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

Kabir, Sadia; Van Cleve, Tim; Khandavalli, Sunilkumar; Medina, Samantha; Pylypenko, Svitlana; Mauger, Scott; Ulsh, Michael; Neyerlin, Kenneth C.

doi:10.1021/acsaem.0c03073

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

Journal Article · Mon Mar 22 00:00:00 EDT 2021 · ACS Applied Energy Materials

DOI:https://doi.org/10.1021/acsaem.0c03073· OSTI ID:1774883

^[1]; ^[1]; ^[1]; Medina, Samantha ^[2]; ^[2]; ^[1]; ^[1]; ^[1]

National Renewable Energy Lab. (NREL), Golden, CO (United States)
Colorado School of Mines, Golden, CO (United States)

This work investigates how local ionomer/platinum (Pt) interactions and ionomer distribution in electrospun Pt/Vulcan nanofiber electrodes impact ionomer coverage, proton accessibility, and oxygen reduction reaction (ORR) performance in proton-exchange membrane fuel cells. Insights from various in situ electrochemical diagnostics were utilized in conjunction with ex situ microscopic characterization to understand how the electrode microstructure—both at the aggregate level and near the ionomer/platinum interface—is affected by electrospinning in comparison to ultrasonic spraying. The effect of the carrier polymer poly(acrylic acid) (PAA) concentration from 5–20 wt % (with respect to total ink solids) on the resulting nanofiber morphology is discussed. Electron microscopy observations and CO displacement measurements indicated that Pt/Vulcan nanofibers prepared with a higher PAA concentration (15 wt %) were conformally coated with a film of ionomer on the exterior of the fiber, which resulted in an overall lower ionomer coverage on both Pt and carbon throughout the fiber diameter. In contrast, 10 wt % PAA leads to a uniform intrafiber distribution of the ionomer within the fibers, increasing the overall ionomer coverage and proton accessibility under both wet and dry conditions. These differences in the local ionomer coverage on Pt between 10 and 15 wt % PAA were also attributed to differences in the adsorption/interaction affinities between PAA and the ionomer onto the catalyst surface in the ink using zeta potential measurements. Additional fuel cell electrochemical tests on the electrospun electrodes show improvements in ORR kinetics and high-current-density H₂/air performance compared to the ultrasonically sprayed electrodes.

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), Advanced Manufacturing Office (EE-5A); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Hydrogen and Fuel Cell Technologies Office (EE-3F)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1774883

Report Number(s):: NREL/JA-5900-79533; MainId:33759; UUID:c9889ad8-e471-46d4-ab1b-2b4da3e645e4; MainAdminID:21202

Journal Information:: ACS Applied Energy Materials, Journal Name: ACS Applied Energy Materials Journal Issue: 4 Vol. 4; ISSN 2574-0962

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (44)

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
Beaded nanofibers formed during electrospinning Fong, H.; Chun, I.; Reneker, D. H. Polymer, Vol. 40, Issue 16 https://doi.org/10.1016/S0032-3861(99)00068-3	journal	July 1999
A review on polymer nanofibers by electrospinning and their applications in nanocomposites Huang, Zheng-Ming; Zhang, Y.-Z.; Kotaki, M. Composites Science and Technology, Vol. 63, Issue 15, p. 2223-2253 https://doi.org/10.1016/S0266-3538(03)00178-7	journal	November 2003
A new type of hydrophilic carbon paste electrodes for biosensor manufacturing: binder paste electrodes Parellada, Josefina; Narváez, Arántzazu; Domínguez, Elena Biosensors and Bioelectronics, Vol. 12, Issue 4 https://doi.org/10.1016/S0956-5663(96)00066-8	journal	January 1997
Effect of particle size on the activity and durability of the Pt/C electrocatalyst for proton exchange membrane fuel cells Xu, Zhuang; Zhang, Huamin; Zhong, Hexiang Applied Catalysis B: Environmental, Vol. 111-112 https://doi.org/10.1016/j.apcatb.2011.10.007	journal	January 2012
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
An in situ technique for analyzing ionomer coverage in catalyst layers Iden, Hiroshi; Ohma, Atsushi Journal of Electroanalytical Chemistry, Vol. 693 https://doi.org/10.1016/j.jelechem.2013.01.026	journal	March 2013
Evaluation of ionomer coverage on Pt catalysts in polymer electrolyte membrane fuel cells by CO stripping voltammetry and its effect on oxygen reduction reaction activity Takeshita, Tomohiro; Kamitaka, Yuji; Shinozaki, Kazuma Journal of Electroanalytical Chemistry, Vol. 871 https://doi.org/10.1016/j.jelechem.2020.114250	journal	August 2020
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
Influence of the composition of isopropyl alcohol/water mixture solvents in catalyst ink solutions on proton exchange membrane fuel cell performance Ngo, Trung Truc; Yu, T. Leon; Lin, Hsiu-Li Journal of Power Sources, Vol. 225 https://doi.org/10.1016/j.jpowsour.2012.10.055	journal	March 2013
Effects of carbon supports on Pt distribution, ionomer coverage and cathode performance for polymer electrolyte fuel cells Park, Young-Chul; Tokiwa, Haruki; Kakinuma, Katsuyoshi Journal of Power Sources, Vol. 315 https://doi.org/10.1016/j.jpowsour.2016.02.091	journal	May 2016
Fabrication of high-performance gas-diffusion-electrode based membrane-electrode assemblies Mauger, Scott A.; Pfeilsticker, Jason R.; Wang, Min Journal of Power Sources, Vol. 450 https://doi.org/10.1016/j.jpowsour.2019.227581	journal	February 2020
Tailoring electrode microstructure via ink content to enable improved rated power performance for platinum cobalt/high surface area carbon based polymer electrolyte fuel cells Van Cleve, Tim; Wang, Guanxiong; Mooney, Mason Journal of Power Sources, Vol. 482 https://doi.org/10.1016/j.jpowsour.2020.228889	journal	January 2021
Durability of platinum-based fuel cell electrocatalysts: Dissolution of bulk and nanoscale platinum Cherevko, Serhiy; Kulyk, Nadiia; Mayrhofer, Karl J. J. Nano Energy, Vol. 29 https://doi.org/10.1016/j.nanoen.2016.03.005	journal	November 2016
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
Utilizing ink composition to tune bulk-electrode gas transport, performance, and operational robustness for a Fe–N–C catalyst in polymer electrolyte fuel cell Osmieri, Luigi; Wang, Guanxiong; Cetinbas, Firat C. Nano Energy, Vol. 75 https://doi.org/10.1016/j.nanoen.2020.104943	journal	September 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
Fabrication Method for Laboratory-Scale High-Performance Membrane Electrode Assemblies for Fuel Cells Sassin, Megan B.; Garsany, Yannick; Gould, Benjamin D. Analytical Chemistry, Vol. 89, Issue 1 https://doi.org/10.1021/acs.analchem.6b03005	journal	December 2016
The Priority and Challenge of High-Power Performance of Low-Platinum Proton-Exchange Membrane Fuel Cells Kongkanand, Anusorn; Mathias, Mark F. The Journal of Physical Chemistry Letters, Vol. 7, Issue 7 https://doi.org/10.1021/acs.jpclett.6b00216	journal	March 2016
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
3D Analysis of Fuel Cell Electrocatalyst Degradation on Alternate Carbon Supports Sneed, Brian T.; Cullen, David A.; Reeves, Kimberly S. ACS Applied Materials & Interfaces, Vol. 9, Issue 35 https://doi.org/10.1021/acsami.7b09716	journal	August 2017
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
Dictating Pt-Based Electrocatalyst Performance in Polymer Electrolyte Fuel Cells, from Formulation to Application Van Cleve, Tim; Khandavalli, Sunilkumar; Chowdhury, Anamika ACS Applied Materials & Interfaces, Vol. 11, Issue 50 https://doi.org/10.1021/acsami.9b17614	journal	November 2019
Effect of the Side-Chain Structure of Perfluoro-Sulfonic Acid Ionomers on the Oxygen Reduction Reaction on the Surface of Pt Kodama, Kensaku; Motobayashi, Kenta; Shinohara, Akihiro ACS Catalysis, Vol. 8, Issue 1 https://doi.org/10.1021/acscatal.7b03571	journal	December 2017
Modifying the Electrocatalyst–Ionomer Interface via Sulfonated Poly(ionic liquid) Block Copolymers to Enable High-Performance Polymer Electrolyte Fuel Cells Li, Yawei; Van Cleve, Tim; Sun, Rui ACS Energy Letters, Vol. 5, Issue 6 https://doi.org/10.1021/acsenergylett.0c00532	journal	April 2020
Boosting Fuel Cell Performance with Accessible Carbon Mesopores Yarlagadda, Venkata; Carpenter, Michael K.; Moylan, Thomas E. ACS Energy Letters, Vol. 3, Issue 3 https://doi.org/10.1021/acsenergylett.8b00186	journal	February 2018
Scientific Aspects of Polymer Electrolyte Fuel Cell Durability and Degradation Borup, Rod; Meyers, Jeremy; Pivovar, Bryan Chemical Reviews, Vol. 107, Issue 10 https://doi.org/10.1021/cr050182l	journal	October 2007
Conductivity and Wettability Changes of Ultrathin Nafion Films Subjected to Thermal Annealing and Liquid Water Exposure Paul, Devproshad K.; Karan, Kunal The Journal of Physical Chemistry C, Vol. 118, Issue 4 https://doi.org/10.1021/jp410510x	journal	January 2014
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
Electrocatalyst approaches and challenges for automotive fuel cells Debe, Mark K. Nature, Vol. 486, Issue 7401 https://doi.org/10.1038/nature11115	journal	June 2012
Unexplained transport resistances for low-loaded fuel-cell catalyst layers Weber, Adam Z.; Kusoglu, Ahmet J. Mater. Chem. A, Vol. 2, Issue 41 https://doi.org/10.1039/C4TA02952F	journal	January 2014
High performance electrospun bipolar membrane with a 3D junction Shen, Chunhui; Wycisk, Ryszard; Pintauro, Peter N. Energy & Environmental Science, Vol. 10, Issue 6 https://doi.org/10.1039/C7EE00345E	journal	January 2017
Just a Dream—or Future Reality? Gasteiger, Hubert A.; Marković, Nenad M Science, Vol. 324, Issue 5923, p. 48-49 https://doi.org/10.1126/science.1172083	journal	April 2009
Morphological Control of Electrospun Nafion Nanofiber Mats Ballengee, J. B.; Pintauro, P. N. Journal of The Electrochemical Society, Vol. 158, Issue 5 https://doi.org/10.1149/1.3561645	journal	January 2011
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
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
Durability of Pt-Co Alloy Polymer Electrolyte Fuel Cell Cathode Catalysts under Accelerated Stress Tests Papadias, D. D.; Ahluwalia, R. K.; Kariuki, N. Journal of The Electrochemical Society, Vol. 165, Issue 6 https://doi.org/10.1149/2.0171806jes	journal	January 2018
Characterizing Electrolyte and Platinum Interface in PEM Fuel Cells Using CO Displacement Garrick, Taylor R.; Moylan, Thomas E.; Yarlagadda, Venkata Journal of The Electrochemical Society, Vol. 164, Issue 2 https://doi.org/10.1149/2.0551702jes	journal	December 2016
Recoverable Performance Loss Due to Membrane Chemical Degradation in PEM Fuel Cells Zhang, Jingxin; Litteer, Brian A.; Coms, Frank D. Journal of The Electrochemical Society, Vol. 159, Issue 7 https://doi.org/10.1149/2.063207jes	journal	January 2012
Power Output and Durability of Electrospun Fuel Cell Fiber Cathodes with PVDF and Nafion/PVDF Binders Brodt, Matthew; Wycisk, Ryszard; Dale, Nilesh Journal of The Electrochemical Society, Vol. 163, Issue 5 https://doi.org/10.1149/2.0711605jes	journal	January 2016
A Systematic Study of Solution and Processing Parameters on Nanofiber Morphology Using a New Electrospinning Apparatus Henriques, C.; Vidinha, R.; Botequim, D. Journal of Nanoscience and Nanotechnology, Vol. 9, Issue 6 https://doi.org/10.1166/jnn.2009.NS27	journal	June 2009

Similar Records

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

Journal Article · Thu Apr 08 20:00:00 EDT 2021 · ACS Applied Polymer Materials · OSTI ID:1779800

Dictating Pt-Based Electrocatalyst Performance in Polymer Electrolyte Fuel Cells, from Formulation to Application

Journal Article · Mon Nov 18 19:00:00 EST 2019 · ACS Applied Materials and Interfaces · OSTI ID:1580098

Related Subjects

25 ENERGY STORAGE
PGM-free catalyst
electrochemical diagnostics
electrospinning
fuel cell
oxygen reduction

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

Citation Formats

References (44)

Similar Records

Related Subjects