Durability of Platinum Overlayers formed By Self-Terminating Electrodeposition

Abstract

In Proton Exchange Membrane Fuel Cell (PEMFC), the membrane electrode assembly (MEA), especially the electrode, is considered 'the heart' and is designed to accommodate the need for efficient transport of electrons, reactants, and heat as well as constraints imposed by the platinum cost. Advances in PEMFC electrode design over the years, which range from using Pt black films with a loading of 10 gpt/cm2 in the 1970s to present-day Pt/ PGM (Platinum Group Metal) nanoparticle coated carbon-black particles (Pt/C) that use about 0.3 mgpt/cm2, have led to significant cost-reduction and performance enhancement. However, durability problems associated with corrosion of carbon support and subsequent loss of active surface area during start-up or shut down cycles have led to renewed interest in carbon-free nanostructured electrodes that employ a thin coating of Platinum or PGM-based catalytic layer on mesostructured conductive support ((Debe 2012), (Liu et al. 2012)).In this context, we carried out systematic ex-situ investigations on the durability of platinum thin films comprising of atomic layers formed by Self-Terminating platinum electrodeposition (Liu et al. 2012). We characterized the sequential growth of platinum film using XPS and AFM measurements; and analyzed the electrocatalytic performance as a function of the number of self-terminating pulses. We found that eight pulses of electrodeposition, corresponding to ~10 nm thick platinum film, can meet stringent ex-situ durability targets set, by the Department of Energy (DOE), USA, for a potential electrocatalyst in Fuel Cell Vehicles (FCVs) application. Our results also show that platinum layers formed using four pulses (< 4 µg/cm2 loading) and even one pulse (< 1 µg/cm2 loading) are electrochemically active. For platinum samples formed using eight or more pulses, we observed ~ 20% loss in Electrochemically Active Surface Area (ECSA) during the first 3000 cycles and 10-15% ECSA loss in the remaining 27000 cycles, indicating stabilization of platinum activity over time. We will present the results of our studies on the minimum number of platinum pulses needed to form a complete overlayer of electrochemically active platinum and discuss the platinum loss during the ex-situ durability tests using ICP-OES and Cyclic Voltammetry measurements. These studies pave the way for an additive, roll-to-roll, and cost-effective manufacturing process of ultra-low platinum loaded MEAs for PEMFCs by building on our earlier results on printing silver nanostructures using a simple inkjet printer by Print-Expose-Develop technique (Parmar and Santhanam 2014) in conjunction with the ability to controllably form atomic layers of platinum on metallic substrates by Self-terminating electrodeposition. Figure 1