5-磺基水杨酸掺杂聚吡咯/ZIF67复合材料的超电容性能

李文青; 王艺锟; 王全璐; 张婷婷; 韩永芹

doi:10.13801/j.cnki.fhclxb.20211216.003

5-磺基水杨酸掺杂聚吡咯/ZIF67复合材料的超电容性能

doi: 10.13801/j.cnki.fhclxb.20211216.003

山东科技大学　材料科学与工程学院，青岛 266590

基金项目: 国家自然科学基金面上项目(52173258)

详细信息

通讯作者:
韩永芹，博士，副教授，博士生导师，研究方向为导电高分子复合材料　E-mail: hanyq@sdust.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2021-10-09
- 修回日期: 2021-11-28
- 录用日期: 2021-12-08
- 网络出版日期: 2021-12-17
- 刊出日期: 2022-12-01

Supercapacitive performances of 5-sulfosalicylic acid doped polypyrrole/ZIF67 composites

College of Materials Science and Engineering, Shandong University of Science and Technology, Qingdao 266590, China

摘要

摘要: 为充分利用金属-有机框架化合物(MOF)丰富的多孔结构与导电聚合物的独特掺杂结构，研究掺杂剂对MOF/导电聚合物复合材料的结构及电化学性能的影响，以实现稳定的化学掺杂。通过调控Co²⁺与2-甲基咪唑的摩尔配比常温反应制备得到三维花状结构的ZIF-67(命名为Z8)；利用简便的原位聚合反应制备得到5-磺基水杨酸(5-SSA)掺杂聚吡咯(PPy)/Z8复合材料。Z8的引入能在一定程度上减少PPy微球的堆积，其与5-SSA之间的多重氢键、共轭效应等有利于PPy实现稳定的化学掺杂，其有利于电子及电解质离子的快速传输，并为PPy提供支撑。电化学测试结果表明，所有的复合材料中，PPy/10wt%Z8可获得最佳的电化学性能，其在1 A·g⁻¹的电流密度下的比电容可达300 F·g⁻¹。以PPy/10wt%Z8为正极，活性炭为负极，柔性碳布作为支撑体，聚乙烯醇(PVA)-H₂SO₄为电解质组装得到柔性非对称超级电容器，在1 mA·cm⁻²的电流密度下，其比电容为200 mF·cm⁻²，能量密度为71 μW·h·cm⁻²，功率密度为800 μW·cm⁻²，并且在10 mA·cm⁻²电流密度下循环10000次后，器件的电容保持率为80.2%，表现出良好的超电容特性。
- 磺基水杨酸 /
- 聚吡咯 /
- Z8 /
- 复合材料 /
- 超级电容器
Abstract: In order to make full use of the structure of the rich porous structure of metal-organic frame material (MOF) and the unique doping structure of conductive polymers, the influence of dopants on the structure and electrochemical properties of MOF/conductive polymer complexes are studied to achieve stable chemical doping. 3D flower-like ZIF-67 (Z8) was firstly prepared by controlling the ratio of Co²⁺ and 2-methylimidazole at room temperature. 5-Sulfosalicylic acid (5-SSA) doped polypyrrole (PPy)/Z8 composites were synthesized via facile in-situ polymerization. The introduction of Z8 can reduce the agglomeration of the obtained PPy microspheres. The stable chemical doping can be achieved by the multiple bonds and the conjugation effects between 5-SSA and Z8. This will be helpful for the fast transfer of electrons and electrolyte ions and the strong support for the PPy chains. The resulted composites with 10wt% Z8 loading (PPy/10wt%Z8) achieves the highest specific capacitance of 300 F·g⁻¹ among the PPy/Z8. The asymmetric supercapacitor assembled by PPy/10wt%Z8 and active carbon on carbon cloth as flexible electrodes demonstrates high areal capacitance (200 mF·cm⁻²), high energy density (71 μW·h·cm⁻²) and power density (800 μW·cm⁻²). Moreover, the flexible supercapacitor provides excellent cycle stability after 10000 cycles (80.2% capacitance retention), indicating good supercapacitive performances.
- 5-sulfosalicylic acid /
- polypyrrole /
- Z8 /
- composites /
- supercapacitor

HTML全文

图 1 PPy/Z8复合材料的合成示意图

Figure 1. Schematic diagram of the synthesis process of PPy/Z8 composite

APS—Ammonium persulfate; 5-SSA—5-sulfosalicylic acid; Z8—ZIF-67 with three-dimensional flower-like structure

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图 2 Z8 (a)、PPy (b)、PPy/5wt%Z8 (c)、PPy/10wt%Z8 (d)、PPy/20wt%Z8 (e) 和PPy/30wt%Z8 (f) 的SEM图像

Figure 2. SEM images of Z8 (a), PPy (b), PPy/5wt%Z8 (c), PPy/10wt%Z8 (d), PPy/20wt%Z8 (e) and PPy/30wt%Z8 (f)

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图 3 PPy/5wt%Z8 (a)、PPy/10wt%Z8 (b)、PPy/20wt%Z8 (c) 和PPy/30wt%Z8 (d) 的TEM图像

Figure 3. TEM images of PPy/5wt%Z8 (a), PPy/10wt%Z8 (b), PPy/20wt%Z8 (c) and PPy/30wt%Z8 (d)

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图 4 Z8、PPy、PPy/5wt%Z8、PPy/10wt%Z8、PPy/20wt%Z8和PPy/30wt%Z8的红外光谱图(a)和XRD图谱 (b)；PPy、PPy/5wt%Z8、PPy/10wt%Z8、PPy/20wt%Z8和PPy/30wt%Z8的Raman图谱(c)和ESR图谱(d)

Figure 4. FTIR (a) and XRD (b) spectra of Z8, PPy, PPy/5wt%Z8, PPy/10wt%Z8, PPy/20wt%Z8 and PPy/30wt%Z8; Raman (c) and ESR (d) spectra of PPy, PPy/5wt%Z8, PPy/10wt%Z8, PPy/20wt%Z8 and PPy/30wt%Z8

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图 5 PPy、PPy/5wt%Z8、PPy/10wt%Z8、PPy/20wt%Z8和PPy/30wt%Z8的XPS全谱图 (a)；PPy (b)、PPy/5wt%Z8 (c)、PPy/10wt%Z8 (d)、PPy/20wt%Z8 (e) 和PPy/30wt%Z8 (f) 的C1s XPS图谱

Figure 5. XPS spectra (a) of PPy, PPy/5wt%Z8, PPy/10wt%Z8, PPy/20wt%Z8 and PPy/30wt%Z8; C1s XPS spectra of PPy (b), PPy/5wt%Z8 (c), PPy/10wt%Z8(d), PPy/20wt%Z8 (e) and PPy/30wt%Z8 (f)

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图 6 PPy (a)、PPy/5wt%Z8 (b)、PPy/10wt%Z8 (c)、PPy/20wt%Z8 (d) 和 PPy/30wt%Z8 (e) 的N1s XPS谱图

Figure 6. N1s XPS spectra of PPy (a), PPy/5wt%Z8 (b), PPy/10wt%Z8 (c), PPy/20wt%Z8 (d) and PPy/30wt%Z8 (e)

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图 7 PPy和PPy/Z8在三电极体系中的CV曲线 (a)； PPy/10wt%Z8在不同扫描速率下的CV曲线 (b)；PPy和PPy/Z8在1 A·g⁻¹下的GCD曲线 (c)；PPy/10wt%Z8在不同电流密度下的GCD曲线 (d)；PPy和PPy/Z8的EIS曲线 (e)；Z8、PPy和PPy/Z8在10 A·g⁻¹下的循环稳定性 (f)

Figure 7. CV curves of PPy and PPy/Z8 in three-electrode system (a); CV curves of PPy/10wt%Z8 at different scanning rates (b); GCD curves of PPy and PPy/Z8 under 1 A·g⁻¹ (c); GCD curves of PPy/10wt%Z8 at different current densities (d); EIS curves of PPy and PPy/Z8 (e); Cyclic stability of Z8, PPy and PPy/Z8 at 10 A·g⁻¹ (f)

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图 8 PPy/10wt%Z8//AC器件在不同电压范围内的CV曲线 (a)；不同电流密度下的GCD曲线 (b) 和比电容值 (c)；EIS曲线 (d)；与文献中数据相比较的Ragone图^[7,29-31] (e)；在10 mA·cm⁻²下的循环稳定性 (f)；点亮LED电路板的照片 (g)

Figure 8. CV curves of PPy/10wt%Z8//AC devices in different voltage ranges (a); GCD curves (b) and specific capacitance (c) under different current densities; EIS curve (d); Ragone plots of the devices comparing with the data previously reported^[7,29-31] (e); Cycle stability at 10 mA·cm⁻² (f); Photo of lit LED circuit board (g)

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表 1 聚吡咯(PPy)/Z8复合材料的命名

Table 1. Naming of polypyrrole (PPy)/Z8 composites

Sample	Mass fraction of Z8/wt%
PPy/5wt%Z8	5
PPy/10wt%Z8	10
PPy/20wt%Z8	20
PPy/30wt%Z8	30

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