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# EE 394V New Topics in Energy Systems

Fall 2012

## Clarifications from Course Introduction

Course Description:
Graduate level course. You are already engineers or hold some other
baccalaureate degree. So you are expected to show a proactive and independent
attitude towards your work. You are expected to also be inquisitive about everything
the instructor says. So please, do ask questions in class.
The courses 2nd goal supports this approach.
The 10 % of the grade for participation also supports this course concept.
The use of a recommended text supported by papers and references in class are
also in line with the courses concept.
Goal #1: To discuss topics related with distributed generation technologies.
Goal #2: To prepare the students to conduct research or help them to improve
their existing research skills.

## Alexis Kwasinski, 2012

Microsources
Most common microsources:
Small wind turbine (<10
kW/turbine)

## Reciprocating Engine e.g.

diesel generator (<100
kVA/unit)
Fuel Cell (<400 kW/unit)
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## PV Module (<250 W/module)

Alexis Kwasinski, 2012

Real microsources

Wind turbines +
PV modules

PAFC
Microturbines

MCFC

http://static.flickr.com/39/101004887_6525c88bfc.jpg

## Alexis Kwasinski, 2012

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

## Fuel Cells Basics

Fuel cells convert chemical energy directly into electrical energy.
Difference with batteries: fuel cells require a fuel to flow in order to produce
electricity.
Heat is produced from chemical reaction and not from combustion.
Types of fuel cells:
Proton exchange membrane (PEMFC)
Direct Methanol fuel cell (DMFC)
Alkaline fuel cell (AFC)
Phosphoric acid fuel cell (PAFC) (*)
Molten-carbonate fuel cell (MCFC) (*)
Solid-oxide fuel cell (SOFC) (*)
(*) Suitable for microgrids.

## Fuel cells operation

Example: PEMFC
The hydrogen atoms electron and proton are separated at the anode.
Only the protons can go through the membrane (thus, the name
proton exchange membrane fuel cell).

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 )

## Fuel cell thermodynamics

The first law of thermodynamics:
The energy of a system is conserved

Q W dE

Change of heat
provided to the
system

Change of
work provided
by the system

Change of
systems total
energy

## 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)

## Fuel cell thermodynamics

For an open system with mass flow across its boundaries (control volume),
such as a steam turbine

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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## 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 ,
In the cathode: 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
temperature T0, the entropy is defined as

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Qrev
T0

Qrev at a

## Fuel cell thermodynamics

In all processes involving energy conversion or interactions S is nonnegative. S is zero only in reversible processes..
For any process then S

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

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## Fuel cell thermodynamics

The maximum possible efficiency for a fuel cell is, then

max

W
Q
1 min
H
H

## An alternative derivation involves using Gibbs Free Energy

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, 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
G

max

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From tables:

H 2 2 H 2e ,
In the anode:

G 0 kJ
G 237.2 kJ / mol

## And from slide #10 H equals 285 kJ/mol. Thus,

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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## Fuel cell thermodynamics

Thus,
G
Eo
2F
and since F = 96,485 C/mole and G = -237.2 kJ/mole, then

(237200)
Eo
1.229 1.23V
(2)(96, 485)

## E0 is also denoted by Er, the reversible voltage.

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.
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## PEMFC output: Tafel equation

The Tafel equation yields the cells output voltage Ec considering additional
loosing mechanisms:

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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## PEMFC output: Tafel equation

In the last equation R is the universal gas constant (8.314 Jmol-1K-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.
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Er = 1.23 V

Maximum power
operating point

Er =1.23V
b=60mV,
i0=10-6.7Acm-2
r=0.2cm2
Activation loss
region

## Ohmic loss region

(linear voltage to current
relationship)
Actual PEMFCs efficiency vary between 35% and 60%

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## 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

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## PEMFC electrical characteristics

A very good dynamic model of a PEMFC is discussed in: Wang, Nehrir, and
Shaw, Dynamic Models and Model Validation for PEM Fuel Cells Using
Electrical Circuits. IEEE Transactions on Energy Conversion, vol 20, no. 2,
June 2005.
Some highlight for this model:
Basic circuit

## Rohm: represents ohmic losses

Ract: represents the activation losses (related with 2nd term in Tafel equation)
Rconc: losses related with mass transport.
C: capacitance related with the fact that there are opposing charges buildup
between the cathode and the membrane.
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## PEMFC electrical characteristics

Model for the internal fuel cell voltage E

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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## PEMFC electrical characteristics

Ed,cell can be calculated from the following dynamic equation:

s
E d ,cell ( s ) e I( s ) e
es 1

dEd ,cell (t ) 1
di (t )

Ed ,cell
(t ) e
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.
Thermodynamic characteristics were introduced in the model through an
analogous electric circuit, as shown in the next slide.
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## PEMFC electrical characteristics

Simulation model and equivalent electric circuit for the thermodynamic block:

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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## Alexis Kwasinski, 2012

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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## Alexis Kwasinski, 2012

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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## Alexis Kwasinski, 2012

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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## PEMFC Technology and issues

Expected life of PEMFC is very short (5,000 hours) and not suitable for DG.
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.
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## Direct Methanol Fuel Cells (DMFC)

The main advantage is that they use a liquid fuel.
Reactions:
Anode CH 3OH H 2O CO2 6 H 6e
Cathode 1/ 2O2 2 H 2e H 2O
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
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## Phosphoric Acid Fuel Cells (PAFCs)

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
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## Alkaline Fuel Cells (AFCs)

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
Developed for the Apollo program.
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

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## Molten Carbonate Fuel Cells (MCFCs)

One of the main advantages is the variety of fuels and catalyst than can be
used.
Reactions:
2

## Anode H 2 CO3 H 2O CO2 2e

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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## Solid Oxide Fuel Cells (SOFCs)

One of the main advantages is the variety of fuels and catalyst than can be
used.
Reactions:
H 2 O 2 H 2 O 2e
Anode

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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## Fuel cell technologies

Comparison of the most common technologies
PEMFC

DMFC

PAFC

MCFC

SOFC

H2

CH3OH

H2

hydrocarbons

hydrocarbons

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

## Unit Size (KW)

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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