Polypyrrole-coated triple-layer yolk-shell Fe₂O₃ anode materials with their superior overall performance in lithium-ion batteries

Abstract

Iron oxide (Fe₂O₃) emerges as a highly attractive anode candidate among rapidly expanding energy storage market. Nonetheless, its considerable volume changes during cycling as an electrode material result in a vast reduced battery cycle life. In this work, an approach is pioneered for preparing high-performance Fe₂O₃ anode materials, by innovatively synthesizing a triple-layer yolk-shell Fe₂O₃ uniformly coated with a conductive polypyrrole (Ppy) layer (Fe₂O₃@Ppy-TLY). The uniform polypyrrole coating introduces more reaction sites and adsorption sites, and maintains structure stability through charge-discharge process. In the uses as lithium-ion battery electrodes, Fe₂O₃@Ppy-TLY demonstrates high reversible specific capacity (maintaining a discharge capacity of 1375.11 mAh·g⁻¹ after 500 cycles at 1 C), exceptional cycling stability (retaining the steady charge-discharge performance at 544.33 mAh·g⁻¹ after 6000 ultrafast charge-discharge cycles at a 10 C current density), and outstanding high current charge-discharge performance (retaining a reversible capacity of 156.75 mAh·g⁻¹ after 10000 cycles at 15 C), thereby exhibiting superior lithium storage performance. This work introduces innovative advancements for Fe₂O₃ anode design, aiming to enhance its performance in energy storage fields.

Keywords

Fe₂O₃ / structure design / anode material / lithium-ion battery

References

[1] J.X. Sun, L.Q. Ye, X.R. Zhao, P.P. Zhang, and J. Yang, Electronicmodulation and structural engineering of carbon-based anodes for low-temperature lithium-ion batteries: A review, Molecules, 28(2023), No. 5, art. No. 2108.

[2] Hu PF, Meng CF, Li FG, et al. . Hierarchical multi-yolk-shell copper oxide@copper-1,3,5-benzenetricarboxylate as an ultrastable anode for lithium ion batteries. J. Colloid Interface Sci.. 2022, 617: 568

[3] L. Chen, M.R. Yang, F. Kong, J.Y. Guo, H.B. Shu, and J. Dai, Metallic penta-graphene/penta-BN₂ heterostructure with high specific capacity: A novel application platform for Li/Na-ion batteries, J. Alloys Compd., 901(2022), art. No. 163538.

[4] Chen JL, Guo XM, Gao MY, et al. . Self-supporting dual-confined porous Si@c-ZIF@carbon nanofibers for high-performance lithium-ion batteries. Chem. Commun.. 2021, 57(81): 10580

[5] Xu JJ, Wang D, Kong SY, Li RZ, Hong ZL, Huang FQ. Pyrochlore phase Ce₂Sn₂O₇ via an atom-confining strategy for reversible lithium storage. J. Mater. Chem. A. 2020, 8(11): 5744

[6] Zhang D, Zhang CY, Zheng X, et al. . Facile synthesis of the Mn₃O₄ polyhedron grown on N-doped honeycomb carbon as high-performance negative material for lithium-ion batteries. Int. J. Miner. Metall. Mater.. 2023, 30(6): 1152

[7] Chen L, Yang MR, Kong F, Du WL, Guo JY, Shu HB. Penta-BCN monolayer with high specific capacity and mobility as a compelling anode material for rechargeable batteries. Phys. Chem. Chem. Phys.. 2021, 23(32): 17693

[8] P. Wang, M.Q. Shen, H. Zhou, C.F. Meng, and A.H. Yuan, MOF-derived CuS@Cu-BTC composites as high-performance anodes for lithium-ion batteries, Small, 15(2019), No. 47, art. No. 1903522.

[9] Yu J, Wei YB, Meng BC, et al. . Homogeneous distributed natural pyrite-derived composite induced by modified graphite as high-performance lithium-ion batteries anode. Int. J. Miner. Metall. Mater.. 2023, 30(7): 1353

[10] K. Cao, L. Jiao, H. Liu, et al., 3D Hierarchical porous α-Fe₂O₃ nanosheets for high-performance lithium-ion batteries, Adv. Energy Mater., 5(2015), No. 4, art. No. 1401421.

[11] Zhao JF, Zhang SC, Liu WB, Du ZJ, Fang H. Fe₃O₄/PPy composite nanospheres as anode for lithium-ion batteries with superior cycling performance. Electrochim. Acta. 2014, 121: 428

[12] B. Li, T. Zhang, S.H. Wei, and W. Gao, Nitrogen-doped carbon hollow spheres packed with multiple nano Sn particles for enhanced lithium storage, Chem. Eng. J., 446(2022), art. No. 136768.

[13] B. Li, W. Zhang, T. Zhang, S.H. Wei, and W. Gao, Accurately tailoring yolk-shell spheres to balance cycling stability and volumetric capacity of lithium storage, J. Alloys Compd., 917(2022), art. No. 165548.

[14] G.L. Xia, Q.L. Gao, D.L. Sun, and X.B. Yu, Porous carbon nanofibers encapsulated with peapod-like hematite nanoparticles for high-rate and long-life battery anodes, Small, 13(2017), No. 44, art. No. 1701561.

[15] Jeong JM, Choi BG, Lee SC, et al. . Hierarchical hollow spheres of Fe₂O₃@Polyaniline for lithium ion battery anodes. Adv. Mater.. 2013, 25(43): 6250

[16] Y.C. Chen, C.X. Kang, L. Ma, et al., MOF-derived Fe₂O₃ decorated with MnO₂ nanosheet arrays as anode for high energy density hybrid supercapacitor, Chem. Eng. J., 417(2021), art. No. 129243.

[17] C. Park, E. Samuel, B. Joshi, et al., Supersonically sprayed Fe₂O₃/C/CNT composites for highly stable Li-ion battery anodes, Chem. Eng. J., 395(2020), art. No. 125018.

[18] Choi YS, Choi W, Yoon WS, Kim JM. Unveiling the genesis and effectiveness of negative fading in nanostructured iron oxide anode materials for lithium-ion batteries. ACS Nano. 2022, 16(1): 631

[19] Chen XY, Sawut N, Chen KA, et al. . Filling carbon: A microstructure-engineered hard carbon for efficient alkali metal ion storage. Energy Environ. Sci.. 2023, 16(9): 4041

[20] H. Kim, J.C. Hyun, D.H. Kim, et al., Revisiting lithium- and sodium-ion storage in hard carbon anodes, Adv. Mater., 35(2023), No. 12, art. No. 2209128.

[21] Han WJ, Qin XY, Wu JX, et al. . Electrosprayed porous Fe₃O₄/carbon microspheres as anode materials for high-performance lithium-ion batteries. Nano Res.. 2018, 11(2): 892

[22] Zhang SY, Zhang PG, Xie AJ, Li SK, Huang FZ, Shen YH. A novel 2D porous print fabric-like α-Fe₂O₃ sheet with high performance as the anode material for lithium-ion battery. Electrochim. Acta. 2016, 212: 912

[23] Huang H, Kong LJ, Shuang W, Xu W, He J, Bu XH. Controlled synthesis of core-shell Fe₂O₃@N-C with ultralong cycle life for lithium-ion batteries. Chin. Chem. Lett.. 2022, 33(2): 1037

[24] X.Y. Hou, J.L. Kang, G. Zhou, and J.T. Wang, Preparation of Fe₂O₃@C composite with octahedron-like Fe₂O₃ embedded in carbon framework as a superior anode for LIBs, Mater. Lett., 313(2022), art. No. 131736.

[25] Z.X. Lu, J. Wang, W.L. Feng, et al., Zinc single-atom regulated hard carbons for high rate and low temperature sodium ion batteries, Adv. Mater., 35(2023), No. 26, art. No. 2211461.

[26] F.P. Chen, Y.J. Di, Q. Su, et al., Vanadium-modified hard carbon spheres with sufficient pseudographitic domains as highperformance anode for sodium-ion batteries, Carbon Energy, 5(2023), No. 2, art. No. e191.

[27] H.Y. Wang, H.X. Chen, C. Chen, et al., Tea-derived carbon materials as anode for high-performance sodium ion batteries, Chin. Chem. Lett., 34(2023), No. 4, art. No. 107465.

[28] C. Zhao, Z.F. Yan, B. Zhou, et al., Identifying the role of lewis-base sites for the chemistry in lithium-oxygen batteries, Angew. Chem. Int. Ed., 62(2023), No. 32, art. No. e202302746.

[29] Zhang LL, Wang T, Gao TN, et al. . Multistage self-assembly strategy: Designed synthesis of N-doped mesoporous carbon with high and controllable pyridine N content for ultrahigh surface-area-normalized capacitance. CCS Chem.. 2021, 3(2): 870

[30] Arrigo R, Hävecker M, Wrabetz S, et al. . Tuning the acid/base properties of nanocarbons by functionalization via amination. J. Am. Chem. Soc.. 2010, 132(28): 9616

[31] Mao JY, Niu DC, Zheng N, et al. . Fe₃O₄-embedded and N-doped hierarchically porous carbon nanospheres as high-performance lithium ion battery anodes. ACS Sustainable Chem. Eng.. 2019, 7(3): 3424

[32] P. Bhattacharya, M. Kota, D.H. Suh, K.C. Roh, and H.S. Park, Biomimetic spider-web-like composites for enhanced rate capability and cycle life of lithium ion battery anodes, Adv. Energy Mater., 7(2017), No. 17, art. No. 1700331.

[33] Yang ZC, Shen JG, Archer LA. An in situ method of creating metal oxide-carbon composites and their application as anode materials for lithium-ion batteries. J. Mater. Chem.. 2011, 21(30): 11092

[34] Yang Y, Li JQ, Chen DQ, Zhao JB. A facile electro-phoretic deposition route to the Fe₃O₄/CNTs/rGO composite electrode as a binder-free anode for lithium ion battery. ACS Appl. Mater. Interfaces. 2016, 8(40): 26730

[35] Ma FX, Wu HB, Xu CY, Zhen L, David Lou XW. Self-organized sheaf-like Fe₃O₄/C hierarchical microrods with superior lithium storage properties. Nanoscale. 2015, 7(10): 4411

[36] Kong LP, Zhu YT, Williams PJ, Kabbani M, Brushett FR, Rupp JLM. Insights into Li⁺ storage mechanisms, kinetics, and reversibility of defect-engineered and functionalized multi-walled carbon nanotubes for enhanced energy storage. J. Mater. Chem. A. 2024, 12(7): 4299

[37] Kim JH, Park GD, Kang YC. Amorphous iron oxide-selenite composite microspheres with a yolk-shell structure as highly efficient anode materials for lithium-ion batteries. Nanoscale. 2020, 12(19): 10790

[38] Huang X, Yu H, Chen J, Lu ZY, Yazami R, Hng HH. Ultrahigh rate capabilities of lithium-ion batteries from 3D ordered hierarchically porous electrodes with entrapped active nanoparticles configuration. Adv. Mater.. 2014, 26(8): 1296

[39] Lee SH, Yu SH, Lee JE, et al. . Self-assembled Fe₃O₄ nanoparticle clusters as high-performance anodes for lithium ion batteries via geometric confinement. Nano Lett.. 2013, 13(9): 4249

[40] Liu L, Yang XF, Lv CX, et al. . Seaweed-derived route to Fe₂O₃ hollow nanoparticles/N-doped graphene aerogels with high lithium ion storage performance. ACS Appl. Mater. Interfaces. 2016, 8(11): 7047

[41] Su LW, Zhong YR, Zhou Z. Role of transition metal nanoparticles in the extra lithium storage capacity of transition metal oxides: A case study of hierarchical core-shell Fe₃O₄@C and Fe@C microspheres. J. Mater. Chem. A. 2013, 1(47): 15158

[42] Yuan TZ, Jiang YZ, Sun WP, et al. . Ever-increasing pseudocapacitance in RGO-MnO-RGO sandwich nanostructures for ultrahigh-rate lithium storage. Adv. Funct. Mater.. 2016, 26(13): 2198

[43] Ma YT, Huang J, Liu X, et al. . 3D graphene-encapsulated hierarchical urchin-like Fe₃O₄ porous particles with enhanced lithium storage properties. Chem. Eng. J.. 2017, 327: 678

[44] H. Wu, G.H. Yu, L.J. Pan, et al., Stable Li-ion battery anodes by in situ polymerization of conducting hydrogel to conformally coat silicon nanoparticles, Nat. Commun., 4(2013), art. No. 1943.

[45] Zhou XS, Wan LJ, Guo YG. Binding SnO₂ nanocrystals in nitrogen-doped graphene sheets as anode materials for lithium-ion batteries. Adv. Mater.. 2013, 25(15): 2152

[46] J.H. Zhao, X.X. He, W.H. Lai, et al., Catalytic defect-repairing using manganese ions for hard carbon anode with high-capacity and high-initial-coulombic-efficiency in sodium-ion batteries, Adv. Energy Mater., 13(2023), No. 18, art. No. 2300444.

[47] Guo JC, Liu Q, Wang CS, Zachariah MR. Interdispersed amorphous MnO_x-carbon nanocomposites with superior electrochemical performance as lithium-storage material. Adv. Funct. Mater.. 2012, 22(4): 803

[48] Santhoshkumar P, Prasanna K, Jo YN, Sivagami IN, Kang SH, Lee CW. A facile and highly efficient short-time homogenization hydrothermal approach for the smart production of high-quality α-Fe₂O₃ for rechargeable lithium batteries. J. Mater. Chem. A. 2017, 5(32): 16712

[49] Hong M, Su YJ, Zhou C, et al. . Scalable synthesis of γ-Fe₂O₃/CNT composite as high-performance anode material for lithium-ion batteries. J. Alloys Compd.. 2019, 770: 116

[50] Huang P, Tao W, Wu HX, et al. . N-doped coaxial CNTs@α-Fe₂O₃@C nanofibers as anode material for high performance lithium ion battery. J. Energy Chem.. 2018, 27(5): 1453

[51] Li M, Du HR, Kuai L, Huang KF, Xia YY, Geng BY. Scalable dry production process of a superior 3D net-like carbon-based iron oxide anode material for lithium-ion batteries. Angew. Chem. Int. Ed.. 2017, 56(41): 12649

[52] Du ZZ, Chen XJ, Hu W, et al. . Cobalt in nitrogen-doped graphene as single-atom catalyst for high-sulfur content lithium-sulfur batteries. J. Am. Chem. Soc.. 2019, 141(9): 3977