Vo[. 135, No.

6 INDIUM TIN OXIDE 1457

(a) Manuscript submitted July 6, 1987; revised manuscript
+ +
-2.
4-
+
received Oct. 19, 1987.
+
+
-3, 4-
The University of Texas at Arlington assisted in meeting
+ the publication costs of this article.
~ zx
z~

-4 g~
+ REFERENCES
-5-
A [1
~ [J C2
1. (a) J. Switzer, This Journal, 133, 722 (1986); (b) J.
Switzer, ACS Meeting, Denver (1987).
s
x 2. H.A. Laitinen and J. M. Conley, Anat. Chem., 48, 1224
-6" []
(1976).
• •
• 3. N. R. Armstrong, A. W. C. Lin, M. Fujihira, and T. Ku-
-7 wama, Anal. Chem., 48, 741 (1976).
1,1 112 1~ 1:4 1~ 4. (a) G. Hodes, L. Thompson, J. Dubow, and K. Rajesh-
O~
o (b) war, J. Am. Chem. Soc., 105, 324 (1983); (b) O. M-R.
+ Chyan and K. Rajeshwar, This Journal, 132, 2109
(1985); (c) O. M-R. Chyan, S-I. Ho, and K. Rajeshwar,
+ zx ~ ibid., 133, 531 (1986); (d) S-I. Ho and K. Rajeshwar,
[]
ibid., 134, 768 (1987).
-5-
5. S. Menezes, A. Heller, and B. Miller, ibid., 127, 1268
+ []
(1980).
A 6. F. Decker, M. Fracastoro-Decker, S. Badawy, K.
Doblhofer, and H. Gerischer, ibid., 130, 2173 (1983).
A 7. D. Belanger, J. P. Dodelet, and B. A. Lambos, ibid.,
+
"6 133, 1113 (1986).
+
8. R. C. Kainthla, B. Zelinay, and J. O'M. Bockris, ibid.,
x 134, 841 (1987).
•
~x 9. A. T. Howe, J. Chem. Soc. Chem. Commun., 1407 (1983).
-7 10. S-I. Ho and K. Rajeshwar, This Journal, 134, 768 (1987).
1,1 1:2 1:3 1:4 l:s 11. (a) G. B. Hoflund, D. F. Cox, and H. A. Laitinen, Thin
Solid Films, 83, 261 (1981); (b) G. B. Hoflund, D. F.
E, V vs SCE
Cox, F. Ohuchi, P. H. Holloway, and H. A. Laitinen,
Fig. 14. Tafel curves for bare, RuOx-modified and Ti-supported RuO~ Appl. Surf. Sci., 14, 281 (1982-1983).
electrodes in |M KOH. Data notation as in Fig. 13. 12. (a) W. Badawy, K. Doblhofer, I. Eiselt, H. Gerischer, S.
Krause, and J. Melsheimer, Electrochim. Acta, 29,
1617 (1984); (b) R. H. Colton and H. E. Hager, This
I n all the cases, the Tafel lines level off at the extremity
Journal, 133, 2530 (1986).
13. J-C. Manifacier, L. Szepessy, J. F. Bresse, M. Perotin,
of the positive polarization limit. Blocking effects from the and R. Stuck, Mater. Res. Bull., 13, 109 (1978).
02 bubbles can be traced as the origin for this anomalous 14. K. S. Kim and N. Winograd, J. Catal., 35, 66 (1974).
trend. Only the higher Tafel slope can be discerned in the 15. L. D. Burke and O. J. Murphy, J. Electroanat. Chem.
neutral pH range (not shown). When the current density Interfacial Electrochem., 96, 19 (1979).
data in the ordinates of Fig. 14a and 15a are recalculated on 16. G.-W. Jang and K. Rajeshwar, This Journal, 134, 1830
the basis of the real surface area (rather than the geometric (1987).
area of the ITO), the Tafel lines for the various catalyst 17. S. Trasatti and G. Lodi, in "Electrodes of Conductive
loadings are almost superimposable (Fig. 13b and 14b). Metal Oxides," Part B, S. Trasatti, Editor, p. 521,
(Ideally, all the plots should exactly coincide if the varying Elsevier: Amsterdam (1981).
surface area had been correctly normalized.) Nonetheless, 18. L. D. Burke, O. J. Murphy, J. F. O'Neill, and S. Ven-
the overall trends in Fig. 13 and 14 lend further credence to katesan, J. Chem. Soc. Faraday Trans. 1, 73, 1659
(1977), and references therein.
the Ru assay technique addressed earlier in this paper. 19. (a) S. Trasatti and W. E. O'Grady, Adv. Electrochem.
Acknowledgment Electrochem. Eng., 12, 177 (1981); (b) L. I. Krishtalik,
Electrochim. Acta, 26, 329 (1981); (c) D. V. Kokoulina,
We are grateful to the Strategic Defense Initiative Office, L. V. Bunakoya, T. I. Khomyakova, and E. B. Sirot-
Innovative Science and Technology Branch and the Texas kina, Electrokhimiya, 22, 24 (1986).
Advanced Technology Research Program for partial sup- 20. M. E. G. Lyons and L. D. Burke, J. Chem. Soc. Faraday
port of this research. Trans. 1, 83, 299 (1987).

Electrolyte Effects on the Switching Reaction of Polyaniline

Jean-Christophe LaCroix and A. F. Diaz*
IBM Research Division, Almaden Research Center, San Jose, California 95120-6099

ABSTRACT
This report describes the electrochemical behavior of polyaniline prepared in aqueous solution with various acid elec-
trolytes. Electroactive polyaniline with two different cyclic voltammograms, i.e., with and without the additional peak at
500 mV, can be produced by controlling the current densities during the preparation. The oxidation reaction is coulombi-
cally reversible, and the rate depends on the acidity of the solution but is i n d e p e n d e n t of the nature of the counter anion.
In solutions more acidic than 0.1M, the charge is linear with time in the initial period. In 10-3M acid solutions, the charge
has a t 1/2 dependence. The films are also electroactive in n o n a q u e o u s solvents, and voltammograms with well-defined
waves result when the solution contains both organic salt and protic acid electrolyte. Polyaniline is stable in the dry state
but not in aqueous electrolyte. TGA shows that the material dehydrates at 80~ and completely decomposes at 185~ SEM
analyses show that the initially deposited film is a continuous film and that the subsequent deposit has a fibril structure.

The electroactive and conductive properties of polyani- development. The electroactive property of polyaniline
line are a subject of investigation in numerous labora- films has been studied for technologies such as electro-
tories. On the whole, the studies reveal a unique balance of chromic displays (1, 2), storage batteries (3), and sensors
effort directed to both the scientific issues and technology (4). These applications require that the material have high
*Electrochemical Society Active Member. reversibility, rapid switching rates, and chemical stability.
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 1458 J. Electrochem. Soc.: ELECTROCHEMICAL SCIENCE AND TECHNOLOGY
Therefore, any attempts to optimize the material requires
good characterization. At present, attempts to compare the
characterization results from the different laboratories can
be difficult because there is a variation in the electrochem-
ical response of the films where some films have additional
redox peaks in the region near 500 mV and some do not.
We now wish to report the results of a study showing
that electroactive polyaniline with two different cyclic
voltammograms, i.e., with and without a reaction at 500
mV, can be prepared by controlling the anodic voltage
and, effectively, the current densities during the prepara-
tion. The switching reaction is coulombically reversible
and the chronocoulometric traces show that the charge
has a t dependence in acidic solutions (>0.1M) and a t 1/~de-
pendence in weakly acidic solutions. Polyaniline is also ac-
tive in several nonaqueous solvents and can be switched
when the solution contains both salt and protic acid elec-
trolyte. Polyaniline is stable to storage in the dry state but
not in aqueous electrolyte. TGA shows that the film dehy-
drates at 80~ and decomposes at 185~
Experimental
All the chemicals used in this study were reagent grade
and were used without further purification unless stated
otherwise. Aniline (Aldrich Chemical Company) was puri-
fied by simple distillation. The electrodes were prepared
by vapor deposition of 5000A of platinum on a glass plate
which was precoated with 500A of chromium as an adhe-
sion layer. The metal deposition was made through a mask
producing a metal surface area equal to 0.5 cm 2.
Polyaniline was prepared using a 0.1M aniline in 2M sul-
furic acid aqueous electrolyte. The films were generated
by sweeping the voltage applied to the electrode between
- 1 0 0 and 900 mV vs. sodium chloride calomel reference
electrode at 50 mV/s, as was previously described (5-7).
During the preparation, the anodic voltage limit is gradu-
ally reduced to 750 mV in order to maintain the current
density at the positive voltage limit to a nearly constant
value (ca. 0.4 mA/cm2). We thus have direct potential con-
trol and indirect current control during deposition. Films
prepared using 33 mC/cm ~ had a corresponding thickness
of 1000A. Unless otherwise specified, all films were pre-
pared with controlled anodic voltage in order to minimize
the formation of oligomers and degradation products.
Samples for thermal analyses were polymerized on a thin
gold wire 0.03 m m diam and 50 cm length.
I I I I I I
400
300 --
< 100
o
-lOO
-200
-300
o 200 400 600 800 lOOO
E/mV
Fig. 1. Cyclic voltammogram of the aniline polymerization reaction
on a platinum electrode using a 2M sulfuric acid aqueous solution con-
taining 0.2M aniline, and with continuous cyclic sweeping at 50 mV/s.
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June 1988
All the electrochemical experiments were made using a
sodium chloride reference electrode and a gold wire coun-
terelectrode. The analyses were performed with IR com-
pensation and using the electrochemical equipment previ-
ously described (8). Samples used for SEM analyses were
precoated with 250A of gold and the measurements were
made using a Hitachi $500. Film thicknesses were mea-
sured by SEM and using a Tencor alfa step instrument.
Thermal gravimetric analyses were made using a du Pont
1090 Thermal Analyzer and 981 Differential Scanning Cal-
orimeter. These analyses were made under a helium atmo-
sphere and using a scan rate of 20~
Results and Discussion
Electropolymerization.--The polyaniline films were pre-
pared in an aqueous solution containing 0.1M aniline plus
2M acid, by sweeping the voltage applied to the platinum
electrode between -100 and 900 mV at 50 mV/s (5). The
preparations produced good quality films without
coloration of the preparative solution. As the film begins to
form, peaks for the redox reaction of polyaniline appear at
250 mV and the anodic voltage limit was gradually re-
duced to 750 mV. A typical preparation voltammogram is
shown in Fig. 1. With sulfuric acid electrolyte, the reaction
is faster on the polymer than on platinum, allowing the
anodic voltage limit to be reduced as soon as the platinum
is covered with polyaniline. The faster charge transfer
rates with a polyaniline/sulfuric acid electrode than with a
platinum electrode have been observed with the polymer-
ization of aniline (5, 6) and in the form of a greater revers-
ibility for the ferrocene, ferrous, and ferrocyanide couples
in aqueous electrolyte (7).
Controlling the anodic voltage limit in order to maintain
the current densities below 0.4 mA/cm 2 produced films
which show the oxidation peak at 250 mV plus the 900 mV
peak only and no peak at 500 mV. On the other hand, films
showing the additional peak at 500 mV in the voltammo-
gram could be prepared by using a higher current density.
Literature reports on polyaniline prepared in aqueous sul-
furic acid parallel these results, and the two kinds of films
generated in different laboratories simply result from the
degree of current density control exercised during the
preparation. Films showing the additional peak at 500 mV
were prepared with cycling to an anodic voltage limit of
0.8V (6) and 0.9V (7), or potentiostatically at 0.9V (4, 7). On
the other hand, polyaniline with only one redox wave at
250 mV was prepared with sweeping to voltages less than
0.8V (5) or galvanostatically with the current density at 0.1
mA/cm a (1).
The ratio of the charge involved in the switching reac-
tion of the polymer (Qs) to the charge involved in the poly-
merization reaction (Qp) was found to be fairly constant
during the preparation. The ratio was determined from a
I
1.5 I
9
1.0
o~
E
0
0.5
I I I
5 10 15
Qp/mC
Fig. 2. Plot of Q, vs. Qp for the data taken from each cycle in Fig. 1
 Vol. 135, No. 6 POLYANILINE 1459

/
.////
1000 1200 1200

8O0 1000
e

800 -.~ 600 1000 < 800

./
600
4OO
200 /
8OO
--~ 600

400 /
I I I I 2OO
0 20 40 60 80 600
400 v/mV/s
20 40 60 80
v/mV/s
<
400
200 i/pA 80 m W s
v,s
60
2O0 40
x'20 20

0
-200
-200

-400
-400
I I I I I
0 200 400 600 800 -600
E/rnV
Fig. 3. Cyclic voltammogram of polyaniline (500~) in 2M aqueous 0 200
400 600 800 1000
sulfuric acid. Film was prepared with controlled current and anodic E/mY
voltage. Fig. 4. Cyclic voltammogram of polyaniline in 2M aqueous sulfuric
acid. Film was prepared without controlling the current density and the
anodic voltage limit.
plot of the total charge against voltage, which was re-
corded during the voltage sweep process. The charge in
the voltage range 200-300 mV was used to estimate Q~. were quite different. The polymerization reaction is slower
F r o m such a plot, the cumulative Qs/Qp ratio was deter- on these polymer surfaces than on platinum, and the
mine d for each successive voltage sweep cycle. The plot of anodic voltage limit could not be reduced during the prep-
Qs vs. Qp is shown in Fig. 2 for a film prepared using 33 aration. The voltammograms of the resulting films showed
sweep cycles. The slope provides a ratio equal to 0.125, and the additional peak at 500 mV along with the peaks at 250
the switching charge/cycle is 0.1 mC/cm2-cycle. The and 800 mV. As with the above acid electrolytes, the Qs/Qp
charge/cycle parameter has been used by Kitani (6) and ratio is constant during the preparation with hydrochloric
Wang (9) as a measure of the polymerization rate and is and trifluoroacetic acid electrolytes and equals 0.125.
found to be in the range 0.06-1.4 mC/cm2-cycle with differ-
ent acid electrolytes. Regarding the efficiency of the reac- Switching reaction.--The switching reaction of polyani-
tion, Oreta and Buttry have shown that the current effi- line prepared with low current/voltage was measured in
ciency for the polymerization reaction (with cycling) is 2M sulfuric acid containing no aniline. The voltammogram
40% where 100% corresponds to 1 electron per aniline unit is reasonably clean and has one oxidation and reduction
deposited (10). peak at 120-250 mV, as can be seen in Fig. 3. The peak for
Polyaniline was prepared in other electrolytes in order the second reaction at 900 mV is also present, although the
to probe the influence of the different acids. Some of these sweep was not extended into this peak during the initial
have been previously used, e.g., hydrochloric (6, 11), nitric analyses because material with an oxidation peak at 500
(6), and perchloric acid (6). Films prepared using hydro- mV is produced. While the voltage used to reverse the
chloric, nitric, fluorosulfonic, and trifluoromethylsulfonic sweep direction is arbitrary, it does affect the coulometric
acid electrolyte had the same electrochemical preparation results because the oxidation of the film appears to be a
characteristics. That is, the anodic voltage limit could be continuous process throughout the voltage range as pro-
reduced during the preparation and the resulting film posed by MacDiarmid (12). The redox peaks for the films
showed only one oxidation peak at 250 mV. The differ- from these preparations are listed in Table I and are la-
ences between these electrolytes was not quantified. Films beled first, second, and third systems in the order of ap-
prepared with hydrofluoric and trifluoroacetic electrolytes pearance in the anodic sweep. The peak heights for the
first oxidation reaction,scale linearly with the sweep rate,
and the cathodic and anodic peak separation remains con-
Table I. Summary of Ep values~ for polyaniline in aqueous acid stant at 130 mV. A voltammogram with this simple form
electrolyte
2.0 i i r i
First system Second system Third system (b) f 9
Acid (2M) Epa Epc Epa Epc Epa Epc
1.5
H2SO4 260 140 540 520 900 870 | |
620 580
HCI 250 110 610b 560b 870 830 1.0
HNO3 250 130 520 500 860 830 0
600 570 03
FSO3H 250 120 540 520 870 830
620 580
CF3SO~H 210 130 540b 490b 810 820 0.0
CF3COOH 210 130 530 510 770 740 0 100 150 0 5 10 15
HF 190 50 300 450 610 510 T/ms tl/2/(ms) 1/2

Fig. 5. Chronocoulometric plots resulting from potential steps from

aValues in millivolts vs. NaSCE measured at 50 mV/s scan rate. - 100 mV to 600 (1), 500 (2), 400 (3), and 300 (4) mV for a polyani-
bGenerated by degradation of polyaniline in aniline-free elec-
trolyte. line film (SO0~) in 2M aqueous sulfuric acid.
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 1460 J. Electrochem. Soc.: E L E C T R O C H E M I C A L
has been reported by Tamura by using a film prepared gal-
vanostatically (1, 2). The shape and position of the first
peak depend on the acidity of the solution. With increasing
sulfuric acid electrolyte, the peak becomes sharper and
shifts linearly to anodic values at the rate of 0.060 mV/pH
unit in the pH range - 1 to 1, with constant ionic strength.
This pH dependence has been reported and ascribed to a
one electron/one proton reaction (11). Therefore, all of the
measurements were made with 2M acid electrolyte in
order to minimize differences resulting from the solution
acidity.
The v o l t a m m o g r a m for a film prepared with no anodic
voltage control shows a peak at 500 mV (second system) as
seen in Fig. 4. This peak is difficult to interpret because it
originates in several ways. The use of high current densi-
ties during the preparation generates oligomers which oxi-
dize in this voltage range. This can be minimized by reduc-
ing the anodic voltage limit or the concentration of aniline.
In addition, voltages anodic of 900 mV degrade the film
and products are generated which oxidize in this voltage
range. Therefore, in order to avoid the appearance of these
signals, it is important to control the voltage and, effec-
tively, the current during a preparation, and the voltage
during analyses. This peak has been reported by several
laboratories and is assigned to the presence of ortho
coupled polymer (13), and degradation products (11). The
vol t am m o g r am s for polyaniline films prepared and tested
in the other acid electrolytes are very similar to the above.
The v o l t am m o g ram s for films prepared and tested in sul-
furic, hydrochloric, nitric, and fluorosulfonic acid electro-
lytes are effectively superimposable. The Ep values are
listed in Table I. With trifluoromethylsulfonic, hydrofluor-
ic, and trifluoroacetic acid electrolytes, the oxidation peak
for the polymer is shifted negatively by 40-60 mV, and with
the latter two electrolytes, the presence of the peak at 500
mV could not be avoided.
The switching reaction corresponds to the oxidationn of
the pi-system of the protonated aniline units in the poly-
mer converting them from benzenoid- to quinoid-like
structures as shown in Eq. [1] (2, 13, 14). In this equation,
only the protonated structures are considered because
they are relevent to the solution conditions in this study.
Thus, Buttrey shows that in 2M sulfuric acid, ca. 50% of the
reduced polymer and 70% of the oxidized polymer is pro-
tonated (10). Unlike polypyrrole and polythiophene, the
oxidation-reduction reaction of polyaniline produces ben-
zenoid- and quinoid-like structures. These structures are
coi~formationally different and have been detected spec-
troscopically using IR and optical absorption (electro-
chemically prepared) (15, 16), and NMR and resonance
Ra m an (chemically prepared) (17, 18). The reaction has a
hysteresis as is observed with many of these polymers (2,
5, 19). The hysteresis has been ascribed to conformational
changes in the redox polymers (2, 19, 20), to changes in the
swelling of the film and to changes in the level of interca-
lation of ions (10, 21). With polyaniline, the conformational
2.0 I
| calculated diffusion coefficients are in the range, 10-l~
15
1.0
0 nol into PMMA (23) and aqueous zinc chloride solution (24)
0.5
i i I I
0.0 100 200 300 400 500
t/ms
Fig. 6. Chronocoulometric plots resulting from o potential step from
- 1 0 0 to 600 mV for a polyaniline film (SO0~) in sulfuric acid; (1)
O.1M, (2) 1M, and (3) 2M.
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SCIENCE AND TECHNOLOGY June 1988
NH2+ ns= 2 NH+
[Q~=fnsFFI
(x+2) [~ NH3+ np=2
I~ ~ \~[" § (2)
/ ;~ [Op=npFmt]
differences between the benzenoid- to quinoid-like forms
of the polymer must be a contributing factor.
The fraction of the aniline units along the chain which
are oxidized (x) was estimated from the switching/
polymerization charge ratio, Qs/Qp. Qs and Qp are defined in
Eq. [1] and [2] and can be related to the electrochemical
stoichiometry (n) ratio for these reactions, nJ%. In Eq. [1],
F is the total surface concentration of polyaniline centers,
x is the fraction of the aromatic units affected by the oxida-
tion reaction, F is the Faraday constant, and ns, the electro-
chemical stoichiometry of the switching reaction, is con-
sidered equal to 2 per 2 aniline units (5). In Eq. [2], mt is the
total moles of aniline reacted to form the polymer, and np
equals 2 per aniline unit. Relating the charge ratio to the
electrochemical stoichiometry ratio as in Eq. [3] provides x
equal to 0.25. This value agrees with the above value con-
sidering that n~ and np differ by a factor of 2. As mentioned
above, this value will depend on the voltage used to re-
verse the direction of the sweep. This factor may explain
w h y our value is lower than the values of 0.33-0.42 charges/
repeating unit reported by Genies (22)
QJQp = xnJnp [3]
Switching Reaction Rate
The chronocoulometric response of the reaction was
measured by stepping the voltage applied to the electrode
from -100 mV to an anodic voltage and back to -100 mV.
The resulting plots for a film (500A thick) prepared on a
platinum electrode are shown in Fig. 5. The rate of
switching is strongly dependent on the anodic voltage
step, and the response does not have simple Fickian be-
havior (Fig. 5b). The response is initially linear with time
and changes to a t 1/2 dependence at longer times. The ini-
tial slope for the voltage step to 600 mV is 35 mC/s and is
the same for films 500-1500A thick. The response is the
same with 2M sulfuric, hydrochloric, or fluorosulfonic acid
electrolyte. Particularly interesting is the fact that the
same Q-t dependence is observed for the reduction reac-
tion (step from 600 to -100 mV) with a small difference in
the slope, since it is not expected from the shape of the cy-
clic voltammogram.
The model normally used to describe the switching rate
of familiar films such as polypyrrole and polythiophene as-
sumes the controlling step of the reaction is assumed to be
the rate of mass transport of ionic species in and out of the
film. Semi-infinite diffusion equations, with t 1/2 depen-
dence, are used to fit the experimental results, and the con-
tribution of migration to mass transport is neglected. The
cm2/s. This model does not explain the Q-t response of the
polyaniline film. Although linear diffusion has not been
observed in electrochemical systems, mass transport con-
trolled p h e n o m e n a with linear kinetics, as opposed to
Fickian, have been observed, e.g., the diffusion of metha-
into a glassy polymer. In these systems, the rate is con-
trolled by the constant velocity of an advancing boundary
resulting from a chemical reaction or a phase transition
and is refered to as Case II diffusion (25). In the case of
polyaniline, if the switching rate is controlled by mass
transport, it may be limited by a process involving a mov-
ing front across the thickness of the film and not by diffu-
sion of ions. While Case II diffusion is consistent with the
linear kinetics, it is not consistent with the recent report by
Glarum indicating that the charge is developed homogene-
ously throughout the film (26).
 Vol. 135, No. 6 POLYANILINE 1461

Table II. Cyclic voltammetry data for polyaniline in several 600

electrolyte solutions

Anodic a Cathodic a 500

Solvent Electrolyte Epb ip/Av~ Epb ip/Av~
Water 2M H2SO4 250 13.5 120 8.5 400
Ethanol 2M H2SO4 380 13 250 12.5
1M CF3COOH/ 170 4.5 80 6 Z
0.1M Bu4NBF4
300
2,2,2-Trifluoro- 2M H2SO4 370 12 230 7.5
ethanol 1M CF~COOH/ 500 8 260 7
0.1M Bu4NBF4
w 200
Acetic acid 2M H2SO4 420 15 320 12.5
1M CF3COOH/ 380 4.8 200 5.5
0.1M Bu4NBF4
Acetonitrile 2M H2SO4 450 13.5 360 12 100 CH3COOH ?2HsOH
1M CF~COOH/ 540 5.5 260 6.5 CH3CN '~ H20
0.1M Bu4NBF4
I III I I
40 50 60
aMeasurements made with IR compensation and sweep rates at
10-100 mV/s. ET/(kcat/mol)
bValues in mV. Fig. 8. Plot of Ep~and Epc values from the cyclic voltammograms of
~Values in mA-s/cm~V.
polyaniline films in various solvents (50 mV/s, NaSCE) vs. ET values
from Ref. (29).
A n alternate e x p l a n a t i o n is that the s w i t c h i n g reaction is
c o n t r o l l e d by the resistance of the cell (solution and film). 1
n e e d e d to distinguish b e t w e e n t h e s e possibilities
I f t h e c u r r e n t and the potential applied to the electrode are
related as in Eq. [4], then, for large I R values, the c u r r e n t
will be fairly c o n s t a n t and i n d e p e n d e n t of k0QRed. It will i = koQRed eXp [~ ~--~(E- IR)] [4]
also be insensitive to the o t h e r cell c o n d i t i o n s s u c h as pH,
a n i o n type, and m a g n i t u d e of the potential step. I n d e p e n - T h e acidity of the solution influences the kinetics of t h e
d e n t of t h e model, t h e observations are that t h e s w i t c h i n g reaction. As s e e n in Fig. 6, the s w i t c h i n g t i m e is a l m o s t
t i m e s for polyaniline are in tens of m i l l i s e c o n d s and are identical for 1-2M sulfuric acid electrolyte and ca. 3 t i m e s
significantly less t h a n for p o l y p y r r o l e ( h u n d r e d s of milli- s l o w e r w i t h 0.1M acid electrolyte. With the 0.1M acid elec-
seconds). T h e difference reflects either the h i g h e r m o b i l i t y trolyte t h e t i m e d e p e n d e n c e of t h e reaction has already
of p r o t o n s and anions in polyaniline, or t h e difference in c h a n g e d significantly and is linear w i t h t 1/2 in t h e r e g i o n
cell resistance b e t w e e n the a q u e o u s and aprotic electro- 20-80% reaction. The D/12 v a l u e calculated for this p o r t i o n
lyte. If the resistance of t h e cell is the controlling p a r a m e - of t h e reaction is 7.85 s -I, and D equals 1.9 • 10 10 cm2/s
ter for the s w i t c h i n g rate of t h e film, it m a y also be the con- (500A film). With a m o r e dilute acid solution, 0.001M sul-
trolling p a r a m e t e r for the other polymers, s u c h as furic acid plus 0.1M s o d i u m sulfate, the D/l 2 v a l u e is 1.4 s -1,
p o l y p y r r o l e and p o l y t h i o p h e n e . Therefore, the interpreta- and D e q u a l s 1.4 • 10 -l~ cm2/s (1000A film). F o r compari-
tions b a s e d on m a s s transport and the v a l u e s of t h e diffu- son, O y a m a (27) reports at t u2 d e p e n d e n c e for the
sion coefficients p u b l i s h e d m a y be in error. More w o r k is s w i t c h i n g reaction in p H 1 solution using a film 0.36 ~ m
1The authors wish to thank the referee for comments regarding t h i c k and a D v a l u e e q u a l to 1.2 • 10 -1~ cm2/s.
the effect of IR losses.
Other solvents.--The m a j o r i t y of the e l e c t r o c h e m i c a l
studies w i t h polyaniline h a v e b e e n p e r f o r m e d in a q u e o u s
I I solutions (1-7, 9, 11, 13, 14), a l t h o u g h . t h e p o l y m e r is also
e l e c t r o a c t i v e in m o i s t acetonitrile, p r o p y l e n e carbonate,
1000
and a n h y d r o u s a m m o n i u m fluoride solutions (13, 22). I n
fact, polyaniline is electroactive in several o t h e r solvents.
This is seen in Table II, w h i c h lists t h e Ep and i,/Av values
800 f r o m v o l t a m m o g r a m s m e a s u r e d in alcoholic, c a r b o x y l i c
acid, and aprotic solvents such as acetonitrile. The ip/Av
v a l u e s are for the s w e e p rate range, 10 to 100mV/s. U n l i k e
600 p o l y p y r r o l e (19) and p o l y t h i o p h e n e (28), v o l t a m m o g r a m s
w i t h well-defined w a v e s result only w h e n b o t h organic salt
and protic acid are p r e s e n t in the electrolyte solution.
400 W i t h o u t t h e p r e s e n c e of b o t h electrolytes, v e r y broad non-
d e s c r i p t w a v e s w e r e produced. T h e position and the w i d t h
,,< 100 mV/s of t h e peaks are also sensitive to the solvent/electrolyte
200 80 c o m b i n a t i o n of the solution, and in general, are consis-
60
40 t e n t l y sharper with sulfuric acid t h a n w i t h the salt/protic
20
acid electrolyte. This is seen in the v o l t a m m o g r a m s mea-
s u r e d in acetic acid w h i c h are s h o w n in Fig. 7. T h e p e a k
w i d t h s at half heights are 90 and 120-200 m V w i t h the sul-
furic acid and trifluoroacetic acid electrolyte, respectively,
-200
Table III. Thermal gravimetic analysis data for polyaniline films
-400 Electrolyte

-600 H2SO4 HC1 FSO3H CF3SO3H

I I
200 400 600 800 1000 Polarization, mV -100 +480 -100 -100 +480 -100 +480
Decomposition 185 195 185 185 195 110 110
E/mY temperature, ~
Water content, 19 40 18 34 41 <1 <1
Fig. 7. Cyclic voltammogram of polyaniline (1000~) in 2M sulfuric %
acid in acetic acid solution.
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 1462 J. Electrochem. Soc.: E L E C T R O C H E M I C A L
I ' "~L. ' I I I
3O
,.;-
~. -10
-20
-30 , I , I , I , I , f , I T I ,
-40 0 40 80 120 160 200 240 280
TemperattJre (~
Fig. 9. Thermal gravimetric and differential scanning calorimetric
plots for polyaniline prepared in aqueous sulfuric acid.
and the difference may result from the presence of small
amounts of water with the sulfuric acid.
The potential for the switching reaction of the polyani-
line film shows a rather large solvent effect. In fact, the
shift in the Ep, and Epc values appear to respond to both the
polarity and the basicity of the solvents. The shifts corre-
late best with the ET values, a solvent polarity parameter
developed by Dimroth and colloborators (29) from spectro-
scopic measurements of the solvent effects on the optical
absorption spectra of phenylpyridinium salts in various
solvents. As seen in Fig. 8, a good linear correlation is ob-
served with both anodic and cathodic peak potentials, and
the solvent sensitivity is comparable. The Ep values also
correlate with the solvent basicity as measured by the pKa
(30) and the photon transfer quotient (31) values of the sol-
vents. In the pica correlation, the values for the three non-
aqueous solvents are linearly related, while the value in
water is displaced 100 mV negative of the extended
straight line.
In these solvents, a second peak is observed in the
anodic region as in the aqueous solutions. However, in
contrast with the reaction in aqueous solutions where
sweeping the potential through the second peak degrades
the film, the film is m u c h more stable. For example,
Fig. 10. Scanning electron micrographs of polyaniline films prepared in 2M sulfuric acid (a and b) and 2M hydrochloric acid (c) with controlled
anodic voltage and current density.
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SCIENCE AND TECHNOLOGY J u n e 1988
I I 100 switching the film up to 1V in aqueous electrolyte pro-
duced a 70% loss of the electroactivity after four cycles.
90 The total resident time of the film in the voltage region
o-e anodic of the second peak is ca. 24s. In acetonitrile
.E
80 ._~ (Bu4NBF4/CF3COOH) solution, films switched for 80 cycles
showed a 10% decrease in electroactivity. During these
runs the total residence time of the film in the voltage
70 range anodic of the second peak was ca. 1000s. From the
\
relative amounts of decomposition and residence times in
\ ......
60 the anodic voltage regions for the two electrolytes, the film
is estimated to be at least 500 times more stable in the non-
aqueous electrolyte. The chronocoulometric experiments
in acetonitrile electrolyte revealed that the switching times
were decreased by a factor of five by changing the voltage
step from 0.5 to 1.4V. However, the switching times remain
smaller than those in 2M sulfuric acid.
Film stability.--The films are quite stable to storage in
the dry state, as measured by the charge in the switching
reaction. Films rinsed with water and stored in ambient
conditions for 40 days remain electroactive and show only
a small broadening in the peak shape. The films are some-
what less stable to storage at 80~ After five days, the films
show a 15% loss in the coulombic capacity and the peaks in
the v o l t a m m o g r a m are broad. Further storage up to 40
days reveals very little change. The films are less stable to
storage in 1M aqueous sulfuric acid solution under open-
circuit conditions. At room temperature the open-circuit
potential of the film shifts positive to 650 mV within an
hour. The film changes color but there is little or no loss of
coulombic capacity. Soaking the film for 4h at 80~ re-
duces the coulombic capacity to 12% and the switching po-
tential is shifted positive by 100 inV. The main decom-
position pathway for the film must be hydrolysis to
produce benzoquinone product (32). The films are also sta-
ble to the switching reaction, as mentioned above, al-
though m u c h better estimates of the reversibility have
been provided by several laboratories from continuous cy-
cling experiments. For example, Genies finds that electro-
polymerized polyaniline can be switched up to 100-2000
cycles with coulombic yield of 1.0 (9), while chemically
polymerized polyaniline maintains coulombic capacity of
93-96% during 200 sweep cycles with low current density
(33, 34).
A more direct measure of the thermal stability of polyan-
iline was determined by thermal gravimetric analysis of
films prepared on a thin gold wire. The analyses were car-
ried out under a helium atmosphere using 5-9 mg film
samples. Polyaniline from sulfuric, fluorosulfonic, and hy-
drochloric acid solutions has a higher decomposition tem-
perature, 185~176 than polypyrrole (19) and polythio-
phene (28). These temperatures are listed in Table III.
Shown in Fig. 9 is the scan for a film which was polarized
 Vol. 135, No. 6
at -100 mV before removing the electrode from the cell.
The sample loses moisture in the temperature range
60~176 as evidenced by the 19% weight loss in the tga and
the en d o t h erm in the DSC. Following the dehydration re-
action there is an exotherm at 80~176 and decom-
position at 185~ A small residue remains after the bulk of
the polymer is volatilized which is eventually r e m o v ed at
higher temperatures. The gold wire is burned clean during
this analysis. Films which were polarized at 480 mV had a
higher moisture content and decomposition temperature,
195~ The films prepared in trifluoromethylsulfonic acid
are different from the rest. They contain very little water
and d eco m p o s e at ll0~ The volatiles liberated from the
sample during heating were analyzed by mass spectros-
copy. In the region below 100~, moisture was the only vola-
tile observed.
The chemical process associated with the exotherm is
not understood. Tetraalkylammonium hydrogen sulfate
and the aniline dimer, the sulfate salt of protonated p-ami-
nodiphenylamine, are both stable up to 250~ and do not
show an e x o t h e r m with heating. Therefore, this reaction
m u s t be characteristic of polyaniline and may be a recrys-
tallization reaction.
Surface micrographs.--Literature reports from different
laboratories describe the polyaniline deposit as a film and
as a powder. As can be seen in Fig. 10a, the first deposit is
continuous film which has a surface roughness on the sub-
micron scale and resembles the surface of films previously
reported (5). These films are adherent, continuous, and
covered the 0.5 cm 2 electrode area fairly evenly with no
visible uncoated areas. No difference was detected be-
t w e en films prepared with sulfuric and hydrochloric acid
electrolyte. Ex t en d i n g beyond this film, a fibril structure
forms (13, 35) (Fig. 10b and 10c), which has been noted as a
p o w d e r (6, 9). The fibers have a diameter of ca. 0.1 ~Lm and
e x t e n d up to ca. 1 ~Lm between branch points. The fiber
content on the film can be controlled by the amount of
charge used in the polymerization reaction. Fiber forma-
tion occurred with all the electrolytes and there is a varia-
tion in the degree of formation with each acid. In particu-
lar the film prepared in trifluoroacetic acid produced
extensive fibril structure, giving the film the appearance of
a powder. Removal of the fibril powder from the continu-
ous film did not alter the voltammogram, except to reduce
the size of the signal; therefore, both materials have the
same electrochemical characteristic. This is not surprising,
since pressed pellets of the powders (6) or of polyaniline
from a chemical preparation (33) have nearly the same
electroactive behavior as the continuous film.
Acknowledgments
The authors wish to acknowledge the technical assist-
ance of R. Siemens, E. Hadziioannou, and J. Duran for
their technical assistance. This work was carried out while
one of us (JCL) was under sponsorship from Elf-
Aquitaine. J C L wishes to thank Professor O. Kahn for
making the necessary arrangements for this sponsorship.
Manuscript submitted Sept. 8, 1986; revised manuscript
received Jan. 6, 1988.
IBM assisted in meeting the publication costs of this ar-
ticle.
REFERENCES
1. T. Kobayashi, H. Yoneyama, and H. Tamura, J. Electro-
anal. Chem., 161,419 (1984).
2. T. Kobayashi, H. Yoneyama, and H. Tamura, ibid., 177,
281 (1984).
3. A. G. MacDiarmid, S.-L. Mu, N. L. D. Somasiri, and W.
Downloaded on 2014-10-19 to IP 155.33.16.124 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
POLYANILINE 1463
Wu, Mol. Cryst. Liq. Cryst., 121, 187 (1985).
4. E. W. Paul, A. J. Ricco, and M. S. Wrighton, J. Phys.
Chem., 89, 1441 (1985).
5. A. F. Diaz and J. A. Logan, J. Electroanal. Chem., 111,
111 (1980).
6. A. Kitani, J. Izumi, J. Yano, Y. Hiromoto, and K. Sas-
aki, Bull. Chem. Soc. Jpn., 57, 2254 (1983).
7. R. Noufi, A. J. Nozik, J. White, and L. F. Warren, This
Journal, 129, 2261 (1982).
8. K. Kanazawa and R. K. Galwey, Anal. Chem., 49, 677
(1977).
9. B. Wang, J. Tang, and F. Wang, Syn. Metals, 13, 329
(1986).
10. D. Orata and D. A. Buttry, J. Am. Chem. Soc., 109, 3574
(1987).
11. T. Kobayashi, H. Yoneyama, and H. Tamura, J. Electro-
anal. Chem.~ 177,293 (1984).
12. W.-S. Huang, B. D. Humphrey, and A. G. MacDiarmid,
J. Chem. Soc. Faraday Trans. 1, 82, 2385 (1986).
13. E. M. Genies and C. Tsintavis, J. Electroanal. Chem.,
195, 109 (1985).
14. D. M. Mohilner, R. N. Adams, and W. J. Argensinger,
Jr., J. Am. Chem. Soc., 84, 3618 (1962). See references
to earlier work on the electrochemistry of aniline.
15. T. Ohsaka, Y. Ohnuki, N. Oyama, G. Katagiri, and K.
Kamisako, J. Electroanal. Chem., 161, 399 (1984).
16. W. R. Salaneck, I. Lundstrom, B. Liedberg, M.A.
Hasan, R. Erlandsson, P. Konradsson, A.G. Mac-
Diarmid, and N. L. D. Somasiri, Springer Ser. Solid
State Sci., 63, 218 (1985).
17. T. Hjertberg, W. R. Salaneck, I. Lundstrom, N. L. D.
Somasiri, and A.G. MacDiarmid, J. Polym. Sci:
Polym. Lett. Ed., 23, 503 (1985).
18. H. Kuzmany, E. M. Genies, and A. Syed, Springer Ser.,
Solid State Sci., 63, 223 (1985).
19. A. F. Diaz and K. K. Kanazawa, in " E x t e n d e d Linear
Chain Compounds," Vol. 3, J . S . Miller, Editor,
p. 417, P l e n u m Press, New York (1983).
20. K. Shigehara, N. Oyama, and F.C. Anson, J. Am.
Chem. Soc., 103, 2552 (1981).
21. S. H. Glarum and J. H. Marshall, This Journal, 134, 142
(1987).
22. E. M. Genies, A. A. Syed, and C. Tsintavis, Mol. Cryst.
Liq. Cryst., 121, 181 (1985).
23. N. Thomas and A. H. Windle, Polymer, 19, 255 (1978).
24. R . P . Burford and E. Harrauer, ibid., 24, 1001 (1983).
25. H. L. Frisa, Polym. Eng. Sci., 20, 1 (1980).
26. S. Gottesfeld, E. Ticianelli, and A. Redondo, Abstract
1395, p. 1909, The Electrochemical Society E x t e n d e d
Abstracts, Vol. 87-2, Honolulu, Hawaii, Oct. 18-23,
1987.
27. N. Oyama, Y. Ohnuki, K. Chiba, and T. Ohsaka, Chem.
Soc. Jpn. Chem. Lett., 1759 (1983).
28. R. J. Waltman, J. Bargon, and A. F. Diaz, J. Phys.
Chem., 87, 1459 (1983).
29. K. Dimroth, C. Reichardt, T. Siepmann, and F.
Bohlmann, Ann. Chem., 661, 1 (1963).
30. N. L. Allinger, M. P. Cara, D. C. DeJongh, C. R. John-
son, N. A. Lebel, and C. L. Stevens, "Organic Chem-
istry," p. 285, Worth Publishers, Inc., New York
(1971).
31. "Physical Chemistry of Organic Solvent Systems,"
A.K. Covington and T. Dickinson, Editors, p. 389,
P l e n u m Press, London and New York (1973).
32. R. L. Hand and R. R. Nelson, J. Am. Chem. Soc., 96, 850
(1974).
33. A. G. MacDiarmid, J. C. Chiang, M. Halpern, W-S.
Huang, S-L. Mu, L.D. Somasiri, W. Wu, and S.I.
Yaniger, Mol. Cryst. Liq. Cryst., 121, 173 (1984).
34. A. G. MacDiarmid, J. C. Chian, M. Halpern, W.S.
Huang, J. R . Krawczyk, R. J. Mammone, S. L. Mu,
N. L. D. Somasiri, and W. Wu, Polym. Prepr. Am.
Chem. Soc. Div. Polym. Chem., 25, 248 (1984).
35. C.M. Carlin, L. J. Kepley, and A. J. Bard, This Journal,
132, 353 (1985).