Surface overpotential losses

Over the past 35 years, much has been learned about the electrooxidation of methanol on the surface of noble metals and metal alloys, in particular platinum and ruthenium [2, 4, 6, 7]. Significant overpotential losses occur in the reaction due to poisoning of the alloy catalyst surface by carbon monoxide. Yet, Pt-based metal alloys are still the most popular catalyst materials in the development of new fuel cell electrocatalysts, based on the expectation that a more CO-tolerant methanol catalyst will be developed. The vast ternary composition space beyond Pt-Ru catalysts has not been adequately explored. This section demonstrates how the ternary space can be explored using the high-throughput, electrocatalyst workflow described above. 

Ohmic losses can result from a variety of causes resistance to ion flow in the electrolyte, resistance in the bus bars, and resistance in membranes used to separate anode and cathode electrolytes. The magnitude of the resistances may change with time as films build up on electrode surfaces or as membranes become contaminated. Surface overpotentials can be estimated from rate expressions such as the Tafel equation, or they can be evaluated from em-... 

The stability and durability of Pt alloys, especially those involving a >d transition metal, are the major hurdles preventing them from commercial fuel cell applications. "" The transition metals in these alloys are not thermodynamically stable and may leach out in the acidic PEM fuel cell environment. Transition metal atoms at the surface of the alloy particles leach out faster than those under the surface of Pt atom layers." The metal cations of the leaching products can replace the protons of ionomers in the membrane and lead to reduced ionic conductivity, which in turn increases the resistance loss and activation overpotential loss. Gasteiger et al. showed that preleached Pt alloys displayed improved chemical stability and reduced ORR overpotential loss (in the mass transport region), but their long-term stability has not been demonstrated. " These alloys experienced rapid activity loss after a few hundred hours of fuel cell tests, which was attributed to changes in their surface composition and structure." ... 

Besides the activation overpotential, mass transport losses is an important contributor to the overall overpotential loss, especially at high current density. By use of such high-surface-area electrocatalysts, activation overpotential is minimized. But since a three-dimensional reaction zone is essential for the consumption of the fuel-cell gaseous reactants, it is necessary to incorporate the supported electrocatalysts in the porous gas diffusion electrodes, with optimized structures, for aqueous electrolyte fuel-cell applications. The supported electrocatalysts and the structure and composition of the active layer play a significant role in minimizing the mass transport and ohmic limitations, particularly in respect to the former when air is the cathodic reactant. In general, mass transport limitations are predominant in the active layer of the electrode, while ohmic limitations are mainly due to resistance to ionic transport in the electrolyte. For the purposes of this chapter, the focus will be on the role of the supported electrocatalysts in inhibiting both mass transport and ohmic limitations within the porous gas diffusion electrodes, in acid electrolyte fuel cells. These may be summarized as follows ... 

Recently in-situ XAS spectra have shown that alloying of Pt with base transition elements such as Co and Cr enable changes in the electronic properties of Pt that in turn shift the onset of Pt-OH formation to higher potentials. This has been shown to enable a lowering of ORR overpotential losses by approximately 50mVs. In this endeavor, however, the surface nature of the cluster is very important and has to be predominantly Pt with the inner core as the alloy. Hence, the methodologies of preparation of these metal clusters are of prime importance. 

High surface activities for the OER/HER reactions need to be established to minimize the interface overpotential losses. 

Based on a co-flow configuration, the effect of various parameters on cell performance has been studied systematically. The study covers the effect of (a) air flow rate, (b) anode thickness, (c) steam to carbon ratio, (d) specific area available for surface reactions, and (e) extend of pre-reforming on cell efficiency and power density. Though the model predicts many variables such as conversion, selectivity, temperature and species distribution, overpotential losses and polarization resistances, they are not discussed in detail here. In all cases calculations are carried for adiabatic as well as isothermal operation, fii calculations modeling adiabatic operation the outer interconnect walls are assumed to be adiabatic. All calculations modeling isothermal operation are carried out for a constant temperature of 800°C. Furthermore, in all cases the cell is assumed to operate at a constant voltage of 0.7 V. 

This multi-electron charge transfer reaction (1.23 V/SHE) depends on the electrolyte nature and the catalysts in form of a well defined surface or faceting nanoparticles, and represents a substantial cathodic overpotential loss of ca. 300 mV on the best catalyst, Pt. This means that its four-electron ORR kinetics is slow with an exchange cnrrent density between 10 to lO ttiA cm depending on the natnre of the exposed surface and electrolyte. The consequence is the generation of intermediate species of the overall reaction (3) that can be depicted by a series of reactions, namely ... 

The electrochemical characterisation studies, discussed in the previous section, showed that a 40 at.% Ru electrode, when subjected to extended electrolysis or potential or current cycling in NaCl solutions and when the chlorine overpotential reaches 300-400mV, behaves like a fresh, low at.% Ru (about 5 at.%) electrode. This strongly suggests that Ru losses from the Ru/Ti oxide coating occur during electrolysis. To determine whether or not the Ru losses in failed anodes take place by uniform dissolution across the entire coating or whether only localised surface... 

Electrochemistry is in many aspects directly comparable to the concepts known in heterogeneous catalysis. In electrochemistry, the main driving force for the electrochemical reaction is the difference between the electrode potential and the standard potential (E — E°), also called the overpotential. Large overpotentials, however, reduce the efficiency of the electrochemical process. Electrode optimization, therefore, aims to maximize the rate constant k, which is determined by the catalytic properties of the electrode surface, to maximize the surface area A, and, by minimization of transport losses, to result in maximum concentration of the reactants. 

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