Assignment

Subject: Electrochemistry

by

M.S Vasudev M230776CY

Submitted to:

Dr. Minimol
Menamparambath

Department of Chemistry
National Institute of Technology
Calicut_673601 (India)

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ELECTROCHEMICAL CAPACITORS

Electrochemical capacitors (i.e., supercapacitors) include electrochemical double -layer

capacitors based on charge storage through ion adsorption and pseudo capacitors based on
charge storage with fast surface redox reactions. The energy storage capacities of
supercapacitors are several orders of magnitude higher than those of conventional dielectric
capacitors, but are significantly lower than those of secondary batteries. They typically have
high power density, long cycle stability and high safety and can therefore be considered as an
alternative or complement to rechargeable batteries in applications that require high power
output or rapid energy harvesting1. Efficient energy storage systems are required to power
hybrid/electric vehicles and the ever-increasing number of electronic devices and to store
energy from intermittent sources such as wind and solar. Powerful energy storage systems are
needed in our daily lives in a connected environment as we all want our electronic devices such
as smartphones and tablets to stay charged and functioning throughout the day. Electrochemical
capacitors (ECs) are playing an increasing role in meeting the demand for rapid generation,
storage, and delivery of electrical energy. Since then, the need for versatile, ubiquitous, high-
performance, high-energy-density storage has only increased 2.
Figure1: The Ragone Plot:

The reason why electrochemical capacitors have been able to attract widespread attention is
illustrated above, in which typical energy storage and conversion devices are represented in the

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so-called “Ragone Plot” in terms of their specific energy and specific power. Electrochemical
capacitors close the gap between batteries and traditional capacitors such as electrolytic
capacitors or metallized film capacitors. This gap spans several orders of magnitude in terms
of both specific energy and specific power 3.

Principle of Electrochemical Capacitors:

Electrochemical capacitors store electrical energy in an electrochemical double layer
(Helmholtz layer), which is formed at an interface between the solid and the electrolyte.
Positive and negative ionic charges within the electrolyte collect on the surfac e of the solid
electrode and compensate for the electronic charge on the electrode surface. The thickness of
the double layer depends on the concentration of the electrolyte and the size of the ions and is
on the order of 5–10 Å for concentrated electrolytes. The double layer capacitance for a smooth
electrode in concentrated electrolyte solution is approximately 10 -20 μF/cm 2 and can be
estimated using the equation. 3
C/A= εo*εr/d
assuming a relative permittivity εr of 10 for water in the double layer. d is the thickness of the
double layer with surface A. The corresponding electric field in the electrochemical double
layer is very high and easily reaches values of up to 10 6 V/cm. Compared to traditional
capacitors, where a total capacitance of pF and μF is typical, the capacitance and energy density
stored in the electrochemical double layer is inherently quite high and the idea of building a
capacitor based on this effect is tempting. To achieve a higher capacitance, the electrode surface
area is additionally increased by using porous electrodes with an extremely large internal
effective surface. Combination of two such electrodes give an electrochemical capacitor of
rather high capacitance. The capacitance of a single electrode can be estimated by assuming a
high surface area carbon of 1000 m 2/g and a double layer capacitance of 10 μF/cm 2. This results
in a specific capacitance of 100 F/g for an electrode. A capacitor requires two electrodes of
twice the weight and half the total capacitance (1/C=1/C1+1/C2), giving 25 F/g active capacitor
mass for the example given below (Fig:2). The difference between the values of individual
electrodes and the specifications given for the entire capacitor is significant. When providing
information about an EC, one should state whether the values correspond to a single electrode
measurement or were calculated for a complete capacitor. The difference between these two
situations is a factor of four and is therefore significant.

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Fig 2: A single-cell double-layer capacitor's working principle and an example of the potential
drop at the electrode/electrolyte interface.

Figure 2 shows a schematic diagram of an electrochemical double layer capacitor consisting of

a single cell with a large surface area electrode material loaded with electrolyte. The electrodes
are separated by a porous separator that contains the same electrolyte as the active material.
The potential drop across the cell is also shown in Figure 2. The maximum energy stored in
such a capacitor is given by W=1/2CU02
With a cell voltage U0 of 1 V (aqueous electrolyte), a specific energy of around 3.5 Wh/kg
active mass is obtained. When using an organic electrolyte with a typical cell voltage of 2.3 V,
approximately 18 Wh/kg active mass is obtained. These values are significantly lower than
with available batteries, but significantly higher than with conventional capacitors. It should
be mentioned that the above values depend on the double layer capacity, the specific surface
area of the respective electrode material, the wetting behavior of the pores and the nominal cell
voltage.
Classification of electrochemical capacitors: Based on Material
Electrochemical capacitors can be differentiated based on several criteria, such as the electrode
material used, the electrolyte or the cell design. There are three main categories of electrode
materials: carbon-based, metal oxides and polymer materials.
Carbon:
Carbon is widely used in electrochemical capacitor electrodes due to its low cost, large surface
area (up to 2500 m²/g), availability and established production methods. It stores charge
primarily via the electrochemical double layer, but also exhibits pseudo capacitance due to
surface functional groups generally present on activated carbons. In cyclic voltammetry (CV),
an ideal rectangular shape is observed in organic electrolytes, while redox peaks from surface

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groups appear in aqueous electrolytes. Oxygen-containing groups can increase the stability of
activated carbon in anodes in organic electrolytes but reduce it of cathodes. Larger surface
areas can reduce the stability and conductivity of activated carbon.

Figure 3. Cyclic voltammograms of activated glassy carbon electrodes at 100 mV/s in 3M

H2SO4 (aqueous) and in 1 M TEABF4 in acetonitrile. Both electrodes received the same
electrochemical activation.
Metal oxides:
RuO₂ and IrO₂ electrodes have almost rectangular CV shapes due to redox reactions and not a
pure double layer charge. Ru can change its valence state from III to VI within a 1 V window,
with proton insertion into the bulk material being the primary charge storage process in acidic
aqueous electrolytes. RuO₂ can achieve high specific capacitance (~750 F/g) and low
resistance, providing high power, but comes at a high cost as 90% of the capacitor cost is in
the electrode material. Attempts to reduce costs include diluting precious metals (e.g.
perovskites) and exploring alternatives such as metal nitrides, although commercial
implementation is limited.
Polymers:
Polymeric materials such as poly(3-arylthiophene), poly(pyrrole), and poly(3-
methylthiophene) are proposed as electrode materials for electrochemical capacitors, although
their cyclic voltammograms (CVs) typically show redox peaks based on the redox potential of
the polymer and not the ideal rectangular shape of capacitors. Recently, polymers with both
anodic and cathodic redox processes have been used on dual electrodes, leading to a debate
about whether such devices should be called capacitors or batteries. Although these materials
offer good energy and power density, they have long-term stability issues due to swelling and
shrinkage during cycling, which can lead to degradation.

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Classification of electrochemical capacitors: Based on Electrolyte
Organic:
Organic electrolytes in electrochemical capacitors allow higher cell voltages, typically up to
2.3 V and briefly even 2.7 V, increasing energy storage due to the squared relationship between
voltage and energy. To achieve even higher voltages (up to 3.2 V), high-purity electrolytes and
corrosion-resistant coatings on carbon electrodes are required. However, organic electrolytes
have a higher resistivity (20-50 times that of aqueous electrolytes), which increases the total
series resistance (ESR) and limits power output. This reduction in power is partially offset by
the higher cell voltage achievable, but efficiency is still compromised.
Aqueous:
Aqueous electrolytes in electrochemical capacitors are limited to a unit cell voltage of about 1
V, which reduces energy storage compared to organic electrolytes. However, they offer
advantages such as higher conductivity (e.g. 0.8 S/cm for H₂SO₄), lower c osts and less
demanding cleaning. NEC and ECOND capacitors, as well as laboratory -developed glassy
carbon-based capacitors, use aqueous electrolytes to achieve high power density. The capacitor
design, including electrode porosity, must match the properties of the electrolyte. To prevent
electrolyte depletion, high concentration is required, particularly for organic electrolytes where
solubility limits can affect performance. 3

PSEUDOCAPACITORS:
The charge storage mechanisms of electrochemical SCs are characterized as follows and shown
in Fig. 1: (i) electric double layer charge storage mechanism (EDL), also known as non -faradaic
charge storage mechanism. Under certain conditions, charge transfer/redox reactions do not
occur in each electrode-electrolyte interface because they are thermodynamically or kinetically
unfavorable. The adsorption-desorption process takes place, which is therefore referred to as
the non-Faradaic process. (ii) The Faradaic charge storage mechanism, which is based on the
oxidation-reduction reaction (redox reaction), is a pseudocapacitive charge storage mechanism.
Electrodes on which Faradaic processes take place are also called charge transfer electrodes.
They are further categorized into intrinsic and extrinsic type pseudocapacitors.4

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Fig 1: Classification of electrochemical capacitors based on charge storage mechanism:
EDLCs, Pseudocapacitors (Intrinsic and extrinsic).
Pseudocapacitance is an electrochemical energy storage mechanism discovered in 1941, which
involves fast, reversible Faradaic reactions at or near the electrode surface. Initially described
by Grahame and later expanded upon by Conway and Gileadi, pseudocapacitance differs from
pure electrostatic double-layer capacitance and traditional battery reactions. In the 1970s,
researchers identified ruthenium oxide (RuO₂) as a promising pseudocapacitive material due
to its reversible surface redox reactions. Later, low-cost alternatives like manganese oxide and
conducting polymers were explored. In the 1990s, the concept was applied to Li⁺ intercalation
materials, further broadening pseudocapacitor research, which now includes materials such as
MXenes. Modern pseudocapacitors integrate nanostructured materials for enhanced surface
area, rapid ion transport, and improved cycling stability. 5
In 1962, Conway and colleagues coined "pseudocapacitance" to describe a unique type of
reversible capacitance related to electrochemical ion adsorption on electrodes, initially defined
by ion monolayer adsorption on platinum. This was termed adsorption pseudocapacitance.
Later, with materials like RuO₂, Conway proposed redox pseudocapacitance, where charge is
stored through surface redox reactions, and intercalation pseudocapacitance, observed in
Nb₂O₅, where ions integrate within the material. These types of pseudocapacitance provide a
linear relationship with potential, showing distinct energy storage benefits, especially in
Faradaic and capacitive contributions. 4

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Fig 2. As per Conway, images depict the illustration of the three types of pseudocapacitive mechanisms:
(a) Adsorption pseudocapacitance, (b) Redox pseudocapacitance, and (c) Intercalation
pseudocapacitance.
Adsorption Capacitance:
According to Conway et al., the first type of pseudocapacitance, adsorption pseudocapacitance, is
represented by the equation given below, the electro-sorption of cation A + onto the surface of the
conductive surface M is assumed to follow the Langmuir-type electro-sorption isotherm:

Where, CA represents the concentration of the cation, the surface coverage of MA ads is θ, the surface
coverage of M is 1 − θ, K represents the ratio of the forward and reverse reaction rate constant, F
represents the Faraday constant, R represents the ideal gas constant, V represents the electrode potential,
and T represents the temperature. and it can lead to Nernst equation except for the ratio of reduced to
oxidized species has been replaced by the extent of adsorbate surface coverage, θ as represented in:

Where E is the equilibrium potential of the redox couple and E 0 is the standard potential of the redox
couple. Assuming the charge required to complete a monolayer coverage of A ads is q, the
pseudocapacitance CΦ can be defined as: It is obvious from above equation that when the θ value = 0.5,
the maximum pseudocapacitance is obtained. As a result, the pseudocapacitance will be a function of
applied voltage and surface coverage for a purely Langmuir-type electro-sorption, as shown
in Fig. 3(a). Fig. 3(b) depicts the deposition of adsorbates at identifiable subsequent phases of
electrochemical adsorption with increasing coverage, resulting in multiple peaks, and/or lateral
repulsive interaction between adsorbates as θ increases, increasing the dependence of CΦ .

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Fig 3: Schematic of cyclic voltammograms of extrinsic and intrinsic pseudocapacitive materials. (a)
Pseudocapacitors indicating no diffusion limitation due to fast ion diffusion, (b) extrinsic
pseudocapacitors show the diffusion limitations, and (c) intrinsic pseudocapacitors. 4
Conway’s work on pseudocapacitance advanced the understanding of charge storage mechanisms in
electrochemical energy storage (EES). He highlighted the reversible nature of pseudocapacitance,
contrasting it with batteries, which rely on irreversible phase changes. Costentin and Savéant expanded
on this by suggesting a double-layer plus Faradaic process for enhanced charge storage, where Faradaic
contributions depend on active surface area. Conway also noted the near-ideal cyclic voltammetry (CV)
curve of pseudocapacitors, signifying low hysteresis and high efficiency. These insights support high-
performance pseudocapacitor development. 4

References:
1. Yongyao Xia, et al; Chem. Soc. Rev., 2016,45, 5925-5950
2. Yury Gogotsi, et al; Nature Materials volume 19, pages1151–1163 (2020)
3. M.Carlen; Elec.Chemica. Acta.3 May 2000, Pages 2483-2498
4. P. Bhojane Journal of Energy Storage 45 (2022) 103654
5. Veronica Augustyn, et al; Chem. Rev. 2020, 120, 6738−6782