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

doi:10.15541/jim20240368

Abstract

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

CLC Number:

TQ152

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.

Figures/Tables 8

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

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

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]

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]

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]

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

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]

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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