Investigation of the Microstructure and Rheology of Iridium Oxide Catalyst Inks for Low-Temperature Polymer Electrolyte Membrane Water Electrolyzers
Abstract
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 themore »
- Authors:
-
- 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)
- Publication Date:
- Research Org.:
- National Renewable Energy Lab. (NREL), Golden, CO (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
- OSTI Identifier:
- 1578258
- Alternate Identifier(s):
- OSTI ID: 1606551
- Report Number(s):
- NREL/JA-5900-74843
Journal ID: ISSN 1944-8244; TRN: US2102202
- Grant/Contract Number:
- AC36-08GO28308; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Applied Materials and Interfaces
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 48; Journal ID: ISSN 1944-8244
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; low-temperature polymer electrolyte membrane exchange water electrolysis; rheology; catalyst inks; iridium oxide; ionomer; catalyst layer
Citation Formats
Khandavalli, Sunilkumar, Park, Jae Hyung, Kariuki, Nancy N., Zaccarine, Sarah F., Pylypenko, Svitlana, Myers, Deborah J., Ulsh, Michael J., and Mauger, Scott A. Investigation of the Microstructure and Rheology of Iridium Oxide Catalyst Inks for Low-Temperature Polymer Electrolyte Membrane Water Electrolyzers. United States: N. p., 2019.
Web. doi:10.1021/acsami.9b14415.
Khandavalli, Sunilkumar, Park, Jae Hyung, Kariuki, Nancy N., Zaccarine, Sarah F., Pylypenko, Svitlana, Myers, Deborah J., Ulsh, Michael J., & Mauger, Scott A. Investigation of the Microstructure and Rheology of Iridium Oxide Catalyst Inks for Low-Temperature Polymer Electrolyte Membrane Water Electrolyzers. United States. https://doi.org/10.1021/acsami.9b14415
Khandavalli, Sunilkumar, Park, Jae Hyung, Kariuki, Nancy N., Zaccarine, Sarah F., Pylypenko, Svitlana, Myers, Deborah J., Ulsh, Michael J., and Mauger, Scott A. Thu .
"Investigation of the Microstructure and Rheology of Iridium Oxide Catalyst Inks for Low-Temperature Polymer Electrolyte Membrane Water Electrolyzers". United States. https://doi.org/10.1021/acsami.9b14415. https://www.osti.gov/servlets/purl/1578258.
@article{osti_1578258,
title = {Investigation of the Microstructure and Rheology of Iridium Oxide Catalyst Inks for Low-Temperature Polymer Electrolyte Membrane Water Electrolyzers},
author = {Khandavalli, Sunilkumar and Park, Jae Hyung and Kariuki, Nancy N. and Zaccarine, Sarah F. and Pylypenko, Svitlana and Myers, Deborah J. and Ulsh, Michael J. and Mauger, Scott A.},
abstractNote = {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.},
doi = {10.1021/acsami.9b14415},
journal = {ACS Applied Materials and Interfaces},
number = 48,
volume = 11,
place = {United States},
year = {2019},
month = {11}
}
Web of Science
Works referenced in this record:
Pure hydrogen production by PEM electrolysis for hydrogen energy
journal, February 2006
- Grigoriev, S.; Porembsky, V.; Fateev, V.
- International Journal of Hydrogen Energy, Vol. 31, Issue 2
A comprehensive review on PEM water electrolysis
journal, April 2013
- Carmo, Marcelo; Fritz, David L.; Mergel, Jürgen
- International Journal of Hydrogen Energy, Vol. 38, Issue 12, p. 4901-4934
PEM electrolysis for production of hydrogen from renewable energy sources
journal, May 2005
- Barbir, Frano
- Solar Energy, Vol. 78, Issue 5
Fuel Cell Catalyst Layers: A Polymer Science Perspective
journal, July 2013
- Holdcroft, Steven
- Chemistry of Materials, Vol. 26, Issue 1
Understanding inks for porous-electrode formation
journal, January 2017
- Hatzell, Kelsey B.; Dixit, Marm B.; Berlinger, Sarah A.
- J. Mater. Chem. A, Vol. 5, Issue 39
Gravure Coating for Roll-to-Roll Manufacturing of Proton-Exchange-Membrane Fuel Cell Catalyst Layers
journal, January 2018
- Mauger, Scott A.; Neyerlin, K. C.; Yang-Neyerlin, Ami C.
- Journal of The Electrochemical Society, Vol. 165, Issue 11
PEM fuel cell electrodes
journal, May 2004
- Litster, S.; McLean, G.
- Journal of Power Sources, Vol. 130, Issue 1-2
Investigations on high performance proton exchange membrane water electrolyzer
journal, January 2009
- Ma, L.; Sui, S.; Zhai, Y.
- International Journal of Hydrogen Energy, Vol. 34, Issue 2
The effects of ionomer content on PEM water electrolyser membrane electrode assembly performance
journal, November 2010
- Xu, Wu; Scott, Keith
- International Journal of Hydrogen Energy, Vol. 35, Issue 21
Influence of Ionomer Content in IrO 2 /TiO 2 Electrodes on PEM Water Electrolyzer Performance
journal, January 2016
- Bernt, Maximilian; Gasteiger, Hubert A.
- Journal of The Electrochemical Society, Vol. 163, Issue 11
Rheological Investigation on the Microstructure of Fuel Cell Catalyst Inks
journal, December 2018
- Khandavalli, Sunilkumar; Park, Jae Hyung; Kariuki, Nancy N.
- ACS Applied Materials & Interfaces, Vol. 10, Issue 50
Can charged (block co)polymers act as stabilisers and flocculants of oxides?
journal, October 1996
- Hoogeveen, Nynke G.; Cohen Stuart, Martien A.; Fleer, Gerard J.
- Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 117, Issue 1-2
Short-range contacts govern the performance of industry-relevant battery cathodes
journal, May 2018
- Morelly, Samantha L.; Alvarez, Nicolas J.; Tang, Maureen H.
- Journal of Power Sources, Vol. 387
The effect of shear-thickening on liquid transfer from an idealized gravure cell
journal, July 2015
- Khandavalli, Sunilkumar; Lee, J. Alex; Pasquali, Matteo
- Journal of Non-Newtonian Fluid Mechanics, Vol. 221
Catalyst Layer Ink Interactions That Affect Coatability
journal, January 2018
- Dixit, Marm B.; Harkey, Brice A.; Shen, Fengyu
- Journal of The Electrochemical Society, Vol. 165, Issue 5
Review on penetration and transport phenomena in porous media during slot die coating
journal, February 2017
- Ding, Xiaoyu; Harris, Tequila A. L.
- Journal of Polymer Science Part B: Polymer Physics, Vol. 55, Issue 22
Understanding the Effect of Kinetic and Mass Transport Processes in Cathode Agglomerates
journal, January 2014
- Moore, M.; Wardlaw, P.; Dobson, P.
- Journal of The Electrochemical Society, Vol. 161, Issue 8
Zeta potential of Nafion molecules in isopropanol-water mixture solvent
journal, January 2007
- Zhang, Haining; Pan, Jingjing; He, Xiuchong
- Journal of Applied Polymer Science, Vol. 107, Issue 5
Inherent Acidity of Perfluorosulfonic Acid Ionomer Dispersions and Implications for Ink Aggregation
journal, July 2018
- Berlinger, Sarah A.; McCloskey, Bryan D.; Weber, Adam Z.
- The Journal of Physical Chemistry B, Vol. 122, Issue 31
Defining Nafion Ionomer Roles for Enhancing Alkaline Oxygen Evolution Electrocatalysis
journal, October 2018
- Li, Guang-Fu; Yang, Donglei; Abel Chuang, Po-Ya
- ACS Catalysis, Vol. 8, Issue 12
Polymer adsorption and electrokinetic potential of dispersed particles in weak and strong electric fields
journal, August 2015
- Barany, Sandor
- Advances in Colloid and Interface Science, Vol. 222
Iridium Oxide for the Oxygen Evolution Reaction: Correlation between Particle Size, Morphology, and the Surface Hydroxo Layer from Operando XAS
journal, September 2016
- Abbott, Daniel F.; Lebedev, Dmitry; Waltar, Kay
- Chemistry of Materials, Vol. 28, Issue 18
Composition and temperature dependence of the dielectric constant of 1-propanol/water mixtures: Experiment and molecular dynamics simulations
journal, July 2016
- Méndez-Bermúdez, José G.; Dominguez, Hector; Pusztai, László
- Journal of Molecular Liquids, Vol. 219
Dispersion of Rod-like Particles of Nafion in Salt-Free Water/1-Propanol and Water/Ethanol Solutions
journal, December 2014
- Yamaguchi, Makoto; Matsunaga, Takuro; Amemiya, Kazuki
- The Journal of Physical Chemistry B
Observation of ionomer in catalyst ink of polymer electrolyte fuel cell using cryogenic transmission electron microscopy
journal, January 2017
- Takahashi, Shinichi; Shimanuki, Junichi; Mashio, Tetsuya
- Electrochimica Acta, Vol. 224
Experimental and Theoretical Analysis of Ink Dispersion Stability for Polymer Electrolyte Fuel Cell Applications
journal, January 2017
- Shukla, S.; Bhattacharjee, S.; Weber, A. Z.
- Journal of The Electrochemical Society, Vol. 164, Issue 6
Electrosteric Stabilization of Colloidal Dispersions
journal, August 2002
- Fritz, Gerhard; Schädler, Volker; Willenbacher, Norbert
- Langmuir, Vol. 18, Issue 16
Impact of Catalyst Ink Dispersing Methodology on Fuel Cell Performance Using in-Situ X-ray Scattering
journal, July 2019
- Wang, Min; Park, Jae Hyung; Kabir, Sadia
- ACS Applied Energy Materials, Vol. 2, Issue 9
Iridium Oxygen Evolution Activity and Durability Baselines in Rotating Disk Electrode Half-Cells
journal, January 2019
- Alia, Shaun M.; Anderson, Grace C.
- Journal of The Electrochemical Society, Vol. 166, Issue 4
CO 2 -Assisted Regeneration of a Polymer Electrolyte Water Electrolyzer Contaminated with Metal Ion Impurities
journal, January 2019
- Babic, Ugljesa; Zlobinski, Mateusz; Schmidt, Thomas Justus
- Journal of The Electrochemical Society, Vol. 166, Issue 10
Shear thickening in colloidal dispersions
journal, October 2009
- Wagner, Norman J.; Brady, John F.
- Physics Today, Vol. 62, Issue 10
Extensional rheology of shear-thickening fumed silica nanoparticles dispersed in an aqueous polyethylene oxide solution
journal, March 2014
- Khandavalli, Sunilkumar; Rothstein, Jonathan P.
- Journal of Rheology, Vol. 58, Issue 2
The non-Newtonian rheology of dilute colloidal suspensions
journal, April 2002
- Bergenholtz, J.; Brady, J. F.; Vicic, M.
- Journal of Fluid Mechanics, Vol. 456
A Mechanism for Non‐Newtonian Flow in Suspensions of Rigid Spheres
journal, March 1959
- Krieger, Irvin M.; Dougherty, Thomas J.
- Transactions of the Society of Rheology, Vol. 3, Issue 1
Intrinsic viscosities and other rheological properties of flocculated suspensions of nonmagnetic and magnetic ferric oxides
journal, October 1979
- Smith, Thor L.; Bruce, Calvin A.
- Journal of Colloid and Interface Science, Vol. 72, Issue 1
Intrinsic viscosity of SiO2, Al2O3 and TiO2 aqueous suspensions
journal, June 2006
- Rubio-Hernández, F. J.; Ayúcar-Rubio, M. F.; Velázquez-Navarro, J. F.
- Journal of Colloid and Interface Science, Vol. 298, Issue 2
Hard sphere colloidal dispersions: Viscosity as a function of shear rate and volume fraction
journal, November 1985
- de Kruif, C. G.; van Iersel, E. M. F.; Vrij, A.
- The Journal of Chemical Physics, Vol. 83, Issue 9
Ink transfer of non-Newtonian fluids from an idealized gravure cell: The effect of shear and extensional deformation
journal, May 2017
- Khandavalli, Sunilkumar; Rothstein, Jonathan P.
- Journal of Non-Newtonian Fluid Mechanics, Vol. 243
Structure, dynamics, and rheology of colloid-polymer mixtures: From liquids to gels
journal, April 2009
- Laurati, M.; Petekidis, G.; Koumakis, N.
- The Journal of Chemical Physics, Vol. 130, Issue 13
Analysis of Linear Viscoelasticity of a Crosslinking Polymer at the Gel Point
journal, April 1986
- Winter, H. Henning; Chambon, Francois
- Journal of Rheology, Vol. 30, Issue 2
Rheology of carbon black suspensions. II. Well dispersed system
journal, July 2003
- Aoki, Yuji; Hatano, Akira; Watanabe, Hiroshi
- Rheologica Acta, Vol. 42, Issue 4
Large amplitude oscillatory shear rheology of three different shear-thickening particle dispersions
journal, May 2015
- Khandavalli, Sunilkumar; Rothstein, Jonathan P.
- Rheologica Acta, Vol. 54, Issue 7
Depletion Attraction Caused by Unadsorbed Polyelectrolytes
journal, September 1998
- Pagac, Edward S.; Tilton, Robert D.; Prieve, Dennis C.
- Langmuir, Vol. 14, Issue 18
Polyelectrolyte adsorption, interparticle forces, and colloidal aggregation
journal, January 2014
- Szilagyi, Istvan; Trefalt, Gregor; Tiraferri, Alberto
- Soft Matter, Vol. 10, Issue 15
Flocculation of Sterically Stabilized Polystyrene Latex Particles by Adsorbing and Nonadsorbing Poly(acrylic acid)
journal, February 1994
- Liang, W.; Tadros, Th. F.; Luckham, P. F.
- Langmuir, Vol. 10, Issue 2
Effect of Nonadsorbed Polymer on the Stability of Weakly Flocculated Suspensions
journal, January 1996
- Ogden, A. L.; Lewis, J. A.
- Langmuir, Vol. 12, Issue 14
Analysis of Inkjet Printed Catalyst Coated Membranes for Polymer Electrolyte Electrolyzers
journal, January 2018
- Mandal, Manas; Valls, Antoni; Gangnus, Niklas
- Journal of The Electrochemical Society, Vol. 165, Issue 7
Performance of a PEM water electrolysis cell using IrxRuyTazO2IrxRuyTazO2 electrocatalysts for the oxygen evolution electrode
journal, September 2007
- Marshall, A.; Sunde, S.; Tsypkin, M.
- International Journal of Hydrogen Energy, Vol. 32, Issue 13
Electrocatalysis in water electrolysis with solid polymer electrolyte
journal, November 2003
- Rasten, Egil; Hagen, Georg; Tunold, Reidar
- Electrochimica Acta, Vol. 48, Issue 25-26