Impact of Electrode Reversal Method on Electrode Degradation By High-Potential Environment in Polymer Electrolyte Membrane Fuel Cells
Authors: Choi Pilsoo , Eom Kwang Sup 
Published: December 2024

Polymer electrolyte membrane fuel cells (PEMFCs) are key energy conversion devices, that address global energy challenges and climate change and are prized for various applications due to their high efficiency, low operating temperature, fast startup, and low toxic emissions. Enhancing PEMFC durability is crucial for advancing commercialization. Thus, prioritizing research on Catalyst Layer (CL) degradation mechanisms of Membrane Electrode Assembly (MEA) and developing analytical methods to understand extreme degradation conditions are becoming imperative.

In PEMFCs’ operational scenarios, various issues deteriorate the membrane electrode assembly (MEA) of PEMFCs, leading to irreversible performance declines. These include Pt dissolution, ionomer degradation, carbon corrosion [1], and occasional membrane mechanical issues. Of these, the electrochemical carbon oxidation reaction is particularly detrimental, causing a significant reduction in electrochemical double layer capacitance (EDLC), the formation of oxygen functional groups in carbon supports, and substantial deterioration in electrochemical surface area (ECSA) [2, 3], ultimately leading to degraded PEMFC performance.

On the other hand, reversible performance degradation occurs during fuel cell operation, which specific operational recovery procedures can rectify. Mechanisms contributing to reversible voltage degradation include the platinum oxide formation, adsorption of impurity ions and contaminants on the catalyst surface, water flooding/dehydration, and oxidation of the carbon support surface to create hydrophilic oxygen-containing groups [4]. Understanding reversible degradation mechanisms and recovery strategies is important for efficient operation, improved durability, and prolonged cell lifespan. Typically, the "electrode reversal" method is practical and economical, allowing power output during recovery without additional equipment, thereby minimizing recovery operation runtime.

In this study, we examine the impact of the electrode reversal method on PEMFC performance and the deterioration tendency of MEA during carbon corrosion of cathode CL (Figure 1). Accelerated stress tests (AST) were conducted at high potentials exceeding 1.0 V (vs. RHE), specifically investigating the relationship between electrode degradation behaviors, porous carbon structural properties including ionic resistance and EDLC, and overall PEMFC performance.

Particularly noteworthy after the electrode reversal recovery method were the discernible variations in degradation behaviors and diverse rates of performance decline observed through electrochemical impedance spectroscopy (EIS) analysis. EIS can be used to isolate the contribution of many processes to performance loss, allowing investigation of the effect of carbon corrosion-induced catalyst layer changes on fuel cell performance [5]. The EIS data underwent evaluation via parametric fitting utilizing the transmission line model (TLM) applied to the EIS spectrum. Furthermore, relaxation time distribution (DRT) analysis was employed to directly analyze internal resistance factors as a diagnostic tool for assessing electrode degradation by enhancing the TLM-based impedance analysis results. During the ASTs, electrochemical measurements (i-V, CV, LSV, and EIS) were performed to estimate the degree of PEMFC degradation, we also conducted ex-situ surface analysis of MEA using SEM, TEM, and XPS to elucidate the specific degradation components.

Fig. 1 Electrode Reversal Recovery method during Anode cycling AST of the PEMFC single cell (a) polarization curves (i-V curves); 10 A constant current test (b)-(d): (b) fresh MEA, (c) after 250 cycles, (d) after 500 cycles of Anode cycling AST

References

[1] Sorrentino, Antonio, Kai Sundmacher, and Tanja Vidakovic-Koch. "Polymer electrolyte fuel cell degradation mechanisms and their diagnosis by frequency response analysis methods: a review." Energies 13.21 (2020): 5825.

[2] Macauley, Natalia, et al. "Carbon corrosion in PEM fuel cells and the development of accelerated stress tests." Journal of The Electrochemical Society 165.6 (2018): F3148.

[3] Kwon, JunHwa, et al. "Identification of electrode degradation by carbon corrosion in polymer electrolyte membrane fuel cells using the distribution of relaxation time analysis." Electrochimica Acta (2022): 140219.

[4] Yang, Wenbin, et al. "Investigation of an electrode reversal method and degradation recovery mechanisms of PEM fuel cell." Electrochimica Acta 449 (2023): 142181.

[5] Kwon, JunHwa, et al. "A Comparison Study on the Carbon Corrosion Reaction under Saturated and Low Relative Humidity Conditions via Transmission Line Model-Based Electrochemical Impedance Analysis." Journal of The Electrochemical Society 168.6 (2021): 064515.

Figure 1