In situ voltammetric de-alloying of fuel cell catalyst electrode layer: A combined scanning electron microscope/electron probe micro-analysis study

By Srivastava, Ratndeep; Mani, Prasanna & Strasser, Peter
Published in Journal of Power Sources NULL 2009

Abstract

In situ voltammetric de-alloying, i.e. partial selective dissolution of less noble alloy components, is a recently proposed, effective strategy to prepare active electrocatalysts for the oxygen reduction reaction (ORR) [S. Koh, P. Strasser, J. Am. Chem. Soc. 129 (2007) 12624–12625; R. Srivastava, P. Mani, N. Hahn, P. Strasser, Angew. Chem. Int. Ed. 46 (2007) 8988–8991]. However, in situ de-alloying of bimetallics inside electrode layers of membrane-electrode-assemblies (MEAs) seems to defy the requirement of keeping the membrane free of cationic contaminants; yet, when followed by ion exchange, de-alloyed cathodes result in previously unachieved single cell activities of polymer electrolyte membrane fuel cell cathode layers of up to 0.4 A mgPt-1 at 900 mV cell voltage. The effects of voltammetric Cu de-alloying on the MEA have never been studied before. In the present study, we therefore address this issue and report detailed scanning electron microscope (SEM) imaging of the morphology and electron probe micro-analysis (EPMA) mapping of a MEA at various stages of the de-alloying and ion-exchange process. We investigate the significant loss of Cu from the cathode particle catalyst after de-alloying, demonstrate how the membrane can be cleaned from Cu-ion contamination using ion exchange with protons from liquid inorganic acids, and show that Cu ion exchange does ultimately not affect the activated catalyst particles inside the cathode layer. We correlate the microscopic study of the MEA with its cyclic voltammetric response curves as well as the single cell polarization data.

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