Proton poly ether sulfone-based

Swier, S., Ramani, V., Fenton, J. M., Kunz, H. R., Shaw, M. T. and Weiss, R. A. 2005. Polymer blends based on sulfonated poly(ether ketone ketone) and poly(ether sulfone) as proton exchange membranes for fuel cells. Journal of Membrane Science 256 122-133. 

C. Liang, H. Hisatani, T. Maruyama, Y. Ohmukai, T. Sotani, H. Matsuyama, Influence of chemical compositions on the properties of random and multiblock sulfonated poly(arylene ether sulfone)-based proton-exchange membranes, J. Appl. Polym. Sci. 116 (1)(2010) 267-279. 

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. 

Sulfonated poly(arylene ether)s (SPAEKs) have also been developed for application in PEMs, with sulfonated poly(ether ether ketone) (SPEEK) (9a) as the archetypical example of this group. The base polymer of SPEEK is commercially available and relatively cheap, and sulfonation is a straightforward procedure using concentrated sulfuric acid. At sufficient levels of sulfonation, proton conductivity values for SPEEK are comparable to or higher than those of Nafion. However, this does lead to random copolymers where there... 

Fu, Y. Z., Manthiram, A. and Guiver, M. D. 2006. Blend membranes based on sulfonated poly(ether ether ketone) and polysulfone bearing benzimidazole side groups for proton exchange membrane fuel cells. Electrochemistry... 

Zhang et al. [128] synthesized a self-humidifying membrane based on a sulfonated poly(ether ether ketone) (SPEEK) hybrid with a sulfated zirconia (SO / ZrO2, SZ) -supported platinum catalyst (Pt-SZ catalyst). This type of composite membrane has a higher proton conductivity than plain SPEEK, due to the effect of the Pt-SZ catalyst the membrane also provided excellent single cell performance at low humidity. 

Wang C, Li N, Shin DW, Lee SY, Kang NR, Lee YM, et al. Ruorene-based poly(arylene ether sulfone)s containing clustered flexible pendant sulfonic acids as proton exchange membranes. Macromolecules 2011 44(18) 7296-306. 

Jang H, Islam MM, Lim Y, Lee S, Hossain MA, Hong T, et al. Synthesis and characterization of sulfonated cardo based poly(arylene ether sulfone) multiblock copolymers for proton exchange membrane. Solid State Ionics 2013. 

Badami AS, Roy A, Lee HS, Li Y, McGrath JE. Morphological investigations of disulfonated poly(arylene ether sulfone)-fe-naphthalene dianhydride-based polyimide multiblock copolymers as potential high temperature proton exchange membranes. J Membr Sci 2009 328 (l-2) 156-64. 

Roy A, Hickner MA, Einsla BR, Harrison WL, McGrath JE. Synthesis and characterization of partially disulfonated hydroquinone-based poly(arylene ether sulfone)s random copolymers for application as proton exchange membranes. J Polym Sci Part A Polym Chem 2009 47(2) 384-91. 

Proton exchange membranes (PEM) were also prepared by solution blending of sulfonated poly(phthalazinone ether ketone) (sPPEK) and various amotmts of sulfonated silica nanoparticles (silica-SOsH) [58]. The solution blending techiuque was also used in combination with compression molding thus, poly(ether ether ketone) (PEEK)-based nanohybrids were fabricated by means of compression molding at 400°C under a pressure of 60 MPa using silica surface-modified with stearic acid and PEEK [59]. 

G. Li, J. Xie, H. Cai, J. Qiao, New highly proton-conducting membrane based on sulfonated poly(arylene ether sulfone)s containing fluorophenyl pendant groups, for low-temperature polymer electrolyte membrane fuel cells, Int. J. Hydrogen Energy 39 (6) (2014) 2639-2648. 

N. Zhang, J. Li, X. Wang, Z. Xia, H. Liu, Preparation and properties of bisphenol A-based sulfonated poly(arylene ether sulfone) proton exchange membranes for direct methanol fuel cell, J. Appl. Polym. Sci. 114 (1) (2009) 304-312. 

R. Mukherjee, A.K. Mohanty, S. Banerjee, H. Komber, B. Voit, Phthalimidine based fluorinated sulfonated poly(arylene ether sulfone)s copolymer proton exchange membranes, J. Memb. Sci. 435 (2013) 145-154. 

More recently, block copolymers with sequenced hydrophilic and hydrophobic units have been developed for the sulfonated poly (arylene ether)s with rather low lEC to show high proton conductivity [5, 6]. They have better-developed hydrophilic/hydrophobic nanophase separation and, accordingly, better-connected ionic channels compared to the conventional random copolymers of the same chemical structure and composition. A typical and well-examined example is block copolymers composed of biphenol-based disulfonated arylene ether sulfone (the so-called BPSH) units and the unsulfonated equivalents (BPS) (Fig. 1) by McGrath s group [7-9]. They have investigated detailed properties of the BPSH block copolymer membranes to obtain the following informative conclusions ... 

McGrath s group has done an extensive and systematic study on their sulfonated poly(arylene ether sulfone) block copolymers (Fig. 7.19) [42-51]. The block copolymers are composed of biphenol-based disulfonated arylene ether sulfone (so-called BPSH) units and the unsulfonated equivalents (BPS). The investigated properties of the block copolymer membranes include synthetic details with different main chain linkages, spectroscopic analyses of the chemical stmcture, water uptake, diffusion of water, proton conductivity at wide range of temperature and... 

Lee H-S, Roy A, Lane O, Drum S, McGrath JE (2008) Hydrophilic-hydrophobic multiblock copolymers based on poly(arylene ether sulfone) via low-temperature coupling reactions for proton exchange membrane fuel cells. Polymer 49 715-723... 

Kreuer et al. [66] doped sulfonated poly(ether ether ketone) (sPEEK) by immersing it into liquid pyrazole and imidazole. A base doping level of 2.3-10, defined as the molar ratio of [C3N2H4]/[-S03H], could be achieved. The intercalation of imidazole and pyrazole into polymers with Brpnsted acid sites is shown to enhance the protonic conductivity. Of the two basic solvents of protons, pyrazole has a lower tendency for the molecular association by hydrogen bonding and therefore a lower proton conductivity, as compared with imidazole. Fu et al. [81, 82] studied acid-base blends based on 2-aminobenzimidazole and sPEEK. They proposed that benzimidazole is protonated by the sulfonic acid, as evidenced by the symmetric stretching of the S-O bonds in FTIR spectra. 

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