23rd International Symposium on Transport Phenomena

Auckland, New Zealand

1922 November 2012

Multi-scale Transport Phenomena Simulations in Fuel Cells Design

C.W. Hong1*, H.S. Liou1, C.H. Cheng2 and K. Fei2

1
Department of Power Mechanical Engineering
National Tsing Hua University, Hsinchu 30013, Taiwan
2
Renewable Energy R&D Center
Chung-Hsin Electric & Machinery MFG Corp., Taoyuan, Taiwan
*cwhong@pme.nthu.edu.tw

Abstract

This paper presents some design simulation techniques on the

multi-scale transport phenomena inside low temperature fuel
cells, such as proton membrane exchange fuel cells (PEMFCs),
direct methanol fuel cells (DMFCs), and high temperature solid
oxide fuel cells (SOFCs). Computational techniques integrate
quantum mechanics, molecular dynamics, lattice Boltzmann
dynamics, computational fluid dynamics, and system dynamics
into one design tool to study the transport phenomena inside
electrolytes, diffusion layers, flow channels and fuel cell stack
systems. This multi-scale simulation tool is capable of screening
conceptual design ideas, from nano-scale materials to meso-scale
components to the macro-scale fuel cell stack, before a prototype
is fabricated. It can be applied to the renewable energy industry
for both performance improvement and new system design.

Introduction Figure 1. Computational multi-scale transport phenomena

This paper is a review of the multi-scale simulation and design of
various fuel cells (both low temperature and high temperature
fuel cells) carried out in the Green Energy & Molecular
Engineering Lab in the National Tsing Hua University in the past
25 years. All the figures are extracted from previously published
journal papers by the corresponding author and his research team
in references [1-20] and many other keynote speeches.
Fuel cells have been recognized as the most promising green
power generator provided that fuels (such as hydrogen, methanol
and some other hydrocarbon gases) are produced in a green way.
This paper reviews some techniques and fundamental theories
developed in our Green Energy & Molecular Engineering to
design the fuel cell stack system, from powder to power and from
quantum to system. We start from the electrolyte materials design,
mainly on the low temperature proton exchange membranes and
high temperature solid oxide ceramics, based on the molecular
dynamics (MD) technique. Subsequently we need the quantum
mechanics technique to set up the molecular structure and also to
evaluate the potential functions between each atom. The
computational quantum mechanics (CQM) technique is
employed to deal with the catalytic process which plays the
major role to promote the electrochemical reaction. When we
deal with the porous catalyst layers and diffusion layers in the
cell assembly, it comes out the meso-scale transport phenomenon,
which can be simulated by the lattice Boltzmann modelling
(LBM) from the academic viewpoint. Computational fluid
dynamics (CFD) plus electrochemistry are employed to predict
the fuel cell I-V performance. Figure 1 shows the schematic flow
chart of the computational multi-scale transport phenomena
simulation of fuel cells design via integration of quantum
mechanics, molecular dynamics, and computational fluid
dynamics with mass transfer plus electrochemistry.
simulation of fuel cells design via integration of quantum
mechanics, molecular dynamics, and computational fluid
dynamics with mass transfer plus electrochemistry
Fundamental theory
Computational multi-scale transport phenomena simulation starts
from the single electron flow simulation, which is described by
the Schrodinger equation as
r
h2 2 r ih (r , t )
2 + V (r , t ) = 2
(1)
8 m t
where is the wavefunction, m is the mass of the electron, h is
the Plancks constant, and V is the potential field. For a multi-
electron flow, which is the realist case, we prefer to use density
functional theory (DFT) to solve the electron density instead of
r
the wavefunction. For a system of n electrons, (r ) represents
r
the total electron density at a particular position r in space.
(2)
The electronic energy, denoted by E[], is considered as a
functional of the electron density. There is a single corresponding
r
electronic energy E[] for a given function (r ) . The
approximate functional E[] can be partitioned into four
components as shown below:
E[] = ET [] + EV [] + EJ [] + EXC[] (3)
where ET indicates the kinetic energy term resulting from
electron motion; EV describes the potential energy of the nuclear-
electron attraction and the repulsion between pairs of nuclei; EJ is
the electron-electron repulsion; and EXC represents the exchange- distribution which makes the most stable structure at the
correlation term which includes the remaining part of the minimum energy as shown in Figure 3. In the catalyst layer, the
electron-electron interactions. oxygen reduction and the proton transfer take place here, which
is a nano-scale reaction. Figure 4 shows the quantum simulation
The density functional theory can be employed to calculate the of the catalytic reaction.
charge distribution of each atom and the potential function
between atoms or molecules. When the molecular structure is
optimized and stabilized, we can employ some semi-empirical
potential functions to replace the time-consuming quantum
computation. This is called molecular dynamics, which treats all
atoms as particles with mass and hence within the range of
Newtonian dynamics. The molecular dynamics technique is
based on the Newtons 2nd law and the Hamiltonian dynamics.
The potential function employed can be described as below:

U total = U int er + U int ra + KE (4)

U int er = U VDW + U elec (5)

U int ra = U bond + U angle + U dihedral (6)
Figure 2. Charge distribution of a model Nafion fragment [1]
When we deal with the micro-channel problem or porous
medium flow, we can treat them as a meso-scale transport
phenomenon simulation (Knudson number Kn>1). The Lattice
Boltzmann modelling (LBM) can be applied in this flow regime.
The general form of the lattice-Boltzmann equation can be
expressed by:
1
f i ( X + e i t , t + t) f i ( X , t ) = [ f i ( X , t ) f i ( eq ) ( X , t )] (7)

where f(X, t) is the distribution function which is a function of
the position vector X and time t. ei is the lattice velocity vector in
the i direction. The superscript eq refers to the equilibrium state
and is the dimensionless collision time. Figure 3. Molecular structure of the model Nafion fragment used
For macro-scale transport phenomena taken place at the manifold in the molecular simulation (F: fluorine; C: carbon; S: sulfur; O2:
and flow channels (including some porous media) in the fuel cell ether-like oxygen atoms in the side chain; O3: oxygen atoms in
stack design, we can use the fundamental laws in the the sulfonic-acid group) [2]
computational fluid dynamics which are expressed by the mass
continuity, momentum transport, species transport, and energy
conservation equations, respectively.
r
+ ( V ) = 0
t (8)
r
V r r v
+ V V = f B
t (9)
i r
+ ( iV Di i ) = mi
t (10)
T r
c v + c v V T ( k T ) = 2 C 2 + q B
t (11)
r Figure 4. Simulation of the O2 reduction and the proton transfer
In which is the density; V is the velocity vector; is the stress process of the first hydronium ion approaches the Pt cluster [3]
r
tensor; f B is the body force; i is the density ratio of specie i
w.r.t. bulk; Di is the mass diffusion coefficient for specie i; m is
the mass generation rate; cv is the specific heat at constant
volume; T is temperature; k is the heat conductivity; is the fluid
viscosity; C is the shear rate; qB is the specific rate of heat
generation per unit volume. In which heat conductivity and fluid
viscosity can be calculated from the molecular dynamics, if a
novel material is designed before fabrication.

Multi-scale simulations
Quantum Simulation (Quantum Scale)
In order to set up the most stable structure of a polymer
membrane, we need to calculate the charge distribution of an
example Nafion model. We can use a semi-empirical quantum
model (e.g. AM1) or the detailed DFT model to calculate the
electron cloud distribution. Figure 2 shows the charge
Figure 5. Snapshots of the Nafion membrane morphology and
hydronium transport ((light blue balls are hydroniums) from the
MD simulation [4]
Figure 6. Schematic diagram of the initial doped ceria (or
zirconia) structure. The Ce4+ (or Zr4+) ions were assigned to the
positions according to the FCC lattice; some of the ions were
randomly substituted by Sm3+ (or Gd3+ or Y3+) ions. The
oxygen ions were assigned to the center surrounded by the Ce (or
Zr) tetrahedron; and some of them were randomly substituted by
vacancies [5]
Figure 7. (a) Density field diagram at each instant of the bubble
flow in the micro-channel (0.1 1.0 g/cm3); (b) corresponding
temperature distribution diagram (simulation conditions are set at
inlet velocity: 250 lm/s; inlet temperature 298 K; outlet
temperature 333 K; the wall temperature varies from 298 to 333
K linearly from the inlet to the exit); (c) an enlarged view of the
velocity vectors superimposed on the bubble density diagram [6]
Molecular Dynamics Simulation (Nano Scale)
The ionic conduction properties of the membrane are closely
related to the internal structure such as the spatial distribution of
ionic sites in the membrane. The snapshots of the membrane
morphology from the MD simulation can be seen in Figure 5.
The hydrated Nafion membrane forms the phase separation in the
hydrophobic and hydrophilic parts. The hydrophobic region is
constituted by the backbone (green cloud) of the polymer, while
the hydrophilic region contains water molecules (gray cloud),
hydronium ions (light blue balls) and sulfonic-acid groups
(yellow and red balls).
Another case is the high temperature fuel cell, such as an SOFC,
which uses different solid structure electrolyte. Figure 6 shows
the schematic diagram of the initial doped ceria (or zirconium)
structure. The Ce4+ (or Zr4+) ions were assigned to the positions
according to the FCC (face centered cubic) lattice; some of the
ions were randomly substituted by Sm3+ (or Gd3+ or Y3+) ions.
The oxygen ions were assigned to the center surrounded by the
Ce (or Zr) tetrahedron; and some of them were randomly
substituted by vacancies. This basic principle and molecular
structure generate the oxygen ion flow across the ceramic
electrolyte and can be visualized from the MD simulation results.
Lattice Boltzmann Simulation (Meso Scale)
When we deal with the porous medium region (catalyst layer and
diffusion layer) or microchannel flow in the flow channels of the
fuel cells (e.g., at the anode of a micro DMFC), it is a two-phase
flow with gas (CO2) and liquid (CH3OH) phases. Figure 7 shows
the density field diagram at each instant of the bubble flow in the
micro-channel (0.1 1.0 g/cm3). The corresponding temperature
distribution diagram (simulation conditions are set at inlet
velocity: 250 lm/s; inlet temperature 298 K; outlet temperature
333 K; the wall temperature varies from 298 to 333 K linearly
from the inlet to the exit) is also displayed. An enlarged view of
the velocity vectors superimposed on the bubble density diagram
shows the detailed flow field within the bubble itself.
Computational Fluid Dynamics Simulation (Macro Scale)
The fuel cell stack design is an excise in macro-scale, which uses
computer aided design package incorporated with a
computational fluid dynamics simulation. Figures 8 and 9 show
that at different flow channel designs (e.g., co-flow, counter-flow,
and cross-flow) in a single cell SOFC, the velocity field,
concentration field, and temperature distribution all show
different characteristics.
Figure 9 shows the most important temperature distribution of the
solid electrolyte. The co-flow design generates a hot area near the
outlet portion, and the max temperature difference is 33 K. The
counter-flow design has a uniform temperature gradient with a
larger temperature difference of 55 K from the inlet to the outlet.
The cross-flow design has the most non-uniform temperature
distribution, and the hot spot is at the corner. We can conclude at
this stage that flow channel configuration has significant
influence on the control of macroscopic temperature distribution
and co-flow design provides the most uniform temperature
distribution for this example YSZ (Yttria stabilized Zirconia)
electrolyte.
Figure 10 shows an example design of a 5-cell SOFC stack,
which includes a hydrogen inlet pipe and an air preheat chamber
with pipes as well. The pressure, velocity, concentration, and
temperature fields can be predicted using the CFD technique.
Figure 11 shows the current density distribution generated at the
electrode surface of the anode and the cathode in the 5-cell stack.
The current can be collected in all 5-cells and the I-V
performance can be calculated and compared with an experiment,
which was conducted on an YSZ SOFC.
Figure 12 shows that the prediction agrees reasonably with the
experiment and if we use SDC (Sm doped Ce) electrolyte to
replace the traditional YSZ, the power density at the same current
can be increased by 33% at the same temperature (873K).
Although YSZ can also achieve a good performance at higher
temperature, we prefer the low (or intermediate) temperature
electrolytes to prevent thermal loading and also to reduce the
start up lag due to high working temperature.
Figure 8. Flow velocity field, concentration field, and
temperature distribution of a co-flow channel design SOFC stack

Figure 10. Grid generation and pressure distribution diagrams of

a 5-cell SOFC stack, including the hydrogen inlet pipe and the air
preheat chamber [8]

Figure 9. Temperature distribution of the electrolyte at (a) co-

flow, (b) counter-flow, and (c) cross-flow designs in an SOFC [7]
Figure 11. Current density contours at the electrode surface of (a)
anode and (b) cathode in the 5-cell stack [8]
 Figure 14. Bond graph of the electrochemical reaction and the
electrical system of the PEMFC [9]

Figure 12. Comparison of the voltage-current density and power-

current density diagrams from multi-scale simulation and from an
experimental measurement [8]

System Dynamics Simulation (System Scale)

Fuel cell systems alone cannot work, normally they are always
equipped with an air compressor, hydrogen supply, cooling
system and start up by a battery (and helped with super-
capacitors), and controlled by a central control unit., especially as
the power-plant for a electric vehicle. Figure 13 shows an
example fuel cell vehicle power-plant system. We can use a
unified bond graph approach to simulate the multi-disciplinary
system, which includes the electrochemical system, gas flow,
mechanical, electromagnetic systems.
Figure 14 shows a typical bond graph simulation of the
electrochemical reaction and the electric system of the PEMFC.
The effort and flow symbols are used to represent the electric
circuit analogy of the multi-domain system. Figure 15 shows the
start-up simulation (a step response) of: (a) the anode pressure, (b)
the cathode pressure, (c) the anode temperature, and (d) the
cathode temperature. This figure indicates that the PEMFC
system can start up in 2-3 seconds, but stabilized after 25 seconds. Figure 15. Start-up simulation a step response of: (a) the anode
A frequency response test of the PEMFC system can also be pressure, (b) the cathode pressure, (c) the anode temperature, and
studied. Figure 16 shows its Bode diagram result, which indicates (d) the cathode temperature [9]
that the bandwidth in this system is around 2 rad/s. That means a
supercapacitor is in need to accelerate the whole system for
vehicle acceleration purpose.

Figure 16. Bode diagram of frequency-response simulation of a

model PEMFC [9]
Figure 13. An example of a fuel cell vehicle power plant system
Conclusions
This paper summarizes the past research carried out at the Green
Energy & Molecular Engineering Lab, led by Prof. Che-Wun
Hong, on the various fuel cells design. We start from the
electrolyte materials design, mainly on the low temperature
proton exchange membranes and high temperature solid oxide
ceramics, based on the molecular dynamics technique.
Subsequently we need the quantum mechanics technique to set
up the molecular structure and also to evaluate the potential
functions between each atom. The computational quantum
mechanics technique using DFT theory has been employed to
deal with the catalytic process which plays the major role to
promote the electrochemical reaction. When we deal with the
porous catalyst layer and the diffusion layers in the fuel cells, it
comes out the meso-scale transport phenomenon, which can be
simulated by the lattice Boltzmann modelling due to the Knudson
number (Kn) is always greater than one in these cases. An
example has been given to the micro-channel flow in a DMFC.
This computational multi-scale transport phenomena simulation
of fuel cells design via integration of quantum mechanics,
molecular dynamics, and computational fluid dynamics with
mass transfer plus electrochemistry, has been carried out to
predict the final I-V, I-P performance of a 5-cell SOFC stack as
an example. The prediction has been proved to agree with the
experimental measurement conducted on the same stack. A
system dynamics simulation, using bond graph approach, to show
the step response and frequency response of the PEMFC has been
demonstrated. All examples show that this multi-scale technique
is a versatile and feasible technology to further improve the fuel
cell performance in the near future.
Acknowledgments
The authors are grateful to the financial support from the
National Science Council of Taiwan and the Chung-Hsin
Electric & Machinery MFG Corp under Contract No. NSC
101-2622-E-007-005-CC2 and NSC 101-2221-E-007-051-MY3.
The computer facilities provided by the National Center for
High-Performance Computing is also acknowledged.
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