JPS6180773A - Organic electrolyte cell - Google Patents

Abstract

PURPOSE:To make compactness, thinness and lightness possible and besides to obtain a secondary cell with large capacity, high output and long life, by using an insoluble and infusible substrate with polyacene system skeleton structure having excellent strength as an electrode. CONSTITUTION:A formed body composed of phenol fiber treated by heating at 150 deg.C or higher or heat-treated substance of fiber structure and an insoluble and infusible substrate with polyacene system skeleton structure, which is obtained by heat-treating a compound body formed from phenol resin and zinc chloride in nonoxidizing atmosphere and has 0.05-0.5 of atomic ratio of hydrogen atom to carbon atom and besides 600m<2>/g or greater of specific surface area value, is used as a positive electrode 1 and/or a negative electrode 21. As electrolytic liquid 4, aprotic organic solvent solution of compound producible of ion capable of doping into the electrode by electrolysis is used. After a cell has been mounted, doping agent is doped with voltage impressed from an external power supply.

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field of the Invention) The present invention relates to an organic electrolyte battery in which an electrode active material is an electrically conductive organic polymer material doped with an electron-donating substance or an electron-accepting substance.

(Technical Background and Problems of the Invention) In recent years, electronic devices have become smaller, thinner, and lighter, and as a result, batteries that serve as power sources have become smaller.

There is a strong demand for thinner and lighter products. Currently, silver oxide batteries are widely used as small, high-performance batteries, and lithium batteries have been developed and put into practical use as thin dry batteries and small, lightweight, high-performance batteries. However, since these batteries are primary batteries, they cannot be used for long periods of time by being repeatedly charged and discharged.

On the other hand, nickel and cadmium batteries have been put into practical use as high-performance secondary batteries, but 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 many 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 G batteries as batteries for electric vehicles.
It was not put into 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. In order to meet these needs, batteries that use desert polyacetylene, which is an organic semiconductor, doped with an electron-donating substance or an electron-accepting substance as an electrode active material have recently been researched and proposed. There is. This battery has high performance as a secondary battery and has the potential to be made thinner and lighter, but there is a big runner-up. The reason is that polyacetylene, which is an organic semiconductor, is an extremely unstable substance that is easily oxidized by reeds and oxygen in the air, and is also deteriorated by heat. Therefore, the battery must be manufactured in an inert gas atmosphere, and there are also restrictions in manufacturing the polyacetylene into a shape suitable for the electrode.

In addition, the present inventors have already proposed a secondary battery using an insoluble and infusible substrate containing a polyacene skeleton structure, which is a type of organic semiconductor, doped with an electron-donating substance or an electron-accepting substance as an electrode active material. and patent application 1984-24165
issue). This battery has high performance, has the potential to be made thinner and lighter, has a high oxidation stability of the electrode active material, and is easy to mold, making it a promising secondary battery. .

However, a molded body of an insoluble and infusible substrate containing a polyacene skeleton structure, which is an active material, has a weak mechanical strength to be used as an electrode, and in this respect, it is still insufficient for practical use.

(Purpose of the Invention) In view of the above-mentioned problems of existing batteries, the present inventors have completed the present invention as a result of intensive research. An object of the present invention is to provide a high-performance organic electrolyte battery using an insoluble and infusible substrate having an excellent polyacene skeleton structure. Another object of the present invention is to provide an insoluble and infusible substrate having a polyacene skeleton that can be formed into any shape such as a film or a plate and has excellent mechanical strength. Further objects and advantages will become apparent from the description below.

(Disclosure of the Invention) The above-mentioned object is to heat-treated a phenolic fiber or a fiber structure heat-treated at a temperature of 150°C or higher, and a composite molded article formed from a phenolic resin and zinc chloride in a non-oxidizing atmosphere. having a polyacene-based skeletal structure in which the atomic ratio of hydrogen atoms/carbon atoms obtained by heat treatment in Achieved by an organic electrolyte battery in which a molded body made of an insoluble and infusible substrate is used as a positive electrode and/or a negative electrode, and an aprotic organic solvent solution of a compound capable of producing ions that can be doped into the electrode depending on W% is used as an electrolyte. be done.

The composite molded article in the present invention is made of 150% phenol fiber.
It is a molded article in any shape such as a 7-lumen shape or a plate shape, which is made of a fibrous heat-treated product obtained by heat treatment at a temperature of .degree. C. or higher, a phenol resin, and zinc chloride. The phenol resin is preferably an uncured condensate of an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde.
Specific examples of aromatic compounds include phenols such as phenol, cresol, and xylenol, and in addition to these, methylene bisphenols, hydroxybiphenyls, and hydroxynaphthalenes are also applicable. Among these compounds, phenols, particularly 7-enol, are preferred from a practical standpoint. Further, as the aldehyde used in the present invention, acetaldehyde and other aldehydes can also be used, but formaldehyde is particularly preferred.

Phenol fibers include, for example, fibers obtained by melt-spinning a novolac type phenol resin and crosslinking it with a curing agent such as formaldehyde under an acid or basic catalyst. Phenol fiber structures include structures made of the above-mentioned phenol fibers, such as Examples include knitted fabrics and nonwoven fabrics.

The heat-treated fiber or fiber structure is a phenolic fiber or fiber structure heated at a temperature of 150°C or higher for 10 minutes to 1 hour.
This can be obtained by heat treatment for 0 hours, and this heat treatment may be performed under either a non-oxidizing atmosphere or an oxidizing atmosphere, but it is preferably performed under a non-oxidizing atmosphere. When the heat treatment temperature is less than 160"C, the heat-treated fiber or fibrous structure (hereinafter abbreviated as fibrous heat-treated product), a composite molded product made of phenol resin and zinc chloride is heat-treated in a non-oxidizing atmosphere to form polyacene. When attempting to obtain a 6-molded body made from a 6-insoluble and infusible substrate having a system skeleton structure, the rate of cracks occurring in the molded body tends to increase.And composite molding made of these materials The body can be obtained, for example, by mixing and molding a fibrous heat-treated material, an uncured phenol resin, and zinc chloride under appropriate conditions, and then curing the mixture.

As a mixing method, any method such as dry mixing or wet mixing may be used as long as the above 8 components can be mixed uniformly.
In order to mix sufficiently and uniformly, it is preferable to make the uncured phenol resin and zinc chloride into a solution by adding a suitable solvent such as water, methanol, acetone, etc., then add and mix the fibrous heat-treated material. If the heat-treated fibrous material is a knitted fabric or felt, a prepreg may be prepared by impregnating it with the above-described solution of uncured phenol resin and zinc chloride. The molding method can be the same as that used for making resin molded products in general, but for example, if a film shape is desired, the above-mentioned 8-component mixed slurry may be formed into a film with an appropriate thickness using an applicator. In order to obtain a plate-shaped body, a wall frame may be made and pressure molded as is generally well known. If the prepreg described above is placed between flat plates of metal or the like and press-formed, a plate of an appropriate thickness can be obtained. As for the curing method, when resol is used as the uncured phenol resin, it is convenient to heat-cure at a temperature of 50 to 20[alpha]C during or after molding. In particular, in a method of press molding using a wall frame or the like, it is possible to heat and harden at the same time as molding. When novolac is used as the uncured phenolic resin, a suitable curing agent, such as hexamethylenetetrami, which itself is a formaldehyde generator and an organic base generator, is mixed in advance. ◇ The composite molded product obtained in this way is composed of a fibrous heat-treated product, a phenol resin, and zinc chloride9, and has an arbitrary shape such as a film shape or a plate shape. It is a molded product with very excellent mechanical strength), and can be processed into shapes such as squares, circles, and rectangles cut into appropriate sizes. This composite molded body is made into an insoluble and infusible substrate having a polyacene skeleton structure by a method described later, and the mechanical strength of this base body is exerted by the fibrous heat-treated material in the composite molded body. In other words, by using the fibrous heat-treated material, the strength of the insoluble and infusible substrate used as the electrode material of the battery is greatly improved.0 The effect can be recognized even with a very small amount of the fibrous heat-treated material in the composite molded product. The weight ratio of fibrous heat-treated product/phenol resin is preferably 0.05 or more, but if it is less than 00.05, the strength of the obtained insoluble and infusible substrate containing a polyacene skeleton structure will be insufficiently increased. Zinc chloride also has a specific surface area value (BET method) of the substrate when these composite molded bodies are made into an insoluble and infusible substrate by the method shown later.
Zinc chloride/(phenol resin ten fibrous heat-treated product)
The weight ratio of is 0.5 to 7. If it is less than 0.5, the effect of zinc chloride addition is poor and it does not contribute much to increasing the specific surface area of the insoluble and infusible substrate. When these substrates are used as battery electrodes, doping or undoping of ions in the electrolyte becomes difficult.

If the amount of zinc chloride exceeds 7, the absolute amount of the phenol resin will decrease, making it difficult to form a film or plate, and hardening or reaction of the uncured phenol resin will become difficult.

Next, these composite molded bodies are heat-treated in a non-oxidizing atmosphere to form an insoluble polyacene skeleton structure with a hydrogen atom/carbon atom atomic ratio of 0.05 to 0.5, preferably 0.1 to 0.86. To produce an infusible substrate, the heat treatment temperature is usually 4
00 to 800'C. Preferred heating conditions for heat treatment vary somewhat depending on the composition ratio, curing conditions, or shape of the composite molded product, but in general, a relatively large temperature increase is required from room temperature to about 800°C. For example, when the temperature reaches 0800°C or higher, which can be set at a rate of 100°C/hour, thermal decomposition of the phenolic resin and the fibrous heat-treated material starts, and water vapor, It is advantageous to raise the temperature at a sufficiently slow rate since gases such as hydrogen, methane, and carbon oxides begin to evolve.

The substrate having a polyacene skeleton structure thus obtained is washed with hot water at 50 to 100°C to remove zinc chloride remaining in the substrate, and dried. The atomic ratio of hydrogen atoms/carbon atoms of the substrate is 0.05 to 0.5. If the atomic ratio exceeds 0.5, the charge efficiency of charging and discharging will be poor when the substrate is used as an electrode for a secondary battery by the method shown later; If it is less than 1, the charge efficiency of charging and discharging decreases.

Further, the specific surface area value of the insoluble and infusible substrate containing a polyacene skeleton structure by the BET method is 600 m/f or more.

If it is less than 600 d19, it will be necessary to increase the charging voltage, for example, when charging a secondary battery using the substrate as an electrode, resulting in a decrease in energy efficiency, etc., and also likely to cause deterioration of the electrolytic solution.

Furthermore, the molded product made of the insoluble and infusible substrate can have any shape such as film, plate, or cylinder shape, but in the present invention, since a fibrous heat-treated product is used, the mechanical strength is It has excellent strength and has sufficient strength for practical use as an electrode for secondary batteries.

In particular, when a heat-treated fibrous material in the form of a knitted fabric or felt is used, not only can the thickness, size, density, etc. of the molded product made of the substrate be set arbitrarily, but also its strength is particularly excellent. Further, the insoluble and infusible substrate having a polyacene skeleton structure has a specific surface area value of 600. m
Because it has a large value of # or more, oxygen gas etc. can enter,
Although it is thought that it is easy to reduce the amount of carbon dioxide, 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 has excellent oxidation stability.

The battery of the present invention has an atomic ratio of hydrogen atoms/carbon atoms of 0.05.
~0.6 Preferably 0.1~0.85, and the specific surface area value by BET method is 600! A molded body made of an insoluble and infusible substrate containing a polyacene skeleton structure of rI/f or more is used as a positive electrode and/or a negative electrode, and a compound that can generate ions that can be doped into the stain electrode by electrolysis is used as an aprotic organic solvent. It is manufactured by forming an electrolytic solution by dissolving it into an electrolyte.

Compounds that can be used in the electrolytic solution and can generate ions that can be doped into the electrode include alkali metal or tetraalkylammonium oxides, perchlorates, 6
Examples include heptafluoride phosphate, hexafluoride arsenate, 4-7fluoride boromate, etc. Specifically, r, ix, NE [4I, L
iclo4, LiASF6, I, 1BF4, KPF@,
NaPF6. (n 04Hg)4NO604, (n
04H9) NAIIF6, (n-04Kg>NPF5,
Examples include (n-CaHy)4NOIO4 and LtEIF2.

As the solvent for dissolving the compound, an aprotic organic solvent is used, such as ethylene carbonate, propylene carbonate, r-butyrolactone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, dimethoxyethane, tetrahydro7rane, methylene chloride, or any of these. However, it is important to select the compound in consideration of the solubility, battery performance, etc. of the compound used as the electrolyte.

The concentration of the compound in the electrolytic solution is preferably at least 0.1%/1 or more in order to reduce the internal resistance caused by the electrolytic solution, and usually 0.2 to 1.5 mol/i gives preferable results. can get.

The battery of the present invention uses a molded body made of an insoluble and infusible substrate containing a polyacene skeleton structure as fl or/and a negative electrode, and uses a doping agent dissolved in an aprotic organic solvent as an electrolyte. O cell operation utilizes electrochemical doping and electrochemical and-doping of a doping agent to an insoluble and infusible substrate used as an electrode. That is, energy is stored or released to the outside by electrochemical doping of a doping agent into an insoluble and infusible substrate, and is taken out as stain energy by electrochemical doping, or Internally (stored.

Batteries according to the invention are divided into two types.

The first type is a battery that uses a molded body made of an insoluble and infusible substrate containing a polyacene skeleton structure for both the positive and negative electrodes, and the second type is a battery that uses a molded body made of an insoluble and infusible base for the positive electrode. There is a battery "'C" which uses a negative electrode made of a fluorine metal or its alloy.Specific examples of such metals include "Tsushima! Examples include rubidium, potassium, sodium, lithium, etc. Among these, -
IJ-thium is most preferred.

The shape and size of the electrode, which is a molded body of an insoluble and infusible substrate placed inside the battery, can be arbitrarily selected depending on the intended battery, but the battery reaction is based on the electrochemical reaction on the electrode surface. Therefore, it is advantageous for the electrode to have as large a surface area as possible.

The base body or a molded body doped with a doping agent may be used as a current collector for extracting current to the outside of the battery. Conductive materials such as carbon, platinum, nickel, stainless steel, etc. can also be used.

Next, one example of an embodiment 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. First, the first type of battery according to the present invention, that is, a molded material made of an insoluble and infusible substrate containing a polyacene skeleton structure in both the positive and negative electrodes. A battery that uses the body will be explained. (
1) is a positive electrode, which is a molded body of an insoluble and infusible substrate containing a polyacene skeleton structure in the form of a film or plate;
It may be doped with a doping agent or may be undoped.

(2) is a negative electrode, which is a molded body of an insoluble and infusible substrate containing a polyacene skeleton structure in the form of a film or a plate, and may be doped with a doping agent or not. After assembling the battery, a voltage is applied from an external power source to dope the battery with a doping agent. For example, when both electrodes are formed from undoped insoluble and infusible substrates, the electromotive force of the battery after battery assembly is Ov, and stain pressure is applied from an external power source to dope the doping agent to both electrodes. In particular, the battery will have an electromotive force. (
3) is a current collector for supplying current to charge the electrochemical doping agent, which takes out current from each electrode to the outside; 6) is a current collector for supplying current to charge the electrochemical doping agent; ) is connected so that no voltage drop occurs. (
4) is an electrolytic solution in which the above-mentioned compound capable of producing ions capable of being doped into both positive and negative electrodes 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.

(5) is nine separators arranged for the purpose of preventing contact between the positive and negative electrodes and retaining the electrolyte. This separator is preferably a non-electrically conductive porous body with continuous pores that is resistant to electrolytic solutions, 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. It is preferable for the separator to be thin in order to reduce the internal resistance of the battery.
It is determined by taking into consideration the amount of electrolyte retained, flowability, strength, etc. Both 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 the electrode can be appropriately determined depending on the shape and performance of the intended battery. For example, film-shaped electrodes are suitable for producing thin batteries, while large-capacity batteries can be achieved by laminating many film- or plate-shaped electrodes alternately with positive and negative electrodes. Next, using FIG. 1, we will discuss the second type of battery according to the present invention, that is, the case where the positive electrode uses an insoluble and infusible substrate medium molded body having a polyacene skeleton structure, and the negative electrode uses an alkali metal or its alloy. explain.

(1) is a positive electrode, which is a molded body of an insoluble and infusible substrate; (2) is a negative electrode, which is an alkali metal or an alloy thereof. Others (3)
-(7) are the same as in the case of the first type.

In this type, ie the second type, the doping mechanism, ie the operating mechanism of the cell, is further divided into two mechanisms.

In the first mechanism, the insoluble and infusible substrate is doped with an electron-accepting doping agent, which corresponds to charging, and the insoluble and infusible substrate is doped, which corresponds to discharging. For example, when a 1 mol/l propylene carbonate solution of LiCIO4 is used as an electrode by electrostatically dissolving a molded body of an undoped insoluble infusible substrate and lithium, the electromotive voltage after battery assembly is 2.5 to 3. It is Ov. Next, when the insoluble and infusible substrate is doped with OIO ions by applying a stain pressure from an external power source, the electromotive voltage becomes 8.5 to 4.6 V. Second.

In the mechanism, doping an insoluble and infusible substrate with an electron-donating doping agent corresponds to discharging, and undoping corresponds to charging. For example, in the battery configuration described above, the electromotive voltage after battery assembly is 2.6 to 8. When lithium ions are doped into the cine-meltable infusible substrate by emitting a current to the outside using OV, the electromotive force is 1.0 to 2.
5V, but when voltage is applied from an external power source and the lithium ion is and-pumped, the electromotive voltage becomes 2.5~a again.
, OV.

Doping or undoping may be carried out either under constant current or under constant voltage or under conditions of varying LtIL and voltage, but the amount of doping agent doped into the insoluble and infusible substrate depends on the substrate. 0.5 to 20% of the number of doped ions per carbon atom
is preferred.

(Effects of the Invention) A battery using the molded body of the insoluble and infusible substrate of the present invention as an electrode is a secondary battery that can be repeatedly charged and discharged.
9. The electromotive voltage varies depending on the configuration of the battery, but for the first type it is 1.0-B, 5V.

8.5 to 4 when using the first mechanism in the second type
．． 5v, and when using the second mechanism in the second type, 2.6 to 8. It is OV. In addition, the battery of the present invention has a particularly high energy density per weight, and if an appropriate amount of doping is carried out, it has a value of 100 to 850 energy density. In addition, although there are differences in power density depending on the structure of the battery, it has a much greater power density than a lead-acid battery. Furthermore, the molded article made of the insoluble and infusible substrate according to the present invention is easy to manufacture, has excellent mechanical strength, does not cause damage to the electrode, and is an extremely stable material. The battery can be charged and discharged repeatedly, and the battery performance does not deteriorate over a long period of time. A molded body made of an insoluble and infusible substrate containing a nine-polyacene skeleton structure with excellent properties and mechanical strength is used as an electrode, and this electrode is doped with an electron-donating or electron-accepting substance as an electrode active material. In addition, the battery uses an electrolyte prepared by dissolving a compound that generates ions that can be doped into the electrode in an aprotic organic solvent, and can be made smaller, thinner, and lighter, and has a high capacity. , a new high-performance secondary battery with high output and long life.

The present invention will be specifically explained below using Examples.

Example 1 A phenol fiber plain weave cloth (manufactured by Nippon Kynor Co., Ltd.) was heat treated in an electric furnace at a temperature of 800° C. in a nitrogen atmosphere for 4 hours to obtain a fibrous heat treated product. This fibrous heat-treated product is impregnated with a solution of resol-type phenol resin (aqueous solution with a concentration of about 65%), water, and chloride 9 mixed in a weight ratio of 1015/26. The cloth was molded and cured under pressure for about 10 minutes using a pressure molding machine for laminates heated to 100° C. to obtain a plate-shaped composite molded product having a thickness of 500 μm. In this composite molded product, the weight ratio of fibrous heat-treated product/phenolic resin was 0.11. Also, the weight ratio of zinc chloride/(phenol resin raw fibrous heat-treated product) was 8.6. After forming a film with the above resol, water and zinc chloride mixed solution using an applicator,
A curing reaction was carried out for about 2° at a temperature of 50°C to obtain a plate-shaped molded product with a thickness of 500 μm. In this plate-shaped molded product, the weight ratio of fibrous heat-treated product/phenol resin is 0, and the weight ratio of zinc chloride/(fibrous heat-treated product + phenol fiber) is 4.
It was 0.

Next, these composite molded bodies were placed in a silicone electric furnace.
The temperature was raised to 560°C in a N2 atmosphere at a speed of about 40°C/h, heat treated, and then heated to 560°C for about 60°C.
A plate-like body made of an insoluble and infusible substrate was obtained by washing for a period of time to remove residual zinc chloride, and then drying under reduced pressure.

Among these plate-shaped insoluble and infusible substrates, the plate-shaped substrates obtained from the composite molded articles using the above-mentioned fibrous heat-treated material of the present invention have excellent mechanical strength and are easy to handle. However, the plate-like substrate obtained from the composite molded body made without using the fibrous heat-treated material had low strength and required careful handling. It is shown in Table 1.

Next, when the insoluble and infusible substrate of the present invention obtained from the composite molded article was subjected to fluorescent X-ray analysis, it was found that zn was 0.01% by weight.
(For the substrate) It was found that the ci was below 0.5% by weight and that almost no zinc chloride remained in the substrate. Also, when this substrate was subjected to X-ray diffraction, it was found that 20
There is a main beak at ~22°, and also at 41-46°.
A small peak was observed in the range of , confirming that the substrate has a polyacene skeleton structure.

Next, elemental analysis and B
The results of measuring specific surface area values by the ET method are also shown in Table 1 as comparative examples.

Next, add LiA8 to sufficiently dehydrated propylene carbonate.
A battery was assembled as shown in FIG. 1 by dissolving F6 into a solution of about 1.0 mol/l, using lithium metal as a negative electrode, and using a plate of an insoluble and infusible substrate as a positive electrode. A platinum mesh gourd was used as the current collector, and felt made of glass fiber was used as the separator. This example is a battery that utilizes the second type of first mechanism of the present invention. In other words, doping an insoluble and infusible substrate with AlF6 ions, which are atom-accepting doping agents, corresponds to charging, and
Ping corresponds to discharge. Furthermore, the amount of doping is expressed by the number of ions doped per carbon atom in the substrate, but in the present invention, the number of ions doped is determined from the value of the IE current flowing through the circuit during doping. It is something.

The voltage immediately after the battery with the above configuration is assembled is the first voltage.
Shown in the table. Next, an external stain pressure is applied to the battery, and a constant current is applied so that the doping amount per hour is 1%.
9. Doping Fj ions into the insoluble and infusible substrate for 8.5 hours. Table 1 shows the open circuit voltage at the end of doping. For another 1 hour, a constant current was applied to the circuit so that the amount of and-ping was 1% for each time, and and-ping of A5F and ions was continued until the open circuit voltage reached the voltage immediately after battery assembly. Table 1 shows the amount of undoing and the amount of doping in this test as charge efficiency.

However, in Table 1, the product of the present invention refers to an insoluble and infusible substrate obtained from a composite molded article made using the heat-treated N&fibrous material, or a battery using the same.

In addition, the comparative product represents an insoluble and infusible substrate prepared in the same manner as in the present invention, except that a fibrous heat-treated product was used, or nine batteries using the same.

As is clear from Table 1, the insoluble and infusible substrate using 7-enol fiber has very good mechanical strength, and it is also easy to assemble the secondary battery made using it. It also shows that it has excellent charge and discharge characteristics of the secondary battery that was its ancestor.

Table 1 Example 2 Phenol fiber felt (manufactured by Nippon Kynor Co., Ltd.) was heat-treated in an electric furnace in a nitrogen atmosphere at a temperature of LOOO'C for 6 hours to obtain a fibrous heat-treated product.

Also, in the same manner as above, the heat treatment temperature was set to 200"c1600".
The temperature was changed to 0,700°C to obtain a fibrous heat-treated product.Furthermore, the above felt was heated in a hot air dryer in an oxidizing atmosphere for 2 hours.
Heat treated at a temperature of 0.00°C for 1 hour and impregnated with a solution of water and subtense chloride in a weight ratio of 10/8/20. The mixture was heated to 100° C. and molded and cured under pressure using a nine-pressure molding machine for about 10 minutes to produce a plate-shaped composite molded product. In these composite molded bodies, the weight ratio of fibrous heat-treated product/phenolic resin was about 0.4, and the weight ratio of zinc chloride/(fibrous heat-treated product + 7 enol resin) was about 2.0. Next, heat treatment, washing, and drying were performed under the same conditions as in Example 1 to obtain a plate-like body of an insoluble and infusible substrate.

An insoluble and infusible substrate prepared using a fibrous heat-treated material heat-treated at a temperature of 100° C. in an atmosphere developed cracks during heat treatment, but no cracks occurred in the other samples. Next, these samples were subjected to elemental analysis and BET
The specific surface area and bending strength were measured using the method. The results are shown in Table 2.

Furthermore, a battery was assembled in the same manner as in Example 1 using the plate-shaped body of the insoluble and infusible substrate, and a charge/discharge test was conducted. As a reminder, in this example, LiCIO4 was used as a substitute for LiAsr. The results are summarized in Table 2.

Table 2: Water U Chloride - Into a solution mixed at a weight ratio of 10/1150, cut 7 eyewear (cut length about 2 cod) of phenol fiber (fiber diameter, about 15 μm) was added to a solution of 800 mm in a nitrogen atmosphere.
After adding the fa fibrous heat-treated material obtained by heat treatment at °C for 4 hours and mixing thoroughly, the mixed slurry was molded for about 10 minutes under pressure using a pressure molding machine heated to about 100 °C. After curing, a film-like composite molded product having a thickness of about 100 μm was obtained. Fibrous heat-treated product in this film-like composite molded product/
The IT ratio of the phenolic resin is 0.05, and the weight ratio of zinc chloride/(phenol resin + fibrous heat treated product) is 0.05.
It was 7. Next, this film-like composite molded body was heat-treated to a predetermined temperature in a silicone electric furnace, and then Example 1
In the same manner as above, the substrates were washed with hot water and dried to obtain film-like insoluble and infusible substrates having different hydrogen/carbon atomic ratios. Elemental analysis, specific surface area value and bending strength measurement by BET method were performed on this substrate. The results are summarized in Table 8. Next, a battery was assembled using the same method as in Saneo's side 1, and the charging and discharging characteristics were examined.

However, in this example, LiBF4 is substituted for LiASFgO.
It was used. The results are summarized in Table 8.

Table 8 In all cases, the mechanical strength of the insoluble and infusible substrate used as the electrode is excellent, making it easy to assemble the battery and preventing electrode damage during charging and discharging. A stable and high-performance secondary battery was obtained.

Example 4 This example relates to the first type of battery according to the present invention, that is, a secondary battery using molded bodies of insoluble and infusible substrates for the positive and negative electrodes.

The positive and negative electrodes used in Example 1 were the NO, 1 insoluble and infusible substrate plates, and the electrolyte was a 1-w/I solution in which Li CIO< was dissolved in Probile/carbonate. A battery was constructed and a charge/discharge test was conducted. The open circuit voltage immediately after the battery was assembled was Ov. Next, a voltage was applied from an external power supply to charge the battery by doping the positive electrode with CIO< ions and the negative electrode with li+ ions.

The charging speed was such that the doping amount per hour was 1%, and the charging was carried out for about 2 hours. At this time, the open circuit voltage was 1.7 V, and discharge was performed by performing and-ping of ago: ions and Li + ions at almost the same speed as during zero-order charging. After 1.5 hours, the open circuit voltage was 0 volts.

[Brief explanation of the drawing]

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

Claims (9)

[Claims] (1) A composite molded article formed from a heat-treated phenol fiber or fiber structure heat-treated at a temperature of 150°C or higher and a phenol resin and zinc chloride in a non-oxidizing atmosphere. A molded article made of an insoluble and infusible substrate having a polyacene skeleton structure with a hydrogen atom/carbon atom atomic ratio of 0.05 to 0.5 and a specific surface area value of 600 m^2/g or more by the BET method. An organic electrolyte battery comprising a positive electrode and/or a negative electrode, and an aprotic organic solvent solution of a compound capable of producing ions that can be doped into the electrode by electrolysis as an electrolyte. (2) The weight ratio of the composite molded body to the phenolic resin is 0.
．． The organic electrolyte battery according to claim (1), which contains a phenol fiber or fiber structure of 0.05 or more. (3) Claims (1) or (2), wherein the composite fiber molded article contains 0.5 to 7 zinc chloride based on the total weight of the phenolic resin and the phenol fiber or fiber structure. The organic electrolyte battery described in . (4) The organic electrolyte battery according to any one of claims (1) to (3), wherein the phenol fiber structure is in the form of a knitted fabric or felt. (5) Any one of claims (1) to (4), wherein the heat-treated composite molded product has an atomic ratio of hydrogen atoms/carbon atoms of 0.10 to 0.35. The organic electrolyte battery described. (6) The organic material according to any one of claims (1) to (5), wherein the positive electrode is an insoluble and infusible substrate having a polyacene skeleton structure, and the negative electrode is an alkali metal or an alloy of alkali metals. electrolyte battery. (7) The organic electrolyte battery according to claim (6), wherein the alkali metal is lithium. (8) Claims (1) to (1) in which the positive electrode and the negative electrode are insoluble and infusible substrates having a polyacene skeleton structure.
The organic electrolyte battery according to any of item 5). (9) A compound capable of generating dopable ions,
LiClO_4, LiAsF_6, LiBF_4, (n
-C_4H_9)_4NClO_4, (n-C_3H_
7) The organic electrolyte battery according to any one of claims (1) to (8), which is _4NClO_4 or LiHF_2.