基于并二噻吩桥联聚吡咯薄膜的微型超级电容器

侯鹏鑫; 姜恺悦; 翟光群; 庄小东

doi:10.14133/j.cnki.1008-9357.20210110001

基于并二噻吩桥联聚吡咯薄膜的微型超级电容器

doi: 10.14133/j.cnki.1008-9357.20210110001

侯鹏鑫^{1, 2,},
姜恺悦²,
翟光群^1, ,,
庄小东^2, ,

1.
常州大学材料科学与工程学院，江苏常州 213164
2.
上海交通大学化学化工学院，金属基复合材料国家重点实验室，上海市电气绝缘与热老化重点实验室，变革性分子前沿科学中心，上海 200240

基金项目: 科技部重点研发计划（2017YFE9134000）；国家自然科学基金（51973114，21720102002，51811530013）；上海市科委科技创新行动计划（19JC412600）

详细信息

作者简介:
侯鹏鑫（1996—），男，硕士生，主要研究方向为二维聚合物与膜。E-mail：18000262@smail.cczu.edu.cn

通讯作者:
翟光群，E-mail：zhai_gq@cczu.edu.cn

庄小东，E-mail：zhuang@sjtu.edu.cn

中图分类号: O631
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出版历程
- 收稿日期: 2021-01-10
- 网络出版日期: 2021-03-02
- 刊出日期: 2021-10-01

Thieno[3,2-b]thiophene-Bridged Polypyrrole Film-Based Micro-Supercapacitors

HOU Pengxin^{1, 2
,},
JIANG Kaiyue²,
ZHAI Guangqun^{1
, ,},
ZHUANG Xiaodong^{2
, ,}

1.
School of Materials Science and Engineering, Changzhou University, Changzhou 213164, Jiangsu, China
2.
Frontiers Science Center for Transformative Molecules, State Key Laboratory of Metal Matrix Composites, Shanghai Key Laboratory of Electrical Insulation and Thermal Ageing, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

摘要

摘要: 将富电子的并二噻吩单元作为吡咯单体的桥联基团，得到具有四臂活性位点的吡咯单体；再利用液液界面的氧化聚合反应，直接制备得到连续、大面积的超薄聚吡咯膜。通过直接激光刻蚀的方法，制备了微型超级电容器，并研究了其通过循环伏安曲线、阻抗测试、相位角测试等表征电容器的电化学性能。结果表明，基于该薄膜的微型超级电容器的面积比电容可达1.10 mF/cm²，体积比电容可达68.4 F/cm³，等效串联电阻为4.2 Ω，最大能量密度为9.50 mW·h/cm³，最大功率密度为1433 W/cm³。
- 聚吡咯 /
- 膜 /
- 界面聚合 /
- 微型超级电容器
Abstract: Polypyrrole, one of the famous conventional conductive polymers, has been well studied in the past decades. Due to the rational controlling methods of morphology and structure, polypyrrole-based materials have shown great potential in the field of energy conversion and storage. For example, polypyrrole could contribute excellent pseudocapacitance as electrode material for supercapacitors. However, synthesis of two-dimensional polypyrrole or ultra-thin films remains a challenge because of the easy aggregation and poor solubility features. In this work, the electron-rich thieno[3,2-b]thiophene unit is used to bridge pyrrole monomers to produce four-armed bipyrrole monomer. At liquid-liquid interface, conventional oxidative polymerization reaction can take place and uniform polypyrrole film with large area can be easily produced. Through directly laser scribing, interdigitated micro-supercapacitors based on Au layer supported polypyrrole film can be produced. After evaluation through cyclic voltammetry curves, impedance curves, etc., the micro-supercapacitors show areal specific capacitance of 1.10 mF/cm², volumetric specific capacitance of 68.4 F/cm³, equivalent series resistance（ESR） of 4.2 Ω. The maximum energy density and power density of as-prepared micro-supercapacitors reach 9.50 mW·h/cm³ and 1 433 W/cm³, respectively.
- polypyrrole /
- film /
- interfacial polymerization /
- micro-supercapacitor

HTML全文

图 1 聚2,5-二（1H-吡咯）-噻吩并[3,2-b]噻吩（PPy-3）的合成路线

Figure 1. Synthesis of poly（2,5-di（1H-pyrrol-1-yl）thieno[3,2-b]thiophene）（PPy-3）

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图 2 平面PPy-3-MSC的制备流程示意图（基底为玻璃片）：（i）通过液液界面聚合得到PPy-3膜；（ii）将PPy-3膜转移至玻璃基底上；（iii）在PPy-3膜上溅射金层；（iv）激光蚀刻制备叉指电极；（v）将LiCl/PVA凝胶电解质滴在Au/PPy-3叉指电极上获得PPy-3-MSC

Figure 2. Schematic illustration of PPy-3-MSC on a glass substrate：（i）Synthesis of PPy-3 film through liquid-liquid polymerization; （ii）Transferring PPy-3 film onto a glass substrate; （iii）Sputtering Au on PPy-3 film; （iv) Preparation of interdigital electrodes by laser scribing; （v) Drop casting LiCl/PVA gel electrolyte onto the Au/PPy-3 interdigital electrodes, then after solidification, PPy-3 film-based MSC can be produced

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图 3 （a）Py-3和PPy-3粉末的FT-IR光谱；（b）不同氧化剂制备的PPy-3薄膜的FT-IR光谱；（c）PPy-3薄膜的GIWAXS分析；（d）平面内（q_z=0附近）和平面外（q_xy=0附近）的GIWAXS曲线

Figure 3. （a）FT-IR spectra of Py-3 and PPy-3 powder; （b）FT-IR spectra of PPy-3 films prepared by different oxidants; （c）GIWAXS analysis of PPy-3 films; （d） GIWAXS profiles in-plane （near q_z=0） and out-of-plane （near q_xy=0）

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图 4 （a）PPy-3膜的电子显微镜照片；（b）PPy-3粉末的TGA曲线；（c）PPy-3粉末的氮吸附和解吸附曲线；（d）由吸附分支计算出的PPy-3粉末的孔径分布曲线

Figure 4. （a）SEM image of PPy-3 film; （b）TGA curve of PPy-3 powder; （c）Nitrogen adsorption and desorption isotherms of PPy-3 powder;（d）Pore size distribution curve of PPy-3 powder calculated from the adsorption branch

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图 5 （a）PPy-3膜的UPS谱图；（b）PPy-3膜的固体UV-Vis谱图；（c）（hvα）²-hv曲线（曲线切线与基线交点为带隙能级E_bg=2.75 eV）

Figure 5. （a）UPS spectra of PPy-3 film; （b）UV-Vis spectrum of PPy-3 film; （c）（hvα）²-hv curve（The value at the intersection baseline and the tangent of the curve is the bandgap energy E_bg=2.75 eV）

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图 6 （a）叉指电极在玻璃基板上的光学显微镜照片；（b）不含PVA/LiCl电解质的PPy-3-MSC横截面的SEM照片

Figure 6. （a）OM image of interdigital finger electrodes patterned on glass substrate; （b）SEM image of cross-section of PPy-3-MSC without PVA/LiCl electrolyte

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图 7 （a）不同扫描速率下PPy-3-MSC在PVA/LiCl凝胶电解质中的CV曲线；（b）不同扫描速率下的面积电容和体积电容；（c）阻抗分析图；（d）阻抗相位角对PVA/LiCl中PPy-3-MSC频率的影响

Figure 7. （a）CV curves of PPy-3-MSC in PVA/LiCl gel electrolyte at different scan rates; （b）Evolution of areal capacitance and volumetric capacitance at different scan rates; （c）Nyquist plot; （d）Effect of impedance phase angle on the frequency of PPy-3-MSC in PVA/LiCl

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图 8 MSC-PPy-3的Ragone曲线图（红色线）

Figure 8. Ragone plots for MSC-PPy-3 in LiCl/PVA electrolyte（red line）

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表 1 PPy-3-MSC与近期报道二维材料的性能对比

Table 1. Performance of recent reported 2D materials and PPy-3-MSC

Electrode	C_A/(mF·cm⁻²)	C_V/(F·cm⁻³)	β/(mV·s⁻¹)	E_V /(mW·h·cm⁻³)	P_V/(W·cm⁻³)	Thickness	Electrolyte	Reference
G-CNTCs	2.16 3.93	1.08 1.96	100 A/cm³ 50 A/cm³	0.16 2.42	115（400 V/s） 135	NA	1 mol/L Na₂SO₄ 1 mol/L BMIMBF4	[28]
RGO	0.51	3.1	20	0.43（1.7 W/cm³）	9.4（0.19 mW·h/cm³）	NA	NO	[29]
PiCBA	0.102	34.1	50	4.7（50 mV/s）	1323（1000 V/s）	30 nm	PVA/H₂SO₄	[30]
mPPy@GO	0.076	NA	10	NA	NA	2 μm	PVA/H₂SO₄	[31]
MPG	0.08	17.9	10	2.5（10 mV/s）	495（0.14 mW·h/cm³）	15 nm	PVA/H₂SO₄	[32]
EG/MXene	NA	184	0.2 A/cm³	3.4（0.2 W/cm³）	1.6（1.4 mW·h/cm³）	2.5 μm	PVA/H₃PO₄	[33]
	3.26	33	5	NA	NA
TaS₂	NA	508	10	58.5	1.316	330 nm	PVA/LiCl	[34]
Graphene	0.89	2	5	1.81	0.297	5 μm	EMIMNTF2	[35]
Graphene	0.338 ^1）	197 ^1）	10	23（0.32 W/cm³）	1 860	NA	Ionogel	[36]
MoS₂	8	178	10	NA	NA	450 nm	Aqueous	[37]
NiCo₂S₄	4000	NA	7 mA/cm²	200 μW·h/cm²	4.4（mW/cm²）	0.5−1.2 mm	1 mol/L KOH	[38]
PPy-3	1.10	68.4	10	9.5（0.34 W/cm³）	1433（0.20 mW·h/cm³）	～160 nm	PVA/LiCl	This work
1） PVA/H₂SO₄ electrolyte

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