EIS - Zidan [Autosaved]

COMPLEXETY AND
ELEGANCE OF EIS
MOUSTAFA ZIDAN
Raise Your Hand If You Love
Electrochemistry
Well.. Whether You like It Or Not,
Electrochemistry Is Important.
Electrochemical Reactions Are At The Root Of Several
Research Areas Including:
- Energy Conversion And Storage

- Corrosion
- Sensors And Biosensing Applications
As Well As The Production Of Commodity Materials Such As

Aluminum And Chlorine.
That’s why many electrochemical techniques were
developed over time such as:
- Cyclic voltammetry
- Chronoamperometry
- Chronopotentiometry
- Scanning electrochemical microscopy
- Electrochemical impedance spectroscopy
- Electrochemical frequency modulation.
WHAT MAKES EIS DIFFERENT?
An electrochemical reaction at an electrode–
electrolyte interface can be decomposed
into a series of multistep processes:
- mass transport
- charge-transfer processes
- Adsorption
The individual steps are time-dependent and
may occur at different timescales (e.g.,
charging of the electrochemical double layer
happens on the microseconds timescale, but
diffusion occurs on hundreds of milliseconds
timescale.)
In EIS, We Use Frequency To Deconvolute Different
Electrochemical Phenomena That Occur At Different
Time Scales And Different Characteristic Frequencies.

HOW EIS WORKS
• The potentiostat applies sinusoidal potential to the system as
excitation and measures sinusoidal current as response
(Potentiostatic EIS) or the inverse (Galvanostatic EIS).
HOW EIS WORKS
• EIS experiment consists of
applying the sinusoidal potential
at multiple frequencies and
measuring the output sinusoidal
current at all those different
frequencies creating a spectrum.
• Fourier transform is applied after
that to all the data converting it
from the time domain to the
frequency domain.
Nyquist Plot Bode Plot
IMPORTANT
CONSIDERATIONS
LINEARITY
• Electrochemistry is non-linear, and circuit theory
is simplified when the system is linear.
• This is because impedance in a linear system is
independent of the excitation amplitude, and
the response of a linear system is at the same
frequency of the perturbation (no harmonics are
generated).
• That’s why we the applied excitation should be
small (in amplitude)
• The choice of an input perturbation magnitude
is a compromise between the need to achieve
linearity and the need for a sufficient signal-to-
noise ratio.
Umm.. Why is electrochemical systems
nonlinear?
Well.. This will be your homework. You
can google it 
Now let’s move on

• Electrochemical systems are not necessarily stable,
and the more stable the system is, the longer you can
run the EIS.
• The constraint of stability means that the response to
a perturbation cannot grow with time.
• EIS must also be causal, that’s the response of the
system is due only to the applied perturbation.
• Thus, EIS measurements should be designed to
conform to the Kramers–Kronig relations
KRAMERS-KRONIG
TRANSFORMATION
• widely used as part of a validation procedure to identify the
frequency ranges that may have been corrupted by instrument
artefacts or by non-stationary behavior.
• were derived under the assumptions that a system is stable, responds
linearly to a perturbation and is causal.
• The imaginary part of the impedance can be calculated from the real
part through:
Direct integration of the
Kramers–Kronig relations for
electrochemical impedance
spectroscopy (EIS)
measurements has been
replaced, in modern use, by
regression of Kramers–Kronig-
consistent circuit models that
provide extrapolation to zero and
infinite frequency limits that are
consistent with the behavior of
electrochemical systems
EXPERIMENTATION
How many electrodes?
Two Electrodes
• used in cases where it is difficult to insert a reference

electrode, such as batteries and fuel cells.
• The measured response is the sum of all contributions
between the working electrode and the counter electrode,
which complicates the interpretation of the impedance
response.
Three Electrodes
• The classic device used for all analytical electrochemical
measurements
• Employs a working electrode, which is the sample of interest, a
counter electrode and a reference electrode.
• The use of a reference electrode enables studying the working
electrode response independent of the processes taking place at the
counter electrode.
Four Electrodes
• Two reference electrodes are positioned on either side of the
interface to measure the potential and the two other electrodes allow
for passage of the current.
• used for the characterization of electrolyte conductivity, free-standing
films, an embedded rebar in concrete and the interface between two
immiscible electrolyte solutions.
COUNTER ELECTRODE
• The area of the counter electrode is normally much larger than that of
the working electrode to minimize its contribution to the cell
impedance.
• sometimes placed in a separate compartment to prevent its reaction
products from interfering with the working electrode.
• This compartment is ionically connected with the working electrode
compartment, usually with a glass/ceramic frit or asbestos threads.
Many Cycles for Each Frequency
• The noise level of the measurement is influenced by the

number of cycles used to measure the impedance at each
frequency.
• This effect from the number of cycles used is particularly
worthwhile at high frequencies because the noise content is
high and the time overhead for repetition is low.
• The typical frequency range for electrochemical
measurements, including energy conversion as well as
storage device and corrosion, is 10 kHz–10 mHz..
• It is preferable to start the measurement from the high-
frequency limit sweeping towards the low-frequency limit,
because the operator can grasp the main behavior of the
system in a short period of time.
Different Graphical Methods for
Results Representation:
• Nyquist representation for mass transfer and kinetic
behaviour.
• Bode representation for frequency-dependent behaviour.
• The admittance format for capacitive behaviour at high
frequency.
• The complex-capacitance format for capacitive behaviour of
a dielectric system.
• Generally, electrolyte resistance dominates at the high-
frequency range, diffusive impedance dominates at the low-
frequency range and interfacial processes dominate at the
intermediate-frequency range.
MECHANISM IDENTIFICATION
• EIS can be employed to identify reaction or failure mechanisms from EIS
signatures or the evolution of EIS features.
• This showed that the development of impedance models from assumed
reaction kinetics is superior to the interpretation of impedance data in
terms of an intuitively assumed electrical circuit.
• One way to validate the proposed mechanism is to check whether a
single set of parameters can describe the current–voltage curve and the
electrochemical impedance measured at different potentials.
• Once the mechanism is identified, EIS can be employed to estimate the
reaction parameters, such as charge-transfer resistance and the diffusion
coefficient
WHY EIS?
• provide an understanding of the electrochemical
mechanisms occurring at an electrified interface in a single
measurement.
• has allowed for better comprehension of intermediate
adsorption on electrode surfaces.
• a technique of choice for the study of porous electrodes
because the output is directly affected by the porosity of the
electrode, which may allow the pore size to be evaluated
Enough for Today :’
Any Questions?

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COMPLEXETY AND

- Energy Conversion And Storage

As Well As The Production Of Commodity Materials Such As

Electrochemical Phenomena That Occur At Different

Time Scales And Different Characteristic Frequencies.

Now let’s move on

• used in cases where it is difficult to insert a reference

• The noise level of the measurement is influenced by the

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