Jesse S. Wainright

Acid doped polybenzimidazoles, a new polymer electrolyte

Polybenzimidazole films doped with phosphoric acid are being investigated as potential polymer electrolytes for use in hydrogen/air and direct methanol fuel cells. In this paper, we present experimental findings on the proton conductivity, water content, and methanol vapor permeability of this material, as well as preliminary fuel cell results. The low methanol vapor permeability of these electrolytes significantly reduces the adverse effects of methanol crossover typically observed in direct methanol polymer electrolyte membrane fuel cells.

Conductivity of PBI Membranes for High-Temperature Polymer Electrolyte Fuel Cells

Polybenzimidazole (PB1) film, a candidate polymer electrolyte membrane (PEM) for high-temperature (120-200°C) fuel cells, was cast from PBI/trifluoacetyl/H 3 PO 4 solution with constant molecular weight PBI powder and various acid doping levels. Conductivity measurements on these membranes were performed using an ac method under controlled temperature and relative humidity (RH). A complete set of conductivity data for H 3 PO 4 acid-doped PBI is presented as a function of temperature (60-200°C), RH (5-30%), and acid doping level (300-600 mol %). A mechanism of conductivity is proposed for the proton migration in this PBI/acid system based on this and previous work. Proton transfer in this system appears to occur along different paths for different doping levels, RHs, and temperatures. Hydrogen bonds immobilize the anions and form a network for proton transfer by a Grotthuss mechanism. The rate of proton transfer involving H 2 O is faster, leading to higher conductivity at higher RH. The order of the rate of proton transfer between various species is H 3 PO 4 (H 2 PO 4 -)...H-O-H> H 3 PO 4 ...H 2 PO - 4 > N-H + ...H 2 PO 4 - + N-H + ...H-O-H > N-H + ...N-H. The upper limit of proton conductivity is given by the conductivity of the liquid state H 3 PO 4 .

A H2O2 fuel cell using acid doped polybenzimidazole as polymer electrolyte

Phosphoric acid doped polybenzimidazole (PBI-poly[2,2′-(m-phenylene)-5,5′-bibenzimidazole]) has been investigated for use in a H2O2 fuel cell. The prototype fuel cell test results show that the PBI fuel cell worked quite well at 150 °C with atmospheric pressure hydrogen and oxygen which were humidified at room temperature. No membrane dehydration was observed over 200 h operating. The maximum power density of this prototype fuel cell was 0.25 W cm−2 at current density of 700 mA cm2. Further improvement of the cell performance is to be anticipated by properly impregnating the electrode structure with the polymer electrolyte. The advantage of the H2O2 fuel cell using PBI as polymer electrolyte is that the cell design and the routine maintenance can be significantly simplified because of the low electro-osmotic drag number and good proton conductivity of the PBI membrane at elevated temperature.

A Polymer Electrolyte for Operation at Temperatures up to 200°C

In developing advanced fuel cells and other electrochemical reactors, it is desirable to combine the advantages of solid polymer electrolytes with the enhanced catalytic activity associated with temperatures above 100 C. This will require polymer electrolytes which retain high ionic conductivity at temperatures above the boiling point of water. One possibility is to equilibrate standard perfluorosulfonic acid polymer electrolytes such as Nafion, with a high boiling point Bronsted base such as phosphoric acid. The Nafion/H[sub 3]PO[sub 4] electrolyte has been evaluated with respect to water content, ionic conductivity and transport of oxygen, and methanol vapor. The results show that at elevated temperatures reasonably high conductivity (>0.05 [Omega][sup [minus]1] cm[sup [minus]1]) can be obtained. Methanol permeability is shown to be proportional to the methanol vapor activity and thus decreases with increasing temperature for a given partial pressure. Comparisons and distinctions between this electrolyte and pure phosphoric acid are also considered.

Evaluation of a Sol-Gel Derived Nafion/Silica Hybrid Membrane for Polymer Electrolyte Membrane Fuel Cell Applications: II. Methanol Uptake and Methanol Permeability

Sol-gel derived Nafion/silica hybrid membranes were investigated as a potential polymer electrolyte for direct methanol fuel cell applications. Methanol uptake and methanol permeability were measured in liquid and vapor phase as a function of temperature, methanol vapor activity, and silica content. Decreased methanol uptake from liquid methanol was observed in the hybrid membranes with silica contents of 10 and 21 wt %. The hybrid membrane with silica content of ≈20 wt % showed a significant lower methanol permeation rate when immersed in a liquid methanol-water mixture at 25 and 80°C. Methanol uptake from the vapor phase by the hybrid membranes appears similar to that of unmodified Nafion. Methanol diffusion coefficients, as determined from sorption experiments, were slightly lower in the hybrid membranes than in unmodified Nafion. However, in direct permeation experiments, significantly lower methanol vapor permeability was seen only in the hybrid membrane with silica content of ≈20 wt %. Based on these results, Nafion/silica hybrid membranes with high silica content have potential as electrolytes for direct methanol fuel cells operating either on liquid or vapor-feed fuels.

Electro‐osmotic Drag Coefficient of Water and Methanol in Polymer Electrolytes at Elevated Temperatures

The electro-osmotic drag coefficient of water in two polymer electrolytes was experimentally determined as a function of water activity and current density for temperatures up to 200 C. The results show that the electro-osmotic drag coefficient varies from 0.2 to 0.6 in Nafion{reg_sign}/H{sub 3}PO{sub 4} membrane electrolyte, but is essentially zero in phosphoric acid-doped PBI (polybenzimidazole) membrane electrolyte over the range of water activity considered. The near-zero electro-osmotic drag coefficient found in PBI indicates that this electrolyte should lessen the problems associated with water redistribution in proton exchange membrane fuel cells.

Evaluation of a Sol-Gel Derived Nafion/Silica Hybrid Membrane for Proton Electrolyte Membrane Fuel Cell Applications: I. Proton Conductivity and Water Content

Sol-gel derived Nafion®/silica hybrid membranes were investigated as a potential polymer electrolyte for fuel cell applications. Membrane proton conductivity and water content were measured as a function of temperature, water vapor activity, and silica content. The hybrid membranes have a higher water content at 25 and 120°C, but not at 150 and 170°C. Despite the higher water content, the proton conductivities in the hybrid membranes are lower than, or equal to, that in unmodified Nafion membranes under all conditions investigated. The proton conductivity of the hybrid membrane decreases with increasing silica content under all conditions.

A direct methanol fuel cell using acid-doped polybenzimidazole as polymer electrolyte

A direct methanol/oxygen solid polymer electrolyte fuel cell was demonstrated. This fuel cell employed a 4 mg cm−2 Pt-Ru alloy electrode as an anode, a 4 mg cm−2 Pt black electrode as a cathode and an acid-doped polybenzimidazole membrane as the solid polymer electrolyte. The fuel cell is designed to operate at elevated temperature (200°C) to enhance the reaction kinetics and depress the electrode poisoning, and reduce the methanol crossover. This fuel cell demonstrated a maximum power density about 0.1 W cm−2 in the current density range of 275–500 mA cm−2 at 200°C with atmospheric pressure feed of methanol/water mixture and oxygen. Generally, increasing operating temperature and water/methanol mole ratio improves cell performance mainly due to the decrease of the methanol crossover. Using air instead of the pure oxygen results in approximately 120 mV voltage loss within the current density range of 200–400 mA cm−2 .

AC Impedance Investigations of Proton Conduction in Nafion

AC impedance spectroscopy has been employed to study the conduction of protons in Nafion 117 polymer electrolyte membranes. Both two- and four-electrode geometries have been used to uniquely distinguish between the membrane impedance and the interfacial impedances. The results show that the impedance of Nafion for frequencies up to 100 kHz is characterized by a pure resistance, similar to conventional liquid electrolytes. The frequency dependent features observed using a two-electrode geometry are shown to be consistent with well-characterized interfacial impedances and do not arise from ionic conduction in the membrane. These results show that previous two-electrode studies reported in the literature have misinterpreted the impedance of the electrode interfaces as belonging to the conduction process in the electrolyte.

Microfabricated fuel cells

One or more microfabricated fuel cells may be integrated into a printed circuit board or a printed wiring board within an electronic device. The electrical energy created by the integrated microfabricated fuel cells within the metal wiring on the PWB may then be used by the electronic components within and on the PWB.