Understanding of TiO₂/Co₃O₄-modified configuration strategy for stabilizing O3-type NaNi_0.4Fe_0.2Mn_0.4O₂ cathodes with enhanced long-term and rate performance

Abstract

Sodium-ion batteries (SIBs) have recently gained wildly interest due to the abundance of sodium, lower production costs, and better low-temperature performance compared to lithium-ion batteries (LIBs). Among various cathode materials of SIBs, O3-type NaNi_0.4Fe_0.2Mn_0.4O₂ (NFM424) demonstrates high capacity and ease of synthesis, yet suffers from structural degradation and sluggish Na⁺ kinetics caused by large ionic radius and strong electrostatic interactions. To overcome these issues, a configuration strategy combined with TiO₂ and Co₃O₄ by a simple solid-state reaction method was introduced to improve structural and electrochemical stability. XRD, SEM, TEM, and various electrochemical characterizations as well as TGA/DSC tests were conducted. The resulting NaNi_0.4Fe_0.2Mn_0.3Co_0.05Ti_0.05O₂ (NFMCT) cathode mitigated Jahn-Teller distortions and Na⁺/vacancy ordering while enhancing phase integrity and diffusion pathways. The obtained NFMCT maintained 93.7 mAh·g⁻¹ after 550 cycles at 1 C, with superior rate capabilities at 2 C and 5 C. These findings deepen the understanding of configuration strategy by using multi-element oxide and highlight a practical strategy for designing high-performance SIB cathodes.

Keywords

sodium-ion batteries / layered oxides / structural instability / configuration strategy / O3-type

References

[1] Z. Sun, Y. Gao, J.J. Yang, Y.X. Chen, and B.H.W. Guo, Development of urban building energy models for Wellington city in New Zealand with detailed survey data on envelope thermal characteristics, Energy Build., 321(2024), art. No. 114647.

[2] A.G. Olabi, T. Wilberforce, E.T. Sayed, et al., Battery energy storage systems and SWOT (strengths, weakness, opportunities, and threats) analysis of batteries in power transmission, Energy, 254(2022), art. No. 123987.

[3] Lei HP, Wei TW, Tu JG, Jiao SQ. Core–shell mesoporous carbon hollow spheres as Se hosts for advanced Al–Se batteries. Int. J. Miner. Metall. Mater., 2024, 31(5899

[4] Y. Lv, Y. Gao, Z. Sun, Z.Y. Tian, and Y.P. Gao, Intraday optimization of photovoltaic and energy storage-driven HVAC systems based on an equivalent RC Model, Int. J. Energy Res., 2025(2025), No. 1, art. No. 5377660.

[5] Y. Gao, Z. Sun, X.X. Lin, C. Wang, Z.Y. Sun, and Y.H. Chen, Designing and optimizing heat storage of a solar-assisted ground source heat pump system in China, Int. J. Photoenergy, 2020(2020), No. 1, art. No. 4102350.

[6] Wang J, Yuan YF, Rao XH, et al.. Realizing high-performance Na3V2(PO4)2O2F cathode for sodium-ion batteries via Nb-doping. Int. J. Miner. Metall. Mater., 2023, 30(101859

[7] Wang MT, Guo XT, Luo R, Jiang XN, Tang YF, Wei T. The nucleation and growth mechanism of spherical lithium for advanced lithium metal anode - A Review. Chem. Commun., 2025, 61(193777

[8] M.T. Wang, T. Wei, J.H. Lu, et al., Bimetallic MOFs-derived NiFe₂O₄/Fe₂O₃ enabled dendrite-free lithium metal anodes with ultra-high area capacity based on an intermittent lithium deposition model, ChemSusChem, 17(2024), No. 21, art. No. e202400569.

[9] T. Wei, X.T. Guo, Y.Y. Zhou, et al., Double three-dimensional structures enabled spherical lithium deposition for advanced lithium metal anode, Next Energy, 7(2025), art. No. 100237.

[10] Wei T, Zhang ZH, Zhang Q, et al.. Anion-immobilized solid composite electrolytes based on metal-organic frameworks and superacid ZrO₂ fillers for high-performance all solid-state lithium metal batteries. Int. J. Miner. Metall. Mater., 2021, 28(101636

[11] C. Sun, J.H. Lu, X.T. Guo, et al., Bimetallic metal-organic frameworks -derived lithiophilic and conductive MnO/Co/C enabled intermittent deposition model for high-performance lithium metal anode, J. Power Sources, 607(2024), art. No. 234597.

[12] Wei T, Zhang Q, Wang SJ, et al.. A gel polymer electrolyte with IL@UiO-66-NH₂ as fillers for high-performance all-solid-state lithium metal batteries. Int. J. Miner. Metall. Mater., 2023, 30(101897

[13] Wu JP, Tian JH, Sun XY, Zhuang WD. Cycling performance of layered oxide cathode materials for sodium-ion batteries. Int. J. Miner. Metall. Mater., 2024, 31(71720

[14] Zhang ZH, Wei T, Lu JH, et al.. Practical development and challenges of garnet-structured Li₇La₃Zr₂O₁₂ electrolytes for all solid-state lithium-ion battery: A review. Int. J. Miner. Metall. Mater., 2021, 28(101565

[15] Sun RM, Dou MY, Zhang YX, et al.. Substituting inert phosphate with redox-active silicate towards advanced polyan-ion-type cathode materials for sodium-ion batteries. Nanoscale, 2023, 15(73345

[16] He L, Di ZX, Li JX, et al.. The effects of fluorinated metal-organic frameworks as additives in polymer-based electrolytes for all-solid-state lithium batteries. Chem. Commun., 2024, 60(9814637

[17] Wang SJ, He L, Wang MT, et al.. A modified PVDF-HFP/PMMA crosslinked Co-polymer for high-performance all-solid-state lithium metal batteries. Particuology, 2024, 93: 203

[18] F. Li, L.F. Wei, M.T. Wang, et al., An ultralight TiO₂-graphene composite layer as separator coating to improve performance of lithium sulfur battery, J. Energy Storage, 125(2025), art. No. 116930.

[19] Sichumsaeng T, Chinnakorn A, Kalawa O, Padchasri J, Kidkhunthod P, Maensiri S. Comparative structural and electrochemical properties of mixed P₂/O₃-layered sodium nickel manganese oxide prepared by sol-gel and electrospinning methods: Effect of Na-excess content. Int. J. Miner. Metall. Mater., 2023, 30(101887

[20] C. Wang, H. Tang, H.Y. Zhu, et al., Polymer organic cathodes enable efficient desolvation for highly stable sodium-ion batteries, J. Power Sources, 546(2022), art. No. 231962.

[21] X.H. Rong, D.D. Xiao, Q.H. Li, et al., Boosting reversible anionic redox reaction with Li/Cu dual honeycomb centers, eScience, 3(2023), No. 5, art. No. 100159.

[22] J. Peng, W. Zhang, Q.N. Liu, et al., Prussian blue analogues for sodium-ion batteries: Past, present, and future, Adv. Mater., 34(2022), art. No. e2108384.

[23] A.K. Yang, K. Yao, M. Schaller, et al., Enhanced room-temperature Na⁺ ionic conductivity in Na_4.92Y_0.92Zr_0.08Si₄O₁₂, eScience, 3(2023), No. 6, art. No. 100175.

[24] E. Gabriel, C.R. Ma, K. Graff, A. Conrado, D.W. Hou, H. Xiong, Heterostructure engineering in electrode materials for sodium-ion batteries: Recent progress and perspectives, eScience, 3(2023), No. 5, art. No. 100139.

[25] R. Liu, L. Yu, X.Y. He, et al., Constructing heterointerface of Bi/Bi₂S₃ with built-in electric field realizes superior sodium-ion storage capability, eScience, 3(2023), No. 4, art. No. 100138.

[26] Liu Y, Luo R, Lu JH, Chen RT, Zhung YX, Wei T. Preparation of sodium-ion cathode materials with excellent performance using a Co₃O₄-modified conformation strategy. Chem. Commun., 2025, 61(193912

[27] Sun X, Jin Y, Zhang CY, et al.. Na[Ni_0.4Fe_0.2Mn_0.4−xTi_x]O₂: A cathode of high capacity and superior cyclability for Na-ion batteries. J. Mater. Chem. A, 2014, 2(4117268

[28] Zhou PF, Zhang J, Che ZN, et al.. Insights into the enhanced structure stability and electrochemical performance of Ti⁴⁺/F⁻ co-doped P2-Na_0.67Ni_0.33Mn_0.67O₂ cathodes for sodium ion batteries at high voltage. J. Energy Chem., 2022, 67: 655

[29] Y.J. Guo, P.F. Wang, Y.B. Niu, et al., Boron-doped sodium layered oxide for reversible oxygen redox reaction in Na-ion battery cathodes, Nat. Commun., 12(2021), No. 1, art. No. 5267.

[30] Liu L, Xin YH, Wang YS, et al.. High-entropy configuration of O3-type layered transition-metal oxide cathode with high-voltage stability for sodium-ion batteries. J. Mater. Chem. A, 2024, 12(3523495

[31] Wang Y, Zhao XD, Jin JT, et al.. Low-cost layered oxide cathode involving cationic and anionic redox with a complete solid-solution sodium-storage behavior. Energy Storage Mater., 2022, 47: 44

[32] W.L. Li, G.H. Chen, G.P. He, et al., Multifunctional role of gallium-doping in O3-type layered-oxide cathodes for sodium-ion batteries: Enhancing bulk-to-surface stability, J. Colloid Interface Sci., 692(2025), art. No. 137484.

[33] Yu Y, Kong WJ, Li QY, et al.. Understanding the multiple effects of TiO₂ coating on NaMn_0.33Fe_0.33Ni_0.33O₂ cathode material for Na-ion batteries. ACS Appl. Energy Mater., 2020, 3(1933

[34] Wan X, Zhang YY, Dong FF, et al.. High-entropy structural modification strategy for O3-type layered sodium-ion cathode materials with enhanced electrochemical performance. ACS Appl. Energy Mater., 2025, 8(106451

[35] Kim UH, Park GT, Son BK, et al.. Heuristic solution for achieving long-term cycle stability for Ni-rich layered cathodes at full depth of discharge. Nat. Energy, 2020, 5(11860

[36] W. Luo, W. Su, M.Y. Hu, and X.F. Wang, Enhancing rate and stability performance of O3-type NiFeMnTi-based layered oxides via Sb/Co dual-doping, J. Electroanal. Chem., 960(2024), art. No. 118212.

[37] Yu TY, Hwang JY, Bae IT, Jung HG, Sun YK. High-performance Ti-doped O3-type Na[Ti_x(Ni_0.6Co_0.2Mn_0.2)_1−x]O₂ cathodes for practical sodium-ion batteries. J. Power Sources, 2019, 422: 1

[38] Song CL, Li ZH, Ma LY, et al.. Single-atom Zinc and anionic framework as janus separator coatings for efficient inhibition of lithium dendrites and shuttle effect. ACS Nano, 2021, 15(813436

[39] Wang QC, Meng JK, Yue XY, et al.. Tuning P2-structured cathode material by Na-site Mg substitution for Na-ion batteries. J. Am. Chem. Soc., 2019, 141(2840

[40] L.B. Yao, P.C. Zou, C.Y. Wang, et al., High-entropy and superstructure-stabilized layered oxide cathodes for sodium-ion batteries, Adv. Energy Mater., 12(2022), No. 41, art. No. 2201989.

[41] Yang J, Maughan AE, Teeter G, Tremolet de villers BJ, Bak SM, Han SD. Structural stabilization of P2-type sodium iron manganese oxides by electrochemically inactive Mg substitution: insights of redox behavior and voltage decay. ChemSusChem, 2020, 13(225972

[42] J.B. Zhao, X. Zhang, Q. Zhao, L.J. Wang, and Y.Z. Wang, Enhanced cyclability and dynamic properties of P2-type Na_0.59Co_0.20Mn_0.80O₂ cathode by B-doping for sodium storage, Chem. Phys., 529(2020), art. No. 110582.

[43] Wan J, Qiu YG, Sun XP, et al.. Modulation of redox chemistry of Na₂Mn₃O₇ by selective boron doping prompted by Na vacancies. ACS Appl. Mater. Interfaces, 2022, 14: 38769

[44] X. Wang, X.P. Dong, X.C. Feng, et al., In-plane BO₃ configuration in P2 layered oxide enables outstanding long cycle performance for sodium ion batteries, Small Methods, 7(2023), No. 1, art. No. 2201201.

[45] J.X. Yu, H.F. Yu, L.L. Zhou, Q.L. Cheng, and H. Jiang, Trace Ti/Mg co-doped O3-type layered oxide cathodes with enhanced kinetics and stability for sodium-ion batteries, Appl. Surf. Sci., 649(2024), art. No. 159121.

[46] Kubota K, Fujitani N, Yoda Y, Kuroki K, Tokita Y, Komaba S. Impact of Mg and Ti doping in O3 type NaNi_1/2Mn_1/2O₂ on reversibility and phase transition during electrochemical Na intercalation. J. Mater. Chem. A, 2021, 9(2112830

[47] S.Y. Zhang, Y.J. Guo, Y.N. Zhou, et al., P3/O3 integrated layered oxide as high-power and long-life cathode toward Na-ion batteries, Small, 17(2021), No. 10, art. No. 2007236.

[48] H.X. Li, M. Xu, Z.A. Zhang, Y.Q. Lai, and J.M. Ma, Engineering of polyanion type cathode materials for sodium-ion batteries: toward higher energy/power density, Adv. Funct. Mater., 30(2020), No. 28, art. No. 2000473.

[49] T. Wei, J.H. Lu, P. Zhang, et al., An intermittent lithium deposition model based on bimetallic MOFs derivatives for dendrite-free lithium anode with ultrahigh areal capacity, Chin. Chem. Lett., 35(2024), No. 8, art. No. 109122.

[50] H.R. Yao, W.J. Lv, X.G. Yuan, et al., New insights to build Na⁺/vacancy disordering for high-performance P2-type layered oxide cathodes, Nano Energy, 97(2022), art. No. 107207.

[51] R. Huang, S.H. Luo, Q. Sun, L.X. Qian, X. Liu, and S.X. Yan, P2/O3 biphasic Fe/Mn based cathodes for simultaneously realizing kinetic-enhancement and air-stabilization, Chem. Eng. J., 510(2025), art. No. 161765.

[52] Sui YL, Hao YY, Zhang XP, et al.. Improved electrochemical performance of vanadium substituted Na_0.67Fe_0.5Mn_0.5O₂ cathode material for sodium-ion batteries. Ceram. Int., 2021, 47(45227

[53] M.H. Chen, F.Q. Luo, Y.C. Liao, et al., Hard carbon derived for lignin with robust and low-potential sodium ion storage, J. Electroanal. Chem., 919(2022), art. No. 116526.

RIGHTS & PERMISSIONS

University of Science and Technology Beijing