JPS63301462A - Organic electrolyte battery including activated carbon-aniline composite as positive electrode - Google Patents

Abstract

PURPOSE:To make it possible to obtain a secondary battery with a high capacity, a high output and good rapid charge/discharge characteristics by using composite of a certain activated carbon and polimerized matter of aniline as active material for a positive electrode, and using solution of compound which can produce ions subject to doping dissolved in aprotic organic solvent as electrolyte. CONSTITUTION:Composite of activated carbon with a specific surface value of 600m<2>/g or over and polimerized matter of aniline is used as activa material for a positive electrode 1, and solution of compound which can produce ions subject to doping to the active material of the positive electrode 1 by electrolysis dissolved in aprotic organic solvent is used as electrolyte 4. The activated carbon may be in the form of powders, grains, fibers, or fabric as far as the specific surface is 600m<2>/g or over, but preferably porous activated carbon obtained by heat processing aromatic condensation polymer at over 800 deg.C shall be used, for example. An organic electrolyte battery with a large capacity, a high energy density and a good rapid charge/discharge characteristics can thus be obtained.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to organic electrolyte batteries.

More specifically, it relates to an organic electrolyte battery in which the positive electrode active material is a composite of activated carbon and an aniline polymer, and the electrolyte is a solution of a compound capable of producing doped ions dissolved in an aprotic organic solvent.

[Prior Art] In recent years, electronic devices have become increasingly smaller, thinner, and lighter, and there is a strong demand for smaller, thinner, and lighter batteries that serve as power sources. Currently, silver oxide batteries are widely used as small, high-performance batteries, and lithium batteries have been developed and put into practical use as thin dry batteries and small, lightweight, high-performance batteries. However, since these batteries are primary batteries, they cannot be used for long periods of time by being repeatedly charged and discharged. On the other hand, nickel-cadmium batteries have been put into practical use as high-performance secondary batteries, but they have become smaller and thinner.
It is still unsatisfactory in terms of weight reduction.

Furthermore, lead-acid batteries have been conventionally used as large-capacity secondary batteries in various industrial fields, but the biggest drawback of these batteries is that they are heavy. This is due to the fact that peroxide and lead are used as electrodes. In recent years, attempts have been made to reduce the weight and improve the performance of batteries for electric vehicles, but they have not been put to practical use. However, there is a strong demand for a large capacity and lightweight secondary battery as a storage battery.

As mentioned above, each of the batteries currently in practical use has advantages and disadvantages, and each is used differently depending on its purpose.
There is a great need for smaller, thinner, and lighter batteries. As a battery that attempts to meet these needs,
BACKGROUND ART Recently, batteries have been researched and proposed in which film-like polyacetylene, which is an organic semiconductor, is doped with an electron-donating substance or an electron-accepting substance as an electrode active material.

Although this battery has high performance as a secondary battery and has the possibility of being made thinner and lighter, it has a major drawback.

The reason is that polyacetylene, which is an organic semiconductor, is an extremely unstable substance that is easily oxidized by oxygen in the air and deteriorated by heat. Therefore, battery manufacturing must be carried out in an inert gas atmosphere, and there are also restrictions on manufacturing polyacetylene into a shape suitable for electrodes.

Further, JP-A-58-35881@ proposes an electrochemical cell using carbon fiber having a specific surface area of i,ooo to 10,000 m2/9 for at least one electrode. According to the detailed description of the invention in the publication, the carbon fibers have a diameter of 10 to 20 μm, and the electrodes are formed from such carbon fibers, for example, in the form of a sheet.

Furthermore, JP-A No. 61-225761@publication discloses (8) having continuous pores with an average pore diameter of 10 μm or less and at least 60 μm.
A porous activated carbon having a specific surface area value of 0 m2/g by the BET method is used as a positive electrode or a negative electrode, and (B) a solution of a compound in an aprotic organic solvent that generates ions that can be doped into the electrode by electrolysis is electrolyzed. An organic electrolyte battery has been proposed that is characterized by being a liquid.

These batteries have high oxidation stability of the electrode active material and are easy to mold, making them promising secondary batteries for the future.

However, several issues remain to be solved in order to put this battery into practical use. The most important of these challenges is improving battery capacity, especially improving the ability to increase the energy density (extraction).

On the other hand, polyaniline, which is a polymer of aniline, is known as an electrode active material with high oxidation stability, and secondary batteries using polyaniline as a positive electrode have been studied.

However, it has poor rapid charging and discharging characteristics, and its range of use is limited.

Problems to be Solved by the Invention] An object of the present invention is to provide an organic electrolyte battery that has a large capacity and weight, has a high energy density, and has good rapid charging and discharging characteristics.

Another object of the present invention is to provide an organic electrolyte battery that is an economical secondary battery that can be made smaller, thinner, lighter, and easier to manufacture.

Still another object of the present invention is to provide a secondary battery with a high electromotive voltage and excellent charge efficiency over a long period of time.

Further objects and advantages of the present invention will become apparent from the description below.

[Means for Solving the Problem] The present inventor has discovered that by using a composite of activated carbon and an aniline polymer as a positive electrode active material, a secondary battery with large capacity and good rapid charge/discharge characteristics can be obtained. I found out. In other words, the present invention uses (A) a composite of activated carbon having a specific surface area of 600/J or more by the BET method and an aniline polymer as a positive electrode active material, and B) doping the positive electrode active material by electrolysis. This organic electrolyte battery is characterized in that the electrolyte is a solution of a compound capable of producing ions in an aprotic organic solvent.

The activated carbon in the present invention has a surface area of 600 by the BET method.
If it is m2/g or more, it can be powdered, granular, fibrous, or woven.
It is possible to use commercially available products in shapes such as shapes. However, when aromatic condensation polymers are used at high temperatures, such as ao
It is preferable to use porous activated carbon obtained by heat treatment to a temperature higher than o'c. This can be made in pairs. First, an initial condensate is made from an aromatic hydrocarbon compound having a phenolic hydroxyl group or an aromatic hydrocarbon compound having no phenolic hydroxyl group and aldehydes, and an aqueous solution containing this initial condensate and a salt is prepared. death,
This aqueous solution is poured into a suitable mold, and then the aqueous solution is heated while suppressing the evaporation of water to harden in the mold into a shape such as a plate, film, or cylinder. The fired product is fired at 800° C. or higher in an oxidizing atmosphere, and then the resulting fired product is washed to remove inorganic salts contained in the fired product, and if necessary, dried.

The above-mentioned inorganic salt used together with the initial condensate is a pore-forming agent that is removed in a later step and used to provide communicating pores to the activated carbon, such as zinc chloride, tin chloride, sodium chloride, sodium phosphate, and sodium hydroxide. Or sodium sulfide, etc.

Among these, zinc chloride is particularly preferably used.

The inorganic salt is, for example, 2.5 to 10 times the weight of the initial condensate.
It can be used in If the amount is less than the lower limit, it is difficult to obtain porous activated carbon having communicating pores, and if it is more than the upper limit (2), the mechanical strength of the porous activated carbon tends to decrease undesirably.

The aqueous solution of the initial condensate and the IN-free salt can be prepared using, for example, 0.1 to 1 times the weight of water as the liA-free salt, although it varies depending on the type of inorganic salt used.

An aqueous solution of an initial condensate of a phenolic resin and an inorganic salt can be prepared as a homogeneous solution by, for example, adding an aqueous solution of zinc chloride to a water-soluble resol and then stirring, or a methanol solution of a resol and a zinc chloride solution can be prepared. A highly viscous slurry can also be prepared by mixing an aqueous solution. At this time, other additives such as hardened phenol resin powder or fibers, cellulose fine particles, etc. may be mixed into the aqueous solution. Further, as mentioned above, an organic solvent such as methanol, ethanol, or acetone may be added for uniform mixing. Thus (q for example 1
An aqueous solution having a viscosity of 0.000 to 100 poise is poured into a suitable mold and heated to a temperature of, for example, 50 to 200°C. During this heating, it is important to suppress evaporation of water in the aqueous solution. It is thought that the initial condensate is heated in an aqueous solution and gradually hardens, growing into a three-dimensional network structure while separating from an inorganic salt solution such as zinc chloride.

By firing the cured body in a non-oxidizing atmosphere, the cured body can be converted into activated carbon. Firing is usually carried out at a temperature of 800°C or higher.

The preferred rate of temperature increase during firing varies somewhat depending on the phenolic resin used or its shape, but generally it is possible to set a relatively high rate of temperature increase from room temperature to a temperature of about 300°C, for example, 100°C. It is also possible to have a rate of 'C/time.

When the temperature exceeds 300°C, thermal decomposition of the resin begins and gases such as water vapor, hydrogen, methane, and carbon oxide begin to be generated, so once the temperature reaches 300°C, the temperature should be raised at a sufficiently slow rate. is advantageous. The non-oxidizing atmosphere is
For example, nitrogen, argon, helium, neon, carbon dioxide, etc. are used, and nitrogen is preferably used. Such a non-oxidizing atmosphere may be stationary or flowing.

The inorganic salts contained in the fired body can be removed by sufficiently washing the fired body with water, dilute hydrochloric acid, or the like. After removing the inorganic salt, if necessary, drying is performed to obtain porous activated carbon with developed communicating pores. When this powder is used, in a secondary battery using a composite of activated carbon and aniline polymer as the positive electrode active material, which will be described later, the electrolyte can sufficiently enter the inside of the positive electrode.
The internal resistance becomes smaller and the dopant is smoothly doped or undoped into the positive active material, allowing rapid discharge. The average particle size of activated carbon powder is 100
There is no particular problem as long as the thickness does not exceed μm, but in consideration of the ease of molding a composite molded body and the strength of the molded body, which will be described later, it is desirable that the thickness be 30 μm.

The activated carbon used in the present invention has a specific surface area value of at least 600 Trt2/g- according to the BET method. When the specific surface area value is less than 600 rrt/g, when a battery is constructed using a composite of the activated carbon and aniline polymer as a positive electrode active material, it is necessary to increase the charging voltage during charging, for example. This is undesirable because it reduces energy efficiency and may cause deterioration of the electrolyte.

Although aniline or aniline derivatives can be used as the anilines in the present invention, aniline is preferred from a practical standpoint. As the aniline derivative, for example, N-methylaniline, p-aminodiphenylamine, p-toluidine, p-phenylenediamine, 0-phenylenediamine, etc. can be used.

The aniline polymer in the present invention is one obtained by chemically or electrochemically oxidatively polymerizing the above-mentioned anilines.

As a chemical polymerization method, it can be produced, for example, as follows. Anilines or water-soluble salts of anilines are oxidatively polymerized in a reaction medium containing a protic acid and an oxidizing agent. As water-soluble salts, mineral acid salts such as hydrochloric acid and sulfuric acid are generally preferred. Further, as an oxidizing agent, for example, chromium oxide (IV
), chromates such as potassium dichromate and sodium dichromate, manganese-based oxidizing agents such as potassium permanganate, ammonium persulfate, and the like can be used. As the protonic acid, sulfuric acid, hydrochloric acid, hydrobromic acid, tetrafluoroboric acid, hexafluorophosphoric acid, perchloric acid, etc. can be used, but in particular, tetrafluoroboric acid, hexafluorophosphoric acid, perchloric acid, etc. It is desirable to use an acid that produces an anion with a large ionic radius. Water is generally used as the reaction medium, but water-miscible organic solvents such as ketones such as azetone, tetrahydrofuran and acetic acid, ethers or organic acids, and water-immiscible organic solvents such as carbon tetrachloride and hydrocarbons are also used. Organic solvents can also be used.

When an aqueous solution of a protonic acidic oxidizing agent is added dropwise to a solution of a water-soluble salt of an aniline or aniline dissolved in a reaction medium at a temperature below the boiling point of the reaction medium, preferably below room temperature, the reaction usually takes about several minutes. After the induction period, the polymer precipitates immediately.The polymer thus removed contains protonic acid anions even after being thoroughly washed with water, and this is thoroughly washed with an alkaline aqueous solution such as aqueous ammonia and then washed again. Needs to be washed with water.

If even a small amount of impurities such as unreacted substances and excessive protonic acid anions remain in the polymer, the self-discharge characteristics of a secondary battery using a composite of these and activated carbon as the positive electrode active material will deteriorate. This may cause a reduction in cycle life, etc.

As an electrochemical polymerization method, for example, "jyJ
a. A counter electrode using an inert metal, such as platinum, in an acidic solution of anilines or a water-soluble salt of anilines and a protic acid in a reaction medium used in the chemical polymerization process described above. , and e.g. AQ/ACI Cρ standard electrode, saturated calomel standard i%
Prepare an electrolytic cell with a standard electrode such as a j-electrode and an electrolyte.The protonic acid at this time is similar to the chemical polymerization method, such as tetrafluoroboric acid, hex]nofluorophosphoric acid, or perchloric acid. Preferred acids that produce anions with large ionic radii, such as

Using the above electrolytic cell, electrolytic polymerization is carried out within an appropriate potential range for reference (*), that is, within a potential range in which only the action of anilines occurs at the working electrode without decomposition reactions of the solvent and protonic acid. As the polymerization method, a constant current electrolysis method, a constant potential scanning method, etc. are known, but any method may be used as long as the potential of the working electrode is maintained within the appropriate potential width as described in (a) above. The polymer obtained by such a method can be made into a polymer free of impurities by post-treatment similar to the chemical polymerization method.

The composite of activated carbon and aniline polymer in the present invention is (1) a composite of activated carbon powder and aniline polymer powder directly or integrated with a binder; (2) a composite of activated carbon powder and aniline polymer powder; It is preferable to combine anilines by electrochemically polymerizing them.

A composite is obtained by thoroughly mixing activated carbon powder and aniline polymer powder. The composite ratio differs depending on the usage of the secondary battery using the composite as a positive electrode active material, but the composite ratio of activated carbon/aniline polymer is 2 by weight.
It is preferably 0 to 0.05. If it is more than this upper limit or less than this lower limit, the advantages of the composite will be lost, which is not preferable.

When using the composite as a positive electrode, it is necessary to mold the composite into a plate, film, cylinder, or other shape.

Generally, when the composite ratio of activated carbon/aniline polymer is about 1 or less, the aniline polymer itself has Il! Since it has a one-stick property, it can be molded as is to form a positive electrode, but if it exceeds about one, the strength or binding properties of the molded product will decrease, so it is necessary to add a binder.

The type of binder is not particularly limited as long as it is insoluble in the electrolyte solution in the present invention described later, but for example, 38R
Rubber binders such as, fluorine resins such as polytetrafluoroethylene, thermoplastic resins such as polypropylene, polyethylene, etc. are preferable, and the mixing ratio thereof is 20% relative to the total weight of the composite ω.
% or less is desirable.

To form a plate, film, cylinder, etc., a mixture of activated carbon, aniline polymer, and optionally a binder may be placed in a mold and pressure molded at room temperature or under heating if necessary. . In addition, the mixture is kneaded with a suitable solvent, such as water, methanol, DMF, carbon tetrachloride, etc., to form a paste, which is then applied onto a hoovering current collector or applied under pressure. It can also be used as a positive electrode by drying it by an appropriate method after adhesion. Furthermore, the mixture may be kneaded together with an electrolytic solution, which will be described later, in a water-free atmosphere such as argon gas, and then applied or adhered under pressure onto a current collector, which will be described later, and used as it is as a positive electrode.

A composite obtained by electrochemically polymerizing anilines on the surface of activated carbon can be produced, for example, in the following manner.

In the present invention, the white of activated carbon in the form of a plate, film, fabric, etc. is used as a working electrode, and then a polymer of anilines is electrochemically applied to the surface of the activated carbon using a method similar to the electrochemical polymerization method of anilines. can be polymerized. In this case, activated carbon having a large number of communicating pores is particularly preferred.

When a substrate has a large number of communicating pores, in addition to the above-mentioned advantages, it is possible to easily polymerize the aniline polymer not only on the outer surface of the substrate but also on the inner surface thereof, making it possible to form a homogeneous composite. .

The composite ratio of activated carbon and aniline polymer can be adjusted by the amount of charge flowing through the circuit in the case of the above electrochemical composite. For example, by simply inserting a coulomb meter into the circuit and proceeding with electrochemical polymerization until the required amount of charge is reached, it is possible to produce a compound with a certain composite ratio (q), and the range of the composite ratio is as described above. It is.

The composite, which has been completed by electrochemical polymerization, is thoroughly washed for the reason described above and dried to become a positive electrode.

The molded composite of the present invention thus obtained does not change its physical properties such as electrical conductivity even when left in air for a long time, and has excellent oxidation stability. In addition, since it has excellent heat resistance and chemical resistance, there is no problem of electrode deterioration when using it as an electrode material to grow batteries.

Compounds that generate ions that can be doped into the positive electrode active material by electrolysis include, for example, alkali metals or
・Ralkylammonium halide perchlorate,
Examples include hexafluorophosphate, hexafluoroarsenate, tetrafluoroborate, and the like. Specifically, Li L Na I
, KI, NH41, LiCρ04 , Li BF4 ,
LI As F6, Li PF6, Na C, Il
04, Na BF4, Na As F6, Na P
F6, KCN O4, K B F4, KAS F6
, K P F6, (C2H5)4NCΩ04, (n
C48g)4NCfI'04, (t-04Hc)>
4 NCΩ04, (C2to15 > 4 NBF4
, (n-C4Hg)4N B F4 ,
(t-C4to19 > 4 NBF4, (C2
H5) 4 NP ``6, (n-C4to19
) 4NPF 6, (t-C4to19>
4 NPF6, Li B (C2 to!5
)4, Li B (C6to15)
4 Mata (MaLi1) F4 etc. are mentioned.

As the solvent for dissolving the compound, an aprotic precipitate solvent is used. Examples include ethylene carbonate, propylene carbonate, γ-butyrolactone, dimedylformamide, dimedylacetamide, dimedyl sulfoxide, acetonitrile, dimethoxyethane, tetrahydrofuran, dioxolane, sulfolane, or mixtures thereof. It is selected from among these in consideration of the solubility of the compound used as an electrolyte, battery performance, etc.

The Qf% of the former compound in the electrolyte is preferably at least 0.1 mol/fJ or more in order to reduce the internal resistance due to the electrolyte, and is usually 0.2 to 1.5 mol/g. More preferred.

The battery action of the battery of the present invention utilizes electrochemical doping and electrochemical and-doping of a doping agent to a composite of activated carbon and aniline polymer used as a positive electrode active material.

Although it is most practical to use an alkali metal or an alkaline earth metal for the negative electrode of the battery according to the present invention, it is also possible to use an insoluble and infusible substrate manufactured as follows, for example.

The insoluble and infusible substrate can be obtained in the same manner as in the method for producing porous activated carbon, except that the heat treatment temperature in the method for producing porous activated carbon is 350° C. to 350° C. to 350° C. to 350° C. to AOO’C.

The insoluble and infusible substrate has (a) an atomic ratio of hydrogen atoms/carbon atoms of 0.5 to 0.05;
(b) has a specific surface area value of at least 600 m/
'? and (C) having continuous pores with an average pore diameter of 10 μm or less.

Examples of alkali metals and alkaline earth metals include cesium, rubidium, potassium, sodium, lithium, barium, strontium, and lucium. Of these, lithium is most preferred. These metals can be used alone or as an alloy.

The shape and size of the electrode made of a composite molded body placed in the battery can be arbitrarily selected depending on the type of battery intended, but since the battery reaction is an electrochemical reaction on the electrode surface, the electrode It is advantageous to have as large a surface area as possible.

As a current collector for extracting current to the outside of the battery, a conductive material v1 that is resistant to corrosion by doping agents and electrolytes, such as carbon, platinum, nickel, stainless steel, etc., can be used.

Next, embodiments of the present invention will be explained with reference to the drawings. FIG. 1 is a basic configuration diagram of a battery according to the present invention.

In FIG. 1, 1 is a positive electrode, which is a composite molded body in the form of a film or plate, and 2 is a negative electrode.
Similarly, alkali metals in the form of films or plates, etc.
These include alkaline earth metals, alloys of these metals and other metals, or the above-mentioned insoluble and infusible substrates.

3.3' is a current collector for taking out current from the outside (for power saving) or supplying current for electrochemical doping, that is, for charging. It is connected to terminals 7 and 7' in such a way that no voltage drop occurs. Reference numeral 4 represents an electrolytic solution in which the compound described above that can generate ions that can be doped into an aprotic organic solvent is dissolved. The electrolyte must normally be in liquid form, but it can also be used in gel or solid form to prevent leakage.

A separator 5 is arranged for the purpose of preventing contact between the positive and negative electrodes and retaining the electrolyte. The separator is a porous material with no electronic conductivity that provides continuous pores that are durable for electrolytes, doping agents, and electrode active materials such as alkali metals, and is usually made of cloth made of glass fiber, polyethylene, or polypropylene. , nonwoven fabric or porous material.

The thickness of the separator is preferably thin in order to reduce the internal resistance of the battery, but it is determined by taking into account the amount of electrolyte retained, flowability, strength, etc. The positive and negative electrodes and the separator are fixed within the battery case 6 so as not to cause any practical problems. The shape, size, etc. of the electrode are determined as appropriate depending on the shape and performance of the intended battery.

For example, film-shaped electrodes are suitable for manufacturing thin batteries, and large-capacity batteries can be achieved by laminating a large number of film-shaped or plate-shaped electrodes alternately with positive and negative electrodes.

For example, lithium is used as the negative electrode, and Li is used as the electrolyte.
When using CfJO41 mol/ρ propylene carbonate solution, the electromotive force after battery assembly is 2.5 to 3.2V.
It is. Next, apply voltage from an external power supply to Cρ04-
When ions are doped into the positive electrode active material, the electromotive force is 3
．． It becomes 5-4.5v.

Furthermore, when a positive electrode active material made of a composite material is doped with lithium ions by discharging a current to the outside, the electromotive force will be 1.0 to 2.5V. -When pinging, the electromotive force becomes 2.5 to 3.2V again.

Doping or undoping may be performed under constant current, constant voltage, or varying current and voltage conditions.

When the above-mentioned insoluble and infusible substrate is used as the negative electrode, the electromotive force is approximately OV, and by applying a voltage from an external power source and doping both electrodes with the doping agent, the electromotive force is 1.0 to 3.5V.
becomes the electromotive force.

In either case, the amount of doping agent doped into the positive electrode active material is 0.5 to 20 as a percentage of the number of ions doped to one carbon atom of the positive electrode active material.
% is preferred.

The battery of the present invention, which uses a composite of activated carbon and a polymer of anilines as a positive electrode active material, is a secondary battery that can be repeatedly charged and discharged.

Furthermore, the secondary battery of the present invention is a high-performance secondary battery with higher capacity and higher output than conventionally known secondary batteries using activated carbon.

It is also a secondary battery that can be made smaller, thinner, and lighter, and its performance will not deteriorate over a long period of time.

Furthermore, the secondary battery of the present invention is a secondary battery with good rapid charging and discharging characteristics.

Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 (1) An aqueous solution prepared by mixing water-soluble resol (approximately 60% depth)/half chloride/water in a ratio of 10/25/4 at a medium omega ratio.
The mixture was poured into a 00 cm x 100 cm Xo, 5 ann mold, covered with a glass plate to prevent moisture from evaporating, and then heated at a temperature of about 100° C. for 1 hour to harden.

The phenolic resin was placed in a siliconite electric furnace and heated at a rate of 40°C/hour under a nitrogen stream to 900'C.
Baked to . Next, the plate-shaped heat-treated product was washed with dilute hydrochloric acid, water, and dried.

The plate-shaped porous body was pulverized with a disk mill to obtain activated carbon powder with an average particle size of 8 μm. Next, when the specific surface area value was measured by the BET method, it was found to be an extremely high value of 1800'rd/9.

(2) 909 g of distilled water and 9.2 ml of concentrated hydrochloric acid were added, and 10 g of aniline was further dissolved to prepare an aqueous aniline hydrochloride solution. Separately, prepare an oxidizing aqueous solution in which 50 m of perchloric acid (60% aqueous solution > 50 m) and 10.5 g of potassium dichromate are dissolved, and dropwise add this to the above-mentioned hydrochloric acid aqueous solution of aniline at room temperature over 40 minutes while stirring. After stirring for another 15 minutes,
The reaction mixture was poured into 1.5 g of acetone and V
After stirring, the polymer was filtered off. Further washing with stirring in distilled water 1
Then, the mixture was stirred and washed in 1N ammonia water, and filtered.
The filtrate was washed with distilled water until it became neutral. 70℃
After drying under reduced pressure for 10 hours, 5.8 g of purple aniline polymer powder was obtained.

(3) Mix 5g each of the activated carbon powder and aniline polymer powder prepared in (1), add tetrafluoroethylene powder 0139, and mix thoroughly.l/100Kg/
Pressure molded at room temperature under cr pressure to a thickness of approximately 300μ
A film of m was obtained.

(4) Next, add L to sufficiently dehydrated propylene carbonate.
A battery was assembled as shown in FIG. 1, using a 1.0 mol/N solution of iC,1104 as an electrolyte, lithium metal as a negative electrode, and the above molded film as a positive electrode. A stainless steel mesh was used as the current collector, and felt made of glass fiber was used as the separator.

Doping m is 1 carbon atom in the polymer of activated carbon and aniline.
It is expressed in terms of the number of ions doped per individual. In the present invention, the number of ions to be doped is determined from the value of the current flowing through the circuit.

The voltage immediately after the battery was assembled was 2.8V.

Next, apply a voltage to the battery externally at 7 JI L, and apply ClO at a constant current so that the doping m per hour is 1%.
The positive electrode was doped with 4-ions for 3 hours.

The open circuit voltage at the end of the doping agent is 4. It was OV.

Next, a constant current is passed through the circuit so that the amount of and-ping per hour is 1%, and and-ping of C, Go4- ions is performed, and the open circuit voltage is 3. The test continued until OV was reached.The value of the undoping amount relative to the doping amount in this test was 80%.

Further, the battery was charged and discharged at 4.0 V at a current density such that the amount of doping or undoped ♀ per hour was 5%.
When tested at ~2.8cm, the capacity was 90% of the 1% capacity, which was large despite its rapid charging and discharging characteristics.

Comparative Example 1 Powder 10 of the aniline polymer obtained in Example 1 (2)
Sj and 0.9 g of carbon black were thoroughly kneaded and pressure-molded into a film with a thickness of about 250 μm.

A test was conducted in the same manner as in Example 1 (4) except for using the film, and when the doping amount or undoping amount per hour was 5%, the volume (2) was 40% compared to when it was 1%. Rapid charge/discharge characteristics were poor.

Example 2 (1) An aqueous solution of a water-soluble resol (approximately 60% si>/m zinc oxide/water mixed in a weight ratio of 10/35/8 was formed into a film on a glass plate using a film applicator. After covering the formed aqueous solution with a glass plate to prevent moisture from evaporating, the film was cured by heating at a temperature of about 100'C for 1 hour.

The phenolic resin composite was placed in a siliconite electric furnace and heated to ambient temperature at a rate of 40'C/hour under a nitrogen stream to 900°C.
Calcined to °C. Next, the heat-treated film was washed with dilute hydrochloric acid, then water, and dried.

Next, when the specific surface area value was measured by the BET method, 18
It was an extremely high value of 00 m/g.

Next, when the pore state of the film-form activated carbon was observed using an electron microscope, it was found that it had fine continuous pores of 10 μm or less, and the thickness of the columns was 10 μm or less (flat and thin).

(2) Next, 5. OJ aniline hydrochloride 100 d 0
．． Dissolved in 4 mol/ρ perchloric acid aqueous solution, and added A to the aqueous solution.
1 to q/8g! Using the standard electrode as a reference electrode, 2 × 2 c
Ni platinum plate was used as the counter electrode, and the 2 × 2 plate obtained in (1)
A CNR activated carbon film with a platinum wire attached using carbon paste was used as a working electrode to form an electrolytic cell.

After applying a voltage of i, ov to the working electrode by a potentiostat for 15 minutes, the film was washed with water, followed by a voltage of 0.5
It was soaked in N ammonia water for 2 hours, rinsed thoroughly with water, and dried under reduced pressure at 60°C for 48 hours.

When the weight was measured, a 20% increase in the weight ω of the activated carbon film before electrolytic polymerization was observed.

(3) An aqueous solution containing water-soluble resol (approximately 60% concentration)/zinc chloride/water mixed in a weight ratio of 10/35/8 was formed into a film on a glass plate using a film applicator. Next, a glass plate was placed over the formed aqueous solution to prevent moisture from evaporating, and then heated at a temperature of about 100° C. for 1 hour to cure it.

The phenolic resin film was placed in a siliconite electric furnace and back-heated at a rate of 40°C/hour under a nitrogen stream to a temperature of 60°C.
Heat treatment was performed to 0°C. Next, the heat-treated product was washed with dilute hydrochloric acid, washed with water, and then dried to form a film-like porous insoluble infusible = 13 H4 body.

(4) The activated carbon film obtained by electrolytically polymerizing the aniline obtained in (2) was used as the positive electrode, the porous film obtained in (3) was used as the negative electrode, and the electrolyte was (C2+-15) 4NC, [+ 04 of 1 Batteries were constructed using mol/Ω propylene carbonate dissolution, and charge/discharge tests 1 to 1 were conducted.

Immediately after assembling the battery, the voltage was OV.

Next, a voltage was applied from an external power source to dope the positive electrode with Cρ04− ions and the negative electrode with (C2)−1,) 4N″ ions, thereby charging the battery.

The charging rate was such that the doping amount per hour was 1%, and the charging was carried out for 3 k'i. The open circuit voltage at this time is 2.
It was 5V. Next, discharging was performed by and-pumping CU O4- ions and (C2H5)4N ions at the same rate as during charging, and continued until the electron voltage reached OV G, :. The relationship between the doping amount and the charge/discharge voltage was almost linear, indicating that the battery had characteristics similar to a capacitor. Considering this battery as a capacitor and calculating the capacitor capacity, it was 30F/!7 per liter (F: Farad) Comparative Example 2 Plain woven fabric of Kynor fiber (fabric of phenolic resin fiber of Japanese Kynor formal dress) was fired to 900°C in a non-oxidizing atmosphere in a siliconite electric furnace to carbonize it, and then activated by blowing steam into the electric furnace at the same temperature for about 1 hour. The specific surface area value determined by the BET method was 1800 yr/g. The fiber diameter was approximately 15 μm, and the woven fabric had almost no mechanical strength.

Next, a battery was assembled using the activated carbon fabric as a positive electrode and a negative electrode in exactly the same configuration as in Example 2, and a charge/discharge test was conducted under the same conditions. Considering the battery as a capacitor and calculating the capacitor capacity, it is 16F/per electrode weight! It was 17.

[Brief explanation of drawings]

FIG. 1 shows the basic configuration of a battery according to the present invention. 1 is a positive electrode, 2 is a negative electrode, 3 is a current collector, 4 is an electrolytic solution, 5 is a separator, 6 is a battery case, and 7 is an external terminal.

Claims (1)

[Claims] 1. A composite of activated carbon having a specific surface area of 600 m^2/g or more by the BET method and an aniline polymer as a positive electrode active material, and ions that can be doped into the positive electrode active material by electrolysis. An organic electrolyte battery characterized in that an electrolyte solution is a solution of a compound capable of producing , in an aprotic organic solvent. 2. The activated carbon is obtained by heat treating an aromatic condensation polymer, has continuous pores with an average pore diameter of 10 μm or less, and has a specific surface area value of at least 600 m^2/g by the BET method. The organic electrolyte battery according to scope 1. 3. The organic electrolyte battery according to claim 1, wherein the aniline is aniline. 4. The polymerization ratio of activated carbon and aniline polymer is 20 to 0.0
5. The organic electrolyte battery according to claim 1. 5. Claim 1, wherein the composite of activated carbon and aniline polymer is a composite of carbonic carbon powder and aniline polymer powder, or a composite of aniline polymerized on the surface of activated carbon. The organic electrolyte battery described in . 6. The organic electrolyte battery according to claim 1, wherein the negative electrode is an alkali metal, an alkaline earth metal, or an alloy thereof. 7. The organic electrolyte battery according to claim 6, wherein the negative electrode is lithium or a lithium alloy. 8. The negative electrode is a heat-treated product of an aromatic condensation polymer that is a condensation product of an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde, and (a) the atomic ratio of hydrogen atoms / carbon atoms is 0. .5 to 0.05, (b) has a specific surface area value of at least 600 m^2/g by the BET method, and (c) has continuous pores with an average pore diameter of 10 μm or less. The organic electrolyte battery according to claim 1, which is an insoluble and infusible substrate. 9. Compounds that can generate ions that can be doped by electrolysis include LiI, NaI, KI, NH_4I, LiClO_4, LiBF_4, LiAs
F_6, LiPF_6, NaClO_4, NaBF_4
, NaAsF_6, NaPF_6, KClO_4, KB
F_4, KAsF_6, KPF_6, (C_2H_5)
_4NClO_4, (n-C_4H_9)_4NClO_4, (t-C_4H_9)_4NClO_4, (C_2H_5)_4NBF_4, (n-C_4H_9
)_4NBF_4, (t-C_4H_9)_4NBF_
4, (C_2H_5)_4NPF_6, (n-C_4H
_9)_4NPF_6, (t-C_4H_9)_4NP
F_6, LiB(C_2H_5)_4, LiB(C_6
The organic electrolyte battery according to claim 1, which is H_5)_4 or LiHF_4. 10, the aprotic organic solvent is ethylene carbonate,
The organic electrolyte battery according to claim 1, which is propylene carbonate, γ-butyrolactone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonitrile, dimethoxyethane, tetrahydrofuran, dioxolane, or sulfolane.