(Invited) Elucidating the Electrochemically Active Site Density of PGM-Free ORR Catalysts in Situ Fuel Cells Using Fourier Transform Alternating Current Voltammetry
Authors: Elbaz Lior , Snitkoff-Sol Rifael Z 
Published: July 2022

The rising interest in polymer electrolyte fuel cell (PEFC) technology, part of the global shift in energy production to clean sources, is accompanied by efforts to drive down the cost of this technology, which focus primarily on the cathode catalyst, the most expensive PEFC component. While platinum-group metals (PGMs) continues to be the materials of choice for oxygen reduction reaction (ORR) catalysts, use of these materials in PEFCs must be significantly reduced or eliminated without a penalty in the overall cell performance for PEFC technology to become fully viable.
The most promising class ORR catalysts that do not utilize PGMs (i.e., PGM-free catalysts), involve first-row transition metals, such as iron and cobalt incorporated in a nitrogen-doped carbon (M-N-C catalysts). While advancements in M-N-C activity have been impressive, the much sought-after improvement in durability has been impeded by limited information on changes in the PGM-free catalyst active site density, activity and its degradation rate during fuel cell testing. Currently, degradation of PGM-free catalysts during fuel cell operation is often quantified using the low-current region of polarization curves. While this approach is well established, it neglects complications from such factors as catalyst pore structure, membrane conductivity, ionomer content, nature of the support, and the inhomogeneity of active sites. Hence, there exists a critical need for a method with high specificity towards catalytic activity.
In this presentation we will report for the first time on the use of Fourier-transform alternating current voltammetry (FTacV) as an electrochemical method for accurately quantifying the electrochemically active site density of PGM-free ORR catalysts and following their degradation in situ during operation of polymer electrolyte fuel cells. Using this method, we were able to detect changes in performance of electrochemically active species (electrocatalytic centers in this case), allowing us to calculate the electrochemical active site density (EASD) for the first time, which is necessary to elucidate the degradation mechanisms of PGM-free ORR catalysts that occur in situ fuel cells. large-amplitude FTacV, a well-established electrochemical method with distinct advantages over dc methods, was utilized to quantify the electrochemically active site density of PGM-free FeNC catalysts in situ in PEFC. First, we will demonstrate that an accurate measurement of the EASD can be made using this method. To further emphasize the strength of the technique, we will present our findings during degradation of commercial FeNC catalysts in operating PEFC. The peak currents from higher harmonics produced by this method are correlated to the fuel cell performance, and decrease after durability tests in a manner that indicates EASD loss may not be the only catalyst degradation mechanism, thus inviting further studies of yet-unknown degradation pathway(s).