Electrode reactions, fuel cells oxygen reduction reaction

Figure 6.5. Impedance spectra for the oxygen reduction reaction at three different electrode potentials a 0.8 V b 0.7 V c 0.6 V. The microporous layer (loading 3.5 mg/cm2) of the electrode has varying PTFE content ( ) 10 ( ) 20 (A) 30 (+) 40 wt% [5], (Reprinted from Journal of Power Sources, 94(1), Song JM, Cha SY, Lee WM. Optimal composition of polymer electrolyte fuel cell electrodes determined by the AC impedance method, 78-84, 2001, with permission from Elsevier and the authors.)...

P. N. Ross Jr, Oxygen reduction reaction on smooth single crystal electrodes, in Handbook of Fuel Cells, Electrocatalysis, John Wiley and Sons, Chichester, 2003, Vol. 2. 

Let us consider the oxygen reduction reaction (ORR) that occurs in the cathode of the polymer electrolyte membrane fuel cell (PEMFC), in an acidic environment. Although a variety of ORR mechanisms have been proposed, the four-electron pathway is primarily used to characterize the behavior of this reaction at a platinum electrode or a glassy carbon electrode coated with a platinum-based catalyst. The overall reaction is given by... 

P.N. Ross, Jr., Oxygen reduction reaction on smooth single crystal electrodes. In Handbook of Fuel Cells — Fundamentals, Technology and Applications, Vol. 2, Part 5 (The Oxygen Re-duction/Evolution Reaction), W. Vielstich, A. Lamm, and H.A. Gasteiger, Eds., Chichester, UK, Wiley, 2003, pp. 465 80... 

The oxygen reduction reaction (ORR) on Pt and Pt-alloys, the slowest of the two electrode reactions of low temperature fuel cells, has been studied for a long time in an effort to fully understand its mechanism and therefore be able to develop improved catalyst materials which may significantly contribute to enhance the overall fuel cell efficiency [1,2]. 

Ohma A, Fushinobu K, Okazaki K (2010) Influence of Nafion film on oxygen reduction reaction and hydrogen ptaoxide formation on Pt electrode for proton exchange membrane fuel cell. Electrochim Acta 55 8829-8838... 

Platinum has a myriad of practical uses, especially in the field of electrochemistry where it is used as a catalyst and as a reference electrode. In particular, platinum is the most active known pure metal for the oxygen reduction reaction (ORR) in which O2 is split and combined with protons to form H2O. This is an important step in low-temperature fuel cells (polymer electrolyte fuel cells, direct methanol fuel cells, etc.) as it often is what limits the total fuel cell efficiency. Furthermore, platinum is rather expensive with the materials cost of its use in fuel cells being roughly half of the total fuel cell cost. Consequently, a great deal of effort is made in order to optimize its use. 

However, for technical use of AFC, the long-term behavior of AFC components is important, especially that of the electrodes. Nickel can be used for the hydrogen oxidation reaction (catalyst in the anode) and on the cathode silver can be used as catalyst (see next section), no expensive noble metal (platinum) is necessary, because the oxygen reduction reaction kinetics are more rapid in alkaline electrolytes than in acids and the alkaline electrochanical environment in AFC is less corrosive compared to acid fuel cell conditions. Both catalysts and electrolyte represents a big cost advantage. The advantages of AFC are not restricted only to the cheaper components, as shown by Giilzow [1996]. 

Electrocatalytic Reduction of Oxygen. Oxygen reduction reaction (ORR) occurs on the cathode side of low temperature fuel cells and heavily loaded Pt/C is the most common electrocatalyst. Replacement of ORR catalysts with less expensive materials would have higher technical impact than for anode catalysts. Transition metals loaded carbides and carbide-metal codeposited carbon have been investigated for ORR application. For example, 40 wt% Pt/WC electrocatalyst prepared with RDE electrode showed a cathodic current (-5 x 10 A) similar to that of 40 wt% Pt/C with 0.5 M H2SO4, 100 mv/s and 2000 rpm (160). Also, 40 wt% Pt/WC exhibited electrochemical stability after 100 cycles of cyclic voltammetry from 0 to 1.4 V (vs RHE), whereas the cathodic current of 40 wt% Pt/C disappeared after 100 cycles. 

Chen YX, Li MF, Liao LW, Xu J, Ye S (2009) A thermostatic cell with gas diffusion electrode for oxygen reduction reaction under fuel cell relevant conditions. Electrochem Commun 11 1434-1436... 

The functions of porous electrodes in fuel cells are 1) to provide a surface site for gas ionization or de-ionization reactions, 2) to provide a pathway for gases and ions to reach the catalyst surface, 3) to conduct water away from the interface once these are formed, and 4) to allow current flow. A membrane electrode assembly (MEA) forms the core of a fuel cell and the key electrochemical reactions take place in the MEA. MEA performance is severely affected by electrode composition, structure, and geometry, and especially by cathode structure and composition, due to poor oxygen reduction kinetics and transport liniitations of the reactants in the cathode catalyst layer. 

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