Effects of Pressure

The change in Gibbs Free Energy with pressure of the fuel

cell reaction H2 + ()O2
H2O is given by
a a1/2

g f = g f RT ln
0 H2 O2

aH 2O

Where R is the universal gas constant 8.314 JK-1mol-1, T

is the absolute temperature in K, g f is the change in
0

Gibbs free energy at standard pressure and at

temperature T, a is the activity of the gas given by P/P0
where P is the pressure or partial pressure of the gas, P0
is the standard pressure, 0.1 Mpa= 1 bar.

S. Rajakaruna 2007 Renewable Energy Systems 402 1

 Effects of Pressure
If the pressure of hydrogen and oxygen increase, g f
becomes more negative and hence releases more
energy become available for conversion to electricity.
If the pressure of steam increases, less energy will be
available for the conversion to electricity.
Note here that the effect of change of temperature is
represented by the change in the value of g with
0
f
changing temperature. The second term only represents
the effect of pressure change.
The effect of temperature on maximum EMF can be
g f
seen by substituting the above equation in E =
2F
S. Rajakaruna 2007 Renewable Energy Systems 402 2
Change in EMF with Pressure -The
Nernst Equation
g 0f
RT a a1/2
RT a a1/2

E= + =E +
H2 O2 H2 O2
ln 0
ln
2F 2 F aH 2O 2 F aH 2O
0
Where E is the maximum EMF at standard pressure
and temperature T (K). Note E 0 drops with the
increasing temperature as seen in Table 2.2. This is
called The Nernst Equation and some of its other forms
are as given below.

S. Rajakaruna 2007 Renewable Energy Systems 402 3

 Nernst Equation
1

P P
H 2 O2 2

P0 P0
E = E0 +
RT
ln
2F PH 2O
P 0

If all the pressures are expressed in bar, then, P0=1. Hence above equation
can be expressed as:

1

E= E +
0 RT PH 2 PO2
ln
( ) 2


2F PH 2O

S. Rajakaruna 2007 Renewable Energy Systems 402 4

 Nernst Equation
In nearly all the cases, pressures of gases in above
equation are partial pressures as there are many gases
in the mix both at anode and cathode.
Furthermore, the overall pressure in the mix of gases at
the cathode and anode is the same. Because this
simplifies the design of the cell. If this system operating
pressure is P, then the partial pressures can be
expressed as a ratio of P.

PH 2 = P PO2 = P PH 2O = P
Where , and are constants depending on the
concentration of gases in the mix.
S. Rajakaruna 2007 Renewable Energy Systems 402 5
 Nernst Equation
1 1
1

RT P
2 2
RT RT
2
E= E + 0
ln =E +0
ln + ln ( P )
2F
2F 4F


This form of Nernst equation gives the effect of system
pressure P on the EMF as a separate term. It also shows
how partial pressures influence the EMF.
Example: On the cathode, oxygen is usually supplied as
air. The partial pressures of air at 0.1MPa are: N2=0.0781
MPa, O2=0.02095 MPa, Argon = 0.00093 MPa etc. Thus,
=0.2095 and P=0.1MPa= 1 bar
The partial pressure of H2 depends on how fuel processor
produces hydrogen.

S. Rajakaruna 2007 Renewable Energy Systems 402 6

 Fuel and Oxygen Utilization
As hydrogen passes through the anode, it is used in the
reaction. So the partial pressure of hydrogen will
progressively decrease as it flows from one end to the
other end of the anode.
The same is true for oxygen. As oxygen flows from one
end to the other on the cathode, its partial pressure will
also gradually decrease.
Since and both decrease, the EMF generated
continues to drop as the gases flow from the entry (inlet)
to the exit (outlet). It will be worst near the outlet.

S. Rajakaruna 2007 Renewable Energy Systems 402 7

 Fuel and Oxygen Utilization
Since the bipolar plates on the electrode are good
conductors, there cannot be different voltages in the
same cell. Therefore, it is the current density that drops
as the gases flow towards outlet.

1

RT 2 + RT ln P
4F ( )
E=E +
0
ln
2 F

Due to the RT term, it is also clear that the effects of
decreasing partial pressures is more at high
temperature fuel cells such as Solid Oxide Fuel Cell.

S. Rajakaruna 2007 Renewable Energy Systems 402 8

 Fuel Utilization
For high fuel efficiency, it is required that all the fuel
supplied to the cell used in the reaction. But at the same
time it can be seen from the above discussion that the
pressure of H2 at outlet should not be reduced to very
low levels. As a result, fuel and oxygen utilization need
careful optimising, especially in high temperature fuel
cells.
Fuel Utilization Ratio (u) is defined as,

N used
N in
N out

u= =
H2 H2 H2
in
N H2 N Hin2
S. Rajakaruna 2007 Renewable Energy Systems 402 9
 Fuel Utilization Ratio
where N is the flow rate in moles/s. For a solid-
oxide fuel cell the desired range of u is from 0.7
to 0.9.
Overused-fuel condition: i.e. u> 0.9, will lead
to fuel starvation near the outlet and cause
permanent damage to cells.
Underused-fuel condition: i.e. u<0.7, will
cause unexpectedly high cell voltages.

S. Rajakaruna 2007 Renewable Energy Systems 402 10

 Terminal Voltage of Practical Cells
g f
The maximum EMF given by the equation E =
2F
is an ideal value assuming there are no losses.
The practical terminal voltage of a fuel cell is
considerably less than the above value due to
various types of losses.
At temperatures below 100C, the maximum EMF
E is about 1.2 V. Figure 3.1 shows the variation of
terminal voltage with current density of a practical
fuel cell operating at 40C and standard pressure.

S. Rajakaruna 2007 Renewable Energy Systems 402 11

 Terminal voltage of a low-
temperature fuel cell

S. Rajakaruna 2007 Renewable Energy Systems 402 12

 Terminal voltage of a low-
temperature fuel cell
Note the following in the figure.
Even the open circuit voltage is less than the
theoretical value.
There is a rapid initial fall in voltage with
increasing current density.
Then there is a range of current density where
drop of voltage is almost linear. In this linear
region, the slope is less than in the initial region.
When current density approaches some high
values, the voltage starts to fall rapidly.
S. Rajakaruna 2007 Renewable Energy Systems 402 13
 Terminal voltage of a high-
temperature fuel cell
As discussed earlier, the maximum EMF (E) falls with
the increasing temperature. At about 800C, E is ab out
1.0 V. Figure 3.2 shows how the terminal voltage of a
practical cell at 800C varies with the current den sity.
Note the following in the figure.
Open circuit voltage is almost equal to the theoretical
value.
There is no rapid drop in voltage at low current densities.
The graph is much more linear.
At about the same high values of current densities, the
voltage starts to fall rapidly.
S. Rajakaruna 2007 Renewable Energy Systems 402 14
 Terminal voltage of a high-
temperature fuel cell

S. Rajakaruna 2007 Renewable Energy Systems 402 15

 Fuel Cell Irreversibilities Causes
of Voltage Drop
There are four main types of irreversibilities that cause
the terminal voltage to drop below the Maximum EMF
(E). E is also called the ideal emf, no-loss emf or the
reversible emf.

1. Activation Loss
2. Fuel Crossover and Internal Currents
3. Ohmic Losses
4. Mass Transport or Concentration Loss

S. Rajakaruna 2007 Renewable Energy Systems 402 16

 Activation Loss
Activation Loss is the main reason for rapid drop in
terminal voltage of low-temperature fuel cells at low
current densities. It is caused by the slowness of the
reactions taking place on the surface of the electrode. A
portion of the available energy is lost in driving the
chemical reaction or to supply the activation energy.
The activation loss of voltage is described by Tafel
Equation as: i
Va = A ln
i0
where A is a constant which is higher for slower
reactions and i0 is a constant higher for faster reactions.

S. Rajakaruna 2007 Renewable Energy Systems 402 17

 Activation Loss
For the slow
reaction A is higher,
i0 is smaller.
For the fast
reaction A is smaller
and i0 is higher.
Due to the
logarithmic function
it is i0 which affects
the voltage drop
more.

S. Rajakaruna 2007 Renewable Energy Systems 402 18

 Activation Loss
The above equation describes the voltage drop only for i
> i0. For i < i0, the voltage drop is zero. Therefore, higher
the value of i0, the lower is the voltage drop.
The constant i0 is called the exchange current density.
This is the current corresponding to the electrode
reaction in equilibrium under open-circuit condition.
Under zero current supplied to the external circuit, the
electrode reaction is still happening, but in both
directions.
+
At the cathode: O2 + 4e + 4 H 2 H 2O
+
At the anode: 2 H 2 4 H + 4e
S. Rajakaruna 2007 Renewable Energy Systems 402 19
 Activation Loss
When the external circuit is switched on, the exchange
current density is readily available so drawing a current
up to i0 will cause no voltage drop.
The anode and cathode have two different i0 values as
i0a and i0c respectively.
For a hydrogen fuel cell, i0c<<i0a. Thus, the activation
voltage drop due to anode is negligible compared to that
at the cathode. But for other types of fuel cells, this may
not be true.
Even if the voltage drop at both electrodes are
considerable the combined effect can still be described
by the Tafel equation.
i
The cell terminal voltage is
then given by,
V = E Va = E A ln
i0
S. Rajakaruna 2007 Renewable Energy Systems 402 20
 Effect of i0

S. Rajakaruna 2007 Renewable Energy Systems 402 21

 Methods to increase i0
1. Increasing the cell temperature: Increase of
temperature increases the reaction under open-circuit
condition. Therefore i0 is higher and the voltage drop is
less. By considering low and high values for i0, the
shapes of V-I characteristics of Figure 3.1 and 3.2 at
low current levels can be described. For a low
temperature cell i0 is about 0.1 mA and that for a
800C cell is about 10 mA, which is 100 times large r.
2. Using more effective catalysts.
3. Increasing the contact area of the electrode.
4. Increasing reactant concentration. Ex. Use pure
oxygen instead of air.
5. Increasing the pressure of reactants.
S. Rajakaruna 2007 Renewable Energy Systems 402 22
 Fuel Crossover and Internal
Currents
Although the electrolyte is not supposed to allow the
passing of the fuel (H2) and electrons between the two
electrodes, a very small leakage does happen in all fuel
cells. Both hydrogen and electron crossovers have the
same effect that they reduce the charges available to the
external circuit.
Although, this leakage current is not large enough to
affect the energy efficiency, it does cause a very
considerable drop in open-circuit voltage.
Because of the leakage, the current produced under
open-circuit condition is not zero.

If in is the internal current density, it can be considered

in the Tafel equation as:
S. Rajakaruna 2007 Renewable Energy Systems 402 23
 Fuel Crossover and Internal
Currents
i + in
V = E A ln
i0
Thus, the open-circuit terminal voltage is given by,

in
VOC = E A ln
i0
Using typical values for a low-temperature cell, E=
1.2v, A=0.06 V, i0=0.04mA.cm-2 and in=3 mA.cm-2, V-I
characteristics can be drawn as below.
S. Rajakaruna 2007 Renewable Energy Systems 402 24
 Activation and Internal Current
Losses

Compare this with Figure 3.1 and see how closely it matches the V-I
characteristic of a practical cell at low current densities.

S. Rajakaruna 2007 Renewable Energy Systems 402 25

 Ohmic Losses
Ohmic losses are due to the resistance to the flow of (a)
electrons through the electrodes, bipolar plates and
other stack connections and (b) ions through the
electrolyte.
In most fuel cells, ohmic loss is mainly due to the
electrolyte.
The voltage drop is directly proportional to the current
density.
Vo = i r
Where i is the current density and r is the resistance
per unit area.

S. Rajakaruna 2007 Renewable Energy Systems 402 26

 Ohmic Losses
Ohmic losses are important in all types of fuel
cells. To reduce the ohmic losses, following
can be done.
1. Use of electrodes with highest possible
conductivity.
2. Good design and use of suitable material for
bipolar plates.
3. Making the electrolyte as thin as practically
possible while making sure no direct contact
between electrodes is possible and enough
physical strength is available in the stack.

S. Rajakaruna 2007 Renewable Energy Systems 402 27

 Mass Transport or Concentration
Loss
As current is drawn to the external circuit, gases are
consumed, thus causing a reduction in pressure of both
hydrogen and oxygen at the electrodes if the gas supply
rates are constant. This reduction in pressure at
electrodes due to consumption is the reason for the
concentration loss.
If il is the limiting current corresponding to zero
pressure at the electrodes, the concentration loss can be
expressed using the Nernst equation as,
i
Vc = B ln 1 for i il
il
S. Rajakaruna 2007 Renewable Energy Systems 402 28
 Concentration Loss

i
V = E + B ln 1 E = 1.2V , il = 1000mA
il
S. Rajakaruna 2007 Renewable Energy Systems 402 29
 Combined Effect of All Losses
The effects on terminal voltage by all the
irreversibilities that were discussed can be
represented by the following equation.
i + in i + in
V = E (i + in )r A ln + B ln 1
i0 il
Where E is the maximum EMF (reversible open-
circuit voltage), V is the terminal voltage, i is the
current density in the external circuit.

S. Rajakaruna 2007 Renewable Energy Systems 402 30

 Typical Values of Parameters

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