Polybenzimidazole blends acidic polymers

The scope of the reviewed R D work is limited to intermediate-T acid-base blend membranes prepared by mixing polybenzimidazoles and sulfonated or phosphonated acidic polymers. Other membrane types, where the acid-base concept was used to improve their relevant... 

Abstract There have been numerous studies on modifying DuPont s Nafion (a perfluorosulfonic acid polymer) in order to improve the performance of this membrane material in a direct methanol fuel cell. Modifications focused on making Nafion a better methanol barrier, without sacrificing proton conductivity, so that methanol crossover during fuel cell operation is minimized. In this chapter, a brief literature survey of such modifications is presented, along with recent experimental results (membrane properties and fuel cell performance curves) for (1) thick Nafion films, (2) Nafion blended with Teflon-FEP or Teflon-PFA, and (3) Nafion doped with polybenzimidazole. 

Acid-Based Blends of Polybenzimidazole and Other Polymers. 91... 

Perfluorinated sulfonic acid polymers, such as Nafion membranes, were the most commonly used materials in practical systems for their high proton conductivity and extremely high oxidative stability. However, due to the poor dimensional stability, low mechanical properties of Nafion at high humidity and high temperature, and high cost, an essential need for cost-effective and reinforced substitutes with improved performance arises [193-195]. Nafion blended with the second component could not only reduce the cost, but also improve the mechanical properties and the dimensional stability. Recently, the reinforced composite membranes based on semi-interpenetrating polymer network (semi-IPN) structures of Nafion , polyimidazole (PI) [196-198], polybenzimidazole (PBI) [199], and poly(vinyIidene fluoride) (PVDF) [200] were reported. As shown in Fig. 2.35, the composite membranes with... 

Poiyphosphazene Biends Blends of sulfonated polyphosphazene, for example, sulfonated poly[bis(3-methylphenoxy)phosphazene] or poly[(bisphenoxy)phosphazene] (see Fig. 29.14) with either an inert organic polymer such as poly(vinylidene fluoride) (Pintauro and Wycisk, 2004 Wycisk et al., 2002) or polyacrylonitrile (Carter et al., 2002) or a reactive polymer (e.g., polybenzimidazole) (Wycisk et al., 2005) have been investigated. The resultant membranes had conductivities of 0.01-0.06 S/cm (in water at 25°C) and equilibrium water swelling from 20 to 60% (at 25°C). Blends of poly[(bisphe-noxy)phosphazene] and polybenzimidazole (where acid-base complexation occurred between the sulfonic acid and the imidazole nitrogen) exhibited good mechanical properties and low methanol permeability. MEAs with this membrane material outperformed Nafion 117 in a DMFC at 60°C with concentrated (5-10 M) methanol feeds. With 1.0 M methanol and 0.5 L/min ambient air at 60°C, the maximum power density was 97 mW/cm and the methanol crossover was 2.5 times lower than that with Nafion 117 (Wycisk et al., 2005). 

To prepare new and inexpensive membranes, various trials have been made 196 sulfonated aromatic polyether membrane such as polyether ketones (PEEK),197 sulfonated polysulfone198 and membranes from sulfonated polyphenylene sulfide,199 phosphoric acid-doped polybenzimidazole, (PBI),200 polybenzimidazole having sulfonic acid groups,201 polybenzimidazole with phosphonic acid groups,202 a blend membrane of polybenzimidazole and sulfonated polysulfone,203 sulfonated phosphazene polymer.204... 

One of the frequently advertised advantages of the phosphoric acid imbibed polybenzimidazole systems is their zero water drag coefficient and their possibihty to operate with dry hydrogen and oxygen. However, a vast literature has been devoted to the study of the proton conduction and the effect of relative humidity on the conductivity of the PBl-phosphoric acid system. The promoting effect and the physicochemical interactions of water vapors with the polymer electrolyte and on the fuel cell performance have been explicitly shown for the PBl/PPy(50)coPSF 50/50 polymer blend imbibed with phosphoric acid under fuel cell conditions. ... 

Kerres et al., among others, developed the acid-base blend membranes from sulfonated polymers and aminated or other basic polymers [98] and concluded that the protonation of the basic groups is incomplete if the base is too weak [99]. Very recently, Frutsaert et al. [70] synthesized novel polymers for the development of high temperature PEMFC membranes comprising a blend of s-PEEK and a fluorinated copolymer bearing imidazole functions as pendant groups. The extensive work on intermediate temperature fuel cell membranes are well reviewed in Chap. 4 of this book including polybenzimidazole as the basic component and sulfonated and phosphonated ionomers of either nonfluorinated or partially fluorinated backbones as the acidic component. 

In the following, those publications dealing with synthesis and characterization of intermediate-T blend membranes from PBI basic polymers and sulfonated or phosphonated polymers utilized as acidic macromolecular cross-linkers in the blends are discussed. In Fig. 4.4, those polybenzimidazoles along... 

The interaction forces between the acidic and basic blend component include electrostatic and hydrogen bridge interaction. The sulfonated poly(ethersulfones) and poly(etherketones) were combined both with commercially available basic polymers (e.g., polybenzimidazole Celazole (Celanese), poly(4-vinylpyridine), polyCethylene imine)), and with self-developed basic polymers derived from poly(ethersulfones) [47] and poly(etherketones), including polymers that carry both sulfonic and basic groups onto the same backbone [48]. A wide variety of acid-base blend membranes with a broad property range were obtained. The most important characterization results of the ionically cross-linked ionomer membranes are... 

C. Hasiotis, Q. Li, V. Deimede, J. K. Kallitsis, C. G. Kontoyannis, N. J. Bjerrum, Development and characterization of acid-doped polybenzimidazole/sulfonated polysulfone blend polymer electrolytes for fuel cells, J. Electrochem. Soc. 148(5) A513-A519 (2001)... 

Composites of zirconium tricarboxybutylphosphonate and polybenzimidazole were prepared by Jang and Yamagnchi [56]. The membranes were thermally stable and the conductivities measured for composites with 50 wt% phosphate were about 3.8 mS cm" at 200°C. Zaidi [57] and Zaidi et al. [58] introdnced boron phosphate to improve the conductivity of SPEEK membranes. By adding polybenzimidazole again the compatibility between the phosphate and the polymer matrix conld be improved. Up to 40% phosphate was added to the polymer matrix. The boron phosphate was synthesized from orthophosphoric and boric acid and added as a solid powder to blends of SPEEK and PBl. 

Savinell and co-workers, [105-107], who have principally studied phosphoric acid doped polybenzimidazole (PBl). Similar systems have been reported by He and co-workers [108], who in addition report the conductivities of PBl based membranes doped with PTA and zirconium hydrogen phosphate [108], Acid-base interactions in entirely polymeric systems have been reported by Kerres and co-workers [102], who prepared and stndied several membranes prepared by blending polymers with acidic (snlfonated-PEEK, sulfonated polyethersulfone) and basic (polybenzimidazole, poly-vinylpyridine) characteristics. Selected acid-base polymer systems are discnssed in the following. 

In contrast to the Nafion-FEP system, in which the immiscibility of the polymer components is clearly shown in Fig. 14.8, greater compatibility of Nafion and polybenzimidazole (PBI) was expected due to acid-base interactions between imidazole nitrogens and sulfonic acid protons. PBI should function in such a system as a crosslinker (see Fig. 14.15), producing a reduction in membrane swelling and permeability by methanol. Although the idea of examining acid-base membrane blends in fuel cells is not new [9,11-13,30], little work has been carried out with Nafion. 

Trogadas and Ramani summarized the modification of PEM membranes, including Nafion modified by zirconium phosphates, heteropolyacids, hydrogen sulfates, metal oxides, and silica. Membranes with sulfonated non-fluorinated backbones were also described. The base polymers polysulfone, poly(ether sulfone), poly(ether ether ketone), polybenzimidazole, and polyimide. Another interesting category is acid-base polymer blend membranes. This review also paid special attention to electrode designs based on catalyst particles bound by a hydrophobic poly-tetrafluoroethylene (PTFE) structure or hydrophilic Nafion, vacuum deposition, and electrodeposition method. Issues related to the MEA were presented. In then-study on composite membranes, the effects of particle sizes, cation sizes, number of protons, etc., of HPA were correlated with the fuel cell performance. To promote stability of the PTA within the membrane matrix, the investigators have employed PTA supported on metal oxides such as silicon dioxide as additives to Nafion. 

Blends of sulfonated PS and sulfonated PPO have been described in several papers as offering a combination of high proton conductivity and low methanol permeability [104, 105]. Optimum conductivity was obtained with a 50/50 blend of the sulfonated polymers, with each having an identical ion exchange capacity [104]. The miscibility of the PS/PPO system appeared to be maintained with the blend of the sulfonated polymers. Polybenzimidazole (PBI) and polysulfone (PSF) are immiscible however, sulfonated PSF is miscible with PBI and showed utility in phosphoric acid based fuel cells operated upto200°C[106]. PEMs comprised of Nafion and a vinylidene fluoride-hexafluoropropylene copolymer blend were evaluated... 

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