Module 1:

Electrode system
Ion selective electrode:
An Ion selective electrode is a sensor which converts the activity of a specific ion (dissolved in a
solution) into a voltage (potential), which can be measured by voltmeter or pH meter. The voltage is
theoretically dependent on the logarithm of the ion activity, as described by the Nernst Equation,

Here,
E= Electrode potential
E0 = Standard Electrode potential
R= Gas constant 8.314 J/K/mol
T= temperature in Kelvin unit 298k
F= Faraday 96,500 C
n = Number of electrons involved
[Mn+] = Concentration of metal ions

Ion-sensitive glass electrodes used for determination of concentration of Hydrogen, lithium, sodium,
ammonium, and other ions. It is simple to operate and can be used in portable instruments, and therefore
extensively used in chemical, industrial, agricultural and biological laboratories.
Ion selective electrode possesses the ability to respond only to certain specific ions present in a mixture,
thereby developing potential w.r.t that ions and ignoring the other ions totally.
For example: Glass electrode used for the detection of H+ ion

Classification of Ion-selective electrode:

1. Solid-state membrane:
Example: a. Lanthanum trifluoride crystal doped with europium difluoride used for detection of
fluoride ion
b. Pressed pellet of silver sulphide and silver chloride used for the detection of chloride ion
2. Liquid State membrane:
Example: a. Iron phenanthroline complex used for the detection of anions (Nitrate ion)
b. Phosphate diesters and neutral monocyclic crown ethers used for the detection of cations (Calcium
ions)

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3. Glass membrane:
Example: Glass electrode used for the detection of H+ ion
4. Heterogeneous membrane
Example: Inorganic materials such as zeolite or CMS particles are embedded in the polymeric matrix.
This heterogeneous membrane used for the detection of sulphates and phosphates.

Glass electrode
A glass electrode is a type of ion-selective electrode made of a doped glass membrane that is sensitive
to a specific ion. Glass electrode used for the detection of H+ ion. The most common application of ion-
selective glass electrodes is for the measurement of pH. The pH electrode is an example of a glass
electrode that is sensitive to Hydrogen ions.
Glass electrodes play an important part in the instrumentation for chemical analysis and
physicochemical studies.

Construction of Glass electrode

▪ The glass electrode consists of a glass bulb made up of a special type of
glass which has a low melting point and relatively high electrical
conductivity.
▪ This glass membrane is made up of a special glass called corning glass
whose composition is 22% Na2O, 6% CaO and 72% SiO2
▪ The glass bulb is filled with a solution of constant pH (0.1M HCl) and
insert with an Ag-AgCl electrode, which acts as internal reference
electrode and also serves for the external electrical contact.
Glass electrode can be represented as,
Ag| AgCl | 0.1M HCl |Glass membrane
▪ The combination of indicator electrode (Glass electrode) and the Reference electrode (Calomel
electrode) measures the electro motive force (EMF) of the cell.

Working of Glass electrode

Glass membrane is found to be sensitive to hydrogen ion of an acidic solution. The membrane undergoes
ion-exchange reaction; the Na+ ions of glass are exchanged with H+ ions

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When a glass bulb containing 0.1 M HCl solution is immersed in an acidic solution (unknown) of
different concentration, a boundary potential (Eb) is developed across the layers of the glass membrane.
This boundary potential (Eb) arises due to difference in the concentration of H+ ion inside and outside
the glass membrane.
Therefore, Boundary potential Eb = E2 - E1……... (1)

0.0591
𝐸1 = 𝐸 0 + log 𝐶1
𝑛
0.0591
𝐸2 = 𝐸 0 + log 𝐶2
𝑛
Where,

C1 = Concentration of H+ inside the bulb, is a Constant

C2 = Concentration of H+ outside the bulb

Substitute the values of E1 & E2 into eqn (1), we get

0.0591 0.0591
𝐸𝑏 = 𝐸 0 + log 𝐶2 − [𝐸 0 + 𝑙𝑜𝑔 𝐶1 ]
𝑛 𝑛

0.0591 0.0591
𝐸𝑏 = log 𝐶2 − 𝑙𝑜𝑔 𝐶1
𝑛 𝑛
Where, n=1 (n=no of electrons involved in the reaction)

𝐸𝑏 = 0.0591 log 𝐶2 − 0.0591 log 𝐶1

Substitute, -0.0591 log C1= K, a constant and C2 = H+

𝐸𝑏 = 𝐾 + 0.0591 log 𝐶2

𝐸𝑏 = 𝐾 + 0.0591 log [𝐻 + ]

𝑬𝒃 = 𝑲 − 𝟎. 𝟎𝟓𝟗𝟏 𝐩𝐇

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Where theoretically, When C1 = C2; Eb =0,
But even when C1 = C2, a small Potential is developed. The reason for this is,
1) Ag-AgCl electrode dipped inside the bulb is 0.1 M HCl develops a potential and behaves as internal
reference electrode and it is given by EAg-AgCl
2) A small potential develops on the glass membrane which is called as Asymmetric Potential (Easy).
This is due to the difference in the radius of curvature of the glass membrane as a result of difference in
strain on the two surfaces of the membrane, and a mechanical abrasion on the outer surface during use.
These two potentials add to glass electrode potential and is given by,
Where EG is Glass electrode potential 𝑬𝑮 = 𝑬𝒃 + 𝑬𝑨𝒈−𝑨𝒈𝑪𝒍 + 𝑬𝒂𝒔𝒚

Substitute Eb value: 𝑬𝑮 = 𝑲 − 𝟎. 𝟎𝟓𝟗𝟏 𝐩𝐇 + 𝑬𝑨𝒈−𝑨𝒈𝑪𝒍 + 𝑬𝒂𝒔𝒚

𝑬𝑮 = 𝑬𝟎𝑮 − 𝟎. 𝟎𝟓𝟗𝟏 𝐩𝐇

where EG0 is combination of three constant terms,

E0G = K + E Ag/AgCl + Easy

Application‒Determination of pH using glass electrode:

Glass membrane is found to be sensitive to hydrogen ion of an acidic solution. The membrane undergoes
ion-exchange reaction; the Na+ ions of glass are exchanged with H+ ions

When a glass bulb containing 0.1 M HCl solution is immersed in an

acidic solution (unknown) of different concentration, a boundary
potential (Eb) is developed across the layers of the glass membrane.
This boundary potential (Eb) arises due to difference in the
concentration of H+ ion inside and outside the glass membrane.
Therefore, Boundary potential Eb = E2 - E1……... (1)

0.0591
𝐸1 = 𝐸 0 + log 𝐶1
𝑛
0.0591
𝐸2 = 𝐸 0 + log 𝐶2
𝑛

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Where,

C1 = Concentration of H+ inside the bulb, is a Constant

C2 = Concentration of H+ outside the bulb

Substitute the values of E1 & E2 into eqn (1), we get

0.0591 0.0591
𝐸𝑏 = 𝐸 0 + log 𝐶2 − [𝐸 0 + 𝑙𝑜𝑔 𝐶1 ]
𝑛 𝑛

0.0591 0.0591
𝐸𝑏 = log 𝐶2 − 𝑙𝑜𝑔 𝐶1
𝑛 𝑛
Where, n=1 (n=no of electrons involved in the reaction)

𝐸𝑏 = 0.0591 log 𝐶2 − 0.0591 log 𝐶1

Substitute ‒0.0591 log C1= K, a constant and C2 = H+

𝐸𝑏 = 𝐾 + 0.0591 log 𝐶2

Note: 𝐸𝑏 = 𝐾 + 0.0591 log [𝐻 + ]

𝑬𝒃 = 𝑲 − 𝟎. 𝟎𝟓𝟗𝟏 𝐩𝐇

Then glass electrode potential EG is,

𝑬𝑮 = 𝑬𝒃 + 𝑬𝑨𝒈−𝑨𝒈𝑪𝒍 + 𝑬𝒂𝒔𝒚

𝑬𝑮 = 𝑲 − 𝟎. 𝟎𝟓𝟗𝟏 𝐩𝐇 + 𝑬𝑨𝒈−𝑨𝒈𝑪𝒍 + 𝑬𝒂𝒔𝒚

𝑬𝑮 = 𝑬𝟎𝑮 − 𝟎. 𝟎𝟓𝟗𝟏 𝐩𝐇

where EG0 is combination of three constant terms, E0G = K + E Ag/AgCl + Easy

To determine the pH of a given solution, the glass electrode is combined with a reference electrode such
as a calomel electrode through a salt bridge.

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The cell is represented as
Hg|Hg2Cl2|KCl||Solution of unknown pH |glass| 0.1M HCl | AgCl |Ag
Glass electrode and calomel electrode are connected to pH meter determine the emf of the cell (Ecell).
By knowing the 𝑬𝟎𝑮 of the glass and potential of the saturated calomel electrode, the PH of unknown
solution is calculated.

The emf of the cell (Ecell) is given by,

𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒

𝐸𝑐𝑒𝑙𝑙 = 𝐸𝐺 − 𝐸𝐶𝑎𝑙

𝐸𝑐𝑒𝑙𝑙 = 𝐸𝐺0 − 0.0591 𝑝𝐻 − 𝐸𝐶𝑎𝑙

at 298K

Advantages
➢ It has simple construction and easy to operate.
➢ It can be used both in oxidizing and reducing agents.
➢ Only a few drops of the liquid are enough to determine the pH.
➢ It can be used in solution with pH values ranging from 0 to 10. with special type of glass even
up to pH 12 can be calculated.
➢ It is simple to operate, hence extensively used in various laboratories
Limitations

➢ Glass electrode cannot be used in presence of fluoride ions.

➢ It cannot be employed in pure ethyl alcohol, acetic acid and gelatin.
➢ Glass electrode cannot be used when pH of the solution is above 12, as it introduces alkaline
error.

Electrolyte Concentration cells

It is an electrochemical cell in which electrolyte present in both half cells are same but only the
concentration of electrolyte is different. In this type of cell, two same electrodes are dipped in a solution
made of electrolyte, which has different concentration levels. This cell type moves electrodes from the

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higher concentration to the lower concentrated solution to form a balance.

Expression for emf of the electrolyte concentration cell

When a metal (M) electrode is dipped in a solution
containing its own ions [Mn+], then a potential (E) is
developed at the electrode, the value of which varies with
the concentration of the electrolyte. Therefore, according
to the Nernst equation.

➢ Consider two copper rods are dipped into their own ionic solutions of C1 and C2
➢ The electrode with lower electrolyte concentration acts as anode and the one with higher
electrolyte concentration acts as cathode.
➢ The two half-cells are internally connected by salt bridge and externally connected to the
electronic voltmeter.
Consider the following concentration cell represented by
2+ 2+
Cu| Cu (C1)
|| Cu (C2)
| Cu
2+
Where C1 and C2 are molar concentrations of the Cu ions in the two half cells.
By electrochemical conventions, if C2 > C1 then, we have the following reactions,

Anode reaction: Cu(s) → Cu2+(C1) + 2e-

Cathode reaction: Cu2+(C2) + 2e- → Cu (s)
The electrode dipped in dilute solution (C1) acts as anode; while other electrode dipped in concentrated
solution (C2) acts as cathode. Here oxidation take place at anode, hence electrons flow from dilute
solution (C1) to concentrated solution (C2).
Then emf of the concentration will be,

𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒

𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑪𝟐 − 𝐸𝑪1

0.0591 0.0591
𝐸𝑐𝑒𝑙𝑙 = [𝐸 0 + log 𝐶2 ] − [𝐸 0 + 𝑙𝑜𝑔 𝐶1 ]
𝑛 𝑛

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 0.0591 0.0591
𝐸𝑐𝑒𝑙𝑙 = log 𝐶2 − 𝑙𝑜𝑔 𝐶1
𝑛 𝑛
𝟎. 𝟎𝟓𝟗𝟏 𝑪𝟐
𝑬𝒄𝒆𝒍𝒍 = 𝐥𝐨𝐠
𝒏 𝑪𝟏

From the equation, following conclusions may be drawn

[Link] C2 = C1, the concentration cell does not generate electrical energy.
2. Higher the ratio of C2/C1, higher is the cell potential

Numericals on concentration cell

1. A concentration cell is constructed by dipping copper rods in 0.001M and O .1 M CuSO4 solutions.
Calculate the emf of the cell at 298 K.

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2. A concentration cell is constructed by immersing two iron electrodes in 0.01 M and 0.1 FeSO4
solution. Represent the cell and calculate EMF of the cell at 298K

3.

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4.

5. The spontaneous galvanic cell Tin / Tin ion (0.02M) // Tin ion (0.06M) / Tin develops an emf of
0.0141V at 298K. Calculate the valency of Tin.

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6.

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 Energy storage systems
What is Battery…?
The battery is a device which consists two or more units of an electrochemical cell which is connected
in series or parallel. The positive terminal of the battery is known as the cathode whereas the negative
terminal of the battery is known as the anode.
Principle components of a battery are:
1. Anode where oxidation occurs.
2. Cathode where reduction occurs.
3. An electrolyte, which is ionically conducting.
4. A separator to separate anode and cathode compartment
Classification of Batteries
Batteries are classified into three types as follows.
a) Primary batteries
b) Secondary batteries
c) Reserve batteries
a) Primary batteries:
• These are the batteries which serve as a source of energy only as long as the active chemical
species are present in the battery or in the cell.
• The cell reactions are irreversible. These are designed for only single discharge and cannot be
charged again. Example: Zinc carbon battery (Dry Cell battery), Alkaline battery, Aluminium
air battery etc.,
b) Secondary Batteries:
• These batteries are chargeable and can be used again and again. The cell reactions are reversible
and are often called reversible batteries.
• During discharging the cell acts like voltaic cell converting chemical energy into electrical
energy.
• During charging the cell acts like electrolytic cell by converting electric energy into chemical
energy, hence these batteries are called as storage battery.
• Primary cells act only as galvanic cell, whereas, a secondary cell can act both as galvanic cell
and electrolytic cell.
Ex: Lead acid Battery, Ni-Cd battery, Li-ion battery, Ni-metal hydride battery, Na-ion battery

1
c) Reserve Batteries:

• The batteries which can be stored in an active state and made ready for use by activating them
prior to the applications (usage) are called as reserved batteries.
• In this battery, one of the key components is stored separately, and is incorporated into battery
when required. When long storage is required, reserve batteries are often used, since the active
component of the cell is separated until needed, thus reducing self-discharge
• The key components of the batteries such as electrolyte etc., is separated from the battery. And
the battery is stored for a longer time. The electrolyte is filled before its usage.
Example: Mg-AgCl battery. They are activated by adding sea water (Electrolyte). These
batteries have high reliability and long shelf life; hence they find applications in missiles and
submarines.
• Another example is Zinc-air batteries where the cell is sealed until use, the seal is removed to
admit air and activate the cell when needed

The advantages of the reserved batteries are,

[Link] can be stored for a longer period.
2. To prevent corrosion at contact points during storage
3. Self-discharging reactions during storage can be eliminated or avoided.
[Link] can be used whenever they are required.
Ex: Mg – salt water activated batteries, Mg- AgCl & Mg – CuCl battery etc.
Characteristics of a battery
The following battery characteristics must be taken into consideration when designing or selecting a
battery like,

• Voltage,
• Capacity,
• Energy density,
• Electricity Storage density,
• Cycle life
• Shelf life

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Voltage:

The term “voltage” refers to the difference in electrical potential between the positive and negative
terminals of a battery.

The voltage of any battery depends on the emf of the cells which constitute the battery system. The emf
of the cell depends on the free energy in the overall cell reactions as given by Nernst equation.

From the above equation, emf of the cell and the voltage available from the battery is dependent on the
standard electrode potential (E0) difference between the cathode and anode, temperature and Q value

Where Q is the ratio of the molar concentrations of product and reactants.

To obtain maximum voltage from a cell

1) To get required high voltage, the standard electrode potential difference between the cathode and
anode should be more.
2) Electrode reactions must be fast.
3) The conductivity of the electrolyte should be high
4) The resistance of the cell must be low.
5) Temperature of the reaction and Q value should be low
6) The voltage drop can be minimized by design the cell by keeping electrodes closely and using an
electrolyte with high conductivity.
2. Capacity:

Battery capacity is defined as the total amount of electricity generated due to electrochemical reactions
in the battery
Capacity is a measure of the amount of electricity that may be obtained from the battery.
The unit of the capacity is “ampere hour” and is briefly expressed by the letters “Ah.”
It is determined by Faraday’s relation,

Where, W is Weight of the active material

n is number of electrons involved in discharge reaction
F is Faraday’s constant, 96500 C/mol,
M is Molar mass of active material

3
Capacity is measured by finding the time t taken for the
battery to reach a minimum voltage, for a fixed current
density. The length of the flat portion of the curve is a
measure of the capacity of the battery.

3. Electricity storage density: Electricity storage density is a measure of charge per unit weight
stored in the battery

It is the measure of charge and it can be expressed in Ah/Kg.

A high storage density depends on a good battery design and also appropriate selection of electrode
materials.

The weight of the battery includes electrolyte, electrodes, terminals, case, etc. Lighter elements leads
to higher electricity storage density.

For example: Li metal anode battery having higher electricity storage density when compared with
Zinc-carbon battery

4. Energy density: Energy density is the total amount of energy stored per unit weight of active
materials of the battery. It is mainly depended on the quality of active material used.

If a system has a high energy density, then it is able to store a lot of energy in a small amount of mass.

Energy density can be expressed in Watt-hour/Kg (Wh/ Kg.) A watt-hour is a measure of electrical
energy that is equivalent to the consumption of one watt for one hour

Battery energy density is crucial because the higher the energy density, the longer the battery.

If a battery can be discharged at a current i and at an average voltage Ecell for a period of time t and the
weight of the battery w then the Energy Density is given by

𝒊 × 𝑬𝒄𝒆𝒍𝒍 × 𝒕
ED =
𝑾
For example:

• Energy density of Lithium-ion batteries, ranges between 260-270 Wh/ kg

• Energy density of Lead-acid batteries range from 30-75 Wh/kg
• Energy density of Nickel-cadmium battery ranges between 45-80 Wh/kg
• Energy density of Nickel-metal hydride battery ranges between 60-120 Wh/kg

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5. Cycle Life:
The number of charge and discharge cycles that are possible in secondary batteries, before the failure of
the battery occurs is called Cycle Life. Secondary batteries should have high cycle life.

The cycle life of a battery is affected by corrosion in contacts and shedding of active materials from
electrodes.

The charge / discharge cycle depends on chemical composition, distribution of active materials in the
cell etc.

Example: Lithium-ion battery having more Cycle life when compared to Lead acid battery. Lithium-
ion batteries have expected life cycle ratings between 1,000-2,000 cycles for a heavily used battery and
Lead acid battery having 500-1000 cycles.

6. Shelf life:
Shelf life is defined as “duration of storage under specific conditions without any loss in performance”.
Shelf life is the period of storage under specified conditions during which a battery retains its ability to
work or to produce energy is called Shelf life.

A good battery should have more shelf life. It depends on self-discharge reactions. The long shelf of
the battery is likely when there is no self-discharge.

For example:
➢ Lithium-ion batteries typically have a shelf life of 3-5 year
➢ Alkaline batteries usually have a shelf life of 7–10 years.
➢ Lead acid batteries have a shelf life of 3–5 years.
➢ Zinc Carbon batteries have a shorter shelf life of 2–3 year

Lead acid battery.

▪ Lead acid battery comes under the secondary batteries and it is rechargeable battery

▪ It holds the capability to deliver increased surge currents (extremely high discharge currents)
generally used in automobiles and inverters.

▪ The sealed lead-acid battery consists of six cells mounted side by side in a single case. The
cells are coupled together, and each 2.0V cell adds up to the overall 12.0V capacity of the
battery.

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Construction of Lead acid battery

▪ A lead acid battery consists of two electrodes,

negative electrode(anode) and positive electrodes
(cathode).

▪ The anode and cathode are made up of Lead grids.

▪ The negative electrode filled with Spongy Lead

(Porous Lead) and positive electrode (cathode) filled
with Lead oxide (PbO2)

▪ Both electrodes are immersed in a electrolytic

solution of 5M sulfuric acid with specific gravity of
1.2 to 1.3 g/cm3.

▪ These two electrodes are separated using a separator which is an insulating material.

▪ Lead acid battery consisting of six electrode pairs give about 12V. Each pair of electrodes
produces 2V and Energy density is about 33Wh/Kg.

▪ Cell representation: Pb, PbSO4 𝐻2 𝑆𝑂4 (5𝑀) 𝑃𝑏𝑆𝑂4 , 𝑃𝑏𝑂2 , 𝑃𝑏

Working:
During Discharge:

▪ This lead acid battery utilizes sponge lead and lead oxide in presence sulfuric acid to convert
chemical energy into electrical energy. The chemical reactions in a battery involve the flow of
electrons from one material (electrode) to another, through an external circuit. The flow of
electrons provides an electric current that can be used to do work

▪ Here the sulfuric acid dissolves, its molecules break into positive hydrogen ions (2H+) and
negative sulphate ions (SO42-).

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 ▪ At the anode, Lead (Pb) oxidizes and combines with SO42- to generate PbSO4 with the liberation
of electron. The liberated electrons (e-) at the anode travel through external circuit towards
cathode.
▪ At Cathode PbO2 undergo reduction with H2SO4 and electrons (2e-) to form PbSO4 and 2H2O
▪ During charging DC current has to supply and at this process water (2H2O) gets dissociate to
form 4H+ and 2O2-. This oxide ion (2O2-) react with PbSO4 to form PbO2 and SO42- with the
giving away 2electrons (2e-).
▪ This liberated 2 electrons(2e-) move towards the anode and at anode PbSO4 converts to Pb and
SO42- ion. This sulphate SO42- ion combines with H+ to form H2SO4. The energy gets stored by
increasing the gravity of sulfuric acid. Hence, H2SO4 is regenerated in the cell
Application of Lead Acid battery

1) Used as a power source for starting, lighting and ignition in automobiles.

2) Used in emergency lighting and in uninterrupted power supplies (UPS).

Construction, working and applications of Modern Battery in Electric vehicles (Li-ion battery).

Lithium-ion battery:

▪ Li-ion batteries are secondary batteries and it is rechargeable battery. The electrochemical
properties of lithium are excellent and it is also a highly reactive material. These properties give
the potential to achieve very high energy density in lithium-ion battery

Construction:

Lithium-ion battery have following main constituents:

Anode: This is the negative electrode of the lithium-
ion battery and it is generally made from Carbon,
normally in the form of Graphite (C6).
Cathode: This is the positive electrode and it is
typically made from a lithium-based metal oxide. The
cathode material is made up from Lithium liberating
compounds, typically the three electro-active oxide
materials like, Lithium Cobalt-oxide (LiCoO2),
Lithium Manganese-oxide (LiMn2O4) Lithium Nickel-
oxide (LiNiO2)
Electrolyte: A solution of Lithium halide (LiCl, LiBr, LiClO4, LiAlCl4 / LiPF6) in an organic solvent
like propylene carbonate/ dimethyl carbonate / ethylene carbonate acts as an electrolyte.
Separator: A separator is placed between the anode and cathode to prevent the touching of two
electrodes. This prevents the direct contact of the two electrodes in the battery.
This separator is a fine porous polymer film like microporous polyethylene or polypropylene membrane
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Current collectors: The commercially available current collectors for cathode and anode are aluminum
and copper. Aluminum used as Cathode current collector and Copper is used as anode current collector
for lithium-ion batteries.

Working:
▪ During discharging, the positive Lithium ion moves from the negative electrode (graphite) and
enters the positive electrode (lithium metal oxide) through the electrolyte solution and separator.

▪ Lithium-ion battery depends on an "intercalation" mechanism. This involves the insertion of

lithium ions into metal oxide (cathode)

▪ Oxidation takes place at the anode and releases Lithium ions (Li+) to the cathode, generating a
flow of electrons that helps to power the relevant device. While the reduction reaction takes
place at the positive electrode (cathode), where Lithium ions are incorporated into metal oxide.

▪ Charging reactions can be run in reverse to recharge the cell. Here electrical energy is used to
induce the migration of electrons from the positive electrode to the negative electrode. In this
instance, at cathode lithium ions leave the lithium metal oxide and migrate back to the anode,
where they are reduced back to neutral lithium and reincorporated into the graphite network.
Thus, the cell voltage increases as the cell is charged

▪ Thus, the lithium ions pass back and forth between the electrodes during charging and
discharging. Hence, the lithium-ion batteries are called ‘Rocking chair Shifting’

Application of Lithium-ion battery

▪ The Li-ion batteries are used in cameras, calculators

▪ They are used in telecommunication equipment, instruments, portable radios and TVs.
▪ Li-ion batteries are used to Store Solar Power
▪ They are used in Aerospace applications

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 ▪ Used in Portable Power banks
▪ Lithium-ion Battery Technology has made it is the favorite power source for Electric Vehicles
and Hybrid Electric Vehicles.

Recycling of Lithium-ion battery:

The recycling of spent Li Batteries is important because of the potential risks associated with the
disposal of lithium batteries to landfills. The risk associated are (i) Lithium batteries can explode when
damaged or exposed to high temperatures (ii) Heavy metals (such as lead, manganese, nickel, copper
and cobalt) used in lithium batteries can contaminate soil and ground water. (iii) The electrolytes used
in the batteries are toxic and flammable.
LIBS contains valuable metals such as lithium, iron, aluminium, cobalt, nickel and copper. The most
valuable metal is cobalt
Therefore, the recycling and reuse of used lithium-ion batteries has been paid more and more attention
by many researchers.
The most commonly used methods to recover valuable metals from lithium-ion batteries (LIBs) are
(i) Hydrometallurgy, (ii) Pyro-metallurgy,
Hydrometallurgy

▪ Hydrometallurgy can be defined as a metal recovery method used to obtain metals from waste
materials using aqueous media by combining water, oxygen, and other chemical reagents

▪ Hydrometallurgical processes include acid leaching, bioleaching, solvent extraction, and

chemical precipitation. Acid leaching relied on dissolving materials from the battery after
mechanical treatment. (Leaching is the conversion of an insoluble metal, into a soluble metal
form.)

▪ Hydrometallurgy works to crush and dissolve spent batteries, and then by using suitable
chemical reagents to selectively separate the metal elements in the leaching solution, yielding
high-grade cobalt metal and lithium carbonate.

▪ Hydrometallurgy is more suitable for recycling spent LIBs with single chemical composition,
and its equipment investment cost is low, suitable for the recycling of small- and medium-scale
spent LIBs. Therefore, this method is widely used at present.

▪ The hydrometallurgy process uses inorganic acids like hydrochloric acid (HCl), nitric acid
(HNO3), sulfuric acid (H2SO4), phosphoric acid (H3PO4), organic acids (malic acid, citric acid,
oxalic acid, and ascorbic acid), and hydrogen peroxide (H2O2) to extract and separate the
cathode metals.

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Hydrometallurgy Process

▪ In this hydrometallurgy process, first spent LIBs are subjected to mechanical treatment
followed by an acid leaching process.

▪ In acid leaching process, HCL was found to be the best leachant, which recovered 99% of Co
and Li using 4 M HCl solution at 80 °C for 1 h reaction. In this step, Graphite is not
recovered and stays in a solid residue after filtration of the leachate.

▪ Cobalt can be recovered as Cobalt hydroxide which can be selectively precipitate by adjusting
the pH using a sodium hydroxide solution

▪ Lithium was recovered in form of lithium carbonate via precipitation using Na2CO3 and
followed by oxidized and roasted with Cobalt hydroxide to form Lithium cobalt oxide. (used as
cathode material for LIBs)

▪ If Copper and Aluminium concentration in the leachate is high, then solvent extraction is
applied for its recovery

▪ Nickel in the leachate is selectively extracted by Dimethylglyoxime near completion

▪ The Manganese in the leachate reacts selectively with the KMnO4 reagent and nears
completion, and the Manganese is recovered as Manganese dioxide (MnO2) and Manganese
hydroxide.

Pyrometallurgy
▪ The word “Pyro” relates to high heat. Pyrometallurgy is a conventional process to recover
precious metals from lithium-ion batteries which uses smelting process and reduction process
for the recovery of metals from the spent LIBs.

▪ Pyrometallurgical processing involves incineration in a plasma arc furnace (electric arc heater).

▪ In this process, disassembled batteries are fed into furnaces where they undergo heating at high
temperature.

▪ In the pyrometallurgy process, the crushed scraps are liquefied in a blast furnace to remove
plastics then mixed with small amounts of coke and limestone followed by heating at a high
temperature.

▪ The furnace was divided into three zones; in the first zone, the batch was preheated in order to
evaporate the electrolyte: the temperature slowly increased but should be less than 300 ℃
(excessive heating temperature may lead to explosion).

▪ The second zone was for plastics pyrolysis: the temperature in this section was 700 ℃, which
caused melting of plastics and the hot gasses emitted in this process were used in the preheating
stage.
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 ▪ In the last zone, smelting and reduction took place. The temperature in this zone was in the range
1200 ℃-1450 ℃. During this process, a slag (containing aluminium, silicon, calcium and iron)
and an alloy (containing copper, cobalt, nickel and lithium) were obtained. Further, metals are
separated by chemical treatment.

Sodium-ion battery
▪ Due to the high cost and scarcity of lithium, exploration of alternative metal-ion battery systems
for cheaper energy storage is becoming increasingly important

Construction:
Sodium ion battery have following main constituents:

▪ Anode: This is the negative electrode of the Sodium

ion battery and it is generally made from Hard
Carbon.
▪ Cathode: This is the positive electrode and it is
typically made from a sodium-based metal oxide.
The cathode material is made up from sodium
liberating compounds, typically electro-active oxide
material like, Sodium Cobalt-oxide (NaCoO2).
▪ Electrolyte: A solution of Sodium
hexafluorophosphate (NaPF6) or Sodium
perchlorate (NaClO4) in an organic solvent like
propylene carbonate/ dimethyl carbonate / ethylene carbonate acts as an electrolyte.
▪ Separator: The positive and negative electrodes are electrically separated by a fine porous
polymer film like microporous polyethylene or polypropylene separator
▪ Current collectors: The current collector is used to provide conduction of electrons from the
electrochemical reaction to the external part.
▪ Aluminium is used in both anode current collector and cathode current collector in Sodium ion
battery

Working:
During discharging, the positive sodium ion Na+ moves from the negative electrode and enters
the positive electrode through the electrolyte solution.
Sodium ion battery also depends up on an "intercalation" mechanism. Where, Na+ ions
intercalate into the cathode via electrolyte and separator.

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 Oxidation takes place at the anode and releases sodium ions Na+ to the cathode, generating a
flow of electrons that helps to power the relevant device. While the reduction reaction takes
place at the positive electrode (cathode), where sodium ions are incorporated into metal oxide.

▪ Charging reactions can be run in reverse to recharge the cell. Here electrical energy is used to
induce the migration of electrons from the positive electrode to the negative electrode. In this
instance, at cathode sodium ions leave the sodium metal oxide and migrate back to the anode,
where they are reduced back to neutral sodium and reincorporated into the Hard carbon. Thus,
the cell voltage increases as the cell is charged

▪ Thus, the Sodium ions pass back and forth between the electrodes during charging and
discharging. Because of this reason, the sodium-ion batteries are called ‘Rocking chair
Shifting’

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 Analytical Techniques
Potentiometry
Principle and instrumentation of Potentiometry; its application in the estimation of iron in
industrial effluent.
The determination of the equivalent point of redox titration on the basis of potential measurement is
called a Potentiometric titration.
Principle
• The principle in Potentiometric titration is the measurement of the emf between two electrodes,
an indicator electrode and a reference electrode. The end point of the titration is detected by
measuring the change in potential between two electrodes.
• When the indicator electrode is combined with a reference electrode to form a cell and thus emf
of the cell is measured during the titration.
• The emf of the cell changes rapidly at very close to the end point.
• The equivalence point of the reaction is revealed by a sudden change in potential in the plot of
emf readings against the volume of titration.
• When emf E is plotted as ordinate (Y-axis) and the volume of titrant added as abscissa (X-axis),
the point of inflection of the curve corresponds to the equivalence point or end point of the
titration.

According to the Nernst equation the potential for the reaction,

Where Eo is the standard reduction potential of the system. The potential of the indicator electrode
changes with change in ratio of these concentrations. During the oxidation of Fe 2+ to Fe 3+ or the
reduction of Cr6+ to Cr3+ the ratio changes and therefore the potential changes more rapidly at the end
point of the reaction.

Instrumentation of Potentiometry
Instrument used- potentiometer.
➢ Electrodes: Indicator electrode eg – platinum
electrode (whose electrode potential depends
on the concentration of ions in a solution)
➢ Reference electrode eg- calomel electrode
➢ The solution to be titrated (Analyte) is taken
in the beaker and titrant is taken in the micro
burette.
➢ Immerse the electrodes in the beaker along with magnetic bead and stirrer
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 ➢ The electrodes are connected to the potentiometer which gives the emf values

Application in the estimation of iron in industrial effluent using standard K2Cr2O7 solution
1. Burette out 25 cm3 of industrial effluent solution into a 100 ml beaker. Add 1 test tube full of
dilute sulphuric acid.
2. Dip the platinum and calomel electrode assembly into the solution & connect to a potentiometer
and measure the potential.
3. Add 0.5 cm3 of K2Cr2O7 from a burette, stir the solution and measure the potential after each
addition.
4. Continue the process till the potential shows a tendency to increase rapidly and carry out the
experiment for five more readings by adding K2Cr2O7 in increments of 0.5 cm3.
5. Plot a graph of ΔE/ΔV against volume of
titrant as shown in the figure and find out end
point.
6. Calculate the normality of the industrial
effluents solution and determine the amount
of iron present in the given solution by using
following formula,

(55.85)

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Conductometry
Principle and instrumentation of Conductometry; its application in the Estimation of weak acid
Principle:
▪ It is an electrochemical method of analysis used for the determination or measurement of the
electrical conductance of an electrolyte solution by means of a conductometer.

▪ The principle states that, during a titration one of

the ions is replaced by the other and these two
different ions differ in their ionic conductance as
well. So, conductivity of the solution differs
during the course of titration. This method
involves movement of the ions that creates the
electrical conductivity. The movement of the ions
depend upon the concentration of the solution.
▪ A graph is plotted between change in conductance
and volume of titrant added. By this graph an
equivalence point can be detected.
▪ The movement of the ions is mainly depended on the concentration of the ions. The electric
conductance in accordance with ohms law.
▪ Ohm’s law states that the current I (amperes) flowing through a conductor is directly
proportional to the applied potential, E(volts) and inversely proportional to the resistance
R(ohms) of the conductor

Instrumentation of Conductometry

➢ It consists of two platinum electrodes of 1 cm2 area and kept 1 cm apart.

➢ Immerse the electrodes in the beaker along
with magnetic bead and stirrer
➢ The electrodes are connected to the
conductometer which gives the emf values
➢ The titrant is added from a burette and the
solution is stirred.
➢ The conductance is measured after the
addition of the titrant at intervals of 0.5 ml.

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Conductometry:- Application in the Estimation of Weak Acid

➢ To estimate the weak acid, collect the weak acid (analyte) in a beaker, dip the electrodes into
the solution, and attach the electrodes to a conductometer.
➢ The NaOH (titrant) is added from a burette and the solution is stirred.
➢ During the titration formation of highly ionizable sodium acetate salt is formed.

➢ Therefore, there is an increase in the conductance of the solution. This continues till the
neutralization point.
➢ After the end point conductance increases due to free OH– ions.
➢ A graph is plotted between change in conductance and volume of titrant added. By this graph an
equivalence point can be detected.
➢ Intersection of two straight lines is the end point of the reaction.
➢ Using formula, normality and amount can be calculated.
(𝑁×𝑉)𝑁𝑎𝑂𝐻
𝑁𝐶𝐻3 𝑂𝑂𝐻 = 𝑉𝐶𝐻3 𝑂𝑂𝐻

Amount = 𝑁𝐶𝐻3 𝑂𝑂𝐻 × Eq Wt of CH3COOH (66)

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