JPS61245468A - Nonaqueous electrolyte storage battery - Google Patents

Abstract

PURPOSE:To prevent droppage of polyaniline thus to enable stable repetition of charge/discharge by forming the macromolecular complex body of positive electrode with complex material of polyaniline and polypyrrol compound for coating said polyaniline. CONSTITUTION:Polyaniline electrolyte 2 is conditioned into an electrolytic tank 1 containing water dissolved with unit quantity aniline and perchloric acid as the supporting electrolyte then a carbon paper positive electrode 31 and two sheets of negative electrodes 32 are immersed to perform electrolysis thus to deposit collected needle polymer or polyaniline onto the surface of electrode 31. Then an electrode where polyaniline is deposited as the positive electrode and carbon paper negative electrodes are immersed into polypyrrol electrolyte where pyrrol unit material and lithium perchlorate as the supporting electrolyte are dissolved into propylene carbonate as the polarity organic solvent thereafter D.C. constant current is fed to deposit polypyrrol onto polyaniline. When employing such macromolecular complex material as the positive electrode, droppage of polyaniline under operation is eliminated resulting in stable repetition of charge/discharge.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a storage battery having a positive electrode body using a conductive polymer such as polyaniline and having high stability during repeated charging and discharging.

[Conventional technology]

Recently, conductive polymer membrane! A polymer compound storage battery with a polar body has been proposed. In this method, a storage battery is formed by using a conductive polymer film with conjugated π (bi) bonds, such as polyacetylene or its derivative polypyrrole, as an electric box and immersing it in an electrolyte solution. .

For example, use a polyacetylene film as the positive electrode.

In a storage battery used as a negative electrode body, by immersing these electrode bodies in an electrolyte solution consisting of lithium perchlorate, the following chemical reaction formula [A] can be achieved.

It is thought that the reaction shown in CB) occurs, and the anions of perchlorate ions or cations of lithium ions become 1 through electrochemical oxidation and reduction, and are doped/undoped into the polyacetylene film.

(However, in the above formula, (OH)n&1 polyacetylene, ago7 represents a perchlorate ion, m Li+ represents a lithium ion, and e- represents an electron.) Both the above formulas (A) and CB) occur reversibly, and the formula 90 (A )
A storage battery is formed in which the reaction of equation 9 (CB) is the positive electrode reaction and the reaction of equation 9 (CB) is the negative electrode reaction.In both cases, charging can be performed by moving the reaction to the right, and discharging can be performed by moving the reaction to the left.

Such polymer compound storage batteries take advantage of the advantages of the polymer compound itself, which has a low specific gravity and is formed in a membrane shape, and can reduce the weight of the electrodes and increase the energy density and power density of the battery. Its completion is awaited.

Many conductive polymers that can be used for the positive electrode body of this storage battery are known, such as polyacetylene, polythiophene, polyvirau μ, Horipa 5-phenylene, and polyaniline. The stability of each of these polymers against charging and discharging [(doping/undoping of anions) depends on the amount of electricity charged and discharged per unit weight of the polymer.

That is, when the amount of charge and discharge electricity per unit weight of the polymer is large, the cycle life of charge and discharge is short.

Conversely, if the amount of electricity charged and discharged is small, the cycle life is long. However, these relationships are not constant among each polymer and vary depending on the polymer used.

For example, in the case of polyacetylene, 0.05 Ah/I
If Psyche/L' is repeated with 10 charges and a complete discharge*1, the cycle life is about 45 cycles, while polythiophon has about 90 cycles with 0.05 Ah/(/), and polypyrrole has about 90 cycles with 0.05 Ah/(/). Ha0.064A
Approximately 300 cycles with an amount of electricity of h/l, polybuffe=V
Approximately 40 cycles with an amount of electricity of uO, 05Ah/7,
For polyaniline, the electricity amount of 0.15Ah/7 is approximately 300
It's a cycle.

As described above, among conductive polymers, polyaniline has a relatively large amount of electricity that can be stably charged and discharged, and has the greatest potential for use as a positive electrode body of a storage battery.

Polyaniline is usually composed of aniline monomer (○-MHz
) It is easily polymerized on the anode by electrolytic oxidation in an acidic aqueous solution containing t-. The polymer thus obtained has needle-shaped precipitates with a large surface area. Therefore, when such a polymer is used as a positive electrode body of a storage battery, it has the advantage that dopant anions can smoothly move in and out during charging and discharging.

However, on the contrary, since it is a needle-shaped polymer, the bonding force between molecules is extremely weak, and a part of one polymer easily detaches from the electrode, and it also has the disadvantage that resistance overvoltage during charging and discharging is large.

[Problem that the invention seeks to solve]

The present invention aims to improve the drawbacks of the conductive polymer used as the positive electrode body, to provide a storage battery that has a positive electrode body with reduced resistance overvoltage and is highly stable during repeated charging and discharging. It is.

[Means for solving problems]

The nonaqueous electrolyte storage battery of the present invention comprises a nonaqueous electrolyte solution containing a supporting electrolyte in a polar organic solvent, a container for storing the nonaqueous electrolyte solution, and a negative electrode at least partially immersed in the nonaqueous electrolyte solution. and a positive electrode body, the positive electrode body comprising a current collecting conductor and a polymer composite in close contact with the current collecting conductor, the polymer composite comprising polyaniline and the polyaniline. It is characterized by consisting of a polymer consisting of one or both of a polypyrrole compound and a linear polythiophene compound coated or bound together.

The present invention will be explained in detail below.

The nonaqueous electrolyte storage battery of the present invention basically consists of a nonaqueous electrolyte solution made of a polar organic solvent containing a supporting electrolyte, a container for storing the solution, and a positive electrode immersed in the solution. It consists of a negative electrode body. In the present invention, the positive electrode body is composed of a current collecting conductor and a polymer composite in close contact with the current collecting conductor. The polymer composite consists of polyaniline and a polymer coated or bonded to it, and the polymer coated or bonded to the polyaniline is one or both of a polypyrrole compound and a polythiophene compound.

The above polymer composite is a polymer that has conductivity due to conjugated R (pi) bonds, and when used in the positive electrode body of the storage battery of the present invention, it undergoes an oxidation/reduction reaction with the supporting electrolyte, that is, an anion of the supporting electrolyte. It is doped/undoped and plays the role of charging and discharging. The shape of the polymer composite is a porous body with a large surface area so that the anions of the supporting electrolyte can be easily doped/undoped without local concentration and the coulombic efficiency of charging and discharging is high. The polymer composite is a state in which a needle-like body of polyaniline, which is a needle-like polymer, is coated with or bound to one or both of a polypyrrole compound or a polythiophone compound, and is made of a continuous fibrous material. It has become a body. In this way, since the polymer covers or binds phoria, the internal resistance is low and polyaniline is less likely to be desorbed. Therefore, the polymer composite has good stability against charging and discharging.

In addition, what is in close contact with the current collecting conductor may be only the polyaniline in the polymer composite, or may be only the polymer that coats or binds to the polyaniline. Furthermore, both the polymer and polyaniline may be in close contact with the current collecting conductor.

The polymer coated or bonded to the Boryanine is.

One or both of a polypyrrole compound and a polythiophon compound.

As the above-mentioned polypyrrole compound, polyvirow/L'
, 'Poly-
N-alkylvirol, polyN-arylvirol, and! The above-mentioned polythiophone compounds include:
Examples include polythiophene and poly-3-alkylvirol. In the present invention, one of these may be used, or a mixed polymer or copolymer of two or more of these may be used.

In addition, the shape of the polymer composite is a membrane-like body.

It is preferable to use it in the form of granules or powder, and among these, it is desirable to use it as a film, which has excellent adhesion to the current collecting conductor when used as a positive electrode. When the polymer composite is used as a film-like body, the thickness of the film-like body is preferably within the range of 1Qlzm to 1cm. A membrane-like material within the above range is easily doped/undoped by the supporting electrolyte.

Further, the ratio of polyaniline in the polymer composite to the polymer coated or bonded thereto is desirably within the range of 3 to 2 Qwt% of the polyaniline.

When the proportion exceeds 20 wt%, the excellent charge and discharge characteristics of polyaniline are not exhibited.

On the other hand, if it is less than 3%, the effect of strengthening the bonding force between polyaniline molecules may be reduced.

Note that when the polymer composite is used in the form of granules or powder, a conductive material such as carbon may be mixed therein and used in the positive electrode body.

The supporting electrolyte in the storage battery of the present invention dissolves in a polar organic solvent and becomes an electrical conductor.

The anion of the dissolved supporting electrolyte undergoes the following chemical reaction formula (0
) and CD), doped/reduced by oxidation/reduction reaction.
It is undoped and then charged and discharged.

(However, in the above formula, P is the above-mentioned polymer complex.

A and B are the anion and cation of the supporting electrolyte, e
″′″ represents an electron. ) That is, both the above formulas (C) and CD) occur reversibly99
The reaction of formula (0) occurs at the positive electrode, and the reaction of formula (1) occurs at the negative electrode, and upon charging, the reaction moves to the right, and at the positive electrode, the anion is doped into the polymer. on the other hand,
By discharging, the reaction moves to the left, and the anions in the polymer are dissolved in the solution again in the positive electrode body, allowing charging and discharging to be performed.

The supporting electrolytes include metal perchlorates, fluoroborates, fluorophosphates, v&acids, iodides, bromides, and the like. As for the above perchlorate.

For example, lithium perchlorate, sodium perchlorate.

Potassium perchlorate, silver perchlorate, etc. are mentioned, and the fluoroborate is lithium tetrafluoroborate.

Examples of the fluorophosphate include sodium tetrafluoroborate, potassium tetrafluoroborate, and the like, and examples of the fluorophosphate include lithium hexafluorophosphate, sodium hexafluorophosphate, potassium hexafluorophosphate, and the like.

For example, when lithium perchlorate is used as the supporting electrolyte, perchlorate ions (CeO,1) serve as dianions, and lithium ions (L i ″) serve as cations, respectively, serving as carriers of charging and discharging.

In the present invention, one or more of the above-mentioned supporting electrolytes are used. Moreover, it is desirable that the compounding amount is 0.01 to 2 moles in the polar organic solvent 1e. If the amount is less than 0.01 mol,
This lowers the resistance of the solution, making it difficult to pass current steadily, and furthermore, the charging and discharging capacity may become smaller. On the other hand, 2
If the mole is exceeded, the supporting electrolyte in the solution becomes saturated.

It becomes difficult to completely dissolve the supporting electrolyte.

The polar organic solvent dissolves the supporting electrolyte and allows current to flow by immersing the positive and negative electrode bodies.
In the present invention, a non-aqueous solvent that does not easily cause oxidation of the positive and negative electrode bodies is used. In other words, this is because when an aqueous solution is used, applying electricity causes electrolysis of water in the aqueous solution, generating oxygen and oxidizing the positive and negative electrode bodies.In addition, the solvent itself is also oxidized. Use materials that do not decompose through reduction. As the polar organic solvent.

Frohilev carbonate. Examples include sulfofane, acetonitrile, benzonitrile, nitrobenzene, nitromethane, dimethoxyethane, dimethyl sulfate, etc., and one or FX or two or more of these are used. Among the above polar organic solvents, propylene carbonate and nullholane are preferable because they are extremely stable against heat generation during charging and discharging.

The positive electrode body in the present invention is composed of a current collecting conductor and a polymer composite as described above. The method for producing the polymer composite is preferably electropolymerization from the viewpoint of electrochemical properties of the polymer composite formed, but synthesis may also be performed using an oxidizing agent, a catalyst, etc.

Next, a method for producing this polymer composite by electrolytic polymerization will be explained in detail.

To explain the case of manufacturing polyaniline, an aniline monomer and a supporting electrolyte are dissolved in water to form an electrodepositing solution for polyaniline synthesis.

The ratio t of this aniline monomer is 0.01 to 1e of water.
The amount is preferably within the range of 10 moles. When the blending amount is less than 0.01 mol or more than 10 mol/l, it is difficult to form a polymer suitable for a positive electrode body of a storage battery.

As an explanation for the above-mentioned supporting electrolyte, it is preferable to use an acid having the same anion as the supporting electrolyte used in the W storage tank, that is, perchloric acid, fluoroboric acid, fluorinated phosphoric acid, sulfuric acid, iodic acid, bromic acid, etc. Yes. In addition, if after synthesizing polyaniline, the anion doped in the same electrodeposition solution is dedoped, and then a polymer consisting of one or both of a polypyrrole compound and a polythiophone compound is electrodeposited on the polyaniline. Other acids such as hydrochloric acid may also be used. The amount of the supporting electrolyte is 0.05/-57 per 1e of water.
It is desirable to be within the range of .

Thereafter, the positive electrode and the negative electrode are immersed in an electrodepositing solution containing an aniline monomer and a supporting electrolyte so as not to come into contact with each other, and a DC voltage is applied between the positive and negative electrodes. is electrolytically reacted with Togane to form a polyaniline film on the positive electrode.

A polyaniline film is deposited on this positive electrode.

Aniline monomer is oxidized. In other words, it is thought that the polymerization reaction progresses on the surface of the positive electrode because polymerization starts when electrons are taken away.

Since the polyaniline electrodepositing solution is an acidic aqueous solution, the above-mentioned positive electrode is a conductor that does not undergo oxidative dissolution in the electrolytic deposit9. For example, platinum, gold, nickel/L/, stainless steel, graphite, carbon , using carbon composite materials, etc. Since a polyaniline film is deposited on the surface of this positive electrode, the shape of the positive electrode may be plate-like, net-like, plated film-like,
It is desirable to use a vapor-deposited film. In addition, the negative electrode is a conductor that does not dissolve in the electrodepositing solution, and is made of platinum.

Examples include stainless steel, 2, KEL, and carbon composite materials.

Further, as conditions for the applied DC voltage, it is desirable that the range provides a current density of 0.1 to 10 M/d per unit area of the positive electrode. When the current density is less than 0.1 mA/d, it takes a long time to synthesize polyaniline;
If it exceeds A/d, there is a risk that the electrical properties and life performance of polyaniline will deteriorate.

Generally, for the same current density, if the 0-current time is longer,
The thickness of the polyaniline film thus formed increases accordingly. Therefore, it is desirable to set the current application time so that the film thickness is within the range of 110 l1 to 1 molar. Note that this polyaniline film is an aggregate of needle-like polymers, and after the synthesis of the polyaniline film, the The film thickness may be controlled within the above range by applying pressure together with the electrode.

Next, a polymer consisting of one or both of a polypyrrole compound and a polythiophone compound is deposited on the synthesized polyaniline Ws (aggregate of acicular polymers) by electrolytic polymerization. Due to the precipitation of this polymer, the polyaniline is coated or bonded with the polymer. In this case, the electrode on which the polyaniline film is formed is used as a positive electrode for the next electrolytic polymerization.

In addition, the polyaniline film was peeled off from the synthesis electrode.

It may also be used as a pole for secondary electrolytic polymerization by closely contacting another conductor. Furthermore, the polyaniline film is made into powder.

Thereafter, it may be pressure-molded into a film-like body on a conductor to serve as an electrode for the next electrolytic polymerization.

The electrolytic polymerization of a polymer consisting of one or both of a polypyrrole compound and a polythiophone compound is described in Japanese Patent Application No. 58-214855 and Japanese Patent Application No. 1983, previously filed by the present applicant.
It is preferable to carry out the method shown in Japanese Patent Application No. 8-254474 and Japanese Patent Application No. 58-247601.

In this method, a negative electrode and a positive electrode made of a conductor to which the polyaniline film is closely attached are immersed in a support chamber non-aqueous electrolyte solution such as perchlorate or fluorophocate.

A DC voltage is applied between the positive and negative electrodes.

As a result, a polymer of one or both of the polypyrrole compound and the polythione compound is deposited on the polyaniline film of the positive electrode.

The conditions for this electrolytic polymerization are preferably similar to those in the three applications mentioned above. Under these conditions, the formed polymer can be smoothly doped/undoped with anions during charging and discharging, and has a long life as a coating material or a binding material for polyaniline.

Since the electrodeposition of a polymer consisting of one or both of a polypyrrole compound and a polythiophone compound onto the polyaniline is carried out from a non-aqueous electrolyte solution, synthesis of polyaniline must be carried out after thoroughly washing and drying the hindlimb polyaniline with distilled water. No.

A polymer complex is formed as described above.

The polymer composite is brought into close contact with a current collecting conductor to produce a positive electrode body for a storage battery according to the present invention. In this case, the polymer composite may be brought into close contact with a current collecting conductor as it is. 9
When used as a granular or powdered material, it may be mixed with a conductive material such as carbon and brought into close contact with a current collecting conductor.

The current collecting conductor is a conductor that does not undergo oxidative dissolution or passivation in the nonaqueous electrolyte solution of the storage battery, and includes platinum, gold, nickel, carbon, and the like. Incidentally, the polymer was used when producing the above-mentioned polymer composite by electrolytic polymerization. [A material similar to the conductor of Wl can be used and therefore used during the production of the polymer composite9
A polymer complex was deposited on the surface! The electrode may be used as it is as the main body of the storage battery. In addition, the shape of the current collecting conductor is preferably plate-like, net-like, plated film-like, vapor-deposited film-like, etc., and its thickness is 0.1 to take advantage of the weight reduction of polymer compound storage batteries. A range of 1.000 pm is desirable.

Methods for bringing the current collecting conductor and the polymer composite of the present invention into close contact include a method that utilizes the fact that the polymer composite is deposited on the positive electrode during electrolytic polymerization, as well as pressure bonding or vapor deposition. There are ways to do this.

As the negative electrode body of the storage battery of the present invention, lithium, potassium,
Conductive polymers that can be doped/undoped with cations of the supporting electrolyte such as alkali metals such as sodium or alloys of these alkali metals with tin, aluminum, magnesium, etc. or ions of the above-mentioned alkali metals can be used. As a molecule, it is polyacetylene.

Examples include polythiophene.

At least a portion of the positive and negative electrode bodies is immersed in the non-aqueous electrolyte solution so that they do not come into contact with each other. In this case, in order to increase the charging and discharging capacity of one storage battery, a plurality of positive and negative electrode bodies may be alternately arranged and immersed.

Furthermore, the container of the storage battery of the present invention is made of a material that is not susceptible to the nonaqueous electrolyte solution and has electrical insulation properties, and is preferably made of polyethylene, polypropylene, glass, or the like. In addition, when arranging multiple positive and negative electrode bodies alternately, divide the storage battery container into several cells,
An electrolyte solution and positive and negative electrode bodies may be placed in each cell, and the cells lv may be connected.

As described above, a storage battery according to the present invention is obtained by storing a non-aqueous electrolyte solution in a container, immersing the positive and negative electrode bodies, and connecting the positive and negative electrode bodies.

In addition, in order to prevent the positive and negative electrode bodies from coming into direct contact in the non-aqueous electrolyte solution, there is a separator between the positive and negative electrode bodies. ! An insulator such as a solution holding material and a spacer may be arranged. When a separator is used among the above-mentioned insulators, it is desirable to use all insulators that do not impede permeation of the electrolyte solution, such as polypropylene nonwoven fabric.

In the storage battery according to the present invention, during charging, the polymer complex of the positive electrode body is oxidized, and a doping reaction of anions in the electrolyte solution to the polymer complex occurs. On the other hand, during discharging, the polymer complex is reduced and the anions doped in the polymer complex are dissolved into the solution again, and charging and discharging are performed by this mechanism.

〔Effect of the invention〕

According to the present invention, since polyaniline used as a positive electrode body is coated with or bonded to a polymer made of one or both of a polypyrrole compound and a polythiophene compound, the intermolecular bonding force of the polyaniline is strong and A storage battery having a positive electrode body with low resistance overvoltage can be provided.

Further, in the storage battery of the present invention, the polyaniline of the positive electrode body does not fall off during operation as in the conventional case, and can be repeatedly charged and discharged stably.

〔Example〕

The present invention will be explained in detail below.

Example 1 FIG. 2 shows an electrolytic cell for synthesizing the polymer composite used for the positive electrode body in this example, and FIG. 1 shows a cross section of a storage battery using the positive electrode body.

First, a polymer composite was formed as follows. A polyaniline electrolyte solution 2 was prepared with water. A positive electrode 31 made of carbon vapor with a length of 50 mm x 50 ff x a thickness of 400 μm and two negative electrodes 32 made of the same material are immersed in this electrodeposition solution so as to face each other.・The negative electrode was connected to a DC power source. This electrolytic cell has a positive tm of 3 mA per unit area.
The total amount of electricity flowing through the constant current tube for 102 minutes at a current density of /d 1
8.4C/C''), electrolysis was performed to deposit polyaniline on the surface of the positive electrode 31.

This polyaniline is 8EM<scanning electron M mirror in Figure 5.
Size 0.03-5 as shown in the photo (3080x magnification)
It is an aggregate of 1 tm needle-like polymers.

After thoroughly washing the polyaniline deposited on this jwLm with distilled water, it was vacuum heated and dried at a temperature of 150°C.
I went between Vf.

Thereafter, using an electrolytic cell similar to that shown in FIG. 2, pyrrole monomer and lithium perchlorate as a supporting electrolyte were added to propylene carbonate 1e as a polar organic solvent at 0.0.
The electrode in which the polyaniline was precipitated as a positive electrode and the negative electrode made of carbon vapor were immersed in a 2 mol polypillow μ electrodeposition solution, and the positive and negative electrodes were connected to a DC power source, and the positive electrode unit was immersed. Per area! A constant current of J 7 mA/d was passed for 2.9 minutes (total electric charge 1.2 c/d) to deposit polypillow on the polyaniline.

The total weight of this polymer composite consisting of polyaniline and polypyrrole is 12. It was a film-like body with a bwy/d-thickness of 4QQμm. Further, the weight ratio of polyaniline and polypyrrole is 95:5. This ε polymer composite is shown in the SPM photograph (magnification: 10500) in Figure 4.
As can be seen in Figure 2), it is coated and bound with the acicular polyaniline polymer capolyhyrol, making it a continuous body of fibrous polymer.

Using this polymer composite, a storage battery according to the present invention shown in FIG. 1 was manufactured. That is, the positive electrode body 4 is composed of the polymer composite 41 and a carbon vapor current collector 42 on which the polymer composite is deposited, and the negative electrode body 5 is composed of a mixture of 80% by weight of lithium and 20% by weight of aluminum. An alloy plate was used.

As the non-aqueous electrolyte solution 6, propylene carbonate 1e
The electrolyte solution 6 was prepared by dissolving 1 moA/liter of lithium perchlorate in the electrolyte solution 6 and stored in a container 7.

The positive electrode body 4 and the negative electrode body 5 are immersed in the solution.

A storage battery according to the present invention was manufactured by inserting a polypropylene nonwoven fabric 8 that served as both a separator and an electrolyte holding material between the positive and negative electrode bodies.

Also, for comparison, no polypyrrole coating was performed.

A positive electrode body in which only polyaniline was deposited on a carbon vapor current collector by electrolytic polymerization (the total amount of electricity during electrolytic polymerization was the same as that during the synthesis of the polymer composite described above, and the weight of polyaniline was 12.6
4/d, it is a film-like body with a film thickness of 40011 m. ) was also used, but a comparative storage battery constructed in the same manner as above was also manufactured.

91 mA/per unit area of positive electrode using the above two types of battery tubes
The battery was charged with a constant amount of electricity (10.IAh per 1 g of polymer composite (polyaniline in the comparative example)) at a constant current of d, and this charge/discharge cycle was repeated to examine the voltage characteristics. The results are shown in the curves indicated by - [present invention] and 2 [comparative example] in Fig. 5.

As is clear from FIG. 5, the storage battery according to the present invention has a small voltage difference between charging and discharging, and exhibits excellent voltage characteristics with a low charging voltage, whereas the comparative storage battery has a small voltage difference between charging and discharging. It can be seen that the voltage difference is large and the voltage efficiency is inferior to that of the present invention.

Example 2 The total weight of polyaniline and polypillow μ is 12°6 #
/d, and the weight ratio of polyaniline and polypyrrole was 97:3.90:1 in the same manner as in Example 1.
Three types of polymer composites (all three types were film-like bodies with a film thickness of 4 Q Q IIm) with a ratio of 0 and 80:20 were formed.

These polymer composites were used for positive electrode bodies in the same manner as in Example 1 to produce two storage batteries of the present invention. Table 1 shows the voltage efficiency when these storage batteries were charged and discharged under the same conditions as in Example 1.

In Table 1, the voltage efficiency of each storage battery of Example 1 a [invention] and 2 [comparative example] is also listed. -, b, of the present invention
It can be seen that the storage batteries c and d have higher υ voltage efficiency and smaller internal resistance than Comparative Example 2. Among them-
0. It can be seen that d has the highest efficiency and the ratio of polyaniline and polypyrrole is optimal.

Table 1 Example 3 After polyaniline was prepared in the same manner as in Example 1, polythiophene was electrodeposited on the polyaniline. Polythiophene was deposited at a constant current of 5 mA/- from an electrodepositing solution in which 0.2 mol each of thiophene monomer and lithium perchlorate as a supporting electrolyte were dissolved in propylene carbonate (1e).

In addition, the total weight of polyaniline and polypyrrole 't 1
2.6 q/d and the weight ratio of polyaniline and polypyrrole to 97:3゜95:5,90 using the above method.
:10, 80:20 (all four types were film-like bodies with a film thickness of 400 μm) were formed. Using each polymer composite as a positive electrode body in the same manner as in Example 1, a storage battery e
, f, g, and h were produced.

Table 2 shows the voltage efficiency when charging and discharging the same as in Example 1 using each of these storage batteries.

As is clear from Table 2, a, f, and g of the present invention.

It can be seen that each of the storage batteries h has a higher stain pressure modulus and a lower internal resistance than the comparative storage battery 2 of Example 1.

Table 2

[Brief explanation of drawings]

FIG. 1 is a sectional view of the storage battery of the present invention in Example 1,
Figure 2 shows an electrolytic polymerization production apparatus for a polymer composite used in the positive electrode body of the storage battery of the present invention, and Figures 3 and 4 respectively show the polyaniline electrolytically polymerized in Example 1 and the polymer composite polymer composite used in the positive electrode body of the storage battery of the present invention. 8EM photographs of molecular structures (magnification is 3 for each
080.10500 times 0)・Figure 5 shows 5i!
1 shows voltage characteristic curves of a storage battery of the present invention and a comparative storage battery in Example 1. 31... Pressure electrode for electrolytic polymerization, 32... Negative electrode for electrolytic polymerization, 4... Positive electrode body of storage battery, 41... Polymer composite, 42... Conductor for current collection, 5 . . . Negative electrode body of storage battery, 6. Electrolyte solution, 8. Separator. (2 stones in the throat)

Claims (4)

[Claims] (1) Consisting of a non-aqueous electrolyte solution containing a supporting electrolyte in a polar organic solvent, a container for storing the non-aqueous electrolyte solution, and a negative electrode body and a positive electrode body at least partially immersed in the non-aqueous electrolyte solution. In the storage battery, the positive electrode body is composed of a current collecting conductor and a polymer composite in close contact with the current collecting conductor, and the polymer composite includes polyaniline and a polypyrrole-based material coated or bonded to the polyaniline. A non-aqueous electrolyte storage battery characterized by comprising a polymer comprising one or both of a compound and a polythiophene-based compound. (2) The non-aqueous electrolyte storage battery according to claim (1), wherein the polymer composite is a membrane-like body and has a thickness of 10 μm to 1 mm. (3) The supporting electrolyte is one or more of metal perchlorates, fluoroborates, fluorophosphates, sulfates, iodides, and bromides. (1
) The non-aqueous electrolyte storage battery described in item 2. (4) The polar organic solvent is propylene carbonate,
The nonaqueous electrolyte storage battery according to claim (1), which is one or more of sulfolane, acetonitrile, benzonitrile, nitrobenzene, nitromethane, dimethoxyethane, and dimethyl sulfate.