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Fuel Cell Technology

Electrolysis

What does this have to do with fuel cells?

By providing energy from a battery, water (H2O)


can be dissociated into the diatomic molecules of
hydrogen (H2)
and oxygen (O2).

Figure 1

Fuel Cell Basics

Put electrolysis in reverse.

The familiar process of electrolysis requires work to proceed, if the process is put in reverse, it should be able to do
work for us spontaneously.
The most basic black box representation of a fuel cell in action is shown below:

work
Figure 2

O2
H2

fuel
cell

heat

H2 O

What is a Fuel Cell?


Quite simply, a fuel cell is a device that converts chemical energy into
electrical energy, water, and heat through electrochemical reactions.
Fuel and air react when they come
into contact through a porous
membrane (electrolyte) which separates
them.
This reaction results in a transfer of
electrons and ions across the electrolyte
from the anode to the cathode.
If an external load is attached to this
arrangement, a complete circuit is formed
and a voltage is generated from the flow
of electrical current.
The voltage generated by a single cell is typically rather small (< 1 volt), so many
cells are connected in series to create a useful voltage.

Fuel Cell Vs. Battery


Basic operating principles of both are very similar, but there are several
intrinsic differences.
Hydrogen fuel cell
Galvanic cell (battery)

Open system
Anode and cathode are gases in
contact with a platinum catalyst.
Reactants are externally supplied,
no recharging required.

Closed system
Anode and cathode are metals.
Reactants are internally consumed,
need periodic recharging.

Fuel Cell Vs. Internal Combustion Engine

Similarities:
Both use hydrogen-rich fuel.
Both use compressed air as the oxidant.
Both require cooling.

Differences:

Fuel cell:

Output is electrical work.


Fuel and oxidant react electrochemically.
Little to no pollution produced.

I.C. Engine:

Output is mechanical work.


Fuel and oxidant react combustively.
Use of fossil fuels can produce significant pollution.

Fuel Cell Basics


Components

Anode: Where the fuel reacts or "oxidizes", and releases electrons.


Cathode: Where oxygen (usually from the air) "reduction" occurs.
Electrolyte: A chemical compound that conducts ions from one electrode to the other inside a fuel cell.
Catalyst: A substance that causes or speeds a chemical reaction without itself being affected.
Cogeneration: The use of waste heat to generate electricity. Harnessing otherwise wasted heat boosts the
efficiency of power-generating systems.
Reformer: A device that extracts pure hydrogen from hydrocarbons.
Direct Fuel Cell: A type of fuel cell in which a hydrocarbon fuel is fed directly to the fuel cell stack,
without requiring an external "reformer" to generate hydrogen.

Fuel Cell Basics


Putting it together.

Figure 3

Animation of PEMFC

What is a hydrogen fuel cell?


Hydrogen fuel cells (HFCs) are a
type of electrochemical cell.
HFCs generate electricity by
reduction and oxidation reactions
within the cell.
They use three main components, a
fuel, an oxidant and an electrolyte.

HFCs operate like batteries,


although they require external fuel.
HFCs are a thermodynamically open
system.
HFCs use hydrogen as a fuel, oxygen
as an oxidant, a proton exchange
membrane as an electrolyte, and

How do they work?

Fuel (H2) is first transported


to the anode of the cell
Fuel undergoes the anode
reaction

Anode reaction splits the


fuel into H+ (a proton) and eProtons pass through the
electrolyte to the cathode
Electrons can not pass
through the electrolyte, and
must travel through an
external circuit which creates
a usable electric current
Protons and electrons reach
the cathode, and undergo the
cathode reaction

Chemistry behind the technology


Oxidation

Reduction

At the anode of the cell,


a catalyst (platinum
powder) is used to
separate the proton from
the electron in the
hydrogen fuel.
Anode half-reaction:
2H2 4H+ + 4eEo = 0.00V

At the cathode of the cell, a


second catalyst (nickel) is
used to recombine the
protons, electrons, and
oxygen atoms to form water.
Cathode half- reaction:
4H+ + O2 + 4e- 2H2O
Eo = 0.68V

In electrochemistry, the Eocell value (energy) of a fuel cell is equal to the


Eo of the cathode half-reaction minus the Eo of the anode half-reaction.
For a hydrogen fuel cell, the two half reactions are shown above. So to
calculate the energy of one fuel cell, we need to subtract the anode
energy from the cathode energy. For a HFC, the Eocell = 0.68V 0.00V
which equals 0.68V

Uses of hydrogen fuel cells


There are many different uses of fuel cells being utilized right now. Some
of these uses are
Power sources for vehicles such as cars, trucks, buses and even boats and
submarines

Power sources for spacecraft, remote weather stations and military


technology

Batteries for electronics such as laptops and smart phones

Problems regarding hydrogen fuel cells


Lack of hydrogen infrastructure

Need for refueling stations


Lack of consumer distribution system

Cost of hydrogen fuel cells


2009 Department of Energy estimated $61/kw

Honda FCX Clarity costs about half a million dollars to make


Carbon cost of producing hydrogen

Problems with HFC cars


Short range (~260 miles)
Warm up time (~5 minutes)

Types of Fuel Cells

The five most common types:

Alkali
Molten Carbonate
Phosphoric Acid
Proton Exchange Membrane
Solid Oxide

Types of Fuel Cells

SOFC

Vorteil: Keine aufwendige Brenngas-Aufbereitung


Nachteil: Hohe Betriebstemperaturen = Hohe System-Kosten
Starke Material-Beanspruchung

Alkali Fuel Cell

compressed hydrogen and oxygen fuel


potassium hydroxide (KOH) electrolyte
~70% efficiency

150C - 200C operating temp.


300W to 5kW output
Figure 4

requires pure hydrogen fuel and platinum catylist ($$)


liquid filled container corrosive leaks

Molten Carbonate Fuel Cell (MCFC)


carbonate salt electrolyte

60 80% efficiency
~650C operating temp.
cheap nickel electrode catylist

up to 2 MW constructed, up to 100 MW designs exist

Figure 5

The operating temperature is too hot for many applications.

carbonate ions are consumed in the reaction inject CO2 to compensate

Phosphoric Acid Fuel Cell (PAFC)

phosphoric acid electrolyte


40 80% efficiency
150C - 200C operating temp
11 MW units have been tested
sulphur free gasoline can be used as a fuel
Figure 6

The electrolyte is very corrosive


Platinum catalyst is very expensive

Proton Exchange Membrane (PEM)

thin permeable polymer sheet electrolyte


40 50% efficiency
50 250 kW
80C operating temperature

Figure 7

electrolyte will not leak or crack

temperature good for home or vehicle use


platinum catalyst on both sides of membrane $$

Solid Oxide Fuel Cell (SOFC)

hard ceramic oxide electrolyte


~60% efficient
~1000C operating temperature

cells output up to 100 kW

Figure 8

high temp / catalyst can extract the hydrogen from the fuel at the electrode
high temp allows for power generation using the heat, but limits use

SOFC units are very large


solid electrolyte wont leak, but can crack

Benefits
Efficient:

in theory and in practice

Portable:

modular units

Reliable:

few moving parts to wear out or break

Fuel Flexible: With a fuel reformer, fuels such as natural gas, ethanol,
methanol,
propane, gasoline, diesel, landfill gas,wastewater,
treatment digester gas, or even ammonia can be used

Environmental:

produces heat and water (less than combustion in both cases)


near zero emission of CO and NOx
reduced emission of CO2 (zero emission if pure H2 fuel)

Fuel cell efficiency is not an completely


defined term yet

Voltage efficiency tends to over estimate the amount of


work based on caloric fuel content

Max voltage = the reversible reaction potential at the operating


conditions
Emax = 100%, not realistic because of heat losses

Vcell
E=V
x100%
voltage
max

Vmax=1.23v @STP

The Change in Gibbs energy and Heat of formation of


water form the basis for the most commonly used
overall efficiency measure
E=

overall

()[Vcell]

x100%

=0.95
=1.48

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
Water
Catalyst (Pt)
Anode (-)

Membrane
(Nafion)

Catalyst (Pt)
Cathode (+)

H 2 2 H 2e

1/ 2O2 2 H 2e 1H 2O
O2 2H 2 2H 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
systems total
energy

Change of heat
Change of
provided to the work provided
system
by the system
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.

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:
In the cathode:

H 2 2 H 2e ,
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 Qrev at a temperature T0,
the entropy is defined as
Q
S rev
T0

Fuel cell thermodynamics


In all processes involving energy conversion or interactions S is non-negative. S
is zero only in reversible processes..

Q
S
T
The = in the above relationship will give us the minimum amount of heat Qmin
required in a process.
For any process then

From the enthalpy definition a fuel cell can be considered as a system like the
following one

Fuel cell thermodynamics


The maximum possible efficiency for a fuel cell is, then
Q
W
max
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
G
processes, such as heat orchemical
energy, into work.
max
H
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

Fuel cell thermodynamics


From tables:

In the anode:
In the cathode:

H 2 2 H 2e ,
1/ 2O2 2 H 2e 1H 2O,

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.

Fuel cell thermodynamics


Thus,
Eo

G
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.

PEMFC electrical characteristics


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%

Mass transport loss region

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