Electrical Energy Storage Systems

(MIET2131)

Session 2: Fuel cell fundamentals

A/Prof. Bahman Shabani

1
Outlines

Fuel cell fundamentals

- Faraday constant
- Hydrogen consumption and production rates http://www.geifuelcells.com/innovation/ht-pem

- Thermodynamic analysis
- Fuel cell efficiency
- Fuel cell performance curve
- Fuel ell heat generation

2
Faraday constant (F)

Faraday Constant (F) = N.e=(6.022*1023)*(1.602*10-19 ) = 96485 C

‘e’ is the electrical charge of an electron and ‘N’ is Avogadro’s number.

Considering the basic equation of the chemical reaction

happens in a fuel cell (e.g. PEM fuel cell) two electrons
pass round the circuit for each water molecule produced
and each hydrogen molecule used. So for one mole of
hydrogen used, 2N electrons pass round the external
circuit (where N is Avogadro’s Number).

IMPORTANT NOTE: 1 Mole = 6.022*1023 molecules

Anode Reaction

H 2 → 2 H + 2e −
+

Cathode Reaction

0.5O2 + 2e− + 2H + → H 2O
Overall Reaction

0.5O2 + H 2 → H 2O

3
PEM Fuel Cells: Real Equation

 λ −1
λ air N 2 + (λ Hydrogen − 1)H 2
3 .76 3 .76
λ Hydrogen H 2 + λ air (0 .5O2 + N 2 ) → H 2 O +  air O 2 +
2  2  2

(λhydrogen −1) H 2 λ hydrogen H 2

 λ −1 3 . 76
λ air ( 0 . 5 O 2 +
3 . 76
N2) H 2 O +  air O 2 + λ air N 2
2  2  2

Important note: Even with the actual above- mentioned equation the overall reaction that happens
inside the fuel cell is the same as that introduced before (see below). In fact the other elements (extra
oxygen, hydrogen and nitrogen) leave the fuel cell untouched.

0.5O2 + H 2 → H 2O

4
Hydrogen Utilisation Coefficient

H2 in

H2 reacted

H2 out

Utilisation coefficient = H2-reacted / H2-in

5
Hydrogen reaction rate

The electrical charge applied= 2F× Number of hydrogen moles

The electrical charge applied/time= 2F× Number of hydrogen moles/time
Electrical current = 2F × Number of hydrogen moles/time

Number of hydrogen moles/time = I/2F (moles/s)

If the stack comprises ‘n’ cells then the reaction rate would be:
nI/2F

This is the reaction rate of hydrogen

This equation can be also expressed based on the stack power (P) and the average
cells’ voltage (Vc):
1 P
H 2 reaction rate = ( moles / s )
2 F Vc
Or
1 P
H 2 reaction rate = ( kg / s )
1000 F Vc
6
Hydrogen reaction rate
Here you need to consider the equation of the actual reaction where the hydrogen
stoichiometry is above 1:

 λ −1
λ air N 2 + (λ Hydrogen − 1)H 2
3 .76 3 .76
λ Hydrogen H 2 + λ air (0 .5O2 + N 2 ) → H 2 O +  air O 2 +
2  2  2

In this case the previous equation for hydrogen reaction rate can be used as below:

λ Hydrogen P
H 2 usage rate = ( kg / s )
1000 F Vc

By measuring the actual consumption (usage) rate you are able to calculate the hydrogen
stoichiometry or the hydrogen utilisation coefficient.

Notes:
- You will practice this in the laboratory activity arranged for this course.
- You can apply all these equations for hydrogen production using an electrolyser

7
Oxygen reaction rate

Similarly the oxygen reaction rate in a fuel cell (moles/s and kg/s) would be:

1 P
O2 reaction rate = ( moles / s )
4 F Vc

This can be represented in (kg/s) by considering the molar mass of oxygen (32 g):

32 × 10 −3 P P
O2 reaction rate = = 8.29 × 10 −8 ( kg / s )
4 F Vc Vc

8
Inlet and exit air
(based on actual equation of the reaction)

 λ −1
O2 + 3.76 λair N 2 + (λ Hydrogen − 1)H 2
3.76
λ Hydrogen H 2 + λair (0 .5O2 + N 2 ) → H 2 O +  air
2  2 

Air contains about 21% (molar proportion) oxygen and about 79% nitrogen, hence the
molar rate of air usage would be:
1 P
λair
4 F Vc
Air usage rate = ( moles / s )
0.21
And considering the molar mass of air (28.97 g), the air usage rate (kg/s) would be:
P
Air usage rate = 3 .57 × 10 − 7 λair ( kg / s )
Vc
The exit air is calculated by removing the mass of the reacted oxygen from the total mass
of air entering the fuel cell:

(
Exit air rate = 3 .57 × 10 − 7 λair − 8.29 × 10 −8 )VP ( kg / s )
c

9
Water consumption and production rates

Now you should be able to repeat similar calculations for water consumptions or
production rates in electrolysers and fuel cells.

Note: The molar mass of water is 18.02 g

10
Fuel cell electrical work

When one mole of hydrogen reacts with oxygen the amount of electrical charge passing the circuit is -2F.

The electrical work is voltage times charge (W=q.V). So:

Charge ×E = electrical work

E: Fuel cell voltage

Electrical work (J/mole of hydrogen consumed)= -2EF

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Output voltage of a 100% efficient fuel cell
In practice and even theoretically a 100% efficient fuel cell is impossible. However, let’s follow this
assumption to see what would be the voltage produced by each cell if a fuel cell is 100% efficient.

The maximum energy that could be released during the burning process is obtained using the fuel
calorific value or changing in enthalpy of formation:
H 2 + 0.5 O2 → H 2O ( Steam) ∆ h f = LHV = −241830 J /( Mole of hydrogen )
H 2 + 0.5 O2 → H 2O ( Liquid ) ∆ h f = HHV = −285840 J /( Mole of hydrogen )

Enthalpy of formation If all the energy released by the fuel calorific value converts into
electricity (a 100% efficient fuel cell) then the fuel cell voltage,
at 298.15 °K (J/mol)
which is also called Electromotive force (E) is:
Water (Steam) -241827
Water (Liquid) -285838
∆h f
Hydrogen 0 ∆ h f = −2 E.F ⇒ Emax,100% eff . = −
Oxygen 0
2F
Nitrogen 0 E = 1 .48 V HHV E = 1 .25 V LHV
Enthalpy of formation (J/mole)
Water (Steam) h f , H 2O = 143 .05T − 46.432T 1.25 + 5.5167T 1.5 − 0.01849T 2 − 253719 .49

Hydrogen h f , H 2 = 56.505T − 88890.4T 0.25 + 116500 LnT + 1121400T −0.5 − 376189.944

Oxygen h f ,O2 = 37 .342T + 8.0408 × 10 −6 T 2.5 + 357140 T −0.5 − 2368800 T −1 − 23884 .22

Nitrogen h f , N 2 = 39 .060T + 1025580 T −0.5 − 10727000 T −1 + 410200000 T −2 − 39677 .027

Sonntag, R. E., C. Borgnakke and G. J. V. Wylen (2003). Fundamentals of Thermodynamics. England, John Wiley & Sons Ltd.

12
Fuel cell energy efficiency
The efficiency of a power production unit is always defined as the ratio of useful energy or power
(target) to the maximum available energy or power from which the useful energy or power is extracted.
So for the fuel cell unit in which extracting the electrical power is the main target the stack energy
efficiency is defined:

electrical energy produced per mole of fuel

η= × 100
Maximum energy that could be released by one mole of fuel

By considering ‘q’ the electrical charge that is released by the reaction between hydrogen and oxygen
(air) and by substituting the actual cell voltage (Vc) and the maximum cell potential:

Vc × q V
η= ×100 ⇒ η = c ×100
Emax × q Emax

For having the maximum electrical energy (theory) the water in the outlet should be is in liquid form.
Clearly, in case of steam in the exit, part of the fuel’s energy has been used for vaporizing water
molecules. So for calculating the stack efficiency the HHV of hydrogen has to be used:
Vc
η=µ ×100
1.48
µ is called hydrogen utilization factor (or Faraday efficiency if the theoretical reaction is considered).
From all the hydrogen fed to stack just part of that is used in the stack and the rest leave the stack
untouched.

13
Maximum theoretical voltage of a fuel cell
The reaction between hydrogen and oxygen (producing water) is exothermic. It means even it is done
electrochemically (no combustion), this heat is still produced. Obviously this amount of hydrogen’s
chemical energy that converts to heat will not contribute in electricity production.

From thermodynamics, this heat is calculated

through the following equation:

Q = T∆s
Hence the amount of energy available per
mole of hydrogen would be:

∆ h f − T∆ s f
It is notable that

h f −T s f
is called Gibbs free energy of formation; hence, the
maximum output voltage of fuel cells can be
calculated by determining the difference between
the Gibbs free energy of formation of products and
reactants:

∆g f
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Maximum theoretical voltage of a fuel cell
Regarding this fact that the fuel cells cannot be 100% efficient if the Gibbs free energy of formation
instead of enthalpy of formation is used, the maximum theoretical voltage supplied by fuel cells can be
calculated as below:
∆g f
∆ g f = −2 E.F ⇒ Emax,theoretical = −
2F
This also called the Reversible Open Circuit Voltage (OCV) of the fuel cell. We will cover the fuel cell
irreversibilities later

Important Note: Gibbs free energy of formation is a function of temperature. Hence the maximum
theoretical voltage supplied by fuel cells is affected by the fuel cell operating temperature. At 25 °C, this
maximum voltage is calculated to be 1.23 V.
T T
d h f ,T = c p .dT ⇒ h f ,T = ∫ c p .dT ⇒ h f ,T = h f , 298.15 + ∫ c p .dT
0 298.15

T
1
g f ,T = h f ,T − T ( s 298 .15 + ∫
298 .15
T
c p .dT )
Sonntag, R. E., C. Borgnakke and G. J. V. Wylen (2003). Fundamentals
of Thermodynamics. England, John Wiley & Sons Ltd.

Enthalpy of Molar entropy

Molar specific heat (J/mol.°K)
formation at 298.15 °K (J/mol.K)
at 298.15 °K (J/mol)
Water (Steam) -241827 188.83 c p , H 2O = 143.05 − 58.040T 0.25 + 8.2751T 0.5 − 0.036989T
Water (Liquid) -285838 70.05 -
Hydrogen 0 130.59 c p , H 2 = 56.505 − 22222.6T −0.75 + 116500T −1 − 560700T −1.5
Oxygen 0 205.14
c p ,O2 = 37.342 + 2.0102 × 10 −5 T 1.5 − 178570T −1.5 + 2368800T −2

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Maximum reversible efficiency
Fuel cell efficiency limits

This can be calculated by dividing the maximum theoretical electrical energy released by the maximum
energy (including heat) that can be released:

∆g f
η max =
∆h f

Example:

Form of Temperature Reversible OCV Maximum open circuit voltage in a Max Eff. (%)

water (°C) (Maximum electromotive Force) 100% efficient fuel cell

product
100 1.17 1.48 79%
Gas

16
Maximum theoretical voltage of a fuel cell
The effect of operating temperature

Form of water product Temperature ∆ g f (kJ/mole) Reversible OCV

(°C) (Maximum Electromotive Force)

25 -237.2 1.23
Liquid
80 -228.2 1.18
Liquid
100 -225.2 1.17
Gas
200 -220.4 1.14
Gas
400 -210.3 1.09
Gas
600 -199.6 1.04
Gas
800 -188.6 0.98
Gas
1000 -177.4 0.92
Gas

Fuel cell systèmes explained , Larminie, Dicks Maximum EMF (reversible open circuit voltage)
atmospheric pressure
1.3
As shown in this table, the reversible OCV of the fuel

(maximum theoretical EMF)

1.2
cell drops when the operating temperature of the fuel

Reversible OCV
cell increases. 1.1

Volt
1

Do you think, overall, decreasing the fuel cell 0.9

operating temperature is a favourable measure to 0.8

enhance the performance of the fuel cell? 0.7
0 200 400 600 800 1000 1200
We will answer this question soon ………. Temperature (C)

17
Polarisation curve
Irreversibilities (Overpotentials)
The theory suggests the voltage of each cell is about 1.2 V, but in practice this voltage is less and even
drops further when an electrical load is connected to the fuel cell.

The result of these fuel cell

irreversibilities is extra heat
generated by the fuel cell that will
be discussed later in this session

These irreversibilities are

known by other terms such as:

• Overvoltage
• Voltage drop
• Overpotential
• Polarisation
• Losses

Source: Fuel cell systems explained,

Larminie and Dicks, 2003 18
Internal current (Fuel crossover)
This happens specially in low-temperature fuel cells whereas
in higher-temperature fuel cells it is usually negligible
(Larminie and Dicks 2003).

When no load is connected to fuel cell, the open circuit

voltage is smaller than the reversible OCV. It indicates that
an internal current is there even before any actual load is
connected to the cell. The effect of this internal current can
be assumed equivalent to fuel wastage through fuel
crossover through the membrane from one electrode to the
other without reaction

How can we measure the fuel cell internal current?

This can be calculated by measuring the hydrogen gas consumption rate at open circuit voltage when no
load is connected to the fuel cell. This consumption can be considered as the result of the current
passing through the fuel cell internally (just through the external circuit: no load). Then we have:

nI
H 2 reaction rate ( moles / s ) =
2F
2 F × H 2 reaction rate
I=
n

19
Activation losses
This loss caused by the limitations on the rates of the reactions taking place on the surface of the
oxygen and hydrogen electrodes. This kind of polarisation occurs in the first part of the polarisation
curve from the left as shown in the following curve. This is basically the potential used to kick start the
fuel cell chemical reaction for transferring the electrons.

∆Vact

20
Ohmic losses
These losses are due to:

• Ionic resistance of electrolyte

• Electrical resistance of electrodes and
bipolar plates
• Electrical resistance of cells
interconnections

That is why the material chosen for

electrodes, bipolar plates, and electrolyte
and also the manufacturing quality of fuel
cells (e.g. the fuel cell interconnections)
are playing important roles in the
performance of the fuel cell.

These losses vary linearly with current as they simply follow

the ohm law (V=RI).

Question: Do you recommend a thinner membrane to reduce Ohmic resistance against the
flow of ions? What kind of challenges might be associated with this solution?

21
Mass transport (concentration) losses
• It happens when higher currents are drawn
from the fuel cell

• This is the result of reduction in the

concentration of oxygen that leads to reduction
in the partial pressure of this reactant

• By using pure oxygen instead of air these

losses are can be reduced

• Increasing the oxygen stoichiometry can help

reduce these losses; however, there would be
some other problems associated with using
extra air (e.g. dry membrane)

• Reduction in the supply pressure of hydrogen

(due to high rate of consumption) also
contributes in these losses.

Source: Fuel cell systems explained,

Larminie and Dicks, 2003 22
Fuel cell performance curve

V = E − ( ∆Vact + ∆Vint + ∆Vohm + ∆Vtrans )

23
Fuel cell heat generation

• Fuel cell irreversibilities are the reasons for heat generation within the fuel cells

• Fuel cells generate more heat at higher currents. When a fuel cell operates at its maximum power point
its heat generate rate is maximum.

This gap
converts to heat

24
Fuel cell heat generation
To calculate the fuel cell heat generation rate, its voltage should be compared the output voltage of a
100% efficient fuel cell (1.48 V per cell).
•
Qtotal = nI ( EMF (100 % efficient cell .liquid water ) − V cell ) = nI (1 .48 − V cell )

The actual voltage of the fuel cell can be obtained from following equation:
Vcell = E − ( ∆Vact + ∆Vint + ∆Vohm + ∆Vtrans )

Hence the maximum heat generated by the fuel cell is:

•
Qtotal = nI (1.48 − E + ∆Vact + ∆Vint + ∆Vohm + ∆Vtrans )

This gap
converts to heat

25
Fuel cell energy flow
(Sankey diagram)

How the generated heat is removed from the 500 W (540 W) PEM BCS
fuel cell (ambient temperature 30, ambient pressure 100 kPa, inlet air
pressure 35 kPa g, inlet hydrogen pressure 35 kPa g, air stoichiometry 2)

26
Fuel cell water management

As discussed earlier the water content of the membrane affects its conductivity against
the flow of ions. The following figures are relating the relative humidity of the exit air with
the conductivity of the membrane and also the over performance of the fuel cell.

Source: Zhang, J., Y. Tang, C. Song, Z. Xia, H. Li, H. Wang and J. Zhang (2008). "PEM fuel cell relative humidity (RH) and its effect on
performance at high temperatures." Electrochimica Acta 53(16): 5315-5321.

Question:
What type of the fuel cell losses is more affected by the humidity level of the fuel cell?

27
Exit air relative humidity
 λ −1
λ air N 2 + (λ Hydrogen − 1)H 2
3 .76 3 .76
λ Hydrogen H 2 + λ air (0 .5O2 + N 2 ) → H 2 O +  air O 2 +
2  2  2
In reality some water molecules enter the stack (because of the
water content of the inlet air), and these water molecules leave the The number of water
stack through the stack’s exit port. This can be reflected in the
above-mentioned equation.
molecules entering the fuel
cell with the inlet air
PH 2O
ϕexit = (nw,in)can be obtained from
Psat the relative humidity and
n w ,exit the pressure of the inlet air.
PH 2O = Pexit , air
nexit ,total
Note: Pw is the water
n w , produced + n w ,in
PH 2O = Pexit , air vapour pressure at the
n w ,in + n w , produced + nO2 ,exit + n N 2 ,exit inlet. Can be calculated by
knowing the relative
Pw humidity and the
(0.42 + )
Pinlet ,air − Pw temperature of the inlet air.
PH 2O = Pexit ,air
Pw
(1 + )λair + 0.21 Pw
Pinlet ,air − Pw ϕin =
Psat
28
Fuel cell heat and water management
• The ideal relative humidity of the exit air is between 80% and 100%
• Relative humidity below 80% for the exit air is the sign of cell dehydration
• Relative humidity above 100% (theoretically, it is meaningless in practice) means the membrane is
flooded
• Inlet air relative humidity, fuel cell operating temperature and air stoichiometry are the key
parameters playing role in the fuel cell’s humidity level.

The results of a
theoretical analysis on
a 500 W BSC fuel
cell. Inlet air relative
humidity 60%,
ambient temperature
30 C. Inlet air and
hydrogen pressures 5
psi. Exit reactants
pressure 3 psi

29