锂离子电容器硬碳负极材料的表面改性及其电化学性能研究

doi:10.11949/0438-1157.20200071

化工学报 ›› 2020, Vol. 71 ›› Issue (6): 2735-2742.DOI: 10.11949/0438-1157.20200071

• 材料化学工程与纳米技术 • 上一篇下一篇

锂离子电容器硬碳负极材料的表面改性及其电化学性能研究

王赫¹(),秦楠^2,³,郭鑫^2,³,郑俊生^2,³(),赵基钢¹()

^1.华东理工大学绿色能源化工国际联合研究中心，上海 200237
^2.同济大学新能源汽车工程中心，上海 201804
^3.同济大学汽车学院，上海 201804

收稿日期:2020-01-17 修回日期:2020-04-08 出版日期:2020-06-05 发布日期:2020-06-05
通讯作者: 郑俊生,赵基钢
作者简介:王赫(1993—)，男，硕士研究生，hewang9999@163.com
基金资助:
国家自然科学基金项目(51777140);科技部科技支撑项目(2015BAG06B00);同济大学中央高校基本科研业务专项资金(22120180519)

Surface modification and electrochemical properties of hard carbon anode material for lithium ion capacitors

He WANG¹(),Nan QIN^2,³,Xin GUO^2,³,Junsheng ZHENG^2,³(),Jigang ZHAO¹()

^1.International Joint Research Center for Green Energy Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
^2.Clean Energy Automotive Engineering Center, Tongji University, Shanghai 201804, China
^3.School of Automotive Studies, Tongji University, Shanghai 201804, China

Received:2020-01-17 Revised:2020-04-08 Online:2020-06-05 Published:2020-06-05
Contact: Junsheng ZHENG,Jigang ZHAO

摘要/Abstract

摘要：

以浓硫酸和浓硝酸为氧化剂，采用超声氧化法对硬碳进行表面氧化处理，并研究其作为锂离子超级电容器负极材料的电化学性能。采用扫描电镜、X射线衍射和X射线光电子能谱等表征手段研究了超声氧化处理对硬碳形貌、结构以及表面含氧官能团相对含量的影响。采用恒电流充放电、循环伏安法及交流阻抗法等电化学测试手段对处理前后硬碳的电化学性能进行研究。结果表明：超声氧化处理能在硬碳表面引入适量的含氧官能团，添加额外的活性中心，提高电子迁移率，进而提高硬碳材料的电化学性能。半电池测试中，在2 A·g^-1的高电流密度下，氧化硬碳的比容量是未处理硬碳的2倍，具有优秀的倍率性能。以氧化硬碳负极和活性炭正极制备出锂离子电容器，能量密度为37.6 W·h·kg^-1，功率密度可达9415 W·kg^-1，在1.0 A·g^-1电流密度下，经过4000次充放电循环后，容量保持率为99.1%，具有良好的循环稳定性。

关键词: 锂离子电容器, 负极材料, 硬碳, 表面, 氧化, 电化学

Abstract:

Concentrated sulfuric acid and concentrated nitric acid were used as oxidants to oxidize the surface of hard carbon by ultrasonic oxidation, and its electrochemical performance as a negative electrode material for lithium ion supercapacitors was studied. The influence of ultrasonic oxidation treatment on the morphology, structure and relative content of oxygen-containing functional groups on the surface were characterized by scanning electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The electrochemical performance of hard carbon before and after treatment was studied by means of galvanostatic charge and discharge, cyclic voltammetry and AC impedance. The results showed that ultrasonic oxidation treatment can introduce appropriate amount of oxygen-containing functional groups on the hard carbon surface, add additional active sites, improve the electron mobility, and then improve the electrochemical performance of hard carbon materials. In the half-cell test, at a high current density of 2 A·g^-1, the specific capacity of oxidized hard carbon is twice that of untreated hard carbon, and it has excellent rate performance. Lithium ion capacitors were fabricated with oxidized hard carbon anode and activated carbon cathode. The energy density is 37.6 W·h·kg^-1, and the power density is 9415 W·kg^-1, the capacity retention rate was 99.1% after 4000 cycles at a current density of 1.0 A·g^-1, showing good cyclic stability.

Key words: lithium ion capacitors, anode materials, hard carbon, surface, oxidation, electrochemical

中图分类号:

O646

王赫, 秦楠, 郭鑫, 郑俊生, 赵基钢. 锂离子电容器硬碳负极材料的表面改性及其电化学性能研究[J]. 化工学报, 2020, 71(6): 2735-2742.

He WANG, Nan QIN, Xin GUO, Junsheng ZHENG, Jigang ZHAO. Surface modification and electrochemical properties of hard carbon anode material for lithium ion capacitors[J]. CIESC Journal, 2020, 71(6): 2735-2742.

图/表 15

图1 HC和OHC的扫描电镜图

Fig.1 SEM images of HC and OHC

图2 HC和OHC的XRD谱图

Fig.2 XRD patterns of HC and OHC

图3 样品的X射线光电子能谱图

Fig.3 XPS spectra of HC and OHC

表1 HC和OHC不同官能团相对含量/%

Table 1 Relative content of different functional groups of HC and OHC/%

Sample	C—C	C—O	CO	O—CO
HC	75.9	12.7	3.8	7.5
OHC	70.7	13.6	7.2	8.3

图4 不同电极的半电池倍率性能图

Fig.4 Half-cell rate capability of different electrodes

图5 不同电极的半电池循环性能图

Fig.5 Half-cell cycling performance of different electrodes

图6 电极在不同扫速下的循环伏安曲线

Fig.6 CV curves of electrodes at different sweep speeds

图7 不同电极的lgIp-lgν关系图

Fig.7 The lgIp-lgν plot of anodic peak current

图8 不同电极的Ip/v1/2和v1/2关系图

Fig.8 The plot of Ip/v1/2versus v1/2 for different electrodes

表2 不同电极的k1和k2系数

Table 2 k1 and k2 coefficients for different electrodes

Sample	k₁/(mA·s·mV^-1)	k₂/(mA·s^1/2·mV^-1/2)	(k₁/k₂)/(s^1/2·mV^-1/2)
HC	1.67	1.30	1.28
OHC	1.91	1.15	1.66

图9 HC和OHC的EIS分析

Fig.9 EIS analysis of HC and OHC

表3 HC和OHC的EIS拟合参数

Table 3 Fitting EIS parameters of HC and OHC

Sample	R₀/Ω	R_SEI/ Ω	R_CT/ Ω	D(Li⁺)/(cm²·s^-1)
HC	4.185	30.88	61.65	4.45^-8
OHC	4.939	26.06	17.77	6.36^-8

图10 LIC-HC和LIC-OHC的倍率性能图

Fig.10 Rate capability of LIC-HC and LIC-OHC

图11 LIC-HC和LIC-OHC的Ragone图

Fig.11 Ragone plots of LIC-HC和LIC-OHC

图12 LIC-HC和LIC-OHC的循环性能图

Fig.12 Cycling performance of LIC-HC和LIC-OHC

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锂离子电容器硬碳负极材料的表面改性及其电化学性能研究

Surface modification and electrochemical properties of hard carbon anode material for lithium ion capacitors

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