1.

6 BATTERY TECHNOLOGY
1.6.1 Introduction
Can you imagine a world without batteries? The clock on your wall requires a battery for it to
work. The watch on your wrist goes on a battery. The motor vehicle needs a battery for it to
start and take you to your destination. Battery is the backbone of UPS to run your computer
without interruption. After a days work, if you pick-up the remote control of the television, it
is again the battery that helps you to change channels of the T.V. Cameras, laptop computers,
cellular phones, key chain laser, heart pacemaker and children toys – they all require batteries.
Batteries are used for so many different purposes and different applications require batteries
with different properties. The battery required to start a car must be capable of delivering a
large electrical current for a short period of time. The battery that powers a cardiac pacemaker
must be small, rugged, leak proof, compact and capable of delivering a steady current for an
extended period of time. In UPS systems, longer and consistent backup is needed. Batteries
for hearing aids must be above all tiny. Batteries for torpedoes and submarines must be stable
during storage and give high power for short times & certainly rechargeable. For a lap-top
computer, a battery in the form of a flexible sheet distributed around the case is much preferred.
Batteries remain an enormous industry with a turnover of billions of pounds worldwide.

1.6.2 Classification of commercial cells

Primary Cells: They are galvanic cells which produce electricity from chemicals that are
sealed into it when it is made. This type of cells cannot be recharged as the cell reaction cannot
be reversed efficiently by recharging. Once the cell reaction has reached equilibrium the cell
must be discarded. No more electricity is generated and we say the battery is ‘dead’. These are
also known as ‘throw – away’ batteries or irreversible batteries.
Eg: Dry cell, Lithium copper sulfide cell
Secondary cells: A secondary cell is rechargeable by passing current through it. In the
charging process, an external source of electricity reverses the spontaneous cell reaction and
restores a non- equilibrium mixture of reactants. After charging, the cell can be used for
supplying current when required, as the reaction sinks toward equilibrium again. Thus as the
secondary cell can be used through a large number of cycles of discharging and charging. Such
cells are also known as rechargeable cells, storage cells, or accumulators.
Eg. Lead-acid batteries, Nickel-cadmium cell, Lithium- ion battery
1.6.2.1 Requirements of Primary Battery:
• Compact, lightweight and must be fabricated from easily available raw materials.

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• Economic and have benign environmental properties
• Should have a high energy density, longer shelf life
• Provide constant voltage and should have a long discharge period
1.6.2.2 Requirements of Secondary Battery
• Long shelf-life in both charged & discharged conditions
• Longer cycle life and design life
• High power to weight ratio
• Short time for a recharge.
• High voltage & high energy density
1.6.2.3 Differences between Primary and Secondary batteries
Primary Batteries Secondary Batteries
1.6.3 1.Cell reaction is irreversible Cell reaction is reversible
2. They must be discarded after its They may be recharged a number of
active elements have been consumed times from an external d.c. source
during its useful life
3. Have a relatively short shelf life Have a very long shelf life
4. Function only as galvanic cells Function as galvanic cells during
discharge as & as electrolytic cells
during the charging process.
5. They cannot be used as energy They can be used as energy storage
storage devices devices (e.g. solar/ thermal energy
converted to electrical energy)
6. They cannot be recharged They can be recharged.
e.g. Dry cell, Li-MnO2 battery e.g. Lead acid battery, Ni-cd battery
Lithium ion cells
Lithium metal cannot be used safely in secondary batteries. Hence, various lithium compounds
have been made, which are used in rechargeable batteries, commonly known as Lithium –Ion
Cells. In these type of batteries, a lithiated metal oxide such as LiCoO2, LiV2O5, LiMn2O4 etc
is inserted into the cathode which consists of a layered graphite crystal. The electrolyte is
normally LiPF6, but LiBF4 can also be used as LiPF6 is not corrosion resistant.
Construction:
The anode is a lithium-carbide intercalate (LixC6). The cathode is a transition metal oxide MO2
of variable oxidation state (MnO2, CoO2, NiO2) which can intercalate lithium usually cobalt
dioxide, CoO2 is used. The electrolyte is usually inert polar dry ether or carbonate (diethyl

2
carbonate or propylene carbonate), in which a conductivity salt such as LiPF6 or LiBF4 is
dissolved.

Figure 1.6.5 Schematic diagram of Rechargeable lithium ion battery

Working: Graphite has a layered structure and its electrochemically reduced in an aprotic
organic electrolyte containing lithium salts and lithium in interclated (or doped) between the
layers of graphite to form Lithium-Graphite interclated compound (GIC). Li-GIC undergoes
oxidation leaving an electron.
At anode:
⚫ LixC6 xLi+(solv) + 6C(s) + xe-………………………….(1)
When a negative electrode is discharged, lithium is deinterclated (undoped) from lithiated
graphite and lithium ions dissolve into the electrolyte. The lithium content in the LiCoO2
electrode reversibly changes during charge and discharge as indicated in the following
equation:
At cathode:
⚫ CoO2(s) + xLi+(solv) + xe- LixCoO2(s)……………….(2)
Net cell reaction:
LixC6(s) + CoO2 Discharge LixCoO2(s) + 6C………………….(3)
Charge
Explanations: It is called as a lithium ion battery to emphasize that it contains no lithium metal.
Both the electrodes are intercalation compounds. The electrode on the left serves as the anode
when the cell discharges. It is a special intercalation compound consisting of a graphite host
into which lithium ions have been electrochemically inserted between the carbon atom layers.
The lithiated graphite is written as LixC6. During the discharge, the lithium ions are extracted
by the half-reaction (1). The electrode that serves as cathode during discharge is normally

3
cobalt dioxide. The reduction half reaction is cathode during discharge is normally cobalt
dioxide. The reduction half reaction shown in equation (2), where cobalt undergoes reduction
from IV to III oxidation state. The overall reaction is shown in equation (3). During discharge
the Li+ ions spontaneously migrate from the lithium graphite anode to the CoO2 cathode
enabling current to flow through the external circuit. When charged, cobalt ions are oxidized
and lithium ions migrate into the graphite, when discharging the battery delivers energy to the
external load and when charging it receives energy from a DC power source. The electrode that
acts as an anode, during discharging becomes a cathode when its charging.
Applications:
• Lithium-ion batteries are most commonly used in applications where one or more of
the advantages (size, weight or energy) outweigh the additional cost, such as mobile
telephones and mobile computing devices.
• Lithium-ion-polymer batteries are used when the battery design matters in a particular
application as different designs are possible (Cylindrical, jelly-roll design, flat
rectangular).
• It is used in current-generation laptops, cellular phones, video-recorders.
• It is also used in portable CD players, televisions and implantable medical devices.
Advantages:
➢ Lithium-ion batteries were designed to overcome the safety problems associated with
the highly reactive properties of Lithium metal.
➢ Long cycle life (400-1200 cycles).
➢ They are smaller, lighter and provide greater energy density than either nickel-cadmium
or nickel-metal-hydride batteries
➢ They can be operated in a wide temperature range and can be recharged before they are
fully charged.
➢ Typically designed to be recharged in the device rather than in an external charger.
➢ The average voltage of a Li-ion battery is equivalent to three Ni-Cd cells.
Disadvantages:
➢ Poor charge retention.
➢ The self-discharge rate is about 10% per month.
➢ It prices are high compared to other types of cells commonly used.
1.7 Fuel cells

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A fuel cell is a galvanic cell of a special type in which chemical energy contained in a fuel –
oxidant system is converted directly into electrical energy in a continuous electrochemical
process. It is an energy conversion device or electricity producer. The fuel cell has two
electrodes and an electrolyte like a primary cell. The reactants (i.e. fuel + oxidant) are
constantly supplied from outside and the products are removed at the same rate as they are
formed.
Cell: Fuel/ electrode/electrolyte/electrode/oxidant.
Anode: Fuel + oxygen ----------->Oxidation products+ ne-
Cathode: Oxidant + ne- ---------->Reduction products
A fuel cell consists of fuel, electrodes, electrolyte, & oxidant. Fuel undergoes oxidation at the
anode and oxidant gets reduced at the cathode. The cell can produce current as long as the
reactants are supplied. Most fuel cells produce low voltages, commonly less than one volt, so
a number of them are connected in series in “fuel batteries.”

Figure 1.7 Fuel cell

Eg:- H2-O2 fuel cell, CH3OH-O2 fuel cell, Solid-oxide fuel cell, Molten carbonate fuel cell
1.7.1 Advantages of fuel cells
• High fuel to electricity conversion efficiency of 70-75 % while a thermal power plant
converts 35-40% chemical energy of coal into electrical energy.
• Fuel cell products do not cause pollution problems such as noise pollution, chemical
pollution and thermal pollution normally associated with conversional power plants.
• Fuel cell power plants can be located near the point of use electricity such as on an
urban location, rather than at a remote place. So transmission and distribution lose
(~30%) could be avoided.
• A fuel cell will produce a steady electric current as long as fresh reactants are available.

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1.7.2 Classification of fuel cells
1. Fuel cell type Electrolyte used
2. Polymer electrolyte Polymer membrane
3. Direct methanol Polymer membrane
4. Alkaline Potassium hydroxide
5. Phosphoric acid Phosphoric acid
6. Molten carbonate Lithium/potassium carbonate
7. Solid oxide Yittria stabilized zirconia

1.7.3 Alkaline fuel cell (AFC)

Construction: Both electrodes are made up of porous carbon impregnated with finally- divided
platinum. Potassium hydroxide is used as electrolyte is placed in the central compartment. The
hydrogen gas is continuously supplied at the anode and pure oxygen gas is continuously
supplied at the cathode form an external reservoir. The cell operates at about 80 oC and the
normal voltage is 1.10 V. At the anode, hydrogen is oxidized to the H+ ions, which are
neutralized by the OH- ions of the electrolyte, forming water and electrons are released. At the
cathode, oxygen and water take electrons to form hydroxide ions. The overall reaction is
equivalent to the combustion of hydrogen. The only product discharge by the cell is water
vapor that escapes through the exhaust point. Note that the gases H2 and O2 diffuse into the
electrode pores and so does the electrolyte solution.

Figure 1.7.3 Alkaline Fuel Cell

Working:

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At Anode:
• H2(g) + 2OH-(aq) 2H2O(l) + 2e-
At Cathode:
1
• O2(g) + H2O(l) + 2e- 2OH-(aq)
2
1
Overall: H2+ O2 H2O(l)
2
Advantages: Desirable attributes of the AFC include its excellent performance on hydrogen
(H2) and oxygen (O2) compared to other candidate fuel cells due to its active O2 electrode
kinetics and its flexibility to use a wide range of electro-catalysts.
Disadvantages:
• The sensitivity of the electrolyte to CO2 requires the use of highly pure oxidant and
fuel.
• As a consequence, the use of a reformer would require a highly effective CO and CO2
removal system.
• If ambient air is used as the oxidant, the CO2 in the air must be removed. While this is
technically not challenging, it has a significant impact on the size and cost of the
system.
Applications: AFC is widely used in US space programs to produce electrical energy and water
on board spacecraft.
1.7.4 Proton exchange membrane fuel cell (PEMFC)

Polymer electrolyte membrane fuel cells – also called proton exchange membrane fuel cells –
deliver high power density and offer the advantages of low weight and volume, compared to
other fuel cells. PEM fuel cells use a solid polymer as an electrolyte and porous carbon
electrodes containing a platinum catalyst. They need only hydrogen, oxygen from the air, and
water to operate and do not require corrosive fluids like some fuel cells. Polymer electrolyte
membrane fuel cells operate at relatively low temperatures, around 80 oC (176 oF).
Low temperature operation allows them to start quickly (less warm-up time) and results in less

wear on system components, resulting in better durability. However, it requires that a noble-

metal catalyst (typically platinum) be used to separate the hydrogen’s electrons and protons,

adding to system cost. The platinum catalyst is also extremely sensitive to CO poisoning,

making it necessary to employ an additional reaction to reduce CO in the fuel gas if the

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hydrogen is derived from an alcohol or hydrocarbon fuel. This also adds cost. Developers are

currently exploring Pt/Ru catalysts that are more resistant to CO.

Role of Proton conducting membranes:

• The membrane function in two ways:

i) It acts as the electrolyte which provides ionic communication between the anode
and the cathode
ii) it serves as the separator for the two-reactant gases.
• Optimized proton and water transport properties of the membrane and proper water
management are crucial for efficient fuel cell operation.
• Dehydration of the membrane reduces the proton conductivity and excess of water can lead
to the flooding of the electrolyte. Both conditions result in poor performance.
• The absence of solution-phase electrolyte in PEF fuel cells, compared to alkaline and
phosphoric acid fuel cells greatly reduces the complexity of the fuel and oxidant flow
controls.
• Polymeric electrolyte is carbon dioxide tolerant.
• The most important breakthrough came with the development of perflourinated membrane
by DuPont. From 1966, the membrane requirements were best met by nafion family of
perfluorinated ionomer membranes. Lifetimes over 60,000 hrs have been achieved at
353 K. Their general formula is
F F F F F F F F F

C C C C C C C C C

F F F F O F F F F

F C F

F C F

F C F

F C F

O=S=O
-
O
+
H

Construction:

Electrolyte:-Ion exchange polymeric membranes. This is an excellent insulator, but an

excellent conductor of H+ ions. The material used, consists of a fluorocarbon polymer
backbone, similar to Teflon, to which sulphonic acid groups are fixed to the polymer and cannot
leak out, but the protons of these groups are free to migrate through the membrane.

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Electrodes:-Typical gas diffusion electrodes, made up of porous C impregnated with Pt
catalyst. Noble metal treated carbon fiber paper/cloth which is directly bonded to the polymer
membrane at an elevated temperature and pressure (The catalytic electrode/membrane
configuration is referred to as membrane electrodes assemble, MEA).
Fuel:- Hydrogen
Oxidant:- Air
Catalyst:-Platinum
Interconnect:- Carbon or metal
Operating temperature:- 40 – 80 oC.
Charge-carrier:-H+
-

Fig.1.7.5.1 schematic of a typical PEMFC electrode, which displays three layers

(i) A Teflonized substrate (typically, carbon cloth)
(ii) A diffusion layer, generally formed by carbon particles of about 0.1 μm size with Teflon.
(iii) An active layer, where Pt catalyst grains are supported on carbon particles (Pt loading is
usually 0.4 mg/cm2or less) with or without Teflon.
Cell reactions and Function of PEMFC:
PEM fuel cells operate at around 80 oC and practical efficiency of 60 %. Power output is in the
range of 5-200 KW. They are ideal for transportation and portable power. Additional
advantages are their high response, small size and low cost. A polymer electrolyte membrane
fuel cell is unusual in that its electrolyte consists of a layer of solid polymer which allows
protons to be transmitted from one fact to the other. Porous carbon is used as the anode and
cathode of the PEMFC, as shown in Fig. It basically requires H2 and O2 as its inputs, though
the oxidant may also be ambient air, and these gases must be humidified. It operates at a low

9
temperature because of the limitations imposed by the thermal properties of the membrane
itself. The operating temperatures are around 90oC and a Pt catalyst is used.

Fig.1.7.5.2 Proton exchange membrane fuel cell

At anode:
• H2(g) 2H+(aq) + 2e-
At cathode
1
• O2(g) + 2H+(aq) + 2e- H2O(l)
2
1
Overall reaction: H2(g) + O(g) H2O(l)
2
Applications:
• PEM fuel cells are used primarily for transportation applications and some stationary
applications.
• Due to their fast startup time, low sensitivity to orientation, and favorable power-to-weight
ratio, PEM fuel cells are particularly suitable for use in passenger vehicles, such as cars and
buses.
Advantages:
• The PEMFC has a solid electrolyte which provides excellent resistance to gas
crossover.
• The PEMFCs low operating temperature allows rapid start-up and, with the absence of
corrosive cell constituents, the use of the exotic materials required in other fuel cell
types, both in stack construction.
• PEMFCs are capable of high current densities of over 2 kW/I and 2 W/cm2.
Disadvantages:

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 • The low and narrow operating temperature range makes thermal management difficult,
especially at very high current densities, and makes it difficult to use the rejected heat
for cogeneration.
• Optimized proton and water transport properties of the membrane and proper water
management are crucial for efficient fuel cell operation. Dehydration of the membrane
reduces the proton conductivity and excess water can lead to the flooding of the
electrolyte. Both the conditions lead to poor performance.
• Perflourinated membranes have a high cost.
• PEMFCs are quite sensitive to poisoning by trace levels of contaminants including CO,
sulfur species and ammonia.
1.7.6 Differences between the fuel cell and galvanic cell:
Sl.No Fuel Cell Galvanic Cell
1 They do not store chemical energy They store chemical energy
2 Reactants are fed from outside the cell The reactants from an integral part of its
continuously construction.
3 Need expensive noble metal catalysts These special conditions are not required
& an optimum to an operative for their
efficient functioning.
4 Do not get discharged and no need of Get-discharged when stored – up energy is
charging exhausted.
5 Such cells never become dead as long Limited life span in use
as fresh reactants are available
6 Useful for long-term electricity Useful as portable power services.
generation.
7 Reaction products must be No such problem
continuously removed
8 No pollutants are generated Pollutants are generated after their useful
(significant environmental benefits) life
9 Produce power from fuels They cannot generate electricity from fuels
10 Significantly higher power densities Lower power density

1.8 Metal finishing

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1.8.1 Introduction

Metal objects such as car components, kitchen utensils, juice cans, window frames, railings
and so on which we see in everyday life will have undergone a surface modification, referred
to as finishing. It covers a wide range of processes carried out to modify the surface properties
of a metal. The process involves deposition of a layer of another metal or a polymer,
conversion of a surface layer of atoms into oxide film or any other inorganic compound film
or any process which can finally improve the surface characteristics. Metal finishing is done
by electroplating, electroless plating, grinding wheels and honing, lapping and burnishing tools
to obtain a smooth surface of a component with desired characteristics. Metal finishing is a
process of electro deposition of an adherent metallic film of uniform thickness on the surface
of the substrate for the purpose of modifying its surface properties.
The metal finishing techniques were originally introduced in the industry for improving the
physical appearance of the metal objects by imbibing a decorative appeal. Since then a wide
range of technological developments in the field was taken place for imparting additional
desirable surface properties to the material other than their intrinsic properties to enhance the
utility of the metal. Some of them are
• Improving resistance to corrosion
• Enhancing resistance to chemical attack, abrasion and wear
• Imparting thermal resistance and resistance to impact
• Improving thermal and electrical properties
• Increasing hardness, thermal and optical reflectivity to the surface
• Making the surface resistant for moisture attack
1.8.2 Electroplating
The techniques of metal finishing include electroplating of metals and alloys and Electroless
plating of a modified surface. Electroplating is the process by which coating metal is deposited
on the base metal by passing a direct current through an electrolytic solution, containing the
soluble salt of the coating metal. It is primarily used for depositing a layer of material to bestow
a desired property (e.g., abrasion and wear resistance, corrosion protection and aesthetic
qualities) to a surface that otherwise lacks that property and sometimes to build up thickness
on undersized parts. The common metals used for coating purpose are Zn, Cu, Ni, Cr, Ag, Au
and Pt.
1.8.3 Theory of electroplating

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Electroplating is the process of coating a metal on a substrate made up of another metal, alloy
or non-metal by the process of electrolysis. The process used in electroplating is called
electrodeposition and the principle is electrolysis. The electroplating device is an electrolytic
cell in which two electrodes (anode and cathode) are dipped in an electrolytic solution. The
part to be plated is the cathode of the circuit. In one technique, the anode is made of the metal
to be plated. Both components are immersed in a solution called an electrolyte containing one
or more dissolved meal salts as well as other ions that permit the flow of electricity. A rectifier
supplies a direct current to the anode, oxidizing the metal atoms that compromise it and
allowing them to dissolve in the solution. At the cathode, the dissolved metal ions in the
electrolyte solution are reduced at the interface between the solution and the cathode, such that
they ‘plate out’ on to the cathode. The rate at which the anode is dissolved is equal to the rate
at which the cathode is plated, ie equal to the current flowing through the circuit. In this
manner, the ions in the electrolyte bath are continuously replenished by the anode. Other
electroplating processes may use an inert anode such as lead or graphite. In these techniques,
ions of the metal to be plated must be periodically replenished to maintain proper coating metal
ion concentration in the bath. The device used for electroplating is an electrolytic cell in the
form of a tank having two electrodes immersed in the electrolyte solution. The schematic
representation of various components of the electroplating unit is shown in Fig. 1.8.3.

Fig. 1.8.3 Schematic of the electroplating bath

Essential components include:
• An electroplating bath containing a conducting salt and the metal to be plated in a soluble
form as well as a buffer and additives.
• The article to be plated - electronically conducting cathode.

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• The electronically conducting anode, the coating metal itself, or an inert material of good
electrical conductance like graphite.
• An inert vessel to contain the above mentioned materials made up of either rubber lined
steel, concrete or wood.
Suppose the anode is made of coating metal itself. During electrolysis, the concentration of the
electrolytic bath remains unaltered, since the metal ions deposited from the bath are replenished
continuously by the reaction of free anions with the anode metal. As an example, if the CuSO4
solution is used as an electrolyte, it ionizes as
CuSO4 → Cu2+ + SO42−
On passing current, Cu2+ ions go to the cathode and get deposited there.
• Cu2+ + 2e − → Cu
The free SO42- ions migrate to the copper anode and dissolve an equivalent amount of copper
to form sulfate.
• Cu + SO42- → CuSO4 + 2e
Thus there is a continuous replenishment of electrolytic salt during electrolysis. If however, the
anode is made of some inert material like graphite, then electrolytic salt is added continuously
in order to maintain proper coating metal ion concentration in the bath. Moreover the process
of electroplating goes on nonstop, since the anode is not consumed and its replacement is not
required. The process involves the passage of current and electrolysis of conducting media.
Three important factors governing the electroplating process include decomposition potential
(ED), polarization and overvoltage.
1.8.3.1 Decomposition Potential (ED):
When an electric current is passed through the electrolyte solution the electrolysis starts and
the products formed, gather around the electrodes. Concentration in the vicinity of the
electrodes changes and a back emf sets in. e.g., in the electrolysis of water, if a small voltage
(~ 0.75V) is applied between two platinum electrodes immersed in the 1M sulphuric acid
solution, the electrolysis starts, proceeds to some extent and then decreases rapidly finally to
stop. The reason for this observation is the initial passage of current causing release of a small
amount of hydrogen and oxygen at the cathode and anode respectively. The gases are adsorbed
at the surface of electrodes and the inactive platinum electrode is converted into active gas
electrodes. This produces a back emf of the polarization current, which resists the emf of the
battery or applied voltage. At potential below 1.7V the back emf counterbalance the effect of
applied emf and the process of electrolysis is not sustained. If the applied voltage is slowly

14
increased, there is a slight increase in the current until the applied voltage just exceeds the back
emf (1.7 V), the current suddenly increases appreciably at that point. Thus, the minimum
external potential or voltage, at which the electrolysis current begins to increase appreciably
and continuous electrolysis sets in is known as decomposition potential of the electrolyte. It is
equal to back emf.
Measurement of decomposition potential (ED):
The schematic diagram for the determination of decomposition potential is shown in
Fig.1.8.3.1a The electrolytic cell consists of two platinum electrodes (E1 and E2) dipped in the
electrolytic solution. The applied voltage (V) is measured at different resistance and the
corresponding current is measured with the help of milliammeter (M).

Fig. 1.8.3.1a Setup for measurement of decomposition potential

A series of readings for current passing through the electrolyte cell at corresponding applied
voltage is recorded and a graph is plotted to measure the electrode potential. A graph between
applied emf and the current density is shown in the following Fig.1.8.3.1b

Fig. 1.8.3.1b A graph of external voltage applied vs current density

The linear portions of the graph are extended, until they intersect. Voltage corresponding to
the point of intersection is the ED of the electrolyte.

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Factors influencing decomposition potential:
Decomposition potentials of different electrolytes are different. Even the ED of an electrolyte
is not a constant. It depends upon the following factors;
• Strength of the current flowing through the cell
• Chemical nature of the electrodes
• Physical nature of the electrodes
• Activity of the electrolyte
• Absolute temperature.
Use of decomposition potential values:
• Knowledge of ED value enables the calculation of actual emf which is required for setting
in continuous electrolytic processes, electroplating and electrorefining.
• It helps in predicting the sequence of discharge process to occur.
• Used in the separation of a mixture of metal ions from a solution by electrolysis.
1.8.3.2 Overvoltage
The decomposition potential of an electrolyte is approximately equal to the emf of the galvanic
cell formed due to the discharge of products at the electrodes. The decomposition of an
electrolyte is therefore expected to start as soon as applied potential reaches the value of
reversible emf of the cell. This is true with respect to metal ions. But when products discharged
at the electrodes are gases, then the actual decomposition potential is invariably much higher
than its theoretical reversible electrode potential. The excess voltage is referred to as
overvoltage (η) of the gas. It may occur at both the electrodes.
Overvoltage (η) is the difference between the actual applied emf to bring about continuous
electrolysis and the theoretical emf needed for such electrolysis. For instance, the reversible
potential of oxygen gas with smooth Pt electrode is 1.23 V. But actual gas evolution takes place
at a potential of 1.68 V. The excess 0.45 V is the overvoltage of oxygen on smooth Pt surface.
The following factors influence the overvoltage of an electrolyte;
• Nature of the electrode surface (or material)
• Current density and temperature
• Nature of the electrolyte
Overvoltage is believed to be a surface phenomenon at the electrodes. Of the many steps
involved in gas evolution at electrodes, at least one is rather a slow process and requires energy.
The extra energy is supplied by the applied voltage and this extra energy is related to
overvoltage.

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e.g., electrolysis of water

(i) H+ (aq.) + e- H (fast)

(ii) H + H H2 (slow)
The step (ii) being slow, consumes energy and accounts for overvoltage. Hydrogen
overvoltage is the measure of the tendency of hydrogen to be liberated at the cathode. Higher
the value of overvoltage more difficult is the liberation of hydrogen on that metal.
1.8.3.3 Polarization
Since the electrolysis is a non spontaneous process, the minimum energy required to carry out
such a process is equal to the free energy increase accompanying the change. However, in
irreversible conditions, the potential to be applied for electrolysis is higher than the reversible
emf of the cell. A cell that requires excess voltage over the theoretical is said to be polarized
and the phenomenon is referred to as polarization. Electrolytic processes occur at the electrodes
of the cell. Polarization sets in the cell when the electrode processes become slow and
irreversible. Thus polarization in the cell is due to polarization at the electrodes. Magnitude of
overpotential is directly proportional to the extent of polarization. The observed polarizations
are of two types.
(a) Concentration polarization (b) Kinetic polarization
Concentration polarization:
An electrochemical reaction occurs only at the surface of the two electrodes. Reactant
concentration decreases in the electrolyte adjacent to the electrode surface. The reactant species
are transported to the electrode surface by processes like diffusion, migration and convection
from the bulk of the solution. When the rate of transport is insufficient to match the rate of
electrode reaction, current flowing through the cell drops. A higher potential than the
theoretical value is required to maintain the current at the necessary level. This phenomenon
is called concentration polarization. The steps involved in electrolytic processes are
(i) Diffusion of reactant species towards the electrode and
(ii) Diffusion of product away from the electrode, cause concentration polarization.
Concentration polarization can be eliminated or at least minimized by increasing the
convection, by raising the temperature or mechanical agitation of the solution.
Kinetic or Activation polarization:
Activation polarization is caused when steps
i) Adsorption of the reactant on the electrode
ii) Charge transfer across the metal-solution interface and

17
 iii) Desorption of the product from the electrode become slow and need activation
energy.
A higher potential than the theoretical value is to be applied to maintain current at the necessary
level. It is not possible to eliminate or minimize kinetic polarization by any means. Activation
polarization is normally very low, when metal deposition or metal dissolution is the electrode
process. When the electrode process is a gas (H2 and O2) evolution, kinetic or activation
polarization is usually very high.
Factors influencing polarization:
• Size and nature of the electrode
• Nature of ions accumulated on electrodes
• Electrolytic concentration
• Temperature
• Conductivity of electrolytic solution
• Stirring of electrolytic solution
• Use of depolarizer
Importance of polarization effect:
An impervious or non-porous film, contributes to the increase of polarization at an electrode.
Considerable polarization effect can also be seen where loosely adhering and even porous films
are formed. Such films either formed naturally (during manufacturing) or artificially (by the
application of special coatings or products of corrosion) are important in determining the rate
of corrosion of a metal or an alloy and also for the protection from corrosion.

1.8.4 Applications of electroplating

• Plating for aesthetic appearance:
• Plating for protection
• For electroforming
• Plating on non-metals

1.8.5 Characteristics of a good deposit

▪ The deposit should be bright and lustrous
▪ The deposit should be continuous, uniform, non porous and adhesive
▪ It should be hard and ductile
▪ It should be of fine grained nature

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1.8.6 Factors influencing the nature of the deposit
There are several factors which affect the nature of an electro deposit.
(a) Current density
Higher the current density, more the deposition rate but will enforce the poor adhesion
and loose and brittle plating quality. There is the possibility of a burnt and spongy deposit.
Whereas low current density takes extra time to finish the job and is uneconomical. Therefore,
optimum moderate current densities should be applied.
(b) Metal ion concentration
As the electroplating involves the discharge of free metal ions, the concentration of free metal
ions plays an important role. If the concentration of metal ion is low the crystal size will be
smaller and a fine adherent film may be coated. Thus the ideal situation is low free metal ion
concentration in a concentrated solution of a metal compound which can be attained by addition
of a compound with a common ion or by the formation of complex compound and ions. e.g.,
when copper is deposited from an electroplating bath containing copper sulphate solution,
sulphuric acid is added to increase the concentration of sulphate ion. The concentration of
cupric ions is reduced due to common ion effect.
(c) Temperature:
Generally, the solution to be deposited is used at room temperature. However, warm baths are
used for increasing solubility of electrolyte and current density. The size of the crystals
increases with increasing temperature and renders lower adherence. But on the other hand the
solubility and metal dissociation increase at higher temperature leading to the higher
conductance of the solution. Also, the mobility of ions increases at a higher temperature and
decreases the viscosity of the electrolyte solution so that the cathode film is replenished at a
faster rate. This increases the current density for a given voltage and reduces the tendency
towards treeing. There are disadvantages also of using high temperatures. Since, the
possibility of corrosion of equipment, decomposition of the organic addition agent and
evolution of hydrogen gas at cathode would increase at a higher temperature. So the optimum
range of temperature needs to be selected.
(d) pH of the electrolyte
The pH of the electrolyte solution should be properly maintained. The range of the pH varies
for different types of the plating bath. If pH is more towards the acidic side the nature of the
deposit will be affected adversely as the evolution of hydrogen gas is expected at cathode
thereby forming a burnt deposit. If pH is more towards the basic side the plating is delayed, so
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uneven and thick deposit is obtained. Suitable buffers may be used for maintaining the
appropriate pH.
(e) Presence of additives:
To obtain electroplate with desire qualities and specifications, additional substances called
additives are added in small quantities to the electrolyte bath. These additives have the capacity
to modify the structure, appearance and characteristics of the deposit. The different types of
additives used are
(i) Complexing agents:
(ii) Brighteners:
(iii) Levellers:
(iv)Wetting agents:
(v) Structure modifiers:
(f) Throwing power of the plating bath
Throwing power is defined as the degree of uniformity of metal distribution or evenness of
deposit thickness obtained on a cathode of irregular shape. If the distribution of the deposit is
uniform throughout the surface of the article to be coated, the throwing power is considered
good.
1.8.7 Methods of cleaning the metal surface
It is essential to clean the surface of base metal before the application of the electroplated
coating. The common impurities found on the metal surface are grease, oil, oxide layer and
other extraneous matters. The following methods are employed to clean the metal surfaces.
(iii) Physical (Solvent) cleaning: - Physical cleaning is done with the help of solvents to
make the surface free from oil, grease, superficial dirt, and buffing, polishing and fatty
substances. The commonly used solvents such as chlorinated hydrocarbons, xylene, toluene,
aqueous cleaning agents are used with or without electric current. Solvent cleaning is made
more effective by vapour degreasing. An organic volatile solvent like trichloroethene is heated
and vapours are passed over the metal surface to be cleaned. The vapours condense on the
surface and condensed liquid dissolves and washes away the oil, grease and other organic
matter from the surface. The emulsifying agents are also added to the solvent to remove
organic impurities from the surface of the metal.
(ii) Chemical (Alkali) Cleaning: It is used to remove the minute residue of soil and grease and
for removal of tarnish and oxide film. The commonly used alkali cleaners consist of a number
of alkalies, soap, chelating agents like Na2O3, sodium phosphates, NaOH etc. Alkali cleaning
is made more effective by passing current through a hot alkaline solution, with the article to be
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cleaned constituting the cathode. The evolution of H2 at the cathode and O2 at the anode, metal
helps to dislodge the greasy substance. It is followed by thorough rinsing with water and then
immersing in a very dilute solution of acids to remove traces of alkali after cleaning is
completed.
(iii) Mechanical Cleaning: Involves removal of the oxide layer (tarnish), loose rust and other
inorganic deposits from the surface to obtain better appearance, protection and optimum
effects. This is done by hand cleaning with bristle brush and some abrasives like sand papers,
polishing tools (grinding with grinding stone), scratch rubbing with chisel, knife, scrapers, wire
brush or a abrasive stone or paper and detergent.
(iv) Pickling: The oxides sometimes cannot be removed by simple alkali or mechanical
cleaning. The extraneous fragments like heavy scales of oxides, scratches and strains can be
removed from the surface by dissolving in the acid solution. The acid pickling involves the
removal of such oxides; rust or tarnish by immersing the material (except Al) in acid like dil.
HCl or dil.H2SO4 or dil. HNO3. Pickling of Al is done in alkaline solution, whereas pickling
of Cu, Ni or brass articles are accomplished in a solution of dil. HNO3 or a mixture of dil.
HNO3 and dil. H2SO4. Pickling is usually followed by polishing and buffing.
(v) Electro polishing: - In this method, the metal to be cleaned is made anode in a suitable
solution. During the process, a surface layer of the metal gets dissolved along with the
impurities. It also helps to remove minor surface irregularities. The most commonly used baths
for electro polishing contain sulphuric acid, phosphoric acid, chromic acid, nitric acid etc.
After the process, the metal is thoroughly rinsed with water, dried and used for electroplating.
1.8.8 Electroplating of chromium
Chromium plating is a finishing treatment utilizing the electrodeposition of a thin layer of
chromium on a metal object. This layer can be decorative or corrosion protective to the base
surface. The process of chromium plating includes degreasing to remove heavy soiling, manual
cleaning to remove all residual traces of dirt and surface contamination and various
pretreatments depending on the objectives of the coating. Different etching solutions such as
hydrochloric, hydrofluoric, sulphuric acid and ferric chloride are used. Further, the treated
base material is placed into the chrome plating bath for electroplating of desired thickness.
• Chromium coatings are generally thinner and have micro pores in it. As the thickness of
the coating increases, cracks develop in the coatings. Hence, chromium coatings are always
plated on nickel/copper undercoates. Ni gives protection and chromium gives a decorative
finish.

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• Chromium anodes are not used in electroplating of chromium on account of two
difficulties. These electrodes become passive in acidic medium and they result in a black
deposit.
• Chromium has higher electrode potential and can be easily coated on the iron to protect
from rusting/corrosion
• The anode efficiency is nearly 100 % whereas cathode efficiency is at best around 20 %. It
may be inferred that metal going into the solution is five times of the metal getting
deposited, resulting in building up of excessive chromic acid concentration. This disturbs
the ratio of Cr(III) to Cr(VI) and the conductivity of the bath and dull deposits called burnt
deposits are obtained. To avoid this, inert material is used as anode and chromium
electrolyte in the bath.
There are two types of chromium plating-Decorative coating and hard coating

Table 1.8.8 Comparison of decorative and hard coating of chromium

Decorative coating Hard coating
Bath Chromic acid (250 g) + Chromic acid (250 g) +
composition H2SO4 (2.5 g) + H2SO4 (2.5 g) +
Trivalent chromium (1g) Trivalent chromium (1 g)
Operating 45 – 55 °C 45 – 55 °C
Temperature
Anode Insoluble anodes like Lead – lead : 6%
Pb – Pb : 6% Sb – Pb: 7%
Sb - Pb--7% Sn
Sn
Cathode Article to be coated Article to be coated
Current 145--430 A/ft2 290--580 A/ft2
density
Cathode 10 – 15 17 – 21
efficiency
Applications Decorative applications with Coating of industrial
corrosion resistance finish on components like gauges,
cycles, automobiles, furniture, dies, cutting tools, piston
household fittings, aircraft, rings and hydraulic rams.
surgical and dental
instruments.

Working-
On passing current, Cr3+ ions go to the cathode and get deposited there.
• Cr3+ + 3e − → Cr

1.8.9 Electroless plating

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Electroless plating is a method of depositing a metal film on a substrate surface (conductor or
non-conductor) from metal salt solution using a suitable reducing agent without using electrical
energy. The reaction can be depicted as
Metal ions + Reducing agent Metal + Oxidized product
The method involves the deposition of metals such as Cu, Ag, Ni, Au or Pd on the surface of
the base material by means of a reducing agent. Electroless plating results in a fine grained
metal deposit that has similar finishing as that of traditional electrodeposit finishing. In
industries, such process is used for plating on non-conductors like plastic, electroformed dies,
hard memory disks, printed circuit boards (PCBs) or to obtain an extremely uniform plate. This
technique is also used for the prevention of corrosion.
Process of electroless plating: The process of electroless plating involves the following steps:
(i) Preparation of active surface: This is the most important step and the surface is activated by
any of the following ways.
(a) etching – by acid treatment
(b) electroplating with a thin layer of metal or insulators like plastic surfaces followed by heat
treatment
(c) Alternate treatment with SnCl2 and PdCl2 on the plastic surface
SnCl2 + PdCl2 Pd + SnCl4
Pd is coated on plastic.
(ii) Preparation of plating bath:
(a) Metal to be coated in the form of chloride or sulphate solution
(b) Reducing agents like formaldehyde and sodium hypophosphate for reduction of metal ion
to metal
(c) Complexing agents like EDTA, tartrates, citrates to form metal complexes to prevent excess
deposition
(d) Stabilizers like thiourea, calcium ions to prevent decomposition of the bath and to impart
stability to the solution
(e) Exaltants (accelerators) like succinates, glycinates and fluorides to increase the rate of
plating
(f) Brighteners like thiosulphate to give a lustrous appearance
(g) Buffers like boric acid to maintain the pH
(iii) Reduction step: Active surface is dipped in the bath and deposition is carried out. The
plating is carried out in a series of tanks where the object is immersed to plate the desired metal.
The rate of deposition is controlled by the amount of reducing agent present and the type of
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chelating agent used. The deposition rate is normally 12.5 – 25 µm, although, it has been done
up to 650 µm in thickness.
Advantages of electroless plating
The following are main advantages of electroless plating
• More uniform coating on the surface of object whatever shape it may have. Even the
objects having irregular shapes, holes, recesses, internal surfaces, valves or threaded
parts get uniform deposit since it has better throwing power than electroplating.
• Electrical power and other accessories are not required.
• Coating is harder than regular plating and better wear resistance.
• Deposits have compatible wettability for oils, inherent lubricity and non-galling
characteristics, unlike electrolytic nickel.
• Deposits are much superior to electroplated nickel and hard chrome, as they are less
porous and provide better corrosion protection to steel substrates.
• Electroless plating of Ni on aluminum substrate enhances the solderability together with
providing a non-magnetic under lay in magnetic components. The deposits are less
porous and possess unique characteristic chemical, mechanical and magnetic
properties.
• Additives or levelers are not required in the process nor the complex filtaration method
requirement.
• It is a simple process, so requires simple equipment.
Disadvantages of electroless plating
The main disadvantages of the process are the following;
• Due to speedy chemical renewal, cost of waste treatment is high.
• The frequency of dumping electroless bath is high as it is sensitive to contamination
• Costs per unit weight of the deposited metal are more.
• It needs pure chemicals.
• Chemical reductants are more expensive than electricity.
• Metal salts and reductant used in electroless plating solutions are thermodynamically
not stable.
• Impurities or dust or colloidal matter (even if present in trace amount) promote the
decomposition of bath components.
1.8.9.1 Electroless plating of Copper

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It is an auto-catalytic reaction used to deposit a coating of copper on a substrate without the
use of electrical energy. It is commonly used to plate plastic for decorative purposes and parts
for engineering applications, particularly to render conductivity for electronic and printed
circuit boards.
Reducing agents generally react with the plating bath, resulting in slow, deposition rates and
poor deposit quality. It can be prevented by rejuvenating the bath at regular intervals. The bath
solution undergoes spontaneous decomposition, resulting in an additional waste stream of
copper and etching solution as copper built up on the tanks from the bath solution, must be
stripped with an etchant such as sulphuric acid and hydrogen peroxide.
Electroless plating bath for copper includes;
• Coating solution : CuSO4 soln
• Reducing agent : HCHO
• Buffer: NaOH & Rochelle salt
• Complexing agent: EDTA di sodium salt
• Optimum pH: 11
• Optimum temperature: 25 °C
The reactions involved at two electrodes are
At cathode:
• Cu2+ (aq) + 2e- Cu (S)
At anode:
• 2HCHO + 4OH-(aq.) 2HCOO-(aq.) + 2H2O(l) + H2(g) + 2e-
Overall reaction:
Cu2+(aq.) + 2HCHO + 4OH-(aq.) 2HCOO-(aq.) + 2H2O(l) + H2(g)
Since Cu2+ ions and HCHO are consumed during the redox reaction, these are replenished
periodically. The redox reaction involves consumption of hydroxyl ions and pH of the
solution decreases as the reaction progresses. Hence addition of buffer is essential. Usual
plating rate is 1-5 µmh-1.
Applications of electroless plating:
• Electroless copper plating is widely used for metalizing printed circuit boards (PCBs)
• It is used as a base coating for subsequent conventional electroplating
• It is used for producing through hole connections and for decorative plating on plastics.
When double sided PCBs are fabricated then holes are drilled for making electrical
connections. These holes are plated by electroless plating.

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1.8.10 Comparison of electroplating and electroless plating
Table 1.8.9 Comparison of electroplating and electroless plating
Property Electroplating Electroless plating
Driving force Electric current Autocatalytic redox reaction
Anode reaction
Cathode Article to be plated Article to be plated with a
catalytic surface
Anode Separate anode Article to be plated
Reducing agent Electrons bring about Chemical reagents bring
about reduction reaction
Anode reactant M or H2O R, the reducing agent in
solution
Nature of deposit Pure metal or alloy Usually metal contaminated
with species derived from
the redox reaction
Thickness limit 1 - 100 1 – 100
(µm)
Applicability Applicable to Can be used for conductors
conductors only and non-conductors
Throwing power Less throwing power; More throwing power and
cannot be used for can be used for irregular and
irregular shapes and uneven shaped objects
intricate parts

*****

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