P-doped CoSe2 nanoparticles embedded in 3D honeycomb-like carbon network for long cycle-life Na-ion batteries

doi:10.1016/j.jmst.2020.10.045

Abstract

Abstract:

We report for the first time a Na-ion battery anode material composed of P-doped CoSe₂ nanoparticles (P-CoSe₂) with the size of 5-20 nm that are uniformly embed in a 3D porous honeycomb-like carbon network. High rate capability and cycling stability are achieved simultaneously. The honeycomb-like carbon network is rationally designed to support high electrical conductivity, rapid Na-ion diffusion as well as the accommodation of the volume expansion from the active P-CoSe₂ nanoparticles. In particular, heteroatom P-doping within CoSe₂ introduces stronger P-Co bonds and additional P-Se bonds that significantly improve the structure stability of P-CoSe₂ for highly stable sodiation/desodiation over long-term cycling. P-doping also improves the electrical conductivity of the CoSe₂ nanoparticles, leading to highly elevated electrochemical kinetics to deliver high specific capacities at high current densities. Benefiting from the unique nanostructure and atomic-level P-doping, the P-CoSe₂(2:1)/C anode delivers an excellent cycle stability with a specific capacity of 206.9 mA h g^-1 achieved at 2000 mA g^-1 after 1000 cycles. In addition, this material can be synthesized using a facile pyrolysis and selenization/phosphorization approach. This study provides new opportunities of heteroatom doping as an effective method to improve the cycling stability of Na-ion anode materials.

Key words: CoSe₂, P-doping, Honeycomb-like carbons, Anodes, Sodium-ion batteries

Jiajia Ye, Xuting Li, Guang Xia, Guanghao Gong, Zhiqiang Zheng, Chuanzhong Chen, Cheng Hu. P-doped CoSe₂ nanoparticles embedded in 3D honeycomb-like carbon network for long cycle-life Na-ion batteries[J]. J. Mater. Sci. Technol., 2021, 77: 100-107.

Figures/Tables 5

Fig. 1. (a) Schematic illustration of the synthesis route of the P-CoSe2(2:1)/C composite. (b) SEM image of the P-CoSe2(2:1)/C composite. (c) XRD patterns of the Co/C, CoSe2/C and P-CoSe2(2:1)/C composites. (d) XRD patterns of the CoSe2/C and P-CoSe2(2:1)/C composites showing the shifts of diffraction peaks induced by P-doping.

Fig. 2. (a) TEM and (b) HRTEM images of the P-CoSe2(2:1)/C composite. (c) HAADF image of the P-CoSe2(2:1)/C composite and its corresponding EDS elemental mappings of C, Co, P and Se. XPS spectra of the CoSe2/C and P-CoSe2(2:1)/C composites: (d) Co 2p, (e) Se 3d and (f) P 2p.

Fig. 3. (a) CV profiles of P-CoSe2(2:1)/C with a scan rate of 0.2?mV s-1. Galvanostatic charge/discharge profiles of (b) CoSe2/C and (c) P-CoSe2(2:1)/C from various cycles at 200?mA g-1. (d) Charge/discharge cycling performance of CoSe2/C, P-CoSe2(1:1)/C, P-CoSe2(2:1)/C, P-CoSe2(3:1)/C and porous C at 200?mA g-1.

Fig. 4. (a) Rate capability of three kinds of P-CoSe2/C samples and porous C. Capacity retention of (b) CoSe2/C and (c) P-CoSe2(2:1)/C anodes at various current densities up to 5000?mA g-1. (d) Charge/discharge cycling performance of CoSe2/C, porous C and P-CoSe2/C at 2000?mA g-1. (e) Nyquist plots and (f) corresponding Z′-ω1/2 curves of CoSe2/C and P-CoSe2(2:1)/C anodes before and after the rating test. (g) GITT potential profiles and (h) calculated Na-ion diffusion coefficients of P-CoSe2(2:1)/C and CoSe2/C during the discharge and charge processes at 100?mA g-1.

Fig. 5. (a) CV profiles at different scan rates and (b) logi versus logv plots of P-CoSe2(2:1)/C. (c) Capacitive contribution (red) to the total current of P-CoSe2(2:1)/C at the scan rate of 0.2?mV s-1 shown in the CV profile and (d) the contribution ratios at various scan rates up to 2.0?mV s-1.

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P-doped CoSe₂ nanoparticles embedded in 3D honeycomb-like carbon network for long cycle-life Na-ion batteries

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