Activation over-potential

Electrochemical Reactions
Electrochemical reactions are redox (reduction-oxidation) reactions that involve transfer of free
electrons at the interface of an electron conductor (e.g. metal surface) and an ionic conductor (e.g.
electrolyte). Such reactions are either driven by externally applied voltage or voltage may be created
by the electro-chemical reaction that occurs spontaneously. The branch of science dealing with
electrochemical reactions is electrochemistry. One point may be noted that in chemical reactions no
transfer of electrons take place whereas in electrochemical reactions involve transfer of free electrons.

Since electrochemistry deals with the transfer of charge between and electrode and a chemical species
in an electrolyte, electrochemical processes are necessarily heterogeneous.
For example
H <-->2H++2e-...................................................................................................................(1)
2

In (1) above reaction, electron transfer takes place at the interface between the electrode (e.g. Pt) and
an electrolyte (e.g. H SO in water). Electrochemical reactions are heterogeneous because H+ cannot
exist inside the electrode and free electrons cannot exist inside the electrolyte. Hence, it is a
heterogeneous reaction.
2

Figure 1: Electrochemical reaction at the electrode-electrolyte interface showing

heterogeneous nature of the reaction
Any electrochemical cell has two electrodes called the anode, where oxidation takes place and the
cathode, where reduction takes place. These reactions occurring at the anode and cathode are called
half-cell reactions which together constitute the full electrochemical cell.
Understanding Potential
A general electrochemical reaction can be displayed as follows:
Ox

species

+e- <--->Re

species

.....................................................................................................(2)

Where Ox
and Re
are the oxidized and reduced form of the same chemical entity. Voltage
(potential) is a measure of electron energy. By manipulating the voltage in an electrochemical reaction,
course of above reaction can be influenced. For example, if the potential in above reaction is made
more negative than the equilibrium potential, then reaction will be biased in the forward direction. On
the other hand, if the electrode potential is made relatively more positive than the equilibrium
potential, the reaction will be biased in the reverse direction. Thus, voltage applied to an
electrochemical cell decides the course a reaction will take.
species

species

Activation Energy
For any reaction to occur spontaneously, the change in Gibbs energy should necessarily be negative.
Even if the Gibbs free energy decreases from reactants to products, the reaction rates are finite
because of impedance which is known as activation barrier (Figure 2). This impedance is a barrier that
needs to be overcome for the chemical reaction to occur (please go to module 5 in-situ analyses for
electrochemical impedance analyses). Lower the activation energy, easier it is for reactants to convert
from reactants to products. Transition state theory states that only a species in activated state can
undergo transition from reactant to product. Hence, it is necessary to first overcome the activation
energy before conversion into products.

Figure 2: Gibbs Energy change for an electrochemical reaction. Activation barrier makes the
reaction rate finite.
Thermodynamic treatment from statistical mechanics tells that probability of finding a species in an
activated nature is exponentially dependant on the size of the activation barrier:

....................................................................................................(3)
Where P* is the probability of finding a reactant species in the activated state, G is the energy
barrier (energy gap between the reactants and the activated species), T is temperature (K) and R is
the universal gas constant.
1

Reaction Rate
For any chemical reaction, it is not just the product that is important but also the rate at which it
forms. Therefore, we need to find out the reaction rate in the forward direction. This can be understood
and calculated as follows:
The reaction rate is the number of reactant species available to participate in the reaction multiplied by
the probability that they will be found in the activated state (because, only these will participate in the
reaction) multiplied by the rate at which these transform into the final products. As such, reaction rate
is given by:
u =C tP*....................................................................................................(4)
1

Where, u is the reaction rate in the forward direction, C is the reactant surface concentration
(mol/cm2) and t is the transformation rate from activated state to final products. However, this is still
not the net reaction rate, because the reverse reaction is happening too.
1

Net Reaction Rate

The net rate of reaction is given by:
Net rate = forward rate reverse rate

u=u -u ....................................................................................................(5)
1

Where, u is the net rate of reaction and u is the rate of reaction in reverse direction. Quite intuitively,
the net reaction rate can be given as (using equation 3, 4 and 5)
2

.................................................................................................(6)
Where, t2 and G2 are the transformation rate and activation barrier for the reverse direction and C p is
the product surface concentration.
Gibbs energy change for the entire reaction can be given as
....................................................................................................(7)
Using equation 7 to substitute G in equation 6 , the net reaction rate can be given as:
2

..................................................................................(8)

Exchange Current Density

Now, we know that current is charge transferred per unit time.
Hence, if Q (coulomb) is the charge transferred in time t (sec), then the current is given by the relation

...................................................................................................(9)
If an electrochemical reaction results in the transfer of n electrons, then

.................................................................................................(10)

Where, F is the Faraday's constant and

is the rate of electrochemical reaction (mol s -1).From (10)
and (6) above relation, the forward current density can be expressed as

....................................................................................................(11)
Similarly, the reverse current density can be given as

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

Note that i is current and j and j is current density. Since electrochemical reaction takes at the
interface of electrolyte-electrode, it is wise to express in terms of current density than simply current.
1

That is current density defined j = (i / A) with a unit (Amp / area).

Also note that at equilibrium, there is no net current density. That is, the forward and reverse current
densities should be equal. This current density at equilibrium is known as the exchange current
density. At this point, no net current is extracted from the cell under operation. Thus one can write,

j =j =j
1

Butler-Volmer Equation:
Generally, in an electrochemical cell, we aim to get some useful net current from the cell under
operation. For this, it is important to deviate from equilibrium, where the energies of the reaction are
balanced. For this, we need to understand the equilibrium state of a reaction by analyzing the energies
of the system. For understanding this approach, we can take the earlier example only (Equation 1)
One of the steps involved here is the chemi-desorption of the adsorbed hydrogen on the catalyst
surface (denoted by cat below)
cat-H --> cat+e++H+
As shown in Figure 3 (a), the chemical free energy of the above reaction step decreases as the

distance from the interface (catalyst-hydrogen) increase. But, the electrical energy increases (Figure 3
(b)) as the distance from in interface increases (development of charge ensues with e- accumulating
up at the electrode and H + in the electrolyte. This charge accumulation continues till the resultant
potential difference () counterbalances the difference in free energies between the reactant and
product state.
The combined effect of these two energies can be seen in figure 3 (c) where the net effect leads to
equal forward and reverse reaction rates.

This build up of the charge, neutralizes the difference between the two reaction rates by decreasing
the activation energy barrier for the reverse reaction and increasing the activation energy barrier for
the forward reaction rate. As such, while the forward reaction rate decreases, the reverse reaction rate
increases. This makes it difficult to extract a net current from the cell.
Now, it can be stated that

.........................................................................................(13)
We know that the sum of interfacial electric potential difference at anode and cathode yield the overall
thermodynamic equilibrium voltage. These anode and cathode interfacial potentials are called Galvani
potentials. The exact magnitude of these Galvani potentials is not known.
We had earlier studied that voltage plays a crucial role in deciding the course of a reaction. This is
because charged species are involved in the reaction and this free charge species are sensitive to
voltage which changes the free energy of these species upon bringing up a change in the voltage. As a
result, this changes the size of the activation barrier. Now, voltage will play a crucial role in extracting a
net current from the electrochemical reaction.
Reducing the Galvani potential at both anode and cathode reduces the forward reaction activation
barrier and at the same time, increases the reverse reaction activation barrier. This results into a net
forward reaction and hence, a net current can be obtained from the electrochemical cell.
By looking at the figure 4(b), it can be seen that if the Galvani potential is reduced by a value of , the
forward reaction activation barrier is reduced by F and the reverse reaction activation barrier is
increased by (1-)F (figure 4(c)). Here, is called the charge transfer coefficient and it denotes how
a change in Galvani potential changes the activation barrier for forward and reverse reactions thus
producing a net cell current.

We already know that at equilibrium, the current density is given by the exchange current density.
Moving away from equilibrium and taking into account the changes in activation barrier, the new

current densities can be written as follows:

...................................................................................................(14)

...................................................................................................(15)
The net current j is therefore, j1-j2 (subtracting eq. 15 from 14)

...................................................................................................(16)
We also need to take into account the change in reactant and product surface concentration; owing to
change in voltage that changes the reaction rate. This change in concentration can be taken care of by
introducing actual surface concentrations C*R and C*P. Accordingly, eq. (16) becomes:

.......................................................................................(17)
Where, j is the current density measured at surface concentrations C and C . Eq. 17 is called
the Butler-Volmer equation and denotes the relationship between current density, surface
concentration and activation voltage loss in an electrochemical loss. We can conclude from the above
equation that the current density increases exponentially with activation over-voltage ().
0

Activation Over-potential
Activation over-potential represents the voltage that is sacrificed to overcome the activation barrier to
extract a net current from an electrochemical reaction. The over-potential is the extra voltage needed
to reduce the energy barrier of the reaction (usually the rate determining step) so that the reaction
proceeds at a desired rate. Thus, higher is the voltage sacrificed, higher is the current density
obtained.
The magnitude of this activation loss is governed by reaction kinetic parameters and j . Having a high
j0 is highly favored. This can also be shown from Figure 5, which shows the plot for cell voltage versus
current density.
0

Figure 5: Voltage versus current density at different exchange current densities

Tafel Equation
The ButlerVolmer equation (17) often is quite complex to deal with owing to its exponential nature.
Thus, it creates unnecessarily complications which can be resolved by making some simplifications
under certain conditions. We consider here two cases:
1. is very small: For small ? (less than 15 mV at room temperature), a Taylor series expansion of the
Butler-Volmer equation (17) yields:

..........................................................................................................(18)
Approximation being made here is that ex1+x for small values of x. Eq. 18 displays linear relationship
between current density and over-potential for small disturbances from equilibrium.

2. is very large: When is very large (> than 50-100 mV at room temperature), only the forward
reaction rate contributes significantly to current density. In other words, the reaction becomes
irreversible and the eq. 17 is simplified to :

.........................................................................................................(19)
Solving for yields,

......................................................................................(20)
A plot of and ln (j) should be a straight line with intercept as - RT/anF *ln(j ) with slope RT/aNF .
Eq. 20 is known as the Tafel equation.
o

Tafel equation is important to calculate transfer coefficient a and exchange current density j from the
slope and intercept as shown in figure 6.
o

Figure 6: plot of activation over-potential and current density. At low over-potential,

Tafelequation deviates from its linear nature.

Significance of exchange current density

The exchange current density, j , is a fundamental characteristic of electrode behaviour that can be
defined as the rate of oxidation or reduction at an equilibrium electrode expressed in terms of current
density. The exchange current density characterizes the absence of net electrolysis and zero
overpotential. The exchange current can be thought of as a background current to which the net
current observed at various overpotentials is normalized. For a redox reaction written as a reduction at
the equilibrium potential, electron transfer processes continue at electrode/solution interface in both
directions. The cathodic current is balanced by the anodic current. This ongoing current in both
directions is called the exchange current density. That is j = j = j ; Exchange current, in fact, is a
misnomer since there is no net current flow. It is merely a convenient way of representing the rates of
oxidation and reduction of a given single electrode at equilibrium, when no loss or gain is experience
by the electrode material. In fuel cell testing, the activation overpotential is started beyond the value
of exchange current density, i.e., there is no overpoential at j0. Thus, higher value of exchange current
density helps to improve kinetic performance of fuel cell.
o

As j represents the rate of exchange between the reactant and product states at equilibrium, it can
be defined from either the forward- or backward-reaction direction of Butler-Volmer equation (BVE). It
depends upon reactant concentration and temperature. Decrease in activation barrier and increase in
no. of reaction sites also improves j as well as fuel cell kinetics (assuming j and BVE are already
defined mathematically). It is obvious from the expression below that
0

exchange current density is function of concentration, temperature, G (activation barrier).

1

1.

j and fuel cell kinetics can be improved by increasing reactant concentration. By operating fuel
cell at higher reactant concentration, proportional improvement of kinetics can be noticeable.
o

Fuel cell using air instead of pure oxygen at the cathode leads to 5 times reduction of oxygen
kinetics compared to pure oxygen operation.
2.

Changing the temperature has an exponential effect on j . By increasing the temperature,

thermal energy available in the system increases and it will reach activated state easily.

3.

A decrease in activation barrier represents the catalytic influence of the surface of the
electrode. A catalytic electrode is one which significantly lowers the activation barrier for the
reaction. It has an exponential effect and small decrease in activation barrier cause large
effect. Using a highly catalytically active electrode therefore provides a way to dramatically
increase j and thus improves cell kinetics. It depends on choice of catalyst.

4.

Current densities are based on projected geometric area of an electrode. If an electrode

surface is extremely rough, the true surface area can be orders of magnitude larger than the
geometric surface area. Thus, by increasing surface roughness, i.e., no. of reaction sites per
unit area, j 0 and cell performance can be improved.

Significance of charge transfer coefficient

The charge transfer coefficient (a) signifies the fraction of the interfacial potential at an electrodeelectrolyte interface that helps in lowering the free energy barrier for the electrochemical reaction. It
expresses how the charge in the interfacial potential changes the sizes of the forward versus reverse
activation barrier. In operating batteries and fuel cells, a is the parameter that signifies the fraction of
overpotential that affects the current density. The value of a depends on the symmetry of the
activation barrier and it is always between 0 and 1.

= 0 is an extreme situation which signifies that there is no decrease in forward activation

barrier from equilibrium value. That means cell is in equilibrium.

= 1 implies that the reduction of activation barrier for the forward reaction is totally
dependent on over potential, ideal for electrochemical operation. Forward is completely
favoured. No backward reaction is taking place.

= 0.5 is for symmetric reactions. Here, the decrease in forward activation barrier is equal to
the increase in reverse activation barrier. The current densities for the forward and reverse
reactions are both given by j . It may be noted that even, at a = 0.5, more forward reaction is
taking place than backward reaction as the forward activation barrier is smaller than the
backward activation barrier.
o

Most electrochemical reactions have values between 0.2 to 0.5.

Concentration Polarization
Transport processes in fuel cells:

By this time, we are aware that in fuel cells the following processes occur simultaneously.

Mass Transport

Heat Transport

Momentum Transport

Charge (electron and ion) Transport

All these processes are very complex and have interlinkages and dependencies to each other as per the scheme
shown.

These transport processes of the fuel cell are equally important and responsible for the desired output of an
efficient fuel cell. The understanding of all the above processes in a fuel cell requires the knowledge
ofmulticomponent, multiphase, and multidimensional transport processes.
The basic knowledge may be gathered from the fundamental books on heat transfer, mass transfer, fluid
mechanics, and mass transfer. However, here we would like to present a simplistic view of the essential knowledge
required to understand the fuel cell.
Objective of this section is to make you understand the various transport processes and their impact on the fuel
cell.
Revisiting some of the basic concepts:

Consider a mixture of volume V, containing N different species. The concentration of a species i may be described
by anyone of the following ways,
molar concentration(Ci)

Where, n represents the number of moles of species i in the mixture and

i

Mass concentration(i)
Where, m represents the number
i

of moles of species i in the mixture and

Where, W represents the molecular weight of species i in the mixture.

i

Mole fraction(Xi)

Where C is total molar concentration.

Mass fraction(Yi)

Where

is the total mass concentration.

Concept of Average and Diffusion Velocity:

V is the velocity (absolute) of different species with respect to the stationary coordinate.
i

The average velocity of the species in the mixture can be defined as:

Mass- average velocity (v)

Thus the mass-average velocity is averaged by the proportional amount of mass of each species in the mixture.

Mass- average velocity (v*)

Thus the molar-average velocity is averaged by the proportional amount of moles of each species in the mixture.
It is to be noted that diffusion is the relative motion of a species with respect to the average motion of a mixture
as a whole. Thus,

Mass- average velocity

Mass- average velocity

Bulk motion: v or v*

Diffusion: vi or vi*

Therefore, the total mass flux and total molar flux of the species i relative to the stationary coordinate become,

Diffusion Law:

Consider a typical case of a fuel cell, which has a non-reacting mixture containing two species i,& j. The rate of
mass transfer for species i diffusing through j follows Ficks Law. For unidirectional flux in x-direction,

The above equation is the Ficks Law in terms of mass flux and conveys that the diffusion mass flux arises from the
mass concentration gradient. The negative sign shows that the diffusion flux is in the direction of decreasing
concentration.In a similar way, the equation can be written for the molar concentration gradient,

The proportionality constant Dij is called binary diffusivity, or the diffusion coefficient of the species i with respect
to species j. The unit of diffusivity is m2/s.
Table:A few relevant values (approx.) of binary coefficient required in fuel cell are shown in table at 25 o C and 1
atm. Pressure.
Species i

Species j

Dij(m2/s)

H2 (g)

Air (g)

0.41 X 10-4

O2 (g)

Air (g)

0.21 X 10-4

C2H5OH (l)

H2O(l)

0.12 X 10-8

CO2 (g)

H2O(l)

0.20 X 10-8

CO2 (g)

H2O(l)

0.24 X 10-8

O2 (g)

H2O(l)

0.63 X 10-8

N2 (g)

H2O(l)

0.26 X 10-8

Now, we would see that the momentum and heat transport laws are very similar to the mass transport and
equivalent laws are Newtons Law and Fourier Law, respectively. Consider a flow situation where the flow is over a
solid surface (x-z plane) in an orderly (laminar) and smooth manner in the x-direction, the velocity, temperature
and concentration of species i changes in the y-direction.
Note: The reader may get the details in any standard book on fluid mechanics, heat transfer, and mass transfer.
Newton's Law of Viscossity (momentum transport)

Where Md,y is the the momentum flux , v is the kinematic viscosity (m 2/s) and v is the velocity in x-direction.
X

The Fourier law can be represented by the following equation for the heat transfer in the y-direction,
Fourier's Law

Where, qy is the heat flux, is the thermal diffusivity (m 2/s).

These transport properties are related to each other by some non-dimensional ratios.After this brief discussion on
the transport properties, we will now focus on concentration polarization in the fuel cell.
Polarization:

Activation Polarization
Concentration Polarization
Ohmic Polarization

Recall that during the explanation of the activation polarization, we have assumed that the concentration of the
reactant is constant and independent of the cell current density. However, in real situation when we draw the
current, the concentration of the reactant decreases at the reaction site. Once the concentration of the reactant
decreases, the low availability of the reactant at the reaction site leads to the reduction of corresponding voltage.
If we further keep on drawing the current the reactant concentration depleted and at a certain current the cell
voltage drops down to zero voltage. This maximum current is known as the limiting current.
The reactant does not continued to be transported to the reaction site because of limitation of the certain
processes. A few major processes include the slow diffusion in the gas phase in the electrode pores (problem
aggravates in case of flooded electrode), slow diffusion of the product through reactant from the active sites and
vice-versa. These losses are known as reaction losses. Moreover, the concentration of the reactant decreases along
the flow channel from inlet to outlet, which adds to the increases in the voltage loss. The combined effect of the
Nernst loss and reaction loss is known as concentration loss or concentration polarization.
Concentration loss = Nernst loss + reaction loss

Quantifying Concentration Polarization

The quantification of the concentration polarization may be done by simplified or by rigorous engineering
approach. In this NPTEL course we will be limited to the simplified approach only.
Consider an electrode prepared with backing layer and catalyst layer. It may be assumed that the catalyst layer is
very thin as compared to the backing layer. Thus the thickness of the catalyst layer may be considered negligible.
The reactant concentration at the inlet is considered to be C o. We know that the reactant is transported from the
flow channel through convection and to the electrode by diffusion. If the concentration of reactant at the end of
the backing layer is Ce, and at the surface of the electrode is C e, the rate of the mass transfer at steady-state can
be calculated as shown below.
The mass transfer rate from flow channel to the electrode surface through convection is,

Where N is the mass transfer rate (mol/s), A is the electrode area and h mis the mass transfer coefficient.
Similarly, the mass transfer rate from electrode surface to the catalyst surface by diffusion is,

Where, Deff is the effective diffusion coefficient as the diffusion will be from the porous media.
In case of a porous electrode with porosity of and without any water flooding D eff will be defined by the
Bruggmanns correlation

At steady state these mass transfer rates will be same thus eliminating C e from the above two equation,

Where, R is the total mass transfer resistant of the reactant to the catalyst layer and defined as,
R=(1/h +1/D )/A
m

eff

We know that due to the different resistances the rate of mass transfer of the reactant to the catalyst site or
reaction site is N. Once the reactant is reached to the reaction site the electrochemical reaction will occur, which
results in the current. We are aware that the current generation and the rate of reactant transport is linked by the
Faradays law,

Where, j is Current Density.

On substituting the value of rate of mass transfer (N) in the above equation,

Thus by the above relation we can find out that the current density is proportional to the reactant concentration
difference in the inlet and the catalyst layer as well as the concentration of the inlet concentration of the reactant.
Here we can see that if the current density increases, C c will reduce and at the maximum current density the value
of Cc becomes zero.Therefore, the maximum possible current density (limiting current density; J L) when all the
reactant supplied to the catalyst layer is consumed by the electrochemical reaction, can be found out at C c = 0,

It can be emphasized at this moment that the limiting current at a particular design and operating condition is
fixed at a certain value. However, by improving the design and operating conditions the limiting current may be
improved by analyzing the above equation. Increase in mass transfer coefficient (h m) will improve J : How to
improve the mass transfer coefficient? The flow conditions must be improved in the flow channel.
L

Increase in effective diffusivity (D eff) will improve j : Issues of design and operating condition! The effective
diffusivity is the function of temperature and porosity of the electrode (or gas diffusion layer) and thus can be
improved by these improving these factors.
On combining J and J ,
L

It is very interesting relation and can easily provide the real concentration of the reactant at the catalyst surface if
the current density and limiting current density are known for a particular fuel cell at the operating conditions. The
above equation may be rearranged to,

Now, to quantify the concentration overpotential, consider Nernst equation for a single reactant species,

If the reactant concentration at the inlet and at the catalyst surface if same then the cell voltage (E) will be
maximum (EO). Thus,

or

A few points must be noted for the previous equation,

1.

The equation is valid at higher current densities.

2.

Reactant transport should be the rate limiting process.

3.

The pores of the gas diffusion layer are assumed to be free of water droplets.

4.

Other physico-chemical processes are ideal and do not affect the system considered.

Note: Detailed knowledge of the concentration polarization in terms of individual mass transport into the fuel
channel, diffusion of the reactant from the fuel channel to the interface of gas diffusion layer and catalyst layer,
and diffusion of the reactant into the catalyst layer (for high and low current densities), removal of the product
from the reaction sites etc. All these processes can evaluated with the complex mathematics along with various
co-relations. These processes are beyond the scope of the NPTEL course.

Transport of Electricity: Ohmic Polarization

The ohmic polarization arises due to electrical resistance in the cell components, including

Resistance to the flow of ions in the electrolyte (ionic resistance)

Resistance to the flow of electrons and ions in the catalyst layer (ionic and electronic
resistance)

Resistance to the flow of electrons through the electrode-backing layer, or gas-diffusion layer
(electronic resistance), and

Resistance to the flow of electrons through the interface contact and the terminal connections
(electronic resistance)

Ohmic polarization can be determined by Ohm's law,

where R is the sum of electronic, ionic, and contact resistance.

For practical fuel cells, ohmic polarization is mainly caused by ionic resistance in the electrolyte.

In fuel cell literature, the use of electrical resistance of the cell components, including
electrolytes, is often avoided and reciprocal resistance or conductance is commonly used. The
conductance is simply the inverse of resistance,

The resistance R depends on the material property as well as the geometry of the conductor as
follows,

Details of Mass and Electricity Transport in Electrolyte

As discussed earlier that the ohmic polarization is contributed by many components. However, in fuel
cell the ohmic polarization is largely contributed by the electrolyte. The electrolyte transports the ions,
that means the mass as well as the charge (or electricity) are transported by the electrolyte.
Therefore, the transport processes in the electrolyte will be discussed in the electrolyte.

The Mass transfer in the electrolyte is very similar to reactant transfer to the electrode as described
earlier. However, only exception is that the mass transfer arises in the electrolyte is by the motion of
mobile ionic species in the electric field set up between the anode and cathode. The motion of charged
species in the electric field is known as migration of the ions.

Thus in order to understand the complex behaviour of transport in the electrolyte, the discussion is
divided into 3 situation to make it simplified.

In the first situation, it will be considered that the mass transfer of the ionic species in the electrolyte
is purely due to the diffusion and there is no electric field between the anode and cathode. In the
second situation, it will be considered that the mass transport of the ionic species in the electrolyte is
due to migration only. That is the transporting species is having charge and electric field is set up
between the anode and cathode. In the third situation, the transport of charged species will be
considered due to simultaneous diffusion and migration.

Based on the previous discussion, the three situations are written below,

1. Mass transfer by diffusion

2. Mass transfer by migration
3.Mass transfer by simultaneous diffusion and migration of ions

All above three situations are described in the following discussion one by one.

Mass transfer in Electrolyte by Diffusion of Ionic Species

Consider the situation of a mobile ionic species, i, that is being discharged at an electrode surface.

The transfer process for the ionic species is thus created by the concentration difference (diffusion
mechanism). A representative concentration profile is shown in the adjacent figure.

The rate of diffusion towards the electrode surface for the ionic species i is, in terms of molar flux
(Ficks law)

D is the diffusion coefficient of the ionic species, i, with respect to the electrolyte solution and is mainly
a function of nature & molecular size of the species, temperature, and electrolyte viscosity.
i

Thus current density corresponding to the rate of ion transport is,

Where, is the thickness of the diffusion layer adjacent to the electrode surface. The typical value of
the diffusion layer is in the rage ~300 micrometer).
i

The limiting current density can be obtained at Ci,s = 0

where is the diffusion layer thickness at limiting current density.

L,i

If the diffusion layer thickness could be assumed almost invariant (which may not be necessarily true),
then i = L,i

Assuming all other processes at the electrode are reversible, the voltage loss due to lowering of the ion
concentration at the electrode surface can be estimated from the Nernst equation,

Mass transfer in Electrolyte by Diffusion of Ionic Species

In the earlier discussion, the charge on the species did not matter. However, while discussing migration
the charge on the species matters. The electrolyte may have positively and negatively charged species
along with the neutral species. Thus,
Electrolyte

Positive ion

Negative ion

Neutral species (eg. water) for electrolyte

Ions are constantly in random thermal motion. However, they start to accelerate in the direction of the
electric field once an external field is set-up across the electrolyte layer.
Acceleration is retarded by: viscous and electrical forces (mainly from ionic interactions).
Terminal velocity: (Driving forces = Retarding forces)

u is the mobility
i

d/dx gradient of the electrical potential

Electrical field is represented by the gradient of the electrical potential in the x-direction
u is the mobility (ionic velocity/potential gradient) of the ion (m2.mol/J.s).
i

The negative sign reflect that positively charge ion (z > 0) moves in the direction of decreasing
potential.
i

The molar flux due to terminal velocity,

Thus the current density arises,

Where, conductivity of the ion i is the transport property of the ion in the electrolyte is defined as

Then,

Which is simply an expression of Ohms law

The eq. is valid when C is uniform throughout
i

At this moment, the question comes that if all the charged species are involved then how to know the
effect of individual species. In this concern, the total current density J resulting from the migration of
all the ions in the electrolyte is equal to the sum of the contribution made by the transport of each of
the ionic species or,

On comparing this equation with the previous one, we can find out that the conductivity of the
electrolyte may be written as,

The migration of each ionic species in the electrolyte contributes to the total current density carried by
the electrolyte. In order to quantify the relative contributions, the transference number of the ionic
species, i, is defined as the fraction of the total current density that is carried by the given ionic
species, i, or

Substituting j and j ,
1

Since k is transport property, t is also a transport property of the electrolyte

If we integrate the equation, across the electrolyte layer thickness, we obtain the ohmic overpotential
due to the electrolyte,

On integration,

The relationship is valid only if the concentration is uniform in the electrolyte.

Mass Transfer by Simultaneous Diffusion and Migration of Ions
Total molar flux for the ion i under the combined effect of diffusion and ion migration,

Corresponding current density,

When a fuel cell reach a steady state, all the current is carried by the transport of ions that participate
in the electrode reactions
For all other ions present in the electrolyte, their flux due to the electric field effect (migration) is
counterbalanced by the flux due to the concentration gradient (diffusion) and no net transport of
electricity arises from the motion of these ions.
At this point we may emphasize that both the diffusion coefficient Di and the ion mobility ui are
the transport property of the ionic species i through the electrolyte solution and they may be related to

each other.
Consider a situation where there is no net current flow (J=0) through the electrolyte, that is, the
current arising from the ion diffusion due to the concentration gradient and from the ion migration in
an applied electric field reaches the same magnitude, but in the opposite direction.
Thus thermodynamic equilibrium is attained and the conc. of the ion i is given by the thermodynamic
Boltzmann distribution.

Where C , is the concentration of the ionic species i corresponding to zero (0) local potential ( ).
i

On the other hand, at j=0 and integrating the below written equation, from Ci, , at =0 to Ci at ,

we obtain,

On comparing with the equation written in the previous slide,

It should be pointed out that the Nernst-Einstein relation is valid even when the total current
through the electrolyte does not reduce to zero value, although it was derived when J=0. This is
because both u and D are the (transport) properties of the ion i in the electrolyte.
i

Considering equations

On rearranging
On integrating from the surface where x=0, =1 and Ci = Ci,s and in the bulk electrolyte sufficiently
away from the electrode surface where = 2 and C =C ,
i,

It may be noted that the above equation is the basis of current interruption method, that we will

discuss in characterization techniques.

At this point we may think if diffusion and migration is considered then why not the convection
process. Of course, we will discuss that also. The mass transfer, that is, the movement of material from
one location in solution to another, arises from atleast by one of them,

1.

Migration

2.

Diffusion

3.

Convection

The mass transfer to an electrode is governed by the Nernst-Planck equation, written for 1-D mass
transfer along the x-axis as,

The above equation is known as Nernst-Planck Equation

FUEL CELL MODELING

Need Of modeling

A virtual prototypes of fuel cell, which helps in fabrication

Insight into the electrochemistry of the fuel cell & processes that takes place in the heart of the
fuel cell

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.
Role of modeling in fuel cell development process [2]

Figure 1: Flow chart of fuel cell development process

Characteristics of a good model [2]
A good model should balances,

Robustness: model should able to predict fuel cell performance under a large range of
operating conditions and physical parameters.

Accuracy: it can be developed by using the correct assumptions, correct physical quantities and
input parameters, correct governing equations, and validation with experimental data.

Computational efforts: time required for calculation should be less, but sometimes for accuracy,
computational efficiency is compromised.

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,
E
=thermodynamically predicted voltage of fuel cell
=activation losses due to reaction kinetics

=ohmic losses from the ionic and electronic resistance

thermo
act

ohmic

conc

=concentration losses due to mass transport

Using the expression for

as,

conc

act

ohmic

from the previous chapter, the net j - v behaviour can br given

................................................(2)

C 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>>j .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: , , , ,,A,R

of ,, are related to and j
A

and j , where the values

ohmic

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)

This model is more sophisticated than the basic model.

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.

The model is well suited for polymer electrolyte fuel cell (PEMFC) and solid oxide fuel cell
(SOFC).

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

Reactants (H , H O, O , N ) transport in flow channel is by convection and in electrodes by diffusion.
2

Electrons transport is through the external circuit, whereas ions transport through membrane
electrolyte.
In membrane, water transport is by electroosmotic drag and back diffusion

Figure 3: Flux detail diagram of PEMFC

PEMFC

Figure 3shows the flux details needed in 1D model. Individual fluxes are represented by the
numbers.

Infuel cells, all species transport flux are related to the single charcter 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)

mathematically,

...........................................................(4)
where, j is the cell current density (A/cm 2), 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

is the net hydrogen flux (in - out) in the anode, i.e., the amount consumer in the oxidation
reaction. Similarly,
is the net flux of oxygen at cathode
rate due to oxygen reduction reaction at cathode.

is the water generation

water flux balance in the PEMFC is given as,

.............................................

...(5)

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.

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

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

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

............................................(9)
SOFC flux balance

Reactants (H , H O, O , N ) transport in flow channel is by convection and in electrodes by

diffusion .
2

Electrons transport is through the external circuit, whereas ions transport through membrane
electrolyte.

Figure 4: Flux detail diagram of SOFC

Figure 4 shows the flux detailed diagram of SOFC.

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

.............................................(10)

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.

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.Bur

here, for iD model convection is not cosidered 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 kinectics 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

Equations that deal specificially with phenomena in a fuel cell are-

Deacy's equation for fluid flow in conduits and porous media,

Fick's law of diffusion,

Stefan-Maxwell equation for multispecies diffusion,

Fourier's Law for heat conduction,

Faraday's Law for relationship between electrical current and consumption of reactants in an
electrochemical reaction,

Butler-Volumer equation for relationship between electrical current and Potential

Ohm's Law of electrical current conduction.

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 ( ), ohmic overpotential ( ), and concentration overpotential ( ).
act

act

act

For the present model, simplified version of equations are used by choosing appropiate assumptions.By
solving these equation we can determine cocentration profiles, activation overpotential( ), ohmic
overpotential ( ), and concentration overpotential( ) .
act

ohmic

conc

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,x i 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, D and void fraction, by Bruggeman's correction,
ij

.......................................................................................(13)
Electrolyte layer
Governing equations for species transport in the electrolyte.is depend on the type of fule 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,

....................................................................
..........(15)
where, LM is the electrolyte thickness, K is the electrolyte conductivity (S/cm) which is given as,
M

...............................................................................(16)
where, A (K/ohm) and activation energy, G (J/mol) are usually determine experimently.
act

For PEMFC, water and proton (H+) both transport through the membrane electrolyte.Proton flux is
given by Eq.(4) nd water flux through the membrane can be describe as combined effect of back
diffusion and electroosomotic drag,

...........................................
.......................(17)

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

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

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

dry

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

...............................................................
...........(20)
Ohmic overpotential is determined as,

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

Resistance of the membrance, R is given by,

m

..............................................................................................
(22)
Membrance conductivity, K for Nafion membrane is expressed as [3],
M

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

M,303 K

()=0.005193-0.00326

where, can be determine using Eq.(20)

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

.........................................................................(24)
For an ideal gas(p=CRT), the above equation becomes,

................................................................(25)
where, p0=1atm
Modeling Examples
1d SOFC Model

Figure 5 shows the 1D schematic of SOFC.

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

...............................................................(26)

................................................(27)

Figure 5: Schematic of SOFC

Using Eq. (10), H , H O flux are related with cell current density.
2

Integrating Eq.(26) and (27), gives linear profile of H ,H O concentration at anode,

2

.....................................................................(28)

......................................................................
(29)
At interface 'a', values of x ,x
H2

H2O

are known. Solving Eqs. (28) and (29) at interface 'b' yields,

....................................................................
(30)

...........................................................
(31)
where, tA is the thickness of the anode
Cathode
Siimilarly, one can obtained oxygen profile at cathode,

....................................................(32)
At interface 'c', Eq. (32) yields,

......................................................(33)
Combine Eqs. (25) and (33), cathode overpotential is given as,

.....................................
(34)
Electrolyte
From Eqs. (15) and (16), ohmic loss is given by,

................................
.(35))
Finally, a real SOFC voltage is written as,

.............................(36)

............................(37)
1D PEMC Model
Figure 6 shows the 1D schematic of PEMFC

Reactants (H , H O, O , N ) transport in flow channel is by convection and in electrodes by

diffusion.

Electrons transport is through the external circuit, whereas ions transport through membrane
electrolyte.

In membrane, water transport is by electroosmotic drag and back diffusion

Anode

Figure 6: Schematic of PEMFC

Similar to SOFC model, H , H O fluxes described as,
2

........................................................................................
(38)

.....................................................................................
......(39)
Using Eq. (9), the solution of the above equations,

........................................................................
..................(40)

........................................................
...............................(41)
here, is unknown.
At interface 'b', Eq. (40) and (41) yields,

.............................................................
.......................(42)

........................................................
.......................(43)
Cathode

Oxygen concentration profile at cathode interface 'c' is expressed as

.....................................................................
..........(44)
water concentration profile at cathode interface 'c' is given as,

..............................................................
.............(45)
where, tc is the thickness of the cathode.
Similar to SOFC model, cathodic overpotential is determine using Eqn (34)
Membrance electrolyte:
To calculate ohmic overpotential, water profile in membrane is required. Substitute Eq. (7) in Eq. (20)
and integrate, Eq.(20) becomes,

......................................................
..(45)

At interface 'b'
.......................................................................(46)

At interface 'c'
.......................................................................(47)
Nation watrer content can be relate with the water activity as,

......................
................................................(48)

......................
................................................(49)

......................................................................(50)
Combining Eqs.(43) and (48) and Eqs. (45) and (49) gives,

...............
......................................................(51)

........................................(52)

From Eqs. (46),(47),(51) and (52), two unknowns, and B

conductivity, K profile in membrance can calculated by Eqs.(23) and (45).

in

Eq.(45),the

Resistance in membrane is calculated by Eq. (22), hence ohmic overpotential is determine as,

..................................................................(53)
Finally, fuel voltage is given as,

.........................................................
....(54)
Direct Methanol Fuel Cell Modeling (DMFC) [4]

Figure 7 shows the schematic diagram of DMFC.

Complete oxidation of methanol (fuel at anode) takes place and product obtained is CO via 6
e- release.

Model consider the mass transport in the anode compartment.

Kinetics and ohmic effect considered in the catalyst layer.

Influence of different parameters on anode performance is investigated.

Figure 7: Schematic diagram of the anode bonded PEM DMFC

Mathematical Model

A membrane region of solid polymer electrolyte (PEM), protons produced at the catalyst layer
are transported via migration through it.

Active catalyst region(catalyst layer) on which oxidation of glucose takes place, it formed as a
thin film of proton conductive ionomer (e.g. Nafion) and carbon supported catalyst (e.g. PtRu/C) uniformly dispersed in the ionomer.

A diffusion region (diffusion layer) composed of highly porous and electronically material
(collect the electrons generated at the catalyst layer into the current collector).

Figure 8 : Schematic illustration of catalyst layer [5]

Model Assumptions

Steady state, isothermal conditions were considered .

Anode and cathode compartment have the same pressure .

Anode and cathode compartment assumed as mixed reactor .

Two phase flow in anode channel is neglected .

The electro-osmotic drag coefficient of the water for PEM is taken as fully hydrated, therefore it
depend only on temperature .

Concentration of oxygen taken high, so assumed constant concentration at cathode

compartment so no need of mass balance .

Electrochemical Cell Reactions

Governing Equations
Methanol transport in flow channel

..........................................................
...........................(55)
Mass transport in diffusion layer
water flux balance equation is given as,

.....................................................................................(56)
Methanol flux equation is expressed as,

........................................
.............................(57)

.........................
........................................(58)

.......................
.......................................(59)
Integrating Eq. (59) gives,

...............................................................
(60)
Combining Eqs. (55) and (66)

................................................................
(61)

where,

is the mass transfer coefficient,

is the superficial velocity of water

Mass transport in catalyst layer
Electrochemical reaction rate described by Tafel type Butler-Volumer Equation,

........................................................
..................(62)
Methanol flux equation given as,

........................
..................................................(63)
Flux balance of water is expressed as,

...........................................................................................(64)
Methonal, flux in catalyst layer decrease along z-axis due to its oxidation at the catalytic site, therefore
material balance of methonol,

.............................................................................................(65))
Anodic over potential at any location within the catayst layer is written as,

............................................................................................
.(66)
Ohm's law for solid phase,

.............................................................................................(67)
Ohm's law for ionomer phase,

.............................................................................................(68)
Variation of the over potential within in the catalyst layer given by,

...................................................................................
..........(69)
Mass transport in PEM
Water transport through the PEM results from both the electro-osmotic drag and diffusion, i.e.

Water flux caused by elctro-osmotic drag, at constant cell temperature is given by,

...................................................................................................
(70)
Water flux caused by water concentration gradient in the PEM,

..................................................................................
..................(71)

At higher current density enhanced water accumulation at cathode reaction raise its concentration on
the cathodic side into fully hydrated state, also anode is in fully hydrated condition, so we can
neglect N
drag

Final water flux equation is expressed as,

............................................................................................(72)
Similarly as anode diffusion layer, methanol flux in membrane given as,

..............................................................
..........................(73)
Solution Procedure

................................(74)

..
.........................................(75)
These equations can br transferred into first order equation as,

.......................................................................................(76)

.......................................................................................(77)

..............................................(78)

..............(79)

Dependent variables:

Boundary Conditions
Diffusion layer is ionically insulated, so that the protonic current density must be zero at the diffusion
layer/catalyst layer interface(z-0),

................................................................................(80)
Material balance of methonal at diffusion layer/catalyst layer interface(z=0)

.........
.......................(81)
In shooting technique appropriate initial guess is given to the variable and iterate it until the final value
due to initial guess will match with the actual final value.
At catalyst layer/PEM interface(z=lc), the protonic current density must be equal to the cell current
density l

.......................................................................................(82)
The flux through the catalyst layer is partly consumed in electrochemical reaction and remaining pass
through the membrane sa menthonol crossover, therefore,

.........................................................(83)
Intial value of i is known , others variables values are unknown so for solve these equations, proper
shooting technique is used.
Base - case parameterrs values

Results [4]
Anode overpotential of DMFC:Catalyst Pt-Ru, Methanol concentration in feed- 2 M

Methanol concentration variation with in the diffusion layer and catalyst layer at various current density

Variation of methanol crossover with current density at various feed concentrations

Effect of current density on anodic overpotential at various current density

Variation of reaction rate within the catalyst layer at different values of

current density of 0.3 A/cm2

Vriation of anodic overpotential with effective protonic conductivity

and

at cell

at different current density

References

1.

Modeling of fuel cell, http://www.aip.org/tip/INPHFA/vol-7/iss-4/p14.pdf

2.

Frano Barbir, PEM Fuel Cells: Theory and Practice, 2005, Elsevier Inc.

3.

Ryan O'Hayre, Suk-Won Cha, Whitney Colella, Fritz B. Prinz, Fuel Cell Fundamentals, 2nd
Edition, 2008, Wiley.

4.

K.T. Jeng, C.W. Chen, Modeling and simulation of a direct methanol fuel cell, Journal of Power
Sources 112 (2002) 376-375.

5.

Lixin You, Hongtan Liu, A parametric study of the cathode catalyst layer of PEM fuel cells using
a pseudo-homogeneous model, International Journal of Hydrogen Energy 26 (2001) 991999