Engineering Chemistry (BCHY101L)

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 reaction
or, conversely, that uses electricity to drive a non-spontaneous redox reaction.
▪ 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 often 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 reaction to electrical energy. ΔG < 0
• Electrolytic cell: Consumes electrical energy from an external source to drive
a non-spontaneous chemical reaction. 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- Reduction: M2n+ + n e- → M2
Overall representation of Galvanic cell
M1 | M1n+ (C1) ║ M2n+ (C2) | M2
Cell Representation
 Cell Representation

Convention Regarding the Sing of EMF:

Cell is not feasible if EMF = -Ve

Cell is feasible if EMF = +Ve

# Electrons flow from anode to cathode while current

flows from cathode to anode. The potential of cathode
is more than the anode. Cell will be feasible only if the
potential of cathode will be more than anode.
To Calculate Standard EMF of Cell (Eo Cell):

Calculate Standard EMF of Cell (Eo Cell) of following cell if standard reduction
potential of Zn and Ag are -0.76 V and + 0.80 V:

Solution:
Example 1:
Example 2:
Nernst Equation:
Numerical Problems:
Numerical Problems:
To Calculate Eq. Const. K:
Problem No.1
Construction of cell
Write the half cell reaction, Construct the cell, and explain the the net reaction and cell
EMF of the following cell:
Cd|Cd2+ (0.01 M)║Cu2+ (0.5 M)|Cu
Cd
The standard reduction potentials are ̶ 0.40 V and 0.34 V respectively.
▪ The half reactions:
At anode: Cd → Cd2+ + 2 e- Standard reduction potential = ̶ 0.40 V CdSO4

At cathode: Cu2+ + 2 e- → Cu Standard reduction potential = 0.34 V

▪ Net reaction: Cd + Cu2+ → Cu + Cd2+
▪ Cell EMF:
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 from molten salt.
▪ Similarly, there is net movement of Cl- ions to the
anode where they are oxidized to Cl2.
▪ Positive terminal of the battery 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.
Steel rod
▪ Here inert electrodes are used. Graphite

Anode: 2 Cl ̶ (l) → Cl2 (g) + 2 e-

Cathode: 2 Na+ (l) + 2 e- → 2 Na (l) Overall: 2 NaCl (l) → 2 Na (l) + Cl2 (g)
Electrolytic Decomposition of Water

▪ A pair of inert electrodes are dipped into the

H2
solution and applying a voltage between them Power
O2
results in the rapid evolution of bubbles of supply

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:
Anode: 2 H2O → O2(g) + 4 H+ + 4 e-

Cathode: 4 H+(aq) + 4 e- → 2 H2(g)

Overall: 2 H2O → O2(g) + 2 H2(g) Platinum electrodes

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 plating:
• Anode reaction: Ni (s) → Ni2+ (aq.) + 2 e-
• Cathode reaction: Ni2+ (aq.) + 2 e- → Ni (s)
• Electrolyte: Aqueous NiSO4 solution
▪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 1: ▪ Silver plating 2:
• 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 K[Ag(CN)2] solution
• Electrolyte: Aqueous AgNO3 solution
E.g. ELECTROPLATING of copper

AIM
(i) To increase the resistance to corrosion and chemical
attack of the plated metal.
(ii) To obtain a polished surface
(iii) To improve hardness and wear resistance

Uses :
(i) It is often used in electronic industries for making
printed circuit boards, edge connectors,
semiconductor lead-out connection
(ii) It is also used in the manufacture of jewelry,
refrigerator, electric iron etc.

19
Electroplating of Cu

PRINCIPLE
Electroplating is the process in which the metal to be coated is deposited on the base
metal (substrate) by passing a direct current in the presence of electrolytic solution
containing the soluble salt of the metal to be coated.

Required materials,
Electrolyte : (3-5%) H2SO4 / (15-30%) CuSO4
Anode : Pure Cu metal or Graphite (inert)
Cathode : Metal part (Object to be coated)
Additive : Boric acid or gelatin 20
Electroplating of Cu

DC battery

Cu (Anode) Steel object

+ ve Cu2+
(cathode) (-ve)
Cu
2+

Cu2+ SO42-
Cu deposited
surface

Process
Ionization reaction of electrolyte:
H2SO4 2H+ + SO42-
CuSO4 Cu2+ + SO42- ;

On passing current: Cu2+ + 2e- Cu (at cathode)

Cu + SO42- CuSO4 + 2e- (at
anode)

21
Factors affecting electroplating

 Surface cleaning – for strong adherent

 Concentration of electrolyte.
 Conductivity and stability of electrolyte
 Thickness of the deposit – for decorative purpose thin
coating and for corrosion protection multiple coating
 Current density (current per unit of the base metal) should
be low for uniform controlled deposition
 Additives: Ensure strong adherence and mirror smooth
coating
 pH of the electrolytic bath

22
Semiconductors
▪ A semiconductor is a substance, usually a solid chemical element or compound that can conduct
electricity under some conditions, 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.

E E E
Conduction
band

Electron Conduction band

distribution Conduction band

Valance band Valance band

Valance band

Insulator Semiconductor Conductor

Semiconductors
Conduction band

Conduction band:
Empty band

Electron energy
First empty band above the Band gap
highest filled band
Outermost band
Partially filled containing electrons
Valence
Valence band: band

Outermost band containing

electrons
Nucleus
Classification of solids:
1. Conductors
2. Insulators Cu
3. Semiconductors
1. Conductors
 Outermost (orbital) band is not completely filled
 Essentially no band gap
easy overlap
lots of available energy states if field is applied
e.g Metals and Alkali metals 24
 2. Insulators 3. Semiconductors:
 Valence band full or nearly full  Similar to insulators but narrow band gap
 At electrical temperatures some electrons can be promoted
 Wide band gap with empty conduction band
to the conduction band
 Essentially no available energy states to which
electron energies can be increased

Conduction band
Empty Conduction band
Almost Empty

Eg Band gap

Eg Wide band gap

Valence band
Almost Full

T > 0K
Valence band Full
Some common band gaps:
Element gap (ev)
Ge 0.6
Si 1.1
GaAs 1.4
25
SiO2 9.0
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
Types of semiconductors:
Intrinsic Semiconductors:

Intrinsic Semiconductors: It is a Pure state (conductive on its own)

E.g. Covalently bonded, tetravalent Si lattice
 Promotion of an electron to the conduction band leaves “hole” in the
valence band (electron-hole pair)
 When an electric field is applied the electron will migrate to positive (+)
terminal
 The hole will migrate to negative (– )terminal
 i.e the electron next to the hole will be attracted to the (+) terminal ,
leaving a hole toward (-) terminal

- +
Ec

Eg

Ev

Net propagation of hole 28

Extrinsic Semiconductor.
▪ Extrinsic semiconductor is an improved intrinsic semiconductor with a small
amount of impurities added by a process called doping, which alters the
electrical properties of the semiconductor and improves its conductivity.
▪ Semiconductors are available as either elements or compounds.
▪ Silicon and Germanium are the most common elemental semiconductors.
▪ Compound Semiconductors include InSb, InAs, GaP, GaSb, GaAs, SiC, and GaN.
▪ Introducing impurities (Doping) into the semiconductor materials can
control their conductivity.
▪
▪ Doping process produces two groups of
semiconductors:
• The negative charge conductor (n-type)
• the positive charge conductor (p-type)
n-type Semiconductor
▪ An n-type semiconductor is an intrinsic semiconductor doped with pentavalent
impurity, such as, P, As, Sb, etc.
▪ If a small amount of phosphorus is added to a pure silicon crystal, one of the
valence electrons of phosphorus becomes free to move around (free electron)
as a surplus electron.
p-type Semiconductor
▪ An p-type semiconductor is an intrinsic semiconductor doped with trivalent
impurity, such as, B, Al, In, etc.
▪ If a small amount of boron is doped to a single crystal of silicon, valence
electrons will be insufficient at one position to bond silicon and boron, resulting
in holes that lack electrons.
Si lattice with n-type dopant

Ec
Ed

Ev

 Localized energy levels

just below conduction
band which facilitates
easy conduction
Si
Ev = Energy level of valence bond
P (Donor atom) Ec = Energy level of conduction band
32
Ed = Energy level of dopant
p-type
Doping of Si with trivalent indium (3 valence electrons)
Incomplete bonding with Si
Nearby electron from Si can fill hole
Majority carriers are holes in the valence band
Minority carriers are electrons in the conduction band
Lattice doped with acceptor atoms
localized energy levels just above valence band

33
Si lattice with p-type dopant

Ec

Ea
Ev

localized energy levels just

above valence band which
makes the conduction easy
Si
Ev = Energy level of valence bond
B (Acceptor atom) Ec = Energy level of conduction band
34
Ea = Energy level of acceptor
 Czochralski crystal pulling technique for Si
▪ Ge or Si obtained by zone refining method is polycrystalline, i.e., there is no regularity in
their crystal structure and contain crystals of different sizes.
▪ This method involves growing the crystal on a single crystal seed; thereby the atoms
reproduce identical atomic arrangement as that of the seed crystal.
Silicon crystal with a
diameter of 300 mm and a
weight exceeding 250 kg
Doping techniques
▪Epitaxy:
• Involves in unified crystal growth or deposition of a thin crystal on another substrate.
• Si or Ge wafer (kept in graphite boat) is placed in a long cylindrical quartz tube reactor,
which is then heated (by RF induction coil). Then gases containing compounds of Ge or
Si mixed with calculated/appropriate quantities of dopant over the wafer results.
• For getting Si epitaxial film, SiCl4, H2 and N2 mixture is used.
• For n-type doping ⇒ above mixture is used with phosphine (PH 3)
• For p-type doping ⇒ Diborane (B2H6) is employed.
▪Diffusion technique:
• Conversion of a region of semiconductor material by solid or gaseous diffusion of
impurity atom into the crystal lattice of the semiconductor material without any
melting and it consists of heating a P-type dopant.
• By this technique, the extent of impurity atoms penetration can be controlled
even less than a few millions of a centimetre.
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.
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.
Evolution of secondary batteries
History of battery specific energy
Future
300

(Wh/kg)
Energy 250 Li-polymer

200
Specific Energy

150 Li-ion

100 Ni-Cd
Lead
50
Acid Ni-MH

0
1850 1900 1950 2000
Year 41
 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 Cha
rgi
lithium metal polyanionic materials ng

(LiFePO4, LiMnPO4, LiFeSO4F, etc.).

Li+
▪ Anode: The negative electrode is made
from graphite, usually with composition
Li0.5C6.
▪ Electrolyte: Mixture of organic carbonates
such as ethylene carbonate, diethyl ng
a rgi
carbonate. Dis
c h

▪ Separator: Prevents touching two

Li+
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.
LiCoO2 Graphite
 Charging and Discharging Reactions

e- e-
e- e-

Charging - Dis-Charging +
- +
Anode Cathode

Co Co

O O

Li+ Li+

LiCoO2 LiCoO2 Graphite

Graphite Li ion
Li ion permeable
permeable membrane
membrane
Electrolyte
Electrolyte
 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 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 LiNiCoAlO2 NCA Electric vehicles
Cobalt Aluminium and grid storage
Oxide
• 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 CO 2 which causes
pressure build up in battery, resulting in a dangerous explosion.
 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.

Ultrathin
supercapacitors for
wearable devices
 Batteries Comparison
▪ Batteries and capacitors do a similar job—
storing electricity—but in completely different Capacitors
ways.
▪ Batteries have two electrical terminals
▪ A capacitor is a device used to store electrical charge
(electrodes) separated by a chemical substance and electrical energy.
called an electrolyte. ▪ Capacitors use static electricity (electrostatics)
▪ When power is on, chemical reactions happen rather than chemical substances to store energy.
involving both the electrodes and the
▪ Inside a capacitor, there are two conducting metal
electrolyte. These reactions convert the
chemicals inside the battery into other plates with an insulating material called a dielectric
substances, releasing electrical energy as they in between them - it's a dielectric sandwich.
go. ▪ Positive and negative electrical charges build up on
▪ Once the chemicals have all been depleted, the the plates and the separation between them, which
reactions stop and the battery is flat. prevents them coming into contact, is what stores
▪ In a rechargeable battery, such as a lithium-ion the energy.
power pack used in a laptop computer or MP3
▪ The dielectric allows a capacitor of a certain size to
player, the reactions can happily run in either
direction so that it is usually charge and store more charge at the same voltage, so it makes
discharge hundreds of times before the battery the capacitor more efficient as a charge-storing
needs replacing. device.
Applications of Supercapacitors and Market
Supercapacitors
▪ 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)
Construction of Supercapacitors (1) Electrodes: The electrodes of the supercapacitor is made
of Activated Carbon material. The electrodes
have Porous nature which helps to store more charge
carriers. if the electrodes are able to store more charge
carrier then the capacitance will be increased. There are two
electrodes one is the positive electrode and another is the
negative electrode.
(2) Current Collectors: The current collectors are used to
connect the electrodes and the terminals of the capacitor. The
- + current collectors are generally made up with foil metals.
Mostly aluminum is used. There are two current collectors
in the supercapacitor one for the positive electrode and
another is the negative electrode.
(3) Separator: The separator is used to provide insulation or

ts,
ar
separate the electrodes to prevent the short-circuit. The
gp separator mainly made up with Kapton material. The
in
low

separator is very thin like paper. The separator provides

ol
ef

insulation between the electrodes but it allows to the flowing

rs
El Sepa urre rod s th

cto

of charge carrier through it.

a

lyt r olle
es
o c lec r h

n
io
Tw E cito

tro ato t c

(4) Electrolyte Solution: Mainly the Acetonitrile or

ut
n
t

ol
Tw apa

propylene carbonate as solvents are used as electrolyte in

eS
c
o

r
1. per

the supercapacitor. The electrolyte solution consists the

Su

ec

charge carriers like positive cations and negative anions.

A
2.
3.
.
Working of Supercapacitors
Charging
▪ 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 -ve electrode +ve electrode
area of the plates increases and as the
distance between the plates decreases. (C α
Area/distance)
Dis-charging
▪ When we apply a voltage across the electrodes
of the supercapacitor then it starts charging.
The electrodes start to attract the ions of opposite
polarity. That means the positive electrode attracts
the negative Ions or charges and the negative
electrode attracts the positive ions or charges. As a
result, the positive ions or charges creates a layer
near the negative electrode and the negative ions
create a layer near the positive electrode.
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 0.1F – 1000F.
 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 ﹣40 to 85℃
℃ ﹣20 to 100℃
℃ ℃
﹣20 to 65℃
temperature
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).
 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.
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 H 2 + O 2 → 2 H 2O
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.
Alkaline Fuel Cells (or) H2- O2 Fuel Cells

H2 O2

An electrochemical cell in which

the energy of a reaction between a
Unreacted
fuel (such as liquid hydrogen) and
Unreacted
H2 + H2O - + Oxygen
an oxidant (such as liquid oxygen)
Vapour e- e- is converted directly and
continuously into electrical energy.
OH-

H2O

K+OH-
Cathode: Porous
Anode : Porous carbon with Pt
carbon with Pt catalyst
catalyst
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
▪ 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.
Polymer Electrolyte Membrane Fuel Cell (PEMFC):
General features:
• Fuel : Hydrogen
• Electrolyte: Ion exchange polymer membrane (Nafion) Nafion is a
perfluorinated cation exchange polymer membrane. It is a solid state
electrolyte.
• Electrodes: Metal based or made of porous carbon
• Catalyst : Platinum

• Operating temperature: 80 °C
• Charge carrier: H+ ions

• Fuel cell efficiency: 60 %

• Size & Cost: Small & Low
• Better performance: If gases are humidified
• Application: Mainly for transportation like Buses & Cars
Polymer Electrolyte Membrane Fuel Cell (PEMFC):
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.
Solid oxide fuel cells (SOFC)

Anode, cathode and electrolyte all made up of ceramic substances and

these cells are generally operated at high temperature. Ceramics are
employed as functional elements. Both electrodes are separated by
Solid Impermeable Electrolyte which conduct oxygen ions from
cathode to anode that reacts chemically with fuel.
Anode: Porous material, made up of oxides of Ni-Zr or Ni-Y stebilized
by zirconium oxide.
Cathode: Thin porous layer made up of lanthanum manganate
(LaMnO3) at which reduction of oxygen takes place.
Electrolyte: YO2 and ZrO2
Construction of SOFC

▪ 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 (The amount of energy reflected back to space)
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

Types of solar energy conversion cells

 Photovoltaic Cells
 Photoelectrochemical cells
 Dye-sensitized solar cells
Photovoltaic Cells Why Silicon?
▪ A solar cell is a device that converts the energy of Silicon is considered as the most suitable material for
sunlight directly into electricity by the solar energy conversion because:
photovoltaic effect.
▪ Second most abundant element (~ 28% by mass) after
▪ The photovoltaic effect involves creation of a oxygen
voltage (or a corresponding electric current) in a
material upon exposure to electro-magnetic ▪ Highly pure silicon can be readily synthesized from
radiation. sand or quartz by heating them at high temperature
in furnace
▪ Though the photovoltaic effect is directly related
to the photoelectric effect, the two processes are
SiO2 + C → Si + CO2
different.

▪ There are several different types of PV cells

which all use semiconductors to interact with ▪ Silicon is an excellent semiconductor with optimum
incoming photons from the Sun in order to band gap of 1.23 eV at 300 K
generate an electric current. ▪ Cost effectiveness
▪ Highly purified silicon (Si) from sand, quartz, etc. ▪ Silicon can be easily doped with phosphorus (P),
is “doped” with intentional impurities at
arsenic (As), antimony (Sb), boron (B), indium (In) or
controlled concentrations often used in
aluminium (Al).
Photovoltaic Cells.
Introduction to Photovoltaic
Consistent annual growth in solar power markets coupled with a global shortage in crystalline silicon
needed for traditional solar power has propelled the market for thin-film photovoltaics (PV), which is
expected to grow from $220 million in 2006 to over $3 billion in 2013 (Ref:NanoMarkets, 2006).
However, for cadmium-telluride (CdTe) thin-film PV, the market projections are tempered by concern
over global environmental policies restricting electronic products containing cadmium, a known
human carcinogen (IARC, 1993).
The global solar energy market was valued at $52.5 billion in 2018 and is projected to reach $223.3 billion by
2026, growing at a CAGR of 20.5% from 2019 to 2026.
Therefore, alternate materials are being searched…….

• The photovoltaic effect was first recognized in 1839 by French

physicist Alexandre-Edmond Becquerel.
• However, it was not until 1883 that the first solar cell was
built, by Charles Fritts, who coated the semiconductor
selenium with an extremely thin layer of gold to form the
junctions. The device was only around 1% efficient.
• Russell Ohl patented the modern solar cell in 1946 (U.S.
Patent 2,402,662)
77
Solar Spectrum

Photons do not have

sufficient energy to free e- Photons have sufficient
from Si energy to free e- from Si

 200 to 2000 nm
 About 46% of the spectral energy is distributed in the visible region
 About 49% in near IR,
 About 3% in UV region and
 Rest in far IR regions
78
Applications of Solar Cells
It is a Renewable energy
It Can be powered for remote locations
No pollution and environmentally friendly etc.,

R15-1200- Rollable Solar Charger

$274.00

79
Photovoltaic effect (cell)
It is a physical phenomenon in which light energy is converted to electrical energy

Photo = light Materials for photovoltaic

i cs Voltaic = Produce Voltage cells-
o lt a
tov 1. Encapsulate
h o 2. Contact Grid
p
e of 3. Antireflective
i pl Coating
i nc 4. N-type Silicon
Pr 5. P-type Silicon
6. Back Contact
Top electrode

e
n-type semi conducting layer -
-
p-type semi conducting layer
+

Bottom electrode

80
Working

3. The photons (yellow dot) carry

their energy down through the
cell.
4. The photons give up their
energy to electrons (green dot)
in the lower, p-type layer.
5. The electrons use this energy
to jump across the barrier into
the upper, n-type layer and
escape out into the circuit.
1. A solar cell is a sandwich of n-
6. Flowing around the circuit, the
type silicon (blue) and p-
electrons make the lamp light
type silicon (red).
up.
2. When sunlight shines on the
cell, photons (light particles)
bombard the upper surface.
81
Efficiency of a solar cell

A solar cell's energy conversion efficiency (η, "eta"), is the percentage of

power converted (from absorbed light to electrical energy) and collected,
when a solar cell is connected to an electrical circuit. This term is
calculated using the ratio of Pm, divided by the input light irradiance
under "standard" test conditions (E, in W/m²) and the surface area of the
solar cell (Ac in m²).

Efficiency (%) : Pm
Pm= Power (W)  
E= irradiance or electromagnetic radiation E x Ac
(W/m2)
Ac= The surface area of the solar cell (m²)

82
Materials for photovoltaic cells

Oxygen 46.1%
Table 1. Natural abundance of elements in earth crust
Silicon 28.2%
Monocrystalline Si, 38% Aluminium 8.2%
Iron 5.6%
Calcium 4.2%
Sodium 2.4%
Magnesium 2.3%
CdS
Potassium 2.1%
Titanium 0.57%
CuGaSe2 Hydrogen 0.14%
ZnO Copper 0.005%
CuInSe2
Materials for solar cell - 2006 Total 99.8%

Silicon is extracted from naturally occurring SiO2 or from its halides. It exists in two
allotropic forms
1. Amorphous – A brown powder
2. Crystalline – grey crystals
3. Single crystal silicon 83
Photovoltaic Cells using silicon: Materials such as silicon, germanium exhibit a property of semi-
conduction and are called semiconductors. These semiconductors have electrical conductivity lower than
metals and higher than insulators.
Silicon is an ideal material for PV as it is a cheap material for fabrication of photovoltaic cells.
(p-type)
When pure silicon is doped with an acceptor element such as boron, it becomes a positively charged (p-
type) semiconductor.
(n-type)
On the other hand, when it is doped with a donor element such as phosphorus, it becomes a negatively
charged (n-type) semiconductor.

Silicon has a valency of

four and each silicon
atom is bonded to four
other silicon atoms as
shown in Figure. When
it is doped with boron
that has a valency of
three, silicon is
replaced with boron as
shown. 84
 Band gap vs Efficiency
The efficiency the materials
increases as the band gap
40 increases but beyond certain
c-Si CdTe value of the band gap the
efficiency decreases – why?
The Shockley–Queisser limit gives the
CZTS maximum possible efficiency of a
single-junction solar cell under un-
Efficiency
concentrated sunlight, as a function of
30 CdS the semiconductor band gap. If the
band gap is too high, most daylight
(%)

CuInSe2 CuGaSe2 photons cannot be absorbed; if it is too

low, then most photons have much
ZnO more energy than necessary to excite
electrons across the band gap, and the
rest is wasted. The semiconductors
commonly used in commercial solar
20 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 cells have band gaps near the peak of
this curve, for example silicon (1.1eV)
Egap (eV) or CdTe (1.5eV).

Efficiency (%) :
Pm
Pm= Power (W)10
E= irradiance or electromagnetic radiation (W/m 2)

Ac= The surface area of the solar cell (m²)
0 E x Ac 85
Unique Features of solar cell

7. Require little maintenance if

1. Have no moving parts (in the
properly manufactured and
classical mechanical
installed
sense) to wear out
8. Can be made from silicon, the
2. Contain no fluids or gases (except in
second most abundant element in
hybrid systems) that can leak out, as
the earth's crust
do some solar-thermal systems
9. Have a relatively high conversion
3. Consume no fuel to operate
efficiency giving the highest overall
4. Have a rapid response, achieving full
conversion efficiency from sunlight
output instantly
to electricity
5. Can operate at moderate
10. Have a high power-to-weight
temperatures
ratio making them suitable for
6. Permitting a wide range of solar-
roof application
electric applications such as
11. Are amenable to on-site
- Small scale for remote applications
installation
and residential use
12. Produce no pollution while
- Intermediate scale for business and producing electricity (but waste
neighborhood supplementary power products from the manufacture, and
- Large scale for centralized energy toxic gases in the event of catastrophic
farms of square kilometers size failure and disposal may be a concern) 86
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.
 Photo Electro Chemical cell (PECs)
It is a cell containing a semiconductor and a metal electrode immersed in an electrolyte solution and
when light falls on the surface of the semiconductor, the light energy is converted in to electrical
energy
The main difference between a PEC cell and the photovoltaic cell
Light
In PEC photo- generated carriers whereas in the later, there
transfer the energy from light to is no such process.
chemical species in the solution
Electricity
Fuels
O2 H2

CO
2
e e
Sugar

sc M
sc M
H2O
H2O
O
2 Semiconductor/Liquid
Photosynthesis Junctions Solar cell Photovoltaic 88
 Photo electrochemical Cells Types

1. Liquid Junction Solar Cell (LJSC)

The cell, which is used for the conversion
of solar energy into electrical energy, with
the help of photoactive semiconductor and
the electrolyte.
-
e

2. Photoelectrosynthesis (PES)
cells
Solar energy is converted into chemical
energy in the form of fuels

89
Photoelectrochemical Cell-LJSC Material requirements
• Band gap must be at least 1.8-
2.0 eV but small enough to
absorb most sunlight
2hν + H2O ---> H2(g) + ½ O2 (g)
• Band edges must straddle
Redox potentials
2H2O + 2e- = 2OH- +H2
• Fast charge transfer
e-
EC H2O/H2
Ehν > Eg • Stable in aqueous solution
• The simplest LJSC consists of
two electrodes (one of them a SC
1.8-2.0 eV and the other a metal) dipped in
an electrolyte containing a
1.23 eV redox couple.
e- Eg Counter
• Both the electrodes must be
electrode
inert, i.e., the electrode material
itself should not take part in the
electrochemical reactions.
EF
H2O/O2 • One of the important
EV h+ requirements for the operation
of a LJSC is the presence of
H2O + 2h+ = 2H+ + 1/2O2 depletion layer at the surface of
h = hole
+ p-type the SC electrode.
semiconductor
Pt wire • For this, the initial Fermi level of
the SC should be above the Eredox.
Light energy is Converted to Electrical+Chemical Energy
 Briefly working of Photo Electro Chemical cell (PECs)

1. A photoelectrochemical cell consists of a photoactive semiconductor (SC) working

electrode (either n- or p-type) and counter electrode made of metal (M) (e.g. Pt). Both
electrodes are immersed in the electrolyte containing suitable redox couples.
2. If the junction of the semiconductor-electrolyte is illuminated with a light having energy
greater than the bandgap of the semiconductor, photogenerated electrons/holes are
separated in the space charge region.

3. With the help of a connecting wire, photogenerated majority carriers are transported via a
load to the counter electrode where these carriers electrochemically react with the
redox electrolyte.

91
Working Contd..(For Reading, Explanation)
1. A typical type of the photocurrent-generated device has a semiconductor in
contact with an electrolyte, and this is often referred as
photoelectrochemical cells.
2. A photoelectrochemical cell consists of a photoactive semiconductor (SC)
working electrode(either n- or p-type) and counter electrode made of metal
(M) (e.g. Pt). Both electrodes are immersed in the electrolyte containing
suitable redox couples.
3. In a metal-electrolyte junction, the potential drop occurs entirely on the
solution side, whereas in a semiconductor-electrolyte junction, the potential
drop occurs on the semiconductor site as well as the solution side.
4. The charge on the semiconductor side is distributed deep in the interior of
the semiconductor, creating a space charge region. If the junction of the
semiconductor-electrolyte is illuminated with a light having energy greater
than the bandgap of the semiconductor, photogenerated electrons/holes are
separated in the space charge region.
5. The photogenerated minority carriers (holes) arrive at the interface of the
semiconductor-electrolyte. Photogenerated majority carriers (electrons)
accumulate at the backside of the semiconductor.
6. With the help of a connecting wire, photogenerated majority carriers are
transported via a load to the counter electrode where these carriers
electrochemically react with the redox electrolyte. 92
Chemical reactions - Working -LJSC
1. Absorption of light near the surface of the semiconductor creates electron-
hole pairs.
The non-equilibrium electrons in the conduction band are produced by
illumination of light will have energy Ehv ≥Eg.
2. Holes (minority carriers) drift to the surface of the semiconductor (the
photo anode) where they react with water to produce oxygen (Oxidation)
2h+ + H2O ----> ½ O2(g) + 2H+
3. Electrons (majority carriers) are conducted to a metal electrode (typically
Pt) where they combine with H+ ions in the electrolyte solution to make H2
(Reduction)
2e- + 2H+ ----> H2(g)
4. Transport of H+ from the anode to the cathode through the electrolyte
completes the electrochemical circuit.
The overall reaction : 2hν + H2O ----> H2(g) + ½ O2 (g)
93
Dye sensitized Solar Cells- Gratzel cells

Professor Michael Gratzel

Swiss Federal Institute of Technology
Lausanne
Switzerland

Michael Grätzel and Brian O’Regan invented “Dye-sensitized solar cells”, also
called “Grätzel cells”, in 1991.

Dr. Brian O’Regan

Research Lecturer
Imperial College London

94
 Difference between PEC and Gratzel Cell

Photo electrochemical cell

1. Semiconductor electrode
2. Counter electrode
3. Electrolyte solution

Gratzel Cell
1. Dye adsorbed Semiconductor
electrode
2. Counter electrode
3. Electrolyte solution (Iodide)
95
Why?/How? - Dye sensitization of a semiconductor for solar energy conversion

 Chlorophyll is a best example for a organometallic (Mg containing organic compound) dye that uses
solar energy for photosynthesis – reported by Moser 1887
 Cue was taken from this and proved that dye adsorbed on semiconductor surface can enhance the
photo-electrochemical cell’s performance for solar energy conversion
 In a dye molecule, the gap between the highest occupied molecular orbital (HOMO) and the lowest
unoccupied level (LUMO) is analogous to the conduction band - valence band gap in a semiconductor
 Dye-sensitized solar cells (DSCs) are potential low-cost solar energy conversion devices
 Efficiency of DSCs is 11.1% at present
 The life time of DSCs exceeds 10 years based on the durability and stability towards light and
chemicals

organometallic porphyrin system

96
▪ 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, TiO 2 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 TiO 2 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 TiO 2.
• LUMO should be placed as close to the surface of the TiO 2, 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.
Construction and Working of Gratzel cell

At Anode Dye+ (adsorbed on TiO2) + 3/2 I-  Dye (adsorbed on TiO2) + 1/2 I3-

SnO2 Coated Single TiO2 Dye molecule - Counter (+ve)

Glass ( -ve Nanoparticl Adsorbed on electrode, Pt
electrode) Electrolyte
e TiO2

e-
CB
e -

e-
e-
Sun e -

light Ef
e- 3I-
e- qV (obtainable I)
e- e-
e -
VB ERedox
I3- e-

e- e-
e-  3 e- 
e- e- 2 e- e-
1
0

At Cathode I3- + 2e-  3I- 101

Working Principle of Gratzel cell

Step 1 Sunlight (photon of light) passes through the titanium dioxide layer and
strikes electrons in the adsorbed dye molecules. Electrons gain this
energy and excited to conduction band.
Step 2 The excited free electrons move through the titanium dioxide
nanoparticle from dye molecule and accumulate at the conducting glass
electrode (-ve plate TiO2-dye plate).
Step3 The free electrons from the negative electrode flows through the
external circuit to the counter electrode which produces electric current
which can be measured.
Step4 On the surface of the counter electrode (+ve) iodide ion (I - reduced
form) receive the electron and gets oxidized to I 3- ion after transferring the
electrons to dye molecule which regains its electron from the iodide electrolyte.
The dye is then regenerated for second cycle.
Step5 The free electrons at the metal/graphite (+ve) plate then reduce the tri-
iodide (I3-) molecules to I-. The dye molecules are then ready for the next
excitation. In the next cycle step1 to step 5 is followed.
102
Dye Sensitized solar cell - working
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 TiO 2
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 (I 3-).
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. 103
 Molecular engineering of dyes.
cis - isomer

0.8
COOH
HOOC COOH

HOOC
N N
Trans - isomer
0.6 N

N Ru
Absorbance

NCS SCN NCS

Ru
N NCS N N

HOOC N

0.4 HOOC OOCH

HOOC

0.2
Very small changes to a dye
structure can have significant
influence on the optical properties.
0.0 In the present case compare the
absorption spectra of two isomers
300 400 500 600 700 of 800
dithiocyanato bis(4,4’-
Energy [nm] dicarboxylic acid-2,2’-bipyridine)
104
ruthenium(II) dye.
Naturally Occurring Dyes
Advantages and disadvantages of DSSC