Electrical Generation from Fuel Cells Systems: A

Multiscale Modeling Approach.

Diana C. Orozco-Gallo, PhD.

Dr. Thomas A. Zawodzinski
Advisor
The University of Tennessee - Knoxville
IV CONGRESO INTERNACIONAL DE INNOVACIÓN Y
TECNOLOGÍA - CAMBIO CLIMÁTICO
UNIMINUTO
November 1st – 2nd , 2018
Introductio to Fuel Cells
 Adjustable power
 Clean energy
 Hydrogen as fuel

x Slow cathode
kinetics
x High catalyst costs
x Durability

DOE, 2017 2
 ¿Why hydrogen?
Multiple sources Three times more energy per
mass!!

DOE, 2017

Multiples apications
3
 Fuel Cells Types

Type Ion Temperature Aplication

Alkaline (AFC) OH- 50-200°C Space ships

Proton Exchange
H+ 30-100°C Automovile
Membrane (PEMFC)
Direct Methanol
H+ 20-90°C Low power systems
(DMFC)
Combined heat and
Phosphoric Acid
H+ ~200°C power systems (CHP)
(PAFC)
200-kW
Molten Carbonate CO32- CHP medium to large,
~650°C
(MCFC) MW
CHP multiple capacity
Solid Oxide (SOFC) O2- 500-1000°C
(2-kW a multi-MW)

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 Fuel Cells Systems

DOE, 2017

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 Fuel Cell Costs

DOE, 2017

Portable units prices are $15.000.00 for 1kW installed

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Why is fuel cell modelling a complicated task?

Macroscopic Fuel Cell Behavior

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 MULTIPLE SCALES AND
METHODOLOGIES CONSIDERED HERE
• Macroscale: 1D MODELING – Finite differences
* Solid Acid Fuel Cells Performance (SAFCs)
* NPMCs PEM Fuel Cells Performance
• Microscale: Density Functional Theory
* Pp/FePp comparison with Pt
• Mesoscale: Molecular Dynamics
* Structural information of FePp system

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Macrohomogeneous Modeling (1D)
NPMCs
Problem to be solved:

• Describing the main parameters

• Identifying main losses: activation, ohmic and
concentration

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 Description of the catalyst in PEMFC
Pt-based
Pt(111), Pt(211)
OH
Most active facets
Adsorption
OOH site
Adsorption
site
ORR: 2e- and 4e- reaction mechanism
Non-Precious Metal - Based

Iron porphyrin

Before pyrolysis
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 How to identify parameters?

Parameter Approach
required
δCL, Catalyst layer MEA with different
thickness loadings
b, Tafel Slope Simultaneous fitting*
Ari*, RCCD, Fitting parameter
roughness corrected i0
pO2, Oxygen partial O2 and Air
pressure
DC*, Permeability Fitting parameter
(Springer, et al., 1993)
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 Results: Macroscopic model

The performance decreases around 66% and 50% with oxygen dilution, for 1mg and
3mg respectively as consequence of the poor catalytic activity mass transport
limitations 12
Results: Overpotential analysis
S. Arisetty, et al., ECS
Transactions, 41 (2011) 797-809

• Activation losses driven system

• Our overpotential values are twice bigger
compare to Pt-based system
• Not an active material towards ORR
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 Microscopic approach

Problems to be solved:

• ORR behavior for Fe/Pp/FePp

• Activity of Fe/Pp/FePp compare to Pt

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 ORR Reaction Pathways
k1(+4e-)
Griffith
O OH 4e-
MZ MZ+2 MZ +2H2O
diff k2(+2e-) k3(+2e-) O 2H+ OH 4H+
O2 (b) O2* H2O2 (a) H2O Pathway I
k-2(-2e-) Peroxide
Pathway IIA
Pauling
2e- Mz +2H2O2
k4 k6 k5 MZ O +1MZ
O +2Mz O
2H+
Direct 4e-
MZ +O2 O O- O-2 4e- Pathway IIB
4H+ Mz +2H2O
Pathway II
H2O2 *
Bridge
MZ
diff O MZ+1 OH 4e-
2MZ +2H2O
O 2H+ MZ+1 OH 4H+
MZ
H2O2 (b) Pathway III

Adsorption Models for O2 and its

Schematic representation of two and four
electrons oxygen reduction reaction mechanism reaction pathway in acid
from Yeager and Adzic approaches electrolytes

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 Oxygen Reduction Reaction
Overall 4e- Reaction ORR Gibbs Energies

Couple four proton-electron

transfers

Simplified Model System

Fundamental Concepts in Heterogenous Catalysis. Norskov, 2014 16

 How are our modeling systems?

Functionals:
PBE
Pseudopotentials:
Norm Conserving PP
Number of atoms:
Pt: 27
Fe: 18
Porphyrin: 26
Fe Porphyrin:25
Pt(111) Fe(111) Porphyrin Fe Porphyrin
Software:
Kinetic Energy Cutoff [Ry] 40 38 38 32 Quantum Espresso
k-points 9x9x9 9x9x9 7x7x7 9x9x9

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 Activation Energies: Iron Porphyrin

• O-Fe bond is weak and the • All the hydrogen bond • H is attracted by the N
OH-H bond breaking breaking occurs on surrounding the
occurs when H is adsorbed Fe. porphyrin center
into Fe. • Oxygen tends to be
desorbed
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 How is Pp and FePp electro catalysis compare to
Pt?
Fe has better
O2 Activation

Fe binds OH
strongly
FePp O2
Pp has activation no
similar O2 favorable ∆G>0
activation no
favorable
Favorable
∆G>0
reduction
steps

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 Scaling Relations and Volcano Plot for (111) Surfaces

Potential Potential
Determining Step Determining Step

• O2 Activation
• Strong OH process
binding energies • Weak surface
• Most difficult to oxygen bond,
remove it from difficult OOH
the surface formation

EOH* EO*
Pt 0.600 -0.700 0.310 0.95 1.61 -1.020 -2.280 -0.920 -0.700 • Phys. Chem. Chem. Phys. 13, 20760-20765. Wang,
S., et al., 2011.
Pp -0.209 -1.421 2.019 0.50 3.23 -1.468 -0.211 -2.989 -0.252
FePp 4.015 3.723 5.098 2.15 5.39 0.184 0.297 -3.497 -1.904 20
 What we learned from the microscale
study of NPMC
• Oxygen activation in Fe porphyrin is not favorable and its activity is
lower than the Porphyrin.
• The presence of the center metal does not imply that the activity will
inherit the metal activity.
• N-O and Fe-O bonding are weak and the bond breaking is promoted
by the N-H interaction.
• This methodology gives us important qualitative information about
the possibility of N-coordinated active sites as the reactive ones.
• Non-pyrolized materials activity is related t0 poor oxygen
activation on the catalytic surface.
• Further coverage dependent studies must be carried on to develop an
appropriate idea of the oxygen Porphyrin and iron center interaction.
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 Mesoscale approach

Problems to be solved:

• NPMCs Active sites final structure

identification
• Oxygen Transport to the active sites

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 Active site unknown: how to define?
Clues/suggestions from the literature
• EXAFS, Mossbauer Spectroscopy • XRD, Raman, XAFS, EXAFS, XPS,
Phys. Chem. Chem. Phys. 16, 13654-13661. C. E. Szakacs, et al., 2014. Fuel, 99, 106. F. Vallejos-Burgos, et al., 2012.

Microstructure Microstructure destruction,

formation Metallic structures

Micropores
Concentration of
sites
4N 5N
5/7 Active
structures

• XPS, XAS, EXAFS, XANES

J. Phys. Chem. C, 118(17), 8999-9008. Mukerjee, et al., 2014

FeNx Moieties and Fe

NPs as active sites How to put all this
information together? 23
 Identifying structures of active sites: Cu-TrPc

Cu
XRD Perfusion Calorimetry

Evidence of structural changes and

ECS Electrochem. Lett. 2014 3(11), G. A. Goenaga et al., 2016
multiple sites with pyrolysis
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Identifying structures of active sites: FePp

XRD SEM

N.M. Cantillo, et al., Journal of Materials Chemistry A, 4 (2016) 15621-15630.

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 Results: Mesoscale Model
Single Iron Porphyrin Molecule How to fill the gap between macroscopic, microscopic and nanoscale
modeling for NPMCs?
• Potential parameters:
MM2, corrected for Iron
Porphyrins (J. Chem.
Soc., Faraday Trans.,
1995,91, 1741-1749,
Marques et. al, 1995)
• Software: LAMMPS
C N Fe
Iron Porphyrin System
Modeling parameteres
ρbulk=2.009 g/cm3
ρsolid,exp=1.1210 g/cm3
ρsolid,cal=1.1218 g/cm3
ε=0.44
Fe=5%
r0=2.84 Å
Number molecules:125
Number atoms:3125 26
 What we learned from the microscale
study of NPMC
• Mesoscale modeling combined with experimental results showed evidence of
both porosity formation and multiple active sites.
• From the calorimetry results, we revealed the presence of at least two types of
adsorption sites. One of these is exothermic and one is endothermic towards
oxygen adsorption.
• XRD results also showed the creation of metal particles and metal oxides for both
catalyst studies in this section.
• Iron Porphyrin as a single molecule and as a system was represented through
MD simulations.
• The final density reaches the experimental value and the Fe-C distances are
reproduced with great accuracy.
• The presence of Fe(110) was not accurate and this is likely a result of the
potential employed in this approach.
• Further studies to find reactive potentials (ReaxFF) are necessary to elucidate
and validate the radial distribution functions obtained in this study. 27
What we learned for NPMCs

Fuel cell low performance is

due to higher activation
overpotentials. Double Tafel
slopes represent two active
sites with different surface
coverage

Fe Porphyrin was emulated and the

Porphyrin and Fe Fe radial distribution was capable
Porphyrin had poor oxygen to describe the C-Fe interactions
activation and OOH* but Fe-Fe interactions are not well
stabilization. Fe Porphyrin captured. To describe the structural
is not active towards ORR. changes as a function of
O-O bond breaking seems temperature it is necessary to
to be a consequence of H-N develop a ReaxFF
interactions.
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 Acknowledgments
 My advisor Dr. Thomas A. Zawodzinski
 Dr. Alex B. Papandrew
 My committee members Dr. Steve Abel, Dr. Siris Laursen, and Dr. Haixuan Xu
 Dr. Nelly Cantillo
 Dr. Gabriel Goenaga
 Dr. Jamie Lawton
 Dr. Shengqian Ma- USF
 Dr. Marshall McDonell, Dr. Nick McNutt, Dr. David Keffer and Dr. Haixuan Xu
 The National Institute for Computational Sciences, NSF grant 1137097— Beacon Project—, the
Newton HPC program at the University of Tennessee, and Extreme Science and Engineering
Discovery Environment (XSEDE), NSF ACI-1548562 for the computational resources.
 The NSF grant EPS-1004083–TN-SCORE—and COLCIENCIAS for funding.
 Colleagues Zawodzinski Group. David Wilson, Luke Severdio and Brian Fane.

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Electrical Generation from Fuel Cells Systems: A
Multiscale Modeling Approach.

Thanks for your attention!!

Diana C. Orozco-Gallo, PhD.
Dr. Thomas A. Zawodzinski
Advisor
The University of Tennessee - Knoxville
IV CONGRESO INTERNACIONAL DE INNOVACIÓN Y
TECNOLOGÍA - CAMBIO CLIMÁTICO
UNIMINUTO
November 1st – 2nd , 2018 31