煤沥青基微晶炭的制备及其储锂性能

doi:10.16085/j.issn.1000-6613.2020-0496

摘要/Abstract

摘要：

以工业副产物煤沥青（coal tar pitch, CTP）为原料，采用高温炭化法制备煤沥青基微晶炭，利用XRD、Raman光谱、SEM、TEM和XPS等手段对其微观结构和表面化学性质进行表征，并探究微晶炭用作锂离子电池负极材料的储锂特性。结果表明，煤沥青经不同温度（800~1100℃）炭化处理后可制备出石墨微晶和无定形炭共存的微晶炭。炭化温度是影响煤沥青基微晶炭的微晶片层、纳米孔道和结构缺陷等微观结构特征和表面化学性质的重要因素。当炭化温度为800℃时，煤沥青基微晶炭CTP-800具有较为有序的石墨微晶片层和丰富的纳米孔道、结构缺陷等无定形炭，且两者有机结合，相互镶嵌，构筑成三维网络结构，同时炭基体表面含有适量氧/氮官能团。该微晶炭用作锂离子电池负极材料时具有优异的储锂特性，在50mA/g电流密度下可逆容量可达305mA·h/g，1000mA/g大电流密度下仍可维持在174mA·h/g，经100次循环后可逆容量保持率超过99.0%，显示出良好的倍率性能和优异的循环稳定性，是一种较为理想的锂离子电池负极材料。煤沥青基微晶炭 CTP-800优异的储锂特性与其炭基体中含有石墨微晶片层与纳米孔道、结构缺陷等无定形炭和炭表面富含氧/氮官能团等因素密切相关。

关键词: 煤沥青, 微晶炭, 负极材料, 储锂性能

Abstract:

In this paper, coal tar pitch (CTP), a by-product of industry, was used as raw material to prepare CTP-based microcrystal carbons by high-temperature carbonization. The microstructure and surface properties of CTP-based microcrystal carbons were characterized by means of X-ray diffraction (XRD), Raman spectrum, scanning electron microscope (SEM), transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS). The lithium storage characteristics of CTP-based microcrystal carbons applied as anode materials were also investigated. The results showed that CTP-based microcrystal carbons coexisting graphite microcrystalline structure and amorphous structure can be prepared by carbonization of coal tar pitch at different temperatures (800—1100℃). Microstructural characteristics such as microcrystalline layers, nanopore channels and structural defects and surface chemical properties of CTP-based microcrystal carbons were strongly dependent on the carbonization temperature. When the carbonization temperature was 800℃, CTP-based microcrystal carbon CTP-800 had a relatively ordered graphite microcrystalline layer and abundant amorphous carbon such as nanopore channels and structural defects, and the two were organically combined and embedded with each other to form a three-dimensional network structure, and the surface of carbon matrix contained appropriate oxygen/nitrogen functional groups. Such CTP-based microcrystal carbon had excellent lithium storage characteristics when it used as anode material for lithium ion batteries. The reversible capacity reached as high as 305mA·h/g at current rate of 50mA/g and still remained 174mA·h/g at current rate of 1000mA/g, and the reversible capacity retention rate was over 99.0% after 100 cycles. Such results indicated that the microcrystal carbon CTP-800 had good rate performance and excellent cycle stability, which might become a promising anode material for lithium ion batteries. The excellent lithium storage characteristics of CTP-800 were strongly depended on their unique microstructure in carbon matrix including graphite microcrystalline layer, amorphous carbon such as nanopore channel and structural defects, and oxygen/nitrogen-rich functional groups on the carbon surface.

Key words: coal tar pitch, microcrystal carbons, anode materials, lithium storage properties

中图分类号:

TQ522.65

王振帅, 邢宝林, 韩学锋, 曾会会, 侯磊, 郭晖, 张传祥, 岳志航. 煤沥青基微晶炭的制备及其储锂性能[J]. 化工进展, 2021, 40(1): 313-323.

Zhenshuai WANG, Baolin XING, Xuefeng HAN, Huihui ZENG, Lei HOU, Hui GUO, Chuanxiang ZHANG, Zhihang YUE. Preparation of coal tar pitch-based microcrystal carbons and their lithium storage properties[J]. Chemical Industry and Engineering Progress, 2021, 40(1): 313-323.

图/表 12

表1 煤沥青的工业分析与XPS元素分析

工业分析/%					XPS元素分析/%
M_ad	A_ad	V_daf	FC_daf		C	O	N	S
0.37	0.21	64.23	35.77		92.89	4.01	2.51	0.59

图1 煤沥青基微晶炭的XRD谱图

表2 煤沥青基微晶炭的微晶结构参数

样品编号	d₀₀₂/nm	L_a/nm	L_c/nm	L_c/d₀₀₂
CTP-800	0.356	16.24	7.95	22.3
CTP-900	0.353	16.19	7.92	22.4
CTP-1000	0.351	14.97	7.32	20.9
CTP-1100	0.349	14.68	7.18	20.6

图2 煤沥青基微晶炭的Raman光谱图

图3 煤沥青和煤沥青基微晶炭的SEM图[(a)~(c）]和TEM图[（d）]

图4 煤沥青基微晶炭的N2吸附/脱附等温线与孔径分布曲线

图5 煤沥青基微晶炭CTP-800和CTP-1000的XPS谱图

图6 煤沥青基微晶炭负极材料在50mA·g-1下的首次恒流充放电曲线

表3 煤沥青基微晶炭负极材料的首次充放电比容量和库仑效率

样品编号	放电比容量 /mA·h·g^-1	充电比容量 /mA·h·g^-1	不可逆比容量 /mA·h·g^-1	库仑效率/%
CTP-800	500	320	180	64.1
CTP-900	442	289	153	65.3
CTP-1000	370	276	94	74.5
CTP-1100	345	251	96	72.6

图7 煤沥青基微晶炭负极材料的循环伏安曲线

图8 煤沥青基微晶炭负极材料的倍率性能

图9 煤沥青基微晶炭负极材料的循环性能

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