锂硫电池正极用钴掺杂空心多孔碳载体材料

doi:10.15541/jim20200161

摘要/Abstract

摘要：

锂硫电池被认为是新一代低成本、高能量密度的储能系统。但由于硫正极导电性差、穿梭效应严重以及氧化还原反应速率慢, 导致电池容量衰减严重, 倍率性能较差。本研究以柠檬酸钠为碳源制备了具有三维中空结构的多孔碳材料, 并在其骨架上负载钴纳米颗粒后作为硫正极的载体。引入的钴纳米颗粒可有效吸附多硫化物, 提升其转化反应的动力学, 进而明显改善电池的循环和倍率性能。所得的钴掺杂复合硫正极在0.5C (1C=1672 mAh·g^-1)的倍率下首圈放电比容量高达1280 mAh·g^-1, 在1C的倍率下稳定循环200圈后可保持770 mAh·g^-1, 并且具有优异的倍率性能, 即使在10C的大电流密度下仍可稳定循环。

关键词: 锂硫电池, 钴纳米颗粒, 转化反应, 硫正极

Abstract:

Lithium-sulfur batteries are deemed to be the next generation of cost-effective and high energy density systems for energy storage. However, low conductivity of active materials, shuttle effect and sluggish kinetics of redox reaction lead to serious capacity fading and poor rate performance. Herein, a sodium citrate derived three-dimensional hollow carbon framework embedded with cobalt nanoparticles is designed as the host for sulfur cathode. The introduced cobalt nanoparticles can effectively adsorb the polysulfides, enhance the kinetics of conversion reaction and further improve the cyclic and rate performance. The obtained cathode delivered a high initial discharge capacity of 1280 mAh·g^-1 at 0.5C, excellent high-rate performance up to 10C and stable cyclic capacity of 770 mAh·g^-1 at 1C for 200 cycles with high Columbic efficiency.

Key words: lithium sulfur battery, cobalt nanoparticle, conversion reaction, sulfur cathode

中图分类号:

TM912

金高尧, 何海传, 吴杰, 张梦源, 李亚娟, 刘又年. 锂硫电池正极用钴掺杂空心多孔碳载体材料[J]. 无机材料学报, 2021, 36(2): 203-209.

JIN Gaoyao, HE Haichuan, WU Jie, ZHANG Mengyuan, LI Yajuan, LIU Younian. Cobalt-doped Hollow Carbon Framework as Sulfur Host for the Cathode of Lithium Sulfur Battery[J]. Journal of Inorganic Materials, 2021, 36(2): 203-209.

图/表 19

Fig. 1 Schematic illustration for the synthesis steps of hollow Co/C composite and its effect for the resulting electrode

Fig. 2 (a) XRD pattern, (b) Raman spectrum, (c) XPS spectrum and (d) N2 adsorption/desorption isotherm of Co/C-700 with insert in (d) showing pore size distribution

Fig. S1 XRD pattern of UWC-700

Fig. S2 (a) TGA curve of Co/C-700 in air and (b) XRD pattern of the final product

Table S1 BET surface area and pore volume distribution of UWC-700, Co/C-700 and HEC-700

Sample	S_BET/(m²∙g^-1)	V_total/(cm³∙g^-1)	Pore volume/%
Sample	S_BET/(m²∙g^-1)	V_total/(cm³∙g^-1)	Micro	Meso	Macro
UWC-700	15.09	0.026	1.76	98.24	0
Co/C-700	376.13	0.52	28.85	62.76	8.49
HEC-700	369.53	0.54	25.47	68.17	6.36

Fig. 3 (a, b) TEM, (c) high-resolution TEM (HRTEM) images and (d) EDS elemental mappings (Co, C and O) of Co/C-700

Fig. S3 N2 adsorption/desorption isotherms (a) and pore size distributions (b) of UWC-700 and HEC-700

Fig. S4 SEM image of Co/C-700

Fig. S5 XRD pattern (a) and SEM image (b) of HEC-700

Fig. S6 TGA curves of S@Co/C-700 and S@HEC-700 under N2 atmosphere

Fig. S7 XPS spectrum of S@Co/C-700 composite

Fig. S8 High resolution XPS spectra of Co/C-700(a) C1s; (b) O1s; (c) Co2p

Fig. 4 High resolution XPS spectra for S@Co/C-700 composites (a) S2p; (b) C1s; (c) O1s; (d) Co2p

Fig. S9 Photograph of static adsorption test of HEC-700 and Co/C-700 after standing for 1 h

Fig. S10 Multi-cycle CV curves of Co/C-700 based symmetric cells at 1 mV?s-1 (a) and increased rates (b), and multi-cycle CV curves of HEC-700 at 1 mV?s-1 (c) and increased rates (d)

Fig. 5 CV curves of (a) Co/C-700 and (b) HEC-700 based symmetric cells with and without 0.2 mol?L-1 Li2S6 at 1 mV?s-1; (c) CV curves and (d) EIS plots of S@Co/C-700 and S@HEC-700 electrodes

Fig. 6 (a) Rate capabilities at various rates from 0.5C to 10C and (b) cycling stabilities at 1C for S@Co/C-700 and S@HEC-700 electrodes

Fig. S11 Voltage profiles of S@HEC-700 (a) and S@Co/C-700 (b) electrodes at various rates from 0.5C to 10C

Fig. S12 (a) Cycling stabilities of S@Co/C-700 and S@HEC-700 electrodes at 2C; (b) Cycling performance of S@Co/C-700 at 5C and 10C

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