定向加压过滤法制备碳纳米管/聚苯胺纸基复合电极材料及其电化学性能

蔡艳芝; 李璇; 任璇璇; 成来飞; 李阳; 刘婷婷; 黄少华

doi:10.13801/j.cnki.fhclxb.20210513.007

定向加压过滤法制备碳纳米管/聚苯胺纸基复合电极材料及其电化学性能

doi: 10.13801/j.cnki.fhclxb.20210513.007

蔡艳芝^1, ,,
李璇^1,,
任璇璇¹,
成来飞²,
李阳¹,
刘婷婷^1,,
黄少华^1,

1.
西安建筑科技大学　材料科学与工程学院，西安 710055
2.
西北工业大学　超高温结构复合材料重点实验室，西安 710012

基金项目: 国家自然科学基金面上项目(51972261)；国家自然科学基金青年项目(51302206)；超高温结构复合材料重点实验室创新基金(6142911020208)

详细信息

通讯作者:
蔡艳芝，博士，教授，研究方向为纳米复合材料　E-mail: 511123589@qq.com

中图分类号: TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2021-03-10
- 修回日期: 2021-04-27
- 录用日期: 2021-05-06
- 网络出版日期: 2021-05-14
- 刊出日期: 2022-02-01

Preparation of carbon nanotubes/polyaniline buckypaper composite electrode by directional pressure filtration and its electrochemical properties

1.
College of Materials Science and Engineering, Xi’an University of Architecture and Technology, Xi′an 710055, China
2.
Science and Technology on Thermostructural Composite Materials Laboratory, Northwestern Polytechnical University, Xi′an 710072, China

摘要

摘要: 采用定向加压过滤技术获得直径约为120 mm、厚度约为10 μm的碳纳米管/聚苯胺(CNT/PANI)自支撑纸基柔性电极。在电极中CNT均匀弥散分布，PANI均匀地嵌入CNT网络中。PANI为纳米至亚微米级球形颗粒，其负载量最高为2.7 mg·cm⁻²。PANI负载量为2.2 mg·cm⁻²的电极的孔隙率为70.33%，密度为0.4 g·cm⁻³，孔面积为67.31 m²·g⁻¹。该电极可紧绕直径为4 mm的玻璃棒数圈而无损伤。该电极在4 mA·cm⁻²的电流密度条件下，单电极比电容为1.88 F·cm⁻²；在充放电1200次循环过程中，比电容先下降后增大，至900次循环时比电容达到2.41 F·cm⁻²，1200次循环时容量保持率为125.78%；经180°弯折500次后，容量保持率为78.43%。该电极所组装的对称三明治结构超级电容器在5 mA·cm⁻²的电流密度条件下比电容为0.48 F·cm⁻²，经1000次充放电循环容量保持率为94.3%，能量密度和功率密度分别为213.75 mW·h·cm⁻³和2163.22 mW·cm⁻³。
- 柔性电极 /
- 聚苯胺 /
- 比电容 /
- 碳纳米管纸 /
- 定向加压过滤
Abstract: Carbon nanotubes/polyaniline (CNT/PANI) buckypaper self-supporting flexible electrodes with a diameter of about 120 mm and a thickness of about 10 μm were obtained by directional pressure filtration technology. CNTs distributed uniformly and dispersed in the electrode, and PANI was uniformly embedded in the CNT network. PANI was spherical particles of nanometer to submicron size, with a maximum loading capacity of 2.7 mg·cm⁻². The electrode with PANI loading of 2.2 mg·cm⁻² has a porosity of 70.33%, a density of 0.4 g·cm⁻³ and a total pore area of 67.31 m²·g⁻¹. The electrode can be wound several times around the glass rod with diameter of 4 mm without damage. At the current density of 4 mA·cm⁻², the specific capacitance of the electrode is 1.88 F·cm⁻². In the process of 1200 charging-discharging cycles, the specific capacitance decreases first and then increases, and reaches 2.41 F·cm⁻² at the 900th cycle, and the capacity retention rate is 125.78% at the 1 200th cycle. After 500 times of bending at 180° angle, the retention rate of capacity is 78.43%. The symmetrical sandwich structure supercapacitor assembled by this electrode has a capacitance of 0.48 F·cm⁻² at a current density of 5 mA·cm⁻². Its capacity retention rate after 1000 charge-discharge cycles is 94.3%. Its energy density and power density are 213.75 mW·h·cm⁻³ and 2163.22 mW·cm⁻³, respectively.
- flexible electrodes /
- polyaniline /
- specific capacitance /
- carbon nanotube buckypaper /
- directional pressure filtration

HTML全文

图 1 CNT/PANI纸的宏观和微观形貌：(a)伸展的CNT/PANI纸及其厚度；(b)卷曲的CNT/PANI纸及其直径；((c)、(d))断面微观形貌

Figure 1. Macroscopic and microscopic morphologies of CNT/PANI buckypaper: (a) Stretched CNT/PANI buckypaper and its thickness; (b) Curled CNT/PANI buckypaper and its diameter; ((c), (d)) Cross-section microscopic morphologies

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图 2 CNT/PANI纸的XRD图谱

Figure 2. XRD pattern of CNT/PANI buckypaper

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图 3 不同PANI含量的CNT/PANI纸的电化学性能：(a)在3 mV·s⁻¹ 扫速条件下的CV曲线；(b)在4 mA·cm⁻²电流密度条件下的GCD曲线

Figure 3. Electrochemical properties of CNT/PANI buckypaper with different PANI content: (a) CV curves at a sweep speed of 3 mV·s⁻¹; (b) GCD curves at a current density of 4 mA·cm⁻²

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图 4 不同PANI含量CNT/PANI纸断面微观形貌：(a) CNT/PANI_21wt%；(b) CNT/PANI_29wt%；(c) CNT/PANI_38wt%；(d) CNT/PANI_43wt%

Figure 4. Cross-section microscopic morphologies of CNT/PANI buckypaper with different PANI contents：(a) CNT/PANI_21wt%; (b) CNT/PANI_29wt%;(c) CNT/PANI_38wt%; (d) CNT/PANI_43wt%

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图 5 CNT/PANI_38wt%纸的电化学稳定性和阻抗测试：(a) 电化学测试前后阻抗变化；(b)扫速1~9 mV·s⁻¹ CV曲线；(c)不同电流密度GCD曲线；(d)不同电流密度容量变化

Figure 5. Electrochemical stability and Impedance test of CNT/PANI_38wt% buckypaper: (a) Impedance change before and after electrochemical test; (b) CV curves at 1-9 mV·s⁻¹ scanning speed; (c) GCD curves at different current density; (d) Capacity change at different current density

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图 6 CNT/PANI_38wt%不同扫速赝电容贡献率柱形图(a)、9 mV·s⁻¹扫速下循环伏安曲线(b)

Figure 6. Column diagram of contribution rate of pseudocapacitance of CNT/PANI_38wt% at different scanning speeds (a), Cyclic voltammetry curve at 9 mV·s⁻¹ scanning speed (b)

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图 7 经180°弯曲500次前后5 mV·s⁻¹扫速下CNT/PANI_38wt%纸循环伏安曲线对比

Figure 7. Cyclic voltammetry curve comparison at 5 mV·s⁻¹scanning speed before and after 180° bending for 500 times for CNT/PANI_38wt% buckypaper

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图 8 4 mA·cm⁻²电流密度下CNT/PANI_38wt%容量变化曲线

Figure 8. Capacity variation curve of CNT/PANI_38wt% at a current density of 4 mA·cm⁻²

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图 9 CNT/PANI_38wt%纸循环测试后断面微观形貌：(a) 300次循环；(b) 600次循环

Figure 9. Cross-section microscopic morphologies of CNT/PANI_38wt% buckypaper after cycle test: (a) 300 cycles; (b) 600 cycles

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图 10 CNT/PANI纸电化学测试前后的孔径分布曲线

Figure 10. Pore size distribution curves of CNT/PANI buckypaper before and after electrochemical test

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图 11 CNT/PANI纸电化学测试后电解液FTIR图谱

Figure 11. FTIR spectrum of electrolyte after electrochemical test of CNT/PANI buckypaper

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图 12 CNT/PANI纸基超级电容器的电化学测试：(a)扫速1-9 mV·s⁻¹循环伏安曲线；(b)不同电流密度恒电流充放电曲线；(c) 5 mA·cm⁻²循环1000次容量保持率

Figure 12. Electrochemical test of CNT/PANI buckypaper-based supercapacitor: (a) Sweep speed 1-9 mV·s⁻¹ Cyclic voltammetry curves; (b) Different current density Constant current charge-discharge curves; (c) 5 mA·cm⁻² cycle 1000 times capacity retention

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表 1 碳纳米管/聚苯胺(CNT/PANI)纸基复合电极材料的组成

Table 1. Composition of carbon nanotubes/polyaniline (CNT/PANI) buckypaper composite electrode

Sample	Mass fraction of CNT/wt%	Mass fraction of PANI/wt%	Specific areal mass loadings of PANI /(mg·cm⁻²)
CNT/PANI_0wt%	100	0	0
CNT/PANI_21wt%	79	21	1.2
CNT/PANI_29wt%	71	29	1.8
CNT/PANI_38wt%	62	38	2.2
CNT/PANI_43wt%	57	43	2.7
Note: Specific areal mass loadings of PANI—Mass fraction of PANI × Mass of buckypaper /Area of buckypaper.

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表 2 近年来文章中碳/赝电容电极材料电化学性能总结

Table 2. Summary of electrochemical performance of carbon/pseudocapacitance electrode materials in recent years

Compound	Specific capacitance	Cycle stability	Energy density	Power density	Electrode thickness/μm	Literature
CNT buckypaper	3.0 F·cm⁻³	90% (10000 cycle)	1.5 mW·h·cm⁻³	4.2 W/cm³		^[19]
CNT/graphene/PANI	10.3 mF·cm⁻²				15	^[32]
PANI/CNT/PVC	298 mF·cm⁻²	86.5% (5 000 cycle)				^[44]
PANI hydrogel	237.7 mF·cm⁻²	90% (1 000 cycle)	27.2 mW·h·cm⁻²	210 mW·cm⁻²	40	^[30]
PANI hydrogel	17.4 F·cm⁻³	82% (5 000 cycle)	6.16 mW·h·cm⁻³			^[45]
CNT/graphene/PANI	261 mF·cm⁻²		36.3 μW·h·cm⁻²	0.17 μW·cm⁻²		^[13]
CNT/MnO₂	135 mF·cm⁻²	86% (10 000 cycle)	0.018 mWh·cm⁻²	0.72 mW·cm⁻²	50	^[12]
PANI/Co(OH)₂	8.14 F·cm⁻²		201.5 μW·h·cm⁻²	3000 μW·cm⁻²		^[46]
VN/CNT	7.9 F·cm⁻³	82% (1 000 cycle)	0.54 mW·h·cm⁻³	0.4 W·cm⁻³	48	^[11]
CNT/PANI buckypaper	2.16 F·cm⁻²	125.78% (1 200 cycle)	213.75 mW·h·cm⁻³ 2.14 mW·h·cm⁻²	2163.22 mW·cm⁻³ 21.6 mW·cm⁻²	10	This work
Notes: PVC—Polyvinyl chloride; VN—Vanadium nitride.

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