JP2519180B2 - Organic electrolyte battery - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to an organic electrolyte battery in which an electroconductive organic polymer material doped with an electron donating substance or an electron accepting substance is used as an electrode active material.

(Prior Art) In recent years, miniaturization, thinning, or weight reduction of electronic devices has been remarkable, and accordingly, there has been a great demand for miniaturization, thinning, and weight reduction of a battery serving as a power source. Currently, silver oxide batteries are widely used as small-sized and high-performance batteries, and lithium batteries have been developed and put to practical use as thinned dry batteries and small-sized and lightweight high-performance batteries. However, since these batteries are primary batteries, they cannot be used for a long time by repeating charge and discharge. On the other hand, nickel-cadmium batteries have been put into practical use as high-performance secondary batteries, but they are still unsatisfactory in terms of size reduction, thickness reduction, and weight reduction. Further, a lead storage battery has been conventionally used in various fields as a large-capacity secondary battery, but the biggest drawback of this battery is that it is heavy.
This is fatal because lead peroxide and lead are used as electrodes. In recent years, attempts have been made to reduce the weight and improve the performance of batteries for electric vehicles, but they have not been put to practical use. However, there is a strong demand for a large-capacity and lightweight secondary battery as a storage battery.

As described above, each of the batteries currently put into practical use has advantages and disadvantages, and they are used differently depending on the application, but there is a great need for making the battery thinner or lighter. As a battery that meets such needs, a battery using an organic semiconductor thin film polyacetylene doped with an electron-donating substance or an electron-accepting substance as an electrode active material has recently been studied and proposed. Although this battery has high performance as a secondary battery and can be thinned and reduced in weight, it has a major drawback. That is, polyacetylene, which is an organic semiconductor, is an extremely unstable substance, which is easily oxidized by oxygen in the air and is also deteriorated by heat. Therefore, the battery must be manufactured in an inert gas atmosphere, and there is a limitation in manufacturing polyacetylene into a shape suitable for an electrode.

Further, the present inventors have previously used a secondary battery in which an insoluble and infusible substrate containing a polyacene-based skeleton which is a kind of organic semiconductor is doped with an electron donating substance or an electron accepting substance as an electrode active material. (Japanese Patent Laid-Open No. 60-
No. 170163). This battery has high performance, has the potential to be thin and lightweight, and has high oxidation stability of the electrode active material.
Furthermore, it is a promising secondary battery because it can be easily molded.

However, a molded body of an insoluble and infusible substrate containing a polyacene skeleton structure which is an electrode active material has a problem in dimensional stability during heat treatment when used as an electrode, and it is difficult to obtain a material having an accurate dimension, Further, when obtaining a molded product of a large size, there remains a problem that cracks occur during heat treatment.

(Problems to be Solved by the Invention) The present inventors have completed the present invention as a result of continuing diligent research in view of the above-mentioned problems of existing batteries, and the purpose thereof is It is intended to provide a high performance organic electrolyte battery using an insoluble and infusible substrate having a polyacene skeleton structure having a large size and accurate dimensions as an electrode. Another object is to provide a secondary battery which is easy to manufacture, economical, and lightweight. Another object is to provide a high-performance secondary battery having a high electromotive voltage, a high charge-discharge charge efficiency and a high energy density. Another object is to provide an insoluble and infusible substrate having a polyacene skeleton which can be formed into an arbitrary shape such as a film shape or a plate shape and has accurate dimensions. Still other objects and effects will be apparent from the following description.

(Means for Solving Problems) The above-mentioned object is to achieve an atomic ratio of hydrogen atoms / carbon atoms of 0.05 to 0.
6, powder of an insoluble and infusible substance having a polyacene skeleton structure having a specific surface area of 600 m ² / g or more by the BET method (A), a phenolic resin (B) and a zinc chloride (C)
The atomic ratio of hydrogen atoms / carbon atoms obtained by heat-treating the composite molded article formed from and in a non-oxidizing atmosphere is 0.05 to
A compound that is 0.6 and has a specific surface area value by the BET method of 600 m ² / g or more as an insoluble and infusible substrate having a polyacene skeleton structure as a positive electrode and / or a negative electrode, and can generate ions that can be doped in the electrode by electrolysis. This is achieved by an organic electrolyte battery using the aprotic organic solvent solution of as an electrolytic solution.

In the above, the insoluble infusible substance powder of the present invention is BE
The specific surface area value by the T method is 600 m ² / g.
It is a powder of a semiconducting or conductive organic polymer material having a polyacene skeleton structure as shown in No. 49, for example, a heat-treated product of an aromatic condensation polymer shown in JP-A-60-152554. Powder and the like are preferable. Particularly, the aromatic condensation polymer is preferably a heat-treated product of a phenolic resin. Further, the atomic ratio of hydrogen atoms / carbon atoms in the powder of the insoluble and infusible substance needs to be in the range of 0.05 to 0.6. If the atomic ratio is less than 0.05, the doping effect tends to be weakened when an insoluble and infusible substrate used as an electrode is prepared by using the powder. On the other hand, if it exceeds 0.60, cracks are likely to occur during heat treatment of a composite molded body produced using the powder. Further, when the specific surface area value of the powder made of the insoluble and infusible substance by the BET method is less than 600 m ² / g, it becomes difficult to dope the dopant having a relatively large ionic radius.

Further, in the present invention, the phenolic resin is a condensate of an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde. As such an aromatic hydrocarbon compound, so-called phenols such as phenol, cresol and xylenol are preferable, but not limited to these. For example, methylene-bis-phenols represented by the following formula can also be used, and such compounds are also included in the aromatic hydrocarbon compound in the present invention.

Similarly, hydroxy-biphenyls and hydroxynaphthalenes are included. Of these, phenols are particularly preferred in practice.

The phenolic resin in the present invention is a modified aromatic polymer which is substituted with an aromatic hydrocarbon compound having no phenolic hydroxyl group, such as xylene or toluene, for example, a modified product of a condensation product of phenol, xylene and formaldehyde. Aromatic polymers can also be used. As the aldehyde, not only formaldehyde but also other aldehydes such as acetaldehyde and furfural can be used, but formaldehyde is preferred. The phenol-formaldehyde condensate may be a novolac type, a resol type or a complex thereof.

The mixing ratio of the powder of the insoluble and infusible substance to the phenol resin is preferably 30/70 to 80/20 by weight.
If the powder ratio is less than 30%, cracks and the like are likely to occur in the molded product in the subsequent heat treatment step, while if it exceeds 80%, the proportion of the resole resin that acts as a binder during the preparation of the composite molded product decreases, and the composite molded product The mechanical strength of the battery electrode material as described above tends to decrease.

Further, zinc chloride used together with the powder of the insoluble infusible substrate and the phenolic resin is removed in the subsequent step, but in order to give the insoluble infusible substrate used as the electrode a high specific surface area value. Used for. The amount of zinc chloride mixed is preferably 0.5 to 7 times the amount of the phenolic resin. If the amount is too small, the specific surface area of the insoluble and infusible substrate used as the electrode is lowered, and when this substrate is used as the electrode, it is difficult to dope or undope the ions in the electrolytic solution. Strength tends to decrease.

Next, the insoluble infusible substance powder, the phenolic resin, and zinc chloride are mixed and molded under appropriate conditions and cured to obtain a composite molded body. The mixing method may be any method such as dry mixing and wet mixing, but an adequate solvent such as water, methanol, or the like can be used for sufficiently uniform mixing.
It is preferable that the phenol resin and zinc chloride are made into a solution using acetone or the like, and then the powder of the insoluble and infusible substance is added and mixed.

As a molding method, generally, the same method as in the case of producing a resin molded product can be used, but for example, in order to obtain a film shape, the above-mentioned three-component mixed slurry may be formed into a film with an appropriate thickness by an applicator. When a plate-like body is to be obtained, a wall frame may be formed and press-formed as generally known.

As a curing method, for example, in the case of using a resole as a phenolic resin, it may be 50 to 200 during or after molding.
It is convenient to heat cure at a temperature of ° C. In particular, in the method of press molding using a wall frame or the like, curing can be performed by heating simultaneously with molding. Further, when novolac is used as the phenolic resin, a suitable curing agent such as hexamethylenetetramine is itself a formaldehyde generator and at the same time an organic base generator is mixed in advance and molded. It may be post-heat cured.

The composite molded body thus obtained is composed of insoluble infusible substance powder, phenolic resin and zinc chloride,
It has an arbitrary shape such as a plate or a cylinder, and can be easily manufactured from a small size to a large size.

Next, these composite compacts are heat-treated in a non-oxidizing atmosphere to produce an insoluble and infusible substrate having a polyacene skeleton structure with an atomic ratio of hydrogen atoms / carbon atoms of 0.05 to 0.6, preferably 0.15 to 0.6. . At this time, the heat treatment temperature is usually 400 to 800 ° C.
The preferable temperature rising conditions of the heat treatment are somewhat different depending on the composition ratio hardening conditions of the composite molded body or its shape, but generally, it is possible to set a relatively large temperature rising rate from room temperature to about 300 ° C. It is also possible to use a speed of 100 ° C./hour, for example. When the temperature reaches 300 ° C or higher, thermal decomposition of the phenolic resin starts, and gases such as steam, hydrogen, methane, and carbon monoxide start to be generated.
It is advantageous to raise the temperature at a sufficiently slow rate.

The substrate having a polyacene-based skeleton structure thus obtained is washed with warm water at 50 to 100 ° C. to remove zinc chloride remaining in the substrate and dried.

In this way, an insoluble and infusible substrate for an electrode, which is composed of an insoluble and infusible substrate having a polyacene skeleton structure, is obtained, and the substrate is composed of two parts. That is, an island portion coming from the powder of the insoluble and infusible substance used in the production of the composite molded body and a sea portion resulting from the thermal decomposition of the phenol resin. These two parts are both composed of an insoluble and infusible substance having a polyacene-based skeleton structure. Although the atomic ratio of hydrogen atom / carbon atom in these two parts may be different, From the viewpoint of uniformity of the substrate, the same value is desirable. The hydrogen atom / carbon atom atomic ratio of the insoluble and infusible substrate for an electrode of the present invention represents the atomic ratio of the matrix composed of these two parts, and the value is in the range of 0.05 to 0.6. It is preferably 0.15 to 0.6, particularly preferably 0.15 to 0.6. When the atomic ratio exceeds 0.6, the charge efficiency of charge and discharge is insufficient when the substrate is used as an electrode of a secondary battery by the method described later, and the atomic ratio of hydrogen atoms / carbon atoms is 0.
Even if it is less than 05, the charge / discharge charge efficiency is insufficient.

That is, when an insoluble infusible substrate having an atomic ratio of hydrogen atoms / carbon atoms of 0.05 to 0.6 is used as an electrode of a secondary battery, preferable battery characteristics are exhibited.

Further, the specific surface area value of the insoluble infusible substrate containing this polyacene skeleton structure by the BET method is extremely large because it is manufactured using zinc chloride, but it should be 600 m ² / g or more. Is preferred. If it is less than 600 m ² / g, for example, it becomes necessary to increase the charging voltage when charging the secondary battery using the substrate as an electrode, and the energy efficiency decreases,
Also, it is unlikely to deteriorate the electrolyte. Further, the molded body composed of the insoluble and infusible substrate used as the electrode of the present invention can be formed into any shape such as a plate shape and a cylindrical shape. Since the powder consisting of is used, the dimensional stability of the molded body during heat treatment is good, and since cracks etc. do not occur, a molded body of an insoluble and infusible substrate for a large size electrode with accurate dimensions can be obtained. It is possible to obtain.

Further, since the insoluble infusible substrate having the polyacene skeleton structure has a very large specific surface area value of 600 m ² / g or more by the BET method, it is considered that a gas such as oxygen penetrates and easily deteriorates. However, in reality, even if left in the air for a long time, the physical properties and the like do not change. For example, even if left in the air for 1000 hours, the electrical conductivity does not change, and the oxidation stability is excellent.

The organic electrolyte battery of the present invention has a hydrogen atom / carbon atom atomic ratio of 0.05 to 0.6, preferably 0.15 to 0.6, and a BET specific surface area value of 600 m ² / g or more containing insoluble infusible structure containing polyacene skeleton structure. It is an organic secondary battery in which a molded body made of a substrate is used as a positive electrode and / or a negative electrode, and a solution in which a compound capable of generating ions that can be doped into the electrode by electrolysis is dissolved in an aprotic organic solvent is used as an electrolytic solution.

Examples of the compound capable of generating ions that can be doped into the electrode include alkali metal or tetraalkylammonium halide perchlorate, hexafluorophosphate, hexafluoroarsenate, tetrafluoroborate, etc. Is mentioned. Specifically, LiI, NaI, NH ₄ I, LiClO ₄ , LiAsF ₆ , LiBF
₄ , KPF ₆ , NaPF ₆ , (n-C ₄ H ₉ ) ₄ NClO ₄ , (C ₂ H ₅ ) ₄ NCl
O ₄ , (C ₂ H ₅ ) ₄ NBF ₄ , (n-C ₄ H ₉ ) ₄ NBF ₄ , (n-C ₄ H ₉ )
₄ NAsF ₆ , (n-C ₄ H ₉ ) ₄ NPF ₆ or LiHF _2, etc. may be mentioned.

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

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

The battery function of the battery of the present invention utilizes the electrochemical doping and the electrochemical undoping of the doping agent to the insoluble and infusible substrate used as the electrode. That is, the energy is stored by the electrochemical doping of the doping agent into the insoluble and infusible substrate, or it is extracted as the electrical energy or stored internally by the electrochemical undoping released to the outside. To be

The batteries according to the present invention are divided into two types. First
The second type is a battery in which an insoluble and infusible substrate is used for both the positive electrode and the negative electrode, and the second type is a battery in which an insoluble and infusible substrate is used for the positive electrode and an alkali metal or an alkaline earth metal is used for the negative electrode. Examples of the alkali metal and alkaline earth metal include cesium, rubidium, potassium, sodium, lithium, barium, strontium, and calcium. Of these, lithium is most preferred. These metals can be used alone or as an alloy.

The shape and size of the electrode made of an insoluble and infusible substrate placed in the battery can be arbitrarily selected according to the type of the target battery, but since the battery reaction is an electrochemical reaction on the electrode surface, Advantageously, the electrodes have as large a surface area as possible. An insoluble and infusible substrate or an insoluble and infusible substrate doped with a doping agent may be used as a current collector for extracting a current from the substrate to the outside of the battery. Other conductive materials having corrosion resistance, such as carbon, platinum, nickel and stainless steel, can also be used.

Next, an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a basic configuration diagram of a battery according to the present invention.

First, a first type of battery according to the present invention, that is, a battery using an insoluble and infusible substrate for both the positive electrode and the negative electrode will be described. In FIG. 1, (1) is a positive electrode, which is a film-like or plate-like insoluble and infusible substrate,
(2) is a negative electrode, which is also an insoluble and infusible substrate having a film shape or a plate shape. All of these may or may not be doped with a doping agent. After assembling the battery, a voltage is applied from an external power source to dope the doping agent. For example, when an undoped insoluble and infusible substrate is used for both electrodes, the electromotive voltage of the battery after assembly of the battery is 0 V, and a voltage is applied by an external power source to dope the electrode with a doping agent. The battery will have an electromotive force. (3)
(3 ') is a current collector for supplying an electric current from each electrode to the outside or supplying an electric current for electrochemical doping, that is, charging, and each electrode and the external terminal (7) are formed by the method described above. It is connected to (7 ') without causing a voltage drop. (4) is an electrolytic solution in which the aforesaid compound capable of generating ions capable of being doped into both positive and negative electrodes is dissolved in an aprotic organic solvent. The electrolytic solution is usually in a liquid state, but it can be used in a gel or solid state in order to prevent liquid leakage. (5) is a separator arranged for the purpose of preventing contact between the positive and negative electrodes and holding the electrolytic solution. The separator is a porous body having continuous pores that is durable to an electrolytic solution or an electrode active material such as a doping agent or an alkali metal and has no electron conductivity, and is usually a cloth made of glass fiber, polyethylene or polypropylene, A non-woven fabric or a porous body is used. The thickness of the separator is preferably thin in order to reduce the internal resistance of the battery, but is determined in consideration of the amount of retained electrolyte, flowability, strength, and the like. The positive and negative electrodes and the separator are fixed in the battery case (6) so as not to cause practical problems. The shape and size of the battery are appropriately determined depending on the shape and performance of the target battery. For example, a film-like electrode is suitable for manufacturing a thin battery, and a large-capacity battery can be achieved by laminating a large number of film-like or plate-like electrodes alternately with both positive and negative electrodes.

Next, the second type of battery according to the present invention, that is, the case where an insoluble and infusible substrate having a polyacene skeleton structure is used for the positive electrode and an alkali metal or an alkaline earth metal is used for the negative electrode will be described. Explaining with reference to FIG. 1, the second type battery is different from the first type battery only in that the negative electrode (2) is an alkali metal or an alkaline earth metal. (3) to (7) have the same meaning as in the case of the first type battery.

In the case of this second type of cell, the doping mechanism, ie the operating mechanism of the cell, is further divided into two mechanisms. First
In the mechanism of (2), the insoluble and infusible substrate is doped with the electron-accepting doping agent for charging, and the undoped one is for discharging. For example, when an undoped insoluble infusible substrate is used as an electrode and LiClO ₄ 1 mol / propylene carbonate solution is used as an electrolytic solution of lithium, the electromotive force after battery assembly is 2.5 to 3.0V. Next, a voltage is applied by an external power source to dope the insoluble and infusible substrate with ClO ₄ ⁻ ions, and the electromotive force becomes 3.5 to 4.5V. In the second mechanism, doping the porous insoluble and infusible substrate with the electron-donating doping agent corresponds to discharging, and undoping corresponds to charging. For example, in the above battery configuration, the electromotive force after battery assembly is 2.5-
It is 3.0 V, and by discharging an electric current to the outside, when the insoluble and infusible substrate is doped with lithium ions, the electromotive force becomes 1.0 to 2.5 V, but a voltage is applied by an external power source,
When undoped with lithium ions, the electromotive force is 2.
It will be 5 to 3.0V.

Doping or undoping may be performed under a constant current or a constant voltage, or under conditions of changing current and voltage. However, the amount of the doping agent doped in the insoluble and infusible substrate is The percentage of the number of doped ions per carbon atom is preferably 0.5 to 20%.

The battery of the present invention using an insoluble and infusible substrate as an electrode is a secondary battery that can be repeatedly charged and discharged.
The electromotive voltage varies depending on the structure of the battery, but is 1.0 to 3.5 V in the first type, 3.5 to 4.5 V in the case of using the first mechanism in the second type, and the second type in the first type. When using two mechanisms, it is 2.5-3.0V. Further, the battery of the present invention has a particularly large energy density per weight, and has a value of about 500 WH / kg based on the weight of the insoluble and infusible substrate when an appropriate amount of doping is performed. Further, although the power density varies depending on the structure of the battery, it has a much higher power density than the lead storage battery. Further, when the insoluble and infusible substrate in the present invention is used as an electrode, a secondary battery having a small internal resistance, capable of being repeatedly charged and discharged, and having no deterioration in battery performance for a long period of time can be manufactured.

The secondary battery manufactured according to the present invention contains a polyacene-based skeleton structure which is excellent in oxidation resistance, heat resistance, moldability, and dimensional stability during heat treatment, as compared with conventionally known organic semiconductors. The organic substrate is used as an electrode, the electrode is doped with an electron-donating or electron-accepting substance is used as an electrode active material, and a compound capable of generating ions that can be doped into the electrode by electrolysis is dissolved in an aprotic organic solvent. It is a battery that uses the above solution as an electrolytic solution, and is a novel high-performance secondary battery that can be processed into any shape and has extremely high capacity, high output, and long life. The present invention will be specifically described below with reference to examples.

Example 1 i) Resol type phenolic resin (about 60% concentration aqueous solution) / water / zinc chloride were mixed at a weight ratio of 25/10/50 to proceed a curing reaction at a temperature of 100 ° C. for 60 minutes, The obtained cured product was pulverized, placed in a siliconit electric furnace, and heat-treated in a nitrogen atmosphere up to 500 ° C. at a heating rate of about 40 ° C./hour. The heat-treated product was pulverized again, washed with a 0.1N hydrochloric acid aqueous solution at 100 ° C. and warm water for 5 hours, and then dried under reduced pressure at a temperature of 70 ° C. for 3 hours to obtain a powder of an insoluble and infusible substance. When the powder was measured by fluorescent X-ray analysis, Zn was 0.01% by weight.
It was found to be less than (against powder), Cl was 0.5% by weight or less, and zinc chloride hardly remained in the substrate. When the powder was analyzed by X-ray diffraction, there was a main peak at 20 to 22 ° at 2θ, and
A small peak was observed in the range of 41 to 46 °, which confirmed that the powder had a polyacene skeleton structure. Further, as a result of measuring the specific surface area by the BET method, it was found that the specific surface area value of the powder was 1000 m ² / g. As a result of elemental analysis, the hydrogen atom / carbon atom ratio of the powder was 0.25.

ii) Resol type phenolic resin (about 60% concentration aqueous solution) / water / zinc chloride mixed at a weight ratio of 25/10/50 to a solution having a specific surface area value of 1000 m ² / The powder of the insoluble and infusible substance which is g is mixed so that the ratio with the solid component of the phenol resin in the solution is 60/40, and then poured into a mold of 50 × 50 × 2 mm, The curing reaction was allowed to proceed for 60 minutes at a temperature of 100 ° C. to obtain a composite molded body (product of the present invention) having a size of about 50 × 50 × 2 mm.

iii) Resol type phenolic resin shown in ii) / water /
The zinc chloride mixed solution was poured as it was into a mold of 50 × 50 × 2 mm, and a compact (comparative product) having a size of about 45 × 45 × 1.8 mm was obtained by the same method as ii).

iv) The molded body obtained in ii) and iii) was put into a siliconit electric furnace and heat-treated in a nitrogen atmosphere up to 500 ° C. at a heating rate of about 40 ° C./hour. In the heat-treated product of the present invention, the dimensions were almost unchanged, and a uniform product was obtained.On the other hand, in the molded product prepared without using the powder of the insoluble and infusible substance, dimensional shrinkage, cracks, etc. were observed. Was given.

v) Next, the heat-treated composite molded article of the present invention was washed with a 0.1 N hydrochloric acid aqueous solution at 100 ° C. and warm water for about 5 hours to remove zinc chloride remaining in the substrate. After washing, it was dried under reduced pressure at a temperature of 70 ° C. for 3 hours to obtain an insoluble and infusible plate-shaped substrate. When the plate-shaped substrate was subjected to X-ray fluorescence analysis, Zn was 0.01% by weight (relative to the substrate) or less, Cl was 0.5% by weight or less, and zinc chloride hardly remained in the substrate. There was found. The X-ray diffraction of the substrate was 20 at 2θ.
There was a main peak at -22 ° and a small peak at 41-46 °, confirming that the substrate had a polyacene skeleton structure. Next, the elemental analysis of the substrate, the electrical conductivity, and the measurement of the specific surface area value by the BET method were carried out. As a result, the hydrogen atom / carbon atom atomic ratio was
The electric conductivity was 0.25, the electric conductivity was 10 ^-5 (Ω · cm) ^-1 , and the specific surface area value by the BET method was 1100 m ² / g.

vi) Next, add fully dehydrated propylene carbonate to Li
A battery was assembled as shown in FIG. 1 in which AsF ₆ was dissolved to form a solution of about 1.0 mol / mol, lithium metal was used as a negative electrode, and a plate-shaped body of an insoluble and infusible substrate was used as a positive electrode. A platinum mesh was used as the current collector and a felt made of glass fiber was used as the separator. This embodiment is the second embodiment of the present invention.
It is a battery utilizing the first mechanism of the type. That is, doping the insoluble and infusible substrate with AsF ₆ ⁻ ions that are electron accepting doping agents corresponds to charging, and undoping corresponds to discharging. Further, the doping amount is represented by the number of doped ions per carbon atom in the substrate, but in the present invention, the number of doped ions is obtained by the current value flowing in the circuit at the time of doping. is there. The voltage immediately after assembly of the battery with the above configuration is 2.
It was 9V.

Next, a voltage was externally applied to this battery, and the insoluble and infusible substrate was doped with AsF ₅ ⁻ ions at a constant voltage for 3.5 hours so that the doping amount per hour was 1%. The open circuit voltage at the end of doping was 4.0V. Next, a constant current was passed through the circuit so that the amount of undoping per hour was 1%, the undoping of AsF ₆ ⁻ ions was performed, and this was continued until the open circuit voltage reached the voltage immediately after the battery was assembled. The charge efficiency was undoped versus undoped in this test, where the charge efficiency was 80%.

It is clear that the secondary battery assembled using the insoluble and infusible substrate in this manner has excellent charge / discharge characteristics.

Comparative Example 1 i) A plain weave cloth made of phenolic fiber (manufactured by Nippon Kynol Co., Ltd., trade name Kynol, basis weight 200 g / m ² ) was placed in a silicon knit furnace and heated up to 500 ° C. at about 40 ° C./in a nitrogen atmosphere.
Heat treatment was performed at a heating rate of time, and the obtained heat-treated product was pulverized to obtain an insoluble and infusible substance powder. When the powder was analyzed by X-ray diffraction, there was a main peak at 20 to 22 ° at 2θ and a small peak in the range of 41 to 46 °, and the powder had a polyacene skeleton structure. It was confirmed that Next, the specific surface area value of the powder by the BET method,
Also, the atomic ratio of hydrogen atoms / carbon atoms was measured by elemental analysis. As a result, the specific surface area value by the BET method was 400 m ² / g, and the atomic ratio of hydrogen atom / carbon atom was 0.42.

ii) Using the powder of the insoluble infusible substance having a specific surface area value of 400 m ² / g obtained in i), and performing the same operation as in ii), iv) and v) of Example 1 Plate-shaped substrate (comparative product)
I got The elemental analysis of the substrate, the electrical conductivity, and the specific surface area value by the BET method were measured. As a result, hydrogen atom /
The atomic ratio of carbon atoms is 0.3 and the electrical conductivity is 10 ^-2 (Ω · cm)
^-1 , The specific surface area value by the BET method was 560 m ² / g.

iii) Next, the insoluble and infusible plate-shaped substrate (comparative product) was doped in the same manner as in vi) of Example 1, but almost no current flowed in the circuit.

Example 2 i) Ratio obtained in i) of Example 1 to a solution in which a resole type phenolic resin (about 60% concentration aqueous solution) / water / zinc chloride was mixed at a weight ratio of 25/12/60. Surface area value is 1000
The powder of the insoluble infusible substance which is m ² / g is mixed so that the ratio with the solid content of the phenol resin in the solution is 60/40, and then the size of 50 × 50 × 2 mm. Pour into the mold of 100 ℃
The curing reaction was allowed to proceed for 60 minutes at the above temperature to obtain a composite molded body having a size of about 50 × 50 × 2 mm.

ii) Next, heat the composite molded body up to the predetermined temperature shown in Table 1.
It was heat-treated at a temperature rising rate of 40 ° C./hour, washed and dried in the same manner as in v) of Example 1 to obtain an insoluble and infusible plate-shaped substrate. In any case, cracks etc. do not occur,
A substrate having the exact dimensions was obtained. The elemental analysis of the substrate, the electrical conductivity, and the specific surface area value by the BET method were measured, and these values are shown in Table 1 together. Further, a battery was assembled using lithium tetrafluoroborate as an electrolyte in the plate-like substrate in the same manner as in vi) of Example 1, and the charge / discharge characteristics were examined. The results are summarized in Table 1.

In any case, when an insoluble and infusible substrate was used as the electrode, a stable and high-performance secondary battery was obtained.

Example 3 i) The ratio obtained in i) of Example 1 to a solution in which a resole type phenol resin (aqueous solution having a concentration of about 60%) / water / zinc chloride was mixed at a weight ratio of 25/10/50. Surface area value is 1000
The powder of the insoluble and infusible substance of m ² / g was mixed in such a ratio that the ratio with the solid content of the phenol resin in the solution was the ratio shown in Table 2, and then 50 × 50 × 2 mm. Pour into the formwork of 100,
The curing reaction was allowed to proceed for 60 minutes at a temperature of ° C to obtain a composite molded body having a size of about 50 x 50 x 2 mm. The composite molded body was prepared as in Example 1 iv).
And a heat treatment, washing and drying by the method shown in v) to obtain an insoluble and infusible plate-shaped substrate. In each case, cracks and the like did not occur, and the size was accurate.

ii) Elemental analysis of the plate-like substrate, electric conductivity, and measurement of specific surface area by BET method were carried out, and these values are collectively shown in Table 2. Next, a battery was assembled in the same manner as in Example 1 vi) using lithium tetrafluoroborate as an electrolyte for the plate-shaped substrate, and the charge / discharge characteristics were examined. The results are shown in Table 2.

Example 4 This example relates to a first type of battery according to the present invention, that is, a secondary battery using an insoluble and infusible substrate for the positive electrode and the negative electrode. A battery was constructed by using the plate-like body of the insoluble and infusible substrate of No. 1 used in Example 3 for the positive electrode and the negative electrode, and using 1 mol / solution of LiClO ₄ dissolved in propylene carbonate as an electrolytic solution. Then, a charge / discharge test was performed.

The open circuit voltage immediately after the battery was assembled was 0V. Next, a voltage is applied from an external power source to generate ClO ₄ ⁻ ions for the positive electrode and Li ⁺ for the negative electrode.
It was charged by doping with ions. The charging rate was such that the doping amount per hour was 1%, and the charging was performed for about 2 hours. The open circuit voltage at this time was 2.5V. Next, undoping of ClO ₄ ⁻ ions and Li ⁺ ions is performed at almost the same rate as during charging, and discharge is performed at an open circuit voltage of 0 V.
It was done until. The charge efficiency was about 80%.

[Brief description of drawings]

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

Claims (8)

(57) [Claims] 1. The atomic ratio of hydrogen atoms / carbon atoms is 0.05 to 0.6.
And a powder (A) of an insoluble and infusible substance having a polyacene skeleton structure having a specific surface area value of 600 m ² / g or more by the BET method, a phenolic resin (B), and zinc chloride (C) The atomic ratio of hydrogen atoms / carbon atoms obtained by heat-treating the formed composite compact in a non-oxidizing atmosphere is 0.05 to 0.
6 and a compound having a specific surface area by BET method of 600 m ² / g or more is an insoluble and infusible substrate having a polyacene skeleton structure as a positive electrode and / or a negative electrode, and can generate ions that can be doped in the electrode by electrolysis An organic electrolyte battery using the aprotic organic solvent solution of 1. as an electrolytic solution. 2. The organic electrolyte battery according to claim 1, wherein the insoluble and infusible substance is a heat-treated phenolic resin. 3. The organic electrolyte battery according to claim 1 or 2, wherein the phenolic resin is phenol formaldehyde resin. 4. A composite molded article formed by 30 to 70 parts by weight of an insoluble and infusible substance powder and 70 to 20 parts by weight of a phenolic resin. The organic electrolyte battery according to any one of 1. 5. The organic electrolyte battery according to any one of claims 1 to 4, wherein the insoluble and infusible substrate has a hydrogen atom / carbon atom atomic ratio in the range of 0.15 to 0.60. 6. The organic electrolyte battery 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 an alkali metal. . 7. The organic electrolyte battery according to any one of claims 1 to 5, wherein the positive electrode and the negative electrode are insoluble and infusible substrates having a polyacene skeleton structure. 8. A compound capable of producing a dopable ion is LiClO ₄ , LiAsF ₆ , LiBF ₄ , (n-C ₄ H ₉ ) ₄ NClO ₄ , (n.
-C ₃ H _{7) 4} organic electrolyte cell according to any one of NClO ₄ or LiHF ₂ a is Claims paragraphs 1 through 6 wherein.