Fc160 Zelenay Myers 2023 o

DOE Hydrogen Program
2023 Annual Merit Review and Peer Evaluation Meeting

June 5 – 8, 2023, Arlington, Virginia
ElectroCat 2.0
(Electrocatalysis Consortium)
Deborah Myers
Argonne National Laboratory
Piotr Zelenay
Los Alamos National Laboratory
Project ID: FC160
This presentation does not contain any proprietary, confidential, or otherwise restricted information
2023 DOE Hydrogen Program Annual Merit Review – Slide 1
Overview
Timeline Laboratory – PI
• Start date: Oct 1, 2020 Los Alamos National Laboratory

• End date: Sep 30, 2025
– Piotr Zelenay
Budget Argonne National Laboratory
• FY23 funding total planned: $4M – Deborah Myers

• Planned FY24 funding: $4M
National Renewable Energy Laboratory
Barriers – Derek Vigil-Fowler
• A. Cost (catalyst)
• D. Activity (catalyst; MEA) Oak Ridge National Laboratory
• B. Durability (catalyst; MEA)
– David Cullen
• C. Power density (MEA)

Relevance and Goals
Heavy-Duty Transportation Fuel Cell Targets (2025) Electrolyzer Stack Goals (2026)
 Durability: 25,000-hour lifetime  Durability: 80,000-hour lifetime
 68% peak efficiency  69% efficiency at 3 A cm-2
 $80/kW fuel cell system cost  $100/kW
 Overall Target: 2.5 kW/gPGM power  Overall Target: $2/kg H2 over
(1.07 A cm-2 current density at 0.7 V after 25,000 hour- 80,000-hour lifetime
equivalent accelerated durability test)
End-of-consortium Goals:
Fuel Cell: H2-air performance of ≥ 100 mA/cm2 at 0.8 V and ≥ 500 mA/cm2 at 0.675 V at beginning of test (BOT) and
≥ 80 mA/cm2 and ≥ 400 mA/cm2 after 30,000 AST cycles (0.6 V to OCV, 3 s each, H2-air), respectively, under integral
conditions for a PEMFC with a PGM-free oxygen reduction catalyst
Electrolyzer: 2.5-fold increase, from 0.2 A/cm2 to 0.5 A/cm2 at 1.8 V and reduction in the voltage loss at a reference
current density of 0.2 A/cm2 from 0.2 mV/h to 0.1 mV/h with alkaline-exchange membrane electrolyzer using a PGM-
free oxygen evolution catalyst

FY23 Q1 Fuel Cell Quarterly Progress Measures Approach
Milestone Name/Description Criteria End Date Type Status

ORR catalyst performance in H2- Current density of ≥ 85 mA cm-2 at 0.80 V and ≤ 45 Partially
air fuel cell mV voltage loss at 0.80 A cm-2 after 10,000 Quarterly Progress Completed
12/31/2022
catalyst AST cycles (LANL). Measure (Regular) see slide
#8
High-throughput evaluation of Complete fabrication of multi-channel flow cell and
ORR activity (shared with verify accuracy and reproducibility compared to Completed
Quarterly Progress
Electrolyzer QPM) RDE. Achieve and agreement of ORR mass 12/31/2022 see slide
Measure (Regular)
activity between the flow cell and RDE results of #22
<5% (ANL).
Model graphene-based catalyst Optimize graphene-based model M-N-C catalyst Partially
development system and image at least ten N-C and ten Fe-N- Quarterly Progress Completed
12/31/2022
C sites by low-voltage imaging and EELS Measure (Regular) see slide
(ORNL). #16
Configuration of Nafion polymer Compute relaxed geometries and charges of
fragments under applied Nafion polymer fragment at 3 values of the applied Completed
Quarterly Progress
potential potential on Fe-N-C catalyst (bulk site) and Pt. 12/31/2022 see slide
Measure (Regular)
Fragment will be place at 3 different locations on #21
Fe-N-C catalyst (NREL).

FY23 Q2 Fuel Cell Quarterly Progress Measures Approach

Computational design of high- Identify the next two most promising high-
throughput synthesis of ANL’s throughput synthesis conditions for Catalyst Completed
Quarterly Progress
System #4 ORR catalysts System 4 to improve its ORR activity and 3/31/2023 see slide
Measure (Regular)
decrease machine learning models uncertainty. #14
(LANL, ANL)
PEFC cathode catalyst ORR Improve ORR activity of high-throughput
activity synthesized catalysts by 30% and stability by 30% Completed
Quarterly Progress
compared to FY22 best-in-class Fe-N-C catalyst 3/31/2023 see slide
Measure (Regular)
with guidance from machine learning activity. #15
(ANL, LANL)
Electron tomography of porous Quantify internal pore size distribution of one
Completed
FeNC catalysts LANL FeNC catalyst derived from soft-template Quarterly Progress
3/31/2023 see slide
synthesis approach using electron tomography. Measure (Regular)
#9
(ORNL)
Effect of explicit water on Compute adsorption energies for single O2, NO,
binding at active site OH, SO4, HSO4, and ClO4 on the Fe bulk under
applied potential and in the presence of explicit
Completed
waters. Determine dominant binding Quarterly Progress
3/31/2023 see slide
configurations in different potential regions. Measure (Regular)
#21
Compare trends in bond length, formal charge,
and spin state with variation of the potential to
EXAFS and Mössbauer data from ANL. (NREL)

FY23 Q3 Fuel Cell Quarterly Progress Measures and Annual Milestones Approach

ORR activity surrogate models Demonstrate (develop and integrate)
first surrogate models of ORR activity into Pareto On track
Quarterly Progress
optimization scheme using DFT model input to 6/30/2023 see slide
Measure (Regular)
identify (atomic and electronic) structural #17
descriptors of activity. (LANL)
PEFC H2-air fuel cell Evaluate 25 variations of ionomer to catalyst ratio
performance improvement and solvent composition of ink for best-in-class
Quarterly Progress
through cathode catalyst layer ANL PGM-free electrode. Characterize structure 6/30/2023 On track
Measure (Regular)
composition optimization of electrode layers using electron microscopy.
(ANL, ORNL)
Effect of Nafion polymer Compute adsorption energies for O2, NO, and OH
fragments on binding at Fe-N-C on the Fe bulk under applied potential and in the Quarterly Progress
6/30/2023 On track
active site presence of Nafion fragments at 3 different Measure (Regular)
locations. (NREL)
ORR catalyst performance in Current density of ≥ 85 mA cm-2 at 0.80 V and
≤ 40 mV voltage loss at 0.80 A cm-2 after 30,000 Annual Milestone
H2-air fuel cell 9/30/2023 On track
catalyst AST cycles. (LANL, ANL, ORNL) (Regular)
Upgrade of ElectroCat Data Hub Complete release of the update to the ElectroCat Annual Milestone
Data Hub, with all data migrated. (NREL) 9/30/2023 On track
(Regular)

Progress in Fe-N-C ORR Performance Accomplishment
Cathode: ca. 4.0 mg cm-2, FY21/22/23 Fe-N-C catalyst, 1700 sccm,

Two-step, two heat-treatment synthesis of Fe-N-C catalyst: 1.0 bar air partial pressure, 100 %RH; Anode: 0.3 mgPt cm-2 Pt/C, H2,
700 sccm, 1.0 bar H2 partial pressure, 100% RH; Membrane: Nafion
 Two-step heat-treatment synthesis of Fe-N-C catalysts to obtain
211; Cell: differential, 5 cm2, Temperature: 80 °C.
nitrogen doped carbon first and after incorporate Fe precursors
 Allows for controlling separately Fe dispersion, morphology, and
composition through use of nitrogen-doped carbons
Denoted “N-C/Fe”
Current density (mA cm-2)

Voltage (V)
FY21 FY22 FY23
0.80 61 79 97
0.675 302 377 435
Highlight: Fe-N-C catalyst (N-C/Fe) developed via a two-step, two heat-treatment approach showing 59% and 44%
performance improvement over the FY21 baseline at 0.80 V and 0.675 V, respectively (23% & 15% improvement over FY22)

Fuel Cell Performance of N-C/Fe Catalyst Accomplishment
Cathode: ca. 4.0 mg cm-2, N-C/Fe catalyst, 1700 sccm, 1.0 bar air partial pressure, 100 %RH; Anode: 0.3 mgPt cm-2 Pt/C, H2, 700 sccm, 1.0 bar H2 partial pressure,
100% RH; Membrane: Nafion 211; Cell: differential, 5 cm2, Temperature: 80 °C. Durability Testing: square-wave cycle from (OCV-0.01) V to 0.60 V
92 mA/cm2 at 0.80 V
0.372 V
92 mA/cm2
0.323 V
45 mA/cm2
Metrics Initial 10k Loss • FY23 Q1 QPM: ≥ 85 mA/cm2 at 0.80 V for initial and
≤ 45 mV loss at 0.80 A/cm2 after 10k cycles
Current density at 0.80 V
92 45 47 • Highlight: 92 mA/cm2 at 0.80 V for initial and 49 mV
(mA/cm2)
loss at 0.80 A/cm2 after 10k cycles, exceeding the
Voltage at 0.80 A/cm2 (V) 0.372 0.323 0.049
activity target in the FY23 Q1 QPM.

New Synthesis Methods for Fe-N-C Catalysts Accomplishment
Hollow Structure of Fe-N-C Catalysts Derived from Tannic Acid-Etched MOF Precursors
Highlight: Developed a new type

of hollow structure for Fe-N-C
catalysts using the approach of
tannic acid etching MOF precursors
to enhance catalyst surface area
• Highlight: Soft-template synthesis of Fe-N-C

catalysts results in enhanced RDE activity using
triblock-PEG template
• Soft-template synthesis with micelle templates

likely introduce mesopores in Fe-N-C catalysts

High-Throughput Synthesis of ORR Catalysts Accomplishment
Catalyst System 2: Physical mixtures (ball milling) of Fe salt, carbon-nitrogen precursor, carbon support (234 samples)
(e.g., Zitolo et al., Nat. Mater., 14, 937, 2015)
•Twenty-five catalyst samples were prepared since the 2022 AMR for further performance optimization based on the ML
findings from catalyst samples with varied phenanthroline-to-ZIF ratios, varied content of Fe in the precursor, varied
pyrolysis temperature and hold time, and varied heating/cooling rate/mode prepared for input into machine learning
algorithms.
Catalyst System 3: Two step synthesis; formation of nitrogen-doped carbon followed by incorporation of Fe (50 samples)
(based on J. Li, D. Myers, Q. Jia et al., J. Am Chem. Soc., 142, 1417, 2020)
• Physical mixtures (ball milling) of carbon-nitrogen precursors pyrolyzed and heat-treated in NH3 to form nitrogen-doped
carbon (N-C)
• Physical mixtures (ball milling) of N-C and Fe salt pyrolyzed; subset also heat treated in NH3
Catalyst System 3b: Chemical vapor deposition of FeCl3 into N-C; 72 unique samples
(based on L. Jiao, D. Myers, Q. Jia et al., Nature Materials, 20 (2021) 1385.)
 Effect of ball-milling time of N-C, ZIF-8, heat treatment temperature, Fe:N-C ratio,
additive (Sn, Co…), carbon coating (Dopamine, propylene cracking, ZIF-8…)
Catalyst System 4: Physical mixtures (ball milling) of Fe2O3 nanoparticles and ZIF-8 pyrolyzed
in fixed-bed reactor (based on University of Buffalo ElectroCat project)
 Effect of Fe content (>40 samples thus far), particle size, phen/ZIF-8 ratio.
 Effect of pyrolysis conditions (temperature, time, heating rate)
 Effect of Fe precursors other than Fe2O3

Machine-Learning Guided Discovery of System 2 Catalysts with Enhanced Activity Accomplishment
• 36 initial samples synthesized and characterized • Achieved ORR activity ~ 600% higher than Fe-N-C ORR
• Synthesized 14 new samples via the adaptive learning catalysts prepared in the same way elsewhere
approach (*2.25 A g-1 at 0.8 V, RDE) * Energy Environ. Sci. 13, 2480 (2020)
Search space involves ~ 1011

possible combinations (~ 106 in
a more conservative scenario)
From 2022 AMR: “…predicted next samples to be synthesized and characterized, with potential increase of activity in > 5%”
Highlight: Significantly exceeded last year’s predicted target by discovering 4 new samples with activity larger
than those in the original dataset, resulting in an activity increase of ~33% (to 16.3 mA/mg @ 0.8 V in RDE).
Highlight: Invited publication in Journal of Power Sources: W. J. M. Kort-Kamp et al., JPS 559, 232583 (2023).

Statistical Analysis of Effects of System 2 Synthesis Conditions on ORR Activity Accomplishment
a Furnace closed b Furnace open Pearson

correlation
1.0
0.5
0.0
-0.5
-1.0
Highlight: Used data-science approaches to uncover the relative importance of synthesis variables
in the activity and demonstrated how other variable relevance is strongly affected by the cooling rate.

ORR Activity of High-throughput System 3b (CVD) Catalysts Accomplishment
Inert gas
ML Descriptors
Quartz reactor
1. ZIF-8 vs N-C (L=30mm, OD=2.6,
Mixing of N-precursors ID=2.0 mm)
2. Grinding vs Ballmilling
3. BM time 16 parallel pyrolysis
FeCl3 + MeClx
4. Fe loading CVD reactors
5. Metal additive FeCl3
+ N-precursors
6. N-Source frit
ZIF-8 or N-C
Inert (Silica, L=8 cm)
Pyrolysis in Ar Frit(20 μm)
(HT fixed bed reactors 7. Pyrolysis temperature
1st cycle 2nd cycle Change
25 25
Natural Cooling
Mass activity (mA/mg)

1st cycle
20 20
2nd cycle
15
15
10
10
5
5
0
0
-5
0.5 0.75 1 1.25
- Bi Gd Mo Pr Ta
FeCl3/N-C Ratio
Highlight: Parallel CVD reactors allow for fast screening of conditions. First iteration
gives maximum mass activity of 23.1 mA/mg @ 0.8 V in RDE (highest achieved in
ElectroCat). Stability improved upon addition of a second metal chloride.

ORR Activity of High-Throughput System 4 Catalysts Accomplishment
25
Vertical furnace
1 • Twenty-six samples in initial synthesis
ML Descriptors N2, H2
20
round
NP Fe2O3 -4
1,10-phenanthroline 1. Weight loading of Fe • Highest activity of these twenty-six for

ZIF-8 2. ZIF-8/phen ratio
15
1.2% Fe + ZIF-8 (no phen) after
Variance (%)
-9
Ball milling pyrolysis at 1050 °C, 10 °C/min 2h

10 -14
3. Heating rate
TC
• Initial and mass activity after five
Pyrolysis in N2
(vertical furnace)
4. Pyrolysis temperature 5 -19 potential cycles included in machine
5. Holding time
learning model
0 -24
Cooling 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26
ORR#1 ORR#5 Variance
• Machine learning has predicted
X-ray absorption spectroscopy synthesis conditions to achieve higher
Higher mass activity
ORR activity
Higher fraction of Fe in Fe-N4 Correlation between ORR mass
20
per Fe at low loading sites at low Fe loading activity and Fe-N4 content
ORR activity at 0.8 V per % Fe (mA/mg)
Fe3C 0.4% Fe 20 0.4
0.8% Fe
15
1.0% Fe
ORR activity at 0.8 V (mA/mg)

15 0.3
1.2% Fe
Fraction of Fe-N4
Fe-N4
10 1.6% Fe
10 0.2
Chi(R)
5 5 0.1
0 0
0 5 10 20
0.4 0.8 1 1.2 1.6 0 1 2 3 4
Pyrolysis Heating rate (oC)
Radial distance (Å)
Highlight: Maximum ORR mass activity of 19.3 mA/mg (0.8 V, RDE) of 26 samples in initial
set. Ten catalysts have no activity loss or improved activity after five potential cycles. Machine
learning has suggested four synthesis conditions to improve ORR activity. (FY23 Q2 QPM)

Increased ORR Activity and Durability through High-Throughput Synthesis Accomplishment
FY23 Q2 QPM: Improve ORR activity of high-throughput synthesized catalysts by 30% and stability by 30% compared
to FY22 best-in-class Fe-N-C catalyst with guidance from machine learning activity
QPM Surpassed: Activity increased by 88% and stability by 78% compared to benchmark
25 100
Mass activity at 0.8V (mA/mg)

88% 90
Activty/Stability Boost (%)

FY22 best-in-class: 20
78%
80
 ML#9 from system 2 62% 70
(ball-milling of Fe acetate, ZIF-8, 15 60
53%
pyrolysis in inert gas, heat treatment in
NH3) 57% 50
 ML#9 chosen due to balance of activity 10 40

and stability 36% 30
 See slide 13 ElectroCat 2022 AMR for 5 20
details on synthesis conditions of ML#9
10
0 0
ORR #1 ORR#2 Activity Boost Stability Boost

Imaging and Automated Spectroscopy of Metal Atom Sites in Model 2D System Accomplishment
• A 2D model system enables

a direct view of transition
a b
metal sites and automated
spectroscopy significantly Fe
improves measurement
statistics.
• The structure and local
composition around
transition metal sites in a 2D
system can be more directly
determined by imaging and
EELS than in a 3D system.
• Automated atom-finding,
probe positioning, and 2 nm
EELS acquisition routine
rapidly provides data from • FY23 Q1 QPM: Optimize graphene-based model M-N-C catalyst system and
large numbers of atoms to image at least ten N-C and ten Fe-N-C sites by low-voltage imaging and EELS
improve statistics. • QPM Partially Completed: A 2D model system was synthesized for advanced
characterization of atomically dispersed transition metal sites, imaging and EELS
were performed, and the system being optimized for increased co-located Fe and N
content.

Multi-Objective (Activity and Stability) Optimization of PGM-free ORR Structures Accomplishment
0.8
MN4C12
0.6
PFeN4C12 = 0.61
0.4
HO-FeN4C10@zig-zag edge
Sactivity
0.2
PHO-FeN4@ZZ = 0.48
0
-0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1
MN4C10-N-MN4C10
-0.2
= previously reported
Pareto front PFeN4-N-FeN4 = 0.61
-0.4
Sstability
Highlight: Demonstrated MN4C12 and μ-nitrido (MN4C10-N-MN4C10) CoN4C10@zig-zag edge

structures have highest combined Pareto scores, P, exceeding HO- PCoN4@ZZ = 0.54
FeN4@zig-zag edge and extending previously reported Pareto
front through increased calculated stability of nitrido structures

DFT-Derived Stability Descriptors Accomplishment
• Calculated dissolution
potential, Udiss, for
FeN4C10, FeN4C12,
FeN4C10 @ zig-zag edge
• Calculated local electron
beam energy threshold
(EBET) and relaxed
structures with lowest
EBET atoms removed
• Calculated Udiss for C/N
EBET structures and calculated degraded structures
values (0 K in red) Hafiz, Zelenay,
• Removal of C/N yields
and Holby, under review, Applied
Catalysis B significant decrease in
Udiss effect to be submitted for calculated Udiss value for
publication ASAP upon acceptance. given structure
Highlight: Identified that in most cases corrosion of local C/N facilitates dissolution of transition metal –
increased graphitization shown to support enhanced dissolution tolerance for Fe  Fe2+ + 2 e- reaction

Effect of Anions on the Fe3+/Fe2+ Redox and ORR Activity of Fe-N-C Accomplishment
Stagnant O2-saturated electrolytes

2 mA HClO4 first, then moved to H2SO4
• Voltammetry shows quick and complete in HClO4_1st

0.57 M HClO4 in H2SO4_2nd
displacement of HClO4 with H2SO4
Fe3+/Fe2+ peak:
• Voltammetry shows slow and incomplete 0.5 µA
0.754 V ORR peak: 0.707 V
displacement of H2SO4 with HClO4
• Results indicate that sulfate/bisulfate anions

0.5 M H2SO4 interact more strongly with Fe center than
perchlorate anions
0.0 0.2 0.4 0.6 0.8 1.0
Fe3+/Fe2+ peak: Potential/V vs RHE
0.622 V ORR peak: 0.716 V
H2SO4 first, then moved to HClO4
0 0.2 0.4 0.6 0.8 1 in H2SO4_1st in H2SO4_1st
Potential /V vs RHE in HClO4_2nd-5min in HClO4_2nd-1h
• ORR occurs at higher potentials in H2SO4 than in HClO4

 H2SO4: ORR peak potential 0.716 V (stagnant), E1/2 in RDE 0.815 V 0.5 µA 0.5 µA
 HClO4: ORR peak potential 0.707 V (stagnant), E1/2 in RDE 0.789 V
• Fe3+/Fe2+ redox occurs at lower potentials in H2SO4 than in HClO4
 H2SO4: 0.622 V HClO4: 0.754 V
Ref: Xiaoping Wang, et al., Electrochim. Acta, 443 (2023) 141934. 0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Potential/V vs RHE Potential/V vs RHE
Highlight: Sulfate or bisulfate anions suppress Fe3+ reduction, enhance

ORR, and interact more strongly with Fe center than perchlorate anions

Modeling Effect of Anions with Explicit Solvation on Fe Redox and ORR Activity Accomplishment
• Modeling results with inclusion of explicit solvation show that ClO4-, HSO4-, and SO42- interact differently with Fe-N-C
 ClO4- and HSO4- interact weakly with Fe center; anions are pulled away from Fe center to liquid phase due to hydrogen bonding
 SO42- interacts directly with the Fe center, even when Fe center is coordinated with an OH ligand
• The different interactions of anions with Fe-N-C impact their effects on Fe2+/Fe3+ redox and ORR activity
 ClO4-: FeN4 center coordinates OH to form FeN4(OH) at 0.69 V; no enhancement of ORR with Fe oxidation
 SO42-: Fe is oxidized at 0.52 V; a significant enhancement in ORR is observed upon Fe oxidation and OH coordination
 These modeling results explain experimental trends of higher ORR activity of Fe-N-C in sulfuric acid electrolyte, but lower
Fe3+/Fe2+ redox potential than in perchloric acid electrolyte

Role of Explicit Water, Ionomer in Quantum-Mechanical Modeling of ORR on Fe-N-C Accomplishment
• Quantum mechanical modeling of Fe-N-C catalyst often does not include catalyst microenvironment
• Two focus areas: impact of potential, explicit waters on binding of common species, ionomer (Nafion) binding on Fe-N-C, Pt
Explicit water effect on binding on FeN4@Graphene Nafion fragment binding on Pt, FeN4@Graphene
Ab-initio MD provides snapshots for water configurations GCDFT predicts more favorable adsorption of SO3-terminated
Solvation method alters Different water configs produce Explicit H2O can induce Nafion fragment binding at more reductive potentials on Pt, Fe site
adsorption energies large variations ORR thermo large structural changes in Fe-N-C. CF3 and HSO3-terminated fragments generally have less
favorable adsorption at more reductive potentials on Fe-N-C.
Implicit
solvation
FY23 Q2 QPM met: “Compute adsorption energies for single O2, NO, OH, SO4, HSO4, and ClO4
on the Fe bulk under applied potential and in the presence of explicit waters.”
Highlight: Quantified effect of explicit water on ORR thermodynamics, binding of common species
Highlight: Established that SO3 binding to Fe is dominant effect of Nafion in non-defected catalyst

Capability Development: High-Throughput Activity Evaluation (also for ORR) Accomplishment
Automated
deposition system
Simultaneous evaluation of ORR and OER activity
of multiple catalysts
Developed a new flow cell comprised of

PEEK blocks using hand micro-pipetting on
the glassy carbon disk while rotating the disk
• FY23 Q1 QPM: Fabrication of multi-channel flow cell

for ORR and OER catalyst activity evaluation to
expedite catalyst evaluation.
• Highlight: Completed fabrication of multi-channel flow
cell and verified accuracy and reproducibility compared
to RDE; achieved agreement of ORR and OER mass
activity between the flow cell and RDE results of < 5%.
Electrolyte flow simulation

LTE Electrolysis
PGM-free OER and HER Electrocatalysts

for AEMWE

FY23 Electrolysis Quarterly Progress Measures Approach

Hybrid DFT calculations of Report calculated work functions and relative O
alloyed NiOOH surfaces vacancy formation energies (neutral charge state) Completed
for NiOOH basal plane systems with and without Quarterly Progress
12/31/2022 see slide
Fe, Mn, and Co metal dopants (treated as Measure (Regular)
substitutional defects) using HSE06 + 15% exact #38
exchange methodology (LANL).
High-throughput evaluation of Demonstrate multi-channel cell accuracy and Completed
LTE OER electrocatalysts in reproducibility in comparison with RDE with Quarterly Progress
aqueous electrolyte agreement of OER potential at 10 mA cm-2 of < 5 Measure (Regular)
mV (ANL). #22
Focused ion beam cross-section Demonstrate direct imaging of electrode/PTL Completed

of electrode/PTL interface interface accessed by automated FIB cross- Quarterly Progress
sectioning on one tested MEA (ORNL). Measure (Regular)
#60
OER performance in liquid OER current density in an aqueous alkaline
electrolyte electrolyte of 10 mA cm-2 at a potential of ≤ 1.55 V Completed
vs. RHE (iR-free) at beginning of test after Quarterly Progress
3/31/2023 see slides
activation and no more than 0.75 mV/h potential Measure (Regular)
loss during 72 h durability test at 10 mA cm-2 #32,33
(LANL, ANL).
In situ Mössbauer of NiFe OER Quantify changes in Fe oxidation state between Completed
Quarterly Progress
catalyst OCV and 1.75 V from Mossbauer spectra obtained 3/31/2023 see slide(s)
Measure (Regular)
using in situ half-cell (ORNL). #43

FY23 Electrolysis Quarterly Progress Measures (continued) Approach

LTE Catalyst Testing in AEM Decide upon baseline materials
MEA (membrane/thickness, PGM/non-PGM catalysts) Completed
Quarterly Progress
and operational parameters to establish a PGM 3/31/2023 see slide
Measure (Regular)
and PGM-free membrane electrode assembly #28
baseline performances (NREL).
Adaptive learning strategy for Based on available experimental data, develop
oxygen evolution catalysts new artificial neural network models for OER On track
activity dependence on synthesis conditions. Use Quarterly Progress
uncertainty quantification and global optimization to Measure (Regular)
identify the next two most promising experiments #36,37
targeting improved OER (LANL, ANL).
High-throughput synthesis of Provide LANL machine learning activity with
Quarterly Progress
OER catalysts for adaptive aqueous electrolyte OER polarization curve data 6/30/2023 On track
Measure (Regular)
learning for 20 unique materials (ANL, LANL).
IL-STEM visualization of catalyst Quantify change in LANL NiFe aerogel catalyst
transformation during composition, morphology, and crystal structure
Quarterly Progress
conditioning before and after cycling in three electrode cell and 6/30/2023 On track
Measure (Regular)
correlate with Mossbauer, XRD, and XAFS
characterization (ORNL).
Water domain structure of AEM Calculate the water domain width in poly(aryl On track
polymer piperidinium)-based polymers as a function of Quarterly Progress
9/30/2023 see slide
hydration. Compare computed scattering functions Measure (Regular)
to existing x-ray scattering data (NREL). #39

FY23 Electrolysis Annual Milestones Approach

OER performance in liquid OER current density in an aqueous alkaline
electrolyte electrolyte of 10 mA cm-2 at a potential of ≤ 1.54 V Completed
vs. RHE (iR-free) at beginning of test after Annual Milestone
activation and no more than 0.5 mV/h potential (Regular)
loss during ≥ 72 h durability test at 10 mA cm-2 #32,33
(LANL, ANL, ORNL).
HER performance in liquid HER current density in an aqueous alkaline
electrolyte electrolyte of 10 mA cm-2 at a potential of
≥ -0.30 V vs. RHE (iR-free) at the beginning of test Annual Milestone
9/30/2023 On track
and no more than 0.8 mV/h potential loss during ≥ (Regular)
48 h durability test at 10 mA cm-2 (LANL, ANL,
ORNL).
LTE Catalyst Testing in AEM Incorporating ElectroCat-developed catalysts,
MEA demonstrate cell overvoltage reduction of more
than 50 mV (HFR-free) compared to commercial
baseline catalysts (NiFeOx, established in Completed
HydroGEN EMN) at 1 A/cm2. Comparisons Annual Milestone
9/30/2023 see slide
between novel and commercial catalysts would (Regular)
maintain consistent supporting electrolytes (1 M #35,62
KOH) and operating conditions, including materials
choices, flow configurations (wet/wet), and
temperature (80 °C) (NREL).

OER and HER Catalyst Development Paths Approach
Oxygen Evolution Reaction (OER)

Catalysts
 La-Sr-Co (LSC perovskite) oxide catalysts (in
collaboration with Pajarito Powder)
 Binary Ni-alloy oxide catalysts, aerogels and
xerogels, using different metal ratios and
heat-treatment temperatures
 Ternary Ni-based catalysts, e.g., NiFeCo
 ZnCoMOF-derived catalysts
 Catalysts from collaborators
Hydrogen Evolution Reaction (HER)

Catalysts
 Binary Ni-alloy catalysts, aerogels and
xerogels, e.g., NiMo, using different metal
ratios and heat-treatment temperatures
 Phosphide-based Ni aerogels
High throughput methods extensively used

MEA Performance Baselines: PGM-free Anode with PGM-free & PGM Cathode Accomplishment
• Baseline Materials: V
PiperION-A TP-85 80 µm membrane HFR-free
PiperION-A TP-85 ionomer, I/C = 0.3
Ni mesh PTL (Bekaert, Currento 2NI 18-0,25)
C paper GDL (Fuel Cell Earth, MGL280)
Voltage (V)
• Cathode Catalysts:
PGM-free: 40% Ni/C (Fuel Cell Store), 4.8 mg/cm2Ni
PGM: 47% Pt/C (TKK), 0.35 mg/cm2Pt
• Anode Catalyst:
NiFe2O4 (US Research Nanomaterials), 0.6 mg/cm2TM PGM-free Benchmark: Ni/C//NiFe2O4
• Operating Parameters: 1.0 A/cm2 at 1.811 V (HFR-free)
1 M KOH, 80 °C
50 mL/min, wet/wet PGM Benchmark: Pt/C//NiFe2O4
Membranes ion exchanged in 3 M KOH for 48 h 1.0 A/cm2 at 1.739 V (HFR-free)
20% compression
5 cm2 active area
Highlight: Met FY23 Q2 QPM for establishing LTE performance baselines (“Decide upon
baseline materials (membrane/thickness, PGM/non-PGM catalysts) and operational parameters
to establish a PGM and PGM-free membrane electrode assembly baseline performances.”)

OER Catalyst Development: La-Sr-Co Oxide Catalysts Accomplishment
La-Sr-Co oxide catalyst from LANL compared with a similar material from Pajarito Powder (LSC-PP-OER49B),
optimized to improve electronic conductivity and surface area, and with a benchmark PGM commercial catalyst IrO2
CV 10 mV/s
1600 rpm
N2-saturated 0.1 M KOH
Loading 0.25 mg/cm2
Catalyst BET S.A. (m2 g-1) Pore V (cm3 g-1)

Pajarito Powder-optimized catalyst showing slightly
LSC-LANL 8.6 0.041 higher surface area and OER activity than original
LSC-PP-OER49 14.4 0.092 LANL material; LSC catalysts activity still trailing that
of IrO2 by ca. 50-75 mV in RDE testing (right)
L. Osmieri et al., J. Power Sources 556 (2023) 232484

OER Catalyst Development: La-Sr-Co Oxide Catalysts (Electrode Fabrication) Accomplishment
2.3
Without binder With binder DI water - BOL
2.2 DI water - after 20 h I/C = 0.2
1% K2CO3
0.1 M KOH
B/I = 0.16
2.1
DI water - EOT
2.0
Voltage (V)
1.9
1.8
No detachment No detachment
1.7
1.6
more degradation and
1.5
catalyst detachment
1.4
0 100 200 300 400 500 600 700 800 900 1000
-2
Current Density (mA cm )
Detachment No detachment 2.3
DI water - BOL
2.2 DI water - after 20 h I/C = 0.4
1% K2CO3 B/I = 0.16
2.1 0.1 M KOH
DI water - EOT
• Ink deposition method important to 2.0
Voltage (V)
ensure uniform coating and high 1.9
catalyst utilization in MEA testing 1.8
• Highlight: Use of binder (Nafion) Detachment No detachment 1.7
preventing catalyst-layer detachment 1.6

less degradation and
• Highlight: Ink formulation (I/C and B/I) I/C: ionomer-to-catalyst ratio 1.5 catalyst detachment
B/I: binder (Nafion)-to-ionomer ratio
impacts performance and durability 1.4
0 100 200 300 400 500 600 700 800 900 1000
L. Osmieri et al., J. Power Sources 556 (2023) 232484 Current Density (mA cm ) -2

NiFe Aerogel Catalyst Characterization (After Testing) Accomplishment
150 °C
150°C
150 °C
500 °C
500°C
• Highlight: Catalyst heat-treated at 150 °C showing

structural change; small crystallites before testing (see
back-up slide #54) converting to highly active
(oxy)hydroxide layered structure. Activation required for
complete transformation into the active phase.
500 °C
• No structural change for catalyst heat-treated at 500 °C,
probably due to the presence of large, morphologically
stable crystallites

OER Catalyst Development: NiFe Aerogel Catalyst Durability Accomplishment
NiFe 2:1 aerogel catalyst heat-treated at 150 °C 72-hour current hold at 10 mA cm-2
25 1.80
t=0 i at 10 mA cm-2
t = 72 h 1.75
20
Staircase voltammetry 10 mV
step, 10 s duration, 1600 rpm 1.70
E vs. RHE (V)

N2-saturated 0.1 M KOH,
i (mA cm-2)
catalyst loading 0.25 mg/cm2

15
1.65
1.529 V (iR-free)
10 at 10 mA cm-2 at 1.60
beginning of test
(t = 0)
1.55
5 1.554 V (iR-free) at
10 mA cm-2 at end 1.50
of test (t = 72 h) 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
0 Time (h)
1.35 1.40 1.45 1.50 1.55 1.60
Highlight: Exceeded FY23 Q2 QPM and OER Annual
EiR-free vs. RHE (V) Milestone with 1.53 V at 10 mA cm-2 at beginning of
Degradation rate: (1554 mV - 1529 mV) / 72 h = 0.35 mV/h (from polarization curves) test and 0.35 mV/h (0.5 mV/h without any interruption)
(1675 mV - 1639 mV) / 72 h = 0.50 mV/h (from continuous life test
without interruption)
in 72 h test (vs. the milestone target of 0.5 mV/h)

OER Catalyst Development: Durable Nanostructured OER Catalyst Accomplishment
Durability of NiFeCo nanostructured OER catalyst 72 h at 10 mA/cm2 in O2-saturated 1.0 M KOH, 1600 rpm, 188 µg cm-2
Highlight: Exceeded FY23 Q1 QPM (and FY23 OER Annual Milestone). OER current density in an
aqueous alkaline electrolyte of 10 mA/cm2 at a potential of ≤ 1.55 V (≤ 1.54 V) vs. RHE at beginning of
test and ≤ 0.75 mV/h (0.5 mV/h) potential loss during 72 h durability test at 10 mA/cm2
ElectroCat FY23 OER performance target met and exceeded with two different electrocatalysts!

OER Catalyst Development: Performance Comparison in AEMWE and RDE Accomplishment
ANL Co-MOF from Di-Jia Liu’s HydroGEN Seedling Project

RDE – 0.1 M KOH AEMWE – 0.1 M KOH AEMWE – DI water
AEMWE test conditions: • Highlight: NiFe 8:1 catalyst, heat-treated at 150 °C, showing best
 Same ionomer and membrane (Versogen) performance of PGM-free ORR catalysts
 Same cathode (PtRu/C, ~1 mgPt cm-2)
• OER activity trends in RDE testing only partially observed in AEMWE
 Same PTL materials at anode (sintered Ti)
and cathode (MGL370 carbon paper) • Despite lower activity in RDE testing, IrO2 performing better in AEMWE
 Same temperature (70 °C) than PGM-free catalysts, likely due to more effective interaction with ionomer
 Different anode catalyst ink formulation • Highlight: Electrode fabrication, activation, and test conditions playing key
(I/C, B/I, catalyst loading) role in maximizing AEMWE performance of catalysts

Progress Towards LTE Performance Milestone of PGM-free OER Catalyst Accomplishment
Milestone (9/30/2023): LTE Catalyst Testing in AEM MEA. Criteria: Incorporating ElectroCat-developed catalysts, demonstrate cell overvoltage
reduction of more than 50 mV (HFR-free) compared to commercial baseline catalysts (NiFeOx, established in HydroGEN EMN) at 1 A/cm2.
Comparisons between novel and commercial catalysts would maintain consistent supporting electrolytes (1 M KOH) and operating conditions,
including materials choices, flow configurations (wet/wet), and temperature (80 °C).
• Highlight: ElectroCat FY23 annual milestone exceeded

by 130 mV with NiFe 8:1 catalyst – 1.559 V vs. 1.739 V
baseline established with NiFe2O4 catalyst
• Highlight: By reaching iR-free voltage of 1.559 V NiFe
System
HFR CLR Tafel VHFR-free (V) 8:1 catalyst also meeting the HydroGEN FY23 Q4
(Ω cm2) (Ω cm2) (mV/dec) at 1.0 A cm-2
milestone: “Demonstrate AEMWE in a supporting electrolyte
NiFe2O4 0.078 0.197 82 1.739
with a cell overvoltage within 50 mV (HFR-free) of
NiFe 8:1 0.082 0.078 69 1.559
commercial Nafion at 1 A/cm2”. (Voltage reached with NiFe
PEM 115 MEA 0.083 0.008 64 1.541
catalyst within 18 mV of the PEM 115 MEA performance.)

Adaptive Learning for Designing OER Electrocatalysts Accomplishment
 Developed an adaptive learning framework for the design of aerogel-derived Ni-based oxide OER catalysts
 Selected four synthesis variables as OER catalyst descriptors: (1) Fe molar ratio, (2) Co molar ratio,
(3) ethanol volume, and (4) polyacrylic acid (PAA) concentration
Composition space
XPAA (mg/ml)
Xethanol (ml)
Initial dataset
Highlight: Designed a matrix with 30 samples for synthesis and characterization in order to build an initial
database for developing machine learning models; samples synthesized; test data being processed

OER Catalyst Development: Laying Ground for Adaptive Learning Work Accomplishment
Effect of heat-treatment temperature (below 150 °C) Effect of multiple gels drying with supercritical (SC) CO2
30 30
NiFe 8:1 500°C Ni - Dry multiple samples
NiFe 8:1 150°C Ni - Dry single sample_2021
Ni - Dry single sample_2022
25 NiFe 8:1 75°C 25 NiFe 8:1 - Dry multiple samples
NiFe 8:1 no heat treatment
NiFe 8:1 - Dry single sample_2022
NiFe 8:1 - Dry single sample_2021
20 Staircase voltammetry: 20
10 mV, 10 s Staircase voltammetry:
1600 rpm 10 mV, 10 s
i (mA cm-2)
i (mA cm-2)
15 N2-saturated 0.1 M KOH 15 1600 rpm
Loading: 0.25 mg/cm2 N2-saturated 0.1 M KOH
Loading: 0.25 mg/cm2
10 10
5 5
0 0
1.30 1.35 1.40 1.45 1.50 1.55 1.60 1.65 1.2 1.3 1.4 1.5 1.6 1.7
EiR-free vs. RHE (V) EiR-free vs. RHE (V)
• Highlight: Heat treatment in air up 150 °C not having an impact on catalytic activity; heat treatment at 500 °C
having negative impact on activity → no heat-treatment temperature included in the adaptive learning (ML) study
• No cross contamination between gels observed when drying numerous samples in the same SC CO2 dryer
chamber, enabling faster sample preparation for the adaptive learning study

Atomic-Scale Models of OER Electrocatalysts Accomplishment
 Applied HSE06 (15% exact exchange) density functional theory (DFT) method to study Fe, Co, Mn doped NiOOH surfaces
 Calculated work function used as activity descriptor – in agreement with known experimental trends in activity
 Calculated O vacancy formation energy suggests mechanisms involving this formation step are energetically unfavorable
FY23 Q1 QPM: “Report calculated work functions and relative O vacancy formation energies (neutral charge state) for
NiOOH basal plane systems with and without Fe, Mn, and Co metal dopants (treated as substitutional defects) using
HSE06 + 15% exact exchange methodology.”
Highlight: QPM met. DFT-based calculations enhancing the understanding of complex OER catalyst surfaces, addressing
model, mechanism, and methodology, along with adaptive learning approaches and synthesis and characterization

MD, ML for Understanding AEMs and Catalyst-Ionomer Interface Accomplishment
 Understanding ionomer, AEMs requires length, time scales beyond quantum-mechanical simulations
 Two focus areas: simulate bulk polymer with classical force fields, develop force fields for interface
 Started with Nafion-platinum due to wealth of characterization data
Bulk-Polymer Modeling: PiperION Nafion-Platinum Interface
Used neural network method, DeePMD,

that generalizes to any polymer/catalyst set
Water
domain size • Highlight: Predicted structure, transport
properties of PiperION AEM
• Future direction: Use DeePMD to
understand polymer-catalyst interface for OER

HER Catalyst Development: Impact of Synthesis Method on Activity (RDE) Accomplishment
HER activity of aerogel-derived catalysts (RDE)

More synthesis variables
to be investigated:
 Ni-to-Mo ratio
 Other than Mo in
~300 mV combination with Ni
(e.g., Nb, Co)
 Heteroatom doping
(N, P, S, etc.)
• Highlight: Heat treatment at high temperature under

reducing atmosphere (5% H2 in N2) – a key factor in
improving HER activity (→ conversion of Ni-oxide to Ni
metal)
Staircase voltammetry:
10 mV, 10 s, 1600 rpm
• Carbon addition further improving activity by helping
N2-saturated 0.1 M KOH with metal particles dispersion
Loading: 0.25 mg/cm2
• Significant performance gap still remaining to the
benchmark PtRu/C catalyst: ca. 300 mV at 10 mA cm-2

HER Catalyst Development: Effect of PGM-free Ni Cathode Loading Accomplishment
V Cathode loading:
HFR-free 0.3 mg/cm2Ni
3.4 mg/cm2Ni
4.8 mg/cm2Ni
Voltage (V)
Cathode loading:
0.3 mg/cm2Ni
3.4 mg/cm2Ni
4.8 mg/cm2Ni
1.25 V
2V
Voltage (V)
• Increased cathode loading from 0.3 to 4.8 mg/cm2Ni:

 Increase in current from 0.70 to 1.28 A/cm2 at 2.0 V
 Decrease in Tafel slope by 25 mV/decade
 Decrease in catalyst-layer resistance by 50%
• Highlight: PGM-free catalyst loading at the cathode
having major impact on electrolyzer performance

HER Catalyst Development: Short-term Anion Exchange Ionomer Degradation Accomplishment
Anode: IrO2 catalyst ~1 mgIr cm-2, spray coating on sintered Ti PTL; Cathode: Pt 20% Ru 10% on C ~0.5 mgPt/cm2, spray coating on MGL370 GDL; Membrane:
Orion Polymer CMX (40 μm); AE ionomer: F7N55 provided by Santosh Adhikari and Yu Seung Kim (LANL); Cell: 5 cm2 electrode area; Temperature: 70 °C
F7N55 F7N55
• Highlight: Ionomer (F7N55) degradation causing degradation of the catalyst-ionomer interface (→ loss of capacitance)
during DI water testing, negatively affecting performance; not observed in 0.1 M KOH due to excess of liquid electrolyte.
• Similar degradation observed with three other alkaline ionomers: FN55 from Santosh Adhikari and Yu Seung Kim at LANL,
and BTN(PIP) and BTN(TMA) by Sariah Marth and Chulsung Bae at Rensselaer Polytechnic Institute (cf., slides #63-65)
• Chemical stability of anion exchange ionomers having major impact on AEMWE durability.

Capability Development: In situ Mössbauer Spectroscopy of OER Catalysts Accomplishment
Ex situ powder
spectrum
Left: Teflon cell for in situ OER Mössbauer spectroscopy, with source Increase of absorption
and drive in foreground. with more cycles
Right: Pump, Mössbauer setup, and potentiostat in shielded enclosure;

Catalyst in the cell on carbon paper with 1 M KOH solution
circulating at 2 mL/min.
Increase in
absorption with
• Designed and built in situ Mössbauer cell. cycling
• Synthesized 57Fe-enriched NiFe OER aerogel catalyst

In situ spectrum
• Highlight: Demonstrated in situ Mössbauer spectroscopy,
of NiFe catalyst
showing predominance of Fe(III) at all potentials and
increase in particle size with OCV cycling. FY23 Q2 met.

Collaboration and Coordination
ElectroCat core national laboratories:

 Los Alamos National Laboratory – ElectroCat co-Lead
 Argonne National Laboratory – ElectroCat co-Lead
 National Renewable Energy Laboratory
 Oak Ridge National Laboratory
Collaborators not directly participating in ElectroCat (no-cost):
 Cornell High Energy Synchrotron Source, Ithaca, New York – X-ray catalyst characterization
 Bar-Ilan University, Israel – aerogels-based catalysts with high active-site density
 Daegu Gyeongbuk Institute of Science and Technology (DGIST), Daegu, South Korea
 – catalyst performance evaluation
 Israeli Fuel Cell Consortium (IFCC) – PGM-free activity indicators and durability
 Pajarito Powder, Albuquerque, New Mexico – catalyst scale-up, PGM-free electrode
design, catalyst commercialization (independent of ElectroCat project)
 Rensselaer Polytechnic Institute (RPI), Troy, New York – alkaline membranes and ionomers
 University at Buffalo, Buffalo, New York – novel PGM-free catalyst synthesis
 University of Warsaw, Warsaw, Poland – role of graphite in PGM-free catalyst design
 Washington State University, Pullman, Washington – OER electrocatalyst development

Response to 2022 Sub-Program Reviewer Comment and 2021 Reviewers’ Comments
• Not reviewed in 2022, however, reviewer comments for the Fuel Cell Technologies Subprogram referred to ElectroCat as follows:
[…] the focus of the ElectroCat consortium could be shifted toward developing PGM-free catalysts for AEM electrolyzers over the
next three to five years.
At its inception in 2020, ElectroCat 2.0’s research portfolio was 75% fuel cells and 25% electrolysis. In 2023, ElectroCat 2.0’s
research portfolio is 50% fuel cells and 50% electrolysis.
2021 Reviewer comments:
• “Validation of DFT predictions with experimental data is limited. The fact that there are some experimental motivations is
understood, but the results need to come back to these to demonstrate causality.”
Models of idealized sites continue to produce testable hypothesis, but the heterogeneous and dynamic nature of real materials often
makes testing these difficult experimentally. These are not single-structure materials and they do evolve in time. Qualitative
trends from computational descriptors have been confirmed experimentally (dependence of metal stability on pH, metal stability in
certain potential ranges at low pH, and identification of spectroscopic signatures, to name a few). In FY22, we have aimed to
improve the predictive value of models to experimental efforts. LANL modeling and ORNL microscopy have collaborated to
determine how TEM could aid in understanding C/N stability against corrosion for directly observed Fe-N sites. ANL/NREL models of
active sites have aided in identifying likely structures for given sites/ligation state as a function of potential as measured with X-ray
spectroscopy. These steps move us closer to understanding what structures are present in real materials and thus linking synthesis
conditions to these structures, though this connection needs to be further strengthened. Our machine learning efforts have focused
on optimizing performance, but we hope to extend to causational relationships based on active site structures. This is a significant
effort, however, and will not be possible in the near term without a significant increase in funding for combined modeling and
experimental efforts to this end. Furthermore, we would highlight that modeling efforts have directly aided experimental work through
“asking better questions” and targeting particular, specific questions that can be motivated by DFT findings. In particular, the
existence and suggestion of possible chemistry of axial 5th ligands and their effect on activity, stability, and spectroscopy originally
came from fundamentally motivated DFT calculations.

Reviewers’ Comments from 2021 Annual Merit Review
• Significant progress has been made in PEMFC development, but there are weaknesses that need to be addressed—particularly,
performance of the catalyst in the electrolyzer setting. The cell voltage of 2.0 V at 600 mA/cm2 is too high. Much more focus should
be put on the study conditions for the electrolyzer performance if the project is ever going to achieve a goal of an 80,000-hour
lifetime. An early understanding of the fundamental mechanisms associated with the IrO2 anode’s operation in the electrolyzer
should be used to guide the catalyst development.
ElectroCat 2.0 is solely focused on electrocatalyst development and implementation. The study of conditions and the understanding
of IrO2 anode operation in acidic electrolyte is one of the focuses of H2NEW. We are collaborating with H2NEW and HydroGEN and
building on the learnings in these two consortia to guide the development of PGM-free OER catalysts for anion-exchange
membrane water electrolyzers.

Selected Accomplishments and Progress
ElectroCat Development and Communication
• Consortium-wide in-person meetings held in Knoxville on October 6-7, 2022, and in Santa Fe on February 13-14, 2023
• 14 papers published and 18 presentations, including 6 invited
• Developed methods for inclusion of explicit solvation in modeling of adsorption and ORR activity
• Designed, constructed, and validated new cell for high-throughput screening of catalysts’ ORR and OER activity
• Developed in situ Mossbauer capabilities for OER catalyst activation and degradation studies
Progress in Performance of PGM-free ORR Catalysts
• Achieved maximum MEA H2-air current densities of 97 mA cm-2 at 0.8 V and 435 A cm-2 at 0.675 V beginning of test and
49 mV loss at 0.8 A cm-2 after 10k AST cycles with initially slightly less active catalyst sample (92 mA cm-2 at 0.8 V)
• MEA H2-air current density at 0.8 V and 0.675 V increased by 23% and 15% vs FY22 results
• Synthesized 64 unique catalysts using high-throughput approach, with 88% enhancement in ORR activity and 78%
enhancement in stability versus FY22 best-in-class high-throughput synthesized Fe-N-C catalysts
Progress in PGM-free OER and HER Catalysts
• LTE performance baselines established with PGM-free anode catalysts and PGM-free and PGM cathode catalysts
• FY22 Go/No-Go OER activity of ≤ 1.6 V vs. RHE at 10 mA cm-2 exceeded with several aerogel-derived NiFe oxides
• FY23 OER Annual Milestone in electrochemical cell of 10 mA cm-2 at ≤ 1.54 V and ≤ 0.5 mV/h potential loss during 72 h
durability test exceeded with two catalysts: aerogel-derived NiFe oxide catalysts and nano-structured NiFeCo catalyst
• ElectroCat FY23 annual AEMWE milestone exceeded by 130 mV with NiFe 8:1 catalyst
• Work functions & O vacancy formation energies for key NiOOH basal plane systems calculated with and without dopants
• Determined dependence of Ni cathode performance as a function of catalyst loading

Remaining Challenges and Barriers
Fuel Cell
• Increasing accessibility of stable active sites in Fe-N-C catalysts
• Increasing the density of stable active sites and oxygen reduction reaction turnover frequency
(TOF) to meet DOE H2-air performance targets
• Gaining fundamental knowledge in electrocatalysis for assuring further progress in catalyst
development
• Developing atomic-level surface techniques for operando studies of surface reactions
Low-Temperature Electrolysis
• Increasing performance of electrolyzer operating with PGM-free anode and cathode catalysts
performance to the level demonstrated with PGM electrodes
• Improving durability of alkaline membrane electrolyzer operating on pure water and at
temperatures of ≥ 60 °C
• Minimizing degradation of anion-exchange ionomers
• Understanding key factors determining performance and durability of PGM-free catalysts in AEM
electrolyzers
• Developing atomic-level surface techniques for operando studies of surface reactions

Proposed Future Work
ElectroCat Development
• Expand capabilities to include methods developed specifically for OER and HER catalyst development, evaluation,
and implementation
• Develop and utilize combinatorial electrolyzer hardware for expediting OER and HER catalyst optimization and
evaluation in MEAs
Improvement in Performance and Durability of Fuel Cell Catalysts and Electrodes

• Advance performance of cathode catalysts by maximizing volumetric density and accessibility of active sites through
alternative synthetic methods, in particular:
 Synthesize catalysts with high density of active sites using Fe doping of nitrogen-doped carbons
 Use pore-former and soft-template synthesis with micelle templates to enhance Fe-N-C catalyst mesoporosity
• Optimize fuel cell performance of the best-in-class high-throughput catalysts using high-throughput ink optimization,
cell testing, and associated ink characterization and cell diagnostics
Electrolyzer Catalysts and Electrodes

• Activate MOF-derived OER catalyst on a porous transport electrode, fabricate and test MEA
• Fabricate and test NiFeCo nanostructured OER catalyst in an MEA
• Further increase activity of high surface-area OER catalyst derived from aerogels and xerogels
• Synthesize OER and HER catalysts with hierarchical porosity
• Introduce atomic-scale modeling into catalyst development and kinetic/transport modeling into electrode development
• Identify and quantify products of anode and cathode catalyst degradation
Any proposed future work is subject to change based on funding levels
Summary
End of Consortium Goals
• Fuel Cell: H2-air performance of ≥ 100 mA cm-2 at 0.8 V and ≥ 500 mA cm-2 at 0.675 V at beginning of test (BOT) and
≥ 80 mA cm-2 and ≥ 400 mA cm-2 after 30,000 AST cycles (0.6 V to OCV, 3 s each, H2-air), respectively, under integral
conditions for a PEMFC with a PGM-free oxygen reduction reaction (ORR) catalyst
• Electrolyzer: 2.5-fold increase, from 0.2 A cm-2 to 0.5 A cm-2 at 1.8 V and reduction in the voltage loss at a reference
current density of 0.2 A cm-2 from 0.2 mV h-1 to 0.1 mV h-1 with alkaline-exchange membrane water electrolyzer using a
PGM-free oxygen evolution reaction (OER) catalyst
Progress in Performance of PGM-free ORR Catalysts for PEMFCs
• Achieved maximum MEA H2-air current densities of 97 mA cm-2 at 0.8 V and 435 A cm-2 at 0.675 V beginning of test and
49 mV loss at 0.8 A cm-2 after 10k AST cycles with initially slightly less active catalyst sample (92 mA cm-2 at 0.80 V)
• MEA H2-air current density at 0.8 V and 0.675 V increased by 23% and 15% vs FY22 results
• Using high-throughput approach, enhanced ORR activity by 88% and stability by 78% versus FY22 best-in-class high-
throughput synthesized Fe-N-C catalystsS
Progress in PGM-free OER Catalysts for Alkaline-Exchange Membrane Water Electrolyzers
• Exceeded FY23 OER Annual Milestone in aqueous electrochemical cell of 10 mA cm-2 at ≤ 1.54 V and ≤ 0.5 mV/h
potential loss during 72 h durability test exceeded with two catalysts: aerogel-derived NiFe oxide catalysts and nano-
structured NiFeCo catalyst
• Demonstrated MEA overvoltage reduction of more than 180 mV (HFR-free) compared to commercial baseline catalysts
(NiFeOx, established in HydroGEN EMN) at 1 A cm-2 with aerogel NiFe 8:1 catalyst (at 0.6 mg cm-2 loading) and 100 mV
(HFR-free) with NiFeCo nanostructured catalyst (at 0.3 mg cm-2 loading).

Co-Authors
PGM-free catalyst development, electrochemical and fuel cell testing, atomic-

scale modeling, machine learning
Piotr Zelenay (PI), Yanghua He, Jeremy Jernigen, Edward (Ted) Holby,
Wilton Kort-Kamp, Luigi Osmieri, John Weiss, Hanguang Zhang
PGM-free catalyst development, high-throughput techniques, atomic-scale

modeling, X-ray studies, aqueous stability studies
Debbie Myers (PI), Ahmed Farghaly, Magali Ferrandon, A. Jeremy Kropf,
Cong Liu, Jae Hyung Park, Xiaoping Wang, Jiayi (Jason) Xu
High fidelity modeling, electrode design and performance evaluation

Derek Vigil-Fowler (PI), Jacob Clary, Shaun Alia, Melissa Kreider
Advanced electron microscopy, atomic-level characterization, XPS studies

Dave Cullen (PI), Lynda Amichi, Raphael Hermann, Xiang Lyu, Jose Arregui Mena,
Shawn Reeves, Alexey Serov, Haoran Yu, Michael Zachman, Amir Ziabari

Technical Back-Up Slides and
Additional Information

ORR Catalyst Development: Synthesis of MOF-derived Fe-N-C Catalysts Accomplishment
Stage 1: Precursor synthesis Stage 2: High-temperature treatment
High-temperature
furnace
gas flow
+ Inlet Outlet
Zn(NO3)2∙6H2O Zn
Fe
N
Fe(NO3)3 ∙ 9H2O
MOF precursor C
One-step heat-treatment synthesis (conventional approach)

Limitations of conventional one-step
high-temperature approach:
treatment
 difficult to modify the structure of catalysts
precursors without affecting Fe dispersion
 modification of catalyst precursors leads to
Catalyst precursor: Fe-N-C catalyst the formation of inactive Fe nanoparticles
Fe, N and C precursor
in catalysts
(Fe/Zn-MOF)

ORR Catalyst Development: Adaptive Learning and Uncertainty Quantification Accomplishment
Bootstrap statistical sampling
+
h1(x)
ML model fitted in
1,000
h2(x)
representative
“copies” of the
original dataset
h3(x)
…
Mean and STD  μ(x), σ(x)
Highlight: Developed and implemented an integrated experimental-machine learning adaptive learning design
loop with uncertainty quantification to model and guide the synthesis of 14 new ORR Fe-N-C electrocatalysts

ORR Catalyst Development: What About the Catalyst Short-term Stability? Accomplishment
a b
ORR 2 = 0.91 ± 0.03 × ORR1 − (0.32 ± 0.19)
99% confidence interval
R2 = 0.95
Initial Adaptive
dataset learning
Furnace closed X
Furnace open X
• Linear correlation between the catalyst activity and short-term stability

• Nonlinear correlations seemingly important in poor-performing samples (non-zero intercept)
• Highlight: All catalysts lose ~10% of their initial activity in the short term regardless of their synthesis process

OER Catalyst Development: La-Sr-Co Oxide Catalysts (Characterization) Accomplishment
200
0.0025 LSC-LANL
180 LSC-LANL LSC-PP-OER49B
LSC-PP-OER49B PDF#00-048-0122 La0.5Sr0.5CoO2.91
160
V adsorbed @ STP (cm3 g-1)
0.0020
LSC-LANL
dV(r) (cm3 Å-1 g-1)
140
0.0015
Counts (a.u.)
120
0.0010
100
80 0.0005
60
0.0000
40 10 100
Half pore width (Å)
20
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 20 30 40 50 60 70 80
Relative Pressure 2θ (°)
• Pajarito Powder catalyst (LSC-PP-OER49B) showing higher surface

area and pore volume due to high micropore (< 0.5 nm) and large-pore
(> 10 nm) content
LSC-PP-OER49B
• XRD spectra typical for La-Sr-Co oxide
• Uniform distribution of La, Sr, and Co observed in LSC-LANL catalyst
• Particles containing only Co oxide detected in LSC-PP-OER49B catalyst
Catalyst BET S.A. (m2 g-1) Pore V (cm3 g-1)

LSC-LANL 8.6 0.041
LSC-PP-OER49 14.4 0.092

NiFe Aerogel Catalysts Characterization Accomplishment
Low-temperature heat treatment (150 °C)

• Small crystallites (< 2 nm)
• High surface area
• High OER activity
• Ni(II)-to-Ni(III) transition during CV
CV 10 mV/s
1600 rpm
N2-saturated 0.1 M KOH
150°C 150°C Loading 0.25 mg/cm2
2 nm
High-temperature heat treatment (500 °C)
500°C
• Large crystallites (> 20 nm)
500°C • NiOx-rich core with FeOx shell
• Low surface area
2 nm
• Low OER activity
• No Ni(II)-to-Ni(III) redox behavior

LANL Sol-Gel Synthesis of OER and HER Catalysts Approach
OER catalysts – synthesis variables explored:

• Ni:Fe ratio
• Heat treatment temperature
• Gel drying method
Supercritical CO2
drying Aerogel
OER catalysts: heat
 NiCl2 + MCl2, M = Fe (OER), Mo (HER)
Solvent removed; treatment in air Aerogel/Xerogel-derived
 Solvent (ethanol)
“gel-like” morphology T = 150 °C, 500 °C NiFe oxide
 Gelation agent (propylene oxide)
maintained
 Carbon added for some HER catalysts
Aging &
Ambient HER catalysts: heat
solvent Aerogel/Xerogel-derived
Sol Gel pressure drying Xerogel treatment in 5% H2
exchange
T = 500 °C Ni and Ni-M particles
Hydrolysis
&
Condensation
HER catalysts – synthesis variables explored:

• Addition of Mo
• Addition of carbon

Synthesis of NiFeCo Nanostructured OER Catalyst Approach
• Nanostructured OER catalysts composed of multi-metal cations: (i) very high (?)
electrochemically active surface area, (ii) good structural stability, (iii) high electrical conductivity
• Tunable electronic structures, large compositional space → excellent candidates for high-
throughput synthesis guided by machine learning modeling

Development of Protocol to Investigate Short-term Durability Approach
Anode: IrO2 catalyst ~1 mgIr cm-2 on sintered Ti PTL; Cathode: Pt Ru/C ~0.5 mgPt/cm2 on MGL370 GDL; Cell: 5 cm2 electrode area; Temperature: 70°C
Day 1
• CV 50 mV/s in DI water, 1.2 – 2.0 V, 70 °C;
• 3x V-I curve in DI water, 0.1-1.0 or 2.0 A/cm2, 0.1 A/cm2 step (10 – 15 points), 3 min/step, 70 °C;
• EIS DI water;
• CV 50 mV/s in 1% K2CO3, 1.2 – 2.0 V, 70 °C;
• V-I curve in 1% K2CO3, 0.1-2.0 A/cm2, 0.1 A/cm2 step until 1.0 A/cm2 , 0.2 A/cm2 step until 2.0 A/cm2 (15 points), 3 min/step, 70 °C;
• EIS 1% K2CO3;
• CV 50 mV/s in 1% K2CO3, 1.2 – 2.0 V, 70 °C;
• CV 50 mV/s in 0.1 M KOH,1.2 – 2.0 V, 70 °C;
• V-I curve in 0.1 M KOH, 0.1-2.0 A/cm2, 0.1 A/cm2 step until 1.0 A/cm2 , 0.2 A/cm2 step until 2.0 A/cm2 (15 points), 3 min/step, 70 °C;
• EIS 0.1 M KOH;
• CV 50 mV/s in 0.1 M KOH, 1.2 – 2.0 V, 70 °C;
• Flush ~2 L DI water;
Leave paused overnight
Day 2
• Same as day 1, except no 1% K2CO3 test
Day 3
• Same as Day 2
Day 4
• 3x V-I curve in DI water, 0.1-1.0 or 2.0 A/cm2, 0.1 A/cm2 step (10 – 15 points), 3 min/step, 70 °C;
• EIS DI water;

Activation of NiFe Aerogel Catalysts Accomplishment
2.8 2.8
#1 #1 Anode: ~1.5 mg cm-2 catalyst on sintered Ti PTL;
NiFe 8:1 – 150°C #2 #2 NiFe 8:1 – 150°C
2.6 #3 2.6
#3
Cathode: Pt 40% Ru 20% on C ~1 mgPt/cm2 MGL370
#4
#5 #4 GDL; Cell: 5 cm2 electrode area; Membrane:
HT 150°C
2.4 #6 2.4 #5 Versogen Piper-Ion (40 µm); Temperature: 70 °C
#7 #6
Voltage (V)
Voltage (V)
#8
2.2 2.2 #7
#9
#10 #8
2.0 2.0 #9
#10
1.8 1.8
• Highlight: High AEMWE
performance of catalyst heat-treated
1.6 1.6
at low temperature (150 °C), further
1.4 1.4 improving over 10 consecutive V-I
0 200 400 600 800 1000 1200 1400 1600 1800 0 200 400 600 800 1000
Time (s) Current Density (mA cm-2)
measurements; catalyst color
2.8 2.8 changing from yellowish before
NiFe 8:1 – 500°C NiFe 8:1 – 500°C
2.6 2.6 testing to black after testing
indicating change in composition (→
2.4 2.4
activation) that results in higher OER
Voltage (V)
activity testing
Voltage (V)
2.2 2.2
2.0 2.0
• AEMWE performance of catalyst
HT 500°C #1 #1
1.8 #2 1.8
#2 heat-treated at 500 °C lower than
#3
1.6
#4
1.6 After testing
#3 that of the material heat-treated at
#5 #4
#5 150 °C, not improving with during V-I
1.4
0 200 400 600 800 1000 1200 1400 1600 1800
1.4
0 200 400 600 800 1000 measurements.
Time (s) Current Density (mA cm-2)
Impact of NiFe Catalyst Drying Method (Aerogel vs. Xerogel) Accomplishment
BET S.A. Pore V 0.020

Catalyst Ni:Fe 8:1 Aerogel 150°C
(m2 g-1) (cm3 g-1)
NiFe 8:1 Aerogel 150°C 382 0.85
Ni:Fe 8:1 Xerogel 150°C
NiFe 8:1 Aerogel 500°C 55 0.21
0.015
NiFe 8:1 Xerogel 150°C 264 0.44
Staircase voltammetry
dV(r) (cm3 Å-1 g-1)

10 mV, 10 s
NiO PDF#00-004-0835 1600 rpm
NiFe 8:1 Aerogel 0.010 N2-saturated 0.1 M KOH
NiFe 8:1 Aerogel 150°C Loading 0.25 mg/cm2
NiFe 8:1 Xerogel 150°C
NiFe 8:1 Aerogel 500°C
Counts (a.u.)
0.005
0.000
10 100
Half pore width (Å)
20 30 40 50 60 70 80 90
Xerogels lacking 15 - 40 nm wide pores Lower OER activity of xerogels vs. aerogels
2θ (°)
• Xerogels showing ca. 30% lower BET surface area and ca. 50% lower pore volume than corresponding aerogels
• XRD data indicating possible presence of larger crystallites in xerogels and aerogels
• Highlight: Large mesopores in aerogels (missing in xerogels) possibly acting as hosts for the OER-active Fe-
containing sites

Accessing Electrode/PTL Interfaces with FIB-SEM Accomplishment
• Focused-ion-beam (FIB) cross sectioning of a NiFe electrode on Ti porous transport layer.

• Catalyst coating follows the rough topography of the PTL surface with thickness ranging from 2 -10 microns.

Gram-Scale Synthesis of MOF-derived OER Catalysts with Improved Activity Accomplishment
Achieved an
Fe-rich OER
catalyst
4-inch-long crystals of Nominal Conc. of Ni

MOF-derived OER catalysts in reaction (mmol)
• Highlight: Developed gram-scale (5-6 grams) synthesis procedure for ZnCoMOF-derived OER
catalysts which showed improved activity vs FY22 MOF-derived OER catalysts.
• Exceeded FY23 Q1 QPM activity target of 10 mA cm-2 at ≤ 1.55 V with activated MOF-derived catalyst.
• Determined that activated catalysts are air-stable and can be used without re-activation after storage.

Progress Towards LTE Performance Milestone of PGM-free OER Catalyst Accomplishment
1 M KOH, 80 °C, 50 mL/min

Versogen 80 um, I/C 0.3
NiFe2O4 – 79 mV/dec
Co – 93 mV/dec
Ni-Fe-Co – 68 mV/dec
Cathode: Pt/C 0.3 mg/cm2

Anodes: 0.3 mg/cm2
Commercial NiFe2O4
Commercial Co
ElectroCat Ni-Fe-Co
V@1
HFR CLR Tafel
A/cm2
• Highlight: At 1 A/cm2, the ElectroCat Ni-Fe-Co (Ω*cm2) (Ω*cm2) (mV/dec)
(HFR-free)
anode catalyst achieves 100 to 120 mV
improvement over commercial catalysts 1.823
NiFe2O4 0.067 0.334 79
(1.755)
• Next steps: increase anode catalyst loading to
1.862
0.6 mg/cm2; durability testing Co 0.086 0.346 93
(1.776)
ElectroCat 1.737
0.082 0.146 68
Ni-Fe-Co (1.654)

HER Catalyst Development: Short-term Anion Exchange Ionomer Degradation (2) Accomplishment
Orion Polymer CMX (40 μm); AE ionomer: BTN(PIP) provided by Sariah Marth and Chulsung Bae (RPI) Cell: 5 cm2 electrode area; Temperature: 70 °C
BTN(PIP) BTN(PIP)
Highlight: As in previous case, degradation of the BTN(PIP) ionomer resulting in severe

degradation of the catalyst-ionomer interface (→ loss of capacitance) in DI water, negatively
affecting performance; not observed in 0.1 M KOH due to large excess of liquid electrolyte

Orion Polymer CMX (40 μm); AE ionomer: FN55 provided by Santosh Adhikari and Yu Seung Kim (LANL); Cell: 5 cm2 electrode area; Temperature: 70 °C
As with other ionomers, also in this case, degradation of the FN55 ionomer results in

Orion Polymer CMX (40 μm); AE ionomer: BTN(PIP) provided by Sariah Marth and Chulsung Bae (RPI) Cell: 5 cm2 electrode area; Temperature: 70 °C
BTN(TMA) BTN(TMA)
As in cases of other ionomers, also here, the BTN(TMA) ionomer degradation is causing

Publications – since 2022 AMR presentation submission
1. H. Wang, L. Osmieri, H. Yu, M. J. Zachman, J. H. Park, N. N. Kariuki, F. C. Cetinbas, S. Khandavalli, S. Mauger, D. J. Myers, D. A. Cullen, K.
C. Neyerlin, “Elucidating the impact of the ionomer equivalent weight on a platinum group metal-free PEMFC cathode via oxygen limiting
current” SusMat (2022) 1.
2. L. Osmieri, Y. He, H. T. Chung, G. McCool, B. Zulevi, D. A Cullen, P. Zelenay, “La–Sr–Co oxide catalysts for oxygen evolution reaction in anion
exchange membrane water electrolyzer: The role of electrode fabrication on performance and durability” J. Power Sources. 556 (2023)
232484.
3. C.L. Vecchio, X. Lyu, I. Gatto, B. Zulevi, A. Serov, V. Baglio, "Performance investigation of alkaline direct methanol fuel cell with commercial
PGM-free cathodic materials" J. Power Sources 561 (2023) 232732.
4. T. Reshetenko, M. Odgaard, G. Randolf, K. K. Ohtaki, J. P. Bradley, B. Zulevi, X. Lyu, D. A. Cullen, C. J. Jafta, A. Serov, A. Kulikovsky, "Design
of PGM-free Cathodic Catalyst Layers for Advanced PEM Fuel Cells" Appl. Cat. B: Environ. 312 (2022) 121424.
5. S. Akula, M. Mooste, B. Zulevi, S. McKinney, A. Kikas, H.-M. Piirsoo, M. Rähn, A. Tamm, V. Kisand, A. Serov, E. B. Creel, D. A. Cullen, K. C.
Neyerlin, H. Wang, M. Odgaard, T. Reshetenko, K. Tammeveski, "Mesoporous textured Fe-N-C electrocatalysts as highly efficient cathodes for
proton exchange membrane fuel cells" J. Power Sources 520 (2022) 230819.
6. X. Wang, M. Ferrandon, J. Hyung Park, J.-J. Shen, A.J. Kropf, H. Zhang, P. Zelenay, D.J. Myers, “Iron redox behavior and oxygen reduction
activity of Fe-N-C electrocatalysts in different electrolytes” Electrochim. Acta 443 (2023) 141934.
7. W.J.M. Kort-Kamp, M. Ferrandon, X. Wang, J. Hyung Park, R. K. Malla, T. Ahmed, E.F. Holby, D.J. Myers, Piotr Zelenay, “Adaptive learning-
driven high-throughput synthesis of oxygen reduction reaction Fe-N-C electrocatalysts” J. Power Sources 559 (2023) 232583.
8. M.S. Ferrandon, J.H. Park, X. Wang, E. Coleman, A.J. Kropf, D.J. Myers, “Enhancing the activity of Fe-N-C oxygen reduction reaction
electrocatalysts by high-throughput exploration of synthesis parameters” Electrochim. Acta 441 (2023) 141850.
9. S. Liu, C. Li, M. J. Zachman, Y. Zeng, H. Yu, B. Li, M. Wang, J. Braaten, J. Liu, H.M. Meyer III, M. Lucero, A. J. Kropf, E.E. Alp, Q. Gong, Q.
Shi, Z. Feng, G. Wang, H. Xu, D.J. Myers, J. Xie, D.A. Cullen, S. Litster, and G. Wu, “Atomically dispersed iron sites with a nitrogen-carbon
coating as highly active and durable oxygen reduction catalysts for fuel cells” Nature Energy, 7 (2022) 652.
10. N. Zion, L. Peles-Strahl, A. Friedman, D.A. Cullen, L. Elbaz, “Electrocatalysis of Oxygen Reduction Reaction in Polymer Electrolyte Fuel Cell
with Covalent Framework of Iron Phthalocyanine Aerogel” ACS Appl. Mater. and Interfaces 14 (2022) 20303.

Publications (continued)
11. R. Z. Snitkoff-Sol, A. Friedman, Y. Yurko, A. Kozhushner, M. J. Zachman, P. Zelenay, A. M. Bond, and L. Elbaz, “Quantifying the
electrochemical active site density of precious metal-free catalysts in situ in fuel cells” Nat. Catal. 5 (2022) 163.
12. Y. Yang, C. R. Peltier, R. Zeng, R. Schimmenti, Q. Li, Xin Huang, Z. Yan, G. Potsi, R. Selhorst, X. Lu, W. Xu, M. Tader, A. V. Soudackov,
Ha. Zhang, M. Krumov, E. Murray, P. Xu, J. Hitt, L. Xu, H.-Y. Ko, B. G. Ernst, C. Bundschu, A. Luo, D. Markovich, M. Hu, C. He, H. Wang, J.
Fang, R. A. DiStasio Jr., L. F. Kourkoutis, A. Singer, K. J. T. Noonan, L. Xiao, L. Zhuang, B. S. Pivovar, P. Zelenay, E. Herrero, J. M. Feliu, J.
Suntivich, E. P. Giannelis, S. Hammes-Schiffer, T. Arias, M. Mavrikakis, T. E. Mallouk, J. D. Brock, D. A. Muller, F. J. DiSalvo, G. W. Coates,
and H D. Abruña, “Electrocatalysis in Alkaline Media and Alkaline Membrane-Based Energy Technologies” Chem. Rev., 122 (2022) 6117.
13. S. Akula, M. Mooste, B. Zulevi, S. McKinney, A. Kikas, H.-M. Piirsoo, M. Rähn, A. Tamm, V. Kisand, A. Serov, E.B Creel, D. A. Cullen, K. C.
Neyerlin, H. Wang, M. Odgaard, T. Reshetenko, and K. Tammeveski, “Mesoporous textured Fe-NC electrocatalysts as highly efficient
cathodes for proton exchange membrane fuel cells” J. Power Sources 520 (2022) 230819.
14. Q. Li, A. M. Villarino, C. R. Peltier, A. J. Macbeth, Y. Yang, M. J. Kim, Z. Shi, M. R Krumov, C. Lei, G. G Rodríguez-Calero, J. Soto, S. H. Yu,
P. F. Mutolo, L. Xiao, L. Zhuang, D. A. Muller, G. W. Coates, P. Zelenay, H. D. Abruña, “Anion Exchange Membrane Water Electrolysis: The
Future of Green Hydrogen” J. Phys. Chem. C. (2023); https://doi.org/10.1021/acs.jpcc.3c00319.

Presentations – since 2022 AMR presentation submission
1. 241st ECS Meeting, Vancouver, BC, Canada, May 29 – June 02, 2022. “La-Sr-Co Oxide Catalysts for Oxygen Evolution Reaction in Anion
Exchange Membrane Water Electrolyzers: The Role of Electrode Fabrication on Performance and Durability” L. Osmieri L., Y He, and P.
Zelenay (invited).
2. 241st ECS Meeting, Vancouver, BC, Canada, May 29 – June 02, 2022. “Towards Entirely Platinum Group Metal-Free Water Electrolyzers:
Innovative Electrocatalysts for Oxygen Evolution and Hydrogen Evolution Reactions” L. Osmieri and P. Zelenay (invited).
3. 241st ECS Meeting, Vancouver, BC, Canada, May 29 – June 02, 2022. “Nitric Oxide Probe Molecule Studies of Iron-Nitrogen-Carbon PEMFC
Oxygen Reduction Electrocatalysts”, D. Myers, M. Ferrandon, A. J. Kropf, P. Zelenay, H. Zhang, E.E. Alp, J. Hyung Park, and X. Wang.
4. 241st ECS Meeting, Vancouver, BC, Canada, May 29 – June 02, 2022. “Optimization of Synthesis Variables Towards Improved Activity and
Stability of Fe-N-C PGM-Free Catalysts”, X. Wang, M. Ferrandon, J. Park, E. C. Wegener, A. J. Kropf, and D. J. Myers.
5. 241st Meeting of the Electrochemical Society, Vancouver, Canada, May 29-June 2, 2022. “Effect of Nanostructure and Surface Chemistry on
Activity and Selectivity of Cu-Based Electrocatalysts for Carbon Dioxide Reduction;” D. J. Myers, M. Ferrandon, A. J. Kropf, P. Zelenay, H.
Zhang, E. E. Alp, J. H. Park, X. Wang.
6. 241st Meeting of the Electrochemical Society, Vancouver, Canada, May 29-June 2, 2022. “Effect of Nanostructure and Surface Chemistry on
Activity and Selectivity of Cu-Based Electrocatalysts for Carbon Dioxide Reduction;” Y. He, P. Zelenay (invited).
7. 3rd International Conference on Electrolysis (ICE 2021), Golden, Colorado, USA, June 19-23, 2022. “Catalyst Development and Electrode
Fabrication for Low-Temperature Water Electrolyzer Operating with Anion Exchange Membrane;” L. Osmieri, Y. He, H. Yu, D. A. Cullen, and P.
Zelenay.
8. 242nd Meeting of the Electrochemical Society, Atlanta, Georgia, October 9-13, 2022. “PGM-Free Catalysts and Electrodes for Anion Exchange
Membrane Water Electrolyzers;” L. Osmieri, Y. He, H. Yu, D. A. Cullen, and P. Zelenay.
9. 242nd Meeting of the Electrochemical Society, Atlanta, Georgia, October 9-13, 2022. “Platinum Group Metal-Free Oxygen Evolution
Electrocatalysts for Alkaline Water Electrolysis;” D.J. Myers, A.A. Farghaly, M. Ferrandon, A.J. Kropf, and D. Cullen.
10. 242nd Meeting of the Electrochemical Society, Atlanta, Georgia, October 9-13, 2022. “Metal Organic Framework-Based Alkaline Oxygen
Evolution Reaction Electrocatalysts: Morphology, Metal Loading, and Durability” A.A. Farghaly, D.A. Cullen, and D.J. Myers.

Presentations (continued)
11. 242nd Meeting of the Electrochemical Society, Atlanta, Georgia, October 9-13, 2022. “Redox Behavior and ORR Catalytic Activity of Fe-N-C
Electrocatalysts in Various Electrolytes and in the Presence of Probe Molecules”, X. Wang, J. Hyung Park, Y. Zeng, M. Ferrandon, G. Wu,
and D. Myers.
12. 242nd Meeting of the Electrochemical Society, Atlanta, Georgia, October 9-13, 2022. “Platinum Group Metal-Free ORR Catalysts for Anion
Exchange Membrane Fuel Cells;” H. Zhang, P. Zelenay.
13. 242nd Meeting of the Electrochemical Society, Atlanta, Georgia, October 9-13, 2022. “Redox Behavior and ORR Catalytic Activity of Fe-NC
Electrocatalysts in Various Electrolytes and in the Presence of Probe Molecules;” X. Wang, J. H. Park, M. Ferrandon, Y. Zeng, H. Zhang, G.
Wu, P. Zelenay, D. J. Myers.
14. 242nd Meeting of the Electrochemical Society, Atlanta, Georgia, October 9-13, 2022. “Exploring PGM-Free Oxygen Reduction Reaction
Active Sites By in Situ molecular Probes;” B. M. Ceballos and P. Zelenay.
15. MAT-SUS, Materials for Sustainable Development Conference, nanoGe Fall Meeting, Barcelona, Spain, October 24-28, 2022. “Atomically
Dispersed MNC Catalysts for Electrochemical Oxygen and Carbon Dioxide Reduction Reactions;” H. Zhang, Y. He, J. C. Weiss, P. Zelenay
(invited).
16. 5th Israeli Fuel Cell Consortium Workshop, Tel Aviv, Israel, November 14-16, 2022. “PGM-free Electrocatalysts for Hydrogen Production in
Low-Temperature Water Electrolyzers;” P. Zelenay (invited).
17. Platinum Group Metal and Platinum Group Metal-free Electrocatalysts: Catalyst/Ionomer Interactions, Telluride, Colorado, March 6-10, 2023.
“Models of Electrocatalysts and the Role of Electrocatalyst/Ionomers;” E. F. Holby (invited).
18. Telluride Science Research Center (TSRC) Workshop; Platinum Group Metal and Platinum Group Metal-free Electrocatalysts:
Catalyst/Ionomer Interactions, Telluride, Colorado, March 6-9, 2023. “PGM-free Electrocatalysts for Anion Exchange Membrane Water
Electrolyzers” L. Osmieri and P. Zelenay (invited).

Technology Transfer Activities
ElectroCat laboratories are actively engaged with industry both within and outside of the consortium partners
and seek to provide ElectroCat developed technology and knowledge to help the fuel-cell community.
Patents
J. Park and D. Myers, Electrode Ink Deposition System For High-throughput Polymer Electrolyte Fuel Cell,
United States Patent No. 11,581,547 16/425,04.7
Continuing License Agreement

License agreement between Los Alamos National Laboratory and Pajarito Powder, LLC for LANL-developed
non-PGM ORR catalysts (inventors: H. T. Chung and P. Zelenay); executed on February 1, 2016.

Reviewer-Only Slide

ElectroCat Status: PGM-free Catalysts in H2-Air Fuel Cells
H2-air fuel cell

Initial After 30k cycles1
Catalyst
i (mA/cm2) V (V) i (mA/cm2) V (V)
0.8 V 0.675 V 0.8 A cm-2 0.8 V 0.675 V 0.8 A cm-2
ANL Fe (N-C) 2021 AMR 55 340 0.56 9 122 0.44
ANL Fe (N-C) 2022 AMR (ML #9) 85 379 0.530 15 122 0.421
ANL Fe (N-C) 2022 AMR (ZIF-8-
88 354 0.516 16 158 0.453
coated ML #9)
LANL ‘Dual-Zone’ Fe-N-C 2021
31 181 0.32 24 170 0.32
AMR3
LANL H2-synthesized “Dual-Zone”
79 381 0.55 33 185 0.50
Fe-N-C 2022 AMR
LANL Fe-doped N-C 2023 AMR 92 0.372 45 0.3235
LANL (AD)Fe1.5-N-C 37 211 0.44 3 47 0.28
LANL CM-PANI-Fe-C(Zn)2,4 105 440 ~ 0.47 not cycled
1 AST cycles in air (0.2 bar partial pressure of O2), voltage range from 0.6 V to OCV-0.01 V
2 Non-differential conditions
3 After 80k AST cycles
4 No AST cycling performed
5 Voltage loss after 10,000 AST cycles

Fc160 Zelenay Myers 2023 o

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Fc160 Zelenay Myers 2023 o

Uploaded by

Copyright:

Available Formats

DOE Hydrogen Program

2023 Annual Merit Review and Peer Evaluation Meeting

Project ID: FC160

• Start date: Oct 1, 2020 Los Alamos National Laboratory

Budget Argonne National Laboratory

• FY23 funding total planned: $4M – Deborah Myers

2023 DOE Hydrogen Program Annual Merit Review – Slide 2

2023 DOE Hydrogen Program Annual Merit Review – Slide 3

Milestone Name/Description Criteria End Date Type Status

2023 DOE Hydrogen Program Annual Merit Review – Slide 4

Milestone Name/Description Criteria End Date Type Status

2023 DOE Hydrogen Program Annual Merit Review – Slide 5

Milestone Name/Description Criteria End Date Type Status

2023 DOE Hydrogen Program Annual Merit Review – Slide 6

Cathode: ca. 4.0 mg cm-2, FY21/22/23 Fe-N-C catalyst, 1700 sccm,

Current density (mA cm-2)

2023 DOE Hydrogen Program Annual Merit Review – Slide 7

2023 DOE Hydrogen Program Annual Merit Review – Slide 8

Highlight: Developed a new type

• Highlight: Soft-template synthesis of Fe-N-C

• Soft-template synthesis with micelle templates

2023 DOE Hydrogen Program Annual Merit Review – Slide 9

2023 DOE Hydrogen Program Annual Merit Review – Slide 10

Search space involves ~ 1011

2023 DOE Hydrogen Program Annual Merit Review – Slide 11

a Furnace closed b Furnace open Pearson

2023 DOE Hydrogen Program Annual Merit Review – Slide 12

Mass activity (mA/mg)

2023 DOE Hydrogen Program Annual Merit Review – Slide 13

Mass activity (mA/mg)

Ball milling pyrolysis at 1050 °C, 10 °C/min 2h

Fe3C 0.4% Fe 20 0.4

ORR activity at 0.8 V (mA/mg)

2023 DOE Hydrogen Program Annual Merit Review – Slide 14

Mass activity at 0.8V (mA/mg)

Activty/Stability Boost (%)

 ML#9 chosen due to balance of activity 10 40

ORR #1 ORR#2 Activity Boost Stability Boost

2023 DOE Hydrogen Program Annual Merit Review – Slide 15

• A 2D model system enables

2023 DOE Hydrogen Program Annual Merit Review – Slide 16

Highlight: Demonstrated MN4C12 and μ-nitrido (MN4C10-N-MN4C10) CoN4C10@zig-zag edge

2023 DOE Hydrogen Program Annual Merit Review – Slide 17

2023 DOE Hydrogen Program Annual Merit Review – Slide 18

Stagnant O2-saturated electrolytes

• Voltammetry shows quick and complete in HClO4_1st

• Results indicate that sulfate/bisulfate anions

• ORR occurs at higher potentials in H2SO4 than in HClO4

Highlight: Sulfate or bisulfate anions suppress Fe3+ reduction, enhance

2023 DOE Hydrogen Program Annual Merit Review – Slide 19

2023 DOE Hydrogen Program Annual Merit Review – Slide 20

2023 DOE Hydrogen Program Annual Merit Review – Slide 21

Developed a new flow cell comprised of

• FY23 Q1 QPM: Fabrication of multi-channel flow cell

Electrolyte flow simulation

2023 DOE Hydrogen Program Annual Merit Review – Slide 22

PGM-free OER and HER Electrocatalysts

2023 DOE Hydrogen Program Annual Merit Review – Slide 23

Milestone Name/Description Criteria End Date Type Status

Focused ion beam cross-section Demonstrate direct imaging of electrode/PTL Completed

2023 DOE Hydrogen Program Annual Merit Review – Slide 24

Milestone Name/Description Criteria End Date Type Status

2023 DOE Hydrogen Program Annual Merit Review – Slide 25

Milestone Name/Description Criteria End Date Type Status