Synthetic Metals 98 Ž1998.

51–55

Energy density and IR spectra of polyaniline synthesized

electrochemically in the solutions of strong acids
Shaolin Mu ) , Jinqing Kan
Department of Chemistry, Teacher’s College, Yangzhou UniÕersity, Yangzhou 225002, China

Received 5 June 1998; revised 14 July 1998; accepted 28 August 1998

Abstract

The electrochemical polymerization of aniline in fluoboric acid, hydrochloric acid, perchloric acid, sulphuric acid and nitric acid was
carried out at a constant potential of 0.75 V Žvs. SCE.. The conductivity of polyaniline synthesized in fluoboric acid is the largest and that
synthesized in nitric acid is the smallest among the above acids used for the polymerization of aniline. The conductivity of polyaniline
synthesized in sulphuric acid is a little higher than that synthesized in nitric acid. Based on the results from the constant current
charge–discharge process, the order of the energy density of polyaniline synthesized in the various acids is as follows: E HBF4 ) E HCl )
E HClO4 ) E H 2 SO4 ) E HNO 3 . This result is similar to the redox charge of polyaniline from the cyclic voltammograms of polyaniline obtained
2y
in various acids at the same polymerization charge. The absorption peaks of BF4y, ClO4y, NOy 3 and SO4 doped in polyaniline are
observed in the IR spectra. There is a relationship between the relative intensity of the absorption peaks of the benzene and quinone rings
to that of the doped anion, i.e., the relative intensity of absorption peaks in IR spectra decreases with increasing conductivity of
polyaniline. q 1998 Elsevier Science S.A. All rights reserved.

Keywords: Aniline in strong acids; Electrochemical polymerization; IR spectra and conductivity; Energy density

1. Introduction We found that the conductivity of polyaniline synthesized

in strong acid solutions was higher than that synthesized in
The electrochemical polymerization of aniline has been
the weak acid solutions. Therefore, polyaniline synthesized
used extensively for the preparation of polyaniline, be-
in strong acids should be a good candidate for the batteries
cause in this manner, the polymerization conditions are
electrodes. Polyaniline is neither soluble nor passive dur-
easily controlled and it is not necessary to employ any
ing the oxidation process, and there is no precipitate to
oxidizer. The properties of polyaniline depends on the
form during the reduction process. These characteristics
polymerization conditions during electrolysis. Therefore,
are very important for recharge batteries. Polyaniline bat-
this method provides a convenient comparison between the
teries have a high recharge cycles with a very high
properties of polyaniline obtained at different conditions of
coulombic efficiency, but have a low capacity density w12x.
electrolysis. Polyaniline can be used for batteries elec-
Thus, the study on factors affecting the energy density of
trodes, electrochromic devices, light-emitting diodes and
polyaniline is very important. The strong acids, such as
immobilization of enzyme w1–6x. The different application
HCl, H 2 SO4 , HClO4 and HBF4 , have been used for the
purposes need the different properties of polyaniline. It is
chemical synthesis of polyaniline, and their effects on
clear that polyaniline synthesized electrochemically can
some properties of polyaniline have been studied w14x. The
meet these needs.
electrochemical polymerization of aniline in various strong
The properties of polyaniline, such as conductivity,
acids and the properties of polyaniline synthesized in the
electrochemical properties and various spectra, were af-
strong acids were reported w9,10x. But these studies were
fected by a acid used for the electrolysis of aniline w7–13x.
carried out at different conditions, it is difficult to make a
clear comparison between their properties, such as the
)
Corresponding author. Fax: q 86-514-7349819; E-mail: energy density and conductivity of polyaniline, and IR
slmu@yzu.edu.cn absorption peak position of anions doped in polyaniline. In

0379-6779r98r$19.00 q 1998 Elsevier Science S.A. All rights reserved.

PII: S 0 3 7 9 - 6 7 7 9 Ž 9 8 . 0 0 1 4 7 - 7
52 S. Mu, J. Kan r Synthetic Metals 98 (1998) 51–55
the latter, most of IR spectra of polyaniline are related to
the chloride anions doped into polyaniline, which was
synthesized in the HCl solution. Since Cly ion has no
special absorption peak in IR spectra, it is not possible to
detect its presence in polyaniline. Polyaniline with high
conductivity contained anions, which decreased to a cer-
tain extent in the reduced polyaniline. This has been
identified by the electrochemical quartz crystal microbal-
ance ŽEQCM. w15x.This give us a clue that there may be a
relationship between the conductivity of polyaniline and
the IR absorption intensity of the anions doped in polyani-
line.
To enhance the energy density of polyaniline is very
important to polyaniline batteries. This has been reviewed
extensively by Novak et al. w16x. In many factors affecting
the energy density, the acid used for the synthesis of
polyaniline plays a decisive role. Thus, we used some
strong acid solutions containing aniline to synthesize
polyaniline. The purpose for this work is to make a
systematic comparison between properties of polyaniline
synthesized electrochemically in different strong acids, to
confirm the energy density of polyaniline synthesized in
which acid is the largest, and to look for the relationship
between the conductivity and the IR absorption peak inten-
sity of the doped anions.
2. Experimental
The chemicals used were all reagent grade. Aniline was
distilled before use. The electrolysis cell consisted of two
platinum foil electrodes and a reference electrode. The area
of the working electrode was 4 = 4 mm2 . All potentials
given here are referred to the saturated calomel electrode
ŽSCE..
A PAR Model 173 potentiostat–galvanostat with a
Model 179 digital coulometer was used for the electro-
chemical polymerization of aniline. The temperature was
controlled at 208C. A DH-1 potentiostat–galvanostat was
used for the cyclic voltammetry of polyaniline films. Their
cyclic voltammograms, after attaining a stable state of
polyaniline film, were recorded using a YEW Model 3036
X-Y recorder. The scan rate was 48 mV sy1 . The sweep-
ing potential range was between y0.2 and 0.80 V. The
charge and discharge processes of polyaniline battery were
Table 1
Conductivity, capacity and energy density of polyaniline synthesized in various acids Žthe battery consisted of a polyaniline positive electrode and a zinc
negative electrode.
Acid Conductivity Average discharge voltage
ŽS cmy1 . ŽV. of the battery
HNO 3 0.13 1.03
H 2 SO4 0.46 1.11
HCl 1.33 1.09
HClO4 4.89 1.04
HBF4 5.90 1.07
carried out using an automatic battery charge–discharge
unit ŽHJ-201B, Japan. and a YEW 3066 pen recorder. A
polyaniline pellet and a zinc foil were used for the positive
electrode and negative electrode of the battery. Polyaniline
for the measurement of conductivity was washed with the
responding acid of 0.2 M, except H 2 SO4 of 0.1 M, and
then dried at 808C for 24 h. The conductivity of polyani-
line was measured by a four-probe technique. IR spectra of
polyaniline were measured on pressed pellets with KBr
using a Nicolet 740 FTIR instrument.
3. Results and discussion
3.1. ConductiÕity of polyaniline
The conductivities of polyaniline synthesized in the
strong acids are listed in Table 1.
From Table 1, we can see that the conductivity of
polyaniline synthesized in fluoboric acid is the largest and
that synthesized in nitric acid is the smallest in the five
kinds of the strong acid. Nitric acid has a strong oxidizabil-
ity, which oxidized further polyaniline during the electro-
chemical polymerization of aniline to decrease conductiv-
ity. The conductivity of polyaniline synthesized in sul-
phuric acid is a little higher than that synthesized in nitric
acid. The results listed in Table 1 are in agreement with
those obtained by Yoshikawa et al. w10x, in which polyani-
line was synthesized electrochemically in HBF4 , HClO4 ,
HCl and HNO 3 .
3.2. Cyclic Õoltammograms of polyaniline films synthesized
in Õarious acids
Polyaniline films used for the cyclic voltammograms
were synthesized in the solutions of 0.2 M aniline in 1 M
HNO 3 , 1 M HCl, 1 M HClO4 , 1 M HBF4 and 0.5 M
H 2 SO4 , respectively. The electrolysis was carried out at
0.75 V. The total amount of charge passed in the electroly-
sis was 0.03 C for all cases, i.e., polyaniline films poly-
Capacity Energy density
ŽA h kgy1 . ŽW h kgy1 .
43.9 45.2
40.9 45.4
66.5 72.5
55.7 59.5
77.6 83.0
 S. Mu, J. Kan r Synthetic Metals 98 (1998) 51–55
Fig. 1. The cyclic voltammograms of polyaniline synthesized in fluoboric
acid. Curves: Ž1. in 1 M NaBF4 solution with pH 4.0, Ž2. in 1 M NaBF4
solution with pH 5.0.
merized on the same piece of platinum foil had the same
polymerization charge. The working electrode area was
4 = 4 mm2 . Their cyclic voltammograms were carried out
in the salt solution of the corresponding acid at pH 4.0 and
pH 5.0, respectively. Fig. 1 shows the cyclic voltammo-
grams of polyaniline film obtained in 1 M HBF4 solution.
Curves 1 and 2 in Fig. 1 show the cyclic voltammograms
of polyaniline film in the solutions of 1 M NaBF4 with pH
4.0 and pH 5.0, respectively. From areas of cyclic voltam-
mograms of curves 1 and 2, we can see that the electro-
chemical activity of polyaniline, i.e., the redox charge
decreases with increasing pH. Fig. 2 shows the cyclic
voltammograms of polyaniline film obtained in 1 M HNO 3
solution. Curves 1 and 2 in Fig. 2 show the cyclic voltam-
mograms of polyaniline in the solutions of 1 M NaNO 3
with pH 4.0 and pH 5.0, respectively. Also we can see that
the redox charge of polyaniline synthesized in HNO 3
solution decreases with increasing pH. From the cyclic
voltammograms, we found that among the above acids
used for the synthesis of polyaniline, the redox charge of
polyaniline synthesized in HBF4 solution is largest, and the
redox charge of polyaniline synthesized in HNO 3 solution
is the smallest. The redox charge of polyaniline synthe-
sized in sulphuric acid is a little lager than that synthesized
in nitric acid, its cyclic voltammograms are omitted here.
This result is similar to that of polyaniline synthesized
Fig. 2. The cyclic voltammograms of polyaniline synthesized in nitric
acid. Curves: Ž1. in 1 M NaNO 3 solution with pH 4.0, Ž2. in 1 M NaNO 3
solution with pH 5.0.
53
chemically in HBF4 , HCl, HClO4, H 2 SO4 and H 3 PO4 w14x,
in which the redox charge was also obtained using cyclic
voltammetry. The redox charge of polyaniline increased
with increasing conductivity. The above results indicate
that the redox charge of polyaniline was affected by the
kind of strong acids used for the synthesis of polyaniline.
3.3. Charge–discharge process
To know the effect of acid used for the polymerization
of aniline on the energy density of polyaniline, a given
weight of polyaniline was pressed on the platinum wire net
to form the polyaniline electrode, and then it was oxidized
and reduced at a constant current. The battery for the
charge and discharge of polyaniline consisted of a polyani-
line electrode, a zinc electrode, a separator and the aque-
ous solution, which consisted of 2.5 M ZnCl 2 , 3.0 M
NH 4 Cl and 0.01% Triton X-100 with pH 4.4. This solution
has a good buffer capacity. The addition of NH 4 Cl is to
prevent the formation of precipitation of zinc chloride at
the zinc electrode during the oxidation of zinc, because of
the formation of the complex, ZnŽNH 3 .42q. Triton X-100 is
a non-ionic surfactant, which plays an important role in
preventing corrosion of the zinc electrode. Fig. 3 shows
the charge and discharge processes of the battery at a
constant current of 1.0 mA. The area of the polyaniline
electrode used in the battery was 1 cm2 , and the weight of
polyaniline used for the fabrication of the electrode was
76.4 mg. In this case, polyaniline was synthesized in the
solution containing aniline and fluoboric acid. The battery
was charged and discharged between 0.75 and 1.50 V.
From the discharge curve shown in Fig. 3, the capacity and
energy density of polyaniline in HBF4 were calculated to
be 77.6 A h kgy1 and 84.6 W h kgy1 , respectively. The
capacity density and energy density of polyaniline synthe-
sized in various acids are listed in Table 1. From Table 1,
we can see that the energy density of polyaniline synthe-
sized in fluoboric acid is the largest and that synthesized in
sulphuric acid and nitric acid is the smallest among the
five kinds of the strong acid. The order of the energy
Fig. 3. Charge and discharge curves of polyaniline in the solution
containing 2.5 M ZnCl 2 , 3.0 M NH 4 Cl and 0.01% Triton X-100, pH 4.4,
polyaniline synthesized in fluoboric acid. Curves: Ž1. charge, Ž2. dis-
charge.
54 S. Mu, J. Kan r Synthetic Metals 98 (1998) 51–55
density of polyaniline synthesized in various acids is as
follows: EHB F4 ) E HCl ) E HClO 4 ) E H 2 SO 4 ) E HNO 3 . This
means that the energy density of polyaniline is affected by
the kind of acid used for the polymerization of aniline. The
results Žin Table 1. from the constant current charge and
discharge are similar to those obtained with the cyclic
voltammetry, in which the redox charge of polyaniline
synthesized in fluoboric acid is also the largest and that
synthesized in nitric acid and sulphuric acid is also small-
est among the five kinds of the strong acid. The results
from both the cyclic voltammograms and charge and dis-
charge processes of polyaniline at a constant current, we
can see that the redox charge and energy density of
polyaniline increased with increasing conductivity except
polyaniline synthesized in perchloric acid. The reason for
the latter is not too clear now.
3.4. Spectra of polyaniline
Fig. 4a and b show the IR spectra of the oxidized state
Žconductivity of 5.9 S cmy1 . and reduced state Žconductiv-
ity of 3.7 = 10y3 S cmy1 . of polyaniline, respectively,
synthesized in fluoboric acid. A sharp peak at 1090 cmy1
with splitting peaks at 1035 and 1115 cmy1 ŽFig. 4a. is
attributed to BF4y, since the BF4y ion has the typical
vibration wave numbers with splitting peaks concentrated
at 1050 cmy1 w17x. This result indicates that BF4y anions
were doped in polyaniline. The splitting peaks at 1035–
1115 cmy1 in Fig. 4a are merged into a sharp peak at 1135
cmy1 ŽFig. 4b., this is caused by the reduction of polyani-
line. It is well known that polyaniline lost anions after
reduction.
Fig. 5a and b show the IR spectra of the oxidized state
Žthe conductivity of 0.128 S cmy1 . and reduced state Žthe
conductivity of 3.2 = 10 y5 S cmy1 . of polyaniline, re-
Fig. 4. IR spectra of polyaniline synthesized in fluoboric acid: Ža.
oxidized form Žemeraldine salt., Žb. reduced form.
Fig. 5. IR spectra of polyaniline synthesized in nitric acid: Ža. oxidized
form Žemeraldine., Žb. reduced form.
spectively, synthesized in nitric acid. The absorption peak
of NOy 3 is at 1350–1420 cm
y1 w
18x. Thus, the two sharp
y1
peaks at 1383.6 cm in Fig. 5a and b are attributed to
that of NOy 3 anions doped in polyaniline. From Fig. 5a
and b, we can see that the intensity of the absorption peak
ŽFig. 5b. at 1383.6 cmy1 is weaker than that in Fig. 5a,
this is also caused by the reduction of polyaniline.
We also found that there are a peak at about 1111.3
cmy1 and a peak at 1120.8 cmy1 for polyaniline synthe-
sized in sulphuric acid and perchloric acid, which are
attributed to the absorption peaks of SO42y anions and
ClO4y anions w18x, respectively. Their IR spectra are saved
here. The above results indicate that the absorption peaks
2y
of BF4y, NOy y
3 , ClO4 and SO4 anions doped in polyani-
line are present in the IR spectra. But no evidence for the
formation of new bonds between the polyaniline chain and
doped anions was observed, that is anions doped in
polyaniline exist as the ion form. Therefore, there is a
anion exchange between polyaniline itself and the solution
during the redox process of polyaniline.
The absorption peaks at 1580–1500 cmy1 shown in
Figs. 4 and 5 are attributed to the C5C stretching vibra-
tions of the benzene ring and quinone ring. From Figs. 4
and 5, we can see that the intensities of the absorption
peaks at 1090 cmy1 ŽFig. 4. and 1383.6 cmy1 ŽFig. 5. for
the reduced states are smaller than those for their oxidized
states, which leads to the relative intensity of the absorp-
tion peaks of the benzene ring and quinone ring to that of
the doped anions increases after the reduction of polyani-
line. We know that the conductivity of polyaniline is
decreased after reduction. Thus, the relative intensity of
 S. Mu, J. Kan r Synthetic Metals 98 (1998) 51–55
the absorption peaks are related to the conductivity of
polyaniline, i.e., the smaller the relative intensity of the
absorption peaks of the benzene ring and quinone ring to
that of doped anions, the greater is the conductivity of
polyaniline.
4. Conclusion
The electrochemical polymerization of aniline in fluo-
boric acid, hydrochloric acid, perchloric acid, sulphuric
acid and nitric acid was carried out at a constant potential
of 0.75 V. The absorption peaks of BF4y, ClO4y, NOy 3 and
SO42y doped in polyaniline were observed in IR spectra.
The relative intensity of the absorption peaks of benzene
ring and quinone ring in polyaniline to that of the doped
anions decreased with increasing conductivity of polyani-
line, but no evidence for the formation of new bends
between the polyaniline chain and doped anions was ob-
served. This indicates that anions doped in polyaniline
existed as the ion form. The energy density of polyaniline
is affected by the acid used for the polymerization of
aniline. The energy density of polyaniline synthesized in
fluoboric acid is the largest among the five kinds of strong
acid. The energy density of polyaniline synthesized in
hydrochloric acid is close to that synthesized in fluoboric
acid. Thus, to enhance the energy density of the polyani-
line battery, the choice of polyaniline synthesized in fluo-
boric acid or hydrochloric acid is more favorable than
other acids.
55
Acknowledgements
This work was supported by the National Natural Sci-
ence Foundation of China.
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