6 - Durable High-Power Density Fuel Cell Cathodes For HeavyDuty Vehicles

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FC327

Durable High-Power Density


Fuel Cell Cathodes for Heavy-
Duty Vehicles
Shawn Litster
Carnegie Mellon University
Pittsburgh, PA

June 8, 2022

This presentation does not contain any proprietary,


confidential, or otherwise restricted information DE-EE0008822
Technical overview and impact
PROJECT GOALS IMPACT

• 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

Barriers Ballard Power Systems, Inc.


B. Cost
– PI: Devproshad Paul
➢ Reduce PEM fuel cell costs by reducing PGM loading
– Co-PI: Alan Young
C. Performance
– Co-PI: Shanna Knights
➢ Increase catalyst activity, utilization, and effectiveness by
increasing solubility and permeability of ionomers
A. Durability M2FCT Consortium
➢ Increase the lifetime of PEM fuel cells by reducing the
loss of efficiency and power

3
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.

The Chemours Company (Industry sub)


Andrew Park (Chemours co-PI), Gerald Brown(Chemours co-PI)
High Oxygen Permeability Ionomer (HOPI) and dispersion
development, synthesis, and experimental characterization.

Ballard Power Systems (Industry sub)


Devproshad Paul (Ballard PI), Alan Young, Shanna Knights
MEA fabrication scale-up analysis and demonstration, testing,
AST development, and durability forecasting

4
Technical Targets, and Status
DOE/Project
D2020 Baseline HOPI Status
Target
Pt/LSAC Pt/HSC Pt/LSAC Pt/HSC

Mass activity (A/mgPt)1 >0.44 0.16 0.30 0.23 0.48


Performance at
0.3 0.33 0.55 0.41 0.58
0.8V(A/cm2)2

Performance loss
<30 62 78 29 53
at 0.8 A/cm2 (mV)2,3,5

Local RO2 (s/cm)4 9 16 21 9 4


CCL Resistance
N/A 110 103 100 93
(mOhm.cm2)1,5
Degradation rate
N/A 2.1 2.3 0.8 1.3
(µV/cycle)3,5
180oC, 100%RH, 280oC, 100%RH, 1.5barg, 335K AST Cycles, 480oC, 60%RH, 50.2mg/cm2 catalyst loading

5
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.

Baseline D2020 protocol for


Define ink processing protocol with concept level ink mixing/coating equipment for 0.05-0.20 mgPt/cm2
M1.2 2 100% 0.05-0.3 mgPt/cm2 defined in
cathode catalyst coated membranes (CCM).
this report
Baseline D2020 MEA testing
Define baseline PFSA ionomer (D2020) capability with 0.20 mgPt/cm2 Pt or PtCo catalyst, optimized for
M1.3 3 100% has been completed at Ballard
ionomer loading. Output will be a metrics table with full analysis of CCL transport properties.
and CMU.
Selection of two HOPI dispersions for 50 cm2 MEA fabrication and testing based on Task 1.1 and 1.2
M1.4 4 100% Completed.
findings
Demonstrate reduction of in-situ local oxygen transport resistance to 9 s/cm with no increase in cathode Target of 9 s/cm local O2
GNG 1 4 100%
protonic sheet resistance. resistance has been met.
Underway with new 1 L batch of
M2.1 Synthesis of improved HOPI scaled-up to 100 g to support expanded MEA testing 5 50% ionomer dispersion delivered to
Ballard
Durability analysis comparing MEAs with HOPIs versus baseline Nafion D2020 for Pt and PtCo. Final
M2.2 6 50% Pt completed in Year 1
output will be a report including failure mode analysis.

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

Existing ASTs demonstrated.


M2.4 Define ASTs for input into forecasting performance at 25,000 h using durability models 8 100%
Forecasting underway
Demonstrate a 2X increase in forecasted lifetime hours using HOPI versus a baseline using D2020
Nafion under identical test conditions with 0.2 mg Pt/cm2 loading. The lifetimes of the HOPI and
Reduced degradation with HOPI
GNG 2 baseline D2020 cases will be defined as time until the power density at 0.7 V decreases to that when 8 100%
demonstrated
the baseline D2020 Nafion electrode had decreased by 10% and will be evaluated by AST
characterization and forecasted durability modeling.
6
Approach

High Oxygen Permeability Ionomer (HOPI)


Traditional PFSA Ionomers1 HOPI-type PFSA

• Heavy duty vehicles requires high efficiency and long lifetimes


at moderate Pt loading
Reprinted with permission from A. Kongkanand and M.F. Mathias, J. Phys. Chem. Lett. 2016 7 (7), 1127-1137.
Copyright 2016 American Chemical Society.
• Increase mass activity for high voltage efficiency
• Reduce local Pt O2 voltage loss with reductions in ECSA over long stack
lifetimes

• Prior work indicates HOPIs reduce O2 transport resistance


and increase air mass activity3
• 20% increase in current at 0.75 V
• 50% increase in 0.85 V mass activity

• Emergent HOPI technology requires development of optimum


integration for durability and manufacturability

HOPI polymers have been specifically engineered for cathode catalyst


layers to reduce mass transport losses associated with local O2 flux on Pt
1. Kongkanand and Mathias, J. Phys. Chem. Lett, 2016. 2. US Patent 9,431,661 B2, 3. Shimizu et al, J. Electrochem. Soc., 2018
7
Relevance
Model Simulation
Modeling the Impact of HOPI Permeability
𝑃 = 𝑆𝐷
Low ECSA Impact
• Permeability (P) is the product of solubility (S) and diffusivity (D) Solubility
• Observed specific ORR activity of catalyst is proportional to O2 solubility of adjacent electrolyte HOPI Solubility +
Diffusivity
• CMU’s multiphase MEA model: O2 solubility and diffusivity of ionomer, catalyst aggregate size, fraction
of internal/external Pt, anion adsorption, and local Pt O2 resistance (see Technical Backup slides).
D2020
• Implemented with 3X permeability assuming 50/50 contribution of solubility and diffusivity (73%
increased solubility and diffusivity)
0.025 mg/cm2 Pt/Vu,
• Provides consistent increase in mass activity and limiting current with literature and preliminary data 1
80oC, 150 kPa
• Preliminary evaluation of increased performance and extended lifetime using ECSA loss as a metric of
lifetime *Neutral gas/solid
interaction case
• Evaluation of 0.7 V power density and ECSA loss associated with 10% power density reduction with
D2020
• D2020 experiences 10% drop with ~25% ECSA loss
• HOPI reduces to same power density at ~60% ECSA loss (doubling of lifetime)
• Substantial increases in voltage efficiency and maximum power density with HOPI

1. Shimizu et al, J. Electrochem. Soc., 2018 8


Technical Accomplishment

Effect of HOPI Side Chain Chemistry & EW


• HOPI dispersions with two different sulfonic acid monomers (“A” or “B”) were fabricated to
understand impact of side chain and evaluate alternate chemistry’s effect on crack formation
• HOPI proton conductivity appears to be a strong function of EW, irrespective of sulfonic acid
monomer moiety
• Zeta potential suggests both dispersions are stable, but that HOPI B may tend to agglomerate
more than HOPI A
• A wide range of HOPI “B” equivalent weights have been synthesized to understand impact of
EW/conductivity on performance of HOPI in electrode layers.

9
Technical Accomplishment

N-Propanol Rich HOPI Dispersions


Reduce or Eliminate Cracking of Films
Higher alcohol content reduces tendency
of neat HOPI cast films to crack
Effect correlates well with early observed
HOPI “A” Film Cracking HOPI “B” Film Cracking trends in catalyst layers
X nPA: 1 H2O ratio (RED is extreme cracking) (RED is extreme cracking)
0
0.43
1
2.33
9

In the remainder of this project, Chemours aims to:


• Continue to understand fundamentals of HOPI catalyst layer cracking Crack-Free film Film with some
cracking
• Prepare additional HOPI variations (EW / polymer composition) as guided
by catalyst application testing
• Plan for continued scale up demonstrations of polymerization capability

10
Technical Accomplishment

All-atom MD of Ionomer-Pt Interface


• MD simulations of ionomer-platinum interfaces
• Comparison of HOPI and D2020 and alternative D2020 with short
side chain (SSC) chemistry
• HOPI exhibits least amount of hydrophilic clustering
• More amorphous structure of HOPI layer
• Increased thickness (lower density) for HOPI relative to D2020

• Density of polymer at the platinum interface is significantly


higher for D2020 compared to HOPI
• This will likely result in improved oxygen solubility/diffusivity
at the interface
Technical Accomplishment

Water clustering and pore-network visualization


• Water clusters in HOPI are more disperse compared to D2020
• D2020 exhibits more continuous pores compared to HOPI
HOPI D2020
Technical Accomplishment

Thin-film Characterization
• HOPI and Nafion D2029 (~900 EW) control analyzed by GISAXS at LBL

• HOPI ionomer films show weaker phase separation compared to Nafion


• Likely result of 3D bulky backbone chemistry

• Similar swelling and water content between HOPI and D2029 at <60% RH

• Reduced swelling and decreased water content at higher relative humidity

• Indicates the more rigid structure of the HOPI ionomer

• May explain the less pronounced RH sensitivity of MEA RO2 to RH with


HOPI vs D2020 Silicon substrates

RH Effect Thickness Effect

13
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,

HOPI vs D2020 Permeability pp. 9853–9858, 2015.


2. J. P. Braaten, X. Xu, Y. Cai, A. Kongkanand, and S. Litster,
“Contaminant Cation Effect on Oxygen Transport through
the Ionomers of Polymer Electrolyte Membrane Fuel Cells,”

• New improved apparatus with integrated oxygen J. Electrochem. Soc., vol. 166, no. 16, pp. F1337–F1343,
2019.

sensor for improved accuracy with high permeability


films and substrates
• Measures permeability of a quasi-free-standing film
by supporting the layer on a nano-porous substrate
without a polarized electrode surface (vs. Pt surface
of RDE, films, etc.)
• Permeability based on current difference between air
and N2 flowing
• Measurements performed with HOPI and D2020
films
30% RH
• As fabricated film thickness measured in dry
condition by profilometer due to sample to sample
and ionomer to ionomer variability
• Increased permeability of 2.6X for HOPI over D2020
• Significant increase in bulk film permeability and not
only a Pt-surface interface effect
Tsample = 50.0±0.1°C, p = 1 atm
Air or N2, 0.2 l/min, 29%RH

14
Technical Accomplishment

Ink and electrode optimization Ink SAXS

• Study of ink composition on agglomeration and


coating quality
• Ionomer type effect: D2020 (1000EW) vs. HOPI (870EW)
• EW effect: DE2029 (880 EW) vs. D2020 & HOPI
• CMU ink agglomeration characterized by USAXS
• No strong effect of nPA:H2O ratio on agglomeration
• Less agglomeration with HOPI vs. D2020
• Coating studies at CMU
• Greater degree of cracking with HOPI vs. D2020/DE2029
• Greater ionomer agglomeration with low nPA:water ratios
• Studies on effect of ionomer, solvent, and I/C ratio
on performance
• Significant 67% increase in mass activity with HOPI
over D2020
• Significant reduction in total non-Fickian (p-indep)
oxygen transport resistance with HOPI

TKK EA 50 (46 wt % Pt/LSAC),


I/C=0.6, 0.20±0.02 mgPt/cm2 (est.)

15
Technical Accomplishment

Nano-CT Imaging of Catalyst Layers


• Nano-CT (CMU) of catalyst layers by phase contrast for pore/crack structure and Cs+-stained
absorption contrast for 3D ionomer mapping
• High agglomeration of electrode structure and ionomer with HOPI
• Cracks present between agglomerations with HOPI
• Mostly continuous film with D2020 with more uniform ionomer distribution
HOPI D2020
Phase Cs+ absorption Phase Cs+ absorption
contrast contrast contrast contrast

Max. resolution of 50 nm (16 nm voxels)


Large-field-of-view imaging with 150 nm
resolution (65 nm voxels) shown here
User facility available to industry, nat’l
38 µm labs, and universities.
40 µm

Green intensity ~ volumetric density of ionomer 16


Technical Accomplishment

Ionomer stability and AST


• Evaluate chemical stability of HOPI via chemical degradation with
OCV holds (28 hr in preliminary test)
• CV ECSA shows the initial loss in surface area over 5 days of
testing
• No increase in electrode proton conduction resistance
• No change in pressure-dependent slope of oxygen transport
resistance
• No change when pressure-independent resistance is corrected
0.5
for ECSA loss 0.45

0.4

HOPI 5003.001 BOL


0.35 HOPI 5003.001 EOL

)
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

Scale-able Electrode Fabrication


Catalyst Layer Roughness Factors (rf) Catalyst Layer Thickness Catalyst Layer Crack Density
vs. Catalyst Loadings vs. Catalyst Loadings vs. Catalyst Loadings

HSA-Pt catalyst, I/C = 0.6 - 1.1

HSA-Pt catalyst, I/C = 0.6 - 1.1


HSA-Pt catalyst, I/C = 0.6 - 1.1

• Catalyst layer was fabricated in the roll-to-roll scale-able coating process


• Catalyst loadings had a good agreement with roughness factors (rf) and thicknesses except HOPI 1036EW deviated
from loading vs thickness trend where high crack density may explain the higher thickness
• HOPI integrated catalyst layers (CLs) had higher crack density at higher catalyst loadings but decreased to similar to
D2020 with decreasing catalyst loadings
• HOPI 870EW had comparatively lower crack density compare to high EW HOPI variant

18
Technical Accomplishment

Electrode Performance – Ionomer Types


100% RH Performance at 80 oC,
250KPa, H2/air • Two HOPI variants were tested and compared performance with D2020 baseline.
• HOPI 870EW variant was the top performing candidate over D2020 and
HOPI 1036EW
• HOPI 870EW variant showed similar cathode catalyst layer resistance (CCL R)
but significant reduction of pressure independent (PI) oxygen transport
resistance and 1.5 times higher mass activity than D2020
• HOPI 1036EW variant suffered with poor performance due to higher CCL proton
45 cm2, HSA-Pt catalyst, I/C = 0.8
& local oxygen transport resistance (EW & high crack density effect)
Ionomer Types, Roughness Mass Activity
EW Factor (A/mgPt at 0.9V)
Current Density (A/cm2) D2020, 1000EW 108 0.3
60% RH Performance at 80 oC, CCLR at 80 oC, different RHs HOPI, 870EW 83 0.48
250KPa, H2/air HOPI, 1036EW 92 0.34

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

45 cm2, HSA-Pt catalyst, I/C = 0.8

Current Density (A/cm2)

19
Technical Accomplishment

Performance – Catalyst & Ionomer Loadings


Performance comparison
100% RH Performance at
PI RO2 at 80 oC, 60% RH at rf = 110
2A/cm2 at 80 oC, 250KPa

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

20
Technical Accomplishment

Electrode Performance – Catalyst Types


Low Current Density Performance High Current Density Performance PI RO2 Comparison
45 cm2, I/C = 0.8, 80oC, 250KPa, 100%RH 45 cm2, I/C = 0.8, 80oC, 250KPa, 100%RH 45 cm2, I/C = 0.8, 80oC, 250KPa, 100%RH

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

21
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

Microscopy Analysis of Degradation


• Microscopy studies on pristine and end of test (EOT)
Pt/HSC samples from Ballard D2020-EOT Pt band HOPI-EOT
• X-ray nano-CT at CMU
• Electron microscopy at ORNL

• Nano-CT shows more significant region of Pt


depletion in D2020 sample as well as a more obvious
Pt band
• Pt located on cathode side of membrane
reinforcement layer
• This AST performed in air results in more diffuse band located
further from cathode than with N2 AST

• Electron microscopy with elemental mapping also Pt depletion


shows enhanced depletion of Pt in first 2 µm of the
cathode adjacent to the PEM
• Fluorine mapping by ORNL also shows the
agglomeration of HOPI as observed by nano-CT

23
Technical Accomplishment

HOPI-enhanced lifetime forecast


• CMU MEA model validated and CMU MEA model validation for RF, ionomer and AST
applied to Pt/LSAC lifetime
forecasting based on Pt dissolution.
• ~7X longer lifetime with HOPI to
reach same EOL power density.
• Ballard lifetime forecasting for
aggressive drive cycle with Pt/HSC Pt/LSAC
Pt/LSAC Pt/LSAC Pt/LSAC
for HOPI vs. D2020.
• For ~10% performance loss at 0.7 V
cell voltage (equivalent roughly to Pt/LSAC estimation using CMU MEA model
1.34 A/cm2), HOPI MEAS showed Pt/LSAC
~4x lifetime improvement Ballard lifetime forecasting model for
Pt/HSA and aggressive drive cycle

24
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.

25
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

26
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

27
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

28
Technical Backup and Additional Slides

29
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

30
MD convergence evaluation
Time evolution of density peaks indicates whether the system is still equilibrating in simulation

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