高性能锂离子电容器正极材料石墨烯-介孔炭复合物的制备及性能分析

doi:10.12096/j.2096-4528.pgt.23099

发电技术 ›› 2024, Vol. 45 ›› Issue (3): 494-507.DOI: 10.12096/j.2096-4528.pgt.23099

高性能锂离子电容器正极材料石墨烯-介孔炭复合物的制备及性能分析

韩秀秀¹, 魏少鑫¹, 汪剑¹, 崔超婕¹^,², 骞伟中¹^,²

^1.清华大学化学工程系, 北京市海淀区 100084
^2.鄂尔多斯实验室, 内蒙古自治区鄂尔多斯市 017000

收稿日期:2023-08-30 修回日期:2023-10-25 出版日期:2024-06-30 发布日期:2024-07-01
通讯作者: 崔超婕
作者简介:韩秀秀(1989)，女，博士，研究方向为碳材料及其在储能领域的应用，hanxiuxiu@tsinghua.edu.cn；
魏少鑫(1998)，男，博士研究生，研究方向为三维泡沫铝基高功率电池型电容器技术的开发；
汪剑(1994)，男，中级工程师，研究方向为碳材料的工艺开发与产品制备以及煤化工催化剂的合成制备；
崔超婕(1987)，女，博士，助理研究员，研究方向为碳材料及其在储能与环保领域的应用，本文通信作者，cuicj06@tsinghua.edu.cn；
骞伟中(1971)，男，博士，教授，研究方向为碳材料及复合材料制备、储能与环境处理应用，新型煤化工催化剂及其产业化，多相流反应器技术，qianwz@tsinghua.edu.cn。
基金资助:
国家自然科学基金项目(22109085)

Preparation and Performance Analysis of High Performance Cathode Material Graphene-Mesoporous Carbon Composites for Lithium-Ion Capacitor

Xiuxiun HAN¹, Shaoxin WEI¹, Jian WANG¹, Chaojie CUI¹^,², Weizhong QIAN¹^,²

^1.Department of Chemical Engineering, Tsinghua University, Haidian District, Beijing 100084, China
^2.Ordos Laboratory, Ordos 017000, Inner Mongolia Autonomous Region, China

Received:2023-08-30 Revised:2023-10-25 Published:2024-06-30 Online:2024-07-01
Contact: Chaojie CUI
Supported by:
National Natural Science Foundation of China(22109085)

摘要/Abstract

摘要：

目的设计同时具有高质量活性和高体积活性的锂离子电容器(lithium-ion capacitor，LIC)复合正极材料。方法借助扫描电子显微镜、透射电子显微镜、康塔全自动比表面和孔径分析仪、四探针测试仪，通过实验分析了颗粒之间的微观形貌、堆叠方式、接触模式和界面特性对复合电极的电导率、电学性质的影响规律。结果将介孔活性炭(mesoporous activated carbon，MC)与单分散石墨烯/单壁碳纳米管杂化物(graphene/single-walled carbon nanotube hybrid，GNH)混合，紧密压缩制成锂离子电容器正极材料。GNH均匀地包裹在MC颗粒表面，与MC面对面接触，增大接触面积；而且GNH在MC颗粒之间形成均匀的三维导电网络，提供了快速的电子传导。另外，GNH具有开放结构，会优先吸附电解液离子，与MC界面间存在浓度梯度；同时，GNH具有较高的导电性，与导电性较差的MC界面间存在接触电势差效应。两者共同促使GNH和MC界面之间形成快速的离子和电子双传输路径，促进离子在MC内部的扩散，从而避免了高电流密度下因离子扩散缓慢而造成的容量损失。结论添加5% GNH提高了倍率性能，并且在不牺牲堆积密度的前提下同时提高质量和体积能量密度。

关键词: 电化学储能, 介孔活性炭, 石墨烯, 锂离子电容器, 接触电势差

Abstract:

Objectives The lithium-ion capacitor (LIC) composite cathode materials with both high mass activity and high volume activity were designed. Methods By scanning electron microscope, transmission electron microscope, Kanta fully automatic specific surface and pore size analyzer, and four-probe tester, the micromorphology, stacking mode, contact mode and interface characteristics between particles were analyzed for the impact of conductivity and electrical properties of composite electrodes. Results Mesoporous activated carbon (MC) and monodisperse graphene/single-walled carbon nanotube hybrid (GNH) were mixed, followed by compressing tightly to prepare the lithium-ion capacitor cathode material. GNH were uniformly wrapped around the surface of MC particles with face-to-face connection, which increases the contact area. Then, the even 3D conductive network constructed by GNH among the individual MC particles provided high electrical conductivity and accelerated electron conduction. In addition, GNH were located at the high ion concentration side due to their exohedral surface structure. Meanwhile, a contact potential difference effect existed between GNH (the easy conductive one) and MC (the poor conductive one). This produced rapid ion and electron dual transport channels at the interface between GNH and MC, and boosted ion diffusion in the porous structure inside MC particles. It will help avoid the loss of capacity from slow ion diffusion at higher current densities. Conclusions The addition of 5% GNH brings about outstanding rate performance, and higher mass and volumetric energy density, but does not reduce the packing density.

Key words: electrochemical energy storage, mesoporous activated carbon, graphene, lithium-ion capacitor, contact potential difference

中图分类号:

TK 02

韩秀秀, 魏少鑫, 汪剑, 崔超婕, 骞伟中. 高性能锂离子电容器正极材料石墨烯-介孔炭复合物的制备及性能分析[J]. 发电技术, 2024, 45(3): 494-507.

Xiuxiun HAN, Shaoxin WEI, Jian WANG, Chaojie CUI, Weizhong QIAN. Preparation and Performance Analysis of High Performance Cathode Material Graphene-Mesoporous Carbon Composites for Lithium-Ion Capacitor[J]. Power Generation Technology, 2024, 45(3): 494-507.

图/表 17

图1 MC材料和极片的形貌结构表征

Fig. 1 Morphology and structure characterization of MC powder and electrode

图2 MC的氮气吸脱附表征

Fig. 2 Characterization of nitrogen adsorption and desorption for MC

图3 GNH材料和极片的形貌结构表征

Fig. 3 Morphology and structure characterization of GNH powder and electrode

图4 GNH的氮气吸脱附表征

Fig. 4 Characterization of nitrogen adsorption and desorption for GNH

图5 复合电极GMC-x的形貌结构表征

Fig. 5 Morphology and structure characterization of GMC-x electrode

图6 5种电极材料在扫描速率为50 mV/s时的CV曲线

Fig. 6 CV curves of five electrode materials at 50 mV/s

图7 GMC-5/AF在不同电流密度下的GCD曲线

Fig. 7 GCD curves of GMC-5/AF at different current densities

图8 5种电极材料在不同电流密度下的质量比电容和线性加和

Fig. 8 Mass specific capacitance and linear weighted sum of five electrode materials at different current densities

图9 从0.02 A/g增大到1 A/g的容量保持率

Fig. 9 Capacitance retention ratio from 0.02 to 1 A/g

图10 复合电极相对于MC的电容增量

Fig. 10 Increment of capacitances relative to MC

图11 复合电极实际比电容与线性加和之间的差值及其占比

Fig. 11 Difference values of specific capacitances between composites and linear weighted sum and its proportion

图12 奈奎斯特图

Fig. 12 Nyquist plots

表1 等效电路拟合结果

Tab. 1 Fitting results of equivalent circuit

材料	R_o	R_ct	Q_ct/(×10^-7)	R_n	C_n	W_o
MC	3.875	20.770	19.000	2.686 00	0.040 00	37.390
GMC-2.5	2.916	12.270	8.588	0.317 15	0.754 41	23.290
GMC-5	2.729	9.688	9.970	0.339 80	0.708 23	21.860
GMC-10	2.712	7.582	11.270	0.360 23	0.628 54	17.400
GNH	2.495	3.197	247.000	4.582 00	0.178 00	7.087

图13 单位质量能量密度与功率密度的比较

Fig. 13 Comparison of energy density and power density per unit mass

图14 GMC-5/AF和MC/AF的循环性能

Fig. 14 Cycling performance of GMC-5/AF and MC/AF

图15 5种电极材料在不同电流密度下的体积比电容

Fig. 15 Volume specific capacitance of five electrode materials at different current densities

图16 单位体积的能量密度与功率密度的比较

Fig. 16 Comparison of energy density and power density per unit volume

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高性能锂离子电容器正极材料石墨烯-介孔炭复合物的制备及性能分析

Preparation and Performance Analysis of High Performance Cathode Material Graphene-Mesoporous Carbon Composites for Lithium-Ion Capacitor

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