Module 1 : ELECTROCHEMISTRY AND ENERGY STORAGE SYSTEM

Free energy:
It has been introduced by Gibbs. It refers to the system only. Gibbs free energy is defined as
“the maximum amount of energy available to a system to perform useful work”. At
constant temperature change in Gibbs free energy is given by ΔG =ΔH-TΔS.
If ΔG = -ve, then the process is spontaneous
If ΔG = +ve, then the process is non-spontaneous
If ΔG = 0, then the process is in equilibrium
A spontaneous process may be defined as a process which proceeds of its own accord, without the help of
any external agency. Non- spontaneous process does not occur of its own.

EMF of the cell:

“EMF is the potential difference between the two electrodes of a galvanic cell which causes
the flow of current from one electrode to other”. EMF = ECathode - EAnode. Standard EMF of the
cell is when the reactants and products of the cell reaction are at unit concentration at 298K and
at a pressure of one atmosphere.
Single electrode potential (E):
It can be defined as “the potential developed at the interface between the metal and solution
when it is in contact with a solution of its own ions”.
Standard electrode potential (Eo):
It can be defined as “Standard electrode potential is the electrode potential when the
electrode is in contact with a solution of unit concentration at 298K”.
Cell potential:
The potential difference between the two electrodes of a galvanic cell which causes the flow of
current from one electrode to the other electrode of a cell is called cell potential.
Cell reactions: At anode : Oxidation - M → Mn+ +ne-
At Cathode : Reduction - Mn+ +ne- → M
Derivation of Nernst equation- Dependence of electrode potential on
concentration
Nernst equation gives a relationship between single electrode potential and standard electrode
potential through concentration of metal ions at a particular temperature. Consider a reversible
electrode reaction-
Mn++ ne- ⇌ M
The reduction electrode reaction is taken in forward direction, because electrode potential is a
measure of reduction tendency.
According to Vant-Hoff reaction isotherm-
ΔG = ΔG0 + RT lnK where K → equilibrium constant, K = [M] / [Mn+]
ΔG → decrease in free energy
ΔG0→ decrease in free energy at standard condition

ΔG = ΔG0 + RT ln
Also decrease in free energy of the system = electrical work done
i.e ΔG = -nfE and ΔG0 = -nfE0

-nFE = -nFE0 + RT ln

Divide by –nF , E = E0 - ln ; [M] =1 for pure metal

= E0 - log

= E0 + log

At 298K , R=8.314 J/K/mol, F =96500 C, E0 →standard electrode potential, n→ valency

E = E0 + log

Nernst equation can also be applied to calculate the emf of a cell. Consider a reaction, aA +bB ⇌cC +dD

Ecell = E0 cell - log

Reference electrodes:
An electrode whose electrode potential is known and which can be used to measure the electrode
potential of another electrode is known as a reference electrode. Eg: Calomel electrode, SHE.
Primary reference electrode: Standard hydrogen electrode whose potential is set to zero,
by convention at all temperatures.
Secondary reference electrode: The electrode potentials of these electrodes are previously
determined against SHE and therefore can be used as a substitute for hydrogen
electrode. Example: Calomel electrode.
Calomel electrode:
I t is a Hg-Hg2Cl2( Mercurous chloride) electrode.
Construction:
Calomel electrode consists of glass tube in which Mercury is placed at the bottom. A paste of
calomel (Hg2Cl2) and Hg is placed on the layer of Mercury. The remaining space is filled with
saturated KCl. A Platinum wire fused in a glass tube is dipped into the Mercury to
provide external electrical contact. This is placed inside an outer jacket with a porous plug and is
filled with saturated KCl.
Representation: Hg/Hg2Cl2/KCl(saturated)

Working: Since it is a reversible electrode, it functions as anode as well as cathode, depending

on the nature of the coupled electrode.
When it functions as cathode, Hg2Cl2 + 2e- → 2Hg + 2Cl-
When it functions as anode, 2Hg + 2Cl- → Hg2Cl2 + 2e-
Net reaction, Hg2Cl2 + 2e- ⇌ 2Hg + 2Cl-

Electrode potential,

Applications: determination of single electrode potential using calomel

electrode:
To determine the electrode potential of zinc electrode, Zinc rod dipped in ZnSO4 solution. It is
connected to saturated calomel electrode through a voltmeter. The cell so formed may
represented as- Zn/ZnSO4// KCl(saturated)/ Hg2Cl2/Hg

EMF of the cell, Ecell = Ecathode - Eanode

2+
Ecell = Ecalomel- E Zn/Zn
2+
E Zn/Zn = Ecalomel- Ecell
2+
E Zn/Zn = 0.2422- Ecell
Types of electrodes:
1. Metal- metal Ion electrode: it consists of a metal dipped in a solution containing its
own ions. Example: Zn/ Zn2+, Cu/ Cu2+
2. Metal- metal salt ion electrode: a metal is in contact with sparingly soluble salt of the
same metal dipped in a solution containing anion of the salt. Example: calomel
electrode, silver- silver chloride electrode
3. Gas electrode: it consists of a particular gas flushed around an inert electrode (Pt) which
is dipped in a solution containing ions to which it is reversible. Example: SHE
4. Redox electrode: potential arises due to the presence of both oxidised and reduced species
of the same metal at an inert electrode. For example: Pt/Fe3+,Fe2+
5. Ion selective electrode: Ion selective electrode is the one which is selectively responds
Specific ion in a mixture and the potential developed at the electrode is a function of the
concentration of that ion in the solution. The electrode generally consists of a membrane
which is capable of exchanging the specific ions with solution with which it is in
contact; therefore these electrons are also called as membrane electrodes.
Glass electrode:
It is pH sensitive electrode, used for pH determination.

Principle:
When two solutions of different pH are separated by thin-walled glass membrane, a difference of
potential develops between the two surfaces of membrane. the magnitude of potential depends
on difference between pH of two solutions. If pH of one of these is held constant, the glass
electrode potential is a linear function of pH of the second solution.
Construction:
The glass electrode consists of glass bulb made up of special type of glass with high electrical
conductance. The glass bulb is filled with solution of constant pH(0.1M HCl) and is inserted
with silver- silver chloride electrode which is the internal reference electrode and also serves for
the external electrical contact. The electrode is dipped in a solution containing H + ions.
Working:
Representation -Ag/AgCl(s)// HCl(0.1M)/ Glass.
The glass membrane exchanges ions with solution
H+(Solution) + MG1(membrane) ⇌ M+(Solution) + HG1(membrane)
The inner gel layer and Outer gel layer are at different potentials due to the difference in the
concentration of the solutions( C1> C2).
The difference in these two potentials is called boundary potential, Eb =E1-E2

C2 = 0.1M is constant, C1 = [H+]

, n=1

When C1 = C2 , Eb = 0. However small additional potential exists due to two reasons.

1. Silver -silver chloride electrode inside the bulb in 0.1 molar HCl develops some
potential and behaves as internal reference electrode
2. Due to unevenness of glass membrane that develops a potential, Easy.
Thus potential of glass electrode Eg has three components-
1. The boundary potential
2. Potential of internal reference electrode silver-silver chloride
3. A small asymmetry potential
EG = Eb + EAg-AgCl +Easym
0
It can be reduced as EG = EG -0.0591pH
 Because EG = Eb + EAg-AgCl + Easy

EG = K - 0.0591 pH + EAg-AgCl + Easy

Since K, EAg-AgCl , Easy are constants, potential can be written as, EG = EG -0.0591pH
0

Where EG = K+ EAg-AgCl + Easy

0

Application of Glass electrode- determination of pH of a solution:

The glass electrode is immersed in a solution of which pH is to be determined. It is combined
with a reference electrode such as a calomel electrode internally and externally through the
potentiometer. The cell assembly is represented as:
Hg | Hg2Cl2 (s) | KCl (sat.) || Solution of unknown pH | glass | HCl (0.1M) | AgCl | Ag(s)
The EMF of the above cell, Ecell is measured using an electronic potentiometer. Ecell measured
is the difference between potential of glass electrode EG and calomel electrode (Ecal). The
potential developed at the indicator glass electrode is higher than the reference calomel electrode
(EG > Ecal).
Hence, Ecell = Ecathode - Eanode
= EG -Ecal
Ecell = [EG0 - 0.0591 pH] - Ecal
(Since, EG = EG0 - 0.0591 pH)
-0.0591pH = Ecell- EG0 + Ecal
pH = EG0 – Ecal- Ecell
0.0591
Energy storage systems
Battery is a device consisting of two or more galvanic cells connected in series or parallel or
both, that can store chemical energy in the form of active materials and on demand convert it into
electrical energy through electrochemical redox reaction. Batteries can thus generate power and
can act as portable sources of electrical energy. Batteries are classified as Primary, Secondary
and Reserve batteries:
Primary battery or primary cells: The batteries in which the cell reaction is not completely
reversible are called primary batteries. They are also referred to as irreversible batteries. They are
not rechargeable and once discharged have no further electrical use. They have no cycle life. Eg;
dry cell or Zn-MnO2 Cell, Li-MnO2 battery.
Secondary battery: The batteries in which the cell reaction is reversible are referred to as
secondary batteries. Secondary batteries after discharge can be recharged electrically to their
original condition by passing electric current through them in the direction opposite to that of
discharge current. They are also referred to as storage batteries or accumulators. They have cycle
life. Eg: Lead – acid battery, Ni – Cd battery.
Reserve Batteries: The batteries, which may be stored in an inactive state and made ready for
use by activating them (by adding an electrolyte, another cell component) prior to application are
referred to as reserve batteries. In these batteries, a key component is separated from the rest
prior to activation and hence the batteries are capable of long – term storage. Eg: Magnesium
water activated batteries, zinc–silver oxide batteries etc.
Construction, working and applications of Li-ion batteries:
Li-ion battery is a rechargeable battery in which lithium ions move from the negative electrode
to the positive electrode during discharge and back when charging.
Construction:
Anode: It is made with graphite, Copper foil is used as current.
Cathode: Lithium cobalt oxide compound. Aluminium foil is used as current collector
Separator: Porous polymer film.
Electrolyte: A lithium salt in an organic solvent. This electrolyte effectively transport Li+ ion to
cathode during discharge of battery. The voltage of LIB is about 3.6-3.7 V
Working:
Discharge reactions: During discharge, Li ions are dissociated from anode and migrate through
the electrolyte and are inserted into the crystal structure of cathode.
At anode,

At cathode,

The net cell reaction during charging and discharging is represented as –

Recharge reactions: During charging an external electrical power source applies a higher
voltage than that produce by the battery, forcing the current to pass in reverse direction. Lithium
ions then migrate from cathode to anode, where they become embed in the porous electrode
material in a process known as intercalation.
Applications of lithium-ion battery:
1. Used in portable devices like cell phones, laptops, digital cameras, flashlights
2. Used in tools such as cordless drills, sanders etc
3. Used in cardian pacemakers and other implantable devices
4. Used in telecommunication equipments, portable radios and TV’s
5. Because of their light weight and high energy density, they are used in electric vehicles
The Li-ion battery advantages include:
Cell voltage: The voltage produced by each lithium ion cell is about 3.6 volts. This has many
advantages. Being higher than that of the standard nickel cadmium, nickel metal hydride and
even standard alkaline cells at around 1.5 volts and lead acid at around 2 volts per cell, the
voltage of each lithium ion cell is higher, requiring less cells in many battery applications. For
smartphones a single cell is all that is needed and this simplifies the power management.
Self-discharge: One issue with many rechargeable batteries is the self discharge rate. 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. It is typically around 5% in the first 4 hours after being
charged but then falls to a figure of around 1 or 2% per month.
High energy density: Energy density is the measure of how much energy a battery contains in
proportion to its weight. This measurement is typicallypresented in Watt-hours per kilogram
(Wh/kg). A battery with high energy density has a longer battery run time in relation to the
battery size. Lithium-ionbattery has highest energy densities of any battery technology today
(100-265Wh/kg or 250-670 Wh/L). The much higher energy density offered by lithium ion
battery is one of the chief advantages to make use in high power applications such as electric
vehicles as an energy storage device.
Recycling of Lithium-ion batteries:
Li-ion batteries are made of materials such as cobalt, graphite and lithium which are considered
as critical minerals and hence Li-ion batteries should be recycled at certified battery electronics
recyclers rather than being discarded in the trash or put in municipal recycling bins. There are
three basic methods to recycle the batteries such as pyrometallurgy (smelting), hydrometallurgy
(leaching), and direct recycling (physical processes). Pyrometallurgy and hydrometallurgy are
the chemical processes being operated at industrial level, and direct recycling is a physical
process done at lab and pilot scale.
Direct recycling method: To reduce this risk, spent LIBs usually need to be discharged before
recycled. Physical processes usually include pretreatment and direct recovery of electrode
materials. These processes usually include disassembly, crushing, screening, magnetic
separation, washing, heating treatment, etc.
Direct recovery is a process of recovering useful components from spent LIBs without using
chemical methods. Before handling LIBs, they were discharged and disassembled into thousands
of cells. Then, the small ells were treated with supercritical CO, and the electrolytes were
extracted and treated in this process. After lowering the temperature and pressure, CO can be
separated from the electrolyte and the electrolyte can be regenerated. The cells were then
disassembled, broken and sorted. Finally, the cathode material was collected and reused.

Sodium-ion battery:

Sodium-ion batteries (SIBs) are energy conversion and storage devices that use sodium-ions to
shuttle positive charge between the anode & cathode in order to convert electrical energy to
chemical energy and vice versa. SIBs generally contain two electrodes, one anode and one
cathode, both consisting of the respective active materials coated on an aluminum foil current
collector. A thin liquid-permeable sheet called the separator is placed between the two electrodes
to keep them electrically insulated from each other, while allowing sodium ions to move freely
between the electrodes. The anode or negative electrode is where the sodium is stored when the
cell is in the charged state, while the cathode or positive electrode, hosts the sodium-ions in the
discharged state. The transport of positively charged sodium ions between the electrodes is
enabled by a solvent salt solution called the electrolyte, while electrons move between the
current collectors through an external circuit.
Sodium-ion battery cells consist of a cathode based on a sodium containing material, an anode
(not necessarily a sodium-based material) and a liquid electrolyte containing dissociated sodium
salts in polar protic or aprotic solvents. During charging, sodium ions are extracted from the
cathode and inserted into the anode while the electrons travel through the external circuit; during
discharging, the reverse process occurs where the sodium ions are extracted from the anode and
re-inserted in the cathode with the electrons travelling through the external circuit doing useful
work.
The sodium-ion battery (SIB) is a type of rechargeable battery analogous to the lithium-ion
battery but using sodium ions (Na+) as the charge carriers. Its working principle and cell
construction are almost identical with those of the commercially widespread lithium-ion battery
types, but sodium compounds are used instead of lithium compounds.
The dominant anode used in commercial lithium-ion batteries, graphite, cannot be used in
sodium-ion batteries as it cannot store the larger sodium ion in appreciable quantities. Instead, a
disordered carbon material consisting of a non-graphitizable, non-crystalline and amorphous
carbon structure (called "hard carbon") is the current preferred sodium-ion anode of choice.
Similar to all lithium-ion cathodes, sodium-ion cathodes also store sodium
via intercalation reaction mechanism. Owing to their high tap density, high operating potentials
and high capacities, cathodes based on sodium transition metal oxides have received the greatest
attention.
Sodium-ion batteries can use aqueous as well as non-aqueous electrolytes
Sodium-ion batteries have received much academic and commercial interest as a possible
complementary technology to lithium-ion batteries, largely due to the uneven geographic
distribution, high environmental impact and high cost of many of the elements required for
lithium-ion batteries. Chief among these are lithium, cobalt, copper and nickel, which are not
strictly required for many types of sodium-ion batteries. The largest advantage of sodium-ion
batteries is the high natural abundance of sodium. This would make commercial production of
sodium-ion batteries less costly than lithium-ion batteries. No electric vehicles use sodium ion
batteries. Challenges to adoption include low energy density and a limited number of charge-
discharge cycles.
Advantages and disadvantage over Li-ion batteries

Sodium-ion batteries have several advantages over competing battery technologies. Compared to
lithium-ion batteries, current sodium-ion batteries have somewhat higher cost, slightly lower
energy density, better safety characteristics, and similar power delivery characteristics. If the cost
of sodium-ion batteries is further reduced, they will be favored for grid-storage and home
storage, where battery weight is not important. If, in addition to cost improvements, the energy
density is increased, the batteries could be used for electric vehicles and power tools, and
essentially any other application where lithium-ion batteries currently serve.
Advantages:
1) Low-cost and environmentally-friendly.
2) Slightly lower energy density and high efficiency.
3) Better safety characteristics.
4) These are high rate batteries and operation at lower temperature
Disadvantages:
1) Batteries are less powerful.
2) Anode graphite absorbs too little sodium.
Applications:
1) Used in cellular phones and laptops.
2) In electric vehicles and power tools.