One-step synthesis of novel core-shell bimetallic hexacyanoferrate for high performance sodium-storage cathode

doi:10.1016/j.jmst.2021.11.020

Abstract

Abstract:

Recently, the design of core-shell hierarchical architecture plays an important role in improving the electrochemical performance of Prussian blue analogue cathodes (PBAs). Unfortunately, the inconvenient stepwise preparation and the strict lattice-matching requirement have restricted the development of core-shell PBAs. Herein, we demonstrate a one-step synthesis strategy to synthesize core-shell manganese hexacyanoferrate (MnFeHCF@MnFeHCF) for the first time. And the formation mechanism of the core-shell hierarchical architecture is investigated by first-principles calculations. It is found that the as-obtained MnFeHCF@MnFeHCF act out the superior intrinsic natures, which not only can obtain a larger specific surface area and lower Fe(CN)₆ vacancies but also can activate more Na-storage sites. Compared with the manganese hexacyanoferrate (MnHCF), the iron hexacyanoferrate (FeHCF), and even the traditional core-shell nickel hexacyanoferrate (FeHCF@NiHCF) prepared by a stepwise method, the MnFeHCF@MnFeHCF demonstrates a superior rate performance, which achieves a high capacity of 131 mAh g^-1 at 50 mA g^-1 and delivers a considerable discharge capacity of about 100 mAh g^-1 even at 1600 mA g^-1. Meantime, the capacity retention can reach up to nearly 80% after 500 cycles. The improved performances could be mainly originated from two aspects: on the one hand, Mn substitution is helpful to enhance the material conductivity; on the other hand, the core-shell structure with matched lattice parameters is more favorable to enhance the diffusion coefficient of sodium ions. Beside, the structural transformation of MnFeHCF@MnFeHCF upon the extraction/insertion of sodium ions is instrumental in releasing the interior stress and effectively maintaining the integrity of the crystal structure.

Key words: Cathode, Prussian blue analogue, Core-shell structure, First-principles calculations, Electrochemical performance

Daxian Zuo, Cuiping Wang, Jiajia Han, Qinghao Han, Yanan Hu, Junwei Wu, Huajun Qiu, Qian Zhang, Xingjun Liu. One-step synthesis of novel core-shell bimetallic hexacyanoferrate for high performance sodium-storage cathode[J]. J. Mater. Sci. Technol., 2022, 114: 180-190.

Figures/Tables 7

Fig. 1. (a) Preparation process of MnFeHCF@MnFeHCF core-shell material; (b) MnFeHCF@MnFeHCF samples synthesized under different Fe/Mn molar ratios; (c) Disordered crystal structure and (f) corresponding charge density difference; (d) The ordered crystal structure and (g) corresponding charge density difference; (e, h) Calculated XRD patterns of ordered and disordered crystal structure.

Fig. 2. (a) XRD patterns of different samples; TG and DTG curves of (b) MnFeHCF@MnFeHCF core-shell material and (e) FeHCF@NiHCF core-shell material; (c, f) FTIR spectra of different materials; (d) Nitrogen adsorption-desorption isotherms of different samples; (g) XPS surveys of all samples; (h) Mn 2p spectrum of MnFeHCF@MnFeHCF core-shell material; (i) Ni 2p spectrum of FeHCF@NiHCF core-shell material.

Fig. 3. Morphology characterizations of MnFeHCF@MnFeHCF core-shell material: (a) SEM image; (b) TEM image; (c) The corresponding SAED patterns; (d, e) STEM images in different modes; (f-k) The energy dispersive spectroscopy mapping images. Morphology characterizations of FeHCF@NiHCF core-shell material: (l) SEM image; (m) TEM image; (n) The corresponding SAED patterns; (o, p) STEM images in different modes; (q-v) The energy dispersive spectroscopy mapping images.

Fig. 4. CV curves of different samples measured at a scan rate of 0.1 mV s-1: (a) MnFeHCF@MnFeHCF core-shell electrode; (b) FeHCF@NiHCF core-shell electrode; (c) FeHCF electrode. (d) Rate performances of different three samples; Corresponding charge and discharge curves of (e) MnFeHCF@MnFeHCF and (f) FeHCF@NiHCF electrodes at different current densities. (g) Cycle performance of different three electrodes at current density of 200 mA g-1.

Fig. 5. GITT curves and corresponding Na+ ion diffusion coefficients upon charging/discharging: (a) MnFeHCF@MnFeHCF core-shell material; (d) FeHCF@NiHCF core-shell material. CV curves of (b) MnFeHCF@MnFeHCF and (e) FeHCF@NiHCF with different scan rates of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1 mV s-1. Linear plots of the relationship between Ip and ν-1/2 for both the anodic and cathodic scans of (c) MnFeHCF@MnFeHCF and (f) FeHCF@NiHCF. Schematic illustration of extraction/insertion process of Na+ ions between shell and core during the first cycle: (g) FeHCF@NiHCF; (h) MnFeHCF@MnFeHCF.

Fig. 6. (a) Ex-situ XRD results of MnFeHCF@MnFeHCF at different charge and discharge states, enlarged view showing the shift of the (220) diffraction peak are on the left column, the charge/discharge voltage curve is on the right column; (b) Schematic diagrams for the phase transformation during charge and discharge; (c, d) The morphologies of MnFeHCF@MnFeHCF core-shell material after 500 cycling; (e) Mn 2p spectrum of MnFeHCF@MnFeHCF core-shell material under different charge and discharge states; (f) Corresponding XRD patterns before and after cycling.

Fig. 7. (a) Total and partial densities of states (DOS) for the Na, Fe and Mn in the Na2FeFe(CN)6 and Na2Mn2/3Fe1/3Fe(CN)6; Band structure of (b) Na2FeFe(CN)6 and (c) Na2Mn2/3Fe1/3Fe(CN)6; Crystal structure of PBA compounds with different sodium concentration, among them, the yellow ball represents the sodium atom: (d) NaxFeFe(CN)6 compound, (e) NaxNiFe(CN)6 compound, (f) NaxFeFe(CN)6@NaxNiFe(CN)6 compound; Electrostatic potential of PBA compounds with different sodium concentration: (g) NaxFeFe(CN)6 compound, (h) NaxFeFe(CN)6@NaxNiFe(CN)6 compound.

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