Documente Academic
Documente Profesional
Documente Cultură
Electrolysis
Figure 1
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
H2
fuel
cell
heat
H2 O
Open system
Anode and cathode are gases in
contact with a platinum catalyst.
Reactants are externally supplied,
no recharging required.
Closed system
Anode and cathode are metals.
Reactants are internally consumed,
need periodic recharging.
Similarities:
Both use hydrogen-rich fuel.
Both use compressed air as the oxidant.
Both require cooling.
Differences:
Fuel cell:
I.C. Engine:
Figure 3
Animation of PEMFC
Reduction
Alkali
Molten Carbonate
Phosphoric Acid
Proton Exchange Membrane
Solid Oxide
SOFC
60 80% efficiency
~650C operating temp.
cheap nickel electrode catylist
Figure 5
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
Benefits
Efficient:
Portable:
modular units
Reliable:
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:
Vcell
E=V
x100%
voltage
max
Vmax=1.23v @STP
overall
()[Vcell]
x100%
=0.95
=1.48
dc current
Heat
Oxygen
Hydrogen
Water
Catalyst (Pt)
Anode (-)
Membrane
(Nafion)
Catalyst (Pt)
Cathode (+)
H 2 2 H 2e
1/ 2O2 2 H 2e 1H 2O
O2 2H 2 2H 2O
(Er 1.23 V )
Q W dE
Change of
systems total
energy
Change of heat
Change of
provided to the work provided
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)
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.
H 2 2 H 2e ,
1/ 2O2 2 H 2e 1H 2O,
H 0 kJ
H 285.8 kJ
Hence, in a PEMFC, 285 kJ/mol are converted into heat (Q) and electricity (W). How
much electricity W can we ideally obtain?
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 Qrev at a temperature T0,
the entropy is defined as
Q
S rev
T0
Q
S
T
The = in the above relationship will give us the minimum amount of heat Qmin
required in a process.
For any process then
From the enthalpy definition a fuel cell can be considered as a system like the
following one
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
G
processes, such as heat orchemical
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
In the anode:
In the cathode:
H 2 2 H 2e ,
1/ 2O2 2 H 2e 1H 2O,
G 0 kJ
G 237.2 kJ / mol
max
G 237.2
0.83
H 285.8
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.
G
2F
(237200)
Eo
1.229 1.23V
(2)(96, 485)
Maximum
power operating
point
Er =1.23V
b=60mV,
i0=10-6.7Acm-2
r=0.2cm2
Activation loss
region
Amrhein and Krein Dynamic Simulation for Analysis of Hybrid Electric Vehicle
System and Subsystem Interactions, Including Power Electronics