ARTICLE IN PRESS

Energy 32 (2007) 269280

www.elsevier.com/locate/energy

Keynote Paper

Computational modelling of polymer electrolyte membrane (PEM) fuel

cells: Challenges and opportunities
N. Djilali
University of Victoria, Institute for Integrated Energy Systems & Department of Mechanical, Engineering, Victoria, BC, Canada V8W 3P6
Received 7 November 2005

Abstract

Fuel cells are still undergoing intense development, and the combination of new and optimized materials, improved product
development, novel architectures, more efcient transport processes, and design optimization and integration are expected to lead to
major gains in performance, efciency, reliability, manufacturability and cost-effectiveness. Computational fuel cell engineering (CFCE)
tools that allow systematic simulation, design and optimization of fuel cell systems would facilitate the integration of such advances,
allow less heavy reliance on hardware prototyping, and reduce development cycles.
CFCE requires the robust integration of models representing a variety of complex multi-physics transport processes characterized by a
broad spectrum of length and time scales. These processes include a fascinating, but not always well understood, array of phenomena
involving uidic, ionic, electronic and thermal transport in concert with electrochemical reactions. In this paper, we report on some
progress in both fundamental modelling of these phenomena, as well as in the development of integrated, computational uid dynamics
(CFD) based models for polymer electrolyte membrane (PEM) fuel cells. A new rational model for coupled protonic and water transport
in PEMS, as well direct numerical simulations of two-phase ow in porous gas diffusion electrodes are discussed. Illustrative applications
of CFD-based simulations are presented for conventional fuel cells and novel micro-structured fuel cells. The paper concludes with a
perspective on some of the remaining theoretical, experimental and numerical challenges to achieve truly functional CFCE tools.
r 2006 Elsevier Ltd. All rights reserved.

Keywords: Fuel cell; Transport phenomena; Two phase ow; Modelling; CFD; Polymer electrolyte membranes; Porous electrodes; Computational design;
Micro-fuel cell; Review

1. Introduction as supplied with a fuel. When fuelled by hydrogen, the only

by-products of a fuel cell are water and heat. In addition to
Fuel cells and hydrogen technologies offer a promising the important question surrounding the development of a
pathway towards sustainable energy systems. They offer hydrogen fuelling infrastructure discussed elsewhere [1], the
the prospect of low to zero emission power generation for main obstacles to the deployment and commercialization
subWatt to MWatt applications in transportation, heating, of polymer electrolyte membrane fuel cells (PEMFCs) are
manufacturing, and communication. However, many en- cost, durability, and performance [2]. In this paper we will
gineering and scientic obstacles (as well as economic and focus on the role of computational tools in addressing
socio-political ones) need to be surmounted before wide some of the technical challenges in the development of
spread adoption of these technologies becomes possible. better performance and affordable PEMFC technology,
The potential of fuel cells for clean and efcient energy the lead contender for replacing the ubiquitous battery and
conversion have long been recognized. Fuel cells are internal combustion engine.
adaptable, have a high theoretical efciency, and, unlike The overall operating principle of a PEMFC is relatively
batteries, they can produce electricity continuously as long simple. Hydrogen is fed to the cell and oxidized at the
anode, while oxygen, usually carried in an air feed stream,
Tel.: +1 250 721 6034; fax: +1 250 721 6323. is reduced at the cathode. The protons produced at the
E-mail address: ndjilali@uvic.ca. anode are conducted through the polymer electrolyte

0360-5442/$ - see front matter r 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.energy.2006.08.007
 ARTICLE IN PRESS
270 N. Djilali / Energy 32 (2007) 269280

Nomenclature S_ source term

s saturation
c molar concentration T Temperature
I, i current; current density u velocity
k permeability e porosity
F Faradays constant F potential
Np protonic ux m viscosity
Nl water ux r density
P pressure s conductivity; interfacial tension

membrane (PEM) to the cathode. Since the membrane is materials or designs. A particularly promising avenue is the
not electronically conductive, the electrons released at the use of micro-structured features [3] as will be discussed
anode have to ow along an external circuit, thereby later. In any case, it is rst necessary to identify the
generating useful electric power, and eventually recombine prevailing limitations and their location, and to understand
with the protons on the cathode side to produce water. their origin. In-situ measurements to obtain the relevant
These reactions and pathways are illustrated schematically information are exceedingly difcult due to the conned
in Fig. 1. and electrochemically active environment of fuel cells, the
Broadly speaking, improved performance in PEMFC complexity of the couplings, and the often transient nature
can be achieved by enhancing the rates of transport and/or of the processes. Rational models based on the funda-
reaction, and by increasing the surface/volume ratio of mental physico-chemical processes together with experi-
interfacial areas where reactions/transport take place. This mental observation are thus an essential tool to gain a
can be achieved by, e.g., engineering the transport proper- more complete understanding of the operation of a fuel
ties or processes in specic areas, or by introducing new cell. Coupling these models with modern computational
uid dynamics (CFD) and multi-disciplinary optimization
methods would allow the creation of powerful computa-
- + tional fuel cell engineering (CFCE) tools that could lead to
V
dramatic reductions in lead times and development costs,
and spur innovative design.
Membrane
Electrode
While much progress has been made in recent years in
Assembly (MEA) CFD based modelling of fuel cells, truly functional and
predictive capabilities remain a challenge due to, amongst
Electrode
others factors:

Anode Cathode
 lack of sufciently general models for ionic and water
transport in polymer membranes;
 deciencies in models for two phase transport in porous
gas diffusion electrodes and gas ow channels;
O2 +4e-
 inadequate macroscopic modelling and resolution of
2H2
catalyst layers;
4e- +4H+ +4H+
2H2O
 limited data for material and transport parameters and
lack of in situ data for validation; and
 existence of a wide range of characteristic length and
time scales.

An excellent overview of the potential gains to be made

by theoretical modelling was recently provided in [4], and
many notable advances in CFD modelling of PEM fuel
Proton Exchange
cells have been made by several groups over the last few
Membrane (PEM)
years [59], and a thorough review was provided in 2004 in
Catalyst Layer [10]. Some representative contributions made since that
Gas Diffusion Layer(GDL) review include parallelized three-dimensional CFD model-
ling [1113]; parametric computational studies in conjunc-
Gas Channel Current Collector tion with experimental validation [14,15]; and develop-
ments addressing the important aspects of two-phase
Fig. 1. Schematic of a PEM fuel cell. transport [16,17] and catalyst layer modelling [18,19].
 ARTICLE IN PRESS
N. Djilali / Energy 32 (2007) 269280 271

A review of challenges and modelling issues in both low  The transport of heat away from the reaction site
and high temperature fuel cells, with particular attention to primarily through the solid matrix.
heat management, appeared recently [20]. In this paper, we  Condensation/evaporation and transport of liquid water
provide an overview focused primarily on recent progress and vapour.
made at the University of Victoria in addressing some of
the key transport phenomena issues and in the develop- Optimal tailoring of an effective electrode requires
ment of CFD based modelling strategies for PEMFCs. The balancing of often conicting requirements. On the
rst part of the paper focuses on fundamental modelling of cathode side for instance, the reaction is prone to mass
specic transport phenomena encountered in component transport limitations at high current densities, when
layers of the membrane electrode assembly (MEA). In the depletion of oxygen in the air stream becomes signicant.
second part, we discuss the integration of some of these This can be further compounded by ooding of the
sub-models into multi-dimensional CFD codes and illus- electrode pores by the product water and blocking of
trate their application in plate and frame unit cells as well pathways for oxygen transport to the reaction sites.
as in novel micro-structured designs. The paper closes with Effective removal of excess water is thus essential, but
a perspective on some of the remaining challenges. must be balanced against the need to prevent drying of the
adjacent proton conducting media (membrane), which not
2. Transport phenomena in PEMFCS only causes deterioration in protonic conductivity (and
thus higher ohmic losses and lower efciency), but also
The cathode side of the MEA, shown schematically in impacts durability.
Fig. 2, provides a good illustration of the complex interplay Computational design of fuel cells with effective reactant
between various transport phenomena. The MEA consists distribution, optimized structures and proper heat and
of a proton exchange membrane sandwiched between water management, requires understanding of the various
catalyst and gas diffusion layers (GDL), with the latter two transport processes in each of the components, the
components essentially forming the electrode. This elec- development of physically representative models for these
trode is a buffer zone that facilitates a number of processes: processes, and, nally, proper coupling of the models.

 The conduction of electrons between the current 2.1. Polymer electrolyte membranes
collectors and the reaction sites.
 The conduction of protons between the membrane and Polymer electrolyte membranes (PEM) provide the key
catalyst layer. functions of conducting protons from anode to cathode,
 The transport of the reactants to the catalyst layer. and of preventing reactant crossover. These membranes
consist of microphase-separated structures, comprising
Proton Carbon hydrophobic polymer chains (PTFE/Teon) and hydro-
Electrically
Conducting Supported philic sulfonic acid groups. A thorough review of transport
Conductive
Media Catalyst phenomena in PEM was recently provided in [21]. The
Fibers
protonic conductivity characteristics of a PEM are strongly
e- dependent on the membrane hydration given in terms of l
(number of sorbed waters per sulfonate head). Excess
HO2 protons in bulk water are primarily in the form of
hydronium ions (H3O+), and higher complexes such as
O2 Eigen ion (H9O4)+ may also participate. A phenomenon
closely linked to membrane conductivity is electro-osmotic
drag (EOD), the process whereby a given number of water
molecules associated with a proton are dragged as the
proton migrates from anode to cathode. This EOD
H+ mechanism plays a major role in determining overall water
balance.
The breadth of PEM transport models proposed to date
ranges from molecular dynamics simulations and statistical
mechanics models, to empirical macroscopic models as
illustrated in Fig. 3. Our focus is on the development of
macroscopic models required for computational simula-
tions of complete fuel cells. The most widely used model to
PEM Catalyst GDL
date for determining membrane conductivity in large scale
Layer
fuel cell models is due to Springer, Zawodzinski and
Fig. 2. Transport of reactants, charged species and products in a PEMFC Gottesfeld [22]. This diffusion model has limited
cathode. predictive abilities as it relies on empirical correlations
 ARTICLE IN PRESS
272 N. Djilali / Energy 32 (2007) 269280

AC impedance conductivity measurements. The BFM2 has

a number of features that make it promising. The model:

 relies on rationally derived transport equations based on

the physics of multi-component transport in the
membrane;
 is not restricted by the assumption of equimolar counter
diffusion;
 accounts for the effect of temperature on the sorption
isotherm;
 is not restricted to Naon, but applies to the entire
family of peruoro-sulfonated membrane.

Fig. 3. Classication of transport models for proton exchange mem- Fig. 4 illustrates the enhanced capabilities of the BFM2
branes.
model in capturing the variation of the conductivity for all
water contents. Fig. 5 illustrates the predicted water
crossover coefcient WC N l I=2F . In the second
obtained for Naon membranes only [23,24], and in
part of this paper, the BFM2 is coupled to a fuel cell model
particular does not perform well under low humidication
and we will see that the resulting overpotentials and overall
conditions [23].
performance predicted by the BFM2 can, for some
A more fundamental and general approach to macro-
operating conditions, differ signicantly from those ob-
scopic modelling transport in membranes requires micro-
tained using the classical Springer model.
scopic consideration of the dominant interactions between
the aqueous system and the polymer and how they affect
the conductivity and transport properties. A general model 2.2. Gas diffusion electrodes
that considers such interactions based on the fundamentals
of multi-component diffusion was recently derived. This The gas diffusion layers (GDLs) consist of an aniso-
model proceeds from a generalization of the StefanMax- tropic brous structure, either in the form of a paper or a
well relations to a free solution in a membrane pore woven cloth, that allows distribution of reactant gases
structure [25]. Specializing this formulation to polymer through the porous matrix and collection of current
electrolyte membranes (specically peruorosulfonic acid through the bres (see Fig. 6). At higher current densities,
membranes) and expressing the electrochemical potential or when local water and heat management is inadequate,
gradient in terms of composition, activity, Gibbs free water condensation takes place leading to potential
energy, and electrical potential yields a general expression ooding within the GDL (and catalyst layer) as
that can be simplied through an order of magnitude discussed earlier. In order to remedy this, GDLs are
analysis [26]. Considering a limiting case scenario with a commonly treated with PTFE (Teon) to impart hydro-
pressure drop of order (5  105 N/m2) and a potential drop phobicity, and force water droplets to agglomerate at the
of order (0.3 V), shows that the dominant driving terms are free surface of the GDL. However, the hydrophilic Naon
the potential and mole fraction gradients, rFm and rX. in the catalyst layer will absorb and retain liquid water.
The resulting simplication and expressing X in terms of
membrane water content l yields the new Binary Friction 7
Membrane Model (BFM2) [26]:
6
" # " # nd
fDpp Dpw  rFm  ou
Conductivity (S/m)

Np 5 erb
pp
c . (1) U
Nw fDwp Dww rl d
4 un
r bo
we
Lo
The BFM2 provides a general constitutive relation 3
r
ge
coupling the protonic ux Np, which is proportional the Sp
rin Thampan
2
ionic current im, to the water ux Nw; c is the molar
concentration of water; f F/(RT), and Fm and l are the 1
membrane potential and water content. The coupling
between the protonic and water transport is through the
0 2 4 6 8 10 12
diagonal transport parameters Dpw and Dwp which are
(mol H2O / molSO3-)
considered to be functions of water content l and
temperature T. A feature of the model is that all Fig. 4. Calculated conductivity using BFM2 (solid) and models of
parameters can be obtained using a simplied version of Springer et al. [22] and Thampan et al. [24] against experimental data
the model obtained in the limit of conditions representing [27] for E-form Naon 117 (dashed bounds).
 ARTICLE IN PRESS
N. Djilali / Energy 32 (2007) 269280 273

Fig. 6. Microscope image depicting the random bre structure of a GDL

formed of Toray carbon paper.

degree on wettability, two-phase ow can exist in three

possible regimes [28].
In PEMFC electrodes, the capillary number (the ratio of
viscous forces to interfacial tension forces) is generally
small and liquid transport is dominated by capillary
diffusion. Extending classical relationships for the hydro-
dynamics of a single-phase in porous media to each phase,
the conservation equations for the gas and liquid phases
take the form [28]:
q1  sl rg
r  rg ug S_ g ,
qt
qsl rl
r  rl ul S_ l , 2
qt
where ug and ul are the gas and liquid phase supercial
Fig. 5. Comparison of water crossover (+ve from anode to cathode) for
velocities, 1  sl  and sl  in the left-hand sides represents
various cathode (la) and anode side (lc) water content boundary
conditions obtained with (a) Springer et al. membrane model; (b) BFM2. the volume of each phase, and S_ g and S_ l are volumetric
sources of gas and liquid.
Similarly, extending the single-phase momentum equa-
Thus, liquid water produced is transported from a tion to a two-phase system yields
saturated catalyst layer to the free surface of the GDL.
A major stumbling block in the reliability of two-phase kg
ug  rPg ,
models that attempt to account for liquid water transport mg
in GDLs is the necessity to rely on empirical correlations kl
and experimental observations obtained in soil and sand ul  rPl , 3
ml
samplesmedia with a structure that differs signicantly
from brous or woven GDLs. where rP is the pressure gradient, kg and kl are phase
The phase distribution in a porous media is potentially specic permeabilities, obtained by correcting the bulk
the result of viscous, capillary, and gravitational forces. permeability (k) for the effect of the reduced area open to
When modelling the diffusion layer of a PEMFC, the each phase due to the presence of the other phase. With ve
second (liquid) phase is taken to consist of a single variables sl ; ug ; ul ; Pg and Pl and only four equations, an
component, with transfer of water only across the phase additional relation is required to close the system. This can
boundary through evaporation/condensation. For porous be obtained by considering the key phenomenon of
media in which the void space is occupied by two-phases, capillarity associated with interfacial tension. The micro-
the bulk porosity e is divided between the liquid e1 and gas scopic capillary pressure is directly proportional to the
eg volume fractions, and the liquid saturation is dened as interfacial tension (s) and inversely proportional to the
s1 1 =. Depending on saturation, and also to some radius curvature of the interface (r), i.e. Pc / s=r.
 ARTICLE IN PRESS
274 N. Djilali / Energy 32 (2007) 269280

Low Capillary Pressure with the capillary diffusivity dened as

Low Non-wetting Pressure  
kl dPc
r1
Dsl . (6)
ml dsl

Pnw = Pw+PC Eqs. (4) are the basis of the most general multi-uid
formulation used so far in complete fuel cell models [29],
Pc /r
and a hierarchy of simplications, ranging from the
r1 > r2 mixture model [30] to simple porosity correction schemes
unw
Pnw, 2 > Pnw, 1 have been proposed [28]. One of the central problems in all
models of two-phase transport in GDLs is the determina-
tion of a constitutive relation for capillary pressure as a
function of saturation, the expected general form of which
is illustrated in Fig. 8. The prescription of the constitutive
r2 relation has so far relied on the so-called Leverett J-
function, specically in the form proposed by Udell [31]:
 
High Capillary Pressure Pc k 1=2
Js , (7)
High Non-wetting Pressure s 
Wetting Phase (Gas in GDL) with
Non-wetting Phase (Liquid Water in GDL)
Js 1:4171  s  2:1201  s2 1:2631  s3 . (8)
Fig. 7. Schematic of capillary diffusion, in which the liquid is the non- This is then used to compute the capillary pressure in
wetting phase. conjunction with the contact angle y
s cosy
A schematic illustration of capillary motion in a pore is Pc Js (9)
shown in Fig. 7. At the end of the pore where the liquid k=1=2
radius is smaller (lower local saturation), the capillary and in turn to determine the capillary diffusivity.
pressure is greater than at the end with the larger liquid There are a number of issues with Udells relation [28],
radius (greater local saturation). Because the liquid not the least of which is that the experimental data upon
pressure is the sum of the capillary pressure and the gas which it is based was obtained in porous samples of soils,
pressure Pc Pl  Pg , the hydrodynamic pressure of the which have a radically different structure from brous
liquid is greater at the end of the pore with the smaller media used in GDLs.
radius. Therefore, the bulk motion of the liquid is toward Another key issue in the application of two-phase
the end with the greater radius (and local saturation). The transport models is the determination of the phase specic
transport of liquid water from low to high saturation, as permeabilities. These must be corrected for the volume
shown in Fig. 7, is counter-intuitive, and illustrates the fractions occupied by different phases. One of the
tendency for water, in hydrophobic media such as those
used for gas diffusion layers, to move to ever-increasing
pore diameters according to the capillary pressures inverse
proportionality to the liquid radius. This analysis will be
instructive in the subsequent interpretation of visualiza-
tions and simulations of ow between the bres that make
up the structure of a GDL.
Introducing the denition of macroscopic capillary
Capillary Pressure

pressure into the momentum equations yields:

kg
ug  rPg ,
mg
kl kl
ul  rPg  rPc . 4
ml ml
The last term in Eq. (4b) represents capillary diffusion.
Assuming the capillary pressure gradient depends solely on
the saturation gradient, the liquid phase momentum
equation can be rewritten as
Sim Saturation
kl
ul  rPg  Dsl rsl , (5)
ml Fig. 8. General form of the capillary pressure curve.
 ARTICLE IN PRESS
N. Djilali / Energy 32 (2007) 269280 275

approaches we have recently used to determine the

functional dependence of relative permeability and capil-
lary pressure on saturation is based on stochastic pore
network model simulations illustrated in Fig. 9. These
simulations consist of building a network of pores and
throats, with distributions of pore radii corresponding to
the porous media of interest, and then solving the
momentum transport equations to account for capillary
dominated drainage and cluster formation as a function of
invading phase saturation. Statistical analysis of the
stochastic realizations allows determination of, e.g., the
variation of the relative phase permeability and of capillary
pressure as a function of saturation.
A more fundamental approach consists of resolving the
two phase transport by performing direct numerical
simulations that explicitly resolve the ow, including
dynamic interface tracking, between the bres. The
equivalent 2D reconstruction of a bre array correspond-
ing to a typical gas diffusion layer is shown in Fig. 10. The
simulation in this systems start with a medium in contact
with a liquid water reservoir at the bottom at a higher
pressure. A volume of uid (VOF) technique in conjunc-
Fig. 10. Computational grid for 2D reconstruction of gas diffusion layer.
tion with sub-models for surface tension and wall adhesion
is used to track the evolution of the two phase ow,
including the interface. The instantaneous pressure eld In recent studies of diffusion layers and two-phase fuel
obtained from such simulations, Fig. 11, shows clearly the cell models [32,33], it was proposed that liquid water in a
two-phase interface. 2D, as well as 3D simulations provide GDL evolves in an inverted tree structure; i.e. a high
fundamental understanding of the two-phase transport, number of small capillaries disperse evenly within the GDL
and parametric simulations that directly account for and eventually converge into larger capillaries and
detailed features, such as degree of hydrophobicity, can eventually result in one very large capillary that breaks
yield data for determining capillary functions that are more through the surface. Analysis of the VOF simulations
representative of GDLs than Eq. (8). together with recent quantitative visualization experiments
performed with laser induced uorescence [34] suggest
fundamentally different transport dynamics.
For a hydrophobically treated GDL, assuming well
dispersed PTFE coating (i.e. uniform contact angle), the
transport within the GDL is a process of pressure buildup
and breakthrough, due to the fact that capillary forces
provide the main resistance to the progression of the
interface in the brous hydrophobic structure. As water is
produced in the catalyst layer, the pressure in the liquid
increases, and the uid surface slowly passes through the
constrictions of the cross-sections generated by intersecting
bers (see Fig. 12). When the water has passed halfway
through each constriction, the curvature of the surface
decreases due to the expanding radius of the surface. Thus,
the liquid pressure at the interface drops and induces
hydrodynamic ow in the direction of the expanding
surface. Subsequently, the liquid expands rapidly above
this cross-section until the uid interface contacts the next
set of ber intersections. The process then begins again.
The uid will preferentially pass through the ber cross-
sections featuring the greatest spacing, as this reduces
capillary pressure resistance. A schematic of the overall
ow mechanism inferred from the analysis of VOF
Fig. 9. Example of invading phase (water) saturation pattern obtained simulations and quantitative visualization [34] is illustrated
using capillary pore network simulations. in Fig. 13, showing a process dominated by ngering and
 ARTICLE IN PRESS
276 N. Djilali / Energy 32 (2007) 269280

Fig. 11. Two phase ow in GDL: instantaneous pressure eld liquid phase (gas phase in blue).

Catalyst Layer Gas Diffusion Layer

Fig. 12. Liquid interface in the cross-section of four intersecting GDL

bers.

channeling, and featuring numerous dead ends where

water transport recedes when an adjacent breakthrough
channel forms.

3. Integration into CFD-based fuel cell models

Fig. 13. Schematic of the mechanism for liquid water transport in PEM
One of the most challenging aspects of computational fuel cell gas diffusion layers.
modelling of PEMFCs is the multi-physics nature of the
transport processes, and the coupling between these effects of a given transport process on other equations. The
processes as illustrated in Fig. 14. Each circle in the gure transport equations for gas species, water in liquid and
represents a transport equation governing a particular solid (membrane) phases, and energy are closely coupled
process, and the arrows pointing outward represent the with all other conservation equations. Among all the
 ARTICLE IN PRESS
N. Djilali / Energy 32 (2007) 269280 277

processes, the transport of water, which exists in the system evaporation, which can be found under the land areas
in the forms of vapour, liquid, and absorbed in the due to the increased pressure drop. The pressure drop, an
polymer, is central to all other transport processes. artifact of the increased resistance to gas transport below
Unsaturated water in the vapour phase affects local relative the land area, reduces the vapour pressure below the
humidity in the vicinity of the membrane and thus water saturation point. Negative values, indicating condensation,
transport across the membrane and protonic conductivity, are most prevalent at the catalyst layer/GDL interface
which in turn impacts the electric potential eld. The because of the oxygen consumption and the production of
transport of liquid water in the porous media affects mass water vapour. The corresponding distribution of liquid
transport of gas species, while liquid water in the gas water saturation in the cathodes GDL, shown on the right-
channels changes the pressure eld and may alter the hand side, indicates maximum saturation levels of about
overall ow distribution in a unit cell. A key aspect of any 10% under the land area at the end of the channel.
simulations involving two-phase transport and phase Transport of water across the membrane links, as noted
change is the proper resolution of heat transfer and earlier, the anode and cathode sides of a fuel cell.
irreversibilities [35]. Polarization curves obtained using a complete fuel cell
Fig. 15 illustrates the predicted distribution of the rate of model that incorporates the binary friction membrane
phase change and of liquid water saturation in the cathode model (BFM2) discussed in Section 2.1 are presented in
of a PEMFC using a 3D coupled implementation of the Fig. 16. A particularly important issue here is the coupling
multi-uid model presented earlier. In this gure, the top
and bottom of the vertical axis correspond to the catalyst
layer/ GDL and gas ow channel/GDL interfaces,
respectively, and the planes correspond to successive Springer, RH = 75/ 25
Springer, RH = 25/ 75
locations from the inlet to the outlet of the fuel cell 0.8 BFM2, RH = 75/ 25 0.8
section. Positive phase change values correspond to BFM2, RH = 25/ 75
cell voltage [V]

0.6 0.6
Temperature
(Energy) Latent heat
i2R, i
0.4 0.4
convection Reaction
mass source rates
Gas species source
Mass & Water Electrical
flux 0.2
Momentum potential 0.2
p Membrane

s source B.C. EOD

convection Water content
Saturation 0
s 0 0.2 0.4 0.6 0.8 1 1.2 1.4
cell current [A /cm2]

Fig. 16. Polarization curve predicted using Springers membrane model

Fig. 14. Coupling of Transport Phenomena in a PEMFC. and BFM2.

Fig. 15. Rate of phase change [kg/(m3 s)] (left) and liquid water saturation (right) inside the cathodic gas diffusion layer at a current density of 0.8 A/cm2.
(Gas channel opening is located between 0.0005 and 0.0015 m of the cell width, and the land areas between 00.0005 and 0.00150.002 m.).
 ARTICLE IN PRESS
278 N. Djilali / Energy 32 (2007) 269280

of water transport within the membrane to water transport

in the electrodes in such a way that mass conservation is
ensured. An empirical relationship between water content
and water activity (membrane sorption isotherm) has to be
enforced to this end. Fig. 16 compares the effects of
different humidication regimes on the anode and cathode
sides (25% and 75% relative humidity). The Springer
model predicts similar polarization curves for both
regimes, while the BFM2 predicts a substantially larger
loss for the RH 25/75 regime (dry anode). An analysis of
the source of this loss reveals that it is primarily due to
larger ohmic losses predicted through the membrane as a
result of drying on the anode side. In this case, there is no
water to hydrate the anode catalyst layer, unlike the case of
the dry cathode (RH 75/25), where the water production
from the oxygen reduction and the cathode-to-anode back- Fig. 17. Schematic of a micro-structured air-breathing PEMFC.
diffusion helps to maintain a more uniform membrane
saturation. This highlights the crucial importance of
membrane modelling, particularly for fuel cell systems that
rely on passive water management, such as air breathing
cells considered next.
Exploitation of microscale transport processes in con-
junction with macro-manufacturing makes it possible to
conceive of very high power density fuel cells [3], which
also have the potential of being signicantly cheaper than
planar plate and frame fuel cells. Micro-fabrication of ow
elds, current collectors, and electrical interconnects have
been used in a number of designs, but these have generally
relied on the traditional planar MEA architecture. Non-
planar designs can achieve much higher active area to
volume ratios, and hence higher volumetric power densi-
ties, as was demonstrated in our waved cell topology [36].
For applications requiring low power, operation in passive
air-breathing mode offers several advantages, including
system simplication resulting from elimination of mani-
folds and ancillaries such as fans and increased volumetric
power density. Mass transfer limitations are however an Fig. 18. Mass fraction distribution of oxygen in three adjacent electrodes.
issue in such designs [37]. The ambient oxygen mass fraction in the convective air ow (top) is 0.23.
Computational modelling has been particularly valuable
in analyzing a concept that exploits the microscale
transport principles in conjunction with an air-breathing The CFD-based tools were adapted to this problem [37]
non-planar patented design illustrated in Fig. 17. The to assess the functionality of the design, determine the
micro-structured electrodes in this design consist of a nano- severity of potential transport limitations, and to identify
porous material featuring mean pore diameters on the design parameters to alleviate these. In addition to the
order of 100 nm, i.e. two orders of magnitude smaller than coupled transport processes discussed earlier, two specic
in typical GDLs (Fig. 6). With comparable levels of process that have to be accounted for in this case are
porosity, the nano-porous GDL can increase the active natural convection in the ambient air, and Knudsen
area of the deposited catalyst by exploiting the surface to diffusion though the GDL.
volume ratio [3]. The higher functionality of such a GDL Fig. 18 illustrates the distribution of oxygen for a system
can be impeded by [37]: consisting of three adjacent electrodes subjected to non-
uniform convective heat and mass transport currents at the
 the inability of nano-scale porous media to effectively top. The catalyst layer is located along the left hand
transport reactant and product gases to the entire active vertical axis for each electrode. A minimum oxygen mass
area; and fraction of 0.089, a 61% drop from the ambient, is
 the limited ability of natural convection to passively obtained in the central cathode. Though the reduction in
regulate temperature and supply adequate amounts of oxygen concentration is signicant, the fuel cell is still far
oxygen to the cathode. from being oxygen starved, indicating that the GDL
 ARTICLE IN PRESS
N. Djilali / Energy 32 (2007) 269280 279

parameters and dimensions considered will not result in molecular dynamic simulations, are required to determine
insurmountable mass transport limitations. the fundamental properties of specic PFSA membranes,
including the diffusion and interaction coefcients, and the
4. Concluding perspective sorption isotherms. Further this model needs to be
extended to liquid water equilibrated membranes and to
Fuel cells are at the vanguard of emerging clean energy account for transients.
technologies, but must surmount a number of key PEMFC catalyst layers consist of a complex composite
challenges in order to successfully compete against incum- structure of interconnected, microporous agglomerates
bents such as IC engines and batteries. The availability of surrounded by macropores. Charged species, heat, liquid
reliable and functional computational tools could help water, and gas all ow through this layer. Modelling and
achieve dramatic reductions in development cycles and experimental characterization of this layer is one of the
costs, and could spur innovative design required to most difcult problems in PEMFCs. Multi-scale modelling
surmount some of the cost and performance challenges. strategies are required to resolve the catalyst structure and
In this paper we have reviewed the array of transport guide the formulation of improved macroscopic models
phenomena encountered in PEM fuel cells, and presented suitable for use in a CFCE framework.
some of the progress made in our laboratory in addressing The functionality and usefulness of computational fuel
some of the fundamental issues that still limit the cell models in a design environment will require the
capabilities of computational fuel cell engineering (CFCE). effective and robust integration of the various submodels
A new model for coupled protonic and water transport in a CFCE framework that will allow not only design
in polymer membranes was presented. This general model analysis, but also systematic optimization. This will
is based on rational and physical consideration, removes necessitate the development of novel algorithms that take
several of the limitations of the empirical models used to into account the specic nature of the couplings, the large
date, and should provide a good foundation for modelling range of scales encountered in PEMFCs fuel cells, and the
all puruoro-sulfonic acid membranes. Approaches com- multi-variable nature of the optimization problems.
bining pore network modelling, direct numerical simula-
tion of two phase ow in reconstructed gas diffusion layers,
and quantitative visualization have been described, and the Acknowledgements
sample results presented revealing fundamental mechan-
isms of liquid water transport in hydrophobic GDLs. The The work presented in this paper is the result of
important issue of integration and coupling was also collaboration with a number of former and current
discussed in the context of CFD-based fuel cell models, and graduate students, research associates and colleagues. The
we have shown that used judiciously, current models and author would like to particularly acknowledge the con-
computational tools can be used in both conventional tributions of: Torsten Berning, Brian Carnes, Jeff Fimrite,
designs and in novel micro-structured fuel cells to provide Shawn Litster, Ged McLean, Bojan Markicevic, Henning
detailed information and to analyze design features. Struchtrup, and Jay Sui.
Numerous outstanding problems need to be resolved Financial support from the following is also gratefully
before truly functional computational fuel cell engineering acknowledged: the MITACS Network of Centres of
capabilities are achieved. The broader applicability of the Excellence; the Natural Sciences and Engineering Research
multi-uid model comes at the cost of solving for an Council (NSERC) of Canada; the Canada Research Chairs
additional set of eld equations and the required coupling program; Angstrom Power Inc.; and Ballard Power
of the phases. This makes the numerical solution less stable Systems.
and more computationally intensive. Alternative models
based on various levels of simplications should be better
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