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Electrolysis
What does this have to do with fuel cells?
Figure 1
Fuel Cell Basics
Put electrolysis in reverse.
The familiar process of electrolysis requires work to proceed, if the process is put in reverse, it should be able to do
work for us spontaneously.
The most basic black box representation of a fuel cell in action is shown below:
work
Figure 2
O2
fuel H2 O
H2
cell
heat
What is a Fuel Cell?
Quite simply, a fuel cell is a device that converts chemical energy into
electrical energy, water, and heat through electrochemical reactions.
Fuel and air react when they come
into contact through a porous
membrane (electrolyte) which separates
them.
Similarities:
Differences:
Fuel cell:
Output is electrical work.
Fuel and oxidant react electrochemically.
Little to no pollution produced.
I.C. Engine:
Output is mechanical work.
Fuel and oxidant react combustively.
Use of fossil fuels can produce significant pollution.
Fuel Cell Basics
Components
Figure 3
Animation of PEMFC
What is a hydrogen fuel cell?
Hydrogen fuel cells (HFCs) are a
type of electrochemical cell.
Alkali
Molten Carbonate
Phosphoric Acid
Proton Exchange Membrane
Solid Oxide
Types of Fuel Cells
SOFC
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
high temp / catalyst can extract the hydrogen from the fuel at the electrode
high temp allows for power generation using the heat, but limits use
SOFC units are very large
solid electrolyte wont leak, but can crack
Benefits
Fuel Flexible: With a fuel reformer, fuels such as natural gas, ethanol, methanol,
propane, gasoline, diesel, landfill gas,wastewater, treatment digester gas, or even ammonia can be used
Environmental: produces heat and water (less than combustion in both cases)
near zero emission of CO and NOx
reduced emission of CO2 (zero emission if pure H2 fuel)
Fuel cell efficiency is not an completely
defined term yet
Voltage efficiency tends to over estimate the amount of
work based on caloric fuel content
Max voltage = the reversible reaction potential at the operating
conditions
Emax = 100%, not realistic because of heat losses
Vcell
E=V x100%
voltage max
Vmax=1.23v @STP
Water
Membrane
Catalyst (Pt) (Nafion) Catalyst (Pt)
Anode (-) Cathode (+)
H 2 2 H 2e 1/ 2O2 2 H 2e 1H 2O
O2 2H 2 2H 2O (Er 1.23 V )
Fuel cell thermodynamics
The first law of thermodynamics:
The energy of a system is conserved
Q W dE
Change of
Change of heat Change of systems total
provided to the work provided energy
system by the system
In conservational fields, potential functions change depend only on initial and final
values. Hence, Q W E
For a closed system (control mass system), such as a piston
E U K P
(The total energy change equals the sum of the change in internal energy, the change
in kinetic energy, and the change in potential energy)
Fuel cell thermodynamics
For an open system with mass flow across its boundaries (control volume), such as a
steam turbine
E U K P ( pV )
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
H U pV
Then,
H E K P
If we use the 1st law of thermodynamics for a stationary control volume (i.e. the
kinetic and potential energies are constant in time, then
H Q W
Thus, the enthalpy is the difference between the heat and the work involved in a
system such as the one defined immediately above.
Fuel cell thermodynamics
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).
H 2 2 H 2e , H 0 kJ
In the anode: 1/ 2O2 2 H 2e 1H 2O, H 285.8 kJ
In the cathode:
Hence, in a PEMFC, 285 kJ/mol are converted into heat (Q) and electricity (W). How
much electricity W can we ideally obtain?
Q
For any process then S
T
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
Q W Q
H
Fuel cell thermodynamics
The definition of entropy is relates with the 2nd Law of Thermodynamics. One of its
interpretations is that it is impossible to convert all the energy related with irreversible
processes, such as heat orchemical
G energy, into work.
max
H
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
Fuel cell thermodynamics
From tables:
H 2 2 H 2e , G 0 kJ
In the anode: 1/ 2O2 2 H 2e 1H 2O, G 237.2 kJ / mol
In the cathode:
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
W G 2 FEo
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.
Fuel cell thermodynamics
Thus,
G
Eo
2F
(237200)
Eo 1.229 1.23V
(2)(96, 485)
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.
PEMFC electrical characteristics
Er = 1.23 V
Maximum
power operating
point
Er =1.23V
b=60mV,
i0=10-6.7Acm-2
r=0.2cm2
Amrhein and Krein Dynamic Simulation for Analysis of Hybrid Electric Vehicle
System and Subsystem Interactions, Including Power Electronics