Super capacitor

Suggested Readings:
1. Supercapacitors: Materials, Systems, and Applications; Francois Beguin
and Elzbieta Frackowiak, Wiley-VCH,2013.

2.Electrochemical Technologies for Energy Storage and Conversion, Ru-

Shi Liu, Lei Zhang, Xueliang Sun, Hansan Liu,and Jiujun Zhang;
Wiley-VCH,2012.
 What is a Supercapacitor?
• A supercapacitor is a specially designed capacitor which has a very large
capacitance.
• Supercapacitors combine the properties of capacitors and batteries into
one device.
• The first Supercapacitor was created by GE (General Electric) in the year
1957. Standard Oil of Ohio (SOHIO) accidentally in 1966, discovered the
double-layer capacitor when working on fuel cells.
• The expression ‘‘supercapacitor’’ was originally coined by Nippon Electric
Company (NEC), who first successfully marketed the device as
SuperCapacitor™ in 1970 for computer memory backup.
• They are also known as double-layer capacitors or ultracapacitors.
• Capacitances achieved using this technology can be as high as 12000 F.
• The self-capacitance of the entire planet Earth is only about 710 µF, more
than 15 million times less than the capacitance of a supercapacitor.
• The surface area of the plates of a supercapacitor is relatively more, while
the distance between the two plates is less as compared to that of normal
electrolytic capacitors.
Characteristics Capacitor Super capacitor

Charge / > 0.95 0.85 – 0.98

Discharge
Efficiency

Operating -20 to 65 °C -40 to 65 °C

Temperature

Advantages *It avoids excessive drawing *Long Life Cycle

of power *High Energy Storage
*Less Battery drain due to a *Fast Charging and Discharging Time
capacitor *High Load Currents
*High Integration Density
*Real and Reactive Power
Control

Working Capacitor store energy in the Super capacitor stores energy

form of electric field. between the ions of the electrolyte &
electrode in a double layer of charge.
Ragone plot of the power-energy density range for different electrochemical
energy storage devices. [The plot is named after David V. Ragone]
super capacitors are positioned between batteries and
conventional capacitors.
The battery has a slight decrease in performance when used to
high power, and conventional capacitors cannot be used because the
energy is too small.
• A supercapacitor device is made up of the
following parts
1. electrode material
2. electrolyte material
3.current collector
4. binder
5. separators.
 Working Principle of a Supercapacitor
• A supercapacitor typically works on the principle of storing
electrical energy between two electrostatic double layers
• It consists of two metal electrode plates that are soaked into an
electrolyte solution and are separated by a thin insulation layer.
• The material used to construct the metal plates of a
supercapacitor is generally coated with porous materials such as
carbon, activated charcoal, etc.
• Capacitor is always directly proportional to the
surface area of its conduction plates, which in
this case is significantly large.
• The value of capacitance is inversely proportional
to the distance between the plates, which in the
case of supercapacitors is considerably less as
compared to the traditional capacitors.
 Working of a Supercapacitor
• When a voltage is applied across the plates of the supercapacitor,
one of the plates tends to develop a positive charge, while the
other plate gets negatively charged.
• This causes the negative ions present in the electrolyte solution to
get attracted towards the positively charged plate and the
positively charged ions to get attracted towards the negative
metal plate.
• A thin layer of ions gets deposited on the inner side of both plates.
This leads to the formation of an electrostatic double layer.
• The overall capacitance of the supercapacitor can be calculated by
Where C is the capacitance, A is the surface area, ε is the relative
dielectric constant of the medium between two layers (electrolyte),
and δ is the distance between two layers (distance from the surface
electrode to the center of the ion layer)
Applications:
• LED flashlights in digital cameras
• For stabilizing power supply in laptops and
handheld devices etc.
• Uninterrupted power supply (UPS)
• Supercapacitors are used in ICs, RAM, CMOS,
Clocks and micro computers etc.
A research team in Germany developed the world's smallest micro supercapacitor, which
can be safely used in the human body.
Electrochemical capacitors (ECs) – sometimes referred to as “electric
double-layer” capacitors – also appear under trade names like
“Supercapacitor” or “Ultracapacitor.”
• They can offer very fast charge and discharge rates relative to
batteries of a comparable volume, but their specific energy is less
than that of batteries.
• Nitrides of molybdenum, titanium and iron, carbon nanotubes
(CNT), and mesoporous carbonaceous materials have been
proposed as electrodes for supercapacitors.
• The electrolytes used are LiClO4, NaClO4, LiAsF6, BF4-, CF3SO3- and
quarternary phosphonium salts.
• ECs can be divided into three main areas, based on their mode of energy
storage and construction:
1. the electric double-layer capacitor (EDLC),
2. the redox EC (also referred to as pseudocapacitor) - The faradaic electrochemical
processes comprise the passage of charge across the double layer, resulting in
faradaic current passing through the supercapacitor cell
3. hybrid systems incorporating combinations of double layer and
pseudocapacitance
 Activated Carbon Materials (ACs)
• Activated carbon, also called activated charcoal

• In 1957, the first supercapacitor was based on a low porous carbon.

• Due to their good electrical conductivity (1250–2500 Sm−1), it is
suitable for SCs.

• Maximum obtainable surface area was estimated by 3000 m2 g−1

• Activated carbon material is made through two processes, namely
carbonation and followed by activation.
1. The carbonization step involves the treatment of precursors in the
exposure of oxidizing gases, such as CO2, steam, and air, at high
temperatures (700–1200 °C) in an inert atmosphere to obtain the
amorphous carbon.
2. In the activation step, the applied temperature is lower (400 to 700
°C). The chemical activation process is carried out in the presence of
the activating agents like carbonates, alkalis, chlorides, or acids such
as NaOH, KOH, ZnCl2, and H3PO4 that lead to having a porous
network in the carbon particles.
• The specific capacitance values for the activated carbon electrodes
in aqueous electrolytes (between 100 to 300 F g−1) is higher than in
organic solution (<150 F g−1).
• Activated carbons are the only supercapacitor electrode material
that succeeded in commercialization due to its high surface area,
controllable pore size distribution, and low-cost compared to other
carbon materials.
• The particle size of the activated carbon used as the electrode of
the supercapacitor also affects the capacitance value.
• smaller the particle size, the more the surface area and provide
greater capacitance values.
• Supercapacitor electrodes can also use materials from carbon
aerogels.
• Aerogel is a suspension of carbon nanoparticles in the gel, and has
a higher surface area, good conductivity, and can be used without
binder.
• The commercially available carbons are as follows:
1. Wood-based activated carbons
2. Coconut-based activated carbons
3. Petroleum-residue-based activated carbon (coke,
coal tar, etc.)
4. Carbohydrate-based activated carbons
5. Ex-resin-activated carbons (e.g., phenolic resin).
 Metal oxide
• Transition metal oxides as the basis for supercapacitors can
be typically divided into two types: noble metal oxides and
base transition metal oxides.
• Noble metal oxides- RuO2 and IrO2. (Ru,Rd,Pd,Ag,Os,Ir,Pt,Au)
• Base transition metal oxides - NiO, Co3O4, Fe3O4 , MnO2, V2O5
and CuO.
• Mixed-MOs such as CuO@NiO, CuO/Cu2O, Cu/Cu2O@TiO2,
Fe2O3@TiO2, ZnO@Co3O4, Fe2O3/Co3O4 , Fe2O3/NiCo2O4,
Co3O4/ZnFe2O4, Co3O4/NiCo2O, ZnO/ZnFe2O4, Cr2O3@TiO2,
NiFe2O4/Fe2O3, NiO@ZnO, and ZnO@ZnCo2O4.
• Higher specific capacitance and lower resistance, as well as
their high conductivity.
• Ruthenium Oxide (RuO2) – It is one of the most studied TMOs for SC
electrodes due to its superior chemical and thermal stability, high
metallic type conductivity, broad potential window (1.2 V), highly
reversible redox reaction, long cycle life, high theoretical
capacitance (1200–2200 F g-1), and good rate capability.
• Manganese Dioxide (MnO2) - low cost, and low environmental
impact, high theoretical specific capacitance (1370 Fg-1) .
• used in biosensor, molecular adsorption, energy storage, ion
exchange, and catalysis
• Nickel Oxide (NiO) - NiO is one of the other promising
pseudocapacitive materials for SCs electrodes owing to its
properties such as, the high theoretical specific capacitance of 2584
Fg-1 , thermal stability, chemical stability, facile synthesis, reasonable
cost, abundance, and being environmentally friendly.
• Vanadium Pentoxide (V2O5) - V2O5 shows an ultra-high theoretical
capacitance of 2120 Fg-1
 Conducting Polymers (CPs)
• CPs can offer a higher capacitance because of the larger surface
areas and redox storage capabilities.
• The CP-based electrodes for SC exist in three various
configurations including,
1. the p–p configuration in which both electrode materials are the
same p-doped polymer.
2. the SCs n-p type in which both electrode materials made from
the same polymers, but one is positively charged (p-doped) and
the other one is negatively charged (n-doped) electrodes.
• p-doped and p–p’ SCs containing two various p-doped CPs with
various oxidation and reduction electro activities.
• Various types of CPs commonly used for SC electrodes,
including Polyaniline (PANI), polythiophene (PTh), PPy,
polyindole (PIND), polyfurane, poly(p-phenylene), poly(p-
phenylenevinylene), poly 3,4-ethylenedioxythiophene (PEDOT).
Advantages:
• high capacitance
• high Energy density
• Adjustable redox activity through chemical
modification
• good conductivity in doped states
• high voltage windows
• low environmental impact
• low cost
Disadvantages:
• low power densities
 Nanostructured Carbon based materials
• H. Becker developed the first EDLC using carbon-based materials in
1975.
• Activated carbons (ACs), templated carbons, carbide-derived carbons
(CDCs), activated carbon fabrics , carbon fibers, carbon aerogels, carbon
nanotubes (CNTs) , carbon nanohorns have been utilized for both
symmetric and asymmetric supercapacitors.
• High electrical conductivity, high specific surface area (SSA), perfect
corrosion resistance, high temperature stability, and tunable porous
structures.
• graphene and graphene-based composites have been investigated
because of their unique structures and high specific surface areas.

carbon nanohorns
• The high surface area, light weight, layered structure makes
graphene a suitable electrode material for the designing of energy
storage devices.
• Theoretically large surface area (2675 m2/g) and higher intrinsic
specific capacitance value (550 F/g), graphene has been chosen as
the suitable material for electrochemical double layered capacitor.
• There are plenty of methods to produce various types of graphene,
such as
1. micromechanical exfoliation,
2. epitaxial growth,
3. chemical vapour deposition,
4. electrochemical and chemical approaches,
5. arch discharge method
6. intercalation techniques in graphite.
• CNTs could be used as electrode material for SCs in
the form of composite along with other materials
such as graphene, metal oxides (MOs) and polymer.
• CNTs can be classified into two main categories such
as SWCNTs and multi-walled carbon nanotubes
(MWCNTs).
• The theoretical SSA for SWCNTs was reported at
about 1315 m2/g, while the SSA for MWCNTs was
smaller than ACs (< 3000 m2 g−1).
 Electric Double Layer Capacitor (EDLC)
• Based on the operating principle of the electric double layer that is
formed at the interface between activated charcoal and an electrolyte.
Structure of EDLC :
• EDLC consists of electrodes, electrolyte (and electrolyte salt), and the
separator, which prevents facing electrodes from contacting each other.
• Activated charcoal is used in its solid form, and the electrolytic fluid is
liquid.
Material Specific capacitance SSA (Specific Surface Area)

Activated carbon 310 F g−1 ∼1500 m2 g−1

graphene 215 F g−1 714 m2 g−1

CNT 160.8 F g−1 1315 m2g−1

graphite 94.4 F g−1 0.6-1.3 m2 /g

Principles of Electrical Double-Layer Capacitors:
• When electrode and electrolyte materials come in contact with
each other, the positive and negative poles are distributed relative
to each other over an extremely short distance. Such a
phenomenon is known as an electrical double-layer.
• By applying voltage to the facing electrodes, ions are drawn to the
surface of the electrical double layer and electricity is charged.
Conversely, they move away when discharging electricity.
• Capacitance is proportional to the surface area of the electrical
double layer. Therefore, using activated carbon, which has large
surface area for electrodes, enables EDLC to have high capacitance
• As each electrode–electrolyte interface represents a capacitor, the
complete cell can be considered as two capacitors connected in
series.
• For a symmetrical capacitor (i.e., identical electrodes) the cell
capacitance (Ccell) will therefore be

• where, C+ and C− represent the capacitance of the positive and

negative electrodes, respectively.
• In a symmetric device the capacitance for the positive electrode (C+)
equals that of the negative one (C−).
• The capacitance of the complete cell becomes half of the capacitance
of each individual electrode; that is

• where Ce = C+ = C−
• relative specific capacitance values, either per unit mass or volume.
The specific (gravimetric) capacitance of an electrode, Ce, is given
by

• where me is the weight of active material (in grams) present in a

single electrode.
• Capacitance may also be reported as normalized capacitance
(capacitance per unit area), defined as

• where SA is the surface area of the active electrode material.

• Basically there are two different types of constructions,
• i. The stacked
• ii. The wound
• The stacked types called “Coin”, generally offer a capacitor voltage
of 5.5V and available with capacities of up to 1.5F.
• The construction of the wound types is similar to the construction of
ordinary radial electrolytic capacitors. Available with a maximum cell
voltage between 2.1V and 3V, capacities of up to 3400F

Wound type
Stacked type
• Comparison With Batteries:

Type Batteries Conventional EDLC

capacitor
Time of charge 1 to 5 h 0.3 to 30 s 1-10 s

Time of discharge 0.3 to 3 h 0.3 to 30 s 1-10 s

Spec. Energy [Wh/Kg] 20 to >100 <10 <0.1
Lifetime [cycles] 1000 Up to 1 Million >500000
Spec. power [ W/Kg] <1000 >1000 >100000
Efficiency 0.7 to .85 0.9 to 0.98 >0.95
Applications
• Solar battery operated circuits: Toys, Lamps, Parking Lot etc
• Electric vehicles: Forklift trucks, Golf cart etc
• Battery backup: PC, Network& Server etc
• White goods: washing machine, Tumble dryer
• Bicycle lamps and photovoltaics, solar-LED- lighting, Road signals
• Windmills
• Recuperation/ start stop: Cars, Trains, Bus
• UPS systems
• Emergency Door actuators
• Safety relevent applications: fire siren, emergency exit light
• Memory backup for video and audio equipment: TV, Digital photo frame
• GPRS/GSM applications
• Heavy lifting
• Metering
• Roller coaster
 Redox Electrochemical Capacitor (Pseudocapacitors)
• The prefix pseudo originates from the Greek “ψευδής/pseudes” and
translates to “false” or “lying.”
• Pseudocapacitive describes an electrochemical mechanism in which
the capacitance originates from charge transfer processes across the
electrode/electrolyte interface.
• The concept of pseudocapacitance emerged by Conway and Gileadi
in the early 1960s to describe surface Faradaic processes.
• Pseudocapacitor Diagram:

• A pseudocapacitor is a hybrid in between a battery & an EDLC (electric

double layer capacitor).
• The storage of charge mainly occurs through chemical & electrostatic
processes.
Working Principle:
• To store electrical energy by transferring electron charge between
electrode & electrolyte through reduction-oxidation reactions.
• The energy storage in Pseudocapacitors can be done throughout the
faradaic reactions.
• Once the voltage is applied to a pseudocapacitor, then both reduction &
oxidation occurs on the material of the electrode.
• Hydrous ruthenium oxide (RuO2·nH2O) has proton–electron mixed-
conductive nature and offers huge pseudocapacitance (>700 F g–1)
Types of Pseudocapacitor:
• Pseudocapacitors are classified into two types based on electrode
materials used to store charge within pseudocapacitors like the
following,
1.Metal oxide
2.Conducting Polymers
1. Metal Oxide
• The discovery of pseudocapacitance in transition metal oxides
happened in 1971 - when the charge storage behaviour of a
ruthenium oxide (RuO2) thin film in sulfuric acid was first reported
by S. Trasatti and G.Buzzanca.
• The most frequently used metal oxides are MnO2, RuO2, NiO,
SnO2, IrO2, Fe3O4, V2O5, Co2O3 & MoO as supercapacitor
electrodes.
• RuO2 is considered as the most promising electrode material
because its high specific capacitance (720 F g−1) and high
electrical conductivity.
• structural water in hydrated RuO2 (RuO2·xH2O) facilitates proton
transport.
• In 1999, the Goodenough group reported that an amorphous,
hydrated MnO2·xH2O showed capacitor-like behaviour.
2. Conducting Polymers:
• A class of materials established by H. Shirakawa, E.J.Louis, A. G.
MacDiarmid, C.K.Chiang, A. J.Heeger were studied since the late
1980s.
• The most frequently used conducting polymers are PPy
(Polypyrrole), PANI (Polyaniline), PTh (Polythiophene), and PPV (p-
Poly p-phenylene vinylene) & PEDOIT (p-poly e-ethylene
dioxythiophene).
• Electron insertion into the conduction band via n-doping
(reduction), and/or removing an electron from the valence band
via p-doping (oxidation) increase charge carrier concentration.
• These materials have some disadvantages like, structural
instability.
Advantages:
• These capacitors have a higher power density.
• They have significantly longer lifetimes.
• As compared to lithium-ion batteries, they charge & discharge very
quickly.
Disadvantages:
• They are not suitable for long-term energy storage devices.
Applications:
• These are used in consumer electronics.
• In wearable or flexible electronics.
• Regenerative braking within automobile applications.
• Kinetic energy (K.E) recovery systems like cranes, elevators, wind
turbines, etc
Current status:
• The Global Supercapacitors Market was valued at USD 549.1 million
in 2021, and it is expected to reach a value of USD 1,114.60 million
by 2027.
• Supercapacitors are replacing traditional electric car batteries with
quick charging and temperature stability.

World’s leading supercapacitor

Maxwell Technologies, USA
World leading Tecate group, USA
Super
capacitor
companies

Murata Manufacturing, Japan Panasonic Corporation, Japan

• Future trends:

scientists from University College London and the Chinese Academy of Sciences
have developed a new flexible graphene-based supercapacitor. This flexible
graphene supercapacitor design can store 10 times more energy than
comparable existing technology.
Printed micro-supercapacitors (MSCs) - record volumetric
capacitance of 338 F cm−3, landmark volumetric energy density of
18.8 mW h cm−3 and power density of 40.9 W cm−3
Yarn based supercapacitors:
Researchers of North Carolina State University researchers found a
way to prevent electrical malfunctions in yarns designed to store
electrical energy.
Short-circuiting in yarns that act as supercapacitors, which are
electrical devices that store energy, could be prevented by wrapping
the yarns with an insulating thread.
Wearable Supercapacitors:
Researchers from Penn State University along with collaborating
researchers from Minjiang University and Nanjing University in China have
developed a self-powered, stretchable micro-supercapacitors that could
be used in wearable health-monitoring and diagnostic devices.
Micro-supercapacitors are miniature versions of supercapacitors and can
range from microns to centimeters.