An Electrochemical Quartz Crystal Microbalance Study of a Prospective Alkaline Anion Exchange Membrane Material for Fuel Cells: Anion Exchange Dynamics and Membrane Swelling

• Published in: Journal of the American Chemical Society 2014-04, Vol.136 (14), p.5309-5322
• Main Authors: John, Jimmy, Hugar, Kristina M, Rivera-Meléndez, Johary, Kostalik, Henry A, Rus, Eric D, Wang, Hongsen, Coates, Geoffrey W, Abruña, Héctor D
• Format: Article
• Language: English
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja4117457

A strategy has been devised to study the incorporation and exchange of anions in a candidate alkaline anion exchange membrane (AAEM) material for alkaline fuel cells using the electrochemical quartz crystal microbalance (EQCM) technique. It involves the electro-oxidation of methanol (CH3OH) under alkaline conditions to generate carbonate (CO3 2–) and formate (HCOO–) ions at the electrode of a quartz crystal resonator coated with an AAEM film, while simultaneously monitoring changes in the frequency (Δf) and the motional resistance (ΔR m) of the resonator. A decrease in Δf, indicating an apparent mass increase in the film, and a decrease in ΔR m, signifying a deswelling of the film, were observed during methanol oxidation. A series of additional QCM experiments, in which the effects of CH3OH, CO3 2–, and HCOO– were individually examined by changing the solution concentration of these species, confirmed the changes to be due to the incorporation of electrogenerated CO3 2–/HCOO– into the film. Furthermore, the AAEM films were found to have finite anion uptake, validating the expected tolerance of the material to salt precipitation in the AAEM. The EQCM results obtained indicated that HCOO– and CO3 2–, in particular, interact strongly with the AAEM film and readily displace OH– from the film. Notwithstanding, the anion exchange between CO3 2–/HCOO– and OH– was found to be reversible. It is also inferred that the film exhibits increased swelling in the OH– form versus the CO3 2–/HCOO– form. Acoustic impedance analysis of the AAEM-film coated quartz resonators immersed in water showed that the hydrated AAEM material exhibits significant viscoelastic effects due to solvent plasticization.