Q) Why does capacitance increase with scan rate?

Popular Answers (1) As the scan rate increases the diffusion of electrolyte ion into
electrode internal structure and pore become difficult (diffusion limitation) and ineffective
interaction between the electrolyte and electrode materials occurs therefore the specific
capacitance is decrease
QWhat is scan rate in voltammetry?

In cyclic voltammetry (CV), the electrode potential ramps linearly versus time in cyclical
phases (Figure 2). The rate of voltage change over time during each of these
phases is known as the experiment's scan rate (V/s)
Q. How do I choose a scan rate?

The choice of scan rates depends upon the information sought:

1. If the aim is to look for anodic and cathodic reversible peaks, scan rate of about 5 mV
per sec is suitable.
2. If the aim is to obtain approximate kinetic parameters, scan rate of 100 mV per sec is
adequate.
Q. What is rate capability of supercapacitor?
Abstract. In the present work, supercapacitors based on graphene /Pt films show
especially high rate capability (120 F g−1 even at 50 A g−1) and cyclability (no
attenuation over 10 000 cycles) and peculiar nanosphere morphology after
electrochemical cycling.
Q. Why does capacitance increase with scan rate .?
Popular Answers (1) As the scan rate increases the diffusion of electrolyte ion into
electrode internal structure and pore become difficult (diffusion limitation) and ineffective
interaction between the electrolyte and electrode materials occurs therefore the specific
capacitance is decrease.
Why Capacitance varies by changing scan rate in cyclic voltammetry ?
As the scan rate increases the diffusion of electrolyte ion into electrode internal structure and pore
become difficult (diffusion limitation) and ineffective interaction between the electrolyte and electrode
materials occurs therefore the specific capacitance is decrease. 
Reasonable scan rate/current density should be used whether reporting
maximum specific capacitance for supercapacitor?
When scan rate is very low, redox behavior will be included. batteries are generally
worked in low scan rates (0.1 mV/s). All the electrochemical behaviors are analysed in
low scan rates. And supercapacitor is associated with fast charge-discharge cycles and
fast scan rate only.
Testing Electrochemical Capacitors Part 1: CV, EIS, and Leakage Current
Introduction
Super-capacitors are energy storage devices similar to secondary batteries. Unlike
batteries, which use chemical reactions to store energy, super-capacitors generally
store energy through the physical separation of electrical charges.

All super-capacitors consist of two electrodes immersed in a conductive liquid or

conductive polymer called the electrolyte. The electrodes are separated by an ionic-
conducting separator that prevents shorts.

Compared to a battery, a super-capacitor has the following advantages:

1. Higher charge and discharge rates (high power density)

2. Longer cycle life (> 100,000 cycles)
3. Materials with low toxicity
4. Operation over a wide temperature range
5. Low cost per cycle
These are offset by some disadvantages:

1. Higher self-discharge rate

2. Lower energy density
3. Lower cell voltage
4. Poor voltage-regulation
5. High initial cost
Current applications for super-capacitors include:

1. Hybrid Electric Vehicles (HEVs)

2. Diesel-engine starting systems
3. Cordless power tools
4. Emergency and safety systems
uperCyclic Voltammetry (CV)
Cyclic Voltammetry (CV) is a widely-used electrochemical technique. Early in a
capacitor development project, CV yields basic information about a capacitive
electrochemical cell including:

 Voltage window
 Capacitance
 Cycle life  
A comprehensive description of Cyclic Voltammetry is well beyond the scope of this
application note. Most books describing laboratory electrochemistry have at least one
chapter discussing CV.
Description of Cyclic Voltammetry
CV plots the current that flows through an electrochemical cell as the voltage is swept
over a voltage range. A linear voltage-ramp is used in the sweep. Often, a CV test
repetitively sweeps the voltage between two limit potentials. A pair of sweeps in
opposite directions is called a cycle.

Figure 1 presents a CV experiment as a plot of capacitor voltage and current versus

time. The darker-colored, saw-toothed waveforms are the voltage applied to the cell; the
lighter-colored waveforms are measured current. This graph shows a CV test with three
and one-half cycles. Each cycle is shown in a different color. 

Figure 1.2: Cyclic Voltammogram of measured current versus applied potential.

This diagram also shows the points where the y-values of peak anodic current
(ipa) and peak cathodic current (ipc) as well as the x-values of peak anodic
potential (Epa) and peak cathodic potential (Epc).

Cyclic voltammetry (CV) is a technique used to study reaction mechanisms that involve

the transferring of electrons. The method involves linearly varying an electrode
potential between two limits at a specific rate while monitoring the current that
develops in an electrochemical cell. This experiment is performed under conditions
where voltage is in excess of that predicted by the Nernst equation (Equation Lab
1.1Lab 1.1).¹ Although CV is best at providing qualitative information about reaction
mechanisms, several quantitative properties of the charge transfer reaction can also be
determined.

E=E°−RTnFlnQ(Lab 1.1)(Lab 1.1)E=E°−RTnFln⁡Q

Cyclic voltammetry involves applying a voltage to an electrode immersed in an

electrolyte solution, and seeing how the system responds. In CV, a linear sweeping
voltage is applied to an aqueous solution containing the compound of interest. A linear
sweeping voltage is defined by the voltage (or potential) being varied linearly at the
speed of the scan rate. The variation of the voltage can be seen in Figure 1.1. The
voltage is initially given by Equation Lab 1.4Lab 1.4 (see below). After the voltage
reaches a certain maximum value, the potential is reversed and the sign of vt reverses
and Ei becomes the maximum voltage, EλEλ. The switch takes place at the peak which
can be seen in Figure 1.1. The process can then be repeated in a periodic, or cyclic
manner. The voltage after the potential sweep direction is switched is given by
Equation Lab 1.5Lab 1.5.

As an important tool for studying mechanisms and rates of oxidation and reduction
processes, CV provides the capability for generating a species during the forward scan
and then probing its fate with the reverse scan or subsequent cycles. This process can
occur within a few seconds. There is a unique aspect of cyclic voltammetry: three
electrodes used. The electrodes are a working electrode, a reference electrode, and a
counter electrode. The working electrode can be seen as a medium whose reductive or
oxidative power can be externally adjusted by the magnitude of the applied potential.
As the potential is increased or decreased linearly versus time, the working electrode
becomes a stronger oxidant or reductant, respectively. Therefore, the working
electrode, which typically consists of a chemically inert conductive material such as
platinum, acts as a donor or acceptor of electrons. The general reaction written in
Reaction Lab 1.2Lab 1.2 refers to the addition of electrons to the oxidized electrode
and the electrode transforming to its most reduced form.

O+ne−→R(Lab 1.2)(Lab 1.2)O+ne−→R

The reference electrode, typically AgCl or calomel, keeps the potential between itself
and the working electrode constant. The potential is measured between the reference
and working electrodes, and the current is measured between the working and counter
electrodes. A counter electrode is employed to allow for accurate measurements to be
made between the working and reference electrodes. The counter electrode's role is to
ensure that the current does not run through the reference electrode since such a flow
would change the reference electrodes potential. A voltage sweep from Ei (initial
voltage) to Ef (final voltage) is produced using a signal generator. The voltage is applied
to the working electrode using a potentiostat. A potentiostat is an external power
source. By sweeping the voltage slowly, information may be extracted from a graph of
potential versus current going through the sample. Polarography utilizes this method of
analysis where the limited current arising from a redox process in the solution during
the sweep. This information is used to quantitatively determine the concentration of
species that are electrochemically active in solution.

CV differs from polarography in two important ways. Firstly, the working electrode at
which the reactions of interest occur has a constant area, not one which changes with
time as in classical polarography. This electrode may be a solid such as graphite or
platinum with a small surface area, or a stationary or hanging mercury drop. The latter
type of electrode may have its surface renewed periodically. The second difference is
that the potential of the working electrode is scanned rapidly over a wide potential
range and then returned to its initial value using an applied potential signal which varies
linearly with time between the initial value and the final value at the limit of the forward
scan. Normally, this technique is applied so that currents due to reduction processes are
observed during the forward scan and those due to oxidation on the reverse scan. The
resulting cyclic voltammogram from a typical potential against time profile is shown
in Figure 1.2.
A galvanostat (also known as amperostat) is a control and measuring device capable of keeping
the current through an electrolytic cell in coulometric titrations constant, disregarding changes in the
load itself.
Its main feature is its nearly "infinite" (i.e. extremely high in respect to common loads) internal
resistance.
The designation "galvanostat" is mainly used in electrochemistry: this device differs from
common constant current sources by its ability to supply and measure a wide range
of currents (from picoamperes to amperes) of both polarities.
The galvanostat responds to changes in the resistance of the cell by varying its output potential:
as Ohm's law shows,
the variable system resistance and the controlled voltage are directly proportional, i.e.
where
  is the electric current that is kept constant
  is the output control voltage of the amperostat
  is the electrical resistance that varies; thus, an increase of the load resistance implies
an increase of the voltage the amperostat applies to the load.
What Does Galvanostatic Mean?
Galvanostatic refers to an experimental technique whereby an electrode is
maintained at a constant current in an electrolyte. This technique is used to
measure corrosion rate and electrochemical reactions.

Galvanostatic, like potentiostatic and potentiodynamic, is a polarization

technique that allows for the controlled polarization of metal surfaces in
electrolytes, in order to directly observe cathodic and anodic behaviors.

In galvanostatic tests, the change is plotted in potential verses time at

constant current. A constant DC current is applied to the metal of interest
while it is immersed in the electrolyte.

The galvanostatic mode is an electrochemical measuring mode for

electrochemical analysis or for the determination of the kinetics and
mechanism of electrode reactions based on the control of the current flowing
through the system. The control apparatus used is called a galvanostat.

The galvanostatic method consists of placing a constant current pulse upon

an electrode and measuring the variation of the resulting current through
the solution. It is used for measuring the rate of an electrochemical reaction.
This technique is used for Tafel curves and linear polarization
measurements, and its applications include corrosion rate measurement.

Galvanostatic polarization is an alternative to potentiostatic polarization. In

galvanostatic polarization measurements, the current between working and
counter electrodes is controlled, and the potential between working and
reference electrodes is automatically adjusted to the value required to
maintain the current. The potentiostatic polarization curve provides
considerably more information about passivity than does the galvanostatic
curve.

In the galvanostatic approach to measure linear polarization resistance:

1. A small current is applied.

2. The electrode potential changes.
3. The potential change is measured.
4. Overvoltage vs. current is plotted and the slope calculated.
Basics of Electrochemical Impedance
Spectroscopy
This tutorial presents an introduction to Electrochemical Impedance Spectroscopy (EIS)
theory and has been kept as free from mathematics and electrical theory as possible. If
you still find the material presented here difficult to understand, don't stop reading. You
will get useful information from this application note, even if you don't follow all of the
discussions.

Four major topics are covered in this Application Note.

 AC Circuit Theory and Representation of Complex Impedance Values

 Physical Electrochemistry and Circuit Elements
 Common Equivalent Circuit Models
 Extracting Model Parameters from Impedance Data
No prior knowledge of electrical circuit theory or electrochemistry is assumed. Each
topic starts out at a quite elementary level, then proceeds to cover more advanced
material
EIS

Electrochemical impedance spectroscopy (EIS) is a powerful technique

used for the analysis of interfacial properties related to bio-recognition
events occurring at the electrode surface, such as antibody–antigen
recognition, substrate–enzyme interaction, or whole cell capturing.

Electroanalytical methods are considered as the most important branch

of analytical chemistry, which determines characteristics along with
quantity of specific analyte(s) present in an electrochemical cell. The
measurement of electrochemical features taking place at the electrode
interface reflects the association between the magnitude of the property
measured and the concentration of particular chemical species.
Compared to other analytical methods, e.g., chromatography or
spectroscopy, electroanalytical techniques are much simpler and easier
to miniaturize as well as being cheaper, which makes them more
appropriate for rapid and accurate detection. Based on the measurable
signals, electroanalytical methods are categorized as follows:

Potentiometric analysis: a reference electrode and an indicator electrode

are allocated in a simple electrochemical cell whereas the difference of
potential between the two electrodes is recorded to provide significant
information about the sample concentration [1]. In the potentiometric
technique, at zero current, the potential changes (vs. a reference
electrode) are correlated to the changes of a concentration of a target
analyte. The EMF of a cell depends on that concentration. Therefore, a
direct calculation is easily obtained from the Nernst correlation
(Equation (1)):

Ecell = E0cell − (RT/nF) ln Q

(1)

where Ecell is the measured cell potential, E0 is the standard cell potential,
R is the universal gas constant, T is the temperature, n is the number of
electron transfer, F is the Faraday constant, and Q is the reaction
quotient that represents the instantaneous ratio of redox-concentrations
between the anode and the cathode.

What is the principle of Electrochemical Impedance Spectroscopy?

Electrochemical impedance spectroscopy (EIS) is a powerful technique that utilizes a
small amplitude, alternating current (AC) signal to probe the impedance
characteristics of a cell. The AC signal is scanned over a wide range of frequencies to
generate an impedance spectrum for the electrochemical cell under test.

Electrochemical Impedance Spectroscopy (EIS) is a highly sensitive

characterization technique used to establish the electrical response of chemical systems
in a nondestructive manner. EIS systems characterize the time response of chemical
systems using low amplitude alternating current (AC) voltages over a range of
frequencies. Using an electrode setup consisting of a working, reference, and counter
electrodes a known voltage is passed from the working electrode through an electrolytic
solution and into the counter electrode. Quantitative measurements are produced by
the EIS and enable the evaluation of small scale chemical mechanisms at the electrode
interface and within the electrolytic solution. Therefore, EIS is useful in determining a
wide range of dielectric and electrical properties of components in research fields
studying batteries, corrosion, etc.
Experimental Set Up

An electrochemical cell is used to house the chemical reaction and is electrically

connected to the electrochemical spectrometer to obtain the electrical response of an
electrolytic solution. EIS systems are operated using computer programs specifically
designed for EIS testing. Therefore, prior to conducting an EIS experiment it is essential
that all components of the system be attained.

Generally, EIS studies utilize a three electrode mode which is comprised of a working
electrode (the sample material), a counter electrode (commonly graphite or platinum),
and a reference electrode. While electrode geometries may vary the general
experimental setup remains similar to the procedure outlined below.

The three electrodes are mounted on an electrode stage and secured. The electrolytic
solution is prepared and transferred to the sample container. A metallic sample
container would provide additional pathways for electrons during experimentation
leading to a reduction in the EIS current response as electrons move into the metal
rather than the reference electrodes. Therefore, the sample container should be
composed of an insulating material, such as glass or plastic, which will not interfere
with the transfer of electrons during testing. The electrode mount is then placed on the
sample container such that a portion of each electrode is submerged in the electrolytic
solution.