JP2001118577A - Method for manufacturing electrode including indole base high polymer and secondary cell using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an indole base high polymer electrode for secondary cell having superior self discharging characteristics. SOLUTION: This secondary cell 10 is constituted by replacing the dopant incorporated in a high polymer with the dopant of anion, whose molecular weight is below 140 per electric charge capacity using polymerization of indole group polymers, laminating positive electrode material 4 which was coated on the charge collection body 1a, by mixing conductive aid agent and electrolyte with the above material and a negative electrode material 4, which was coated on the charge collection body 1b and has electrolyte impregnated inside with a separator 3 between them, and sealing the cell with a gasket 5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an electrode containing a conductive polymer and a secondary battery using the same, and more particularly to a method for producing an electrode containing an indole polymer as a conductive polymer and using the same. Related to the secondary battery that was used.

[0002]

2. Description of the Related Art Conventionally, a polymer secondary battery using a conductive polymer such as polyaniline or a quinone-based polymer as an active material for a positive electrode material or a negative electrode material has been disclosed in JP-A-6-302316 and JP-A-11-126609. Etc. In addition to these conductive compounds, attempts have been made to use indole polymers as electrode materials for polymer batteries.

[0003]

The indole polymer has a high oxidation-reduction potential of 900 to 1200 mV (based on a silver-silver chloride standard electrode (hereinafter referred to as an Ag / AgCl standard electrode standard)) and a theoretical capacity. The cathode active material is as large as 96 mAh / g, which is a very good cathode active material. There were drawbacks.

The present inventor has found that the use of an indole polymer having a small anion having a molecular weight per charge of 140 or less as a dopant solves the above-mentioned drawbacks of the electrode using the indole polymer. This has led to the present invention.

It is an object of the present invention to provide a secondary battery using an indole polymer as an active material for an electrode and using protons as charge carriers.

[0006]

According to the present invention, there is provided a method for producing an electrode containing an indole polymer, wherein the indole polymer is formed by chemical or electrolytic polymerization of an indole compound. After exchanging the dopant with an anionic dopant having a molecular weight per charge of 140 or less, the polymer is formed on the first current collector.

The indole polymer used in the present invention is represented by the following chemical formula.

[0008]

Embedded image

R is a hydrogen atom, a halogen atom, a nitro group,
Represents a group such as a cyano group, an amino group, and a sulfone group.

[0010] In the present invention, a conductive additive made of at least one carbon material selected from graphite, carbon black, acetylene black and carbon fiber is added to the indole polymer formed on the current collector. In addition, the conductivity of the indole polymer electrode can be improved.

In the present invention, the method of exchanging the dopant in the indole polymer formed by chemical polymerization or electrolytic polymerization with a dopant of the anion having a molecular weight per charge of 140 or less includes the chemical polymerization or the anion. After treating the electrolytically polymerized indole-based polymer with an aqueous alkali solution, a chemical treatment method of treating the indole-based polymer with an acidic aqueous solution containing the anion having a molecular weight per charge of 140 or less or the indole-based polymer with a molecular weight per charge Is 1
An electrochemical treatment method in which an oxidation-reduction treatment is performed in an acidic aqueous solution containing 40 or less of the above anions can be used.

[0012] The secondary battery of the present invention comprises a positive electrode material comprising an electrode in which an electrolyte is impregnated into an indole polymer formed on the first current collector, and a second electrode comprising: Film,
A negative electrode material impregnated with the electrolytic solution is laminated via a separator such that the electrode material is on the inside.

[0013] The secondary battery of the present invention is prepared by using a chemical or electrochemical method to intentionally inject an indole polymer, which is an active material of a positive electrode, into a dopant of 140 or less per charge using a chemical or electrochemical technique. By changing to a small dopant composed of an anion having a molecular weight, expansion and contraction of the positive electrode material can be suppressed, and a secondary battery having excellent self-discharge characteristics and cycle characteristics can be provided.

[0014]

Next, embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 is a structural sectional view of a secondary battery using an indole polymer according to an embodiment of the present invention as a positive electrode material. In the figure, reference numerals 1a and 1b denote current collectors made of a conductive rubber or the like, 2 denotes a mixture of an indole polymer to which a dopant (anion) having a molecular weight per charge of 140 or less is added, a conductive auxiliary and an electrolytic solution. A positive electrode material is formed on the current collector 1a, 3 is a separator impregnated with an electrolytic solution, and 4 is a negative electrode material.
In the secondary battery 10, the gasket 5 is disposed on the side surface, and the current collector 1a on which the positive electrode material 2 is formed and the current collector 1b on which the negative electrode material 4 is formed are disposed above and below the gasket 5 via the separator 3 and heated. It is configured to be pressurized and integrated.

The indole polymer used for the electrode (positive electrode) according to the embodiment of the present invention is represented by the following chemical formula.

[0016]

Embedded image

In the above formula, R is a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amino group, a sulfone group or the like, but is not limited thereto.

The polymerization of the indole polymer is carried out by chemically or electrochemically oxidizing an organic compound having an indole skeleton or a similar structure. After polymerization, the dopant is chemically or electrochemically exchanged. It is possible.
Chemically, after doping treatment with an alkali solution, the type of dopant can be changed by re-doping treatment using an acid solution. As the alkaline solution, a solution having a pH of 10 or more such as an aqueous solution of sodium hydroxide (NaOH) or an aqueous solution of potassium hydroxide (KOH) is preferable. Examples of the acid solution include a sulfuric acid aqueous solution, a nitric acid aqueous solution, and perchloric acid (HCl
O ₄₎ solution, borofluoride hydrochloric acid (HBF _4), but such an aqueous solution and the like, the molecular weight per charge anions 140
The following is assumed. Further, electrochemically, by repeating the oxidation-reduction reaction of the indole-based polymer, anions in the solution are taken in and the dopant species can be changed. Examples of the solution include an aqueous solution of sulfuric acid, an aqueous solution of nitric acid, and an aqueous solution of perchloric acid. As in the case of the chemical dopant exchange treatment, the molecular weight per anion is 140 or less.

When the resistance of the cathode material of the indole polymer is high, a conductive auxiliary made of a carbon material such as graphite, carbon black, acetylene black or carbon fiber can be added to increase the conductivity.

As the negative electrode material, a conductive polymer such as polyquinoxaline to which a dopant has been added can be used, and a conductive auxiliary of the above-mentioned carbon material is added thereto, and an electrolyte is mixed to form a film on the current collector. Is done.

The separator may be a porous insulating film, a solid electrolyte, a gel electrolyte, etc., as long as it has conductivity of protons or other ions involved in redox and electrically insulates the positive electrode and the negative electrode. .

The electrolyte may be in a liquid, solid, or gel state as long as it can supply protons or other ions involved in redox. The anion ion preferably has a molecular weight of 140 or less, such as sulfuric acid. Can be used.

The indole polymer causes a two-step reaction given by the following reaction formulas (1) and (2).

[0024]

(Equation 1)

[0025]

(Equation 2)

FIG. 2 shows a cyclic voltammogram obtained when the indole polymer was polarized in 4 M sulfuric acid. The reaction given by the reaction formula (1) is mainly 200 to 800 mV
On the low potential side (based on the Ag / AgCl standard electrode), the reaction given by the reaction formula (2) is mainly 800 to 1200 m
Occurs on the high potential side of V (based on the Ag / AgCl standard electrode). In the reaction formula (1), at the time of charging, the anion (X ⁻ )
Doping and emission of electrons (e ⁻ ) occur. Further, since the anion is doped between the main chains of the indole polymer, the space between the main chains expands, and the volume of the electrode expands. At the time of discharging, a phenomenon opposite to that at the time of charging occurs, and the anion is eliminated from between the main chains of the indole polymer, so that the space between the main chains is narrowed and the volume of the electrode is reduced.

In the reaction formula (2), the proton (H
⁺ ) And the emission of electrons (e ⁻ ) occur. The proton has a smaller ionic radius than the dopant anion, the space between the polymer main chains hardly changes, and no expansion of the electrode is observed.

These reaction formulas (1) and (2)
Is basically a reversible reaction and can be used as an active material of a secondary battery.

In the above, since the discharge reaction in the reaction formula (2) proceeds by adsorption of protons to the electrode, the state of charge is unstable in an acidic solution having a high proton concentration, self-discharge is large, and There was a problem when used. In addition, due to the expansion and contraction of the electrode seen in the reaction formula (1), there is a problem that the capacity of the secondary battery is significantly reduced after 10,000 cycles or more.

In the present invention, by setting the molecular weight per charge of the dopant anion to 140 or less, a secondary battery having excellent self-discharge characteristics and cycle characteristics can be provided.

In the above reaction formula (2), protons are desorbed during the charge reaction, and protons are adsorbed during the discharge reaction. When the reaction formula (2) proceeds, the dopant anion (X ⁻ ) has already been doped in the indole polymer. By limiting the molecular weight per charge of the dopant anion (X ⁻ ) to 140 or less, the spread between the indole-based polymer main chains can be suppressed. As a result, the entry of protons is restricted, the discharge reaction of the reaction formula (2) is less likely to occur, and the electrode retains electric potential. Therefore, it is possible to provide a secondary battery which is excellent in characteristics with small self-discharge.

When an indole polymer is used as a positive electrode material for a battery, the reaction formula (2) on the high potential side is mainly used.
However, the reaction formula (1) does not occur at a completely independent potential, and the reaction formula (2) does not occur at a completely independent potential. The reaction formula (2) shown in FIG. 2 has a region of 800 to 1200 mV (based on an Ag / AgCl standard electrode). Even when the charge and discharge are performed at the potential, the reaction formula (1) partially proceeds at the same time. Therefore, the charge and discharge are represented by the reaction formula (2).
Even when the potential region is limited to the above range, the volume of the electrode changes due to doping and undoping of the dopant anion shown in the reaction formula (1). Therefore, by limiting the dopant in the indole-based polymer or the anion in the electrolytic solution so that the molecular weight per charge is 140 or less, it is possible to suppress a change in the volume of the electrode, and to improve the cycle characteristics. A secondary battery can be provided.

Next, the embodiments of the present invention will be described in detail. However, the structure and the constituent materials of the battery are not limited to those described here. (Example 1) Poly-5-cyanoindole was polymerized using 5-cyanoindole as a starting material, cupric trifluoromethanesulfonate as an oxidizing agent, and acetonitrile as a solvent. 10 wt% of crystalline carbon was added to the obtained polymer, N, N'-dimethylformamide was added to form a paste, and a film was formed on a carbon sheet and dried to prepare a re-doping electrode. This electrode was polarized 50 times at 0 to 1000 mV (based on an Ag / AgCl standard electrode) in a 1M aqueous solution of ammonium hydrochloride to exchange the dopant. By this operation, the dopant of poly-5-cyanoindole is converted from trifluoromethanesulfonate ion to chloride ion (Cl ⁻ : molecular weight of 35.5 per charge).
Changed to 5).

The mixture of poly-5-cyanoindole and crystalline carbon was peeled off from the electrode for re-doping, and 4 M sulfuric acid was added to the washed and dried powder to form a paste. This was used as a positive electrode material of a battery.

As the negative electrode material, polyphenylquinoxaline represented by the following chemical formula was used.

[0036]

Embedded image

Similarly to the positive electrode, 10 wt% of crystalline carbon was added to the polyphenylquinoxaline, and 4M sulfuric acid was mixed to form a paste to prepare a negative electrode material paste.

After forming a paste of these positive electrode material and negative electrode material on a conductive rubber (current collector) with a gasket having a thickness of 500 μm, a pressure of 14 kgf / cm ² was applied to remove excess sulfuric acid. To form an electrode. These electrodes were opposed to each other via a separator impregnated with sulfuric acid and sealed with a gasket to obtain a battery shown in FIG.

The produced battery was charged to 1.2 V at a current density of 10 mA / cm ² , and then the battery was left in an open circuit state, and the voltage change was measured for 24 hours. FIG. 3 shows the change with time of the voltage. In the battery obtained by the method of Example 1, the change in voltage was small, and almost no self-discharge was observed.

Next, after holding in an open circuit for 24 hours,
The battery was discharged at 0 mA / mA / cm ² and the discharge capacity was determined.
The measurement results of the discharge capacity are shown in Table 1. As for the battery of this example (Example 1), a remaining capacity of 22.4 mAh / g was obtained.

Further, in order to examine the cycle characteristics of the batteries fabricated in the process of this Example 1 was charged at a current density of 10 mA / cm ² to 1.2V, 0.8 V at a current density of 10 mA / cm ² Discharge was carried out until. This is one cycle. This charge / discharge cycle was repeated to measure the change in capacity. FIG. 4 shows the remaining capacity ratio for each cycle, with the initial capacity being 100%. The battery manufactured by the manufacturing method of Example 1 has a capacity of 85% or more of the initial capacity even after 30,000 cycles, indicating that a battery having extremely excellent cycle characteristics can be manufactured. Was. It was found that the voltage change and the residual capacity of this embodiment are considerably superior to those of Examples 1 and 2 shown below.

Example 2 In the same manner as in Example 1, poly-5-cyanoindole was polymerized. The obtained polymer was stirred in a 2M aqueous NaOH solution for 30 minutes at room temperature, and trifluoromethanesulfonic acid ion as a dopant was dedoped. After the polymer was filtered and washed,
The mixture was stirred at room temperature for 30 minutes in a 5M aqueous solution of LiClO ₄ to re-dope perchlorate ions. With this operation,
The dopant for poly-5-cyanoindole is trifluoromethanesulfonate ion to perchlorate ion (Cl
O ₄ ⁻ : molecular weight per charge 99.5).
10 wt% of crystalline carbon was added to the poly-5-cyanoindole that had been subjected to the re-doping treatment, and 4 M sulfuric acid as an electrolytic solution was mixed to form a paste.

In the negative electrode material, 10 wt.
A battery was manufactured in the same procedure as in Example 1 using polyphenylquinoxaline to which% crystalline carbon was added.

The prepared battery was charged to 1.2 V at a current density of 10 mA / cm ² , and then the battery was left in an open circuit state, and the voltage change was measured for 24 hours. The change over time of the voltage is shown by the curve of Example 2 in FIG. In addition, Table 1 shows a list of the remaining capacity after being held in the open circuit for 24 hours.

The battery manufactured by the method of Example 2 had a slight decrease in voltage and remaining capacity after 24 hours as compared with Example 1, but was considerably superior to the comparative example shown below. According to the manufacturing method of this example, a battery having excellent self-discharge characteristics could be manufactured.

Example 3 In the same manner as in Example 1, poly-5-cyanoindole was polymerized. 10 wt% of crystalline carbon was added to the obtained polymer, and N, N ′ was added.
-Dimethylformamide was added to form a paste, formed into a film on a carbon sheet, and dried to prepare a re-doping electrode.
This electrode was placed in a 0.5 M HBF ₄ aqueous solution for 0-100.
Polarization was performed 50 times at 0 mV (based on an Ag / AgCl standard electrode) to exchange the dopant. By this operation, the dopant of poly-5-cyanoindole was changed from trifluoromethanesulfonate ion to tetrafluoroboron ion (BF4 ₋ : molecular weight per charge: 86.8).

The mixture of poly-5-cyanoindole and crystalline carbon was peeled off from the electrode for re-doping, and 4 M sulfuric acid was added to the washed and dried powder to form a paste. This was used as a positive electrode material for a battery.

The negative electrode material was 10 wt.
A battery was manufactured in the same procedure as in Example 1 using polyphenylquinoxaline to which% crystalline carbon was added.

The prepared battery was charged to 1.2 V at a current density of 10 mA / cm ² , and then the battery was left in an open circuit state, and the voltage change was measured for 24 hours. FIG. 3 (see the curve of Example 3) shows the change with time of the voltage. In addition, Table 1 shows a list of the remaining capacity after being held in the open circuit for 24 hours.

The battery manufactured by the method of the third embodiment has a capacity of 24
Both the voltage and the remaining capacity after the time were equivalent to those of Example 1 and were excellent. According to the manufacturing method of this example, a battery having excellent self-discharge characteristics could be manufactured.

Example 4 Poly-6-nitroindole was polymerized using 6-nitroindole as a starting material, cupric trifluoromethanesulfonate as an oxidizing agent and acetonitrile as a solvent. The obtained polymer was stirred at room temperature for 30 minutes in a 2M aqueous NaOH solution to dedope trifluoromethanesulfonic acid ion as a dopant. After filtering and washing the polymer, 0.5M concentration LiC
The mixture was stirred in an aqueous solution of 104 for 30 minutes at room temperature, and was re-doped with perchlorate ions. By this operation, the dopant of poly-6-nitroindole was changed from trifluoromethanesulfonate ion to perchlorate ion (ClO 4 ⁻ : molecular weight per charge 99.5). 10 wt% of crystalline carbon was added to the poly-6-nitroindole which had been subjected to the re-doping treatment, and 4 M sulfuric acid as an electrolytic solution was mixed to form a paste.

In the negative electrode material, 10 wt.
A battery was manufactured in the same procedure as in Example 1 using polyphenylquinoxaline to which% crystalline carbon was added.

The prepared battery was charged to 1.2 V at a current density of 10 mA / cm ² , and then the battery was left in an open circuit state, and the voltage change was measured for 24 hours. FIG. 3 shows the change with time of the voltage. In addition, Table 1 shows a list of the remaining capacity after being held in the open circuit for 24 hours.

In Example 4, unlike other Examples or Comparative Examples, poly-6-nitroindole was used as the positive electrode active material. The change with time of the voltage shown in FIG.
And the residual capacity after 24 hours showed a value equivalent to that of the example, which was superior to comparative examples 1 and 2 shown below. According to the manufacturing method of Example 4, a battery having excellent self-discharge characteristics could be manufactured.

Comparative Example 1 Polymerization of poly-5-cyanoindole was carried out in the same manner as in Example 1. Dedoping and re-doping of the obtained polymer were not particularly performed. Therefore, the dopant is trifluoromethanesulfonic acid ion (CF ₃ SO ₃ ⁻ : molecular weight per charge 149). 10 wt% of crystalline carbon was added to the poly-5-cyanoindole, and 4 M sulfuric acid as an electrolyte was mixed to form a paste.

As in Example 1, 10 wt.
A battery was manufactured in the same procedure as in Example 1 using polyphenylquinoxaline to which% crystalline carbon was added.

The fabricated battery was charged to 1.2 V at a current density of 10 mA / cm ² , and then the battery was left in an open circuit state, and the voltage change was measured for 24 hours. FIG. 3 shows the change with time of the voltage. In Comparative Example 1, the voltage drop was large and the self-discharge characteristics were inferior to Examples 1 to 4.
The voltage after 24 hours was 200 to 3 in comparison with Examples 1 to 4.
00mV lower.

After holding for 24 hours in an open circuit,
The battery was discharged at 0 mA / mA / cm ² and the discharge capacity was determined.
Table 1 shows a list of discharge capacities. The discharge capacity after holding in the open circuit state for 24 hours was about half as compared with Examples 1-4.

Comparative Example 2 Poly-5-cyanoindole was polymerized in the same manner as in Example 1. The obtained polymer was stirred at room temperature for 30 minutes in a 2M aqueous NaOH solution to dedope trifluoromethanesulfonic acid ion as a dopant. After filtering and washing the polymer, 10w
The mixture was stirred in a t% aqueous solution of poly-styrene sulfonic acid for 30 minutes at room temperature, and red-doped with poly-styrene sulfonic acid ions. By this operation, the dopant of poly-5-cyanoindole is converted from trifluoromethanesulfonic acid ion to poly-styrenesulfonic acid ion (CH (CH ₂ ) C ₆
H ₄ SO ₃ ⁻ : molecular weight per charge 183). 10 wt% of crystalline carbon is added to the poly-5-cyanoindole which has been subjected to the re-doping treatment, and 4M as an electrolytic solution is added.
The sulfuric acid was mixed into a paste.

As in the case of Example 1, 10 wt.
A battery was manufactured in the same procedure as in Example 1 using polyphenylquinoxaline to which% crystalline carbon was added.

The fabricated battery was charged to 1.2 V at a current density of 10 mA / cm ² , and then the battery was left in an open circuit state, and the voltage change was measured for 24 hours. FIG. 3 shows the change with time of the voltage. In Comparative Example 2, the voltage drop was large and the self-discharge characteristics were inferior to Examples 1 to 4.

After holding for 24 hours in an open circuit,
The battery was discharged at 0 mA / mA / cm ² and the discharge capacity was determined.
Table 1 shows a list of discharge capacities. The discharge capacity after holding in the open circuit state for 24 hours was less than half that of Examples 1-4.

Comparative Example 3 Poly-5-cyanoindole was polymerized in the same manner as in Example 1. 10 wt% of crystalline carbon was added to the obtained polymer, and N, N ′ was added.
-Dimethylformamide was added to form a paste, formed into a film on a carbon sheet, and dried to prepare a re-doping electrode.
The electrode was placed in a 1M aqueous solution of ammonium chloride at 0 to 1%.
Polarization was performed 50 times at 000 mV (based on an Ag / AgCl standard electrode) to exchange the dopant. By this operation, the dopant of poly-5-cyanoindole is converted from trifluoromethanesulfonic acid ion to chloride ion (Cl ⁻ :
The molecular weight per charge was changed to 35.5). The poly-5-cyanoindole and the crystalline carbon mixture are peeled off from the electrode for re-doping, and the washed and dried powder is added in an amount of 10 wt.
% Poly-styrenesulfonic acid aqueous solution was added to form a paste. This was used as a positive electrode material for a battery. As the negative electrode material, polyphenylquinoxaline to which 10% by weight of crystalline carbon was added as in Example 1 was used, and 10% by weight was used.
% Poly-styrenesulfonic acid aqueous solution was added to form a paste.

Thereafter, a battery was prepared in the same manner as in Example 1, except that the electrolytic solution was changed from 4M sulfuric acid (anion was SO ₄ ²⁻ , and the molecular weight per charge was 96) to 10 wt% poly-styrenesulfonic acid (anion). Is CH (CH ₂ ) C ₆ H ₄ SO ₃
^- , The molecular weight per charge has been changed to 183).

The battery fabricated in Comparative Example 3 was charged at 10 mA / c
It was charged to 1.2V at a current density of m ^2, 10 mA /
Discharge was performed to 0.8 V at a current density of cm ² . This is one cycle. By repeating this charge / discharge cycle,
The change in capacity was measured. FIG. 4 shows the results.

The battery manufactured in Comparative Example 3 had 20,000
Cycles reduced capacity by 20% and 30,000 cycles reduced capacity by 45%. The battery manufactured in Example 1 was 3000
Even at 0 cycles, the capacity was reduced by only 15%. In both Example 1 and Comparative Example 3, the initial dopant is perchlorate ion. However, the anion in the electrolytic solution was a sulfate ion in Example 1, whereas the comparative example 3 was an ion having a higher molecular weight than poly-styrenesulfonic acid ion in Comparative Example 3.

As charge and discharge are repeated, anions in the electrolytic solution are incorporated into the indole polymer as a dopant. In the cycle test, set the lower limit of the discharge voltage to 0.8
Despite the regulation to V, the above reaction formula (1)
As a result, the replacement of the dopant was carried out, and the dopant was replaced with poly-styrenesulfonate ion from perchlorate ion.
The deterioration of the cycle characteristics is larger than that of

[0068]

[Table 1]

[0069]

As described above, according to the present invention, when an indole polymer as a cathode material is polymerized, a polymer-doped anion having a high molecular weight of 140 wt.
The following effects can be obtained by exchanging with the following anions. (1) The spread of the polyindole polymer and the entry of protons are restricted, and the self-discharge reaction can be reduced. (2) As a result, a secondary battery having excellent self-discharge characteristics and excellent cycle characteristics can be provided.

[Brief description of the drawings]

FIG. 1 is a structural sectional view of a secondary battery using an indole polymer according to an embodiment of the present invention as a positive electrode material.

FIG. 2 is a cyclic voltammogram of a cathode material of an indole-based polymer according to an embodiment of the present invention in a 4M aqueous sulfuric acid solution.

FIG. 3 is a time change curve of a voltage showing a self-discharge characteristic of a secondary battery using the indole polymer positive electrode material according to the embodiment of the present invention.

FIG. 4 is a capacity change curve in a charge / discharge cycle test of a secondary battery using the indole-based polymer cathode material according to the embodiment of the present invention.

[Explanation of symbols]

 1a, 1b Current collector 2 Positive electrode material 3 Separator 4 Negative electrode material 5 Gasket 10 Secondary battery

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masaki Fujiwara 5-7-1 Shiba, Minato-ku, Tokyo NEC Corporation (72) Inventor Manabu Harada 5-7-1 Shiba, Minato-ku, Tokyo Japan Inside Electric Company (72) Inventor Shinako Kaneko 5-7-1 Shiba, Minato-ku, Tokyo NEC Corporation Inside (72) Inventor Yuji Nakagawa 5-7-1 Shiba, Minato-ku, Tokyo NEC Corporation F term in the formula company (reference) 4J002 CE001 DA017 DA027 DA037 DE056 DE196 DF036 DG046 FA047 FD117 FD206 GQ02 4J032 BA12 BC01 BC21 BC32 BD02 BD03 BD05 CG01 5H003 AA03 AA04 BA02 BA03 BA07 BB12 BB15 BB34 BB47 BD00

Claims (11)

[Claims] 1. An indole polymer formed by chemical or electrolytic polymerization of an indole compound, wherein the dopant added to the polymer has a molecular weight of 1 per charge.
A method for producing an electrode containing an indole-based polymer, wherein the polymer is formed on the first current collector after exchanging with an anion dopant of 40 or less. 2. The method for producing an electrode containing an indole polymer according to claim 1, wherein the indole polymer is represented by the following chemical formula. Embedded image (R is a hydrogen atom, a halogen atom, a nitro group, a cyano group,
Represents a group such as an amino group or a sulfone group. ) 3. The method for producing an electrode containing an indole polymer according to claim 1, wherein a conductive auxiliary is added to the indole polymer formed on the current collector. 4. The method according to claim 3, wherein at least one kind of carbon material selected from graphite, carbon black, acetylene black, and carbon fiber is used as the conductive auxiliary agent. 5. The method of exchanging the dopant in the indole polymer formed by chemical polymerization or electrolytic polymerization with a dopant of the anion having a molecular weight per charge of 140 or less according to the chemical polymerization or the electrolytic polymerization. The indole polymer according to claim 1, wherein the indole polymer is treated with an alkaline aqueous solution, and then treated with an acidic aqueous solution containing the anion having a molecular weight per charge of 140 or less. Manufacturing method of electrode. 6. A method of exchanging said dopant in said indole polymer formed by chemical polymerization or electrolytic polymerization with a dopant of said anion having a molecular weight per charge of 140 or less, wherein the molecular weight per charge is 140 or less. 2. The method for producing an electrode containing an indole polymer according to claim 1, comprising subjecting the indole polymer to a redox treatment in the following acidic aqueous solution containing the anion. 7. The anion having a molecular weight of 140 or less per charge is Cl ⁻ , ClO ₄ ⁻ , SO ₄ ²⁻ , or BF ₄ ^−.
The method for producing an electrode containing the indole-based polymer according to claim 1, 5 or 6, wherein 8. Manufacturing by the manufacturing method according to claims 1 to 7,
A positive electrode material in which an electrolyte is impregnated in an electrode containing an indole polymer formed on the first current collector, and a negative electrode in which a film is formed on a second current collector and impregnated with the electrolyte A secondary battery characterized in that it is formed by laminating materials with a separator interposed therebetween such that these electrode materials are inside. 9. The secondary battery according to claim 8, wherein a sulfuric acid aqueous solution is used as the electrolyte. 10. The secondary battery according to claim 8, wherein polyphenylquinoxaline is used as the negative electrode material. 11. The negative electrode material according to claim 8, wherein a conductive auxiliary agent made of at least one carbon material selected from graphite, carbon black, acetylene black and carbon fiber is added. The secondary battery according to one of the above.