PBI phosphoric acid

Overture The Early History of PBI/Phosphoric Acid Membranes... 

Jalani NH, Ramani M, Ohlsson K et al (2006) Performance analysis and impedance spectral signatures of high temperature PBI-phosphoric acid gel membrane fuel cells. J Power Sources 160 1096-1103... 

In this chapter, the early work on PBI-phosphoric acid systems that demonstrates the general appUcability of this polymer-acid membrane to high-temperature PEM operation will be reviewed. Two different PBI poly-... 

Asensio et al. [71] also developed a method for producing acid-doped membranes by direct casting from an AB-PBI/phosphoric acid (PA)/methane-sulfonic acid (MSA) solution. The methanesulfonic acid was evaporated to produce a very homogenous, nearly transparent film with controlled composition and up to 3 moles PA/BI. This method of preparation was much more convenient than the typical multi-step, organic solvent based process. 

Similar to that observed for pure phosphoric acid, the transport properties of PBI and phosphoric acid are also dependent on the water activity, i.e., on the degree of condensation (polyphosphate formation) and hydrolysis. There is even indication that these reactions do not necessarily lead to thermodynamic equilibrium, and hydrated orthophosphoric acid may... 

Figure 22. Proton conductivity of PBI nH3P04 adducts, as a function of temperature T and relative humidity RH for a given phosphoric acid concentration.

Fig. 4. Effects of phosphoric acid (PA) treatment on the thermo-oxidative stability of PBI and PBI/PEI blend films aged in air at 315 °C...

PBI (see chemical structure above) is a hydrocarbon membrane that has been commercially available for decades. Free PBI has a very low proton conductivity ( 10 S/cm) and is not suitable for PEM fuel cell applications. However, the proton conductivity can be greatly improved by doping PBI with acids such as phosphoric, sulfuric, nitric, hydrochloric, and perchloric acids. The PA-doped PBI membrane is the most popular one in PEM fuel cell applications because H3PO4 is a nonoxidative acid with very low vapor pressure at elevated temperature. Savinell et al. and Wainright et al. first demonstrated the use of PBI-PA for HT fuel cells in 1994.270 272 since then, there has been a significant amount of research on the PBI-based membrane because of its low cost and good thermal and chemical stabil-... 

Figure 10.8 Chemical structure of (a) polybenzimidazole (PBI) and (b) phosphoric acid-doped PBI.

An electro-osmotic drag due to proton migration is defined as the number of water molecules moved with each proton in the absence of a concentration gradient For comparison, the electro-osmotic drag coefficient for vapor or liquid-equilibrated Nafion membranes ranges from 0.9 to 3.2 at room temperature [146]. For phosphoric acid-doped PBI membranes, however, the water drag coefficient is dose to zero [149,... 

As expected, the confinement of phosphoric acid in the PBI matrix does not give rise to any relevant electroosmotic drag. Of course, the main reason is the fact that proton conductivity is dominated by structure diffusion, that is the transport of protonic charge carriers and phosphoric acid are effectively decoupled. The other reason is that protonic charge carriers are produced by self-dissociation of the proton solvent (phoshoric acid), that is the number of positively and negatively... 

As for pure phosphoric acid, the transport properties of PBI and phosphoric acid also depend on the water activity, this is on the degree of condensation (polyphosphate formation) and hydrolysis. There is even indication that these reactions do not necessarily lead to thermodynamic equilibrium, and hydrated orthophos-phoric acid may coexist with polyphosphates in heterogeneous gel-like microstructures [99]. There is not much known on the mechanism of proton transport in polymer adducts with polyphosphates and/or low hydrates of orthophosphoric acid. Whether the increased conductivity at high water activities is the result of the plasticizing effect of the water on the phosphate dynamics, thereby assisting proton transfer from one phosphate to the other, or whether the water is directly involved in the conduction mechanism has not been elucidated. 

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