Impregnation of ionic liquid into porous Fe-N-C electrocatalyst to improve electrode kinetics and mass transport for polymer electrolyte fuel cells

doi:10.1016/S1872-2067(25)64654-7

Abstract

Abstract:

Developing efficient and stable non-precious metal catalysts is essential for replacing platinum-based catalysts in polymer electrolyte membrane fuel cells (PEMFCs). The transition metal and nitrogen co-doped carbon electrocatalyst (M-N-C) is considered an effective alternative to precious metal catalysts. However, its relatively poor performance in acidic environments has always been a problem plaguing its practical application in PEMFCs. This study presents a sequential deposition methodology for constructing a composite catalytic system of Fe-N-C and ionic liquid (IL), which exhibits improved performance at both half-cell and membrane electrode assembly scales. The presence of IL significantly inhibits H₂O₂ production, preferentially promoting the 4e^- O₂ reduction reaction, resulting in improved electrocatalytic activity and stability. Additionally, the enhanced PEMFC performance of IL containing electrodes is a direct result of the improved ionic and reactant accessibility of the pore confined Fe-N-C catalysts where the IL minimizes local resistive transport losses. This study establishes a strategic foundation for the practical utilization of non-precious metal catalysts in PEMFCs and other energy converting technologies.

Key words: Fuel cell, Electrocatalysis, Oxygen reduction reaction, Ionic liquid, Non-platinum group metal

Siming Li, Enyang Sun, Pengfei Wei, Wei Zhao, Suizhu Pei, Ying Chen, Jie Yang, Huili Chen, Xi Yin, Min Wang, Yawei Li. Impregnation of ionic liquid into porous Fe-N-C electrocatalyst to improve electrode kinetics and mass transport for polymer electrolyte fuel cells[J]. Chinese Journal of Catalysis, 2025, 72: 277-288.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64654-7

https://www.cjcatal.com/EN/Y2025/V72/I5/277

Figures/Tables 5

Fig. 1. (a) Schematic representation of the sequential deposition process of the IL [BMIM][beti] on porous Fe-N-C material. S 2p (b) and F 1s (c) XPS spectra, respectively, for Fe-N-C (below) and Fe-NC/IL (above). (d) HAADF image and S and F EDS mapping of Fe-N-C/IL.

Fig. 2. (a) ORR polarization curves for Fe-N-C and Fe-N-C/IL before and after ADT. (b) Nyquist diagrams of the ORR on Fe-N-C and Fe-N-C/IL at potential of 0.3 V vs. RHE. (c) H2O2 yield for Fe-N-C and Fe-N-C/IL (above) and corresponding electron transfer number (below) during RRDE test in O2-saturated 0.1 mol/L HClO4 at 900 r/min. (d) Five-axespider-web diagram used to evaluate the O2 reduction performance of Fe-N-C and Fe-N-C/IL; (e) ORR kinetic current density, jk, at 0.8 V vs. RHE before and after ADT. (f) ICP-MS measurement of concentration of dissolved Fe in aged electrolyte after ADT.

Fig. 3. (a) H2/O2 polarization curves measured at 80 °C for MEAs fabricated with Fe-N-C and Fe-N-C/IL under 100%/100% RH, 75%/75% RH, and 50%/50% RH. (b) Comparison of the current density measured at 0.30 V of the MEAs at different RHs. (c) Ratio of the current density at 0.3 V of the MEAs at different RHs.

Fig. 4. Nyquist plots of the H2/N2 EIS of the MEAs at 100%/100% RH (a) and 50%/50% RH (b). (c) Comparison of the proton-transfer resistance of the cathode catalyst layers (CCLs) at different RHs. (d) Schematic diagram of proton transport at different RHs.

Fig. 5. (a) Schematic diagram of ORR limiting current measurement. (b) CVs of MEA (GDL+Fe-N-C/IL GDE) under 150 kPa in different RHs. (c) CVs of MEA (2GDL, GDL+Fe-N-C GDE, and GDL+Fe-N-C/IL GDE) under 150 kPa in 50% RH. (d) Rtotal for Fe-N-C and Fe-N-C/IL under different RHs. (e) Comparison of Rtotal for Fe-N-C and Fe-N-C/IL under 150 kPa in different RHs. (f) The distribution of O2 density on the Fe-N-C surface was calculated for two cases: with or without IL [BMIM][beti]. (g) MD simulation models of O2 molecular distribution on Fe-N-C surface with and without IL [BMIM][beti].

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