JPH0740493B2 - Non-aqueous solvent secondary battery - Google Patents

Description

TECHNICAL FIELD The present invention has a high energy density, a small self-discharge,
The present invention relates to a non-aqueous solvent secondary battery having a long cycle life and excellent charge / discharge efficiency (Coulomb efficiency).

2. Description of the Related Art A so-called polymer battery using a polymer compound having a conjugated double bond in its main chain as an electrode is expected as a high energy density secondary battery. Many reports have already been made on polymer batteries, for example, PJ Nigley et al., Journal of the Chemical Society, Chemical Communication, 1979, 594.
Page (PJ Nigrey et al, JCS, Chem. Commun., 1979 , 59
4], Journal Electrochemical Society, 1981, p. 1651 [J. Electrochem. Soc., 1981 , 165.
1), JP-A-56-136469, 57-121168, 59-3870
Issue 59-3872, Issue 59-3873, Issue 59-196566, Issue 59-
196573, 59-203368, 59-203369, etc. can be mentioned as a part thereof.

In addition, it has already been proposed to use polyaniline obtained by oxidative polymerization of aniline, which is a kind of conjugated polymer, as an electrode of a battery of an aqueous solution system or a non-aqueous solvent system.・ Preprints, Volume 25, Number 2, Page 248 (1984) [AGMac
Diarmid et al, Polymer Preprints, 25 , No.2,248 (198
4)], Sasaki et al., Electrochemical Society 50th Annual Meeting, 123
(1983), Electrochemical Society of Japan 51st Annual Meeting, 228 (198
Four)〕.

Problems to be Solved by the Invention Oxidized polymers of aniline compounds are produced by oxidative polymerization methods such as electrochemical polymerization and chemical polymerization. But,
Oxidized polymers of aniline-based compounds produced by these methods are obtained in an oxidized state to some extent,
When the oxidized polymer was used as it was or after being treated with alkali for the positive electrode of the battery, the doping level was at most about 50 mol%, and it was difficult to obtain a secondary battery with higher energy density.

The present inventors have found that as a method of increasing the doping level,
A method has already been proposed (Japanese Patent Application No. 60-247985) in which an oxidized polymer of an aniline-based compound is chemically reduced in advance with a reducing agent and then used for the positive electrode. According to this method, the doping level of the oxidized polymer of the aniline compound can be increased and the energy density of the battery can be improved.
High energy density, (ii) low self-discharge, (iii) high charge
The discharge efficiency and (iv) long cycle life were not always satisfied at the same time.

Therefore, an object of the present invention is to overcome the drawbacks of the secondary battery using the above-mentioned conventional oxidized polymer of an aniline-based compound as a positive electrode, have a high energy density, a small self-discharge, a long cycle life, and a long charging life. -To provide a non-aqueous solvent secondary battery with good discharge efficiency.

Means for Solving the Problems As a result of intensive investigations by the present inventors to obtain a non-aqueous solvent secondary battery that simultaneously satisfies the above four battery performances, as a result, an oxidation polymer of an aniline-based compound was previously chemically treated with a reducing agent. Of the aniline-based compound is significantly reduced, and the oxidation capacity of the aniline-based compound is significantly improved by using a product obtained by subjecting the oxidative polymer to heat treatment in a specific temperature range as a positive electrode active material. It was found that a secondary battery which has reached the above-mentioned condition can be obtained, and has reached the present invention.

That is, the present invention uses a polyaniline-based compound for the positive electrode,
Non-aqueous using (i) a light metal, (ii) a light metal alloy, (iii) a conductive polymer, (iv) a light metal or a composite of a light metal alloy and a conductive polymer, or (v) an intercalation compound for the negative electrode. In a solvent secondary battery, the polyaniline-based compound is an oxidized polymer of an aniline-based compound represented by the following general formula, and after the oxidized polymer is chemically reduced by a reducing agent, 100 to 400 ° C. The present invention relates to a non-aqueous solvent secondary battery, which is heat-treated in the temperature range of 1.

[In the formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different,
A hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is shown. ] The oxidation polymer of the aniline compound used in the present invention is
It is obtained by oxidative polymerization of the aniline compound represented by the above general formula.

Representative examples of the aniline-based compound represented by the general formula, aniline, ortho or metatoluidine, xylidine, ortho or metaanisidine, 2,5-dimethoxyaniline, 2,5-diethoxyaniline, 3,5-dimethoxyaniline, Although 2,6-dimethoxyaniline and the like can be mentioned, use of aniline is preferable from the viewpoint of obtaining a non-aqueous solvent secondary battery having high energy density.

The oxidative polymer of the aniline compound can be produced by either an electrochemical polymerization method or a chemical polymerization method.

When the electrochemical polymerization method is used, the aniline compound is polymerized by anodic oxidation. To do this, for example,
A current density of 20mA / cm ² is used. In most cases, a voltage of 1 to 300 V is applied. The polymerization is preferably carried out in the presence of an auxiliary liquid in which the aniline compound is soluble. for that purpose,
Water or a polar organic solvent can be used, but it is preferable to carry out in an aqueous solution.

The pH of the suitable electrolytic solution is not particularly limited, but the pH is preferably 3 or less, particularly preferably 2 or less. Specific examples of the acid used to adjust the pH include HCl, HBF ₄ , CF ₃ COOH, H ₂ SO ₄
And HNO _{3 and the} like, but are not particularly limited thereto. When using a solvent miscible with water, a small amount of water may be added. A good organic solvent is
Alcohols, ethers such as dioxane or tetrahydrofuran, acetone or acetonitrile, benzonitrile, dimethylformamide or N-methylpyrrolidone.

The polymerization is carried out in the presence of a complexing agent. This is Ani
BF as on , AsF , ASF , SbF , SbCl^-, PF , Cl
O , HSO ， SO_Four ^2-And CH₃ SO Means a salt containing a group of.

These salts include, for example, a proton (H ⁺ ) as a cation,
It contains quaternary ammonium cations, lithium ions, sodium ions or potassium ions. The use of compounds of this kind is known and is not the subject of the present invention. These compounds are usually used in an amount such that the oxidized polymer contains the anionic complex compounding agent in an amount of 20 to 100 mol%. The oxidation polymer of the aniline compound obtained by this method is a complex compound due to the corresponding anion.

When the oxidized polymer of the aniline compound is produced by a chemical polymerization method, the aniline compound can be polymerized in an aqueous solution with a strong acid such as hydrochloric acid and an inorganic peroxide. Among the inorganic peroxides, ammonium persulfate is preferable. According to this method, the oxidized polymer is obtained in the form of fine powder. Since salts are also present in this method, the oxidized polymer is complexed with the corresponding anion.

In addition, in both cases of the electrochemical polymerization method and the chemical polymerization method, it is possible to polymerize by adding other additives such as carbon black, Teflon powder, polyethylene glycol, polyethylene oxide, etc. to the polymerization electrolyte. Is.

The oxidative polymer of the aniline compound thus obtained is then chemically reduced by a reducing agent, but it is preferable to previously compensate the oxidative polymer of the aniline compound with a base before reducing the oxidative polymer of the aniline compound. .

Examples of the base used for this compensation include inorganic bases such as aqueous ammonia, sodium carbonate, potassium hydroxide and sodium hydroxide, and organic bases such as lower aliphatic amines such as triethylamine. Water is preferred.

The method of chemically reducing the oxidative polymer of the aniline compound that has been compensated with a base by a reducing agent is not particularly limited, but usually the oxidative polymer is immersed in a solution of the reducing agent,
A method of stirring or applying ultrasonic vibration is adopted.

As the reducing agent, hydrazines such as hydrazine, hydrazine hydrate and phenylhydrazine, metal hydrides such as lithium aluminum hydride and sodium borohydride, and mercaptans can be used. Among these reducing agents, hydrazines are preferable, and phenylhydrazine and hydrazine are particularly preferable.

The amount of the reducing agent to be used is not particularly limited, but it is usually at least an amount that provides 1 atom of hydrogen to 1 atom of nitrogen contained in the oxidation polymer of the aniline-based compound, preferably 1.5 of the nitrogen atoms contained in the oxidation polymer. Used to be ~ 3 times the atomic weight. The time required for the reduction reaction is usually several tens of minutes to several hours,
In most cases, it is sufficient to react for 2 to 3 hours. Since the reduction reaction proceeds sufficiently quickly even at room temperature, heating is not particularly required, but the reduction reaction may be performed under heating if necessary. After completion of the reduction reaction, the oxidation polymer of the aniline-based compound is thoroughly washed with the same solvent as the reaction solution to remove the reducing agent, and then the temperature range of 100 to 400 ° C., preferably 200.
It heat-processes in the temperature range of -400 degreeC, Especially preferably, the temperature range of 200-350 degreeC. When the heat treatment temperature is lower than 100 ° C., impurities such as water and low molecular weight substances are not sufficiently removed, and when the heat treatment temperature is higher than 400 ° C., deterioration of the oxidized polymer occurs, which is not preferable. . The heat treatment may be performed in an inert gas atmosphere or under a vacuum.

The thus obtained reduction-treated and heat-treated oxidized polymer of the aniline-based compound (hereinafter referred to as the treated oxidized polymer of the aniline-based compound) is, for example, polyaniline, an emerald compound represented by the following formula (I). The leuco emeraldine structure of the following formula (II) in which the din structure is reduced, or the structure containing 50 mol% or more of the reduced structure between the following formula (I) and the following formula (II).

This treated oxidative polymer of aniline-based compound can obtain the remarkable effect of the present invention when used alone as a positive electrode, but further increases the conductivity and strength of the oxidative polymer of treated aniline-based compound. To this oxidation polymer,
It is preferable to mix and use a conductive agent and a binder. For example, as the conductive agent, carbon black, acetylene black, metal powder, metal fiber, carbon fiber and the like can be mentioned. Examples of the binder include thermoplastic resins such as polyethylene, modified polyethylene, polypropylene, poly (tetrafluoroethylene), ethylene-propylene-diene-terpolymer (EPDM), and sulfonated EPDM.

The content of the conductive agent is 5 to 30 parts by weight, preferably 5 to 100 parts by weight of the treated aniline-based compound oxidation polymer.
~ 20 parts by weight. If the amount of the conductive agent is less than 5 parts by weight, the conductivity of the electrode does not increase so much, and if the amount of the conductive agent is more than 30 parts by weight, the weight of the oxidized polymer of the treated aniline compound in the electrode is high. Becomes smaller, which is disadvantageous in terms of energy density.

The binder content is 2 to 20 parts by weight, preferably 5 parts by weight, based on 100 parts by weight of the treated aniline-based compound oxidation polymer.
~ 10 parts by weight. If the blending amount of the binder is less than 2 parts by weight, the electrode tends to collapse, which is not preferable. Further, if the amount of the binder compounded exceeds 20 parts by weight, the electric conductivity of the electrode becomes small, and it is disadvantageous in terms of energy density.

As a method for producing a composite consisting of an oxidized polymer of a treated aniline compound, a conductive agent and a binder, for example, a mixture of an oxidized polymer of the treated aniline compound, a conductive agent and a binder is used. A method of compression molding under pressure and heating can be mentioned. The mixture at this time may be kneaded with water or an organic solvent such as acetone, ethyl alcohol, or xylene.

The pressure during compression molding is preferably within the range of 10 to 10,000 kg / cm ² . The heating temperature during compression molding is
It is preferably in the range of room temperature to 300 ° C.

The operation during compression molding is preferably carried out in an inert gas atmosphere such as nitrogen gas or argon gas in order to prevent the oxidized polymer of the treated aniline compound from being oxidized.

The composite obtained by compression molding is preferably dried under reduced pressure at a temperature of room temperature to 300 ° C. and then used as the positive electrode.

The negative electrode used in the non-aqueous solvent secondary battery of the present invention has (i)
Light metal, (ii) alloy of light metal, (iii) conductive polymer,
(Iv) A complex of a light metal or an alloy of a light metal and a conductive polymer, or (v) an intercalation compound. Two or more kinds of these negative electrodes may be used in combination.

Examples of the (i) light metal used as the negative electrode of the non-aqueous solvent secondary battery include alkali metals such as lithium, sodium and potassium, aluminum and the like, and (ii) alloys of the light metal include lithium-aluminum alloy and lithium. -Zinc alloy, lithium-tin alloy, lithium-aluminum-magnesium alloy, and the like. Also,
(Iii) Examples of the conductive polymer include polypyrrole and polypyrrole derivatives, polythiophene and polythiophene derivatives, polyquinoline, polyacene, polyparaphenylene and polyparaphenylene derivatives, and polyacetylene. Further, (iv) as a complex of a light metal or an alloy of a light metal and a conductive polymer, a complex of aluminum or a lithium-aluminum-magnesium alloy and polyacetylene, polyparaphenylene or a polyparaphenylene derivative, a lithium-aluminum alloy And a polyacetylene, polyparaphenylene or a polyparaphenylene derivative. The term "composite" as used herein means a uniform mixture of a light metal or an alloy of a light metal and a conductive polymer, a laminate, and a modified product obtained by modifying a component serving as a substrate with another component. (V) An intercalation compound includes Fe ₂ O ₃ .

Among the above negative electrodes, (ii), (iii) and (iv) are preferable, and (iv) is particularly preferable.

An alkali metal salt is used as the supporting electrolyte of the electrolytic solution of the non-aqueous solvent secondary battery of the present invention. Examples of the alkali metal of the alkali metal salt include Li, Na and K metals,
Li metal is preferable.

A typical anion component of the supporting electrolyte is, for example, Cl.
O , PF , AsF , AsF ， SO₃CF , BF , And BR (However
R is an alkyl group having 1 to 10 carbon atoms, or aryl
Group) and the like.

Specific examples of the alkali metal salt as the supporting electrolyte,
_{LiPF 6, LiSbF 6, LiClO 4} , LiAsF 6, CF 3 SO 3 Li, LiBF 4, Li
B (Bu) ₄ , LiB (Et) ₂ (Bu) ₂ , NaPF ₆ , NaBF ₄ , NaAsF ₆ , NaB (B
u) ₄ , KB (Bu) ₄ , KAsF _{6 and the} like can be cited, but the invention is not necessarily limited to these. These alkali metal salts may be used alone or in combination of two or more.

The concentration of the alkali metal salt varies depending on the type of the oxidized polymer of the treated aniline-based compound used for the positive electrode, the type of the cathode, the charging conditions, the operating temperature, the type of the supporting electrolyte and the type of the organic solvent. However, it is generally preferred to be in the range of 0.5 to 10 mol / l. The electrolytic solution may be homogeneous or heterogeneous.

Examples of the organic solvent used alone or as a mixture as the solvent of the electrolytic solution of the non-aqueous solvent secondary battery of the present invention include the following.

Alkylene nitrile: eg, crotonitrile (liquid range, −51.1 ° C. to 120 ° C.) Trialkyl borate: eg, trimethyl borate, (CH ₃
O) ₃ B (liquid range, −29.3 ° C. to 67 ° C.) Tetraalkyl silicate: eg, tetramethyl silicate, (CH ₃ O) ₄ Si (boiling point, 121 ° C.) Nitroalkane: eg, nitromethane, CH ₃ NO ₂ (Liquid range, -17 ° C to 100.8 ° C) Alkyl nitrile: Example, acetonitrile, CH ₃ CN (Liquid range, -45 ° C to 81.6 ° C) Dialkylamide: Example, dimethylformamide, HCON (C
H _{3) 2} (liquid range, -60.48 ℃ ~149 ℃) Monocarboxylic acid ester: eg, ethyl acetate (liquid range,
-83.6 to 77.06 ° C) Orthoester: eg, trimethyl orthoformate, HC
(OCH ₃ ) ₃ (boiling point, 103 ° C) Dialkyl carbonate: eg, dimethyl carbonate, OC (OCH ₃ ) ₂ (liquid range, 2 to 90 ° C) Monoether: eg, diethyl ether (liquid range, -11
6-34.5 ° C) Polyether: eg, 1,1- and 1,2-dimethoxyethane (liquid range, -113.2-64.5 ° C and -58-83, respectively)
C.) Cyclic ether: eg, tetrahydrofuran (liquid range, −
65-67 ℃): 1,3-dioxolane (liquid range, -95-78)
℃) Nitro aromatics: eg, nitrobenzene (liquid range, 5.7-2
Aromatic carboxylic acid halide: eg, benzoyl chloride (liquid range, 0 to 197 ° C.), benzoyl bromide (liquid range, −24 to 218 ° C.) Aromatic sulfonic acid halide: eg, benzenesulfonyl chloride ( Liquid range, 14.5-251 ℃) Aromatic phosphonic acid dihalide: eg, Benzenephosphonyl dichloride (boiling point, 258 ℃) Aromatic thiophosphonic acid dihalide: eg, benzene
Thiophosphonyl dichloride (boiling point, 124 ° C at 5 mm) Alkyl sulfonic acid halide: eg, methane sulfonyl chloride (boiling point, 161 ° C) Alkyl carboxylic acid halide: eg, acetyl chloride (liquid range, -112 to 50.9 ° C), acetyl bromide (liquid range, -96 to 76 ° C) ), Propionyl chloride (liquid range, -94
~ 80 ° C) Saturated heterocyclic compound: eg, tetrahydrothiophene (liquid range, -96 to 121 ° C): 3-methyl-2-oxazolidone (melting point, 15.9 ° C) Dialkylsulfamic acid halide: eg, dimethyl sulfamyl chloride ( Boiling point, 80 ° C at 16 mm) Alkyl halosulfonate: eg, ethyl chlorosulfonate (boiling point, 151 ° C) Unsaturated heterocyclic carboxylic acid halide: eg, 2-furoyl chloride (liquid range, -2 to 173 ° C) 5 member Unsaturated heterocyclic compounds: eg, 1-methylpyrrole (boiling point, 114 ° C), 2,4-dimethylthiazole (boiling point, 144
° C), furan (liquid range, -85.65 to 31.36 ° C), ester and / or halide of dibasic carboxylic acid: eg, ethyl oxalyl chloride (boiling point, 135
℃) Mixed alkyl sulfonic acid halide / carboxylic acid halide: eg, chlorosulfonyl acetyl chloride (boiling point, 98 ° C at 10 mm) Dialkyl sulfoxide: eg, dimethyl sulfoxide (liquid range, 18.4 to 189 ° C) Dialkyl sulfate: eg, dimethyl Sulfate (liquid range, −31.75 to 188.5 ° C.) Dialkyl sulfite: Ex., Dimethyl sulfite (boiling point, 126 ° C.) Alkylene sulfite: Ex., Ethylene glycol sulfite (liquid range, −11 to 173 ° C.) Halogenated alkane: Example, methylene chloride (liquid range,-
95-40 ℃, 1,3-dichloropropane (liquid range, -99.5
The preferred organic solvent is sulfolane, crotonitrile, nitrobenzene, tetrahydrofuran, methyl-substituted tetrahydrofuran, 1,3-dioxolane, 3-methyl-2-oxazolidone, propylene or ethylene carbonate, sulfolane, γ-butyrolactone. , Ethylene glycol sulfite, dimethyl sulfite,
Dimethyl sulphoxide and 1,1- and 1,2-dimethoxyethane, particularly preferably mixed solvents of propylene carbonate and 1,2-dimethoxyethane and sulfolane and 1,2-dimethoxyethane. Because they appear to be the most chemically inert to battery components and have a wide liquid range,
In particular, these allow the positive electrode active material to be utilized highly efficiently.

In the non-aqueous solvent secondary battery of the present invention, the amount of the dopant doped into the oxidized polymer of the treated aniline-based compound of the positive electrode is 0.2 with respect to 1 atom of N atom in the oxidized polymer.
˜1.0 mol, preferably 0.2 to 0.8 mol.

The doping amount can be freely controlled by measuring the amount of electricity that flows during electrolysis. Doping may be performed under a constant current or a constant voltage, or under any conditions where the current and the voltage change.

In the present invention, if necessary, a synthetic resin porous membrane such as polyethylene or polypropylene or natural fiber paper may be used as the diaphragm.

Further, since some of the electrodes used in the non-aqueous solvent secondary battery of the present invention may react with oxygen or water to deteriorate the performance of the battery, the battery should be a sealed type and substantially non-existent. It is desirable to be in an oxygen and anhydrous state.

EFFECTS OF THE INVENTION The non-aqueous solvent secondary battery of the present invention has high energy density, high charge / discharge efficiency, long cycle life, small self-discharge rate, and good flatness of voltage during discharge. . In addition, the non-aqueous solvent secondary battery of the present invention is lightweight, small in size, and has a high energy density, and is therefore optimal as a portable device, an electric vehicle, a gasoline vehicle, and a battery for storing electric power.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

Example 1 [Production and reduction of aniline oxide polymer, heat treatment] To a glass container, deoxygenated distilled water, HBF ₄ , and aniline were added, and the concentration of HBF ₄ was 1.5 mol and the concentration of aniline was 0.35.
It was prepared to have a molar content. Two platinum electrodes of 6 cm ² each were placed in the aqueous solution at intervals of 2 cm, and then electrolyzed under stirring with an electric quantity of 120 amper-seconds. At this time, a dark green aniline oxide polymer was deposited on the anode plate. The coated anode was repeatedly washed with distilled water three times and then air-dried, and then the produced aniline oxide polymer film was peeled off from the platinum plate. The peeled oxidized polymer was immersed in 28% ammonia water, left overnight, washed repeatedly with distilled water three times, and then heat-treated under vacuum at 250 ° C. for 15 hours.

The obtained reddish purple film was immersed in a diethyl ether solution (10 cc) in which 1 g of phenylhydrazine was dissolved under a nitrogen gas atmosphere and ultrasonically vibrated for 1 hour. Then, the diethyl ether solution was removed, and the mixture was washed with diethyl ether under a nitrogen gas atmosphere until the liquid was not colored, further washed with 1,2-dimethoxyethane, and heat-treated under vacuum at 250 ° C. for 15 hours. The elemental analysis value of the obtained off-white film is C
+ H + N weight% is 99.88%, the composition ratio is C: H: N
= 6.00: 5.07: 0.99, indicating that the oxidized polymer of aniline represented by the structure represented by the formula (II) is in a completely reduced state.

[Production of Membrane Acetylene High Polymer]

In a glass reaction vessel with an internal volume of 500cc under a nitrogen gas atmosphere
1.7 cc of titanium tetrabutoxide was added, dissolved in 30 cc of anisole, and then 2.7 cc of triethylaluminum was added with stirring to prepare a catalyst solution.

The reaction vessel was cooled with liquid nitrogen, and the nitrogen gas in the system was exhausted with a vacuum pump. Then the reaction vessel is placed at -78 ° C.
Then, the catalyst solution was kept still, and purified acetylene gas having a pressure of 1 atm was blown thereinto.

Immediately, polymerization occurred on the surface of the catalyst solution, and a film-like acetylene high polymer was produced. 30 minutes after the introduction of acetylene, the acetylene gas in the reaction vessel system was exhausted to stop the polymerization. After removing the catalyst solution with a syringe under a nitrogen gas atmosphere,
While keeping the temperature at ℃, 100cc of purified toluene was repeatedly washed 5 times. The filmy acetylene high polymer swollen with toluene is
It was a uniform membranous swelling in which the fibrils were tightly intertwined. Then, the swollen material was heat-treated under vacuum to obtain a filmy acetylene high polymer having a metallic luster and a red-purple thickness of 180 μm and a cis content of 98%. The bulk density of this filmy acetylene high polymer was 0.30 g / cc, and its electric conductivity (DC four-terminal method) was 3.2 × 10 ⁻⁹ S / cm at 20 ° C.

[Battery experiment]

The treated oxidized polymer film of aniline obtained in the above [Production and Reduction of Aniline Oxidized Polymer, and Heat Treatment] was pulverized in an agate mortar under a nitrogen gas atmosphere to obtain a fine powder. To 100 parts by weight of this fine powder, 8.0 parts by weight of carbon black and 10.0 parts of poly (tetrafluoroethylene)
Parts by weight were mixed and kneaded. The resulting kneaded product was subjected to a nitrogen gas atmosphere at room temperature using a molding tablet machine with a diameter of 20 mmφ at 10,000
A composite was prepared by compression molding at a pressure of kg / cm ² to obtain a positive electrode active material. The bulk density of this composite is 0.55 g / cc, and its electrical conductivity (DC four-terminal method) is 5.9 × 10 ^-3 S / cm at 20 ° C.
Met.

On the other hand, a disk having a diameter of 20 mmφ was cut out from the filmy acetylene high polymer obtained in the above [Production of filmy acetylene high polymer] to obtain a negative electrode active material.

A battery was constructed using the positive electrode active material and the negative electrode active material.

FIG. 1 is a schematic cross-sectional view of a battery cell for measuring characteristics of a non-aqueous solvent secondary battery, which is one embodiment of the present invention, where 1 is a platinum lead wire for a negative electrode, 2 is a platinum mesh for a negative electrode having a diameter of 20 mm and 80 mesh Current collector, 3 is a disk-shaped negative electrode having a diameter of 20 mm, 4 is a circular porous polypropylene diaphragm having a diameter of 20 mm, and has a thickness sufficient to impregnate the electrolytic solution, 5 is a disk-shaped positive electrode having a diameter of 20 mm, 6 is a platinum net current collector for positive electrode having a diameter of 20 mm and 80 mesh, 7 is a positive electrode lead wire, and 8 is a screw type Teflon container.

First, the platinum net current collector 6 for the positive electrode is placed in a Teflon container 8
Of the positive electrode 5 on the platinum net current collector 6 for the positive electrode, the porous polypropylene diaphragm 4 on the positive electrode 5 and the electrolyte solution sufficiently impregnated, and then the negative electrode 3 is overlaid.
Further, the platinum net current collector 2 for the negative electrode was placed thereon, and the Teflon container 8 was tightened to manufacture a battery.

As the electrolytic solution, a 1.5 mol / l solution of LiAsF ₆ dissolved in a mixed solvent (volume ratio 1: 1) of propylene carbonate distilled and dehydrated according to a conventional method was used.

Using the battery thus manufactured, the amount of electricity corresponding to the doping amounts of 60 mol% and 6 mol% in the positive electrode and the negative electrode, respectively, under a constant current (3.0 mA / cm ² ) in an argon gas atmosphere was obtained. It was drained and charged. Immediately after charging, discharge the battery under constant current (5.0mA / cm ² ) and the battery voltage is 1.0V.
When a repeated charge / discharge test was conducted under the same conditions as above, the charge / discharge efficiency was reduced to 50%.
It recorded 710 times.

The energy density at the 5th repetition is 158 W · hr.
The maximum charge / discharge efficiency was 100% in kg / kg. Also, when left for 60 hours while being charged, the self-discharge rate is 1.
It was 3%.

Comparative Example 1 In the production of [aniline-oxidized polymer, reduction, and heat treatment] of Example 1, the reduced aniline-oxidized polymer was added to 80%.
Heat treatment was performed at ℃. Hereinafter, a composite was obtained by compression molding in the same manner as in Example 1 except that this treated aniline oxidation polymer was used.

A [battery experiment] was performed in the same manner as in Example 1 except that the composite obtained by the above method was used as the positive electrode active material. As a result, the number of charge / discharge cycles was 537, and the energy density at the fifth cycle was 156 W · hr.
The maximum charge / discharge efficiency was 99% in / kg. Also, when left for 60 hours while being charged, its self-discharge rate is 2.
It was 7%.

Comparative Example 2 In the production of [aniline-oxidized polymer, reduction, and heat treatment] of Example 1, the aniline-oxidized polymer was heat-treated without reduction treatment. Hereinafter, a composite was prepared in exactly the same manner as in Example 1 except that this heat-treated oxidized polymer of aniline was used. A [battery experiment] was performed in the same manner as in Example 1 except that this composite was used as a positive electrode active material. As a result, the charge / discharge efficiency is only 83% at maximum,
At the 39th time, the charge / discharge efficiency dropped below 50%.

Example 2 [Production of aniline-oxidized polymer, reduction, and heat treatment] 400 cc of previously deoxygenated distilled water and 100 cc of 42% HBF ₄ aqueous solution were added to 1 part.
The mixture was placed in a three-necked flask and the mixture was bubbled with nitrogen gas for about 1 hour while stirring. After that, place the system in a nitrogen gas atmosphere, attach a thermometer and condenser, and warm the solution with water.
It was set to 40 ° C. Then, 20 g of aniline was added thereto. While stirring, 46 g of ammonium persulfate was added to this aniline aqueous solution.
Was added dropwise to 200 cc of 1N HCl aqueous solution over about 2 hours, and then reacted at 40 ° C. for 3 hours.

After the reaction was completed, the dark green reaction liquid was passed, and the obtained dark green aniline oxidation polymer was immersed in 500 cc of 28% ammonia water and left overnight. After that, add 20
It was repeatedly washed 3 times with 0 cc of distilled water and then heat-treated under vacuum at 80 ° C. for 15 hours. 18 g of the obtained reddish purple powder
Met. 1.5 g of this reddish purple powder was added to 50 cc of a diethyl ether solution of 3 g of phenylhydrazine under a nitrogen gas atmosphere, and the mixture was stirred at room temperature for 1 hour and then separated. Then, wash with diethyl ether until the liquid becomes colorless, and then 1,2-
It was washed with dimethoxyethane and heat treated under vacuum at 235 ° C for 2 hours. The elemental analysis value of the obtained off-white powder is C +
The weight percentage of H + N is 99.18%, and its composition ratio is C: H: N =
It was 6.00: 5.01: 0.98.

[Battery experiment]

A composite was obtained by molding and drying in exactly the same manner as in Example 1 except that the powder of the treated aniline oxidized polymer obtained in the above [Production and reduction of aniline oxidized polymer, heat treatment] was used. It was The bulk density of the obtained composite was 0.56 g / cc, and its electrical conductivity (DC four-terminal method) was 4.1 × 10 at 20 ° C.
It was ^-3 S / cm.

A battery experiment was conducted in the same manner as in Example 1 except that the composite material obtained by the above method was used as the positive electrode active material. As a result, the number of repetitions until the charge / discharge efficiency dropped to 50% was recorded as 801 times. The energy density of this battery is 157
The maximum charge / discharge efficiency was 100%.
Further, when left for 60 hours while being charged, the self-discharge rate was 1.5%.

Comparative Example 3 In the production of [aniline-oxidized polymer, reduction and heat treatment] of Example 2, the reduced aniline-oxidized polymer was treated at 80 ° C.
It heat-processed. A composite was obtained by compression molding in the same manner as in Example 1 except that the treated aniline oxidation polymer was used.

A battery experiment was conducted in the same manner as in Example 1 except that the composite material obtained by the above method was used as the positive electrode active material. As a result, the number of repetitions until the charge / discharge efficiency dropped to 50% was recorded as 520 times. The energy density of this battery is 156W
・ It was hr / kg, and the maximum charge / discharge efficiency was 99%. When left for 60 hours while being charged, the self-discharge rate was 3.1%.

Example 3 In Example 1, instead of the acetylene high polymer used for the negative electrode, the bulletin of the chemical society of Japan, Vol. 51, p. 2091 (1978) [Bul]
l.Chem.Soc.Japan., 51, 2091 (1978 ) ] obtained by molding the poly-p-phenylene prepared at a pressure of 1 ton / cm ² into a disc-shaped 20mmφ by the method described in (10% carbon A battery experiment was conducted in exactly the same manner as in Example 1 except that (including black) was used as the negative electrode. As a result, the number of repetitions until the charge / discharge efficiency dropped to 50% was recorded as 798 times. The energy density of this battery was 153 W · hr / kg, and the maximum charge / discharge efficiency was 100%. When left for 60 hours while being charged, the self-discharge rate is 1.5%.
Met.

Example 4 In the same manner as in Example 1, except that a Li-Al alloy (atomic ratio of 1: 1) was used as the negative electrode instead of the acetylene high polymer used in the negative electrode in Example 1, [battery Experiment] was performed. As a result, the number of repetitions until the charge / discharge efficiency dropped to 50% was recorded at 839 times. The energy density of this battery is 203W · hr / kg, and the maximum charge / discharge efficiency is 100%.
Met. Further, when left for 60 hours while being charged, the self-discharge rate was 1.1%.

Example 5 In Example 1, instead of the acetylene high polymer used for the negative electrode, the polyparaphenylene and Li-Al alloy used in Examples 3 and 4 were mixed in a weight ratio of 8: 2. A battery experiment was conducted in exactly the same manner as in Example 1 except that a composite (containing 10% of carbon black) molded into a disk shape of 20 mmφ at a pressure of 1 ton / cm ² was used for this mixture. . As a result, the number of repetitions until the charge / discharge efficiency dropped to 50% was recorded as 903 times. The energy density of this battery is 178W · hr / kg, and the maximum charge / discharge efficiency is 100%.
Met. Further, when left for 60 hours while being charged, the self-discharge rate was 1.1%.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of a battery cell for measuring characteristics of a non-aqueous solvent secondary battery that is one specific example of the present invention. DESCRIPTION OF SYMBOLS 1 ... Platinum lead wire for negative electrode 2 ... Platinum net current collector for negative electrode 3 ... Negative electrode 4 ... Porous polypropylene diaphragm 5 ... Positive electrode, 6 ... Platinum net current collector for positive electrode 7 ... Positive electrode lead wire, 8 ... Teflon container

Claims (1)

[Claims] 1. A polyaniline compound is used for the positive electrode, and (i) a light metal, (ii) a light metal alloy, (iii) a conductive polymer, (iv) a light metal or a light metal alloy and a conductive polymer are used for the negative electrode. In the non-aqueous solvent secondary battery using the composite or (v) intercalation compound, the polyaniline-based compound is an oxidation polymer of an aniline-based compound represented by the following general formula, and the oxidation polymer is a reducing agent. A non-aqueous solvent secondary battery, which is chemically reduced by means of heat treatment at a temperature of 100 to 400 ° C. [In the formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. ]