Electrocatalyst degradation

Taniguchi, A. et ah. Analysis of electrocatalyst degradation in PEMFC caused by cell reversal during fuel starvation, J. Power Sources, 130, 42, 2004. 

Figure 17.3. The time-dependent changes of the anode and cathode potential during the cell voltage reversal experiment [19]. (Reprinted from Journal of Power Sources, 130(1-2), Taniguchi A, Akita T, Yasuda K, Miyazaki Y, Analysis of electrocatalyst degradation in PEMFC caused hy cell reversal during fuel starvation, 42-9, 2004, with permission from Elsevier.)...

Electrocatalyst Degradation in PEM Fuel Cells Caused by Cell Voltage Reversal During Fuel Starvation... 

Although there are still some challenges regarding this methodology and room for improvements, non-destructive IL-TEM has already brought new incentives to the characterization of electrocatalyst degradation and will continue to complement fundamental electrochemical studies. 

Key words proton exchange membrane fuel cells, durability, durability testing protocols, PEM degradation, electrocatalyst degradation, carbon support... 

To test the degradation of fuel cell catalyst and assess the carbon support degradation effect on fuel cell performance, many diagnostic tools are available. These tools may test the morphology of the catalyst support directly or may evaluate the carbon corrosion indirectly through the fuel cell overall performance. Common parameters analyzed to evaluate the electrocatalyst degradation include measurement of the catalyst layer areas (cross-sectional and smface area), the ECSA, fuel cell current density, surface morphology, and elemental composition of material or effluent gas. 

The porous electrodes in PEFCs are bonded to the surface of the ion-exchange membranes which are 0.12- to 0.25-mm thick by pressure and at a temperature usually between the glass-transition temperature and the thermal degradation temperature of the membrane. These conditions provide the necessary environment to produce an intimate contact between the electrocatalyst and the membrane surface. The early PEFCs contained Nafton membranes and about 4 mg/cm of Pt black in both the cathode and anode. Such electrode/membrane combinations, using the appropriate current coUectors and supporting stmcture in PEFCs and water electrolysis ceUs, are capable of operating at pressures up to 20.7 MPa (3000 psi), differential pressures up to 3.5 MPa (500 psi), and current densities of 2000 m A/cm. ... 

Electro-catalysts which have various metal contents have been applied to the polymer electrolyte membrane fuel cell(PEMFC). For the PEMFCs, Pt based noble metals have been widely used. In case the pure hydrogen is supplied as anode fuel, the platinum only electrocatalysts show the best activity in PEMFC. But the severe activity degradation can occur even by ppm level CO containing fuels, i.e. hydrocarbon reformates[l-3]. To enhance the resistivity to the CO poison of electro-catalysts, various kinds of alloy catalysts have been suggested. Among them, Pt-Ru alloy catalyst has been considered one of the best catalyst in the aspect of CO tolerance[l-3]. 

Similarly, Pd, Ag, and Pd-Ag nanoclusters on alumina have been prepared by the polyol method [230]. Dend-rimer encapsulated metal nanoclusters can be obtained by the thermal degradation of the organic dendrimers [368]. If salts of different metals are reduced one after the other in the presence of a support, core-shell type metallic particles are produced. In this case the presence of the support is vital for the success of the preparation. For example, the stepwise reduction of Cu and Pt salts in the presence of a conductive carbon support (Vulcan XC 72) generates copper nanoparticles (6-8 nm) that are coated with smaller particles of Pt (1-2 nm). This system has been found to be a powerful electrocatalyst which exhibits improved CO tolerance combined with high electrocatalytic efficiency. For details see Section 3.7 [53,369]. 

Several other polypyridyl metal complexes have been proposed as electrocatalysts for C02 reduction.100-108 For some of them HCOO- appears as the dominant product of reduction. It has been shown for instance that the complexes [Rhin(bpy)2Cl2]+ or [Rh n(bpy)2(CF3S03)2]+ catalyze the formation of HCOO- in MeCN (at —1.55 V vs. SCE) with a current efficiency of up to 80%.100,103 The electrocatalytic process occurs via the initially electrogenerated species [RhI(bpy)2]+, formed by two-electron reduction of the metal center, which is then reduced twice more (Rlr/Rn Rh°/Rh q. The source of protons is apparently the supporting electrolyte cation, Bu4N+ via the Hoffmann degradation (Equation (34)). 

On the negative side, materials problems related to corrosion, electrode degradation, electrocatalyst sintering and recrystalhzation, and electrolyte loss by evaporation are all accelerated at higher temperatures. 

The stability of electrocatalysts for PEMFCs is increasingly a key topic as commercial applications become nearer. The DoE has set challenging near-term durability targets for fuel cell technology (automotive 5,000 h by 2010 stationary 40,000 h by 2011) and has detailed the contribution of the (cathode) catalyst to these. In particular, for automotive systems as well as steady-state stability, activity after simulated drive cycles and start-stop transients has been considered. In practice, both these treatments have been found to lead to severe degradation of the standard state-of-the-art Pt/C catalyst, as detailed next. 

This volume of Modern Aspects of Electrochemistry is intended to provide an overview of advancements in experimental diagnostics and modeling of polymer electrolyte fuel cells. Chapters by Huang and Reifsnider and Gu et al. provide an in-depth review of the durability issues in PEFCs as well as recent developments in understanding and mitigation of degradation in the polymer membrane and electrocatalyst. 

Fig. 11.13 Stability analysis of the most active ternary composition, Pt14Co63Ru23, shown in Fig. 11.17. (a) Location of the electrocatalyst within the ternary composition map. (b) Comparison of the XRD profile of the electrocatalyst before and after screening. The dominant diffraction peak shifts slightly to larger lattice parameters, indicating leaching of cobalt. Significant intensity degradation (relative to the Ti electrode) has occurred after screening. Diffraction of a bare Ti electrode is shown for comparison.

Other technical hurdles must be overcome to make fuel cells more appealing to automakers and consumers. Durability is a key issue and performance degradation is usually traceable to the proton exchange membrane component of the device. Depending on the application, 5,000 40,000 h of fuel cell lifetime is needed. Chemical attack of the membrane and electrocatalyst deactivation (due to gradual poisoning by impurities such as CO in the feed gases) are critical roadblocks that must be over come. 

As part of the early work to find alloys ofplatinum with higher reactivity for oxygen reduction than platinum alone, International Fuel Cells (now UTC Fuel Cells, LLC.) developed some platinum-refractory-metal binary-alloy electrocatalysts. The preferred alloy was a platinum-vanadium combination that had higher specific activity than platinum alone.25 The mechanism for this catalytic enhancement was not understood, and posttest analyses26 at Los Alamos National Laboratory showed that for this binary-alloy, the vanadium component was rapidly leached out, leaving behind only the platinum. The fuel- cell also manifested this catalyst degradation as a loss of performance with time. In this instance, as the vanadium was lost from the alloy, so the performance of the catalyst reverted to that of the platinum catalyst in the absence of vanadium. This process occurs fairly rapidly in terms of the fuel-cell lifetime, i.e., within 1-2000 hours. Such a performance loss means that this Pt-V alloy combination may not be important commercially but it does pose the question, why does the electrocatalytic enhancement for oxygen reduction occur ... 

Stevens, D.A. and Dahn, J.R., Thermal degradation of the support in carbon-supported platinum electrocatalysts for PEM fuel cells. Carbon, 43, 179, 2005. 

Mechanism of the Corrosion and the Degradation of Activity at Nanoparticle Electrocatalysts... 

The use of a PPy film as a convenient matrix for dispersing an oxygen reduction electrocatalyst is questionable since the PPy matrix can react itself with O2, leading to H2O2 by a two-electron transfer reaction [13,15]. Hydrogen peroxide can then oxidize the PPy film, leading to degradation of the polymer and to a decrease of the electrocatalytic activity with time. 

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