An external reference electrode was used to monitor individually the evolution of the anodic and cathodic potentials during the stationary as well as oscillatory operation of a Direct Formic Acid Fuel Cell (DFAFC) and a Direct Methanol Fuel Cell (DMFC). Besides evidencing the large activation loss in both cells, we were able to observe how the oscillatory operation of such devices affects their cathodes. In fact, cathodic oscillations synchronized with the cell voltage dynamics were observed, hitherto never reported on fuel cells. We have addressed these phenomena taking into account two main coupling processes: through the proton concentration and a global coupling stemming from the control mode (potentiostatic or galvanostatic).

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Chemical gardens are macroscopic structures that form when a salt seed is submerged in an alkaline solution. Their thin precipitate membranes separate the reactant partners and slow down the approach toward equilibrium. During this stage, a gradual thickening occurs, which is driven by steep cross-membrane gradients and governed by selective ion transport. We study these growth dynamics in microfluidic channels for the case of Ni(OH) 2 membranes. Fast flowing reactant solutions create thickening membranes of a nearly constant width along the channel, whereas slow flows produce wedge-shaped structures that fail to grow along their downstream end. The overall dynamics and shapes are caused by the competition of reactant consumption and transport replenishment. They are reproduced quantitatively by a two-variable reaction−diffusion−advection model which provides kinetic insights into the growth of precipitate membranes.