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1 Daria Vladikova IEES - BAS, 10 Acad. G. Bonchev St., 1113 Sofia, BULGARIA Centre of Excellence “Portable and Emergency Energy Sources” E-mail: d.vladikova@bas.bg IEES-BAS Centre of Excellence

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2 IEES-BAS Centre of Excellence “a,b,c” Impedance is an introductory course, which aims at giving basic knowledge in the field of electrochemical impedance spectroscopy. The course offers general information concerning: principle of the impedance spectroscopy; basic definitions; structural modelling – main electrical and electrochemical elements and their physical meaning, models of basic electrochemical phenomena. “a,b,c” Impedance can be regarded as a necessary prerequisite for the next group of lectures on advanced impedance techniques (non-stationary and differential impedance analyses).

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3 IEES-BAS Centre of Excellence ntroduction5 2.What is Electrochemical Impedance Spectroscopy10 3. Impedance of Electrochemical Systems13 3.1. Basic Hypotheses14 3.2. Impedance Presentation and Monitoring 3.3. Advantages and disadvantages of Electrochemical Impedance Spectroscopy 20 4.Main Steps in the Classical Impedance Investigation21 5.Impedance Models 24 5.1. Impedance Elements 25 5.1.1. Lumped Elements 26 Resistance26 Capacitance28 Inductance 30 5.1.2. Frequency Dependent Elements 32 Warburg Element 32

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4 IEES-BAS Centre of Excellence Bounded Constant Phase Element 42 5.2. Simple Calculations 46 Basic Electrochemical elements 50 5.3.1. Main Structures of the Electrochemical Models 50 5.3.2. Model Description Conventions 52 5.3.3. Models without Diffusion Limitations 53 Ideally Polarizable Electrode 53 Modified Ideally Polarizable Electrode 54 Polarizable Electrode 55 Modified Polarizable Electrode 58 Faradaic Reaction with One Adsorbed Species 59 5.3.4. Models with Diffusion Limitations 60 Randles Model 60 Modified Randles model 62

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5 2001 Established European Impedance Internet Centre with base organization IEES - BAS 2001 Workshop – ITALY 2002 Workshop – SZECHIA 2003 Sofia Impedance Days CHAINS EVENTS Internat. Mycrosymp on EIS (every 3 years ) Ist – 1987 - RUSSIA IInd - 1990 - BULGARIA IIIrd - 1993 - BULGARIA IVth – 1996 - POLAND Vth – 1999 - HUNGARY VIth - 2002 - CZECHIA VIIth – 2005 – CZECHIA Internat. Symp. on EIS (every 3 years ) Ist –1989 - FRANCE IInd –1992 - USA IIIrd – 1995 - BELGIUM IVth – 1998 - BRAZIL Vth – 2001 - ITALY VIth – 2004 - USA VIIth – 2007 - FRANCE IEES-BAS Centre of Excellence 1. INTRODUCTION

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6 UNIQUE POSSIBILITY to separate different steps in the total process under investigation EASY PERFORMANCE of experiments with accessible digital instrumentation MATURITY in the software exploitation EASY PERFORMANCE of VIRTUAL impedance data analysis (e- data analysis) From SCIENTIFIC point of view From APPLIED point of view IMPEDANCE IMPEDANCE OFFERS IMPORTANT ADVANTAGES COVERS WIDE RANGE OF OBJECTS SERVES & UNITES a great variety of research & applied areas IEES-BAS Centre of Excellence 1. INTRODUCTION

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7 BASIC IMPEDANCE LITERATURE IEES-BAS Centre of Excellence 1. INTRODUCTION D. C. Graham, Chem. Rev., 1947, 41, 441. P. Delahay, New Instrumental Methods in Electrochemistry, 1965, Wiley-Interscience, New York. P. Delahay, Double Layer and Electrode Kinetics, 1965, Wiley-Interscience, New York. D. E. Smith, Electroanalytical Chem. 1966, 1,1(Eds. A. J. Bard, Marcel Dekker), New York. M. Sluyters-Rehbach and J. H. Sluyters in On the impedance of galvanic cell. The potential dependence of the faradaic parameters for electrode processes with coupled homogeneous chemical reactions, Electroanalytical Chem. 1970, 4,1(Eds. A. J. Bard, Marcel Dekker), New York. J. R. Macdonald in Superionic Conductors, (Eds. G. D. Mahan, W. L. Roth), Plenum Press, New York, 1976, p.81. J. R. Macdonald in Electrode Processes in Solid State Ionics, (Eds. M. Kleitz and J. Dupuy), Reidel, Dordrecht, Holland, 1976, p.149. M. C. H. McKubre and D. D. Macdonald in A Comprehensive Treatise of Electrochemistry, (Eds. J. O’M Bockris, B. E. Conway and E. Yeager), Plenum Press, New York, 1977. D. D. MacDonald, Transient Techiques in Electrochemistry, Plenum Press, New York, 1977. R. D. Armstrong, M. F. Bell and A. A. Metcalfe, Electrochem. Chem. Soc. Spec. Rep. 1978, 6, 98. W. I. Archer and R. D. Armstrong, Electrochem. Chem. Soc. Spec. Rep. 1980, 7, 157. C. Gabrielli, Identification of Electrochemical Process by Freguency Response Analysis, Monograph Reference 004 /83, Solartron Instr.Group, Farnsborough, England, 1980. D. D. Macdonald and M. C. H. McKubre, Electrochemical Impedance Technigues in Corrosion Science: Electrochemical Corrosion Testing, STP 272, ASTM, Philadelphia, PA, 1981. J. R. Macdonald, IEEE Trans. Electrical Insulation EI-15, 1981, 65. D. D. Macdonald and M. C. H. McKubre, Modern Aspects of Electrochemistry, (Eds. J. O’M Bockris, B. E. Conway and R. E. White), Plenum Press, New, 1982, 14, 61. M. Sluyters-Rehbach and J. H. Sluyters in Comprehensive Treatise of Electrochemistry, (Eds. E. Yeager, J. O. ’ M. Bockris, B. E. Conway and S. Sarangapani), Plenum Press, New York, 1984, p. 177.

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8 BASIC IMPEDANCE LITERATURE IEES-BAS Centre of Excellence 1. INTRODUCTION C. Gabrielli, Identification of Electrochemical Processesby Frequency Respose Analysis, Technical Report № 004, Solartron, Hampshire, 1984.(can be dounloaded from http://accessimpedance.iusi.bas.bg) J. R. Macdonald (Ed.), Impedance Spectroscopy - Emphasizing Solid Materials and Systems, Wiley-Interscience, New York, 1987. C. Gabrielli, Use and Applications of Electrochemical Impedance Tecniques, Technical Report № 024, Solartron, Hampshire, 1990. Z. Stoynov, B. Grafov, B. Savova-Stoynova and V. Elkin, Electrochemical Impedance, 1991, Publishing House Science, Moscow (in Russian). D. D. Macdonald in Tecniques for Characterization of Electrodes and Electrochemical Processes, (Eds. H. R. Varma and J. R. Selman, J.Wiley&Sons), New York, 1991, p.515. F. Mansfeld and W. J. Lorenz in Tecniques for Characterization of Electrodes and Electrochemical Processes, (Eds. H. R. Varma and J. R. Selman, J.Wiley&Sons), New York, 1991, p.581. C. M. A. Brett and A. M. Oliveira Brett, Electrochemistry, Principles, Methods and Applications, 1993, Oxford University Press. A. Lasia, Electrochemical Impedance Spectroscopy and Its Applications, Modern Aspects of Electrochemistry, B. E. Conway, J. Bockris, and R. White, Edts., Kluwer Academic/Plenum Publishers, New York, 1999, Vol. 32, p. 143-248. http://www.wkap.nl/prod/b/0-306-45964-7 http://www.wkap.nl/prod/b/0-306-45964-7 Second International Symposium on Electrochemical Impedance Spectroscopy, Electrochimica Acta, 38, 14, 1993. Third International Symposium on Electrochemical Impedance Spectroscopy, Electrochimica Acta, 41, 7/8, 1996.Electrochimica Acta EIS’98 Proceedings – Impedance Spectroscopy” Electrochimica Acta, 44, 24, 1999.Electrochimica Acta Fifth International Symposium on Electrochemical Impedance Spectroscopy, Electrochimica Acta, 47, 13/14, 2002.Electrochimica Acta R. Cottis and St. Turgoose, Electrochemical Impedance and Noise, Eds. B. C. Syrett, NACE International, 1440, South Greek Drive, Houston, TX77084, 1999.

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9 2. WHAT IS ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY 2. WHAT IS ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY IEES-BAS Centre of Excellence The Electrochemical Impedance Spectroscopy is based on the classical method of the TRANSFER FUNCTION (TF) Linear System Sinwave input x( i ) = A sin t Sinwave output y( i ) = B sin ( t Principle: 1. If the system under investigation is LINEAR (LS), LS is perturbed with sinwave input x (i ) and the response y ( i ) is measured; The response y( i ) is also sin wave with the same freqiency and different amplitude and phase; 2.The ratio output / input signal determines the complex transfer coefficient for the corresponding frequency: k( i ) = y( i ) / x( i )

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10 2. WHAT IS ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY 2. WHAT IS ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY IEES-BAS Centre of Excellence k( i ) = y( i ) / x( i ) Linear System Principle: 3. If the input is composed by sin wave signals X (i i ) and the output Y (i i ) – by the same set of frequencies ( 1 - n ), the ratio between the two vectors H(i i ) = Y (i i ) / X (i i ) is the Transfer Function H(i i ) TF describes the frequency dependence of the transfer coeffcient k( i) 4. The transfer from the time-domain to the frequency domain is performed by LAPLAS transform. For steady state linear systems it is replaced by FOURIER transform Complex number (Re; Im) Depends on and the object’s properties X (i i ) = Sinwave input ( 1 - n ) Y (i i ) = Sinwave output ( 1 - n )

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11 2. WHAT IS ELECTROCHEMICAL IMPEDANCE SPECTSCOPY 2. WHAT IS ELECTROCHEMICAL IMPEDANCE SPECTSCOPY IEES-BAS Centre of Excellence Principle: 5. TF is impedance H(i i ) = Z (i i ) when the input signal is current (I) and the output signal is voltage (U) 6. TF is admittance H(i i ) = Y (i i ) = Z -1 (i i ) when the input signal is voltage (U) and the output signal is current (I) 7. When the frequency range ( 1 - n ) is large and covers all the properties of the system, the system is observable, otherwise S is partially observable. Conclusion: The Transfer Function H(i i ) describes totally a linear, steady-state and observable system.

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12 3. IMPEDANCE OF ELECTROCHEMICAL SYSTEMS IEES-BAS Centre of Excellence Electrochemical systems behave as big, non-linear, non-steady state, semi-irreversible systems with distributed parameters in macro-and micro scales. During operation or investigation processes of mass- and energy transfer take place. Obviously the application of the TF approach needs a number of simplifications and assumptions. They are generalized in few BASIC WORKING HYPOTHESES They can be divided in 2 groups: 1. Working hypotheses from system analysis point of view 2. Working hypotheses from electrochemical point of view.

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13 3. 1. Basic Working Hypotheses IEES-BAS Centre of Excellence 2.1.1. Working hypotheses from system analysis point of view I. Linearity: This requirement is fulfilled if the input perturbation signal is small enough to keep the state of the investigated system unchanged. The requirement for a small signal covers the potential, the current, as well as the quantity of electricity for half a period (very important at low frequencies ! ). Verification of the hypothesis for linearity: the measured impedance should not depend on the amplitude of the signal. Experimental verification: Consecutive impedance measurements in the full frequency range with decreasing amplitude and analysis of the weighted differences. Small signal : - depends on the investigated system; in some cases 3-5 mV, in others 50-100 V

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14 IEES-BAS Centre of Excellence 2.1.1. Working hypotheses from system analysis point of view II. Causality: This requirement means that all the changes in the investigated system are caused by the perturbation signal, i.e. the output signal is a result of only the input signal and can not appear if there is no input signal. III. Single input, single output: This requirement could be achieved if the rest of the parameters (temperature, concentration, d.c. signal, pH etc.) are kept constant by passive or active conditioning. IV. Observability: This requirement postulates, that all the phenomena under study can be observed in the measured frequency range. 3. 1. Basic Working Hypotheses

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15 IEES-BAS Centre of Excellence 2.1.1. Working hypotheses from system analysis point of view V. Lack of memory effects: This requirement means that the investigated system dos not “remember” the history of the experiment. That means that the result does not depend on the order of the measurements. This property could be expected form entirely reversible systems. Experimental verification: Performance of two consecutive impedance measurements - the one with scanning from high to low frequencies and the other – on the opposite – from low towards high frequencies, followed by and analysis of the weighted differences. 3. 1. Basic Working Hypotheses

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16 IEES-BAS Centre of Excellence 2.1.1. Working hypotheses from electrochmical point of view Additiveness of the Faradaic current and the charging current of the double layer Electrical neutrality of the electrolyte – the total density of the charges in every point of the solution is zero Lack of convection and migration – i.e. there are no changes in the local concentration of the electrolyte Lack of lateral mass and charge fluxes at the electrode surface. Conclusion: The performance of a precise impedance investigation strongly depends on the correctly organized experimental setup, experimental conditions and measuring technique and on the careful preparation of the object. Some of the electrochemical simplifications help for the construction of the models 3. 1. Basic Working Hypotheses

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17 3. 2. Impedance Presentation and Monitoring IEES-BAS Centre of Excellence 3.2.1. Impedance presentation Z (i i ) = Y (i i ) / X (i i ) = U (i i ) / I (i i )complex number Presentation in Cartesian coordinates: Z (i i ) = Re i + iIm i i = (-1) 1/2 ; i = 1, 2,….n – denotes the frequency range N d – frequency density (measured frequencies in one decade; 3-5 for screening; 10-15 for precise measurements; Down scanning – from high to low frequencies Presentation in Polar coordinates: Z (i i ) = = Z Z = (Re i 2 + iIm i 2 ) 1/2 - modulus ; i = Arc tan Im i /Re i - phase

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18 3. 2. Impedance Presentation and Monitoring IEES-BAS Centre of Excellence 3.2.1. Impedance monitoring (graphical visualization) The problem of impedance monitoring comes from the 3-dimensional nature of the data, which should be plotted in a 2-dimensional pattern. The most common presentations are the complex plane (Nyquist) plot (in Cartesian coordinates) and Bode plots (in polar coordinates). Bode plots Recalculated 3Dset of data: D 3 [ i, Z i, i i = 1, 2,..n Coordinates: x i = lg i ; y1 i = Z i;, y2 i = i Complex plane (Nyquist) plot Experimental 3D set of data: D 3 [ Re i, Im i, i i = 1, 2,..n Coordinates: x i = Re; y i = - Im

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19 3.3. ADVANTAGES AND DIADVANTAGES OF ELECROCHEMICAL IMPEDANCE SPECTROSCOPY IEES-BAS Centre of Excellence From one side the impedance (or admittance) functions contain all the information for the investigated system (if the working hypotheses are fulfilled at the selected working point). From another side this information has to be extracted from the data, i.e. the data analysis is an identification procedure. Advantage: The electrochemical impedance has the unique possibility to separate the kinetics of the different steps involved in the total process under investigation, because as a transfer function it is a local, linear an full description of the system under study. A number of processes are taking place, caused by the perturbation signal. The impedance, however, does not measure them, i.e. it is not a physical reality, but information property of the object. Disadvantage: Since impedance is not a physical reality, the interpretation of the experimental data is based on the construction of a working model, following a preliminary working hypothesis, which should be identified. This introduces a subjective component in the analysis.

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20 IEES-BAS Centre of Excellence 4. MAIN STEPS IN THE CLASSICAL IMPEDANCE INVESTIGATION I STAGE DATA MONITORING MEASUREMENT D 3 [ Re i, Im i, i ]

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21 II STAGE – DATA ANALYSIS Choice of a Hypothetical Model IEES-BAS Centre of Excellence 4. MAIN STEPS IN THE CLASSICAL IMPEDANCE INVESTIGATION P = Par.Ident. { i, Re i, Im i, I M [ S ] } estimated parameters supposed model Parametric Identification (CNLS) 1. Z i = Simulation { M [S,P ] I i, } given 2. Choice of measure for proximity (distance between measured and estimated data) 3. Evaluation of the distance for “Best fit” Model Validation Data Analysis will be given in the lectures on the Workshop

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22 ( D 3 [ i, Re i, Im i ] ) IEES-BAS Centre of Excellence 4. MAIN STEPS IN THE CLASSICAL IMPEDANCE INVESTIGATION - Example I. Measurement & Data Monitoring II. Data Analysis R1R1 CPE R2R2 3. R1R1 CPE R2R2 1. C R 2 C 1 R 3 C 2 R 1 2. 1.Choice of Hypothetical models P(S) = R 1, R 2, C (estimated values) P(S) = R 1, R 2, C 1, R 3, C 2 P(S) = R 1, R 2, CPE NO R1R1 CPE R2R2 3. R1R1 CPE R2R2 1. C R 2 C 1 R 3 C 2 R 1 2. 3. Models Validation2. Parametric Identification (CNLS) YES

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23 IEES-BAS Centre of Excellence 5. IMPEDANCE MODELS There are few approaches for presentation of the impedance models. The electrical circuit modelling approach is very convenient for impedance studies of electrical properties. In this case the electrical circuit has a response identical to that obtained from the measurement of the investigated system. The electrical circuit can be regarded as a construction of different electrical and electrochemical elements (structural elements) connected under given laws. If the model is not formal, the values of its elements could give a significant contribution to the physical understanding of the investigated system.

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24 IEES-BAS Centre of Excellence 5.1. IMPEDANCE ELEMENTS Impedance elements are described with one or more parameters, which determine their dimensions. Impedance elements can be divided it 2 basic groups: Lumped elements: resistance R; capacitance C; inductance L. They are directly adopted form electrotechniques, i.e. they are electrical elements and can describe homogeneous systems. Frequency dependent elements – they describe frequency unhomogeneity. They are developed for descrption of some electrochmical processes, i.e. they are electrochemical elements.

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25 IEES-BAS Centre of Excellence 5.1.1. LUMPED ELEMENTS RESISTANCE R R is the simplest modelling element 1.Modelling in the time (t) domain – follows Ohm’s Law: U R =R.I (U R - voltage drop; I – current) Dimensions: ohm (Ω) = VA -1 = m 2 kgA -2 s -3

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26 IEES-BAS Centre of Excellence 5.1.1. LUMPED ELEMENTS RESISTANCE R 3. Physical meaning: description of: energy losses; dissipation of energy; potential barrier; electronic conductivity or conductivity of very fast carriers Electrolyte resistance - Z s (i ) = R s - for water based electrolytes Ohmic resistance - R R s R m (R m - R of metallic leads) 2. Modelling in the frequency ( ) domain: Z R (i ) = R only real part (Re=R; Im = 0) R Impedance diagram in the frequency range 10 5 -10 Hz

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27 IEES-BAS Centre of Excellence 5.1.1. LUMPED ELEMENTS CAPACITANCE C 1.Modelling in the time (t) domain – Capacitance C can be regarded as a proportionality coefficient between the voltage U c and the integral of the current i running through the capacitance : Dimensions: F = sΩ -1

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28 IEES-BAS Centre of Excellence 5.1.1. LUMPED ELEMENTS CAPACITANCE C 3. Physical meaning: modelling of : mass and charge accumulation, dielectric polarization, integral relation between parameters; Double layer capacitance C dl. The impedance of the double layer has a capacitive character. C 1 = 1E-4 C 2 = 1E-3 Impedance diagram in the frequency range 10 5 -10 Hz C only imaginary part (Re = 0) The impedance decreases with the increase of the frequency. 2. Modelling in the frequency ( ) domain:

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29 IEES-BAS Centre of Excellence 5.1.1. LUMPED ELEMENTS INDUCTANCE L 1.Modelling in the time (t) domain – The Inductance L can be regarded as a proportionality coefficient between the voltage U L and the derivative of the current i: Dimensions: H = Ωs

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30 IEES-BAS Centre of Excellence 5.1.1. LUMPED ELEMENTS INDUCTANCE L 3. Physical meaning: Modelling of : self inductance of the connecting cables, the measuring cell and investigated objects, self inductance of current flow or of charge carriers movement; accumulation of magnetic energy; Impedance diagram in the frequency range 10 5 -10 Hz L L 1 = 1E-4 L 2 = 1E-3 only imaginary part (Re = 0) The impedance increases with the increase of the frequency. 2. Modelling in the frequency ( ) domain:

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31 IEES-BAS Centre of Excellence 5.1.2. FREQUENCY DEPENDENT ELEMENTS WARBURG ELEMENT W 1.Modelling in the time (t) domain Warburg element (1896 year) is the first electrochemical element introduced for impedance description of linear semi-infinite diffusion, which obeys the second Fick’s low:

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32 IEES-BAS Centre of Excellence 5.1.2. FREQUENCY DEPENDENT ELEMENTS WARBURG ELEMENT W Impedance diagram in the frequency range 10 5 -10 Hz with W = 100 ohm.s 1/2 W 2. Modelling in the frequency ( ) domain: Re = Im - phase shift = 45 0 and frequency independent W is a proportionality coefficient known as Warburg coeffcient Dimensions: Ωm 2 s 1/2

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33 IEES-BAS Centre of Excellence 5.1.2. FREQUENCY DEPENDENT ELEMENTS WARBURG ELEMENT W REMARK: The applied frequencies should ensure conditions at which the sin wave should not reach the end of the diffusion layer. Thus Warburg impedance is a one port element – it has only one input. This property does not allow the introduction of another element after Warburg impedance.

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34 IEES-BAS Centre of Excellence 5.1.2. FREQUENCY DEPENDENT ELEMENTS CONSTANT PHASE ELEMENT CPE 1.Modelling : CPE represents an empirical relationship; CPE describes frequency dependent impedance caused by surface roughness or non-uniformly distributed properties of the irregular electrode surface. A – proportional factor [Ωm -2 s n ]; n – exponential coefficient (CPE exponent) corresponding to the phase angle n п/2

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35 IEES-BAS Centre of Excellence 5.1.2. FREQUENCY DEPENDENT ELEMENTS CONSTANT PHASE ELEMENT CPE n = 0.45 n = 0.2 n = 0.8 n = 0.9 CPE Impedance diagram in the frequency range 10 5 -10 Hz 2. CPE is a generalized element. Its properties depend on the value of n. for n = 0.5 CPE corresponds to diffusion with deviations from the second Fick’s law; for n = 0 CPE models distorted resistance( n < 0 is related to inductive energy accumulation); for n = 1 – CPE models distorted capacitance; for n = -1 + CPE gives distorted inductance. For integer values of n ( n = 1, 0, -1) CPE models respectively the lumped elements C, R and L.

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36 IEES-BAS Centre of Excellence 5.1.2. FREQUENCY DEPENDENT ELEMENTS CONSTANT PHASE ELEMENT CPE 3. Physical meaning of CPE. CPE may have direct physical meaning : the generalized resistance n = 0 - 0.2 may model conductance of ionic clouds or conductance connected with accumulation of magnetic or electrostatic energy; the generalized capacitance n = 0.8 - 1 may model surface roughness of the electrode or distribution of the charge carrier density, i.e. a double layer with complicated stricture; The generalized Warburg n = 0.4 - 0.6 may present non-ideal geometry of the diffusion layer; presence of migration or convection; diffusion connected with energy loses or accumulation of charges; constrains of the host matrix to the diffusion of species,unhomogeneous diffusion; CPE may be also used for formal better modelling of an external similarity with the measured impedance.

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37 IEES-BAS Centre of Excellence 5.1.2. FREQUENCY DEPENDENT ELEMENTS CONSTANT PHASE ELEMENT CPE 3. Physical meaning of CPE. REMARK: In general CPE is semi-infinite element. It models the impedance of homogeneous semi-infinite layer, i.e. of a layer with a thickness bigger than the penetration depth of the perturbation signal. Thus the CPE has only an input with the exception in the cases when n = 1, 0, -1 and CPE has the features of lumped elements.

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38 IEES-BAS Centre of Excellence 5.1.2. FREQUENCY DEPENDENT ELEMENTS BOUNDED ELEMENTS In real systems very often at low frequencies the perturbation signal penetrates to the end of the layer, which behaves as a layer with a finite thickness. For more precise modelling of such systems bounded electrochemical elements are introduced.

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39 IEES-BAS Centre of Excellence 5.1.2. FREQUENCY DEPENDENT ELEMENTS BOUNDED WARBURG ELEMENT BW 1.Modelling Bounded Warburg element describes the impedance of a linear diffusion in a homogeneous layer with finite thickness: R 0 is the total resistance[Ω] of the layer at = 0 At high frequencies ( ) BW behaves as Warburg element.

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40 IEES-BAS Centre of Excellence 5.1.2. FREQUENCY DEPENDENT ELEMENTS BOUNDED WARBURG ELEMENT BW BW R 0 = 100 R 0 = 200 R 0 = 300 R 0 = 400 W = 0.01 Impedance diagram in the frequency range 10 5 -10 Hz

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41 IEES-BAS Centre of Excellence 5.1.2. FREQUENCY DEPENDENT ELEMENTS BOUNDED CONSTANT PHASE ELEMENT BCP 1.Modelling BCP represents the impedance of a bounded homogeneous layer with CPE behaviour of the conductivity in the elementary volume and a finite conductivity R 0 at d.c. ( ): n and A are the CPE coefficients.

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42 IEES-BAS Centre of Excellence 5.1.2. FREQUENCY DEPENDENT ELEMENTS BOUNDED CONSTANT PHASE ELEMENT BCP 4. Properties of BCP element – the most generalized element R 0 = 100 R 0 = 200 R 0 = 300 R 0 = 400 n = 0.45 A = 0,01 BCP Impedance diagram in the frequency range 10 5 -10 Hz For high enough frequencies a BCP tends to the classical CPE: The error is small. For frequencies below a given limit b the element displays a behavior of pure resistance R 0 : The frequency limits a and b are obtained with a relative error 1%: a =( 2.7A -1 R 0 -1 ) n-1 b =(0.14A -1 R 0 -1 ) n-1

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43 IEES-BAS Centre of Excellence 5.1.2. FREQUENCY DEPENDENT ELEMENTS BOUNDED CONSTANT PHASE ELEMENT BCP criterion for verification of BCP: ( and are the angles of the diagram’s asymptotes respectively at low and high frequencies. 4. Properties of BCP element R o = 400 A = 0.01 n = 0.3 BCP Impedance diagram in the frequency range 10 5 -10 Hz = 2 n /2)

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44 IEES-BAS Centre of Excellence 5.1.2. FREQUENCY DEPENDENT ELEMENTS BOUNDED CONSTANT PHASE ELEMENT BCP Remark: BCP can be applied for n = 0 – 0.6 because of the initial assumption that the investigatd object is regarded as a conductor. Obviously at higher values for n the system demonstrates capacitive behaviour.

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45 IEES-BAS Centre of Excellence 5.2. SIMPLE CALCULATIONS EXAMPLE ON R AND C ELEMENTS The impedance calculations of the combinations of elements follows some rules: 1.When the elements are connected in series, their impedance are added to each other: 2.When the elements are connected in parallel, their admitances, i.e. the reciprocals of the impedance are added : Z IPE (i ) = Z R (i ) + Z C (i ) 1/Z PE (i ) =1/ Z R (i ) +1/ Z C (i )

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46 IEES-BAS Centre of Excellence 5.2. SIMPLE CALCULATIONS EXAMPLE ON R AND C ELEMENTS Connections between elements: R + C Z C (i ) = -i C) -1 Z R (i ) = R C R Series connection: Z (i ) = Z R (i ) + Z C (i ) R C Parallel connection: 1/Z (i ) =1/ Z R (i ) +1/ Z C (i )

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47 IEES-BAS Centre of Excellence 5.2. SIMPLE CALCULATIONS EXAMPLE ON R AND C ELEMENTS C R Series connection: Z (i ) = Z R (i ) + Z C (i ) = R + (i C) -1 = R - i( C) -1

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48 IEES-BAS Centre of Excellence 5.2. SIMPLE CALCULATIONS EXAMPLE ON R AND C ELEMENTS + Z (i ) = + i Paralel connection: 1/Z (i ) =1/ Z R (i ) +1/ Z C (i ) Z C

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49 IEES-BAS Centre of Excellence 5.3. BASIC ELECTROCHEMICAL MODELS 5.3.1. MAIN STRUCTURES OF ELECTROCHEMICAL MODELS 1.Voigt’s Structure – consists of meshes with impedances Z k (i ), connected in series. The flowing current is equal for all meshes. The phenomena modelled by each mesh start instantaneously. Their rates depend on their own time- constants. Voigt’s model structure is applied for impedance description of solid state samples R1R1 C1C1 R2R2 C2C2

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50 IEES-BAS Centre of Excellence 5.3. BASIC ELECTROCHEMICAL MODELS 5.3.1. MAIN STRUCTURES OF ELECTROCHEMICAL MODELS 1.Ladder Structure – consists of a number of kernels corresponding to the modelled phenomena. The modelled phenomena occur consequently. The model has a typical “ladder”structure 2. Application – description of processes at the electrode interface. C1C1 C2C2 R2R2 R1R1 Z(i ) = Z 1 (i ) + { Z 2 ( i ) + [ Z 3 (i ) + Z 4 (i ) + …) -1 ] -1 } -1

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51 IEES-BAS Centre of Excellence 5.3. BASIC ELECTROCHEMICAL MODELS 5.3.2. MODEL DESCRIPTION CONVENTIONS 1.Structures: La: - ladder;Vo: - Voigt 2. Elements: R, C, L, W, BW, CPE, BCP 3. Connections: “ “ – in series; “/” – in parallel 4. Parameters: dimensions in SI ; delimiters – “;”; multiple parameters separator – “\” Example: La: R R/CPE par: 120; 200; 0.01\0.9

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52 IEES-BAS Centre of Excellence 5.3.3. MODELS WITHOUT DIFFUSION LIMITATIONS – IDEALLY POLARIZABLE ELECTRODE (IPE) C DL =0.01 R S =10E+3 R S =20E+3 R S =30E+3 R S =40E+3 C DL RSRS Impedance diagram in the frequency range 10 5 -10 Hz IPE describes a case when there is absence of any process at the electrode surface. 1.Structure: La: R s C dl The structural elements have a direct physical meaning and correspond to the electrochemical parameters: the electrolyte impedance is presented as resistance (R s ) the double layer is presented as simple capacitance C dl 2. Impedance: Z IPE (i ) = R s – i( C dl ) -1

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53 IEES-BAS Centre of Excellence 5.3.3. MODELS WITHOUT DIFFUSION LIMITATIONS – MODIFIED IDEALLY POLARIZABLE ELECTRODE (MIPE) The modelling of the double layer with pure capacitance is a simplification, reasonable for concentrated electrolytes. 1.Modified Structure: La: R s CPE dl When the electrode surface is inhomogeneous or rough, the impedance diagram is deformed because of geometrical factors; For more complicated structures of the double layer C dl is presented as CPE of capacitive nature 2. Impedance: Z MIPE (i ) = R s + A -1 (i ) -n R S = 100 A = 0.01 A = 0.01 n = 1 n = 1 n = 0.8 n = 0.8 CPE RSRS Impedance diagram in the frequency range 10 5 -10 Hz

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54 IEES-BAS Centre of Excellence 5.3.3. MODELS WITHOUT DIFFUSION LIMITATIONS – POLARIZABLE ELECTRODE (PE) The model of polarizable electrode, known also as simple Faradaic reaction gives a simple impedance description of an electrochemical reaction at the electrode surface. 1.Structure: La: R s C dl /Z F the current corresponding to the reaction is treated as additive to the current of the double layer charging(working hypothesis); C DL RSRS ZFZF the model includes additional (Faradaic) impedance in parallel to C dl the model works in the absence of diffusion limitation and the presence of a single step electrochemical reaction. As a result Z F is simplified to a resistance, called charge transfer resistance R ct and the model becomes: La: R s C dl / R ct R ct

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55 IEES-BAS Centre of Excellence 5.3.3. MODELS WITHOUT DIFFUSION LIMITATIONS – POLARIZABLE ELECTRODE (PE) R s = 100 C DL = 1E-4 R ct = 200 C DL RSRS R ct Impedance diagram in the frequency range 10 5 -10 Hz 2. Impedance diagram: Geometrically the impedance diagram is presented as an ideal semicircle with a diameter R ct ; for the semi-circle intercepts the real axis in R s for the intercept is in a point with value R s + R ct the imaginary component reaches a maximum at the so called characteristic frequency 0 0 = (C dl R ct ) –1 = T -1 (T is the time-constant)

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56 IEES-BAS Centre of Excellence 5.3.3. MODELS WITHOUT DIFFUSION LIMITATIONS – POLARIZABLE ELECTRODE (PE) R S = 100 C DL = 1E-4 R ct = 200 R ct = 300 R ct = 400 R ct = 500 C DL RSRS R ct Impedance diagram in the frequency range 10 5 -10 Hz 4. Physical meaning – the structural parameters have direct physical meaning (R s, R ct,C dl ) for partially reversible charge transfer reaction at equilibrium R ct = (RT/nF)(1/I 0 ) (I 0 - exchange current) R ct depends on the rate of reaction, which is potential dependent and thus R ct vary with the potential, i.e.the diameter of the semi- circle changes. 3. Impedance: Z PE (i ) = R s + R ct (1 + ) -1 -i R ct T (1 + ) -1

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57 IEES-BAS Centre of Excellence 5.3.3. MODELS WITHOUT DIFFUSION LIMITATIONS – MODIFIED POLARIZABLE ELECTRODE (MPE) 1. Structure: La: R s CPE dl / R ct 2. Application: one of the most applied model structures, which describes the depression of the semicircle often observed in real systems. 3. Physical meaning: the application of the MPE model may be a better, but formal description of the investigated system, or it may have a physical meaning – description of the electrode’s surface roughness. CPE RSRS R ct R ElS = 100 R ct = 200 A = 0.01 n = 1 n = 0.8 Impedance diagram in the frequency range 10 5 -10 Hz

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58 IEES-BAS Centre of Excellence 5.3.3. MODELS WITHOUT DIFFUSION LIMITATIONS – FARADAIC REACTION WITH ONE ADSORBED SPECIES R 1 = 50 R 2 = 100 C 1 = 1E-3 R 3 = 200 C 2 = 1E-2 C 2 = 3E-3 C 2 = 1E-3 C 2 = 3E-4 Impedance diagram in the frequency range 10 5 -10 Hz R1R1 C1C1 C2C2 R3R3 R2R2 1.Structure: La: R 1 C 1 /R 2 C 2 /R 3 The model describes a heterogeneous reaction occurring in two steps with adsorption of the intermediate product and absence of diffusion limitations: B X + estep I X P + e step II 2. Physical meaning: the structural parameters have direct physical meaning: R 1 = R S ; C 1 = C DL ; R 2 = R ct ; C 2 = C ad

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59 IEES-BAS Centre of Excellence 5.3.4. MODELS WITH DIFFUSION LIMITATIONS – RANDLES MODEL 1.Structure: La: R S C dl /R ct W The model is based on the assumptions of the polarizable electrode with account of the diffusion limitations. 2. Impedance: Z RNS (i ) = R S + [i C dl + (R ct + W iW C DL RSRS R ct W R S =100 R ct = 5E+3 W = 100 C DL =3E-4 C DL =1E-3 C DL =3E-3 C DL =1E-2 Impedance diagram in the frequency range 10 5 -10 Hz

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60 IEES-BAS Centre of Excellence 5.3.4. MODELS WITH DIFFUSION LIMITATIONS – RANDLES MODEL 3.Relation between the structural parameter W and the electrochemical parameters: W = R ct [k f (D O ) -1/2 + k b (D R ) -1/2 ] (k f, k b – reaction rates of the “forward”and “backward” reactions; D O and D R – diffusion coefficients of the species) The structural model has 4 parameters, which can be determined from the impedance (R S, R ct, C dl, W), while the electrochemical impedance model has 7 parameters (R S, C dl, I 0, k f, k b, D R, D O ), which can not be determined directly.

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61 IEES-BAS Centre of Excellence 5.3.4. MODELS WITH DIFFUSION LIMITATIONS – MODIFIED RANDLES MODEL (MRN) 1.Sructure: La: R S C dl /R ct CPE MRN describes geometrical or activation inhomogeneity of the surface or deviations from the linear diffusion process. That happens very often when the diffusion occurs in a diluted solution or in case that the diffusion does not obey Fick’s law. C DL RSRS R ct W CPE R S =20 R ct = 150 C DL =1E-2 A = 0.1 n = 0.5 n = 0.45 n = 0.4 n = 0.3 Impedance diagram in the frequency range 10 5 -10 Hz C DL RSRS R ct W CPE C DL RSRS R ct W CPE BCP

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