摘要
质子交换膜燃料电池（PEMFC）是具有极大潜在应用价值的新能源电池。其核心组件为质子交换膜（PEM），而PEM的电导率对于PEMFC的性能至关重要。组成PEM的材料，无论是全氟磺酸（Nafion）或是碳氢基离子聚合物，饱和湿度下都具有分相的两相结构特征，包含一个亲水相和一个憎水相，而质子是在由亲水相组成的曲折通道中传递的。为了提高PEM电导率，人们提出了控制聚合物微相形态的新思路，试图通过控制PEM的憎水、亲水两相形态得到直通的亲水相质子通道。本文在使用电场构筑PEM内垂直方向取向的质子通道方面进行了探索和尝试。
使用分相的浑浊溶液铸膜是本文的创新点之一。因为发现电场只能对分相体系有取向作用，所以我们在Nafion/DMF的均相溶液中添加了低极性的非溶剂组分CCl4，使溶液呈现出浑浊的非均相状态，人为制造出分相界面。对此非均相溶液施加垂直方向的电场铸膜，PEM中的离子通道实现了在垂直方向的取向，小角X光和广角X光测试证明了聚合物分子的规整排列形态，垂直方向的电导率也因此得到提高。由非均相铸膜液挥发溶剂制得的PEM的断裂强度为9.2-11.8MPa，膜的强度并没有因为溶剂的溶解性差而降低，反而因为电场下Nafion分子的规整排列提高了聚合物膜的结晶度，增强了膜的强度。更特别的是我们发现仅在Nafion/DMF的均相溶液中添加低极性的非溶剂组分就可以使PEM的电导率提高达60%左右，这种简单易行的方法具有很高的应用价值。
通过控制自由基聚合反应，我们首次合成了两种新的嵌段共聚物聚（1H,1H-五氟-正丙基丙烯酸酯-b-苯乙烯磺酸）和聚（丙烯酸烯丙酯-b-苯乙烯磺酸）。聚（1H,1H-五氟-正丙基丙烯酸酯-b-苯乙烯磺酸）具有典型的两性嵌段共聚物的自组装特性，以聚合物的水溶液挥发溶剂铸膜可以得到规整的分相结构形态。在电场的作用下可以实现该规整相形态的取向控制，垂直向电场处理使相应方向的PEM电导率增加了两倍。聚（丙烯酸烯丙酯-b-苯乙烯磺酸）分子中带有大量的双键交联基团，交联后可以大大提高膜的强度和耐溶剂溶解性能。交联膜的IEC为2.3时室温饱和湿度的电导率比商品Nafion膜提高一倍，具有耐甲醇、水溶解，吸水率高，合成工艺简单，原材料价格便宜、易得的特点。
实际利用电场对PEM内质子通道的取向作用，我们对于TiO2纳米颗粒掺杂的磺化聚醚醚酮（SPEEK）的溶液施加了一个垂直方向的电场。经电场处理的PEM的垂直向电导率提高了75%。掺杂在铸膜液中的TiO2无机颗粒通过垂直方向上的往复运动避免了颗粒的沉降和团聚，从而被分散的更加均匀，因此提高了掺杂膜的机械强度。我们还探索了使PEM内导电通道取向的最优化电场施加参数，结果表明，施加低频率、高强度的交流电场更有利于实现PEM中亲水通道的取向。
Polymer exchange membrane fuel cells (PEMFC) are considered to be a very promisingalternative power source for a wide spectrum of applications. As one of the key components inPEMFCs, the proton exchange membranes (PEMs) consist of a hydrophilic proton conductivephase and a hydrophobic non-conductive phase. These two phases are randomly distributed inhydrated PEMs, and the hydrated hydrophilic phase forms tortuous channels for protontransportation within the PEMs. One attractive new approach of improving conductivity ofPEMs is to construct straight proton conducting channels. In this work a new method of electricfield treatment is proposed and tested to prepare PEMs with oriented proton channels.
As the phase separation has been found a critical factor for the external electric field to beeffective, a novel solution casting method of membrane preparation is explored to improve theconductivity of PEMs. A high AC electric field is applied to a heterogeneous Nafion solutionwhile evaporating the solvents, leaving aligned proton channels in the solidified membrane, andthe SAXS and WAXS have been given as direct evidences. Therefore, the trans-planeconductivity of the PEM is increased. A Non-solvent of low polarity carbon tetrachloride (CCl4)causes phase separation in the casting solution, which facilitates the Nafion ionomer to respondto the applied electric field. Despite the severe phase separation in the casting solution, theresultant electro-casting membrane shows a high mechanical strength of11.8MPa, as a resultof the orientation induced high crystallinity fo the molecular chains. The most interestingdiscovery is that the conductivity of PEMs can be increased by60%by just adding somenon-solvent into the casting solution, such a great improvement by the cheap and conveniencemethod.
Two diblock copolymers of poly(1H,1H-pentafluoro-n-propyl acrylate-b-sulfonate styrene acid)(Polymer1) and poly (allyl acrylate-b-sulfonate styrene acid)(Polymer3) have beensynthesized by RAFT polymerization which can be used as PEMs. Polymer1is a typicalamphiphilic diblock copolymer which can be self-assembled into some ordered phase structures,and an external electric field makes the hydrophilic phase oriented in the trans-plane direction.The trans-plane conductivity of PEM increases by200%after the electric field treatment.Polymer3contains plenty of allyl groups as cross-linker in the diblock copolymer, which can beused to improve the solvent resistance and mechanical property of PEM. The Polymer3with anIEC of2.3can have a conductivity twice as that of Nafion at room temperature saturatedhumidity after cross-linking.
With the aim to improve the conductivity of PEMs, an external AC electric field is applied to asulfonated poly (ether ether ketone)(SPEEK)-titanium (IV) dioxide (TiO2) hybrid castingsolution during solvent evaporation, and resulting in increased conductivity by75%in thetrans-plane direction versus normal methods. In addition, reciprocation of TiO2under the ACelectric field prevents the nanoparticles from aggregating and improves mechanical strength ofthe PEMs. Factors affect the proton channels’ alignment degree such as the applied fieldmagnitude and frequency are also investigated, and an AC electric field of low frequency andhigh magnitude which make the electric field more effective has been suggested.
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