Fuel Cell Systems Explained - 2003 - Larminie - Appendix 2 Useful Fuel Cell Equations

Appendix 2
Useful Fuel Cell Equations
A2.1 Introduction
In this appendix, many useful equations are derived. They relate to
• oxygen usage rate
• air inlet flow rate
• air exit flow rate
• hydrogen usage, and the energy content of hydrogen
• rate of water production
• heat production.
In many of the sections that follow, the term stoichiometric is used. Its meaning could
be defined as ‘just the right amount’. So, for example, in the simple fuel cell reaction
2H2 + O2 → 2H2 O
exactly two moles of hydrogen would be provided for each mole of oxygen. This would
produce exactly 4 F of charge, since two electrons are transferred for each mole of hydro-
gen. Note that either or both the hydrogen and oxygen are often supplied at greater than
the stoichiometric rate. This is especially so for oxygen if it is being supplied as air. If
it was supplied at exactly the stoichiometric rate, then the air leaving the cell would be
completely devoid of oxygen. Note also that reactants cannot be supplied at less than the
stoichiometric rate.
This stoichiometry can be expressed as a variable, and the symbol λ is normally used.
Its use can be put like this. If the rate of use of a chemical in a reaction is ṅ moles per
second, then the rate of supply is λṅ moles per second.
To increase the usefulness of the formulas, they have been given in terms of the
electrical power of the whole fuel cell stack Pe , and the average voltage of each cell in
Fuel Cell Systems Explained, Second Edition James Larminie and Andrew Dicks
© 2003 John Wiley & Sons, Ltd ISBN: 0-470-84857-X
10.1002/9781118878330.app2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/9781118878330.app2 by UFMA - Universidade Federal do Maranhao, Wiley Online Library on [08/04/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
396 Fuel Cell Systems Explained
the stack Vc . The electrical power will nearly always be known, as it is the most basic
and important information about a fuel cell system. If Vc is not given, it can be assumed
to be between 0.6 and 0.7 V, as most fuel cells operate in this region (see Figures 3.1 and
3.2). If the efficiency is given, then Vc can be calculated using equation 2.5. If no figures
are given, then using Vc = 0.65 V will give a good approximation. Estimate somewhat
higher if the fuel cell is pressurised.
A2.2 Oxygen and Air Usage

From the basic operation of the fuel cell, we know that four electrons are transferred for
each mole of oxygen. (Look back to equation 1.3.) So
charge = 4F × amount of O2
Dividing by time, and rearranging
I
O2 usage = moles s−1
4F
This is for a single cell. For a stack of n cells
In
O2 usage = moles s−1 [A2.1]
4F
However, it would be more useful to have the formula in kg s−1 , without needing to
know the number of cells, and in terms of power, rather than current. If the voltage of
each cell in the stack is Vc , then
Power, Pe = Vc × I × n
So,
Pe
I=
Vc × n
Substituting this into equation A2.1 gives
Pe
O2 usage = moles s−1 [A2.2]
4 · Vc · F
Changing from moles s−1 to kg s−1
32 × 10−3 · Pe
O2 usage = kg s−1
4Vc F
Pe
= 8.29 × 10−8 × kg s−1 [A2.3]
Vc
Useful Fuel Cell Equations 397
This formula allows the oxygen usage of any fuel cell system of given power to be
calculated. If Vc is not given, it can be calculated from the efficiency, and if that is not
given, the figure of 0.65 V can be used for a good approximation.
However, the oxygen used will normally be derived from air, so we need to adapt
equation A2.2 to air usage. The molar proportion of air that is oxygen is 0.21, and the
molar mass of air is 28.97 × 10−3 kg mole−1 . So, equation A2.2 becomes
28.97 × 10−3 × Pe
Air usage = kg s−1
0.21 × 4 × Vc × F
Pe
= 3.57 × 10−7 × kg s−1
Vc
However, if the air was used at this rate, then as it left the cell it would be completely
devoid of any oxygen – it would all have been used. This is impractical, and in practice
the airflow is well above stoichiometry, typically twice as much. If the stoichiometry is
λ, then the equation for air usage becomes
Pe
Air usage = 3.57 × 10−7 × λ × kg s−1 [A2.4]
Vc
The kilogram per second is not, in fact, a very commonly used unit of mass flow. The
following conversions to ‘volume at standard conditions related’ mass flow units will be
found useful. The mass flow rate from equation A2.4 should be multiplied by
• 3050 to give flow rate in standard m3 h−1

• 1795 to give flow rate in SCFM (or in standard ft3 min−1 )
• 5.1 × 104 to give flow rate in slm (standard L min−1 )
• 847 to give flow rate in sls (standard L s−1 )
A2.3 Air Exit Flow Rate

It is sometimes important to distinguish between the inlet flow rate of the air, which is
given by equation A2.4 above, and the outlet flow rate. This is particularly important
when calculating the humidity, which is an important issue in certain types of fuel cells,
especially proton exchange membrane (PEM) fuel cells. The difference is caused by the
consumption of oxygen. There will usually be more water vapour in the exit air, but we
are considering ‘dry air’ at this stage. Water production is given in Section A2.5. Clearly
Exit air flow rate = Air inlet flow rate − oxygen usage
Using equations A2.3 and A2.4 this becomes

Pe Pe
Exit air flow rate = 3.57 × 10−7 × λ × − 8.29 × 10−8 × kg s−1
Vc Vc
Pe
= (3.57 × 10−7 × λ − 8.29 × 10−8 ) × kg s−1 [A2.5]
Vc
A2.4 Hydrogen Usage

The rate of usage of hydrogen is derived in a way similar to oxygen, except that there
are two electrons from each mole of hydrogen. Equations A2.1 and A2.2 thus become
In
H2 usage = moles s−1 [A2.6]
2F
and
Pe
H2 usage = moles s−1 [A2.7]
2Vc F
The molar mass of hydrogen is 2.02 × 10−3 kg mole−1 , so this becomes
2.02 × 10−3 · Pe
H2 usage =
2Vc F
Pe
= 1.05 × 10−8 × kg s−1 [A2.8]
Vc
at stoichiometric operation. Obviously, this formula only applies to a hydrogen-fed fuel
cell. In the case of a hydrogen/carbon monoxide mixture derived from a reformed hydro-
carbon, things will be different, depending on the proportion of carbon monoxide present.
The result can be transformed to a volume rate using the density of hydrogen, which is
0.084 kg m−3 at normal temperature and pressure (NTP).
In addition to the rate of usage of hydrogen, it is often also useful to know the electrical
energy that could be produced from a given mass or volume of hydrogen. The list provided
in Table A2.1 gives the energy in kilowatthour, rather than joules, as this is the measure
usually used for electrical power systems. In addition to the ‘raw’ energy per kilogram and
standard litre, we have also given an ‘effective’ energy, taking into account the efficiency
of the cell. This is given in terms of Vc , the mean voltage of each cell. If an equation
with the efficiency is needed, then use the formula derived in Section 2.5,
Vc
efficiency =
1.48
Table A2.1 ‘Raw’ and effective energy content of hydrogen fuel. To

obtain the lower heating value, multiply the HHV figures given by 0.846
Form Energy content
Specific enthalpy (HHV) 1.43 × 108 J kg−1

Specific enthalpy (HHV) 39.7 kWh kg−1
Effective specific electrical energy 26.8 × Vc kWh kg−1
Energy density at STP (HHV) 3.20 kWh m−3 = 3.20 Wh SL−1
Energy density at NTP (HHV) 3.29 kWh m−3 = 3.29 Wh SL−1
Note: higher heating value, HHV; standard temperature and pressure, STP.
Useful Fuel Cell Equations 399
A2.5 Water Production

In a hydrogen-fed fuel cell, water is produced at the rate of one mole for every two
electrons. (Revisit Section 1.1 if you are not clear why.) So, we again adapt equation A2.2
to obtain
Pe
Water production = moles s−1 [A2.9]
2 · Vc · F
The molecular mass of water is 18.02 × 10−3 kg mole−1 , so this becomes
Pe
Water production = 9.34 × 10−8 × kg s−1 [A2.10]
Vc
In the hydrogen-fed fuel cell, the rate of water production more or less has to be
stoichiometric. However, if the fuel is a mixture of carbon monoxide with hydrogen, then
the water production would be less – in proportion to the amount of carbon monoxide
present in the mixture. If the fuel was a hydrocarbon that was internally reformed, then
some of the product water would be used in the reformation process. We saw in Chapter 7,
for example, that if methane is internally reformed, then half the product water is used in
the reformation process, thus halving the rate of production.
It is sometimes useful to give an example figure to clarify a formula such as this. Let
us take as an example a 1-kW fuel cell operating for 1 h, at a cell voltage of 0.7 V. This
corresponds to an efficiency of 47% (ref. HHV) (from equation 2.5). Substituting this into
equation A2.9 gives
1000
The rate of water production = 9.34 × 10−8 ×
0.7
= 1.33 × 10−4 kg s−1
So the mass of water produced in 1 h is
= 1.33 × 10−4 × 60 × 60 = 0.48 kg
Since the density of water is 1.0 g cm−3 , this corresponds to 480 cm3 , which is almost
exactly 1 pint. So, as a rough guide, 1 kWh of fuel cell generated electricity produces
about 1 pint or 0.5 L of water.
A2.6 Heat Produced

Heat is produced when a fuel cell operates. It was noted in Chapter 2, section 2.4, that if
all the enthalpy of reaction of a hydrogen fuel cell was converted into electrical energy
then the output voltage would be
1.48 V if the water product was in liquid form
or 1.25 V if the water product was in vapour form.
It clearly follows that the difference between the actual cell voltage and this voltage
represents the energy that is not converted into electricity – that is, the energy that is
converted into heat instead.
The cases in which water finally ends in liquid form are so few and far between
that they are not worth considering. So we will restrict ourselves to the vapour case.
However, please note that this means we have taken into account the cooling effect of
water evaporation. It also means that energy is leaving the fuel cell in three forms: as
electricity, as ordinary ‘sensible’ heat, and as the latent heat of water vapour.
For a stack of n cells at current I , the heat generated is thus
Heating rate = nI (1.25 − Vc ) W
In terms of electrical power, this becomes
1.25
Heating rate = Pe −1 W [A2.11]
Vc

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Appendix 2

Useful Fuel Cell Equations

A2.2 Oxygen and Air Usage

Dividing by time, and rearranging

Substituting this into equation A2.1 gives

Changing from moles s−1 to kg s−1

• 3050 to give ﬂow rate in standard m3 h−1

A2.3 Air Exit Flow Rate

Using equations A2.3 and A2.4 this becomes

A2.4 Hydrogen Usage

Table A2.1 ‘Raw’ and effective energy content of hydrogen fuel. To

Form Energy content

Speciﬁc enthalpy (HHV) 1.43 × 108 J kg−1

A2.5 Water Production

The molecular mass of water is 18.02 × 10−3 kg mole−1 , so this becomes

So the mass of water produced in 1 h is

= 1.33 × 10−4 × 60 × 60 = 0.48 kg

A2.6 Heat Produced

Heating rate = nI (1.25 − Vc ) W

In terms of electrical power, this becomes

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