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化学进展 2021, Vol. 33 Issue (10): 1841-1855 DOI: 10.7536/PC200862 前一篇   后一篇

• 综述 •

聚(3,4-乙烯二氧噻吩)∶聚苯乙烯磺酸/无机纳米复合材料的制备及应用

谭莎1,2, 马建中1,2,*(), 宗延1,2,*()   

  1. 1 陕西科技大学轻工科学与工程学院 西安 710021
    2 西安市绿色化学品与功能材料重点实验室 西安 710021
  • 收稿日期:2020-08-24 修回日期:2020-10-23 出版日期:2021-10-20 发布日期:2020-12-28
  • 通讯作者: 马建中, 宗延
  • 基金资助:
    国家重点研发计划(2017YFB0308602); 国家自然科学基金项目(51903143)
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Preparation and Application of Poly(3,4-ethylenedioxythiophene)∶Poly(4-styrenesulfonate)/Inorganic Nanocomposites

Sha Tan1,2, Jianzhong Ma1,2(), Yan Zong1,2()   

  1. 1 College of Bioresources Chemical and Materials Engineering, Shaanxi University of Science and Technology, Xi'an 710021, China
    2 Xi'an Key Laboratory of Green Chemicals and Functional Materials, Xi'an 710021, China
  • Received:2020-08-24 Revised:2020-10-23 Online:2021-10-20 Published:2020-12-28
  • Contact: Jianzhong Ma, Yan Zong
  • Supported by:
    National Key Research and Development Program of China(2017YFB0308602); National Natural Science Foundation of China(51903143)

聚(3,4-乙烯二氧噻吩)∶聚(苯乙烯磺酸)(PEDOT∶PSS)是一种水溶性导电高分子体系,具有易加工、高透光率及柔韧性等优点,但其应用范围仅限于作为电子器件的柔性电极材料。为了进一步扩大PEDOT∶PSS的应用范围,将无机纳米材料引入该体系实现材料的多功能化是较为有效的方法。本文首先介绍了PEDOT∶PSS/无机纳米复合材料最常用的四种制备方法,即原位法、共混法、自组装法、插层复合法,分别介绍了每种制备方法的原理和特点,并阐述了研究人员对复合材料的结构设计思路及引入的无机相对材料性能的影响。随后,综述了PEDOT∶PSS/无机纳米复合材料在传感器、太阳能电池、超级电容器、热电发电机等领域中应用的最新进展。最后指出了目前在PEDOT∶PSS/无机纳米复合材料的研究中面临的挑战,并对该材料的研究方向和发展趋势进行了展望。

关键词： 聚(3,4-乙烯二氧噻吩), 无机纳米材料, 传感器, 太阳能电池, 超级电容器, 热电发电机

The complex of poly(3,4-ethylenedioxythiophene)∶poly(4-styrenesulfonate)(PEDOT∶PSS) is a water-soluble conducting polymer system with many advantages such as easy processability, high transmittance and flexibility. Its application, however, is only limited as flexible electrode material in some electronic devices. To solve this, introducing inorganic nanomaterials into PEDOT∶PSS complex to realize multifunctional materials is a relatively effective method to further expand its application. In this review, four most commonly used strategies to prepare PEDOT∶PSS/inorganic nanocomposites, including in-situ method, blending method, self-assembly method and intercalation method are summarized at first. Following this, each of the methods is detailed with their mechanism and experimental features, and the structural design of the nanocomposites as well as the structure-property relationships that affected by introduced inorganic nanofillers are also elucidated. Then the latest research progress of applications in sensors, solar cells, supercapacitors, thermoelectric generators of PEDOT∶PSS/inorganic nanocomposites are reviewed. Finally, the existing challenges in PEDOT∶PSS/inorganic nanocomposites studies are pointed out, and the future perspectives are provided for the research direction and potential progress and trends of these materials.

Contents

1 Introduction

2 Preparation of PEDOT∶PSS/inorganic nanocomposites

2.1 In-situ method

2.2 Blending method

2.3 Self-assembly method

2.4 Intercalation preparation method

3 Applications of PEDOT∶PSS/inorganic nanocomposites

3.1 Sensors

3.2 Solar cells

3.3 Supercapacitors

3.4 Thermoelectric generators

3.5 Other applications

4 Conclusion and outlook

Key words: PEDOT, inorganic nanomaterials, sensors, solar cells, supercapacitors, thermoelectric generators
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图式1 PEDOT∶PSS的化学结构
Scheme 1 Chemical structure of PEDOT∶PSS
图1 PEDOT∶PSS包覆Cu7Te4/PEDOT∶PSS包覆Te复合薄膜的制备示意图[38]
Fig. 1 Schematic of the fabrication of the PEDOT∶PSS-coated Cu7Te4/PEDOT∶PSS-coated Te composite film. Reprinted with permission from [38]. Copyright 2018, American Chemical Society
图2 PEDOT∶PSS/石墨烯/MWCNTs复合材料的直接原位合成示意图[55]
Fig. 2 Synthetic scheme of direct in-situ synthesis of PEDOT∶PSS/graphene/MWCNTs composites. Reprinted with permission from [55]. Copyright 2013, Royal Society of Chemistry
图3 PEDOT∶PSS/Au纳米复合材料的制备示意图[57]
Fig. 3 Schematic of the preparation of PEDOT∶PSS/Au nanocomposites. Reproduced from reference [57]. Copyright 2007, American Chemical Society
图4 (a)Ag/PEDOT∶PSS复合界面制备示意图;(b)X射线光电子能谱((a)纯PEDOT∶PSS和(b)Ag/PEDOT∶PSS);(c)透射光谱;(d)纯PEDOT∶PSS薄膜和Ag/PEDOT∶PSS薄膜的紫外光电子能谱图;(e)带有ITO/PEDOT∶PSS或Ag/PEDOT∶PSS/Ag结构的装置在暗处的log(J)-log(V)表征。所有复合膜掺杂Ag的体积百分比为5%[81]
Fig. 4 (a) Schematic of the preparation of Ag/PEDOT∶PSS composite interface;(b) X-ray photoelectron spectroscopy(XPS)((a) pristine PEDOT∶PSS and(b) Ag/PEDOT∶PSS);(c) transmittance spectra; and(d) ultraviolet photoelectron spectroscopy(UPS) images of pristine PEDOT∶PSS and Ag/PEDOT∶PSS films;(e) log(J)-log(V) characterization of the device with a structure of ITO/PEDOT∶PSS or Ag/PEDOT∶PSS/Ag in the dark. The doping content of Ag is 5% in volume ratio for all of the composite films. Reprinted with permission from [81]. Copyright 2019, American Chemical Society
图5 单层Co-Ni LDH和PEDOT∶PSS组装示意图[92]
Fig. 5 Schematic of the assembly of CoNi LDH monolayers and PEDOT∶PSS[92]. Copyright 2015, John Wiley & Sons
图6 PEDOT∶PSS/氧化铁纳米复合薄膜转移到不同衬底上:(a)PVA支撑层溶解后漂浮在水上的含5 mg/mL氧化铁纳米粒子的无支撑PEDOT∶PSS/氧化铁纳米薄膜(2 cm×1 cm);(b)钢丝网上的含1 mg/mL氧化铁纳米粒子的PEDOT∶PSS/氧化铁纳米薄膜的SEM照片(比例尺为100 μm);(c)在聚四氟乙烯螺钉上;(d)在纸上;(e)在塑料管上;(f)在柔性PDMS上,(g)在纸上收集的纳米薄膜边缘的SEM照片,显示了纳米薄膜符合纸纤维结构(比例尺为50 μm)[110]
Fig.6 PEDOT∶PSS/iron oxide composite nanofilms transferred to various substrates:(a) freestanding PEDOT∶PSS/NP5 nanofilm(2 cm×1 cm) floating in water after PVA dissolving.(b) SEM micrographs showing PEDOT∶PSS/NP1 nanofilm collected onto a steel mesh(scale bar: 100 μm). Nanofilms collected onto(c) Teflon screw,(d) paper,(e) plastic tube, and(f) flexible PDMS. In(g), an SEM picture of the edge of ananofilm collected on paper showing the paper fiber structure to which the nanofilm conforms(scale bar: 50 μm). Reprinted with permission from [110]. Copyright 2013, American Chemical Society
图7 倒置平面钙钛矿太阳能电池的结构示意图[120]
Fig. 7 Inverted planar perovskite solar cell[120]
图8 制备RuO2/PEDOT∶PSS/石墨烯丝网印刷电极的步骤和丝网印刷电极的数码相机图[123]
Fig. 8 Overall procedure for fabricating RuO2/PEDOT∶PSS/graphene screen-printed electrode and digital camera image of screen-printed electrode. Reprinted with permission from [123]. Copyright 2015, American Chemical Society
图9 杂化热电材料和热电装置的制备示意图:步骤(1),一锅原位合成PEDOT∶PSS/Bi2Te3杂化纳米线;步骤(2),纳米线嵌入PEDOT∶PSS纳米膜作为热电性能测试样品的自组装三维网络结构的制备;步骤(3),用于大规模的低温能量采集的热电绝缘管装置的制备[138]
Fig. 9 Schematic showing the processing steps of the hybrid TE material and device: step(1), one-pot synthesis of the in situ PEDOT∶PSS/Bi2Te3 hybrid nanowire; step(2), fabrication of the self-assembled 3D network of nanowire-embedded PEDOT∶PSS nanofilms as TE test specimen; and step(3), construction of the insulator-pipeline TE device for large-scale deployment of low-temperature energetic harvesting. Reprinted with permission from [138]. Copyright 2019, American Chemical Society
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