JPS62264561A - Nonaqueous solvent secondary battery - Google Patents

Abstract

PURPOSE:To obtain a battery having high energy density, high chargedischarge efficiency, low self discharge, and long cycle life by using a positive active material obtained by chemically reducing an oxidationpolymerization product of aniline compound, and conducting heattreatment in a specified temperature range. CONSTITUTION:A polyaniline compound which is an oxidation-polymerization product of aniline compound indicated in the formula (R1-R4 show H, alkyl group,or alkoxy group having C1-10) is chemically reduced with a reducing agent, and heated at 100-400 deg.C, then used as a positive electrode. A light metal, light metal alloy, conductive polymer, a composite of light metal or light metal alloy and a conductive polymerm, or an intercalation compound is used as a negative electrode. A platinum net current collector 6 of positive electrode is placed on the lower part of a Teflon container 8, then a positive electrode 5, a porous polypropylene separator 4 containing electrolyte, and a negative electrode 3 are placed thereon in order, and a platinum net current collector 2 for negative electrode is placed thereon, then the container 8 is fastened to form a battery.

Description

[Detailed Description of the Invention] LL Utate ■ Yu 11 The present invention has high energy density, low self-discharge,
The present invention relates to a non-aqueous solvent secondary battery with a long one-night life and good charge/discharge efficiency (Coulombic efficiency).

A so-called polymer battery using a polymer compound having a conjugated double bond in its main chain as an electrode is expected to be a high energy density secondary battery.

Many reports have already been made regarding polymer batteries, such as B.J. Nigley, G.N.
of the chemical society.

Chemical Communication, 1979, No. 59
4 pages (Pl, Nigrey at al, J, C, S
,, Cheap, Co+uun,.

594), Journal Electrochemical Society, 1981, p. 1651 (J
, Electrochem, Soc, -Mon 381
1651), JP-A-56-136469, JP-A No. 57
-121168, 59-3870, 59-38
No. 72, No. 59-3873, No. 59-196566, No. 59-196573, No. 59-203368,
No. 59-203369 and the like can be mentioned as a part of this.

In addition, there have already been proposals to use polyaniline, which is obtained by oxidative polymerization of aniline, which is a type of conjugated polymer, as an electrode for aqueous or non-aqueous solvent batteries (
Polymer pre-prep fluids such as A.G. Mac Diarmid. Volume 25, number 2. Page 248 (1984
) [A, G, HacDiarmidat al.
Polymer Preprints, 25. N
o, 2.248 (1'J84)], Sasaki et al., Abstracts of the 50th Electrochemical Society Box Meeting, 123 (1983)
, Electrochemical Society Tsutsu 51st Conference Abstracts East, 228 (198
4) ).

I'm going to do it.

Oxidized polymers of aniline compounds are produced by oxidative polymerization methods such as electrochemical polymerization and chemical polymerization. but,
Since the oxidized stone aggregates of aniline compounds produced by these methods are obtained in a somewhat oxidized state,
When an oxidized polymer is used as it is or after being treated with an alkali for a positive electrode of a battery, the doping level is about 50 mol% at most, making it difficult to obtain a secondary battery with higher energy density.

The inventors have proposed that as a way to increase the doping level,
A method has already been proposed in which an oxidized polymer of an aniline compound is chemically reduced with a reducing agent and then used as a positive electrode (Japanese Patent Application No. 247985/1985).

According to this method, it is possible to increase the doping level of the oxidized polymer of the aniline compound and improve the energy density of the battery.
) low self-discharge, (iii) B charge/discharge efficiency, and (iv)
It has not always been possible to simultaneously satisfy long cycle life.

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

II゛Ruta No-1 The present inventors conducted five studies in 12 years in order to obtain a non-aqueous solvent secondary battery that satisfies the above four battery performances at the same time. By chemically reducing the oxidized polymer and then heat-treating it at a specific temperature range, the oxidized polymer is used as the primary active material.
The inventors have discovered that the charging capacity (1) of an oxidized polymer of an aniline compound can be significantly improved, and that a secondary battery can be obtained that extremely effectively achieves the above object, and has thus arrived at the present invention.

That is, the present invention uses a polyaniline compound for the positive electrode,
The negative electrode contains (i) a light metal, (ii) an alloy of light metals, (mountain) 8 conductive molecules, (iv) a complex of a light metal or an alloy of light metals and a conductive polymer, or (v) a non-aqueous material using an intercalation compound. In the solvent secondary battery, the +1ri polyaniline compound is an oxidized polymer of an aniline compound represented by the following general formula C1, and after the oxidized polymer is chemically reduced with a reducing agent, the temperature is reduced to 100°C to 400°C. The present invention relates to a non-aqueous solvent secondary battery that is heat-treated in a temperature range of .

[In the formula, R+, R2, R3 and R1 may be the same or different and represent a hydrogen atom, an aruyl group having 1 to 10 carbon atoms, or a flukoxy group having 1 to 10 carbon atoms. ] The oxidized 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.

Typical examples of aniline compounds represented by the above general formula include aniline, ortho- or meta-toluidine, xylidine, ortho- or meta-anisidine, 2.5-dimethoxyaniline, 2.5-jethoxyaniline, 3.5-dimethoxy Examples include aniline, 2,6-dimethoxyaniline, etc., but it is preferable to use aniline from the viewpoint of obtaining a non-aqueous solvent secondary battery with high energy density.

Oxidized polymers of aniline compounds can be produced by either electrochemical polymerization or chemical polymerization.

When electrochemical polymerization is used, the aniline compound is polymerized by anodic oxidation. For that purpose, for example 1
A current density of ~207 WA/32 is used. Most are 1
A voltage of ~300 μ is applied.

The polymerization is preferably carried out in the presence of an auxiliary liquid in which the aniline compound is soluble. For this purpose, water or a polar organic solvent can be used, preferably in an aqueous solution.

Although there is no particular restriction on the suitable pH of the Ti electrolyte, the pH is preferably 3 or less, particularly preferably 2 or less. p
Specific examples of acids used to adjust H include 1-1cfJ,
HBF4, CF3 C0OH, H2804 and HNO
Examples include, but are not limited to, three examples. When using a solvent that mixes with water,
A small amount of water may be added. Suitable organic solvents are alcohols, ethers such as dioxane or tetrahydrofuran, acetone or acetonitrile, benzonitrile, dimethylformamide or N-methylpyrrolidone.

Polymerization is carried out in the presence of a complexing agent. This includes BFi, AsF:, ASFi as anions.

3b Fi, Sb Cρ-, PFii, CJIOi.

means a salt containing a group of

These salts can be used as cations such as H”
), quaternary ammonium cations, lithium ions, sodium ions or potassium ions. The use of compounds of this type 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 20 to 100 mol% of the anionic complexing agent. The oxidized polymer of the aniline compound obtained by this method is a complex compound with the corresponding anion.

When producing an oxidized polymer of an aniline compound by a chemical polymerization method, the aniline compound can be polymerized in an aqueous solution using a strong acid such as hydrochloric acid and an inorganic peroxide. Among the inorganic peroxides, ammonium persulfate is preferred. According to this method, the oxidized polymer is obtained in the form of a fine powder. Since a salt is present in this method as well, the oxidized polymer is a complex compound with the corresponding anion.

In addition, in both the electrochemical polymerization method and the chemical polymerization method, other additives, such as carbon black, def1con powder, polyethylene glycol, polyethylene oxylide, etc., are added to the polymerization electrolyte and polymerized. It is also possible.

The oxidized polymer of the aniline compound thus obtained is then chemically reduced with a reducing agent, but before reducing the oxidized polymer of the aniline compound, the oxidized polymer is
! Preferably, compensation is provided by an f group.

Bases used for this compensation include inorganic bases such as aqueous anhydride, sodium carbonate, potassium hydroxide, and sodium hydroxide, and organic bases such as lower aliphatic amines such as triethylamine. Ammonia water is preferred.

The method of chemically reducing the oxidized polymer of the aniline compound supplemented with a base with a reducing agent is not particularly limited, but usually, the oxidized polymer is immersed in a solution of the reducing agent,
A method of applying stirring or 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 preferred, and phenylhydrazine and hydrazine are particularly preferred.

There is no particular limit to the use of the reducing agent m, a, IJ, but usually, for each nitrogen atom contained in the oxidized polymer of the aniline compound,
In order to give one atom of hydrogen, it is preferably used so that the number of atoms is 1.5 to 3 times that of the nitrogen atom contained in the oxidized polymer. The time required for the reduction reaction is usually several tens of minutes to several hours, and in most cases, a reaction time of 2 to 3 hours is sufficient. The reduction reaction proceeds quickly enough even at room temperature, so
Although heating is not particularly required, the reduction reaction may be carried out under heating if necessary. After the completion of the reduction reaction, the oxidized polymer of the aniline compound is thoroughly washed with the same solvent as the reaction solution to remove the reducing agent, and then heated in a temperature range of 100 to 400°C, preferably in a temperature range of 200 to 400°C. The heat treatment is particularly preferably performed at a temperature range of 200 to 350°C. When the heat treatment temperature is lower than 100° C., impurities such as moisture and low molecular weight substances are sufficiently removed.

Furthermore, if the heat treatment temperature is higher than 400°C, the oxidized polymer will deteriorate, which is not preferable. The heat treatment may be performed either in an inert gas atmosphere or under vacuum.

Taking polyaniline as an example, the oxidized polymer of the aniline compound that has been subjected to the reduction treatment and the heat treatment (hereinafter referred to as the oxidized polymer of the treated aniline compound) is one of the following formula (I). The leucoemeraldine structure of the formula (I[) in which the meraldine structure is reduced or the reduced state of 13i!i between the formula (I) and the formula (IF>) is 5
It has a structure containing 0 mol% or more.

(I) (If) This treated oxidized polymer of aniline compound can obtain the remarkable effects of the present invention even when used alone as a positive electrode, but the treated oxidized polymer of aniline compound ijl
In order to further increase the conductivity and strength, it is preferable to use the oxidized polymer in combination with a conductive agent and a binder.

To illustrate, examples of the conductive agent include carbon black, acetylene black, metal powder, and metal 1111.
! , script fiber, etc. In addition, as a binder,
Polyethylene, modified polyethylene, polypyrene, poly(tetrafluoroethylene), ethylene-propylene-dieneter polymer (EPDM), sulfonated EP
Examples include thermoplastic resins such as DM.

The amount of the conductive agent to be blended is 5 to 30 parts by weight, preferably 5 to 20 [1 part] based on 100 parts by weight of the treated oxidized polymer of aniline compound. If the amount of the conductive agent is less than 5 parts by weight, the conductivity of the electrode will not increase significantly, and if the amount of the conductive agent is more than 30 parts by weight, the oxidized polymer of the treated aniline compound in the electrode will The weight is smaller,
It is disadvantageous in terms of energy density.

The blending amount of the binder is 2 to 20 parts by weight, preferably 5 to 1 part by weight, per 100 parts by weight of the oxidized polymer of the treated aniline compound. If the amount of the binder is less than 2 parts by weight, the electrode will easily collapse, which is not preferable. Furthermore, if the amount of the binder exceeds 20 parts by weight, the electric 31 degree of the electrode decreases and is disadvantageous in terms of energy density.

As a method for producing a composite consisting of a treated oxidized polymer of an aniline compound, a conductive agent, and a binder, for example, a mixture consisting of a treated oxidized polymer of an aniline compound, a conductive agent, and a binder is prepared. Examples include a method of compression molding under pressure and heat.

The mixture at this time may be one kneaded with water or an organic solvent such as acetone, nibble alcohol, or xylene.

The pressure during compression molding is 10 to 10. OOONg/n2
It is preferable that it is within the range of . Moreover, the heating temperature during compression molding is preferably within the range of room temperature to 300°C.

The compression molding operation is preferably carried out under an inert gas atmosphere such as nitrogen gas or argon gas in order to prevent the treated oxidized polymer of the 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 before use as a positive electrode.

The negative electrode used in the nonaqueous solvent secondary battery of the present invention includes (i)
Light metals, (ii) alloys of light metals, (iii) conductive polymers, (iv) composites of light metals or alloys of light metals and conductive polymers, or (v) WJ intercalation compounds.

Two or more types of these negative electrodes may be used in combination.

Examples of (i) light metals used as the negative electrode of the non-aqueous solvent secondary battery include alkali metals such as lithium, sodium and potassium, aluminum, etc.;
Examples of light metal alloys include lithium-aluminum alloy,
Examples include lithium-zinc alloy, lithium-tin alloy, lithium-aluminum-magnesium alloy, and the like. Examples of the conductive polymer (iii) include boribiol and polypyrrole derivatives, polythiophene and polythiophene derivatives, polyquinoline, polyacene, polyvaracene, polyvaraphenylene derivatives, and polyacetylene. Furthermore, (iv) composites of light metals or light metal alloys and conductive polymers include composites of aluminum or lithium-aluminum-magnesium alloys and polyacetylene, polyparaphenylene or polyparaphenylene derivatives, and lithium-aluminum alloys. and polyacetylene, polyvaraphenylene, or a polyvaraphenylene derivative. The term "composite" as used herein refers to a homogeneous mixture of a light metal or an alloy of light metals and a conductive polymer, a laminate, and a modified product in which a base component is modified with another component. (V) An example of the intercalation compound is Fe2O3.

Among the above negative electrodes, (ii), (iii) and (i)
v) is preferred, and (iv) is particularly preferred.

An alkali metal salt is used as the 'Fi electrolysis supporting electrolyte of the non-aqueous solvent secondary battery of the present invention. Examples of the alkali metal of the alkali gold m salt include li, Na and K metals, preferably li gold metal.

support? [[Representative anion components of I include, for example, Cjl O; , PFi, As Fi, As
F″4゜803 CFi, BFi, and BRi
(However, R is an alkyl group having 1 to 10 carbon atoms or an aryl group).

Specific examples of alkali metal salts as supporting electrolytes include:
LiPFe, LiSbFa.

Li CjlOi, Li As Fa, CF380
3Li.

L, i BF4, L, i B (Bkl)4゜1i
B (El)2 (Bjl)z, Na PFs
.

NaBF4, NaAsFe, NaB
(BLI)4.

KB (Blj), 1. Examples include KAsFe, but are not necessarily limited to these. These alkali gold 1i11! ! may be used alone or in combination of two or more.

The concentration of the alkali metal salt varies depending on the type of oxidized polymer of the treated aniline compound used in the positive electrode, the type of cathode, charging conditions, operating temperature, type of supporting electrolyte, type of organic solvent, etc. cannot be specified, but is generally preferably within the range of 0.5 to 10 mol/1. The electrolyte may be homogeneous or heterogeneous.

Examples of the organic solvent C used alone or in combination as a solvent for the electrolyte of the non-aqueous solvent secondary battery of the present invention include the following.

Alkylene nitrile: Examples, crotonitrile (liquid range, -51.1°C to 120°C) two trialkyl borates, trimepuru borate, (Ct130)3B (liquid range, -29.3°C to 67°C) tetraalkyl Silicates: e.g., tetramethyl silicate, (C1130)4S
i (boiling point, 121°C) two ditroalkanes, nitromethane, C1h NO2 (liquid range, -17°C to 100.8°C)
Alkyl nitrile: e.g., acetonitrile, 0113ON
(Liquid range, -45°C to 81.6°C) Two dialkylamides, dimethylformamide, HCON (CH3)2 (Liquid range, -60,48°C to 149°C) Two lactams, N-methylpyrrolidone (Liquid range , -16℃~202℃) Two examples of monocarboxylic acid esters, ethyl acetate (liquid range,
-83,6~77,06℃) Two examples of orthoesters, trimethyl orthoformate, l-10 (OCH: + >3
(Boiling point, 103°C) Lactone: e.g., γ-butylactone dialkylnate, QC (OCH3)2 (Liquid range, 2-9
0℃) Alkylene carbonate: e.g., propylene carbonate, mono-, 1-thyl: e.g., diethyl ether (liquid range, -
116-34.5°C) polyether biside, 1.1- and 1.2-dimethoxyethane (liquid range, -113.2-64, 5°C, respectively)
and -58-83°C) Two examples of cyclic ethers, tetrahydrofuran (liquid range, -
65-61℃): 1,3-dioxolane (liquid range, -
95-78°C) Nido[1 Aromatic: Example, Nitrobenzene (Liquid range, 5.7-210.8°C) Aromatic carboxylic acid halide 2 examples, Benzoyl chloride (Liquid range, 0-210.8°C)
197°C), benzoyl bromide (liquid range, -24 to 21
8°C) Two aromatic sulfonic acid halides, benzenesulfonyl dichloride (liquid range, 14.5-251°C) Aromatic phosphonic acid dihalides: e.g., benzenephosphonyl dichloride (boiling point, 258°C) aromatic Thiophosphonic acid halides: e.g., benzene thiophosphonyl
Dichloride (boiling point, 124°C at 5M) (melting point, 22°C) 3-methylsulfolane (v&point, -1°C) Alkyl
Sulfonic acid halide: VA, methane sulfonyl
Chloride (boiling point, 161°C) Alkyl carboxylic acid halides: Examples, acetyl chloride (liquid range, -112 to 50.9°C), acedel bromide (
liquid range, -96 to 76°C), p[1-pionyl chloride (liquid range, -94 to 80°C), saturated heterocyclic compounds: e.g., tetrahydrolobofene (liquid range, -96 to 121°C): 3-noble 2-oxazolidone (melting point, 15.9°C) dialkyl sulfamic acid halide: e.g., dimethyl sulfur 7 mil
Ride (boiling point, 16-80°C) Alkyl halosulfonate: e.g., ethyl chlorosulfonate (boiling point, 151°C) Unsaturated? I ring carboxylic acid halides, 2 examples, chloride 2
-furoyl (liquid range, -2 to 173°C) five-membered unsaturated polycyclic compound: @, 1-methylpyrrole (boiling point, 114
℃), 2,4-dimethylthiazole (boiling point, 144℃)
, furan (liquid range, -85.65 to 31.36°C), esters of dibasic carboxylic acids and/or halides: e.g., ethyl oxychloride (boiling point, 135°C) mixed alkylsulfonic acid halides/ Carboxylic acid halides: Examples, chlorosulfonylacedel chloride (boiling point, 98°C at 10°C), two dialkyl sulfoxides, dimethyl sulfoxide (liquid range, 18°4-1
89℃) Two dialkyl sulfates, dimethyl sulfide (Liquid range, -31.75~188.5℃) Two dialkyl sulfites, dimethyl sulfide (
(boiling point, 126℃) two alkylene rylphites, nibrene gellicol
Sulfide (liquid range, -11~173℃) Two halogenated alkanes, methylene chloride (liquid range, -
95-40°C), 1,3-dichloropropane (liquid range, -9.5-120.4°C) Among the above, preferred organic solvents include sulfolane, crotonitrile, nitrobenzene, tetrahydrofuran, methyl-substituted tetrahydrofuran, .3-dioxolane, 3-methyl-2-oxazolidone, propylene or ethylene carbonate, sulfolane, γ-butyrolactone, ethylene glycol
Zulfite, dimethyl sulfide, dimethyl sulfoxide, and 1,1- and 1,2-dimethoxyethane, particularly preferably propylene carbonate and 1,2-dimethoxyethane, and sulfolane and 1,2-dimethoxyethane.
A mixed solvent of dimethoxyethane can be mentioned. This is because they are believed to be the most chemically inert towards battery components and have a wide liquid range, especially since they allow for high and efficient utilization of cathode active materials. It is.

In the non-aqueous solvent secondary battery of the present invention, the dopant concentration doped into the oxidized polymer of the treated aniline compound of the positive electrode is 0.00% per N atom in the oxidized polymer.
The amount is 2 to 1.0 mol, preferably 0.2 to 0.8 mol.

The fear of doping can be freely controlled by measuring the amount of electricity flowing during electrolysis. - Doping may be carried out under any method, such as under a constant current, under a constant voltage, or under conditions where the AT current and voltage vary.

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

In addition, some of the electrodes used in the non-aqueous solvent secondary battery of the present invention may react with oxygen or water and reduce the performance of the battery, so the battery should be sealed so that it is virtually free of charge. Oxygen and anhydrous conditions are desirable.

1. The non-aqueous solvent secondary battery of the present invention has a high energy level of 1! - It has high density, high charge/discharge efficiency, long cycle l, low self-discharge rate, and good flatness of voltage during discharge. In addition, the non-aqueous solvent secondary battery of the present invention is compact, compact, and has a high energy density, so it is suitable for use in portable hoeing equipment, electric vehicles, gasoline-powered vehicles, and power storage batteries.

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

Example 1 [Manufacture, reduction, and heat treatment of aniline oxidized polymer] Distilled water that had been deoxygenated in advance, HBF4, and aniline were added to a glass container, and the concentration of HBF4 was 1.5 T-L and the concentration of aniline was 0.35 mol. It was prepared so that 2 in aqueous solution
6c each at cm intervals! After charging the two platinum electrodes of R2, electrolysis was carried out at a current of 120 amperes/second.

At this time, a dark green oxidized polymer of aniline was deposited on the anode plate.

The coated anode was repeatedly washed three times with distilled water, and after air drying, the resulting aniline oxidized polymer film was peeled off from the platinum plate. This exfoliated oxidized polymer was immersed in 28% ammonia water, left overnight, and then soaked in distilled water for 30 minutes.
It was washed several times and then vacuum dried at 250°C for 15 hours.

The resulting reddish-purple film was dissolved in diethyl ether solution containing 1 g of phenylhydrazine under a nitrogen gas atmosphere.
It was placed in CC and subjected to ultrasonic vibration for 1 hour. Thereafter, the diethyl ether solution was removed, and the solution was washed with di-1-thyl ether under a nitrogen gas atmosphere until the quenching solution was no longer colored, further washed with 1,2-dimethoxyethane, and vacuum-dried at 250° C. for 15 hours. Elemental content of the obtained Ic gray-white film: 4
1'1fri has a tffi% of C+ H+ N of 99.
88%, and its composition ratio is C: 1'': N = 6
．． 00:5.07:0.9, indicating that the oxidized polymer of aniline as represented by the structure shown in the above formula (If) was in a completely reduced state.

[Production of film-like acetylene polymer]

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

This reaction vessel was cooled with liquid nitrogen, and the nitrogen gas in the system was exhausted using a vacuum pump. Next, this reaction vessel was
The solution was cooled to 0.degree. C., and while the catalyst solution remained stationary, purified acetylene gas was blown in at a pressure of 1 atmosphere.

Immediately, polymerization occurred on the surface of the catalyst solution, producing a film-like acetylene high polymer. Thirty minutes after the acetylene was added, the acetylene gas in the reaction vessel system was exhausted to stop the polymerization. After removing the catalyst solution with a syringe under nitrogen gas atmosphere,
Washing was repeated five times with 100 cc of purified toluene while maintaining the temperature at -78°C. The film-like acetylene polymer swollen with toluene was a uniform film-like swollen product with densely intertwined fibrils.

Next, this swollen product was vacuum-dried to obtain a reddish-purple film with a metallic luster, a thickness of 180 μm, and a cis content of 98%. Moreover, the height density of this film-like acetylene high polymer is 0.307/CC, and its electrical conductivity r! 1 (DC four terminal method) is 3゜2X 1G'S at 20℃
/α.

(Pond experiment) Above (manufacture, reduction, and heat treatment of aniline oxidized polymer)
The treated oxidized aniline polymer film obtained in step 1 was ground into a fine powder in an agate mortar under a nitrogen gas atmosphere. For every 100 parts of this fine powder, 8.0 ffl parts of carbon black and poly(tetrafluoroethylene')
>IQ, (11 parts) were blended and kneaded.The resulting mixture was compression molded under a nitrogen gas atmosphere using a tablet machine with a diameter of 20agφ at room temperature at a pressure of 10,000Kg/crm2 to form a composite. It was prepared and used as a positive electrode active material.The height density of this composite is 0.55 tJ/CC, and its electrical conductivity (DC four-terminal method) is 5.9x 1O-3 at 20°C.
It was S/as.

-・In the above (manufacture of film-like acetylene polymer), (1
Diameter 20IJwRφ from film-like acetylene polymer
The inner plate was cut and used as a negative electrode active material.

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

The figure is a schematic cross-sectional view of a battery for measuring the characteristics of a non-aqueous solvent secondary battery, which is a specific example of the present invention, in which 1 is a platinum lead wire for the negative electrode, 2 is a platinum lead wire for the negative electrode with a diameter of zoiuR, and an ao mesh. w4 Tokyo Electric Power Co., 3 is a disc-shaped negative electrode with C1 diameter of 20 mm, 4 is a circular porous polypropylene diaphragm with a diameter of 20 m, and is thick enough to be sufficiently impregnated with electrolyte, 5 is a disc-shaped with a diameter of 20 m Positive electrode, 6 G, L diameter 20 #1111180 mesh platinum wire mesh current collector for positive electrode, 7 is a positive electrode lead wire, 8 is a screw-in Teflon container.

First, the platinum wire mesh current collector 6 for the positive electrode is placed in a Teflon container 8.
Further, the positive electrode 5 is placed on the platinum wire mesh current collector 6 for the positive electrode, the porous polypropylene diaphragm 4 is placed on top of it, and after sufficiently impregnated with the electrolyte, the negative electrode 3 is placed on top of the positive electrode 5.
Furthermore, there is a platinum wire mesh for the negative electrode on top! ! The electric body 2 was placed at position a, and the Teflon container 18 was tightened to produce a battery.

The electrolyte was a mixed solvent of propylene carbonate and 1,2-dimethoxyethane that had been distilled and dehydrated according to a conventional method (
A 1.5 mol/1 solution of 1-iAsFe dissolved in a volume ratio of 1:1 was used.

Using the battery prepared in this way, an electrical surface with a doping amount of 60 mol% and 6 mol% for the positive and negative electrodes was obtained under a constant current (3.0 mA/rJ2) in an argon gas atmosphere. I drained it and charged it. After charging is finished,
When the battery was immediately discharged under a constant current (5,0 rrt A/cIR2) and when the battery voltage reached 1.OV, it was charged again under the same conditions as above. The number of repetitions of charging and discharging was recorded as 710 times before the discharge efficiency decreased to 50%.

Also, the energy density at the 5th repetition is 158W
-hr/icy, maximum charging efficiency is 100
%Met. Furthermore, when the battery was left charged for 60 hours, its self-discharge rate was 1.3%.

Comparative Example 1 In Example 1 [manufacture, reduction, and heat treatment of aniline oxidized polymer], the reduced 7 niline oxidized polymer was
Heat treated at ℃. Thereafter, a composite was obtained by compression molding in exactly the same manner as in Example 1, except that this treated oxidized aniline polymer was used.

[Battery experiment] was conducted in exactly 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 repetitions of charging and M-electricity was recorded as 537, and the energy density at the fifth repetition was 156.
At W-hr/K9, the maximum charge/discharge efficiency was 99%. Furthermore, when the battery was left charged for 60 hours, its self-discharge rate was 2.7%.

Comparative Example 2 In [Production, reduction, and heat treatment of oxidized aniline polymer] in Example 1, the oxidized aniline polymer was heat treated without being subjected to reduction treatment. A composite was produced in exactly the same manner as in Example 1, except that this heat-treated oxidized aniline polymer was used. [Battery experiment] was conducted in the same manner as in Example 1 except that this composite was used as the positive electrode active material. As a result, the maximum charging/discharging efficiency was only 83%, which was 39%.
The charging/discharging efficiency became less than 50% on the second occasion.

Example 2 [Manufacture, reduction, and heat treatment of aniline oxidized polymer] 400 cc of distilled water deoxygenated in advance and 10 ml of 42% HBF4 aqueous solution
0 cc was placed in a three-necked flask, and nitrogen gas was bubbled through it for about 1 hour while stirring. Thereafter, the inside of the system was placed under a nitrogen gas atmosphere, a thermometer and a condenser were attached, and the solution was heated to 40° C. with hot water.

Aniline 209 was then added to this. A solution of 46 g of ammonium persulfate dissolved in 200 cc of a 1N HC, 1L aqueous solution was added dropwise to this aniline aqueous solution with stirring over about 2 hours, and then the reaction was allowed to proceed at 40° C. for 3 hours.

After the reaction is completed, the dark green reaction liquid is filtered, and the obtained dark green aniline oxidized polymer is added to 500 cc of 28% ammonia water.
It was soaked in water and left overnight. After filtration, the aniline oxidized polymer was washed three times with 200 cc of distilled water and then vacuum dried at 80° C. for 15 hours. 1q of reddish-purple powder was 18g. 1.5 g of this reddish-purple powder was added to 50 cc of a solution of 3 LJ of phenylhydrazine in diethyl ether under a nitrogen gas atmosphere, stirred at room temperature for 1 hour, and then erased. Next, the solution was washed with diethyl ether until the solution became colorless, and further washed with 1,2-diphthyl thiecene, and vacuum-dried at 235° C. for 2 hours. The element system analysis value of the gray-white powder obtained was that the weight percent of C+14 +N was 99.1.
8%, and its composition ratio is C: II: N = = 6
．． 00:5.01:0.98.

[Battery experiment]

[Manufacture, reduction, and heat treatment of aniline oxidized polymer]
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 Example 1 was used. The height density of the obtained composite is 0.56 g/c
c, and its electrical conductivity (DC four-terminal method) was 4.1xlO-''S/cj+ at 20°C.

A battery experiment was conducted 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 repetitions until the charging/discharging efficiency decreased to 50% was recorded as 801 times. The energy density of this battery is 157W-hr/Ng, and the maximum charge/discharge efficiency is 1
It was 00%. When the battery was left charged for 60 hours, its self-discharge rate was 1.5%.

Comparative Example 3 In Example 2 [manufacture, reduction, and heat treatment of aniline oxidized polymer], the reduced aniline oxidized polymer was heated to 80°C.
heat treated. Thereafter, a composite was obtained by compression molding in exactly the same manner as in Example 1, except that the prepared oxidized aniline polymer was used.

A battery experiment was conducted 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 repetitions until the charging/discharging efficiency decreased to 50% was recorded as 520 times. The energy density of this battery is 1
56W-hr/Kg, and the maximum charge/discharge efficiency is 9
It was 9%. Furthermore, when the battery was left charged for 60 hours, the self-discharge rate was 3.1%.

Example 3 In Example 1, instead of the acetylene polymer used for the negative electrode, Bridge of the Chemical Society, Vol. 51 was used.

Page 2091 (1978) (Bull, Che
ll, Soc, Japan.

51, 2091 (1ri 78)), which was formed into a disk shape of 1 tb φ (containing 10% carbon black), was used as the negative electrode. A battery experiment was conducted in exactly the same manner as in Example 1. As a result, the number of repetitions until the charging/discharging efficiency decreased to 50% was recorded as 198 times. The energy density of this battery is 153W-h
r/Kg, and the maximum charge/discharge efficiency was 100%. Further, when the battery was left charged for 60 hours, its self-tll current rate was 1.5%.

Example 4 A battery was prepared in exactly the same manner as in Example 1, except that a Li-A1 alloy (atomic ratio of 1:1) was used as the negative electrode instead of the acetylene polymer used in the negative electrode. experiment] was conducted. As a result, the number of repetitions until the charging/discharging efficiency decreased to 50% was recorded as 839 times. The energy density of this battery was 203 W-hr/Npi, and the maximum charging efficiency was 100%. When the battery was left charged for 60 hours, its self-discharge rate was 1.1%.

Example 5 In Example 1, instead of the acetylene high polymer used for the negative electrode, polyparaphenylene and 1-Al1 alloy used in Examples 3 and 4 were mixed so that the If ratio was 8:2. did. A battery experiment was conducted in exactly the same manner as in Example 1, except that a composite (containing 10% carbon black) formed by molding this mixture into a disk shape of 204111φ at a pressure of 1 ton/C1n2 was used as the negative electrode. . As a result, the number of repetitions until the charging/discharging efficiency drops to 50% is:
He recorded 903 times.

The energy density of this battery was 178 W-hr/Kg, and the maximum charge/discharge efficiency was 100%. When the battery was left charged for 60 hours, its self-discharge rate was 1.1%.

[Brief explanation of drawings]

The figure is a schematic cross-sectional view of a battery cell for measuring characteristics of a non-aqueous solvent secondary battery, which is a specific example of the present invention. 1... Platinum lead wire for negative electrode 2... Platinum wire mesh current collector for negative electrode 3... Negative electrode

Claims (1)

[Claims] A polyaniline compound is used for the positive electrode, and (i) a light metal, (ii) an alloy of light metals, (iii) a conductive polymer, and a negative electrode.
(iv) A composite of a light metal or an alloy of light metals and a conductive polymer, or (v) In a non-aqueous solvent secondary battery using an intercalation compound, the polyaniline compound is an aniline compound represented by the following general formula. A non-aqueous solvent secondary, which is an oxidized polymer, and the oxidized polymer is chemically reduced with a reducing agent and then heat-treated at a temperature of 100 to 400°C. battery. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2, R_3 and R_4 may be the same or different, and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a carbon number 1 to 10 alkyl group. Indicates an alkoxy group. ]