钠离子电池正极材料循环稳定性提升策略及产业化进程

doi:10.15541/jim20240368

无机材料学报 ›› 2025, Vol. 40 ›› Issue (4): 348-362.DOI: 10.15541/jim20240368 CSTR: 32189.14.10.15541/jim20240368

钠离子电池正极材料循环稳定性提升策略及产业化进程

张继国(), 吴田, 赵旭, 杨钒, 夏天, 孙士恩()

浙江省白马湖实验室有限公司, 杭州 310051

收稿日期:2024-08-12 修回日期:2024-11-05 出版日期:2025-04-20 网络出版日期:2024-11-29
通讯作者: 孙士恩, 正高级工程师. E-mail: shiensun@126.com
作者简介:张继国(1988-), 男, 工程师. E-mail: zhangjiguo@zjenergy.com.cn
基金资助:
国家重点研发计划(2023YFB2504100);浙江省重点研发计划(2023C01246);浙江省白马湖实验室项目(ZB-24-DC-O-F-G-002-B)

Improvement of Cycling Stability of Cathode Materials and Industrialization Process for Sodium-ion Batteries

ZHANG Jiguo(), WU Tian, ZHAO Xu, YANG Fan, XIA Tian, SUN Shien()

Zhejiang Baima Lake Laboratory Co., Ltd., Hangzhou 310051, China

Received:2024-08-12 Revised:2024-11-05 Published:2025-04-20 Online:2024-11-29
Contact: SUN Shien, professor. E-mail: shiensun@126.com
About author:ZHANG Jiguo (1988-), male, engineer. E-mail: zhangjiguo@zjenergy.com.cn
Supported by:
National Key Research and Development Program of China(2023YFB2504100);Key Research and Development Program of Zhejiang Province(2023C01246);Project of Zhejiang Baima Lake Laboratory Co., Ltd.(ZB-24-DC-O-F-G-002-B)

摘要/Abstract

摘要：

与传统锂离子电池相比, 钠离子电池因其成本优势与可持续的资源供应, 被看作是锂离子电池的理想替代品。现阶段主流钠离子电池正极材料包括过渡金属氧化物、聚阴离子型化合物以及普鲁士蓝化合物。然而, 正极材料存在不可逆相转化、Jahn-Teller效应及界面不稳定等问题, 这严重影响了钠离子电池的循环稳定性。本文系统介绍了钠离子电池正极材料循环稳定性提升策略的研究进展与产业化进程。首先, 详细分析了正极材料的结构、优缺点, 并对比了结构稳定性、成本以及循环性能等。其次, 详细阐述了结构优化与化学元素掺杂策略在提升正极材料循环性能方面的最新研究进展, 探索了结构稳定性、电子电导率、离子迁移速率等与电化学性能之间的相互影响关系。然后, 归纳总结了钠离子电池的发展历程与近年来国内外的产业化进展。最后, 梳理了钠离子电池正极材料及钠离子电池体系仍需关注的问题并展望了其发展前景, 以期推进钠离子电池产业稳步、健康发展。

关键词: 钠离子电池, 过渡金属氧化物, 聚阴离子型化合物, 普鲁士蓝化合物, 循环稳定性, 产业化, 综述

Abstract:

Compared with traditional lithium-ion batteries, sodium-ion batteries are an ideal alternative due to their cost advantages and sustainable resource supply. At present, the cathode materials for sodium-ion batteries mainly include transition metal oxides, polyanionic compounds and Prussian blue analogues. However, irreversible phase conversion, Jahn-Teller effect and interface instability of cathode materials seriously affect the cycling stability of sodium-ion batteries. In this paper, the research progress and industrialization process of strategies for improving cyclic stability of cathode materials for sodium-ion batteries are systematically introduced. Firstly, the structure as well as advantages and disadvantages of cathode materials is analyzed in detail, and the structural stability, cost and cycling performance are compared. Secondly, the latest research progress of structure optimization and chemical element doping strategies in improving the cycling stability of cathode materials is elaborated in detail, and the interaction between structural stability, electronic conductivity, ion intercalation/deintercalation of cathode materials and electrochemical performance is revealed. Then, the development process and industrialization progress of sodium-ion batteries are summarized. Finally, the significant problems that still need to be addressed for cathode materials and systems for sodium-ion batteries are sorted out and their future developments are prospected, aiming to propel the steady and healthy development of sodium-ion battery industry.

Key words: sodium-ion battery, transition metal oxide, polyanionic compound, Prussian blue analogue, cycling stability, industrialization process, review

中图分类号:

TQ152

张继国, 吴田, 赵旭, 杨钒, 夏天, 孙士恩. 钠离子电池正极材料循环稳定性提升策略及产业化进程[J]. 无机材料学报, 2025, 40(4): 348-362.

ZHANG Jiguo, WU Tian, ZHAO Xu, YANG Fan, XIA Tian, SUN Shien. Improvement of Cycling Stability of Cathode Materials and Industrialization Process for Sodium-ion Batteries[J]. Journal of Inorganic Materials, 2025, 40(4): 348-362.

图/表 8

图1 锂/钠离子电池原材料价格对比[5]

Fig. 1 Costs of Li+/Na+ battery raw materials[5]

表1 锂离子与钠离子作为电荷载体的性能对比[6-7]

Table 1 Comparison of characteristics of Li+ and Na+ as charge carriers[6-7]

Charge carrier	Li⁺	Na⁺
Ionic radius/Å	0.76	1.02
Electronic polarizability of ion/Å³	0.03	0.2-0.3
Relative atomic mass	6.94	23.00
Ionization energy/eV	5.39	5.14
Melting point/℃	180.5	97.7
Desolvation-energy in propylene carbonate/ (kJ·mol^-1)	215.8	158.2
E⁰/V(vs. SHE)	-3.04	-2.71
Electronegativity	0.98	0.93
Molar mass/(g·mol^-1)	6.9	23.0

图2 钠离子电池正极材料的性能及结构[10,13⇓⇓⇓ -17]

Fig. 2 Properties and structures of cathode materials for Na+ battery[10,13⇓⇓⇓ -17] (a) Properties of cathode materials[13-14]; (b) Classification and phase transition processes of layered materials[10]; (c) Structures of (c1) maricite NaFePO4[15], (c2) olivine NaFePO4[15] and (c3) NASICON-Na3V2(PO4)3[16]; (d) Framework of Prussian blue analogues[17]

图3 结构优化策略[34⇓⇓⇓-38,40,42⇓⇓ -45]

Fig. 3 Strategies of structural optimization[34⇓⇓⇓-38,40,42⇓⇓ -45] (a1) Crystal structure schematic of MTS15 and (a2) cycling performance of MTS15, MTS25, MTS35, and MTS45[34]; (b1) Selected area electron diffraction pattern of P2-NCLMO[35]; (b2) In situ XRD patterns and corresponding volume variations of P2-NCLMO electrode in the first cycle at 0.2C[35]; (c) Calculated diffusion coefficient of Na+ in P2/O3-NaMnNiCuFeTiOF[36]; (d) High-resolution ex situ solid-state 23Na nuclear magnetic resonance spectra of Na3(VOPO4)2F/8% Ketjen black electrode under various states[37]; (e1) Bright field TEM image of nanosized Na4Fe3(PO4)2(P2O7) plates (NFPP-E) with carbon layers and (e2) volume change details during the charge/discharge process of NFPP-E[38]; (f) Cycling performance of full-cell based on MnHCF-S-170 cathode and soft carbon anode[40]; (g) Charge-discharge curves of KMF in different cycles at 0.1 A·g−1[42]; (h) Rate performances of pristine and HT samples under current densities from 0.1C to 20C[43]; (i) Unit volume of SC-HEPBA during charge and discharge process[44]; (j1) In-situ synchrotron-based powder XRD patterns with charge-discharge curves and (j2) cycling performance under 150 mA·g−1 and different temperatures[45]

图4 化学元素掺杂策略[16,46⇓⇓⇓⇓ -51]

Fig. 4 Strategies of chemical elements doping[16,46⇓⇓⇓⇓ -51] (a1) Initial charge-discharge curves of CNFM, Na0.89Li0.05Cu0.11Ni0.11Fe0.3Mn0.43O2 (LCNFM), and LCNFMF at 0.1C in a voltage range of 1.5-4.0 V with inset showing quantitative analysis results of reversible capacity contributions[46]; (a2) Changes of a/c-lattice parameters in three samples obtained by fitting in situ XRD data[46]; (b) Charge-discharge curves of Ni30MgTi[47]; (c1) STEM-HAADF image of interface between preconstructed layer and bulk phase and (c2) corresponding sodium ion diffusion coefficients of P2-NaMNNb calculated from GITT (galvanostatic intermittent titration technique) formula under 25 and −40 ℃[48]; (d) Cycling performance of NFVNP//HC at 5C in a voltage range of 1.5-3.8 V[49]; (e) Galvanostatic charge-discharge profiles at 0.5C in different voltage windows of 1.7-3.8 V and 1.7-4.3 V[16]; (f) Galvanostatic charge/discharge profiles of Fe-rich electrode at 0.1C from 1.5 V to 4.2 V[50]; (g) CV curves of NVTAP at 0.2 mV·s-1[51]

表2 不同种类钠离子电池正极材料性能汇总[64⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓-82]

Table 2 Comprehensive overview of various cathode materials for sodium-ion batterio[64⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓-82]

图5 钠离子电池国外产业化进展[83,85 -86,90 -91]

Fig. 5 International Industrialization process of sodium-ion batteries[83,85 -86,90 -91] (a) Worldwide development history of sodium-ion batteries[85]; (b1) Charge/discharge profiles of Faradion’s second-generation cathode material at 0.2C within different voltage windows[86]; (b2) Fast-charge performance of Faradion’s second-generation cathode material||HC 0.1 Ah full cell, charging at 4C (15 min total charge) without obvious capacity drop[86]; (b3) Faradion 3.0 Ah Na-ion pouch cell with 400 Wh battery pack system[86]; (c1) Discharge voltage profiles at different discharge rates as a function of relative energy accessed under 25 ℃ (1C/1C=100%) and (c2) cycling life measured on different versions of Tiamat Na-ion cells at 25 ℃ and 100% DOD[90]; (d1) Discharge voltage profiles of Natron cell at various discharge C rates as a function of percentage of discharge capacity accessed at 1C/1C and (d2) cycling performance at 25 ℃, 10C/10C, and 100% DOD performed in Natron’s lab with inset showing photo of ABB-Natron pluggable battery module containing 32 Natron’s 4.6 Ah sodium-ion pouch cells[91]; (e1) Cycling performance, (e2) rate capability at room temperature and (e3) safety evaluation of Novasis pouch cells[83]

图6 钠离子电池国内产业化进展[97,99⇓ -101,104 -105,107]

Fig. 6 Domestic industrialization process of sodium-ion batteries[97,99⇓ -101,104 -105,107] (a) Companies dedicated to advancing sodium-ion batteries[97]; (b1) Typical first charge/discharge profiles of several Cu-based oxide cathode materials[99], (b2) rate capability at various constant rates from 0.1C to 1C[100] and (b3) first 30 kW/100 kWh Na-ion battery system for energy storage[101]; (c1) Cycling performance of Na1+xFe[Fe(CN)6] electrodes[104], (c2) digital images of synthesis of Prussian white Na2−xFeFe(CN)6 in 100 L reactor and powder of final product and (c3) cycling performance of pouch full cell[105]; (d1-d3) Practical application of sodium-ion batteries with polyanionic materials as cathodes[107]

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钠离子电池正极材料循环稳定性提升策略及产业化进程

Improvement of Cycling Stability of Cathode Materials and Industrialization Process for Sodium-ion Batteries

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