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Electrochimica Acta
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Article history: A non-isothermal, single phase membrane electrode assembly (MEA) mathematical model accounting
Received 30 June 2014 for most applicable heat sources, viz., reversible, irreversible, ohmic heating, phase change, heat of sorp-
Received in revised form 8 September 2014 tion/desorption, is presented. The mathematical model fully couples a thermal transport equation with
Accepted 14 September 2014
an MEA model and allows the study of non-isothermal effects, such as thermal osmosis through the
Available online 19 September 2014
membrane, local relative humidity variations in the catalyst layers and water sorption into the mem-
brane. A detailed breakdown of various heat sources in the MEA at different current densities is provided
Keywords:
and the impact of various thermal effects previously neglected in the literature such as thermal-osmosis,
Polymer electrolyte fuel cell
Membrane electrode assembly
reversible heat distribution, and heat of sorption are studied. Results show that sorption heat cannot
Non-isothermal be neglected as it contributes up to 10% of the total heat under normal operating conditions. Reversible
Open-source heat distribution can significantly affect the temperature distribution shifting the hottest location of the
Macro-homogeneous model cell from anode and cathode. Analyzing the water transport across the membrane, results show that
Sorption heat thermal-osmosis contributes up to 25% of the water flux inside the membrane at moderate and high
Reversible heat current densities.
Thermal osmosis © 2014 Elsevier Ltd. All rights reserved.
Finite elements
http://dx.doi.org/10.1016/j.electacta.2014.09.051
0013-4686/© 2014 Elsevier Ltd. All rights reserved.
M. Bhaiya et al. / Electrochimica Acta 147 (2014) 294–309 295
simulation of the MEA. Ostrovskii and Gostev [9] has shown that the
Nomenclature enthalpy of sorption decreased from 68 kJ/mol (at 0) to nearly
45 kJ/mol (at 5), but values below the latent heat of water vapor-
S Change in entropy per mole of fuel, J/(mol · K) ization are not reached. On considering the enthalpy of sorption the
T̂ Temperature, ◦ C same as the latent heat of vaporization, the heat term correspond-
Sorbed water content ing to sorption/desorption of water is observed to be of similar
F Universal Faraday’s constant, A · s/mol magnitude as the irreversible heat in a two-dimensional thermal
H+ Proton model [10]. The model however does not solve for transport of other
k Thermal conductivity, W/(cm · K) species (except temperature) and reaction kinetics.
ptot Total pressure, Pa The reversible heat release in the fuel cell is usually accounted
Qrev Reversible heat released per mole of fuel, J/mol for in most non-isothermal models. The total entropy change asso-
T Temperature, K ciated to the overall reaction producing liquid water per unit mole
xH2 O Water mole fraction of fuel (H2 ), S, is well known in the literature [11]. At T = 353 K, it
ACL Anode Catalyst Layer results in a reversible heat release of 55.99 kJ/mol-H2 inside the fuel
CCL Cathode Catalyst Layer cell. However, this heat is not evenly distributed amongst the anode
CGDL Cathode Gas Diffusion Layer and cathode reactions. Efforts to determine the entropy changes
CMPL Cathode Microporous Layer in a single half cell reaction are marred with difficulties because
FEM Finite Element Method of a lack of reliable knowledge of the entropy values of hydro-
GDL Gas Diffusion Layer nium ions (H3 O+ ) and electrons (e− ). To date, most non-isothermal
HOR Hydrogen Oxidation Reaction models in the literature assume that almost all of the reversible
MEA Membrane Electrode Assembly heat is produced inside the cathode electrode. This might not be
ML Membrane Layer the case. Ramousse et al. [12] reported a wide discrepancy in the
MPL Microporous Layer literature data for the hydrogen oxidation reaction (HOR), from -
ORR Oxygen Reduction Reaction 133.2 J/(mol-K) (Exothermic) to 84.7 J/(mol-K) (Endothermic). The
PEMFC Polymer Electrolyte Membrane Fuel Cell HOR half cell reaction is reported to be slightly exothermic [13],
RH Relative Humidity athermic [14] and slightly endothermic [15]. On studying proton
solvation in water, Ramousse et al. [12] calculated that the entropy
change is -133.2 J/(mol-K) (highly exothermic). These values are
all heat generation terms with an accurate membrane water trans- opposite to the normally modelled values in the literature. Kjel-
port model has not yet been developed. The development of such strup et al. [16] performed experiments on a hydrogen-hydrogen
a model would allow researchers to better understand the relative cell under the Soret equilibrium conditions (no current is being
importance of each heat generation term and the impact of thermal generated in the cell). They reported that at 340 K, the entropy
management on water transport in the cell. change for the HOR is −66 ± 5 J/(mol-K). However, it is also con-
Even though several non-isothermal models have been pro- cluded that as current is being generated in the cell (moving away
posed in the literature, the analysis of the relative importance of from the Soret equilibrium), there can be a considerable enthalpy
each heat generation term in the MEA has only seldom been ana- transport along with water and protons shifting the reversible heat
lyzed. Ju et al. [7] estimated the distribution of major heat source production towards the cathode side. Hence there is ambiguity in
terms, viz., reversible heat, irreversible heat, and ohmic heating. the literature for the reversible heat production distribution inside
They found the distribution of major heat sources to be roughly the cell. Therefore, the impact of the reversible heat distribution
35%, 45%, and 17% respectively at cell voltage of 0.6 V under 75%/0% should be studied.
anode/cathode RH conditions. However, water sorption effects Thermal and water management must be studied simulta-
were neglected and the reversible heat term was formulated for liq- neously since they severely affect one another. It has been
uid water product even though the model was single phase, thereby shown that water sorption/desorption will release/absorb energy.
over-predicting the heat generated in the cell. For a single phase Temperature gradients across the membrane also affect water
model to be consistent, a heat sink due to complete evaporation of management across the membrane. Water in sorbed phase is trans-
water should be included in the model, which is ignored in their ported under temperature gradients inside the polymer electrolyte
work. membrane [17,18]. This so-called thermal osmosis effect can be
Ramousse et al. [8] introduced the heat source/sink term cor- explained by the second law of thermodynamics, since water
responding to sorption/desorption of water into the electrolyte moves from the cold side (ordered state inside the hydrophillic
taking place at the catalyst layers in a one-dimensional heat transfer membranes) to the hot side in order to increase the entropy.
Table 1
Summary of non-isothermal models in the literature with respect to various heat source terms and other limitations.
3. Thermal Transport Equation humidified air primarily consisting of oxygen, nitrogen and water
is supplied. Therefore, in the cathode side porous diffusion media,
In order to develop an implementation of the thermal math- four species, viz., oxygen, water vapour, nitrogen and electrons
ematical model for the MEA, the following assumptions will be are transported. Moreover no electrochemical reactions take place
considered: inside the layers, thus there are no additional heat and work terms,
i.e., Sheat = 0 and Ẇelectrical = 0. The thermal transport equation in
1. Steady state model. expanded form is therefore given by,
2. Ideal gas mixtures.
∇ · keff ∇ T − ∇ · H O2 JO2 − ∇ · H H2 O JH2 O − ∇ · H N2 JN2
3. Soret and Dufour effects are neglected.
4. Very low Brinkmann number flow, hence heat production due
− ∇ · H e− Je− = 0. (11)
to viscous dissipation is negligible [29].
5. Pressure gradients are negligible, i.e., the system is isobaric.
6. Two-phase flow and condensation are not considered in the If the gas mixture velocity is negligible (non-convective system),
model, therefore the gas phase is allowed to be in super- the mixture velocity and molar flux are zero, and the species molar
saturated form (higher than 100% RH values) flux and inter-species diffusion molar flux are equivalent such that,
7. Gas and solid phases are in thermal equilibrium because porous Ntot = NN2 + NO2 + NH2 O = 0, (12)
layers, such as GDL, MPL, and CL, have very high interstitial sur-
face area between the fluid (gas) phase and the solid phase, Ji = Ni . (13)
and therefore, there should be enough convective heat transfer The second, third, fourth and fifth terms in equation (11) can be
between the two phases. re-written as,
In order to satisfy the assumptions made in the model, the fuel ∇ · H i Ji = Ji · ∇ H i + H i ∇ · Ji , (14)
cells are studied only under high temperature, i.e., 80 ◦ C and above, where for a non-convective, non-reactive system, mass conserva-
and low relative humidity, i.e., 70% and below, operating conditions. tion dictates that the last term must be zero.
Weber and Hickner showed that at 80 ◦ C, even under fully humidi- Then, equation (11) can be further re-arranged as,
fied conditions, the amount of water removed from the cell by the
liquid phase is less than 20% [30]. ∇ · keff ∇ T − JO2 · ∇ H O2 − JH2 O · ∇ H H2 O − JN2 · ∇ H N2
The transport equation for a representative elementary volume
− Je− · ∇ H e− = 0. (15)
of the porous media under the assumptions above is [26,31],
O(convection):O(diffusion):O(conduction)∼10−6 :10−2 :100 . (9) The species diffusive molar flux can be replaced by the expres-
sion above in equation (11) resulting in,
The transient and convective heat transport terms are therefore
neglected in equation (8) resulting in
∇ · keff ∇ T − ctot DO2 ,N2 ∇ xO2 · (∇ H O2 − ∇ H N2 )
− ctot DH2 O,N2 ∇ xH2 O · (∇ H H2 O − ∇ H N2 ) − Je− · ∇ H e− = 0, (19)
∇ · keff ∇ T − ∇ · H i Ji + Sheat − Ẇelectrical = 0, (10)
where terms H i , molar enthalpy of species i, are a function of tem-
where different species transport, and heat sources vary with var- perature and are given by expression provided by Sonntag et al.
ious layers of the PEMFC. Hence the thermal transport equation [32]. Applying differentiation rules and re-arranging, the following
is derived separately for various PEMFC layers and described in expression is obtained,
subsequent sections.
∂H O2 ∂H N2
∇ · keff ∇ T + DOeff ,N ctot − ∇ T · ∇ xO2
3.1. Thermal transport equation in porous diffusion media
2 2 ∂T ∂T
eff ∂H H2 O ∂H N2
This section deals with the porous diffusion media inside the + DH ctot − ∇ T · ∇ xH2 O − Je− · ∇ H e− = 0. (20)
2 O,N2 ∂T ∂T
PEMFC, viz., GDL and MPL. Considering the cathode electrode,
298 M. Bhaiya et al. / Electrochimica Acta 147 (2014) 294–309
The last term in the equation still contains the diffusive flux where H sorption is molar enthalpy change (heat released) corre-
of electrons in the electronically conductive phase which is not sponding to sorption of water vapour into the electrolyte and H H2O
a primary variable. Electron movement inside the porous layer is is molar enthalpy of the water vapour. Based on the literature, the
governed by Ohm’s law, value of H sorption is taken to be constant at 45 kJ/mol in this work
eff [12]. Since the flux of sorbed water in the membrane is described
s
Je − = + ∇ s . (21) in the MEA model as,
F
eff eff
Further, in an adiabatic system, the molar enthalpy of an elec- m dry eff D
J = nd ∇ m + D ∇ + T ∇T (29)
tron can be simplified using electrochemical potentials [26] such F EW MH2 O
that,
and there is no sorption/desorption of water, the thermal transport
∇ H e− = −F ∇ s . (22) equation inside the membrane layer can be finally expressed as a
function of the primary variables of the problem as [26],
According to the last two equations, the diffusive enthalpy trans-
port due to electron movement term simplifies to irreversible
heating source (Ohmic or Joule heating),
eff
nd m ∂H dry eff ∂H
∇ · keff ∇ T + ∇ T · ∇ m + D ∇T · ∇
eff
F ∂T EW ∂T
−∇ · Je− H e− = −Je− · ∇ H e− = s (∇ s · ∇ s ) . (23)
1 eff ∂H eff
+ D ∇ T · ∇ T + m (∇ m · ∇ m ) = 0. (30)
Replacing the last equation in equation (20), a governing equa- MH2 O T ∂T
tion for heat transport in the cathode GDL or MPL is obtained
that is only a function of the primary variables of the problem,
i.e., 3.3. Thermal transport equation in the catalyst layers
∂H O2 ∂H N2 In the catalyst layers, all phases co-exist, i.e. gas, electron and
∇ · keff ∇ T + DOeff ,N ctot − ∇ T · ∇ xO2 + DHeff O,N ctot proton conducting. The electrochemical reactions also take place.
2 2 ∂T ∂T 2 2
Therefore, in order to derive the governing equations, all the terms
are considered including, Sheat and Ẇelectrical in equation (10). The
∂H H2 O ∂H N2
× − ∇ T · ∇ xH2 O + seff (∇ s · ∇ s ) = 0. (24) heat generation corresponding to the electrochemical reactions
∂T ∂T includes reversible and irreversible terms, however it will be seen
that the reversible term is automatically included due to the elec-
Following a similar process for GDL and MPL in the anode, a
trical work term. In order to derive a governing equation that is
governing equation can be obtained that is a function only of the
only a function of the primary variables, first the irreversible heat
primary variables. In the anode, humidified hydrogen (binary mix-
source and electrical work terms will be discussed in detail, and
ture of hydrogen and water vapour gases) is supplied to the gas
then the inter-species diffusion flux terms will be expanded fol-
channels. Assuming the gas mixture is infinitely dilute and consists
lowing a similar approach to that in sections 3.1 and 3.2.
primarily of hydrogen gas, water vapour transport can be approxi-
Inside the catalyst layers, energy is lost due to the activation
mated as a diffuse species moving in hydrogen according to Fick’s
polarization associated with the electrochemical reactions. It is
law. The thermal transport equation in the anode GDL or MPL is
irreversibly generated as waste heat given as [7],
derived as,
Sirrev = j = j Eeq − Vcell , (31)
∂H H2 O ∂H H2
∇ · keff ∇ T + DHeff O,H ctot − ∇ T · ∇ xH2 O where j is the current density, is the overpotential, Eeq is the
2 2 ∂T ∂T
equilibrium cell potential, and Vcell is the actual cell voltage. This
eff
+ s (∇ s · ∇ s ) = 0. (25) overall irreversible heat release can be broken down into localized
irreversible heat generation corresponding to the ORR and HOR in
the respective catalyst layers,
3.2. Thermal transport equation in the membrane Sirrev,ORR = −j = −j (s − m − EORR ) , (32)
last term in the equation (14) is not zero. For the CCL, on utiliz-
ing the source terms given in the equations (3)-(7) and the latent
heat of vaporization for expressing enthalpy of water vapour in
terms of liquid water enthalpy, the last term can be expanded
as,
j
1 j
H i ∇ · Ji = − H O2 − H H2 O(l) + 2H e− + 2H H + + H
2F 2 (g) 2F lv
k dry
− eq − (H H2 O − H ), (36)
EW
xH2 O ◦
= xH ,
∂H H2 O ∂H H2 2 O,a
∇ · k ∇T eff eff
+ DH O,H ctot − ∇ T · ∇ xH2 O
2 2 ∂T ∂T −n ·
eff
s ∇ s = 0,
eff
nd m ∂H dry eff ∂H 1 eff ∂H (41)
+ ∇ T ·∇ + D ∇ T ·∇ + D ∇ T ·∇ T −n ·
eff
m ∇ m = 0,
F ∂T EW ∂T MH2 O T ∂T
j eff
+ j (s − m − EHOR ) − T (1 − fORR )S overall + m (∇ m · ∇ m )
eff
dry eff D
eff
2F −n · nd m ∇ m + D ∇ + T ∇T = 0,
F EW MH2 O
k dry
eff
+ s (∇ s · ∇ s ) + eq − H sorption = 0 (40)
EW −n · keff ∇ T = 0,
300 M. Bhaiya et al. / Electrochimica Acta 147 (2014) 294–309
Table 3 interface until the variable is solved. For example, all electrolyte
Geometric dimensions of the computational domain
potential boundaries are applied at MPL-CL interfaces. At the gas
Parameters Value, (cm) channel/GDL interfaces, the water molar fraction is specified that
lGDL 2.5 × 10−2 results in the given relative humidity for the operating tempera-
lMPL 5 × 10−3 ture and pressure of the cell. The relative humidity is calculated
lACL 3.33 × 10−4 locally using the ratio of the water partial pressure and the satura-
lCCL 1 × 10−3 tion pressure. If the temperature of the gas at the interface increases
lML 2.5 × 10−3
due to non-isothermal effects, the relative humidity in the channel
lRib 5 × 10−2
lChannel 5 × 10−2 is slightly reduced, e.g., at 2100 mA/cm2 it is 47.3% instead of 50%.
The system of governing equations is non-linear, therefore a
Newton’s iterative method is employed to solve the problem where,
◦
where n is the unit surface normal, and, xH , is determined based
2O
starting with an initial guess, a solution update is obtained at each
on the operating conditions [35]. iteration by solving a linearized form of the governing equations.
The boundary conditions at AGDL-Bipolar plate boundary are The solution variables are then updated accordingly, and the pro-
given by, cess is repeated. In the case of openFCST, the L2 norm of the residual
corresponding to all equations is computed at every iteration step
−n · Deff ∇ xO2 = 0, and the simulation terminates when the L2 norm has reached the
tolerance value of 10−8 .
−n · Deff ∇ xH2 O = 0, The linearized form of the governing equations in this case
is obtained analytically using calculus of variations, see refer-
s = 0, ence [35]. The linearized system of equations is discretized using
(42) Galerkin weighted residuals method with continuous second order
eff
−n · m ∇ m = 0, Lagrange finite elements for test and solution approximation func-
tions. The global system matrix and the right hand side vectors are
eff
dry eff D
eff assembled using Gaussian numerical quadrature. A direct solver,
−n · nd m ∇ m + D ∇ + T ∇T = 0, namely UMFPACK [37], is used to solve the linear system since the
F EW MH2 O
global system matrix is non-symmetric.
T = Tcell , The governing equations are solved in a discretized domain
using an unstructured quadrilateral mesh. Once a converged solu-
where Tcell is the cell operating temperature applied at the bipolar tion is achieved, the mesh is adaptively refined to two more levels
plates. of refiniment utilizing the adaptive error estimator by Kelly et al.
The boundary conditions at CGDL-Gas channel boundary are [38], provided in the deal.II [39,40], in order to achieve a grid-
given by, independent solution. The last solution has 125,718 degrees of
xO2 ◦
= xO , freedom.
2 ,c
Parameters for electron, proton, gas, and sorbed water transport
xH2 O ◦
= xH ,
2 O,c
are detailed in Bhaiya [26], adapted from [27,41]. The electro-
osmotic drag coefficient, nd , is considered to be one based on the
eff
−n · s ∇ s = 0, data by Ren and Gottesfeld [42]. The water diffusion coefficient, D ,
is obtained using the functions proposed by Motupally et al. [43].
−n ·
eff
m ∇ m = 0, (43) Correlations for thermo-osmotic diffusion coefficients are used
from Kim and Mench [19]. The GDL effective thermal conductivity
in the through-plane direction is given by [44],
eff eff
dry eff D
−n · nd m ∇ m + D ∇ + T ∇T = 0,
F EW MH2 O kthrough = M −7.166 × 10−6 T̂ 3 +2.24 × 10−3 T̂ 2 −0.237T̂ +20.1
eff
−n · keff ∇ T = 0,
× W/(m − K), (45)
where ◦
xO
is determined based on the operating conditions [35].
2
The boundary conditions at CGDL-Bipolar plate boundary are where T̂ is the temperature in degree-Celsius and M is the heat
given by, barrier resistance coefficient. Fitting to the data by Zamel et al. [44],
−n · Deff ∇ xO2 = 0,
M = −1.495 × 10−11 T̂ 5 + 2.601 × 10−9 T̂ 4 − 6.116 × 10−8 T̂ 3
−n · Deff ∇ xH2 O = 0,
− 9.829 × 10−6 T̂ 2 + 8.754 × 10−4 T̂ + 0.0664. (46)
s = Vcell ,
(44)
eff The GDL effective thermal conductivity in the in-plane direction
−n · m ∇ m = 0,
is given by [45],
eff eff
dry eff D kin−plane = −7.166 × 10−6 T̂ 3 + 2.24 × 10−3 T̂ 2 − 0.237 T̂
eff
−n · nd m ∇ m + D ∇ + T ∇T = 0,
F EW MH2 O
+ 20.1 W/(m − K). (47)
T = Tcell ,
Table 4
Effective thermal conductivity, W/(cm-K)
Layers Value
Table 5
Operating conditions
Parameters Value
Fig. 3. Polarization curve for the 50% RH and 2 atm case where solid red line repre-
5. Results and Discussion sents the non-isothermal case, solid blue line represents the isothermal case, and dark
green triangle points represents the experimental data [41]. The point at which the
5.1. Non-isothermal effects on performance under different model predicts non-physical RH values (more than 100%) is denoted by × symbol,
and the polarization curves are dashed line afterwards.
operating conditions
Fig. 2. Polarization curve for the 50% RH and 1 atm case where solid red line repre-
sents the non-isothermal case, solid blue line represents the isothermal case, and dark
green triangle points represents the experimental data [41]. The point at which the
log10 (psat ) = −2.1794 + 0.02953 (T − 273.15) − 9.1837
model predicts non-physical RH values (more than 100%) is denoted by × symbol,
× 10−5 (T − 273.15)2 + 1.4454 × 10−7 (T − 273.15)3 . (49)
and the polarization curves are dashed line afterwards.
302 M. Bhaiya et al. / Electrochimica Acta 147 (2014) 294–309
Fig. 6. Temperature distribution plots in the MEA under 50% RH and 1 atm condi-
tions at: (a) 1000 mA/cm2 , and (b) 2100 mA/cm2 .
Fig. 8. Plot of maximum temperature in the MEA versus the current under different Fig. 9. Plot of magnitudes of individual heat terms in the MEA versus the current,
operating conditions. for the 50% RH and 1 atm case.
is now removed in the gas phase remains inside the cell. Third, in
distribution in the anode, membrane and cathode catalyst layers. the case of Thomas et al. [48], supply gases were heated to 80 ◦ C
At 1000 mA/cm2 , the CCL region under the rib is the hottest due to before feeding into the cell. This will result in a convective heat
water sorption in the membrane as will be discussed in detail in flux into the channel boundary, in contrast to the no heat flux
section 5.4. At 2100 mA/cm2 however, the hottest region switches assumption used in our model. To study the feasibility of second
to the region under the channel. This is due to the fact that current hypothesis, the proposed model was solved without accounting
production is limited to the under-the-channel region at high for water vaporization, i.e., assuming all water leaves in liquid form
current densities. It is also observed that the CCL (right side) is without affecting transport. In this case, at 1000 mA/cm2 , the tem-
generally hotter than the ACL (left side), since there are a number of perature rise inside the cell increased to 2.8 ◦ C. This result highlights
significant heat sources in the CCL, such as, irreversible, reversible that thermal and water management are closely interconnected.
and protonic ohmic heating. Experimental studies at low relative humidity would be beneficial
Fig. 8 illustrates the maximum temperature in the MEA at dif- as they would allow researchers to study thermal and water man-
ferent current densities at the four different operating conditions agement independently of two-phase flow, an area that is still not
under study. The maximum temperature increases by up to 13 ◦ C at well understood in fuel cells.
high current densities. Based on these results, it is difficult to justify
the isothermal assumption generally used in the PEMFC modelling 5.3. Heat source distribution
literature. The lowest temperature in all three cases is 353.15 K
(80 ◦ C). This temperature is observed at the Dirichlet boundaries In order to understand the heat distribution inside the cell and
(bipolar plates). Higher temperatures are observed when the cell its main contributors, the heat source/sink distribution in the MEA
operates at 2 atm since higher current densities are achieved; how- is studied. The magnitudes of the individual heat terms in the MEA
ever, the temperature rise is steeper in the 1 atm cases because of are plotted in Fig. 9, for the 50% RH and 1 atm case, in the whole
the higher overpotential losses, i.e., higher irreversible heat pro- range of current densities. The fraction of the total reversible heat
duction. released in the cathode during the ORR, fORR , is considered to be
Temperature measurements inside the PEMFC have been 1. Irreversible heating due to the overpotential in the CCL dom-
reported by Vie and Kjelstrup [3], Zhang et al. [47] and Thomas inates the bulk of heat release in the cell, followed by protonic
et al. [48] for a fuel cell operating at 64 ◦ C, 50 ◦ C and 60 ◦ C under ohmic heating and reversible heat generation. The reversible heat
fully humidified conditions, respectively. At 1000 mA/cm2 , they released by to ORR is mostly counterbalanced (roughly 80 %) by the
report a cell temperature rise of approximately 5 ◦ C, 5 ◦ C and 3.5 ◦ C,
respectively. Due to the single-phase assumption in the proposed
model, fuel cells under fully humidified conditions cannot be stud-
ied, therefore only a qualitative assessment can be performed. At
1000 mA/cm2 , the proposed model predicts a temperature rise of
about 2 ◦ C under any of the operating conditions under study,
thereby under predicting the maximum temperature recorded
experimentally. The under prediction might be due to several rea-
sons. First, the geometry and fuel cell materials are different in this
study and the experimental studies discussed above. Second, at the
operating conditions under study, the proposed model predicts the
complete vaporization of water produced during the reaction. This
acts as a considerable heat sink in the CCL, as it almost counter-
balances the reversible heat released during the reaction, see Figs. 9
and 10. In fully humidified cells, complete evaporation of water will
not take place inside the CCL as the gas phase is already near sat-
uration. Finally, due to the fully humidified conditions, additional
condensation of water will take place in the GDL as the tempera-
ture in the GDL is lower, resulting in heat release in the GDL due Fig. 10. Plot of magnitudes of individual heat terms in the MEA versus the current,
to phase change and hence higher temperatures as the energy that upto 1200 mA/cm2 , for the 50% RH and 1 atm case.
304 M. Bhaiya et al. / Electrochimica Acta 147 (2014) 294–309
Fig. 11. Temperature (T) distribution plots in the ACL + ML + CCL, under 50% RH Fig. 12. Temperature (T) distribution plots in the ACL + ML + CCL, under 70% RH
and 1 atm operating conditions at 1000 mA/cm2, (a) with heat of sorption, and (b) and 1 atm operating conditions at 1200 mA/cm2, (a) with heat of sorption, and (b)
without heat of sorption. without heat of sorption.
Fig. 13. 50% RH and 1 atm case temperature distribution in the ACL + ML + CCL, at 1000 mA/cm2 , for: (a) fORR = 1.0, (b) fORR = 0.5, (c) fORR = 0.0, and (d) fORR = −0.385; and at
2100 mA/cm2 , for: (e) fORR = 1.0, (f) fORR = 0.5, (g) fORR = 0.0, and (h) fORR = −0.385.
Fig. 14. Variation of reversible, irreversible and water vaporization heat terms in
the CLs with current for fORR = −0.385.
Fig. 15. Polarization curve for the 50% RH and 1 atm case, where solid blue line rep-
resents the case of fORR = 1.0, and dotted red line represents the case of fORR = −0.385.
Fig. 17. 50% RH and 1 atm case sorbed water content () plots in the ACL + ML +
CCL, for the isothermal case at: (a) 1000 mA/cm2 , and (c) 2100 mA/cm2 ; and for the
non-isothermal case at: (b) 1000 mA/cm2 , and (d) 2100 mA/cm2 .
Fig. 16. 50% RH and 1 atm case sorbed water content () plots in the CCL, for
the isothermal case at: (a) 1000 mA/cm2 , and (b) 2100 mA/cm2 ; and for the non-
isothermal case at: (c) 1000 mA/cm2 , and (d) 2100 mA/cm2 .
Fig. 19. ˇ versus the current in 50% RH and 1 atm case, where dashed blue line represents the isothermal model, solid red line represents the non-isothermal model without
thermal osmosis, and dash-dot green line represents the non-isothermal model with thermal osmosis.
Fig. 20. ˇ versus the current in 70% RH and 1 atm case, where dashed blue line represents the isothermal model, solid red line represents the non-isothermal model without
thermal osmosis, and dash-dot green line represents the non-isothermal model with thermal osmosis.
per one mole of electron produced in the reaction. Figs. 19 and 20 Water flux across the membrane at higher temperatures are
plots the ˇ as the current density increases, for 50% and 70% RH, not usually reported. Yan et al. [49] reported water fluxes at
1 atm cases. Thermal osmosis is not usually accounted for in MEA 500 mA/cm2 under different channel humidity conditions. In order
models. In order to assess the impact of thermal osmosis on the non- to qualitatively validate the proposed water flux model, the MEA
isothermal model, simulations are performed with the isothermal model was used to simulate water transport under the follow-
model, the non-isothermal model and the non-isothermal model ing conditions: 30%/70%, 50%/70% and 70%/70% cathode and anode
with the thermal osmosis term switched OFF. For all three cases, ˇ relative humidity values, respectively. To better compare to the
increases as the current density is increased from low to medium model, the membrane properties were changed to those used in
current densities. In the isothermal model, ˇ is the smallest due to the study, i.e., Nafion® 117, by modifying the thickness and using
higher water accumulation in the CCL thereby increasing back dif- the proton conductivity, water diffusion coefficient and electro-
fusion. For the isothermal case, the water flux also starts dropping osmotic drag coefficient from Springer et al. [28] and sorption
at medium current density, as back diffusion counteracts electro- isotherm from Hinatsu et al. [50]. The ˇ values reported by Yan
osmotic drag. It can be seen that the isothermal model predicts zero et al. [49] were 0.21, 0.12 and -0.01 while the numerical values
ˇ value at around 1500 mA/cm2 for 70% RH case. However as cur- obtained from our model are 0.57, 0.51 and 0.43. Even though the
rent density is increased further, electro-osmotic drag continues numerical predictions for the ˇ are much higher, the same trend
to increase while back diffusion has reached its maximum value with decreasing cathode humidity is observed. Given the low sto-
thereby resulting in a rapid rise in water flux. The non-isothermal ichiometries, which challenge the assumption of constant reactant
models on the other hand predict a steady rise in water flux from the concentration along the channel used to formulate an across the
ACL to the CCL. This is due to the fact that the CCL is drier (due to the channel model, and that the GDL and CL properties are not reported
increased temperatures), hence back diffusion does not completely by Yan et al. and hence, it could not be modelled accurately, only
counterbalance the electro-osmotic drag. qualitative agreement could be expected.
Comparing the two non-isothermal models, it is clear that the
introduction of thermal osmosis in the mathematical model results 6. Conclusions
in a significant increase in water flux predictions from anode to
cathode. In the 50% RH case, the water flux increases by as much as A single-phase, non-isothermal model of a polymer electrolyte
15 % due to thermal osmosis at medium to high current densities. In membrane electrode assembly has been developed in the open-
the 70% RH case, thermo-osmosis causes the water flux to increase source software, openFCST [25]. The model takes into account all
by 10% at low to medium current densities, but the effect is more the relevant non-isothermal effects such as anisotropic heat trans-
pronounced at high current densities, i.e., more than 2000 mA/cm2 , port, irreversible, ohmic, phase change, reversible, sorption heating
where water flux increases by as much as 30%. It is noteworthy that effects and thermal osmosis. The model was shown to reproduce
temperature differences between the ACL and the CCL are expected the performance curves observed experimentally at a variety of
to be higher with the introduction of a two-phase model. This will operating pressures and temperatures. At high oxygen concentra-
further enhance the water flux due to thermal osmosis. Thermal tions the predictions are in excellent agreement. At low oxygen
osmosis effects are therefore significant and cannot be neglected pressures, results are in agreement at low and moderate current
when analyzing water management in an MEA. densities but differ at high current density most likely due to mass
308 M. Bhaiya et al. / Electrochimica Acta 147 (2014) 294–309
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