Dayananda Sagar Academy of Technology and Management (DSATM)

Presentation on
Electrochemistry and Energy storage systems

by

Dr. Jagadeesh N M. M.Sc., Ph.D., PDF(South Korea)

Assistant Professor
Department of Chemistry
DSATM-Bangalore
 ELECTROCHEMISTRY
Definition:
Electrochemistry is a branch of chemistry that deals with the interconversion of chemical and electrical energies
and behavior of electrolytes.

or Study of electron movement in an oxidation or reduction reaction at a polarized electrode surface.

It focuses on the interaction between chemical reactions and electrical energy, as well as the conversion of
chemical energy into electrical energy and vice versa.

Ex: in a battery, Chemical energy is converted to electrical energy. Whereas in electroplating/electrolysis electrical energy
is converted to chemical energy.

Electrochemical processes are fundamental in various fields, including energy storage and conversion, corrosion
prevention, sensors, and electroplating.

Anode: It is the electrode at which oxidation occurs.

Cathode: It is the electrode at which reduction occurs.

Redox reaction: A chemical reaction in which both oxidation and reduction reaction occur simultaneously.
Electrode :
Electrodes are conductive materials used in electrochemical cells to facilitate electron transfer. The anode is the
electrode where oxidation occurs, while the cathode is the electrode where reduction occurs.

Electrode Potential (E) or Cell potential :

It is defined as the potential developed at the interface between the metal and solution when it is in contact with a solution of
its own ion.

Std Electrode Potential (Eo):

The potential developed at the interface between the metal and the solution when it is in contact with a solution of
unit concentration at 298K at 1 atm pressure is called standard electrode potential.

Electrolyte:
The substance which conduct electricity in molten state or in aqueous solution.
Electrolysis:
The chemical decomposition of an electrolyte upon passing electric current.
 Electrochemical cell
A device that can generate electrical energy from the chemical reactions occurring in it, or use the
electrical energy supplied to it to facilitate chemical reactions is called Electrochemical cell.

Ex: Std 1.5-volt cell which is used to power many of home appliances

Galvanic Cell
A galvanic cell is an electrochemical cell in which the electrons are transferred due to redox
reaction to get electrical energy. In a galvanic cell, two different electrodes are kept immersed in their
respective salt solutions and connected by means of a salt bridge

Ex: Daniel cell

 Cell representation:

When a zinc rod in contact with 1M ZnSO4 and a Cu rod in contact with 1M CuSo4 are connected, Zn goes
into the solution as Zn2+ ions and the electrons released flows through the external wire reaches the copper electrode
where Cu2+ gets reduced/deposited.
A salt bridge is used to maintain the electrical continuity between the two half cells, also it eliminates the
liquid junction potential.

Electrolytic cells

Electrolytic cells are a class of electrochemical cells that use electric currents to facilitate the cell reaction.

The chemical reaction that occurs inside such cells is commonly referred to as electrolysis.

Ex: Electrolytic cells can be used to break down bauxite into aluminum and other components.
Electrolytic cell can also be employed for the electrolysis of water into hydrogen and oxygen.
Types of electrodes.
1. Metal-metal ion electrode:
This type of electrode consists of a metal in contact with a solution of its own ions. At the surface of the electrode, a
potential arises.

For example: 1. Zinc in a solution of zinc sulphate.

2. Copper in a solution of copper sulphate.

2. Metal-metal insoluble salt electrode:

This type of electrode consists of a metal in contact with one of its sparingly soluble salts and a solution of a soluble
salt having a common anion with the sparingly soluble salt.

For example: 1. Calomel electrode Hg / Hg2Cl2 / Cl-

2.Silver-Silver chloride electrode Ag / AgCl (s) / Cl-

3. Gas electrode:
A gas electrode consists of a particular gas flushed around an inert electrode (Pt), which is dipped in a solution
containing ions to which gas is reversible. Inert metal is used to make electrical contact because gases cannot conduct
electricity. The electrode potential value depends on the pressure of the gas and activity of the solution.

For example: 1. Hydrogen electrodes Pt / H2 (1atm) / H+ (1M).

2. Oxygen electrodes Pt / O2 (1atm) / OH- (1M).
4. Redox Electrode:
This type of electrode consists of an inert electrode (Pt or Au) develops potential due to the presence of oxidized
and reduced forms of the same substances in solution.

For example: 1. Pt / Fe2+, Fe3+ 2. Pt / Sn2+: Sn4+

5. Ion Selective Electrode:

Electrodes which have the ability to respond to certain specific ions in a mixture of ions in a solution are called ion
selective electrodes. This electrode contains suitable non-porous membrane separates two solutions, containing similar ions of
different concentrations and acts as an electrochemical membrane.

The potential developed at the electrode depends on the concentration of that particular ionic species.

For example: Glass electrode, crystalline membrane electrode, Solid state membrane electrode.

6. Amalgam electrode:
Amalgam is the alloy of any metal with mercury. An amalgam electrode is a modification of metal-metal ion
electrode. It is formed by placing the metal-amalgam in contact with a solution of metal ion. In place of a metal, its solution in
mercury is used.

For example: 1. Zinc amalgam electrode 2. Ag-amalgam electrode.

Reference Electrode:
Reference electrodes is an electrode which has a stable and known electrode potential with reference to which the
electrode potential of any other electrode can be determined.
Criteria:
i. Potential should be known under the conditions of utility.
ii. It should show minimum variation with respect to temperature.
Types:
I. Primary reference electrode:
Standard hydrogen electrode (SHE) is the only primary reference electrode (gas electrode).
Represented as Pt/H2(g)(1 atm) / HCl(1M)
The potential of SHE is taken as zero by convention. Therefore, potential values of all other electrodes are expressed w.r.t. this
electrode.
Limitations of SHE:
a) Construction and maintenance is difficult since it’s a gas electrode.
b) Pt metal used in the electrode is easily poisoned by any impurity present in the system.
c) Cannot be used in the presence of oxidizing agents like nitrates, H2S, chlorides, etc. as they poison Pt.
d) Difficulty in maintaining pressure at 1 atm.
II. Secondary reference electrode
These are the electrodes whose potential is measured w.r.t. SHE and then can be used as reference electrode
for measuring potentials of other electrodes.
Eg: Calomel electrode, silver-silver chloride electrode

Construction:
• Calomel electrode is a metal-metal salt ion electrode.
• The electrode consists of a narrow glass tube with two side tubes.
• A little Hg is placed at the bottom of the glass tube followed by a layer of
Hg2Cl2 (Mercurous chloride or calomel) and Hg.
• The remaining part of the glass tube is filled with KCl solution of definite
concentration.
• The thin glass tube with a platinum wire is then inserted, taking care that
the platinum wire drips into mercury.

Representation:
Hg|Hg2Cl2|KCl(sat)
Working Principle:
The calomel electrode can act as anode or cathode depending on the nature of another electrode of the cell.

As anode: As cathode:
2Hg Hg2+ + 2e- Hg2Cl2 Hg2+ + 2Cl-
Hg2+ + 2Cl- Hg2Cl2 Hg2+ + 2e- 2Hg
2Hg + 2Cl- Hg2Cl2 + 2e-
Hg2Cl2 + 2e- 2Hg + 2Cl-

Electrode Potential of calomel electrode is given by:

ECE = EoCE -0.0598 log [Cl-] at 298 K

• Calomel electrode is reversible with respect to Cl- ions

• Potential value of calomel electrode decreases with increase in concentration of KCl as fallows.

Name Decinormal CE Normal CE Saturated CE

Conc of KCl 0.1 N 1.0 N Saturated
Potential of 0.3335 0.281 0.242
CE in V
Example: Measurement of electrode potential(Zinc) using Calomel electrode:

Ecell is measured using a potentiometer:

Ecell = Ecathode – Eanode

= ESCE – EZn2+/Zn
EZn2+/Zn = ESCE – Ecell
ESCE = 0.2422 V
Therefor, EZn2+/Zn = 0.2422 V – Ecell
Advantages: Disadvantages:
a) Easy to set up and operate. a) Calomel electrode should not be used at above 50
b) Potential values do not vary much with variation in oC because the mercurous chloride breaks down
temperature. yielding unstable readings.
c) Not poisoned by oxidizing impurities. b) Since mercury is toxic this electrode losing its
d) They are calibrated with respect to SHE. popularity.

Application:
• Used as a reference electrode in PH meter.
• Used to measure the potential of any other electrode.
 Ion selective electrode:
Ion selective electrodes are the electrode that generates potential in the response to the presence of a solution of a
specific ion.

Principle:
It works on the principle of the ion exchange mechanism in which no redox reaction takes place, but the potential
is generated in the response to the presence of the solution of specific ion. It consists of passive membrane function by ion-
exchange mechanism, but no electron transfer takes place. The potential is determined by the relative concentration of an
analyte on each side of the membrane.

External Solution Internal Internal

Membrane

reference to be analyzed standard reference

electrode (analyte)
solution electrode
[Mn+] = C2 [Mn+] = C1

Cell representation
Applications of Ion-selective electrode:
1. It is used in the cosmetics and pharmaceutical industries.
2. To determine various ions in aqueous solutions.
3. To monitor pollutants/ions in natural water, soil and air.
4. To measure the pH of the solution.
5. To determine fluoride ions in drinking water and other drinks.
6. As a chemical sensor for research purposes

Advantages of ion selective electrode:

1. Simple, low-cost, and easy to handle.
2. Direct measurement of a wide range of ions
3. More Precise, High efficiency and short response time.
4. It can be miniature, and non-destructive.
Limitations of ion selective electrode:
1. Inability to measure below 2-3 ppm solution.
2. It can’t be used for a long time due to the deterioration of the membrane.
Glass Electrode :
Glass electrode is pH sensitive electrode which can selectively detect and measures H+ ions in a system. Thus, it is
widely used for pH measurements. A glass electrode is a type of ion selective electrode where a thin bulb shape glass
membrane is used as a sensing material. It is sensitive to hydrogen ions in the solution. When a thin glass membrane separates
two electrolytes, a potential is developed across the membrane.

Construction:
Glass electrode consists of a long glass tube with a thin-walled glass bulb at one end. It is made up of special glass
of low melting point and high electrical conductance. [corning glass 22% Na2O, 6% CaO and 72% SiO2]. The bulb is filled
with 0.1M HCl. Ag/AgCl electrode (internal reference electrode) is placed in the solution provides an electrical contact. The
bulb of the glass electrode is dipped into any solution containing hydrogen ions. If the hydrogen ion concentrations of the
solution inside and outside the glass membrane are different then the potential develops across the glass membrane.

Glass electrode can be represented as

Ag│ AgCl │ 0.1 M HCl │ Glass membrane

Working :
When the glass electrode is dipped in the test solution
(xM), the Na+ ions of the glass membrane are exchanged for H+
ions of the solution inside & outside. The reaction is ion-
exchange.

The boundary potential Eb is established due to the above reaction.

The glass electrode potential EG is given by.
Advantages of Glass Electrode:
1. It is portable and compact
2. Even in very dilute solutions, it gives accurate result
3. It can be used in the presence of viscous biological fluids
4. Environmental analysis
5. Measurement of soil pH level by glass electrode is an important process to observe soil acidity

Limitations of Glass Electrode:

1. It should be handled with care as the glass membrane is thin and fragile
2. Fluoride ions in the sample attack the glass surface and alter the composition of the membrane
3. It shows alkaline error when the solution pH is 11 or more. Above this pH, it shows selectivity towards not
only H+ ions but also Na + ions of the alkali
 ENERGY STORAGE DEVICES

BATTERY:.

A battery is a device that consists of two or more galvanic cells connected in series or parallel or both,
which converts chemical energy onto electrical energy through redox reactions.

Example: Lead-Acid battery, Nickel-Cadmium battery

Uses:

Batteries are used in calculators, watches and pacemakers for heart, hearing aids, computers, car engines,
stand by power supplies, emergency lightning in hospitals, electroplating, industries, military and space
applications.

Batteries have revolutionized the telecommunication system and are upshering a new era of transportation
with the possible replacement of petrol driven automobiles by the electrically powered ones. In modern
days portability of electronic equipment's in the form of handsets has been made possible by batteries.
 Basic Components of a Battery
Basic components of battery:
1.The anode: It releases electrons into the external circuit by undergoing oxidation.

M Mn++ ne-
The anode selected with the following properties in mind; efficiency as a reducing agent, high coulombic output (Ah/g) good
conductivity , stability, ease of fabrication and low cost.

2.The Cathode: It accepts electrons coming from anode through external circuit. Thereby reduction of the active species occurs at cathode.

M n++ ne- M
The cathode must be an efficient oxidizing agent ,be stable when in contact with the electrolyte ,and have a useful working
voltage.

3.Electrolyte : The electrolyte must have good ionic conductivity but not be electrically conductive. As this would cause internal short
circuiting. Electrolyte should be non reactive with the electrode materials and safe to handle . It is commonly a solution (or slurry) of an
acid, alkali or salts.

4.Containers: Must be resistance to corrosion from both inside and outside the cell.

5. Separator : Anode and cathode are separated by a separator like cellulose, Polypropylene, nefion membrane. This will prevent the
internal short circuit.
 CLASSIFICATION OF BATTERIES:

• The batteries are classified as

Primary battery or Primary cells:

A primary cell is the one in which electrical energy can be obtained at the expense of chemical
energy only as long as the active materials are still present. i.e., cells in which the cell reaction is
not completely reversible. These are not rechargeable and once discharged have no further electrical
use.
Eg: dry cell or Zn-MnO2 Cell
2. Secondary battery or Secondary Cells
The cell reaction occurring in secondary cells is reversible and these are rechargeable. They are
also referred to as storage cells. Secondary cells can be recharged with the help of external source of
electricity.
The charge-discharge cycle can be repeated several hundred times.
Eg: Lead storage cell and nickel cadmium cell.
3.Reserve Batteries:
In these batteries, a key component is separated from the rest of the battery prior to activation. Usually,
the electrolyte is the component that is isolated. In this condition, chemical deterioration or self- discharge is
essentially eliminated and the battery is capable of long- term storage.
Reserve batteries are primary cells designed for emergency use particularly in military applications.
Eg: Magnesium water activated batteries, zinc – silver oxide batteries etc.
 Working of a battery:

Discharging: During discharge, oxidation takes place at the anode and reduction takes place at the cathode. The
reactions are spontaneous. Chemical energy is converted into electrical energy. It acts as a galvanic cell during
discharge.
At anode: M Mn++ ne-
At cathode: M n++ ne- M

Charging: During charging, reverse reactions take place. The reverse reactions are non- spontaneous reactions.
The battery is connected to an external d.c. power supply. Electrical energy is converted into chemical energy.
During charging it acts as an electrolytic cell.
At anode: M n++ ne- M
At cathode: M Mn++ ne-
 BATTERY CHARACTERSTICS:

1. Energy density:
Energy density is a crucial parameter for batteries as it measures the
amount of energy a battery can store relative to its size or weight. It is
typically expressed in units such as watt-hours per kilogram (Wh/kg) for
weight-based energy density or watt-hours per liter (Wh/L) for volume-based
energy density.
Energy density is a key factor in determining the suitability of a
battery for various applications, particularly in areas where size and
weight constraints are important.
2. Life Cycle:
Is the number of times a battery can be charged or
discharged before the failure of a battery occurs is the life cycle.
Some of the factors which cause the failure are 1.Short circuit, 2.
Corrosion of contents, 3. falling of active materials from the battery
causing unavailability of them for charging. The cycle life depends
upon how effectively this is achieved. Also depends upon the depth
of each discharge attempts to discharge totally damaging to the
electrodes.
3. Shelf Life:
The shelf life of a battery refers to the period during which a battery
can be stored, unused, and still maintain a reasonable level of its original
capacity and performance. Several factors can influence the shelf life of
batteries, including the battery type and storage conditions(temperature,
humidity, Charge level, packaging), and the manufacturer's
recommendations.
For critical applications like emergency power supplies, it's
important to regularly check and replace batteries to ensure they perform as
expected when needed.
 Sodium Ion Batteries
Definition:
Sodium ion batteries are a type of rechargeable battery that uses sodium ions as a charge carriers.
Characteristics:
• These batteries are relatively young compared to other type of battery type.
• The battery-grade salts of sodium are cheap and abundant, much more than those of lithium.
• The first successful attempt of a sodium battery was undertaken in 1967 by a Ford Motor Company in
the sodium-sulfur battery.
• The factors like price, abundance and size, make sodium-ion batteries particularly interesting for large
scale grid storage applications.
• They have shown great promise for large-scale storage of renewable energy.
• Prototype made with sodium had more charge cycles than Lithium-ion. It also charged faster and
delivered energy more quickly.
• Sodium-ion batteries(SIBs) are cheaper and last longer than cells currently used in gadgets and are light
weight compared to Li-ion batteries.
Characteristics (Cont..)
• SIBs cells have been reported with voltage of 3.6 volts, able to maintain Ah/kg after 50 cycles.
• SIBs are nonflammable and there is no thermal runaway compared to Li-ion batteries.
• The raw material is 1000 times more common than Lithium and safer.

Construction:
Cells have been built and evaluated with Electrode and electrolyte materials as follows.
• Anode: Hard-carbon (C6)/Na intercalated Carbon
• Cathode: Layered transition metal oxides(Layered transition metal dioxides, NaMO2, where M = Fe, Ni,
Mn, Co etc.,), Ex: NaCoO2
• Electrolyte: Sodium salts (NaPF6) and Prussian blue and its analogues dissolved in a binary organic solvent
such as ethylene carbonate dimethyl carbonate.
• Separator : Polypropylene
Sodium-Ion Battery:
Working mechanism:

During discharging, electrons flow from anode to cathode through external circuit. Na+ ions move
through the electrolyte and separator to reach anode.
At cathode, Na+ ions are reduced to sodium and are inserted into the layered structure of metal
oxide.
When the battery is charging the Na+ ions de-intercalte from cathode and migrate towards anode.
Meanwhile charge balance electron pass from the cathode through external circuit containing the charger and
into the anode.
Reaction:
Advantages of sodium ion battery:
• Rechargeable sodium ion for energy storage
• Easier to recycle
• Low market prices Capable of working at room temperature
• Good efficiency.

Disadvantages of sodium ion battery:

• It requires more time for recharging if in case it is fully discharged.
• It is not suitable at low temperature.
• Lower operating voltage
 Vanadium Redox Flow battery (VRB)

A Vanadium Redox Flow Battery (VRFB) is a type of rechargeable flow battery. It employs
vanadium ions as a charge carriers. The battery uses vanadium’s having the ability to exist in a solution in
four different oxidation state (V2+, V3+, V4+ and V5+) to charge and discharge.
Vanadium ions changes color depending upon the valencey.

Construction:
1. Positive Electrode (Cathode): The positive electrode in a VRFB typically consists of a porous
conductive material like carbon felt or graphite felt. This electrode is in contact with the electrolyte
containing vanadium in its higher oxidation state (V5+).
2. Negative Electrode (Anode): The negative electrode in a VRFB also consists of a porous conductive
material, often made of carbon felt or graphite felt. This electrode is in contact with the electrolyte
containing vanadium in its lower oxidation state (V2+).
3. Electrolyte: VRFBs use a vanadium-based electrolyte solution. Typically, two separate electrolyte tanks are
used, one with vanadium in its reduced form (V2+) and the other with vanadium in its oxidized form (V5+). The
two electrolytes are pumped through a cell stack where the electrochemical reactions take place.

VANADIUM REDOX FLOW BATTERY

Working:
Vanadium redox flow batteries (VRFBs) operate based on redox (reduction-oxidation) reactions involving
vanadium ions in two different oxidation states, V2+ (reduced) and V5+ (oxidized).
These reactions occur in two separate electrolyte solutions (one for each oxidation state) and are typically
housed in separate tanks.
When the battery discharges, electrons flow through an external circuit, and vanadium ions in the electrolytes
undergo redox reactions to generate electrical energy.
When the battery charges, the reverse reactions occur.
Discharge (Power Generation):
At the positive (catholyte) electrode: V5+ ions from the oxidized electrolyte gain electrons and are reduced to
V4+, V5+ + e⁻ → V4+
At the negative (anolyte) electrode: V2+ ions from the reduced electrolyte lose electrons and are oxidized to
V3+, V2+ → V3+ + e⁻
Overall cell reaction during discharge: V5+ + V2+ → V4+ + V3+.
Charge (Energy Storage):
During charging, the reactions proceed in the reverse direction, with V4+ and V3+ ions in the
electrolytes being reconverted to V5+ and V2+ ions, respectively. These redox reactions allow VRFBs to store
electrical energy in the form of chemical potential energy in the vanadium ions, which can be readily converted
back into electrical energy when needed.

Advantages:
• It is used as energy storage for solar grids and in windmills.
• Safe, non-flammable aqueous electrolyte.
• Long duration of charge and discharge cycle life, it can go up to years.
• No noise emission
• Mixing of electrolyte causes no permanent damages.
• It can remain completely discharged without any damage.
Disadvantages:
• Vanadium oxides are more expensive.
• Vanadium is toxic compound.
• It requires more space.
• Weight of the aqueous electrolyte is heavy.