Electrochemical energy systems

Batteries and fuel cells

When testing the capacity of a
NiMH or NiCd battery a cut-off voltage of 1.0 V is normally
used.
0.9V is normally used as the cut-off voltage of an alkaline cell.

Devices that have too high cut-off voltages may stop operating
while the battery still has significant capacity remaining.
Nominal voltage: 3.6V
Nominal capacity: 2,400mAh
Discharge current (continuous):
100mA
Discharge current (pulse): 200mA
Cut-off voltage: 2V
Operating temperature: -55 to +85
degrees Celsius
 Nominal Voltage 10.8V
Cut off voltage 2.0V(at 1mA
discharge)
Capacity loss after storage x 100/Capacity before storage
Primary batteries
Dry or leclanche cell
Alkaline battery
Lithium batteries
Secondary batteries – rechargeable batteries
Lead acid
Nickel-Cadmium
Advanced secondary batteries
Nickel Metal hydride
Lithium ion
Lithium batteries
 Lithium batteries
• are disposable (primary) batteries that
have lithium metal or lithium compounds as
an anode.
• They stand apart from other batteries in their high
charge density (long life) and high cost per unit.
• Depending on the design and chemical
compounds used, lithium cells can produce
voltages from 1.5 V (comparable to a zinc–
carbon or alkaline battery) to about 3.7 V.
 Advantages and uses

►Advantages of lithium ion batteries are

- High energy density
- Long shelf life
- Low self discharge
- Need less maintenance
- Can provide very high current
►Uses
Used in auto focus cameras etc.
 Lithium ion batteries
►The main attractions of lithium
as anode material is
– It is the most electronegative metal in the
electrochemical series
– It has very low density
– Means, the largest amount of electrical energy per
unit weight
►But Li cannot be used with the traditional
aqueous electrolytes
– due to the very vigorous corrosive reaction
between Li and water
– with flammable hydrogen as the product.
Cathode materials
• The most common compounds used for
cathode materials are LiCoO2, LiNiO2
and LiMn2O4.
• Of these, LiCoO2 has the best
performance but is very high in cost, is
toxic and has a limited lithium content
range over which it is stable.
• LiNiO2 is more stable, however the
nickel ions can disorder.
• LiMn2O4 is generally the best value for
money, and is also better for the
environment.
 Anode material and electrolyte
• The anode material is carbon based. Li0.5C6.

• This lithium content is lower than would be ideal, however

higher capacity carbons pose safety issues.

Electrolyte

• Since lithium reacts violently with water, and the cell voltage is
so high that water would decompose, a non-aqueous electrolyte
must be used.

• A typical electrolyte is LiPF6 dissolved in an ethylene carbonate

and dimethyl carbonate mixture.
Discharging

The following reactions take place upon discharge:

► At the anode: LixC6→ xLi+ + 6C + xe-
► At the cathode: xLi+ + Mn2O4 +xe-→ LixMn2O4
► Overall: LixMn2O4 + 6C → LixC6 + LixC6
 Rocking chair battery
• Anode here is a non-metallic compound, e.g.
carbon, which can store and exchange lithium
ions.
• A lithium ion-accepting material, for example
CoO2, is then used as the cathode material, and
lithium ions are exchanged back and forth
between the two during discharging and
charging. These are called intercalation
electrodes.
• This type of battery is known as a “rocking chair
battery” as the ions simply “rock” back and forth
between the two electrodes.
► Hydrogen (through anode) and oxygen (through cathode)
gases are bubbled through the respective compartments.
► Electrode – cathode porous, good conducting, excellent
catalyst for the reactions that take place on their surfaces,
not deteriorating by the electrolyte heat or electrode
reactions.
► Anode Graphite impregnated with finely divided platinum, or
alloy of Pd, Ag and Ni serves the purpose if hydrogen is the
fuel.
► Electrolyte - aqueous KOH or H2SO4.
Applications:
►Auxiliary energy source in space
vehicles, submarines or
other military-vehicles.
►Source of fresh water
 Alkali Fuel Cell Technology
Alkali fuel cells operate on compressed hydrogen and oxygen
and generally use a solution of potassium hydroxide in water
as their electrolyte. Operating temperatures inside alkali cells
are around 150 to 200 degrees C (about 300 to 400 degrees
F).

In these cells, hydroxyl ions (OH-) migrate from the cathode to

the anode. At the anode, hydrogen gas reacts with the OH-
ions to produce water and release electrons. Electrons
generated at the anode supply electrical power to an external
circuit then return to the cathode. There the electrons react
with oxygen and water to produce more hydroxyl ions that
diffuse into the electrolyte
 Solid oxide fuel cells
o SOFC employ a solid ceramic electrolyte.
o Most popular electrolyte material is Yttria-stabilized
zirconia (YSZ)which is an oxygen ion conductor.
[

o Since O2- is the conductor in this case, the anodic

and cathodic reactions are:

o Anode : H2 + O2- H2O + 2

o Cathode : ½ O2 + 2 e- O2-

o In SOFC, water is produced at the anode, rather than

at the cathode.
o The most common anodic material in SOFC is a
Nickel-YSZ cermet (a cermet is a mixture of ceramic
and metal).
o The cathode is usually a mixed ion-conducting and
electronically conducting ceramic material.
o Typical cathodes are strontium doped lanthanum
manganite (LSM), Lanthanum-strontium ferrite (LSF),
Lanthanum-strontium cobaltite (LSC), Lanthanum
-strontium cobaltite ferrite (LSCF).
► Anode : porous, to allow the fuel to flow to the electrolyte – Nickel
mixed with ceramic material of the electrolyte

► Cathode: Thin porous layer where oxygen reduction occurs

► Electrolyte : Solid oxide or ceramic electrolyte - Dense layer of

oxygen conducting ceramic. - mixture of ZrO and CaO coated on
either side by porous electrode materials. Others include yttrium
stabilized zirconia (YSZ) and gadolinium doped ceria (GDC)

Operating conditions:
► Operate at temperatures as high as1000oC
► Can be configured as rolled tubes or flat plates
► Oxygen ions diffuse through the electrolyte from cathode and
oxidize hydrogen fuel at the anode. This reaction produces oxygen
and electricity.
 Advantages / Disadvantages
► High efficiency
► Long term stability
► Fuel flexibility
► Low emissions
► High operating temp – longer start up times
► Mechanical / Chemical compatibility issues.

Applications:
► Auxiliary power units in vehicles
► Stationary power generation
► By product gases – channeled to turbines to generate more
electricity – cogeneration of heat and power and improves overall
efficiency
• A portable fuel cell developed by NASA/JPL
SOFC stack arrangement
 Solar Cells
• Types of solar cells –
• Why silicon?
• Comparison among single crystal,
polycrystalline and amorphous silicon
materials
• Dye sensitized solar cells - working principle
with a diagram, characteristics and
applications
 The solar spectrum
The energy in solar irradiation comes in
the form of electromagnetic waves of a
wide spectrum.
Longer wavelengths have less energy
(for instance infrared) than
shorter ones such as visible light or UV.

oAbout 46% of the spectral

energy is distributed in the visible
region
oAbout 49% in near IR

oAbout 3% in UV region and rest

(2%) in far IR region

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 A solar cell, or photovoltaic cell, is an electrical device that converts
the energy of light directly into electricity by the photovoltaic effect,
which is physical and chemical phenomenon
 The photovoltaic effect involves creation of a voltage (or a
corresponding electric current) in a material upon exposure to
electro-magnetic radiation.
 Though the photovoltaic effect is directly related to the photoelectric
effect, the two processes are different.
 In the photoelectric effect electrons are ejected from a material's
surface upon exposure to radiation of sufficient energy.
 It is a form of photoelectric cell, defined as a device whose electrical
characteristics, such as current, voltage, or resistance, vary when
exposed to light.
 Individual solar cell devices can be combined to form modules, otherwise known
as solar panels. In basic terms a single junction silicon solar cell can produce a
maximum open-circuit voltage of approximately 0.5 to 0.6 volt
Energy Conversion Materials
 •System converts light energy
to electricity
•Solar cells are described as
being photovoltaic irrespective of
whether the source is sunlight or
an artificial light

•Applications in Aerospace &

Satellite etc

The operation of a photovoltaic (PV) cell requires three basic

attributes:
The absorption of light, generating either electron-hole pairs
or excitons.
The separation of charge carriers of opposite types.
The separate extraction of those carriers to an external circuit.

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The most commonly known solar cell is configured as a large-area p–n
junction made from silicon.
Other possible solar cell types are organic solar cells, dye sensitized solar cells,
perovskite solar cells, quantum dot solar cells etc.
The illuminated side of a solar cell generally have a transparent conducting film
for allowing light to enter into active material and to collect the generated charge
carriers.
Typically, films with high transmittance and high electrical conductance such
as indium tin oxide, conducting polymers or conducting nanowire networks are
used for the purpose.[
 Solar energy conversion devices
Methods of tapping solar energy
A. Photosynthesis B. Water heaters C. Photovoltaic cells D. Chemical routes
Plants Flat plate, tube p/n Si, Si, GaAs
(Visible light ) (IR radiation) (Visible light)
η = 2-4% η = 12-26%

D2: PEC cells

D1: Biomimetism
Mimicking
Photosynthesis
via chemicals
b. Photoelectrosynthesis
a. LJSC (PES) cells
(i) Photoassisted
(i) Sc/Elect/M
electrolysis cells
η= 13-14% η= 13.3%
(ii) Photogalvanic cells (ii) Photoassisted
M/Elect/M electrosynthesis
cells
η= 0.01%
eg. CO2 CH3OH
N2 NH3
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Types of solar energy conversion cells

• Photovoltaic Cells
• Photoelectrochemical cells
• Dye-sensitized solar cells
• Solar cells can be classified into first, second and third generation cells.
• The first generation cells—also called conventional, traditional or wafer-based
cells—are made of crystalline silicon, the commercially predominant PV
technology, that includes materials such as polysilicon and monocrystalline
silicon.

• Second generation cells are thin film solar cells, that include amorphous
silicon, CdTe cells and are commercially significant in utility-scale photovoltaic
power stations, building integrated photovoltaics or in small stand-alone power
system.

• The third generation of solar cells includes a number of thin-film technologies

often described as emerging photovoltaics—most of them have not yet been
commercially applied and are still in the research or development phase. Many
use organic materials, often organometallic compounds as well as inorganic
substances. Despite the fact that their efficiencies had been low and the stability
of the absorber material was often too short for commercial applications, there
is a lot of research invested into these technologies as they promise to achieve
the goal of producing low-cost, high-efficiency solar cells
 Why Silicon?

o Silicon is a very common element abundant in nature. It is the

main element in sand and quartz.
o Silicon is considered as the most suitable material for solar
energy conversion because of
o 1. Most abundance (~ 28% by mass) after oxygen
o 2. Optimum band gap of 1.23 eV at 300 K
o 3. Cost effectiveness
o 4. Interestingly, silicon has a greater density in a liquid state
than a solid state.

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65
Structure of Silicon : The crystal structure, or atomic arrangement, of any
material has a great deal to do with its electrical properties.
Different types of silicon:

• Single crystal silicon - In its crystalline form, a material is characterized

by an ordered array of component atoms. This array is repetitive with
displacement through the material sample.
• Polycrystalline silicon - Where a polycrystalline material is concerned,
the object is composed of a number of sub-sections, each of which is
crystalline in form. These subsections, however, are independently
oriented so that at their interfaces the atomic order and regularity
undergo sharp discontinuities.
• Amorphous silicon (non-crystalline for higher light absorption) - The
final category, the amorphous material, displays no atomic regularity
of arrangement on any macroscopic scale.

Single crystal silicon Polycrystalline silicon Amorphous

 Classification of Photoelectrochemical cells

PEC cells are Classified into two types according to

their application.

1. Liquid Junction Solar Cell (LJSC) –

This cell is used to convert solar energy into electrical
energy

2. Photoelectrosynthesis (PES) cells –

In this class of cells, solar energy is converted into
chemical energy in the form of fuels.

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 Conditions for Efficient Solar Energy Conversion –
Electrodes

 The requirements for the electrode materials are:

(1) Band gap (Eg) should be optimum

(2) The doping level should be optimum, so that there will be a

good spatial separation of the photo-generated carriers and
hence, high quantum efficiency.
(3) Should have large values of absorption co-efficient (α). This is
usually found for direct band gap SC’s.

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 Dye Sensitization - Grätzel cell
1. Sunlight energy (photon of light) passes through the titanium dioxide layer
and strikes electrons within the adsorbed dye molecules. Electrons gain this
energy and become excited because they have the extra energy.
2. The excited electrons escape the dye molecules and leave free electrons.
These free electrons move through the titanium dioxide and accumulate at
the -ve plate (dyed TiO2 plate).
3. The free electrons then start to flow through the external circuit to
produce an electric current. This electric current powers the light bulb.
4. To complete the circuit, the dye is regenerated. The dye regains its lost
electrons from the iodide electrolyte. Iodide (I-) ions are oxidised (loss of 2
electrons) to tri-iodide (I3-). The free electrons on the graphite plate then
reduce the tri-iodide molecules back to their iodide state. The dye
molecules are then ready for the next excitation/oxid/red cycle.
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70
 Construction of a Grätzel cell
o In Grätzel cell a range of organic dyes are used.
o Examples: Ruthenium-Polypyridine, Indoline dye & metal free organic dye.
o These dyes are extractable from simple foods such as hibiscus tea, tinned summer
fruits, blackberries.

Construction:
o Two transparent glass plates are perforated on one side with a transparent thin layer of
a conducting material.
o Onto the conducting sides, one plate is coated with graphite and the other plate is
coated with titanium dioxide (TiO2).
o A dye is then adsorbed onto the TiO2 layer by immersing the plate into a dye solution of
10-4M in alcohol for 10 min. (approx.)
o The plates are then carefully sandwiched together and secured using a paper clip.
o To complete the cell a drop of iodide electrolyte is added between the plates.
o Figure shows a Grätzel cell prepared from hibiscus tea.
o The upper plate is the TiO2 plate, dyed with hibiscus tea and the lower plate is coated
with graphite.

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 The Grätzel Cell

Upper Plate :
Dye coated TiO2
Plate (-Ve)

Lower Plate :
Graphite coated
conductor (+Ve)

By Hermetic sealing

Prepared Grätzel cell

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 Working Principle of Grätzel Cell
o Sunlight energy passes through the titanium
dioxide layer and strikes electrons within the
adsorbed dye molecules.
o Electrons gain this energy and become excited
o The excited electrons escape from the dye
molecules to become free electrons.
o These free electrons move through theTiO2 and
accumulate at the –ve plate (dyed TiO2 plate).
o The free electrons then start to flow through the
external circuit to produce an electric current.
o This electric current powers the light bulb.
o To complete the circuit, the dye is regenerated.
o The dye regains its lost electrons from the iodide
electrolyte.
o Iodide (I-) ions are oxidised to tri-iodide (I3-).
o The free electrons at the graphite plate then reduce
the tri-iodide molecules back to their iodide state.
o The dye molecules are then ready for the next
excitation/oxidation/reduction cycle.

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