EIS INTRODUCTION AND BASIC CONCEPTS

Impedance definition: concept of complex impedance Almost everyone knows about the concept of electrical resistance. It is the 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. R E ! I While this is a well known relationship, it's use is limited to only one circuit element the ideal resistor. An ideal resistor has several simplifying properties! " It follows Ohm's #aw at all current and voltage levels. " It's resistance value is independent of fre$uency. " A% current and voltage signals keep in phase with each other. &he real world contains circuit elements that e'hibit much more comple' behavior. &hese elements force us to abandon the simple concept of resistance. In its place we use impedance, which is a more general circuit parameter. #ike resistance, impedance is a measure of the ability of a circuit to resist the flow of electrical current. (nlike resistance, impedance is not limited by the simplifying properties listed above. Electrochemical impedance is usually measured by applying an A% potential to an electrochemical cell and measuring the current through the cell. )uppose that we apply a sinusoidal potential e'citation. &he response to this potential is an A% current signal, containing the e'citation fre$uency and it's harmonics. Electrochemical Impedance is normally measured using a small e'citation signal of *+ to ,+ m-. In a linear .or pseudo linear/ system, the current response to a sinusoidal potential will be a sinusoid at the same fre$uency but shifted in phase.

"i#$re % )inusoidal %urrent 0esponse in a #inear )ystem 1

&he e'citation signal, e'pressed as a function of time, has the form

E.t/ is the potential at time tr Eo is the amplitude of the signal, and w is the radial fre$uency. &he relationship between radial fre$uency 1.e'pressed in radians2second/ and fre$uency f .e'pressed in hert3/ is!

In a linear system, the response signal, It, is shifted in phase .4/ and has a different amplitude, Io!

An e'pression analogous to Ohm's #aw allows us to calculate the impedance of the system as!

&he impedance is therefore e'pressed in terms of a magnitude .modulus/ 565, and a phase shift, 4. (sing Eulers relationship,

it is possible to e'press the impedance as a comple' function. &he potential is described as,

and the current response as,

&he impedance is then represented as a comple' number,

Data Presentation #ook at last e$uation in the previous section. &he e'pression for 6.1/ is composed of a real and an imaginary part. If the real part is plotted on the 6 a'is and the imaginary part on the 7 a'is of a chart, we get a 89y$uist plot8. )ee :igure ;. 9otice 2

that in this plot the y a'is is negative and that each point on the 9y$uist plot is the impedance at one fre$uency.

"i#$re & :igure ; ; has been annotated to show that low fre$uency data are on the right side of the plot and higher fre$uencies are on the left. &his is true for EI) data where impedance usually falls as fre$uency rises .this is not true of all circuits/. On the 9y$uist plot the impedance can be represented as a vector of length <6<. &he angle between this vector and the ' a'is is 4. 9y$uist plots have one ma=or shortcoming. When you look at any data point on the plot, you cannot tell what fre$uency was used to record that point. &he 9y$uist plot in :igure ; results from the electrical circuit of :igure >. &he semicircle is characteristic of a single 8time constant8. Electrochemical Impedance plots often contain several time constants. Often only a portion of one or more of their semicircles is seen. "i#$re '

Another popular presentation method is the 8?ode plot8. &he impedance is plotted with log fre$uency on the ' a'is and both the absolute value of the impedance .<6< @6+ / and phase shift on the y a'is. &he ?ode plot for the electric circuit of :igure > is shown in :igure A. (nlike the 9y$uist plot, the ?ode plot e'plicitly shows fre$uency information. "i#$re (

Electrical Circ$it Elements EI) data is commonly analy3ed by fitting it to an e$uivalent electrical circuit model. Bost of the circuit elements in the model are common electrical elements such as resistors, capacitors, and inductors. &o be useful, the elements in the model should have a basis in the physical electrochemistry of the system. As an e'ample, most models contain a resistor that models the cell's solution resistance. )ome knowledge of the impedance of the standard circuit components is therefore $uite useful. &able * lists the common circuit elements, the e$uation for their current versus voltage relationship, and their impedance. Ta)le %

9otice that the impedance of a resistor is independent of fre$uency and has only a real component. ?ecause there is no imaginary impedance, the current through a resistor is always in phase with the voltage. &he impedance of an inductor increases as fre$uency increases. Inductors have only an imaginary impedance component. As a result, an inductor's current is phase shifted C+ degrees with respect to the voltage. &he impedance versus fre$uency behavior of a capacitor is opposite to that of an inductor. A capacitor's impedance decreases as the fre$uency is raised. %apacitors also have only an imaginary impedance component. &he current through a capacitor is phase shifted C+ degrees with respect to the voltage.

Serial and Parallel Com)inations of Circ$it Elements -ery few electrochemical cells can be modeled using a single e$uivalent circuit element. Instead, EI) models usually consist of a number of elements in a network. ?oth serial and parallel combinations of elements occur. :ortunately, there are simple formulas that describe the impedance of circuit elements in both parallel and series combinations.

"i#$re *

:or linear impedance elements in series you calculate the e$uivalent impedance from!

"i#$re +

:or linear impedance elements in parallel you calculate the e$uivalent impedance from!

P,-sical Electroc,emistr- and E.$i/alent Circ$it Elements

Electrol-te Resistance )olution resistance is often a significant factor in the impedance of an electrochemical cell. A modern > electrode potentiostat compensates for the solution resistance between the counter and reference electrodes. Dowever, any solution resistance between the reference electrode and the working electrode must be considered when you model your cell. &he resistance of an ionic solution depends on the ionic concentration, type of ions, temperature and the geometry of the area in which current is carried. In a bounded area with area A and length l carrying a uniform current the resistance is defined as!

where E is the solution resistivity. &he conductivity of the solution, F , is more commonly used in solution resistance calculations. Its relationship with solution resistance is!

)tandard chemical handbooks list F values for specific solutions. :or other solutions, you can calculate k from specific ion conductances. &he units for k are siemens per meter .)2m/. &he siemens is the reciprocal of the ohm, so * ) @ *2ohm. (nfortunately, most electrochemical cells do not have uniform current distribution through a definite electrolyte area. &he ma=or problem in calculating solution resistance therefore concerns determination of the current flow path and the geometry of the electrolyte that carries the current. A comprehensive discussion of the approaches used to calculate practical resistances from ionic conductances is well beyond the scope of this manual. :ortunately, you don't usually calculate solution resistance from ionic conductances. Instead, it is found when you fit a model to e'perimental EI) data.

Do$)le 0a-er Capacitance A electrical double layer e'ists at the interface between an electrode and its surrounding electrolyte. &his double layer is formed as ions from the solution 8stick 7

on8 the electrode surface. %harges in the electrode are separated from the charges of these ions. &he separation is very small, on the order of angstroms. %harges separated by an insulator form a capacitor. On a bare metal immersed in an electrolyte, you can estimate that there will be appro'imately ;+ to G+ H: of capacitance for every cm; of electrode area. &he value of the double layer capacitance depends on many variables including electrode potential, temperature, ionic concentrations, types of ions, o'ide layers, electrode roughness, impurity adsorption, etc. C,ar#e Transfer Resistance A resistance is formed by a single kinetically controlled electrochemical reaction. In this case we have a single reaction at e$uilibrium. %onsider a metal substrate in contact with an electrolyte. &he metal molecules can electrolytically dissolve into the electrolyte, according to!

or more generally!

In the forward reaction in the first e$uation, electrons enter the metal and metal ions diffuse into the electrolyte. %harge is being transferred. &his charge transfer reaction has a certain speed. &he speed depends on the kind of reaction, the temperature, the concentration of the reaction products and the potential. &he general relation between the potential and the current is!

with,
io @ e'change current density %o @ concentration of o'idant at the electrode surface %oI @ concentration of o'idant in the bulk %0 @ concentration of reductant at the electrode surface

: @ :aradays constant & @ temperature 0 @ gas constant a @ reaction order n @ number of electrons involved h @ overpotential . E E+ /

When the concentration in the bulk is the same as at the electrode surface, %o@%oI and %0@%0I. &his simplifies previous e$uation into!

&his e$uation is called the ?utler -olmer e$uation. It is applicable when the polari3ation depends only on the charge transfer kinetics. )tirring will minimi3e diffusion effects and keep the assumptions of %o@%oI and %0@%0I valid. When the overpotential is very small and the electrochemical system is at e$uilibrium, the e'pression for the charge transfer resistance changes into!

:rom this e$uation the e'change current density can be calculated when 0ct is known. Diff$sion Jiffusion can create an impedance known as the Warburg impedance. &his impedance depends on the fre$uency of the potential perturbation. At high fre$uencies the Warburg impedance is small since diffusing reactants don't have to move very far. At low fre$uencies the reactants have to diffuse farther, thereby increasing the Warburg impedance. &he e$uation for the 8infinite8 Warburg impedance is!

On a 9y$uist plot the infinite Warburg impedance appears as a diagonal line with a slope of +.,. On a ?ode plot, the Warburg impedance e'hibits a phase shift of A,K. 9

L is the Warburg coefficient defined as!

In which,
1 @ radial fre$uency JO @ diffusion coefficient of the o'idant J0 @ diffusion coefficient of the reductant A @ surface area of the electrode n @ number of electrons transferred %I @ bulk concentration of the diffusing species .moles2cm>/

&his form of the Warburg impedance is only valid if the diffusion layer has an infinite thickness. Muite often this is not the case. If the diffusion layer is bounded, the impedance at lower fre$uencies no longer obeys the e$uation above. Instead, we get the form!

with,
N @ 9ernst diffusion layer thickness J @ an average value of the diffusion coefficients of the diffusing species

&his more general e$uation is called the 8finite8 Warburg. :or high fre$uencies where 1 approaches infinity, or for an infinite thickness of the diffusion layer, the above e$uation simplifies to the infinite Warburg impedance. Constant P,ase Element %apacitors in EI) e'periments often do not behave ideally. Instead, they act like a constant phase element .%OE/ as defined below. &he impedance of a capacitor has the form!

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When this e$uation describes a capacitor, the constant A @ *2% .the inverse of the capacitance/ and the e'ponent P @ *. :or a constant phase element, the e'ponent is less than one. &he 8double layer capacitor8 on real cells often behaves like a %OE instead of like like a capacitor. )everal theories have been proposed to account for the non ideal behavior of the double layer but none has been universally accepted. 1irt$al Ind$ctor &he impedance of an electrochemical cell can also appear to be inductive. )ome authors have ascribed inductive behavior to adsorbed reactants. ?oth the adsorption process and the electrochemical reaction are potential dependent. &he net result of these dependencies can be an inductive phase shift in the cell current . Common E.$i/alent Circ$it 2odels In the following section we show some common e$uivalent circuits models. &hese models can be used to interpret simple EI) data. &o elements used in the following e$uivalent circuits are presented in &able ; ;. E$uations for both the admittance and impedance are given for each element. &able ; %ircuit Elements (sed in the Bodels

Bodel Q*

A Ourely %apacitive %oating

A metal covered with an undamaged coating generally has a very high impedance. &he e$uivalent circuit for such a situation is in :igure R.

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"i#$re 3

&he model includes a resistor .due primarily to the electrolyte/ and the coating capacitance in series. A 9y$uist plot for this model is shown in figure S. In making this plot, the following values were assigned! 0 @ ,++ .a bit high but realistic for a poorly conductive solution/ % @ ;++ p: .realistic for a * cm; sample, a ;, Hm coating, and er @ G / :i @ +.* D3 .lowest scan fre$uency a bit higher than typical/ :f @ *++ kD3 .highest scan fre$uency/ "i#$re 4

&he value of the capacitance cannot be determined from the 9y$uist plot. It can be determined by a curve fit or from an e'amination of the data points. 9otice that the intercept of the curve with the real a'is gives an estimate of the solution resistance.

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&he highest impedance on this graph is close to *+ *+ Ohm . &his is close to the limit of measurement of most EI) systems. &he same data are shown in a ?ode plot in :igure C. 9otice that the capacitance can be estimated from the graph but the solution resistance value does not appear on the chart. Even at *++ kD3, the impedance of the coating is higher than the solution resistance. "i#$re 5

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Bodel Q;

0andles %ell

&he 0andles cell is one of the simplest and most common cell models. It includes a solution resistance, a double layer capacitor and a charge transfer or polari3ation resistance. In addition to being a useful model in its own right, the 0andles cell model is often the starting point for other more comple' models. &he e$uivalent circuit for the 0andles cell is shown in :igure*+. &he double layer capacity is in parallel with the impedance due to the charge transfer reaction. "i#$re %6

:igure ** is the 9y$uist plot for a typical 0andles cell. &he parameters in this plot were calculated assuming a * cm; electrode undergoing uniform corrosion at a rate of * mm2year. 0easonable assumptions were made for the b coefficients, metal density and e$uivalent weight. &he polari3ation resistance under these conditions calculated out to ;,+ . A capacitance of A+ H:2cm; and a solution resistance of ;+ were also assumed. "i#$re %%

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&he 9y$uist plot for a 0andles cell is always a semicircle. &he solution resistance can found by reading the real a'is value at the high fre$uency intercept. &his is the intercept near the origin of the plot. 0emember this plot was generated assuming that 0s @ ;+ Ohm and 0p@ ;,+ Ohm. &he real a'is value at the other .low fre$uency/ intercept is the sum of the polari3ation resistance and the solution resistance. &he diameter of the semicircle is therefore e$ual to the polari3ation resistance .in this case ;,+ Ohm/. :igure *; is the ?ode plot for the same cell. &he solution resistance and the sum of the solution resistance and the polari3ation resistance can be read from the magnitude plot. &he phase angle does not reach C+K as it would for a pure capacitive impedance. If the values for 0s and 0p were more widely separated the phase would approach C+K.

"i#$re %&

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Bodel Q>

Bi'ed Tinetic and Jiffusion %ontrol

:irst consider a cell where semi infinite diffusion is the rate determining step, with a series solution resistance as the only other cell impedance. A 9y$uist plot for this cell is shown in :igure*>. 0s was assumed to be ;+ Ohm. &he Warburg coefficient calculated to be about *;+ sec *2; at room temperature for a two electron transfer, diffusion of a single species with a bulk concentration of *++ HB 16

and a typical diffusion coefficient of *.G '*+ , cm;2sec. Impedance appears as a straight line with a slope of A,K. "i#$re %'

9otice that the Warburg

Adding a double layer capacitance and a charge transfer impedance, we get the e$uivalent circuit in :igure *A "i#$re %(

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&his circuit models a cell where polari3ation is due to a combination of kinetic and diffusion processes. &he 9y$uist plot for this circuit is shown in :igure ; ;+. As in the above e'ample, the Warburg coefficient is assumed to be about *,+ W sec *2;. Other assumptions! 0s @ ;+ , 0ct @ ;,+ , and %dl @ A+ H:. "i#$re %*

&he ?ode plot for the same data is shown in :igure*G. &he lower fre$uency limit was moved down to *mD3 to better illustrate the differences in the slope of the magnitude and in the phase between the capacitor and the Warburg impedance. 9ote that the phase approaches A,K at low fre$uency. "i#$re %+

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Extractin# 2odel Parameters from Data Bodeling Overview EI) data is generally analy3ed in terms of an e$uivalent circuit model. &he analyst tries to find a model whose impedance matches the measured data. &he type of electrical components in the model and their interconnections controls the shape of the model's impedance spectrum. &he model's parameters .i.e. the resistance value of a resistor/ controls the si3e of each feature in the spectrum. ?oth

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these factors effect the degree to which the model's impedance spectrum matches a measured EI) spectrum. In a physical model, each of the model's components is postulated to come from a physical process in the electrochemical cell. All of the models discussed earlier in this chapter are physical models. &he choice of which physical model applies to a given cell is made from knowledge of the cell's physical characteristics. E'perienced EI) analysts use the shape of a cell's EI) spectrum to help choose among possible physical models for that cell. :or an e'cellent discussion on fitting a physical model to your EI) data, see the Application 9ote on E$uivalent %ircuit Bodeling. Bodels can also be partially or completely empirical. &he circuit components in this type of model are not assigned to physical processes in the cell. &he model is chosen to given the best possible match between the model's impedance and the measured impedance. An empirical model can be constructed by successively subtracting component impedances from a spectrum. If the subtraction of an impedance simplifies the spectrum, the component is added to the model, and the ne't component impedance is subtracted from the simplified spectrum. &his process ends when the spectrum is completely gone .6@+/. As we shall see, physical models are generally preferable to empirical models.

9on linear #east )$uares :itting Bodern EI) analysis uses a computer to find the model parameters that cause the best agreement between a model's impedance spectrum and a measured spectrum. :or most EI) data analysis software, a non linear least s$uares fitting .9##)/ #evenberg Bar$uardt algorithm is used. 9##) starts with initial estimates for all the model's parameters which must be provided by the user. )tarting from this initial point, the algorithm makes changes in several or all of the parameter values and evaluates the resulting fit. If the change improves the fit, the new parameter value is accepted. If the change worsens the fit, the old parameter value is retained. 9e't a different parameter value is changed and the test is repeated. Each trial with new values is called an iteration. Iterations continue until the goodness of fit e'ceeds an acceptance criterion, or until the number of iterations reaches a limit. 9##) algorithms are not perfect. In some cases they do not converge on a useful fit. &his can be the result of several factors including! " An incorrect model for the data set being fitted. " Ooor estimates for the initial values. " 9oise

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In addition, the fit from an 9##) algorithm can look poor when the fit's spectrum is superimposed on the data spectrum. It appears as though the fit ignores a region in the data. &o a certain e'tent this is what happens. &he 9##) algorithm optimi3es the fit over the entire spectrum. It does not care if the fit looks poor over a small section of the spectrum.

(ni$ueness of Bodels &he impedance spectrum shown in :igure *R shows two clearly defined time constants. "i#$re %3

&his spectrum can be modeled by any of the e$uivalent circuits shown in :igure*S

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"i#$re %4

As you can see, there is not a uni$ue e$uivalent circuit that describes the spectrum. 7ou cannot assume that an e$uivalent circuit that produces a good fit to a data set represents an accurate physical model of the cell. Even physical models are suspect in this regard. Whenever possible, the physical model should be verified before it is used. One way to verify the model is to alter a single cell component .for e'ample increase a paint layer thickness/ and see if you get the e'pected changes in the impedance spectrum. Empirical models should be treated with even more caution. 7ou can always get a good looking fit by adding lots of circuit elements to a model. (nfortunately, these elements will have little relevance to the cell processes that you are trying to study. Jrawing conclusions based on changes in these elements is especially dangerous. Empirical models should therefore use the fewest elements possible. #iterature &he list below gives some te't books and papers that we find basic in the field, but is in no way e'haustive. Bost book titles can not be achieved in the library of &( Warsaw. Impedance )pectroscopyU &heory, E'periment, and Applications, ;nd ed. , E. ?arsoukov, V.0. Bacdonald, eds., Wiley Interscience Oublications, ;++,. Electrochemical BethodsU :undamentals and Applications, A.V. ?ard, #.0. :aulkner, Wiley Interscience Oublications ;+++. 22

Electrochemical Impedance! Analysis and Interpretation, V.0. )cully, J.%. )ilverman, and B.W. Tendig, editors, A)&B, *CC>. Ohysical %hemistry, O.W. Atkins, O'ford (niversity Oress ,*CC+. )ignals and )ystems, A.-. Oppenheim and A.). Willsky, Orentice Dall, *CS>. %omprehensive &reatise of ElectrochemistryU -olume C Electrodics! E'perimental &echni$uesU E. 7eager, V.O'B. ?ockris, ?.E. %onway, ). )arangapani, %hapter A 8A% &echni$ues8, B. )luyters 0ehbach, V.D. )luyters, Olenum Oress, *CSA. Bansfeld, :., 8Electrochemical Impedance )pectroscopy .EI)/ as a 9ew &ool for Investigation Bethods of %orrosion Orotection8, Electrochimica Acta, >, .*CC+/, *,>>. Walter, W.W., 8A 0eview of Impedance Olot Bethods (sed for %orrosion Oerformance Analysis of Oainted Betals8, %orrosion )cience, ;G .*CSG/ GS*. Tendig, B., V. )cully, 8?asic Aspects of Electrochemical Impedance Application for the #ife Orediction of Organic %oatings on Betals8, %orrosion, AG .*CC+/ ;;. :letcher, )., X&ables of Jegenerate Electrical 9etworks for (se in the E$uivalent %ircuit Analysis of Electrochemical )ystemsY, V. Electrochem. )oc., *A* .*CCA/ *S;>.

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