Effect of Dispersion Medium Composition and Ionomer Concentration on the Microstructure and Rheology of Fe–N–C Platinum Group Metal-free Catalyst Inks for Polymer Electrolyte Membrane Fuel Cells

Khandavalli, Sunilkumar; Iyer, Radhika; Park, Jae Hyung; Myers, Deborah J.; Neyerlin, Kenneth C.; Ulsh, Michael; Mauger, Scott A.

doi:10.1021/acs.langmuir.0c02015

Title: Effect of Dispersion Medium Composition and Ionomer Concentration on the Microstructure and Rheology of Fe–N–C Platinum Group Metal-free Catalyst Inks for Polymer Electrolyte Membrane Fuel Cells

Journal Article · Thu Sep 24 00:00:00 EDT 2020 · Langmuir

DOI:https://doi.org/10.1021/acs.langmuir.0c02015· OSTI ID:1677432

^[1]; Iyer, Radhika ^[1]; Park, Jae Hyung ^[2];

^[2];

^[1];

^[1]

National Renewable Energy Lab. (NREL), Golden, CO (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)

In this paper, we present an investigation of the microstructure and rheological behavior of catalyst inks consisting of Fe–N–C platinum group metal-free catalysts and a perfluorosulfonic acid ionomer in a dispersion medium (DM) of water and 1-propanol (nPA). The effects of the ionomer-to-catalyst (I/C) ratio and weight percentage of water (H₂O %) in the DM on the ink microstructure were studied. Steady-shear and dynamic-oscillatory-shear rheology, in combination with synchrotron X-ray scattering, was utilized to understand interparticle interactions and the level of agglomeration of the inks. In the absence of the ionomer, the inks were significantly agglomerated, approaching a gel-like microstructure for catalyst concentrations as low as 2 wt %. The effect of H₂O % in the DM on particle agglomeration was found to vary with particle concentration. In concentrated inks (≥2 wt % catalyst), increasing H₂O % was found to increase agglomeration because of the hydrophobic nature of the catalysts. In dilute inks (<1 wt % catalyst), the trend was reversed with increasing H₂O %, suggesting that electrostatic interactions are dominating the behavior. In inks with 5 wt % catalyst, the addition of an ionomer was found to significantly stabilize the catalyst against agglomeration. Maximum stability was observed at 0.35 I/C for all DM H₂O % studied. At high ionomer concentrations (I/C > 0.35), interesting differences were observed between nPA-rich inks (H₂O % ≤ 50%) and H₂O-rich (82% H₂O) inks. The nPA-rich inks remained predominantly stable—ink viscosity only weakly increased with I/C and the Newtonian behavior was maintained for I/C up to 0.9. In contrast, the H₂O-rich inks exhibited a significant increase in viscoelasticity with increasing I/C, suggesting flocculation of the catalyst by the ionomer. These differences suggest that the nature of the interactions between the ionomer and catalyst is highly dependent on the H₂O % in the DM.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE Office of Science (SC); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office; Electrocatalyst Consortium (ElectroCat)

Grant/Contract Number:: AC36-08GO28308; AC02-06CH11357

OSTI ID:: 1677432

Alternate ID(s):: OSTI ID: 1777373

Report Number(s):: NREL/JA-5900-77134; MainId:26080; UUID:c530e011-d122-420a-a426-99c1ac904cf2; MainAdminID:18598

Journal Information:: Langmuir, Vol. 36, Issue 41; ISSN 0743-7463

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Effect of Dispersion Medium Composition and Ionomer Concentration on the Microstructure and Rheology of Fe–N–C Platinum Group Metal-free Catalyst Inks for Polymer Electrolyte Membrane Fuel Cells

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