微纳米结构导电聚合物合成方法研究进展

具有纳微米结构的导电聚合物作为一种重要的新型有机功能材料,近年来已迅速发展成为有机聚合物材料科学领域的主要研究热点之一。本文从化学法和电化学法两种主要的可控合成方法角度,详细综述了具有不同形貌及尺寸微纳米结构的导电聚合物的合成方法与合成过程的研究进展。在这两种合成方法中,又进一步分为硬模板法、软模板法和无模板自组装法三个重要方面。另外,讨论了目前文献中对这些方法得到的微纳米结构导电聚合物的形成机理。     

柔性导电高分子复合材料在应变传感器中的应用*

柔性和可穿戴传感器最近十几年来的发展,使得它们在个性化医疗、人机交互和智能机器人等方面拥有良好的应用前景。由导电材料和弹性聚合物组成的柔性导电高分子复合材料具有高的可拉伸性、良好的柔韧性、优异的耐久性等优点,可用来制备传感范围宽、灵敏度高的柔性应变传感器。本文综述了基于柔性导电高分子复合材料的可拉伸应变传感器的分类(填充型、三明治型、吸附型应变传感器)和传感机理(隧穿效应,分离机制,裂纹扩展),并详细介绍了传感器所用复合材料的结构设计,包括内部结构(双逾渗网络、隔离、多孔、“砖混”结构)、表面结构(微裂纹、褶皱结构)和宏观结构(纤维状、网状、薄膜结构)。内部结构设计可降低材料的逾渗阈值,表面结构设计可提高传感器性能,每个宏观结构都有自己的特点。最后对应变传感器的材料选择、制备工艺、结构设计、附加性能、集成技术和应用方向等方面进行了展望。     

导电聚合物的纳米结构及其在生物医学领域的应用

由于表面效应、小尺寸效应和量子效应,使纳米结构的导电聚合物材料与传统聚合物材料相比,显示出更优越的性能。基于神经组织对电场和电刺激敏感性,使得导电聚合物纳米材料在生物医学应用方面很有前景。本文综述了纳米结构的导电聚合物的合成方法,及其在生物医学领域的应用。合成方法主要关注于硬模板法、软模板法和无模板自组装法,以及这些方法中导电聚合物纳米结构的形成机理。总结了具有纳米结构的导电聚合物,如纳米颗粒、纳米纤维和纳米管等作为神经电极涂层材料和生物传感器等方面的应用。     

超级电容器用炭/导电聚合物复合材料*

炭/导电聚合物复合材料是近年来发展起来应用于超级电容器的一种新型电极材料。炭材料与氧化物的复合材料,或者炭材料与导电聚合物的复合材料,能够将双电层电容与法拉第电容结合,既可提高超级电容器的比电容,改变其充放电电压,又可提高其循环性能。本文综述了近年来国内外各种炭材料,如活性炭,碳纳米管等与导电聚合物复合材料的研究进展,认为炭与导电聚合物的复合材料,尤其是性能优良的炭气凝胶,模板法制备的中孔炭,以及由金属或非金属碳化物与氯气等刻蚀剂反应制备的骨架炭与导电聚合物的复合材料是超级电容器电极材料研究的一个重要发展方向。     

共轭聚合物复合材料的结构和性能

对聚苯胺、聚吡啶等共轭聚合物与非导电聚合物材料的复合体系的结构和性能进行了综述。不同方法制备的复合材料在结构和性能上各有特点。一般共轭聚合物与非导电高分子材料相容性差、尤其是低极性高分了。     

一维纳米纤维构筑的导电聚合物三维结构及其可控的浸润性

微/纳米结构的导电聚合物由于具有高导电性、易合成以及优异的环境稳定性从而在许多先进的研究领域备受关注,并有望在分子导线、化学和生物传感器、发光器件等领域获得广泛应用。 特别是,复杂的三维自组装结构在获得高性能和功能化的材料方面提供了巨大的潜在应用价值。本文主要介绍了我们利用胶束的软模板和自组装驱动力的协同效应,实现由一维纳米结构组装的三维微米结构导电聚合物方面的研究进展。该制备技巧在于低表面自由能的含氟有机酸具有软模板、掺杂剂、自组装驱动力,以及诱导超疏水性的多重作用实现导电聚合物三维结构的组装和多功能化。介绍了利用环境湿度调整分子的自组装驱动力,实现导电聚合物由一维纳米结构向三维微米结构的组装。此外,还介绍了利用导电聚合物可逆的化学掺杂/脱掺杂机制,实现导电聚合物表面浸润性的可逆转化。最后介绍了在液/液/固三相体系中,通过外加电场刺激,可实现油滴在导电聚合物表面的浸润性和黏附力的控制。     

微孔发泡聚合物基导电复合材料的研究进展

概述了用超临界流体作为物理发泡剂对聚合物基导电复合材料进行微孔发泡的基本原理,总结了聚合物基导电复合材料及其微发泡复合材料的几种导电机理,简要介绍了近年来微孔发泡聚合物基导电复合材料电学性能的研究现状。并从微发泡聚合物基导电复合材料的基体特性、所使用的导电填料类型、导电填料的含量、填料在基体中的分散方法及微发泡复合材料的泡孔形态等几个方面,分析了影响微孔发泡聚合物基导电复合材料电学性能的主要因素,并展望了新型微孔发泡聚合物基导电复合材料的研究和发展趋势。     

共轭聚合物微纳晶的制备与表征及其在场效应晶体管器件中的应用

导电聚合物是20世纪70年代发展起来的一个新兴研究领域,因其在有机光电子学中诱人的应用前景备受关注.但是,目前大部分的聚合物光电器件都是基于薄膜构筑的,大量的缺陷及无规的分子排列不利于我们对材料本征性能的评估及高性能光电器件的构筑.有机单晶具有分子长程有序、低缺陷和无晶界等优点,是用来解决这些问题的最佳选择,但是高质量聚合物单晶的获得一直都是一个挑战性的问题.本文综述了目前有关共轭聚合物微纳晶的制备、表征及其在场效应晶体管器件应用中的研究进展,并对共轭聚合物微纳晶材料与器件的发展前景和面临的一些问题做了简要的讨论.     

基于微纳结构的高灵敏度柔性压力传感器

近年来,随着互联网和人工智能的发展和普及,轻薄便捷、电子性能优异的柔性压力传感器作为可穿戴电子设备的核心器件,拥有了越来越广阔的市场。柔性压力传感器具有灵活柔韧、可折叠、传感性能优异等优点,因而在电子皮肤、运动检测、医疗监测和人机界面等方面已引起广泛的关注。构筑微纳结构是提高压力传感器灵敏度和传感性能的关键。基于此,本文首先总结了高灵敏度压力传感器的传感机制(压阻式、电容式、压电式和摩擦电式)和关键性能参数(灵敏度、压力检测范围、检测限、响应/恢复时间、循环稳定性和线性度等),然后归纳了利用基材构建表面微纳结构(微凸结构、荆棘结构和褶皱结构)和利用导电材料构建微纳结构(微球结构、海胆状结构、蜂窝状结构)的柔性压力传感器的研究进展及其优缺点,总结了基于微纳结构的高灵敏度柔性压力传感器在脉搏监测、电子皮肤、运动检测和人机界面等方面的应用现状。最后,从今后应用的角度出发,概述了高灵敏度柔性压力传感器即将面临的挑战及未来发展方向。     

高分子基导电复合材料气敏响应机理研究

高分子基气敏导电材料是近年来发展起来的一种新型功能高分子复合材料.本文介绍了以炭黑(CB)为导电填充剂的复合传感材料的气敏响应机理的体积膨胀模型、结晶模型和氢键模型,并讨论了逾渗阀值、CB及聚合物微观结构与性能、以及CB与聚合物和溶剂三者之间相互作用等因素对该类材料气敏响应性的影响.     

A new method of growing crystalline networks in polymer matrices by simultaneous CT complex formation and in situ crystallization

A new method of preparing conductive polymer composites by growing crystalline networks of conductive additives in polymer matrices (reticulate doping) is described. The method consists of treating the polymer containing molecularly dispersed donor additive with acceptor/solvent vapors. In the swollen polymer layer simultaneously CT complex formation and crystallization takes place which for proper conditions leads to the formation of a network of the CT complex crystallites, making the film surface-conducting. The preparation and properties of surface conductive films using several electron donors and an iodine acceptor are described. The films obtained show surface resistivities of 10⁴–10⁶ ohm and are generally stable under ambient conditions.     

具有隔离结构的导电高分子复合材料的研究进展

导电高分子复合材料(Conductive Polymer Composites,CPCs)研究的重点和热点之一是如何控制导电粒子的分布,有效降低CPCs逾渗值,提高CPCs综合性能,其中具有隔离结构的CPCs因能大大降低复合材料的逾渗值而受到研究者的广泛关注。本文综述了制备隔离结构CPCs的方法,包括机械共混法、溶液共混法、乳液法等,分析了此类材料具有较低逾渗值的机理,总结了此类材料对温度、溶剂等外场的响应规律。根据复合材料微观结构指出提高此类材料力学性能是推进此类材料应用的关键。     

Permanent antistatic phthalocyanine/epoxy nanocomposites - Influence of crosslinking agent, solvent and processing temperature

Cross-linked epoxy matrices containing small amounts of semi-conductive phthalocyanine (Phthalcon) nanoparticles were prepared using different crosslinking agents and processing temperatures. A starting mixture containing an optimum dispersion of these nanoparticles and with an almost equal and large Hamaker constant was always used. Nevertheless large differences in the relation between the volume conductivity σ_v and the particle concentration φ were found and this relation appeared to be sensitive to small changes in processing temperature and the application of a post-cure. Also the amine crosslinker chosen and the initial amount of solvent (catalyst) in the starting dispersion had a major effect. It was shown that these changes influence strongly the formation of and the final conductive fractal particle network morphology through the polymer matrix. During processing a local relaxation of the initially formed fractal particle network into another fractal particle network was often observed, which introduced or enlarged the amount of isolating material between the particles of the conductive network and changed the fractality and structure of the conductive backbone of the particle network. This local relaxation lowered the σ_v at each phthalcon concentration and enlarged φ_c by several orders of magnitude. The occurrence of local relaxation is dependent on the rate of viscosity change during the crosslinking of the polymer matrix components, the way the fractal conductive particle network is formed during processing (universal or non-universal) and the amount of solvent present. Local relaxation may even occur after the gel point of the polymer matrix. A severe post-cure may be needed to stop this local relaxation. To our knowledge local relaxation of a (fractal) nanoparticle network in a polymer matrix during processing is a new phenomenon, not reported before for polymer composites containing (conductive) nanoparticles.     

Investigation of the role of template features on the electrically induced structure formation (EISF) for a faithful duplication

Electrically induced structure formation, as a physical approach to fabricate micro/nanostructures, has attracted much attention because of the simple process, low‐cost, high‐efficiency, and wide applications on electronics, microfluidics, and so forth. Hitherto, the influence of some process parameters, such as voltage, air gap, film thickness, polymer properties, on the polymeric behavior, and the structure formation has been explored, neglecting the effects of the template features, which affect the polymer deformation. Especially for the conductive protrusions directly contacting the polymer, the phenomenon of electric breakdown may occur, leading to a failure of structure formation. The limitation of the research on the template features triggers the necessity to study its influence for a faithful deformation. In this paper, three types of patterned template are studied based on the electric field at the air‐polymer interface, consisting of completely conductive template, partially conductive template, and dielectric template. Comprehensive consideration of the electric intensity for a sufficient driving pressure and the leaky current for preventing damaging the polymer, some guiding opinions on the template material and geometry can be provided to design the patterned template for the electrically induced structure formation process with a purpose for a faithful structure.     

一维聚苯胺纳米材料的制备方法研究进展

一维聚苯胺纳米材料具有电导率高、环境稳定性好、分散性好、比表面积大、扩散路径短等独特性能以及易于大量生产和成本相对低廉等优点,在传感器与传动器、防腐涂料、电磁屏蔽等领域应用潜力大,成为目前研究最为广泛的导电聚合物纳米材料之一,其制备方法也日益成为研究的热点。综述了近年来一维聚苯胺纳米材料制备方法的最新研究进展,介绍了模板法、非模板法和电纺法等制备方法,并对各种不同制备方法的优缺点进行了比较分析。     

Ionic/electronic conductivity regulation of n-type polyoxadiazole lithium sulfonate conductive polymer binders for high-performance silicon microparticle anodes

Low-cost silicon microparticles(SiMP),as a substitute for nanostructured silicon,easily suffer from cracks and fractured during the electrochemical cycle.A novel n-type conductive polymer binder with excellent electronic and ionic conductivities as well as good adhesion,has been successfully designed and applied for high-performance SiMP anodes in lithium-ion batteries to address this problem.Its unique features are attributed to the stro ng electron-withdrawing oxadiazole ring structure with sulfonate polar groups.The combination of rigid and flexible components in the polymer ensures its good mechanical strength and ductility,which is beneficial to suppress the expansion and contraction of SiMP s during the charge/discharge process.By fine-tuning the monomer ratio,the conjugation and sulfonation degrees of the polymer can be precisely controlled to regulate its ionic and electronic conductivities,which has been systematically analyzed with the help of an electrochemical test method,filling in the gap on the conductivity measurement of the polymer in the doping state.The experimental results indicate that the cell with the developed n-type polymer binder and SiMP(~0.5 μm) anodes achieves much better cycling performance than traditional non-conductive binders.It has been considered that the initial capacity of the SiMP anode is controlled by the synergetic effect of ionic and electronic conductivity of the binder,and the capacity retention mainly depends on its electronic conductivity when the ionic conductivity is sufficient.It is worth noting that the fundamental research of this wo rk is also applicable to other battery systems using conductive polymers in order to achieve high energy density,broadening their practical applications.     

Electrochemical Pseudocapacitors Based on Ternary Nanocomposite of Conductive Polymer/Graphene/Metal Oxide: An Introduction and Review to it in Recent Studies

This review gives an overview of the synthesis, surface and electrochemical investigations over ternary nanocomposite of conductive polymers in the development of new supercapacitors. They utilize both Faradaic and non‐Faradaic procedures to store charge, leading to higher specific capacitance and energy density, higher cell voltage, longer life cycle and moderated power density. Owing to a unique combination of features such as superb electrical conductivity, corrosion resistance in aqueous electrolytes, highly modifiable nanostructures, long cycle life and the large theoretical specific‐surface area, the use of ternary nanocomposites as a supercapacitor electrode material has become the focus of a significant amount of current scientific researches in the field of energy storage devices. In these nanocomposites, graphene not only can be utilized to provide a substrate for growing nanostructured polymers in a polymer‐carbon nanocomposite structure in order to overcome the insulating nature of conductive polymers at dedoped states, but also is capable of providing a platform for the decoration of metal oxide nanoparticles to avoid their agglomeration. In this regard, synthesis, characterization and performance of different ternary nanocomposites of conductive polymer/graphene/metal oxide are discussed in detail. These remarkable results demonstrate the exciting commercial potential for high performance, environmentally friendly and low‐cost electrical energy storage devices based on ternary nanocomposite of conductive polymer/graphene/metal oxide.     

Electromagnetic Interference Shielding Polymers and Nanocomposites - A Review

Intrinsically conducting polymers (ICP) and conductive fillers incorporated conductive polymer-based composites (CPC) greatly facilitate the research in electromagnetic interference (EMI) shielding because they not only provide excellent EMI shielding but also have advantages of electromagnetic wave absorption rather than reflection. In this review, the latest developments in ICP and CPC based EMI shielding materials are highlighted. In particular, existing methods for adjusting the morphological structure, electric and magnetic properties of EMI shielding materials are discussed along with the future opportunities and challenges in developing ICP and CPC for EMI shielding applications.     

Mechanical and rheological properties of poly(ethylene-co-ethyl acrylate) as a function of carbon black content

Carbon black (CB) filled poly(ethylene-co-ethyl acrylate) (EEA-CB) is used as conductive phase in conductive polymer composites (CPC). Electrical conductivity of CPC obtained from blends of immiscible polymers results from CB particles localization within the material, which depends on composition and processing conditions. It is particularly important to control viscosity of such systems as this parameter determines both the phase morphology and conductive pathway structure. The small scale, at which CB particle aggregation/dispersion phenomena occur within CPC, makes direct observations difficult. But the effect of carbon black particles/polymers interactions is clearly visible by means of rheological measurements. A strong reinforcing effect of CB on CPC in both solid and liquid states has been noticed. This phenomenon has been analyzed using classical models as a function of temperature and CB content. The results confirm the necessity of CPC rheology control especially during the process to achieve good reproducibility of electrical properties.     

HDPE/EPDM/CB复合物的PTC效应

聚合物正温度系数 (PTC)材料 ,是由聚合物基体与炭黑、碳纤维、金属粉末等导电填料共混而成的一种功能导电复合材料 ,其特点是 :当温度升高时 ,在聚合物结晶熔点附近 ,材料的电阻率随温度升高急剧增加 ,可发生几个数量级的突跃 .聚合物 PTC材料可用作自限温加热器、过电流保护器、传感器等 ,有广阔的发展前景 .目前对聚合物 PTC材料的研究主要以聚乙烯 [1～ 5]、乙烯 -醋酸乙烯酯共聚物[6] 、偏氟乙烯 [7] 等单一组分聚合物作为基体材料 .本文研究了以高密度聚乙烯 (HDPE) /三元乙丙胶(EPDM)共混物为基体材料的炭黑 (CB)导电复合材…