JPS63218157A - Organic electrolyte battery - Google Patents

Abstract

PURPOSE:To obtain an organic electrolyte battery with high battery voltage and high capacity by using an organic semiconductor comprising an insoluble and infusible substrate having a specific polyacetylene type skeleton structure as an electrode active substance. CONSTITUTION:By previously doping electron doner type substances or cations into an insoluble and infusible substrate containing polyacetylene type skeleton structure, which is a heat-treated aromatic condensation polymer, obtained by condensation of aromatic hydrocarbon compounds having phenol hydroxide group and aldehydes, with the number ratio of H atom/C atom of 0.05-0.5 and the specific surface area (BET method) of 600 m<2>/g or more, positive electrode 1 and negative electrode 2 are obtained. An electrolytic solution 4 contains a non-proton type organic solvent and an electrolyte that enables ions, which are doped into these electrodes 1, 2 by electrolysis, to generate. By such arrangement that the previously doped insoluble and infusible substrate is used for the positive electrode 1 and negative electrode 2, a high capacity and a broad actuating potential range can be achieved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to organic electrolyte batteries. More specifically, an insoluble and infusible substrate having semiconductor properties is doped with cations in advance, used as a positive electrode and a negative electrode, and an electrolytic solution is prepared by dissolving a compound capable of producing doped ions in an aprotic organic solvent. The present invention relates to an organic electrolyte battery.

[Background Art] In recent years, electronic devices have become increasingly smaller, thinner, and lighter, and there is a strong demand for batteries that serve as power sources to be smaller, thinner, and lighter. Currently, silver oxide batteries are widely used as small, high-performance batteries, and lithium oxide 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, 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 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 exchange. 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.

In addition, Japanese Patent Application Laid-Open No. 60-17016 filed by the present applicant
The specification of No. 3 describes a heat-treated product of an aromatic condensation polymer consisting of carbon, hydrogen, and oxygen, in which the atomic ratio of hydrogen atoms/carbon atoms is 0.05 to 0.5, and the BET
An aprotic organic solvent of a compound capable of producing ions that can be doped into the electrode by electrolysis, using an insoluble and infusible substrate having a polyacene skeleton structure with a specific surface area of 600 TIt/g or more as a positive electrode and/or a negative electrode. An organic electrolyte battery characterized by using a solution as an electrolyte has been proposed.

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 is easily molded, making it a promising secondary battery. However, several issues remain to be solved in order to put this battery into practical use. Among these problems were the relatively low battery operating voltage and relatively small capacity.

[Problems to be Solved by the Invention] An object of the present invention is to provide an organic electrolyte battery using an organic semiconductor composed of an insoluble and infusible substrate having a polyacene skeleton structure as an electrode active material, which has a high battery voltage and a large capacity. Our goal is to provide large organic electrolyte batteries.

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. Another object of the present invention is to provide a secondary battery that has low internal resistance and low self-discharge, and can be charged and discharged for a long period of time.

[Means and effects for solving the problems] The above object of the present invention is to: A) (a) produce an aromatic condensation polymer which is a condensation product of an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde; A heat-treated product, (b) having a polyacene skeleton structure with an atomic ratio of hydrogen atoms/carbon atoms of 0.5 to 0.05, and c) having a specific surface area of 600 TIi by the BET method.
/g or more; (d) an insoluble infusible substrate doped with an electron-donating substance or a cation in advance as a positive electrode and a negative electrode, and B) capable of generating ions that can be doped into the electrode by electrolysis. This is achieved by an organic electrolyte battery characterized in that the electrolyte is a solution containing an electrolyte and an aprotic organic solvent.

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 such aromatic hydrocarbon compounds, for example, so-called phenols such as phenol, cresol, and xylenol are suitable; ], methylene-bisphenols, hydroxybiphenyls, and hydroxynaphthalenes can also be used. Among these, phenols, particularly phenol, are practically preferred.

The aromatic integrated polymer in the present invention is a modified aromatic polymer in which a part of the above-mentioned aromatic hydrocarbon compound having a phenolic hydroxyl group is replaced with an aromatic hydrocarbon compound not having a phenolic hydroxyl group, such as xylene, toluene, etc. It is also possible to use polymers, for example condensates of phenol, xylene and formaldehyde.

As the aldehyde, aldehydes such as formaldehyde, acetaldehyde, and furfural can be used, and formaldehyde is preferred. The phenol formaldehyde condensate may be a novolac type, a resol type, or a mixture thereof.

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

An initial condensate is prepared from an aromatic hydrocarbon compound having a phenolic hydroxyl group or a mixture of this and an aromatic hydrocarbon compound not having a phenolic hydroxyl group, and aldehydes, and an aqueous solution of this initial condensate and an inorganic salt is prepared. This aqueous solution is poured into a suitable mold and heated to harden in the mold into a plate-like, film-like or cylindrical shape, for example, and then the cured product is heated to 350 to 350 cm in a non-oxidizing atmosphere.
The heat-treated body obtained is then washed to remove inorganic salts contained in the heat-treated body.

The above-mentioned inorganic salt used together with the initial condensate is to be removed in a later step, and is added to the insoluble and infusible substrate of the present invention by
It is an auxiliary agent for providing a specific surface area of 100 g or more. Examples of inorganic salts that can be used include zinc chloride, sodium phosphate, potassium hydride, and potassium sulfide. Among these, zinc chloride is particularly preferred. Inorganic salt is the first tn
It can be used in an amount of, for example, 0.05 to 10 times the weight of the condensate.

However, if the amount is less than the lower limit, the specific surface area value will not be 600 Trt/9 or more, and if the amount is more than the upper limit, the mechanical strength of the final molded product 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 can be prepared using, for example, 0.1 to 1 times as much water as the inorganic salt, and the aqueous solution is poured into a suitable mold. For example, it hardens when heated at a temperature of 50 to 200°C.

Phenolic fibers (for example, Kynol (trademark) fibers manufactured by Nippon Kynol Co., Ltd.) may be mixed into the aqueous solution of the above-mentioned initial condensate and inorganic salt. Alternatively, a prepreg may be prepared by sufficiently impregnating cloth, felt, etc. made of phenolic fiber with the above aqueous solution, and then molded and cured.

The thus obtained 1q 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 400 to 600° C., for heat treatment.

The preferred rate of temperature increase during heat treatment varies somewhat depending on the aromatic condensation polymer used, the degree of its curing treatment, its shape, etc., but in general, a relatively high rate of temperature increase from room temperature to a temperature of about 300''C. For example, it is possible to set the rate at 100°C/hour.When the temperature reaches 300'C or higher, the aromatic condensation polymer starts to thermally decompose, producing water vapor, hydrogen, and methane. , - It is advantageous to raise the temperature at a sufficiently slow rate since gases such as carbon oxides begin to evolve.

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

The inorganic salts contained in the heat-treated body can be removed by sufficiently washing the heat-treated body with water or dilute hydrochloric acid, and then the body is dried. In this way, the atomic ratio of hydrogen atoms/carbon atoms (hereinafter referred to as H/C ratio) is 0.5 to 0.05, preferably 0.35 to 0.1.
An insoluble and infusible substrate having a polyacene skeleton structure and a specific surface area of 600 TIt/9 or more by the BET method can be obtained. According to X-ray diffraction (Cu Kα), the main
The peak position is expressed in 2θ between 20.5 and 23.5°, and in addition to the main peak, there are also peak positions between 41 and 46°.
There are other broad peaks in between.

That is, it is understood that the above-mentioned insoluble and infusible substrate is one in which the polycyclic structure of boriacene-based benzene is evenly and appropriately developed between the boriacene-based molecules.

If the H/C ratio exceeds 0.5 or is smaller than 0.05, the efficiency of charging and discharging will decrease when the substrate is used as an electrode of a secondary battery according to the method shown later, which is not preferable. In addition, the specific surface area value of the insoluble and infusible substrate containing the polyacene skeleton structure by the BET method is extremely large because it is manufactured using an inorganic salt such as zinc chloride, and in the present invention, the specific surface area value is 600 m/g. The above is used.

If it is less than 600 butts/g, it is not preferable because it is necessary to increase the charging voltage when charging a secondary battery in which the substrate is connected to an electrode, resulting in a decrease in energy density, etc., and deterioration of the electrolyte solution.

In addition, Japanese Patent Application Laid-Open No. 61-21806 filed by the present applicant
As described in Publication No. 0, an inorganic salt is converted into an initial condensate of 2
．． The viscosity of the aqueous solution is 100.000-100.000 times the amount by 5-10 times.
When heat-treated in a non-oxidizing atmosphere using a molded body adjusted to 100 centipoise and cured to prevent moisture evaporation during heating, it becomes porous, insoluble, and infusible with continuous pores with an average pore diameter of 10 μ or less. A sexual substrate is obtained. It is more preferable to use the base as an electrode because the electrolyte can easily enter and exit through the communicating holes to the smallest detail.

The electrical conductivity of the above-mentioned insoluble and infusible substrate is usually 10-11 to 1.
01Ω-1,,-1, but by doping with electrolyte ions, the electrical conductivity increases from 10-2 to 102Ω-
Increases to 1 cm-1. In the present invention, as described later,
Since the above-mentioned insoluble and infusible substrate is doped with a cation or electron-donating substance and has high conductivity, it is used as an electrode material that also has current collecting properties. You can also do that.

Furthermore, since the insoluble and infusible substrate of the present invention can be made into various forms such as films and plates, it can be used for small batteries,
Suitable as an electrode material for thin or lightweight batteries.

The porous insoluble and infusible substrate used in the present invention has a
Although it has a large specific surface area of Trt/g or more, it has excellent oxidation stability, and its physical properties such as electrical conductivity do not change even if it is left in the air for a long time. Furthermore, since it has excellent heat resistance and chemical resistance, there is no problem of electrode deterioration when used as an electrode material.

In the organic electrolyte battery of the present invention, the insoluble and infusible substrate described above is doped with an electron-donating substance or a cation in advance, and the insoluble and infusible substrate is used as a positive electrode and a negative electrode, and ions that can be doped into the electrode can be generated by electrolysis. It is characterized in that the electrolyte is a solution in which a compound is dissolved in an aprotic organic solvent.

The electron donating substance to be doped in advance is L.
i1Na, K are preferred, and the cations include Ll, N
a, K, (CH3)4N 1(C2H5)4N+,
(03H5>4 N+ can be used. By doping 0.5 to 3.0% by weight of these electron-donating substances or cations to the insoluble and infusible substrate of the present invention, the absolute potential of the electrode can be changed. Although the reason is unclear, by lowering the absolute electrode potential of the insoluble and infusible substrate, the operating voltage +1 of the battery increases and the discharge capacity increases. The fusible substrates were used as positive and negative electrodes, and the electrolyte was the most standard LiCρ04/propylene carbonate (
The organic electrolyte battery of the present invention in which the insoluble and infusible substrate of the present invention, which has been doped in advance, is used as the positive electrode and negative electrode is compared with the organic electrolyte battery in which the insoluble substrate of the present invention is doped in advance.
It has a discharge capacity of 5 to 2 times, and the operating voltage is 1.2 to 1.
Expands seven times.

That is, the organic electrolyte battery of the present invention, which uses a pre-doped insoluble and infusible substrate as a positive electrode and a negative electrode, has a larger capacity than a conventional organic monolithic battery and has a wide range of operating potential.

As a method for doping the insoluble and infusible substrate with an electron donating substance or cation, any of the known electrolytic methods, gas phase methods, liquid phase methods, and ion implantation methods can be used. For example, when doping cations by electrolytic method, an insoluble and infusible substrate is immersed as a working electrode in an electrolytic solution containing cations, and a current is passed or a voltage is applied between it and a counter electrode in the same electrolytic solution. . Furthermore, when using a gas phase method, the insoluble and infusible substrate is exposed to, for example, the vapor of the above-mentioned electron donating substance.

In addition, when using a liquid phase method, for example, an insoluble and infusible substrate is impregnated with the liquid of the above-mentioned electron donating substance, or a mirror body containing the above-mentioned electron donating substance and an insoluble infusible substrate are impregnated. You may also react. Examples of mirrors used in this reaction include, but are not limited to, alkali metal naphthalene complexes and alkoxides.

The amount by which the insoluble and infusible substrate is doped with the electron donating substance or cation in advance is preferably 0.5 to 3% by weight. When the doping amount is 3% or more, the electrode potential is too low, while when it is 0.5% or less, the electrode potential is too high, and the effect of increasing the capacity and widening the operating potential is not significant.

Further, as a solvent constituting the electrolytic solution used in the present invention, an aprotic organic solvent is used. Examples of aprotic organic solvents include ethylene carbonate, propylene carbonate, γ-butyrolactone, dimethylformamide, dimethylacetamide, dimethylsulfoxide,
Any of acetonitrile, dimethoxyethane, tetrahydrofuran, dioxolane, methylene chloride, sulfolane, or a mixture of two or more of these aprotic organic solvents may be used.

Further, the electrolyte to be dissolved in the above-mentioned mixed or single solvent may be any electrolyte that can generate ions that can be doped into the doped insoluble and infusible substrate of the present invention by electrolysis. Such an electrolyte is, for example, Lt L
NaI, NH41, LiC,ll04, Li
AS F6, L+ BF4, KP F6,
Na PF6, (C2F15) 4N
C, C04, (rl-C4Hg) 4 NGρ04,
(C2 (5) 4 N B F4 , (n-CI-1
) NBF4. (n C4t-1g) 4 NAS F6, (n
C4Hg)4PF6 or LiHF2.

The above electrolyte and solvent are mixed in a sufficiently dehydrated state to form an electrolyte solution, and the concentration of the first electrolyte in the electrolyte solution is at least 0.1 mol/ρ in order to reduce the internal resistance caused by the electrolyte solution. It is desirable to set it to above, and usually 0.2 to
More preferably, the amount is 1.5 mol/.12.

Charging and discharging of the battery of the present invention is performed by electrochemical doping and electrochemical undoping of the above-mentioned electrolyte ions onto a previously doped insoluble and infusible substrate used as an electrode. That is, energy is stored by doping the insoluble and infusible substrate, and is taken out as electrical energy by undoping.

The shape and size of the electrode, which is made of a pre-doped insoluble and infusible substrate placed inside the battery, can be arbitrarily selected depending on the type of battery intended, but the battery reaction is based on the electrochemical reaction on the electrode surface. Since this is a kinetic reaction, it is advantageous for the electrode to have as large a surface area as possible. In addition, the insoluble and infusible substrate itself can be used as a current collector for extracting current from the substrate to the outside of the battery, but conductive materials that are resistant to corrosion by the electrolytic solution, such as carbon, platinum, nickel, and stainless steel, may also be used. etc. can also be used.

Next, embodiments of the present invention will be explained with reference to the drawings. FIG. 1 is a basic structural diagram of a battery according to the present invention. In Figure 1,
Reference numeral 1 denotes a positive electrode, which is a film-like or plate-like insoluble and infusible substrate which has been doped in advance. Reference numeral 2 denotes a negative electrode, which is likewise a film-like or plate-like insoluble and infusible substrate which has been doped in advance. Immediately after the battery is assembled, the electromotive voltage of the battery is 0 to 1 V, although it varies depending on the amount of dopant 1 to 1 with which the insoluble and infusible substrate is doped in advance. By applying voltage from an external power supply,
By charging, the battery has a high electromotive force. Reference numeral 3.3' denotes a current collector for extracting current from each electrode to the outside or supplying current for charging, and is connected to external terminals 7 and 7'. 4 is an electrolytic solution, and 5 is a separator arranged for the purpose of preventing contact between the positive and negative electrodes and retaining the electrolytic solution. The separator is a durable porous body with no electronic conductivity and has continuous pores, and is usually made of glass fiber, polyethylene, polypropylene, or the like, a nonwoven fabric, or a porous body.

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 electrode, negative electrode, and separator are fixed in the battery case 6 so as not to cause any practical problems. The shape, size, etc. of the battery are determined as appropriate depending on the shape and performance of the intended battery. For example, when producing a thin battery, a film-shaped electrode is suitable, and when producing a large-capacity battery, this can be achieved by alternately stacking a large number of film-shaped or plate-shaped positive and negative electrodes.

Charging or discharging may be performed under a constant current, a constant voltage, or under conditions where the current and voltage vary, but the amount of doping agent doped into the insoluble and infusible substrate during charging depends on the The number of doped ions expressed as a percentage per carbon atom is preferably 0.5 to 20%.

The battery of the present invention, which uses an insoluble and infusible substrate doped in advance as an electrode, is a secondary battery that can be repeatedly charged and discharged, and its electromotive voltage varies depending on the charging period of the battery, but is 1.0 to 3. .5V.

Since the specific gravity of the insoluble and infusible substrate and electrolyte that constitute the battery of the present invention is small, the capacity per weight is large.

Furthermore, although there are differences in power density depending on the structure of the battery, it has a much higher power density than a lead-acid battery. Further, when the insoluble and infusible substrate which has been doped in advance according to the present invention is used as an electrode, it is possible to produce 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 secondary battery of the present invention has a porous insoluble and infusible substrate containing a polyacene bone+8 structure that has superior oxidation resistance, heat resistance, moldability, and mechanical strength compared to conventionally known organic semiconductors. Alternatively, the secondary battery uses an electrode doped with an electron-donating substance in advance, and can be made smaller, thinner, and lighter, and has a high capacity, high electromotive force, and high output.

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

Example 1 (1) An aqueous solution containing water-soluble resol (approximately 60% concentration)/zinc chloride/water mixed in a weight ratio of 10/25/4 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 heated at a rate of 40°C/hour under a nitrogen stream to 500°C.
Heat treatment was performed to ℃. Next, the heat-treated product was washed with dilute hydrochloric acid, water, and then dried to obtain a porous film. The thickness of the film was approximately 200 μm, the apparent density was 0.35 g/cffl, and the film had excellent mechanical strength. Next, the electrical conductivity of the film was measured at the lowest temperature using the DC 4-terminal method, and the result was 10'.
(Ω・cmVl. Also, when elemental analysis was performed, the atomic ratio of hydrogen atoms/carbon atoms was 0.27.X
The shape of the peaks from line diffraction is a pattern based on the polyacene skeleton structure, with a broad main peak around 20-22° at 2θ, and a small peak around 41-46°. . Further, when the specific surface area value was measured by the BET method, it was found to be an extremely large value of 2100'rIi/9.

Next, in order to observe the pore state of the film-like insoluble and infusible substrate, an electron micrograph of a cross section of the film was taken.
It was found that it was a porous body having fine interconnected pores with an average diameter of 10 μm or less.

(2) Next, a solution prepared by dissolving LiC, 1104 at a concentration of 1 mol/Ω in sufficiently dehydrated propylene carbonate is used as the electrolyte, the sufficiently dried insoluble and infusible substrate is used as the working electrode, and lithium is used as the counter electrode. l- to the insoluble and infusible substrate as
i Electrolytic doping of cations was performed. The doping amount was expressed as the number of ions doped per carbon atom of the porous film substrate, and the number of doped ions was determined from the value of the current flowing through the circuit. Before starting electrolytic doping, the voltage of the insoluble and infusible substrate to the Li counter electrode was 2.95V. Next, using an external power supply, the voltage to the Li counter electrode of the insoluble and infusible substrate was set to 2.3
When the setting was set to (2), a current began to flow from the insoluble and infusible substrate to the lithium electrode. After about one hour, the current flowing through the circuit decreased to several tens of microamperes, so electrolytic doping was stopped, and the potential of the insoluble and infusible substrate relative to the lithium counter electrode was measured and found to be about 2.3V. Calculating from the amount of current flowing through the circuit up to this point, the amount of lithium cations electrolytically doped into the insoluble and infusible substrate was about 1.2%.

Next, the insoluble and infusible substrate doped with lithium was used as a positive electrode and a negative electrode, and L i C4! was added to sufficiently dehydrated propylene carbonate. A battery was assembled as shown in FIG. 1 using a solution containing 04 dissolved at a concentration of 1 mol/ρ as an electrolyte. A stainless steel mesh was used as the current collector, and felt made of glass fiber was used as the separator.

The voltage immediately after the battery was assembled was OV. Next, a voltage of 2.5V was applied from an external power source to charge the battery for about 1 hour. Naturally, the electromotive voltage of the battery was 2.5V.

Next, when the battery was discharged at a rate such that the amount of and-ping per hour was 3%, the voltage of the battery returned to OV in about 1 hour.

Next, when the battery was charged again using an external power supply with a current that gave a charge amount of 1% per hour, the battery was charged at approximately 3.5%.
After charging, the battery voltage became 3V. Next, when discharging was performed using the same current as during charging, it took about 3 hours and 20 minutes until the battery voltage reached Ov.

The charge efficiency was calculated from the time required for charging and the time required for discharging and was approximately 95%. From this, battery voltage 3
．． It turns out that 0V is in the white range of operating potentials.

Comparative Example 1 A battery was assembled in the same manner as in Example 1 except that an insoluble and infusible substrate that had not been doped in advance was used as a positive electrode and a negative electrode. The voltage immediately after the battery was assembled was Ov. Next, we applied a voltage of 2.5μ using an external power source, charged the battery for about 1 hour, and discharged it at a rate of 3% discharge per hour.The battery voltage returned to OV in about 1 hour. .

Next, the battery was charged by an external power source with a current that would give a charge amount of 1% per hour, and the voltage of the battery became 3V at about 3.5% charge. Next, when discharging was performed using the same current as during charging, the amount of discharge was 3.0%, and the charge efficiency was 85%.

Examples 2 and 3 The insoluble and infusible substrate obtained in Example 1 (1) was doped with lithium cations to a predetermined amount shown in Table 1 by an electrolytic method. Next, a battery was assembled using these pre-doped insoluble and infusible substrates as a positive electrode and a negative electrode, and the charge efficiency in charging and discharging up to 3V was measured in the same manner as in Example 1.

These results are shown in Table 1.

Table 1

[Brief explanation of the drawing]

FIG. 1 is a basic configuration diagram of a battery according to the present invention, where 1 is a positive electrode, 2 is a negative electrode, 3.3' is a current collector, 4 is an electrolytic solution, 5 is a separator, 6 is a battery case, and 7°7 ' represents an external terminal.

Claims (1)

[Scope of Claims] 1. 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, the atomic ratio of hydrogen atoms to carbon atoms being 0.
．． 05 to 0.5 and a specific surface area of 600 m^2/g or more by the BET method.An insoluble and infusible substrate is doped with an electron-donating substance or a cation in advance. An organic electrolyte battery characterized in that a substrate is used as a positive electrode and a negative electrode, and an electrolytic solution is a solution containing an electrolyte and an aprotic organic solvent that can generate ions that can be doped into the electrodes by electrolysis. 2. The organic electrolyte battery according to claim 1, wherein the aromatic condensation polymer is a condensate of phenol and formaldehyde. 3. The organic electrolyte battery according to claim 1, wherein the atomic ratio of hydrogen atoms/carbon atoms is 0.1 to 0.35. 4. The organic electrolyte battery according to claim 1, wherein the insoluble and infusible substrate has a large number of communicating pores with an average pore diameter of 10 μm or less. 5. The insoluble and infusible substrate is doped with an electron-donating substance or cation in units of quantity (1 carbon atom of the insoluble and infusible substrate).
2. The organic electrolyte battery according to claim 1, wherein the positive electrode and the negative electrode are insoluble and infusible substrates doped with 0.5 to 3% (expressed as a percentage of the number of ions doped per cell). 6. The electron-donating substance pre-doped into the insoluble and infusible substrate is selected from Li, Na, and K, and the cation is Li.
^+, Na^+, K^+, (CH_3)_4N^+, (C_2H_5_)4N^+
, (C_3H_5)_4N^+. 7. The organic electrolyte battery according to claim 1, wherein the positive and negative electrodes are insoluble and infusible substrates doped with cations in advance by an electrolytic method. 8. A compound that can generate ions that can be doped is L
iI, NaI, NH_4I, LiClO_4LiASF
_6, LiBF_4, KPF_6, NaPF_6, (C
_2H_5)_4NClO_4, (n-C_4H_9)
_4NClO_4, (C_2H_5)_4NBF_4, (n-C_4H_9
)_4NBF_4, (n-C_4H_9)_4NASF
_6, (n-C_4H_9)_4PF_6 or LiHF
The organic electrolyte battery according to claim 1, which is _2. 9. The aprotic organic solvent is ethylene carbonate, propylene carbonate, γ-butyrolactone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, dimethoxyethane, tetrahydrofuran, dioxolane, methylene chloride, sulfolane, or any of these aprotic organic solvents. The organic electrolyte battery according to claim 1, which is a mixed solution.