Cyclic voltammetry is the most widely used technique for acquiring qualitative information about electrochemical reactions. The power of cyclic voltammetry results from its ability to rapidly provide considerable information on the thermodynamics of redox processes and the kinetics of heterogeneous electron-transfer reactions and on coupled chemical reactions or adsorption processes. Cyclic voltammetry is often the first experiment performed in an electroanalytical study. In particular, it offers a rapid location of redox potentials of the electroactive species and convenient evaluation of the effect of media upon the redox process.

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Shri Shivaji Education Society, Amravati’s
Shri Shivaji Science College
Shivaji Nagar, Nagpur Road, Amravati (MS) 444603
Affiliated to Sant Gadge Baba Amravati University, Amravati (MS) India.
Short Term Course on
Nanomaterial Synthesis and
Charachrization Techniques (NSCT-
2021)

2. Cyclic
Voltammetry
Dr. Vaishali Deshmukh
Assistant Professor
Dept. of Physics
Shri Shivaji Science College, Amravati (MS)

3. Outline
3
Electrochemical Technique.
Introduction
01
Types of Voltammetric Techniques
Electrochemical Characterizations
02
Principle, Experimental Set Up: Electrochemical Cell, Applications
Cyclic Voltammetry
03
Conclusion and References
04

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Introduction
CV is the basic electrochemical test for materials. In this, the current
is recorded by sweeping the potential back and forth (from positive to
negative and negative to positive) between the chosen limits. The
information obtained from CV can be used to learn about the
electrochemical behaviour of the material.
It is an important technique to characterize the electrochemical
performance and reaction kinetics in electrical and electrochemical
energy storage devices under various conditions.
During a scan, the chemical either loses an electron (oxidation) or
gains an electron (reduction) depending on the direction of the
ramping potential.
In the general sense, voltammetry is any technique where the current
is measured while the potential between two electrodes is varied.

5. Types of Voltammetry
◈ Polarography
◈ Differential Pulse
Voltammetry
◈ Hydrodynamic Voltammetry
◈ Stripping Voltammetry
◈ Square-Wave Voltammetry
◈ Staircase Voltammetry
◈ Cyclic Voltammetry
Electrochemical Characterization
Electrochemical Techniques
◈ Voltammetry Technique
◈ Electrochemical Impedance
Spectroscopy
◈ Galvanostatic ChargeeDischarge
◈ Chronopotentiometry
◈ Chronoamperometry Coulometry
◈ Chronocoulometry
◈ Scanning Electrochemical Microscope
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1
Linear Sweep and Cyclic Voltammetry: The Principles
✓Linear sweep voltammetry (LSV) is a voltammetric method where the current at a working electrode is
measured while the potential between the working electrode and a reference electrode is swept linearly
in time.
✓The voltage scan rate (v) is calculated from the slope of the line. The characteristics of the linear
sweep voltammogram recorded depend on a number of factors including: 1. The rate of the electron
transfer reaction(s). 2. The chemical reactivity of the electroactive species. 3. The voltage scan rate

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If the scan rate is altered the current response also changes. The figure below shows a series of
linear sweep voltammograms recorded at different scan rates. Each curve has the same form but it
is apparent that the total current increases with increasing scan rate.

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Cyclic Voltammetry: Principle
✓Cyclic voltammetry (CV) is very similar to LSV. In this
case the voltage is swept between two values at a fixed
rate, however now when the voltage reaches V2 the scan
is reversed and the voltage is swept back to V1.
✓For a reversible electrochemical reaction the CV recorded
has certain well defined characteristics,
✓I) The voltage separation between the current peaks is
✓II) The positions of peak voltage do not alter as a function
of voltage scan rate
✓III) The ratio of the peak currents is equal to one
✓IV) The peak currents are proportional to the square root
of the scan rate

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Cyclic Voltammogram
As voltage is applied to a supercapacitor, ions in
the electrolyte solution diffuse into the pores of
the electrode of opposite charge. Charge
accumulates at the interface between the
electrodes and the electrolyte, forming two
charged layers (double layer) with an extremely
small separation distance. This is the distance
between the electrode surfaces to the center of
the ion layer.

10. The Nernst equation can be used to determine the relative concentration of analyte X
that can be reduced to X– at the electrode at every electrode potential (E) encountered on
the sweep (if the wave is reversible).
10 Fig: Electron transfer at the electrode
X + e– ⇆ X–
Where E is the electrode
potential (in Volts), E0 is the
standard reduction potential
of the X/X– couple (in Volts),
R is the gas constant (8.315
J K–1 mol–1), T is the
temperature (in Kelvin), n is
the number of electrons
transferred (1 in this case),
and F is Faraday’s constant
(96,485 C mol–1), and CX (or
CXˉ) is the concentration of
the respective species (X or
X–) at the electrode (mol L–1).

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Experimental Setup
The Electrochemical Cell
An electrochemical cell is a device in which a
chemical reaction generates an electrical
response or, conversely, an electrical current is
used to trigger a chemical reaction. The
simplest possible electrochemical cell consists
of two connected electrodes in an electrolyte
solution. In cyclic voltammetry, three
electrodes are used.
The working electrode, where the compound
of interest is reduced (C n+ → C (n−1)+ ) or
oxidised (Cn+ → C(n+1)+).
The counter electrode, which completes the
circuit with the potentiostat.
The reference electrode, used to measure the
potential.

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Reference Electrode
A reference electrode is an electrode whose
electrode potential is stable and it is also a
nonpolarizable electrode. It is used as a
reference against which the potential of
other working electrodes can be measured
in an electrochemical cell. The most
common reference electrodes are the
standard calomel electrode, the normal
hydrogen electrode, the silver/silver
chloride (Ag/AgCl) electrode in saturated
potassium chloride and the Ag/Ag+ (0.01M,
usually AgNO3) electrode in acetonitrile.

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Counter and working Electrode
◈ The counter electrode is used in an electrochemical
cell to complete the electrical circuit. Current is
recorded between the working and counter
electrode. Typical examples of counter electrodes
are large area Pt electrode, mesh type Pt electrode.
◈ A working electrode is the electrode of interest,
where the electrochemical reaction is occurring. A
potentiostat is used to control the applied potential
of the working electrode as a function of the
reference electrode potential. The electrode must
be such that it should not have any redox properties
on its own. Typical examples of working electrodes
are Gold electrode, Platinum electrode, Glassy
carbon electrode, Graphite electrode,etc.

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15. Cyclic Voltammetry uses for…..
Determining the reversibility of a reaction
Determining the formal reduction potential of a species
Measuring electron transfer kinetics
Determining the energy levels of semiconducting polymers
Assignment and characterisation of coupled reaction
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16. Applications
Supercapacitors
& Batteries
Sensors Coatings
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Conclusion
Various basic electrochemical characterization techniques are used for the analysis of
electrochemical parameters. Electrochemical reactions taking place during the
electrochemical characterization are responsible for the various phenomena that take place in
the cell.
During electrochemical characterization, the nature of the material, the local environment,
and the reaction parameters are responsible for the various output responses.
Cyclic voltammetry is very frequently used because it offers a wealth of experimental
information and insights into both the kinetic and thermodynamic details of many chemical
systems.
various applications of electrochemical characterizations, such as supercapacitors,
batteries, sensor studies, and coatings, where these characterizations prove to be really
useful for electrochemical studies.
The future of the relatively recent marriage between voltammetry and materials research
appears bright.
The combination of modern electroanalytical techniques with surface spectroscopy,
microscopy, and diffraction methods provides powerful methodology for the exploration of
redox properties of advanced materials.

18. References
◈ B.E. Conway, Electrochemical Supercapacitors: Scientific Fundamentals and
Technological Applications, Springer, 1999.
◈ H. Girard, H. Wang, A. Entremont, L. Pilon, J. Phys. Chem. C, 119 (2015) 11349 –
11361.
◈ R. Farma, M. Deraman, Awitdrus, I. A. Talib, R. Omar, J.G. Manjunatha, M. M.
Ishak, N. H. Basri, B. N. M. Dolah, Int. J. Electrochem. Sci., 8 (2013) 257 - 273.
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All Birds find shelter during
a rain. But Eagle avoids rain
by flying above the clouds.

20. Thank You!
Any questions?
You can find me at:
vaishalideshmukh027@gmail.com
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