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420 Journal of The Electrochemical Society, 147 (2) 420-426 (2000)

S0013-4651(99)03-018-9 CCC: $7.00 © The Electrochemical Society, Inc.

Electrochemistry of Poly(1,5-diaminoanthraquinone) and Its Application


in Electrochemical Capacitor Materials
Katsuhiko Naoi,*,z Shunzo Suematsu,** and Ari Manago
Department of Applied Chemistry, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588, Japan

A poly(1,5-diaminoanthraquinone) [poly(DAAQ)], which is a conducting polymer condensed with 1,4-benzoquinone, was studied
electrochemically and was proposed as a new category of electrochemical capacitor material. In common nonaqueous media, the
poly(DAAQ) showed two sets of reproducible redox couples for repeated cycles. The potential window of the material was in the
range from ca. 21.5 to 11.0 V (vs. Ag/AgCl). In situ UV-visible spectroscopy suggested that the redox couple observed around
21.5 V is responsible for the quinone group and that around 11.0 V is due to the p-conjugated system. The poly(DAAQ) showed
high conductivity (0.3–2.0 Ω21 cm21) over a wide range of potential (22.0 to 0.8 V), which suggests extension of the p-conju-
gated system. It is proposed here that one can construct an electrochemical capacitor device by utilizing poly(DAAQ) as both pos-
itive and negative electrodes. We constructed the poly(DAAQ)/poly(DAAQ) electrochemical capacitor for test purposes. The
poly(DAAQ)/poly(DAAQ) electrochemical capacitor exhibited high specific energy (25–46 Wh kg21) and high specific power
(10,200–30,500 W kg21) at discharge rates from 30 to 90 C.
© 2000 The Electrochemical Society. S0013-4651(99)03-018-9. All rights reserved.

Manuscript submitted March 1, 1999; revised manuscript received September 15, 1999.

p-Conjugated conducting polymers have been investigated for use capacity (238 Ah kg21), (ii) wide potential window (ca. 2.3 V), (iii)
as electrode materials for secondary batteries1-7 and more recently, fast redox, and (iv) high electric conductivity.
electrochemical capacitors.8-12 Among them, polypyrrole, polyani- The thin film of the poly(DAAQ) was electrochemically prepared
line, and polythiophene derivatives have been studied extensively. for the investigations of its structure, electrochemical properties, and
The conducting polymers can be positively or negatively charged electric conductivity. An electrochemical capacitor using the
with ion insertion in the polymer matrix to balance the injected poly(DAAQ) films as both anode and cathode [hereafter abbreviated as
charge. This behavior is called p- or n-doping, respectively. The a poly(DAAQ)/poly(DAAQ) electrochemical capacitor] was construct-
potentials of these doping processes are determined by the electron- ed. The charge-discharge property of the poly(DAAQ)/poly(DAAQ)
ic state of p electrons. The polypyrrole and polyaniline cannot n- electrochemical capacitor was examined for its feasibility.
dope since their n-doping potential is much lower than the reduction
potential of common electrolyte solutions. Polythiophene and its Experimental
derivatives are both n- and p-dopable. Rudge et al. proposed n- and Reagent-grade DAAQ (Tokyo Kasei), tetraethylammonium per-
p-dopable polythiophene derivatives as the electrode materials for chlorate (TEAClO4, Tokyo Kasei), and trifluoroacetic acid
both the anode (p-doping) and the cathode (n-doping) in an electro- (CF3COOH, Kanto Chemicals) were used as received. Battery-grade
chemical capacitor device (type III). Such a device leads to very high propylene carbonate (PC, Mitsubishi Chemicals) was used without
specific energy and power.9,10 further purification.
The maximum charge-discharge capacity of the conventional A standard three-electrode, two-compartment electrochemical
conducting polymers is generally not higher than 100 Ah kg21. The cell was used for all the electrochemical experiments. The Pt elec-
capacity is determined entirely by the electrochemical redox reac- trode (electrode area 0.02 cm2), Pt wire, and an Ag/AgCl electrode
tion of the p-conjugated system. To increase the specific capacity, were used as working, counter, and reference electrodes, respective-
we have been attempting to combine the redox of the p-conjugated ly. Poly(DAAQ) was potentiostatically electropolymerized at
system with that of the other electroactive moieties. A hybridization 11.5 V (vs. Ag/AgCl) at the Pt electrode in a PC solution containing
of other electroactive moieties of high specific capacity, for example, 10 mM DAAQ monomer 1 0.1 M TEAClO4 1 0.5 M CF3COOH.
disulfide (S–S/S2)13,14 or quinone (Q/Q•2/Q22),15-17 into a p-con- Electropolymerization and cyclic voltammetry were employed
jugated system should give even larger specific capacity than just the on a potentiostat (PS-07, Toho Technical Research). The charge con-
mixture of them or the conducting polymer alone. As an example of sumed during electropolymerization was monitored and controlled
this hybridization, we previously introduced poly(2,29-dithiodiani- by a coulometer (model 3320, Toho Technical Research). The ob-
line) [poly(DTDA)] which has polyaniline main chains sandwiched tained poly(DAAQ) film has been characterized by Fourier trans-
by disulfide (S–S) bonds. We studied its electrochemical properties form infrared (FTIR) spectroscopy on a Perkin-Elmer System 2000.
to confirm the enhancement of the specific capacity for the material. The FTIR transmission spectra were obtained by a KBr disk method.
The redox mechanism involves both formation/cleavage of the S–S The electronic structure of the poly(DAAQ) was measured by in situ
bonds and p-doping for the p-conjugated system, both reactions UV-visible (UV-vis) spectroscopy using a MultiSpec-1500 (Shi-
occuring at almost same potential. Its feasibility as the electrode madzu) and the potentiostat.
material, for example, in rechargeable lithium batteries, was also dis- For the construction of an electrochemical capacitor, Pt substrates
cussed in the same papers.18 (electrode area 1.0 cm2) were employed for both anode and cathode.
In this study, the authors focused on another example, namely, The poly(DAAQ) films were electropolymerized on the Pt electrodes
1,5-diaminoanthraquinone (DAAQ) having a moiety of 1,4-benzo- and washed with ethanol. A 1.0 M TEAClO4/PC solution was used as
quinone condensed between two moieties of aniline. We investigat- electrolyte. A preliminary discharge test of the cell was carried out
ed poly(1,5-diaminoanthraquinone) [poly(DAAQ)], which is elec- with Nagano BTS-2004 charge-discharge equipment. All experi-
tropolymerized from DAAQ. Poly(DAAQ) has the following advan- ments were run under a nitrogen atmosphere at room temperature.
tages over conventional conducting polymers: (i) high specific
Results and Discussion
** Electrochemical Society Active Member.
Figure 1 shows FTIR spectra for a monomeric DAAQ and an as-
** Electrochemical Society Student Member. grown poly(DAAQ) obtained by electrochemical polymerization,
*z E-mail: naoi_lab@cc.tuat.ac.jp
and Table I shows their main FTIR bands and possible assignments.

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kg21, including the weight of the dopant. If the two redox reactions
occurred in the separate potential, the theoretical specific capacities
are calculated to be 80 and 107 Ah kg21 for the redox for the p-con-
jugated system and that for the quinone group, respectively.
Figure 2 shows cyclic voltammograms (CVs) for the poly(DAAQ)
film (Fig. 2a) in a TEAClO4/PC solution. The CV for the poly(DAAQ)
has two sets of redox responses, one appearing in a very negative
potential range, viz., from 20.7 to 21.8 V vs. Ag/AgCl, and the other
in a more positive range, viz., from 10.1 to 11.0 V. When the applied
potential was scanned from 0 down to 21.2 V, a reduced peak (Pc1)
and the corresponding oxidation peak appeared as shown in Fig. 2b.
As the potential was taken more negative, from 21.2 V to 21.8 V,
another reduction peak (Pc2) appeared at ca. 21.4 V (see Fig. 2c).
However, only a single oxidation peak appeared at the same potential
as observed in Fig. 2b. To investigate the redox behavior of the
poly(DAAQ) in Fig. 2c, CVs for two reference compounds, namely,
an anthraquinone (Fig. 2d) and a DAAQ monomer (Fig. 2e), were
obtained and compared with that of poly(DAAQ). Both these CVs
give two consecutive redox couples in more or less the same potential
range (from 21.0 to 21.5 V) as the poly(DAAQ) in Fig. 2c. These two
kinds of redox responses are considered to correspond to the quinone
group, which is the common redox site in these three compounds. By
analogy with the redox responses of the reference compounds, the
poly(DAAQ) has a two-electron process involving a quinone/quinone
radical anion (Q/Q•2) process at PC1 which is followed by a radical
anion/dianion (Q•2/Q22) conversion at PC2. As shown in Fig. 2c, no
oxidation peak corresponding to the Q22 couple was observed, but an
increase in current density of the oxidation peak corresponding to the
Q•2 couple was observed upon comparing the CV in Fig. 2b. The be-
havior suggests that the quinone dianion species (formed by the elec-
trochemical reduction at the potential of Pc2) are very likely to be
chemically modified to produce some form of species. The species is
Figure 1. FTIR transmission spectra for (a) monomeric DAAQ and (b) elec- (are) electrochemically oxidized at the potential of Pc1, leading to the
tropolymerized poly(DAAQ) using the potassium bromide (KBr) disk increase in the first oxidation peak. It is speculated that the chemical-
method. ly modified species could be the Q•2 formed from the electrochemi-
cally reduced Q22 species. The Q22 species are speculated to be
chemically oxidized or reacted to three possible species as follows
Absorption peaks at 1580, 1500, and 1100 cm21 are attributed to the
structure of quinoid, benzenoid, and perchlorate anions (ClO2 4 ), Q22 1 (2)H1 r HQ2(H2Q) [1]
respectively. These assignments suggest that the DAAQ was poly-
merized mainly at 1,4 and 5,8 positions, the bonding manner of
which is similar to that of an electroactive polyaniline having head- Q22 1 Q r 2Q•2 [2]
to-tail structure.21-26 An absorption peak at 1610 cm21, attributed to
C5O bonding, is observed in the spectrum for the poly(DAAQ) as Q22 1 O2 r Q•2 1 O•2
2 [3]
well as in that for the monomeric DAAQ. With such a structural
feature of poly(DAAQ), two types of redox reactions are expected to The hydroquinone formed through Reaction 1 cannot be electro-
occur in the polymer, viz., the redox reaction for the p-conjugated chemically oxidized in the potential range from 0 to 21.8 V. Thus,
system and that for the quinone groups. Assuming that the Reaction 1 is a failure mode. In contrast, Reactions 2 and 3 are not
poly(DAAQ) exchanges three electrons, viz., both redox of the p- failure modes, because the chemically formed Q•2 species are elec-
conjugated system and the quinone groups occurred in the same trochemically oxidized in the same potential range. In order to inves-
potential, the theoretical specific capacity is calculated to be 238 Ah tigate the loss of charge due to a failure mode, a charge balance (a

Table I. Main FTIR peaks of monomeric DAAQ and electropolymerized poly(DAAQ) and their possible assignments.

Possible assignments Monomeric DAAQ Poly(DAAQ)

C5O (quinone) 1610 1610


C5N stretch (quinoid structure) 1580
N–H deformation 1550 (Primary amine) 1500 (Secondary amine)
C–N stretch 1290 1250
N–H stretch
gasym(NH2) 3410 (Strong)
gsym(NH2) 3310 (Strong) 3170 (Weak)
N–H stretch (secondary amine) 3430
C–H out-of-plane bending vibration
of 2H 1850 1830
of 3H 1710-810 1710-820
ClO24 (dopant anion) 1100

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422 Journal of The Electrochemical Society, 147 (2) 420-426 (2000)
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charge ratio of oxidation to reduction) is calculated to be 95%. The


value suggests that 5% of the charge is lost due to a failure mode,
which may lead to deterioration of the cycle life.
We now focus on another redox observed in the higher potential
range (0–1.0 V) in Fig. 2a. The redox involves two sets of oxidation-
reduction waves. Similar response was observed when the scanning
potential was restricted from 0 to 11.0 V (see Fig. 2f). No such re-
sponse was observed in the CVs (see Fig. 2d and 2e) for the an-
thraquinone and monomeric DAAQ in the same potential range.
FTIR spectroscopy confirms that the structure of poly(DAAQ) in-
volves that of the electroactive polyaniline.21-26 Thus, the responses
for the poly(DAAQ) in the higher potential range may be attributed
to the redox reactions for the π-conjugated system in the polymer.
A good cyclability was observed in Fig. 2b (102–103 cycles) and
2f (>103 cycles). The two sets of redox couples for the poly(DAAQ)
were separated each other by ca. 2.3 V. An electrochemical capaci-
tor using poly(DAAQ) as both anode and cathode may well have a
potential window of ca. 2.3 V, while that for n- and p-dopable poly-
thiophene derivatives have from 2.8 to 2.9 V.30

Figure 3. (a) In situ UV-vis spectra for the poly(DAAQ) in the potential range
21.8 to 0 V and (b) absorbance at 670 nm replotted by the results from (a) vs.
potential. Electrolyte solution 0.1 M TEAClO4/PC, scan rate 10 mV s21.

To confirm the redox reactions for the poly(DAAQ), the electron


structure for the poly(DAAQ) was estimated with in situ UV-vis
spectroscopy. Figure 3a shows the UV-vis spectra for the
poly(DAAQ) in the potential range from 0 to 21.8 V. Absorption
peaks at ca. 670 nm were observed at each potential. These peaks
may be attributed to the radical species of the quinone groups.19,20
The absorbance at 670 nm is plotted against the potential as shown
in Fig. 3b. As the potential is taken further negative, an increase in
the absorbance was observed. When the potential is taken further
negative than 21.4 V, the peak strength remains essentially constant.
This result suggests that the Q•2 species exist even at the potential at
which the Q22 species form.
The redox mechanism for the negative potential response is sum-
marized in Scheme 1. At potentials more positive than ca. 0 V, the
quinone groups of the poly(DAAQ) are most likely the neutral
quinone (Q) species such as structure A. In the potential range from
0 down to PC1, the Q species are partly reduced into the Q•2 species.
In the potential range from PC1 down to PC2, the structure B is
reduced to form some Q22 species (see structure C). The amount of
the Q•2 species of the structure C is considered equal to that of the
structure B. In the states of structures B and C, the cations in an elec-
trolyte compensate for the negative charges of the Q•2 and/or Q22
species.
Figure 4a shows the UV-vis spectra for the poly(DAAQ) in the
potential range 0 to 11.0 V. The absorption peaks at ca. 520 and 640
nm were observed at each potential. The absorbance peaks at 640 nm
are plotted against the potential as shown in Fig. 4b. As the potential
is taken further positive than 0 V, the absorbances for the peaks in-
Figure 2. CVs for the poly(DAAQ) film at a potential range of (a) 21.8 to crease. As the potential is taken further positive than ca. 0.7 V (Pa1),
11.0, (b) 0 to 21.3, (c) 0 to 21.8, and (f) 0 to 11.0 V. (d) The anthraquinone the peak strength remains essentially constant. Since this peak is
(21.8 to 11.0 V) and (e) the monomeric DAAQ (21.8 to 11.0 V) in 0.1 M caused by the formation of radical cation (polaron) in the p-conju-
TEAClO4/PC. Substrate Pt, scan rate 10 mV s21. gated system of the poly(DAAQ), the polaron concentration may be

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Journal of The Electrochemical Society, 147 (2) 420-426 (2000) 423
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Figure 4. (a) In situ UV-vis spectra for poly(DAAQ) at the potential range 0 to
11.0 V and (b) absorbance at 640 nm replotted by the results from (a) vs.
potential. Electrolyte solution 0.1 M TEAClO4/PC. scan rate 10 mV s21.

It has been well established that conventional p-conjugated con-


ducting polymers such as polyaniline, etc., become insulating at the
lower potential range less than ca. 0 V. 27,28 The occurrence of redox
response of the poly(DAAQ) at the reduced state is a peculiar fea-
Scheme 1. Speculated redox reactions for the poly(DAAQ) at more negative ture. This suggests that the poly(DAAQ) film has high conductivity,
potential than 0 V. even at the reduced states.
In a separate experiment, the four-point probe method was used
to measure the conductivity of the poly(DAAQ) at several potentials
between 22.0 and 0.8 V. The plot of conductivity of the poly(DAAQ)
considered to increase with an increase in the potential, and the con- film vs. the potential obtained by this experiment are shown in Fig. 5.
centration is almost constant in the potential range from Pa1 to Pa2. Conductivity values from 0.3 to 2.0 Ω21 cm21 (S cm21) in the
The redox reactions for the p-conjugated system are shown in potential range from 22.0 to 0.8 V were obtained. These values are
Scheme 2. We suggest that the reactions basically resemble those for much higher than those of the polyaniline at the reduced states. We
the electroactive polyaniline in the nonaqueous solution.29 In the suppose that there are two main factors for the higher conductivity of
first oxidation process, the poly(DAAQ) is oxidized to form the rad- the poly(DAAQ) in the lower potential range. One is that the p elec-
ical cations (polarons) at the polyaniline structure, and the anions in trons in the poly(DAAQ) are delocalized at the reduced states
the electrolyte are considered to compensate the positive charges (p- because the radical anion species in the quinone group behave as the
doping). Since it is reported that the polyaniline is not fully p-dop- charge carriers. The radical anion species exist even at the more neg-
ing in the oxidation process, the structure of the poly(DAAQ) after ative potential than Pc2 due to the electron exchanges in the same
the first oxidation is considered to have structure D in Scheme 2. In macromolecules. The other is the structural factor, that is, two- or
the second oxidation, structure D is oxidized to form the imine struc- three-dimensional expansion of the p-conjugated system. Since the
ture in some places, produced with anion insertion. The polaron con- poly(DAAQ) is polymerized at mainly 1,4 and 5,8 positions, the p-
centration of the poly(DAAQ) in the second oxidation state is near- conjugated system expands not only in the direction of the polyani-
ly equal to that in the first state, which is different from the case of line structure but also in the direction of the quinone groups. In other
the polyaniline. Thus, the structure of E is formed after the oxidation words, the p-conjugated system expands in two dimensions. Fur-
of that of D. thermore, it is reported that the structure of oxidized DAAQ

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424 Journal of The Electrochemical Society, 147 (2) 420-426 (2000)
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monomers involves both p-p stacking and hydrogen bonding.29


Assuming that the poly(DAAQ) has the same structure, its p-elec-
trons can undergo both interchain and intrachain movement. In other
words, p-electrons move three-dimensionally.
By using the poly(DAAQ) films as both anode and cathode, one
can construct a novel type of electrochemical capacitor device
(capacitor A) as shown in Fig. 6a. The charge-discharge tests for the
practically constructed capacitor A were run at the charge and dis-
charge current density from ca. 0.3 to 1.0 mA cm22 (the rate from
ca. 30 to 90 C rate). Figure 7 shows a typical discharge curve for
capacitor A (the discharge density is 0.3 mA cm22). The shapes of
the discharge curve for the capacitor A are similar to those for the
electrochemical capacitors (so called type III electrochemical capac-
itors) using n- and p-dopable polythiophene derivatives as both
anode and cathode. Figure 8 shows a Ragone plot for capacitor A in
which it exhibited specific energy and power from 25 to 46 Wh kg21
and from 10,200 to 30,500 W kg21, respectively. The values were
more or less than that (specific energy and power from ca. 20 to
Figure 5. Electric conductivity for poly(DAAQ) at several potentials be-
tween 22.0 and 0.8 V obtained by the four-point probe method.

50 Wh kg21 and from 2000 to 20,000 W kg21, respectively) for the


electrochemical capacitors based on polythiophene derivatives.33

Figure 6. Charge/discharge mechanism for electrochemical capacitors using


(a) poly(DAAQ) as both anode and cathode (capacitor A) and (b)
Scheme 2. Speculated redox reactions for poly(DAAQ) at more positive poly(TMAPT) anode and poly(DAAQ) cathode (capacitor B) in nonaqueous
potential than 0 V. solutions.

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Figure 7. The discharge curve for capacitor A (electrolyte solution 1 M TEA- Figure 8. Ragone plot for capacitor A at the range of discharge current den-
ClO4/PC). The charge and discharge current density 0.3 mA cm22. sity from 0.3 to 1.0 mA cm22 (the rate from ca. 30 to 90 C).

The values were calculated on the basis of active materials including and that for the quinone groups, and that the electrochemical win-
anode and cathode, not including electrolyte. These values were dow was ca. 2.3 V. The poly(DAAQ) has high conductivity even at
compared to the type III electrochemical capacitors.31,32 Uptaking the reduced states due to the presence of charge carriers in a wide
anions and cations into both electrodes during the charging process potential range and to the two- or three-dimensional expansion of the
consumes the electrolyte in the solution. Hence, the construction of p-conjugated system. By using the poly(DAAQ) films as both anode
capacitor A is an electrolyte-consuming system. Many other combi- (redox of the quinone group) and cathode (redox of the p-conjugat-
nations are possible to construct an electrochemical capacitor which ed system), one can construct a novel type of electrochemical capac-
is not electrolyte consuming. As shown in Fig. 6b, an anion-shuttle itor device. The poly(DAAQ)/poly(DAAQ) capacitor exhibited high
capacitor (capacitor B) can be constructed using the poly(DAAQ) specific energy and power from 25 to 46 Wh kg21 and from 10,200
film as a cathode and an anion-exchanging (self n-doping) polymer to 30,500 W kg21, respectively. By combining the poly(DAAQ)
anode, for example, a poly(3-[4-trimethylaminophenyl]thiophene) cathode with the other anion-exchanging conducting polymer anode,
(poly(TMAPT)) film which has been proposed by Ferraris.33 Such a one could construct an electrochemical capacitor which is not elec-
construction is more advantageous than capacitor A with respect to trolyte consuming. In this sence, the poly(DAAQ) film can also
specific energy and power. Capacitor B is not electrolyte consuming. serve as a polymer cathode in rechargeable polymer battery systems.
The specific capacity of capacitor B is calculated to be max 16 Ah
kg21 per cell including anode, cathode, and electrolyte of 1 M solu- Acknowledgment
tions.34 The value for capacitor B is ca. 1.2 times larger than that of
capacitor A (13 Ah kg21 per cell). As for capacitor B, the working A part of this study was financially supported by a Grant-in-Aid
voltage is calculated to be ca. 3.5 V from the redox potentials of the for Scientific Research (A) from the Ministry of Education, Science,
poly(DAAQ) (11.0 V vs. Ag/AgCl) and poly(TMAPT) (22.5 V vs. Sports and Culture of Japan, project no. 10,131,219 (1998-1999).
Ag/AgCl). The working voltage for capacitor B is ca. 1.5 times
wider than that (ca. 2.3 V) of capacitor A. From the values of the Tokyo University of Agriculture and Technology assisted in meeting the
specific capacities and the working voltages, the specific energies publication costs of this article.
for capacitor B and A are calculated to be 57 Wh kg21 and 31 Wh
kg21, respectively. References
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426 Journal of The Electrochemical Society, 147 (2) 420-426 (2000)
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