Engineering Chemistry

Module 4

Prepared by Dr. Arup Sinha

SJT 710-A3
arup.sinha@vit.ac.in
 Energy devices
▪ Electrochemical and electrolytic cells
▪ Electrode materials with examples
• Semi-conductors
▪ Electrode- electrolyte interface
▪ Chemistry of Li ion secondary batteries,
▪ Supercapacitors
▪ Fuel cells: H2-O2 and solid oxide fuel cell (SOFC);
▪ Solar cells: Photovoltaic cell (silicon based), Photoelectrochemical
cell, 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.
• Electrolytic cell: Consumes electrical energy from an external source to drive
a non-spontaneous chemical reaction
 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
 Anode is where oxidation happens. Here electrolyte is getting oxidized and anode it getting reduced itself

Cathode is where reduction happens. Here electrolyte is getting reduced and cathode it getting oxidised itself
Working mechanism of Galvanic cell
 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:

▪ For equimolar solution of electrolytes corresponding to M1 and M2:

1. Write the half cell reaction, the net reaction and cell EMF of the following cell:
Cd|Cd2+ (0.01 M)║Cu2+ (0.5 M)|Cu
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
At cathode: Cu2+ + 2 e- → Cu Standard reduction potential = 0.34 V
▪ Net reaction: Cd + Cu2+ → Cu + Cd2+
▪ Cell EMF:
 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
 Electrolytic cell
▪ Electrochemical cells use external electrical energy to induce non-spontaneous reactions
▪ Here, the anode is positive and cathode is the negative electrode
▪ The reaction at the anode is oxidation and that at the cathode is reduction

ΔG >0
 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: 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
electrodeposition 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: ▪ 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
Types of semiconductors:
 Intrinsic Semiconductor
▪ Intrinsic semiconductor material is chemically very pure and possesses poor conductivity.
▪ It has equal numbers of negative carriers (electrons) and positive carriers (holes)

Absence of Presence of
electrical field electrical field
 Extrinsic Semiconductor.
▪ Extrinsic semiconductor is an improved intrinsic semiconductor with a small amount
of impurities added by a process, known as doping, which alters the electrical
properties of the semiconductor and improves its conductivity
▪ Introducing impurities into the semiconductor materials (doping process) can control
their conductivity
▪ Doping process produces two groups of semiconductors:
• The negative charge conductor (n-type)
• the positive charge conductor (p-type)
▪ 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, GaN.
 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.
 Preparation of Semiconductors: ~ 99.9999% pure Si and Ge
▪ Distillation:
• Separation of materials is based on the difference in boiling points
• For Ge ⇒ GeCl4 and for Si ⇒ SiHCl3
• As is removed from GeCl4 (b.p. 83.1 0 C) with the help of HCl
• Pure GeCl4 is obtained by fractional distillation in presence of chlorine
• After cooling, the pure GeCl4 is treated with extra pure water to get germanium oxide
• Subsequent reduction of GeCl4 with pure hydrogen affords highly pure elemental Ge

GeCl4 + 2 H2O → GeO2 + 4 HCl

GeO2 + 2 H2 → Ge + 2 H2O

• Similarly, distilled trichloro silane (SiHCl3) is employed to get silicon of high purity.
 Zone refining
▪ Difference between solubility of impurities in the molten and solid phases is used to
concentrate impurities at the end section of the ingots
▪ The technique is based on the principle that when an impure metal in a molten state is
allowed to cool, only the metal crystallizes while the impurities remain present in
the molten state (mass) or melt
▪ Used for the purification of germanium, silicon, gallium etc.
 Czochralski crystal pulling technique
▪ 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
 Electrode-electrolyte interface
▪ When two dissimilar phases come into contact, charge separation occurs in the
interfacial region which results in the generation of an interfacial potential difference
or electric field.
▪ An electrode in contact with a solution of an electrolyte acquires a charge when
• Atoms escape into the solution as cations, leaving behind a negative charge
• Cations get attached to the surface of the electrode creating a positive charge.
▪ At the interface forces experienced by ions and solvent dipoles are no longer isotropic
and homogeneous and the solution side of the interface becomes electrified.
▪ Once the solution side of the interface becomes electrified (acquires a net or excess
charge), an electric field will operate across the phase boundary.
▪ Since the metallic phase contains charged particles, the latter will respond to this E field.
The free electrons will move away from or move towards the interface depending on the
direction of the E field.
▪ Thus a net charge will be induced on the metal, which will be equal in magnitude and
opposite in sign to that on the solution side of the in magnitude and opposite in sign to
that on the solution side of the phase boundary.
▪ Thus charge separation occurs across the M/S interface, and this gives rise to an
interfacial potential difference. gives rise to an interfacial potential difference.
 Electrical double layer
▪ In the electrical double layer model it is supposed that there is a sheet of positive charge
at the surface of the electrode and a sheet of negative charge next to it in the solution
▪ An electrical double layer is often called an electrical diffuse double layer, since the
distribution of counter ions in the ionic cloud takes a diffusive structure due to thermal
motion of ions.
 Theories of structure of double layer
▪ Helmholtz-Perrin model (or) Parallel Plate condenser model:
• Helmholtz considered the double layer consisting of two oppositely charged layers at a
fixed distance a part. Solvated ions lie along the surface of the electrode but are held
away from it by their hydration spheres
• The electrified interface consists of two sheets of charges, one on the electrode (rigidly
held layer) and the other in the solution (layer of oppositely charged ions)
• According to Helmholtz model, the variation of potential of the double layer with
distance into the solution is linear
• The electrical double layer leads to difference of potential between the solid and the
liquid. The potential difference across the two layers is given as:

d = distance between two layers

dQ = charge density on each layer.
ε = dielectric constant of the medium.
▪ Outer Helmholtz plane (OHP): the plane running through the solvated ions
▪ Inner Helmholtz plane (IHP): The inner layer which isclosest to the electrode. This layer
contains solvent molecules and specifically non-hydrated adsorbed ions
 Limitations of Helmholtz-Perrin model
▪ Helmholtz model assumes a fixed layer of oppositely charged ions in solution. But in
solution, due to thermal motion of liquid molecules such a rigid array of charges at an
interface may not exist.
▪ Helmholtz parallel plate condenser model predicts a constant capacity (C) [that is, one
which does not change with potential] for the electrical double layer.
▪ Experimentally it is found that the capacity of the double layer is not constant with cell
potential

▪ It does not take into account the variation of the properties of double layer with
concentration of electrolyte and temperature.
 Guoy-Chapmann’s Model or Diffuse charge Model
▪ According to this model, there is an electrical double layer at the interface which is not
sharp but diffuse double layer.
▪ One layer is fixed on the electrode and the oppositely charged layer is diffused or mobile
on the electrolyte. The solution side of the double layer is not near one molecule in
thickness but extends to some distance into the liquid phase.
▪ The ions are spread out into the solution. The distribution of +ve and ve charges in this
region is not uniform due to thermal agitation and the free movement of ions present in
the solution.
▪ The electrostatic attraction between opposite charges at the interface try to bring out
orderliness while thermal agitation tends to bring disorderliness.
▪ In this respect, the diffuse double layer theory is similar to the Dubye-Huckel concept of
ionic atmosphere surrounding a given ion.
▪ The diffused charge can be considered as a sheet of charge Qd placed at a distance κ–1
from the electrode surface
▪ The potential change from one layer to another is not linear and it is exponential. The
potential drop in the diffused layer is given as
Ψd = potential at a distance d into the solution.
Ψ0 = potential at d = 0 that at a electrode surface.
κ–1 = reciprocal of the thickness of diffused double layer
▪ Success of Guoy-Chapmann model
• The properties of the double layer change with electrolyte concentration and
temperature. Guoy and Chapmann made an attempt to relate the charge density (σ) in
the double layer to the solution composition.
• It gives better explanation of electrokinetic phenomenon than Helmholtz-Perrin model.
It is useful in understanding the stability of colloids, and electrodics (electrode kinitics).
 Stern theory (or) Stern model of double layer
▪ This theory combines the essentials
of both Helmholtz-Perrin and
Guoy-Chapmann theories
▪ According to this theory, the
double layer has two layers. One
layer is fixed on the electrode and
the oppositely charged layer
consists of two parts
▪ One part which remains almost
fixed to the solid surface
(Helmholtz view). This is called
stern layer.
▪ Beyond that plane the ions are
dispersed as in the Gouy-Chapman Fixed layer Diffused double layer
model Helmholtz view Guoy-Chapmann model
 Basic assumptions in Stern model

▪ Under all conditions the interface as a whole should be electrically neutral.

QM = –QS = –(QH + QG)
QM = the net charge density on the metal side
QS = the net charge density on the solution side
QH = Charge on electrode and QG = Charge of diffuced layer
 Electrokinetic potential or zeta potential (ζ)
▪ Whenever charges are separated potential
drop results Stern model suggest that there
should be two potential drops.
▪ Potential fall between the outer limit of the
fixed part of the double layer and the interior
of the bulk of the solution.
▪ That is, between the fixed part and the
diffused mobile part of the system.
▪ It is known as electrokinetic potential or zeta
potential (ζ)
▪ In the Hemholtz region, theret is a shape and
linear change in potential. In the diffused
region, there is a gradual exponential change
in the potential.
 Success of Stern model
▪ The capacity values calculated on the basis of Stern model agrees well with experimental
value
▪ It also shows that the capacity of interface depends on the electrode potential and on the
concentration of electrolyte solution.
▪ According to Stern model, the total capacity of double layer (C) is composed of the
capacitance of the Helmholtz region [CH] and the capacity of Guoy-Chapmann model [CGC]
of the double layer in series

▪ In dilute solution: the double layer is essentially all diffused ⇒ C ≈ CGC

▪ At high concentrations: the double layer is essentially all fixed ⇒ C ≈ CH
▪ Stern theory was able to account for the change in sign of the zeta potential that takes
place if capillary active substances are present in the solution.
 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
Theoretical capacity
Qtheoretical = (nF)

(3600*Mw) mAh g-1

Theoretical capacity of

Li-ion battery
Li-air battery
Zn-air battery
Mg-air battery
Li-S battery
 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.
▪ The technology of Li-ion
batteries is based on the
ability of Li+ ions to be
inserted into and removed
from certain layered solids.
▪ The anode is made of
graphite, which contains
layers of sp2 bonded carbon
atoms.
▪ The cathode is made of a
transition metal oxide that
also has a layered structure.
▪ The two electrodes are
separated by an electrolyte,
which functions like a salt
bridge by allowing Li+ ions to
pass through it.
Charging Reaction and Discharging
 Charging Reaction and Discharging
Charging Reaction: Disharging Reaction:
▪ When the cell is being charged, cobalt ▪ Li+ ions move out of the anode and
ions are oxidized and release electrons migrate through the electrolyte
▪ Simultaneously Li+ ions migrate out of where they enter the spaces between
LiCoO2 and into the graphite. the cobalt oxide layers
▪ Electrons flow from the positive ▪ Simultaneously electrons flow through
electrode to the negative electrode. the external circuit
▪ The electrons and Li+ ions combine at ▪ Electrons reduce cobalt at ions at the
the negative electrode positive electrode to regenerate LiCoO2

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 Cellphones, 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-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
▪ 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: Under overheated Dimethyl carbonate decompose to form CO2
which causes pressure build up in battery, resulting in a dangerous explosion
 Lithium polymer (Poly-Carbon Monofluoride) batteries
▪ PCM cells have an output of 2.8 V and moderately high energy density
▪ Commercial Li/CFx battery:
• Cathode: Composite of CFx, (x = 0.5–1)
conductive additive and a polymeric binder,
• Anode: Lithium
• Polypropylene separator and a non-aqueous
electrolyte (such as LiBF4 in γ-butyrolactone)
▪ (Dis)charge reaction:
CFx + xLi + xS → C(Li+SF-)x
C(Li+SF-)x → C + xLiF + xS
▪ Advantages: high specific energy and energy
density, very low self-discharge, wide operating
temperature range and abuse tolerance
 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.
 How do supercapacitors compare to 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.
 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
Schematic representation of a unit cell
 Nernst Equation of Electrochemistry
∆G is Gibbs free energy
∆G = -nFE0
n is no. of electron
F is Faraday Constant
E0 = -∆G/(nF) E0 Standard electrode potential
Proton Exchange Membrane (PEM)
Water Electrolyzer
e e
- - Anode
Cathode Anode 2H2O O2(g) + 4H+ + 4e- ∆GH2O = -237.13 kJ.mol-1

-
4e
+
4H+ H H+ 2H2O Cathode
4e- + 4H+ 2H2
+ O2 -
+ 4e
2H2 H H

+ Total E0 = E0 (anodic) - E0 (cathodic)

4H
E0 = +1.23 – (0)
E0 = +1.23 V

4
 Nernst Equation of Electrochemistry
∆G is Gibbs free energy
∆G = -nFE0
n is no. of electron
F is Faraday Constant
E0 = -∆G/(nF) E0 Standard electrode potential

Proton Exchange Membrane (PEM)

Water Electrolyzer
Anode
e e 2H2O O2(g) + 4H+ + 4e- ∆GH2O = -237.13 kJ.mol-1
- -
Cathode Anode E0 = - (-237.13)/nF = +1.228 V
Cathode
- 4e- + 4H+ 2H2 E0 = -0/nF = 0 V
4e
+
4H+ H H+ 2H2O

+ O2 -
+ 4e
2H2 H H Total E0 = E0 (anodic) - E0 (cathodic)
E0 = +1.23 – (0)
+ E0 = +1.23 V
4H

4
 Nernst Equation of Electrochemistry
Alkaline Electrolyte Membrane (AEM)
Water Electrolyzer
Anode
e- -
e 4OH- 2H2O + O2(g) + 4e-
∆GOH- = -157.30 kJ.mol-1 and

Cathode Anode

Cathode ∆GH2O = -237.13 kJ.mol-

4e- + 4H2O 4OH + 2H2
+
4e- 2H2O
- - -
OH OH 4OH
O2
- - 4e-
2H2 OH OH
- 2H2O
4OH
Total E0 = E0 (anodic) - E0 (cathodic)

E0 = +0.40 – (-0.8284)
E0 = +1.23 V
 Nernst Equation is used to solve the real assembly

 To design the new energy devices

5
 Nernst Equation of Electrochemistry
Alkaline Electrolyte Membrane (AEM)
Water Electrolyzer
e - -
e Anode
4OH- 2H2O + O2(g) + 4e- ∆GH2O = -237.13 kJ.mol-1
Cathode Anode
∆GOH- = -157.30 kJ.mol-1

4e- 2H2O E0 = - (- (4*-157.30) –(2*-237.13)/nF

- - - = +0.4000073 V
OH OH 4OH
O2 Cathode
- - 4e-
2H2 OH OH 4e- + 4H2O 4OH+ + 2H2
- 2H2O
4OH E0 = - ((4*-237.13)- (4*-157.30)/nF
= -0.8284 V
Total E0 = E0 (anodic) - E0 (cathodic)

E0 = +0.40 – (-0.8284)
E0 = +1.23 V
 Nernst Equation is used to solve the real assembly

 To design the new energy devices

5
 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
 Alkaline fuel cells (AFCs)
▪ Alkaline fuel cells consume hydrogen and pure oxygen producing potable water, heat,
and electricity.
▪ Structure:
• Anode and cathode: inert and porous graphite electrode impregnated with finely
divided platinum catalyst or alloy of Pd, Ag and Ni serves the purpose if hydrogen is
the fuel.
• Hydrogen (through anode) and oxygen (through cathode) gases are bubbled through
the respective compartments.
• Electrolyte: 25% KOH hot solution (alkaline).
• Hydroxyl ions (OH-) migrate from the cathode to the anode.
• At the anode, hydrogen gas reacts with the OH- ions to produce water and release
electrons.
• Released electrons supply electrical power to an external circuit then return to the
cathode where electrons react with oxygen and water to produce more hydroxyl ions
 Chemistry
▪ H2 gas and pure O2 gas are bubbled through the anode and cathode respectively, and the
fuel cell produces power through a red-ox reaction between H 2 and O2

▪ At anode:
2 H2 (g) + 4 OH- (aq) → 4 H2O (I) + 4 e-
EAnode˚= -0.83 V
▪ At cathode:
O2 (g) + 2 H2O (I) + 4 e- → OH- (aq)
ECathode˚= 0.40 V
▪ Net reaction:
O2 (g) + 2 H2 (g) → 2 H2O (I)
ECell˚= 1.23 V
Acid fuel cells (AFCs)
 Chemistry
▪ Sulphuric acid fuel cell.
▪ Phosphoric acid fuel cell (PAFC)
▪ 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

The nominal voltage generated by a single cell is typically rather small (< 1 volt),
▪ 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.
• The by-products are environmentally acceptable.
• Maintenance cost is low for these fuels.
• 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.
▪ Application:
• 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.

▪ Limitations:
• The life time of fuel cells is not accurately known
• It cannot store electricity
• Electrodes are expensive ad short lived.
• Storage and handling of H2 gas is dangerous because it is inflammable
 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
▪ Advanced PEMFC:
• A variant of the PEMFC which operates at elevated temperatures is known as
the high temperature PEMFC (HT PEMFC).
• By changing the electrolyte from being water-based to a mineral acid-based
system, these can operate up to 200 °C.
• This overcomes some of the current limitations with regard to fuel purity
• Electrolyte in HT-PEM is phosphoric acid.
• Membrane is polybenzimidazole (PBI) or pyridine based
 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 also 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
 Methods of Harvesting Sunlight
▪ Photosynthesis
▪ Traditionally, solar energy is used for
• Drying of clothes
• Food grains
• Preservation of food
• Salt – sea water
• Solar devices
▪ Active and Passive solar heating systems for houses
▪ Solar heating systems like solar cooker, solar water heater, solar furnace, Solar Thermal
Power Plant
▪ Solar cells or photovoltaic cells for electricity generation
▪ Last two points utilizes solar energy conversion devices
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 of
▪ 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 + CO 2

▪ 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)
▪ 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 “thin film”, easily deposited on a wide range of surface types
 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.
p-n junction
Photovoltaic (PV) Scheme
 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
▪ 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.
 Dye-Sensitized Solar Cell (DSSC)
▪ These are based on a semiconductor formed between a photo-sensitized anode
and an electrolyte, a photoelectrochemical system

▪ These are also known as Grätzel Cells;

named after the Swiss chemist Michael
Grätzel
▪ The DSSC device consists of 4 components:
▪ Semiconducting electrode or working
electrode
▪ Dye-sensitizer
▪ Redox mediator or electrolyte
▪ Counter electrode
Prof. Michael Gratzel
Construction and Working of DSSCs
▪ 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 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
Photosensitizer or Dye
Metal free Dyes
Naturally Occurring Dyes
▪ 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 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)
▪ Construction:
• Two transparent glass plates are perforated on one side with a transparent
thin layer of a conducting material.
• Onto the conducting sides, one plate is coated with graphite and the other
plate is coated with titanium dioxide (TiO2).
• A dye is then adsorbed onto the TiO2 layer by immersing the plate into a dye
solution of 10-4 M in alcohol for 10 min. (approx.)
• The plates are then carefully sandwiched together and secured using a paper
clip.
• To complete the cell a drop of iodide electrolyte is added between the plates.
• Figure shows a Grätzel cell prepared from hibiscus tea.
• The upper plate is the TiO2 plate, dyed with hibiscus tea and the lower plate
is coated with graphite.
Working Principle
 Working Principle
The working principle of DSSC iInvolves 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 nanoporous 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)

▪ These injected electrons are transported between TiO2 nanoparticles and
diffuse towards conducting glass or substrate
▪ Through the external circuit, electrons reach at the counter electrode or the
cathode
▪ The electrons at the counter electrode gets reduced I3− to I−
▪ The regeneration of the ground state of the dye takes place due to the
acceptance of electrons from I− ion redox mediator
▪ In this regeneration process of the dye I− gets oxidized to I3−
▪ Again, the oxidized mediator (I3−) diffuses towards the counter electrode and
reduces to I− ion

I 3− + 2 e − → 3 I −
3 I− + Dye*+ → Dye + I3−
Advantages and disadvantages of DSSC
 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.