EC-Lab – Application Note #42

08/2012

The modified inductance element La

I – INTRODUCTION respectively, with 0 < a ≤ 1. Again, ZLa(f) = ZL(f)
It is convenient to use a Constant Phase Ele- for a = 1.
ment (CPE) instead of a capacitor when for This application note introduces a few
instance the Nyquist diagram of the impe- practical examples for which the modified
dance of a system shows a semi-circle whose inductance component can lead to a much
center is located below the Real axis, instead better fit of impedance data.
of on the Real axis.
II – HIGH-FREQUENCY INDUCTANCE IN
The difference between a capacitor C and a LI-ION BATTERIES
CPE Q is that the expression of the impedance Figure 1 shows the Nyquist impedance
of a CPE contains an additional parameter a: diagram of an LiPF6 Li-ion battery with a
capacity of 60 Ah and a nominal voltage of
1 3.2 V. An inductive behaviour can be seen at
ZQ ( f ) = (1)
Q ( j 2π f )
a
high frequencies (f > 22 Hz), most likely due to
the connection cables to the battery. This
whereas the expression of the impedance of behaviour is more visible in cells with low
the capacitor is : apparent resistance such as batteries. As
shown by the least square linear fit in Fig. 1,
1 these high frequency data points are on a
ZQ ( f ) = (2) straight line that is not perpendicular to the x-
C ( j 2π f )
axis. Consequently, this behaviour cannot be
represented by a simple inductance.
with C and Q the value of the capacitor in F
and of the CPE in F s(a-1) with 0 < a ≤ 1. It is
important to note that Z(f)Q = Z(f)C for a = 1. A
CPE is physically interpreted as an effect of the
surface roughness of the sample, leading to an
heterogeneity of the capacitance.
Analogously, the modified inductance La can
be used to represent the presence of an
unusual inductance in the Nyquist diagram.
The expression of the impedance of an
inductance is :

Z L ( f ) = Lj 2π f (3)

The expression of the impedance of the Figure 1 : Nyquist impedance diagram of an LiPF6
battery for frequencies ∈ [0.1 , 2000] Hz.
modified inductance La is :
Figure 2 shows the equivalent circuit chosen
Z La ( f ) = La ( j 2π f )
a
(4) to fit the data shown in Fig. 1.

with L and La the value of the inductance in H

and of the modified inductance in H s(a-1),

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 EC-Lab – Application Note #42
08/2012

of the fitting of the battery impedance in Fig.

1 using the modified inductance in series with
a Randles equivalent circuit. In this case, χ2 is
lower and hence better than the χ2 factor
obtained with an equivalent circuit containing
Figure 2 : Randles equivalent circuit with a modified
a simple inductance (cf. Table 1). Further-
inductance in series. more, in Table I, it can be seen that the values
of C1, R2 and W1 are different, which shows
It is a Randles circuit with an inductance La in that using a modified inductance leads to a
series. The simple L is a particular example of better determination of the characteristic
the inductance La. As stated above, if a=1, parameters of the system.
La≡L. R1 is associated to the internal
resistance of the battery, C1 to the double
layer capacitance, R2 to the charge transfer 0,2
resistance and W, the Warburg component, to 0
the semi-infinite diffusion.
Figure 3 shows the fitting curve obtained -0,2

-Im(Z)/mOhm
using the equivalent circuit shown in Fig. 2 -0,4
with a simple inductance. Fig. 4 shows the
same results but with a modified inductance -0,6

La. A comparison of the results of the two -0,8

fitting, i.e. the values of the parameters and of
-1
χ2 (an estimation of the goodness of the fit [1])
are given in Table 1. -1,2

1,5 2 2,5
Re(Z)/mOhm
0,2
Figure 4 : Fitting results of the graph in Fig. 1 using
0 the equivalent circuit : La1+R1+C1/(R2+W1).
-0,2
Table I : Values of the parameters for the equivalent
-Im(Z)/mOhm

-0,4 circuits used in Fig. 3 and Fig. 4.

Parameter Using L (Fig. 3) Using La (Fig. 4)
-0,6
L1 /µHs (a-1)
0.14 0.48
-0,8 a1 1 0.84
R1 /mΩ 2 2
-1 C1 /F 109 429
-1,2 R2 /µΩ 14.3 50.3
s1 /mΩ s-1/2 0.17 0.158
1,5 2 2,5
Χ2 0.53x10-6 2.67x10-9
Re(Z)/mOhm

Figure 3 : Fitting results of the impedance diagram

in Fig. 1 using the equivalent circuit : III – LOW FREQUENCY INDUCTIVE
L1+R1+C1/(R2+W1). BEHAVIOR OF A FREELY CORRODING
METAL
If, instead of an inductance L, a modified Another example of a system for which the
inductance La is used as shown in Fig. 3, it is component La can be used is a metal corro-
possible to fit the non-vertical high frequency ding in an acidic solution. In this case, the
part of the impedance. Fig. 4 shows the results reduction reaction is the proton reduction,

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 EC-Lab – Application Note #42
08/2012

which involves an adsorption step, following the circuit R1+Q2/R2 in Fig. 6 by R1/(R2+La2)
the Volmer-Heyrovský mechanism [2, 3]. Fig. as shown in Fig. 7.
5 shows the impedance graph obtained on a
partially painted Zn sample immersed in
0.5 mol L-1 H2SO4 and the corresponding
fitting curve using the equivalent circuit
shown in Fig. 6.
In this equivalent circuit, Q1/R1 is associated
to the larger semi-circle in Fig. 5 (possibly
related to the coated part of the sample),
Figure 6: Equivalent circuit used in Fig. 5.
Q2/R2 to the inductive semi-circle (related to
an adsorption process at the rough metal Table II : Values of the parameters for the equivalent
surface) and Q3/R3 to the third semi-circle circuits used in Fig. 5.
(also possibly related to the bare metal). The Parameter Fig. 5 Red
solution used in this example was not a Q1 /µF s (a-1)
65.5
perfect ionic conductor but its resistance of a1 0.982
around 1 Ω was considered negligible. R1 /Ω 298
Another way to interpret the impedance Q2 /F s(a-1) -0.015
diagram is to consider a Volmer-Heyrovský a2 0.907
chemical desorption mechanism. R2 /Ω -75.1
Q3 /F s(a-1)
0.168
a3 0.826
R3 /Ω 122
150 Χ2 325

100 In Fig. 8, the blue curve shows the

-Im(Z)/Ohm

experimental data, the red curve, the fitting

50 curve obtained using the equivalent circuit in
Fig. 7 with a simple inductance (a2 = 1) and the
0 green curve, the fitting curve obtained using
the equivalent circuit in Fig. 7 with a modified
-50 inductance.
0 100 200 300
As can be seen in Table III, all the elements of
Re(Z)/Ohm the equivalent circuit have now positive
Figure 5 : Blue : Nyquist diagram of the impedance values. In terms of choosing the best
of a partially coated Zn sample immersed in 0.5 mol equivalent circuit, it seems the red curve fit
L-1 H2SO4 for frequencies ∈ [10x10-3 , 200x103] Hz. less tightly to the real data than the green
Red :Fitting curve using Q1/(R1+Q2/R2+Q3/R3).
curve, which shows that the modified induc-
tance increases the goodness of the fit (see
In the fitting results shown in Table II, the
elements Q2/R2 correspond to the inductive
loop and have negative values. It might be
difficult for the user to handle and interpret
negative values. It is then possible to use an
equivalent circuit for which the elements have
positive values. This can be done by replacing

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 EC-Lab – Application Note #42
08/2012

inset of Fig. 8). This is confirmed by the values IV – CONCLUSION

of the χ2 shown in Table 3. The new element La is a modified inductance
element. It can be used to fit impedance
characteristics related to either an unusual
connection inductance at high frequencies,
mostly visible in batteries or a heterogeneous
adsorption mechanism at low frequencies,
mostly visible in corrosion.

REFERENCES
1) EC-Lab User’s Manual p. 113
Figure 7: Equivalent circuit used in Fig. 8.
2) M. Keddam, Thèse, Paris, 1968, no.
AO2192.
3) J.-P. Diard, P. Landaud, B. Le Gorrec, C.
Montella, J. Electroanal. Chem., 255 (1988) 1.

Data files can be found in :

Fig. 1 :
C:\Users\xxx\Documents\EC-
Lab\Data\Samples\Battery\ AN42_battery
Fig. 5:
C:\Users\xxx\Documents\EC-
Lab\Data\Samples \Corrosion\AN42_coating

APPENDIX
1) It is noteworthy that if the inductive loop in
Figure 8: Blue : Nyquist diagram of the impedance of a
Fig. 5 could be fitted with an R/C instead of an
partially coated Zn sample immersed in 0.5 mol L-1 R/Q (i.e. if a2 was equal to 1) then an R+L
H2SO4.Fitting curve using Red :Q1/(R1/(R2+L2)+Q3/R would be enough and R+La unnecessary.
3), Green : Q1/(R1/(R2+La2)+Q3/R3). 2) Furthermore, to widen the perception of
what an equivalent circuit is, it is worth noting
Table III : Values of the parameters for the equivalent that ZQ(f) = ZLa(f) with aQ = -aLa and Q = 1/La,
circuits used in Fig. 8.
aQ being the a parameter for the element Q
Parameter Using L Using La
and aLa for the element La.
Fig. 8 Red Fig. 8 Green
If we replace in Eq. 4, a by -aQ :
Q1 /µF s(a-1) 65.9 74
Z La ( f ) = La ( j 2π f )
− aQ
a1 0.981 0.958 (5)
R1 /Ω 299 313 La
L2 /H s (a-1)
1464 837 Z La ( f ) = (6)
( j 2π f )
aQ

a2 1 0.645
R2 /Ω 1118 1.33 x10-9 1
Z La ( f ) = (7)
Q ( j 2π f )
aQ
Q3 /F s (a-1)
0.348 0.020
a3 1 0.718
1
R3 /Ω 87.5 325 With La =
Χ2 277 60 Q
Z La ( f ) = Z Q ( f ) (8)

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 EC-Lab – Application Note #42
08/2012

Finally, the impedances of the C, L, Q and La

elements are all particular forms of the
general expression :

Z ( f ) = A ( j 2π f )
m
(9)

with A the value of the component and

m ∈ [-1,0[ ∪ ]0,1].
If m = 0, then the impedance Z is a simple
resistance.

Revised in 08/2019

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