Professional Documents
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1
Distributed Generation Technologies
Microturbines
Reciprocating Engines
Advanced Turbines
Fuel Cells
Photovoltaics Wind turbines 2
Basic Gas Turbine
= $37,300/yr
7
Solution
c) The utility electricity savings = 105 kW X 8000 h/yr X
$0.08/kWh = $67,200/yr
The cathode, the positive post of the fuel cell, has channels etched into it
that distribute the oxygen to the surface of the catalyst. It also conducts the
electrons back from the external circuit to the catalyst, where they can
recombine with the hydrogen ions and oxygen to form water.
11
Parts of a fuel cell
• The electrolyte is the proton exchange membrane.
This specially treated material, which looks something
like ordinary kitchen plastic wrap, only conducts
positively charged ions. The membrane blocks electrons.
12
Parts of a fuel cell
Figure on page 10 shows the pressurized hydrogen gas (H2) entering
the fuel cell on the anode side. This gas is forced through the catalyst
by the pressure. When an H2 molecule comes in contact with the
platinum on the catalyst, it splits into two H+ ions and two electrons (e-
). The electrons are conducted through the anode, where they make
their way through the external circuit (doing useful work such as turning
a motor) and return to the cathode side of the fuel cell.
Meanwhile, on the cathode side of the fuel cell, oxygen gas (O2) is
being forced through the catalyst, where it forms two oxygen atoms.
Each of these atoms has a strong negative charge. This negative
charge attracts the two H+ ions through the membrane, where they
combine with an oxygen atom and two of the electrons from the
external circuit to form a water molecule (H2O).
13
Phosphoric Acid (PAFC).
Phosphoric acid fuel cells are
commercially available today. Hundreds of
fuel cell systems have been installed in 19
nations - in hospitals, nursing homes,
hotels, office buildings, schools, utility
power plants, landfills and waste water
treatment plants. PAFCs generate
electricity at more than 40% efficiency –
and nearly 85% of the steam this fuel cell
produces is used for cogeneration - this
compares to about 35% for the utility
power grid in the United States.
Phosphoric acid fuel cells use liquid
phosphoric acid as the electrolyte and
operate at about 450°F.
One of the main advantages to this type of fuel cell, besides the nearly 85%
cogeneration efficiency, is that it can use impure hydrogen as fuel. PAFCs
can tolerate a CO concentration of about 1.5 percent, which broadens the
choice of fuels they can use. If gasoline is used, the sulfur must be removed.
14
Proton Exchange Membrane
(PEM)
• These fuel cells operate at relatively
low temperatures (about 175°F), have
high power density, can vary their
output quickly to meet shifts in power
demand, and are suited for
applications, such as in automobiles,
where quick startup is required.
According to the U.S. Department of
Energy (DOE), "they are the primary
candidates for light-duty vehicles, for
buildings, and potentially for much
smaller applications such as
replacements for rechargeable
batteries." This type of fuel cell is
sensitive to fuel impurities. Cell
outputs generally range from 50 watts
to 75 kW. 15
Solid Oxide Fuel Cells(SOFC)
• Solid oxide fuel cells use a hard,
non-porous ceramic compound as
the electrolyte, and operate at
very high temperatures - around
1800°F. One type of SOFC uses
an array of meter-long tubes, and
other variations include a
compressed disc that resembles
the top of a soup can. Tubular
SOFC designs are closer to
commercialization and are being
produced by several companies
around the world. SOFCs are
suitable for stationary applications
as well as for auxiliary power units
(APUs) used in vehicles to power
electronics. 16
Molten Carbonate (MCFC)
Molten carbonate fuel cells use an
electrolyte composed of a molten
carbonate salt mixture suspended in a
porous, chemically inert matrix, and
operate at high temperatures –
approximately 1,200ºF. They require
carbon dioxide and oxygen to be
delivered to the cathode. To date, MCFCs
have been operated on hydrogen, carbon
monoxide, natural gas, propane, landfill
gas, marine diesel, and simulated coal
gasification products. 10 kW to 2 MW
MCFCs have been tested on a variety of
fuels and are primarily targeted to electric
utility applications. 17
Summary of Fuel Cell Types
18
Fuel Cell Thermodynamics –
Enthalpy of Formation
The fuel cell shown on page 10 is described by the following pair of
Reactions:
H2 + (1/2)O2 H2O
One way to think about enthalpy is that it is a measure of the energy that it
takes to form that substance out of its constituent elements. The difference
between the enthalpy of the substance and the enthalpies of its elements is
called the enthalpy of formation (∆H).
19
Enthalpy of formation for selected
substances (At 250C and 1 atm)
20
Electrochemical reactions in fuel
cells
21
Enthalpy of formation of water
Analyzing the reactions on page 21, the enthalpies of H2 and O2 are
zero so the enthalpy of formation is simply the enthalpy of the resulting
H2O. Noticing table on page 20, the enthalpy of H2O depends on
whether it is liquid water or gaseous water vapor. When the result is
liquid water:
The negative signs for the enthalpy changes in above tells us these
reactions are exothermic: that is, heat is released.
22
Example
Find the HHV of methane (CH4) in kJ/mol and kJ/kg when it is oxidized to CO2
and liquid H2O.
SOLUTION
The reaction is written below, and beneath it are enthalpies.
Notice that we must balance the equation so that we know how many
moles of each constituent are involved.
CH4(g) + 2O2(g) CO2(g) + 2 H2O(l)
(-74.9) 2X(0) (-393.5) 2X(-285.8)
Notice, too, that we have used the enthalpy of liquid water to find HHV.
The difference between the total enthalpy of the reaction products and the
reactants is
∆H = [(-393.5) + 2 X (-285.8)] – [(-74.9) + 2 X (0)] = -890.2 kJ/mol of CH4
Since the result is negative, heat is released during combustion; that is, it is
exothermic. The HHV is the absolute value of ∆H which is 890.2 kJ/mol.
Since there are 12.011 + 4X1.008 = 16.043 g/mol of CH4, the HHV can be
Written as
HHV = (890.2 kJ/mol) / (16.403 g/mol) X1000 g/kg = 55,490 kJ/kg23
Entropy and Theoretical Efficiency
of Fuel Cells
The reactions H2 + 1/2O2 H2O(l) and Enthalpy
H2 + 1/2O2 H2O(g) act as a source of enthalpy H in H
that can be converted to heat and work. The cell
generates an amount of electricity We and rejects an
amount of thermal energy Q to its environment. Fuel We
Since there is heat transfer and it is a real system, Cell
there must be an increase in entropy. We can write
the entropy appearing in the rejected heat as Enthalpy
∆S=Q/T. However there is no entropy associated Output
Rejected
with the work done We as there is no heat transfer. Heat Q
According to 2nd law of thermodynamics,
Entropy gain ≥ Entropy loss
24
Q ≥ T(ΣSreactants - ΣSproducts )
Entropy and Theoretical Efficiency
of Fuel Cells
Above equation tells us that the minimum amount of heat
that must appear in the fuel cell. That is we cannot convert
all of the fuel’s energy into electricity – we are stuck with
some thermal losses.
We can now easily determine the maximum efficiency of
the fuel cell. From the figure in page 24, the enthalpy
supplied by the chemical reaction ∆H equals the electricity
produced We plus the heat rejected Q:
∆H = We + Q
Since it is the electrical output that we want, we can write
the fuel cell’s efficiency as
η= We/∆H = (∆H – Q)/∆H = 1 – Q/∆H
25
Example
Suppose a fuel cell that operates at 250C (298K) and 1 atm
forms liquid water (that is we are working with the HHV of
the hydrogen fuel):
H2 + (½ )O2 H2O(l) ∆H = -285.8 kJ/mol of H2
26
Solution
a) From the reaction, 1 mole of H2 reacts with ½ mole of O2 to
produce 1 mole of liquid H2O. The loss of entropy by the reactants per
mole of H2 is found as follows:
ΣSreactants = 0.13 kJ/mol-K X 1mol H2
+ 0.205 kJ/mol-K X (1/2) mol O2 = 0.2325 kJ/K
The gain in entropy in the product water is
ΣSproduct = 0.0699 kJ/mol-K X 1mol H2O = 0.0699 kJ/K
b) The enthalpy made available during the formation of liquid water from
H2 and O2 is H = 285.8 kJ/mol of H2.
The maximum efficiency possible occurs when Q is a minimum; thus 27
ηmax = 1 – Qmin/H = 1 – 48.45/285.8 = 0.83 = 83%
Gibbs Free Energy and Fuel Cell
Efficiency
The chemical energy released in a reaction can be thought of as
consisting of two parts: an entropy-free part, called free energy ∆G, that
can be converted directly into electrical or mechanical work, plus a part
that must appear as heat Q. The free energy G is the enthalpy H
created by the chemical reaction, minus the heat that must be liberated,
Q=T∆S, to satisfy the 2nd law.
28
Example
What is the maximum efficiency at STP of a proton-
exchange –membrane (PEM) fuel cell based on the higher
heating value (HHV) of hydrogen ?
SOLUTION
The HHV corresponds to liberated water in the liquid state
so that the appropriate reaction is
H2 + (½ )O2 H2O(l) ∆H = -285.8 kJ/mol of H2
30
Electrical Output of an Ideal Cell
If n is the rate of flow of hydrogen into the cell (in mol/s), we can
therefore write that the current flowing through the load will be
I(A) = n (mol/s). 6.022X1023(molecules of H2/mol).
2 (electrons/molecules H2) . 1.602X10-19(coulombs/electron)
= 192945n A
The ideal power (watts) delivered to the load will be 237.2 kJ/mol of H2
times the rate of hydrogen use:
P(W) = 237.2 (kJ/mol) . n (mol/s) . 1000
= 237200n W
And the reversible voltage produced across the terminals of this ideal
fuel cell will be,
VR = P(W)/ I(A) = 237200n/192945n
= 1.229 V
31
Electrical Characteristics of
Fuel Cells
Usually real fuel cells do not deliver the full Gibbs free energy.
Activation losses result from the energy required by the catalysts to
initiate the reactions. The relatively slow speed of reactions at the
cathode, where oxygen combines with protons and electrons to form
water, tends to limit the fuel cell power. Ohmic losses result from
current passing through the internal resistance posed by the electrolyte
membrane, electrodes, and various interconnections in the cell.
Another loss, referred to as fuel crossover, results from fuel passing
through the electrolyte without releasing its electrons to the external
circuit. And finally, mass transport losses result when hydrogen and
oxygen gasses have difficulty reaching the electrodes. This is
especially true at the cathode if water is allowed to build up, clogging
the catalyst. For these and other reasons, fuel cells, in general,
generate only about 60-70% of the theoretical maximum.
32
Electrical Characteristics of
Fuel Cells
Figure shows the relationship
between current and voltage for a 1.229 V
typical fuel cell. Notice that the 0.9V
voltage at zero current, called the
open circuit voltage, is a little
less than 1V, which is about 25%
0.85V
lower than the theoretical value
of 1.229 V. Over most of the 0.25 V/(A/cm2)
length of the fuel cell I-V graph,
voltage drops linearly as current
increases. This suggests a
Simple equivalent circuit consisting
of a voltage source in series with
some internal resistance.
Fitting the V-I curve in the ohmic region for the fuel cell,
V = 0.85 – 0.25J = 0.85 – (0.25/A)I
where A is the cell area (cm2), I is current (A) and J is current density(A/cm2). 33
Energy storage
• Why energy storage?
• Utility load levelling: to improve load factors,
reduce pollution in populated urban areas and to
make better use of available plants and fuels
• Utilization of renewable energy in its various
forms to relieve the burden on finite fossil fuel
resources and to improve the environment
• Storage for remote users
• Uninterruptible power supplies
34
Pumped Storage Systems
Pumped Storage balances
supply and demand by moving
water between reservoirs (70%
efficient for water) construct a
reservoir above a source of H2O.
In times of slack demand, use
electricity to pump water to the
reservoir. When you need
electricity, run water through
turbines to generate it. It can be
used to increase base load,
decrease peak load....is this
good?
Pumped water storage is used in Michigan (2000 MWe plant in Ludington)
Pennsylvania (870 MWe).
Can also do this for air at about 90% efficiency. In 2000 the US had about 20GW of
pumped storage capability. 35
Superconductors
• What is a superconductor?
Materials in which the electrical resistance disappears at some
critical temperature (Mercury Tc = 4.2K; Niobium-Tin Tc = 23K).
of the bridge.
winding
39
Flywheels
• A wheel winds up through some system of gears and
then delivers rotational energy until friction dissipates it
• Stored energy = sum of kinetic energy of individual mass
elements that comprise the flywheel
• Kinetic Energy = (1/2)*Iω2
• I = moment of inertia ability of an object to resist
changes in its rotational velocity
• ω = rotational velocity
• To optimize the energy-to-mass ratio, the flywheel needs
to spin at the maximum possible speed. This is because
kinetic energy only increases linearly with mass but goes
as the square of the rotation speed.
40
Flywheels
• Rapidly rotating objects are subject to centrifugal forces
that can rip them apart. Centrifugal force for a rotating
object goes as: MRω2
• Thus, while dense material can store more energy it is
also subject to higher centrifugal force and thus fails at
lower rotation speeds than low density material.
• Tensile Strength is More important than density of
material.
• Long rundown times are also required. Frictionless
bearings and a vacuum to minimize air resistance can
result in rundown times of 6 months steady supply of
energy.
• Flywheels are about 80% efficient (like hydro)
• Flywheels do take up much less land than pumped hydro
systems 41
Batteries
• The oldest electrical storage device is the battery. The lead-acid
battery in a car is capable of producing 50-100W/kg for a total stored
energy of 25-35 Wh/kg.