生物质衍生没食子酸增强PEDOT:PSS膜导电性能及其调控机制

徐慧民; 李莉娟; 欧阳新华; 霍延平; 陈礼辉; 黄六莲; 倪永浩; 胡会超

doi:10.13801/j.cnki.fhclxb.20201126.003

生物质衍生没食子酸增强PEDOT:PSS膜导电性能及其调控机制

徐慧民^1,,
李莉娟^1,,
欧阳新华^1, ,,
霍延平^2,,
陈礼辉^1,,
黄六莲^1,,
倪永浩^{1, 3,},
胡会超^1, ,

1.
福建农林大学　材料工程学院，福州 350002
2.
广东工业大学　轻工化工学院，广州 510006
3.
新布伦瑞克大学　化学工程系，弗雷德里克顿，P.O. Box 4400

基金项目: 国家自然科学基金(31700507；21674123)；国家重点研发计划项目(2019YFC1905903；2017YFB0307900)

详细信息

通讯作者:
欧阳新华，博士，教授，博士生导师，研究方向为光电材料与光电器件　 E-mail：hhc_huichao@163.com，ouyangxh@fafu.edu.cn

胡会超，博士，副教授，硕士生导师，研究方向为生物质精炼与生物质基材料

中图分类号: TB332
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出版历程
- 收稿日期: 2020-09-09
- 录用日期: 2020-11-07
- 网络出版日期: 2020-11-25
- 刊出日期: 2021-07-14

Enhanced conductivity and regulated mechanism of PEDOT:PSS film with biomass-derived gallic acid

1.
College of Material Engineering, Fujian Agriculture and Forestry University, Fuzhou 350002, China
2.
School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China
3.
Department of Chemical Engineering, University of New Brunswick, Fredericton P.O. Box 4400, Canada

摘要

摘要: 聚3, 4-乙烯二氧噻吩(PEDOT)因其具有柔性可拉伸、生物相容性高、导电及功函数可调控等优势在柔性可穿戴电子器件中显示出广阔的应用前景。近年来，随着资源危机的日益凸显，针对PEDOT:聚苯乙烯磺酸(PSS)体系，研究开发高效绿色可持续的生物质基掺杂剂，已引起相关研发人员的高度关注。本研究首次报道了采用生物质芳香弱酸−没食子酸(GA，pKa为4.41)掺杂制备高性能PEDOT导电膜的新途径。GA独特的邻多酚羟基结构创造了稳定的GA-PSSH双氢键，使得GA-PSSH的分子结合能显著高于GA的石油基强酸异构体(2, 4, 6-三羟基苯甲酸，pKa=1.68)与PSSH的分子结合能。GA掺杂不仅可实现PEDOT-PSS的高效相分离，而且优化了PEDOT分子链的构象、聚集结构的形貌及其排列方向。这赋予GA具有很高的掺杂效率，当GA掺杂量为1.2%时，PEDOT导电膜的电导率可提升三个数量级，达到1050 S/cm，导电性能达到已报道的生物质基掺杂剂的最高水平，且掺杂效率明显优于其它生物质基掺杂剂及其石油基强酸异构体。
- 没食子酸 /
- 导电膜 /
- 聚3, 4-乙烯二氧噻吩 /
- 电导率 /
- 掺杂剂
Abstract: Since poly(3, 4-ethylenedioxythiophene) (PEDOT) has advantages of flexible stretchable, high biocompatibility, and controllable conductivity and work function, it has emerged extensive application prospects in the flexible wearable electronic devices. In recent years, as the increasingly resources crisis, research and development of the high efficient, green, and sustainable bio-based dopant for PEDOT: PSS (polystyrene sulfonate) system has attracted serious concerns of the relevant researchers. For the first time, this work reported a new approach to prepare high-performance PEDOT conductive film using biomass-derived aromatic weak acid, i.e., gallic acid (GA, pKa of 4.41). Its special structure of adjacent multiple phenolic hydroxyl groups created a stable dual-hydrogen bonds combination with PSSH. The binding energy of GA-PEDOT is significantly higher than that of its petroleum-based strong acidic isomer (2, 4, 6-trihydroxybenzoic acid with pKa of 1.68, ) with PEDOT. GA doping not only realized the high efficient phase separation of PEDOT-PSS, but also optimized the conformational of PEDOT molecular chain, the optimal morphology and orientation of aggregation structure. This endowed GA with high doping efficiency, and the conductivity of PEDOT conductive film can be upgraded by three orders of magnitude to 1050 S/cm, only with 1.2% of doping amount of GA. That has reached the highest conductive feature in all reported bio-based dopants, and the doping efficiency of GA is significantly higher than that of bio-based dopant and its petroleum-based strong acidic isomer.
- gallic acid /
- conductive film /
- poly(3, 4-ethylenedioxythiophene) /
- conductivity /
- dopant

HTML全文

图 1 生物质基GA掺杂制备高导电PH1000纳米膜的路径(a)、GA掺杂与去离子水后处理对导电膜聚集结构的作用机制(b)以及GA、2,4,6-三羟基苯甲酸与PEDOT、PSS/PSSH间的静电与氢键作用(c)

Figure 1. Pathway of high-conductive PH 1000 nanofilm prepared by doping with bio-based GA (a), interaction mechanism of GA doping and DI water post-treatment on aggregation structure of conductive film (b), electrostatic and hydrogen bond interaction of GA, 2,4,6-THBA with PEDOT and PSSH/PSS (c)

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图 2 退火温度、时间与去离子水后处理时间对PEDOT:PSS导电膜电导率的影响(a)以及没食子酸掺杂与去离子水后处理对PEDOT:PSS膜电导率和厚度的影响(b)

Figure 2. Effect of DI water post-treatment time, annealing time and temperature on conductivity of PEDOT:PSS conductive film (a), andinfluence of GA doping and DI water post-treatment on its conductivity and thickness (b)

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图 3 没食子酸与导电膜PH1000、PH1000/GA、PH1000/GA-W的红外谱图

Figure 3. FTIR spectra of gallic acid and conductive films of PH1000, PH1000/GA and PH1000/GA-W

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图 4 导电膜PH1000、PH1000/GA和PH1000/GA-W的拉曼光谱

Figure 4. Characterization on conductive films of PH1000, PH1000/GA, and PH1000/GA-W by Raman spectrum

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图 5 导电膜PH1000、PH1000/GA和PH1000/GA-W的XPS(a)与UV-Vis(b)谱图

Figure 5. Characterization on conductive films of PH1000, PH1000/GA, and PH1000/GA-W by XPS (a), and UV-Vis (b)

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图 6 导电膜PH1000、PH1000/GA和PH1000/GA-W的AFM表面形貌图((a)-(c))和相图((d)-(e))

Figure 6. AFM iamges of surface topography ((a)-(c)) and phase mapping ((d)-(e)) of conductive films of PH1000, PH1000/GA and PH1000/GA-W

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图 7 没食子酸、2,4,6-三羟基苯甲酸和单宁酸掺杂量对纳米膜电导率的影响

Figure 7. Dependence of conductivity on doping amount of gallic acid, 2,4,6-trihydroxybenzoic acid, and tannin acid.

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S1 FTIR spectra of films fabricated by gallic acid, PH1000 and PH1000/GA with or without post-treatment.

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S2 Raman spectra of conductive films fabricated by PH1000, PH1000/GA with or without post-treatment

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S3 PEDOT-PSS/PSSH, GA-PEDOT/PSSH和2,4,6-THBA-PEDOT/PSSH的稳定结构和氢键长(单位: 0.1 nm)

S3. Stable conformations and hydrogen bond distances (Unit: 0.1 nm) of PEDOT-PSS/PSSH, GA-PEDOT/PSSH, and 2,4,6-THBA-PEDOT/PSSH

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表 1 没食子酸、2,4,6-三羟基苯甲酸和单宁酸掺杂制备纳米膜的导电性能对比

Table 1 Comparison on conductivity of nanofilms prepared by doping with GA, 2,4,6-THBA, and tannin acid.

Additives	Melting point/℃	pKa	Addition	Post-soaking with DI water	Thickness / nm	σ/(S·cm⁻¹)
Tannic acid	218	6	1.0%	No^[14]	135.9±1.2	2.48±0.6
			1.0%	5 min	67.6±2.7	65.7±2.5
			2.5%	No^[14]	250.2±3.5	25.0±28
			2.5%	60 min^[14]	110.0±1.3	453.0±21
Gallic acid	252	4.41	1.0%	No	90.8±4.0	563±30
			1.0%	5 min	68.2±2.2	961±32
			1.2%	5 min	69.3±0.6	1050±27
2,4,6-THBA	210	1.68	1.0%	5 min	46.5±1.3	411±12

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表 2 典型结合结构的氢键作用与分子结合能

Table 2 Hydrogen bonds and molecular binding energies of typical binding structure

Binding structure		H-bond distance /10^-1nm	Coulomb force /nN	Binding energy /eV
PEDOT	PSSH	2.633	0.192	−0.425
	PSSH	2.634 (2.889)	0.272 (0.201)	−0.425
	PSS	2.874 (2.589)	0.213 (0.271)	−0.872
	PSS	2.522 (2.975)	0.292 (0.187)	−0.872
2,4,6-THBA	PSSH	1.667	1.511	−0.787
2,4,6-THBA	PEDOT	2.848 (2.467)	0.234 (0.369)	−0.343
GA	PSSH	1.714 (1.653)	1.530 (1.574)	−1.168
GA	PEDOT	2.495 (2.324)	0.350 (0.396)	−0.314

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S1 添加或不添加去离子水后处理后的GA掺杂导电膜的厚度和电导率

S1 Thickness and conductivity of GA-doping conductive films with or without DI water post-treatment

Content of GA/%	PH1000/GA		PH1000/GA-W
Content of GA/%	Thickness/nm	Conductivity/(S·cm⁻¹)	Thickness/nm	Conductivity/(S·cm⁻¹)
0.0	65.0±0.62	0.93±0.02	58.7±3.64	0.93±0.07
0.2	65.3±1.59	43.9±1.02	59.8±4.31	125.8±11.57
0.4	70.1±2.68	186.3±4.63	64.8±1.57	364.8±11.62
0.6	75.0±2.49	296.3±14.53	67.5±2.77	618.9±21.19
0.8	80.1±4.37	543.5±35.36	68.1±2.43	799.2±20.89
1.0	90.7±3.97	563.4±29.9	68.2±2.16	961.5±32.04
1.2	–	–	69.3±0.60	1050.5±27.31
1.4	–	–	69.3±2.48	1041.6±28.49
1.5	–	–	69.6±1.06	1039.9±35.69
1.8	–	–	69.7±0.8	1032.7±35.66
2.0	–	–	69.1±1.26	1040.9±36.22

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S2 2,4,6-THBA掺杂的DI水后处理导电膜的厚度和电导率

S2 Thickness and conductivity of 2,4,6-THBA-doping conductive films with DI water post-treatment

2,4,6-TBHA/%	Thickness/nm	Conductivity/(S·cm⁻¹)
0.0	58.7±3.64	0.93±0.02
0.5	50.6±1.71	322.6±14.1
1.0	46.5±1.33	411.0±4.12
1.5	44.0±1.70	657.1±6.91
2.0	40.9±1.31	810.6±5.09
2.5	45.3±1.72	1031.6±8.84
2.75	45.9±2.65	1007.9±30.7
3.0	45.6±1.85	983.5±30.8
4.0	46.1±1.87	1001.7±30.1

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