Reporte sobre COMSOL: Simulaciones

de Fuel-Cells
Anlisis de los siguientes Model Libraries:
1)Tutorial Models: Fuel Cell cathode.
2)PEMFC:pem gdl species transport 2d.
3)PEMFC: passive pem.
4)PEMFC: ht pem.
Se da un introduccin a cada modelo y las
variantes que se podran realizar.
Antonio Zegarra Borrero

1)Tutorial Models: Fuel Cell cathode.

One of the most important and complicated
parameters to model in a fuel-cell is the MASS
TRANSPORT through the GDL (Gas Diffusion
Layers) and RL (Reactive Layers). The
concentrations of the gases (on the cathode we have
O_{2}, H_{2}O y N_{2} and at the anode H_{2})
are relatively high and are affected by chemical
reactions (Reduction of Oxygen at the Cathode and
Oxidation of Hydrogen at the Anode). These
conditions make Fickian diffusion inappropriate to
model mass transport and one has to rely on the more
elaborated Maxwell-Stefan equation.

In this case the cathode of a fuel-cell with perforated

current collectors is investigated. Due to the perforation
layout a 3D model is needed to study the mass transport,
current and reaction distributions.

This model investigates such a geometry and the mass

transport that occurs through Maxwell-Stefan diffusion. It
couples this mass transport to a generic, Tafel-like
electrochemical kinetics in the reaction term at a cathode.

Physical Interfaces used:

The electronic and ionic current balances are

modeled using a Secondary Current Distribution
interface.
The species (mass) transport is modeled by the
Maxwell-Stefan equations for oxygen (Species 1)
and water (Species 2) in the gas phase using a
Transport of Concentrated Species interface.
Mass transport is solved for in the electrode
domain only.
The velocity vector is solved for using a Darcys
law interface.

Results presented

Isosurfaces of the weight fraction of oxygen at a total

potential drop over the modeled domain of 190 mV.

Velocity field for the gas phase in the cathodes porous

reactive layer. There is a significant velocity peak at the edge
of the inlet orifice caused by the contributions of the reactive
layer underneath the current collector because in this region
the convective flux dominates the mass transport.

The electrochemical reaction rate, represented by the local

current density, is related to both the local overvoltage and
oxygen concentration. The next figure depicts the local
overvoltage, which is rather even throughout the cathode.
This is caused by the high electronic conductivity in the
porous material. Another observation is that the maximum
overvoltage is -180 mV. This means that there is a voltage
loss of 10 mV in the electrolyte layer.
Although the local overvoltage distribution is rather even,
the concentration of oxygen is not. This means that the
reaction rate is nonuniform in the reactive layer. One way to
study the distribution of the reaction rate is to plot the ionic
current density at the bottom boundary of the free
electrolyte.

The local overvoltage is rather even because the

porous electrode is a conductor.

The current-density
distribution shows that
the variations are rather
large. The reaction rate
and the current
production are higher
beneath the orifice and
decrease as the
distance to the gas inlet
increases. This means
that the mass transport
of reactant dictates the
electrodes efficiency
for this design at these
particular conditions.

Now, an analysis of the ways to

introduce modifications to the
instructions in the manual

The simulation starts by adding a SECONDARY

CURRENT DISTRBUTION Interface and a
Stationary Study to set up and solve for a current
distribution model of the cell.
At this stage we don't consider the influence of
chemical species yet because we want to analyze the
current distribution only considering a voltage
difference between the electrolyte and the current
collector.
Because of the geometry we need a 3D-model.

GEOMETRY 1

Use blocks to define the electrolyte and the porous

electrode domains. Then use a workplane to draw the
inlet hole at the top of the porous electrode. Facilitate
geometry selection later (when setting up the physics) by
enabling Create Selections and renaming the geometry
objects.
Block1: Electrolyte, Block 2: Porous Electrode, WorkPlane-->Circle : Inlet. Then use Form Union.

GLOBAL DEFINITIONS

Load the model parameters and variables from text

files (We can change these parameters to adapt them to
a particular material/experiment).

Parameters: fuel_cell_cathode_parameters.txt.

Variables: fuel_cell_cathode_variables.txt.
EXPLICIT

Manually add selections for the bottom electrolyte and

top current collector boundaries:

Explicit 1---> Boundary 3---> Electrolyte Boundary.

Explicit 2---> Boundary 7---> Current Collector.

SECONDARY CURRENT DISTRIBUTION

Now start defining the physics for the current distribution

model. Add a porous electrode and specify the electrode
reaction parameters, then add potential boundary nodes
for both the electrolyte and the electrode phase. Note that
an Electrolyte node already has been added automatically
by default.
Physics Toolbar-->Porous Electrode 1--> Domain
Selection: Porous Electrode. No correction for the
effective conductivities.
Porous Electrode 1--->Porous Electrode Reaction 1--->
Model Inputs---> T, i0, S (We can change this!)
Potentials at the electrolyte and current collector: 0 at the
electrolyte and E_pol at the current collector. Provide
initial values to reduce computational time.

MATERIALS

The Materials node is marked with a red cross. This indicates that
there are material parameters missing in the model. Add two
different material nodes for the electrolyte and the porous
electrode, and specify the conductivity values.

Model Builder--->Component 1---->Materials---->New

Material--->Geometric Entity Selection---->
Electrolyte----->Electrolyte Conductivity: sigmal= 5
[S/m].
Model Builder--->Component1---->Materials---->New
Material--->Geometric Entity Selection---->Porous
Electrode----->Electrolyte Conductivity: sigmal= 1
[S/m], Electrical conductivity sigma=sigma_s.

MESH 1

Use the default mesh sequence that will be induced by

the physics, but change to a finer size.
Model Builder--->Component 1---->Mesh 1--->Element Size---->Fine (Here we can increase the
accuracy by choosing Extra Fine)--->Build All.

STUDY 1: Home Toolbar--->Compute (=).

RESULTS: Electrolyte potential plots are created by default.
Now create a plot of the local overpotential by first adding a
plot group, followed by a volume plot.

Add Plot Group----> 3D Plot Group, then

Model Builder---->Results---->3D Plot
Group---->Volume----->Expression---->
Replace Expression: Overpotential
(siec.eta_per1)---->Plot----> Rename 3D Plot
Group 3----> New Name: Local Overpotential.

Your overpotential plot should now look like this (We

have not included the effects of mass transport yet):

Data Sets: Create a data set with a selection on the

bottom electrolyte boundary only. Then use this data set to
plot a surface plot of the normal electrolyte current
density.

Results Toolbar----->More Data Sets--->Solution.

Model Builder----->Results---->Data Sets: Right
click Solution 2--->Add Selection. Selection
settings window----->Geometric Entity
Selection----->Geometric Entity Level:
Boundary------>Selection: Electrolyte
Boundary---->Select "Propagate to lower
dimensions".

3D Plot Group 4

Home toolbar---->Add Plot Group----> 3D Plot

Group----> Data Section---> Data Set: Solution 2.
Right Click Results-----> 3D Plot Group 4-->Surface----->Expression Section---->Replace
Expression: Normal electrolyte current density
(siec.nIl) ----->abs(siec.nIl) (we plot the absolute
value)------>Plot.
Model Builder----> right click 3D Plot Group
4-----> Rename ----> Electrolyte Current Density.

Now change to second order elements in the finite element

discretization. This will increase the accuracy of the
solution and render a smoother plot. (Alternatively you
could increase the resolution of the mesh).

Model Builder----> Show button (the "eye")--->Select Discretization.

Secondary Current Distribution settings
window----> Discretization Section ------>
Electrolyte potential: Quadratic, Electric potential:
Quadratic.

Study I: Home toolbar---->Compute(=)

Results: Your current density plot should now look

like this:

We have little current at the inlet because there is like

a hole and the current comes from the electrolyte to
the current collector. We have no added oxygen yet!

COMPONENT 1

Now, add more physics to the model by adding a

Transport of Concentrated Species interface for gas
phase mass transport and a Darcy's law interface for
the convective flow.
Add Physics---->Chemical Species Transport--->Transport of Concentrated Species (chcs)---->Dependent Variables------>Number of
species=3-----> Add to Component.
Add Physics---->Fluid Flow---->Porous Media and
Subsurface Flow-----> Darcy's Law (dl)----->Add to
Component.

Transport of Concentrated Species

Model Builder---->Component 1---->Transport of

Concentrated Species----->Domain Selection: Porous
Electrode---->Transport Mechanisms----->Diffusion
model: Maxwell-Stefan.

Convection and Diffusion 1

Model Builder----->Transport of Concentrated

Species----->Convection and Diffusion 1---->Density--->M_n2, M_o2, M_h2o----->Diffusion
(Enter the Data on the Table for D_{i,k})---->Model
Inputs---->u list: Darcy's velocity field (dl/dlm1)--->T--->p: Pressure (dl/dlm1)----> p_{ref}: p_atm.

Porous Electrode Coupling 1

Use a porous electrode coupling to create a mass sink in the

domain corresponding to the oxygen leaving the gas phase
due to the electrochemical reactions.
Physics Toolbar---->Domains---->Porous Electrode
Coupling----->Domain Selection: Porous Electrode.

Reaction Coefficients 1

Model Builder----->Component 1---->Transport of

Concentrated Species---->Porous Electrode Coupling 1----> Reaction Coefficients----> Model Inputs---->i_{v}: Local
current source (siec/pce1/per1)----> Stoichiometric
Coefficients: n_{m}=4 ------> \nu_{wo2}= -1 (Oxygen is
consumed during the Rxn).

Initial Values 1

Model Builder----->Component 1---->Transport of

Concentrated Species ----> Initial Values 1-----> Initial
Values: w_o2_ref, w_h2o_ref.

Inflow 1

Physics Toolbar------>Boundaries----->Inflow---->Bondary Selection: Inlet----->Inflow: w_o2_ref,

w_h2o_ref.

Darcy's Law: Now do the settings for Darcy's law.

Also here the electrochemical currents will result in a
mass sink due to the oxygen molecules leaving the
domain.
Model Builder---->Component 1---->Darcy's
Law----->Domain Selection------>Selection list:
Porous Electrode.

Fluid and Matrix Properties 1

Model Builder----->Darcy's Law---->Fluid and Matrix

Properties 1---->Fluid Properties----->Density: User
Defined: chcs.rho----> Dynamic viscosity: User
Defined: mu ----->Matrix Properties: e_por-->permeability (\kappa)=perm.

Porous Electrode Coupling 1

Physics toolbar----->Domains---->Porous Electrode

Coupling------>Domain Selection----->Selection List:
Porous Electrode------>Species: Add, Add--->Species
Table:

Reaction Coefficients 1

Model Builder---->Porous Electrode Coupling 1---->Reaction Coefficients 1----->Model Inputs---->i_{v}:Local

current source (siec/pce1/per1)------>Stoichiometric
Coefficients---->n_{m}=4---->\nu_{2}=-1.

Inlet 1

Physics toolbar---->Boundaries---->Inlet----->Boundary
Selection---->Selection List: Inlet----->U_{0}: v_in.

SECONDARY CURRENT DISTRIBUTION

Porous Electrode Reaction 1: Finalize the physics

settings by modifying the porous electrode reaction
current density to depend on the oxygen concentration.

Model Builder----->Component 1---->Secondary Current

Distribution---->Porous Electrode 1----->Porous Electrode
Reaction 1-----> Electrode Kinetics----->Kinetics
expression type: Concentration dependent kinetics----->
C_{0}=chcs.c_w_o2/c_o2_ref (chcs.c_w_o2 is the molar
concentration variable defined by the Transport of
Concentrated Species interface).

STUDY 1: Add a second study step that solves for all

physics. Modify the first study step so that it only
solves for the current distribution interface.

Step 1: Stationary

Study Toolbar---->Study Steps---->Stationary--->Physics and Variables Selection---->Table:

Home Toolbar---->Compute (=).

RESULTS: Considering now the presence of Oxygen

and its reduction-reaction.

We notice that there is a higher Overpotential at the inlet,

but the variation is not very large over the porous electrode
because of its conductivity.

We notice that the current density (at the electrolyte) is higher

at the inlet and decreases as the distance from the inlet
increases. The reaction rate (proportional to the current
density) is related to both the local overvoltage and the
concentration of oxygen, and since the local overvoltage is
rather even, we expect the concentration of oxygen to show a
dependence similar to that exhibited by the current density.

3D Plot Group 5: Create a plot of the mass

fraction of oxygen in the gas phase as follows.

Results------>Add Plot Group---->3D Plot Group---->Results:

3D Plot Group 5----->Isosurface: Expression----->Replace
Expression: Mass fraction (w_o2)------>Levels: Total Levels =
10------>Plot----->Rename 3D Plot Group: Oxygen Mass
Fraction.

3D Plot Group 6: Create a slice plot of the gas

velocity magnitude as follows.

Results------>Add Plot Group---->3D Plot Group-->Results---->3D Plot Group 6---->Slice ----->Slice:

Expression------>Replace Expression: Darcy's velocity
magnitude (dl.U).
Right click Results----->3D Plot Group 6----->Slice
1----->Duplicate---->Plane Data----->zx-planes---->Inherit style section------>Plot List: Slice 1----->Plot----->Rename 3D Plot Group: Oxygen Mass Fraction.

Variantes q se pueden realizar:

Change the geometrical arrangement: the size and shape of

the inlet.
Change the Parameters (modify the text-file). The surface
Specific Area is very important and depend on the
nanomaterial.
Material Properties: change conductivities of the free
electrolyte, porous electrode and pore-electrolyte. We can
also change the porosity and permeability (materialdependent).
Change the Discretization of the Mesh (Both are equivalent)
to improve accuracy.
Change the kinetics....perhaps...but Maxwell-Stefan is the
best suited for this system. However the M-S Diffusivity
matrix can be analyzed in more detail.