煤基球形多孔碳用于锂离子电池负极材料的性能研

doi:10.15541/jim20160655

摘要/Abstract

摘要：

因具有较短的锂离子扩散路径、大的比表面积等优势, 球形碳材料在锂离子电池负极材料中展露出良好的应用前景。研究以新疆库车产煤为原料, 采用电弧放电法及化学活化法制备出了具有多孔结构的煤基球形碳。通过X射线衍射(XRD)、扫描电镜(SEM)、拉曼光谱(Raman)、氮气吸脱附法和恒电流充放电等测试手段对材料结构、形貌和电化学性能进行了表征。结果表明, 在100 mA/g的电流密度下, 煤基球形多孔碳的首次放电比容量可达到1188.9 mAh/g, 远高于商业石墨负极372 mAh/g的理论比容量。此外, 该材料还表现出了良好的循环稳定性, 经历200圈循环后的放电比容量为844.9 mAh/g。煤基球形多孔碳优异的电化学性能得益于活化过程所产生的分级孔道结构能为锂离子提供更多储存空间, 从而提高了电极的容量及循环稳定性。

关键词: 煤基, 球形多孔碳, 锂离子电池, 负极

Abstract:

Spherical porous carbon nanomaterials is a promising candidate as anode materials for next-generation LIBs due to its large specific surface area which decreases the lithium ion transport distance. Spherical porous carbon nanomaterials with uniform morphology were prepared by arc-discharging followed by chemical activation using coal as precursor. The as-prepared spherical porous carbon samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), Raman spectrope (Raman), the nitrogen adsorption-desorption, galvanostatic charge and discharge method and so on. The result indicated that the spherical porous carbon materials have high specific capacity of 1188.9 mAh/g, which exceeds the commercial mesophase carbon spheres (372 mAh/g). Moreover, the spherical porous carbon nanomaterials also afford excellent cyclic stability and a reversible capacity of 844.9 mAh/g remains ever after 200 charge/discharge cycles at current density of 100 mA/g. The excellent electrochemical performance of coal based spherical porous carbon may be originated from the graded pore structure, which can provide more storage space for lithium ion, thus improving the capacity and cycle stability of the electrode.

Key words: coal-derived, sphere porous carbon, lithium ion battery, anode

中图分类号:

O643

李君, 曹亚丽, 王鲁香, 贾殿赠. 煤基球形多孔碳用于锂离子电池负极材料的性能研[J]. 无机材料学报, 2017, 32(9): 909-915.

LI Jun, CAO Ya-Li, WANG Lu-Xiang, JIA Dian-Zeng. Performance of Coal-derived Spherical Porous Carbon as Anode Materials for Lithium Ion Batterie[J]. Journal of Inorganic Materials, 2017, 32(9): 909-915.

图/表 8

图1 CSC和 CSPC-n的(a)XRD图谱, (b)Raman图谱

Fig. 1 XRD patterns (a) and Raman spectra (b) of CSC and CSPC-n

图2 (a)CSC,(b)CSPC-1,(c)CSPC-2, (d)CSPC -3和(e)CSPC-4的FESEM照片以及(f)CSPC-3的TEM照片

Fig. 2 FESEM images of (a) CSC, (b) CSPC-1, (c) CSPC-2, (d) CSPC-3, and (e) CSPC-4, and the TEM image of CSPC-3 (f)

图3 (a~e)CSC及CSPC-n的氮气吸脱附等温线, (f)CSC及CSPC-n的DFT孔径分布图

Fig. 3 Nitrogen sorption isotherms of (a-e) CSC and CSPC-n, (f) DFT pore size distributions of CSC and CSPC-n

表1 CSC及CSPC-n的比表面积和孔结构参数

Table 1 The pore structure parameters of CSC and CSPC-n

Sample	S_BET /(m²·g^-1)	V_BJH /(cm³·g^-1)	V_micro /(cm³·g^-1)	(V_micro/V_t)/%
CSC	117.17	0.35	0.01	3.48
CSPC-1	442.81	0.40	0.07	17.44
CSPC-2	464.18	0.44	0.08	18.05
CSPC-3	534.83	0.37	0.12	31.83
CSPC-4	810.42	1.33	0.31	23.30

图4 CSC及CSPC-n的首次(a)和第二次(b)充放电曲线

Fig. 4 Charge/discharge curves in the first cycle (a) and (b) the second cycle of CSC and CSPC-n electrodes

表2 CSPC-n电极的充放电数据

Table 2 Charge/discharge capacity and the efficiency of the CSPC-n electrodes

Sample	First specific discharge capacity /(mAh·g^-1)	First specific charge capacity /(mAh·g^-1)	First coulombic efficiency/%	Second specific discharge capacity /(mAh·g^-1)	Second specific charge capacity /(mAh·g^-1)	Second coulombic efficiency/%	The 20th specific discharge capacity /(mAh·g^-1)	The 20th specific charge capacity /(mAh·g^-1)
CSC	426.4	174.0	40.8	193.9	158.4	81.7	151.2	175.5
CSPC-1	817.8	355.9	43.5	361.1	322.3	89.2	306.7	576.0
CSPC-2	802.4	348.9	43.5	350.4	313.6	89.5	307.7	587.7
CSPC-3	1188.9	497.5	41.8	535.2	471.6	88.1	398.4	844.9
CSPC-4	600.2	244.1	40.7	240.4	215.6	89.7	194.0	327.1

图5 CSC及CSPC-n的容量循环次数关系图

Fig. 5 Cyclic performance of CSC and CSPC-n electrodes

图6 (a) CSPC-3的循环伏安曲线(内插图为局部放大图)和(b)CSPC-3的交流阻抗曲线

Fig. 6 (a) Cyclic voltammetry curves of CSPC-3 electrodes (insert showing the detail with enlarged scale) and (b) Nyquist plots for CSPC-n electrodes

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