Synergistic engineering of cobalt selenide and biomass-derived S, N, P co-doped hierarchical porous carbon for modulation of stable Li-S batteries

doi:10.1016/j.jmst.2022.06.024

Abstract

Abstract:

Hierarchical porous carbon co-doped with heterogeneous atoms has attracted much attention thanks to sizable internal void space accommodating electrolyte, high-density microporous structure physically confining polysulfides (LPS), and heterogeneous atoms serving as active sites to capture LPS. However, solely relying on carbon material defects to capture LPS proves ineffective. Hence, metal compounds must be introduced to chemisorb LPS. Herein, cobalt ions are in-situ grown on the polydopamine layer coated on the surface of biomass-derived S, N, P co-doped hierarchical porous carbon (SNP-PC). Then a layer of nitrogen-doped porous carbon (MPC) dotted with CoSe nanoparticles is acquired by selenizing. Thus, a strong-polar/weak-polar composite material of SNP-PC studded with CoSe nanoparticles is obtained (SNP-PC@MPC@CoSe). Button cells assembled with SNP-PC@MPC@CoSe-modified separator enable superb long-cycle stability and satisfactory rate performance. An excellent rate capacity of 796 mAh g⁻¹ at a high current rate of 4 C with an ultra-low capacity fading of 0.06% over 700 cycles can be acquired. More impressively, even in a harsh test condition of 5.65 mg cm⁻² sulfur loading and 4 μL mg⁻¹ ratio of electrolyte to active materials, the battery can still display a specific capacity of 980 mAh g⁻¹ (area capacity of ∼5.54 mAh cm⁻²) at 0.1 C. This work provides a promising route toward high-performance Li-S batteries.

Key words: Lithium-sulfur battery, Biomass conversion, S, N, P-codoped porous carbon, CoSe modulation, Multifunctional separator, Synergism of strong and weak polarity

Yang Lin, Song He, Zhiyong Ouyang, Jianchao Li, Jie Zhao, Yanhe Xiao, Shuijin Lei, Baochang Cheng. Synergistic engineering of cobalt selenide and biomass-derived S, N, P co-doped hierarchical porous carbon for modulation of stable Li-S batteries[J]. J. Mater. Sci. Technol., 2023, 134: 11-21.

Figures/Tables 8

Fig. 1. Characterization of resultant products. (a) Schematic illustration for the synthesis process of SNP-PC@MPC@CoSe. (b) XRD pattern. (c-e) FESEM images of SNP-PC, SNP-PC@MPC, and SNP-PC@MPC@CoSe. (f) TEM bright-field image of SNP-PC@MPC@CoSe. (g) SAED pattern. (h) HRTEM image and (i) corresponding FFT pattern of a single CoSe nanoparticle. (j) Element mapping patterns of SNP-PC@MPC@CoSe.

Fig. 2. N2 adsorption-desorption isotherms, and their corresponding pore size distribution of (a) SNP-PC, (b) SNP-PC@MPC, and (c) SNP-PC@MPC@CoSe. (d) Raman scattering pattern of all samples.

Fig. 3. High-resolution XPS spectra of SNP-PC@MPC. (a) C 1s. (b) N 1 s. (c) P 2p. (d) S 2p.

Fig. 4. (a) Optical image of the results of LPS adsorption tests (From left to right are SNP-PC@MPC@CoSe, SNP-PC@MPC, and pristine Li2S6-DOL/DME solution, respectively). High-resolution XPS spectra of (b) Co 2p and (c) Se 3d of SNP-PC@MPC@CoSe before and after absorption of Li2S6.

Fig. 5. (a) SEM image of the surface of pristine PP separator. (b) SEM images of cross-sections of SNP-PC@MPC@CoSe-modified separator and PP separator (inserted image). (c) Digital photos of back and front of the SNP-PC@MPC@CoSe-modified separator. (d) Optical images of SNP-PC@MPC@CoSe-modified separator after contacting with electrolyte and folding. (e) Contact angle of pristine PP, SNP-PC@MPC-modified, and SNP-PC@MPC@CoSe-modified separators.

Fig. 6. (a) CV curves of the Li-S cell with SNP-PC@MPC@CoSe-modified separator at various scan rates. (b-d) CV peak current values of A1, C1, and C2 for the cells with SNP-PC@MPC@CoSe-modified, SNP-PC@MPC-modified, and pristine PP separators versus the square root of scan rates. (e) Histogram comparison of the Li + diffusion coefficient of batteries assembled with different separators. (f) CV curves of Li2S6 symmetrical cells with different electrodes at a scan rate of 10 mV s?1. (g) EIS spectra of Li2S6 symmetric cells. The potentiostatic discharge curves of cells assembled with (h) SNP-PC@MPC@CoSe electrodes and (i) SNP-PC@MPC electrodes with Li2S8-Tetraglyme catholyte at 2.05 V.

Fig. 7. (a) Typical CV curves at a scan rate of 0.1 mV s?1. (b) Part of the initial discharge/charge curve at 0.1 C.

Fig. 8. (a) Rate performance. (b) Charge-discharge curve of the cell with SNP-PC@MPC@CoSe-modified separator at various current densities. (c) Cycling performances of Li-S batteries assembled with various separators at 0.2 C. (d) Long-cycle stability of Li-S cells with SNP-PC@MPC@CoSe-modified separator at 1 C. (e) 4 C. (f) Cycling performance of Li-S cell with high sulfur loading cathode of 5.13 mg cm?2 and SNP-PC@MPC@CoSe-modified separator at 0.2 C. (g) Digital photo of 47 LEDs lighted by 4 batteries with SNP-PC@MPC@CoSe-modified separator. (h-j) Optical photos of the Li anode disassembled from cell with PP separator, SNP-PC@MPC, and SNP-PC@MPC@CoSe-modified separator, respectively. (k-m) Corresponding SEM images and EDS mapping patterns (insert). (n) Schematic diagram of synergistic enhancement mechanism of fast conversion, powerful capture, and shuttle suppression for the Li-S battery with SNP-PC@MPC@CoSe-modified separator.

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