Poljwrr International 31 ( 1993) 45-50

Electrochemical, FTIR and

Morphological Study of
Polypyrrole-Polystyrenesu I phonate
Conducting Films
M. J. Gonzalez-Tejera," M. A. de la Plaza,b E. Sanchez de la Blanca"
& I. Hernandez-Fuentes"
"

Departamento dc Quimica Fisica I, Facultad de Ciencias Quimicas, Universidad Complutense, 28040 Madrid, Spain
* Departamento de Quimica Fisica, Universidad Nacional de Educacion a Distancia, 28040 Madrid, Spain
(Received 18 December 1991; revised version received 21 April 1992; accepted 28 May 1992)
Abstract: The electrochemical bchaviour, FTIR spectrum and the morphology of
polypyrroleepolystyrenesulphonate (PPy-PSS) films obtained potentiostatically
at 0.6V in a 0.05~
Py + 1.7 x ~ O - * MNaPSS medium have been analysed. Different

electrochemical parameters have been modified in order to establish the first

polaron formation, the reversibility of the redox process and the doping
nicc h a n ism.
The FTIR spectrum confirms the existence of C=O groups in the film structure
and two possible explanations are suggested. SEM reveals a higher homogeneity in
these films than in PPy films doped with smaller counterions.
K q . iiwh: conducting polymer, polypyrrole, electrochemical and FTIR study.

The stability of the membrane generated depends on

the degree of entanglement of the polymeric counterions
a n d the polypyrrole structure which is enhanced as the
oxidation state increases.
In order to establish better knowledge of the electrochemical mechanism of PPy-PSS membrane generation,
the aim of this paper has been focused on producing
different internal oxidation states by cyclic voltammetry.
This technique also gives information about the reversibility of the redox process a n d the porosity of the
composite film generated. Its morphology has been
analysed using scanning electron microscopy and its
conductivity by the four-probe method.
Spectroscopic methods have been used to elucidate the
structure of PPy films obtained with different counterions
such as BF,,14 C10,'5*'6 and KNO3.l7There are several
differences, but the C=O groups presence in the film
structure is the most significant. The FTIR spectrum of
PPy-PSS has been studied to clarify the presence of the
C=O groups.

INTRODUCTION

Polypyrrole (PPy) is the most common conducting

polymer because of its application to battery electrode
material and electrochroniic devices. The characteristics
of the resulting polymeric material depend o n the
electrochemical conditions of synthesis. In this sense PPy
has been obtained in aqueous and non-aqueous media by
several authors,' - 3 and the influence of the counterion
(e.g. size, geometry, charge, organic o r not organic nature,
etc.) has been studied in some cases.4"
Composite systems can be prepared by the electrochemical polymerization of PPy in the presence of a
soluble anionic polyelectrolyte such as sodium polystyrenesulphonate (NaPSS)." l 3 Using this polyelectrolyte
it is possible to have a charge controllable membrane in
which the fixed charges are controlled electrochemically.6
The membrane electroneutrality is preserved by the
penetration of the electrolyte cation ( N a + ) into the
PPy-PSS matrix producing a pseudo-cathodic doping.697
~

45
Poljwrr. InternarionalO959-8103/93/$06.000 1993 SCI.Printed in Great Britain

46

M . J . Gnnzulez-Tcyera, M . A . de la Pluzu, E. Sanchez de la Blunca, I . Hernundez-Fucntes

EXPERlM ENTAL

PPy films were obtained potentiostatically at 0.6 V using

times from 600 s to 4 h. Film thickness was determined by
weighing using the PPy density given by Diaz & Hall.18
The anodic deposition and the electrochemical characterization of PPy films were carried out in two different
cells. with ii compartment and three electrodes in each
one. A saturated calomel electrode (SCE) was employed
as a reference electrode. The electrical contact between
working and refercnce electrodes was through a Luggin
capillary. A Pt-mesh counter-electrode of large area was
employed and a platinum sheet 10 x 20mm2 was used as
the working electrode. Before each electrodeposition the
working electrode was sonicated in acetone ( 5 min) after
being treated with hot and concentrated sulphuric acid
and rinsed copiously with ultrapure Milli-Q water.
P j ri-ole (Pyj (Aldrich Chemical Co.) was previously
distillod under vacuum and stored in the dark under
reduced pressure at low temperature. The electrolyte used
was sodium polystyrenesulphonate (NaPPS) (Aldrich
<.liemicnl Co.). The solution concentration was 0 . 0 5 ~
Py + 1.7 x 10- 'M NaPSS. The solution was slightly acidic
in order to improve the quality of the deposits5 and was
dcosygenated with nitrogen. The experiments were run at
room tcmper;iture i n a nitrogen atmosphere.
Cjclic voltammot ric nieasurenieiits were performed
\vith ;I Wenking 6XFR 0.5 potentiostat in conjunction
u i t h ii triangular wave generator Wenking model VS G72
and a Sefram X Y type Yt 25 recorder.
FTlR spectra of the films in the oxidized solid state
werc dctorniined froni it pressed disc of the sample mixed
with K B r powder, using a Nicolet 60 SX.
A n SEM IS1 DS-130 with an R-X spectrometer (EDX)
Kwex XOOO I I and a Si/Li detector were used to analyse
the morphology of the polymeric films formed.
The conducti\.ity o f the films was measured by the fourprobe method.
RESULTS A N D DISCUSSION
Figure I shows cyclic voltammograms of a PPy film
potcntiosta~icallygrown in the conditions mentioned in
the Experimental section and recorded in the same
medium. The voltammograms were obtained by potential
sweeping between -0.8 and +0.6V at a scan rate, of
30mV s - I . Four peak potentials are observed in Fig. 1.
I n the anodic sweep two different oxidation states were
detected in the PPy matrix (peaks A and B). Peak A
(E,(A) = -0.75 V) (where E, = peak potential) represents
a weak oxidation state (polaron state) generated in the
PPy matrix, i n which electroneutrality was conserved by
penetration of PSS anions from the electrolytic solution.
The valuc of this first oxidation potential is much lower
than that of polypyrrole films prepared using low
molecular weight electrolyte' and we can attribute this
effect to the macromolecular nature of the counterion. A
11,

P
S 1.7.lO-'M
PP
Py
y ll N
Naa P
PS
SS
1.7.10-' M
v = 30 mVs-1

4
4 55- 1

30 -

'E 15-

E
n-

0-

-15

-30

'

- 0.5

0
E/V (SCE)

0.5

Fig. 1. Cyclic charactcriration voltammograms of PPy in 1.7 x

1 o - ' M NaPSS.

redox couple at peak A is not formed because thc

oxidation state generated is very weak and unstable. At
highcr positive potential peak B appears (E,,(B)= 0.12 V),
which corresponds to a more intense oxidation state of
PPy and consequently to a higher incorporation of PSSanions, producing an intricate entanglement of PPy and
PSS- backbones similar to a m e m b r a r ~ e . ~').20
. ~ . ' Further
studies by electron microscopy must be done in order to
analyse the PSS- distribution in PPy films.
In thccathodiccycle twopeaksarcalso present. Peak C
(E,(Cj= -0.7V) is related to the oxidized species
generated in peak B (AE,(B - C) = 0.58 V). According to
Genies & Syed?' there is a clear irreversibility in the
formation of oxidized and reduced species, but i,,c/ip,13
remains close to unity, suggesting that the reaction is
almost reversible (where i,,c and i,,13are peak C and peak
B current density respectively).' Finally, peak D (E,(D) =
f 0 . 1 V) can be attributed to the penetration of the Na
cation into the PPy- PSS membrane (pseudo-cathodic
doping) when the membrane is organized.
PSS- incorporated during either electrochemical
polymerization or oxidation processes does not experience any redox reaction.
With cycling, the current densities of peaks B and C
decrease, because of the loss ofelectroactivity of thc PPyPSS membrane in the highest oxidation state, while the
current densities of peaks A and D increase.
The influence of the value of the positive and negative
end potentials at \ ' = 30mVs-' on the electrochemical
behaviour of PPy films has been studied. Figure 2 shows
cyclic voltammograms obtained using a constant initial
potential (El= -0.8V) and a variable positive end
potential, from 0.08 to 0.85V. QJQ, ratios have been
calculated in all cases and the corresponding values were
very close to unity, indicating that all the PPy oxidized
POLYMER INTERNATIONAL VOL. 31, NO. 1,1993

47

Polypyrrole-polystyrenesulphonate conducting Jilms

I

FPy11710'2M NaPSS

5
a

E.

10 125 mA

cni

PPy I NoPSS

30 mV

I
-0 5

5-1

O5

EIV ISCEI

Fig. 2. Cyclic voltammograms of a 1.13pm standard PPy layer

in 1.7 x 10 2~ NaPSS with different Ef.

was reduced (where Q, and Q, are cathodic and anodic

charge respectively).
The negative end potential has also been modified, see
Fig. 3, in the range -0.1 to -1.OV. The end positive
potential was maintained constant in all cases
(E,= 0.55 V). From Fig. 3 it can be seen that peak A
clearly appears only when the sweep begins at Ei< 0.7 V

-50
-10

-0 5

05

E/V (SCEI

Fig. 4. Effect of potential scan rate on the cyclic voltammo30; ....... 50.
grams shape: -,
, 70.,
, 90.,
_ _ _ - , 110 m V s - ' .
9

POLYMER INTERNATIONAL VOL. 31, NO. 1,1993

________

and this is the reason why in previous studies of PPyPSS- films this peak has not been de~cribed.~.'The
evolution of ip,c/ip.8ratios over the different voltammograms shows a slow increase of resistivity in the polymer
film, which means a higher degree of oxidation as the
cathodic potential reaches a more negative value. Finally,
the evolution of hydrogen when the sweep begins at
Ei = - 1.OV can be observed.
The variation of the potential scan rate can give further
insight into the mechanism of charge transport and
electrode processes. Potential scan rate was varied in the
range 10-130mV s - l and the anodic peak potential shifts
positively, as shown in Fig. 4. The peak's current increases
as the scan rate rises. A plot of the anodic (B) and cathodic
peak (C)current as a function of v ' ' ~is represented in Fig.
5. A linear relationship with a slope very close to 0-5 is
found, which is an indication that the electron transfer
process is controlled by a semi-infinite diffusion
condition.2.22-24

E I V ISCEI

Fig. 3. Cyclic voltammograms of a 1.13pm standard PPy layer

in 1.7 x 1 0 - 2NaPSS
~
with different E,.

I
D3

loo0

",,*

I I I

10000

Fig. 5. Plot of i, as a function of v"*: --------, ip.B; -,

ips?

M . J. Gonzalez-Tejera, M . A . de la Plaza, E. Sanchez de la Blanca, I. Hernandez-Fuentes

48

500

r-----l
0

50

100

150

v / rnv s-1

Fig. 6. Capacitivecurrent versus scan rate plot for a 0 8 pm PPy

film to a constant potential (0.35 V).

In agreement with KO er a/. we have observed in our

cyclic voltammograms recorded at different scan rates a
decay in the faradaic currents after oxidation peak
potential. All the oxidation processes finished in the
region of 0.35 V and the current measured should arise
from a capacitive component of the current density.
Currents measured in this potential region (0.35 V) show
linear relationships with scan rates (Fig. 6). From the
slope of this line the PPy film capacitance was calculated,

C = 0.27 mFcm-2. The comparison between the value of

the capacitance determined by us in PPy-PSS films and
the corresponding magnitude for PPy films with similar
thickness doped with ClO, anions2 indicates that the PPy
films electropolymerized in NaPSS medium are less
porous. With regard to the assumption that the PPy films
are composed of many essentially identical noninterconnected channelsz5our lower capacitance value is
an indication that the polymeric counteranion closes
some of the channels, improving the film homogeneity.
Figure 7 shows SEM pictures of the PPy-PSS deposits
obtained during 30 and 240min with thicknesses of 1.13
and 13.4pm,respectively. The homogeneity of both films
is higher than that obtained for PPy films in other
electrolytes with smaller counter ion^^^-^' and is in
agreement with the film porosity discussed above.
The measured electronic conductivity of the film of
13.4pm thickness was 10.8 Scm- . No change in the film
conductivity after 3 months in contact with air was found.
FTIR SPECTRUM

Figure 8 shows the FTIR spectrum of the oxidized

PPy-PSS films ( E , = 0 5 5 V). The spectrum was measured
from 4000 to 400cm- In the high frequency region NH
and CH stretching bands are observed. The region below
1800cm- was specially analysed because the most
significant bands of the film studied appear there. The
main characteristic bands observed are included in Table
1, together with the literature FTIR results for PPy films
doped with ClO, counterions.I6
Analysis of the FTIR PPy-PSS spectrum reveals the
following characteristics. Vibrations due to CH out-ofplane bending are observed about 916,951 and 762cm-.
A band appears at around 1025 cm- ,which is attributed
to the NH in-plane bending vibration. In the region
121( r l 182 cm - can be found two CH in-plane bendings,
one about 1204cm- assigned to the CH bending of the

95.6I

(b)

Fig. 7. SEMs ofPPy films potentiostatically obtained in NaPSS

medium. Time deposit: (a) 30min; (b) 240min.

78.2 I
1860

1700

1560

1380
1220
1060
WAVENUMBERS

9M

7LO

5r

Fig. 8. FTIR spcctrum ofa PPy film generated in 1.7 x IO-M

NaPSS medium.
POLYMER INTERNATIONAL VOL. 31, NO. 1,1993

49

Polypyrrok-polystyrenesulphonate conducting films

TABLE 1. FTIR data of PPy system
PPy-PSS

Mode

(C-0) stretching
(C- C) stretching pyrrole ring
Ring stretching

(C-H)
(N-H)
(C-H)

bending
bending deformation
out-of-plane

C--C stretching of C,H,-C-C

R-SO;
characteristic band

group

polymer neutral state and the other about 1182cm-'

assigned to the oxidized polymer state.
PPy ring stretching characteristic bands can be found at
1466, 1380 and 1319-1300cn1-' and the most characteristic one, a very strong band, at about 1559cm-'.
The band assignments mentioned are in agreement
with the literature results for PPy films doped with ClO,
(see Table I)."
The presence of R-SO; groups can be justified by the
strong band that appears at 1204cm-'; there is also a
weak band at around 1636cm-' that could be attributed
to a C-C stretching band belonging to the C,H,C=C
group. This is a confirmation of the presence of PSS
groups in the polymer.
The weak band that appears at approximately
1700cm-' is attributed to the existence of C=O groups
in the structure. This is in accord with the results obtained
using others counter ion^,'^^'^.^^ and was also confirmed
in the UV region in the case of polymerization in aqueous
solution." The intensity of this band can be understood
as a consequence of the very low percentage of C=O
groups in the PPy structure.
The presence of C=O groups and the electroactivity
lost could mean either a nucleophilic attack by water
molecules and/or hydroxylic groups belonging to the
medium that break the n-conjugated structure of the
polymer, or possible PPy ring r ~ p t u r e . ~
CONCLUSIONS

Two oxidation states have been detected by cyclic

voltammetry in PPy-PSS- films. The first, appearing at
very low values of the oxidation potential, corresponds to
a weak oxidation state; the second corresponds to more
intense oxidation. PSS- has become entangled with the
PPy matrix producing a polymeric membrane which is
very homogeneous at the highest oxidation potential and
with a conductivity value above that of semiconductor
materials.
POLYMER INTERNATIONAL VOL. 31, NO. 1, 1993

1700cm-'
1559
1466
1380
1319-1 300
1204-1 182
1025
951
91 6
762
1636
1 370-1 300.
1200-1 180

PPy-cIo;
(from Ref. 16)
1 717 cm-'
1567
1482
1360
1302
1191-1 178
1040-1 035
965-964
91 0-900
781-776

The FTIR spectrum confirms the existence of a

characteristic band belonging to C=O stretching vibrations. This means that C=O groups are produced in the
PPy-PSS film structure, as well as in PPy films generated
in ClO, and NO, aqueous media, and two possible
explanations are suggested.
ACKNOWLEDGEMENTS

The authors wish to thank DGICYT (Spain) (Project

PB89-0089) for financial support. Thanks are due to Drs
D. Rueda and C. Arribas (Instituto de la Materia, CSIC)
for the conductivity measurements and to Dr J. Palacios
and Mrs Bajon (Instituto de Catalisis, CSIC) for the
SEMs.
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M . J. Gonzalez-Tejera, M . A . de la Plaza, E, Sanchez de la Blanca, I. Hernandez-Fuentes

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POLYMER INTERNATIONAL VOL. 31, NO. 1,1993