PERGAMON Electrochimica Acta 44 (1999) 2095±2103

a.c. Electrogravimetry on conducting polymers. Application

to polyaniline
C. Gabrielli, M. Keddam, N. Nadi, H. Perrot *
UPR15 du CNRS, Physique des Liquides et EÂlectrochimie, Universite Pierre et Marie Curie, Tour 22, 4 Place Jussieu, 75252 Paris
Cedex 05, France
Received 27 July 1998

Abstract

A simpli®ed model of the charge carriers in a conducting polymer (polyaniline) is presented here. It takes into
account the di€usion of the electrons, anions and cations. Simultaneous measurements of the electrochemical
impedance and of the electrogravimetric transfer function were carried out on a polyaniline ®lm. The impedance
allows the electron transport to be characterized and the electrogravimetric transfer function leads to a description
of the insertion law of the ions. # 1999 Elsevier Science Ltd. All rights reserved.

Keywords: Electrochemical impedance; Electrogravimetric transfer function; A.c. Quartz crystal microbalance; Conducting polymer

1. Introduction copper electrodeposition [7], gold oxidation in acidic

Impedance properties of conducting polymers have
been extensively studied these last years [1 and refer-
ences therein]. The electric current inside the polymer
®lm is supposed to be transferred by both electronic
and ionic charge carriers. [1±5] In particular,
Vorotyntsev et al. [1] proposed a detailed model where
both di€usion and migration transport mechanisms
were considered but the contribution of co-ions to the
current was neglected. However, even if this model can
explain the measured impedance, both anions and cat-
ions contributions have to be taken into account as
shown by a.c. electrogravimetry [6]. This mass/poten-
tial transfer function measurement through the use of
a quartz crystal microbalance in a.c. regime, combined
with electrochemical impedance measurement, allows
the anion and cation ¯uxes to be calculated individu-
ally. Data obtained by this way demonstrated that
neither the anion incorporation ¯ux nor the cation
expulsion ¯ux becomes negligible in the potential range
studied. This technique was also fruitful in other ®elds:
* Corresponding author.
medium [8], ionic insertion in WO3 [9, 10] or passivity
of iron in sulfuric medium [11].
In this paper a model taking into account the di€u-
sion of both anions and cations, in the conducting
polymer ®lm is proposed. Its validity is checked by
means of the classical electrochemical impedance spec-
troscopy and a.c. electrogravimetry.
2. Theory
On the modi®ed electrode by a conductive polymer
layer of thickness d, two interfaces are de®ned: metal/
polymer and polymer/electrolyte (see Fig. 1). The ®rst
interface is an ion blocking electrode and the second
interface is an electron blocking interface. A one
dimensional model is considered, i.e. the metal/polymer
interface is located at x = 0 and the polymer/electolyte
interface is located at x = d.
It is supposed that the electric current is carried in
the ®lm by electrons and ions.
The hypothesis of a simpli®ed model are the follow-
ing:

0013-4686/99/$ - see front matter # 1999 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 3 - 4 6 8 6 ( 9 8 ) 0 0 3 1 7 - X
2096 C. Gabrielli et al. / Electrochimica Acta 44 (1999) 2095±2103
   
CA aF
JA …d† ˆ KA exp ÿ E ÿ1 …6†
CAS RT
where C AS is the anion concentration at equilibrium.

2.1. Steady-state

In steady-state conditions (@/@t00), Eq. (2) leads to:

Ji …x† ˆ a where a is a constant.
As the constant value of the ¯uxes is zero because of
the boundary conditions [Ji(0) = 0], the steady state
current is also zero, whereas the concentrations and
the potential are constants inside the ®lm and equal to:
Fig. 1. Scheme of the electrode/polymer/solution electrochemi-  
cal system. ka ka F
Ce ˆ ˆ 0 exp ES …7†
kc kc 0 RT
Electrons (e ÿ ), anions (A ÿ ) and cations (M + ) are
 
transported through the polymer by di€usion. So, the F
CA ˆ CAS exp ES : …8†
classical di€usion equations are de®ned as following: RT
@Ci
Ji ˆ ÿDi …1†
@x
2.2. Dynamic behaviour
and
@Ci @Ji When a small sine wave potential change DE is
ˆÿ …2† imposed across the metal/®lm/electrolyte system, low
@t @x
amplitude sine wave concentrations, DCi, and ¯uxes,
where Ci is the concentration of e ÿ , A ÿ or M + and DJi, are observed from Eqs. (1) and (2):
Di is the di€usion coecient of species i. Fluxes Ji of
@DCi
species i are positive in the increasing x direction as it DJi ˆ ÿDi …9†
@x
is depicted in Fig. 1.
The following boundary conditions are applied: At @DJi
joDCi ˆ ÿ : …10†
the metal/polymer interface, which is an ion blocking @x
electrode, for monovalent species: From the boundary conditions:
IF At x = 0,
x ˆ 0 Je …0† ˆ and JA …0† ˆ JM …0† ˆ 0 …3†
F DIF
DJe …0† ˆ ; DJA …0† ˆ DJM …0† ˆ 0 …11†
where electron transfer is supposed to give a Faradaic F
current density, IF, equal to: where
IF =F ˆ ka ÿ kc Ce …4† DIF ˆ Rÿ1
t DE ÿ FAkc DCe …0† …12†

where ka and kc are the rate constants. and

ki ˆ kio exp…bi E† Rÿ1
t ˆ FA…ba ka ÿ bc kc Ce †:

where bi are Tafel coecients. At x = d,

At the polymer/electrolyte interface, which is an DIF
DJe …d† ˆ 0; ÿDJA …d† ‡ DJM …d† ˆ …13†
electron-blocking interface: F
IF where
x ˆ d Je …d† ˆ 0 and ÿ JA …d† ‡ JM …d† ˆ …5†
F DJA …d† ˆ KDCA …d† ‡ GDE …14†
as outward positive ¯uxes gives a negative current for
where
anions and positive currents for cations, and where the  
insertion rate of the anions from the electrolyte is sup- KA aFE
Kˆ exp ÿ
posed to be given by: CAS RT
 C. Gabrielli et al. / Electrochimica Acta 44 (1999) 2095±2103 2097

DIF
and Be ˆ ÿ r  r  …19†
  jo jo
aF CA aFE FDe exp ÿ 2d ÿ1
Gˆÿ KA exp ÿ : De De
RT CAS RT
By substituting DCe(0) in Eq. (12) by its value taken
from Eq. (18):
 r
jo
2FAkc DIF exp ÿ d
De
3. Electrochemical impedance  r
DIF ˆ Rÿ1
t DE ‡
jo …20†

cosh d
De
For small potential perturbations, Eqs. (1) and (2)
r  r 
give for the electron transport in the polymer: jo jo
FDe exp ÿ 2d ÿ1
d2 DCe De De
joDCe ˆ De …15†
dx2  r
jo
whose the general solution is: cosh d
Ak c DIF D e
 r  r ˆ Rÿ1
t DE ÿ r  r …21†
jo jo jo jo
DCe …x† ˆ Ae exp x ‡ Be exp ÿ x …16† De sinh d
De De De De
By using the boundary conditions, at x = d Therefore, the Faradaic impedance, ZF, is equal to:
r  r 
dDCe …d† jo jo DE
ˆ Ae exp d ÿBe exp ÿ ZF ˆ
dx De De DIF
 r
r jo
jo  coth d 
d …17† De
De ZF ˆ Rt 1 ‡ Akc p …22†
joDe
As from Eq. (13)
In this model, the Faradaic impedance depends only
dDCe …d† on the electron kinetics.
ˆ0:
dx
 r  r
jo jo
Ae exp d ˆ Be exp ÿ d
De De
 r
jo 3.1. Asymptotic values
Ae ˆ Be exp ÿ 2d
De
The high and low frequency behaviours of ZF(o) are
therefore: now investigated.
 r 
jo
DCe …x† ˆ 2Be exp ÿd
cosh …x ÿ d (i) High frequency limit:
De
r When y 4 1 coth y 4 1
jo
† : …18† hence when o 4 1:
De  
Akc
At x = 0 ZF …o†1Rt 1 ‡ p …23†
joDe
r
dDCe …0† jo which leads to a Warburg like behaviour in the higher
ˆ …Ae ÿ Be †
dx De frequency range.
As from Eq. (11) (ii) Low frequency limit:
When y 4 0 coth y11y + y3
dDCe …0† DIF hence when o 4 0:
ˆÿ :
dx FDe  
r  r dAkc Akc
  ZF …o†1Rt 1 ‡ ‡ …24†
jo jo DIF 3De jod
Be exp ÿ 2d ÿ1 ˆÿ
De De FDe
This is the impedance of a series resistance±capacity
i.e. circuit (Rp±C ef) such as:
2098 C. Gabrielli et al. / Electrochimica Acta 44 (1999) 2095±2103

Fig. 3. Electrochemical impedance of a non uniform polymer

Fig. 2. Electrochemical impedance calculated for the following ®lm for the same value of the parameters as in Fig. 2 and
values of the parameters: R el = 0.18 O cm 2, Rt = 0.4 O cm2, De = 10 ÿ 7 cm2 s ÿ 1, s = 4.835.
d = 5 mm, A = 0.2 cm2, kc = 0.016 mol s ÿ 1, De = 10 ÿ 7 cm2
s ÿ 1, Cd = 10 mF cm ÿ 2.
Then, the observed impedance Z is such as:
 
dAkc … Demax
Rp ˆ Rt 1 ‡
3De Zÿ1 ˆ Zÿ1
F p…De † dDe …27†
0
d
Cef ˆ …25† Fig. 3 shows the global electrochemical impedance,
Rt Akc
DE/DI (i.e. Z//Cd + R el) of a non-homogeneous ®lm
Fig. 2 shows the global electrochemical impedance cal- coating onto the electrode surface. A tilting of the low
culated, DE/DI (i.e. ZF//Cd + R el, where R el and Cd frequency branch is observed in agreement with the ex-
are the electrolyte resistance and the double layer ca- perimental data.
pacity). The low frequency branch is vertical in contra-
diction with experiments. It should be noted that the
impedance derived by Vorotyntsev et al. [1] also shows 4. Electrogravimetric transfer function
the same feature.
From Eqs. (1) and (2), the change of the concen-
3.2. Non uniform structure of the polymer tration of the anions (A) and cations (M) are governed
by:
If the polymer ®lm is supposed to be non-uniform, a
log-normal probability law p(De) can be considered to d2 DCi
joDCi ˆ Di i ˆ A; M …28†
describe a random distribution of the di€usion coe- dx2
cient to take into account the random non-homogene- whose general solution is such as:
ities of the polymer structure all over the electrode  r  r
surface [12]: jo jo
DCi …x† ˆ Ai exp x ‡ Bi exp ÿ x …29†
 2 Di Di
 log De ÿ log D e 
1 At x = 0, DJi(0) = 0
p…De † ˆ p exp ÿ …26†
2Ps2 De 2s2 then
r
Eq. (26) gives the probability distribution of the elec- dCi …0† jo
ˆ …Ai ÿ Bi † ˆ 0
tron di€usion coecient around a mean value De. dx Di
 C. Gabrielli et al. / Electrochimica Acta 44 (1999) 2095±2103 2099

Therefore: Table 1

Ai ˆ Bi …30†
DE Dm DQ Real part of Dm/DE
so
 r Positive (+) Gain (+) Anion entry (ÿ) Positive (+)
jo
DCi …x† ˆ 2Ai cosh x …31† Positive (+) Loss (ÿ) Cation exit (ÿ) Negative (ÿ)
Di
Current of anion entries or cation exits >0
At x = d
From Eq. (14): A
Dmi ˆ ÿ mi DJi …d† …41†
 r jo
jo
DJA …d† ˆ 2KAA cosh d ‡ GDE …32†
DA which means that positive outward ¯uxes give a loss of
the ®lm mass. Note that the de®nition of positive
also, from equation(9): ¯uxes in the opposite direction lead to a di€erent re-
r  r lationship in [6].
jo jo
DJA …d† ˆ ÿ2DA AA sinh d …33† As in addition, from Eq. (13), the ¯ux of cations is
DA DA
equal to:
therefore: DJM …d† 1 DJA …d†
ˆ ‡ …42†
GDE DE FZF DE
AA ˆ ÿ   r  r
p jo jo therefore:
2 joDA sinh d ‡ K cos h d
DA DA  
Dm A DJA …d† mM
…34† ˆÿ …mA ‡ mM † ‡ : …43†
DE jo DE FZF
and:
Table 1 presents the sign of the near part of Dm/DE
 r
p jo according to the anion entry on cation exit.
G joDA sinh d
DJA …d† DA
ˆ  r  r 4.1. Asymptotic values
DE p jo jo
joDA sinh d ‡ K cosh d
DA DA DJA …d†
Considering DE , similarly to ZF: when o 4 1
…35†
DJA …d† G
i.e. 1
DE K
1 ‡ p
DJA …d† G joDA
ˆ r …36†
DE jo i.e.
coth d
D
1 ‡ K p A DJA …d†
lim
joDA o41 ˆG
DE
The change of the mass, Dm, of the anions and cations when o 4 0
in the ®lm, with atomic mass, mA, and atomic mass,
DJA …d† G
mM, for anions and cations respectively, is such as: 1
DE dK K
1‡ ‡
Dm ˆ DmA ‡ DmM …37† 3DA jod

X …d lim DJA …d†

o40 ˆ0
Dm ˆ A mi DCi dx …38† DE
iˆA;M 0 DJM …d†
Now for DE :
Then, from Eq. (10), for each species i: when o 4 1
… DJM …d† G 1
A d dDJi 1 ‡  
Dmi ˆ ÿ mi dx i ˆ A; M …39† DE K Akc
jo 0 dx 1 ‡ p FRt 1 ‡ p
joDA joDe
 
A lim DJM …d† 1
ˆÿ mi DJi …d† ÿ DJi …0† …40† o41 ˆG‡
jo DE FRt
As Ji(0) = 0: when o 4 0
2100 C. Gabrielli et al. / Electrochimica Acta 44 (1999) 2095±2103

DJM …d† G 1
1 ‡  
DE dK K dAK Akc
1‡ ‡ FRt 1 ‡ ‡
3DA jod 3De jod
DJM …d†
lim
o40 ˆ0
DE
Concerning Dm
DE :
when o 4 1
 
Dm A G mM
1ÿ …mA ‡mM † ‡  
DE jo K Akc
1‡ p FRt 1‡ p
jodA joDe
lim Dm
o40 ˆ0
DE
when o 4 0
Dm A
1ÿ
DE jo
 
G mM
…mA ‡ mM † ‡  
dK K dAkc Akc
1‡ ‡ FRt 1‡ ‡
3DA jod 3De jod
 
lim Dm …mA ‡ mM †G mM
o40 ˆ ÿAd ‡
DE K FRt Akc

Table 2 summarizes the asymptotic values of the

quantities of unrest

Table 2

lim lim
Quantity o40 o41
 
ZF Rt 1 ‡ dAk
3De
c
‡ Akc
jod Rt
DJA …d†
DE 0 G
DJM …d† 1
0 G ‡ FR
DE   t

Dm
DE ÿAd …mA ‡m
K
M †G
‡ mM
FRt Akc 0

Fig. 4 shows the calculated anion DJA/DE(o) and cat-

ion DJM/DE(o) ¯ux/potential transfer functions and
the electrogravimetric, Dm/DE(o), transfer function.
In the anodic range, anions are inserted (negative
¯ux), as DJA/DE(o) is negative. Cations have a mixed Fig. 4. Anion, DJA/DE, and cation, DJM/DE, ¯ux/potential
and electrogravimetric, Dm/DE, transfer functions calculated
behaviour with a negative ¯ux in the low frequency
for the following values of the parameters, in addition to
range (insertion) preceded by a transient expulsion those used in Fig. 2: mA = 35 g, mM = 1 g, G = ÿ2.4  10 ÿ 5,
(positive high frequency ¯ux limit). K = ÿ 5  10 ÿ 4, DA = 10 ÿ 7 cm2 s ÿ 1.
 C. Gabrielli et al. / Electrochimica Acta 44 (1999) 2095±2103 2101

Fig. 5. Scheme of experimental arrangements.

5. Experimental

The electrochemical quartz crystal microbalance

takes advantage of the change of the resonance fre-
quency of a 6 MHz ``AT-cut'' quartz crystal (CQE,
Troyes, France) due to a minute mass change of one
of its electrodes exposed to solution. Two 0.2 cm2 gold
electrodes were deposited on the opposite faces of the
quartz crystal: they allowed electric connections to an
oscillator circuit whereas the electrode exposed to sol-
ution was used as the working electrode. The reference
electrode is a saturated calomel electrode (SCE) and
the potential are referred to it (V vs SCE). The fre-
quency response to an added mass is described by the
Sauerbrey's law [13]. A calibration procedure was pre-
viously performed by using silver electrodeposition.
Faraday's law allows the experimental sensitivity,
equal to ÿ5.2  107 Hz cm2/g, to be determined.
In order to use the EQCM in the a.c. mode, the
modi®ed working electrode was polarized and a small
amplitude potential sinusoidal perturbation was super-
imposed. The frequency response, Df, corresponding to Fig. 6. Experimental electrochemical impedance of PANI ®lm
the mass modulation, Dm, of the modi®ed working in HCl at 0.4 V prepared during 6 h compared with calculated
electrode, was measured simultaneously with the cur- diagram.
2102 C. Gabrielli et al. / Electrochimica Acta 44 (1999) 2095±2103

1 1
rent response of the electrode. The resulting signals are ˆ ÿ joCd
sent to a four-channel Frequency Response Analyzer ZF Zexp ÿ Rel
(Solartron 1254), which allowed the electrogravimetric where R el and Cd are the electrolyte resistance and the
transmittance, Dm/DE, to be simultaneously obtained double layer capacity.
with the impedance, Z exp, of the sample. Fig. 5 shows The experimental changes of anions and cation
the block diagram of the experimental set-up. ¯uxes, (DJA/DE)exp and (DJM/DE)exp, with potential
The Faradaic impedance, ZF, is obtained from the are calculated from Eqs. (13), (37) and (41), through:
measured impedance, Z exp, through: mA Dm
  ÿjo
DJM ZF F DE
ˆ ;
DE exp m A ‡m M

mM Dm
  ÿjo
DJA ZF F DE
ˆÿ :
DE exp mA ‡mM

6. Results

The PANI ®lm was prepared in HCl 1.0 M,

C6H5NH2 (aniline) 0.15 M by potential sweep (9 mV
s ÿ 1 rate) between ÿ0.2 V and 0.7 V/SCE during 6 h.
Then, measurements were carried out in HCl 1.0 M at
0.4 V/SCE.
Fig. 6 shows the measured electrochemical impe-
dance compared with the calculated one according to
the previous model. We can observe a good compat-
ibility in term of shape and frequency distribution.
Fig. 7 shows the DJA(o)/DE and DJM(o)/DE transfer
functions. Fig. 8 shows Dm/DE electrogravimetric

Fig. 7. Anion, DJA/DE, and cation, DJM/DE, ¯ux/potential Fig. 8. Experimental electrogravimetric transfer function, Dm/
transfer functions compared with calculated diagrams. DE, compared with the calculated diagram.
 C. Gabrielli et al. / Electrochimica Acta 44 (1999) 2095±2103
transfer function. These experimental data are com-
pared with calculations derived from the model. In the
analyzed frequency range the agreement between ex-
perimental data and calculated data is fairly good.
7. Conclusion
Simultaneous measurements of the electrochemical
impedance and electrogravimetric transfer function
lead to a better understanding of the transport of the
charge carriers species. The impedance allows the elec-
tron transport to be characterized by the parameters
AKc/d, Rt, De/d 2 estimated for calculating the impe-
dance deduced from the model and the electrogravi-
metric transfer function leads to a description of the
insertion law of the ions (estimated parameters: K/d,
G).
The simpli®ed model presented here allows the mean
features of the experimental data to be interpreted.
However, to describe in details the processes involved,
it will be necessary to take into account the migration
¯uxes of both the anions and the cations in the trans-
port laws and, may be, the transport of the solvent.
2103
References
[1] M.A. Vorotyntsev, L.I. Daikin, M.D. Levi, J.
Electroanal. Chem. 364 (1994) 37.
[2] C. Deslouis, M. Musiani, B. Tribollet, J. Phys. Chem.
100 (1996) 8994.
[3] C. Deslouis, T. El. Mousta®d, M. Musiani, B. Tribollet,
Electrochim. Acta 41 (1996) 1343.
[4] C. Deslouis, M. Musiani, B. Tribollet, M.A.
Vorotyntsev, J. Electrochem. Soc. 142 (1995) 1902.
[5] A. Benyaich, C. Deslouis, T. El. Mousta®d, M. Musiani,
B. Tribollet, Electrochim. Acta 41 (1996) 1781.
[6] S. Cordoba-Torresi, C. Gabrielli, M. Keddam, H.
Takenouti, R. Torresi, J. Electroanal. Chem. 290 (1990)
261.
[7] S. Bourkane, C. Gabrielli, M. Keddam, Electrochim.
Acta 34 (1989) 1081.
[8] S. Bourkane, C. Gabrielli, F. Huet, M. Keddam,
Electrochim. Acta 38 (1993) 1023 and 1827.
[9] C. Gabrielli, M. Keddam, H. Perrot, R. Torresi, J.
Electroanal. Chem. 378 (1994) 85.
[10] O. Bohnke, B. Vuillemin, C. Gabrielli, M. Keddam, H.
Perrot, H. Takenouti, R. Torresi, Electrochim. Acta 40
(1995) 2755 and 2765.
[11] C. Gabrielli, M. Keddam, F. Minou¯et, H. Perrot,
Electrochim. Acta 41 (1996) 1217.
[12] C. Gabrielli, H. Takenouti, O. Haas, A. Tsukada, J.
Electroanal. Chem. 302 (1991) 59.
[13] G. Sauerbrey, Z. Phys. 155 (1955) 206.