Recent advances and perspective in electrode materials

for electrochemical energy storage devices

(Supercapacitors)
Online Lecture Series
Organized by
The Department of Physics, St. Anthony’s College, Shillong
24th April 2021

Presenter:
Tolendra Kshetri, PhD
Post Doctoral Researcher
Department of Nano Convergence Engineering
Jeonbuk National University, Republic of Korea
 Contents:

1. Introduction

2. Fundamentals of energy storage systems

3. Electrochemical energy storage devices

4. Supercapacitor (Electrochemical capacitor)

5. Importance of electrode materials in Supercapacitor

6. Electrode materials for Supercapacitor

7. Conclusion
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1. Introduction

The Nobel Prize in Chemistry 2019 was awarded jointly to John B. Goodenough,
M. Stanley Whittingham and Akira Yoshino "for the development of lithium-ion batteries."

John B. Goodenough M. Stanley Whittingham Akira Yoshino

John Goodenough was born to American parents in
Jena, Germany. After studying mathematics at Yale
University, he served during the Second World War
as a meteorologist in the US Army. He then studied
at the University of Chicago, receiving a doctorate
in physics there in 1952. He subsequently worked
at the Massachusetts Institute of Technology and
Oxford University in Great Britain. Since 1986 he
has been a professor at the University of Texas at
Austin.
The Nobel Prize in Chemistry 2019. NobelPrize.org. Nobel Media AB 2021. Fri. 2 Apr 2021. <https://www.nobelprize.org/prizes/ch
emistry/2019/summary/>
Stanley Whittingham was born in Nottingham in
Great Britain. He studied at Oxford University and
completed his doctorate there in 1968. After a
postdoctoral fellowship at Stanford University in
the United States, he worked for the Exxon and
Schlumberger oil companies before becoming a
professor at the State University of New York at
Binghamton in 1988.
Akira Yoshino was born in Suita, Japan. After
studying technology at Kyoto University, he
began working at the Asahi Kasei chemical
company in 1972, with which he has been
associated throughout his non-academic
career. Since 2005 he has headed his own
laboratory at Asahi Kasei. Yoshino received
his doctorate at Osaka University in 2005
and has been a professor at Meijo
University in Nagoya since 2017.
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1. Introduction
Energy, particularly electrical energy, is indispensable to maintain our standard of living.

However, Fossil fuels are the dominant primary energy resources.

Currently, coal’s share in power generation in the US is over 35%, while it exceeds 70% in India
and China. Globally, coal was responsible for 40% of electricity produced in 2016 and is expected
to provide more than 30% in 2040.

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Energy Environ. Sci., 2018, 11, 2696--2767
1. Introduction
Effects of fossil fuel-based energy sources
Fossil fuels emit more than just carbon dioxide when burned. Coal-fired power plants generate
dangerous mercury emissions, sulfur dioxide emissions (which contribute to acid rain) and most
of the soot (particulate matter) in our air.
Fossil fuel–powered cars, trucks, and boats are the main contributors of poisonous carbon
monoxide and nitrogen oxide, which produces smog (and respiratory illnesses).

 global warming

 Air pollution

 Acid rain

 Health problem

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1. Introduction
Practical ways to reduce CO2 emission and pollutants
 To increase renewable sources of energy
 Electric vehicles

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1. Introduction
Applications of energy storage devices
 Uninterrupted power supply
 Electronic devices
 Smart Phone
 Tablet
 Laptop
 Electric vehicles
 Electric bike
 Electric car
 Electric bus
 Medical instruments
Sustainability 2020, 12, 10511

 Military equipment

 Renewable sources of energy

 Wind energy
 Solar energy

https://www.dnv.com/events/energy-storage- 19
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europe-has-been-postponed-164855
2. Fundamentals of energy storage systems
The first law of thermodynamics (or the law of conservation of energy) states that in a closed
system, the total energy is fixed, and energy can neither be created nor destroyed. It can only be
converted from one form to another.

This fundamental concept serves as the foundation of nearly all forms of energy conversion and
storage.

Most energy storage technologies fall into four generalized categories,

mechanical energy storage, chemical energy storage, electrochemical energy storage, and
electrical energy storage.

The maximum amount of electrical work that can be extracted from a storage system is given by
the thermodynamic equation,

G = H - TS
here,
G is Gibbs free energy,
H is enthalpy,
T is temperature, and *In other words, G represents the maximum energy available to do
S is entropy. either mechanical or electrical work.
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Energy Environ. Sci., 2018, 11, 2696--2767
2. Fundamentals of energy storage systems
Classifications of energy storage technologies (ESTs) by the form of stored energy

Mechanical Electrical

 A. Pumped Hydro-PHS  Capacitor

 B. Compressed Air-CAES  Superconducting magnetic-
 Flywheel- FES SMES

Electrochemical Thermal

 Batteries  Sensible/Latent
 Supercapacitors  Heat Storage

Thermochemical
 Solar Fuels
 Solar Hydrogen

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Sustainability 2020, 12, 10511
3. Electrochemical energy storage devices (EESDs)
Electrochemical energy storage devices are systems which convert chemical energy contained
in its active materials into electric energy by an electrochemical reaction.
The underlying operating principle for electrochemical and photoelectrochemical devices
involves three major process steps:
namely, separation (or, ionization) of charge, transport of charged species, and recombination of
charge.
This basic principle governs the operation of a wide range of devices including batteries, fuel cells
, supercapacitors, electrolytic capacitors, photoelectrochemical and photovoltaic devices.

Figure 3.1. Basic operating principle of electrochemical energy storage, illustrating (a) electrical energy to
chemical energy conversion, and (b) chemical energy back to electrical conversion for reaction A + B = C.
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3. Electrochemical energy storage devices (EESDs)

Lead acid battery Nickel cadmium battery Li-ion battery Supercapacitor

Battery Vs Supercapacitor

ACS Nano 2018, 12, 2081−2083 19

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Energy Environ. Sci., 2018, 11, 2696--2767
3. Electrochemical energy storage devices (EESDs)
When choosing an ESD, what characteristics should be considered?

 storage capacity  environmental effects

 specific energy  capital/operating/maintenance cost

 specific power  Safety

 Efficiency

 Charging-discharging rates

 Self-discharge rate

 Sensitivity to heat

 Charge-discharge rate life-time

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4. Supercapacitors

Figure 4.1. Brief history of supercapacitors Chem. Rev. 2018, 118, 9233−9280

 Electricity storage and delivery via electric double layer (EDL) was first proposed by Becker in 1957
(U.S. Patent 2 800 616).

 The resulting supercapacitors are then called electric double layer capacitors (EDLCs).

 High‐surface‐area activated carbon (AC) is normally used in the system as the working medium.
Because of their huge surface area

 Supercapacitor can store much more electricity and are usually evaluated in Farads (F), whereas
conventional dielectric capacitors are evaluated in picofarads (pF) and microfarads (μF).
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Energy Environ. Sci., 2018, 11, 2696--2767
4. Supercapacitor

 The capacitance of a capacitor is defined as the charge stored per unit potential difference change
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4. Supercapacitor
Types of supercapacitor
Supercapacitors can be classified into three types based on the charged storage mechanism:

 Double layer capacitors (EDLC)

 Pseudocapacitors

 Hybrid capacitors

Figure 4.2. Classification of supercapacitor based on charged storage mechanism 19

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wikipedia
4. Supercapacitor
Working principle of Electric double layer capacitor

Electric double layer (EDL) refers to the two charged layers formed at the resulting potential‐dep
endent charge storage ability is ascribed to electric double layer capacitance. The earliest model
of EDL is usually attributed to Helmholtz27, 28 and thus EDL is also referred to as Helmholtz dou
ble‐layers. Later, the Gouy–Chapman model and the of EDLs.26, 29

Figure 4.3 . Schematic representation of a supercapacitor

 Electric double layer (EDL) refers to the two

charged layers formed at the electrode/electrolyte
Figure 4.4. (a) the initial Helmholtz model, (b) the Guoy–Chapman
interfaces. model and (c) the Gouy-Chapman-Stern model,

 The resulting potential‐dependent charge storage ability is ascribed to electric double layer
capacitance.

 The earliest model of EDL is usually attributed to Helmholtz, and thus EDL is also referred to
as Helmholtz double‐layers.

 Later, the Gouy–Chapman model and the Gouy–Chapman‐Stern model were developed to
more accurately describe the detailed structure of EDLs. 19
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Adv. Energy Mater. 2015, 5, 1401401
4. Supercapacitor
Working principle of pseudocapacitor
 Pseudocapacitance arises at the electrode surfaces, where
the charges are stored by Faradaic process
Electric double layer (EDL) refers to the two charged layers formed at /and the resulting potenti
 Stemming from
al‐dependent thermodynamic
charge reasons,
storage ability the faradaic
is ascribed charge double layer capacitance. The earliest
to electric
transfer process across the electric double layer leads to a
model of EDL is usually attributed to Helmholtz27, 28 and thus EDL is also referred to as Helmho
special potential‐dependent charge accumulation or release
ltz phenomenon
double‐layers.
suchLater,
that the Gouy–Chapman
the derivative dq/dV ismodel andto‐Stern model were developed to more a
equivalent
a capacitance. ccurately describe the detailed structure of EDLs.26,Charging
29
MnO2/M MnO2 + M+ + e-
 It is manifested by the triangular shape of charge/discharge Discharging
curves at constant current density and the rectangular shape
of cyclic voltammograms for pseudocapacitors (PCs). where M+ is a cation
 Such faradaic charge transfer process was introduced by Trasatti et al., attributed to the highly reversible
surface redox reaction.

 Normally during charging, the surface region of redox‐active electrode materials, i.e., RuO2, MoxN or
MnO2, are reduced to lower oxidation states coupled with adsorption/insertion of cations from the
electrolyte at/near the electrode surfaces.

 Upon discharge, the process can be almost fully reversed.

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Adv. Energy Mater. 2015, 5, 1401401
5. Importance of electrode materials
Supercapacitor performance  The main target of research on supercapacitor is to
enhance the energy density (E) of supercapacitor.

𝑪𝑪𝒔𝒔 X 𝑉𝑉 2
E=
2
Where Cs is the specific capacitance (F g-1), and V is the potential
window in volt.

Cs can be increased by increased by two ways:

1) To increase the specific surface area of the electrode
material by developing nanostructured electrode materials.

2) By using pseudo capacitive electrode-materials

V can be increased in two ways:

1) Using organic electrolyte

2) Fabrication of asymmetric supercapacitor/hybrid
supercapacitor
Where Cs is the specific capacitance (F g-1), and V is the potential
window in volt.
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Adv. Energy Mater. 2015, 5, 1401401
6. Electrode materials for supercapacitor
Properties of the electrode materials

 High surface area  Surface wettability

 High porous structure  Mechanical resilience

 High electrical conductivity  Cost effective

 Thermodynamic stability  Environmental friendliness

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Sustainable Energy Fuels, 2017, 1, 1857-1874
6. Electrode materials for supercapacitor
Electrode materials for different types of supercapacitor

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Supercapacitors: A Brief Overview; Marin S. Halper, James C. Ellenbogen.)
6. Electrode materials for supercapacitor
Important electrode materials of double layer capacitor
Activated carbon-based electrode
 Activated carbon

 carbon fibers

 Graphite nanoparticles

 carbon nanotubes

 graphene

 carbon aerogels

https://www.mmcorporation.in/overview.html
 Their composites
Carbon fiber-based electrode

Science Advances 17 Apr 2020:Vol. 6, no. 16, eaaz0906 19

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6. Electrode materials for supercapacitor
Graphite nanoparticle-based electrode

Heliyon 4 (2018) e00862

.
Carbon composite-based electrode

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Chemical Engineering Journal 345 (2018) 39-47
6. Electrode materials for supercapacitor
Important electrode materials of pseudocapacitor

 Transition metal oxides,

 Transition metal nitrides,

 Transition metal carbides

 Transition metal sulfides

 Conducting polymers,

 Composites of transition-based materials with carbon materials

Important methods or techniques used in fabrication of electrode materials

 Hydrothermal  Wet chemical method  Spin coating

 Chemical vapor deposition  Self assembly  Spray coating

 Electrospinning  Electrochemical method  Atomic layer deposition

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The Canadian Journal of Chemical Engineering , Vol. 89, December 2011
6. Electrode materials for supercapacitor
Transition metal-based electrodes

Electrochimica Acta 376 (2021) 137987

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Adv. Energy Mater. 2018, 8, 1702014
6. Electrode materials for supercapacitor
Conducting polymer-based electrodes

J. Mater. Chem. A, 2018, 6, 22123-22133

Li et al. Nanoscale Research Letters (2019) 14:2265 19

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6. Electrode materials for supercapacitor
Composite-based electrodes

small 2017, 13, 1701275

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New J. Chem., 2017, 41, 11731-11741 small 2017, 13, 1701275
7. Conclusions
 Electrochemical energy storage devices (EESDs) play an important role in modern society.

 Significant advances have been made in EESDs in the last few decades.

 It is anticipated that the current worldwide efforts in this field will make electro-mobility a
strong and feasible economic reality, which will promote the transition from an energy
economy based on fossil fuels to sustainable energy.

 A better world free from air pollution, global warming depends crucially on our success in
developing effective, safe and cheap new power sources.

 Above this, in the next few years, flexible and wearable electronic devices will be seen in the
market.

 This area of research is fascinating because it requires a very good balance between very
deep and basic science, the use of the best analytical tools and practical studies.

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Materials Today. Volume 17, Number 3. April 2014
Text book for electrochemical supecapacitor

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