FUEL CELL MODELING

Need Of modeling Role of modeling in fuel cell

development process [2]
o A virtual prototypes of fuel cell, which helps in fabrication
o Insight into the electrochemistry of the fuel cell &
processes that takes place in the heart of the fuel cell
o Optimize the design parameters of fuel cell system

A combination of modeling and experimentation can reduce

the cost and accelerate the pace of building and
understanding prototype systems[1]. This will further help
in commercialization of fuel cell.

Characteristics of a good model [2]

A good model should balances,
o Robustness: model should able to predict fuel cell performance
under a large range of operating conditions and physical parameters.
o Accuracy: it can be developed by using the correct assumptions,
correct physical quantities and input parameters, correct governing
equations, and validation with experimental data.
o Computational efforts: time required for calculation should be less,
but sometimes for accuracy, computational efficiency is Figure 1: Flow chart of fuel cell development
compromised. process
A basic fuel cell model[3]
The real output voltage (V) of fuel cell can be calculated subtracting all the overvoltage losses from
the thermo-dynamically predicted voltage

......................................(1)
where,
Ethermo =thermodynamically predicted voltage of fuel cell
ηact =activation losses due to reaction kinetics
ηohmic =ohmic losses from the ionic and electronic resistance
ηconc =concentration losses due to mass transport

Using the expression for ηconc , ηact , ηohmic from the previous chapter, the net j - v behaviour can
br given as,

......................................(2)
Cont.
Co is the concentration of the reactant, t is the thickness of the electrode.
o Here we use the Tafel equation for the fuel cell kinetics, therefore Eq.(2) means this model is
only valid for j>>jo.For modelling at low current density region, full form of Butler - Volmer
equation should be used.
o In this model there are seven fitting parameters: μA, μC,βA, βC,γ,A,Rohmicand jL, where the values
of μ,β,γ are related to α and j0

Graphical representation of the factors

that contributes to fuel cell
performance

Figure 2: Graphical representation of

all the losses
A 1D FUEL CELL MODEL (ANALYTICAL)
o This model is more sophisticated than the basic model.
o It is based on the flux balance concept. Flux balance allows us to keep tracks of all the species
flowing in, out and through the fuel cell.
o The model is well suited for polymer electrolyte fuel cell (PEMFC) and solid oxide fuel cell
(SOFC).
o In the present models, we only concentrated on fuel cell species transport and determine the
species concentration profiles, electrochemical losses and j-V curve.

Flux Balance in Fuel Cells

o Reactants (H2 , H2 O, O2 , N2 )
transport in flow channel is by
convection and in electrodes by
diffusion.
o Electrons transport is through the
external circuit, whereas ions transport
through membrane electrolyte.
o In membrane, water transport is by
electroosmotic drag and back diffusion

Figure 3: Flux detail diagram of PEMFC

PEMFC
o Figure 3shows the flux details needed in 1D model. Individual fluxes are represented by the
numbers.
o In fuel cells, all species transport flux are related to the single character flux-the current
density or charge flux of the fuel cell. From the figure 2 one can write as,

flux-flux5=flux1 - flux4 = flux8 - flux 13 .................................(3)

.................................(4)

where, j is the cell current density (A/cm2), F is Faraday's constant (96,484 C/mol), N is the
molar flux (mol/s.cm2) , r is the generation term due to electrochemical reaction

o is the net hydrogen flux (in - out) in the anode, i.e., the amount consumer in the oxidation reaction.

o Similarly, is the net flux of oxygen at cathode is the water generation rate due to oxygen
reduction reaction at cathode.
o water flux balance in the PEMFC is given as,
Cont.
o water flux through the membrane is given by the balance between electro-osmotic drag and
back diffusion water fluxes. Flux 5 represent the flux due to water generation. Mathematically
above equation can be written as,

......................(6)

where, is the net flux into the anode catalyst layer, across the membrane layer, and into

the cathode catalyst layer respectively and j/2F term represent the water generation rate.

o Let ς (unknown) is the ratio between the water flux across membrane and charge flux
across the membrane is given as,

......................(7)

Putting Eq. (7) in Eq. (6) one can gets,

......................(8)
Cont.
On combining eq. (5) - (8), all the flux in the fuel given as,

...................(9)

SOFC flux balance

o Reactants (H2 , H2 O, O2 , N2 ) transport in flow
channel is by convection and in electrodes by diffusion .
o Electrons transport is through the external circuit,
whereas ions transport through membrane electrolyte.

o Figure 4 shows the flux detailed diagram of SOFC.

o Similar to PEMFC model, the flux balance equation
for SOFC is given as,

...................(10) Figure 4: Flux detail diagram of SOFC

o Overall flux balance in SOFC is simpler compared to PEMFC because water produced at the anode and does
not transport through the membrane, hence no need of water balance . The water flux at the anode equal to
the charge flux. The species transport through membrane is only of oxygen ions (O2-). Water flux at the
cathode is zero. The water generates at the anode is in vapor form because of high temperature.
o In PEMFC model, water present in liquid form and transport through the membrane. So, water balance across
the membrane is necessary.
Model Assumptions
To simplify the model, some assumptions are made which are as follows:
1. convective transport is ignored. Although, convection is dominant phenomena in fuel cells. But
here, for iD model convection is not considered along x-axis .
2. Diffusion transport in flow channel is ignored. Convection is dominant phenomena in flow
channel, since convection is ignored (assumption 1)) in flow channel , diffusion can also be
ignored.
3. Ohmic losses only due to electrolyte membrane.
4. For H2 - O2 fuel cells, anode activation losses is much smaller than cathode activation losses.
Hence, anode reaction kinetics is ignored.
5. Catalyst layer are assumed as extremely thin like 'interface'(no thickness).Hence convection,
diffusion and conduction processes in catalyst layer are ignored.
6. Water assumed to be exists as water vapor. For SOFC, this assumption is valid because SOFC
operates at high temperature. In PEMFC, water exist in water vapor and in liquid form.
Governing Equations
o Equations that deal specifically with phenomena in a fuel cell are-
o Decay's equation for fluid flow in conduits and porous media,
o Fick's law of diffusion,
o Stefan-Maxwell equation for multispecies diffusion,
o Fourier's Law for heat conduction,
o Faraday's Law for relationship between electrical current and consumption of reactants in an electrochemical
reaction,
o Butler-Volumer equation for relationship between electrical current and Potential
o Ohm's Law of electrical current conduction.
o For the present model, simplified version of equations are used by choosing appropriate
assumptions. By solving these equations we can determine concentration profiles, activation
overpotential (ηact), ohmic overpotential (ηact), and concentration overpotential (ηact).
o
o For the present model, simplified version of equations are used by choosing appropriate
assumptions. By solving these equation we can determine concentration profiles, activation
overpotential(ηact), ohmic overpotential (ηohmic), and concentration over potential(ηconc) .

Electrode layer
Species transport (H2,O2,N2,H2O) in this layer is given by simlified Fick's Law of diffusion,

...............................(11)
In case of gaseous reactants, above equation can be written as,

...............................(12)

where, Ni is the molar flux (mol/s-cm2) of the species i, Ci is the concentration (mol/cm3) of the
species i,pi=pxi is the partial pressure (Pa) of the species i,p is the total pressure of the gas,xi is the mole
fraction of the species I, is the effective binary diffusivity (cm2/s) between species i and j, it can be determine using the
nominal binary diffusity, Dij and void fraction, ε by Bruggeman's correction,
................................(13)
Electrolyte layer
Governing equations for species transport in the electrolyte.is depend on the type of fuel cell
(PEMFC or SOFC)
For SOFC, only oxygen ions (O2-) is transport through the electrolyte. From Eq.(10) oxygen ion
flux can be given as,
........................(14)

From assumption 3, ohmic overpotential is given by,

where, LM is the electrolyte thickness, KM is the electrolyte conductivity (S/cm) which is given as,

........................(15)
where, A (K/ohm) and activation energy, ΔGact(J/mol) are usually determine experimentally.
For PEMFC, water and proton (H+) both transport through the membrane electrolyte. Proton flux
is given by Eq.(4) and water flux through the membrane can be describe as combined effect of
back diffusion and electro-osomotic drag,

........................(16)
 ..........................................(18)

..........................................(19)

...................................(20)

Where, ndrag is the electroosmotic drag coefficient, Ρdry is the density (g/am3) of dry membrane, Mm
is the molecular weight, Dmis the diffusivity(cm2/s) of water inmembrane, λ is the water content
membrane.

Sustitute Eqs. (18) and (19) in Eq. (17), one gets,

..........................................(21)

Ohmic overpotential is determined as,

..........................................(22)
Resistance of the membrance, Rm is given by,
....................................(22)

Membrance conductivity, KM for Nafion membrane is expressed as [3],

KM,303 K (λ)=0.005193λ-0.00326
where, λ can be determine using Eq.(20)
Catalyst layer

Cathode side kinetics is represented by modified form of Butler-Vilmer equation,

....................................(23)

For an ideal gas(p=CRT), the above equation becomes,

....................................(24)
where, p0=1atm
Modeling Examples
1d SOFC Model

o Figure 5 shows the 1D schematic of SOFC.

o Anode: H2,H2O transport is given by Eq. (12)

Using Eq. (10), H2, H2O flux are related with cell current
density.

Integrating Eq.(26) and (27), gives linear profile of H2,H2O

concentration at anode,
Figure 5: Schematic of SOFC