JPH0616867A - Conductive composite and its production - Google Patents

Abstract

PURPOSE:To obtain a conductive composite which is an electrolyte having sulfo groups and has a high Li ion availability by polymerizing a monomer that gives a polymer having conjugated double bonds in the main chain in the presence of a low-molecular anionic compd. and an oxidizing agent. CONSTITUTION:A conductive composite is obtd. by polymerizing a monomer that gives a polymer having conjugated double bonds in the main chain in the presence of a low-molecular anionic compd. having one or two sulfo groups and an oxidizing agent. The composite, when used as the material of a positive electrode of a secondary cell, improves the energy density and ion availability of the cell, thus improving its performance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel conductive composite and a method for producing the same, and the conductive composite of the present invention is advantageous as an excellent electrode material applicable to, for example, secondary batteries.

[0002]

2. Description of the Related Art Composites containing a polymer compound having a conjugated double bond in the main chain and a polymer electrolyte having an anion group as an active ingredient have hitherto been known by electrolytic polymerization [eg,
P. Aldebert et al. Phys. Franc
e, 49 , 2101 (1988)] and chemical polymerization methods are known. For example, a polymer electrolyte composed of a complex of an anionic polymer compound having a sulfonic acid group and a polymer compound having a conjugated double bond in its main chain is known.

[0003]

However, in the conductive composite obtained by the above-mentioned conventional method, when used as an electrode material of a secondary battery, the utilization rate of Li ions (Li ⁺ ions and ClO ₄ at the time of charging / discharging) is used. ^- Although ions into and out of the composite film, the ratio of the Li ⁺ ions to the total amount of ions in and out of time) is low. In order to increase the energy density and reduce the weight of a battery, it is necessary to use a conductive composite having a high Li ion utilization rate, and its development is desired. In view of the above situation, the present invention has been made to solve the problems with the structure of a conductive composite having an electrolyte having a sulfonic acid group and a higher utilization rate of Li ions and a method for producing the same.

[0004]

The present invention solves the above problems.
Never use Li as a secondary battery positive electrode material ⁺
New electrolyte and its production that can improve the ion utilization rate
It provides the law. That is, the present invention
Anionic low molecular weight compound having one or two acid groups
From a polymer compound having a conjugated double bond in the main chain
Provided is an electrically conductive composite. Also, the present invention
In the method for producing the conductive composite of, the main chain has a conjugated double bond.
The sulfonic acid group is added to the raw material monomer of the polymer compound
Low-molecular-weight compound having one or two and
It is characterized in that an oxidizing agent is added to cause a polymerization reaction.

[0005]

When the molecular weight of the polymer compound portion corresponding to one sulfonic acid group in the polymer electrolyte having a sulfonic acid group becomes smaller than that by the conventional method, the present inventors
It was thought that the utilization rate of Li ⁺ ions could be improved, and the research was repeated with a subject of the composite having such a structure and its manufacturing method. As a result, instead of the conventional polymer electrolyte having a sulfonic acid group, a low molecular weight anionic compound having 1 or 2 sulfonic acid groups is combined with a polymer compound having a conjugated double bond in the main chain. The above-mentioned problems can be solved by forming the body, and in order to realize this structure, the raw material monomer of the polymer compound having a conjugated double bond in the main chain and the anionic low molecular weight compound are present in the presence of an oxidizing agent. The inventors have found that it is sufficient to polymerize, and have reached the present invention. In the chemical polymerization method adopted in the present invention, in the polymerization process of the raw material monomer of the polymer compound having a conjugated double bond in the main chain, the polymer compound is positively charged and the reaction system is kept in order to maintain electrical neutrality. The anionic low-molecular weight compound having one or two sulfonic acid groups present therein forms an ion pair, so that the polymer compound having a conjugated double bond in the main chain and the sulfonic acid group
Complex with one or two anionic low molecular weight compounds.

In the present invention, an anionic low molecular weight compound having one or two sulfonic acid groups is mixed with a raw material monomer of a polymer compound having a conjugated double bond in the main chain,
Further, an oxidizing agent is added to cause the above monomers to undergo a polymerization reaction. Examples of the raw material monomer of the present invention include compounds having a conjugated double bond such as aniline, pyrrole, thiophene, 3-alkylthiophene and azulene. As the polymer compound portion in the conductive composite, polyalinine,
Examples thereof include polypyrrole, polythiophene, poly-3-alkylthiophene and the like.

Further, examples of the anionic low molecular weight compound having one or two sulfonic acid groups used in the present invention include aliphatic or aromatic mono- or disulfonic acid compounds, and particularly preferably: Examples thereof include low molecular weight compounds represented by the general formula. Formula _{C n H 2n + 1 SO 3} - - O 3 S (CH 2) 2n SO 3 - C n-1 H 2n-1 PhSO 3 - - O 3 SPhSO 3 - PhNHPhSO 3 - CH 3 NpSO 3 - ( wherein In each formula, 1 ≦ n ≦ 20, Ph represents a benzene ring, and Np represents a naphthalene ring.)

More specifically, the compound represented by the above general formula of the present invention is an alkyl monosulfonic acid compound or a salt thereof, for example, methanesulfonic acid, ethanesulfonic acid, sodium 1-butanesulfonate, 1-
Sodium heptanesulfonate, sodium 1-decanesulfonate, sodium 1-heptadecanesulfonate, etc., as an alkyldisulfonic acid compound or a salt thereof,
For example, sodium 1,4-butanesulfonate, 1,2-
Aromatic monosulfonic acids or salts thereof such as sodium ethanesulfonate, sodium 1,8-octanesulfonate, sodium 1,12-dodecanesulfonate, etc., such as sodium benzenesulfonate, sodium 2,4-dimethylbenzenesulfonate, Sodium 4-diphenylamine sulfonate, sodium n-dodecylbenzene sulfonate, sodium 1-naphthalene sulfonate,
Aromatic disulfonic acid or a salt thereof such as sodium 2-naphthalenesulfonate, sodium p-toluenesulfonate, sodium 2,5-dimethylbenzenesulfonate, and the like, for example, disodium m-benzenedisulfonate,
3,5-Disulfonebenzoic acid disodium salt, 1,5-
Naphthalene disulfonic acid disodium, anthraquinone-1,5-disulfonic acid disodium salt and the like can be mentioned.

Examples of the oxidizing agent used in the present invention include ammonium persulfate, potassium persulfate, rubidium persulfate, cesium persulfate and iron (III) chloride.

The ratio of the sulfonic acid compound or the sulfonic acid salt to the starting material monomer is preferably an equimolar amount to twice the molar amount. When the sulfonic acid salt is used, the reaction may be performed in a hydrochloric acid solution of 2 N or more. is necessary. The amount of the oxidizing agent used is an equimolar amount of the raw material monomer, the reaction time is 4 hours to 6 hours, and the reaction temperature is 0 to -10 ° C as general conditions of the production method of the present invention. The conductive composite obtained by this oxidative polymerization method has a polymer compound having an average molecular weight of 1
The number of carbon atoms (molecular weight) per sulfonic acid group is generally 10 to 1,000,000 and 13 to 20 (200 to 300).

[0011]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these.Example 1 Of the complex of alkyl sulfonic acid compound and polyaniline
Synthesis 3.7 g of aniline and methanesulfone in 150 ml of distilled water
11.5 g of acid was dissolved. Hold the aqueous solution at 0 ° C
Under stirring, 1.6 mol / liter ammonium persulfate
68.3 g of an aqueous solution of water was added dropwise over 1 hour. Dripping
After stirring for another 3 hours, filter with G4 filter
It was After washing the filtrate with acetone, reduce the temperature at 40 ° C overnight.
Pressure dried. The dry weight of the filtrate was 3.0 g. Well
As a result of elemental analysis of the filtered product, the element ratio S / N ratio was 0.3.
It was 6/1. According to the infrared absorption spectrum,
1,290 cm, which is unique to polyaniline^-1, 1,48
0 cm^-1Each peak of
Unique 1,030 cm ^-1That the peak of
From the synthesis of polyaniline / methanesulfonic acid complex
confirmed. Table 1 shows the polyaniline / methanesulfon.
The elemental analysis results of the acid complex are shown in Fig. 1, and the infrared absorption spectrum is shown in Fig. 1.
Indicates a vector. Other alkyl sulfonic acids, i.e.
Polyaniline /
The ethanesulfonic acid complex can be synthesized and the element ratio S / N ratio is
It was confirmed to be 0.35 / 1. Obtained polyani
Table 1 shows the results of elemental analysis of the phosphorus / ethanesulfonic acid complex.
The infrared absorption spectrum is shown in FIG.

[0012]

[Table 1]

Example 2 Preparation of Complex of Alkyl Sulfonic Acid Compound and Polyaniline
Aniline (5.6 g) and sodium 1-butanesulfonate (5.0 g) were dissolved in a synthetic 3 mol / liter hydrochloric acid aqueous solution (300 ml). While maintaining the hydrochloric acid aqueous solution at 0 ° C., 32.8 g of 1.6 mol / liter ammonium persulfate aqueous solution was added dropwise over 1 hour with stirring. After dropping, the mixture was further stirred for 3 hours and then filtered through a G4 filter. The filtered product was washed with acetone and then dried under reduced pressure at 40 ° C. for one day. The dry weight of the filtrate was 2.2 g. As a result of elemental analysis of the filtered material, the element ratio S / N was 0.32 / 1. According to infrared absorption spectrum, 1,290Cm ^-1 is specific to polyaniline, observed each peak 1,480Cm ^-1, also show a peak of 1,030Cm ^-1 is specific to 1-butanoic acid By being
The synthesis of polyaniline / 1-butanesulfonic acid complex was confirmed. A polyaniline / alkylsulfonic acid complex can be synthesized under the same conditions using other sodium alkylsulfonates, that is, sodium 1-heptanesulfonate, sodium 1-decanesulfonate, and sodium 1-heptadecanesulfonate, and the element ratio S / N is 0.3
It was confirmed to be 3/1, 0.37 / 1, 0.34 / 1.

Example 3 Complex of alkyldisulfonic acid compound and polyaniline
Synthesis of 3 mol / liter hydrochloric acid aqueous solution 100 ml aniline 1.8 g, sodium 1,4-butanedisulfonate 5.
0 g was dissolved. While maintaining the hydrochloric acid aqueous solution at 0 ° C,
With stirring, 20.5 g of a 1.6 mol / liter ammonium persulfate aqueous solution was added dropwise over 1 hour. After dropping, the mixture was further stirred for 3 hours and then filtered through a G4 filter. The filtered product was washed with acetone and then dried under reduced pressure at 40 ° C. for one day. The dry weight of the filtrate was 2.2 g. The results of elemental analysis of the filtered product are shown in Table 2, and the element ratio S / N ratio was 0.38 / 1. According to the infrared absorption spectrum as shown in FIG. 3, 1,290cm ^-1 is specific to polyaniline, observed each peak 1,480Cm ^-1, also specific to the 1,4-disulfonic acid 1 , The peak at 030 cm ^-1 is seen,
The synthesis of polyaniline / 1,4-butanedisulfonic acid complex was confirmed. Other sodium alkyldisulfonate,
That is, sodium 1,2-ethanedisulfonate, 1,
A polyaniline / alkyldisulfonic acid complex can be synthesized under the same conditions using sodium 8-octanedisulfonate and sodium 1,12-dodecanedisulfonate, and the elemental ratios S / N of each of the elemental analysis results shown in Table 2 are 0.
It was confirmed to be 16/1, 0.25 / 1, 0.29 / 1. The infrared absorption spectrum of the obtained polyaniline / ethanedisulfonic acid composite is shown in FIG.

[0015]

[Table 2]

Example 4 Preparation of Complex of Aromatic Sulfonic Acid Compound and Polyaniline
Aniline 5.6g Synthesis 3 mol / liter hydrochloric acid 300 ml, it was dissolved sodium benzenesulfonate 6.0 g. While maintaining the hydrochloric acid aqueous solution at 0 ° C. under stirring,
1.6 mol / liter ammonium persulfate aqueous solution 3
2.8g was added dropwise over 1 hour. 3 more after dropping
After stirring for hours, it was filtered with a G4 filter. The filtered product was washed with acetone and then dried at 40 ° C. for 24 hours. The dry weight of the filtrate was 4.6 g. As a result of elemental analysis of the filtered material, the element ratio S / N was 0.35 / 1. According to infrared absorption spectrum, 1,290Cm ^-1 is specific to polyaniline, observed each peak 1,480Cm ^-1, also specific to the benzenesulfonic acid 1,0
The peak at 30 cm ^-1 was confirmed to confirm the synthesis of the polyaniline / benzenesulfonic acid complex. Other aromatic sodium sulfonates, namely sodium 2,4-dimethylbenzenesulfonate, sodium 4-diphenylaminesulfonate, sodium n-dodecylbenzenesulfonate, sodium 1-naphthalenesulfonate, sodium 2-naphthalenesulfonate, p -A polyaniline / aromatic sulfonic acid complex can be synthesized under the same conditions using sodium toluenesulfonate and sodium 2,5-dimethylbenzenesulfonate, and the element ratio S / N
Are 0.38 / 1, 0.35 / 1, 0.39 / respectively
1, 0.31 / 1, 0.34 / 1, 0.33 / 1, 0.
It was confirmed to be 37/1.

Example 5 Compound of sodium aromatic disulfonate and polyaniline
Synthesis of coalescence aniline 5.6 g, m-benzenedisulfonic acid disodium salt 8. in 3 mol / liter hydrochloric acid aqueous solution 300 ml.
0 g was dissolved. While maintaining the hydrochloric acid aqueous solution at 0 ° C,
With stirring, 32.8 g of a 1.6 mol / liter ammonium persulfate aqueous solution was added dropwise over 1 hour. After dropping, the mixture was further stirred for 3 hours and then filtered through a G4 filter. The filtered product was washed with acetone and then dried at 40 ° C. for 24 hours. The dry weight of the filtrate was 5.2 g. As a result of elemental analysis of the filtered material, the element ratio S / N ratio was 0.39 / 1. According to infrared absorption spectrum, 1,290cm ^-1 is specific to polyaniline, 1,480cm ^-1
By observing the respective peaks of ¹ , and the peak of 1,030 cm ⁻¹ which is unique to benzenedisulfonic acid, the synthesis of the polyaniline / benzenedisulfonic acid complex was confirmed.

Example 6 Synthesis of Complex of Alkyl Sulfonic Acid and Polypyrrole 4.0 g of methanesulfonic acid was dissolved in 0.8 ml / liter iron (III) chloride aqueous solution. While maintaining the iron (III) chloride aqueous solution at 0 ° C., 6.2 g of pyrrole was added at once with stirring. After charging, the mixture was stirred for 2 hours and then filtered with a G4 filter. The filtered product was washed with distilled water and acetone, and then dried at 40 ° C. for 24 hours. The dry weight of the filtrate is 6.
It was 3 g. As a result of elemental analysis of the filtered material, the element ratio S / N was 0.48 / 1. According to the infrared absorption spectrum, 1,550c which is peculiar to polypyrrole
The peak at m ^{−1 and} the peak at 1,030 cm ⁻¹ , which is unique to methanesulfonic acid, are
The synthesis of polypyrrole / methanesulfonic acid complex was confirmed.

[0019]Application example 1 of the present invention Filters from polyaniline and alkyl sulfonic acid composites
Rum molding Polyaniline / methanesulfonic acid compound synthesized in Example 1
1g of coalesced powder dissolved in 1.8% ammonium hydroxide acetone
The solution was poured into 250 ml and stirred at room temperature for 2 hours. Stirring
After that, filter with a G4 filter and wash the filtered product with acetone.
Clean After washing, vacuum dry at 40 ° C for 24 hours, and treat with alkali.
Prepare the treated polyaniline / methanesulfonic acid composite powder
Made The dry weight was 0.78 g. The alkali
As a result of elemental analysis of the treated powder, the element ratio S / N is 0.42.
It was / 1. According to the infrared absorption spectrum,
1,290 cm, which is unique to lianiline^-1, 1,480
cm^-1Each peak of
Yes 1,030 cm ^-1Because the peak of
, Polyaniline / methanesulfonic acid after alkaline treatment
It was confirmed to be a complex. The alkali-treated powder 2
0 mg is N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP)
It is added to 1 ml and stirred at 20 ° C for 9 hours.
After preparing an NMP solution, cast it on a stainless steel thin plate.
Then, immediately dry under reduced pressure at 80 ° C. for 8 hours to remove the complex.
Just film was created. Synthesized in Examples 1 and 2
Other polyaniline / alkyl sulfonic acid composite powder
Powder, that is, polyaniline / ethanesulfonic acid composite powder
Powder, polyaniline / 1-butanesulfonic acid complex powder,
Polyaniline / 1-heptanesulfonic acid complex powder, po
Lianiline / 1-decanesulfonic acid complex powder, polya
Using Niline / 1-heptadecane sulfonic acid complex powder
The alkaline treatment under the same conditions.
Prime ratio S / N is 0.63 / 1, 0.67 / 1, 0 respectively
Confirmed to be 61/1, 0.67 / 1, 0.62 / 1
I confirmed. The alkali-treated powder is treated with an alkali-treated polyaniline.
Dissolves in NMP as well as phosphorus / methane sulfonic acid complex powder
And cast the composite film into polyaniline.
/ Methanesulfonic acid composite film
It was

Application Example 2 of the Present Invention Complex of Polyaniline and Alkyldisulfonic Acid Compound
From the polyaniline synthesized in Example 3
1.8% of 1 g of 1,4-butanedisulfonic acid complex powder
The mixture was poured into 250 ml of an ammonium hydroxide acetone solution and stirred at room temperature for 2 hours. After stirring, the mixture was filtered through a G4 filter, and the filtered substance was washed with acetone. After washing, it was dried under reduced pressure at 40 ° C for 24 hours and treated with alkali, polyaniline / 1,
A 4-butanedisulfonic acid complex powder was prepared. The dry weight was 0.82 g. As a result of elemental analysis of the alkali-treated powder, the element ratio S / N was 0.39 / 1.
According to infrared absorption spectrum, 1,290Cm ^-1 is specific to polyaniline, observed each peak 1,480Cm ^-1, also 1,4-butane peak of disulfonic acid 1,030Cm ^-1 is unique Is seen,
After the alkali treatment, it was confirmed to be a polyaniline / 1,4-butanedisulfonic acid complex. 20 mg of the alkali-treated powder was added to 1 ml of NMP, an NMP solution was prepared by stirring at 20 ° C. for 9 hours, then cast on a stainless steel thin plate, and immediately dried under reduced pressure at 80 ° C. for 8 hours to cast the composite. I made a film. Other polyaniline / alkyldisulfonic acid composite powders synthesized in Example 3, namely polyaniline / 1,2-ethanedisulfonic acid composite powder, polyaniline / 1,8-octanedisulfonic acid composite powder, polyaniline / 1,12- Using dodecanedisulfonic acid complex powder, alkali treatment was performed under the same conditions, and it was confirmed that the element ratios S / N after the alkali treatment were 0.29 / 1, 0.38 / 1, and 039/1, respectively. . The alkali-treated powder was dissolved in NMP in the same manner as the alkali-treated polyaniline / 1,4-butanedisulfonic acid complex powder, and the cast film of the complex was treated in the same manner as the polyaniline / 1,4-butanedisulfonic acid complex film. Created.

Application Example 3 of the Present Invention A complex of polyaniline and an aromatic sulfonic acid compound,
Complex of polyaniline and aromatic disulfonic acid compound
The film forming Example 4 synthesized polyaniline / benzenesulfonic acid complex powder 1g was introduced into 1.8% ammonium hydroxide in acetone 250ml from, and stirred at room temperature for 2 hours. After stirring, the mixture was filtered through a G4 filter, and the filtered substance was washed with acetone. After washing, it was dried under reduced pressure at 40 ° C. for a whole day and night to prepare an alkali-treated polyaniline / benzenesulfonic acid complex powder. The dry weight was 0.78 g. As a result of elemental analysis of the alkali-treated powder, the element ratio S / N is 0.5.
It was 5/1. According to the infrared absorption spectrum,
1,290 cm ^-1 , 1,48 which is peculiar to polyaniline
Each peak at 0 cm ^{−1 and} the peak at 1,030 cm ⁻¹ , which is unique to benzenesulfonic acid, were confirmed to confirm that the polyaniline / benzenesulfonic acid complex was present even after the alkali treatment. 20 mg of the alkali-treated powder was added to 1 ml of NMP, an NMP solution was prepared by stirring at 20 ° C. for 9 hours, then cast on a stainless steel thin plate, and immediately dried under reduced pressure at 80 ° C. for 8 hours to cast the composite. I made a film. Example 4,
Other polyaniline / aromatic sulfonic acid composite powders and polyaniline / aromatic disulfonic acid composite powders synthesized in Example 5, namely polyaniline / 2,4-dimethylbenzenesulfonic acid composite powder, polyaniline / 4
-Diphenylamine sulfonic acid complex powder, polyaniline / n-dodecylbenzene sulfonic acid complex powder, polyaniline / 1-naphthalene sulfonic acid complex powder, polyaniline / 2-naphthalene sulfonic acid complex powder, polyaniline / p-toluene sulfonic acid complex Body powder, polyaniline / 2,5-dimethylbenzenesulfonic acid complex powder, and polyaniline / benzenedisulfonic acid complex powder were subjected to alkali treatment under the same conditions, and the element ratio S / N after alkali treatment was 0. 37/1, 0.33 /
1, 0.37 / 1, 0.34 / 1, 0.33 / 1, 0.
It was confirmed to be 36/1, 0.38 / 1, 0.35 / 1. The alkali-treated powder was dissolved in NMP in the same manner as the alkali-treated polyaniline / benzenesulfonic acid composite powder, and a cast film of the composite was prepared in the same manner as the polyaniline / 1,4-butanedisulfonic acid composite film.

Application Example 4 of the Present Invention Compressive formation of a composite of polypyrrole and alkyl sulfonic acid
The synthesized polypyrrole / methanesulfonic acid complex powder 20mg placed on a stainless mesh in the form Example 6, 20
It was compression-molded at 230 ° C. and 230 kg / cm ² .

Comparative Example 1 Polyaniline / Polyvinylsulfur
Synthesis of phosphonic acid complex Synthesis of polyaniline / polyvinylsulfonic acid complex 2.5 g of aniline and 2.5 g of sodium polyvinylsulfonate synthesized in Synthesis Example 1 described later were dissolved in 200 ml of a 2 mol / liter hydrochloric acid aqueous solution. While maintaining the hydrochloric acid aqueous solution at 0 ° C., 16.4 g of a 1.6 mol / liter ammonium persulfate aqueous solution was added dropwise over 1 hour with stirring. After dropping, the mixture was further stirred for 3 hours and then filtered with a G4 filter. After washing the filtrate with acetone, 4
It was dried under reduced pressure overnight at 0 ° C. The dry weight of the filtrate is 2.1.
It was g. Moreover, as a result of elemental analysis of the filtered material, the element ratio S
/ N was 0.36 / 1. Also, according to the infrared absorption spectrum, 1,290 cm, which is peculiar to polyaniline
The respective peaks at ⁻¹ and 1,480 cm ⁻¹ were observed, and the peak at 1,030 cm ⁻¹ , which is peculiar to polyvinyl sulfonic acid, was observed, thus confirming the synthesis of the polyaniline / polyvinyl sulfonic acid complex.

Synthesis Example 1 Poly (vinyl sulfonate) sodium
Synthesis 25 wt% sodium vinylsulfonate solution 40g of beam was carried out for 1 hour bubbling with nitrogen gas. Also potassium peroxodisulfate / sodium sulfite (molar ratio 1: 1)
A redox initiator was prepared by dissolving 0.86 g in 15 g of distilled water bubbled with nitrogen gas. The redox initiator was added to an aqueous solution of sodium vinyl sulfonate, and the mixture was stirred for 6 hours while bubbling nitrogen gas. After the reaction, the reaction solution was added to 1 liter of methanol with stirring to precipitate a product. The product was washed with methanol and acetone, dried under reduced pressure at 40 ° C for one day, and identified by elemental analysis, infrared absorption spectrum and NMR spectrum. In elemental analysis, the element ratio C: H:
S became 1: 3.0: 0.49. In the infrared absorption spectrum, S = of the sulfonic acid group at 1,200 cm ^-1
An absorption peak due to O stretching vibration appeared. In the NMR spectrum, broad absorption peaks due to the methylene proton and the methine proton appeared at around 2.2 ppm and around 3.5 ppm, respectively. As a result of the above elemental analysis, infrared absorption spectrum, and NMR spectrum, it was confirmed that the product was sodium polyvinylsulfonate. The viscosity average molecular weight of the sodium polyvinylsulfonate was 1,700.

Comparative Example 2 Synthesis of Polyaniline / Polystyrene Sulfonic Acid Composite The same as Comparative Example 1 except that commercially available sodium polystyrene sulfonate (average molecular weight 70,000) was used in place of sodium polyvinyl sulfonate in Comparative Example 1. A polyaniline / polystyrene sulfonic acid composite was synthesized by the method. The dry weight of the filtered material was 2.6 g, and the element ratio S / N was 0.49 / 1 as a result of elemental analysis of the filtered material. Also, in the infrared absorption spectrum of the filtrate,
1,290 cm ^-1 , 1,48 which is peculiar to polyaniline
The synthesis of the polyaniline / polystyrene sulfonic acid complex was confirmed by the respective peaks of 0 cm ^{−1 and} the peak of 1,030 cm ⁻¹ which is unique to polystyrene sulfonic acid.

[0026]Comparative Example 3 Synthesis of polypyrrole / polyvinyl sulfonic acid composite Instead of methanesulfonic acid in Example 6, synthesized in Synthesis Example 1
Except for using sodium polyvinyl sulfonate
Polypyrrole / polyvinyls were prepared in the same manner as in Example 6.
The rufonic acid complex was synthesized. The dry weight of the filtrate is 6.8.
g, and as a result of elemental analysis of the filtrate, the element ratio S /
N was 0.53 / 1. In addition, infrared absorption
1,55 which is peculiar to polypyrrole
0 cm ^-1The peak of
Which is peculiar to 1,030 cm^-1The peak of
Of the polypyrrole / polyvinyl sulfonic acid composite
Confirmed synthesis.

Application Example 5 by Comparative Example Film of polyaniline / polyvinylsulfonic acid composite
1 g of the polyaniline / polyvinylsulfonic acid composite powder synthesized in Molding Comparative Example 1 was treated with alkali in the same manner as in Application Example 1 to prepare an alkali-treated polyaniline / polyvinylsulfonic acid composite powder. The dry weight was 0.57 g. As a result of elemental analysis of the alkali-treated powder, the element ratio S / N
Was 0.35 / 1. Further, according to the infrared absorption spectrum, 1,290 cm ^-1 , which is peculiar to polyaniline,
Seen the peak of 1,480Cm ^-1, also by the peak of 1,030Cm ^-1 is specific polyvinyl sulfonic acid is observed, it was confirmed that after the alkali treatment is also polyaniline / polyvinyl sulfonic acid complex . The same method as in Application Example 1 of the present invention except that the alkali-treated polyaniline / polyvinylsulfonic acid composite powder is used instead of the alkali-treated polyaniline / methanesulfonic acid composite powder in Application Example 1 of the present invention. , A polyaniline / polyvinylsulfonic acid composite cast film was prepared.

Application Example 6 of Comparative Example Filling of polyaniline / polystyrene sulfonic acid composite
Creating the alkali treatment polyaniline / polystyrene sulfonate complex powder polyaniline / polystyrene sulphonic acid complex powder 1g synthesized in beam shaping Comparative Example 2 and alkali treatment in the same manner as Application Example 1 of the present invention. Dry weight is 0.61g
Met. As a result of elemental analysis of the alkali-treated powder,
The element ratio S / N was 0.34 / 1. Further, according to the infrared absorption spectrum, 1,2 which is peculiar to polyaniline
90cm ^-1, observed each peak of 1,480cm ^-1, also specific to the polystyrene sulfonic acid 1,030cm
It was confirmed that the polyaniline / polystyrenesulfonic acid complex was present even after the alkali treatment by the peak of ^-1 . The same method as in Application Example 1 of the present invention except that the alkali-treated polyaniline / polystyrenesulfonic acid composite powder is used instead of the alkali-treated polyaniline / methanesulfonic acid composite powder in Application Example 1 of the present invention. A cast film of polyaniline / polystyrene sulfonic acid composite was prepared.

COMPARATIVE EXAMPLE 7 COMPRESSION MOLDING OF POLYPYROL / POLYVINYL SULFONIC ACID COMPOSITE In place of the polypyrrole / methanesulfonic acid composite powder in Application Example 4, the polypyrrole / polyvinylsulfonic acid composite powder synthesized in Comparative Example 3 was used. A polypyrrole / polyvinylsulfonic acid composite powder was compression-molded in the same manner as in Application Example 4 except that it was used.

The effects of the present invention were confirmed by measuring the energy density and ion operation rate of the composite films and compression molded products produced in the above-mentioned Application Examples 1 to 7. (1) Polyaniline / anionic compound composite film Table 3 shows energy densities of various polyaniline / anionic compound composite films prepared in Application Examples 1 to 3 of the present invention and Application Examples 5 and 6 according to Comparative Examples. Show. All energy densities were measured under the same conditions. That is, 1 mol / liter propylene carbonate solution of lithium perchlorate was used as the electrolytic solution and lithium was used as the negative electrode, and the current density was evaluated at 0.1 A / cm ² . Polyaniline of the present invention /
The energy density of the film composed of the anionic low molecular weight compound composite is the energy of the film composed of the polyaniline / anionic polymer compound composite such as the comparative polyaniline / polyvinylsulfonic acid composite or the polyaniline / polystyrenesulfonic acid composite. It was higher than the density. Table 3 also shows the utilization rate of Li ⁺ ions. Here, the Li ⁺ ion utilization rate means that Li ⁺ ions and ClO ₄ ⁻ ions move in and out of the composite film during charge and discharge, and L is based on all ions that move in and out at this time.
Says the proportion of i ⁺ ions.

[0031]

[Table 3]

The utilization rate of Li ⁺ ions in the film of the polyaniline / anionic low molecular weight compound composite of the present invention is the same as that of polyaniline / anionic polyaniline / polyvinylsulfonic acid composite film or polyaniline / polyvinylsulfonic acid composite film. It was higher than the Li ⁺ ion utilization rate of the polymer compound film.
By increasing the Li ⁺ ion utilization rate, it is possible to reduce the amount of electrolyte in the battery, and it is possible to increase the energy density of the battery.

Among the anionic compounds used in the polyaniline / anionic low molecular weight compound composite film of the present invention, methanesulfonic acid, ethanesulfonic acid, 1,
For 2-ethanedisulfonic acid and 1,4-butanedisulfonic acid having a low molecular weight and a small molecular weight per sulfonic acid group, the sulfonic acid group is selectively ion-paired to the + charged portion of polyaniline during charging. And the utilization rate of Li ⁺ ions increased. Moreover, when the molecular weight per sulfonic acid group was small, the energy density of the composite film became high and appeared. From the above, in any case, the polyaniline / anionic low molecular weight compound composite film of the present invention could realize high performance as a battery electrode.

(2) Polypyrrole / anionic compound compound
Compression-molded product of coalescence Table 4 shows the energy density and Li ⁺ ion utilization rate of the compression-molded product of the polypyrrole / anionic compound composite prepared in Application Example 4 of the present invention and Application Example 7 of the comparative example. The measurement conditions were the same as those of the polyaniline / anionic compound composite of (1) above. The compression molded product of the polypyrrole / anionic low molecular weight compound composite of the present invention has higher energy density and higher Li ⁺ ion utilization rate than the compression molded product of the polypyrrole / polyvinylsulfonic acid composite according to the comparative example.

[0035]

[Table 4]

Similar to the above (1), among the anionic compounds used in the polypyrrole / anionic low molecular weight compound composite film of the present invention, the anionic compound has a low molecular weight such as methanesulfonic acid and has a molecular weight per sulfonic acid group. In the case of a small one, the sulfonic acid group has a strong tendency to selectively form an ion pair in the + charged portion of polypyrrole during charging,
It appeared that the Li ⁺ ion utilization rate increased. From the above, the molded product of the polypyrrole / anionic low molecular weight compound composite of the present invention was able to realize high performance as a battery positive electrode.

[0037]

Industrial Applicability The present invention provides a complex of a polymer compound having a conjugated double bond group and an anionic compound having one or two sulfonic acid groups, and a method for producing the same. By using the conductive composite as a positive electrode material of a secondary battery, the effect of improving the energy density and the ion operating rate can be obtained, and the battery performance can be improved.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum diagram of a polyalinine / methanesulfonic acid composite according to the present invention.

FIG. 2 is an infrared absorption spectrum diagram of a polyalinine / ethanesulfonic acid complex according to the present invention.

FIG. 3 is an infrared absorption spectrum of the polyalinine / 1,4-butanedisulfonic acid complex according to the present invention.

FIG. 4 is an infrared absorption spectrum diagram of a polyalinine / 1,2-ethanedisulfonic acid complex according to the present invention.

Claims (2)

[Claims] 1. A conductive composite composed of an anionic low molecular weight compound having one or two sulfonic acid groups and a polymer compound having a conjugated double bond in the main chain. 2. A polymerization reaction by adding an anionic low molecular weight compound having one or two sulfonic acid groups and an oxidizing agent to a raw material monomer of a polymer compound having a conjugated double bond in the main chain. With 1 sulfonic acid group
A process for producing a conductive composite, which comprises an anionic low molecular weight compound having one or two and a polymer compound having a conjugated double bond in the main chain.