Elucidating mechanistic background of the origin and rates of peroxide formation in low temperature proton exchange fuel cells

Degradation of electrode-membrane assembly of the low-temperature hydrogen fuel cells represents one of the main obstacles in wider adoption of these clean and efficient electrochemical sources of electrical energy. Chemical degradation of proton exchange membrane is initiated by hydrogen peroxide formation, which forms in the fuel cell as a by-product to water in oxygen reduction reaction and decomposes to reactive radical species, damaging to the membrane chemical structure. Depending on the operating conditions of the fuel cell, the source of hydrogen peroxide can be either cathode, anode, or, as we argue in the paper, also the Pt particles in the membrane, which originate from the cathode catalyst dissolution, diffusion into the membrane and redeposition of Pt ions inside the membrane. In the paper we propose a mathematical model of intertwined physical processes in membrane and catalyst layer, aimed at unifying the description of hydrogen peroxide formation throughout entire membrane-electrode assembly at any fuel cell operating conditions. The model results, compared to experimental data, indicate that Pt particles inside the membrane can indeed be an important source of hydrogen peroxide in aged fuel cells. For a fresh fuel cell, numerical simulation using proposed model show that hydrogen peroxide can be formed at either cathode or anode, depending on the fuel cell operating condition, but with anode production being more prominent in standard fuel cell operating conditions.