JPS63314759A - Organic electrolyte cell using metal oxide composite material as positive electrode - Google Patents

Abstract

PURPOSE:To obtain a secondary cell with a large capacity and little capacity reduction at the quick charge and discharge by using a composite material of a specific insoluble and infusible material and a metal oxide as a positive electrode active material. CONSTITUTION:A composite material of a metal oxide and an insoluble and infusible material which is the heat-treated material of aromatic condensation polymer which is a condensed material of an aromatic hydrocarbon compound with phenol hydroxyl group and aldehyde and has the polyacen skeleton structure with the atom ratio between the hydrogen atom/carbon atom of 0.05-0.5 and has the specific surface area value by the BET method of at least 600m<2>/g is used as the active material of a positive electrode 1. A nonproton organic solvent solution 4 of a compound capable of generating ions doped with the positive electrode active material by electrolysis is used as an electrolyte 4. The electrochemical doping of a doping agent and the electrochemical undoping on the composite material of the positive electrode active material are utilized to obtain the cell function.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to organic electrolyte batteries. More specifically, the positive electrode active material is a composite of an insoluble infusible substance with semiconductor properties and a metal oxide, and the electrolyte is a solution in which a compound capable of producing ions that can be doped is dissolved in an aprotic organic solvent. The present invention relates to an organic electrolyte battery.

[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 alloys 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, although nickel-cadmium batteries have been put into practical use as high-performance secondary batteries, they are still unsatisfactory in terms of miniaturization, thinness, and weight reduction.

Furthermore, lead-acid batteries have conventionally been used as large-capacity secondary batteries in various industrial fields, but the biggest drawback of these batteries is that they are heavy. This is fateful since 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 that has a large capacity and is of great use as a storage battery.

As mentioned above, the batteries that are currently in practical use each have their advantages and disadvantages, and are used differently depending on the purpose.
There is a great need for smaller, thinner, and lighter batteries. As a battery that meets these needs, a battery that uses a thin film of polyacetylene, which is an organic semiconductor, doped with an electron-donating substance or an electron-accepting substance as an electrode active material has recently been researched and proposed. Although this battery has high performance as a secondary battery and has the potential to be made thinner and lighter, it has a major drawback. The reason is that polyacetylene, which is an organic semiconductor, is an extremely unstable substance, easily oxidized by oxygen in the air, and deteriorated by heat. Therefore, the battery manufacturing step 1 must be carried out in an inert gas atmosphere, and there are also restrictions on manufacturing polyethylene into a shape suitable for electrodes.

In addition, the applicant has previously developed a secondary electrode active material in which an insoluble and infusible substrate containing a polyarene skeleton structure, which is a type of organic semiconductor, is doped with an electron-accepting substance or an electron-accepting substance. proposes a battery (Unexamined Japanese Patent Publication No. 60-1
No. 70163). This battery has high performance, has the possibility of being made thinner and lighter, has a high oxidation stability of the electrode active material, and can be easily molded, making it a promising secondary battery. 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.

By the way, gold RM compounds such as V205 are known as positive electrode materials, and secondary batteries using such metal oxides as positive electrodes have been studied. However, in batteries using such metal oxides as positive electrode materials, the capacity decreases significantly when rapid charging and discharging is performed, making them impractical.

[Problems to be Solved by the Invention] In view of the above-mentioned problems of existing batteries, an object of the present invention is to provide an organic electrolyte battery that has a large capacity and exhibits little capacity loss, especially during rapid charging and discharging. shall be.

Still 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 that has a high electromotive voltage, a low internal resistance, and can be charged and discharged over a long period of time.

Other objects and advantages of the invention will become apparent from the following description.

[Means for Solving the Problems] The present inventor has proposed that by using a composite of a specific insoluble and infusible substance and a metal oxide as a positive electrode active material, the capacity can be increased and the capacity can be reduced especially during rapid charging and discharging. It has been found that a secondary battery with a small amount of energy can be obtained.

The capacity of the battery is significantly greater than when using a positive electrode active material consisting of an insoluble and infusible substance alone or a metal oxide alone.

In other words, the present invention provides (A) (a) a heat-treated product of an aromatic condensation polymer which is a condensation product of an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde; It has a boriacene skeleton structure with an atomic ratio of O, OS ~ 0.5, and has a specific surface area value of at least 600TIi by the BET method.
/g and (b) a composite of a metal oxide as a positive electrode active material, and (B) an aprotic organic solvent of a compound that can generate ions that can be doped into the positive electrode active material by electrolysis. This is an organic electrolyte battery characterized by using a solution as an electrolyte.

The aromatic condensation polymer in the present invention is a condensate of an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde. As the aromatic hydrocarbon compound, so-called phenols such as phenol, cresol, and xylenol are suitable, but are not limited thereto. For example, the following formula (where X and y are each independently 0.1 or 2
It is. ), or may also be hydroxybiphenyls or hydroxynaphthalenes. Among these, phenols, particularly phenol, are preferred from a practical standpoint.

As the aromatic condensation polymer in the present invention, one of the above-mentioned aromatic hydrocarbon compounds having a phenolic water M group is used.
A modified aromatic polymer in which the phenolic water group is substituted with an aromatic hydrocarbon compound such as xylene, toluene, aniline, etc., such as a modified aromatic polymer that is a condensation product of phenol, xylene, and formaldehyde. Alternatively, a modified aromatic polymer substituted with melamine or urea can also be used.

As the aldehyde, formaldehyde, ace1-aldehyde, furnral, etc. can be used, and formaldehyde is preferred. The phenolaldehyde condensate may be a novolac type, a resol type, or a composite thereof. A spherical phenol resin (spherical diameter of about 100 μm or less) commercially available as Bell Pearl R (trademark: manufactured by Kanebo Co., Ltd.) can also be used.

The insoluble and infusible substance according to 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 described above. As for the mixing method, the aromatic integrated polymer may be dissolved in a solvent such as methanol, azetone, or water, and then the above-mentioned inorganic substance may be added and thoroughly mixed. Further, if the aromatic condensation polymer is meltable such as novolak, it may be mixed under heating. The mixing ratio of the aromatic condensation polymer and the above-mentioned inorganic substance varies depending on the type and shape of the polymer and inorganic substance to be mixed, but is preferably 10/1 to 1/7 in terms of weight.

Next, the mixture is formed into a film, plate, fiber, 'l'li.
It hardens into solid, granular, or a mixture thereof. The molding method is by spinning if it is a fibrous material, by using an applicator if it is a film material, or by press molding using a mold if it is a plate material.

Then heat for 2-60 minutes at 50-180'C or 2-60 minutes at a temperature of 50-150'C in the presence of a curing agent and catalyst.
Curing is possible by heating for ~90 minutes.

Moreover, if it is desired that the insoluble and infusible substance has a large number of communicating pores with an average pore diameter of 0.03 to 10 μm, a cured molded body may be produced, for example, in the following manner.

Prepare the initial condensate of the aromatic condensation polymer described above, prepare an aqueous solution containing this initial condensate and an inorganic salt, pour this aqueous solution into a suitable mold, and then heat the aqueous solution while suppressing water evaporation. Then, it is cured in the mold into a plate-like, film-like, or cylindrical shape, for example.

The inorganic salt can be used in an amount of, for example, 2.5 to 10 times the weight of the initial condensate. If the amount is less than the lower limit, it will be difficult to obtain a porous body having communicating pores, and if the amount is more than the upper limit, the density of the final material will tend to decrease, which is not desirable. The aqueous solution of the initial condensate and inorganic salt varies depending on the type of inorganic salt used, but for example, the aqueous solution of the inorganic salt
It can be adjusted using 1 small amount of water.

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

The preferred temperature increase rate during heat treatment varies somewhat depending on the aromatic condensation polymer used, the degree of curing treatment, its shape, etc., but in general, a relatively large temperature increase from room temperature to about 300°C is required. A temperature rate of, for example, 100°C/hour is also possible. When the temperature reaches 300'C or more, the aromatic condensation polymer starts to thermally decompose and gases such as water, hydrogen, methane, and carbon oxide begin to be generated, so the temperature should be raised at a sufficiently slow rate. is advantageous.

Such heat treatment of the aromatic condensation polymer is carried out under a non-oxidizing atmosphere. Non-oxidizing atmospheres include, for example, nitrogen, argon, helium, neon, carbon dioxide atmosphere,
or vacuum, with nitrogen being preferably used. Such a non-oxidizing atmosphere may be static or fluid.

By thoroughly washing the obtained heat-treated body with water or dilute hydrochloric acid, the inorganic salts contained in the heat-treated body can be removed. After that, drying this heat-treated body will remove the inorganic salts that have a large specific surface area and, in some cases, the communication pores. A developed insoluble and infusible substance can be obtained.

The insoluble and infusible substance has a polyacene skeleton structure with an atomic ratio of hydrogen atoms/carbon atoms (hereinafter referred to as 1/C ratio) of 0.5 to 0.05, preferably 0.35 to 0.05. However, in some cases, an insoluble and infusible material having communicating pores with an average pore diameter of 10 μm or less, for example, an average pore diameter of 0.03 to 10 μm, can be obtained.

According to X-ray diffraction (CUKα), the main peak position exists between 20.5 and 23.5° expressed in 2θ,
In addition to the main peak, there are other broad peaks between 41° and 46°. Also, according to the infrared absorption spectrum, D(=D2900~294°/D156
The absorbance ratio of 0 to 1640) is usually 0.5 or less, preferably 0.3 or less.

In other words, the above-mentioned insoluble and infusible substance has a polycyclic structure of polyacene-based benzene that is uniformly and moderately distributed between polyacene-based molecules.
It is understood that it is a developed thing.

If the 1-1/C ratio exceeds 0.5, the charge efficiency of charging and discharging a secondary battery using a composite of the substance and a metal oxide as an electrode will deteriorate, which is not preferable. A hydrogen atom/carbon atom atomic ratio of less than 0.05 is also undesirable because it causes some problems in charging and discharging charge efficiency. That is, hydrogen atom/
When an insoluble and infusible substance having an atomic ratio of carbon atoms of 0.05 to 0.5 is used, preferable battery characteristics are exhibited. or,
B of the insoluble and infusible substance containing the polyacene skeleton structure
The specific surface area value determined by the ET method is extremely large because it is produced using an inorganic salt, and those having a specific surface area of 600 butts/g or more are particularly preferred. If it is less than 600 m2/g, it will be necessary to increase the charging voltage when charging a secondary battery using a composite of the substance and metal oxide as a positive electrode active material, resulting in a decrease in energy efficiency, etc. This is undesirable as it may cause deterioration. The insoluble and infusible material containing the polyacene skeleton structure has a specific surface area value of 60 according to the BET method.
Because it has a large value of 0/9 or more, it is thought that oxygen gas etc. can enter and deteriorate easily, but in reality, there is no change in physical properties such as electrical conductivity even if it is left in the air for a long time, and it is stable due to oxidation. It has excellent characteristics.

The metal oxide used in the present invention is one capable of intercalating or diintercalating lithium ions. Particularly preferred are transition metal oxides. Note that doping in the present invention also includes the intercalation mechanism. As the transition metal oxide, oxides of metals such as vanadium, chromium, manganese, molybdenum, copper, and bismuth can be used. for example,
Examples include V2O5, V6O13, and Cr3O8.

In addition, AgCr o3, B I 2 Pb 203,
A composite oxide of two or more metals such as Cu 2 V207 can also be used. The metal oxide may be in a crystalline state or may be made into an amorphous state by heat treatment or the like.

The composite of an insoluble and infusible substance and a metal oxide in the present invention can be obtained, for example, using these powders in the following manner.

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

In particular, it is desirable to use a molded body of an insoluble and infusible material, such as a granular or plate-shaped body having a large number of communicating holes, crushed into powder. When this powder is used, in a secondary battery that uses a composite of this powder and a metal oxide as a positive electrode active material, the electrolyte sufficiently enters the inside of the positive electrode, so that the dopant can be smoothly doped or undoped into the positive electrode active material. This enables rapid charging and discharging. There is no particular problem with the average particle size of the powder of the insoluble and infusible substance as long as it does not exceed 100 μm, but the ease of molding of the composite body described later,
Considering the strength of the molded body, it is desirable that the thickness be 30 μm or less.

Further, it is desirable that the metal oxide powder has a thickness of 30 μm or less in consideration of doping efficiency and molding.

A composite can be obtained by sufficiently mixing the above two types of powders. Although the composite ratio depends on the usage of a secondary battery using the composite as a positive electrode active material, it is desirable that the weight pressure of insoluble and infusible material/metal oxide is 9515 to 15/85. If the metal oxide is reduced beyond 9515, the effect of increasing the capacity due to compounding will be reduced, and if the metal oxide is increased below 15/85, the rapid charge/discharge characteristics will be lost. It is not desirable because it is stored away. Preferably, this ratio is between 90/10 and 30/70.

When the composite is used as a positive electrode, it is generally desirable to form it into a plate, film, cylinder, or the like. Molding can be performed by appropriate means such as pressurization and sintering. The molded composite has an electrical conductivity of 10-53.
/cm or more, more preferably 10-3S/cm or more, and a conductive agent may be added at the time of molding. The type of conductive agent is not particularly limited, and may be metal powder such as metal nickel, but examples include activated carbon, carbon black,
Carbon-based materials such as acetylene black and graphite are particularly preferred. The mixing ratio varies depending on the electrical conductivity of the insoluble and infusible substance, the composite ratio of the composite, etc., but it is 4% based on the total weight of the composite.
It is appropriate to add 0 to 2%.

It may be preferable to add a binder during pressure molding. The type of binder is not particularly limited as long as it is insoluble in the electrolytic solution in the present invention described later, but examples include rubber binders such as SBR, fluororesins such as polytetrafluoroethylene, and thermoplastics such as polypropylene and polyethylene. Resins are preferred, and their mixing ratio is preferably 20% or less based on the total weight of the composite.

A mixture of the above-mentioned insoluble and infusible material powder, total oxide powder, and optionally a conductive agent and a binder is formed into a plate, film, cylinder, or the like. As for the molding method, for example, the mixture 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. with a relatively low boiling point to form a paste, which is then applied (later) onto a hoovering current collector or under pressure. It can also be used as a positive electrode by adhering the top layer and then drying it by an appropriate method. Furthermore, after kneading the mixture together with an electrolytic solution, which will be described later, in a water-free atmosphere such as argon gas, it may be applied or adhered to a current collector under pressure, and used as it is as a positive electrode. can.

The thus obtained positive electrode has excellent oxidation stability, with no change in physical properties such as electrical conductivity even when left in air for a long time. In addition, since it has excellent heat resistance and chemical resistance, when it is used as an electrode material to construct a battery, there is no problem of electrode deterioration.

Examples of compounds that can generate ions that can be doped into the positive electrode active material by electrolysis in the organic electrolyte battery of the present invention include L + I, L i Cf1O4, L!
BF4, L! AS F6, L! PF6, L!
B (C21-15>4, Li B (C6H5)
4 or L! Examples include HF2.

An aprotic organic solvent is used as the solvent for dissolving the compound. Examples include ethylene carbonate, propylene carbonate, γ-buburolactone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonitrile, dimethoxyethane, tetrahydrofuran, dioxolane, sulfolane, or mixtures thereof. It is selected from these in consideration of the solubility of the compound used as an electrolyte, battery performance, etc.

The concentration of the former compound in the electrolytic solution is preferably at least 0.1 mol/g or more in order to reduce the internal resistance caused by the electrolytic solution, and usually 0.2 to 1.5 mol/ρ is more preferable. preferable.

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 an insoluble infusible material and a metal oxide 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, the above-mentioned insoluble and infusible substances can also be used.

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

the shape of the electrode made of the above-mentioned composite placed in the battery;
The size can be arbitrarily selected depending on the type of battery intended, but since the battery reaction is an electrochemical reaction on the surface of the electrode, it is advantageous to make the surface area of the electrode as large as possible.

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

Next, the actual tM aspect 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 product in the form of a film or a plate, and 2 is a negative electrode, which is also a film or plate shaped composite material. These include earth metals, alloys of these metals with other metals, and insoluble and infusible substances. 3.3' is a current collector for extracting current from each electrode to the outside or supplying current for electrochemical doping, that is, charging;
Each electrode and external terminal 7, 7' are connected so as not to cause a voltage drop. 4 is an electrolytic solution in which the above-mentioned compound capable of producing ions that can be doped is dissolved in an aprotic organic solvent. The electrolyte is usually in liquid form, but it can also be used in gel or solid form to prevent leakage. Reference numeral 5 denotes a separator arranged for the purpose of preventing contact between the positive and negative electrodes and retaining the electrolyte. The separator is a non-electron conductive porous body with continuous pores that is resistant to electrolytes, doping agents, and electrode active materials such as alkali metals, and is usually made of cloth made of glass fiber, polyethylene, polypropylene, etc. Nonwoven fabric or porous material is used. 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 electrolyte retention capacity, 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 producing thin batteries, and production of large-capacity mother batteries can be achieved by alternately stacking a large number of film-shaped or plate-shaped electrodes with both positive and negative electrodes.

For example, lithium is used as the negative electrode and V is used as the metal oxide.
2O5 and a L i CN 041 mol/g propylene carbonate solution as the electrolyte, the electromotive force after battery assembly is 3.0 to 3.5 .

Next, when a voltage is applied from an external power source to dope the positive electrode active material with cuO4- ions, the electromotive force is 3.5~
It becomes 4.5 ■. Furthermore, when a positive electrode active material made of a composite is doped with lithium ions by discharging a current to the outside, the electromotive force becomes 1.0 to 2.5μ, but when a voltage is applied from an external power source, lithium ions are When doped, the electromotive force becomes 3.0 to 3.5 ■ again. Doping or undoping may be performed under constant current, constant voltage, or varying current and voltage conditions. When an insoluble and infusible substance is used for the negative electrode, the electromotive force is approximately 0.5V, and by applying a voltage from an external power source and doping both electrodes with a doping agent, the electromotive force is approximately 1.0V.
The electromotive force is ~3.5■.

The battery of the present invention, which uses a composite of an insoluble and infusible substance and a metal oxide as a positive electrode active material, is a secondary battery that can be repeatedly charged and discharged.

The battery of the present invention has a high capacity, and is characterized by a small decrease in capacity even when it is rapidly charged and discharged. Furthermore, the battery of the present invention is a secondary battery that has a low internal resistance, can be repeatedly charged and discharged, and does not deteriorate in battery performance over a long period of time.

The present invention will be specifically explained below using Examples.

Example 1 (1) Water-soluble resol (approximately 90% concentration)/Silium chloride
An aqueous solution of water mixed in a weight ratio of 10/40/8 was poured into a mold of 100 CItX 100αX 0.5 m, and heated at 100°C for 1 hour with a glass plate placed over it to prevent moisture from evaporating. The mixture was cured to obtain a precursor.

The precursor was placed in a siliconite electric furnace and heated under a nitrogen stream for 4 hours.
Heat treatment was performed by increasing the temperature at a rate of 0°C/hour to 500°C. Next, the heat-treated product was washed with dilute hydrochloric acid, then water, and then dried to obtain a plate-like porous structure. The porous body was pulverized with a disk mill to obtain a powder of an insoluble and infusible material with an average particle size of 10 μm. The powder had a specific surface area value of 2200 m/9, which was an extremely large value determined by the BE 1-method.

Further, elemental analysis revealed that the atomic ratio of hydrogen atoms/carbon atoms was 0.23.

The shape of the peaks from X-ray diffraction is a pattern based on the boria skeleton structure, with a broad main peak around 20-22° at 2θ, and a small peak around 41-46°. Ta.

(2) Commercially available Cr3O8 was ground in a disk mill to obtain metal oxide powder with an average particle size of 10 μm.

(3) Powder of the insoluble and infusible substance specified in (1),
The metal oxide powder obtained in (2) was mixed at the predetermined ratio shown in Table 1, and the mixture was further mixed with 201 f
After adding 1% carbon black and 10% by weight polytetrafluoroethylene powder and thoroughly kneading,
Pressure molding was carried out at room temperature at a pressure of Kg/cIlt to form a film with a thickness of about 300 μm.

(4) Next, add L to sufficiently dehydrated propylene carbonate.
A battery was assembled as shown in Figure 1, using a 1.0 mol/ρ solution of iCJO4 as an electrolyte, Lichi's Kumu Kinku as a negative electrode, and the above-mentioned molded film as a positive electrode.As a current collector. A stainless steel mesh was used, and felt made of glass fiber was used as a separator.

(5) Next, a voltage was applied externally to this battery, and the molded film was doped with (1104- ions) at a constant current.The current value at this time was the value (m 8).

Positive electrode active material surrounding (Irtg) x - The open circuit voltage at the end of doping was 4■.

Next, the battery was discharged at the same current value as during charging, and the discharge was continued until the battery voltage reached 2■. The results are summarized in Table 1.

Table 1 However, in Table 1, the mixing ratio represents the weight ratio of the insoluble and infusible substance to the metal oxide. Despite the rapid charging and discharging described above, a high capacity secondary battery was obtained.

Comparative Example 1 An experiment was conducted in the same manner as in Examples 1 (3) to (5) using only the powder of the insoluble and infusible substance obtained in the same manner as in Example 1 (1). The electrical conductivity of the formed film was 3 x 1O-3S/ctrt, and the time required for discharge was 0.75 hours.

Comparative Example 2 A molded film obtained by conducting an experiment in the same manner as in Examples 1 (3) to (5) using only the metal oxide powder obtained in the same manner as in Example 1 (2). The electrical conductivity was 5×10'S/cm, and the time required for discharge was 0.60 hours.

The results of Example 1 and Comparative Examples 1 and 2 are summarized in FIG. 2. In FIG. 2, the horizontal axis represents the weight ratio of the insoluble and infusible material in the composite, and the vertical axis represents the time required for the discharge to reach 2V. The capacity was significantly increased when the composite of the present invention was used as the positive electrode active material, compared to when an insoluble and infusible substance alone (Comparative Example 1) or a metal oxide alone (Comparative Example 2) was used. That is clear.

Example 2 A powder of an insoluble and infusible substance obtained in the same manner as in Example 1 (1) and a metal oxide with an average particle size of 10 μm or less obtained by pulverizing V2O5 in a disc mill. powder,
The mixing ratio of the insoluble and infusible substance powder to the metal oxide powder is 7.
A film-like electrode was formed in the same manner as in Example 1-(3) except that the thickness was 0/30. A battery was assembled using the film electrode in the same manner as in Example 1-(4) except that Li As F6 was used as the electrolyte.

The battery was charged for 1 hour by applying a voltage of 4V from the outside. Next, the battery was discharged at the same current value as in Example 1 (5) and at a current value 115 times the current value, and the discharge was continued until the battery voltage reached 2V. As a result, each discharge is 1.06
It took 6 hours, and the capacity ratio was 0.88.

Example 3 Using the same composite molded body as used in Example 2 for the positive electrode,
A film made from the powder of the insoluble and infusible substance in Comparative Example 1 was used for the negative electrode, and the electrolyte was L; Batteries were constructed using propylene carbonate dissolution and charge/discharge tests were conducted. The voltage immediately after the battery was assembled was 0.5V. Next, 2
A voltage (2) was applied to dope the positive and negative electrodes for about 1 hour. Naturally, the electromotive voltage of the battery was 2■.

Next, when the battery was discharged at a constant current in the same manner as in Example 1 (5), the voltage of the battery reached O in about 0.8 hours. The battery was charged and discharged 100 times between 2 and OV, but the performance of the battery did not deteriorate.

[Brief explanation of drawings]

FIG. 1 shows the basic configuration of a battery according to the present invention, where 1 is a positive electrode, 2 is a negative electrode, 3.3' is a Tokyo Electric body, 4 is an electrolyte, 5 is a separator, 6 is a battery case, 7, 7' represents an external terminal. FIG. 2 shows the relationship between the weight ratio of the insoluble and infusible material in the positive electrode active material and the discharge time in a battery according to the present invention and a comparative battery.

Claims (1)

[Scope of Claims] 1. (A) (a) A heat-treated product of an aromatic condensation polymer which is a condensation product of an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde, which has hydrogen atoms/carbon atoms. has a polyacene skeleton structure with an atomic ratio of 0.5 to 0.05, and has a specific surface area value of at least 6 by the BET method.
00m^2/g and (b) a composite of a metal oxide as a positive electrode active material, and (B) an aproton of a compound that can generate ions that can be doped into the positive electrode active material by electrolysis. 1. An organic electrolyte battery characterized in that an electrolyte is an organic solvent solution. 2. Weight ratio of insoluble and infusible substance to metal oxide is 95:5
15:85. The organic electrolyte battery according to claim 1. 3. The organic electrolyte battery according to claim 1, wherein the composite of an insoluble and infusible substance and a metal oxide is a composite of an insoluble and infusible substance powder and a metal oxide powder. 4. A patent claim in which the composite is a mixture containing an insoluble and infusible substance powder, a metal oxide powder, a conductive agent, and an optional binder formed into a film, plate, or cylinder shape. The organic electrolyte battery according to scope 3. 5. The organic electrolyte according to claim 4, wherein the conductive agent is activated carbon, carbon black, acetylene black, graphite, or metal powder, and the mixing ratio thereof is 40 to 2% based on the total weight of the composite. battery. 6. The organic electrolyte battery according to claim 1, wherein the metal oxide is a transition metal oxide. 7. Claim 6, wherein the transition metal oxide is vanadium oxide, chromium oxide and/or molybdenum oxide
The organic electrolyte battery described in section. 8. Transition metal oxides are V_2O_5, V_6O_1_3
, Cu_2V_2O_7 and Cr_3O_8. The organic electrolyte battery according to claim 7. 9. The organic electrolyte battery according to claim 1, wherein the aromatic condensation polymer is a condensate of phenol and formaldehyde. 10. Specific surface area value of insoluble and infusible substance by BET method is 8
00 to 3000 m^2/g, the organic electrolyte battery according to claim 1. 11. The organic electrolyte battery according to claim 1, wherein the insoluble and infusible substance has a large number of communicating pores with an average pore diameter of 0.03 to 10 μm. 12. The organic electrolyte battery according to claim 1, wherein the insoluble and infusible substance has a hydrogen atom/carbon atom atomic ratio of 0.5 to 0.15. 13. The organic electrolyte battery according to claim 1, wherein the negative electrode is selected from alkali metals, alloys thereof, alkaline earth metals, and alloys thereof. 14. The organic electrolyte battery according to claim 13, wherein the negative electrode is lithium or a lithium alloy. 15. A heat-treated product of an aromatic condensation polymer in which the negative electrode 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. ~0.05, (b) has a specific surface area value of at least 600 m^2/g by the BET method, and (c) is insoluble and infusible, having communicating pores with an average pore diameter of 10 μm or less. The organic electrolyte battery according to claim 1, which is a substance. 16. Compounds that can generate ions that can be doped by electrolysis are LiI, LiClO_4, LiBF_4, L
iAsF_6, LiPF_6, LiB(C_2H_5)
_4, LiB(C_H_6H_5)_4 or LiHF_
2. The organic electrolyte battery according to claim 1, which is 17, the aprotic organic solvent is ethylene carbonate,
The organic electrolyte battery according to claim 1, which is propylene carbonate, γ-butyrolactone, dimethylformamide, dimebracetamide, dimethyl sulfoxide, acetonitrile, dimethoxyethane, tetrahydrofuran, dioxolane, sulfolane, or a mixture thereof.