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2222材料工程  2019, Vol. 47 Issue (5): 145-152    DOI: 10.11868/j.issn.1001-4381.2016.001494
  研究论文 本期目录 | 过刊浏览 | 高级检索 |
以预锂化多壁碳纳米管为负极的锂离子电容器性能
蔡满园, 孙晓刚(), 陈玮, 邱治文, 陈珑, 刘珍红, 聂艳艳
南昌大学 机电工程学院, 南昌 330031
Performance of lithium-ion capacitors using pre-lithiated multiwalled carbon nanotubes as negative electrode
Man-yuan CAI, Xiao-gang SUN(), Wei CHEN, Zhi-wen QIU, Long CHEN, Zhen-hong LIU, Yan-yan NIE
School of Mechatronics Engineering, Nanchang University, Nanchang 330031, China
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摘要 

采用内部短路方式对多壁碳纳米管负极进行不同程度的预嵌锂处理,预嵌锂时间为5,30,60min,以预嵌锂多壁碳纳米管极片作为负极,活性炭极片作为正极,组装成锂离子电容器。利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)对多壁碳纳米管及电极极片进行表征分析,采用恒流充放电(GCD)和交流阻抗谱(EIS)研究预嵌锂多壁碳纳米管负极和未预嵌锂处理多壁碳纳米管负极锂离子电容器的性能。电化学测试结果表明,多壁碳纳米管负极预嵌锂大幅提高了电容器充放电性能,对比未嵌锂多壁碳纳米管电容器,在相同的电流密度下(100mA/g),能量密度提高400%。预嵌锂60min,电流密度100mA/g时,其比容量达到57F/g。在电流密度为100~3200mA/g范围内,其最高能量密度与功率密度分别达到90Wh/kg,4130W/kg。1000次充放电循环后,容量保持率维持在85%以上,表现出良好的超级电容器性能。

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蔡满园
孙晓刚
陈玮
邱治文
陈珑
刘珍红
聂艳艳
关键词 预嵌锂负极多壁碳纳米管活性炭锂离子电容器    
Abstract

Pre-lithiated multiwalled carbon nanotube anode was prepared by internal short approach(IS) for 5min, 30min and 60min. Lithium ion capacitors (LICs) were assembled using pre-lithiated multiwalled carbon nanotubes as cathode and activated carbon(AC) as anode. The structure characterization of multiwalled carbon nanotubes and electrodes were investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The electrochemical performance of pre-lithiated multiwalled carbon nanotube electrodes and pure multiwalled carbon nanotubes electrodes were tested by galvanostatic charge/discharge and electrochemical impedance spectrum. The electrochemical tests indicate that the charge-discharge performance of LIC is greatly improved by pre-lithiation of multiwalled carbon nanotubes. The energy density reaches about 4 times over conventional electric double-layer capacitors (EDLCs) at the current density of 100mA/g. The LICs achived a specific capacitance of 57F/g at the current density of 100mA/g with 60min pre-lithiatiation process. The maximum energy density and power density reach 90Wh/kg and 4130W/kg respectively in the current range of 100-3200mA/g. The capacity retention rate remains more than 85% after 1000 cycles. The LIC shows excellent supercapacitor performance.

Key wordspre-lithiatiation    anode    multiwalled carbon nanotubes(MWCNTs)    activated carbon(AC)    lithium-ion capacitor
收稿日期: 2016-12-12      出版日期: 2019-05-17
中图分类号:  O646  
基金资助:江西省科技厅科研项目(20142BBE50071);江西省教育厅(KJD13006)
通讯作者: 孙晓刚     E-mail: xiaogangsun@163.com
作者简介: 孙晓刚(1957-), 男, 博士, 教授, 研究方向为碳纳米管及锂离子电池, 联系地址:江西省南昌市红名滩新区学府大道999号南昌大学前湖校区机电工程学院(330031), E-mail:xiaogangsun@163.com
引用本文:   
蔡满园, 孙晓刚, 陈玮, 邱治文, 陈珑, 刘珍红, 聂艳艳. 以预锂化多壁碳纳米管为负极的锂离子电容器性能[J]. 材料工程, 2019, 47(5): 145-152.
Man-yuan CAI, Xiao-gang SUN, Wei CHEN, Zhi-wen QIU, Long CHEN, Zhen-hong LIU, Yan-yan NIE. Performance of lithium-ion capacitors using pre-lithiated multiwalled carbon nanotubes as negative electrode. Journal of Materials Engineering, 2019, 47(5): 145-152.
链接本文:  
http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2016.001494      或      http://jme.biam.ac.cn/CN/Y2019/V47/I5/145
Fig.1  内部短路预嵌锂结构示意图
Fig.2  碳纳米管SEM(a)、TEM(b)图像,活性炭正极极片(c)和碳纳米管负极极片SEM图(d)
Fig.3  CNTs XRD(a)和拉曼图谱(b)
Fig.4  不同预理化碳纳米管负极颜色的变化图像
Fig.5  碳纳米管电极预嵌锂前首次充放电曲线图(a)和不同预嵌锂时间首次充电曲线图(b)
Fig.6  碳纳米管负极预嵌锂前后锂离子电容器在不同电流密度下的恒流充放电曲线
(a)未预锂化处理; (b)预锂化时间为5min; (c)预锂化时间为30min; (d)预锂化时间为60min;(e)不同电流密度比电容曲线;(f)功率密度-能量密度曲线
Current density/ (mA·g-1)LIC0 LIC5 LIC30 LIC60
Csp/ (F· g-1) Psp/ (W· kg-1) Esp/ (Wh· kg-1) Csp/ (F· g-1) Psp/ (W· kg-1) Esp/ (Wh· kg-1) Csp/ (F· g-1) Psp/ (W· kg-1) Esp/ (Wh· kg-1) Csp/ (F· g-1) Psp/ (W· kg-1) Esp/ (Wh· kg-1)
  100 14.64 148 29.3 33.42 153 53.85 42.45   148 67 57   148.6 90
  200 12.4 294 19.2 32.5 288 51.66 41.3   297 63 53.9   293.3 82.2
  300 10.2 436 14.9 27.6 483 43.57 40.43   434 60.8 51   436.4 76
  400   8.9 575 12.6 25.4 585 39.3 34.8   850 50.5 50   583 75
  800   7.1 1109 8.6 17.2 1170 26 29.3 1143 39.7 47.6 1145 65.5
1200 - - - 17.1 1731 25 26.6 1672 33.9 44.8 1684 56.6
2000 - - - - - - - - - 29.5 2720 29.5
3200 - - - - - - - - - 24.7 4130 22.1
Table 1  多壁碳纳米管负极锂离子电容器在不同电流密度下的比容量、功率密度、能量密度对比数据
Fig.7  LIC60循环前后交流阻抗(a)和等效电路模型和拟合曲线(b)
Sample RsSEI layer Charge transfer
R1 CPE1/F Rct CPEd1/F
Before cycling 3.405 10.33 0.2267 26.67 1.09×10-4
After cycling 4.292 14.46 0.0811 37.08 1.33×10-4
Table 2  LIC60锂离子电容器循环前后拟合参数
Fig.8  不同预嵌锂程度锂离子电容器的充放电循环性能
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