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EA-15159; No. of Pages 5
Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta
a r t i c l e i n f o a b s t r a c t
Article history: The Fletcher’s proposition [S. Fletcher, Electrochemistry Communications 3 (2001) 692–696] to repre-
Received 20 July 2009 sent a three-terminal electrochemical cell by its two-terminal electrical equivalent for the purpose of
Received in revised form 29 October 2009 the analysis of its electrical responses helps significantly to elucidate peculiarities of the electrochemical
Accepted 3 November 2009
impedance (EI) such as inductive or capacitive artifacts. The Fletcher’s two-terminal equivalent cell of
Available online xxx
3rd order appears however to be redundant as including more circuit elements then necessary to rep-
resent the 2nd order impedance of the electrochemical cell. As the alternative to this we recommend
Keywords:
two equivalent circuits of 2nd order, both simpler then the original Fletcher’s circuit and both better
Electrochemical impedance
Equivalent circuit
candidates to play the role of the canonical electrical model. Transformation from three-terminal to
Inductive artifact two-terminal circuit done here with Mathematica® program appeared relatively simple and it was also
Capacitive artifact possible to relax Fletcher’s restraint of representing the working electrode by single resistance. Instead,
we used two-terminal electrical models with the working electrode represented by series resistance,
double layer capacitance and charge transfer resistance. EI spectra of such extended configuration also
present capacitive and inductive artifacts referred to by Fletcher in his model. These artifacts do depend
on the impedance of the working electrode.
© 2009 Elsevier Ltd. All rights reserved.
0013-4686/$ – see front matter © 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2009.11.008
Please cite this article in press as: A. Sadkowski, J.-P. Diard, On the Fletcher’s two-terminal equivalent network of a three-terminal electrochemical
cell, Electrochim. Acta (2009), doi:10.1016/j.electacta.2009.11.008
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G Model
EA-15159; No. of Pages 5
2. Circuit transformations three-terminal to twoterminal With lumped elements considered as constant parameters we
solved equations (2a)–(2g) for variables (i, i1 , i2 , i3 , i4 , i5 , i6 ) using
Fig. 1 presenting the diagram of the three-terminal electro- the command Solve of Mathematica® program [9]. The solution
chemical cell is the same as the one shown as Fig. 1 in [4] and shows presents the whole information on currents and voltages in the
all terminals (nodes) and paths of external current, branch cur- three-terminal network. From this we can calculate the measured
rents and loop voltages. The impedance was defined as the ratio of “impedance” according to Eq. (1) as the function of complex angular
variable p = i ω:
1 + pC5 (R2 R3 /R1 + R2 + R3 )
ZWE (p) = R1 (3)
1 + p(C4 (R1 + R2 ) + C6 (R1 + R3 ) + C5 (R2 + R3 )) + p2 (C5 C6 + C4 (C5 + C6 ))(R2 R3 + R1 (R2 + R3 )))
This expression has the structure of the normalized [10] rational
function of complex variable p:
voltage difference between WE and Ref nodes and the current
from WE to CE terminal. It is assumed that no external current 1 + a1 p
ZWE (p) = R1 (4)
flows to or from the Ref node. 1 + b1 p + b2 p2
(R1 iR1 + R2 iR2 ) with R1 , a1 , b1 , b2 –constants composed from elements of the net-
ZWE = (1)
i work in Fig. 1.
It may be noted in passing that definition of Eq. (1) is not an On current perturbation it relaxes as the system of 2nd order
impedance sensu stricto, because it is not related to the unique according to the denominator of the 2nd order with respect to
two-pole and the numerator and the denominator of this equation variable p.
are related to different points of the network in Fig. 1. Therefore The electrical equivalent should have the same normal form
it should be rather referred to as a specific transfer function of the as in Eq (4) and can be assembled as the 2-pole with resistors,
network in Fig. 1 and not its impedance. capacities and/or inductances without any preference as to the kind
The easiest way to solve the circuit in Fig. 1 for its currents and of reactances (capacities and/or inductances) applied. The equiva-
voltages is to solve equations for zero net currents at 4 nodes WE, lence (degeneracy) of various structures of electrical models was
CE, Ref and O and for zero net voltages around 3 loops with capac- justly discussed also by Fletcher in his earlier publication [11].
ities C4 , C5 and C6 and resistors R1 , R2 and R3 . These equations are For unknown reason the two-terminal equivalent circuit pro-
as follows: posed by Fletcher was more complex as is shown in Fig. 2. Its
normalized impedance Z2 presents the rational function of the 3rd
i = iC6 + iR1 + iC4 (2a) order of the structure:
i = iC6 + iR3 + iC5 (2b) 1 + a1 p + a2 p2
Z2 (p) = R1 (5)
iC5 = iC4 + iR2 (2c) 1 + b1 p + b2 p2 + b3 p3
that is of the order by one higher then the impedance defined by
iR1 = iR2 + iR3 (2d)
Eq. (1) for three-terminal network of electrochemical cell.
iC4 = pC4 (R1 iR1 + R2 iR2 ) (2e) Only on introduction of suitable formulae for elements of the
circuit in Fig. 2 in [4] (details given in Fletcher’s paper and not
iC5 = pC5 (R3 iR3 − R2 iR2 ) (2f)
invoked here) it is “automatically” reduced down by one order
iC6 = pC6 (R1 iR1 + R3 iR3 ) (2g) and attains the structure of Eq. (4) and impedance function of 2nd
degree strictly corresponding to Eq. (3). The conclusion is that in
its general form the equivalent two-pole in Fig. 2 is too complex
to be applied as a canonical equivalent of the ZWE impedance in
three-terminal electrochemical cell in Fig. 1. Only due to special
combination of elements constituting the two-pole circuit the order
of its impedance is reduced properly from 3 to 2 without any change
of its impedance spectrum.
One can put forward simpler electrical two-poles of the 2nd
order with normalized structures as in Eq. (4) and impedances of
Please cite this article in press as: A. Sadkowski, J.-P. Diard, On the Fletcher’s two-terminal equivalent network of a three-terminal electrochemical
cell, Electrochim. Acta (2009), doi:10.1016/j.electacta.2009.11.008
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G Model
EA-15159; No. of Pages 5
r1 = R1 (7a)
C4 C6
c1 = C4 + C6 + (7b)
C5
Fig. 3. Two-terminal circuit modeling the impedance in Fig. 1 measured according
to Eq. (2) with impedance function of 2nd order according to Eq. (4). (R2 C5 − R1 C6 )(C5 R3 − C4 R1 )
l1 = (7c)
C5
(C6 R1 − C5 R2 )(C4 R1 − C5 R3 )
r2 = (7d)
(C4 (C5 R2 − C6 R1 ) + C5 (C6 R3 + C5 (R2 + R3 )))
They are obtained as solution of equations with coefficients at
various degrees of the variable p in numerator and denominator of
Eqs (3) and (6). This solution was also found using command Solve
of the Mathematica® software.
One should stress that the presence of inductance in network
in Figs. 2 and 3 does not mean that inductive artifact is inevitably
present in the experimental data. It simply means that impedance
Fig. 4. Another two-terminal circuit modeling the impedance in Fig. 1 measured as a function of variable p in a three-pole cell in Fig. 1 and of two-
according to Eq. (2) with impedance function of 2nd order according to Eq. (4). pole electrical equivalent involving inductance are the same. The
selection of a particular type of the electrical model, in particular
the choice between model in Fig. 3 (inductive element) and Fig. 4
the form given by Eq. (3). These circuits are shown in Figs. 3 and 4. (capacitive element) is a matter of convenience and of the free will
The working electrode is represented by simple resistor but in fur- of the researcher and in no way does it suggest the inductive instead
ther extension of our models it was substituted by combination of capacitive behavior of the electrode.
of R1 + (Cd ||Rt ) denoted here by r1 , c4 and r7 . The only restriction
imposed by 3-node electrochemical cell in Fig. 1 on these 2-node 2.2. The second two-pole equivalent circuit
models is that they all have to contain the shunting capacitance par-
allel to the rest of the network. This is required by the numerator in The second two-pole equivalent to the impedance function in
the impedance equation by one order higher than the denominator Eq. (3) is shown in Fig. 4.
in Eq. (4) and its extension with R1 + (Cd ||Rt ) in place of R1 . This cor- It differs from the one in Fig. 3 by the presence of capacitance
responds to the purely capacitive character of the impedance at the in place of inductance but the structure of normalized impedance
high frequency limit, which can be also considered as the capaci- equations are the same and given by Eq. (4). The impedance Z4 of
tive artifact imposed by the form of the three-terminal network in this network is:
Fig. 1. r1 + r2 + pc2 r1 r2
Z4 (p) = (8)
1 + p(c2 r2 + c1 (r1 + r2 )) + p2 c1 c2 r1 r2
2.1. The first two-pole equivalent circuit By comparing coefficients at p in numerator and denominator in
this equations and Eq (3) one finds the values of elements in Fig. 4:
The first two-pole network equivalent to the impedance func-
tion in Eq. (3) is shown in Fig. 3. It differs from this in Fig. 2 by C4 C6
c1 = C4 + C6 + (9a)
elimination of the branch containing C** and R** elements in series. C5
Fig. 5. EI spectra of the sole working electrode (R1 –C7 ||R4 , ZEL )—dotted line (orange in the on-line version); complete three-terminal electrochemical cell ZWE with ZEL in
place of R1 (solid line, blue in the on-line version). (a) complex polar coordinates (Nyquist, −ZIm ()–ZRe (), (b) Bode phase coordinates (degrees–log (/s−1 )) and (c) Bode
amplitude (log (|Z|())–log (/s−1 )) coordinates. Values of parameters: R1 = 100 , R2 = 100 , R3 = 100 , R4 = 1000 , C4 = 10−11 F, C5 = 10−11 F, C6 = 10−11 F, C7 = 4 × 10−4 F
correspond to purely capacitive artifact with the whole Nyquist plot in the 1st quadrant. No overlap of ZEL with artificial part of the spectrum allowing their easy separation.
Please cite this article in press as: A. Sadkowski, J.-P. Diard, On the Fletcher’s two-terminal equivalent network of a three-terminal electrochemical
cell, Electrochim. Acta (2009), doi:10.1016/j.electacta.2009.11.008
ARTICLE IN PRESS
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EA-15159; No. of Pages 5
Fig. 6. EI spectra of the sole working electrode (R1 –C7 ||R4 , ZEL )—dotted line (orange in the on-line version); complete three-terminal electrochemical cell ZWE with ZEL
in place of R1 (solid line, blue in the on-line version). (a) complex polar coordinates (Nyquist, −ZIm ()–ZRe ()), (b) Bode phase coordinates (degrees–log (/s−1 )) and (c)
Bode amplitude (log (|Z|())–log (/s−1 )) coordinates. Values of parameters: R1 = 10 , R2 = 100 , R3 = 100 , R4 = 4 , C4 = 10−11 F, C5 = 10−11 F, C6 = 10−11 F, C7 = 4 × 10−4 F
correspond to purely capacitive artifact with the whole Nyquist plot in the 1st quadrant. No overlap of ZEL with artificial part of the spectrum allowing their easy separation.
Fig. 7. EI spectra of the sole working electrode (R1 –C7 ||R4 , ZEL )–dotted line (orange in the on-line version); complete three-terminal electrochemical cell ZWE with ZEL in
place of R1 (solid line, blue in the on-line version). (a) complex polar coordinates (Nyquist, −ZIm ()–ZRe ()), (b) Bode phase coordinates (degrees–log (/s−1 )) and (c) Bode
amplitude (log (|Z|())–log (/s−1 )) coordinates. Values of parameters: R1 = 2 , R2 = 100 , R3 = 100 , R4 = 40 , C4 = 10−6 F, C5 = 10−6 F, C6 = 10−6 F, C7 = 4 × 10−4 F correspond
to mixed capacitive and inductive artifact with the Nyquist plot in the 1st and 2nd quadrant. Overlap of ZEL with artificial part of the spectrum making impossible their easy
separation.
Please cite this article in press as: A. Sadkowski, J.-P. Diard, On the Fletcher’s two-terminal equivalent network of a three-terminal electrochemical
cell, Electrochim. Acta (2009), doi:10.1016/j.electacta.2009.11.008
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EA-15159; No. of Pages 5
b2 = (C4 C5 + C4 C6 + C5 C6 )(R1 R2 + R1 R3 + R2 R3 ) + R4 (R1 C7 (C4 + C6 ) in the Fletcher’s circuit (R2 , R3 , C4 , C5 and C6 ) should be in most
cases limited to the high frequency part of the spectrum. In case of
+R2 C4 (C5 + C6 + C7 ) + R2 C5 (C6 + C7 ) + R3 (C4 C5 + C4 C6 + C5 C6 well separate time constants of the WE and internal time constants
+C5 C7 + C6 C7 )) (10d) of parasitic elements, the high frequency deformation (capacitive
or inductive) is situated out of the experimentally accessible fre-
quency range f > 106 Hz (Figs. 5 and 6). This allows to limit the usable
b3 = C7 R4 (R1 R2 + R1 R3 + R2 R3 )(C4 C5 + C4 C6 + C5 C6 ) (10e) range of the spectrum to the part where ZWE approaches ohmic
resistance R1 and to delete the distorted higher frequency part.
Impedance of the two-pole model as in in Fig. 3 turns now to: In case of superposition of frequency ranges (Fig. 7), the practical
1 + a1 p + a2 p2 recommendation may be to minimize the parasitic time constants
Z3 (p) = (r1 + r4 ) (11) Ri Cj so, to shift the distorted part of the spectrum out of the range
1 + b1 p + b2 p2 + b3 p3
covered by ZEL .
and new coefficients are:
c7 r1 r2 r4 + l1 (r1 + r2 + r4 ) 4. Conclusions
a1 = (11a)
r2 (r1 + r4 )
The two-terminal network in Fig. 2 proposed by Fletcher [4] as a
c7 l1 r4 (r1 + r2 )
a2 = (11b) lumped electrical model of a typical three-terminal electrochemical
r2 (r1 + r4 )
cell cannot be considered a canonical circuit because it is unneces-
l1 + r2 (c7 r4 + c1 (r1 + r4 )) sarily complex. It contains two capacities and inductance, hence it
b1 = (11c)
r2 is of the 3rd order with single shunting capacitance. The three ter-
minal network in Fig. 1 representing the electrochemical cell with
c7 l1 r4 + c1 (c7 r1 r2 r4 + l1 (r1 + r2 + r4 ))
b2 = (11d) resistances as WE, Ref and CE electrodes has impedance defined
r4
by Eq. (2) which is the 2nd order function of complex frequency
c1 c7 l1 r4 (r1 + r2 ) and has to be modeled by any lumped circuit of the 2nd order. We
b3 = (11e)
r2 have presented here two such circuits and we have shown that
The impedance of the model from Fig. 4 turns to: their impedance is the same as impedance defined by Eq. (2) for
three-terminal electrochemical cell in Fig. 1.
1 + a1 p + a2 p2 To make the mathematical analysis tractable the interfacial
Z4 (p) = (r1 + r2 + r4 ) (12)
1 + b1 p + b2 p2 + b3 p3 impedances of WE, Ref and CE in [4] were assumed to be pure resis-
c7 r4 (r1 + r2 ) + c2 r2 (r1 + r4 ) tances. We relaxed this restriction and calculated the impedance
a1 = (12a) of the network including working electrode modeled by com-
r1 + r2 + r4
monly used circuit R1 + (Cd || Rt , impedance ZEL ). We have shown
c2 c7 r1 r2 r4 that capacitive and inductive artifacts originated in stray capaci-
a2 = (12b)
r1 + r2 + r4 ties of CE and Ref and inter-electrode resistances are present also
b1 = c2 r2 + c7 r4 + c1 (r1 + r2 + r4 ) (12c) here with the most conspicuous effect of the capacitive limit of the
measured impedance at high frequency.
b2 = c2 c7 r2 r4 + c1 (c7 r4 (r1 + r2 ) + c2 r2 (r1 + r4 )) (12d)
The voltage-to-current ratio defined in Eq. (2) should not
b3 = c1 c2 c7 r1 r2 r4 (12e) be—strictly speaking—considered as impedance because the cur-
rent and voltage are not referred to the same terminals. This is
All these functions present capacitive response at high fre- rather a transfer function of a 3-node network in which voltage
quency limit as all their electrical models include purely capacitive is sensed inside the two-pole (WE–CE) electric circuit divider.
shunting. The impedance at high frequency limit tends therefore It has to be noted, that all considerations here and in Ref. [4]
to zero, but in the intermediate frequency range it may have either are limited to the isolated electrochemical cell and in some cases
capacitive or inductive character, this being the manifestation of recommendations related to polarizing source (potentiostat) may
the capacitive or inductive artifacts. be in conflict with these discussed here.
To illustrate effects of these artifacts we show in Figs. 5–7 the
EI spectra of the electrical equivalent circuit representing working References
electrode (dotted lines – R1 + (Cd ||Rt ), ZEL given by Eq. (13)) together
with EI spectra of the whole Fletcher’s 3-node network as in Fig. 1 [1] G. Fafilek, Solid State Ionics 176 (2005) 2023.
with ZEL in place of R1 or r1 (solid lines). [2] H. Goehr, M. Mirnik, C.A. Schiller, J. Electroanal. Chem. 180 (1984) 273.
[3] S. Cherchilian, P. Eichner, M. Keddam, H. Takenouti, H. Mazzile, Electrochim.
1 + p(C7 R1 R4 /R1 + R4 ) Acta 35 (1990) 1131.
ZEL = (R1 + R4 ) (13) [4] S. Fletcher, Electrochem. Commun. 3 (2001) 692.
1 + pC7 R1
[5] V. Horvat-Radosevic, K. Kvastek, Electrochim. Acta 52 (2007) 5377.
Values of the electrical elements were chosen close to those [6] V. Horvat-Radosevic, K. Kvastek, J. Electroanal. Chem. 613 (2008) 139.
[7] V. Horvat-Radosevic, K. Kvastek, J. Electroanal. Chem. 631 (2009) 10.
experimentally observed in typical electrochemical experiment [8] L.O. Valoen, A. Lasia, J.O. Jensen, R. Tunold, Electrochim. Acta 47 (2002) 2871.
(units are Ohms and Farads) and it can be seen that at low fre- [9] S. Wolfram, Mathematica, 7th ed., 2008.
quencies all solid lines (Fletcher’s network) cover exactly the [10] J.-P. Diard, B. Le Gorrec, C. Montella, Cinetique Electrochimique, Hermann, Paris,
1996.
corresponding dotted lines (only working electrode) and diverge at
[11] S. Fletcher, J. Electrochem. Soc. 141 (1994) 1823.
high frequencies. This proves that influence of parasitic elements
Please cite this article in press as: A. Sadkowski, J.-P. Diard, On the Fletcher’s two-terminal equivalent network of a three-terminal electrochemical
cell, Electrochim. Acta (2009), doi:10.1016/j.electacta.2009.11.008