In-situ encapsulation of α-Fe2O3 nanoparticles into ZnFe2O4 micro-sized capsules as high-performance lithium-ion battery anodes

doi:10.1016/j.jmst.2020.10.039

Abstract

Abstract:

Transition metal oxides as anode materials for high-performance lithium-ion batteries suffer from severe capacity decay, originating primarily from particle pulverization upon volume expansion/shrinkage and the intrinsically sluggish electron/ion transport. Herein, in-situ encapsulation of α-Fe₂O₃ nanoparticles into micro-sized ZnFe₂O₄ capsules is facilely fulfilled through a co-precipitation process and followed by heat-treatment at optimal calcination temperature. The porous ZnFe₂O₄ scaffold affords a synergistic confinement effect to suppress the grain growth of α-Fe₂O₃ nanocrystals during the calcination process and to accommodate the stress generated by volume expansion during the charge/discharge process, leading to an enhanced interfacial conductivity and inhibit electrode pulverization and mechanical failure in the active material. With these merits, the prepared α-Fe₂O₃/ZnFe₂O₄ composite delivers prolonged cycling stability and improved rate capability with a higher specific capacity than sole α-Fe₂O₃ and ZnFe₂O₄. The discharge capacity is retained at 700 mAh g^-1 after 500 cycles at 200 mA g^-1 and 940 mAh g^-1 after 50 cycles at 100 mA g^-1. This work provides a new perspective in designing transition metal oxides for advanced lithium-ion batteries with superior electrochemical properties.

Key words: α-Fe₂O₃/ZnFe₂O₄ ceramic composite, Co-precipitation process, Confinement effect, Interfacial effect, Grain growth, High conductivity, Lithium-ion battery anodes

Wei Wu, Yongshan Wei, Hongjiang Chen, Keyan Wei, Zhitong Li, Jianhui He, Libo Deng, Lei Yao, Haitao Yang. In-situ encapsulation of α-Fe₂O₃ nanoparticles into ZnFe₂O₄ micro-sized capsules as high-performance lithium-ion battery anodes[J]. J. Mater. Sci. Technol., 2021, 75: 110-117.

Figures/Tables 5

Fig. 1. Illustration of the synthesis process of the capsule-like α-Fe2O3/ZnFe2O4 micro-sized composite.

Fig. 2. (a) XRD patterns of the as-prepared α-Fe2O3, α-Fe2O3/ZnFe2O4 and ZnFe2O4 under varied thermal-annealing temperatures. XPS spectra of the α-Fe2O3/ZnFe2O4 composite: (b) survey scan, (c-e) Fe 2p, Zn 2p and O 1s spectra with high-resolution, respectively.

Fig. 3. SEM images of (a) α-Fe2O3 annealed at 350 ℃, (b) α-Fe2O3/ZnFe2O4 composite annealed at 450 ℃, and (c) ZnFe2O4 annealed at 550 ℃. (d, e) TEM and HRTEM images of α-Fe2O3/ZnFe2O4, respectively. (f-i) HAADF image and the EDS elemental mappings of Fe, Zn, O of α-Fe2O3/ZnFe2O4, respectively.

Fig. 4. (a-c) Charge/discharge profiles of α-Fe2O3, ZnFe2O4, and α-Fe2O3/ZnFe2O4, respectively, for the initial cycles between 0.01 and 3 V at 200 mA g-1. (d) CV profile of α-Fe2O3/ZnFe2O4 with the first 6 cycles between 0.01 and 3 V at a scan rate of 0.2 mV s-1. (e) Impedance spectra (inset shows the enlargements) and (f) the fitting of electron mobility for α-Fe2O3/ZnFe2O4, α-Fe2O3 and ZnFe2O4 electrodes. (g) Rate capability tested under different specific currents and (h) cycling performances of α-Fe2O3/ZnFe2O4 comparing with α-Fe2O3 and ZnFe2O4 at 200 mA g-1 for 500 cycles. (i) Cycling stability test of α-Fe2O3/ZnFe2O4 under different mass loadings and areal capacities at 100 mA g-1 for 50 cycles. (j) Areal capacity versus mass loading for the data shown in f, and the fit slope indicates the specific capacity. (k) CV curves at various sweep rates from 0.05 to 1.6 mV s-1. (l) The determination of b-value using the linear fitting plot of the peak currents to sweep rates of α-Fe2O3/ZnFe2O4.

Fig. 5. SEM images of the α-Fe2O3/ZnFe2O4 after (a, b) 100 cycles, (c, d) 200 cycles, (e, f) 500 cycles.

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In-situ encapsulation of α-Fe₂O₃ nanoparticles into ZnFe₂O₄ micro-sized capsules as high-performance lithium-ion battery anodes

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