[J].Energy Storage Materials,2025,74:103920.
[28] Zhu T,Liu W,Liao X B,et al.A novel NASICON-type Na3.5MnCr0.5Ti0.5(PO4)3 nanofiber with multi-electron reaction for high-performance sodium-ion batteries[J].Advanced Fiber Materials,2024,6(2):561-569.
[29] Jiang C X,Yu Q Q,Ding Y L.Enabling high working voltage and rate capability of NASICON cathode via moderately regulating coordination environment[J].Journal of Energy Storage,2025,119:116398.
[30] Mei J B,Li B,Zhang S,et al.Enhanced performance of ternary NASICON-type Na3.5-xMn0.5V1.5-xZrx(PO4)3/C cathodes for sodium-ion batteries[J].Acta Physico-Chimica Sinica,2024,40(12):2407023.
[31] Zhang W,He L,Li J T,et al.Configurational entropy-tailored NASICON cathode redox chemistry for capacity-dense and ultralong cyclability[J].Energy & Environmental Science,2025,18(14):7278-7290.
[32] Ahsan M T,Ali Z,Wang J J,et al.Robust sodium storage enabled medium entropy Na3.5V0.5Mn0.5Fe0.5Ti0.5(PO4)3 NASICON with multielectron reaction for sodium-ion battery[J].Rare Metals,2025,44(4):2328-2339.
[33] Zhang H W,Li R,Ji Y,et al.A dual-carbon encapsulation architecture boosted charge transfer and cycling stability of sodium vanadium/manganese phosphate cathode for sodium-ion batteries[J].Journal of Electroanalytical Chemistry,2025,985:119085.
[34] Deng M T,Sui Y L,Rao K X,et al.Realizing reasonable redistribution of platform capacity through valence structure optimization for low strain Na3MnZr(PO4)3 cathode material[J].Chemical Engineering Journal,2024,499:156347.
基金资助
固体推进全国重点实验室稳定支持项目(SY41YYF202510)
PDF
