A Tutorial on Electrochemical Impedance Spectroscopy

Mark Orazem, Bernard Tribollet

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Mark Orazem, Bernard Tribollet. A Tutorial on Electrochemical Impedance Spectroscopy. Chem-
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A Tutorial on Electrochemical Impedance Spectroscopy

Mark E. Orazem* · Bernard Tribollet

Received: date / Accepted: date

Abstract Electrochemical impedance spectroscopy is

presented as a transfer-function technique that is ap-
plied to electrochemical systems. Examples are pro-
vided that show the unique capability of the technique
to provide valuable information that may otherwise be
difficult or impossible to obtain.

Keywords Transfer Functions · Corrosion · Fuel Fig. 1 Representation of a black box. Taken from Orazem
Cells · Oxide Films and Tribollet.[1]

Impedance spectroscopy is an electrochemical tech-

nique with broad applications that is used in fields such
as corrosion, biomedical devices, semiconductors and
solid-state devices, sensors, batteries, fuel cells, electro- Consider the system with unknown properties that
chemical capacitors, dielectric measurements, coatings, is shown in Figure 1 and labeled “black box”. The
electrochromic materials, analytical chemistry, electro- objective of the exercise is to learn the properties of
catalysis, and imaging. The objective of this tutorial is the box in an effort to understand what it is. A series
to provide a brief and somewhat qualitative introduc- of measurements may be considered to interrogate the
tion to the subject of electrochemical impedance spec- black box by imposing an input and measuring the re-
troscopy. This material, presented at the “First Work- sulting output. For example, imagine that the box is
shop of Material Science for Corrosion Protection” in placed in a dark room and is then subject to light of
Santiago, Chile, November, 2017, is an extension of an a specified wavelength. If a response is seen, such as
introductory chapter presented in Orazem and Tribol- an electrical current, the contents of the box may be
let[1]. considered to be photoactive. To explore the kinetics
associated with the discharge of current from absorbed
paper published as M. E. Orazem and B. Tribollet, “A Tu- photons, the light intensity could be modulated. An
torial on Electrochemical Impedance Spectroscopy,” invited alternative approach could be to impose an electrical
paper, ChemTexts, 6, 12 (2020). potential and to observe the resulting current. Modu-
*Corresponding author. Mark E. Orazem lation of the input signal would allow exploration of
Department of Chemical Engineering, University of Florida, the influence of storage of charge within the box and
Gainesville, FL, 32611, USA the kinetics of processes that transform the potential
Tel.: +1-352-392-6207
Fax: +1-352-392-9513
to current.
E-mail: [email protected]
Bernard Tribollet The relationship between input and output is called
Sorbonne Université, CNRS, Laboratoire Interfaces et a “transfer function”. Impedance spectroscopy is a spe-
Systémes Electrochimiques, LISE, F-75005, Paris, France cial case of a transfer function.
2 Mark E. Orazem*, Bernard Tribollet

where Re is the ohmic resistance, given for a disk elec-

trode in units of Ω as[2]
1 ρ
Re = = (2)
4κr0 4r0

(a) or, in units of Ωcm2 , as

πr0 ρ
Re = (3)
4
For the parameters given, the time constant is τC =
0.04 ms. The corresponding characteristic angular fre-
(b) quency is given by
1
Fig. 2 Representation of the system response Y (t) to X(t) ωC = (4)
defined as: a) step change input; and b) sinusoidal input with τC
frequency ω. Taken from Orazem and Tribollet.[1]
and, in units of Hz,
1
1 Transfer Function fC = (5)
2πτC

The transfer function provides a compact description Thus, for a time constant τC = 0.04 ms, the character-
of the input-output relation for a linear time-invariant istic frequency is 4.1 kHz.
(LTI) system. Due to the fact that most signals can The time constant for a faradaic reaction is given
be decomposed into summation of sinusoids via Fourier by
series, the response of a system is characterized by the
τ t = C 0 Rt (6)
frequency response of the system. A generalized system
is illustrated in Figure 2(a). The response to a step where Rt is the charge-transfer resistance, given, for
input signal X(t) shows different long and short time linear kinetics on a disk electrode, by
behaviors that can be represented as the dependence of
the transfer function on frequency. RT
Rt = (7)
The short-time behavior corresponds to high fre- nFi0
quencies, and the long-time behavior corresponds to Equations (6) and (7) yield a time constant of 0.51 ms
low frequencies. For an electrochemical system, charg- and a characteristic frequency of 310 Hz.
ing of the electrode-electrolyte interface occurs rapidly The time constant for diffusion to a rotating disk
and is associated with the high-frequency or short-time electrode is given by
response. Diffusion is a slower process with a large time
2
constant and correspondingly a smaller characteristic δN
τD = (8)
frequency. Di
The appropriate frequency range for the measure- where Di is the diffusion coefficient for the reacting
ment is determined in accordance to the system un- species and δN is the diffusion layer thickness given as
der study. For example, the phenomena associated with a function of rotation speed by
a typical electrochemical system include double-layer
charging, faradaic reactions, and diffusion.  1/3
3 1
r
ν 1
r
ν
Consider, for example, a disk electrode with radius δN,i = Γ (4/3) = 1.61
a Sci 1/3 Ω Sci 1/3 Ω
r0 = 0.25 cm and a capacity C0 = 20 µF/cm2 . The disk
(9)
is immersed in an electrolyte of resistivity ρ = 10 Ωcm.
Assume that the faradaic reaction has an exchange cur- where Sci = ν/Di is the Schmidt number which has
rent density i0 = 1 mA/cm2 and that the disk is rotat- a value Sci = 1000 for ν = 10−2 cm2 /s and a typical
ing at Ω = 400 rpm. The kinematic viscosity of the diffusivity Di = 10−5 cm2 /s. The time constant for dif-
electrolyte is ν = 10−2 cm2 /s. fusion of a species with a diffusivity of 10−5 cm2 /s is
The time constant for charging the electrode surface equal to 0.41 s. The corresponding characteristic fre-
is given by quency is 0.4 Hz.
Thus, the frequency range for an impedance mea-
τC = C0 Re (1) surement for disk electrode can be from 10 kHz to
A Tutorial on Electrochemical Impedance Spectroscopy 3

yields the magnitude of the transfer function. The phase

angle in units of radians can be obtained as
∆t
ϕ(ω) = 2π (14)
T
If ∆t = 0, the phase angle is equal to zero. Similarly,
the phase angle is equal to zero if ∆t = T as the phase
angle in equation (14) is a full period 2π. As shown in
Figure 3, the output lags the input, and the phase angle
has a positive value.
The transfer function is, therefore, characterized by
two parameters: the gain
Fig. 3 Schematic representation of the calculation of the  
transfer function for a sinusoidal input at frequency ω. The Y (ω)
e 
|Y |  
time lag between the two signals is ∆t and the period of the |H(ω)| = =   (15)
signals is T . Taken from Orazem and Tribollet.[1] |X| X(ω)
e 


and the phase shift ϕ(ω). These two parameters can

10 mHz. The frequency range may be limited by instru- be written in the form of a complex number with a
ment and wiring limitations that constrain the high- magnitude |H(ω)| and a phase ϕ(ω) or with a real part
frequency limit and by nonstationary processes that expressed as |H(ω)| cos (ϕ(ω)) and an imaginary part
constrain the low-frequency limit. |H(ω)| sin (ϕ(ω)).
Experiments are conducted in the time domain. If Generally the input signal is considered to be a ref-
the input signal is sinusoidal, as shown in Figure 2(b), erence for the phase. In this case, the corresponding
complex number for the input is real, i.e., X(ω)
e and
X(t) = X + |∆X| cos(ωt) (10)
the output signal is a complex number Y (ω) with a
e
magnitude Ye (ω) and a phase ϕ(ω). Thus,
 
where X is the steady-state or time-invariant part of
the signal, and |∆X| represents the magnitude of the  
oscillating part of the signal. When |∆X| is sufficiently Y (ω)
e
e
 Y (ω)


small that the response is linear, the output will have H(ω) = =   (cos ϕ(ω) + j sin ϕ(ω)) (16)
the form of the input and be at the same frequency, i.e., X(ω)
e X(ω)
e 


Y (t) = Y + |∆Y | cos(ωt + ϕ) (11) For an electrical or an electrochemical system, the input
is usually a potential, the output is a current, and the
where ϕ is the phase lag between the input and out- transfer function is called admittance. In the particular
put signals. An alternative representation of the time- case where the input is a current and the output is a
domain expressions is potential, the transfer function is an impedance. The
transfer function is, however, a property of the system
X(t) = X + Re{X
e exp(jωt)} (12) that is independent of the input signal. As the admit-
tance is the inverse of the impedance,
and
Ve (ω)
Y (t) = Y + Re{Ye exp(jωt)} (13) Z(ω) = (17)
ei(ω)

respectively, where X e and Ye are complex quantities Generally only the impedance is considered even if the
called phasors that are functions of frequency but are measurement corresponds to an admittance. The mea-
independent of time. The transfer function is a func- sured impedance can have a strong dependence on the
tion of frequency and is independent of both time and applied frequency. By analyzing the impedance as a
the magnitude of the input signal. While the measure- function of frequency, a transfer-function model could
ments are made in time domain, the determination of be defined which takes into account all time constants
the transfer function is obtained from subsequent anal- of the corresponding system.
ysis. Impedance spectroscopy is much more than a simple
The calculation of the transfer function at a given application of Ohm’s law, i.e., V = IR. The expres-
frequency ω is presented schematically in Figure 3. The sion V = IR represents a steady-state measurement.
ratio of the amplitudes of the output and input signals For a system consisting of a resistor, shown in Figure
4 Mark E. Orazem*, Bernard Tribollet

from which the contributions of Re and Rt cannot be

distinguished and the contribution of the parallel capac-
itance cannot be discerned. In contrast, the impedance
response may be expressed as

Ve Rt
Z= = Re + (24)
I
e 1 + jωR t Cdl
(a) from which the parameters Re , Rt , and Cdl may be
obtained easily by using graphical methods.[1, 3]

2 Applications of Impedance Spectroscopy

Impedance spectroscopy has been applied to many elec-

trochemical systems. The examples given below are in-
tended to demonstrate the power of impedance spec-
troscopy. The discussion of the influence of adsorbed in-
(b)
termediates on impedance response suggests that some
Fig. 4 Electrical systems: a) a resistor and b) a resistor in properties can be studied only by measurement of the
series with the parallel combination of a capacitor and a re- electrochemical impedance. Impedance spectroscopy can
sistor. Taken from Orazem and Tribollet.[1] be used to measure rates of corrosion that are too small
to be assessed by weight loss measurements. Impedance
spectroscopy also can provide an inexpensive way to
4(a), the measurement of current at an applied poten-
determine the thickness of oxide layers. The analyses
tial yields the value of the resistor, i.e., V /I = Re . For
presented in this section are qualitative. The reader is
potentiostatic impedance measurements, application of
directed to the cited literature for more detailed math-
an oscillatory potential
ematical treatments.
V = V + |∆V | cos(ωt) (18)

yields a current 2.1 Presence of Adsorbed Intermediates

I = I + |∆I| cos(ωt + ϕ) (19) Some properties can be studied only by measurement of

the electrochemical impedance. For example, impedance
where ϕ is the phase lag between the current and po-
may be used to demonstrate the existence of an ad-
tential. Equation (18) is mathematically equivalent to
sorbed reaction intermediate in the form of a fraction
V = V + Re{Ve exp(jωt)} (20) of monolayer in the case of iron dissolution in sulphuric
acid. A current-potential curve obtained on a station-
and equation (19) is mathematically equivalent to ary iron electrode in 0.5 M sulfuric acid solution is pre-
sented in Figure 5(a).[4] The scan rate was 2 mV/sec.
I = I + Re{Ie exp(jωt)} (21) The potential was applied to the iron electrode from
The impedance for the resistor shown in Figure 4(a), the open-circuit potential, activating the iron electrode,
expressed as to a higher potential, passivating the electrode surface.
The potential E = −0.925 V (SSE) in Figure 5(b) rep-
Ve resents a steady-state condition for which impedance
Z= = Re (22) measurements were performed.
Ie
Bockris and coworkers[5] proposed a reaction model
yields the same information that could be obtained in which two consecutive steps are coupled by an ad-
from the steady-state measurement V /I = Re . sorbed intermediate. The anodic dissolution of iron can
The circuit presented in Figure 4(b) may be con- be described in simplified form as
sidered to represent a simple potential-dependent elec-
K −
trochemical reaction. The steady-state measurement of 1
Fe −→ Fe+
ads + e (25)
current at an applied potential yields
and
V K
= Re + Rt (23) Fe+ 2 2+
+ e−
I ads −→ Fe (26)
A Tutorial on Electrochemical Impedance Spectroscopy 5

(a)

Fig. 6 Electrochemical impedance response for a pure iron

electrode in 0.5 M H2 SO4 measured at a potential E =
−0.925 V(SSE) as indicated in Figure 5(b). Data taken from
Wu et al.[4].

on steady-state potential as

∂iF ∂ γ̇
A= (28)
∂γ ∂V
(b)
where
Fig. 5 The polarization curve for a stationary iron electrode
in 0.5 M H2 SO4 : a) a scan including both the active and ∂γ i(25) − i(26)
passivated regions; b) zoomed portion of part (a) showing γ̇ = = (29)
∂t ΓF
the potential at which the impedance measurement was per-
formed. Data taken from Wu et al.[4].
When A = 0, the time-rate-of-change of fractional cov-
erage is independent of steady-state potential, and only
a single capacitive loop is seen in the impedance re-
The iron first oxidizes and forms a monovalent inter-
sponse. When A > 0, a low-frequency inductive loop is
mediate adsorbed on the electrode surface. This re-
visible, as is shown in Figure 6. The global impedance
action is followed by the oxidation of the intermedi-
response given in Figure 6 shows a low-frequency induc-
ate. The ferrous ion is soluble and diffuses away from
tive loop which may be associated with the formation
the electrode. Epelboin and Keddam[6], Armstrong et
of Fe(I) species adsorbed on the electrode surface.
al.[7], and Epelboin et al.[8] showed that the induc-
tive loops observed in the low-frequency impedance re- While the mathematical development is found else-
sponse could be attributed to partial coverage of the where, the results presented here show, from a qualita-
iron surface by an adsorbed intermediate. Such a film tive perspective, that the low-frequency inductive loop
is too thin to be observed directly. may be attributed to the coupling of electrochemical
reactions through an intermediate. In the case of the
The faradaic impedance for this system can be ex-
iron system, the reactions (25) and (26) are coupled
pressed as
through an adsorbed intermediate. A similar coupling
of elementary reactions has been proposed for corrosion
1 of magnesium.[9]
ZF = (27)
1 A Other forms of coupling may also be envisioned. Roy
+
Rt,eff B + jω et al.[10] suggested that low-frequency inductive loops,
often observed in proton-exchange-membrane (PEM)
where Rt,eff represents the effective charge-transfer re- fuel cells, may be attributed to oxidation of the plat-
sistance for reactions (25) and (26). The inductive term inum catalyst. The platinum dissolution was assumed
is scaled by a constant A that can be expressed in terms to occur by a reaction scheme similar to that reported
of the dependence of the steady-state faradaic current by Darling et al.,[11] by an electrochemical reaction
on the fractional coverage of the surface and the depen-
dence of the time-rate-of-change of fractional coverage Pt + H2 O  PtO + 2H+ + 2e− (30)
6 Mark E. Orazem*, Bernard Tribollet

in which PtO is formed, followed by a chemical disso-

lution reaction

PtO + 2H+ → Pt+2 + H2 O (31)

The formation of the platinum oxide was proposed to

have an indirect influence on the oxygen-reduction re-
action at the cathode by changing the effective rate
constant for the reaction. Thus,

Keff = KPt + (KPtO − KPt )γPtO (32)

where KPt is the rate constant on a platinum site and Fig. 7 Electrochemical impedance response for a 5 cm2 nom-
KPtO is the rate constant on a platinum oxide site. The inal surface area PEM fuel cell at a current of 0.2 A/cm2 .
The line represents a model calculation based on the cou-
oxygen-reduction reaction was assumed to take place
pling of electrochemical reactions through the oxidation of a
according to platinum catalyst. The diamond  is the polarization resis-
tance obtained from the slope of the polarization curve. Data
O2 + 4H+ + 4e− → 2H2 O (33) taken from Roy et al.[10].

with a steady-state current density given by

iO2 = −Keff cO2 (0) exp (−bO2 ηO2 ) (34)

where Keff is defined by equation (32).

Roy et al.[10] measured the impedance of a PEM
fuel cell. The membrane electrode assembly (MEA) was
a 0.0308 mm (2 mil) thick Nafion N112 membrane with
a Pt catalyst loading of 0.4 mg/cm2 on both the anode
and the cathode sides. The flow channel employed a
single-channel horizontal serpentine flow configuration
with the outlet lower than the inlet to facilitate removal
of condensed water. The active surface area of the MEA
was 5 cm2 .
A Scribner Associates 850C fuel cell test station was
used to control reactant flow rates and temperatures.
The test station was connected to a computer by an
interface for data acquisition. The 0.1 L/min hydrogen
gas flow to the anode was held at a temperature of 40 ±
0.1◦ C, and the 0.5 L/min compressed air gas flow to the
cathode was held at a temperature of 35 ± 0.1◦ C. The
gas flows were humidified to 100% relative humidity at
Fig. 8 C 1s high-resolution spectra obtained from un-used
the respective temperatures. The cell temperature was and used (after 600 hours of operation) MEA cathode catalyst
held at 40 ± 0.1◦ C. layers. Taken from Roy et al.[12]
A typical result is shown in Figure 7. The line rep-
resents a model calculation based on the coupling of
electrochemical reactions through the oxidation of a These results can be used to motivate new experimental
platinum catalyst. The diamond  is the polarization observations.
resistance obtained from the slope of the polarization Roy et al.[12] report, for example, the results of X-
curve. Ray Photoelectron Spectroscopy obtained from the un-
The one-dimensional model does not provide an ex- used and used MEA cathode catalyst layers. The high-
act fit to the experimental result that was obtained resolution spectra from the C-1s region, shown in Figure
for a system that, given the serpentine gas flow, had 8, revealed two Nafionr -related carbon peaks between
a nonuniform current and potential distribution. The binding energies of 291 and 294 eV. On the un-used
model suggests, however, that the coupling of electro- catalyst, the ratio of support carbon to Nafionr carbon
chemical reactions through the oxidation of the Pt cat- was higher than on the used catalyst. This could be due
alyst can give rise to low-frequency inductive loops. to migration of Nafionr onto the catalyst layer from the
A Tutorial on Electrochemical Impedance Spectroscopy 7

Electrochemical impedance spectroscopy provides a

powerful in-situ tool to explore the coupling of electro-
chemical reactions, yielding insight into reaction mech-
anisms for electrochemical systems. Indeed, the cou-
pling through adsorbed intermediates can be studied
only by measurement of the electrochemical impedance.
The interpretation of impedance spectra in terms of a
proposed model can be used, as shown in the work pre-
sented here for the PEM fuel cell, to guide selection of
ex-situ experiments that can be used to either support
or reject the proposed mechanism.

2.2 Identification of Small Rates of Corrosion

In the special case that both the anodic and the ca-
thodic reactions are controlled by kinetics, the rate of
corrosion may be determined from impedance measure-
ments made under the open-circuit condition, or the
corrosion potential. The corrosion current may be ex-
tracted from the polarization or effective charge-transfer
resistance using the Stern–Geary relation[16]
Fig. 9 Pt 4f high-resolution spectra obtained from un-used
and used (after 600 hours of operation) MEA cathode catalyst −βc βa
layers. Taken from Roy et al.[12] icorr = (35)
2.303 × 103 Rt,eff (βa − βc )
where βa and βc are the Tafel slopes for anodic and
cathodic reactions, respectively, and
Nafionr membrane due to membrane degradation or to
carbon support corrosion. Rt,a Rt,c
Rt,eff = (36)
The high-resolution spectra of the Pt 4f region are Rt,a + Rt,c
presented in Figure 9. The binding energies of the Pt is the effective resistance associated with the parallel
4f peaks (∼ 71 eV) were consistent with those reported contributions of the charge-transfer resistances for the
for Pt metal [13]. Since the spectra have been normal- anodic and cathodic reactions. Equation (35) applies
ized, the lower Pt content on the un-used catalyst layer for systems such as the corrosion of iron in anaerobic
is evident in the lower signal-to-noise ratio of the spec- electrolytes, but does not apply for more complicated
trum obtained from this sample. In addition to a higher systems, for example, in aerated electrolytes, where the
Pt content on the used cathode catalyst layer, the Pt reactions are not strictly kinetically controlled. In more
4f peaks are broader compared to the un-used cathode complex systems, the steady-state corrosion current may
catalyst layer. There is a significant shoulder at higher be obtained from the charge-transfer resistance of the
binding energies compared to Pt metal. This is indica- corrosion reaction, i.e.,
tive of Pt oxidation. Roy et al.[12] observed that the
Pt 4f spectrum obtained from 3 monolayers of PtOx on βa
ia = (37)
Pt(100), prepared using atomic oxygen, was very sim- 2.303 × 103 Rt,a
ilar to the spectrum obtained from the used catalyst
A sophisticated model may be needed to differentiate
layer.[14] They concluded that, after extended opera-
the corrosion process from the other phenomena and
tion in the fuel cell, some of the platinum in the catalyst
reactions in the system.
layer was oxidized.
An example is provided by Frateur et al.[17], who
The attribution of the low-frequency inductive loop explored the corrosion of cast iron in EvianTM drinking
to PtOx formation is sensitive to the reversibility of water. A film is formed on the cast iron electrodes that
PtOx formation as a function of potential. While the includes a porous electrode and porous ferrous films.
reversibility of PtOx formation was not addressed by As the electrolyte is aerated, the cathodic reaction is
Roy et al.[12], Mathias et al.[15] reported that the re- reduction of oxygen, which is influenced by mass trans-
action is reversible. fer to the pore walls. The anodic reaction is dissolution
8 Mark E. Orazem*, Bernard Tribollet

of the cast iron. For this complex system, the corrosion

rate was determined from equation (37).
The work of Frateur et al.[17] was motivated by the
need to measure the very small internal corrosion rate
of cast iron drinking water pipes, used, for example,
for the water distribution network in France. While the
rate of corrosion is too small to pose structural prob-
lems for the pipe network, the small rate of corrosion
is sufficient to reduce the concentration of free chlo-
rine (FCl, the sum of hypochlorous acid HOCl and
hypochlorite ions ClO− ) introduced in water at the
treatment plant in order to maintain microbiological
quality. Frateur et al.[17] reported the results of elec-
trochemical impedance measurements that, by use of a
model that accounted for anodic metal dissolution, the
progressive development of a porous film composed of
corrosion product, and oxygen reduction, allowed esti-
mation of corrosion rates. After 28 days of immersion in
EvianTM water, the corrosion rate of the cast iron was
observed to be about 10 µm/year. This work was sup-
ported by surface analyses which showed the presence of
corrosion products but could not assess the rate. A cor-
rosion rate this small cannot be assessed by weight-loss
measurements. As reported by the authors, “the cor-
rosion of pipes is not a problem itself but it induces a Fig. 10 Impedance data for free-machining 18/8 stainless
steel in an electrolyte consisting of 22 g/L boric acid with
consumption of FCl, which is the real concern of drink- NaOH added, about 6 g/L, to bring the pH to 7.2 (at the
ing water professionals.” edge of buffering region). Data are presented for the steel
in as-received condition and after a proprietary treatment to
increase the chromium content of the oxide film. Data taken
2.3 Measurement of Film Thickness from Orazem et al.[23]

Impedance spectra usually are influenced by distribu-

tions of time constants that can often be described in with a value close to unity.
terms of a constant-phase element (CPE). Jorcin et Equation (39) may be a considered a single equa-
al.[18] and Hirschorn et al.[19] suggested that interpre- tion with known values for Q and α and unknown val-
tation of the CPE requires consideration of the nature ues for ε, δ, and ρδ . In practice, however, ε is generally
of the time-constant distribution. A modified power-law known for a given oxide film, and ρδ may be obtained
distribution of time constants through the thickness of by calibration.[22] The application of equation (39) was
a film was shown by Hirschorn et al.[20,21] to yield a explored by Orazem et al.[23], who reported impedance
CPE. responses for free-machining 18/8 stainless steel (18 Cr-
The CPE parameters, obtained from 8Ni), also known as 303 stainless steel, in an electrolyte
consisting of 22 g/L boric acid with NaOH added, about
R||
Z = Re + (38) 6 g/L, to bring the pH to 7.2 The results are presented
1 + (j2πf )α R|| Q in Table 1. As shown in Table 2, application of equa-
in terms of ohmic resistance Re , a parallel resistance tion (39) yielded film thicknesses in close agreement
R|| , and CPE parameters α and Q, were expressed in to values obtained from ex-situ XPS. The power-law-
terms of film thickness δ, dielectric constant ε, and the model analysis is now used commercially for screening
resistivity at the film–electrolyte interface as ρδ as raw materials. Riemer and Orazem[24] reported that
“The impedance based screening of raw materials has
(εε0 )α a tremendous positive impact in an industry where the
Q= (39)
gδρ1−α
δ state of the oxide film on stainless steel strongly influ-
where ε0 is the permittivity of vacuum, and ences process and product performance. Having a fast,
inexpensive and accurate measure of the film thickness
g = 1 + 2.88(1 − α)2.375 (40) is of great benefit in the manufacturing process. With
A Tutorial on Electrochemical Impedance Spectroscopy 9

Table 1 Regression results for free-machining 18/8 stainless References

steel in an electrolyte consisting of 22 g/L boric acid with
NaOH added to bring the pH to 7.2. Data taken from Orazem 1. M.E. Orazem, B. Tribollet, Electrochemical Impedance
et al.[23] Spectroscopy, 2nd edn. (John Wiley & Sons, Hoboken,
2017)
As Received After Treatment 2. J.S. Newman, Journal of the Electrochemical Society
Re , Ωcm2 15.3 13.3 113(5), 501 (1966)
R|| , MΩcm2 2.33 16.8 3. M.E. Orazem, N. Pébère, B. Tribollet, Journal of the
α 0.91 0.91 Electrochemical Society 153, B129 (2006)
4. S.L. Wu, M.E. Orazem, B. Tribollet, V. Vivier, Journal
Q, µF/s(1−α) cm2 11 30.5
of the Electrochemical Society 156(7), C214 (2009)
δ by XPS, nm 6.3 2.5
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Acknowledgements The authors thank Prof. Mamie Sancy 22. M.E. Orazem, B. Tribollet, V. Vivier, D.P. Riemer, E.A.
(Pontificia Universidad Católica) and Prof. Maritza Paez (Uni- White, A.L. Bunge, Journal of the Brazilian Chemical
versidad de Santiago de Chile) for the opportunity to present Society 25, 532 (2014)
the present work at the “First Workshop of Material Science 23. M.E. Orazem, B. Tribollet, V. Vivier, S. Marcelin,
for Corrosion Protection” held in 2017 in Santiago, Chile. The N. Pébère, A.L. Bunge, E.A. White, D.P. Riemer,
authors thank Prof. Dr. Fritz Scholz (Universität Greifswald) I. Frateur, M. Musiani, Journal of the Electrochemical
for the invitation to submit this tutorial. Mark Orazem ac- Society 160, C215 (2013)
knowledges financial support from the University of Florida 24. D.P. Riemer, M.E. Orazem, ECS Interface 23(3), 63
Foundation Preeminence and the Dr. and Mrs. Frederick C. (2014)
25. A. Lasia, Electrochemical Impedance Spectroscopy and
Edie term professorships.
Its Applications (Springer, New York, 2014)
26. V.F. Lvovich, Impedance Spectroscopy: Applications
to Electrochemical and Dielectric Phenomena (Wiley,
Conflict of interest Hoboken, 2015)
27. E. Barsoukov, J.R. Macdonald (eds.), Impedance Spec-
The authors declare that they have no conflict of inter- troscopy: Theory, Experiment, and Applications, 3rd
est. edn. (John Wiley & Sons, Hoboken, 2018)