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Difference with batteries: fuel cells require a fuel to flow in order to produce
electricity.
Water
Membrane
Catalyst (Pt) (Nafion) Catalyst (Pt)
Anode (-) Cathode (+)
H 2 2 H 2e 1/ 2O2 2 H 2e 1H 2O
O2 2 H 2 2 H 2O (Er 1.23 V )
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.
5 Alexis Kwasinski, 2012
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).
In the anode: H 2 2 H 2e , H 0 kJ
In the cathode: 1/ 2O2 2 H 2e 1H 2O, 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?
From the enthalpy definition a fuel cell can be considered as a system like the
following one
Q W Q
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 or chemical energy, into work.
Hence, for fuel cells, the electrical work represents the Gibbs Free Energy
and the maximum possible energy conversion efficiency is G
max
H
8 Alexis Kwasinski, 2012
Fuel cell thermodynamics
From tables:
In the anode: H 2 2 H 2e , G 0 kJ
In the cathode: 1/ 2O2 2 H 2e 1H 2O, G 237.2 kJ / mol
G 237.2
max 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.
9 Alexis Kwasinski, 2012
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.
Ec Er b log(i / i0 ) ir
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)
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.
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
Equal to Er
where, f1 ( I , T )
N cell RT
2F
ln pH* 2 pO* 2 N cell k E (T 298)
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.
16 Alexis Kwasinski, 2012
PEMFC electrical characteristics
Ed,cell can be calculated from the following dynamic equation:
s dEd ,cell (t ) 1 di (t )
E d ,cell ( s ) e I( s ) e (t ) e
Ed ,cell
es 1 dt e dt
where e is the overall flow delay.
In steady state, both derivatives are zero, so Ed,cell = 0. But when the load
changes, di(t)/dt is not zero, so Ed,cell will be a non-trivial function of time that will
affect the fuel cell internal output voltage.
When considering fuel cells dynamic behavior, they all tend to have a slow
response caused by the capacitance effect in slide 19, the flow delays, the
mechanical characteristics of the pumps, and the thermodynamic
characteristics.
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:
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.
Since an effort (i.e. work) needs to be done to keep hydrogen stored, storing
hydrogen implies loosing efficiency.
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
One of their main advantages is their long life in the order of 40,000 hours.
The reactions are the same than in a PEMFC. Hence, the reversible voltage is
1.23 V
The main advantage is that their cost is relatively low (when considering the
fuel cell stack only without accessories.
Reactions: H 2 2OH 2 H 2O 2e
Anode 1/ 2O2 2 H 2O 2e 2OH
Cathode
Very sensitive to CO2 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
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.
Issues:
Extremely slow startup
Very slow dynamic response
They operate at high temperature with the same plus and minus than in
MCFCs.
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
Unit Size (KW) 0.1 500 << 1 <5 5 2000 800 2000 > 2.5
Installed Cost
($/kW) 4000 > 5000 * Without
< 1000*purifier 3000 3500 800 2000 1300 - 2000
All fuel cells occupy a lot of space. Much more than any of the other types of
microsources