Lecture - Fuel Cells

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 Need Of Energy Storage Devices
Solar power is an intermittent energy source, meaning that solar
power is not available at all times, and is normally supplemented
by storage or another energy source, for example with wind
power and hydropower.
Wind power is an intermittent energy source, meaning that wind
is not available at all times, and thus needs to be supplemented by
storage or another energy source, for example with solar power
and hydropower.
Under circumstances of peak power consumption, load
shedding is done to meet the grid power supply. Under these
condition one may like to switch to storage power supply.
From very small devices such as wrist watches to sophisticated
devices such as powering of space shuttles rely on power storage
devices. 2
Energy Storage Systems

Fuel Cells
Hydrogen production and Storage
Li-ion batteries

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 About Fuel Cell
A fuel cell is an electrochemical device that converts the fuel into
an electric current. Electricity is generated through chemical
reactions between the fuel and an oxidant.

The reactants flow into the cell, and the reaction products flow
out of the cell while the electrolyte remains within it.

Fuel cells consume reactant from an external source, which must be

replenished .

Many combinations of fuels and oxidants are possible. A

hydrogen fuel cell uses hydrogen as its fuel and oxygen (usually
from air) as its oxidant. Other fuels include hydrocarbons and
alcohols. Other oxidants include chlorine and chlorine dioxide.
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 Design Of Fuel Cell
Fuel cells are available in a number of varieties. However the way of their
functioning is almost identical.
Each type of Fuel cell consists of 3 parts : (1) An anode (2) An electrolyte, and
(3) A cathode.
The most common fuel used in the cells is hydrogen.
The anode catalyst is usually made
up of very fine platinum powder. The
anode catalyst, accelerates up the
dissociation of the fuel into electrons
and ions.
The cathode catalyst is often made
up of nickel which converts the ions
into the waste chemicals like water
or carbon dioxide.
A typical fuel cell produces a voltage from 0.6 V to 0.7 V at full rated load. 5
Performance and efficiency of Fuel cell
Energy conversion of a fuel cell may be represented as :

Chemical energy of fuel = Electrical energy + Heat energy

Electricity: Energy =
Hydrogen V·I·t
Fuel Cell Heat (byproduct)
Oxygen Water (byproduct)

The input energy is the energy produced during reactions at the

electrodes.
The above energy balance could be explained using the first and
second laws of thermodynamics.
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 Types of Fuel Cells
Polymer Electrolyte Membrane Fuel
Cell (PEMFC)

Alkaline Fuel Cell (AFC)

Phosphoric Acid Fuel Cells (PAFC)
Molten Carbonate Fuel Cells (MCFC)

Solid Oxide Fuel Cells (SOFC)

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 Polymer Electrolyte Membrane fuel cell
Polymer electrolyte membrane (PEM) fuel cells are also called
proton exchange membrane fuel cells.

These cells use a solid polymer as an

electrolyte and porous carbon electrodes
containing a platinum catalyst.

H2: Fed on Anode

Air (O2): Fed on Cathode

Polymer electrolyte membrane fuel

cells operate at relatively low
temperatures, around 80°C.
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Polymer electrolyte membrane (PEM) Fuel Cell
It deliver high-power density and offer the advantages of low weight and volume,
compared with other fuel cells.

PEM fuel cells are used primarily for transportation applications such as cars
and buses and some stationary applications due to their fast startup time, low
sensitivity to orientation, and favourable power-to-weight ratio.

It requires a noble-metal catalyst (typically platinum) to separate the hydrogen's

electrons and protons, adding to system cost.

A limitation is hydrogen storage. Most fuel cell vehicles (FCVs) powered by

pure hydrogen must store the hydrogen on-board as a compressed gas in
pressurized tanks. Due to the low-energy density of hydrogen, it is difficult to
store enough hydrogen on-board to allow vehicles to travel the same distance
as gasoline-powered vehicles before refuelling, 300–400 miles.

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 Solid Oxide Fuel Cells
The cell is consists of two porous electrodes
which sandwich an electrolyte.

Air flows along the cathode. When an oxygen

molecule from air comes in contact with
cathode-electrolyte interface, it catalytically
acquires four electrons from the cathode and
splits into two oxygen ions.

O2 + 4e-  2O2-

The oxygen ions diffuse into the electrolyte material and migrate to the other
side of the cell where they encounter the anode.

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 Solid Oxide Fuel Cells
The oxygen ions encounter the fuel
at the anode/electrolyte interface
and react catalytically, giving off
water, carbon dioxide, heat, and --
most importantly -- electrons.

The electrons transport through the

anode to the external circuit and
back to the cathode, providing a
source of useful electrical energy in
an external circuit.

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 Components of SOFC
Electrolyte: Ceramic material, Yttrium-doped zirconium oxide (YSZ) is the
potential electrolyte in SOFCs because of its sufficient ionic conductivity,
chemical stability, and mechanical strength. The only drawback of stabilized YSZ
is the low ionic conductivity in the lower cell operation temperature regime,
below about 750oC.

Cathode: The oxidant gas is air or oxygen at the SOFC cathode. Calcium or
Strontium substituted Lanthanum manganite has good electronic conduction,
porosity, thermal stability and thermal expansion match to YSZ.

Anode: Nickel-YSZ composites are the most commonly used anode materials for
SOFCs. Nickel is an excellent catalyst for fuel oxidation. YSZ in the anode
constrains nickel aggregation, decreases the effective thermal expansion
coefficient bringing it closer to that of the electrolyte, and provides better
adhesion of the anode with the electrolyte.
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 Design Configurations of SOFC
Two design configurations for
SOFCs have emerged:
A planar design: In the planar design,
the components are assembled in flat
stacks, with air and fuel flowing
through channels built into the
cathode and anode.
Planar design SOFC
A tubular design :In the tubular design,
components are assembled in the form
of a hollow tube, with the cell
constructed in layers around a tubular
cathode. Air flows through the inside of
the tube and fuel flows around the
exterior.
Tubular design SOFC 13
Optional

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Main markets for fuel cell technology
1. Stationary power includes any application in which the fuel
cells are operated at a fixed location, either for primary or for
backup power, or for combined heat and power generation(CHP).

2. Transportation applications include motive power for cars,

buses and other fuel cell vehicles (FCV) and auxiliary power units
(APUs) for highway and off-road vehicles, as well as specialty
vehicles.

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HYDROGEN
PRODUCTION
AND
STORAGE
 INTRODUCTION
Hydrogen can be produced from a variety of feedstocks. These
include fossil resources such as natural gas and coal and also
renewable resources such as biomass and water with input from
renewable energy sources (e.g. sunlight, wind, wave or hydro-power).

The technologies for hydrogen production include reforming of

natural gas; gasification of coal and biomass; and the splitting of
water by water-electrolysis, photo-electrolysis, photo-biological
production and high temperature decomposition.
Each technology is in a different stage of development and
offers unique opportunities and benefits.

Water electrolysis and natural gas reforming are the technologies of

choice in the current and near term. These are proven technologies
usable in the early phases of building a hydrogen infrastructure for
the transport sector.
An overview of the various feedstocks
and process technologies
 HYDROGEN FROM FOSSIL FUELS
Production from natural gas: Hydrogen can currently be produced
from natural gas by means of three different chemical processes:
1. Steam reforming (steam methane reforming – SMR).
2. Partial oxidation (POX).
3. Autothermal reforming (ATR).
1. Steam Methane Reforming: Steam reforming involves the endothermic conversion
of methane and water vapour into hydrogen and carbon monoxide (Eqn. 1). The heat is
often supplied from the combustion of some of the methane feed-gas. The process
typically occurs at temperatures of 700 to 850 °C and pressures of 3 to 25 bar (mm of
Hg). The product gas contains approximately 12 % CO, which can be further converted
to CO2 and H2 through the water-gas shift reaction (Eqn. 2).

CH4 + H2O + heat  CO + 3H2 (1)

CO + H2O  CO2 + H2 + heat (2)

 H2 Production from natural gas
2. Partial oxidation of natural gas:
Partial oxidation of natural gas is the process whereby partial combustion of
methane with oxygen gas yields carbon monoxide and hydrogen ( Eqn 3).
CH4 + 1/2O2 CO + 2H2 + heat (3)

The above reaction is exothermic and heat is generated. Hence no external heating is
required and comparatively more compact design of reactor is feasible. The CO
produced is further converted to H2 as described in equation (2).

3. Autothermal reforming

Autothermal reforming is a combination of both steam reforming (Eqn. 1) and

partial oxidation (Eqn. 3). The total reaction is exothermic, and so it releases
heat. The outlet temperature from the reactor is in the range of 950 to 1100
°C, and the gas pressure can be as high as 100 bar. Again, the CO produced is
converted to H2 through the water-gas shift reaction (Eqn. 2).
 HYDROGEN FROM FOSSIL FUELS
H2 Production from Coal
Hydrogen is produced from coal through gasification process. A typical
reaction for the process is represented by equation (4), wherein carbon is
converted to carbon monoxide and hydrogen.

C(s) + H2O + heat  CO + H2 (4)

This reaction is endothermic hence additional heat is required for carrying

out the hydrogen production process. The CO is further converted to CO2
and H2 through the reaction, described in equation (2).

Hydrogen production from coal is commercially mature, but it is more

complex than the production of hydrogen from natural gas. The cost of the
hydrogen produced is also higher.
 HYDROGEN PRODUCTION FROM
SPLITTING OF WATER
Hydrogen can be produced from the splitting of water through
various processes. These are:

1. Water electrolysis
2. Photo-electrolysis
3. Photo-biological production
4. High-temperature water decomposition.
 Water electrolysis
Water electrolysis is the process whereby water is split into
hydrogen and oxygen through the application of electrical energy,
as in equation (5).

H2O + electricity  H2 + 1/2O2 (5)

Future potential costs for

electrolytic hydrogen are
presented in Figure,
where the possibilities to
considerably reduce the
production cost are
evident.
 HYDROGEN STORAGE SYSTEMS
Hydrogen storage can be considered for onboard vehicular, portable,
stationary, bulk, and transport applications, i.e. for fuel cell or ICE/electric
hybrid vehicles.

The three principal forms of hydrogen storage (gas, liquid, and solid),
with a focus on the technology gaps and R&D priorities related to the
various approaches will be discussed.
 GASEOUS HYDROGEN
The most common method to store hydrogen in gaseous form is in
steel tanks, although lightweight composite tanks designed to
endure higher pressures are also becoming more and more
common.
Cryogas, gaseous hydrogen cooled to near cryogenic
temperatures, is another alternative that can be used to increase
the volumetric energy density of gaseous hydrogen.
A more novel method to store hydrogen gas at high pressures is
to use glass microspheres.
Two of the most promising methods to store hydrogen gas
under high pressure:
Composite tanks
Glass microspheres.
 Composite Hydrogen Storage tanks

Design of composite hydrogen Storage Tank.

There are several advantages with such
composite tanks.

Their low weight meets key targets, and

the tanks are already commercially
available, well-engineered and safety-
tested.

Composite tanks require no internal heat

exchange and may be usable for cryogas.

Their main disadvantages are the large physical volume required (which does not meet
targets).

There are also some safety issues that still have not been resolved, such as the problem of
rapid loss of H2 in an accident.
Glass Microspheres for Hydrogen Storage
The basic concept for hydrogen gas storage in glass microspheres can be described in
three steps:

Charging, filling and discharging.

First, hollow glass spheres are filled with H2 at

high pressure (350-700 bar) and high
temperature (300 °C) by permeation in a high-
pressure vessel.

Next, the microspheres are cooled down to

room temperature and transferred to the low-
pressure vehicle tank.

Finally, the microspheres are heated to 200-

300 °C for controlled release of H2 to run the
vehicle.
 Glass Microspheres for Hydrogen Storage
Limitations
The main problem with glass microspheres is the inherently low achievable
volumetric density and the high pressure requirement for filling.

The glass microspheres slowly leak hydrogen at ambient temperatures.

Another challenge is the need to supply heat at temperatures higher than those
available from the PEM fuel cell (70-80 °C). The required high temperature (300 °C) also
makes rapid response-control difficult.

Advantages
Glass microspheres have the potential to be inherently safe as they store H2
at a relatively low pressure onboard and are suitable for conformable tanks.

This allows for low container costs.

Hydrogen storage in the form of LIQUID HYDROGEN
The most common way to store hydrogen in a liquid
form is to cool it down to cryogenic temperatures (–
253 °C). The three most promising methods are:

1. Cryogenic Hydrogen

2. Hydrogen as a constituent in NaBH4 solutions.

3. Hydrogen as a constituent in Rechargeable

organic liquids.
 Cryogenic liquid hydrogen (LH2)
Cryogenic hydrogen, usually simply referred to as liquid hydrogen (LH2), has a density of
70.8 kg/m3 at normal boiling point (–253 °C).

The theoretical gravimetric density of LH2 is 100%, but only 20 wt. % H2 of this can
be achieved in practical hydrogen storage systems today. This means that liquid
hydrogen has a much better energy density than the pressurised gas solutions.

About 30-40% of the energy is lost when LH2 is produced.

Main disadvantage with LH2 is the boil-off loss during dormancy, and requirement of
super-insulated cryogenic containers for storage.

The main advantage with LH2 is the high storage density that can be reached at
relatively low pressures.

Liquid hydrogen has been demonstrated in commercial vehicles (particularly by BMW),

and in the future it could also be co-utilized as aircraft fuel, since it provides the best
weight advantage of any H2 storage.
 SOLID HYDROGEN
Storage of hydrogen in solid materials has the potential to become a
safe and efficient way to store energy, both for stationary and
mobile applications.
There are four main groups of solid materials suitable for this
purpose:
1. Carbon and other high surface area materials
2. H2O-reactive chemical hydrides
3. Thermal chemical hydrides
4. Rechargeable hydrides
 Carbon and other high surface area materials
Carbon-based materials (nanotubes and graphite
nanofibers)
Carbon-based materials, such as nanotubes and graphite nanofibers, have received
a lot of attention in the research community and in the public press over the last
decade.

Pure H2 molecular physisorption has been clearly demonstrated, but is useful only
at cryogenic temperatures (up to 6 wt.% H2), and extremely high surface area
carbons are required.

Pure atomic H-chemisorption has been demonstrated to 8 wt.% H2, but the
covalent-bound H is liberated only at impractically high temperatures (above 400
°C).

Room temperature adsorption up to a few wt.% H2 is occasionally reported,

but has not been reproducible.
 Rechargeable hydrides
The two main reversible hydriding reactions in rechargeable
metal hydride batteries are shown in Figure.
From this it becomes clear that the complex hydrides provide the
hope for the future, particularly the non-transition metal types
such as borohydrides, alanates and amides.
Comparison between various Storage
Techniques
Comparisons between the three basic storage options shows that
the potential advantages of solid H2-storage compared to
gaseous and liquid hydrogen storage are:
Lower volume.
Lower pressure (greater energy efficiency).
Higher purity H2 output.

Compressed gas and liquid storage are the most commercially

viable options today, but completely cost-effective storage
systems have yet to be developed.

The safety aspects with all storage options, particularly the novel
hydride storage options, must not be underestimated.
 Definition of Battery
A battery is a device that converts chemical energy to electrical
energy.
A battery is composed of two electrodes (cathode and anode)
and an ionically conductive material called electrolyte.

When these electrodes are connected by means of an external

load or device, electrons spontaneously flow from negative to
more positive potential and ions migrate through the electrolyte
maintaining the charge balance, and electrical energy can be
trapped by the external circuit.

Two or more electrochemical cells can be connected in series or

parallel combination to form a battery depending up on the
required energy and voltage.
 About Battery
A battery’s characteristics depend upon the internal chemistry,
current drain and temperature.
The amount of energy per unit mass or volume (Watt. hours/kg or
Watt. hours/litre) that a battery can deliver depends significantly
on the cell’s voltage and capacity, which are dependent on the
chemistry of the system.
Another important parameter is power which depends partly on
the battery’s engineering but crucially on the used chemicals in
that battery.

Based on the usage and principle of operation, batteries are

categorized mainly in two groups, namely primary (disposable)
and secondary (rechargeable) and manufactured in various
shapes and sizes according to usage.
 Primary Batteries (Disposal)
Primary batteries are manufactured to be used once only because
its active material (chemicals) is consumed in a single discharge via
an irreversible electrochemical reaction.

These batteries are usually of low price, easy to carry because of

light-weight, exhibit high energy density at low to moderate
discharge, require minimum maintenance and are easy to use.

The most common primary cells that are being used commercially,
Zinc-MnO2 (1.5 V) and Li-MnO2 (3.0 V).

Depending upon their usage, different shape and sizes are available
in market like, button and coin cells are widely used in watches,
calculators, CD players and other portable appliances.
Different kinds of primary batteries and their
applications
Primary Merits and/or applications
Zinc-carbon battery Midium cost, used in light drain application.
Zinc-chloride battery Similar to zinc-carbon but slightly longer life.
Long life, widely used in both light-drain and heavy-drain
Alkaline/manganese battery application.

Commonly used in hearing aids, watches, and calculators

Silver oxide battery
Lithium-Thionyl Chloride Industrial applications, including computers, electric meters
battery and other devices which contain volatile memory circuits and
act as a carryover voltage to maintain the memory in the
event of main power failure. These are relatively expensive.
Digital watches, radiocommunications, and portable
Mercury battery electronic instruments. Manufactured only for specialist
applications due to toxic nature of mercury.
High-temperature reserve.
Thermal battery
 Secondary Batteries (Rechargeable)
These can be re-charged by applying the electrical current, which
reverses the chemical reactions that occur during its use and
regenerate its active material for further use. These batteries are
also known as storage batteries or accumulators.

Therefore, the rechargeable batteries are considered as eco-

friendly alternative to the primary batteries as far as metal
pollution is concerned.
Many reclamation companies recycle batteries to reduce the
number of batteries going in to land fills.

Primary batteries have created many environmental concerns,

mainly toxic metal pollution.
Key Parmeters that should be met with
secondary batteries
• Energy densities
– Gravimetric (Wh/kg)  lighter weight
– Volumetric (Wh/l)  smaller size Optimised
“Speck”
• Power (W) Effects available
battery
capacity
– Potential (V)
– Current (I)
• Recharge conditions and limits
– cell protection
• Fabrication of micro-batteries
 Secondary Batteries Energy Densities

• Nickel Cadmium (Ni-Cd)

– 1.2V, 400 Cycles 1000
Smaller Thin Film

Volumetric Energy Density (Wh/l)

– Inexpensive − Simple charging 900 Li / Li-ion

– low energy density − Memory effect 800

– high self discharge (20% month) 700

– Toxic 600
500
Li-ion

• Nickel Metal Hydride (Ni-MH) 400

– 1.2V, 600 Cycles 300 Ni-Cd

Ni-
Li-
polymer
– Simple to charge, 200
MH Lighter
100
– High self discharge (30% month) 0
Pd-acid

– reduced memory effect − Less-toxic 0 50 100 150 200 250 300 350 400

• Silver Zinc (AgZn)

Gravimetric Energy Density (Wh/kg)

– 1.5 V, 300 Cycles

– Low energy density − Very difficult to recharge
• Lithium Ion (Li-ion) based
– 3.5V, 2000+ Cycles
– Higher energy density − No memory effect − Low self discharge
– Lower toxicity − More expensive − More complex charging
– Continuous current limited to 1.5C
 Principle of “Rocking chair” Li-ion Battery

e- e-

- +
Li+
charge

e- e-

Li+ discharge

LixC6 Graphite Li+ conducting electrolyte LiCoO2

• Electrode redox reactions on charge:

Cathode oxidation : LiCoO2  Li1-xCoO2 + xLi+ + xe-
Anode reduction : xLi+ + xe- + C6  LiC6 discharge is the opposite
 Principle of Operation of LIBs
Rechargeable LIBs involve a reversible insertion/extraction of Li ions (guest
species) in to/from a host electrode material during discharge/charge.

The Li intake/uptake process happening with a flow of ions through the

electrolyte is accompanied by a redox (reduction/oxidation) reaction of the host
matrix assisted with a flow of electrons through the external circuit.

In the commercial LIBs, Li-containing metal oxides (LiCoO2, LiNiO2, LiMn2O4,

and LiFePO4) are employed as cathodes (positive electrode).

Graphitic carbons (MCMB: mesocarbon microbeads) or amorphous Sn-Co-C

composite are used as anodes (negative electrode).
The electrolyte allows the flow of Li-ions between the electrodes but prevents
the electron flow. Due to the reversible motion of Li-ions between cathode
and anode through electrolyte, the LIBs are also known as rocking chair, swing
and shuttle-cock batteries.
Voltage vs. capacity (mAh/g) of electrode materials for LIB. The output
voltage values for Li-ion cells or those with Li-metal anodes are represented.
 Advantages of LIB
Wide variety of shapes and sizes efficiently fitting the devices they power.

Much lighter than other energy-equivalent secondary batteries.

High open circuit voltage in comparison to aqueous batteries (such as

lead acid, nickel-metal hydride and nickel-cadmium).

This is beneficial because it increases the amount of power that can be

transferred at a lower current.

No memory effect.

Self-discharge rate of approximately 5-10% per month, compared to

over 30% per month in common nickel metal hydride batteries.
 Disadvantages
Shelf life
Charging forms deposits inside the electrolyte that inhibit ion transport. Over
time, the cell's capacity diminishes. The increase in internal resistance reduces
the cell's ability to deliver current. This problem is more pronounced in high-
current applications. The decrease means that older batteries do not charge as
much as new ones (charging time required decreases proportionally).

Internal resistance
The internal resistance of lithium-ion batteries is high compared to other
rechargeable chemistries such as nickel-metal hydride and nickel-cadmium.
Internal resistance increases with both cycling and age. Rising internal
resistance causes the voltage at the terminals to drop under load, which
reduces the maximum current draw. Eventually increasing resistance means
that the battery can no longer operate for an adequate period.

Safety Issues: Li-ion batteries are not as durable as nickel metal hydride or nickel-
cadmium designs and can be dangerous if mistreated. They may suffer cell
rupture if overheated or overcharged.
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