JP2882892B2 - Method for forming conductive polymer / polymer electrolyte composite film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a conductive polymer / polymer electrolyte composite film of the present invention, and more particularly to an electrode material, a sensor material, a conductive paint, an electromagnetic shielding material, an electronic element, which is applied to a positive electrode of a battery. The present invention relates to a method which can be advantageously applied to the production of an electrochromic material and an ion selective permeable membrane.

[0002]

2. Description of the Related Art Films containing a conductive polymer / polymer electrolyte composite have hitherto been obtained only by an electrolytic polymerization method. Aldebert et al. Phys, F
lance, 49 , 2101 (1988)}. However, the electrolytic polymerization method is not suitable for producing a large amount of a conductive polymer / polymer electrolyte composite film.

[0003]

In order to synthesize a large amount of a conductive polymer / polyelectrolyte complex, a chemical polymerization method using an oxidizing agent can be employed. However, the conductive polymer / polyelectrolyte composite synthesized by the chemical polymerization method can be obtained only in powder form. The molded body is brittle and difficult to handle simply by pressing the powder as it is, and when used as a battery positive electrode, the conductivity decreases due to the penetration of the electrolyte between the powders, and the energy density is improved. Therefore, it is necessary to improve the positive electrode for a battery. Therefore, a method for forming a conductive polymer / polymer electrolyte composite film is an issue.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a conductive polymer /
The following two methods were employed to produce a polymer electrolyte composite film. (1) Film forming method of conductive polymer / polymer electrolyte composite using solubilized conductive polymer as binder Soluble conductive polymer insoluble in organic solvent in organic solvent
Performs a process of, organic solvent a conductive polymer which is the solubilized
Dissolve in the medium . After the conductive polymer / polymer electrolyte composite powder is uniformly dispersed in this solution, it is cast on a substrate.
Then the organic Solvent was evaporated, the conducting polymer / polyelectrolyte complex film was formed on a substrate to produce a functional device.

[0005] (2) an organic solvent insoluble conductive polymer / insoluble conductive polymer / polyelectrolyte complex powder according solubilized cast film molding method organic solvent polyelectrolyte complex It performs a process of solubilizing the organic solvent, after dissolving the powder in an organic solvent medium, casting the solution on a substrate. Thereafter, the organic solvent is evaporated to form the film on the base material, whereby a functional element is manufactured.

[0006]

The two techniques adopted in the present invention, namely, (1)
A method of forming a cast film of a conductive polymer / polymer electrolyte composite using a solubilized conductive polymer as a binder, and (2) a method of forming a conductive polymer / polymer electrolyte composite insoluble in an organic solvent. The conductive polymer / polyelectrolyte composite film produced by the cast film forming method by solubilization has a higher strength than the direct compression molded product of the conductive polymer / polyelectrolyte composite powder. And the energetic density increases.

The following are examples of the conductive polymer / polymer electrolyte composite insoluble in an organic solvent, which is the object of the present invention. Polyaniline / polyvinylsulfonate, polyaniline / polystyrenesulfonate, polyaniline / perfluorosulfonate, polypyrrole / polyvinylsulfonate, polypyrrole / polystyrenesulfonate, polypyrrole / perfluorosulfonate, polythiophene / polyvinylsulfonate , Polythiophene / polystyrene sulfonate ion, polythiophene / perfluorosulfonic acid ion, poly (3-methylthiophene) / polyvinyl sulfonate ion, poly (3-methylthiophene) / polystyrene sulfonate ion, poly (3-methylthiophene) / Perfluorosulfonic acid ion, poly (3-butylthiophene) / polyvinylsulfonic acid ion, poly (3-butylthiophene) ) / Polystyrenesulfonic acid ion, poly (3-butylthiophene) / perfluorosulfonic acid ion,

[0008]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Synthesis Example 1 Synthesis of Polyaniline / Polyvinylsulfonate Ion Complex Using Perchloric Acid Aqueous Solution
06M, 0.03M of sodium polyvinyl sulfonate having an average molecular weight of 1,000 was dissolved. While maintaining the perchloric acid aqueous solution at −3 ° C., 50 ml of a 1.8 mol / l aqueous solution of ammonium persulfate was added dropwise over 1 hour with stirring. After stirring for another 3 hours after dropping, the mixture was filtered through a glass filter. The filtrate was washed with distilled water and acetonitrile, and then dried under vacuum at 40 ° C. for 24 hours. The dry weight of the filtrate was 4.1 g. As a result of elemental analysis of the filtrate, the S / N ratio was 1.12 / 1. According to the infrared absorption spectrum, peaks of 1,290 cm ⁻¹ and 1,480 cm ⁻¹ characteristic of polyaniline are observed, and 1,030 cm ⁻¹ characteristic of sulfonic acid ion are observed.
The synthesis of the polyaniline / polyvinylsulfonate ion complex was confirmed by the peak at ^-1 .

Synthesis Example 2 Synthesis of polyaniline / polyvinyl sulfonic acid ion complex using aqueous hydrochloric acid solution Synthesis Example 1 was repeated except that 300 ml of a 2 mol / l aqueous hydrochloric acid solution was used instead of 300 ml of a 2 mol / l aqueous perchloric acid solution. A polyaniline / polyvinyl sulfonic acid ion complex was synthesized in exactly the same manner. The dry weight of the synthetic filtrate was 4.6 g. As a result of elemental analysis of the filtrate, the S / N ratio was 1.24 / 1. According to the infrared absorption spectrum, 1,1, which is specific to polyaniline,
290 cm ^-1, is observed each peak of 1,480cm ^-1,
Further, the peak of 1,030 cm ⁻¹ characteristic of sulfonic acid ions was observed, thereby confirming the synthesis of the polyaniline / polyvinyl sulfonic acid ion complex.

Synthesis Example 3 Synthesis of polyaniline / polystyrenesulfonate ion complex using perchloric acid aqueous solution Except for using sodium polystyrenesulfonate in place of sodium polyvinylsulfonate in Synthesis Example 1, the same method as in Synthesis Example 1 was used. Was used to synthesize a polyaniline / polystyrene sulfonic acid ion complex. The average molecular weight of the sodium polystyrene sulfonate used here was 5,000.
Met. The dried weight of the filtrate was 5.9 g, and as a result of elemental analysis of the filtrate, the S / N ratio was 0.81 / 1. In the infrared absorption spectrum of the filtrate, 1,290 cm ⁻¹ , 1,480
observed each peak cm ^-1, but also by the peak of 1,030Cm ^-1 is unique is seen sulfonate ion was confirmed the synthesis of polyaniline / polystyrene sulfonate ion complex.

Synthesis Example 4 Synthesis of polyaniline / polystyrene sulfonate ion complex using aqueous hydrochloric acid solution Synthesis Example 2 was repeated except that sodium polystyrene sulfonate having an average molecular weight of 5,000 was used instead of sodium polyvinyl sulfonate in Synthesis Example 2. A polyaniline / polystyrene sulfonic acid ion complex was synthesized in exactly the same manner. The dried weight of the filtrate was 6.1 g, and the S / N ratio was 0.83 / 1 as a result of elemental analysis of the filtrate.
In addition, in the infrared absorption spectrum of any filtrate,
1,290 cm ^-1 , 1,48 unique to polyaniline
The synthesis of the polyaniline / polystyrene sulfonic acid ion complex was confirmed by each peak at 0 cm ^{-1 and} the peak at 1,030 cm ^-1 characteristic of sulfonic acid ions.

Synthesis Example 5 Synthesis of Polypyrrole / Polyvinylsulfonate Ion Complex In 300 ml of 0.8 mol / l aqueous solution of iron (III) chloride, 0.04 M of sodium polyvinylsulfonate having an average molecular weight of 1,000 was dissolved. 0 ° C.
While stirring, 0.1 M of pyrrole was added all at once. After the addition, the mixture was stirred for 2 hours and filtered with a glass filter. The filtrate was washed with distilled water and acetonitrile, and then dried under vacuum at 40 ° C. for 24 hours. The dry weight of the filtrate was 7.3 g. As a result of elemental analysis of the filtrate, the S / N ratio was 0.76 / 1. Further, in the infrared absorption spectrum, 1,5
Show a peak of 50 cm ^-1, and by the peaks of 1,030Cm ^-1 is unique is seen sulfonate ion was confirmed the synthesis of polypyrrole / poly vinyl sulfonic acid ion complex.

Synthesis Example 6 Synthesis of Polypyrrole / Polystyrene Sulfonate Ion Complex In the same manner as in Synthesis Example 5, except that sodium polystyrene sulfonate having an average molecular weight of 70,000 was used instead of sodium polyvinyl sulfonate in Synthesis Example 5. A polypyrrole / polystyrene sulfonic acid ion complex was synthesized. The dry weight of the filtrate was 7.4 g. As a result of elemental analysis of the filtrate, the S / N ratio was 0.80 / 1. Also, in the infrared absorption spectrum of the filtrate, a peak at 1,550 cm ^-1 characteristic of polypyrrole was observed, and a peak of 1,030 cm ^-1 characteristic of sulfonic acid ions was observed.
The synthesis of polypyrrole / polystyrenesulfonate ion complex was confirmed by the peak of ^-1 .

Synthesis Example 7 Synthesis of polyaniline 2 ml / l hydrochloric acid aqueous solution 300 ml aniline 0.06 M
Was dissolved. While stirring the aqueous hydrochloric acid solution at -3 ° C, a 1.8 mol / l aqueous ammonium persulfate solution 5 was stirred.
0 ml was added dropwise over 1 hour. After stirring for another 3 hours after dropping, the mixture was filtered through a glass filter. The filtrate was washed with distilled water and acetonitrile, and then dried under vacuum at 40 ° C. overnight. The dry weight of the filtrate was 4.2 g. In addition, in the infrared absorption spectrum of the filtrate, 1,290 cm ⁻¹ , 1,480 c
The synthesis of polyaniline was confirmed by observing each peak of m- ¹ .

Example 1 Formation of Polyaniline / Polyvinylsulfonate Complex Film by Procedure 1 The polyaniline powder synthesized in Synthesis Example 7 was N-methyl-2.
Hardly soluble in organic solvents such as pyrrolidone; Then, 2 g of the polyaniline powder synthesized in Synthesis Example 7 was put into 200 ml of a 3% ammonium hydroxide aqueous solution, and the bath temperature was changed to 120 ml.
Reflux at 2 ° C. for 2 hours. After the reflux, the mixture was filtered through a glass filter, and the filtrate was washed with ethanol, distilled water, and acetonitrile. After washing, vacuum drying was performed at 40 ° C. for 24 hours to prepare an alkali-treated polyaniline. The dry weight of the alkali-treated polyaniline was 1.6 g. The alkali-treated polyaniline could be dissolved in N-methyl-2-pyrrolidone (NMP). A 10% NMP solution of alkali-treated polyaniline was prepared and used as a binder solution. After pouring 0.18 g of the polyaniline / polyvinyl sulfonic acid ion composite powder synthesized in Synthesis Example 1 into 2 ml of the binder solution, the powder was stirred and homogeneously dispersed. This solution 1
After casting 00 μl on a stainless steel plate, it was vacuum-dried at 80 ° C. for 24 hours to form a polyaniline / polyvinyl sulfonic acid ion composite film.

Example 2 Formation of Polyaniline / Polystyrene Sulfonate Ion Composite Film by Method 1 Instead of the polyaniline / polyvinyl sulfonate ion composite powder used in Example 1, polyaniline / polystyrene sulfone synthesized in Synthesis Example 3 A polyaniline / polystyrene sulfonate ion composite film was formed in exactly the same manner as in Example 1 except that the acid ion composite powder was used.

Example 3 Formation of Polypyrrole / Polyvinylsulfonate Ion Composite Film by Method 1 Instead of the polyaniline / polyvinylsulfonate ion composite powder used in Example 1, polypyrrole / polyvinylsulfone synthesized in Synthesis Example 5 A polypyrrole / polyvinylsulfonate ion composite film was formed in exactly the same manner as in Example 1 except that the acid ion composite powder was used.

Example 4 Polypyrrole / polystyrenesulfonate ion composite film formation by Method 1 Instead of the polyaniline / polyvinylsulfonate ion composite powder used in Example 1, polypyrrole / polystyrenesulfonate synthesized in Synthesis Example 6 A polypyrrole / polystyrenesulfonate ion composite film was formed in exactly the same manner as in Example 1 except that the ion composite powder was used.

Example 5 Alkali-treated polyaniline / polyvinyls according to technique 2
Film formation of sulfonic acid ion complex Polyaniline / polyvinyl sulfone synthesized in Synthesis Example 2
1 g of acid ion composite powder in 3% aqueous ammonium hydroxide
Put into 100 ml of liquid and reflux at bath temperature of 120 ° C for 2 hours
did. After reflux, the solution is filtered through a glass filter, and the filtrate is distilled.
Washed with water, acetonitrile. All day and night at 40 ° C after washing
Vacuum dried, alkali treated polyaniline / polyvinyls
A sulfonate ion composite powder was prepared. Dry weight is 0.
57 g. The alkali-treated polyaniline / poly
Elemental analysis of vinyl sulfonate ion composite powder
As a result, the S / N ratio was 0.98 / 1. Also infrared absorption
According to the spectrum, 1,2 is characteristic of polyaniline.
90cm^-1, 1,480cm ^-1Each peak of
1,030cm which is peculiar to the sulfonic acid ion^-1No
Can be seen even after alkali treatment.
Phosphorus / polyvinyl sulfonate ion complex
confirmed. The alkali-treated polyaniline / polyvinyl
10 mg of sulfonic acid ion complex powder to 1 ml of NMP
And stirred at 20 ° C for 3 hours to dissolve NMP.
After preparing the solution, it was cast on a stainless steel sheet and immediately
Vacuum dried at 0 ° C for 8 hours to cast-fill the composite
Formed.

Example 6 Film formation of alkali-treated polyaniline / polystyrenesulfonate ion composite by Method 2 1 g of the polyaniline / polystyrenesulfonate ion composite powder synthesized in Synthesis Example 4 was alkali-treated in the same manner as in Example 5 to give an alkali. A treated polyaniline / polystyrenesulfonate ion composite powder was prepared. Dry weight is 0.5
9 g. As a result of elemental analysis of the alkali-treated polyaniline / polystyrenesulfonate ion composite powder, the S / N ratio was 0.77 / 1. According to the infrared absorption spectrum, 1,2, which is specific to polyaniline,
90cm ^-1, observed each peak 1,480Cm ^-1, also by the peak of 1,030Cm ^-1 is specific to sulfonate ion is observed, after the alkali treatment at polyaniline / polystyrene sulfonate ion complex Confirmed that there is. A polyaniline / polystyrenesulfonate ion was prepared in the same manner as in Example 5 except that the alkali-treated polyaniline / polystyrenesulfonate ion composite powder was used instead of the alkali-treated polyaniline / polyvinylsulfonate ion composite powder. A composite cast film was formed.

Example 7 Preparation of Oxidized Polyaniline / Polyvinylsulfonate Ion Composite Film A cast film of the alkali-treated polyaniline / polyvinylsulfonate ion composite prepared in Example 5 was prepared as follows.
C., immersed in a 0.5 mol / l aqueous solution of perchloric acid for 1 hour, washed with distilled water, vacuum-dried at 80.degree.
An oxidized polyaniline / polyvinyl sulfonic acid ion composite film was formed.

Example 8 Preparation of Oxidized Polyaniline / Polystyrenesulfonate Ion Composite Film Instead of the alkali-treated polyaniline / polyvinylsulfonate ion composite film prepared in Example 7, the alkali-treated polyaniline / polystyrenesulfonate ion composite film prepared in Example 6 was prepared. An oxidation-treated polyaniline / polystyrenesulfonate ion composite film was formed in the same manner as in Example 7, except that the polystyrenesulfonate ion composite film was used.

Example 9 Formation of a film of a phenylhydrazine-treated polyaniline / polyvinylsulfonate complex according to Method 2 200 mg of the alkali-treated polyaniline / polyvinylsulfonate complex powder prepared in Example 5 was put into 100 ml of phenylhydrazine. And stirred at 20 ° C. for 3 hours. After stirring, the mixture was filtered with a glass filter, and the filtrate was washed with methanol. After washing, vacuum drying was performed at 40 ° C. for 24 hours to prepare a phenylhydrazine-treated polyaniline / polyvinylsulfonic acid ion complex. Dry weight is 150
mg. As a result of elemental analysis of the phenylhydrazine-treated polyaniline / polyvinyl sulfonic acid ion composite powder, the S / N ratio was 0.92 / 1. According to the infrared absorption spectrum, peaks of 1,290 cm ⁻¹ and 1,480 cm ⁻¹ characteristic of polyaniline are observed, and 1,030 cm ⁻¹ characteristic of sulfonic acid ion are observed.
The peak at ^-1 confirmed that the polyaniline / polyvinylsulfonate ion complex was obtained even after the phenylhydrazine treatment. 10 mg of the phenylhydrazine-treated polyaniline / polyvinylsulfonate ion complex powder was added to 1 ml of NMP, and stirred at 20 ° C. for 3 hours to prepare an NMP solution. Vacuum drying was performed for 8 hours to form a cast film of the composite.

Example 10 Molding of a phenylhydrazine-treated polyaniline / polystyrenesulfonate ion composite film by Procedure 2 In place of the alkali-treated polyaniline / polyvinylsulfonate ion composite powder in Example 9, the alkali prepared in Example 6 was used. A phenylhydrazine-treated polyaniline / polystyrenesulfonate ion composite powder was prepared in exactly the same manner as in Example 9 except that the treated polyaniline / polystyrenesulfonate ion composite powder was used. The dry weight was 160 mg. As a result of elemental analysis of the phenylhydrazine-treated polyaniline / polystyrene sulfonic acid ion composite powder, the S / N ratio was 0.71 / 1. According to infrared absorption spectrum, 1,290Cm ^-1 is specific to polyaniline, observed each peak 1,480Cm ^-1, also the peak of 1,030Cm ^-1 is specific to sulfonate ion is observed As a result, it was confirmed that the polyaniline / polystyrene sulfonic acid ion complex was obtained even after the phenylhydrazine treatment. Example 9
And the phenylhydrazine-treated polyaniline / polystyrenesulfonate ion composite powder is used instead of the phenylhydrazine-treated polyaniline / polystyrenesulfonate ion composite powder. A cast film of the acid ion complex was formed.

COMPARATIVE EXAMPLE 1 Compression molding of polyaniline / polyvinyl sulfonic acid ion composite powder Untreated, alkali-treated, and phenylhydrazine-treated polyaniline / polyvinyl sulfonic acid synthesized or prepared in Synthesis Example 1, Example 5, and Example 9 Ion composite powder 10
mg on a stainless steel mesh, 20 ° C, 230k
It was compression molded at g / cm ² .

Comparative Example 2 Compression molding of polyaniline / polystyrenesulfonate ion composite powder Synthesis Example 3 was used instead of the untreated, alkali-treated, and phenylhydrazine-treated polyaniline / polyvinylsulfonate ion composite powders in Comparative Example 1. Embodiment 6 and Embodiment 10
The polyaniline / polystyrenesulfonate ion composite powder is compression-molded in exactly the same manner as in Comparative Example 1 except that the untreated, alkali-treated, and phenylhydrazine-treated polyaniline / polystyrenesulfonate ion composite powders synthesized or prepared in Step 1 are used. did.

Comparative Example 3 Compression Molding of Polypyrrole / Polyvinylsulfonate Complex Powder 10 mg of the polypyrrole / polyvinylsulfonate complex powder synthesized in Synthesis Example 5 was placed on a stainless steel mesh and compressed at 20 ° C. and 230 kg / cm ² . Molded.

COMPARATIVE EXAMPLE 4 Compression molding of polypyrrole / polystyrene sulfonate ion composite powder Instead of polypyrrole / polyvinyl sulfonate ion composite powder in Comparative Example 3, polypyrrole / polystyrene sulfonate ion composite powder synthesized in Synthesis Example 6 The polypyrrole / polystyrenesulfonate ion composite powder was compression-molded in exactly the same manner as in Comparative Example 3 except for using.

Table 1 shows the energy densities of the various conductive polymer / polymer electrolyte composite films formed by the method 1. Table 2 shows the energy densities of various conductive polymer / polymer electrolyte composite films formed by the method 2. For comparison, Table 3 shows the energy densities of various conductive polymer / polymer electrolyte composite powder compacts. All the energy densities were performed under the same conditions. That is, 1 mol / l of propylene carbonate solution of lithium perchlorate was used as an electrolyte and lithium was used as a negative electrode, and the current density was evaluated at 0.1 mA / cm ² . The energy density of the conductive polymer / polymer electrolyte composite film of the present invention is higher than the energy density of any molded product obtained by compression molding the conductive polymer / polymer electrolyte composite powder. As a result, the performance was improved as a positive electrode for a battery.

[Table 1]

[Table 2]

[Table 3]

[0030]

According to the present invention, it is possible to form a conductive polymer / polymer electrolyte composite film having improved energy density.

Claims (2)

(57) [Claims] 1. A variable non soluble conductive polymer in an organic solvent
And solubilizing treatment is dissolved in an organic solvent, after which the conducting polymer / polyelectrolyte complex powder was uniformly dispersed in the organic solvent, it was cast on the substrate surface, and evaporated thereafter organic solvent A method for forming a conductive polymer / polymer electrolyte composite film, comprising forming a film on a substrate surface. 2. A method for solubilizing a conductive polymer / polymer electrolyte composite powder insoluble in an organic solvent, dissolving the powder in an organic solvent, casting the powder on a substrate surface, and evaporating the organic solvent. A method for forming a conductive polymer / polyelectrolyte composite film, comprising forming a film on the surface of a substrate by heating.