Engineering Chemistry

Module 4

Energy Devices
 Contents…. (6 hours)
Electrochemical and electrolytic cells
Electrode materials with examples
• Semi-conductors
Chemistry of Li ion secondary batteries
Supercapacitors
Fuel cells: H2-O2 and solid oxide fuel cell (SOFC)
Solar cells: Photovoltaic cells (silicon based), Photoelectrochemical
cells, Dye- sensitized cells.
 Electrochemical Cell
▪ A device that is used to generate electricity from a spontaneous redox reac7on
or, conversely, that uses electricity to drive a non-spontaneous redox reac7on.
▪ An electrochemical cell typically consists of
• Two electronic conductors (also called electrodes >> anode and cathode)
• An ionic conductor (called an electrolyte)
• the electron conductor used to link the electrodes is oAen a metal wire,
such as copper wiring
▪ The electrochemical cells are broadly classified into two types:
• Galvanic or voltaic cell: Converts the energy released by a spontaneous
chemical reac7on to electrical energy. ΔG < 0
• Electroly7c cell: Consumes electrical energy from an external source to drive
a non-spontaneous chemical reac7on. ΔG > 0
 Galvanic or voltaic cell
A galvanic cell uses the energy released during a spontaneous redox reaction
(ΔG < 0) to generate electricity.
This type of electrochemical cell is also called a voltaic cell after its inventor, the
Italian physicist Alessandro Volta.
Anode is written on the left-hand side >> oxidation occurs
Cathode is written on the right-hand side >> reduction occurs
Electrode on the left Electrode on the right
Metal (or solid phase)| Electrolyte (whole Electrolyte (whole formula or ion) | Metal
formula or ion) (or solid phase)
Zn|Zn(NO3)2 (1M) Cu(NO3)2 (1M)|Cu
Oxidation: M1 → M1n+ + n e- ReducFon: M2n+ + n e- → M2
Overall representation of Galvanic cell
M1 | M1n+ (C1) ║ M2n+ (C2) | M2
 Daniel Cell
Invented by British chemist John Frederic
Daniell.
Zn Electrode dipped in ZnSO4 solution:
• Oxidation: Zn → Zn2+ + 2 e-
Cu Electrode dipped in CuSO4 solution:
• Reduction: Cu2+ + 2 e- → Cu
Each electrode is referred to as half cell which
are connected through a salt bridge
Salt bridge: KCl or NH4Cl in a gelatine form
Maintains the charge balance in the two half
cells
Minimizes or eliminates the liquid junction
potential
Cell emf = 1.1 V
 EMF of Electrochemical Cell
The electromotive force (EMF): Maximum potential difference between two electrodes
of a galvanic or voltaic cell.
This quantity is related to the tendency for an element, a compound or an ion to acquire
(i.e. gain) or release (lose) electrons.
Cell reaction is feasible when Ecell has positive value.
Cell EMF in terms of Nernst Equation:
 The Electrolysis of Molten NaCl
Here Na+ ions gain electrons and are reduced
to Na at the cathode.
As Na+ ions near the cathode are depleted,
additional Na+ ions migrate in.
Similarly, there is net movement of Cl- ions to
the anode where they are oxidized to Cl2.
Positive terminal is connected to the anode.
The negative terminal is connected to the
cathode which forces electrons to move from
the anode to the cathode.
Electrolysis is performed at ~ 801 °C.
Here inert electrodes are used.

Cathode: 2 Na+ (l) + 2 e- → 2 Na (l)

Overall: 2 NaCl (l) → 2 Na (l) + Cl2 (g)
Anode: 2 Cl ̶ (l) → Cl2 (g) + 2 e-
 Electrolytic Decomposition of Water
A pair of inert electrodes are dipped into the
solution and applying a voltage between
them results in the rapid evolution of bubbles
of H2 and O2.
Due to very poor electrical conductivity of
pure water, a small amount of an ionic solute
(such as H2SO4 or Na2SO4) is added to increase
its electrical conductivity.
The electrolytes are chosen such a way that
the ions that are harder to oxidize or reduce
than water:
Cathode: 4 H+(aq) + 4 e- → 2 H2(g)
Anode: 2 H2O → O2(g) + 4 H+ + 4 e-
Overall: 2 H2O → O2(g) + 2 H2(g)
 Electroplating
Uses electrolysis to deposit a thin layer of one metal on another metal to improve beauty
or resistance to corrosion.
Electroplating was first discovered by Luigi Brugnatelli in 1805 through using the
electrode position process for the electroplating of gold.
Both ferrous and non-ferrous metals are plated with Ni, Cr, Cu, Zn, Pb, Al, Ag, Au, Sn etc.
The base metal to be plated is made
cathode of an electrolytic cell.
The anode is either made of the coating
metal itself or an inert material of good
electrical conductivity.
A water-soluble salt of the plating metal is
used as electrolyte.
Often non-participating electrolytes, such
as, Na2SO4, are added to the bath solution
to increase the conductivity of the medium.
 Copper plating:
• Anode reaction: Cu (s) → Cu2+ (aq.) + 2 e
• Cathode reaction: Cu2+ (aq.) + 2 e → Cu (s)
• Electrolyte: Aqueous CuSO4 solution
▪Nickel pla7ng:
• Anode reacFon: Ni (s) → Ni2+ (aq.) + 2 e
• Cathode reacFon: Ni2+ (aq.) + 2 e → Ni (s)
• Electrolyte: Aqueous NiSO4 soluFon

Gold plating:
• Anode reaction: Au (s) → Au+ (aq.) + e
• Cathode reaction: Au+ (aq.) + e → Au (s)
• Electrolyte: Aqueous K[Au(CN)2] solution
Silver plating: Silver plating:
• Anode reaction: Ag (s) → Ag+ (aq.) + e • Anode reaction: Ag (s) → Ag+ (aq.) + e
• Cathode reaction: Ag+ (aq.) + e → Ag (s) • Cathode reaction: Ag+ (aq.) + e → Ag (s)
• Electrolyte: Aqueous AgNO3 solution • Electrolyte: Aqueous K[Ag(CN)2] solution
 Semiconductors
A semiconductor is a substance, usually a solid chemical element or compound that
can conduct electricity under some conditions but not others, making it a good medium
for the control of electrical current.
It has almost filled valence band, empty conduction band and very narrow energy gap
i.e., of the order of 1 eV. Energy gap of Silicon (Si) and Germanium (Ge) are 1.0 and 0.7 eV
respectively. Consequently Si and Ge are semiconductors.
 Effect of temperature on conductivity of semiconductors:
At 0 K electrons freeze at valence band and hence all semiconductors are insulators.
Electrical conductivity of a semiconductor material increases with increasing temperature
as resistivity decreases.
At higher temperature transition from the valence band to the conduction band gets
facilitated ⇒ higher conductivity or lower resistivity.

Temperature
 Battery
Battery is a device that consists of one or more electrochemical cells connected in series or
parallel or both and converts the chemical energy into electrical energy.
The cell consists of three major components:
• The anode: Reducing electrode which gives up electrons to the external circuit
• The cathode: Oxidizing electrode which accepts electrons from the external circuit
• The electrolyte: It is the ionic conductor
Types of Cells/Batteries:
• Primary battery (Primary cells): The cell reaction is not reversible. When all the reactants
have been converted to product, no more electricity is produced and the battery is dead.
Example: Lechlanche Cell (Dry Cell), Alkaline Cell and Lithium batteries.
• Secondary battery (secondary cells): The cell reactions can be reversed by passing electric
current in the opposite direction. Example: Lead acid batteries, Ni-Cd batteries, Ni-Metal
Hydride batteries, Lithium ion batteries.
• Flow battery and fuel cell: Materials (reactants, products, electrolytes) pass through the
battery. Example: Hydrogen-oxygen fuel cell (HOFC), Solid oxide fuel cell(SOFC), etc.
 Construction of Lithium-Ion (Li ion) Batteries
Cathode: This is the positive electrode and
it is typically layers of lithium-metal oxide
(LiCoO2, LiNiO2, LiMn2O4, LiNiMnCoO2) and
lithium metal polyanionic materials
(LiFePO4, LiMnPO4, LiFeSO4F, etc.).
Anode: The negative electrode is made
from graphite, usually with composition
Li0.5C6.
Electrolyte: Mixture of organic carbonates
such as ethylene carbonate, diethyl
carbonate.
Separator: Prevents touching two
electrodes. This absorbs the electrolyte, and
enables the passage of ions, but prevents
the direct contact of the two electrodes
within the lithium in cell.
 Lithium-ion (Li-ion) battery LIB
• LIB’s are one of the most popular types of rechargeable batteries for portable electronics, with
a high energy density and low self-discharge.
• The essential feature of the Lithium ion battery is that lithium ions move from the negative
electrode to the positive electrode during discharge and back when charging
• To facilitate such Li ion movement, LIB’s use an intercalated lithium compound as one
electrode material
• Lithium-ion batteries thus operate based on what is sometimes called the "rocking chair" or
"swing" effect.
• This involves the transfer of Lithium ions back and forth between the two electrodes.

Lithium (blue spheres) Lithium cobalt oxide consists of layers of

intercalated between graphene lithium (show here as purple spheres) that lie
sheets between slabs formed by cobalt and oxygen
atoms (shown here as connected red and
blue spheres).
 Charging Reaction and Discharging
Charging Reaction: Discharging Reaction:
When the cell is being charged, cobalt Li+ ions move out of the anode and
ions are oxidized and release migrate through the electrolyte
electrons. where they enter the spaces between
Simultaneously Li+ ions migrate out of the cobalt oxide layers.
LiCoO2 and into the graphite. Simultaneously electrons flow through
Electrons flow from the positive the external circuit.
electrode to the negative electrode.
Electrons reduce cobalt at ions at the
The electrons and Li+ ions combine at positive electrode to regenerate LiCoO2.
the negative electrode.
Anode: LiCoO2 → Li1-nCoO2 + n Li+ + n e- Anode: LinC6 → C6 + n e- + n Li+
Cathode: C6 + n e- + n Li+ → LinC6 Cathode: Li1-nCoO2 + n Li+ + n e- → LiCoO2

LiCoO2 + C6 → Li1-nCoO2 + LinC6 Li1-nCoO2 + C6Lin → LiCoO2 + C6

 Lithium-ion battery applications
Portable power packs: Li-ion batteries are lightweight and more compact than other
battery types, which makes them convenient to carry around within cell phones, laptops
and other portable personal electronic devices.
Uninterruptible Power Supplies (UPSs): Li-ion batteries provide emergency back-up power
during power loss or fluctuation events to guarantee consistent power supply.
Electric vehicles: As Li-ion batteries can store large amounts of energy and can be recharged
many times, they offer good charging capacity and long life spans which creates high
demand for Li-ion battery packs for electric, hybrid or plug-in hybrid electric vehicles.
Marine vehicles: Li-ion batteries are emerging as an alternative to gasoline and lead-acid
batteries in powering work or tug boats and leisure craft like speed boats and yachts.
Personal mobility: Lithium-ion batteries are used in wheelchairs, bikes, scooters and other
mobility aids for individuals with disability or mobility restrictions.
Renewable energy storage: Li-ion batteries are also used for storing energy from solar
panels and wind turbines as they can be charged quickly. They are lighter, more compact
and can hold higher amounts of energy than lead-acid batteries.
 Advantages & Disadvantages of Lithium Ion BaIery
Advantages:
• High energy density: High energy density is one of the biggest advantages of lithium ion
battery technology. This higher power density offered by lithium ion batteries is a great
advantage for their use in electronic gadgets and electric vehicles.
• Low self-discharge: Lithium ion cells is that their rate of self-discharge is much lower than
that of other rechargeable cells such as Ni-Cad and NiMH forms.
• Low maintenance: Lithium ion batteries do not require active maintenance.
• High cell voltage: The voltage produced by each lithium ion cell is about 3.6 volts. This
ensure less number of cells in many battery applications.
• Variety of types available: There are several types of lithium ion cell available. This ensures
the right technology can be used for the particular application needed.
• No requirement for priming: Lithium ion batteries are supplied operational and ready to
go.
• Load characteristics: These provide a reasonably constant 3.6 volts per cell before falling
off as the last charge is used.
 Disadvantages:
• Protection required: Lithium ion cells and batteries are not as robust as some other
rechargeable technologies. They require protection from being over charged and
discharged too far.
• Ageing: Lithium ion batteries suffer from ageing. Often batteries will only be able to
withstand 500-1000 charge discharge cycles before their capacity falls.
• High Cost: A major lithium ion battery disadvantage is their cost. Typically they are around
40% more costly to manufacture than Nickel cadmium cells.
• Chances of explosion:
• Bad design or manufacturing defects: In that case, there wasn’t enough space for the
electrodes and separator in the battery. When the battery expanded a little as it charged,
the electrodes bent and caused a short circuit.
• Overcharging: When overcharged, lithium cobalt oxide releases oxygen which can react
with flammable electrolyte leading to overheating.
• Electrolyte breakdown: On overheating, Dimethyl carbonate decompose to form CO2
which causes pressure build up in battery, resulting in a dangerous explosion.
• The anode of a Lithium-ion battery is composed of Lithium, dissolved as ions, into a carbon based electrode
• The cathode material is made up from Lithium liberating compounds, typically the three electro-active oxide
materials, Lithium Cobalt-oxide LiCoO2 , Lithium Manganese-oxide LiMn2O4 , and Lithium Nickel-oxide
LiNiO2
• 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.
 Electrode reactions

• Anode here is a non-metallic compound, e.g. carbon, which can store and exchange lithium ions.
• A lithium ion-accepting material (Intercalation), for example CoO2, is then used as the cathode material, and
lithium ions are exchanged back (deintercalation) and forth between the two during discharging and
charging. These are called intercalation electrodes.
 Lithium-ion Polymer batteries
• Lithium-ion polymer batteries use Lithium-ion electrochemistry in a matrix of ion conductive polymers that
eliminate free electrolyte within the cell.
• The electrolyte thus plasticises the polymer, producing a solid electrolyte that is safe and leak resistant.
• A polymer matrix, such as polyvinylidene fluoride (PVdF) or poly(acrylonitrile) (PAN), gelled with
conventional salts and solvents, such as LiPF6 is used as the electrolyte
• These cells have not reached full commercialization and are still a topic of research
 Fuel cells
An electrochemical cell in which the energy of a reaction between a fuel (such as hydrogen) and an
oxidant (such as oxygen) is converted directly and continuously into electrical energy.

• Fuel cells are different from batteries in requiring a continuous source of fuel and oxygen or air to sustain the
chemical reaction
• They are also known as flow cells
• Fuel cells consist of an anode, a cathode, and an electrolyte that allows positively charged hydrogen ions (or
protons) to move between the two sides of the fuel cell
• The anode and cathode contain catalysts that cause the fuel to undergo oxidation reactions that generate
positively charged hydrogen ions and electrons.
• The hydrogen ions are drawn through the electrolyte after the reaction.
• Electrons are drawn from the anode to the cathode through an external circuit, producing direct current
electricity.
• At the cathode, hydrogen ions, electrons, and oxygen react to form water.

Classification : 1. Low Temperature fuel cells (< 100oC)

based on 2. Moderate Temperature fuel cells (100
to 250oC)
temperature of 3. High Temperature fuel cell (> 500oC)
operation 4. Solid Oxide Fuel Cell (SOFC) (1000oC)
A typical fuel cell consists of :
• The electrolyte substance. The electrolyte substance usually defines the type of fuel cell.
• The fuel that is used. The most common fuel is hydrogen.
• The anode catalyst breaks down the fuel into electrons and ions. The anode catalyst is usually
made up of very fine platinum powder.
• The cathode catalyst turns the ions into the waste chemicals like water or carbon dioxide. The
cathode catalyst is often made up of nickel but it can also be a nanomaterial-based catalyst.
• A typical fuel cell produces a voltage from 0.6 V to 0.7 V

Based on the electrolytes used, fuels cell types are

1. Alkaline fuel cells
2. Phosphoric acid fuel cells
3. Molten carbonate fuel cells
4. Polymer electrolyte membrane fuel cells
5. Solid oxide fuel cells
6. Biochemical fuel cells
 Alkaline Fuel Cells (or) H2- O2 Fuel Cells
• Also known as the Bacon fuel cell after its British inventor, Francis Thomas Bacon
• The cell consists of two porous carbon electrodes impregnated with a suitable catalyst such as Pt, Ag, CoO,
etc.
• The space between the two electrodes is filled with a concentrated solution of KOH or NaOH which serves as
an electrolyte.
• H2 gas and O2 gas are bubbled into the electrolyte through the porous carbon electrodes.
• The overall reaction involves the combination of hydrogen gas and oxygen gas to form water.
• This type of cell provides a potential of about 0.9 V

Anode 2H2 + 4 OH- H2O + 4e-

Cathode O2 + 2H2O + 4 e- 4OH-

Net reaction 2H2 + O2 2H2O

• Hydrogen (diffused through anode) and oxygen (through cathode) gases are bubbled through the respective
compartments.
• Electrode – porous , good conducting, excellent catalyst for the reactions that take place on their surfaces, not
deteriorating by the electrolyte heat or electrode reactions.
• Graphite impregnated with finely divided platinum, or alloy of Pd, Ag and Ni serves the purpose if hydrogen is the
fuel.
• Electrolyte - aqueous 30-40% KOH or H2SO4

Applications:
Auxiliary energy source in space vehicles, submarines or other military-vehicles.
 Solid oxide fuel cells (SOFC)
• Anode, cathode and electrolyte all made up of ceramic substances
• 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
• Oxide ions transport through the solid electrolyte to the anode for oxidation along with the fuel
• Proton transporting electrolytes have also been studied
• Popular electrolyte materials include yttria-stabilized zirconia (YSZ), scandia stabilized zirconia (ScSZ) and gadolinium doped
ceria (GDC)
• Operate at temperatures as high as1000°C to avoid expensive Pt catalysts
• Can be configured as rolled tubes or flat plates

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

Anode 2H2 4H+ + 4e-

Cathode O2 + 4H+ + 4 e- 2H2O

Net reaction 2H2 + O2 2H2O

 Polymer membrane fuel cells
• The proton exchange membrane fuel cell (PEMFC) uses a water- based, acidic polymer membrane as its
electrolyte, with platinum-based electrodes.
• PEMFC cells operate at relatively low temperatures (below 100 degrees Celsius)
• PEMFC cells are currently the leading technology for light duty vehicles and materials handling vehicles, and
to a lesser extent for stationary and other applications.
• The PEMFC fuel cell is also sometimes called a polymer electrolyte membrane fuel cell (also PEMFC)
To function, the membrane must
• conduct hydrogen ions (protons) but not electrons as this would in effect "short circuit" the fuel
cell.
• also not allow either gas to pass to the other side of the cell, a problem known as gas crossover
• be resistant to the reducing environment at the cathode as well as the harsh oxidative
environment at the anode.

WORKING
• Hydrogen fuel is processed at the anode where electrons are separated from protons on the surface of a
platinum-based catalyst.
• The protons pass through the membrane to the cathode side of the cell while the electrons travel in an external
circuit, generating the electrical output of the cell.
• On the cathode side, another precious metal electrode combines the protons and electrons with oxygen to
produce water, which is expelled as the only waste product; oxygen can be provided in a purified form, or
extracted at the electrode directly from the air.
The most commonly used membrane is Nafion which is a sulfonated tetrafluoroethylene based
fluoropolymer-copolymer

Alternatives to Nafion include

1) PVDF (Poly VinyliDene Fluoride),
2) heterocyclic polymers such as PBI (Polybenzimidazole)
3) sulfonated aromatic hydrocarbons (SAPs).
 Solar cells
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 the creation of voltage and electric current in a material upon exposure to light

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

1. The absorption of light, generating electron-hole pairs

2. The separation of charge carriers of opposite types.
3. The separate extraction of those carriers to an external circuit.
 How Do Silicon Solar Cells Work?

• Pure crystalline silicon is a poor conductor of electricity as it is a semiconductor material at its core.
• When trivalent impurities like boron or gallium are doped, it results in p-type Si material
• When pentavalent impurities like Phosphorous or arsenic are doped , we get n-type Si
• In a solar cell, the layers are positioned next to each other and that way an electric field is created.
• When the sunlight hits the solar cell, the energy stimulates electrons that leave holes behind.
• These migrate to the electrodes in the cell because of the presence of the electric field. In this way,
electricity is generated.

Cross section of a solar cell

 Types of Silicon Solar Cells
Monocrystalline Solar Cells

• Monocrystalline solar cells, also called "single crystalline" cells are identified by their dark black colour.
• Monocrystalline solar cells are made from a very pure type of silicon, which makes them the most efficient
material for converting sunlight into electricity.
• In addition, monocrystalline solar cells are also the most space-efficient.
• Another advantage of monocrystalline cells is that they last the longest of all types - many manufacturers
offer warranties of up to 25 years on these types of photovoltaic systems.
• Monocrystalline cells are the most expensive option, mostly because the four sided cutting process results
in wasting a lot of silicon, sometimes more than half.
• The cheaper alternatives for consumers would be polycrystalline cells.
Polycrystalline Solar Cells
• Polycrystalline solar cells, also known as polysilicon and multi-silicon cells, were the first solar cells
presented to the industry, in the beginning of the 1980s.
• Polycrystalline cells do not undergo the cutting process used for monocrystalline cells. Instead, the silicon
is melted and poured into a square mould, hence the square shape of polycrystalline.
• This makes polycrystalline solar cells much more affordable, as hardly any silicon is wasted during the
manufacturing process.
• On the minus side, they are less efficient and require more space than single crystalline cells, due to the
fact that the purity level is lower in polycrystalline cells.
• Another disadvantage is that polycrystalline has lower heat tolerance than monocrystalline, meaning that
they are unable to function as efficiently in high temperatures.
 Amorphous Solar Cells
• The silicon is not structured or crystalline.
• In the past, amorphous solar cells were used for smaller-scale applications, such as pocket calculators,
because their power output was relatively low.
• Amorphous silicon solar panels are a powerful and emerging line of photovoltaic systems that differ from
crystalline silicon cells in terms of their output, structure, and manufacture.
• The material costs are reduced since amorphous silicon only requires about 1% of the silicon that would
have been used to produce a crystalline-silicon based solar cell.
• The development process of amorphous silicon solar panels has made them more flexible and lightweight,
which makes the transportation and installation of the panels less risky.
• A flexible thin-film module renders amorphous solar cells suitable even for curved surfaces.
• One of the drawbacks is the lower efficiency rate of amorphous thin-film solar cells. However, the
technology is new, and efficiency rates are thought to increase with technological breakthroughs in the near
future.
 Dye sensitized solar cells
• This new class of advanced solar cell can be likened to artificial photosynthesis due to the way in which it
mimics nature’s absorption of light energy.
• Manufacturing of DSCs is simple, mostly low cost, and incorporate environmentally friendly materials.
They have a good efficiency (about 10-14 %) even under low flux of sunlight.

• The anode of a DSC consists of a glass plate which is coated with a transparent
conductive oxide (TCO) film. Indium tin oxide (ITO) or fluorine doped tin oxide
are most widely used. A thin layer of titanium dioxide (TiO2) is applied on the
film. The semiconductor exhibits a high surface area because of its high porosity.

• The anode is soaked with a dye solution which bonds to the TiO2.In some
laboratory cells plain fruit juice which contain pigments can be used. These
pigments are able to convert light energy into electrical energy.

• The cathode of a DSC is a glass plate with a thin Pt film which serves as a
catalyst. An iodide/triiodide solution is used as the electrolyte.

• Both electrodes are pressed together and sealed so that the cell does not leak.
An external load can be powered when light shines on the anode of the dye
solar cell.
• The dye is the photoactive material of DSSC, and can produce electricity once it is sensitized by light
• The dye catches photons of incoming light (sunlight and ambient artificial light) and uses their energy to
excite electrons, behaving like chlorophyll in photosynthesis
• The dye injects this excited electron into the Titanum Dioxide (a white pigment commonly found in white
paint)
• The electron is conducted away by nanocrystalline titanium dioxide (a nano-scale crystallized form of the
titanium dioxide).
• A chemical electrolyte in the cell then closes the circuit so that the electrons are returned back to the dye
• It is the movement of these electrons that creates energy which can be harvested into a rechargeable
battery, super capacitor or another electrical device.

The energy level diagram

The set up
The DSSC has a number of attractive features;
• it is simple to make using conventional roll-printing techniques,
• is semi-flexible and semi-transparent which offers a variety of uses not applicable to glass-based systems,
and
• most of the materials used are low-cost.

Disadvantages

• The major disadvantage to the DSSC design is the use of the liquid electrolyte, which has temperature
stability problems
• Another disadvantage is that costly ruthenium (dye), platinum (catalyst) and conducting glass or plastic
(contact) are needed to produce a DSSC.
• A third major drawback is that the electrolyte solution contains volatile organic compounds (or VOC's),
solvents which must be carefully sealed as they are hazardous to human health and the environment
 Supercapacitor or Ultracapacitors
A supercapacitor is a type of capacitor that can store a large amount of energy, typically
10 to 100 times more energy per unit mass or volume compared to electrolytic capacitors.
These can deliver and accept charge more quickly than batteries.
 BaIeries and capacitor
Batteries and capacitors do a similar job—storing electricity—but in completely different
ways.
Batteries have two electrical terminals (electrodes) separated by a chemical substance
called an electrolyte.
When power is on, chemical reactions happen involving both the electrodes and the
electrolyte. These reactions convert the chemicals inside the battery into other
substances, releasing electrical energy as they go.
Once the chemicals have all been depleted, the reactions stop and the battery is flat
In a rechargeable battery, such as a lithium-ion power pack used in a laptop computer or
MP3 player, the reactions can happily run in either direction so that it usually charges
and discharges hundreds of times before the battery needs replacing.
 Capacitors
A capacitor is a device used to store electrical charge
and electrical energy.
Capacitors use static electricity (electrostatics)
rather than chemical substances to store energy.
Inside a capacitor, there are two conducting metal
plates with an insulating material called a dielectric in
between them - it's a dielectric sandwich.
Positive and negative electrical charges build up on
the plates and the separation between them, which
prevents them coming into contact, is what stores the
energy.
The dielectric allows a capacitor of a certain size to
store more charge at the same voltage, so it makes
the capacitor more efficient as a charge-storing
device.
 Advantages of capacitors over batteries:
Capacitors have many advantages over batteries: they weigh less, generally don't
contain harmful chemicals or toxic metals, and they can be charged and discharged
zillions of times without ever wearing out.
But they have a big drawback too: their basic design prevents them from storing
anything like the same amount of electrical energy as batteries.
A supercapacitor differs from an ordinary capacitor in two important ways:
• Its plates effectively have a much bigger area and the distance between them is much
smaller, because the separator between them works in a different way to a
conventional dielectric.
• Although the words "supercapacitor” and "ultra capacitor” are often used
interchangeably, there is a difference: they are usually built from different materials
and structured in slightly different ways, so they store different amounts of energy.
Like an ordinary capacitor, a supercapacitor has two plates that are separated.
The plates are made from metal coated with a porous substance such as powdery,
activated charcoal, which effectively gives them a bigger area for storing much more
charge
Unlike capacitor, in a supercapacitor, there is no dielectric as such. Instead, both plates
are soaked in an electrolyte and separated by a very thin insulator (which might be made
of carbon, paper, or plastic)
 How do Supercapacitors Work?
▪When the plates are charged up, an opposite charge forms on either side of the
separator, creaSng what's called an electric double-layer.
▪This is why supercapacitors are oTen referred to as double-layer capacitors, also called
electric double-layer capacitors or EDLCs).
▪The capacitance of a capacitor increases as the area of the plates increases and as the
distance between the plates decreases.
 Characteristics of Supercapacitors
Fast charging speed and it can reach more than 95% of its rated capacity within minutes
Cycle life is long and the number of charge and discharge cycles can reach 10,000 to
500,000 times.
The high current discharge capacity is super strong, the energy conversion efficiency is
high, the process loss is small, and the high current energy cycle efficiency is ≥90%;
High power density, up to 300W/KG ~ 5000W/KG, equivalent to 5~10 times of battery;
The raw material composition, production, use, storage and dismantling process of the
product are not polluted, and it is an ideal green environmental protection power source;
The charging and discharging circuit is simple, no charging circuit like rechargeable
battery is needed, and the safety factor is high, and the maintenance is long-term
maintenance-free;
Good ultra-low temperature characteristics, temperature range -40 °C - +70 °C;
Easy to detect, the remaining power can be read directly;
The capacity range is usually 0.1 F – 1000 F.
 Comparison of supercapacitors with batteries and ordinary capacitors
Unlike battery, supercapacitors can store and release energy almost instantly.
That's because a supercapacitor works by building up static electric charges on solids,
while a battery relies on charges being produced slowly through chemical reactions.
Batteries have a higher energy density (they store more energy per unit mass) but
supercapacitors have a higher power density (they can release energy more quickly).
Supercapacitors are suitable for quick storing and releasing large amounts of energy.
Although supercapacitors work at relatively low voltages (maybe 2–3 volts), they can be
connected in series (like batteries) to produce bigger voltages for use in more powerful
equipment.
Since supercapacitors work electrostatically, rather than through reversible chemical
reactions, they can theoretically be charged and discharged any number of times.
They have little or no internal resistance, which means they store and release energy
without using much energy—and work at very close to 100 percent efficiency.
 Comparison of Supercapacitor, Ordinary Capacitor and Battery
Parameter Super Capacitor Ordinary Capacitor Battery
Energy storage Watt-second energy Watt-second energy Watt-hour energy
Power supply Fast discharge, linear or Fast discharge, linear or Maintain a constant
exponential voltage decay exponential voltage decay voltage for a long time
Charging/discharging milliseconds to seconds Picosec. to milli sec. 1 to 10 hours
time
Dimensions Small Small to Large Large
Weight 1g to 2g 1g to 10kg 1g to ＞10kg
Energy density 1 to 5Wh/kg 0.01 to 0.05Wh/kg 8 to 600Wh/kg
Power density High, ＞4000W/kg High, ＞5000W/kg Low, 100-3000W/kg
Operating voltage 2.3V to 2.75V 6V to 800V 1.2V to 4.2V
Life ＞100,000 cycles ＞100,000 cycles 150 to 1500 cycles
Working temperature ﹣40 to ﹢85℃ ﹣20 to ﹢100℃ ﹣20 to ﹢65℃
 Application of Supercapacitors
Supercapacitors have been widely used as the electrical equivalents of flywheels in
machines—"energy reservoirs" that smooth out power supplies to electrical and
electronic equipment.
Supercapacitors can also be connected to batteries to regulate the power they supply.
In wind turbines, where very large supercapacitors help to smooth out the intermittent
power supplied by the wind.
In electric and hybrid vehicles, supercapacitors are increasingly being used as temporary
energy stores for regenerative braking (where the energy a vehicle would normally
waste when it comes to a stop is briefly stored and then reused when it starts moving
again).
 Elaborated slides
courtesy: VIT Vellore
 Lithium-Ion (Li ion) Batteries
Lithium-ion battery is a secondary battery.
It does not contain metallic lithium as anode.
As the name suggests, the movement of lithium ions are responsible for charging &
discharging.
Lithium ion battery technology was first proposed in the 1970s by M Whittingham who
used titanium sulphide for the cathode and lithium metal for the anode.
The Nobel Prize in Chemistry 2019 is awarded to John B. Goodenough, M. Stanley
Whittingham and Akira Yoshino.
 Why lithium?
Currently, most portable electronic devices, including cell phones and laptop
computers, are powered by rechargeable lithium-ion (Li-ion) batteries, because:
Lithium is a very light element.
Li-ion batteries achieve a high specific energy density which is the amount of energy
stored per unit mass.
Because Li+ has a very large negative standard reduction potential, Li-ion batteries
produce a higher voltage per cell than other batteries.
A Li-ion battery produces a maximum voltage of 3.7 V per cell, nearly three times
higher than the 1.3 V per cell that nickel–cadmium and nickel–metal hydride
batteries generate.
As a result, a Li-ion battery can deliver more power than other batteries of
comparable size, which leads to a higher volumetric energy density—the amount of
energy stored per unit volume.
 Construction of Lithium-Ion (Li ion) Batteries
Cathode: This is the positive electrode and
it is typically layers of lithium-metal oxide
(LiCoO2, LiNiO2, LiMn2O4, LiNiMnCoO2) and
lithium metal polyanionic materials
(LiFePO4, LiMnPO4, LiFeSO4F, etc.).
Anode: The negative electrode is made
from graphite, usually with composition
Li0.5C6.
Electrolyte: Mixture of organic carbonates
such as ethylene carbonate, diethyl
carbonate.
Separator: Prevents touching two
electrodes. This absorbs the electrolyte, and
enables the passage of ions, but prevents
the direct contact of the two electrodes
within the lithium in cell.
Charging Reaction and Discharging
 Charging ReacPon and Discharging
Charging Reaction: Discharging Reaction:
When the cell is being charged, cobalt Li+ ions move out of the anode and
ions are oxidized and release migrate through the electrolyte
electrons. where they enter the spaces between
Simultaneously Li+ ions migrate out of the cobalt oxide layers.
LiCoO2 and into the graphite. Simultaneously electrons flow through
Electrons flow from the positive the external circuit.
electrode to the negative electrode.
Electrons reduce cobalt at ions at the
The electrons and Li+ ions combine at positive electrode to regenerate LiCoO2.
the negative electrode.
Anode: LiCoO2 → Li1-nCoO2 + n Li+ + n e- Anode: LinC6 → C6 + n e- + n Li+
Cathode: C6 + n e- + n Li+ → LinC6 Cathode: Li1-nCoO2 + n Li+ + n e- → LiCoO2

LiCoO2 + C6 → Li1-nCoO2 + LinC6 Li1-nCoO2 + C6Lin → LiCoO2 + C6

 Lithium ion battery variants
NAME CONSTITUENTS ABBREVIATION MAJOR APPLICATIONS
CHARACTERISTICS

Lithium Cobalt LiCoO2 LCO High capacity Cell phones, laptops,

cameras

Lithium Manganese LiMn2O4 LMO Lower capacity Power tools, medical,

Oxide hobbyist

Lithium Iron LiFePO4 LFP Lower capacity Power tools, medical,

Phosphate hobbyist

Lithium Nickel LiNiMnCoO2 NMC Lower capacity Power tools, medical,

Manganese Cobalt hobbyist
Oxide
Lithium Nickel Cobalt LiNiCoAlO2 NCA Electric vehicles and
Aluminium Oxide grid storage
• Lithium polymer (Poly-Carbon monofluoride) batteries have an output of 2.8 V and
moderately high energy density.
 Lithium-ion battery applications
Portable power packs: Li-ion batteries are lightweight and more compact than other
battery types, which makes them convenient to carry around within cell phones, laptops
and other portable personal electronic devices.
Uninterruptible Power Supplies (UPSs): Li-ion batteries provide emergency back-up power
during power loss or fluctuation events to guarantee consistent power supply.
Electric vehicles: As Li-ion batteries can store large amounts of energy and can be recharged
many times, they offer good charging capacity and long life spans which creates high
demand for Li-ion battery packs for electric, hybrid or plug-in hybrid electric vehicles.
Marine vehicles: Li-ion batteries are emerging as an alternative to gasoline and lead-acid
batteries in powering work or tug boats and leisure craft like speed boats and yachts.
Personal mobility: Lithium-ion batteries are used in wheelchairs, bikes, scooters and other
mobility aids for individuals with disability or mobility restrictions.
Renewable energy storage: Li-ion batteries are also used for storing energy from solar
panels and wind turbines as they can be charged quickly. They are lighter, more compact
and can hold higher amounts of energy than lead-acid batteries.
 Advantages & Disadvantages of Lithium Ion Battery
Advantages:
• High energy density: High energy density is one of the biggest advantages of lithium ion
battery technology. This higher power density offered by lithium ion batteries is a great
advantage for their use in electronic gadgets and electric vehicles.
• Low self-discharge: Lithium ion cells is that their rate of self-discharge is much lower than
that of other rechargeable cells such as Ni-Cad and NiMH forms.
• Low maintenance: Lithium ion batteries do not require active maintenance.
• High cell voltage: The voltage produced by each lithium ion cell is about 3.6 volts. This
ensure less number of cells in many battery applications.
• Variety of types available: There are several types of lithium ion cell available. This ensures
the right technology can be used for the particular application needed.
• No requirement for priming: Lithium ion batteries are supplied operational and ready to
go.
• Load characteristics: These provide a reasonably constant 3.6 volts per cell before falling
off as the last charge is used.
 Disadvantages:
• Protection required: Lithium ion cells and batteries are not as robust as some other
rechargeable technologies. They require protection from being over charged and
discharged too far.
• Ageing: Lithium ion batteries suffer from ageing. Often batteries will only be able to
withstand 500-1000 charge discharge cycles before their capacity falls.
• High Cost: A major lithium ion battery disadvantage is their cost. Typically they are around
40% more costly to manufacture than Nickel cadmium cells.
• Chances of explosion:
• Bad design or manufacturing defects: In that case, there wasn’t enough space for the
electrodes and separator in the battery. When the battery expanded a little as it charged,
the electrodes bent and caused a short circuit.
• Overcharging: When overcharged, lithium cobalt oxide releases oxygen which can react
with flammable electrolyte leading to overheating.
• Electrolyte breakdown: On overheating, Dimethyl carbonate decompose to form CO2
which causes pressure build up in battery, resulting in a dangerous explosion.
 Fuel Cells
A fuel cell is a device that converts chemical potential energy (energy stored in molecular
bonds) into electrical energy
Electricity is generated without combustion by combining hydrogen and oxygen to
produce water and heat
They offer higher electrical efficiency (≥ 40%) compared to conventional power
generation systems.
 Principle of Operation
A fuel cell is a device that uses hydrogen (or hydrogen-rich fuel) and oxygen to
create electricity by an electrochemical process.
Hydrogen and oxygen (air) are supplied to anode and cathode, respectively.
When hydrogen is led to the anode, the hydrogen molecules are split into
proton and an electron.
The protons migrate through the electrolyte to the cathode, where they react
with oxygen to form water.
At the same time, the electrons are forced to travel around the electrolyte to
the cathode side, because they cannot pass through the electrolyte. This
movement of electrons thus creates an electrical current.
 Types of Fuel Cells
There are eight main types of fuel cells, based mainly on the type of electrolyte:
• PEMFCs, proton exchange membrane or polymer electrolyte membrane fuel
cells
• AFCs, alkaline fuel cells
• PAFCs, phosphoric acid fuel cells
• MCFCs, molten carbonate fuel cells
• SOFCs, solid oxide fuel cells
• DMFCs, direct methanol fuel cells
• DAFCs, direct ammonia fuel cells
• DCFCs, direct carbon fuel cells
Apart from DAFCs, DMFCs, and DCFCs, other types of fuel cells are fed with
hydrogen.
 Hydrogen – oxygen fuel cells (HOFC)
This cell is a common type of fuel cell. Similar to a galvanic cell, fuel cell also
have two half cells.
Both half cells have porous graphite electrode with a catalyst (platinum, silver
or a metal oxide).
The electrodes are placed in the aqueous solution of NaOH or KOH (alkaline
fuel cells-AFC) or H2SO4 (acidic fuel cell) which acts as an electrolyte.
Hydrogen and oxygen are supplied at anode and cathode respectively at about
50 atmospheric pressure, the gases diffuse at respective electrodes.
The overall chemical reaction in a hydrogen fuel electrochemical cell involves
the oxidation of hydrogen by oxygen to produce only water.
2 H2 + O2 → 2 H2O
 Proton exchange membrane fuel cell (PEMFC)
or
Polymer electrolyte membrane fuel cells (PEMFC)
This type of fuel cell utilize water-based, acidic polymer electrolyte
membranes (PEMs), such as Nafion, to conduct protons for ion exchange
purposes.
PEMFC cells operate at relatively low temperatures (< 80°C).
Due to the relatively low temperatures and the use of precious metal-based
electrodes, these cells must operate on pure hydrogen.

Nafion
 Process
Hydrogen fuel is processed at the anode where electrons are separated from
protons on the surface of a platinum-based catalyst.
The protons pass through the membrane to the cathode side of the cell while
the electrons travel in an external circuit, generating the electrical output of the
cell.
On the cathode side, another Pt electrode combines the protons and electrons
with oxygen to produce water.

• At anode: H2 (g) → 2 H+ + 2 e-
• At cathode: O2 (g) + 4 H+ + 4 e- → 2 H2O
• Net reaction: O2 (g) + 2 H2 (g) → 2 H2O (I)
ECell˚= 1.23 V
PEMFC
Advantages
• The energy conversion is very high (75-82%).
• Fuel cell minimizes expensive transmission lines and transmission losses.
• It has high reliability in electricity generation and the by-products are environmentally
acceptable.
• Maintenance cost is low for these fuels and they save fossil fuels.
• Noise and thermal pollution are very low.
Disadvantages:
• The major disadvantage of the fuel cell is the high cost and the problems of durability and
storage of large amount of hydrogen.
• The accurate life time is also not known and It cannot store electricity.
• Electrodes are expensive ad short lived.
• Storage and handling of H2 gas is dangerous because it is inflammable.

Applications:
• The most important application of a fuel cell is its use in space vehicles, submarine or military
vehicles.
• The product H2O is valuable source of fresh water for the astronauts.
• Fuel cell batteries for automotive will be a great boon for the future.
 Solid Oxide Fuel Cell (SOFC)
SOFC is a high-temperature FC that utilizes solid ceramic inorganic oxide as an
electrolyte; e.g., zirconium oxide stabilized with yttrium oxide, instead of a
liquid or membrane, also known as Yttria-stabilized Zirconia (YSZ).
SOFC is also referred to as ceramic FC.
Both hydrogen and carbon monoxide are used as fuels.
Solid oxide fuel cells work at very high temperatures, the highest of all the fuel
cell types at around 800 °C to 1,000 °C.
Efficiency: over 60% when converting fuel to electricity
This cell relatively resistant to small quantities of sulphur in the fuel, compared
to other types of fuel cell, and hence can be used with coal gas.
 Structure of SOFC
Anode or fuel electrode:
• Nickel mixed with YSZ (Yttria stabilized Zirconia) or called Nickel-YSZ cermet (a
cermet is a mixture of ceramic and metal).
• It is a porous ceramic layer to allow the fuel to flow towards electrolyte.
Cathode or air electrode:
• The cathode is usually a mixed ion-conducting and electronically conducting ceramic
material.
• It is a thin porous ceramic layer coated over the solid electrolyte where oxygen
reduction takes place. One example being, strontium doped lanthanum manganite
(LSM).
Electrolyte:
• Oxide ion (O2-) conducting ceramic.
• The most popular electrolyte material is a bilayer composite electrolyte (YSZ layer +
gadolinium doped CeO2) (GDC) layer) or a mixture of ZrO and CaO.
At anode (oxidation):
H2 (g) + CO (g) + 2 O2- → H2O (g) + CO2 (g) + 4e-
At cathode (reduction):
O2 (g) + 4e- → 2 O2-
Net reaction:
H2 (g) + CO (g) + O2 (g) → H2O (g) + CO2 (g)
 Advantages of SOFC:
• SOFCs have a number of advantages due to their solid materials and high
operating temperature.
• Since all the components are solid, as a result, there is no need for electrolyte
loss maintenance and electrode corrosion is eliminated.
• Also because of high-temperature operation, the SOFC has a better ability to
tolerate the presence of impurities as a result of life increasing.
• High efficiencies: Due to high-quality waste heat for cogeneration
applications and low activation losses, the efficiency for electricity
production is great.
• Low emissions. Releasing negligible pollution. It is the cleanest among all fuel
cells.
 Disadvantages:
• High operating temperature (500 to 1,000 °C) which results in longer start up
times and mechanical/chemical compatibility issues.
• The cost and complex fabrication are also significant problems that need to be
solved.

• Applications:
• SOFCs are being considered for a wide range of applications, such as working
as power systems for trains, ships and vehicles; supplying electrical power for
residential or industrial utility.
• Stationary power generation
• By product gases are channeled to turbines to generate more electricity:
cogeneration of heat and power and improves overall efficiency.
• Auxiliary power units in vehicles
Differences between Primary, Secondary and Fuel cells
 Solar Energy Potential
Theoretical: 1.2x105 TW solar energy potential
(1.76 x105 TW striking Earth; 0.30 Global mean albedo)
Energy in 1 hr of sunlight ↔ 14 TW for a year
Practical: ≈ 600 TW solar energy potential (50 TW - 1500 TW depending on land fraction
etc.; WEA 2000)
Onshore electricity generation potential of ≈ 60 TW (10% conversion efficiency)
Photosynthesis: 90 TW
 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
77
 Types of solar energy
conversion cells

• Photovoltaic Cells
• Photoelectrochemical cells
• Dye-sensitized solar cells
 Photovoltaic Cells
A solar cell is a device that converts the energy of sunlight directly into electricity
by the photovoltaic effect.
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.
There are several different types of PV cells which all use semiconductors to
interact with incoming photons from the Sun in order to generate an electric
current.
Highly purified silicon (Si) from sand, quartz, etc. is “doped” with intentional
impurities at controlled concentrations often used in Photovoltaic Cells.
 Why Silicon?

Silicon is considered as the most suitable material for solar energy conversion because:
Second most abundant element (~ 28% by mass) after oxygen
Highly pure silicon can be readily synthesized from sand or quartz by heating them
at high temperature in furnace

SiO2 + C → Si + CO2

Silicon is an excellent semiconductor with optimum band gap of 1.23 eV at 300 K

Cost effectiveness
Silicon can be easily doped with phosphorus (P), arsenic (As), antimony (Sb), boron
(B), indium (In) or aluminium (Al).
 Semiconductor-Grade Silicon
!"#$%&"D&()"G+,+,-&!#.+/D,01/"DO&POG0#&!+4+/D,&R!P!S&
!"#$& 7#%/O+$"+D,&D8&9OD/#%%& :#G/"+D,&

#$%C'()"G)H,--'$./(,-".$,C)"
!" M/-/(%1"OP45S"78"9),H/1." 5/;"OMS"<"5/=>"OMS"!"5/&O-S"<"5/=O.S"<";="O.S"
M/-/(,":/H9"(,$7%1"
#'$/?8"P4"M/-/(%1"H9$%'.9","
(9)G/(,-"$),(H/%1"H%"@$%C'()"
>" 5/"OMS"<"CB;-"O.S"!"5/B;-C&O.S"<"B>"O.S"<"9),H"
,"M/-/(%1A7),$/1.".,M"%?"
H$/(9-%$%M/-,1)"O5/B;-CS"
5/B;-C",1C"98C$%.)1"$),(H"/1"
,"@$%()MM"(,--)C"5/)G)1M"H%"
C" >5/B;-C"O.S"<">B>"O.S"!">5/"OMS"<"aB;-"O.S"
%7H,/1"@'$)"M)G/(%1C'(H%$A"
.$,C)"M/-/(%1"O545S"
"
Czochralski
(CZ) crystal
growing

• Si is purified from SiO2 (sand) by refining, distillation and CVD.

• It contains < 1 ppb impurities. Pulled crystals contain O (~1018 cm-3) and C
(~1016 cm-3), plus dopants placed in the melt.
 CZ Crystal Puller

Crystal puller
and rotation Crystal seed
mechanism

Single Molten
crystal polysilicon
silicon
Quartz Heat shield
crucible
Carbon heating
Water jacket
element
Figure 4.10
• All Si wafers come
from “Czochralski”
grown crystals.
• Polysilicon is melted,
then held just below
1417 °C, and a single
crystal seed starts the
growth.
• Pull rate, melt
temperature and
rotation rate control
the growth
Silicon Ingot Grown by CZ Method

Photograph courtesy of Kayex Corp., 300 mm Si ingot

Photo 4.1
 Types PV based on the structure of silicon: Crystal structure, or atomic
arrangement in a material plays crucial role in its electrical properties.
• 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.
• 15–18% efficient, typically expensive to make (grown as big crystal)
• Poly-crystalline 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.
• 12–16% efficient, slowly improving and cheaper to make (cast in ingots)
• Amorphous silicon (non-crystalline)
• The final category, the amorphous material, displays no atomic regularity of
arrangement on any macroscopic scale.
• 4–8% Efficient and cheapest per Watt
• Called as “thin film” and easily deposited on a wide range of surface types
p-n junction
•System converts light energy to electricity

•Applications in Aerospace & Satellite etc 92

93
 Disadvantages of Solar Photovoltaic Cell
Some toxic chemicals, like cadmium and arsenic, are used in the PV production
process. These environmental impacts are minor and can be easily controlled
through recycling and proper disposal.
The conversion of light energy into heat energy is one of the limitations.
Solar energy is somewhat more expensive to produce than conventional
sources of energy due in part to the cost of manufacturing PV devices
Solar power is a variable energy source, with energy production dependent on
the sun.
Solar panels efficiency levels are relatively low (between 14%-25%) compared
to the efficiency levels of other renewable energy systems.
Solar panels are fragile and can be damaged relatively easily.
 Photoelectrochemical cells
Photoelectrochemical cell is a photocurrent generated device which is made up
of an electrolyte and a photoactive semiconductor electrode.
Types of Photoelectrochemical cells:
• Liquid Junction Solar Cell (LJSC) –
This cell is used to convert solar energy into electrical energy
• Photoelectrosynthesis (PES) cells –
In this class of cells, solar energy is converted into chemical energy in the form
of fuels.
 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.

96
 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 become 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.
97
98
Transparent and Conductive Substrate
• Substrate for the deposition of the semiconductor and catalyst, acting also as
current collectors
• Characteristics of a substrate:
More than 80% of transparency
Should have a high electrical conductivity.
• The fluorine-doped tin oxide (FTO, SnO2: F) and indium-doped tin oxide (ITO,
In2O3: Sn) are usually applied as a conductive substrate in DSSCs.
• These substrates consist of soda lime glass coated with the layers of ITO and
FTO.
• The ITO films have a transmittance > 80% and 18 Ω /cm2 of sheet resistance,
• FTO films show a lower transmittance of ~ 75% in the visible region and sheet
resistance of 8.5 Ω /cm2
Working Electrode (WE)
• Working electrodes (WE) are prepared by depositing a thin layer of oxide
semiconducting materials such as TiO2, Nb2O5, ZnO, SnO2 (n-type), and NiO
(p-type) on a transparent conducting glass plate made of FTO or ITO
• These oxides have a wide energy band gap of 3 – 3.2 eV
• Due to its non-toxicity, and easy availability, TiO2 is mostly used as a
semiconducting layer
• To enhance its activity the TiO2 semiconducting layers are immersed in a
mixture of a photosensitive molecular sensitizer and a solvent
• Due to highly porous structure and the large surface area of the electrode, a
high number of dye molecules get attached on the nanocrystalline TiO2
surface, and thus, light absorption at the semiconductor surface increases.
 Photosensitizer or Dye
• Dye are responsible for the maximum absorption of light.
• These should have the following photophysical and electrochemical properties:
• Dyes should be luminescent.
• Their absorption spectra should cover UV-vis and NIR regions.
• The HOMO should be located far from the surface of the conduction band of TiO2.
• LUMO should be placed as close to the surface of the TiO2, and should be placed
higher than the TiO2 conduction band potential.
• The periphery of the dye should be hydrophobic to enhance the long-term stability of
cells.
• Co-absorbents like chenodeoxycholic acid (CDCA) or anchoring groups like alkoxy-silyl,
phosphoric acid, and -COOH should be present to avoid the aggregation of the dye
over the TiO2 surface.
 Electrolyte
• An electrolyte, such as I−/I3−, Br−/Br2−, SCN−/SCN2, and Co(II)/Co(III) has five
main components, i.e., redox couple, solvent, additives, ionic liquids, and
cations.
• The following properties should be present in an electrolyte: :
• Redox couple should be able to regenerate the oxidized dye efficiently.
• Should have chemical, thermal, and electrochemical stability.
• Should be non-corrosive with DSSC components.
• Should be able to permit fast diffusion of charge carriers, enhance
conductivity, and create effective contact between the working and counter
electrodes.
Counter Electrode (CE)
• CE in DSSCs are mostly prepared by using Pt, C, CoS, Au/GNP, alloy CEs like
FeSe, and CoNi0.25.
Photosensitizer or Dye
Naturally Occurring Dyes
 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.

105
 Construction of a Grätzel cell
In Grätzel cell a range of organic dyes are used.
Examples: Ruthenium-Polypyridine, Indoline dye & metal free organic dye.
These dyes are extractable from simple foods such as hibiscus tea, tinned
summer fruits, blackberries.

Upper Plate :
Dye coated TiO2
Plate (Anode)

Lower Plate :
Graphite coated
conductor (Cathode)
 Working Principle
The working principle of DSSC involves four basic steps: light absorption, electron injection,
transportation of carrier, and collection of current.

Sunlight energy (photon of light) passes through the titanium dioxide layer and absorbed
by the photosensitizer
Due to the photon absorption, electrons get promoted from the ground state (Dye) to
the excited state (Dye*) of the dye
Excited electrons with a lifetime of nanosecond range are injected into the conduction
band of nano-porous TiO2 electrode which lies below the excited state of the dye.
As a result, the dye gets oxidized.

Dyeo + hν → Dye*

Dye* → Dye*+ + e- (TiO2)

Advantages and disadvantages of DSSC
 Supercapacitor or Ultracapacitors
A supercapacitor is a type of capacitor that can store a large amount of energy, typically
10 to 100 times more energy per unit mass or volume compared to electrolytic capacitors.
These can deliver and accept charge more quickly than batteries.
 Batteries and capacitor
Batteries and capacitors do a similar job—storing electricity—but in completely different
ways.
Batteries have two electrical terminals (electrodes) separated by a chemical substance
called an electrolyte.
When power is on, chemical reactions happen involving both the electrodes and the
electrolyte. These reactions convert the chemicals inside the battery into other
substances, releasing electrical energy as they go.
Once the chemicals have all been depleted, the reactions stop and the battery is flat
In a rechargeable battery, such as a lithium-ion power pack used in a laptop computer or
MP3 player, the reactions can happily run in either direction so that it is usually charge
and discharge hundreds of times before the battery needs replacing.
 Capacitors
A capacitor is a device used to store electrical charge
and electrical energy.
Capacitors use static electricity (electrostatics)
rather than chemical substances to store energy.
Inside a capacitor, there are two conducting metal
plates with an insulating material called a dielectric in
between them - it's a dielectric sandwich.
Positive and negative electrical charges build up on
the plates and the separation between them, which
prevents them coming into contact, is what stores the
energy.
The dielectric allows a capacitor of a certain size to
store more charge at the same voltage, so it makes
the capacitor more efficient as a charge-storing
device.
 Advantages of capacitors over batteries:
Capacitors have many advantages over batteries: they weigh less, generally don't
contain harmful chemicals or toxic metals, and they can be charged and discharged
zillions of times without ever wearing out.
But they have a big drawback too: their basic design prevents them from storing
anything like the same amount of electrical energy as batteries.
A supercapacitor differs from an ordinary capacitor in two important ways:
• Its plates effectively have a much bigger area and the distance between them is much
smaller, because the separator between them works in a different way to a
conventional dielectric.
• Although the words "supercapacitor” and "ultra capacitor” are often used
interchangeably, there is a difference: they are usually built from different materials
and structured in slightly different ways, so they store different amounts of energy.
Like an ordinary capacitor, a supercapacitor has two plates that are separated.
The plates are made from metal coated with a porous substance such as powdery,
activated charcoal, which effectively gives them a bigger area for storing much more
charge
Unlike capacitor, in a supercapacitor, there is no dielectric as such. Instead, both plates
are soaked in an electrolyte and separated by a very thin insulator (which might be made
of carbon, paper, or plastic)
 How do Supercapacitors Work?
When the plates are charged up, an opposite charge forms on either side of the
separator, creating what's called an electric double-layer.
This is why supercapacitors are often referred to as double-layer capacitors, also called
electric double-layer capacitors or EDLCs).
The capacitance of a capacitor increases as the area of the plates increases and as the
distance between the plates decreases.
 Characteristics of Supercapacitors
Fast charging speed and it can reach more than 95% of its rated capacity within minutes
Cycle life is long and the number of charge and discharge cycles can reach 10,000 to
500,000 times, without "memory effect“.
The high current discharge capacity is super strong, the energy conversion efficiency is
high, the process loss is small, and the high current energy cycle efficiency is ≥90%;
High power density, up to 300W/KG ~ 5000W/KG, equivalent to 5~10 times of battery;
The raw material composition, production, use, storage and dismantling process of the
product are not polluted, and it is an ideal green environmental protection power source;
The charging and discharging circuit is simple, no charging circuit like rechargeable
battery is needed, and the safety factor is high, and the maintenance is long-term
maintenance-free;
Good ultra-low temperature characteristics, temperature range -40 °C - +70 °C;
Easy to detect, the remaining power can be read directly;
The capacity range is usually 0.1 F – 1000 F.
 Comparison of supercapacitors with batteries and ordinary capacitors
Unlike battery, supercapacitors can store and release energy almost instantly.
That's because a supercapacitor works by building up static electric charges on solids,
while a battery relies on charges being produced slowly through chemical reactions.
Batteries have a higher energy density (they store more energy per unit mass) but
supercapacitors have a higher power density (they can release energy more quickly).
Supercapacitors are suitable for quick storing and releasing large amounts of energy.
Although supercapacitors work at relatively low voltages (maybe 2–3 volts), they can be
connected in series (like batteries) to produce bigger voltages for use in more powerful
equipment.
Since supercapacitors work electrostatically, rather than through reversible chemical
reactions, they can theoretically be charged and discharged any number of times.
They have little or no internal resistance, which means they store and release energy
without using much energy—and work at very close to 100 percent efficiency.
 Comparison of Supercapacitor, Ordinary Capacitor and Battery
Parameter Super Capacitor Ordinary Capacitor Battery
Energy storage Watt-second energy Watt-second energy Watt-hour energy
Power supply Fast discharge, linear or Fast discharge, linear or Maintain a constant
exponential voltage decay exponential voltage decay voltage for a long time
Charging/discharging milliseconds to seconds Picosec. to milli sec. 1 to 10 hours
time
Dimensions Small Small to Large Large
Weight 1g to 2g 1g to 10kg 1g to ＞10kg
Energy density 1 to 5Wh/kg 0.01 to 0.05Wh/kg 8 to 600Wh/kg
Power density High, ＞4000W/kg High, ＞5000W/kg Low, 100-3000W/kg
Operating voltage 2.3V to 2.75V 6V to 800V 1.2V to 4.2V
Life ＞100,000 cycles ＞100,000 cycles 150 to 1500 cycles
Working temperature ﹣40 to ﹢85℃ ﹣20 to ﹢100℃ ﹣20 to ﹢65℃
 Application of Supercapacitors
Supercapacitors have been widely used as the electrical equivalents of flywheels in
machines—"energy reservoirs" that smooth out power supplies to electrical and
electronic equipment.
Supercapacitors can also be connected to batteries to regulate the power they supply.
In wind turbines, where very large supercapacitors help to smooth out the intermittent
power supplied by the wind. In electric and hybrid vehicles, supercapacitors are
increasingly being used as temporary energy stores for regenerative braking (where the
energy a vehicle would normally waste when it comes to a stop is briefly stored and then
reused when it starts moving again).