碳纤维支撑柔性碳硫复合电极的制备、物性及电池性能研究

doi:10.15541/jim20180236

摘要/Abstract

摘要：

锂硫电池作为极具潜力的下一代二次电池受到广泛关注。然而, 对于含硫正极的研究仍处于实验探索阶段, 商业化的碳纤维毡应用于硫正极鲜有报道。本研究制备了锂硫电池用碳纤维支撑柔性碳硫复合电极, 并对其进行了物性及电池性能的研究。结果发现, 碳纤维毡具有多孔隙的三维网络结构, 与具有微孔结构的多孔碳共同构成正极支撑体, 能够物理固定正极材料, 有助于提高电池的能量密度和锂硫正极的导电性, 界面电阻由原来的97.9 Ω降到22.6 Ω。进一步研究表明, 碳纤维毡做集流体的样品在首圈0.05C倍率下, 具有996.7 mAh/g的放电比容量, 在2C高倍率下循环140圈后仍保持666.7 mAh/g的放电比容量, 而铝箔样品仅为772.9和471.6 mAh/g。同时, 本研究使用的LA132水系粘结剂、super-P导电剂价格低廉, 球磨制备工艺可规模化生产、安全环保, 可以为锂硫电池工业化生产和应用提供参考。

关键词: 锂硫电池, 碳纤维支撑, 柔性, 传统铝箔

Abstract:

Lithium sulfur battery has attracted extensive attention as highly promising next generation of rechargeable battery. However, lithium sulfur battery, especial the sulfur cathode, is still under experimental exploration, and the commercial carbon fiber felt is rarely reported to apply in the sulfur cathode. Herein, the flexible carbon-fiber- supported carbon-sulfur electrode was prepared, and its physical properties and electrochemical performance were characterized. The results showed that the interface resistance was reduced from 97.9 Ω to 22.6 Ω, due to porous three-dimensional network of the carbon fiber felt and micropore of the porous carbon which benefited energy density of the battery and conductivity of the sulfur cathode. Furthermore, the initial discharge capacity at 0.05C rate was 996.7 mAh/g and the discharge capacity at 2C rate after 140 cycles was 666.7 mAh/g when carbon fiber felt serves as current collector, while their counterparts with aluminum foil as the current collector were 772.9 and 471.6 mAh/g, respectively. Furthermore, the environmental-friend and low-cost binder LA132, super-P, and the ball-milling technique are beneficial to mass synthesis, suitable for the industrial production and the application of lithium sulfur battery.

Key words: lithium-sulfur battery, carbon-fiber supported, flexible, traditional aluminum foil

中图分类号:

TQ174

李亚东, 李伟平, 王琴, 郑道光, 王建新. 碳纤维支撑柔性碳硫复合电极的制备、物性及电池性能研究[J]. 无机材料学报, 2019, 34(4): 373-378.

Ya-Dong LI, Wei-Ping LI, Qin WANG, Dao-Guang ZHENG, Jian-Xin WANG. Flexible Carbon-fiber Supported Carbon-sulfur Electrode: Preparation, Physical Property and Electrochemical Performance[J]. Journal of Inorganic Materials, 2019, 34(4): 373-378.

图/表 9

图1 (a)升华硫、(b)多孔碳、(c)CS和(d)CSv的XRD图谱

Fig. 1 XRD patterns of (a) sublimed sulfur, (b) porous carbon, (c) CS and (d) CSv

图2 多孔碳和碳硫粉热重(TG)测试

Fig. 2 Thermal weight (TG) test of porous carbon and carbon- sulfur composites

图3 (a)CSv和(b)多孔碳的氮气吸附-脱附等温曲线

Fig. 3 N2 adsorption-desorption isotherms of (a) CSv and (b) porous carbon

表1 多孔碳的结构特性

Table 1 Texture properties of porous carbon

Sample	Surface area/(m²?g^-1)			Volume/(cm³?g^-1)		Average pore diameter/nm
Sample	S_BET	S_micro	S_external	V_total	V_micro	BJH
Porous carbon	1734.7242	1041.1364	693.5878	0.848649	0.472287	2.2930
CS_v	7.4587	1.3661	6.0926	0.008040	0.000438	7.1043

图4 (a)~(c)碳纤维毡、(d)多孔碳、(e) CS、(f)~(g) CSv的SEM照片; (h)~(i) 250 ℃处理碳硫粉的EDX图谱以及(j)表面元素含量((g)中标识区域)

Fig. 4 SEM images of (a-c) CFF, (d) porous carbon, (e) CS, and (f-g) CSv, and EDX elemental maps of (h) carbon, (i) sulfur, and (j) the corresponding mass percentage in the area marked with a rectangle in (g)

图5 (a)~(e)碳纤维支撑和(f)~(g)铝箔支撑的(a)~(c)正极数码和(d)~(g)SEM照片,

Fig. 5 (a-c) Digital and (d-g) SEM images of (a-e) CFF/CSv and (f-g) Al/CSv cathodes

图6 CFF/CSv为正极的电池循环伏安曲线

Fig. 6 Typical cyclic voltammograms of devices with CFF/CSv as cathode

图7 碳纤维毡和铝箔分别做集流体的电池阻抗, 插图为等效电路图

Fig. 7 Electrochemical impedance plots of the batteries with Al/CSv and CFF/CSv as the current collectors with inset showing equivalent circuit

图8 碳纤维毡和铝箔分别做集流体的电池在(a)0.2C~5C和(b)2C下的循环性能曲线; 不同硫负载量碳纤维毡做集流体的电池在(c)0.2C下的循环性能曲线和(d)首圈0.05C下的充放电曲线

Fig. 8 Cycle performance of CFF/CSv and Al/CSv batteries at (a) 0.2C-5C rates and (b) 2C rate, (c) Cycle performance of CFF/CSv batteries with different S load at 0.2C rate, and (d) charge-discharge performance of the CFF/CSv batteries with different S load at 0.05C rate

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