Microstructure controlled synthesis of Ni, N-codoped CoP/carbon fiber hybrids with improving reaction kinetics for superior sodium storage

doi:10.1016/j.jmst.2021.05.034

Abstract

Abstract:

Transition-metal phosphides (TMPs)-based hybrid structure have received considerable attention for efficient sodium storage owing to their high capacity and decent reversibility. However, the volume expansion & the poor electronic conductivity of TMPs, the poor-rate capability, and fast capacity decay greatly hinder its practical application. To address these issues, a low-cost and facile strategy for the synthesis of Ni, N-codoped graphitized carbon (C) and cobalt phosphide (CoP) embedded in carbon fiber (Ni-CoP@C-N⊂CF) as self-supporting anode material is demonstrated for the first time. The graphitized carbon and carbon fiber improve the electrical conductivity and inhibit the volume expansion issues. In addition to that, the microporous structure, and ultrasmall sized Ni-CoP offer a high surface area for electrolyte wettability, short Na-ion diffusion path and fast charge transport kinetics. As a result, outstanding electrochemical performance with an average capacity decay of 0.04% cycle^-1 at 2000 mA g^-1, an excellent rate capability of 270 mAh g^-1@2000 mA g^-1 and a high energy density of ~231.1 Wh kg^-1 is achieved with binder-free self-supporting anode material. This work shows a potential for designing binder-free and high energy density sodium-ion batteries.

Key words: Ultrasmall Ni-CoP, Carbon shell, Microporous structure, High Na⁺ diffusion coefficients, Sodium-ion batteries

Huijun Li, Xiaomin Wang, Zhenxin Zhao, Rajesh Pathak, Siyue Hao, Xiaoming Qiu, Qiquan Qiao. Microstructure controlled synthesis of Ni, N-codoped CoP/carbon fiber hybrids with improving reaction kinetics for superior sodium storage[J]. J. Mater. Sci. Technol., 2022, 99: 184-192.

Figures/Tables 7

Fig. 1. (a) Illustrates the preparation process for Ni-CoP@C-N?CF electrode; (b) The XRD pattern of Ni-CoP@C-N; (c) The SEM images and EDS map of Ni-CoP@C-N; The TEM images: (d) low-resolution of Ni-CoP@C-N, (e) high-resolution of Ni-CoP@C-N; (f) N2 adsorption desorption isotherms and pore size distribution of Ni2P@C-N, Ni-CoP@C-N and CoP@C-N.

Fig. 2. (a) SEM and elemental mapping images; (b) XRD patterns of Ni-CoP@C-N?CF and CF; XPS spectrum: high-resolution XPS spectrum (c) Co 2p, (d) Ni 2p and (e) P 2p.

Fig. 3. (a) Cycling performance of Ni-CoP@C-N?CF, Ni-CoP@C-N, CoP@C-N and Ni2P@C-N; (b) Comparison data of cycle performance in different literatures [[35], [36], [37], [38], [39], [40], [41], [42], [43], [44], [45]]; (c) Rate capability of Ni-CoP@C-N?CF, Ni-CoP@C-N, CoP@C-N and Ni2P@C-N; (d) Comparison data of rate performance in different literatures [10,35,[42], [43], [44], [45], [46], [47], [48], [49], [50]] and (e) The long cycling performance of Ni-CoP@C-N?CF at current density of 2000 mA g-1.

Fig. 4. (a) Contour plots and (b) stacked patterns of in situ XRD patterns of Ni-CoP@C-N on aluminum foil during the first discharging/charging.

Fig. 5. (a) SEM images of Ni-CoP@C-N?CF after 300 cycles; (b-c) TEM image of Ni-CoP@C-N?CF after 300 cycles; (d) Schematic illustration of the sodiation-desodiation process of Ni-CoP@C-N?CF.

Fig. 6. (a) CV curves of Ni-CoP@C-N?CF at various scan rates; (b) Relationship between lg (v) and lg (i); (c) The capacitive fraction of Ni-CoP@C-N?CF at 0.6 mV s-1; (d) Fraction of capacitive and diffusion-controlled behavior of Ni-CoP@C-N?CF at various sweep rates.

Fig. 7. (a) Schematic of the full cell assembled with Ni-CoP@C-N?CF and NVP; (b) the charge/discharge curves of Ni-CoP@C-N?CF and NVP in Na+ half-cell; (c) Cycling performance of Ni-CoP@C-N?CF//NVP at current density 200 mA g-1; (d) Ragone plots of the Ni-CoP@C-N?CF//NVP [48,[58], [59], [60], [61], [62]] and a digital image lit by Ni-CoP@C-N?CF//NVP full cell.

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