JP2616775B2 - Organic electrolyte battery with ternary composite as cathode - Google Patents

Description

The present invention relates to an organic electrolyte battery. More specifically, the present invention relates to an organic electrolyte battery in which a ternary composite is used as a positive electrode active material, and a solution in which a compound capable of generating ions that can be doped is dissolved in an aprotic organic solvent is used as an electrolyte.

[Prior Art] In recent years, the miniaturization, thinning or weight reduction of electronic devices has been remarkable.
There is a great demand for weight reduction. At present, silver oxide batteries are frequently used as small and high-performance batteries, and lithium batteries have been developed and commercialized as thin dry batteries and small and lightweight high-performance batteries. However, since these batteries are primary batteries, they cannot be repeatedly used and used for a long time. On the other hand, nickel-cadmium batteries have been put into practical use as high-performance secondary batteries.
It is still unsatisfactory in terms of weight reduction.

In addition, lead storage batteries have conventionally been used in various industrial fields as large capacity secondary batteries, but the biggest disadvantage of these batteries is that they are heavy. This is fatal because lead 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 secondary battery having a large capacity and light weight as a storage battery.

As described above, the batteries currently in practical use have respective advantages and disadvantages and are used properly according to the respective applications. However, there is a great need for a smaller, thinner, or lighter battery. In recent years, as a battery that meets such needs, a battery using, as an electrode active material, a thin-film polyacetylene that is an organic semiconductor doped with an electron donor or an electron acceptor has been studied and proposed. Although this battery has high performance as a secondary battery and has the potential of being thinner and lighter, it has major drawbacks. That is, polyacetylene, which is an organic semiconductor, is a very unstable substance, is easily oxidized by oxygen in the air, and is transformed by heat. Therefore, the battery must be manufactured in an inert gas atmosphere, and there is a limitation in manufacturing polyacetylene into a shape suitable for an electrode.

Further, Japanese Patent Application Laid-Open No. 61-218060 filed by the applicant of the present application
Japanese Patent Application Laid-Open Publication No. H11-163556 discloses (A) a heat-treated product of an aromatic condensation polymer which is a condensate of an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde, wherein (a) the atomic ratio of hydrogen atoms / carbon atoms is (B) having a specific surface area value of at least 600 m ² / g by the BET method, and (c) having a communicating hole having an average pore diameter of 10 μm or less, insoluble and infusible. (B) a solution obtained by dissolving a compound capable of generating ions that can be doped into the electrode by electrolysis in an aprotic organic solvent is used as an electrolytic solution. Organic electrolyte batteries have been proposed.

In addition, a patent application filed on May 30, 1987, which was unpublished at the time of filing the present application, "Organic electrolyte battery using an aniline composite as a positive electrode"
Discloses a secondary battery using a composite of an aniline polymer and the insoluble and infusible substrate as a positive electrode active material. The battery has high capacity, high energy density, excellent rapid charge / discharge characteristics, has the possibility of thinning and lightening, has high oxidation stability of the electrode active material, and is easy to mold. It is a promising secondary battery. However, some problems remain in promoting the practical use of the battery. The most important of these is that when the battery is packaged in a practical size such as a coin-type battery, sufficient performance cannot be exerted due to a shortage of ions doped into the positive electrode of the battery.

On the other hand, among the inorganic compounds, transition metal oxides represented by V ₂ O ₅ , Cr ₃ O _8, etc. have been attracting attention as positive electrode active materials for lithium secondary batteries, and energetically studied. Although the operation mechanism of the battery is based on the intercalation of lithium ions, it has not been put to practical use yet because of the problem of cycle characteristics that the capacity is reduced by repeated charging and discharging.

[Problems to be Solved by the Invention] In view of the problems of the various batteries described above, an object of the present invention is to provide a high-capacity, compact package of a practical size, no capacity reduction due to repeated charging and discharging, and rapid charging and discharging characteristics. An object of the present invention is to provide an organic electrolyte battery having excellent performance.

Still another object of the present invention is to provide an organic electrolyte battery which is an economical secondary battery which can be reduced in size, thickness, or weight and is easy to manufacture.

Still another object of the present invention is to provide a secondary battery having a high electromotive voltage, a low internal resistance, and capable of being charged and discharged for a long time.

Still other objects and advantages of the present invention will be apparent from the following description.

[Means for Solving the Problems] The present inventor can use a composite of a specific insoluble and infusible substance, an aniline polymer and a transition metal oxide as a positive electrode active material, thereby enabling compact packaging. It has been found that a secondary battery having a large capacity, maintaining a large capacity after repeated charge / discharge, and having a small capacity decrease in rapid charge / discharge can be obtained.

That is, the present invention provides (A) (a) a heat-treated product of an aromatic condensation polymer which is a condensate of an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde, and has an atomic ratio of hydrogen atom / carbon atom. B having a polyacene-based skeleton structure in which is 0.05 to 0.5
An insoluble and infusible substance having a specific surface area of at least 600 m ² / g by the ET method, (b) an aniline polymer, and (c) a transition metal oxide capable of intercalating or deintercalating lithium ions. (B) an electrolyte in which a solution of a compound capable of generating ions that can be doped into the positive electrode active material by electrolysis is used as an electrolyte. It is an electrolyte battery.

The aromatic condensation polymer in the present invention is a condensate of an aromatic hydrocarbon compound having a phenolic hydroxyl group with an aldehyde. As the aromatic hydrocarbon compound,
For example, so-called phenols such as phenol, cresol, and xylenol are suitable, but not limited thereto. For example, (Where x and y are each independently 0, 1 or 2
It is. ), Or hydroxybiphenyls or hydroxynaphthalenes. Of these, phenols, particularly phenol, are practically preferred.

As the aromatic condensation polymer in the present invention, the above-mentioned aromatic hydrocarbon compound having a phenolic hydroxyl group is partially modified with an aromatic hydrocarbon compound having no phenolic hydroxyl group, such as xylene, toluene, or aniline. An aromatic polymer, for example, a modified aromatic polymer which is a condensate of phenol, xylene, and formaldehyde can be used, and a modified aromatic polymer substituted with melamine or urea can also be used.

As the aldehyde, formaldehyde, acetaldehyde, furfural and the like can be used, and formaldehyde is preferred. The phenol aldehyde condensate may be any of a novolak type, a resol type, or a composite thereof. A spherical phenol resin (sphere diameter of about 100 μ or less) commercially available as Bellpearl R (trade name, manufactured by Kanebo Co., Ltd.) can also be used.

The insoluble infusible substance in the present invention is a heat-treated product of the aromatic polymer as described above, and can be produced, for example, as follows.

An inorganic substance such as zinc chloride, sodium phosphate, potassium hydroxide or potassium sulfide is mixed into the aromatic condensation polymer. As a mixing method, an aromatic condensation polymer may be dissolved in a solvent such as methanol, acetone or water, and then the above-mentioned inorganic substance may be added and sufficiently mixed.
Further, if the aromatic condensation polymer is a meltable material such as novolak, it may be mixed under heating. The mixing ratio between the aromatic condensation polymer and the above-mentioned inorganic substance varies depending on the type and shape of the polymer to be mixed and the inorganic substance, but is preferably from 10/1 to 1/7 by weight.

Next, the mixture is cured into a film, plate, fiber, cloth, granule or a mixture thereof. The forming method is press forming by spinning a fibrous body, using an applicator for a film-like body, or using a mold for a plate-like body. Next, heat at 50 to 180 ° C for 2 to 60 minutes, or at 50 to 150 ° C in the presence of a curing agent and a catalyst.
Curing is possible by heating at a temperature of 2 to 90 minutes.

When it is desired that the insoluble and infusible substance has a large number of communication holes having an average pore diameter of 0.03 to 10 μm, for example, a cured molded body may be manufactured as follows.

Prepare an initial condensate of the aromatic condensation polymer described above,
An aqueous solution containing this initial condensate and an inorganic salt is prepared, and the aqueous solution is poured into an appropriate mold, and then the aqueous solution is heated while suppressing evaporation of water to form a plate, a film, or a cylinder in the mold. It cures to a shape such as a shape.

The inorganic salt can be used in an amount of, for example, 2.5 to 10 times by weight of the precondensate. If the amount is smaller than the lower limit, it is difficult to obtain a porous body having communication holes, and if the amount is larger than the upper limit, the density of the finally obtained porous body tends to decrease, which is not desirable. The aqueous solution of the initial condensate and the inorganic salt varies depending on the type of the inorganic salt used, but for example, 0.1 to 1
It can be adjusted using water by weight.

The cured product thus obtained is then heated in a non-oxidizing atmosphere to a temperature of from 350 to 800C, preferably from 350 to 700C, particularly preferably from 400 to 600C.

The preferred heating rate during the heat treatment varies somewhat depending on the aromatic condensed polymer used, or the degree of its curing treatment or its shape, but generally a relatively large heating rate from room temperature to about 300 ° C. And, for example, a rate of 100 ° C./hour. When the temperature reaches 300 ° C. or higher, thermal decomposition of the aromatic condensation polymer starts, and gas such as water vapor, hydrogen, methane, and carbon monoxide starts to be generated. Therefore, it is advantageous to raise the temperature at a sufficiently low rate. It is.

Such a heat treatment of the aromatic condensation polymer is performed in a non-oxidizing atmosphere. The non-oxidizing atmosphere is, for example, a nitrogen, argon, helium, neon, carbon dioxide atmosphere, or a vacuum, and nitrogen is preferably used. Such a non-oxidizing atmosphere may be stationary or flowing.

By sufficiently washing the obtained heat-treated body with water or diluted hydrochloric acid, it is possible to remove the inorganic salt contained in the heat-treated body, and thereafter, when this is dried, it has a large specific surface area, and in some cases, the communication hole. A developed insoluble and infusible material can be obtained.

The insoluble infusible substance has an atomic ratio of hydrogen atoms / carbon atoms (hereinafter referred to as H / C ratio) of 0.5 to 0.05, preferably 0.35 to 0.
Having a polyacene-based skeletal structure of 05, and in some cases communicating holes having an average pore size of 10 μm or less, for example, an average pore size of 0.03 to
An insoluble and infusible substance having a communication hole of μm is obtained.

According to X-ray diffraction (CuKα), the position of the main peak is represented by 2θ between 20.5 and 23.5 °, and in addition to the main peak, another peak which is broad between 41 and 46 ° Exists. According to the infrared absorption spectrum,
D (= D ₂₉₀₀ to ₂₉₄₀ / D ₁₅₆₀ to ₁₆₄₀ ｝) The absorbance ratio is usually 0.5
Or less, preferably 0.3 or less.

That is, it is understood that the insoluble and infusible substance is one in which the polycyclic structure of polyacene-based benzene is uniformly and appropriately developed between polyacene-based molecules.

When the H / C ratio exceeds 0.5, the charge efficiency of charge / discharge of a secondary battery using a composite of the substance, a polymer of an aniline compound and a transition metal oxide as an electrode deteriorates, which is not preferable. If the atomic ratio of hydrogen atoms / carbon atoms is less than 0.05, it is not preferable because some problems occur in charge efficiency of charge and discharge. Further, the specific surface area value of the insoluble infusible substance containing the polyacene-based skeleton structure by the BET method becomes an extremely large value because it is produced using an inorganic salt, and those having a specific surface area of 600 m ² / g or more are particularly preferable. . If it is less than 600 m ² / g, it is necessary to increase the charging voltage at the time of charging a secondary battery using the compound, a composite of an aniline polymer and a transition metal oxide as a positive electrode active material, so that energy efficiency and the like need to be increased. And the electrolyte solution is less likely to deteriorate.

As the aniline in the present invention, aniline or an aniline derivative can be used, but aniline is practically preferable. As the aniline derivative, for example, N-methylaniline, p-aminodiphenylamine, p-toluidine, p-phenylenediamine, o-phenylenediamine and the like can be used.

The aniline polymer can be produced by chemically or electrochemically oxidatively polymerizing the aniline. As the chemical polymerization method, for example, it can be produced as follows. The aniline or a water-soluble salt of the aniline is oxidatively polymerized in a reaction medium containing a protonic acid and an oxidizing agent.
In general, mineral salts such as hydrochloric acid and sulfuric acid are desirable as the water-soluble salt. Examples of the oxidizing agent include chromium (IV) oxide, potassium dichromate, chromates such as sodium dichromate, and manganese-based oxidizing agents such as potassium permanganate;
Ammonium persulfate or the like can be used. Sulfuric acid, hydrochloric acid, hydrobromic acid, tetrafluoroboric acid, hexafluorophosphoric acid, perchloric acid and the like can be used as the protic acid, and in particular, tetrafluroboric acid, hexafluorophosphoric acid, perchloric acid, etc. It is desirable to use an acid that generates an anion having a large ionic radius. Water is generally used as a reaction medium, but water-miscible organic solvents such as ketones such as acetone, tetrahydrofuran and acetic acid, ethers or organic acids, and water-immiscible organic solvents such as carbon tetrachloride and hydrocarbons. Can also be used.

When an aqueous solution of a aniline or a water-soluble salt of an aniline is dissolved in an aqueous solution of a protonic acid oxidizing agent at a temperature lower than the boiling point of the reaction medium, and preferably lower than room temperature, an induction time of about several minutes is usually passed. Later, the polymer precipitates immediately. The polymer thus obtained contains the protonic acid anion even after being sufficiently washed with water, and it is necessary to sufficiently wash this with an aqueous alkaline solution such as aqueous ammonia and then again with water.

If impurities such as unreacted substances and protonic acid anion-excess oxidizing agent remain in the polymer even in a small amount, the self-discharge characteristics and cycle of the secondary battery using the composite made as a positive electrode active material It may cause shortening of the service life and the like.

The electrochemical polymerization method can be produced, for example, as follows. A aniline or a water-soluble salt of an aniline and a protonic acid are dissolved in a reaction medium used in the above-described chemical polymerization method in a protic acid acidic solution, and a counter electrode using an inert metal such as platinum, and Ag / A
a reference electrode such as a gCl standard electrode, a saturated calomel standard electrode,
Further, an electrolytic cell provided with a working electrode is prepared. The protonic acid at this time is preferably a protonic acid that generates an anion having a large ionic radius, such as tetrafluoroboric acid, hexafluorophosphoric acid, and perchloric acid, as in the case of the scientific polymerization method.

Using the above-mentioned electrolytic cell, the electrolytic polymerization is performed within a potential range suitable for the reference electrode, that is, within a potential range in which only the polymerization of anilines occurs on the working electrode without causing the decomposition reaction of the solvent and the protonic acid. As the electropolymerization method, a constant current electrolysis method, a constant potential scanning method and the like are known, and any method may be used as long as the potential of the working electrode is maintained within the above-described appropriate potential width. The polymer obtained by such a method can be converted into a polymer containing no impurities by the same post-treatment as in the chemical polymerization method.

As the transition metal oxide in the present invention, an oxide which can be reversibly put in and out by lithium ion intercalation or deintercalation is used. still,
The doping in the present invention includes the intercalation mechanism. As the transition metal oxide, a metal oxide such as vanadium, chromium, manganese, molybdenum, and bismuth can be used. For example, V ₂ O ₅ ,
V ₆ O ₁₃ and Cr ₃ O ₈ are mentioned. AgCrO ₃ , Bi ₂ Pb ₂ O ₃ ,
A composite oxide of two or more metals such as Cu ₂ V ₂ O ₇ can also be used. The metal oxide may be in a crystalline state or in an amorphous state by heat treatment or the like.

The composite of the insoluble infusible substance, the aniline polymer and the transition metal oxide in the present invention can be obtained, for example, by using these powders as follows.

As the insoluble and infusible substance produced by the above-described method, a substance obtained in a powder form may be used as it is, or a substance obtained in the form of a molded body may be crushed into a powder form using a mill or the like.

In particular, it is desirable to use an insoluble and infusible substance having a large number of communication holes, for example, a molded product such as a granule or a plate which is ground into a powder. In a secondary battery using the composite made with the powder as a positive electrode active material, the dopant is smoothly doped or undoped into the positive electrode active material when the electrolyte sufficiently enters the inside of the positive electrode. It becomes possible. The average particle size of the powder of the insoluble and infusible substance is
There is no particular problem as long as the thickness does not exceed 100 μm, but it is preferable that the thickness be 30 μm or less in consideration of the ease of molding of the composite molded article described later and the strength of the molded article.

As the aniline polymer powder and the transition metal oxide powder, commercially available or synthesized ones may be used as they are, but in consideration of doping efficiency and molding, 100 μm
It is desirable that the thickness be 30 μm or less.

A composite can be obtained by sufficiently mixing the above three powders. The composite ratio depends on the use of a secondary battery using the composite as a positive electrode active material, but the aniline polymer is 5 to 30% by weight based on the total positive electrode active material, and the transition metal oxide is the total positive electrode active material. It is desirable to account for 5 to 40% by weight of the substance.

When the aniline polymer exceeds 30% by weight, sufficient performance cannot be obtained when a battery of a practical size is assembled. When the content of the transition metal oxide exceeds 40% by weight, the rapid charge / discharge characteristics deteriorate, and the capacity decreases with repeated charge / discharge.
5% by weight each of aniline polymer and transition metal oxide
Below, the significance of combining these is less.

When the composite is used as a positive electrode, it is generally desirable to form the composite into a shape such as a plate, a film, or a cylinder. The molding can be performed by an appropriate means such as pressurization and sintering. A conductive agent can be added during molding. The type of the conductive agent is not particularly limited, and a carbon-based material such as activated carbon, carbon black, acetylene black, and graphite is particularly preferable. The mixing ratio varies depending on the composite ratio of the composite and the like, but it is appropriate to add 40 to 2% to the total weight of the composite.

In the case of pressure molding, it may be preferable to add a binder. The type of the binder is not particularly limited as long as it is insoluble in the electrolytic solution of the present invention described later,
For example, rubber-based binders such as SBR, fluorine-based resins such as polytetrafluoroethylene, and thermoplastic resins such as polypropylene and polyethylene are preferable, and their mixing ratio is desirably 20% or less based on the total weight of the composite.

The insoluble infusible substance powder, the aniline polymer powder and the transition metal oxide powder as described above, and optionally a mixture to which a conductive agent and a binder are added, are formed into a plate, film, cylinder or the like. As a molding method, for example, the mixture may be placed in a mold and subjected to pressure molding at room temperature or, if necessary, under heating.

For example, in the case of a small electrode such as an electrode for a button type battery, 1
It is also possible to press-mold each one with a press machine, but from an industrial point of view, continuously press-mold a plate-like material using a roller or the like, and then punch out to an appropriate size. The scrap can be reused after re-grinding and is very economical.

In the case of a thin or wrap-around battery electrode, for example, it can be formed by the following method. The kneaded material described above or, if necessary, kneaded with an appropriate solvent such as water, methanol, DMF, or a solvent having a relatively low boiling point such as carbon tetrachloride and the like to form a paste, is collected as described later. It can also be used as a positive electrode by applying it on a conductor or bonding it under pressure and then drying it by an appropriate method. Further, after kneading the mixture together with an electrolytic solution to be described later in an atmosphere containing no water such as argon gas, the mixture can be applied to a current collector to be described later or adhered under pressure and used as it is as a positive electrode.

In the organic electrolyte battery of the present invention, the compound capable of generating an ion that can be doped into the positive electrode active material by electrolysis includes a halide of an alkali metal, perchlorate, hexafluorophosphate, hexafluoroarsenate, Tetrafluoroborates and the like, for example, LiI, NaI, KI, LiClO ₄ , LiBF ₄ , L
iAsF ₆ , LiPF ₆ , NaClO ₄ NaBF ₄ , NaAsF ₆ , NaPF ₆ , KClO ₄ , K
BF ₄ , KAsF ₆ , KPF ₆ , LiB (C ₂ H ₅ ) ₄ , LiB (C ₆ H ₅ ) ₄ or
LiHF _2, and the like.

An aprotic organic solvent is used as a solvent for dissolving the compound. For example, ethylene carbonate, propylene carbonate, γ-butyrolactone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonitrile, dimethoxyethane, tetrahydrofuran, dioxolan, sulfolane, or a mixture thereof can be used. Among them, the material is selected in consideration of the solubility of the compound used as the electrolyte, battery performance, and the like.

The concentration of the compound in the electrolytic solution is preferably at least 0.1 mol / or more, and more preferably 0.2 to 1.5 mol /, in order to reduce the internal resistance due to the electrolytic solution.

It is most practical to use an alkali metal or an alkaline earth metal or an alloy thereof for the negative electrode of the battery according to the present invention, but the above-mentioned insoluble and infusible substances can also be used.
Lithium and lithium alloys are preferred.

As a current collector for extracting a current to the outside of the battery, a conductive substance having corrosion resistance to a doping agent and an electrolytic solution, for example, carbon, platinum, nickel, aluminum, stainless steel, or the like can be used.

When constructing a battery, the separator that spins the short circuit between the positive electrode and the negative electrode is a porous material that has continuous pores that are durable with respect to the electrolyte or an electrode active material such as a doping agent or alkali metal and has no electron conductivity. Usually, cloth, nonwoven fabric or porous body made of glass fiber, polyethylene or polypropylene is used.

When assembling a battery of a practical size, the separator can be made as thin as possible to reduce the internal resistance and obtain a high capacity battery.

As described above, the organic electrolyte secondary battery of the present invention has the advantages that it can be compactly packaged, has a high capacity, has a small capacity decrease due to repeated charge and discharge, and has a small capacity decrease due to rapid charge and discharge.

Hereinafter, the present invention will be described specifically with reference to examples. In the examples, parts are parts by weight.

Example 1 (1) An aqueous solution obtained by mixing a water-soluble resol (about 60% concentration) / zinc chloride / water at a weight ratio of 10/40/8 was 100 cm × 100 c.
The mixture was poured into a m × 2 mm mold, and was heated and cured at 100 ° C. for 1 hour in a state in which a glass plate was placed thereon to prevent moisture from evaporating, thereby obtaining a precursor.

The precursor is placed in a siliconite electric furnace under a nitrogen stream.
The temperature was increased at a rate of 40 ° C./hour, and heat treatment was performed up to 500 ° C. Next, the heat-treated product was washed with dilute hydrochloric acid, washed with water, and then dried to obtain plate-like porosity. When the electrical conductivity of the porous body was measured at room temperature by a DC four-terminal method,
It was 10 ^-3 S / cm. The porous body is pulverized with a disc mill,
A powder of an insoluble and infusible substance having an average particle size of 20 μ was obtained. Of the powder
The specific surface area by the BET method was an extremely large value of 2500 m ² / g. Elemental analysis revealed that the atomic ratio of hydrogen atoms / carbon atoms was 0.24.

The shape of the peak from X-ray diffraction was a pattern derived from the polyacene-based skeleton structure. A broad main peak was present at about 20 to 22 ° at 2θ, and a small peak was found at about 41 to 46 °.

(2) To 90 g of distilled water, add 9.2 ml of concentrated hydrochloric acid, and further add aniline 10
g was dissolved to prepare an aniline hydrochloride aqueous solution. Separately, 50 ml of perchloric acid (60% aqueous solution) and 10.5 g of kalim dichromate
An oxidizing aqueous solution in which was dissolved was prepared, and this was dropped into the above-mentioned aqueous solution of aniline in hydrochloric acid at room temperature over 40 minutes while stirring. After stirring for another 15 minutes, the reaction mixture was
After stirring for 1.5 hours, the polymer was filtered off. Further, after stirring and washing in distilled water, washing with stirring in 1N aqueous ammonia was performed, followed by filtration, and further washing with distilled water until the filtrate became neutral. After drying under reduced pressure at 70 ° C. for 10 hours, 5.8 g of purple aniline polymer powder was obtained.

(3) the powder of the insoluble and infusible substance obtained in (1) and (2)
Was mixed with a commercially available powder of V ₂ O _{5 at} a weight ratio of 60/20/20.

Further, carbon black 10 per 100 parts of the mixture
Parts, 10 parts of an aqueous dispersion of polytetrafluoroethylene (60% concentration) were added, and after sufficiently kneading, pressure molding was performed under heating at 100 ° C. under a pressure of 100 kg / cm ² to obtain a 15 mm diameter × 900 μm A disk-shaped compact was obtained. The apparent density of the molded product was 0.6 g / cm ³ .

(4) The disk-shaped molded body obtained in (3) was used as a positive electrode,
As a negative electrode, lithium metal of μm, and a 1.5 mol / solution of LiClO ₄ dissolved in sufficiently dehydrated propylene carbonate as an electrolyte, type 2016 as shown in FIG. 1 (diameter 20 mm, thickness 1.
6mm) coin battery. In FIG. 1, 1 is a negative electrode box, 2 is a negative electrode, 3 is a separator, 4 is a positive electrode, 5 is a positive electrode box, and 6 is an insulating packing. As the separator, a felt made of glass fiber having a thickness of 100 μm was used. The current collection on the positive electrode side was performed by vapor-depositing aluminum on one side of the positive electrode and pressing it on the positive electrode housing, and the current collection on the negative electrode side was performed by directly pressing lithium on the negative electrode housing. The positive electrode housing and the negative electrode housing were made of stainless steel, and an insulating packing was inserted between the two joints to prevent a short circuit.

The battery was charged for 1 hour by externally applying a voltage of 4V. The electromotive force after charging was 4.0V. Then 6mA
Was performed until the battery voltage reached 2.0 V, and the discharge time was about 80 minutes. That is, the capacity was high despite such rapid charge and discharge.

The internal resistance during this test was as small as 7Ω. The same charge / discharge was repeated 40 times, but the discharge time hardly changed.

Comparative Example 1 (excluding transition metal oxide) The powder of the insoluble and infusible substance of Example 1 and the powder of the aniline polymer were mixed at a weight ratio of 60/20. 10 parts of carbon black and 10 parts of an aqueous dispersion of polytetrafluoroethylene (concentration: 60%) were added to 100 parts of the mixture, and after sufficiently kneading,
Pressure molding at 100 kg / cm ² under heating at ℃, 15mm diameter × 900μ
m was obtained.

The capacity was measured in the same manner as in Example 1 (4) except that the molded body was used as a positive electrode. Despite charging at 4V, the battery's electromotive force was 3.8V. When a constant current discharge of 6 mA was performed until the battery voltage reached 2.0 V, the discharge time was only about 60 minutes.

Comparative Example 2 10 parts of carbon black and 10 parts of a polytetrafluoroethylene aqueous dispersion (concentration: 60%) were added to 100 parts of the same V ₂ O ₅ powder as used in Example 1 (3), After kneading, 100 ℃
Pressure molding was performed under heating at 100 kg / cm ² to obtain a disk-shaped molded body having a diameter of 15 mm × 900 µm.

The capacity was measured in the same manner as in Example 1 (4) except that the molded body was used as a positive electrode. 6mA constant current discharge with battery voltage of 2.0
The discharge time was about 60 minutes when the operation was performed until the voltage reached V. The discharge time after repeating charge and discharge 40 times was also about 30 minutes.

Example 2 Example 1 except that Cr ₃ O ₈ was used as the transition metal oxide.
The capacity was measured in exactly the same manner as in. The discharge time was as high as about 85 minutes. Even after 40 times of charge / discharge, there was almost no decrease in capacity. Also, when the charging time is 30 minutes,
The discharge time was about 80 minutes, and there was almost no decrease in capacity due to rapid charging.

Example 3 The insoluble infusible substance, the aniline polymer and V ₂ O ₅ used in Example 1 were mixed at various ratios, and a positive electrode was produced in the same manner as in Example 1 (3). The mixing ratio is represented by the weight% of the aniline polymer and V ₂ O ₅ with respect to the total weight of the three positive electrode active materials. 1.5 mol / L as electrolyte
A battery was constructed in the same manner as in Example 1 (4) except that iPF ₆ / propylene carbonate dissolution was used. The discharge time after 40 charge / discharge cycles are shown as numerical values in the diagram of FIG. The horizontal axis in the figure is the V ₂ O ₅ ratio, and the vertical axis is the aniline polymer ratio. When the sum of the two is subtracted from 100%, the ratio of the insoluble and infusible substance is obtained.

 In the figure, the mixing ratio of the region surrounded by the dotted line is preferable.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view of a coin-type battery according to an embodiment of the present invention, wherein 1 is a negative electrode box, 2 is a negative electrode, 3 is a separator,
4 represents a positive electrode, 5 represents a positive electrode box, and 6 represents an insulating packing. FIG. 2 is a diagram showing discharge time (minutes) at various positive electrode active material component ratios.

Claims (15)

(57) [Claims] (A) (a) A heat-treated product of an aromatic condensation polymer which is a condensate of an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde, wherein the hydrogen atom /
It has a polyacene skeleton structure in which the atomic ratio of carbon atoms is 0.5 to 0.05 and has a specific surface area value of at least 600 by the BET method.
A composite of an insoluble infusible material of m ² / g and a transition metal oxide capable of intercalating or deintercalating (b) an aniline polymer and (c) lithium ion is used as a positive electrode active material. (B) A rechargeable organic electrolyte battery characterized by using, as an electrolytic solution, an aprotic organic solvent solution of a compound capable of generating ions that can be doped into the positive electrode active material by electrolysis. 2. The organic electrolyte battery according to claim 1, wherein the aniline polymer is 5 to 30% by weight and the transition metal oxide is 5 to 40% by weight based on the total weight of the positive electrode active material. . 3. The organic electrolyte battery according to claim 1, wherein the composite is a composite of an insoluble infusible substance powder, an aniline polymer powder and a metal oxide powder. 4. A composite comprising a mixture containing an insoluble infusible substance powder, an aniline polymer powder, a metal oxide powder, a conductive agent and an optional binder, is formed into a film, plate, or cylinder. The organic electrolyte battery according to claim 3, wherein the organic electrolyte battery is formed into a shape. 5. The organic electrolyte battery according to claim 1, wherein the aromatic condensation polymer is a condensate of phenol and formaldehyde. 6. The organic electrolyte battery according to claim 1, wherein a specific surface area of the insoluble and infusible substance by a BET method is 800 to 3000 m ² / g. 7. The organic electrolyte battery according to claim 1, wherein the insoluble and infusible substance has a large number of communication holes having an average pore diameter of 0.03 to 10 μm. 8. The organic electrolyte battery according to claim 1, wherein the aniline polymer is an aniline polymer. 9. The organic electrolyte battery according to claim 1, wherein the transition metal oxide is a vanadium oxide, a chromium oxide and / or a molybdenum oxide. 10. The transition metal oxide is V ₂ O ₅ , V ₆ O ₁₃ , Cu ₂ V ₂ O ₇
And organic electrolyte battery Claims paragraph 9, wherein the selected from Cr ₃ O _8. 11. The organic electrolyte battery according to claim 1, wherein the negative electrode is selected from an alkali metal, an alloy thereof, an alkaline earth metal or an alloy thereof. 12. The organic electrolyte battery according to claim 11, wherein the negative electrode is lithium or a lithium alloy. 13. A heat-treated product of an aromatic condensed polymer in which the negative electrode is a condensate of an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde, wherein (a) the atomic ratio of hydrogen atoms / carbon atoms is An insoluble infusible material having a polyacene skeleton structure of 0.5 to 0.05, (b) having a specific surface area value of at least 600 m ² / g by the BET method, and (c) having communicating holes having an average pore diameter of 10 μm or less. The organic electrolyte battery according to claim 1, wherein 14. The compound capable of forming ions which can be doped by electrolysis is LiI, NaI, KI, LiClO ₄ , LiBF ₄ , LiA
_{sF 6, LiPF 6, NaClO 4} , NaBF 4, NaAsF 6, NaPF 6, KClO 4, K
BF ₄ , KAsF ₆ , KPF ₆ , LiB (C ₂ H ₅ ) ₄ , LiB (C ₆ H ₅ ) ₄ or
The organic electrolyte battery according to paragraph 1 claims a LiHF _2. 15. The aprotic organic solvent is ethylene carbonate, propylene carbonate, γ-butyrolactone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonitrile, dimethoxyethane, tetrahydrofuran, dioxolan, sulfolane or a mixture thereof. Item 2. The organic electrolyte battery according to Item 1.