6 - Durable High-Power Density Fuel Cell Cathodes For HeavyDuty Vehicles
6 - Durable High-Power Density Fuel Cell Cathodes For HeavyDuty Vehicles
6 - Durable High-Power Density Fuel Cell Cathodes For HeavyDuty Vehicles
June 8, 2022
• Facilitate low platinum loadings in an advanced fuel • New ionomers developed specifically for electrode
cell membrane electrode assembly (MEA) cathode demands
catalyst layer (CCL) for heavy-duty vehicles (HDVs). • New insights on HOPI-Pt interfacial structure
• Synthesize and implement electrode-specific • Significant increase in BOL performance due to
ionomers that permit enhanced oxygen transport to increased mass activity and reduced local oxygen
the platinum surface for improved performance and transport resistance
durability.
• Significant reductions in degradation rates and
• Demonstrate the ionomer approach will yield required extended lifetimes
reduction in oxygen transport resistances in an MEA.
• Optimize the design of the ionomer for
commercialization, demonstrating significant
reductions in CCL platinum content while targeting
≤0.2 mg/cm2 Pt catalyst loading and 25,000 hr
lifetime set point.
2
Overview
Timeline and Budget Project Lead
• Project Start Date: 10/01/2019 Carnegie Mellon University
• Project End Date: 1/31/2023 – PI: Shawn Litster
• Total Project Budget: $2,500,000 – Co-PI: Zack Ulissi
• Total Recipient Share: $500,000
• Total Federal Share: $2,000,000 Partners
• Total DOE Funds Spent*: $974,243 The Chemours Company
*As of 12/31/2021 – PI: Andrew Park
– co-PI: Gerald Brown
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Project Team and Scope
Carnegie Mellon University (University prime)
Shawn Litster (PI), Zack Ulissi (Co-PI)
Electrode design, electrode fabrication, fuel cell testing, X-ray
and electron imaging, AST development, multi-scale modeling,
molecular-scale modeling, project management.
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Technical Targets, and Status
DOE/Project
D2020 Baseline HOPI Status
Target
Pt/LSAC Pt/HSC Pt/LSAC Pt/HSC
Performance loss
<30 62 78 29 53
at 0.8 A/cm2 (mV)2,3,5
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Year 1 & 2 Milestones and Go/No-Go Decision Points
Milestone Number* Milestone Description Quarter Percent
Progress notes
(Go/No-Go Number) (Go/No-Go Decision Criteria) complete
Delivery of >200 mL (>10% solids) HOPI dispersion to project partners for thin-film characterization, 350 ml of HOPI delivered to
M1.1 1 100%
ink studies, and MEA development project partners this quarter.
Demonstrate single cell with HOPI-enhanced cathode with 0.2 mg Pt/cm2 having a mass activity of 0.44
M2.3 7 100% Achieved with Pt/HSC
mA/mg PGM at 0.9 VIR-free
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Technical Accomplishment
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Technical Accomplishment
Thin-film Characterization
• HOPI and Nafion D2029 (~900 EW) control analyzed by GISAXS at LBL
• Similar swelling and water content between HOPI and D2029 at <60% RH
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Method and apparatus
Technical Accomplishment 1. H. Liu, W. K. Epting, and S. Litster, “Gas Transport
Resistance in Polymer Electrolyte Thin Films on Oxygen
Reduction Reaction Catalysts,” Langmuir, vol. 31, no. 36,
• New improved apparatus with integrated oxygen J. Electrochem. Soc., vol. 166, no. 16, pp. F1337–F1343,
2019.
14
Technical Accomplishment
15
Technical Accomplishment
0.4
)
2
0.3
0.25
0.2
0.15
80°C, 100% RH, 150 kPaabs
0.2/0.2 SLPM N2/H2 0.1
0.05
80°C, 100% RH, 150 kPaabs
0.2/0.2 SLPM N2/H2
0
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07
2
)
17
Technical Accomplishment
18
Technical Accomplishment
PI RO2 at 80 oC,
different RHs
45 cm2, HSA-Pt catalyst, I/C = 0.8
45 cm2, HSA-Pt catalyst, I/C = 0.8
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Technical Accomplishment
45 cm2, HSA-Pt
catalyst
45 cm2, HSA-Pt
catalyst
• Various catalyst loadings and three I/C ratios were investigated based on HSA-Pt catalyst
• I/C = 0.8 was the optimum for both D2020 and HOPI 870EW performance and PI RO2
Compared to D2020 ionomer, HOPI 870EW showed:
• Performance gain at high current density and reduction of oxygen transport resistance with decreasing roughness factor
• 30 mV performance gain at rf=110 with optimum I/C ratio
• 60 mV performance gain at rf=30 with same optimum I/C ratio
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Technical Accomplishment
PI RO2 (s/cm)
• Three catalysts including LSA-Pt, HSA-Pt, HSA-PtCo were investigated with both 45 cm2, I/C = 0.8
D2020 and HOPI 870EW ionomers
• HSA-Pt catalyst is the top performer at high current density
• Regardless of catalyst types, HOPI 870EW showed over D2020 - Mass Activity
• 10-20 mV kinetic performance improvement due to the mass activity Comparison
improvement
• Significant mass-transport related high current density performance
improvement due to reduction of PI RO2
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Technical Accomplishment
Electrode Durability
RF with Pt Dissolution AST Cycles In comparison to D2020, HOPI 870EW showed:
• Minor change in rf loss but major reduction of MEA performance degradation
rate for both LSA-Pt and HSA-Pt catalyst
• For HSA-PtCo catalyst, major reduction in rf loss and performance
degradation at 0.1A/cm2 but negative impact on degradation at high current
density, possibly due to faster changes of CL morphology during AST cycling
because of high crack density: 32% in HSA-PtCo/HOPI vs 4% in HSA-
PtCo/D2020
45 cm2, I/C=0.8
35K cycles, 80 oC, air/H2, 250KPa, 100% RH Performance Degradation Rate Performance Degradation Rate
at 0.1A/cm2 at 1A/cm2
- 16%
RF Degradation 32%
41% 23% 45%
7%
61%
20%
Technical Accomplishment
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Technical Accomplishment
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Reponses to Last Year AMR Reviewers’ Comments
We thank the reviewers for the many positive comments. Below we address only questions, suggestions, and comments of concern.
“…primary unknowns of the approach are how central catalyst degradation will be in HD systems and how chemically robust the HOPIs are in use.”, “…Additional studies investigating the
HOPI membrane for bulk properties such as water uptake, permeability, conductivity, and durability to radical attack would be good inclusions.”, “…inclusion of membrane studies on free-
standing films of HOPIs would provide valuable insight”, & “…HOPI ionomer chemistry adds additional ether linkages in the passive repeating unit of the polymer…effort should be focused on
fully characterizing the stability of this ionomer against chemical/electrochemical degradation.”
A new ionomer chemical AST has been established in the past year and preliminary results are encouraging showing no loss in ionomer performance. LBL has performed several
characterizations of HOPI thin films. Oxygen permeability of quasi free-standing films has been measured.
“…unclear whether HOPIs are needed or helpful at 0.2 mgPt/cm2. A significant impact would be expected at lower loadings (<0.1 mgPt/cm2). Modeling at lower loadings should also be
considered.” & “…at the end of the day for the high-roughness-factor MEAs was just not there …minute improvements over the D2020 baseline when the roughness factor is >100. This begs
the question of whether some other factor is dominating the performance of the catalyst layer, such as the catalyst layer resistance being higher for the HOPI, or the optimal ionomer-to-catalyst
ratio being different for the HOPI, as compared to D2020, possibly because the density of D2020 is higher.”
Low loading has been modeled and validated in the past year. At 0.2 mgPt/cm2 the benefits of HOPI are increased mass activity and retention of performance over the stack
lifetime as RF decreases.
“…project should focus on high-surface-area-carbon-type (HSC-type) supports, as these work the best at a low loading.
Catalysts with HSC supports has been a major focus of the past year.
“…threefold improvement in oxygen permeability is meaningful, but it is not clear how well it will be maintained over time or whether there are other degradation phenomena that may be worse
in HOPI than in other PFSAs. The HOPI approach also requires that Pt ECSA loss be treated as a significant degradation concern because it cannot be addressed either by novel catalysis
approaches or by systems controls. This is a worthwhile project, but it is not enough by itself to fully cover durability concerns.”
Startup/shutdown ASTs for carbon corrosion have also shown significant reductions in degradation rate despite same ECSA loss with D2020 and HOPI.
“…difficulty in performing all the needed catalyst layer optimizations to properly demonstrate the improvement in the catalyst layer performance using a HOPI.”
This challenge is addressed by performing small-scale studies at CMU with larger parameter ranges in the ink composition and evaluation of loading at larger scale at Ballard.
“…they could provide direct evidence by looking at the MEA performance as a function of oxygen partial pressure in the cathode. This would prove that it is the high oxygen
solubility/concentration in the ionomer that is the source of the performance enhancement. This is important, as it will guide further development of this ionomer, as well as others.”
This is a good suggestion for an approach to addressing a key objective in Year 3.
“…HOPI will likely benefit light-duty applications in the near term. Constraining development to HD targets does not seem like a logical first step”, “…should estimate the cost increase relative to
D2020”, and “…Since HD applications typically use higher Pt loadings, degradation studies are critical. For this application, the implementation of HOPI will be
highly dependent on cost. Perhaps the investigators can discuss cost impacts in future disclosures.”
Costs associated with the ionomer are an important consideration.
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Future Work
Year 3 Optimizing Performance and Durability for HDVs with HOPIs
• Ink optimization for new HOPI variants with higher equivalent weight and
chemistry
• Molecular dynamics simulations of alternative HOPI backbone and sidechain
chemistries
• Separate quantification of diffusivity and solubility vs. permeability for HOPI
• Anion adsorption impact on activity analysis
• Crack mitigation strategies (solvents, drying, additives)
• Understanding HOPI impact on degradation with HSC supports and PtCo catalyst
• Completion of ionomer AST studies
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Summary
Approach Collaboration and Coordination with Other Institutions
An integrated approach to advancing HDV fuel cell efficiency and durability with • Experienced industrial partners in fuel cells for HDVs and PFSA ionomers
advanced electrode ionomers coupled with advanced diagnostics, modeling, and imaging.
• Tight coordination of ionomer development with requirements for industry-
1. HOPIs for durable high efficiency with low Pt loading through higher scale MEA fabrication.
solubility and diffusivity. Tuning of ionomer synthesis and dispersions with • Integration of industry PFSA chemistry library and synthesis with molecular
guidance from molecular modeling and colloidal studies. simulation to investigate promising material sets.
2. Optimization of the catalyst|ionomer interface through colloidal studies, • Collaboration with M2FCT for USAXS of inks (ANL), electrode fabrication and
small-scale electrode testing, cell to molecular-scale modeling. testing with PtCo/HSC (NREL), ionomer evaluation (LBNL – in progress), and
upcoming imaging with ORNL.
3. Scale-able high-performance electrode fabrication with HOPIs through small-
scale evaluation and medium-scale electrode casting in an industry format. Relevance/Potential Impact
4. ASTs and 25,000 hr performance forecasting to guide the development of fuel • HOPIs yield longer lifetimes by minimizing voltage loss as ECSA decreases
cells with adequate performance and lifetime for HDVs. over longer HDV lifetimes.
• Reduce loss in maximum power density with ECSA loss
• New HOPI chemistries with high O2 solubility provide a catalyst independent
Accomplishments and Progress to date pathway to higher efficiency through higher mass activity.
• Synthesis of a chemstable HOPI and distribution to project partners.
• Evaluation of HOPI catalyst ink preparation and deposition and comparison Proposed Future Work
with D2020 baseline. • Ink optimization for new HOPI variants
• Scaled-up evaluation of HOPI-based cathodes prepared by roll-to-roll • MD simulations of alternative HOPI backbone and sidechain chemistries
deposition. • Separate quantification of diffusivity and solubility vs. permeability for HOPI
• Significant reduction in local oxygen transport losses, meeting Year 1 goal. • Anion adsorption impact on activity analysis
• Up to 67% increase in mass activity for Pt on Vulcan and LSAC.
• Crack mitigation strategies (solvents, drying, additives)
• 60-70% reduction in degradation rate with HOPI in Pt dissolution AST
• MD studies of HOPI and D2020 elucidating the open structure of HOPI films • Understanding HOPI impact on degradation with HSC supports and PtCo
on Pt surfaces. catalyst
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Acknowledgements Million Mile Fuel Cell Truck (M2FCT) Consortium
National Renewable Energy Laboratory
Carnegie Mellon University KC Neyerlin
Jonathan Braaten
Guanxiong Wang
Jiawei Liu
Zakar White Argonne National Laboratory
Shohei Ogawa Deborah Myers
Juan Mesa Nancy Kariuki
Zachary Ulissi (co-PI) Jae Hyung Park
Nicholas Tiwari Lawrence Berkeley National Laboratory
Xiaoxia Wang Ahmet Kusoglu, A. Bird, J. Petrovik,
Sudheesh Ethirajan A. Katzenburg, A. Weber
Chemours Company Oak Ridge National Laboratory
Andrew Park (Chemours co-PI) Dave Cullen
Gerald Brown (Chemours co-PI) DOE Hydrogen and Fuel Cell Technologies Office
Scott Blackburn Gregory Kleen (Technology Manager)
Austin Plymill Elliot Padgett
Ballard Power System Dimitrios Papageorgopoulos
Devproshad Paul (Ballard PI) Sunita Satayapal
Alan Young Dan Berletti
Shanna Knights
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Technical Backup and Additional Slides
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𝑃 = 𝐾𝐷
Cell Modeling of HOPI Impact
• Permeability is the product of solubility and diffusivity
• Ionomer permeability can be increased in two ways:
• Higher diffusivity through greater porosity, lower tortuosity, and favorable gas-
polymer interactions
• Higher solubility through favorable solvation and polymer interaction as well as
*Neutral gas/solid
greater porosity interaction case
• Approaches to increased permeability can have distinct impacts on fuel
cell performance
• Higher diffusivity yields higher O2 concentrations at the Pt catalyst at high
current density and increases maximum power density
• Higher solubility increases O2 concentration at the Pt interface with ionomer at
ALL currents, increasing efficiency and power density
• Cell-scale modeling to understand impact of ionomer properties
• CMU’s cathode model accounts for the following aspects related to HOPIs
• Fraction of external Pt in contact with ionomer
• Transport resistance to internal Pt through carbon support
• Reduced activity of ionomer in contact with ionomer due to possible anionic
poisoning
• Solubility of O2 in ionomer and water
• Local resistance of ionomer due to:
1. Diffusion through bulk ionomer film
2. Diffusion through densified interfacial zones due to ionomer-Pt interaction
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MD convergence evaluation
Time evolution of density peaks indicates whether the system is still equilibrating in simulation
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