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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