Sodium thiosulfate-assisted synthesis of high-Pt-content intermetallic electrocatalysts for fuel cells

doi:10.1016/S1872-2067(24)60127-0

Abstract

Abstract:

Carbon supported Pt-based intermetallic compounds (IMCs) with high activity and durability are the most competitive cathode catalysts for the commercialization of proton exchange membrane fuel cells (PEMFCs). The synthesis of Pt-based intermetallics with a good balance between small size and high metal loading remains challenging because of the high-temperature annealing that is generally required to form intermetallic phases. We developed a sodium thiosulfate-assisted impregnation strategy to synthesize small-sized and highly ordered PtM IMCs catalysts (M = Co, Fe, Ni) with high-Pt-content (up to 44.5 wt%). During the impregnation process, thiosulfate could reduce H₂PtCl₆ to form uniformly dispersed Pt colloid on carbon supports, which in turn prevents the aggregation of Pt at the low-temperature annealing stage. Additionally, the strong interaction between Pt and S inhibits particle sintering, ensuring the formation of small-sized and uniform PtM intermetallic catalysts at the high-temperature annealing stage. The optimized intermetallic PtCo catalyst delivered a high mass activity of 0.72 A mg_Pt^-1 and a large power performance of 1.17 W cm^-2 at 0.65 V under H₂-air conditions, along with 74% mass activity retention after the accelerated stress test.

Key words: Sodium thiosulfate, Small-sized, Pt-based intermetallic compound, High-Pt-content, Proton exchange membrane fuel cells

Shi-Yi Yin, Shi-Long Xu, Zi-Rui Li, Shuai Li, Kun-Ze Xue, Wanqun Zhang, Sheng-Qi Chu, Hai-Wei Liang. Sodium thiosulfate-assisted synthesis of high-Pt-content intermetallic electrocatalysts for fuel cells[J]. Chinese Journal of Catalysis, 2024, 66: 292-301.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60127-0

https://www.cjcatal.com/EN/Y2024/V66/I11/292

Figures/Tables 6

Fig. 1. Schematic illustration of the Pt-M (M = Co, Fe, and Ni) IMCs catalysts formation with or without Na2S2O3 by an industrially relevant impregnation-reduction approach.

Fig. 2. XRD patterns of PtM-S and PtM (M = Co, Fe, and Ni). XRD patterns of PtCo (a), PtFe (b), and PtNi (c) prepared with or without Na2S2O3. Asterisks marked in (a-c) are the characteristic super-lattice peaks of ordered intermetallic structures. (d-f) The (111) diffraction peaks originate from the magnified region in the red box of (a-c). The insets show the particle size and distribution estimation by XRD results (order from left to right: dark blue represents Pt-rich phase, purple represents M-rich phase, and light blue represents single M phase).

Fig. 3. HAADF-STEM images and particle size distributions of PtM-S and PtM (M = Co, Fe, and Ni). HAADF-STEM images and particle size distribution of PtCo (a), PtFe (b), PtNi (c), PtCo-S (d), PtFe-S (e), and PtNi-S (f). (g) Violin plots of number-average particle size distributions for between PtM-S and PtM catalysts (M = Co, Fe, and Ni). (h) Violin plots of number-average particle size distributions for PtCo-S and PtCo catalysts with various Pt loading from 27.1 wt% to 44.5 wt%. (i) Comparison of Pt-based intermetallic size between our work and the state-of-art in the literature. The red shaded areas represent the size distribution range of PtCo-S IMCs with different loadings prepared in our work.

Fig. 4. Formation mechanism of PtCo-S IMCs. (a) UV-vis spectra of the H2PtCl6·6H2O solution, Na2S2O3 solution, and the mixture solution of H2PtCl6·6H2O and Na2S2O3. The photographs showed the color change of Na2S2O3 with H2PtCl6 after 24 hours. (b) Comparison of XPS results of the Pt 42f of PtCo-S/C precursor powder and PtCo/C precursor powder. (c) XANES spectra of PtCo-S/C precursor powder, PtCo/C precursor powder, PtS2 and Pt foil. XRD patterns of Pt/C (d), Pt-S/C (e), and PtCo-S/C (f) were prepared under elevated temperatures. (g) EXAFS spectra at Pt L3-edge for PtCo-S/C catalysts at 300 and 900 °C, referenced PtO2, PtS2 and Pt foil. XPS spectra of Pt 4f (h) and S 2p (i) for PtCo-S catalysts from 300 to 900 °C.

Fig. 5. Structure evolution of PtCo-S catalyst after post-treatment with H2O2 oxidation, H2SO4 etching and H2 reduction treatment. (a) Schematic illustration of structure evolution of PtM-S (M = Co, Fe, Ni) IMC catalyst from L10-Pt1M1 to Pt1M1@Pt core-shell structure. (b) Comparison of XRD patterns of PtCo-S IMC catalyst after post-treatment. (c) The change of ordering degree and atom ratio of Pt/Co for PtCo-S IMC catalyst after post-treatment. Atomic-resolution HAADF-STEM image (d) and corresponding line-profile (e) taken from red region of (d), and EDS line scanning (f) of Pt1Co1@Pt core-shell structure.

Fig. 6. MEA performance. H2-air single-cell polarization curves and power density plots of the PtCo-S (a) and TKK-Pt/C (b) cathodes under beginning-of-life (BOL) and end-of-life (EOL) after 30000 AST. Test conditions: cathode loading of 0.1 mgPt cm-2, 80 °C, 100% relative humidity, 150 kPaabs; H2 and air flow rates were fixed at 0.5 and 2.0 L min-1, respectively. Current density and power density of PtCo-S (c) and TKK-Pt/C (d) cathodes at BOL and EOL. (e) MA at 0.9?V in H2-O2 fuel cells and the voltage at 0.8 A?cm-2 in H2-air fuel cells at BOL and EOL. (f) ECSA was measured by CO stripping at BOL and EOL.

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