JPH03233861A - Organic electrolyte battery - Google Patents

Abstract

PURPOSE:To make possible charge and discharge of an organic electrolyte battery over a long period by using lithium as negative electrode active material, and using as a negative electrode a heat treated specific aromatic condensed polymer consisting of carbon, hydrogen and oxygen. CONSTITUTION:An organic electrolyte battery is provided with a positive electrode 1, a negative electrode 2 and an electrolyte 4 and a heat treated aromatic condensed polymer consisting of carbon, hydrogen and oxygen is used as the negative electrode 2. The aromatic condensed polymer is selected from among (a) a condensate of an aromatic hydrocarbon compound having phenol hydroxyl group and aldehyde, (b) a condensate of an aromatic hydrocarbon compound having phenol hydroxyl group, an aromatic hydrocarbon compound not having phenol hydroxyl group, and aldehyde, and (c) furan resin. When an insoluble and infusible base substance containing polyacene skeleton structure in which the ratio of hydrogen to carbon is 0.50 to 0.05 after heat treatment is molded suing a thermoplastic resin binder, of after the base substance is molded, a molding of an insoluble and infusible base substance heat treated at temperature above the melting point of the thermoplastic resin is made to carry lithium therein by more than 3mol%. The long-range cycle characteristic of the battery is thereby bettered.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an organic electrolyte battery, and more specifically, as a negative electrode, an insoluble and infusible substrate having a polyacene skeleton structure is molded using a thermoplastic resin binder. It is possible to use a molded body that has been heat-treated above the melting point during or after molding and supports lithium on it! Regarding electrolytes.

(Prior Art) In recent years, batteries using conductive polymers, transition metal oxides, or activated carbon as positive electrodes have been proposed. When lithium is used as the negative electrode of these batteries, secondary batteries for energy sources with high voltage, capacity, and energy density can be obtained. However, when such a battery using lithium as a negative electrode is put into practical use, there is a problem in that the charge/discharge cycle life is reduced due to the generation of dendrites. Dendrites are dendritic or moss-like lithium crystals that form on the surface of a lithium negative electrode during charging. The dendrites lengthen with repeated charging and discharging, and eventually both poles are short-circuited, resulting in the end of the cycle life. Therefore, it is important to suppress the generation of dendrites when putting the battery into practical use.

Recently, research has been progressing on lithium batteries in which lithium is supported on carbon materials such as graphite, and conductive polymers such as polyacetylene and polyparaphenylene. However, although the generation of dendrites is extremely small, there is a problem in that the structure changes significantly when lithium is added or removed, resulting in a decrease in cycle characteristics.

In general, battery electrodes use active materials in the form of powders, such as polytetrafluoroethylene binder polyethylene,
Kneading with thermoplastic resin binder such as polypropylene,
Pressure molded products are
Preferably used.

However, when lithium is supported on a compact formed by molding the above-mentioned insoluble and infusible substrate in powder form using the above method, the electrode becomes significantly loose, and problems remain with battery characteristics, especially rapid discharge characteristics and cycle characteristics. .

(Problems to be Solved by the Invention) The present inventors have completed the present invention as a result of diligent research in view of the above-mentioned problems.The purpose of the present invention is to enable charging and discharging over a long period of time. To provide secondary batteries.

Another object of the present invention is to provide a secondary battery with good rapid discharge characteristics.

Still another object of the present invention is to provide a secondary battery that is easy to manufacture.

<Means for Solving the Problems> The above object of the present invention is to use an organic electrolyte 1 including a positive electrode, a negative electrode, and an electrolytic solution containing a solution of a lithium salt dissolved in an aprotic organic solvent in a battery. A heat-treated product of an aromatic condensation polymer using lithium as an active material and carbon, hydrogen, and oxygen as a negative electrode, the aromatic condensation polymer comprising (a) an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde. (b) a condensate of an aromatic hydrocarbon compound having a phenolic hydroxyl group, an aromatic hydrocarbon compound having no phenolic hydroxyl group and an aldehyde, and (c) a furan resin; The atomic ratio of hydrogen atoms/carbon atoms is 0.5
0-0.05 when molding an insoluble and infusible substrate containing a polyacene skeleton structure using a thermoplastic resin binder, or by heat-treating it at a temperature higher than the melting point of the thermoplastic resin after the bottom shape. This is achieved by an organic electrolyte battery characterized by using a base molded body supporting lithium in a molar percentage of 3% or more.

The insoluble and infusible substrate containing a polyacene skeleton structure (hereinafter referred to as PAS) in the present invention is an aromatic condensation polymer described in JP-A-59-3806 filed by the applicant of the present application. Obtained by heat treatment under specific conditions.

In addition, PAS having a specific surface area of 600 m"/g or more by the BET method is
It is obtained by the method described in Japanese Patent No. 170163.

Specifically, when a high specific surface area is not required, aromatic condensation polymers used in the present invention include (a) aromatic hydrocarbon compounds and aldehydes having phenolic hydroxyl groups, such as phenol-formaldehyde resins; (b) Aromatic hydrocarbon compounds with phenolic hydroxyl groups, such as xylene-modified phenol, formaldehyde resin (phenol partially replaced with xylene), aromatic compounds without phenolic hydroxyl groups Suitable examples include condensates of hydrocarbon compounds and aldehydes and (c) furan resins.

The aromatic condensation polymer is gradually heated to a suitable temperature of 400°C to 1000°C, preferably 600°C to 800°C, in a non-oxidizing atmosphere (including a vacuum state) to form hydrogen atoms/carbon atoms. The atomic ratio (hereinafter referred to as H/C) is 0.
PAS is obtained when the heat-treated product has a molecular weight of 50 to 0.05, preferably 0.35 to 0.10. In the case of PAS having a specific surface area determined by the BET method of 600 m"/g or more, an inorganic salt such as zinc chloride or sodium phosphate is mixed with the above-mentioned aromatic condensation polymer. The amount to be mixed is
Although it varies depending on the type and the shape and performance of the intended electrode,
The weight ratio (1) is preferably 0/1 to 1/7.

The mixture of inorganic salt and aromatic condensation polymer thus obtained is usually cured by heating at a temperature of 50 to 180°C for 2 to 90 minutes, although this varies depending on the composition of the polymer, the type of inorganic salt, etc. The obtained cured product is then heated to a temperature of 350 to 800°C, preferably 400 to 750°C in a non-oxidizing atmosphere, and the obtained heat-treated product is thoroughly washed with water or dilute hydrochloric acid. , to remove inorganic salts contained in the heat-treated body.

After that, when this is dried, H/C=0.50~0,0
5 preferably 0.35-0. 600m”/g of IO
PAS having the above specific surface area can be obtained.

It is preferable that the PAS used in the present invention has a main peak position of 24° or less in 2θ in xi diffraction (CuKα ray) and shows a broad peak between 41° and 46°C in 2θ.

Further, in the present invention, PAS is determined from an infrared absorption spectrum and is expressed by the following formula (D): D=Dteem-tvae/Drsha-
Iham, D. 1,4° is the absorbance determined from the maximum absorption peak in the range of 2,900 to 2,940 Kaiser in the infrared absorption spectrum, and DI56° to 1° is the absorbance determined from the maximum absorption peak in the range of 1,560 to 1,640 Kaiser in the infrared absorption spectrum. The required absorbance is
is preferably 0.5 or less, particularly 0.3 or less.

(Details of the method for calculating the above absorbance ratio (D) are described in Example 1 of JP-A-59-3806.) PAS has a suitably developed aromatic polycyclic structure, and It is suggested that the average distance of the planar polyacene skeleton structure is relatively large, and lithium can be stably supported.

When the above-mentioned average distance is small, that is, as it approaches the graphite crystal, changes are more likely to occur in the substrate structure when lithium is supported or when lithium is put in and taken out (during charging and discharging), and the cycle characteristics deteriorate.

In addition, if the aromatic polycyclic structure is not developed, lithium cannot be stably supported, and a battery manufactured using a negative electrode in which lithium is supported on this straight PAS will have a large self-discharge.

The negative electrode in the present invention is made of powder, short 1. ll PAS manufactured in the shape of fibers, etc. or manufactured in an appropriate shape and processed into powder, short fibers, etc.
is molded with a thermoplastic resin binder. Lithium is supported on a molded rod that has been heat-treated above the melting point of the thermoplastic resin.

The thermoplastic resin in the present invention is not particularly limited, but
It is insoluble in the electrolyte described later, and the operating temperature range of the battery is
Specifically, it is preferable to use a material that does not soften or become brittle at -30°C to 80°C, and in addition to the above properties, it is practically
More suitable results can be obtained by using a material that melts at 300° C., such as polyethylene, polypropylene, polystyrene, etc.

The amount of thermoplastic resin binder in the present invention is 5% to 50%, preferably 10 to 30% by weight based on PAS, but the appropriate amount is determined by the shape of PAS, the type of binder, and the amount of lithium supported. .

In the present invention, heat treatment at a temperature above the melting point is an important step for imparting strength to the electrode. When the above thermoplastic resin is generally used as a binder, the thermoplastic resin powder,
A method is known in which fibers and the like are mixed in an amount of several percent to several tens of percent by weight with respect to the active material, and then pressure molded, or heat and pressure molded for a short time. Conventional methods require a large amount of thermoplastic resin binder to obtain strength, which naturally reduces the amount of active material in the electrode, leading to a decline in battery characteristics such as capacity. When lithium is supported on a PAS-shaped body, the electrode becomes loose and the internal resistance of the battery increases compared to when a plate-like or film-like PAS is used as a lithium-supporting material, making rapid discharge difficult. Cycle characteristics cannot be obtained.

The heat treatment in the present invention must be performed at a temperature higher than the melting point of the thermoplastic resin used. In other words, by performing the heat treatment at a temperature higher than the melting point, part or all of the thermoplastic resin is melted, and the mixture becomes more homogeneous and mixed. When the shape of resin powder or fibers is distorted, P
Because it adheres to AS, a PAS molded body with high strength and less loosening of the electrode when lithium is supported can be obtained.

The heating method used in the present invention includes a method in which a mixture of PAS and a thermoplastic resin binder is pressure-molded simultaneously, and a method in which a mixture of PAS and a thermoplastic resin binder is heat-treated in an electric furnace or the like after pressure-molding. It is necessary to do this until it melts. The temperature for 1 hour varies depending on the type of resin, amount, heating method, etc., but it is important to determine the temperature so that the above-mentioned molten state is obtained.

The negative electrode in the present invention may be formed by supporting lithium on a PAS body obtained by the method described above.

The supporting method at this time may be appropriately selected from known methods such as electrolytic method, gas phase method, liquid phase method, and ion implantation method.For example, when supporting lithium by electrolytic method, lithium ions are It is immersed as an electrode for a PAS pot-shaped body in an electrolytic solution containing the electrode, and a current is passed or a voltage is applied between it and a counter electrode in the same electrolytic solution.

It can also be supported by a method in which an appropriate amount of lithium foil is brought into direct contact with the molded body.

When using a gas phase method, for example, lithium vapor is added with P.
The AS molded body is exposed, or when a liquid phase method is used, for example, a complex containing lithium ions is reacted with an insoluble and infusible substrate. Examples of the complex used in this reaction include, but are not limited to, alkali metal naphthalene complexes and alkoxides.

The amount of lithium supported on PAS by the above method is 3% or more, preferably 10% or more, expressed as a molar percentage (percentage of lithium to one carbon atom of PAS). The amount of lithium varies depending on the specific surface area of PAS, and it is desirable to carry lithium so that the PAS on which lithium is carried is in a bowl-shaped position with a ratio of 1.0 to 0v with respect to Li/Li. If the amount is too low, the capacity of the battery of the present invention will decrease, and if it is too much, excess lithium will be exposed to the surface of the PAS, which is not preferable.

In particular, when PAS with a high specific surface area is used, the amount of lithium supported increases, so the electrode tends to loosen in the conventional method, and the effects of the present invention are noticeable. i.e. 600
PAS, which has a specific surface area determined by the BET method of m'/g or more, has a high diffusion rate of Lj in the substrate, so it is possible to reduce the internal resistance of the battery! ! However, by using the method of the present invention, a high-performance secondary battery can be obtained.

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

Further, the electrolyte dissolved in the above mixed or single solvent may be any electrolyte capable of producing lithium ions. Such an electrolyte may be, for example, Lit LiC10.
, , LiAsFa, LiBFi, or LiHF.

The above electrolyte and solvent are mixed in a sufficiently dehydrated state to form an electrolytic solution.
The concentration of IT solute is preferably at least 0.1 mol/1 or more in order to reduce the internal resistance due to the electrolyte.
It is usually more preferable to set it as 0.2-1.5 mol/1.

As the positive electrode of the organic electrolyte battery of the present invention, for example, conductive polymers, metal oxides, metal sulfides, activated carbon, etc. which can be electrochemically doped and undoped, which will be described later, can be used.

Conductive polymers that can be electrochemically doped and undoped include polyacetylene, polythiophene,
Examples include polyacene organic semiconductors, which are heat-treated products of polyaniline and aromatic condensation polymers. When used as an electrode material, stability and bottom shape are extremely important from a practical standpoint, and from this viewpoint, polymers of polyacene-based organic semiconductors and anilines are preferred.

Metal oxides that can be preferably used as the positive electrode include vanadium, chromium, and manganese, which can reversibly introduce and remove lithium ions by intercalating or deintercalating silane (referred to as doping or and-doping in the present invention). , molybdenum, and bismuth.

For example, VzOs, Van's, CrxO@,
Mn01. One or more types of MoO3°CuzVxOq are used. The fill structure of these transition metal oxides may be in a crystalline state or may be made into an amorphous state by heat treatment or the like.

Gold can be preferably used as a positive electrode! Examples of sulfides include Ti5t, Mo5t, and Mo5s. The structure of these gold r/1kfi compounds may be in a crystalline state or an amorphous state.

Among the positive electrodes mentioned above, the most preferred is a polyacene organic semiconductor (Japanese Patent Application Laid-open No. 170163/1983). This semiconductor has particularly excellent stability, and the use of this semiconductor as a positive electrode is 4.0 It is also possible to create a high-voltage battery having a voltage of

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

Next, an example of an embodiment of the present invention will be explained with reference to the drawings. 1st
The figure pertains to the invention! This is a basic configuration diagram of a pond. In FIG. 1, (1) is the positive electrode, and (2> is the negative electrode).
(3) and (3') are current collectors, which are connected to each electrode and external terminals (7) and (7') so as not to cause a voltage drop. (4) is an electrolytic solution in which the aforementioned compound capable of generating ions to be doped is dissolved in an aprotic organic solvent. ! Thawing is usually done in liquid form, but it can also be used in gel or solid form to prevent leakage. (5) is a separator placed for the purpose of preventing contact between the positive and negative electrodes and retaining the electrolyte.

The separator is a porous body with no electronic conductivity and has continuous pores that are durable against the electrolytic solution or the t-electrode active material, such as a doping agent or an alkali metal. Generally, cloth, nonwoven fabric, or porous material made of glass fiber, polyethylene, polypropylene, etc. 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 consideration the amount of electrolyte retained, flowability, strength, etc. The positive and negative electrodes and the separator are fixed in the battery case (6) so as not to cause any practical problems.

The shape, size, etc. of pole 1 can be appropriately determined depending on the shape and performance of the intended battery.

(Effects of the Invention) The AT electrolyte battery of the present invention is characterized by the fact that when the insoluble and infusible substrate containing a polyacene skeleton structure is shaped into a bottom using a thermoplastic resin binder, or after the bottom is formed, the melting point of the thermoplastic resin is By using the above-heat-treated molded rod on which lithium is supported as the negative electrode, the secondary battery has excellent rapid discharge characteristics and long-term cycle characteristics.

The present invention will be specifically explained below using Examples.

Example (1) Method for producing PAS 1 Novolak type phenolic resin silicone was placed in an electric furnace and heated at 650°C (PASI-1) and 800°C (
PAS powder was obtained by heat treatment at a temperature increase rate of 10° C./hour to PASI-2) and pulverization with a disk mill.

(2) PAS manufacturing method 2 An aqueous solution of a water-soluble resol (approximately 60% concentration), zinc chloride, and water mixed in a weight ratio of 10:25:4 is applied onto a glass plate using a film applicator. filmed zero-order r
Ii. A glass plate was placed over the filmed aqueous solution to prevent moisture from evaporating, and then heated at a temperature of about 100° C. for 1 hour to cure it.

The phenol resin film was placed in a siliconite electric furnace and heated to 550°C under a nitrogen stream at a rate of 1007 hours.
(PAS2-1>, heat treatment was performed to 750'C (PAS2-2).

Next, the nuclear heat treated product was washed with dilute hydrochloric acid, then water, and then dried to obtain a PAS film with a high specific surface area.

PAS powder was obtained by pulverizing this PAS film with a disk mill.

(PAS manufacturing method 3...positive electrode) A film is formed on a glass plate using a film applicator with an aqueous solution containing water-soluble resol (approximately 60% concentration), zinc chloride, and water mixed in a weight ratio of IO:25:4. The first aqueous solution was covered with glass to prevent moisture from evaporating, and then heated at a salinity of about 100° C. for 1 hour to harden 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 produce a soo
The heat-treated product was washed with dilute hydrochloric acid, water, and then dried to obtain an insoluble and infusible substrate.

Powder 100 obtained by pulverizing the insoluble and infusible substrate with a disk mill
After thoroughly kneading 15 parts of acetylene black and 10 parts of tetrafluoroethylene powder, a film of about 500 μm was formed using a roller.

(PAS3) (Negative electrode manufacturing method 1) PAS 1-1. PASL-2 each powder 1
00 parts, 20 parts (per weight) of polypropylene powder were mixed, pressure molded at a pressure of 200 kg/cm'', heat treated at 250°C for 2 hours in a nitrogen atmosphere,
A PAS precipitate of 0μ was obtained. An electrochemical cell was assembled using the molded body as a working electrode, lithium metal as a counter electrode and a reference electrode, and a 1 mol/1 solution of LiCI Oa dissolved in sufficiently dehydrated brobylene carbonate as an electrolyte. By applying a voltage of 0.2 V to lithium for 12 hours, lithium was supported on the insoluble and infusible substrate.

The amount of lithium supported is expressed as a percentage of the number of lithium to one carbon atom of PAS, and 35% and 31% of lithium were supported on the PASI-1 and PASI-2 base bodies (respectively). l, basis 2).

(Negative electrode manufacturing method 2) PAS2-1. 25 parts (per weight) of polyethylene powder was mixed with 100 parts of each powder of PAS2-2, and after pressure molding at a pressure of 200 kg/cm'', heat treatment was performed at 200°C for 2 hours in a nitrogen atmosphere to form a 500μ PAS of
A molded body was obtained.

A 300μ Li metal foil (approximately 8 lithium-carrying openings) was placed on the molded body.
0%) and 1 mol/l (,1C1
When left in the 0a propylene carbonate solution for 48 hours, the Li metal foil completely disappeared and all Ij was PAS7i! It was possible to carry it in the form.

The PAS2-1 bottom body had a potential of 0.46 V, and the PAS2-2 bottom body had a potential of 0.34 V (VSLi/Li") 0) as a negative electrode (negative electrodes Na3 and Na4, respectively).

(Preparation of battery) A battery was assembled as shown in FIG. 1 by using PAS3 as a positive electrode and combining it with negative electrodes m1 to m4.

A stainless wire mesh was used as the current collector, and felt made of glass fiber was used as the separator. Also, as an electrolyte, 1 mol/j! LiCj! A battery was assembled using a 0° propylene carbonate solution.

(Measurement of cycle characteristics) A voltage of 4.Ov was applied to the above battery from an external power supply for about 1 hour to charge it, and then it was discharged at a current density of 1 mA/cm" to 2.0μ to determine the initial capacity. This charge/discharge cycle was further repeated, and the number of times the capacity reached 80% of the initial capacity was measured.

(Measurement of rapid discharge characteristics) The charging method was the same as the measurement of cycle characteristics.
Discharge at a current density of 1 mA until the current density is 2.0 cm.
/CM! The capacity was compared with that during discharge.

The result is (capacity at 5mA/cm)/(1mA/c
m 1 hour capacity).

Table 1 summarizes the physical properties of PAS, and Table 2 summarizes the test results of the present invention.

No. table Table 2 Comparative example A ] A.S. ~ 2.

A negative electrode was prepared in the same manner as in the example except that the powder of PAS2-2 was not heat-treated (designated as negative electrode Nal' to 4'), and its cycle characteristics and rapid discharge characteristics were examined. The results are shown in Table 3.

Table 3 Comparative Example 2 After mixing and kneading 10 parts (per weight) of polytetrafluoroethylene (PTFE) powder to 10 parts of powder of PAS2-2, roll bottom shape was applied to a film of 500 μm. did.

When lithium was supported by the method in negative electrode manufacturing method 2,
Its potential was 0.41V. A battery was assembled in the same manner as in the example, and cycle characteristics and rapid discharge characteristics were measured.

After 172 cycles, the initial capacity reached 80%, and the ratio during rapid discharge was 0.38.

[Brief explanation of drawings]

FIG. 1 is a basic configuration diagram of a battery according to the present invention, in which (1) is a positive electrode, (2) a negative electrode, (3) and (3') are current collectors, and (
4) is an electrolyte, (5) is a separator, and (6) ! The case (7) and (7') represent external terminals. Figure Procedural Amendment (Spontaneous) April I5, 1991 1, Indication of the case Flat-bottomed 2-year patent application No. 29889 2, Name of the invention Organic electrolyte battery 3, Person making the amendment Relationship to the case Patent applicant address 5-17-4 Sumida, Sumida-ku, Tokyo 534 1-5-90 Tomobuchi-cho, Bejima-ku, Osaka Kanebo Co., Ltd. Patent Department Telephone (06) 921-1251 5. Specification to be amended "Scope of Claims ” and “Detailed Description of the Invention” Column 6, Contents of Amendment (1) The description in the “Claims” column of the specification has been amended as shown in the attached appendix (“Amended Scope of Claims”). first. (2) The description in column ``Detailed Description of the Invention j'' of the specification will be amended as follows. The text ``Substrate j'' has been corrected to ``Insoluble and infusible substrate j containing a polyacene skeleton structure.'' ■ On page 4, line 18 of the same page, ``The negative electrode active material is lithium and 1 has been deleted. 7. List of attached documents (1) Attachment (“Amended Claims”) One or more attachments (“Amended Claims 1fflj)” (1) The positive electrode, the negative electrode, and the lithium salt are aprotic. In an organic electrolytic 1Xt cell equipped with an electrolytic solution containing a solution dissolved in an organic solvent, a heat-treated product of an aromatic condensation polymer consisting of carbon, hydrogen and oxygen is used as a negative electrode, the aromatic condensation polymer is (a) (b) A condensate of an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde, (b) an aromatic hydrocarbon compound having a phenolic hydroxyl group, a condensate of an aromatic hydrocarbon compound having no phenolic water M group, and an aldehyde; (c) selected from furan resins, and the atomic ratio of hydrogen atoms/carbon atoms of the heat-treated product is 0.50 to 0.
．． When molding an insoluble and infusible substrate containing a polyacene skeleton structure of 05 using a thermoplastic resin binder,
Or add 3% lithium in mole percentage to an insoluble and infusible base molded body that has been heat-treated above the melting point of the thermoplastic resin after the bottom shape.
An organic electrolyte battery characterized by using the above supported material.

Claims (1)

[Claims] (1) In an organic electrolyte battery equipped with a positive electrode, a negative electrode, and an electrolytic solution containing a solution of a lithium salt dissolved in an aprotic organic solvent, the negative electrode active material is lithium, and the negative electrode is an aromatic compound consisting of carbon, hydrogen, and oxygen. A heat-treated product of an aromatic condensation polymer, the aromatic condensation polymer comprises (a) a condensate of an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde, (b) an aromatic hydrocarbon compound having a phenolic hydroxyl group, Aromatic hydrocarbon compounds having no phenolic hydroxyl groups and condensates of aldehydes and (c
) A thermoplastic resin binder is used to prepare an insoluble and infusible substrate containing a polyacene skeleton structure selected from furan resins and having an atomic ratio of hydrogen atoms/carbon atoms of the heat-treated product of 0.50 to 0.05. An organic electrolyte battery characterized by using an insoluble and infusible base molded body which is heat-treated at a temperature higher than the melting point of the thermoplastic resin during molding or after molding and supports lithium in a molar percentage of 3% or more.