Fuel Cell Thermodynamics

Fuel Cells Basics

Fuel cells convert chemical energy directly into electrical energy.

Difference with batteries: fuel cells require a fuel to flow in order to produce
electricity.

Heat is produced from chemical reaction and not from combustion.

Types of fuel cells:
Proton exchange membrane (PEMFC)
Direct Methanol fuel cell (DMFC)
Alkaline fuel cell (AFC)
Phosphoric acid fuel cell (PAFC) (*)
Molten-carbonate fuel cell (MCFC) (*)
Solid-oxide fuel cell (SOFC) (*)
(*) Suitable for microgrids.
Fuel cells operation
Example: PEMFC
The hydrogen atoms electron and proton are separated at the anode.
Only the protons can go through the membrane (thus, the name
proton exchange membrane fuel cell).
Hydrogen
Oxygen
Water
2
2 2 H H e
+
+
Heat
2 2
1/ 2 2 2 1 O H e H O
+
+ +
Membrane
(Nafion)
Catalyst (Pt)
Anode (-)
Catalyst (Pt)
Cathode (+)
dc current
2 2 2
2 2 ( 1.23 )
r
O H H O E V + =
Fuel cell thermodynamics
The first law of thermodynamics:
The energy of a system is conserved






In conservational fields, potential functions change depend only on initial and
final values. Hence,

For a closed system (control mass system), such as a piston


(The total energy change equals the sum of the change in internal energy, the
change in kinetic energy, and the change in potential energy)
Q W dE o o =
Q W E = A
Change of heat
provided to the
system
Change of
work provided
by the system
Change of
systems total
energy
E U K P A = A + A + A
Fuel cell thermodynamics
For an open system with mass flow across its boundaries (control volume),
such as a steam turbine


pV represents the work to keep the fluid flowing (p is pressure and V is
volume). Hence, if a magnitude called enthalpy H is defined as


Then,


If we use the 1
st
law of thermodynamics for a stationary control volume (i.e.
the kinetic and potential energies are constant in time, then



Thus, the enthalpy is the difference between the heat and the work involved
in a system such as the one defined immediately above.
( ) E U K P pV A = A + A + A + A
H U pV = +
H E K P A = A A A
H Q W A =
If the change in enthalpy is negative, heat is liberated and the reaction occurs
spontaneously (contrary to endothermic reactions that requires to apply heat in
order for the reaction to occur).

In the anode:
In the cathode:

Hence, in a PEMFC, 285 kJ/mol are converted into heat (Q) and electricity
(W).

Entropy: it is a property that indicates the disorder of a system or how
much reversible is a process. This last definition relates entropy to
energy quality.

In a reversible isothermal process involving a heat transfer Q
rev
at a
temperature T
0
, the entropy is defined as
Fuel cell thermodynamics
2
2 2 , 0 H H e H kJ
+
+ A =
2 2
1/ 2 2 2 1 , 285.8 O H e H O H kJ
+
+ + A =
0
rev
Q
S
T
A =
In all processes involving energy conversion or interactions S is non-
negative. S is zero only in reversible processes..

For any process then

The = in the above relationship will give us the minimum amount of heat
Qmin required in a process.

From the enthalpy definition a fuel cell can be considered as a system like the
following one

Fuel cell thermodynamics
Q
S
T
A >
H
Q Q W
Fuel cell thermodynamics
The maximum possible efficiency for a fuel cell is, then



An alternative derivation involves using Gibbs Free Energy

The definition of entropy is relates with the 2
nd
Law of Thermodynamics. One
of its interpretations is that it is impossible to convert all the energy related with
irreversible processes, such as heat or chemical energy, into work.

Hence, it is possible to define a magnitude with units of energy called Gibbs
Free Energy that represents the reversible part of the energy involved in the
process.

Hence, for fuel cells, the electrical work represents the Gibbs Free Energy and
the maximum possible energy conversion efficiency is

max
G
H
q
A
=
A
min
max
1
Q W
H H
q = =
A A
From tables:

In the anode:
In the cathode:

And from slide #6 H equals 285 kJ/mol. Thus,




The Gibbs Free Energy can also be used to calculate the output voltage of an
ideal fuel cell. Since the Gibbs Free Energy equals the electrical work, and the
electrical work equals the product of the charge and voltage, then



where F is the Faraday constant (charge on one mole of electrons) the factor
of two represents the fact that two electrons per mole are involved in the
chemical reaction.
2
2 2 , 0 H H e G kJ
+
+ A =
2 2
1/ 2 2 2 1 , 237.2 / O H e H O G kJ mol
+
+ + A =
Fuel cell thermodynamics
max
237.2
0.83
285.8
G
H
q
A
= = ~
A
2
o
W G FE = A =
Fuel cell thermodynamics
Thus,



and since F = 96,485 C/mole and G = -237.2 kJ/mole, then





E
0
is also denoted by E
r
, the reversible voltage.

This is the voltage that can be obtained in a single ideal PEMFC when the
thermodynamic reaction limitations are taken into account. I.e., this is the
output voltage of a single ideal PEMFC when it behaves as an ideal voltage
source. However, additional energy loosing mechanisms further reduce this
voltage.

2
o
G
E
F
A
=
( 237200)
1.229 1.23
(2)(96, 485)
o
E V

= = ~
The Tafel equation yields the cells output voltage E
c
considering additional
loosing mechanisms:



The first term is the reversible cell voltage (1.23V in PEMFCs)

The last term represents the ohmic losses, where i is the cells current density,
and r is the area specific ohmic resistance.

The second term represent the losses associated with the chemical kinetic
performance of the anode reaction (activation losses). This term is obtained
from the Butler-Volmer equation and its derivation is out of the scope of this
course.
In the second term, i
0
is the exchange current density for oxygen reaction and
b is the Tafel slope:
log( )
RT
b
n e |
=
PEMFC output: Tafel equation
0
log( / )
c r
E E b i i ir =
In the last equation R is the universal gas constant (8.314 Jmol
-1
K
-1
), F is the
Faraday constant, T is the temperature in Kelvins, n is the number of electrons
per mole (2 for PEMFC), and is the transfer coefficient (usually around 0.5).
Hence, b is usually between 40 mV and 80 mV.

The Tafel equation assumes that the reversible voltage at the cathode is 0 V,
which is only true when using pure hydrogen and no additional limitations, such
as poisoning, occur.

The Tafel equation do not include additional loosing mechanisms that are
more evident when the current density increases. These additional mechanisms
are:
Fuel crossover: fuel passing through the electrolyte without reacting
Mass transport: hydrogen and oxygen molecules have troubles reaching
the electrodes.

Tafel equation also assumes that the reaction occurs at a continuous rate.
PEMFC output: Tafel equation
PEMFC electrical characteristics
Maximum power
operating point
E
r
= 1.23 V
Activation loss
region
Ohmic loss region
(linear voltage to current
relationship)
Mass transport loss region
E
r
=1.23V
b=60mV,
i
0
=10
-6.7
Acm
-2
r=0.2cm
2
Actual PEMFCs efficiency vary between 35% and 60%
PEMFC electrical characteristics
This past curve represent the steady state output of a fuel cell.

The steady state output depends on the fuel flow:
Amrhein and Krein Dynamic Simulation for Analysis of Hybrid Electric Vehicle
System and Subsystem Interactions, Including Power Electronics
Hydrogen production
Hydrogen needs to be produced, and sometimes it also needs to be
transported and/or stored. Hydrogen is not a renewable source of energy.
Hence, FC are alternative sources of energy.

Methods for hydrogen production:
Methane Steam Reforming (MSR)
It uses natural gas
Two-step process:
1)
endothermic reaction (needs heat)
2)
exothermic reaction (provides heat)
75 % to 80 % efficient.
Partial oxidation (POX)
It also uses natural gas or other hydrocarbon
and/or
POX is compact and has faster dynamic response than MSR, but MSR
provides higher hydrogen concentration.
4 2 2
3 CH H O CO H + +
2 2 2
CO H O CO H + +
4 2 2
1/ 2 2 CH O CO H + +
4 2 2 2
2 CH O CO H + +
Hydrogen production
More methods for hydrogen production:
Electrolysis of water
Water molecules can be separated using electricity. But we use electricity
to produce hydrogen to produce electricity again.
Pure water is in many places an scarce resource.
The electricity for the electrolysis needs to be produced and the water
needs to be purified (soft de-ionized water is needed).
Reaction:


Electricity can be obtained at a large scale from nuclear reactors but the
hydrogen needs to be stored and transported, and nuclear fuel is not a
renewable source of energy.
At a VERY small scale wind or solar power can be used, but this energy is
available only when there is wind or sunlight.
Gasification of Biomass, Coal or Wastes
These methods are still a long way into the future.
2 2 2
2 2 H O O H +
Hydrogen Storage
Hydrogen atoms are the lightest and smallest of all elements. For this reason,
it is very difficult to keep hydrogen from escaping confined environments such
as tanks or pipes.

Since an effort (i.e. work) needs to be done to keep hydrogen stored, storing
hydrogen implies loosing efficiency.

Some storage methods:
Pressure Cylinders: Some efficiency is lost in the compressing
process
Liquid Hydrogen: it requires lowering the hydrogen temperature to
20.39 K. This process already reduces 1/3 of the efficiency.
Metal Hydrides: These are compounds of hydrogen and Magnesium,
titanium and other metals. Efficiency is low to medium and lot of heat is
generated when the hydrogen is released, but these compounds are
very easy to store in the form of soils.
Carbon nano-fibers: New technology.
PEMFC Technology and issues
Expected life of PEMFC is very short (5,000 hours).

The most commonly used catalyst (Pt) is very expensive.

The most commonly used membrane (Nafion a sulfonated tetrafluorethylene
copolymer is also very expensive).

PEMFCs are very expensive.

CO poisoning diminishes the efficiency. Carbon monoxide (CO) tends to bind
to Pt. Thus, if CO is mixed with hydrogen, then the CO will take out catalyst
space for the hydrogen.

Hydrogen generation and storage is a significant problem.

Additional issues to be discussed when comparing other technologies:
dynamic response and heat production.
The main advantage is that they use a liquid fuel.
Reactions:
Anode
Cathode

Voltages: 0.046 V at anode, 1.23 V at cathode, 1.18 V overall.

Methanol has high energy density so DMFC are good for small portable
applications.

Issues:
Cost
Excessive fuel crossover (methanol crossing the membrane)
Low efficiency caused by methanol crossover
CO poisoning
Low temperature production
Considerable slow dynamic response
Direct Methanol Fuel Cells (DMFC)
3 2 2
6 6 CH OH H O CO H e
+
+ + +
2 2
1/ 2 2 2 O H e H O
+
+ +
One of their main advantages is their long life in the order of 40,000 hours.

The phosphoric acid serves as the electrolyte.

The reactions are the same than in a PEMFC. Hence, the reversible voltage is
1.23 V

The most commercially successful FC: 200 kW units manufactured by UTC

They produce a reasonable amount of heat

They support CO poisoning better than PEMFC

They have a relatively slow dynamic response

Relative high cost is an important issue



Phosphoric Acid Fuel Cells (PAFCs)
The main advantage is that their cost is relatively low (when considering the
fuel cell stack only without accessories.
Reactions:
Anode
Cathode

Developed for the Apollo program.

Very sensitive to CO
2
poisoning. So these FCs can use impure hydrogen but
they require purifying air to utilize the oxygen.

Issues:
Cost (with purifier)
Short life (8000 hours)
Relatively low heat production
Alkaline Fuel Cells (AFCs)
2 2
2 2 2 H OH H O e

+ +
2 2
1/ 2 2 2 2 O H O e OH

+ +
One of the main advantages is the variety of fuels and catalyst than can be
used.
Reactions:
Anode
Cathode

They operate at high temperature. On the plus side, this high temperature
implies a high quality heat production. On the minus side, the high temperature
creates reliability issues.

They are not sensitive to CO poisoning.

They have a relatively low cost.

Issues:
Extremely slow startup
Very slow dynamic response
2
2 3 2 2
2 H CO H O CO e

+ + +
2
2 2 3
1/ 2 2 O CO e CO

+ +
Molten Carbonate Fuel Cells (MCFCs)
Solid Oxide Fuel Cells (SOFCs)
One of the main advantages is the variety of fuels and catalyst than can be
used.
Reactions:
Anode
Cathode

They operate at high temperature with the same plus and minus than in
MCFCs.

They are not sensitive to CO poisoning.

They have a relatively low cost.

They have a relatively high efficiency.

They have a fast startup

The electrolyte has a relatively high resistance.
2
2 2
2 H O H O e

+ +
2
2
1/ 2 2 O e O

+
Comparison of the most common technologies














PEMFC DMFC AFC PAFC MCFC SOFC
Fuel H
2
CH
3
OH
H
2
H
2

H
2
, CO, CH
4
,
hydrocarbons
H
2
, CO, CH
4
,
hydrocarbons
Electrolyte
Solid polymer
(usually Nafion)
Solid polymer
(usually Nafion)
Potasium
hydroxide
(KOH)
Phosporic
acid (H
3
PO
4

solution)
Lithium and
potassium
carbonate
Solid oxide
(yttria,
zirconia)
Charge carried in
electrolyte
H
+
H+ OH
-
H
+
O
2-

Operational
temperature (
o
C) 50 100 50 - 90 60 - 120 175 200 650 1000
Efficiency (%) 35 60 < 50 35 55 35 45 45 55 50 60
Unit Size (KW) 0.1 500 << 1 < 5 5 2000 800 2000 > 2.5
Installed Cost ($/kW) 4000 > 5000 < 1000* 3000 3500 800 2000 1300 - 2000
Fuel cell technologies
2-
3
CO
* Without purifier