Advances in the preparation of wet-spun PEDOT:PSS-based fibers and its application in flexible electronic devices
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摘要: 近年来，导电聚合物材料在柔性可穿戴电子领域的应用越来越瞩目。与薄膜材料相比，纤维材料在柔性、可织造等方面有着先天的优势，湿法纺丝技术是连续制备导电纤维的主要手段，PEDOT:PSS基纤维具有柔性、高导电性、比表面积大、可纺性等优势。然而，PEDOT主链的刚性使纤维的拉伸性和导电性无法同时满足，使其在柔性可穿戴电子领域的应用受到限制。因此，经湿法纺丝制备高性能导电纤维的研究成为了时下的热点和难点。通过对湿法纺丝过程中的关键步骤进行优化，可以有效提高纤维的综合性能，从而为导电纤维在未来柔性电子领域的应用提供新的可能性。本文总结了当前湿法纺丝PEDOT:PSS基纤维的制备策略,包括纺丝液设计、凝固浴调控及后处理优化三个关键步骤，分析了PEDOT:PSS基纤维在柔性电子器件领域中的应用和存在的问题，展望了PEDOT:PSS基纤维在新一代纤维基柔性电子器件中的性能表现和发展方向。Abstract: In recent years, the application of conductive polymer materials in the field of flexible wearable electronics has been increasingly prominent. Compared with film materials, fibers have inherent advantages in flexibility, weavability, etc. Wet spinning technology is the main means of continuous preparation of conductive fibers, and the PEDOT:PSS-based fibers have the advantages of flexibility, high electrical conductivity, large specific surface area, spinnability, and so on. However, the rigidity of the PEDOT main chain prevents the simultaneous satisfaction of fiber stretchability and conductivity, limiting its application in the field of flexible wearable electronics. Therefore, research on wet spinning to prepare high-performance conductive fibers has become a current focus and challenge. By optimizing the key steps in the wet spinning process, the comprehensive performance of fibers can be effectively enhanced, thereby providing new possibilities for the application of conductive fibers in the future field of flexible electronics. In this review, we summarize the current preparation strategy of wet spinning PEDOT:PSS-based fibers, including the three key steps of spinning solution design, coagulation bath regulation and post-treatment optimization, analyze the applications and challenges of PEDOT:PSS-based fibers in the field of flexible electronic devices, and provide prospects for the performance and development direction of PEDOT:PSS-based fibers in next-generation fiber-based flexible electronic devices.
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图 1 (a) 湿法纺丝连续制备PEDOT:PSS基纤维的工艺示意图，(b) PEDOT:PSS分子结构式
Figure 1. (a) The technical diagram for the continuous preparation of PEDOT:PSS-based fibers by wet spinning, (b)The molecular structure of PEDOT:PSS
图 4 H2SO4处理PEDOT:PSS纤维增强的机制[45]
(a) 湿法纺丝PEDOT:PSS纤维硫酸后处理工艺 (b)纤维经H2SO4处理前后的应力应变曲线 (c) H2SO4处理前后PEDOT:PSS纤维的S2 p XPS谱图 (d) 在900-1700 cm−1和(e) 1380-1480 cm−1波数范围内，H2SO4处理前后PEDOT:PSS纤维的拉曼光谱 (f) 未处理和 (g) H2SO4处理的PEDOT:PSS纤维的广角X射线散射(WAXS)图谱 (h) PEDOT:PSS纤维中PEDOT链堆积排列示意图
Figure 4. Mechanism of performance enhancement of PEDOT:PSS fiber after H2SO4 post-treatment[45]
(a) the post-treatment of wet-spun PEDOT:PSS fibers with H2SO4 (b) stress-strain curves of fibers before and after treatment with H2SO4 (c) S2 p XPS spectra of the PEDOT:PSS fiber before and after H2SO4 treatment. Raman spectra of the PEDOT:PSS fiber before and after H2SO4 treatment in the wavenumber ranges of (d) 900-1700 cm−1 and (e) 1380-1480 cm−1. WAXS patterns of (f) untreated and (g) H2SO4-treated PEDOT:PSS fibers. (h) schematic diagram of the chain packing alignment of PEDOT in the PEDOT:PSS fiber.
图 5 拉伸对湿纺PEDOT:PSS纤维性能的影响[48]
(a)PEDOT:PSS膜 (b) 对PEDOT:PSS纤维进行拉伸 (c) 进一步拉伸的WAXS分析，(d) 归一化强度(相对于PSS宽峰)与2 θ的关系，(e) PEDOT:PSS晶体结构的示意图，(f)(100)反射和(g)(020)反射的方位角的函数，(h)电导率(i)杨氏模量与聚合物链取向的关系，(j) 电导率与杨氏模量的关系
Figure 5. Effect of drawing on the properties of wet-spun PEDOT:PSS fibers [48]
2 D WAXS pattern of (a) PEDOT:PSS film, (b) drawing on PEDOT:PSS fibers (c) further drawing (d) normalized intensity (concerning the PSS broad hump) versus 2θ (e) scheme of the PEDOT:PSS crystal structure Intensity as a function of azimuthal angle for (f) (100) reflections and (g) (020) reflections correlation between (h) electrical conductivity and (i) Young’s modulus versus polymer chain orientation (j) correlation between electrical conductivity versus Young’s modulus.
图 6 (a) 红外灯照射PEDOT:PSS基纤维图示，(b) 纤维在不同距离下的电阻变化，(c)纤维电阻变化的响应时间( D = 20 cm , T = 50℃)，(d) 纤维在相同距离( D = 20 cm , T = 50℃)红外灯的100次周期性开/关下的传感性能，(e) 纤维用于仿生手臂感知压力和温度的概念应用[49]。
Figure 6. (a) Demonstration of PEDOT:PSS-based fibers irradiated by infrared lamp (b) resistance changes of fibers at different distances (c) response time of fibers resistance change (D = 20 cm, T = 50℃) (d) the sensing performance of composite fibers during 100 lamp on-off cycles at the same distance (D = 20 cm, T = 50℃) (e) fibers are used for concept application of bionic arms sensing pressure and temperature[49]
表 1 后处理策略提升湿法纺丝纤维性能的方法和机制
Table 1. Approaches and mechanisms of post-treatment to enhance the performance of wet-spun fibers
Post-treatment strategy Common methods Principles of Performance Enhancement Solution treatment EG(Ethylene glycol)、H2SO4(Sulfuric acid)、EtOH(ethanol)/H2O、DMF(N,N-Dimethylformamide)、DMSO(Dimethyl sulfoxide) Removal of residual polymers, organic solvents, and non-conductive components of PSS(Polystyrene sulfonate)to improve fiber crystallinity and surface flatness Tensile treatment Physical tensile Align the main chains of PEDOT(Poly(3,4-ethylenedioxythiophene)) and PSS in the direction of the fiber axis, reduce defects, and improve the conductivity and thermal stability of the fibers Heat treatment Heating or insulation treatment Heating promotes the orderly arrangement of fiber molecular chains, improves the intermolecular packing density, and increases the crystallinity of fibers, changing the structure and morphology of fibers Light treatment UV or infrared light exposure Improvement of fiber conformation and fiber surface morphology to promote charge transport and carrier generation, further improving fiber conductivity and stability 
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