2.2.

Pseudo capacitors

Pseudo capacitors achieve the electrochemical storage of electrical energy by faradaic redox
reactions with charge transfer. In pseudo capacitors, when an electric potential is applied across the
electrodes/plates, electrolyte ions move towards oppositely charges electrodes and create double
layer in such a way that a single layer of solvent molecules behave like a separator. Pseudo
capacitors involves the fast and reversible faradaic chemical reactions accompanied by charge
transfer between electrode and electrolyte across the double layer. This phenomenon is similar to
charging/discharging of batteries except that adsorbed ions does not undergo any chemical reaction
with the electrode active material. Thus, only charge transfer process occurs in pseudo capacitors.
Such capacitance arises because of specific thermodynamic conditions where electrode potential
(V) is defined as a function of the charge (Q) accumulated on the electrodes. Voltage derivative of
charge (dQ/dV) is the measure of capacitance in pseudo capacitors. The strength of electrode
materials to achieve the pseudo capacitance is measured by the chemical affinity of electrodes with
adsorbed ions, porosity and structure of electrode material, availability of redox centers and
possibility of intercalation.

The faradaic pseudocapacitive reactions can occur both on the surface of electrodes and on the
bulk of electrode material. The materials that exhibit the redox behavior suitable to be used as
electrode in pseudo capacitors are transition metal oxides such as MnO2, IrO2, RuO2 etc. doped in
to the conductive electrode materials like active carbon. Let us consider an example of MnO2, the
pseudocapacitive charge storage mechanism can be described as follows:

On the surface of electrode material, faradaic redox reaction involves the adsorption of electrolytic
cations C+ such as H+, Li+, Na+ and K+:

(MnO2)surface + C+ + e- → (MnOOC)surface ……….(11)

On the bulk of electrode material, faradaic redox reaction involves the intercalation and
deintercalation of electrolytic cations C+ such as H+, Li+, Na+ and K+ in the bulk of MnO2:

MnO2 + C+ + e- → MnOOC ……….(12)

The electrons which are involved in the faradaic processes move to and from the valence electron
orbitals of the redox electrode reagent. The electrons enter the negative electrode and flow towards
positive electrode via external circuit. At the positive electrode, a double layer with an equal
number of anions is created. The electrons arriving at positive electrode do not transfer to the anions
forming the double layer. Rather, they remain in highly ionized and electron deficit transition metal

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ions of electrode surface.

Figure 4. double-layer with specifically adsorbed ions in pseudo capacitors

In comparison to the EDLCs, Pseudo capacitors provide much higher capacitance per unit area.
Reason being, pseudo capacitive reactions occur with de-solvated electrolyte ions which are much
smaller than solvated ions of EDLCs and pseudo capacitive reactions occur on both the electrode
surface & bulk of electrode material resulting in larger capacitance values. However, due to
sluggish faradaic processes, pseudo capacitors exhibit relatively low power density than EDLCs
and due to redox reactions at electrodes, pseudo capacitors lack the long term cyclability compared
to EDLCs.

2.3. Hybrid Capacitors

The Hybrid capacitors are designed as an attempt to combine the advantages and disadvantages of
EDLCs and pseudo capacitors in such a way that hybrid product provides better performance
characteristics in comparison to EDLCs and Pseudo capacitors. A hybrid capacitor is combination
of two electrodes, one that stores the charge faradaically and other stores the charge electrostatically.
Thus, Hybrid capacitors combine a faradaic with an electrostatic electrode to produce the combined
characteristics of EDLCs and pseudo capacitors which improves the performance. Hybrid
capacitors provide higher energy density and higher specific power than EDLCs and pseudo
capacitors.

3. Components of Supercapacitor
Generally, supercapacitors consist of two conducting plates/electrodes separated by an

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electrolyte/dielectric media. There has been a lot of research work being carried out to improve the
performance characteristics of the supercapacitors by utilizing different electrode-electrolyte
configuration. Some of the typical electrode-electrolyte configuration in use for different categories
of supercapacitors are as provided below:

3.1. Electrolyte

The electrolyte is made up of a solvent and chemicals dissolved in that solvent which breaks down
in to positive cation and negative anions imparting the properties of electrical conduction to
electrolytes. The conductivity of an electrolyte is directly proportional to its ionic concentration.
The electrolyte in a supercapacitor should be chemically inert and should not alter the material
properties of supercapacitor to ensure long term stable behavior of electrical parameters of
supercapacitor. The viscosity of an electrolyte should be low enough to wet the porous and spongy
structure of electrodes. The Performance characteristics of the supercapacitors can be changed by
adjusting the nature of electrolyte. Both, aqueous and organic electrolytes can be used in a
supercapacitor. The choice of an electrolyte is often dependent on the intended application of the
supercapacitor.

3.1.1. Aqueous Electrolytes

Aqueous electrolytes consist of water as solvent and dissolved inorganic chemicals. H2SO4 and
KOH are typical aqueous electrolytes being used in supercapacitors. They have lower ESR, offer
higher conductivity and require smaller minimum pore sizes on electrode material. Breakdown
voltage of aqueous electrolytes is relatively smaller and operating temperature range is also lower
compared to organic electrolytes. The aqueous electrolytes are chosen for the supercapacitors with
low specific energy and high specific power.

3.1.2. Organic Electrolytes

Electrolytes with organic solvents such as propylene carbonate, acetonitrile, diethyl carbonate,
tetrahydrofuran etc. and solutions with alkyl ammonium salts or quaternary ammonium salts (such
as NMe(Et)3BF4 or N(Et)4BF4) offers higher breakdown voltage and larger temperature range
compared to aqueous electrolytes. However, organic electrolytes offer lower electrical conductivity
and high cost in comparison to aqueous counterparts. The organic electrolytes are chosen for the
supercapacitors with high specific energy and low specific power.

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3.2. Electrodes

3.2.1. Electrostatic double layer capacitors (EDLCs)

While the nature of electrolyte is of considerable importance in the design of supercapacitors,

EDLCs have been subdivided based on the form of carbon they use for electrode material.
Generally, carbon electrode materials have lower cost, higher surface area and more proven
fabrication technology than other materials such as metal oxides and polymers. The different form
of the carbon materials that are in use to store charges in EDLCs are activated carbon, carbon
nanotubes and carbon aerogel.

3.2.1.1. Activated Carbon

Activated carbon is very commonly used as electrode material in EDLCs because of its higher
surface are and low cost compared to other carbon-based materials. It utilizes a complex porous
structure consisting of differently sized micropores (<20 Å), Mesopores (20-500Å) and macro
pores (>500Å) to achieve their higher surface areas. Although, the capacitance is proportional to
the surface area of the electrodes, however, empirical studies have suggested that not all of
electrode surface area contributes for the capacitance. This discrepancy is due to the electrolyte
ions which are too large to diffuse into the small micropores and hence preventing some of the
micropores to contribute towards charge storage. Research has also suggested an empirical
relationship that energy density and power density are directly proportional to the pore sizes.

3.2.1.2. Carbon Aerogels

Carbon aerogels also have been subject of interest to be used as electrode materials in EDLCs.
They are formed by creating a continuous network of conducting carbon nanoparticles with
scattered mesopores. Owing to their continuous structure and their ability of chemical bonding
with current collector, carbon aerogels do not need additional adhesives for binding. Due to
absence of adhesive binding agents, carbon aerogels exhibit lower ESR as compared to activated
carbon electrodes. This lower ESR yields higher power as per eq. (4) and this is one of the main
areas of research in supercapacitors involving carbon aerogels.

3.2.1.3. Carbon Nanotubes

Carbon nanotubes are another common electrode material being used for making EDLCs, due to
their high surface area, electronic conductivity, good chemical stability and unique internal

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structure. In contrast to other carbon-based electrodes, mesopores in carbon nanotubes are
interconnected causing distribution of charge which helps in utilizing almost all available surface
area. This highly efficient utilization of surface area causes higher effective capacitance compared
to other carbon-based electrode of same area.

Since the electrolyte ions can diffuse more easily into the mesoporous network, these electrodes
also possess higher ESR compared to activated carbon electrodes. Further, to reduce the ESR,
different fabrication techniques have been developed such as growing the carbon nanotubes on to
the current collectors and subjecting them to heat treatment process or casting them into the
colloidal suspension thin films.

3.2.2. Pseudo capacitors

There are mainly two electrode materials which are being used as electrodes in pseudo capacitors:
conducting polymers and metal oxides.

3.2.2.1. Conducting Polymers

Conducting polymers are used as electrode material in pseudo capacitors because they mainly offer
capacitance through redox processes. It is possible to introduce positive (p-doped) and negative
charge (n-doped) centers on electronic conjugated polymer chains through electrochemical redox
reactions which makes them viable material for supercapacitors. Also, the conducting polymers
can be charged positively/negatively along with ion insertion to balance the injected charges. The
redox reactions take place throughout the entire bulk of material and also these charge/discharge
processes are highly reversible because of no phase change involvement. The most common
conducting polymers used as supercapacitor electrode materials are polyaniline (PANI), polypyrrol
(PPy), polythiophene (PTh), poly(3,4-ethylene-dioxythiophene) (PEDOT) etc.

Conducting polymers possesses relatively high conductivity and capacitance along with low ESR
and cost compared to other carbon-based electrodes. Particularly, the p-n doped polymer
configuration with one positively charged (p-doped) and one negatively charged (n-doped)
conducting polymer electrode has helped to achieve high potential energy and high-power density
but lack of an efficient n-type conducting polymer material has restricted these supercapacitors
from reaching their potential. Further, it has been found that cyclic stability of conducting polymer
electrodes has been limited by the mechanical stress which is generated on the conducting polymers
when reduction-oxidation reactions takes place.

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3.2.2.2. Metal Oxides

The metal oxides are considered as most promising next generation electrochemical supercapacitor
electrode materials, since they can provide higher energy density than conventional carbon-based
double-layer capacitors, and better electrochemical stability than conducting polymer-based
materials. The mechanism of charge storage in metal oxides is pseudocapacitive which involves
faradaic redox reactions within appropriate voltage windows and also exhibit some bit of double
layer charge storage mechanism. The prerequisite for the metal oxides to be used as supercapacitor
electrode materials are:

i. The metal must have at least two oxidation states that can co-exist within a continuous
voltage range, with no phase change or irreversible structure change.

ii. The metal oxide itself must be electronically conductive.

iii. The protons or alkali cations should be absorbed on the oxide surface or intercalate into
their lattice easily during charge and discharge.

Until now, the most extensively investigated materials include ruthenium oxide, manganese oxide,
vanadium oxide etc.

3.2.3. Hybrid capacitors

Based on the electrode configuration, Hybrid capacitors have been divided into three categories
namely composite, asymmetric and battery type.

3.2.3.1. Composite

Composite electrodes consist of carbon-based electrodes integrated with either conducting polymer
of metal oxides and make use of both physical and chemical charge storage mechanism in a single
electrode. The carbon-based materials in the electrodes facilitate the double layer charge
mechanism and provides high surface electrode area which increases the contact between deposited
pseudocapacitive material and electrolyte. Further, pseudocapacitive material also facilitates to
increase the capacitance of composite electrode due to faradaic reactions.

3.2.3.2. Asymmetric

Asymmetric hybrid capacitors use combination of faradaic and non-faradaic processes by coupling
an EDLC and pseudo capacitor electrodes. As discussed in section 3.2.2(a), lack of an efficient n-
type conducting polymer material has restricted the conducting polymer pseudo capacitors from

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reaching their potential. Use of a negatively charged activated carbon electrode in place of n-type
conducting polymer material attempts to resolve this problem. While conducting polymer
electrodes have lower ESR and higher capacitance in comparison to activated carbon electrode
materials, they also have less cyclic stability and lower maximum voltage. Asymmetric hybrid
capacitors mitigate this tradeoff to achieve high power density and energy density by coupling
these two electrodes. This also result in better cyclic stability than pseudo capacitors.

3.2.3.3. Battery type

Similar to asymmetric hybrids, battery type hybrids also couple two different electrodes:
supercapacitor electrode and battery electrode. They combine the energy characteristics of batteries
with power, cyclic stability and recharge time of supercapacitors. Primary research has focused on
using nickel hydroxide, LTO (Li4Ti5O12) and lead dioxide as one electrode and activated carbon as
other electrode. The research has suggested that battery type hybrids may be able to bridge the gap
between batteries and supercapacitors thus providing more scope of research in supercapacitor
field.

3.3. Separators

In supercapacitors, separators serve as an inactive fundamental component, and plays an important

role in determining the device performance. A separator is a porous membrane/mat sandwiched
between two electrodes. Its main function is to physically separate the two opposite electrodes to
avoid electrical short circuits, and also provide a way for ionic charge carriers transport in liquid
electrolyte throughout the interconnected porous separator. The separators are chosen as very
porous to minimize ESR and chemically inert to protect the electrolyte's conductivity and stability.
The sophisticated designs use woven glass fibers or porous woven ceramic fibers, nonwoven
porous polymeric films like polyacrylonitrile or Kapton as separators while open paper capacitors
are used as separator material in inexpensive designs.

3.4. Current Collectors

In a supercapacitor, current collectors are used to connect the capacitor terminals to the electrodes.
Generally, the metal foils are used as current collector or collector is sprayed on the electrodes
sometimes.

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4. Supercapacitors vs other energy storage technologies
“Ragone plot” showing the performance improvement of supercapacitors in comparison to other
energy storage technologies is shown in Fig. 5. Ragone plot is a graph which shows power density
of various energy storage technologies measured along vertical axis versus their energy densities
which are measured along horizontal axis. It can be observed from the ragone plot that even though
supercapacitor provide greater capacitance than conventional capacitors, yet they have not met the
energy densities of mid to high end batteries and fuel cells.

Figure 5. Ragone plot of various energy storage technologies

The following table provides the general summary of some of the critical parameters of each energy
storage technology:

Property Supercapacitors Capacitors Fuel Cells Batteries

Charge/Discharge Milliseconds to Picoseconds to 10 to 300 hours. 1 to 10 hours
Time Seconds Milliseconds Instant charge
(Refuel)
Operating -40°C to +85°C -20°C to +100°C +25°C to +90°C -20°C to +65°C
Temperature
Operating 2.3 V to 2.75 V 6 V to 800 V 0.6 V 1.25 V to 4.2 V
Voltage
Capacitance 100 mF to 1500 F 10 pF to 2.2 mF NA NA
Life Cycle 50,000+ hours, >100,000 cycles 1500 to 10,000 150 to 1500
Unlimited cycles hours cycles
Weight 1 g to 230 g 1 g to 10 Kg 20 g to >5 Kg 1 g to >10 Kg
Power Density 10 to 120 kW/Kg 0.25 to 10,000 0.001 to 0.1 0.005 to 0.4
kW/Kg kW/Kg kW/Kg
Energy Density 1 to 10 Wh/Kg 0.01 to 0.05 300 to 3000 8 to 600 Wh/Kg
Wh/Kg Wh/Kg
Pulse Load Up to 100 A Up to 1000 A Up to 150 Up to 5 A

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 mA/cm2

5. Future of supercapacitor research

Over the past several years, research has been focused upon efforts to improve the capacitance of
the electrode material and to develop improved quantitative model. However, recently R&D efforts
concerning hybrid capacitors, electrolyte optimization, ESR and self-discharge are likely to be new
area of research for performance advancement in supercapacitors.

5.1. Hybrid Capacitors

Hybrid capacitors have combined the best features of EDLCs and pseudo capacitors in a unified
supercapacitor and have exhibited the combination of performance characteristics which was
unattainable with EDLCs and pseudo capacitors as an individual supercapacitor. Thus R&D efforts
to fabricate the improved hybrid capacitors and developing more accurate quantitative model is
continuously increasing. Because of features such as high cycle life, high energy density along
with flexibility in tuning the performance and design of hybrid capacitors is leading them to take
over the EDLCs and pseudo capacitors as the most promising class of supercapacitors.

5.2. Electrolyte Optimization

Electrolyte optimization has been constantly emphasized as the critical step towards
supercapacitors improvement by researchers. While the operating voltage and ionic concentration
of an electrolyte can limit the energy density, its resistivity can limit the power density of
supercapacitor. Despite the effects of electrolytic properties on supercapacitor performance,
research to improve electrolytes have not yet become as popular as that of electrodes. However,
many researchers believe necessary to encourage more R&D effort towards electrolyte
optimization to keep better synergy between electrode and electrolyte improvements.

5.3. Equivalent Series Resistance (ESR)

ESR plays an important role in achieving higher power density and thus R&D efforts to lower the
ESR of supercapacitors is becoming an important area of research. Methods such as bonding the
electrode chemically to current collector, using colloidal thin film suspensions and surface
polishing of current collator has already been developed to improve the ESR of supercapacitors.
Further, there is a lot of research scope to determine the intrinsic ESR of various electrolytes and

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finding the relation between pore size of electrode material and ESR. Improvement in ESR will
result in supercapacitors with much higher power density than contemporary supercapacitors.

5.4. Ameliorating Self-Discharge

One of the major drawback supercapacitors possesses is their tendency to self-discharge. Since
charged supercapacitors have higher potential energy than discharged supercapacitors, there is a
thermodynamic pressure to discharge for a supercapacitor. This pressure often manifests itself into
an undesirable process called as self-discharge which occurs when a supercapacitor discharges
internally with open circuit condition. Although, self-discharge is a common phenomenon in all
electrochemical energy storage devices such as batteries, capacitors; however, self-discharge rate
has been very high in supercapacitors tending to be more detrimental. This is because
supercapacitors do not have an intrinsic barrier to stop the supercapacitors operating in reverse
while in chemical reaction-based energy storage systems, reverse process is restricted due to
thermodynamic or kinetic barriers in absence of any external connection between electrodes.
Further, supercapacitors electrodes possess high potential difference across a very small separation.
Due to these reasons, supercapacitors have relatively much higher self-discharge rate than that of
batteries and capacitors.

Thus, ameliorating the self-discharge of supercapacitors is one of the main areas of research in the
supercapacitors field. There are various mechanisms for self-discharge but most common one is
the result of uncontrollable faradaic reactions such as oxidation and reduction of impurities in
electrode material. Thus, material purity improvement has been identified as one of the important
research areas to improve the self-discharge of supercapacitors.

References
1. http://www.cap-xx.com/resource/energy-storage-technologies/
2. Hao, Xihong. "A review on the dielectric materials for high energy-storage application." Journal of
Advanced Dielectrics V. 3, 2013
3. Zhang Y, Feng H, Wu X, Wang L, Zhang A, Xia T, "Progress of electrochemical capacitor electrode
materials: A review," International Journal of Hydrogen Energy, V. 34, No. 11, 2009, pp.4889-99
4. Ma, Guofu, et al. "A redox mediator doped gel polymer as an electrolyte and separator for a high-
performance solid-state supercapacitor." Journal of Materials Chemistry A 3.7 (2015): 4035-4041.

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