JPH0630260B2 - Organic electrolyte battery - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an organic electrolyte battery. More specifically, the present invention relates to an organic electrolyte battery in which an insoluble and infusible substrate having semiconductor properties is used as a positive electrode and / or a negative electrode, and a solution in which a compound capable of generating an ion that can be doped is dissolved in an aprotic organic solvent is used as an electrolytic solution. .

[Conventional technology]

In recent years, the miniaturization, thinning, or weight reduction of electronic devices has been remarkable, and along with this, the miniaturization, thinning of batteries that are power sources,
There is a great demand for weight reduction. Currently, silver oxide batteries are widely used as small size and high performance batteries, and lithium batteries have been developed and put into practical use as thin dry batteries and small and lightweight high performance batteries. However, since these batteries are primary batteries, they cannot be used for a long time by repeating charging and discharging. Meanwhile, nickel-cadmium batteries have been put into practical use as high-performance secondary batteries, but they are still unsatisfactory in terms of downsizing, thinning, and weight reduction.

Further, lead-acid batteries have been conventionally used in various industrial fields as large-capacity secondary batteries, but the biggest drawback of these batteries is that they are 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 into 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 according to their respective applications.
There is a great need for making batteries smaller, thinner, and lighter. As a battery that tries to answer these needs,
Recently, batteries using an organic semiconductor thin film polyacetylene doped with an electron-donating substance or an electron-accepting substance as an electrode active material have been studied and proposed. The battery has high performance as a secondary battery and has the possibility of being thin and lightweight, but has a serious drawback. That is, polyacetylene, which is an organic semiconductor, is an extremely unstable substance and 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 it is also restricted to manufacture polyacetylene into a shape suitable for an electrode.

Further, Japanese Patent Application No. 59-24165, which is a prior application filed by the same applicant as the applicant of the present application, has not yet been published, but the specification of the same application discloses that an aroma composed of carbon, hydrogen and oxygen. A heat-treated product of a group condensation polymer, wherein the atomic ratio of hydrogen atoms / carbon atoms is 0.05 to 0.5, and B
The insoluble and infusible substrate having a polyacene-based graded structure having a specific surface area value of 600 m ² / g or more by the ET method is used as a positive electrode and /
Alternatively, an organic electrolyte battery has been proposed which is characterized by using a solution of an aprotic organic solvent of a compound capable of generating ions capable of being doped in the electrode by electrolysis as a negative electrode.

The battery is a promising secondary battery having high performance, possibility of thinning and weight saving, high oxidative stability of electrode active material, and easy molding thereof. However, some problems remain for the practical application of the battery. The most important of these problems is to improve the battery capacity, in other words, to increase the doping amount and the energy density that can be taken out.

An object of the present invention is to provide an organic electrolyte battery.

Another object of the present invention is to provide an organic electrolyte battery having a large capacity per unit weight and a high energy density.

Yet another object of the present invention is to provide an organic electrolyte battery using an organic semiconductor composed of an insoluble and infusible substrate having a polyacene skeleton structure as an electrode active material.

Still another object of the present invention is to provide an organic electrolyte battery which is an economical secondary battery which can be miniaturized, thinned or lightened and is easy to manufacture.

Still another object of the present invention is to provide a secondary battery having a high electromotive voltage, a low internal resistance, and capable of being charged and discharged for a long period of time.

Further objects and advantages of the present invention will be apparent from the following description.

[Means and Actions for Solving Problems] According to the present invention, such an object and advantage of the present invention are (A) an aromatic compound which is a condensate of an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde. A heat-treated product of a group-type condensation polymer, wherein the atomic ratio of (a) hydrogen atom / carbon atom is 0.5 to 0.05.
And (b) the specific surface area by BET method is at least 600 m ² /
and (c) an insoluble and infusible substrate having communicating pores having an average pore size of 10 μm or less as a positive electrode and / or a negative electrode, and (B) a compound capable of generating ions that can be doped into the electrode by electrolysis. Is used as an electrolytic solution, and a solution of the above is dissolved in an aprotic organic solvent.

The aromatic condensation polymer in the present invention is a condensation product 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, the following formula Here, x and y are each independently 0, 1 or 2 and may be a methylene-bisphenol represented by the following, or a hydroxy-biphenyl or a hydroxynaphthalene. Of these, phenols are particularly suitable for practical use.

The aromatic condensation polymer in the present invention further includes 1 of aromatic hydrocarbon compounds having a phenolic hydroxyl group.
It is also possible to use a modified aromatic polymer in which a portion is substituted with an aromatic hydrocarbon compound having no phenolic hydroxyl group, such as xylene or toluene, for example, a modified aromatic polymer which is a condensate of phenol, xylene and formaldehyde. 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 novolak type, a resol type, or a composite thereof.

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

Preparing an initial condensation product of an aromatic hydrocarbon compound having a phenolic hydroxyl group or an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aromatic hydrocarbon compound not having a phenolic hydroxyl group and an aldehyde, and the initial condensation product An aqueous solution containing an inorganic salt is prepared, and the aqueous solution is poured into a suitable mold, and then the aqueous solution is heated while suppressing evaporation of water to form a plate-shaped, film-shaped, or cylindrical shape in the mold. After curing and conversion, the cured product is heated to a temperature of 350 to 800 ° C. in a non-oxidizing atmosphere to be heat-treated, and then the obtained heat-treated product is washed to remove inorganic salts contained in the heat-treated product. To do.

The above-mentioned inorganic salt used together with the initial condensate is a pore-forming agent which is removed in a later step and is used for imparting communicating pores to the cured body, and examples thereof include zinc chloride, sodium phosphate, potassium hydroxide or potassium sulfide. . Of these, zinc chloride is particularly preferably used. The inorganic salt can be used in an amount of, for example, 2.5 to 10 times the initial condensation product. If the amount is less than the lower limit, it is difficult to obtain a porous body having communicating pores, and if the amount is more than the upper limit, the mechanical strength of the finally obtained porous body tends to decrease, which is not desirable. The aqueous solution of the initial condensate and the inorganic salt varies depending on the type of the inorganic salt used, but can be prepared using, for example, 0.1 to 1 times the weight of water of the inorganic salt. Thus, for example, 10
The aqueous solution having a viscosity of 10,000 to 100 centipoise is poured into a suitable mold and heated to a temperature of 50 to 200 ° C, for example. At the time of this heating, it is important to suppress evaporation of water in the aqueous solution. That is, it is considered that the initial condensate is gradually hardened by being heated in the aqueous solution and grows into a three-dimensional network structure while being separated from zinc chloride and water.

The cured product thus obtained is then subjected to a temperature of 350 to 800 ° C., preferably 350 to 700 ° C., particularly preferably 400 to 6 in a non-oxidizing atmosphere (including a vacuum state).
It is heated to a temperature of 00 ° C. and heat-treated.

The preferable heating rate during the heat treatment varies slightly depending on the aromatic condensation polymer used, the degree of the curing treatment or the shape thereof, etc., but generally a relatively large temperature rise from room temperature to about 300 ° C. It is possible to use a speed, for example, a speed of 100 ° C./hour. At a temperature of 300 ° C. or higher, thermal decomposition of the aromatic condensation polymer starts, and gases such as steam (H ₂ O), hydrogen, methane, and carbon monoxide start to be generated, so that the temperature rises at a sufficiently slow rate. It is advantageous to heat.

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

By thoroughly washing the obtained heat-treated body with water or dilute hydrochloric acid, the inorganic salts contained in the heat-treated body can be removed, and then, when this is dried, communication holes have developed and a specific surface area is increased. It is possible to obtain a porous cured condensate having a large size.

Thus, by the above heating and heat treatment, the atomic ratio of hydrogen atoms / carbon atoms (hereinafter referred to as H / C ratio) is 0.5 to 0.0.
An insoluble and infusible substrate having a polyacene skeleton structure of 5, preferably 0.35 to 0.1 and a communicating hole having an average pore diameter of 10 μm or less, for example, an average pore diameter of 0.03 to 10 μm can be obtained. Further, the atomic ratio of oxygen atom / carbon atom (O
/ C ratio) is usually 0.06 or less, preferably 0.03 or less. According to X-ray diffraction (CuKα), the position of the main peak is in the range of 20.5 to 23.5 ° represented by 2θ, and 41 to 46 in addition to the main peak.
There is another broad peak between °. Moreover, according to the infrared absorption spectrum, D (= D _{2000 to 2940} / D
The absorbance ratio of _{1560 to 1640} ) is usually 0.5 or less, preferably 0.3 or less.

That is, it is understood that the insoluble and infusible substrate has a polyacene-based benzene polycyclic structure uniformly and moderately developed among polyacene-based molecules.

When the H / C ratio is more than 0.5 or less than 0.05, the charge / discharge efficiency decreases when the substrate is used as an electrode of a secondary battery according to the method described later, which is not preferable. Further, the specific surface area value of the insoluble and infusible substrate containing the polyacene skeleton structure by the BET method is extremely large because it is manufactured using an inorganic salt such as zinc chloride,
In the present invention, those having a density of 600 m ² / g or more are used.
When it is less than 600 m ² / g, for example, when charging a secondary battery using the substrate as an electrode, it is necessary to increase the charging voltage, which lowers the energy density and is likely to prevent deterioration of the electrolytic solution. Absent.

The insoluble and infusible substrate used in the present invention is a porous body having communicating pores having an average pore diameter of 10 μm or less as described above,
Further, since it has a three-dimensional mesh structure, the electrolytic solution can easily flow in and out of details through the communication hole.

The above-mentioned porous insoluble and infusible substrate is also characterized in that it has fine communication holes with uniform pore diameters, that is, in a sharp state of pore diameter distribution as described above.

The insoluble and infusible substrate used in the present invention is a porous body having fine communication holes, and thus has an advantage that the electrolyte solution easily penetrates into the details, and also has a high specific surface area value. As described above, there is an advantage that the electrolyte ions can be doped smoothly and in a large amount. Therefore, the secondary battery of the present invention having small internal resistance, high capacity, and high energy density can be realized.

The electric conductivity of the insoluble and infusible substrate is usually 10 ^−11.
It is -10 ¹ Ω ^-1 cm ^-1 . Then, as will be described later, in the case of using it as an electrode material by doping with electrolyte ions, the conductivity is greatly increased, so that the electrode material also has a current collecting property.

The insoluble and infusible substrate has an apparent density of 0.2 to 0.6 g / cm ³ , for example. That is, a material having a relatively high porosity to a material having a relatively low porosity can be used. The mechanical strength depends on the apparent density, but is 0.2 g / cm ³
It has a practically sufficient strength even though it has an apparent density of. Since the insoluble and infusible substrate can take various forms such as a film, a plate, a fiber, a cloth, a non-woven fabric or a composite thereof, when used as an electrode material, a small battery, a thin battery or a lightweight battery, etc. Is possible.
The porous insoluble and infusible substrate used in the present invention is 600
Despite having a large specific surface area value of m ² / g or more, in reality, even if it is left in the air for a long time, the physical properties such as electric conductivity do not change, and it has excellent oxidation stability. Further, since it has excellent heat resistance and chemical resistance, it does not cause the problem of electrode deterioration when used as an electrode material to construct a battery.

As described above, the organic electrolyte battery of the present invention uses the above-mentioned porous insoluble and infusible substrate as a positive electrode and / or a negative electrode, and dissolves a compound capable of generating ions that can be doped in the electrode by electrolysis in an aprotic organic solvent. This is an organic secondary battery using the prepared solution 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,
Examples thereof include hexafluoroarsenate and tetrafluoroboronate.
Specifically, LiI, NaI, NH ₄ I, LiClO ₄ , L
iAsF ₆ , LiBF ₄ , KPF ₆ , NaPF ₆ , (n-C
₄ H ₉ ) ₄ NClO ₄ , (C ₂ H ₅ ) ₄ NClO 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.

An aprotic organic solvent is used as a solvent for dissolving the compound. For example, ethylene carbonate, propylene carbonate, γ-butyrolactone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonitrile, dimethoxyethane, tetrahydrofuran, methylene chloride, sulfolane, or a mixture thereof can be used. It is selected from among these in consideration of the solubility of the compound used as the electrolyte, the 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 of the electrolytic solution, and more preferably 0.2 to 1.5 mol / usually.

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. The first type is a battery in which a porous insoluble and infusible substrate is used for both the positive electrode and the negative electrode, and the second type is in which a porous insoluble and infusible substrate is used for the positive electrode and an alkali metal or alkaline earth metal is used for the negative electrode. This is the electrode used. Examples of alkali metals and alkaline earth metals include cesium, rubidium, potassium, sodium, lithium, barium, strontium, and calcium. Of these, lithium is most preferred. These metals can be used alone or as an alloy.

The shape 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 intended battery, but the battery reaction is an electrochemical reaction on the surface of the electrode. It is advantageous to have as large a surface area as possible. Further, an insoluble and infusible substrate or an insoluble and infusible substrate doped with a doping agent can be used as a current collector for extracting a current from the substrate to the outside of the battery, but it has corrosion resistance to the doping agent and the electrolytic solution. Other conductive materials such as carbon, platinum, nickel, stainless steel, etc. 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, reference numeral 1 is a positive electrode, which is a film-shaped or plate-shaped insoluble infusible substrate, and 2 is a negative electrode, which is also a film-shaped or plate-shaped insoluble infusible substrate. . Each 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 OV, and a voltage is applied by an external power source to dope the electrodes with a doping agent. The battery will have thermal power. 3 and 3'extract current from each electrode to the outside, electrochemical doping,
That is, it is a current collector for supplying a current for charging, and is connected to each electrode and the external terminals 7, 7'by the method described above so as not to cause a voltage drop. Reference numeral 4 denotes an electrolytic solution, in which an aprotic organic solvent is dissolved with the above-mentioned compound capable of generating ions that can be doped into both positive and negative electrodes. The electrolytic solution is usually liquid, but it may be used in the form of gel or solid to prevent liquid leakage. Reference numeral 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 electrolyte retained, flowability, strength, and the like. The positive and negative positive electrodes and the separator are fixed in the battery case 6 so as not to cause any practical problems. The shape and size of the electrode are appropriately determined according to the shape and performance of the target battery. For example, a film-shaped electrode is suitable for manufacturing a thin battery, and a large-capacity battery can be achieved by laminating a large number of film-shaped or plate-shaped 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, this second type battery is different from the first type battery only in that the negative electrode 2 is made of an alkali metal or an alkaline earth metal. 7 has 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. In the first mechanism, the insoluble and infusible substrate is doped with the electron-accepting doping agent for charging, and the undoped one is for discharging. For example, as an electrode, an undoped insoluble infusible substrate and lithium as an electrolytic solution
When 1 mol of LiClO ₄ / propylene carbonate solution is used, the electromotive force after battery assembly is 2.5 to 3.0V. Then a voltage is applied by the external power supply Cl ▲ O ^- Doping to ₄ ▼ ions insoluble and infusible base, the electromotive force becomes 3.5～4.5V. 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-mentioned battery configuration, the electromotive voltage after battery assembly is 2.5 to 3.0 V, and when the insoluble and infusible substrate is doped with lithium ions by discharging an electric current to the outside, the electromotive force is 1.0. The voltage is up to 2.5 V, but when a voltage is applied by an external power source and lithium ions are undoped, the electromotive force becomes 2.5 to 3.0 V again.

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 to be doped into the insoluble and infusible substrate depends on the carbon of the substrate. The percentage of the number of doped ions with respect to one atom is preferably 0.5 to 20%.

The battery of the present invention using a porous insoluble and infusible substrate as an electrode is a secondary battery that can be repeatedly charged and discharged, and its electromotive voltage varies depending on the structure of the battery, but is 1 in the first type. 0 to 3.5 V, 3.5 to 4.5 V when the first mechanism is used in the second type, and 2.5 to 4.5 V when the second mechanism is used in the second type. 3.0V
Is. 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. Regarding the power density, the power density is much higher than that of the lead storage battery, although there is a difference depending on the structure of the battery. Further, when the above porous insoluble and infusible substrate in the present invention is used as an electrode, it is possible to manufacture a secondary battery having a small internal resistance, capable of repeated charging and discharging, and having no deterioration in battery performance over a long period of time.

The secondary battery produced by the method of the present invention is a porous insoluble insoluble polymer containing a polyacene skeleton structure which is superior in oxidation resistance, heat resistance, moldability and mechanical strength as compared with conventionally known organic semiconductors. The fusible substrate is used as an electrode, and the electrode is doped with an electron-donating or electron-accepting substance as an electrode active material.
It is a battery that uses a solution in which a compound capable of generating ions that can be doped in the electrode by electrolysis is dissolved in an aprotic organic solvent as an electrolytic solution, and can be miniaturized, thinned, and lightened, and is extremely high. It is a new high-performance secondary battery with high capacity, high output and long life. The present invention will be specifically described below with reference to examples.

In addition, in the present specification, the average pore diameter of the communicating holes is measured and defined as follows.

An electron micrograph of the sample is taken at a magnification of 1,000 to 10,000, for example. If an arbitrary straight line is drawn on this photograph and the number of holes intersecting the straight line is n, the average pore diameter () is calculated by the following formula.

Here, li is a length cut by a hole where straight lines intersect, Is the sum of the cut lengths for n holes, and n
Is the number of holes intersecting the straight line, where n is a value of 10 or more.

Example 1 (1) An aqueous solution prepared by mixing water-soluble resol (about 60% concentration) / zinc chloride / water at a weight ratio of 10/25/4 was formed on a glass plate with a film applicator. Next, a glass plate was covered on the formed aqueous solution to prevent water from evaporating, and then heated at a temperature of about 100 ° C. for 1 hour to be cured.

The phenol resin film was placed in a silicon nitride electric furnace and heated at a rate of 40 ° C./hour under a nitrogen stream to obtain 500
Heat treatment was performed up to ℃. Next, the heat-treated product was washed with dilute hydrochloric acid, washed with water, and then dried to obtain a film-shaped porous body. The thickness of the film was about 200 μm, the apparent density was about 0.35 g / cm ³ , and the film was excellent in mechanical strength. Next, the electric conductivity of the film was measured at room temperature by a direct current four-terminal method and found to be 10 ⁻⁴ (Ω
・ Cm) ^-1 Further, when an elemental analysis was performed, the atomic ratio of hydrogen atoms / carbon atoms was 0.27. The shape of the peak from X-ray diffraction is a pattern based on the polyacene skeleton structure, and a broad main peak was present at around 20 to 22 ° at 2θ, and a small peak was confirmed at around 41 to 46 °.

Moreover, when the specific surface area value was measured by the BET method, 2
It was a very large value of 100 m ² / g.

Next, in order to observe the pore state of the film-shaped semiconductor, an electron micrograph of the film cross section was taken. It is shown in FIG.
As is clear from FIG. 2, the three-dimensional mesh structure is 10 μm.
It was a porous body having the following fine ventilation holes.

(2) Next, add L to thoroughly dehydrated propylene carbonate.
A battery was assembled as shown in FIG. 1 in which a 1.0 mol / solution of iClO ₄ was used as an electrolytic solution, lithium metal was used as a negative electrode, and the above-mentioned porous film substrate was used as a positive electrode. A stainless mesh was used as the current collector, and a felt made of glass fiber was used as the separator.

The doping amount is represented by the number of doped ions per carbon atom of the porous film substrate.
In the present invention, the number of ions to be doped is obtained from the current value flowing through the circuit.

Then by applying a voltage from the outside to the battery, the doping amount per hour of 1% and becomes such a current density in Cl ▲ O ^- ₄ ▼
The porous insoluble and infusible film substrate was doped with ions for about 5 hours and charged. Then, the battery was discharged at the same current density and continued until the battery voltage reached 2.5V.

Next, a predetermined amount of doping was performed at the same current density as described above, and after charging, discharging was performed at the same rate, and the voltage was returned to 2.5V. These results are shown in FIG. When 8% is doped, the electromotive voltage is about 4.5 V and the charging / discharging efficiency (discharge amount /
The amount of charge was about 80% and the capacity was about 150 mAH / g. However, the semiconductor weight was taken as the weight standard. The energy density was calculated to be about 500 WH / kg on the basis of the same weight. Further, the internal resistance of the battery during these tests was a good value of about 20Ω even though the electrode area was as small as about 2 cm ² .

Examples 2 to 4 (1) A phenol resin film having a thickness of about 200 μm obtained in the same manner as in Example 1 was heated in a nitrogen electric current furnace at a rate of about 30 ° C./hour in a silicon electric furnace and shown in Table 1. Heat treatment was performed by heating to various predetermined temperatures. Thereafter, the film was washed with dilute hydrochloric acid and water, and dried to obtain a porous insoluble and infusible substrate film. The obtained porous substrate film was subjected to elemental analysis and specific surface area measurement by the BET method. The results are summarized in Table 1.

(2) Next, add L to thoroughly dehydrated propylene carbonate.
iBF ₄ was dissolved to give a solution of about 1.0 mol / mol.
Then, a battery was assembled using lithium metal as a cathode, the above solution as an electrolytic solution, and a porous substrate film as an anode.

Next, a voltage was applied from an external power source and charging was performed for 6 hours at a current density at which the doping amount per hour was 1%. The voltage at that time is shown in Table 1. Then, the battery was discharged at the same current density and continued until the voltage became equal to the voltage immediately after the battery was assembled.
The ratio of the discharged amount to the charged amount is shown in Table 1 as the charge efficiency.

Example 5 (1) A phenol resin film having a thickness of about 200 μm obtained in the same manner as in Example 1 was washed with water to remove a part of zinc chloride contained therein. Then, it was put in a silicon electric furnace, heat-treated in the same pattern as in Example 1, then washed and dried.

The apparent density of the porous sample was about 0.40 g / cm ³ , the film was excellent in mechanical strength, and the electric conductivity was 10 ⁻⁶ (Ω · cm) ⁻¹ . In addition, elemental analysis showed that the atomic ratio of hydrogen atoms / carbon atoms was 0.32.
The specific surface area value by the T method was 800 m ² / g.

(2) Next, a battery similar to that of Example 1 was assembled using the porous substrate. At this point the cell had a voltage of 2.8V. Next, the battery was charged for 6 hours at a rate that the doping amount per hour was 1%. The electromotive voltage was 4.3V. Then discharge at the same rate and continue until 2.8V. It was possible to discharge for about 5 hours.

Example 6 Example 6 relates to a battery of the first type of the present invention, that is, a secondary battery using the porous insoluble and infusible substrate of the present invention for the positive electrode and the negative electrode.

The same porous substrate as used in Example 1 was used for the positive electrode and the negative electrode, and a battery was constructed using 1 mol of (C ₂ H ₅ ) ₄ NClO ₄ dissolved in propylene carbonate as an electrolyte, and a charge-discharge test was conducted. I went. The voltage immediately after the battery was assembled was 0V. Next, apply a voltage of 2.5 V from an external power source to about 1
Time to the positive electrode Cl ▲ O ^- ₄ ▼ doped ions, the negative electrode _{(C 2 H 5) 4 N} + ions. The electromotive voltage of the battery was 2.5 V as a matter of course. Next, when the battery was discharged at a rate at which the amount of undoping per hour was 3%, the voltage of the battery returned to 0 in about 1 hour.

Next, the charge / discharge test as described above was continued, and a repeated durability test was performed about 1000 times. No deterioration in battery performance was observed.

[Brief description of drawings]

FIG. 1 shows the basic structure of a battery according to the present invention, in which 1 positive electrode, 2 negative electrode, 3 and 3'collector, 4 electrolytic solution, 5 separator, 6 battery case, 7, 7'denotes an external terminal. FIG. 2 is an example of an electron micrograph of the particle structure (porous structure) of the cross section of the porous insoluble and infusible substrate film used in the present invention. In the photograph, the length of the bar line shown in the lower right is 5μ. FIG. 3 is an example of a charge / discharge curve of the organic electrolyte battery of the present invention. The vertical axis represents the open circuit voltage of the battery, and the horizontal axis represents the doping amount. White circles correspond to charging and black circles correspond to discharging. Is the discharge curve after 2% doping, is the discharge curve after 4% doping, is the discharge curve after 6% doping and is the discharge curve after 8% doping.

Continuation of the front page (56) Reference JP-A-58-209864 (JP, A) JP-A-59-157974 (JP, A) JP-A-60-5011 (JP, A) JP-A-58-35881 (JP , A)

Claims (13)

[Claims] 1. A heat-treated product of (A) an aromatic condensation polymer, which is a condensation product of an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde, and (a) an atomic ratio of hydrogen atom / carbon atom. Is 0.5 to 0.05
And (b) the specific surface area by BET method is at least 600 m ² /
g, and (c) an insoluble and infusible substrate having communicating pores having an average pore diameter of 10 μm or less is used as a positive electrode and / or a negative electrode, and (B) a compound capable of generating ions that can be doped into the electrode by electrolysis. An organic electrolyte battery characterized in that a solution dissolved in an aprotic organic solvent is used as an electrolytic solution. 2. The organic electrolyte battery according to claim 1, wherein the aromatic condensation polymer is a condensation product of phenol and formaldehyde. 3. The organic electrolyte battery according to claim 1, wherein the atomic ratio of hydrogen atoms / carbon atoms of the insoluble and infusible substrate is 0.35 to 0.1. 4. The specific surface area value of the insoluble and infusible substrate by the BET method is 800 to 3000 m ² / g.
The organic electrolyte battery according to item. 5. The insoluble and infusible substrate has an average pore size of 0.03 to 10
The organic electrolyte battery according to claim 1, which has a large number of communication holes of μm. 6. The organic substance according to claim 1, wherein the insoluble and infusible substrate has a polyacene skeleton structure in which an atomic ratio of oxygen atom (O) / carbon atom (C) is 0.06 or less. Electrolyte battery. 7. An insoluble and infusible substrate is formed through a large number of communicating holes.
The organic electrolyte battery according to claim 1, which has a three-dimensional network structure. 8. The organic electrolyte battery according to claim 1, wherein the insoluble and infusible substrate is a positive electrode, and the alkali metal or alkaline earth metal is a negative electrode. 9. The method according to claim 8, wherein the negative electrode is an alkali metal and the alkali metal is lithium or a lithium alloy.
The organic electrolyte battery according to item. 10. The organic electrolyte battery according to claim 1, wherein the insoluble and infusible substrate serves as a positive electrode and a negative electrode. 11. A compound capable of forming an ion that can be doped is LiI, NaI, NH ₄ I, LiClO ₄ , Li.
_{AsF 6, LiBF 4, KPF 6} , NaPF 6, (C 2 H 5) 4
NClO ₄ , (n-C ₄ H ₉ ) ₄ NClO ₄ , (C ₂ H ₅ ) ₄ N
BF ₄ , (n-C ₄ H ₉ ) ₄ NBF ₄ , (n-C ₄ H ₉ ) ₄ NA
_{sF 6, (n-C 4} H 9) 4 PF 6 or organic electrolyte cell according to paragraph 1 claims a LiHF _2. 12. The aprotic organic solvent is ethylene carbonate, propylene carbonate, γ-butyrolactone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonitrile, dimethoxyethane, tetrahydrofuran, methylene chloride or sulfolane. The organic electrolyte battery described in 1. 13. An insoluble and infusible substrate is a film, a plate, a fiber,
The organic electrolyte battery according to claim 1, which is in the form of a cloth, a nonwoven fabric, or a composite thereof.