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Inkjet printing of 2D polyaniline for fabricating flexible and patterned electrochromic devices

用于柔性和图案化电致变色器件的二维聚苯胺的喷墨打印研究

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Abstract

Conjugated organic polymer (COP)-based electrochromic devices (ECDs) exhibit promising applications in digital and color displays. However, fabricating COP-based ECDs integrated with excellent electrochromic performance, customized patterns, and flexibility remains challenging. In this study, we report inkjet-printed, flexible, and patterned ECDs based on two-dimensional (2D) polyaniline (PANI) sheets, which are evenly dispersed in formic acid (FA) enabling high-precision, stable inkjet printing. The pristine lamellar structure of PANI sheets, which combine nanoscale thickness and an appropriate doping ratio, and the additive-free ink composition endow the printed PANI electrodes and ECDs with high performance. The fabricated PANI electrode exhibits a high optical contrast (76% at a wavelength of 750 nm), a good coloration efficiency (CE) of 259.1 cm2 C−1, and a short coloration/bleaching time (1.8/2.4 s), simultaneously integrated with pseudocapacitance and mechanical flexibility. Moreover, the 2D lamellar PANI ink developed in this study can be printed into various designed patterns, particularly for electrochemically controlled, addressable electrochromic displays. This work highlights 2D lamellar PANI as a promising electrochromic material for flexible and patterned ECDs.

摘要

基于有机共轭聚合物的电致变色器件(ECD)在数字和彩色显示器中具有广阔的应用前景. 然而, 制备兼具优异电致变色性能、 柔韧性和定制化图案的ECD仍然是一个挑战. 本文报道了利用喷墨打印技术制备二维层状聚苯胺(PANI)基柔性图案化ECD的方法. 层状PANI均匀分散在甲酸中, 能够实现高精度、 稳定的喷墨打印. 同时, 层状PANI的纳米级厚度、 适当的掺杂比例, 以及无添加剂的墨水成分, 使得打印后的PANI电极和器件保持较高的电致变色性能和电化学特性. 喷墨打印所得电极不仅表现出优异的光学对比度(76%, 750 nm波长)、 良好的着色效率259.1 cm2 C−1、 较短的着色/褪色时间(1.8/2.4 s), 而且具有赝电容特性与机械柔韧性. 此外, 本文所开发的二维层状PANI墨水可以定制化设计并打印成各种图案, 并以此制备电化学控制的可寻址电致变色显示器. 这种二维层状PANI电致变色材料可进一步用于柔性和图案化ECD, 在新型光电显示领域具有较好的应用前景.

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Acknowledgements

This work was supported by the International Cooperation Fund of the Science and Technology Commission of Shanghai (19520744500), the National Natural Science Foundation of China (51903045 and 52173031), the Program of Shanghai Academic/Technology Research Leader (20XD1400100), the Basic Research Project of the Science and Technology Commission of Shanghai (21JC1400100), and the Fundamental Research Funds for the Central Universities and Graduate Student Innovation Fund of Donghua University (CUSF-DH-D-2020048). We thank Dr. Renwei Liu (Shimadzu) for the help in AFM and XPS characterizations.

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Authors and Affiliations

  1. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai, 201620, China

    Xiangyu Huang  (黄翔宇), Jie Chen  (陈杰), Hongjie Xie  (谢鸿杰), Feixiang Zhao  (赵飞翔), Suna Fan  (范苏娜) & Yaopeng Zhang  (张耀鹏)

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  1. Xiangyu Huang  (黄翔宇)
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  2. Jie Chen  (陈杰)
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  3. Hongjie Xie  (谢鸿杰)
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  4. Feixiang Zhao  (赵飞翔)
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  5. Suna Fan  (范苏娜)
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  6. Yaopeng Zhang  (张耀鹏)
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Contributions

Author contributions Zhang Y and Fan S conceived and directed this research; Huang X performed the experiments, analyzed the data, and wrote the manuscript; Chen J conducted TEM and SAED measurements of PANI; Xie H performed the tensile and torsional experiments of ECDs; Zhao F constructed the screen-printed conductive silver line in the seven-segment display. The manuscript was written through the contributions of all authors. All authors gave approval to the final version of the manuscript.

Corresponding authors

Correspondence to Suna Fan  (范苏娜) or Yaopeng Zhang  (张耀鹏).

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Conflict of interest The authors declare that they have no conflict of interest.

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Supplementary information Supporting data are available in the online version of the paper.

Xiangyu Huang is a PhD candidate at the College of Materials Science and Engineering, Donghua University (DHU). His current research interests are electrochromic devices and dynamic optical devices based on conjugated polymers.

Suna Fan is an associate professor at the College of Materials Science and Engineering, DHU. She received her PhD degree in materials physics and chemistry from Jilin University, in 2017. From 2017 to 2018, she was an assistant professor at Wenzhou Institute of Biomaterials and Engineering, Chinese Academy of Sciences (CAS) (renamed as Wenzhou Institute, University of CAS in 2019). She joined DHU in 2018. Her interest is focusing on conducting polymers and silk-based smart materials.

Yaopeng Zhang is a professor at the State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, DHU. He received his PhD degree in materials science from DHU in 2002. From 2004 to 2007, he was a postdoctoral research fellow at Kawamura Institute of Chemical Research, Japan. He served as a visiting scholar at Akita University, Japan, and Stony Brook University, USA, respectively. His current research is focusing on silk materials for bioelectronic and biomedical applications.

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Huang, X., Chen, J., Xie, H. et al. Inkjet printing of 2D polyaniline for fabricating flexible and patterned electrochromic devices. Sci. China Mater. 65, 2217–2226 (2022). https://doi.org/10.1007/s40843-022-2037-4

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