(Electrochemical )Impedance Spectroscopy

Ohms Law and why we use EIS??

Ohms law Z= E/I

• Ability of a circuit element to resist the flow of electrical current. Ohm's

law defines resistance in terms of the ratio between voltage, E, and
current, I.

• Limited to only one circuit element –Under the ideal resistor conditions

• It follows Ohm's Law at all current and voltage levels.

• Its resistance value is independent of frequency.
• AC current and voltage signals though a resistor are in phase with each
other.

https://www.gamry.com/application-notes/EIS/basics-of-electrochemical-impedance-
spectroscopy/
 What is Electrochemical Impedance
Spectroscopy?

 Exploit Faraday’s Law to characterize a chemical process

in terms of electrical measurements.

 Electrochemical impedance is the response of an

electrochemical system (cell) to an applied potential.

 The frequency dependence of this impedance can reveal

underlying chemical processes.
 What is Electrochemical Impedance
Spectroscopy?

 The response of electrochemical systems is very nonlinear.

 We interrogate the impedance in a perturbative manner:ƒ Small

amplitude (~10 mV) AC ripple on top of the controlled DC
polarization potential with varying frequency (mHZ to MHz)

 Frequency (High-Fast electrode kinetics and low frequency- Slow

process such as diffusion )

 At high frequency the reactants do not have enough time to diffuse

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 Resistors, capacitors and Inductors

• Impedance of a resistor is independent of frequency

• Impedance of the capacitor is inversely proportional to frequency

(Phase=90˚) ; Capacitor behavior occurs at low and mid frequency region)

• Impedance of inductor is in direct proportional to frequency(Phase = -90˚)

• Inductance phenomena occurs at high and mid frequency
 Impedance values changes with that changes with frequency and has phase shift.

 impedance drops with frequency and the current leads voltage by 90 degrees, it is
capacitance

 impedance rises with frequency and the current lags voltage by 90 degrees, it is
inductance

Component Impedance as
complex form
resistor Z=R

inductor Z = jωL

capacitor Z = 1/jωC
 Analyzing EIS: Modeling

• Electrochemical cells can be modeled as a

network of passive electrical circuit elements.
• A network is called an “equivalent circuit”.
• The EIS response of an equivalent circuit can
be calculated and compared to the actual EIS
response of the electrochemical cell.

R Capacitance Inductor
Constant phase
Warburg element
 Nyquist and its corresponding bode planes

R independent of “f”
1 Log IzI Zim

Log f
Zreal

2 Log IzI
Zim

Log f
Zreal

3 Log IzI
Zim
Log f
Zreal

Similar to capacitor- however, ideally it deviates

 Electrochemistry as a Circuit
Helmholtz region

Diffuse region
• Double Layer
Capacitance
• Electron
Transfer
Resistance
• Uncompensate
d (electrolyte) Randles Cell
Resistance (Simplified)
Working electrode
DLC
Including diffusion region in equivalent circuit
 Nyquist, Bode and Phase angle of a simple
Randles circuit

Low freq.
High freq.

Rs
Rct

https://www.gamry.com/application-notes/EIS/basics-of-electrochemical-impedance-
spectroscopy/
 Randles with diffusion impedance

Warburg

Rs Rct

https://www.gamry.com/application-notes/EIS/basics-of-electrochemical-impedance-
spectroscopy/
Inductance
Exercise
Files --- Examples
Ignoring Rs
Including Rs
THANK YOU
ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY
EIS – Mass Transfer Controlled Process

Nyquist
Bode
Impedance

Bode
Phase
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Mixed kinetics
ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY

Bode
Impedance
(Magnitude

Nyquist

Bode Phase
Angle
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