Professional Documents
Culture Documents
Fall 2012
Microsources
Most common microsources:
Small wind turbine (<10
kW/turbine)
Real microsources
Wind turbines +
PV modules
PAFC
Microturbines
MCFC
http://static.flickr.com/39/101004887_6525c88bfc.jpg
Ideal sources
Characteristics:
For a voltage (current) source, the internal impedance is zero (infinity):
No internal losses.
Instantaneous dynamic response.
For an ideal voltage source, current has no effect on the voltage output:
The output voltage value and waveform are always the same regardless
of the load.
For current sources replace current by voltage in the last statement.
An ideal capacitor with an infinite capacitance behaves as a dc voltage
source.
dv
q
iC
dt
L
i
di
vL
dt
dc current
Heat
Oxygen
Hydrogen
Catalyst (Pt)
Anode (-)
Membrane
(Nafion)
Water
Catalyst (Pt)
Cathode (+)
H 2 2 H 2e
1/ 2O2 2 H 2e 1H 2O
O2 2 H 2 2 H 2O
(Er 1.23 V )
Q W dE
Change of heat
provided to the
system
Change of
work provided
by the system
Change of
systems total
energy
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.
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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
temperature T0, the entropy is defined as
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Qrev
T0
Qrev at a
Q
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
11
max
W
Q
1 min
H
H
max
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H 2 2 H 2e ,
In the anode:
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.
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(237200)
Eo
1.229 1.23V
(2)(96, 485)
Ec Er b log(i / i0 ) ir
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, i0 is the exchange current density for oxygen reaction and
b is the Tafel slope:
RT
b
n log(e)
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Maximum power
operating point
Er =1.23V
b=60mV,
i0=10-6.7Acm-2
r=0.2cm2
Activation loss
region
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Amrhein and Krein Dynamic Simulation for Analysis of Hybrid Electric Vehicle
System and Subsystem Interactions, Including Power Electronics
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Equal to Er
N cell RT
where, f1 ( I , T )
ln pH* 2 pO* 2 N cell k E (T 298)
2F
f 2 ( I ) N cell Ed ,cell
Comments:
The voltage drop related with fuel and oxidant delay is represented by
Ed,cell.
The fuel cell output voltage depends on hydrogens and oxygens pressure
The fuel cell output voltage also depends on the temperature.
The time constants for these chemical, mechanical, and thermodynamic
effects are much larger than electrical time constants.
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s
E d ,cell ( s ) e I( s ) e
es 1
dEd ,cell (t ) 1
di (t )
Ed ,cell
(t ) e
dt
e
dt
Fuel cells have a slow dynamic response, as shown in the next figure that
evaluates the response of a fuel cell to multiple fast step load changes:
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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) CH 4 H 2O CO 3H 2
endothermic reaction (needs heat)
2) CO H 2O CO2 H 2
exothermic reaction (provides heat)
75 % to 80 % efficient.
Partial oxidation (POX)
It also uses natural gas or other hydrocarbon
CH 4 1/ 2O2 CO 2 H 2 and/or CH 4 O2 CO2 2 H 2
POX is compact and has faster dynamic response than MSR, but MSR
provides higher hydrogen concentration.
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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:
2 H 2O O2 2 H 2
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.
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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.
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2
Cathode 1/ 2O2 CO2 2e CO3
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
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2
Cathode 1/ 2O2 2e O
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.
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DMFC
PAFC
MCFC
SOFC
H2
CH3OH
H2
Solid polymer
(usually Nafion)
Solid polymer
(usually Nafion)
Potasium
hydroxide
(KOH)
Phosporic
acid (H3PO4
solution)
Lithium and
potassium
carbonate
Solid oxide
(yttria,
zirconia)
H+
H+
OH-
H+
CO32-
O2-
Operational
temperature (oC)
50 100
50 - 90
60 - 120
175 200
650
1000
Efficiency (%)
35 60
< 50
35 55
35 45
45 55
50 60
0.1 500
<< 1
<5
5 2000
800 2000
> 2.5
Installed Cost
($/kW)
4000
> 5000
800 2000
1300 - 2000
Fuel
Electrolyte
Charge carried in
electrolyte
AFC
H2
* Without
< 1000*purifier 3000 3500
All fuel cells occupy a lot of space. Much more than any of the other types of
microsources
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