The performance of anion exchange membrane fuel cells (AEMFC) has dramatically progressed in the past few years, with initial power performance matching, if not exceeding, those of proton exchange membrane fuel cells (PEMFC). The remaining challenges are i) the replacement of platinum-group-metal catalysts by catalysts based on Earth-abundant elements, ii) improved durability, and iii) the carbonatation issue when the cathode is fed with natural air. Compared to PEMFCs, the water management of AEMFC is more challenging, due to higher flux of water transported from one electrode to the other for a given current density, but also due to the high swelling of anion exchange ionomer (AEI) [1]. An optimized water management was shown to be not only critical for AEMFC power performance [2], but also for the cell stability. The chemical stability of AEM and AEI was recently shown to decrease dramatically with decreasing relative humidity [3]. During AEMFC operation, low humidity is expected on the cathode due to water consumption by the oxygen reduction reaction and due to electroosmotic drag from cathode to anode. While the water management of AEMFC is a recognized challenge, only few works have hitherto investigated it with operando techniques [4-5].
In this presentation, we will discuss the application of humidity sensors to measure on-line the relative humidity of the gas outlets of a single-cell AEMFC, allowing us to derive the water balance at each electrode (Figure 1a). The setup was applied to study the water balance and understand how it affects the AEMC power performance, focusing on one type of membrane-electrode assembly, comprising of a state-of-art anode (PtRu/C), cathode (Fe-N-C) and AEM/AEI (low density polyethylene/ethylenetetrafluoroethylene). The effect of dew point, backpressure and flow rates on cell performance and water transport were investigated. As an example of the type of results that can be obtained, Figure 1b shows the water balance at the anode and cathode as a function of time (blue and red curves, respectively), for different galvanostatic holds of 5 min each, from 0.2 to 1.2 A cm-2, at otherwise fixed conditions. As expected, the water balance is positive at the anode, and increases fairly linearly with the current density. Importantly, the water balance at the anode is always lower than the anode water balance expected if all the produced water (through the hydrogen oxidation reaction) would stay in the anode. This implies that the electroosmotic drag effect of water transport from cathode to anode is minor, and that the transport of water from anode to cathode (via back-diffusion, or other mechanism) is significant. As a result, the water balance is also positive at the cathode. Figure 1b shows also the total water balance (green curve), and that it matches with the theoretical total simply derived from the cell current density (black curve). In fact, for all operating conditions tested, the water balance was positive at the cathode, implying that the so-called cathode dry-out seldom occurs in AEMFC. The results also generally show that anode flooding is strongly connected with the maximum current density at which an AEMFC can stably operate. In conclusion, the use of humidity sensors can provide quantified insights on water dynamics in operating AEMFC, providing a tool for understanding optimized operating conditions, or for optimizing materials and components when they are designed to improve water management.
References
[1] J. R. Varcoe et al, Anion-exchange membrane in electrochemical energy systems, Energy & Environ. Science 7 (2014) 3135-3191
[2] N. Ul Hassan, M. Mandal, G. Huang, H. A. Firouzjaie, P. A. Kohl, W. E. Mustain, Achieving high performance and 200 h stability in anion exchange membrane fuel cells by manipulating ionomer properties and electrode optimization, Adv. Energy Materials 10 (2020) 2001986.
[3] D. R. Dekel, M. Amar, S. Willdorf, M. Kosa, S. Dhara, C. E. Diesendruck, Effect of water on the stability of quaternary ammonium groups for anion exchange membrane fuel cell applications, Chem. Mater. 29 (2017) 4425-4431.
[4] X. Peng et al, Using operando techniques to understand and design high performance and stable alkaline membrane fuel cells, Nature Commun. 11 (2020) 3561.
[5] B. Eriksson, H. Grimler, A. Carlson, H. Ekström, R. Wreland Lindström, G. Lindbergh, C. Lagergren, Quantifying water transport in anion exchange membrane fuel cells, Int. J. Hydrogen Energy 44 (2019) 4930-4939.
Acknowledgments
This study was supported by the European Union’s Horizon 2020 research and innovation programme under grant agreement CREATE [721065]. We are grateful to Prof. John R. Varcoe (Univ. Surrey, UK) for providing the ionomer and membrane