Elettrochimica
per la caratterizzazione
di materiali funzionali avanzati
3. Spettroscopia dimpedenza elettrochimica
Electrochemistry
for the characterization
of advanced functional materials
3. Electrochemical Impedance Spectroscopy (EIS)
Prof. Patrizia R. Mussini
Dipartimento di Chimica Fisica ed Elettrochimica,Via Golgi 19, 20133 Milano
patrizia.mussini@unimi.it
Alternating voltage and current
IE E = E0sin(t)
E0
I0
t
T
I = I0sin(t+)
E = XL I I = BL E
XL= inductive
reactance
BL = inductive
susceptance
t
= L =1/ L I = I0sin(t /2)
E is 90 ahead of I
= /2
Capacitance C: I E E = E0sin(t)
E = XC I I = BC E
XL = capacitive BC = inductive
reactance susceptance t
C
= 1/ = C
I is 90 ahead of E I = I0sin(t + /2)
= /2
Impedance of a circuit including the three basic elements in series
The vector combination of the resistive effects of all the circuit elements
is the circuit impedance Z, and its reciprocal is admittance Y.
R L C In a SERIES circuit the current through each of the components is the same,
while the total voltage is the sum of the voltages across each component
(proportional to the corresponding resistance or reactance). Accordingly, in
order to find the global potential/current relationship it is convenient to perform
a vector analysis of the voltage contributions, taking as a reference the I vector.
X is the total reactance, i.e. the vector sum of inductive reactance and
IXL capacitive reactance, perpendicular to ohmic resistance and pointing upwards
for prevailing inductive reactance, downwards for prevailing capacitive
IZ reactance. For XL = XC total reactance is 0; therefore the circuit has purely ohmic
IX
resistance and current is in phase with voltage, no matter how large XL and XC
(resonance condition).
IR
The vectorial sum of R, ohmic resistance, and X, total reactance
IXC I (vectorial sum of capacitive and inductive reactances), is the
circuit Z impedance.
Dividing all terms by current I we obtain the impedance triangle of the circuit:
R
For an RC parallel
C
Y Y = Y+iY
Y in particular, here
BC = Y = G + iC = 1/R + i
C
C
G
Y
The principle of Electrochemical Impedance Spectroscopy (EIS) measurements (I)
The necessary condition is to be able to discriminate within the global impedance each
single contribution and assign it to the right step/obstacle, or identify a circuit model
corresponding to the electrochemical system and providing a simulated impedance
spectrum faithfully reproducing the experimental one.
To this aim it is necessary to repeat the impedance measurement at different frequencies
(i.e., on a whole frequency spectrum) of the alternating voltage; in fact all resistive terms
in the circuit excepting ohmic resistances have their own dependency on frequency; for
instance, capacitive reactances tends to zero at high frequencies.
The principle of Electrochemical Impedance Spectroscopy (EIS) measurements (II)
Electrochemical system,
with a given relationship
between potential and
current (see voltammetry)
4. Complete 3D
diagram 5. Real time plot: Lissajous curves
(-Z vs vs Z)
Z = R i/(C) = R + 1/(iC)
Nyquist: Bode modulus: Bode phase:
0 Z |Z| =(R2 +1/(C)2) =1/(RC)
tg
ZR 0 |Z| 1/(C) 0 90
ln|Z| / ln(
) 1
0
ln|Z| lnR
Nyquist admittance
Corresponds to electron transfer at the interphase in the
RC parallel absence of mass transfer control (like the Butler and Volmer
equation; faradaic impedance) also taking into account the
double layer capacitance (like the background in CV)
F (1 ) F
i = i0 exp exp
RT RT
Parallel we consider the conductive terms in terms of complex number,
In this example with building admittance as the sum of ohmic conductance (real term) and capacitive
susceptance (imaginary positive term), then we invert it to achieve impedance.
Slope 1 (Capacitance)
Bode modulus
RCT (100 )
Rs (10 )
= 45
Bode phase
=0 =0
It can be demonstrated that,
determining the charge
transfer resistance and the
Warburg impedance as a
function of the electrode
potential,
2 zF (1 2 ) zF
( E E 20 ) ( E E 20 )
v2 = k e
0
2 B
RT
k a e
0
2 s C
RT
B
Y = A+
i + C
f = zF/(RT)
= occupied sites/total sites
ififBB==00simple
simple
RC semicircle
RC semicircle
B<0 B>0
Case of two adsorbed species
Effect of non ideality of solid electrodes: the phase constant element CPE
On solid electrodes deviations are often observed from ideal behaviour, particularly a
dispersive effect on frequencies and therefore on the time constants, as a consequence of (a)
microscopic roughness, resulting in coupling between solution resistance and surface capacity
and in (b) slow adsorption of ion and other molecules at the interphase.
For this reason the observed impedances cannot be represented as combination of simple R, C,
and L elements, but, as in the case of the Warburg element, by an infinite series of RC parallels
(distributed element) or by an ad hoc new element, which is called constant phase element
CPE, with equation:
1 1
Z CPE = that is Z CPE = cos( 2 ) i sin ( 2 )
T (i) T
where T is a constant in F cm-2 s-1 and is related to the rotation angle in the complex
plane with respect to a purely capacitive characteristics:
= (90)(1 )
It is worthwhile noticing that the equation can represent:
a pure capacity for = 1
a non ideal solid electrode for 1> > 0.5
Warburg impedance for = 0.5
a pure ohmic resistance for = 0
a pure inductance for = -1
a) Case of an ideally polarizable
electrode: the straight line angle will
be no more 90 but a smaller one.
b) Case of an electron
transfer in parallel
with the double layer
capacitance: the half
circle appears
depressed (or, better,
partially rotated below
the first quadrant)
The extension of the CPE in the case of finite diffusion is the Bounded Constant Phase
element BCP
Z BCP =
1
T (i)
[
tanh RsT (i)
]
At high frequencies the equation becomes a simple CPE, reducing to Rs at low frequencies.
For = 0.5 it is shaped similarly to impedance in the finite diffusion case.
As for = 0.5 CPE represents semi infinite diffusion, for the same value BCP represents
finite diffusion.
Adsorption effects
The frequency dispersion resulting from surface irregularities is not found working on
monocrystalline Au(111) and Au(100) electrodes. However it is found even on such well
defined electrodes, in the presence of specifically adsorbable ions, such as halide anions, and
has been attributed to slow adsorption, diffusion and phase transitions at the surface
(reconstructions).
A fractal approach to surface roughness
Some researchers have elaborated impedance models for rough surfaces starting
from a fractal approach.
Zooming on a normal object will uncover finer, previously invisible,
new structure. When the same is done on a fractal object, however,
no new detail appears; nothing changes and the same pattern
repeats over and over. This feature is called auto similarity.
The fractal term has been coined in 1975 by Benot Mandelbrot,
from Latin fractus (broken), like fraction; actually mathematics
considers fractal images as objects having fractional dimensions..
Porous electrodes
Porous electrodes are frequently adopted in electrocatalysis to increase the active surface.
In order to deal with pores they are usually assumed to have cylindrical shape with l length
and r radius.
Two cases can be considered:
a) Porous electrodes in stationary conditions, without internal
diffusion. In other words, we can assume their internal
concentrations to be constant. The axially flowing dc
current, I, which enters the pore, flows towards the walls
and its value decreases with the distance x from the pore
orifice.
b) Porous electrodes in the presence of axial diffusion (during
electrolysis, concentration changes in the pores).
Both the electric potential and the electroactive species
concentration are assumed to depend only on the distance
from the pore orifice; moreover, an excess of supporting
electrolyte is also assumed to be present (so that migration
can be neglected). Pore model
1) Porous electrodes in
stationary conditions
In an electrolysis process
concentration in pores changes.
The presence of a concentration
gradient in pores results in two
semicircles modulated by the
overpotential.
Real case are much more complicated, involving a lot of pores of which morphology and
dimensional distribution are hardly known.
Other shapes than the cylindric one result in changes of the impedance spectrum:
Examples of applicative cases
Impedance of a protective coating in optimum conditions
Dealing with this case as with an ideal
capacity the fitting is not quite satisfactory.
This depends on the electrode roughness
However,
substituting C with
a CPE the fitting is
very good.
The presence of pores in the
protective layer changes the
situation drastically.
Impedance of a galvanic cell: two electrode
reactions (corresponding to two RC parallel
time constants)