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Title: Investigation of high temperature polymer electrolyte membrane fuel cells
Authors: Mamlouk, Mohamed
Issue Date: 2008
Publisher: Newcastle University
Abstract: the major issues limiting the introduction of polymer electrolyte membrane fuel cells (PEMFC) is the low temperature of operation which makes platinum-based anode catalysts susceptible to poisoning by trace amounts of CO, typically present in reformed fuel. In order to alleviate the problem of CO poisoning and improve the power density of the cell, operating at temperature above 100°C is preferred. Nafion® type perfluorosulphonated polymers have been typically used for PEMFC but cannot function at temperatures above 100°C. In addition, higher temperatures will enable more effective cooling of the cell stacks and provide a means for combined electrical and heat energy generation. The solution to improved PEMFCs technology is to develop a new polymer electrolyte membrane which exhibits stability and high conductivity in the absence of liquid water. A HighTemperature PEMFC based on a Phosphoric acid (H3P04) doped Polybenzimidazole poly[2,2- (m-phenylene)-5,5 bibenzimidazole] (PBI) membrane has been developed and demonstrated as an alternative to Nafion® for operation at temperatures up to 200°C. PBI membranes, when doped with phosphoric acid, do not rely on hydration for conductivity; a significantly lower water content of the membrane, compared to Nafion, is required for proton transport. The resulting system improvements include; high CO tolerance, simple thermal and water management, excellent oxidative and thermal stability, and good proton conductivity at elevated temperatures. Two issues associated with phosphoric acid in the PBI based fuel cell are the lower activity of the electrocatalysts and the potential loss of the acid into the fuel cell gas/vapour exhaust streams. The limited oxygen permeability and slow oxygen reduction kinetics in phosphoric acid is a major limitation for the performance ofPBI based PEMFCs. The kinetics of oxygen reduction in PBVH3P04 has been studied in electrochemical single electrode cells. Several Membrane Electrode Assemblies (MEAs) have been manufactured to allow optimisation of the electrode performance. Various electrochemical techniques such as chronoamperometry, polarisation curves and Frequency Response Analysis (FRA) were used to study and separate the effects of the various phenomena taking place at the electrode surface: IR losses, mass transport and kinetics. A new Electrode structure utilizing PTFE has been developed allowing higher oxygen permeability and therefore enhanced performance of 0.55 W cm-2 with oxygen and 0.27 W cm-2 with air (atm) at temperature as low as 120 ·C. The Platinum loading was reduced to 0.4 mgpt cm-2 at the cathode and 0.2 mgpt cm-2 at the anode. Further reduction of cathode platinum loading to 0.2 mgPI cm-2 was achieved without dramatic drop in the performance by utilising Pt based binary alloy catalyst (Pt-Co/C). A simplified thin film steady-state, isothermal, one dimensional model of a proton exchange membrane fuel cell (PEMFC), with a polybenzimidazole (PBD membrane, was developed. The electrode kinetics were represented by the Butler-Volmer equation, mass transport was described by the multi-component Stefan Maxwell equations and Fick's law, and the ionic and electronic resistances described by Ohm's law. The model incorporated the effects of temperature and pressure on the open circuit potential, the exchange current density and diffusion coefficients, together with the effect of water on the acid concentration and ionic conductivity. The polarisation curves predicted by the model were validated against experimental data for a PEMFC which included the effect of temperature and oxygen/air pressure on cell performance. An additional problem which faces the introduction ofPEMFC technology is that of supplying or storing hydrogen for cell operation, especially for vehicular applications. Consequently the use of alternative fuels such as methanol and ethanol is of interest, especially if this can be used directly in the fuel cell, without reformation to hydrogen. A limitation of the direct use of alcohol is the lower activity of oxidation in comparison to hydrogen, and hence to improve activity and power output higher temperatures of operation are preferable. The performance of a high temperature direct methanol fuel cell (DMFC) using PBI based electrode assemblies was investigated. The performance of the system was limited by poor methanol oxidation kinetics in a phosphoric acid environment and consequently power performance was inferior to that achieved with low temperature DMFCs based on Nafion membranes.
Description: PhD Thesis
Appears in Collections:School of Chemical Engineering and Advanced Materials

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