Three-fold optimization of Pt/ionomer interface by ionic liquid-modified MOF-808 in cathode of proton exchange membrane fuel cells

doi:10.1016/S1872-2067(25)64662-6

Abstract

Abstract:

The large-scale commercialization of proton exchange membrane fuel cells (PEMFCs) has been hindered by the high demand of platinum (Pt) in the cathode due to the sluggish kinetics of the oxygen reduction reaction. Reducing the amount of Pt would worsen the problems caused by the adsorption of perfluorinated sulfonic acid (PFSA) ionomers to Pt via the side chains, namely, blocking the active sites of Pt and inducing densely packed layers of fluorocarbon backbones on Pt surface to obstruct local O₂ transport at the Pt/PFSA interfaces. This work aims at optimizing the Pt/ionomer interface to mitigate the sulfonate adsorption and in the meantime to reduce the local O₂ transport resistance (R_local), by using a porous composite of 1-butyl-3-methylimidazolium hydrogen sulfate ionic liquid (IL) modified MOF-808 (BMImHSO₄@MOF-808) as additive in cathodic catalyst layer (CCL). Through detailed physical, spectroscopic and electrochemical characterizations, we demonstrate a three-fold optimization mechanism of Pt/ionomer interface structure by BMImHSO₄@MOF-808: the unsaturated metal sites in MOF-808 effectively inhibit the sulfonate adsorption on Pt through coordination with the sulfonates of PFSA, thereby improving catalyst utilization; the pores in MOF-808 establish efficient transport channels for gaseous oxygen, significantly reducing R_local; the IL modification layers facilitate the formation of continuous proton transport networks, increasing proton conductivity. The incorporation of BMImHSO₄@MOF-808 in a low-Pt CCL (0.1 mg_Pt cm^-2) yields a peak power density of 1.9 W cm^-2 for PEMFC under H₂-O₂ condition, and ca. 20% increase of power density under H₂-air condition as compared with conventional CCL, indicating the prospect of IL-MOF composites as an efficient additive to enhance the performance of PEMFCs.

Key words: Proton exchange membrane fuel cells, Pt/ionomer interface, Local oxygen transport, MOF-808, Ionic liquid, Sulfonate adsorption

Yan Huangli, Yu Chengwen, Zhang Xianming, Tang Meihua, Chen Shengli. Three-fold optimization of Pt/ionomer interface by ionic liquid-modified MOF-808 in cathode of proton exchange membrane fuel cells[J]. Chinese Journal of Catalysis, 2025, 75: 84-94.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64662-6

https://www.cjcatal.com/EN/Y2025/V75/I8/84

Figures/Tables 7

Scheme 1. The synthesis route of MOF-808, BMImHSO4@MOF-808 and BSO3HMImHSO4@MOF-808.

Fig. 1. XRD patterns (a) and FT-IR (b) and TGA (c) of MOF-808, BSO?HMImHSO4@MOF-808 and BMImHSO4@MOF-808.

Fig. 2. (a) H2-air fuel cell performance of MOF-808 free, MOF-808, BSO3HMImHSO4@MOF-808 and BMImHSO4@MOF-808. The cell temperature, feeding gas pressure, RH are 80 °C, 250 kPaabs, and 100%, respectively; Nyquist plots corresponding to polarisation curves at 0.5 A cm-2 (b) and 3 A cm-2 (c).

Fig. 3. H2-air fuel cell performance for different MEAs: (a) MOF-808 free and BMImHSO4@MOF-808 with different BMImHSO4 loadings and (b) different BMImHSO4@MOF-808 addition amount in CCL. The cell temperature, feeding gas pressure, RH are 80 °C, 250 kPaabs, and 100%, respectively.

Fig. 4. (a) H2-O2 cell performance of MOF-808 free, MOF-808 and BMImHSO4@MOF-808. The temperature, operating pressure, RH are 80 °C, 250 kPaabs, and 100%, respectively. (b) EIS analysis corresponding to polarisation curves at 0.5 A cm-2. CV curves (c) and ECSA (d) of the cells.

Fig. 5. (a) Pt 4f XPS spectra of BMImHSO4@MOF-808-Nafion-Pt/C, MOF-808-Nafion-Pt/C, Nafion-Pt/C and JM Pt/C in the catalyst layer. (b) CO displacement results at 0.45 V. CO stripping curves (c) and the sulfonate group coverage on Pt (in percent) (d) for BMImHSO4@MOF-808-Nafion-Pt/C, MOF-808-Nafion-Pt/C and Nafion-Pt/C.

Fig. 6. (a) Rtotal of MEA with MOF-808 free, MOF-808 and BMImHSO4@MOF-808 plotted versus the absolute gas pressure. RH+ at different humidity: 100% RH (b); 40% RH (c); dry proton accessibility analysis (d).

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