JPS60150563A - Manufacture of polymer compound storage battery - Google Patents

Abstract

PURPOSE:To economically manufacture a storage battery with a simplified process by directly utilizing the battery case and positive, negative electrodes used for combining a polymer film at the surface of positive electrode as the lead storage battery case and positive, negative electrodes. CONSTITUTION:A monomer and polymer support electrolyte are dissolved into polarity organic solvent within a battery case 4 in order to form non aqueous electrolyte solution for polymerization. A positive electrode 1 consisting of a substance having resistivity to oxidation such as platinum and carbon etc. and a negative electrode 3 consisting of metallic or carbonic material such as iron or copper, etc. are at least partly immersed into non aqueous electrolyte solution for polymerization in such a manner that they are separated each other and a polymer film of monomer is precipitated on the surface of positive electrode 1 through electrolytic polymerization by supply an electrolytic current through application of a DC voltage across the positive and negative electrodes 1 and 3. The non-aqueous electrolyte solution for polymerization is taken out from the battery case 4 and the non-aqueous electrolyte solution obtained by dissolving supply electrolyte for battery into the polarity organic solvent is supplied to the battery case 4.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a storage battery with a positive electrode body using a conductive polymer compound, a high Coulombic efficiency in charging and discharging, and a length of 4 cm in a simple process. be.

As storage batteries, alkaline storage oil or lead storage batteries are common, but recently a polymer compound storage battery that uses a conductive polymer compound as a film-like material has been proposed. .

This method attempts to form an S battery by using a membrane of a conductive polymer compound having a conjugated π (pi) bond such as polyvirau/I/ as an electrode body and immersing the electrode body in an electrolyte solution. .

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

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

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

(CH) n + Cdo4-r±(OH) n"'
ClO4-10e CA) (CH)n+L+ + e
(CH)n-・Li+CB'), -1---2- (However, in the above formula, (CH)n is polyacetylene, Ce0a- is a perchlorate ion, Li+ is a lithium ion, and e- is (Represents an electron.) Both formulas (A) and CB) above occur reversibly, and a storage battery is formed in which the reaction of formulas (A) and CB) is the positive electrode reaction, and the reaction of formula 9CB) is the negative electrode reaction. Charging can be performed by moving to the left, and discharging can be performed by moving to the left.

This type of polymer compound storage battery takes advantage of the polymer compound itself, which has a low specific gravity and is formed into a membrane shape, and can reduce the weight of the electrodes and increase the energy density and power density of the battery. Conceivable.

By the way, as a conventional method for producing a storage battery having a polymer compound film on an electrode body, the polymer compound film is synthesized outside the battery case using a Tiegts-Natsuta type catalyst, etc., and 1! It has been proposed that the material be molded into a shape suitable for a pole body and then assembled as a battery electrode.

However, this method requires a complicated process of taking out the synthesized polymer film and assembling it into an electrode body, and when assembling this electrode body.

There is a problem in that the polymer film is susceptible to external influences and may undergo oxidative decomposition. For example, the polyacetylene membrane synthesized by the conventional method described above contains impurities such as residual catalyst, and is extremely unstable in the air and susceptible to oxidative decomposition reactions. All steps up to assembly must be performed under an inert gas atmosphere.

As mentioned above, the conventional manufacturing method for polymer compound storage batteries requires a large number of steps because it must be carried out under strict conditions that do not affect the monopolymer.

The cost will be very high.

The present invention overcomes the drawbacks of the above-mentioned conventional methods, synthesizes a polymer compound film that can be used as a positive electrode body for a storage battery, uses the film in a storage battery without being affected by external influences, and requires fewer manufacturing steps. It is an object of the present invention to provide a method of manufacturing a storage battery at low cost.

That is, 1. The method for manufacturing a polymer compound storage battery of the present invention is as follows:
A monomer and a supporting electrolyte for polymerization are dissolved in a polar organic solvent in a container to form a non-aqueous electrolyte solution for polymerization, and oxidation-resistant materials such as platinum and carbon are added to the non-aqueous electrolyte solution for polymerization. A positive electrode made of a substance such as iron, a negative electrode made of a metal such as iron or copper, or a carbon-based material are immersed at least partially so that they do not come into contact with each other, and a DC voltage is applied between the positive and negative electrodes. a first step of depositing a polymer film of the monomer on the surface of the positive electrode through an electrolytic polymerization reaction by applying an electrolytic current;

A second step of taking out the polymerization non-aqueous electrolyte solution from the battery container and injecting a battery non-aqueous electrolyte solution in which a battery supporting electrolyte is dissolved in a polar organic solvent into the battery container. It is something.

According to the method of the present invention, when synthesizing a single polymer film, the battery container and the positive and negative 1! This is because the coffin is used as it is as a storage battery container and positive and negative electrode bodies, and a storage battery is formed by simply replacing the non-aqueous electrolyte solution.

A storage battery can be moved sideways through a simple process and at low cost. Furthermore, the battery container is sealed.

It is not necessary to carry out the process under an inert gas atmosphere as in the conventional case.

In addition, in this method, the polymer film is formed by electrolytic polymerization reaction, so compared to that synthesized using a conventional Ziegts-Natsuta type catalyst.

There is no contamination due to residual catalyst, and the polymer film has excellent electrical properties, and the positive electrode body of a storage battery using the polymer film can have extremely stable electrical properties.

In this way, in the method of the present invention, all you have to do is replace the non-aqueous solute solution! The container for depolymerization can be directly applied to a storage battery.1 Since there is no need to directly handle the synthesized polymer membrane, it can be used as the main body of a storage battery without damaging the polymerization process. can. Also, electric f
Just by providing a replacement port for the non-aqueous electrolyte solution in the II, you can!
No matter what shape the tank has, it is possible to form an accumulator in a simple way.

The present invention will be explained in more detail below.

The polymer compound storage oil produced by the method of the present invention is:

In principle, it consists of a non-aqueous electrolyte solution made of a polar organic solvent containing a supporting electrolyte, a battery container in which the solution is stored, and positive and negative electrode bodies immersed in the solution. It uses a polymer membrane of a compound. The polymer film is a film of a polymer compound that has conductivity due to conjugated π (pi) bonds, etc., and when used in the positive electrode of a storage battery, performs oxidation and reduction reactions and plays a role in charging and discharging. It is. That is, the anions of the supporting electrolyte in the non-aqueous electrolyte solution are doped/undoped with the polymer membrane of the positive electrode body, and the cations are doped/undoped with the negative electrode body through oxidation/reduction reactions as shown in the following chemical reaction formulas [C) and CD), respectively. The battery is then charged and discharged.

P + h-;== p+ -A + e-LC)+ 13 + e'' (p) (However, in the above formula, P is a polymer membrane, and A-1B+ is an anion and a cation of the supporting electrolyte, respectively.

e- represents an electron. ) Both the above formulas (C) and CD) occur reversibly, the reaction of formula 0 (C) occurs on the positive electrode body, and the reaction of formula 1 (D) occurs on the negative electrode body, and the reaction moves to the right from the charging riko.

In the positive electrode body, the anion A- is doped into the polymer film.

On the other hand, by discharging, the reaction moves to the left, and in the positive electrode body, the anion A- in the polymer film is dissolved in the solution again.
Can be charged and discharged.

In the present invention, it is desirable to use a polypillow θ-based compound or a polythiophene-based compound as the polymer compound, and either one or both of them may be used.

In the first step of the present invention, the above polymer film is formed by electrolytic polymerization reaction. First, in a container made of a material such as polyethylene or polypropylene, a monomer that forms a polymer film by an electrolytic polymerization reaction and a support polymer for polymerization are dissolved in a polar organic solvent. Form a water electrolyte solution.

The monomer is preferably a virol compound or a thiophene compound, and either one or both of them may be used. Examples of the virol compound include virol and N-alkylvirol.

In the present invention, it is N-arylvirol.

One of these or 2 m or more is used. In other words, the thiophene compound is thiophene or 8-alkylthiophene, and one or both of these are used. For example, if only a hahilol compound or a thiophene compound is used, the amount to be mixed is 1 g of polar organic solution K. 0.01-1% of a monomer of a virol-based compound or a monomer of a 1,000-ohne-based compound, respectively.
It is desirable to blend within the range of 0 mol. In addition, when using both a virol compound and a thiophene compound, use a polar organic solvent. 0.0 pyrrole compounds
5~lO-! : Jv, thiophone compound from 0.01
It is preferable to mix within a range of 6 moles.

If the amount is smaller than the above range, it is difficult to form a polymer film with a large surface area suitable for the positive electrode body of a storage battery, and if it is larger than the above range.

There is a possibility that the dissolved amount of the supporting electrolyte for polymerization coexisting in the nonaqueous electrolyte solution decreases.

The supporting electrolyte for polymerization becomes an electrical conductor when dissolved in a polar organic solvent, and includes metal chlorates, fluoroborates, fluorophosphates, sulfates, and the like. Examples of the above-mentioned perchlorates include lithium perchlorate, sodium perchlorate, potassium perchlorate, silver perchlorate, etc., and examples of the fluoroborates include lithium tetrafluoroborate,
Examples of the fluorophosphate include sodium tetrafluoroborate, potassium tetrafluoroborate, etc., and examples of the fluorophosphate include lithium hexafluorophosphate, sodium hexafluorophosphate, potassium hexafluorophosphate, and the like. In the present invention.

One or more types of these supporting electrolytes are used. Preferably, Q uses lithium perchlorate, which has stable electrical characteristics.

In addition, the amount of the polar organic solvent 11) is 0.01~
It is desirable that the amount is 2 moles. The blending amount is 0.0
If the amount is less than 1 mol, the resistance of the solution will be so large that it will be difficult to pass current steadily, while if it exceeds 2 mol, it will be difficult to completely dissolve the supporting electrolyte in the solution. .

In the present invention, the polar organic solvent dissolves the monomer and the supporting electrolyte, and immerses the positive and negative electrode bodies in the polar organic solvent to allow current to flow therethrough.

A nonaqueous solvent with a high decomposition voltage of <<1 is used to cause oxidation of the positive and negative electrode bodies. For example, when an aqueous solution is used, electrolysis of water occurs in the aqueous solution when electricity is applied, oxygen is generated, oxidizes the positive and negative electrodes, and the decomposition voltage of this water limits the voltage. This is because batteries of this voltage may not be manufactured.

Examples of the polar organic solvent include propylene carbonate and sulfone. Examples include acetonitrile, benzonitrile, nitrobenzene, nitromethane, dimethoxyethane, dimethyl sulfate, etc., and one or more of these may be used. Note that 9 of the polar organic solvents above generate heat when energized.

Preferred is propylene carbonate, sulfophane, which is very stable.

Further, 1 Dendan container is not affected by the non-aqueous electrolyte solution,
It is made of a material having electrical insulation properties, and polyethylene, polypropylene, glass, etc. are preferable.

Thereafter, at least a portion of the positive electrode and the negative electrode is immersed in a non-aqueous electrolyte solution for polymerization containing the monomer and supporting electrolyte so that they do not come into contact with each other, and a DC voltage is applied between the positive and negative electrodes. , the monomer is subjected to an electrolytic polymerization reaction to form a polymer film of the monomer! Perform the process of forming on the extreme surface. in this case,
In order to form multiple polymer films in a single electrolytic polymerization operation,
A plurality of positive and negative electrodes may be arranged alternately and immersed in the electrolyte solution. Furthermore, the battery container may be divided into several cells, and the electrolyte solution and the positive electrode may be arranged in each cell/L/. - You may insert a negative electrode and connect the terminal.

The positive electrode is a conductor that does not undergo oxidative dissolution or passivation in a non-aqueous electrolyte solution.

For example, platinum, gold, nickel, stainless steel, graphite, carbon, carbon composite material, etc. are used.

Since a polymer film of the above monomer is precipitated on the surface of this positive electrode, it is desirable to use a plate-like, net-like, plating-like, or vapor-deposited shape as the shape of the positive electrode. . Further, the negative electrode is also a conductor that does not undergo oxidative dissolution or passivation in a non-aqueous electrolyte solution, such as platinum, aluminum, or magnesium.

Iron, copper, nickel, carbon composite materials, etc. are banned. The thicknesses of the positive and negative electrodes are set to 0 and 1, respectively, in order to take advantage of the weight reduction when forming a polymer compound storage battery.
It is desirable that the distance be within the range of ~100011 m.

Note that the positive and negative electrodes are directly connected in a non-aqueous electrolyte solution.

To prevent contact, place a separator between the positive and negative electrodes.
! An insulator such as a solution holding material and a spacer may be arranged. When using a separator among the above insulators,
It is desirable to use a material that does not impede permeation of the electrolyte solution, such as polypropylene nonwoven fabric.

By connecting the positive electrode and the negative electrode to a DC power source and applying a DC voltage, the monomers in the solution cause an electrolytic polymerization reaction. Through this polymerization reaction, a polymer film of the above monomer is deposited on the surface of the positive electrode. This is positive because polymerization begins by oxidation of the monomer, that is, the loss of electrons! This is thought to be due to the polymerization reaction proceeding on the extreme surface.

For example, when a pyrrole compound and a thiophene compound are used as monomers, one or both of the mixed polymer or copolymer consisting of the polypyrrole compound and the polythiophene compound is formed on the positive WL electrode surface by this polymerization reaction. It is thought that a polymer film consisting of

The conditions for this electrolytic polymerization are positive tf@0 per unit area.
．． It is desirable to apply a current with a current density of 1 to 1 OmA/d. If the current density is less than 01 mA/d, @
The electrical properties and life performance of the formed polymer will be lowered, and on the other hand, if tomA/1ffl is exceeded, there is a possibility that the polymer film will not be formed.

Note that even if the flow density is 10 mA/cd or more! The potential of the positive electrode may affect polymer formation, so a silver electrode (Aflo, o l M
The potential of the positive electrode when using Alcloa) is 2,5
It is desirable to make it V or more. If the potential exceeds 25V, a good polymer film may not be formed.

In addition, the zero current conduction time varies depending on the current density, but
In general, when the polymer film formed for one current application time at the same current density is made of a polypyrrole-based compound or a polythiophene-based compound.

It is desirable to set current conditions so that the polymer film has a thickness of 1 to 110007z and a bulk density of each film of 0.4 to 1.8Q/Cd. When the polymer film formed under these conditions is applied to the positive electrode body of a storage battery.

The coulombic efficiency of charging and discharging is high, almost 100%.

Moreover, the overvoltage is small even after repeated charging and discharging.
It is stable.

In the second step of the present invention, the non-aqueous electrolyte solution for polymerization is taken out from the container container in which the 9-polymer membrane obtained in the first step is synthesized, and placed in the container container.

Simply inject a non-aqueous battery electrolyte solution in which a supporting electrolyte for batteries is dissolved in a polar organic solvent, and use the other battery containers and positive and negative WLfM as they are for storage battery containers and positive and negative electrode bodies. It forms the

As the supporting electrolyte for the battery, metal perchlorate, fluoroborate, fluoride! p salt, sulfate, etc. are used. However, 'I! The supporting electrolyte for the pond may be the same compound as the supporting electrolyte for polymerization used in the first step, or may be a different compound. Also.

It is desirable that the blending amount is the same as in the previous V pigeon weighing.

Also, as the polar organic solvent, the r@sexual #! used in the first step may also be used. As well as solvents, propylene carbonate, sulfone, acetonitrile, benzonitrile, nitrope, nitrogen, dimethoxyethane.

In the present invention, one or more of these are used.

In this second step,! The reason for replacing the non-aqueous electrolyte solution in the tank container is that the above monomer may remain in the non-aqueous electrolyte solution during the synthesis of the polymer membrane, and this residual monomer may affect the charging and discharging of the storage battery. This is because it is thought that there is a risk that the electrical characteristics of 1W may be lowered.

As a way to replace the upper rudder non-aqueous laxative solution.

By providing two entrances and exits in the container, one for the solution and one for the solution, you can drain and pour the solution naturally, or use vacuum or pressure to increase the rate of exchange. It may be forcibly discharged or injected.

By connecting the positive and negative electrode bodies in the manner described above, a polymer compound storage battery is obtained. In addition, when a plurality of positive and negative electrodes are arranged alternately in order to form a large amount of polymer film in a single electrolytic polymerization operation during the synthesis of the polymer film described in +i+1, a high-capacity single cell battery can be obtained.

In addition, high capacity, high voltage multiple cell/I/cell batteries can be easily produced.

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

Hereinafter, the present invention will be explained in detail.

Example 1 A schematic diagram of a storage battery manufactured in this example is shown in FIG.

Correct! ! 5 pieces of carbon cloth l with a thickness of 11007z as poles
0 pieces. 99 sheets of polypropylene nonwoven fabric 2, which also serves as a separator and an electrolyte holding material, and 50 sheets of aluminum plate 8 with a thickness of 100 μm for the negative electrode are stacked one after another, and these are placed in a polyethylene battery case equipped with a drain port 41. container 4
The upper end 11 of the Carpore cloth fJ and the upper end 81 of the aluminum plate were sandwiched and attached with a stainless steel strap 5. Next, attach the polyethylene lid 6 with the injection port 61 with only the upper end of the strap exposed.
The space between the battery container and the lid was sealed.

A nonaqueous electrolyte solution for polymerizing propylene carbonate 1e as a polar organic solvent with a monomer to form a polymer film was injected into this container from the injection port 61 until the strap 5 was immersed in the nonaqueous electrolyte solution. .

Next, the electrolytic cell was connected to a DC power source so that the carbon cloth was polarized positively and the aluminum plate was polarized negatively.

A constant current of 7 mA/cd per unit area of the positive electrode was applied for 60 minutes, and positive! Polypyrrole polymer film on the extreme surface.

Lithium was deposited on the surface of each negative electrode. The polymer film had a bulk density L of 26 f/d and a thickness of about 70 Jim.

The carbon cloth on which this polymer film was deposited and the aluminum plate on which lithium was deposited were used as positive and negative electrode bodies for storage batteries, respectively. A non-aqueous battery electrolyte solution in which 240 moles of lithium perchlorate as a battery supporting electrolyte was dissolved in propylene carbonate 11 as an organic solvent was injected from the injection port 61 to produce a storage battery according to the present invention. A potential difference of about 8 μm was generated between the positive and negative electrodes of this ':# battery.

The storage battery is discharged with a constant current of tmA/d per unit area of the positive electrode (discharged until the potential difference between the positive and negative electrodes becomes IV), and then with a constant current of 1mA/d. (The doping amount of perchlorate ions is 20% of the number of monomer molecules constituting the polymer.) Charge/discharge cycles were repeated to examine the life performance. The results are shown in curve A in FIG. From FIG. 2, it can be seen that the storage battery according to the present invention has a high coulombic efficiency and can be repeatedly charged and discharged about 800 times.

Example 2 The same polar organic solvent 1 polymerization support S! as in Example 1 except that NJ tilpyrrole monomer was used as the monomer for forming the polymer film. Solyte, prepare a non-aqueous electrolyte solution for polymerization with the blended amount, and! When electricity is applied during depolymerization, the polymer film of tilvirol is
Lithium was deposited on the surface of the negative electrode. The polymer film had a bulk density of 127y7cm and a thickness of about 807zm.

Next, in the same manner as in Example 1, the non-aqueous electrolyte solution in the battery container was replaced to produce a storage battery according to the present invention. Using this storage battery, a charge/discharge test was conducted in the same manner as in Example 1, and its life performance was evaluated. The results are shown in curve B in FIG. From FIG. 2, the storage battery according to the present invention has a high coulombic efficiency and can be repeatedly charged and discharged.

It can be seen that it has a long life.

Example 8 Propylene carbonate 16 as a polar organic solvent, 0.1 mol each of virol monomer and thiophene monomer, and 0 lithium perchlorate as supporting electrolyte for polymerization.
A non-aqueous electrolyte solution for polymerization was prepared by dissolving 2 moles of the solution, and the solution was poured into the same container as in Example 1, and a current density of 8 mA/d per unit area of the positive electrode was applied for 80 minutes to conduct electrolytic polymerization. A storage battery according to the present invention was manufactured by replacing the non-aqueous electrolyte solution. The positive electrode body of the storage battery has a bulk density L 10 f /cd and a film thickness of about 80 μm on the surface of the positive electrode for 9 polymerization.
A polymer film consisting of polybillow and polythiophene was deposited.

Using the storage battery, a charge/discharge test was conducted in the same manner as in Example 1, and its life performance was measured. The results are shown in curve C in FIG.

From Figure 2, it can be seen that the storage battery of this invention has a high coulombic efficiency and can be repeatedly charged and discharged.

Example 4 A schematic diagram of a storage battery manufactured in this example is shown in FIG. A polypropylene nonwoven fabric with a size of Iomxlm that doubles as a separator and electrolyte holding material! One sheet of 1!0, thickness 10011 m, size 121 as a positive electrode
: One sheet of carbon cloth 10 of x1m, one sheet of polypropylene non-woven fabric 20 similar to the above, and one aluminum plate 80 of thickness 1007ztn and size 12(7) x1m as a negative electrode were stacked one after the other and rolled up. . Put this into a polyethylene ring tube 7 equipped with a drain lower 1, and fill it with an inlet 8.
Attach the stainless steel vxtBco top lid 8 equipped with 1 so as to be in contact with the aluminum plate of the negative electrode, and similarly attach the stainless steel bottom lid 82 so as to be in contact with the carbon cloth of the positive electrode.
The top cover and bottom cover are each used as a terminal and sealed.

A WL tank was formed.

Next, propylene carbonate as a polar organic solvent) 1
A non-aqueous electrolyte solution for polymerization in which 0.2 moles each of virol monomer and lithium perchlorate as a supporting electrolyte for polymerization are dissolved in 1 is injected into the container through the injection port 81 until the top lid comes into contact with the solution. did. Connect the top and bottom lids of the battery to the bus terminal and negative terminal of a DC power source, respectively, and apply a constant current of qmh/cA per unit area to the positive terminal for 80 minutes. Lithium was deposited on the plate surface. The polymer film had a bulk density of 1.26y7 cm and a film thickness of about 9071 m.

The non-aqueous electrolyte solution for polymerization was taken out from the drain lower 1 of this container using a pachyme, and then from the injection port 81 in Example 1.
Inject a non-aqueous battery electrolyte 'Ift solution under pressure,
A storage battery according to the present invention was manufactured by replacing the nonaqueous electrolyte solution and using a carbon cloth on which the above polymer 1 pattern was deposited and an aluminum plate on which lithium was deposited as a positive electrode body and a negative electrode body, respectively.

The accumulation'F! ! A charging and discharging test was conducted using a pond as in Example 1, and its life performance was measured. The result is shown by curve p) in FIG.

From FIG. 2, it can be seen that the KW cell according to the present invention has a high coulombic efficiency and can be repeatedly charged and discharged.

Example 5 The same polar organic solvent 1 as in Example 4 except that N-4,000 rubyroyl monomer was used as the monomer for forming the polymer film.
A non-aqueous electrolyte solution for polymerization was fabricated using the supporting electrolyte for polymerization and the blended amount. A storage battery according to the present invention was manufactured by replacing the non-aqueous electrolyte solution.

The positive electrode body of the storage battery has a bulk density of 1 on the surface of the positive electrode for polymerization.
A polymer film of polyN-methylpyrrole with a film thickness of about 7011 m and a film thickness of 2 sf/d was deposited.

Using the storage battery, a charge/discharge test was conducted in the same manner as in Example 1, and its life performance was measured. The results are shown in curve E in FIG.

It can be seen from FIG. 2 that the storage battery according to the present invention has a high coulombic efficiency and can be repeatedly charged and discharged.

Example 6 In propylene carbonate 11 as a polar organic solvent, 0.1 mole each of virol monomer and thiophene monomer were added, and 0.01 mole of lithium perchlorate was added as a supporting electrolyte for polymerization.
1! in the same manner as in Example 4, except that a non-aqueous electrolyte solution for polymerization was prepared by dissolving 2 moles! A storage battery according to the present invention was manufactured by depolymerizing and replacing the nonaqueous electrolyte solution.

The positive electrode body of the storage battery has an overlapping degree of 1 on the surface of the positive electrode for polymerization.
．． A polymer film consisting of polypyrrole and polythiophene with a film thickness of 121/CtA and 7Q7zm was precipitated.

Using the storage battery, a charge/discharge test was conducted in the same manner as in Example 1, and its life performance was measured. The results are shown in curve F in FIG.

It can be seen from FIG. 2 that the storage battery according to the present invention has a high coulombic efficiency and can be repeatedly charged and discharged.

[Brief explanation of drawings]

FIG. 1 and FIG. 8 show Example 1, respectively. FIG. 2 is a schematic diagram of the storage battery according to the present invention in Example 4, and shows the charging/discharging life performance curve of the storage VL battery in Examples 1 to 6t. 1, 10... Positive electrode, l 20... Separator and electrolyte holding material, 3,130... Negative wL electrode 4.7...
・ Battery container, 41.71... Drain port 81.81...
・Inlet Figure 3 Figure 2 Cycle hot times

Claims (1)

[Claims] (11 [In a tank container, a monomer and a supporting electrolyte for polymerization are dissolved in a polar organic solvent to form a non-aqueous electrolyte solution for polymerization, and in the non-aqueous electrolyte solution for polymerization, A positive electrode made of an oxidation-resistant substance such as platinum or carbon, and a negative electrode made of a metal such as iron or copper or a carbon-based material are immersed at least partially so that they do not come into contact with each other. A first step of depositing a polymer film of the monomer on the surface of the electrode by electrolytic polymerization reaction by applying a DC voltage between the electrodes and passing an electrolytic current. A second step of removing the non-aqueous electrolyte solution for polymerization from the tank container and injecting a non-aqueous battery electrolyte solution in which a supporting electrolyte for batteries is dissolved in a polar organic solvent into the battery container. A method for manufacturing a molecular compound storage battery. (2) The monomer is one or both of a pyrrole compound and a thiophene compound.
A method for manufacturing a polymer compound storage battery as described in . (8) The supporting electrolyte for polymerization is a metal perchlorate. 1f of fluoroborates, fluorophosphates, and sulfates
The method for manufacturing a polymer compound storage battery according to claim (1), wherein fi or two or more types. (4) The supporting electrolyte for batteries is a metal perchlorate. The polymer compound storage battery according to claim 1, which is one or more of fluoroborates, fluorophosphates, and sulfates! Il construction method. (5) The polar organic solvent is propylene carbonate. Sulfide, acetonitrile IV, benzonitrile. Nitrobenzene, nitromethane, dimethoxyethane, F
The method for producing a polymer compound storage battery according to claim (1), wherein one or more of dimethyl i and dimethyl chloride is used. (6) What is the electrolytic current? The method for producing a polymer compound storage battery according to claim 11, wherein the positive Wl electrode has a positive Wl electrode of 0.1 to 1 OmA/d per unit area.