Toward Optimizing Electrospun Nanofiber Fuel Cell Catalyst Layers: Polymer–Particle Interactions and Spinnability

Khandavalli, Sunilkumar; Sharma-Nene, Nisha; Kabir, Sadia; Sur, Samrat; Rothstein, Jonathan P.; Neyerlin, Kenneth C.; Mauger, Scott A.; Ulsh, Michael

doi:10.1021/acsapm.0c01354

Toward Optimizing Electrospun Nanofiber Fuel Cell Catalyst Layers: Polymer–Particle Interactions and Spinnability

Journal Article · Fri Apr 09 00:00:00 EDT 2021 · ACS Applied Polymer Materials

DOI:https://doi.org/10.1021/acsapm.0c01354· OSTI ID:1779800

^[1]; Sharma-Nene, Nisha ^[1]; Kabir, Sadia ^[1]; Sur, Samrat ^[2]; Rothstein, Jonathan P. ^[2]; ^[1]; ^[1]; ^[1]

National Renewable Energy Lab. (NREL), Golden, CO (United States)
Univ. of Massachusetts, Amherst, MA (United States)

We investigate the effect of the poly(acrylic acid) (PAA) carrier polymer concentration on the microstructure and rheological properties of catalyst inks for electrospun polymer–electrolyte membrane fuel-cell catalyst layers. Characterization of an ink microstructure using oscillatory shear rheology showed that the catalyst particles (platinum on carbon) are significantly agglomerated in the absence of PAA or an ionomer. Both the ionomer and PAA promoted the stability of the particles against agglomeration via electrosteric stabilization by adsorbing onto the particle surface. Increasing the PAA concentration increased the stability of the particles (or reduced the agglomerated structure) due to increasing PAA coverage onto the free surface area of the particles. However, beyond a certain increase in concentration, PAA was found to predominantly remain as an excess free polymer in the ink due to an insufficient free/available surface area on the particles for further PAA coverage. Extensional rheology measurements demonstrated that PAA enhances the extensional viscosities of the inks. Consequently, increasing the PAA concentration in the ink promoted the evolution of uniform nanofibers. However, beyond a certain concentration, a significant increase in the shear viscosities of the inks led to defective fiber morphologies because of the onset of flow instabilities. Electrochemical performance comparisons between catalyst layers with different PAA concentrations showed maximum performance at the PAA concentration that led to the least agglomerated structure of the catalyst, most uniform fiber morphologies, and low concentrations of free (non-adsorbing) PAA in the electrode. These results provide a rationale for optimization of electrospun catalyst nanofibers for both spinnability and electrochemical performance.

View Accepted Manuscript (DOE)

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1779800

Report Number(s):: NREL/JA--5900-79228; MainId:33454; UUID:c2fe02fe-38af-48f2-a59c-ab3e2c5afdb1; MainAdminID:21274

Journal Information:: ACS Applied Polymer Materials, Journal Name: ACS Applied Polymer Materials Journal Issue: 5 Vol. 3; ISSN 2637-6105

Publisher:: ACS PublicationsCopyright Statement

Country of Publication:: United States

Language:: English

References (52)

Dispensing of rheologically complex fluids: The map of misery Clasen, Christian; Phillips, Paul M.; Palangetic, Ljiljana AIChE Journal, Vol. 58, Issue 10 https://doi.org/10.1002/aic.13704	journal	December 2011
Instabilities in polymer processing Petrie, Christopher J. S.; Denn, Morton M. AIChE Journal, Vol. 22, Issue 2 https://doi.org/10.1002/aic.690220202	journal	March 1976
Electrospun Fiber Mat Cathode with Platinum‐Group‐Metal‐Free Catalyst Powder and Nafion/PVDF Binder Slack, John; Halevi, Barr; McCool, Geoff ChemElectroChem, Vol. 5, Issue 12 https://doi.org/10.1002/celc.201800283	journal	April 2018
High-Performance Nanofiber Fuel Cell Electrodes Zhang, Wenjing; Pintauro, Peter N. ChemSusChem, Vol. 4, Issue 12 https://doi.org/10.1002/cssc.201100245	journal	November 2011
Electrochemical Characterization of Pre-conditioning Process of Electrospun Nanofiber Electrodes in Polymer Electrolyte Fuel Cells Si, D.; Zhang, S.; Huang, J. Fuel Cells, Vol. 18, Issue 5 https://doi.org/10.1002/fuce.201700209	journal	July 2018
Extension rate of the straight jet in electrospinning of poly( N -isopropyl acrylamide) solutions in dimethylformamide: Influences of flow rate and applied voltage Wang, Yu; Hashimoto, Takeji; Li, Chang-Chou Journal of Polymer Science Part B: Polymer Physics, Vol. 56, Issue 4 https://doi.org/10.1002/polb.24544	journal	November 2017
Instabilities in viscoelastic flows Larson, R. G. Rheologica Acta, Vol. 31, Issue 3 https://doi.org/10.1007/BF00366504	journal	January 1992
The extensibility of macromolecules in solution; A new focus for macromolecular science Keller, A.; Odell, J. A. Colloid & Polymer Science, Vol. 263, Issue 3 https://doi.org/10.1007/BF01415506	journal	March 1985
Filament stretching of carbon nanotube suspensions Ma, Anson W. K.; Chinesta, Francisco; Tuladhar, Tri Rheologica Acta, Vol. 47, Issue 4 https://doi.org/10.1007/s00397-007-0247-y	journal	January 2008
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
Some investigations on the fiber formation by utilizing a side-by-side bicomponent electrospinning approach Gupta, Pankaj; Wilkes, Garth L. Polymer, Vol. 44, Issue 20 https://doi.org/10.1016/S0032-3861(03)00616-5	journal	September 2003
Effect of a spectrum of relaxation times on the capillary thinning of a filament of elastic liquid Entov, V. M.; Hinch, E. J. Journal of Non-Newtonian Fluid Mechanics, Vol. 72, Issue 1 https://doi.org/10.1016/S0377-0257(97)00022-0	journal	September 1997
Application of electrospinning for the fabrication of proton-exchange membrane fuel cell electrodes Waldrop, Krysta; Wycisk, Ryszard; Pintauro, Peter N. Current Opinion in Electrochemistry, Vol. 21 https://doi.org/10.1016/j.coelec.2020.03.007	journal	June 2020
A high-performance PEM fuel cell with ultralow platinum electrode via electrospinning and underpotential deposition Hong, Shaojing; Hou, Ming; Zhang, Hongjie Electrochimica Acta, Vol. 245 https://doi.org/10.1016/j.electacta.2017.05.066	journal	August 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
High voltage stability of nanostructured thin film catalysts for PEM fuel cells Debe, Mark K.; Schmoeckel, Alison K.; Vernstrom, George D. Journal of Power Sources, Vol. 161, Issue 2 https://doi.org/10.1016/j.jpowsour.2006.05.033	journal	October 2006
Electrospray deposition of catalyst layers with ultra-low Pt loadings for PEM fuel cells cathodes Martin, S.; Garcia-Ybarra, P. L.; Castillo, J. L. Journal of Power Sources, Vol. 195, Issue 9 https://doi.org/10.1016/j.jpowsour.2009.11.092	journal	May 2010
Improving the bulk gas transport of Fe-N-C platinum group metal-free nanofiber electrodes via electrospinning for fuel cell applications Kabir, Sadia; Medina, Samantha; Wang, Guanxiong Nano Energy, Vol. 73 https://doi.org/10.1016/j.nanoen.2020.104791	journal	July 2020
Role of chain entanglements on fiber formation during electrospinning of polymer solutions: good solvent, non-specific polymer–polymer interaction limit Shenoy, Suresh L.; Bates, W. Douglas; Frisch, Harry L. Polymer, Vol. 46, Issue 10 https://doi.org/10.1016/j.polymer.2005.03.011	journal	April 2005
The role of elasticity in the formation of electrospun fibers Yu, Jian H.; Fridrikh, Sergey V.; Rutledge, Gregory C. Polymer, Vol. 47, Issue 13 https://doi.org/10.1016/j.polymer.2006.04.050	journal	June 2006
Electrospinning jets and polymer nanofibers Reneker, Darrell H.; Yarin, Alexander L. Polymer, Vol. 49, Issue 10 https://doi.org/10.1016/j.polymer.2008.02.002	journal	May 2008
Theory and kinematic measurements of the mechanics of stable electrospun polymer jets Helgeson, Matthew E.; Grammatikos, Kristie N.; Deitzel, Joseph M. Polymer, Vol. 49, Issue 12 https://doi.org/10.1016/j.polymer.2008.04.025	journal	June 2008
Colloidal Suspension Rheology Mewis, Jan; Wagner, Norman J. https://doi.org/10.1017/CBO9780511977978	book	January 2011
The stress generated in a non-dilute suspension of elongated particles by pure straining motion Batchelor, G. K. Journal of Fluid Mechanics, Vol. 46, Issue 4 https://doi.org/10.1017/S0022112071000879	journal	April 1971
Power Laws Dominate Shear and Extensional Rheology Response and Capillarity-Driven Pinching Dynamics of Entangled Hydroxyethyl Cellulose (HEC) Solutions Dinic, Jelena; Sharma, Vivek Macromolecules, Vol. 53, Issue 9 https://doi.org/10.1021/acs.macromol.0c00077	journal	April 2020
Toward Optimizing Electrospun Nanofiber Fuel Cell Catalyst Layers: Microstructure and Pt Accessibility Kabir, Sadia; Van Cleve, Tim; Khandavalli, Sunilkumar ACS Applied Energy Materials, Vol. 4, Issue 4 https://doi.org/10.1021/acsaem.0c03073	journal	March 2021
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
Designing the 3D Architecture of PGM-Free Cathodes for H ₂ /Air Proton Exchange Membrane Fuel Cells Li, Jingkun; Brüller, Sebastian; Sabarirajan, Dinesh C. ACS Applied Energy Materials, Vol. 2, Issue 10 https://doi.org/10.1021/acsaem.9b01181	journal	September 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
Elucidating the Dynamic Nature of Fuel Cell Electrodes as a Function of Conditioning: An ex Situ Material Characterization and in Situ Electrochemical Diagnostic Study Kabir, Sadia; Myers, Deborah J.; Kariuki, Nancy ACS Applied Materials & Interfaces, Vol. 11, Issue 48 https://doi.org/10.1021/acsami.9b11365	journal	November 2019
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
Surface Tension of Alcohol Water + Water from 20 to 50 .degree.C Vazquez, Gonzalo; Alvarez, Estrella; Navaza, Jose M. Journal of Chemical & Engineering Data, Vol. 40, Issue 3 https://doi.org/10.1021/je00019a016	journal	May 1995
Correlations of Solution Rheology with Electrospun Fiber Formation of Linear and Branched Polyesters McKee, Matthew G.; Wilkes, Garth L.; Colby, Ralph. H. Macromolecules, Vol. 37, Issue 5 https://doi.org/10.1021/ma035689h	journal	March 2004
Electrospinning and Solution Properties of Nafion and Poly(acrylic acid) Chen, Hong; Snyder, Joshua D.; Elabd, Yossef A. Macromolecules, Vol. 41, Issue 1, p. 128-135 https://doi.org/10.1021/ma070893g	journal	January 2008
Formation of beads-on-a-string structures during break-up of viscoelastic filaments Bhat, Pradeep P.; Appathurai, Santosh; Harris, Michael T. Nature Physics, Vol. 6, Issue 8 https://doi.org/10.1038/nphys1682	journal	June 2010
Electrospinning: designed architectures for energy conversion and storage devices Cavaliere, Sara; Subianto, Surya; Savych, Iuliia Energy & Environmental Science, Vol. 4, Issue 12 https://doi.org/10.1039/c1ee02201f	journal	January 2011
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
Effects of particle stiffness on the extensional rheology of model rod-like nanoparticle suspensions Lang, Christian; Hendricks, Jan; Zhang, Zhenkun Soft Matter, Vol. 15, Issue 5 https://doi.org/10.1039/c8sm01925h	journal	January 2019
The hydrodynamic stress in a suspension of rods Shaqfeh, Eric S. G.; Fredrickson, Glenn H. Physics of Fluids A: Fluid Dynamics, Vol. 2, Issue 1 https://doi.org/10.1063/1.857683	journal	January 1990
On the breakup of viscous liquid threads Papageorgiou, Demetrios T. Physics of Fluids, Vol. 7, Issue 7 https://doi.org/10.1063/1.868540	journal	July 1995
Highly efficient nonprecious metal catalyst prepared with metal–organic framework in a continuous carbon nanofibrous network Shui, Jianglan; Chen, Chen; Grabstanowicz, Lauren Proceedings of the National Academy of Sciences, Vol. 112, Issue 34 https://doi.org/10.1073/pnas.1507159112	journal	August 2015
A review on electrospinning design and nanofibre assemblies Teo, W. E.; Ramakrishna, S. Nanotechnology, Vol. 17, Issue 14 https://doi.org/10.1088/0957-4484/17/14/R01	journal	June 2006
Electrospun Nafion Nanofiber for Proton Exchange Membrane Fuel Cell Application Bajon, R.; Balaji, S.; Guo, S. M. Journal of Fuel Cell Science and Technology, Vol. 6, Issue 3 https://doi.org/10.1115/1.3005577	journal	May 2009
Elasto-capillary thinning and breakup of model elastic liquids Anna, Shelley L.; McKinley, Gareth H. Journal of Rheology, Vol. 45, Issue 1 https://doi.org/10.1122/1.1332389	journal	January 2001
How dilute are dilute solutions in extensional flows? Clasen, C.; Plog, J. P.; Kulicke, W. -M. Journal of Rheology, Vol. 50, Issue 6 https://doi.org/10.1122/1.2357595	journal	November 2006
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
Drop breakup dynamics of dilute polymer solutions: Effect of molecular weight, concentration, and viscosity Sur, Samrat; Rothstein, Jonathan Journal of Rheology, Vol. 62, Issue 5 https://doi.org/10.1122/1.5038000	journal	September 2018
Determination of Electrode Sheet Resistance in Cathode Catalyst Layer by AC Impedance Liu, Yuxiu; Murphy, Michael; Baker, Daniel 212th ECS Meeting, ECS Transactions https://doi.org/10.1149/1.2780961	conference	January 2007
Study on the Cathode Fabricated by Spinning Process and Its Performance in PEFC Kotera, Seigo; Watabe, Hiroyuki; Fujii, Katsuya ECS Transactions, Vol. 25, Issue 1, p. 821-830 https://doi.org/10.1149/1.3210635	journal	January 2009
Nanofiber Fuel Cell MEAs with a PtCo/C Cathode Slack, J. J.; Gumeci, C.; Dale, N. Journal of The Electrochemical Society, Vol. 166, Issue 7 https://doi.org/10.1149/2.0151907jes	journal	January 2019
Fabrication, In-Situ Performance, and Durability of Nanofiber Fuel Cell Electrodes Brodt, Matthew; Han, Taehee; Dale, Nilesh Journal of The Electrochemical Society, Vol. 162, Issue 1 https://doi.org/10.1149/2.0651501jes	journal	November 2014
Electrospinning deposition of poly(acrylic acid): platinum/carbon catalyst ink to enhance polymer electrolyte membrane fuel cell performance Chen, Guan Hao; Kelly, Danielle; Shine, Audrey MRS Communications, Vol. 9, Issue 4 https://doi.org/10.1557/mrc.2019.144	journal	October 2019

Similar Records

Toward Optimizing Electrospun Nanofiber Fuel Cell Catalyst Layers: Microstructure and Pt Accessibility

Journal Article · Sun Mar 21 20:00:00 EDT 2021 · ACS Applied Energy Materials · OSTI ID:1774883

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

Journal Article · Wed Nov 06 19:00:00 EST 2019 · ACS Applied Materials and Interfaces · OSTI ID:1578258

Related Subjects

25 ENERGY STORAGE
catalyst inks
electrospinning
extensional rheology
fuel cells
nanofibers
poly(acrylic acid)

Toward Optimizing Electrospun Nanofiber Fuel Cell Catalyst Layers: Polymer–Particle Interactions and Spinnability

Citation Formats

References (52)

Similar Records

Related Subjects