Sodium storage properties of Fe, Ni-bimetallic doped carbon-modified NaTi₂(PO₄)₃

Abstract

NaTi₂(PO₄)₃ (NTP) is a material with a NASICON structure, a three-dimensional open type skeleton, and suitable negative voltage window, which is widely regarded as a magnetic anode material for aqueous sodium ion batteries (ASIBs). However, NTP’s intrinsically poor conductivity hampers their use in ASIBs. Herein, bimetallic doped carbon material was designed and combined with the sol–gel method to prepare NaTi₂(PO₄)₃–C–FeNi (NTP–C–FeNi) composite materials. This bimetallic doped carbon composite NTP material not only has a large specific surface area, but also effectively improves conductivity and promotes rapid migration of Na⁺. Following the rate performance test, NTP–C–FeNi retained a reversible capacity of 116.75 mAh·g⁻¹ at 0.1 A·g⁻¹, representing 95.9% of the first cycle capacity. After 500 cycles at 1.5 A·g⁻¹, the cycle fixity was 85.3%. The enhancement of electrochemical performance may owe to the widening of pathways and acceleration of Na⁺ insertion/extraction facilitated by FeNi–C doping, while the carbon coating effectively promotes electrode charge transfer. The results indicate that the bimetallic doped carbon composite NaTi₂(PO₄)₃ holds potential for practical applications in novel aqueous sodium ion battery systems.

Keywords

aqueous sodium-ion batteries / NaTi₂(PO₄)₃ / bimetallic doped carbon / electrochemical performance

References

[1] FujitaT, ChenH, WangKT, et al.. Reduction, reuse and recycle of spent Li-ion batteries for automobiles: A review. Int. J. Miner. Metall. Mater., 2021, 282179.

[2] G.Q. Yang, C. Lee, X.X. Qiao, S.K. Babu, U. Martinez, and J.S. Spendelow, Advanced electrode structures for proton exchange membrane fuel cells: Current status and path forward, Electrochem. Energy Rev., 7(2024), No. 1, art. No. 9.

[3] ShiMJ, ZhuHT, ChenC, JiangJT, ZhaoLP, YanC. Synergistically coupling of graphene quantum dots with Zn-intercalated MnO₂ cathode for high-performance aqueous Zn-ion batteries. Int. J. Miner. Metall. Mater., 2023, 30125.

[4] ZhaoY, WangB, ShiMJ, AnSB, ZhaoLP, YanC. Mg-intercalation engineering of MnO₂ electrode for high-performance aqueous magnesium-ion batteries. Int. J. Miner. Metall. Mater., 2022, 29111954.

[5] LiangYL, YaoY. Designing modern aqueous batteries. Nat. Rev. Mater., 2023, 82109.

[6] LanDY, QuXF, TangYT, LiuLY, LiuJ. Acetate solutions with 3.9 V electrochemical stability window as an electrolyte for low-cost and high-performance aqueous sodium-ion batteries. J. Electrochem., 2022, 28158

[7] B. Li, P.C. Ruan, X.Y. Xu, et al., Covalent organic framework with 3D ordered channel and multi-functional groups endows Zn anode with superior stability, Nano-Micro Lett., 16(2024), No. 1, art. No. 76.

[8] HanY, LiuSY, CuiL, et al.. Graphene-immobilized flowerlike Ni₃S₂ nanoflakes as a stable binder-free anode material for sodium-ion batteries. Int. J. Miner. Metall. Mater., 2018, 25188.

[9] C.S. Ding, Z. Chen, C.X. Cao, Y. Liu, and Y.F. Gao, Advances in Mn-based electrode materials for aqueous sodium-ion batteries, Nano-Micro Lett., 15(2023), No. 1, art. No. 192.

[10] W. Li, J.P. Li, R.R. Li, et al., Study on sodium storage properties of manganese-doped sodium vanadium phosphate cathode materials, Battery Energy, 2(2023), No. 2, art. No. 20220042.

[11] S.Z. Zhao, H.Y. Che, S.L. Chen, et al., Research progress on the solid electrolyte of solid-state sodium-ion batteries, Electrochem. Energy Rev., 7(2024), No. 1, art. No. 3.

[12] XuT, YuJJ, MaJC, RenW, HuML, LiXF. The critical role of water molecules in the development of aqueous electrolytes for rechargeable metal-ion batteries. J. Mater. Chem. A, 2024, 122313551.

[13] DelmasC, CherkaouiF, NadiriA, HagenmullerP. A nasicon-type phase as intercalation electrode: NaTi₂(PO₄)₃. Mater. Res. Bull., 1987, 225631.

[14] S.I. Park, I. Gocheva, S. Okada, and J.I. Yamaki, Electrochemical properties of NaTi₂(PO₄)₃ anode for rechargeable aqueous sodium-ion batteries, J. Electrochem. Soc., 158(2011), No. 10, art. No. A1067.

[15] S.Y. Lee, D. Park, B.S. Yoon, Y.S. Lee, Y.I. Park, and C.H. Ko, Atomic layer deposition-based synthesis of TiO₂ and Al₂O₃ thin-film coatings on nanoparticle powders for sodium-ion batteries with enhanced cyclic stability, J. Alloy. Compd., 897(2022), art. No. 163113..

[16] W.J. Wang, J.T. Wu, and C.L. Zeng, New construction of polypyrrole interphase layers to improve performance stability of NaTi₂(PO₄)₃ anode for aqueous Na-ion batteries, Solid State Ionics, 397(2023), art. No. 116259.

[17] BirkL, Rener-SitarK, BenčinaM, JunkarI. Dental silicate ceramics surface modification by nonthermal plasma: A systematic review. Dent. Mater., 2024, 403531.

[18] LiuXH, XuXT, XuanXX, et al.. Unlocking enhanced capacitive deionization of NaTi₂(PO₄)₃/carbon materials by the yolk–shell design. J. Am. Chem. Soc., 2023, 145169242.

[19] LuDH, ZhangJJ, WeiZB, WangZB. Reducing atmosphere improves the conductivity of NaTi₂(PO₄)₃/C material for hybrid aqueous rechargeable lithium-ion battery anode. Ceram. Int., 2022, 481826408.

[20] QinXH, DuYH, ZhangPC, et al.. Layered barium vanadate nanobelts for high-performance aqueous zinc-ion batteries. Int. J. Miner. Metall. Mater., 2021, 28101684.

[21] WuJT, YangLX, LiuHJ, et al.. Effect of Al doping on electrochemical performance of NaTi₂(PO₄)₃/C anode for aqueous sodium ion battery. J. Appl. Electrochem., 2022, 52111563.

[22] LiuXJ, LiZF, ZhongXH, WangCX, DmytroS. Dual strategy of La³⁺ doping and carbon coating enhancing the rate performance of NaTi₂(PO₄)₃ anode materials. Ionics, 2024, 3031437.

[23] Z. Tang, S.Y. Zhou, Y.C. Huang, et al., Improving the initial coulombic efficiency of carbonaceous materials for Li/Na-ion batteries: Origins, solutions, and perspectives, Electrochem. Energy Rev., 6(2023), No. 1, art. No. 8.

[24] T. Xu, M.S. Zhao, Z. Li, et al., A high rate and long cycling performance NaTi₂(PO₄)₃ core–shell porous nanosphere anode for aqueous sodium-ion batteries, Energy Technol., 10(2022), No. 11, art. No. 2200970.

[25] M.L. Lu, T. Li, X.Q. Yang, Y. Liu, and X.D. Xiang, A liquidphase reaction strategy to construct aqueous sodium-ion batteries anode with enhanced redox reversibility and cycling stability, Chem. Eng. Sci., 274(2023), art. No. 118700.

[26] WuC, KopoldP, DingYL, van AkenPA, MaierJ, YuY. Synthesizing porous NaTi₂(PO₄)₃ nanoparticles embedded in 3D graphene networks for high-rate and long cycle-life sodium electrodes. ACS Nano, 2015, 966610.

[27] Y.L. Wu, Q. Zou, C.L. Li, and W.H. Wang, Structural reinforced NaTi₂(PO₄)₃ composite by pillar effects for constructing a high-performance rocking-chair desalination battery, Chem. Eng. J., 480(2024), art. No. 147965.

[28] GuJJ, ZhangSJ, ZhangXY, et al.. NaSn_0.02Ti_1.98(PO₄)₃/C as a promising anode material with high performance for sodium-ion batteries. J. Solid State Electrochem., 2024, 2872093.

[29] S. Difi, I. Saadoune, M.T. Sougrati, R. Hakkou, K. Edstrom, and P.E. Lippens, Role of iron in Na_1.5Fe_0.5Ti_1.5(PO₄)₃/C as electrode material for Na-ion batteries studied by operando Mössbauer spectroscopy, Hyperfine Interact., 237(2016), No. 1, art. No. 61.

[30] J.T. Wu, H.J. Liu, H.P. Bu, et al., Manganese-based NASICON structured Na_1+2xMn_xTi_2−x(PO₄)₃ as promising cathode in aqueous sodium ion battery, J. Alloy. Compd., 934(2023), art. No. 167872.

[31] Y.K. Xi, X.X. Wang, H. Wang, et al., Optimizing the electron spin states of Na₄Fe₃(PO₄)₂P₂O₇ cathodes via Mn/F dual-doping for enhanced sodium storage, Adv. Funct. Mater., 34(2024), No. 16, art. No. 2309701.

[32] WeiP, LiuYX, SuYR, et al.. F-doped NaTi₂(PO₄)₃/C nano-composite as a high-performance anode for sodium-ion batteries. ACS Appl. Mater. Interfaces, 2019, 1133116.

[33] WangQC, HeS, ChenH, et al.. Tailoring the electronic structure of the NaTi₂(PO₄)₃ anode for high-performing sodium-ion batteries via defect engineering. Green Chem., 2024, 2642114.

[34] B. He, K.B. Yin, W.B. Gong, et al., NaTi₂(PO₄)₃ hollow nanoparticles encapsulated in carbon nanofibers as novel anodes for flexible aqueous rechargeable sodium-ion batteries, Nano Energy, 82(2021), art. No. 105764.

[35] A. Mukherjee, S. Banerjee, and S.B. Majumder, Improvement of sodium storage performance of N-doped carbon coated NaTi₂(PO₄)₃ derived from polyvinyl pyrrolidone, J. Mater. Sci. Mater. Electron., 34(2023), No. 21, art. No. 1602.

[36] J.R. He and A. Manthiram, 3D CoSe@C aerogel as a host for dendrite-free lithium-metal anode and efficient sulfur cathode in Li–S full cells, Adv. Energy Mater., 10(2020), No. 41, art. No. 2002654.

[37] J. Qin, T.S. Wang, D.Y. Liu, et al., A top-down strategy toward SnSb in-plane nanoconfined 3D N-doped porous graphene composite microspheres for high performance Na-ion battery anode, Adv. Mater., 30(2018), No. 9, art. No. 1704670.

[38] RenWN, ZangWJ, ZhangHF, et al.. PtCo bimetallic nanoparticles encapsulated in N-doped carbon nanorod arrays for efficient electrocatalysis. Carbon, 2019, 142206.

[39] Y. Liu, X. Liu, X.Y. Wang, et al., Synergistic bimetallic effects of BiSb anodes enable long-stable sodium storage, Adv. Funct. Mater., 35(2025), No. 6, art. No. 2415092.

[40] CaoKZ, MaJH, DongYL, et al.. Graphitic carbons: Preparation, characterization, and application on K-ion batteries. Rare Met., 2024, 4394056.

[41] LiJB, LiZQ, TangSC, et al.. Sodium titanium phosphate nanocube decorated on tablet-like carbon for robust sodium storage performance at low temperature. J. Colloid Interface Sci., 2023, 629121.

[42] X. Liu, M.L. Zhang, X.Y. Wang, et al., Evidence of quasi-Na metallic clusters in sodium ion batteries through in situ X-ray diffraction, Adv. Mater., 37(2025), No. 1, art. No. 2410673.

[43] PlečkaitytėG, PetrulevičienėM, StaišiūnasL, et al.. Understanding and mitigation of NaTi₂(PO₄)₃ degradation in aqueous Na-ion batteries. J. Mater. Chem. A, 2021, 92112670.

[44] B. Luo, W.G. Wang, Q. Wang, et al., Facilitating ionic conductivity and interfacial stability via oxygen vacancies-enriched TiO₂ microrods for composite polymer electrolytes, Chem. Eng. J., 460(2023), art. No. 141329.

[45] H. Gao, W.L. Gao, and M. Pumera, 3D-printed nanostructured copper substrate boosts the sodiated capability and stability of antimony anode for sodium-ion batteries, Adv. Funct. Mater., 34(2024), No. 19, art. No. 2310563.

[46] UbbinkRF, GudjonsdottirS, VogelYB, HoutepenAJ. Numerical model to simulate electrochemical charging of nanocrystal films. J. Phys. Chem. C, 2023, 127209896.

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