Introduction to Electrochemical Impedance Spectroscopy


Syllabus and Tentative Schedule:
No. Topic
1. Introduction: Introduction to electrochemistry, electrode-electrolyte interface, EIS basics, graphical representation of impedance data
2. Experimental details: Instrumentation, role of supporting electrolyte, single and multi-sine inputs, linearity and stability
3. Data validation: Kramers Kronig Transforms (KKT), applications and limitations, Alternatives: measurement model analysis and linear KKT
4. Data analysis: Electrical Equivalent Circuits, choice of circuits, distinguishability, zeros and poles representation. Reaction mechanism analysis, linearization of governing equations, reactions with intermediates, identification of mechanism from data
5. Physical Phenomena: Origin of constant phase elements behavior, diffusion effects, Warburg Impedance, porous electrodes, passivation and film formation
6. Selected applications of EIS: Corrosion, biosensors, materials characterization, fuel cells and batteries
7. Variations of EIS: Local EIS, Nonlinear EIS, higher harmonics, noise based techniques
Assignments:
  1. Assignment 01
  2. Assignment 02
  3. Assignment 03
  4. Assignment 04
  5. Assignment 05

References :

    Books

  1. Electrochemical Impedance Spectroscopy , by Mark E. Orazem and Bernard Tribollet
  2. Impedance Spectroscopy , by E. Barsoukov and James Ross Macdonald
  3. Electrochemical Impedance Spectroscopy and its applications , Andrzej Lasia
  4. Impedance Spectroscopy , by V.F. Lvovich

    5. Online Resources

    1. Basics of EIS , in Gamry website
    2. Introduction to EIS , maintained by IVIUM.
    3. Introduction to EIS by Prof. Rusling, University of Connecticut.
    4. Check out the application notes and tutorials, in Biologic website.
    5. A detailed Introduction by Andrzejf Lasia, who has also written one of the books listed above.
    6. Application notes in Solartron Analyitical . In particular, look for "Identification of electrochemical processes by frequency response analysis" by Gabrielli. Note: Solartron is with AMETEK group now, and you may have to register, to access these notes

      7. There are many other resources on EIS, available online. You can search in google with specific queries and sift through the results.


    Class Notes

    1. Introduction to electrochemistry (Not yet ready)
    2. Introduction to EIS
    3. Time domain response of a simple electrical circuit. Data visualization options
    4. Outline of a few other electrochemical techniques, and experimental aspects in EIS
    5. Application of FFT to transfer time domain data to frequency domain
    6. Multisine waves. Harmonics and non-harmonics. Advantages and pitfalls.
    7. Spectral Leakage. Data validation using KKT , with examples
    8. KKT, Measurement model approach, linear KKT . Basics and illustrations
    9. Linear KKT illustrations. Next, EEC. An introduction to EIS data modeling using equivalent electrical circuit (EEC)
    10. EEC - modeling data set. How can we choose 'the best circuit'? Akaike Information Criterion (AIC)
    11. Equivalent electrical circuit or EEC - Some circuits cannot be distinguished. Zero pole representation. Concept of writing the impedance of a reaction
    12. Equivalent electrical circuit or EEC and RMA . EEC analysis - how to use Rt and Rp to guess initial values. Next, Reaction mechanism analysis of a simple electron transfer reaction
    13. Reaction Mecanism Analysis. Simple electron transfer reaction. Next, a two step reaction
    14. Mechanistic Analysis, Two step reaction, with and adsorbe intermediate . First step is an electrochemical reaction, 2nd step is a chemical reaction
    15. Two step reaction, both are electrochemical steps Reaction Mecanism Analysis. Illustration showing inductive loop at one potential and capacitive loop at another potential
    16. E-EAR Reaction. Reaction Mecanism Analysis. Illustration showing negative (differential) impedance
    17. Reaction with two adsorbed intermediates. Mecanistic Analysis of a three step reaction. A variety of patterns in complex plane plots are possible
    18. Catalytic reaction, explained with illustrations Faradaic impedance in high overpotential showing negative (differential) impedance

Mark Distribution:

  1. Mid Sem: 30
  2. Home Work: 30
  3. Final Exam : 40