Investigation of the Microstructure and Rheology of Iridium Oxide Catalyst Inks for Low-Temperature Polymer Electrolyte Membrane Water Electrolyzers

Khandavalli, Sunilkumar; Park, Jae Hyung; Kariuki, Nancy N.; Zaccarine, Sarah F.; Pylypenko, Svitlana; Myers, Deborah J.; Ulsh, Michael J.; Mauger, Scott A.

doi:10.1021/acsami.9b14415

Investigation of the Microstructure and Rheology of Iridium Oxide Catalyst Inks for Low-Temperature Polymer Electrolyte Membrane Water Electrolyzers

Journal Article · Thu Nov 07 00:00:00 EST 2019 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.9b14415· OSTI ID:1578258

^[1]; Park, Jae Hyung ^[2]; Kariuki, Nancy N. ^[2]; Zaccarine, Sarah F. ^[3]; ^[3]; Myers, Deborah J. ^[2]; ^[1]; ^[1]

National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)
Colorado School of Mines, Golden, CO (United States)

Here, we present an investigation of the structure and rheological behavior of catalyst inks for low-temperature polymer electrolyte membrane water electrolyzers. The ink consists of iridium oxide (IrO₂) catalyst particles and a Nafion ionomer dispersed in a mixture of 1-propanol and water. The effects of ionomer concentration and catalyst concentration on the microstructure of the catalyst ink were studied. Studies on dilute inks (0.1 wt % IrO₂) using zeta potential and dynamic light scattering measurements indicated a strong adsorption of the ionomer onto the catalyst particles which resulted in an increase in the ..zeta..-potential and the z-average diameter. Steady-shear and dynamic-oscillatory-shear rheological measurements of concentrated IrO₂ dispersions (35 wt % IrO₂) indicated that the particles are strongly agglomerated in the absence of the ionomer. The addition of even a small amount of the ionomer (2.4 wt % with respect to total solids) caused the rheology to transition from shear thinning to Newtonian because of the reduction in agglomerated structure due to stabilization of the aggregates by the ionomer, consistent with the behavior of dilute inks. At intermediate ionomer loadings, between 2.4 and 9 wt %, the viscosity increased with increasing ionomer wt %, though remained Newtonian, predominantly due to the increasing ionomer volume fraction in the ink. For ionomer loadings greater than 9 wt %, the particles were found to be flocculated, likely induced by a dispersed ionomer. The flocculated inks exhibited strong shear-thinning and gel-like behaviors in steady-shear and oscillatory-shear rheology. The onset of flocculation was found to be sensitive to the catalyst concentration, where below 35 wt % of IrO₂, flocculation was not observed. The rheological observations were further verified by ultra-small-angle X-ray scattering.

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

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office; USDOE Office of Science (SC); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

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

OSTI ID:: 1578258

Alternate ID(s):: OSTI ID: 1606551

Report Number(s):: NREL/JA--5900-74843

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 48 Vol. 11; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (59)

The effect of shear-thickening on the stability of slot-die coating Khandavalli, Sunilkumar; Rothstein, Jonathan P. AIChE Journal, Vol. 62, Issue 12 https://doi.org/10.1002/aic.15336	journal	June 2016
Zeta potential of Nafion molecules in isopropanol-water mixture solvent Zhang, Haining; Pan, Jingjing; He, Xiuchong Journal of Applied Polymer Science, Vol. 107, Issue 5 https://doi.org/10.1002/app.27473	journal	January 2007
Review on penetration and transport phenomena in porous media during slot die coating Ding, Xiaoyu; Harris, Tequila A. L. Journal of Polymer Science Part B: Polymer Physics, Vol. 55, Issue 22 https://doi.org/10.1002/polb.24307	journal	February 2017
Liquid Film Coating: Scientific principles and their technological implications Kistler, Stephan F.; Schweizer, Peter M. https://doi.org/10.1007/978-94-011-5342-3	book	January 1997
Rheology of carbon black suspensions. II. Well dispersed system Aoki, Yuji; Hatano, Akira; Watanabe, Hiroshi Rheologica Acta, Vol. 42, Issue 4 https://doi.org/10.1007/s00397-003-0298-7	journal	July 2003
Large amplitude oscillatory shear rheology of three different shear-thickening particle dispersions Khandavalli, Sunilkumar; Rothstein, Jonathan P. Rheologica Acta, Vol. 54, Issue 7 https://doi.org/10.1007/s00397-015-0855-x	journal	May 2015
Intrinsic viscosities and other rheological properties of flocculated suspensions of nonmagnetic and magnetic ferric oxides Smith, Thor L.; Bruce, Calvin A. Journal of Colloid and Interface Science, Vol. 72, Issue 1 https://doi.org/10.1016/0021-9797(79)90176-0	journal	October 1979
Can charged (block co)polymers act as stabilisers and flocculants of oxides? Hoogeveen, Nynke G.; Cohen Stuart, Martien A.; Fleer, Gerard J. Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 117, Issue 1-2 https://doi.org/10.1016/0927-7757(96)03699-0	journal	October 1996
The Calculation of Zeta Potential Hunter, Robert J. Zeta Potential in Colloid Science, p. 59-124 https://doi.org/10.1016/B978-0-12-361961-7.50007-9	book	January 1981
Polymer adsorption and electrokinetic potential of dispersed particles in weak and strong electric fields Barany, Sandor Advances in Colloid and Interface Science, Vol. 222 https://doi.org/10.1016/j.cis.2014.09.009	journal	August 2015
Electrocatalysis in water electrolysis with solid polymer electrolyte Rasten, Egil; Hagen, Georg; Tunold, Reidar Electrochimica Acta, Vol. 48, Issue 25-26 https://doi.org/10.1016/j.electacta.2003.04.001	journal	November 2003
Observation of ionomer in catalyst ink of polymer electrolyte fuel cell using cryogenic transmission electron microscopy Takahashi, Shinichi; Shimanuki, Junichi; Mashio, Tetsuya Electrochimica Acta, Vol. 224 https://doi.org/10.1016/j.electacta.2016.12.068	journal	January 2017
Pure hydrogen production by PEM electrolysis for hydrogen energy Grigoriev, S.; Porembsky, V.; Fateev, V. International Journal of Hydrogen Energy, Vol. 31, Issue 2 https://doi.org/10.1016/j.ijhydene.2005.04.038	journal	February 2006
Performance of a PEM water electrolysis cell using IrxRuyTazO2IrxRuyTazO2 electrocatalysts for the oxygen evolution electrode Marshall, A.; Sunde, S.; Tsypkin, M. International Journal of Hydrogen Energy, Vol. 32, Issue 13 https://doi.org/10.1016/j.ijhydene.2007.02.013	journal	September 2007
Investigations on high performance proton exchange membrane water electrolyzer Ma, L.; Sui, S.; Zhai, Y. International Journal of Hydrogen Energy, Vol. 34, Issue 2 https://doi.org/10.1016/j.ijhydene.2008.11.022	journal	January 2009
The effects of ionomer content on PEM water electrolyser membrane electrode assembly performance Xu, Wu; Scott, Keith International Journal of Hydrogen Energy, Vol. 35, Issue 21 https://doi.org/10.1016/j.ijhydene.2010.08.055	journal	November 2010
A comprehensive review on PEM water electrolysis Carmo, Marcelo; Fritz, David L.; Mergel, Jürgen International Journal of Hydrogen Energy, Vol. 38, Issue 12, p. 4901-4934 https://doi.org/10.1016/j.ijhydene.2013.01.151	journal	April 2013
Intrinsic viscosity of SiO2, Al2O3 and TiO2 aqueous suspensions Rubio-Hernández, F. J.; Ayúcar-Rubio, M. F.; Velázquez-Navarro, J. F. Journal of Colloid and Interface Science, Vol. 298, Issue 2 https://doi.org/10.1016/j.jcis.2006.01.009	journal	June 2006
The effect of shear-thickening on liquid transfer from an idealized gravure cell Khandavalli, Sunilkumar; Lee, J. Alex; Pasquali, Matteo Journal of Non-Newtonian Fluid Mechanics, Vol. 221 https://doi.org/10.1016/j.jnnfm.2015.03.007	journal	July 2015
Ink transfer of non-Newtonian fluids from an idealized gravure cell: The effect of shear and extensional deformation Khandavalli, Sunilkumar; Rothstein, Jonathan P. Journal of Non-Newtonian Fluid Mechanics, Vol. 243 https://doi.org/10.1016/j.jnnfm.2017.02.005	journal	May 2017
PEM fuel cell electrodes Litster, S.; McLean, G. Journal of Power Sources, Vol. 130, Issue 1-2 https://doi.org/10.1016/j.jpowsour.2003.12.055	journal	May 2004
Short-range contacts govern the performance of industry-relevant battery cathodes Morelly, Samantha L.; Alvarez, Nicolas J.; Tang, Maureen H. Journal of Power Sources, Vol. 387 https://doi.org/10.1016/j.jpowsour.2018.03.039	journal	May 2018
Composition and temperature dependence of the dielectric constant of 1-propanol/water mixtures: Experiment and molecular dynamics simulations Méndez-Bermúdez, José G.; Dominguez, Hector; Pusztai, László Journal of Molecular Liquids, Vol. 219 https://doi.org/10.1016/j.molliq.2016.02.053	journal	July 2016
PEM electrolysis for production of hydrogen from renewable energy sources Barbir, Frano Solar Energy, Vol. 78, Issue 5 https://doi.org/10.1016/j.solener.2004.09.003	journal	May 2005
Colloidal Suspension Rheology Mewis, Jan; Wagner, Norman J. https://doi.org/10.1017/CBO9780511977978	book	January 2011
The non-Newtonian rheology of dilute colloidal suspensions Bergenholtz, J.; Brady, J. F.; Vicic, M. Journal of Fluid Mechanics, Vol. 456 https://doi.org/10.1017/s0022112001007583	journal	April 2002
The effect of Brownian motion on the bulk stress in a suspension of spherical particles Batchelor, G. K. Journal of Fluid Mechanics, Vol. 83, Issue 1 https://doi.org/10.1017/s0022112077001062	journal	November 1977
Iridium Oxide for the Oxygen Evolution Reaction: Correlation between Particle Size, Morphology, and the Surface Hydroxo Layer from Operando XAS Abbott, Daniel F.; Lebedev, Dmitry; Waltar, Kay Chemistry of Materials, Vol. 28, Issue 18 https://doi.org/10.1021/acs.chemmater.6b02625	journal	September 2016
Inherent Acidity of Perfluorosulfonic Acid Ionomer Dispersions and Implications for Ink Aggregation Berlinger, Sarah A.; McCloskey, Bryan D.; Weber, Adam Z. The Journal of Physical Chemistry B, Vol. 122, Issue 31 https://doi.org/10.1021/acs.jpcb.8b06493	journal	July 2018
Impact of Catalyst Ink Dispersing Methodology on Fuel Cell Performance Using in-Situ X-ray Scattering Wang, Min; Park, Jae Hyung; Kabir, Sadia ACS Applied Energy Materials, Vol. 2, Issue 9 https://doi.org/10.1021/acsaem.9b01037	journal	July 2019
Rheological Investigation on the Microstructure of Fuel Cell Catalyst Inks Khandavalli, Sunilkumar; Park, Jae Hyung; Kariuki, Nancy N. ACS Applied Materials & Interfaces, Vol. 10, Issue 50 https://doi.org/10.1021/acsami.8b15039	journal	December 2018
Defining Nafion Ionomer Roles for Enhancing Alkaline Oxygen Evolution Electrocatalysis Li, Guang-Fu; Yang, Donglei; Abel Chuang, Po-Ya ACS Catalysis, Vol. 8, Issue 12 https://doi.org/10.1021/acscatal.8b02217	journal	October 2018
Fuel Cell Catalyst Layers: A Polymer Science Perspective Holdcroft, Steven Chemistry of Materials, Vol. 26, Issue 1 https://doi.org/10.1021/cm401445h	journal	July 2013
Dispersion of Rod-like Particles of Nafion in Salt-Free Water/1-Propanol and Water/Ethanol Solutions Yamaguchi, Makoto; Matsunaga, Takuro; Amemiya, Kazuki The Journal of Physical Chemistry B https://doi.org/10.1021/jp506814m	journal	December 2014
Flocculation of Sterically Stabilized Polystyrene Latex Particles by Adsorbing and Nonadsorbing Poly(acrylic acid) Liang, W.; Tadros, Th. F.; Luckham, P. F. Langmuir, Vol. 10, Issue 2 https://doi.org/10.1021/la00014a018	journal	February 1994
Effects of Phase Behavior on the Drying of Colloidal Suspensions Haw, M. D.; Gillie, M.; Poon, W. C. K. Langmuir, Vol. 18, Issue 5 https://doi.org/10.1021/la0110951	journal	January 2002
Electrosteric Stabilization of Colloidal Dispersions Fritz, Gerhard; Schädler, Volker; Willenbacher, Norbert Langmuir, Vol. 18, Issue 16 https://doi.org/10.1021/la015734j	journal	August 2002
Effects of Perfluorosulfonic Acid Adsorption on the Stability of Carbon Black Suspensions Mizukawa, Hiroki; Kawaguchi, Masami Langmuir, Vol. 25, Issue 20 https://doi.org/10.1021/la9025188	journal	September 2009
Effect of Nonadsorbed Polymer on the Stability of Weakly Flocculated Suspensions Ogden, A. L.; Lewis, J. A. Langmuir, Vol. 12, Issue 14 https://doi.org/10.1021/la950953o	journal	January 1996
Depletion Attraction Caused by Unadsorbed Polyelectrolytes Pagac, Edward S.; Tilton, Robert D.; Prieve, Dennis C. Langmuir, Vol. 14, Issue 18 https://doi.org/10.1021/la980058f	journal	September 1998
Polyelectrolyte adsorption, interparticle forces, and colloidal aggregation Szilagyi, Istvan; Trefalt, Gregor; Tiraferri, Alberto Soft Matter, Vol. 10, Issue 15 https://doi.org/10.1039/c3sm52132j	journal	January 2014
Understanding inks for porous-electrode formation Hatzell, Kelsey B.; Dixit, Marm B.; Berlinger, Sarah A. J. Mater. Chem. A, Vol. 5, Issue 39 https://doi.org/10.1039/c7ta07255d	journal	January 2017
Structure, dynamics, and rheology of colloid-polymer mixtures: From liquids to gels Laurati, M.; Petekidis, G.; Koumakis, N. The Journal of Chemical Physics, Vol. 130, Issue 13 https://doi.org/10.1063/1.3103889	journal	April 2009
Shear thickening in colloidal dispersions Wagner, Norman J.; Brady, John F. Physics Today, Vol. 62, Issue 10 https://doi.org/10.1063/1.3248476	journal	October 2009
Hard sphere colloidal dispersions: Viscosity as a function of shear rate and volume fraction de Kruif, C. G.; van Iersel, E. M. F.; Vrij, A. The Journal of Chemical Physics, Vol. 83, Issue 9 https://doi.org/10.1063/1.448997	journal	November 1985
High-concentration zeta potential measurements using light-scattering techniques Kaszuba, Michael; Corbett, Jason; Watson, Fraser Mcneil Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 368, Issue 1927 https://doi.org/10.1098/rsta.2010.0175	journal	September 2010
Small-Angle Scattering from Polymeric Mass Fractals of Arbitrary Mass-Fractal Dimension Beaucage, G. Journal of Applied Crystallography, Vol. 29, Issue 2 https://doi.org/10.1107/s0021889895011605	journal	April 1996
An in situ USAXS–SAXS–WAXS study of precipitate size distribution evolution in a model Ni-based alloy Andrews, Ross N.; Serio, Joseph; Muralidharan, Govindarajan Journal of Applied Crystallography, Vol. 50, Issue 3 https://doi.org/10.1107/s1600576717006446	journal	May 2017
Extensional rheology of shear-thickening fumed silica nanoparticles dispersed in an aqueous polyethylene oxide solution Khandavalli, Sunilkumar; Rothstein, Jonathan P. Journal of Rheology, Vol. 58, Issue 2 https://doi.org/10.1122/1.4864620	journal	March 2014
A Mechanism for Non‐Newtonian Flow in Suspensions of Rigid Spheres Krieger, Irvin M.; Dougherty, Thomas J. Transactions of the Society of Rheology, Vol. 3, Issue 1 https://doi.org/10.1122/1.548848	journal	March 1959
Analysis of Linear Viscoelasticity of a Crosslinking Polymer at the Gel Point Winter, H. Henning; Chambon, Francois Journal of Rheology, Vol. 30, Issue 2 https://doi.org/10.1122/1.549853	journal	April 1986
Gravure Coating for Roll-to-Roll Manufacturing of Proton-Exchange-Membrane Fuel Cell Catalyst Layers Mauger, Scott A.; Neyerlin, K. C.; Yang-Neyerlin, Ami C. Journal of The Electrochemical Society, Vol. 165, Issue 11 https://doi.org/10.1149/2.0091813jes	journal	January 2018
Understanding the Effect of Kinetic and Mass Transport Processes in Cathode Agglomerates Moore, M.; Wardlaw, P.; Dobson, P. Journal of The Electrochemical Society, Vol. 161, Issue 8 https://doi.org/10.1149/2.010408jes	journal	January 2014
Catalyst Layer Ink Interactions That Affect Coatability Dixit, Marm B.; Harkey, Brice A.; Shen, Fengyu Journal of The Electrochemical Society, Vol. 165, Issue 5 https://doi.org/10.1149/2.0191805jes	journal	January 2018
Influence of Ionomer Content in IrO ₂ /TiO ₂ Electrodes on PEM Water Electrolyzer Performance Bernt, Maximilian; Gasteiger, Hubert A. Journal of The Electrochemical Society, Vol. 163, Issue 11 https://doi.org/10.1149/2.0231611jes	journal	January 2016
Iridium Oxygen Evolution Activity and Durability Baselines in Rotating Disk Electrode Half-Cells Alia, Shaun M.; Anderson, Grace C. Journal of The Electrochemical Society, Vol. 166, Issue 4 https://doi.org/10.1149/2.0731904jes	journal	January 2019
CO ₂ -Assisted Regeneration of a Polymer Electrolyte Water Electrolyzer Contaminated with Metal Ion Impurities Babic, Ugljesa; Zlobinski, Mateusz; Schmidt, Thomas Justus Journal of The Electrochemical Society, Vol. 166, Issue 10 https://doi.org/10.1149/2.0851910jes	journal	January 2019
Experimental and Theoretical Analysis of Ink Dispersion Stability for Polymer Electrolyte Fuel Cell Applications Shukla, S.; Bhattacharjee, S.; Weber, A. Z. Journal of The Electrochemical Society, Vol. 164, Issue 6 https://doi.org/10.1149/2.0961706jes	journal	January 2017
Analysis of Inkjet Printed Catalyst Coated Membranes for Polymer Electrolyte Electrolyzers Mandal, Manas; Valls, Antoni; Gangnus, Niklas Journal of The Electrochemical Society, Vol. 165, Issue 7 https://doi.org/10.1149/2.1101807jes	journal	January 2018

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Investigation of the Microstructure and Rheology of Iridium Oxide Catalyst Inks for Low-Temperature Polymer Electrolyte Membrane Water Electrolyzers

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