JPS62180957A - Secondary cell with nonaqueous solvent - Google Patents

Abstract

PURPOSE:To attain properties such as high energy density and low self- discharge, by adding an electroconductive agent and a binder to an oxidized polymer of an aniline compound chemically reduced by a reducing agent, to make a positive electrode for a secondary battery having a nonaqueous solvent. CONSTITUTION:A positive electrode is made of a complex material having an electric conductivity of 10<-4>S/cm or more and comprising a binder, an electroconductive agent and an oxidized polymer of an aniline compound chemically reduced by a reducing agent and represented by a formula wherein R1-R4 denote the same thing or different things, which are a hydrogen atom, an alkyl group of 1-10 in number of carbon atoms or an alkoxy group of 1-10 in number of carbon atoms. The positive electrode is combined with a negative electrode of a light metal, a light metal alloy, an electroconductive high- molecular substance or the like to constitute a secondary cell having a nonaqueous solvent. The secondary cell is thus made of the complex material of high electric conductivity and provided with high energy density, low self- discharge, high charge/discharge efficiency and long cycle life.

Description

[Detailed description of the invention] The present invention has high energy density, low self-discharge,
The present invention relates to a non-aqueous solvent secondary battery with a long cycle 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, for example, BJS, Ibley et al., Journal of the Chemical Industry, Chemical Communication, 1979.

Page 594 (P.J., Nigrey et al.
J.C.S., Chem.

C0mm1In,, 1979 594), Di1-Inu Lu, T-Rekl-Lochemical Tree Adi, 1
981, No. 1651 (J, Electrochem)
, S, oc, , -υ381 1651 ) , 11f
No. 56-13G469, No. 57-121168,
No. 59-31370, No. 59-3872, No. 59-
No. 3873, No. 59-196566, No. 59-1.9
No. 6573, No. 59-203368, No. 59-203
No. 369 can be cited 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 batteries [A.G.・Preblinz, Volume 25, Number 2. Page 248 (1984) [A, G, HacDiarmide at,
PolyIler Prepr+nts, 25. N
o, 2.248 (1984)], Sasaki et al., Proceedings of the 50th Conference of the Electrochemical Society, 123 (1983),
Proceedings of the 51st Conference of the Electrochemical Society, 228 (1911
14) ).

Oxidized polymers of aniline compounds are produced by oxidative polymerization methods such as electrochemical polymerization and chemical polymerization. but,
Oxidized polymers 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. Therefore, a method has been proposed in which an oxidized polymer of an aniline compound is chemically reduced in advance using a reducing agent and then used for the positive electrode. However, the oxidized polymer of the reduced aniline compound obtained by this method has a low electrical conductivity of 10'510n or less, and when a conductive agent is added,
Even if the conductivity is increased to IQ-48/cm or higher, (+)
No material has been obtained that simultaneously satisfies high energy density, (ii) low self-discharge, (iii) high charge/discharge efficiency, and (iV) long cycle life.

Therefore, an object of the present invention is to overcome the drawbacks of the conventional secondary batteries using oxidized polymers of aniline compounds as positive electrodes, and to achieve high energy density, low self-discharge, long cycle life, and rechargeable batteries. - To provide a non-aqueous solvent secondary battery with good discharge efficiency.

As a result of intensive study to obtain a non-aqueous solvent secondary battery that simultaneously satisfies the above four battery performances, the inventors of the present invention have found that the oxidized polymer of the aniline compound is chemically reduced with a reducing agent in advance. Then, by adding an appropriate conductive agent and a binder to this oxidized polymer to form a highly conductive composite, this is used as a positive electrode active material to increase the charge capacity of the oxidized polymer of aniline compound. It has been discovered that a secondary battery can be obtained which is greatly improved and achieves the above objectives very effectively,
We have arrived at the present invention.

That is, according to the present invention, an aniline-based compound represented by the following general formula that has been chemically reduced with a reducing agent and has an electrical degree of 1O-
Using a composite of 4S/cm or more as a positive electrode, (i) I! 1. A non-aqueous solvent secondary battery characterized in that a negative electrode is made of a metal alloy, (iii) a conductive polymer, or (1v) a light metal or a composite of a light metal alloy and a conductive polymer. is provided.

In the 2RI 3R4 C formula, R+, R2, R3 and R4 may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy 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-dime-1- Examples include xyaniline and 2,6-dimethoxyaniline, but aniline is preferably used 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 ~20 mA/cm2 is used. In most cases, a voltage of 1 to 300\l is applied.

The procedure is preferably carried out in the presence of an auxiliary liquid in which the aniline compound is soluble. For this purpose, water or polar I3
Although a solvent can be used, it is preferably carried out in an aqueous solution.

The pl+ of a suitable electrolytic solution is not particularly limited, but 111N is preferably 3 or less, particularly preferably 2 or less. 1] As a specific example of the acid used for adjusting 11, HC
ρ, HBF4, CF3 C0OH, H2804 and H
Examples include NO3, but are not particularly limited to these. When using a solvent that mixes with water, a small amount of water may be added. Suitable organic solvents are alcohols, ethers such as dioquiline or de-1-lahydrofuran, acetone or acetonitrile, benzoni-1-helyl, dimethylbormamide or N-methylpyrrolidone.

Polymerization is carried out in the presence of a complexing agent. This includes BF, As Fi, and ASFi as anions.

Sb Fi, Sb C1! -, PFii
, CηOl.

It means a salt containing ζ1 of 0.

These salts contain cations such as pro1-(+-
1”), quaternary ammonium cation, lithium ion,
Contains sodium or potassium ions. The use of compounds of this type is known and is not a counter-stain of the present invention. These compounds are usually used when 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 amorphous peroxide. Preferred among the amorphous peroxides is ammonium perammonium. 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 electrochemical polymerization and chemical polymerization, it is also possible to add other additives to the polymerization electrolyte, such as carbon black, Teflon powder, polyethylene glycol, polyethylene oxide, etc. It is.

When producing an oxidized polymer of the reduced aniline compound used in the positive electrode of the non-aqueous solvent secondary battery of the present invention, it is preferable to compensate the oxidized polymer with a base in advance.

The bases used in this MA include aqueous ammonia, sodium carbonate, hydrium hydroxide, sodium hydroxide, and other non-I11 bases, lower aliphatic amines such as triethylamine, etc. Among these, Anjonia water is preferred.

The method of chemically reducing the oxidized polymer of the aniline compound compensated with a base using a reducing agent is not particularly limited, but usually the polymer is immersed in a solution of the reducing agent and then stirred or ultrasonically applied. A method of providing imaging is adopted.

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

There is no particular restriction on the amount of the reducing agent used, but it is preferable that the amount of nitrogen contained in the oxidized polymer of the aniline compound is usually 1 atom of hydrogen for each 1 atom of nitrogen contained in the oxidized polymer of the aniline compound. 1.5 to 3 [Δ nuclear power is used. The time required for the reduction reaction is usually several tens of minutes to several hours, and in many cases, one hour is sufficient3.The reduction reaction proceeds quickly even at seedling temperature, so
Although zero heat is not required, the reduction reaction may be carried out under heating if necessary. After the reduction reaction is completed, the oxidized polymer of the aniline compound is thoroughly washed with a solvent of the same type as the reaction solution to remove the unifier, and then dried.

The electrical conductivity of the oxidized polymer of the aniline hazardous compound chemically reduced with the reducing agent thus obtained is 1O-4S/c.
A secondary battery that simultaneously satisfies the four battery performances mentioned above has a low value of m-vortex-free, and when only the oxidized polymer of the 7-component aniline compound is used as the positive electrode, the strength is low. is not obtained.

Therefore, in the present invention, an oxidized polymer of reduced aniline compound is mixed with a conductive agent and a bonding agent. If a conductive agent and a binder are not used together, the significant effects of the present invention cannot be obtained. Examples of the Vl) fiI agent used in the present invention include carbon black, acetylene black, metal powder, metal fiber, and carbon fiber. Also,
As a binder, polyethylene, modified polyethylene, polypropylene, poly(tetrafluoroethylene), ethylene-propylene-diene polymer (EPDM),
Examples include thermoplastic resins such as sulfone-7 EPDM.

The amount of the conductive agent is preferably 5 to 20 parts by weight per 100 parts by weight of the oxidized polymer of the reduced aniline compound (the number of affected areas is 5 to 10 parts). If the conductive agent is less than 1O-4S/cm, it is not preferable.If the amount of the conductive agent is more than 20m, the weight of the oxidized polymer in the electrode will decrease, and the energy density will decrease. This is disadvantageous in some respects.

The blending amount of the binder is 2 to 20 parts by weight, preferably 5 to 10 parts by weight, based on 100 parts by weight of the reduced oxidized polymer of the aniline compound. If the amount of the binder is less than 2 parts by weight, the electrode tends to collapse, which is not preferable. If the amount of the binder exceeds 20 parts by weight, the electrical conductivity of the electrode will decrease, and this will be disadvantageous in terms of energy density.

As a method for producing a composite consisting of an oxidized polymer of a reduced aniline compound, a conductive agent, and a binder, for example, a mixture consisting of an oxidized polymer of a reduced 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 obtained by kneading water or a potent solvent such as acetone.

The pressure during compression molding is 10-10,0OOK9/c
The heating humidity during compression molding is preferably within the range of room temperature to 300°C.

The compression molding operation is preferably carried out under an atmosphere of an inert gas such as nitrogen gas or argon gas in order to prevent the 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.

If the electrical conductivity of the composite obtained by blending the oxidized polymer of the reduced aniline compound with a conductive agent and a binder and molding it is less than 10-48/'Cm, it is not sufficient to use it as a positive electrode. does not show satisfactory battery performance. The reason is not clear, but it is thought that the voltage during charging increases and the electrolyte decomposes, etc., and the charging density increases to 1TI'.
This phenomenon is remarkable when LΔ/cm2 or more.

t! used in the non-aqueous solvent secondary battery of the present invention! The J pole is (
,i) 'F! Gold metal (ii) Alloy of light metal, (i
ii) "A conductive polymer or (1v) a composite of a light metal or an alloy of light metals and a conductive polymer."

Used as a gi electrode in the above non-aqueous solvent secondary battery (1)
Examples of light metals include alkali metals such as lithium, sodium and potassium, aluminum, etc. (ii)
Examples of light metal alloys include lithium-aluminum alloy, lithium-zinc alloy, lithium-tin alloy, and the like. (iii) Examples of the conductive polymer include polypyrrole and polypyrrole derivatives, polythiophene and polythiophene derivatives, polyquinoline, boriacene, polyparaphenylene and polyparaphenylene derivatives, polyacetylene, and the like. In general, (iv) a composite of a light metal or an alloy of light metals and a conductive polymer,
Examples include composites made of aluminum and polyacetylene, polyparaphenylene, or polyparaphenylene derivatives/conductors, lithium-aluminum alloys, and composites made of gold and polyacetylene, polyparaphenylene, or polyparaphenylene derivatives. The term "composite" as used herein refers to a uniform mixture of a light metal or an alloy of light metals and a conductive polymer, a laminate, and an ice-decorated body in which a base component is modified with another component.

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

As the supporting electrolyte of the electrolyte solution of the non-aqueous solvent secondary battery of the present invention, an alkaline gold salt is used. Examples of the alkali metal of the alkali metal salt include li, Na and K metals, preferably 1 metal.

Typical anion components of the supporting electrolyte include, for example, C
uOi, PFi, △S Fi, As Fi.

803 CFi, BFi, and BRli (However, R
is an alkyl group having 1 to 10 carbon atoms or an aryl group)
etc. can be mentioned.

Specific examples of alkali metal salts as supporting electrolytes include:
l-i Pl”e, li 31) Fa.

Li CfJ 04, Li As Fo, CF38
03 Li.

Li BF4, Li B (BLI) 4.

Li B (Eth (BLI)2, Na PF
Q.

NaBF4, NaAsFa,
Na B (Bll)4.

KB (Bu)4. Examples include KAs Fe, but are not necessarily limited to these. These alkali metal salts may be used alone or in combination of two or more.

The concentration of alkali metal salt depends on the type of composite used for the positive electrode,
54i! depending on the type of shade, charging conditions, operating humidity, type of supporting electrolyte, type of organic solvent, etc. Therefore, it is not possible to make a general rule 1-, but in general, 1. tO,5~1
It is preferably within the range of 0 mol/p. The electrolyte may be homogeneous or heterogeneous.

Examples of the gM solvents 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: e.g., chloro-1-nitrile (liquid range, -51,1°C to 120°C) Trifurkyl borate: e.g., trimyl borate, (CI-430) 38
(Liquid range, -29.3°C to 67°C) Two tetraalkyl silicates, tetramethyl silicate, (CH30)
4 Si (boiling point, 121°C) nitroalkane: e.g.
Nido-O-methane, CH3NO2 (liquid range, -17°C to 100.8°C) alkylni-1-lyl: e.g., acetonitrile, CH3CN
(Liquid range, -45°C to 81.6°C) Dialkylamide: Example, dialkylamide, HCON (CH3)2 (Liquid range, -60,48°C to 149°C) Two lactams, N-methylpyrrolidone monocarbon Acid esters: e.g. ethyl acetate (liquid range,
-83,6~7706°C) Two orthoesdels, to trimethylorthoforme-1, 1''C (○C1-13)3
(Boiling point, 103°C) Lactone: Example, γ-butyrolactone dialkyl carbonate 2 examples, dimethyl carbonate, QC (OCI-13) 2 <Liquid range, 2-90
°C) 2 alkylene carbonates, propylene carmonoether: example, diethyl ether (liquid range, -116 to 34,5 °C) 2 polyethers, 1,1-3 and 1,2-dimethoxyethane (liquid range, -113, 2 to 64 respectively.
5°C J'3 and -58~83°C> Two cyclic ethers, detrahydrofuran (liquid range, -65~67°C): 1.
3-Dioxolane (liquid range, -95 to 78°C) Nitroaromatics: e.g., nitrobempine (liquid range, 5.7 to 210.8°C) Aromatic carboxylic acid halides: e.g., benzoyl chloride, liquid range, 0 to 191°C), benzoyl bromide (liquid range, -24 to 218°C), two aromatic sulfonic acid halides, benzenesulfonyl chloride (liquid range, 14.5 to 251°C), aromatic phosphonic acid dihalide :Example, benzenephosphonyl dichloride (boiling point, 258°C), two aromatic thiophosphonic acid dihalides, benzene thiophosphonyl dichloride (boiling point, 124°C at 5#) (melting point, 22°C) 3-methylsulforane (melting point, -1°C) Alkyl sulfonic acid halides: e.g., methane sulfonyl chloride (boiling point, 161°C) Alkyl carboxylic acid halides: e.g., acetyl chloride (liquid range, -112 to 50,9°C), acetyl bromide (
Liquid range, -96 to 76°C), propionyl chloride (liquid range, -94 to 80°C), two saturated heterocyclic compounds, tetrahydrodiophene (liquid range, -96 to 121°C): 3-methyl-2 -Oxazolidone (melting point, 15,9°C) dialkyl sulfamic acid halides: e.g. dimethyl sulfamyl chloride (boiling point, 80°C at 16M) 1-2 alkyl halosulfones, edyl chlorosulfonate (boiling point, 151°C) unsaturated Heterocyclic carboxylic acid halides: e.g., 2-furoyl chloride (liquid range, -2 to 173°C), two five-membered unsaturated heterocyclic compounds, 1-methylvirol (boiling point, 114°C)
, 2.4-dimethylthiazole (boiling point, 144°C),
Furan (liquid range, -85,65 to 31,36 °C), esters and/or halides of dibasic carboxylic acids: e.g., ethyl oxalyl chloride (boiling point, 135 °C), mixed alkylsulfonic acid halides/carboxylic acids Two halides, chlorosulfonylacedel chloride (boiling point, 98°C at 10 mm) dialkyl sulfoxides: e.g., dimethyl sulfoxide (liquid range, 184-1
89°C) 2 dialkyl sulfates, dimethyl nalphate (liquid range, -31,75~1f18.5°C) 1-2 dialkyl sulfites, sitatyl sulfide (boiling point, 126°C) Alkylene sulfide: e.g., ethylene glycol
Sulfide (liquid range, -11 to 173°C) Halogenated alkanes: e.g., methylene chloride (liquid range, -173°C)
95-40°C), 1,3-dichloropropane (liquid range, -919.5-120.4°C): , 1 Among the above, preferred! Solvents are: sulfolane, crotonitrile, nitrobenzene, terahydrofuran, methyl-substituted detrahydrofuran, 1,3-dioxolane,
Particularly preferred are 3-methyl-2-oxazolidone, propylene or ethylene carbonate, sulfolane, gamma-nibutyrolactone; ethylene glycol sulfide, sitatyl sulfide, dimethyl sulfoxide, and 1,1- and 1,2-dimethoxyethane. Examples include mixed solvents of propylene carbonate and 1,2-dimethoxyethane, and sulfolane and 1,2-dimethoxyethane. This is because these are thought to be the least inactive towards battery components,
This is also because they have a wide liquid range, and they also allow active substances to be used highly and efficiently.

In the non-aqueous solvent secondary battery a5 of the present invention, the dopant i~ doped into the R1 polymer of the aniline compound in the positive electrode composite is as follows:
The amount is 0.2 to 1.0 mol, preferably 0.2 to 0.8 mol.

The doping temperature can be freely controlled by measuring the amount of electricity that flows during electrolysis. The doping may be carried out either under constant current, constant voltage or under varying conditions of current and voltage.

In the present invention, if necessary, a porous membrane A5 natural fiber N paper made of synthetic resin such as polyethylene or polypropylene may be used as the diaphragm.

Furthermore, 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. ! It is desirable that the water be in a substantially oxygen-free and water-free state.

The non-aqueous solvent secondary battery of the present invention has high energy density, high charge/discharge efficiency, long cycle life, low self-discharge rate, and good voltage flatness during discharge. It is. Furthermore, the non-aqueous solvent secondary battery of the present invention is lightweight, compact, and has a high energy density, making it ideal for portable equipment, electric vehicles, gasoline vehicles, and power storage batteries.

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

Example 1 [Production and treatment of aniline oxidized polymer] In a glass container,
Add pre-deoxygenated distilled water, HBF4, and aniline, and
The concentration of BF4 is 1.5 mol, and the concentration of aniline is 0.35.
The sea urchin was prepared in moles. Two platinum electrodes of 6 cm2 each were placed with a spacing of 2 cm in the aqueous solution, followed by electrolysis with an electric fi of 120 ampere-seconds while stirring. On this occasion,
A dark green oxidized polymer of aniline was deposited on the anode plate.

The coated anode was washed three times with distilled water, and then the aniline oxidized polymer film formed was peeled off from the platinum plate. The peeled oxidized polymer was soaked in 28% ammonia water. After being immersed in water and left overnight, the sample was washed three times with distilled water, and then vacuum-dried at 80°C for 15 hours.

A diethyl ether solution containing 1 J of phenylhydrazine dissolved in 10% of the damaged reddish-purple film was prepared under a nitrogen gas atmosphere.
It was hung in CC and subjected to ultrasonic vibration for 1 hour. After the corrosion, the diethyl ether solution was removed, and the solution was washed with diethyl ether under a nitrogen gas atmosphere until it was no longer colored, and then washed with 1,2-xyethane, and heated at 80°C for 15 minutes.
Vacuum dried for hours.

The element b) digit value of the obtained gray-white film is C+ 1-
(The weight percent of 10N is 99.88%, and its composition ratio is C
:H: N= 6.00: 5.07: 0
．． 99, indicating that the aniline oxidation polymer represented by the formula shown below was in a completely reduced state.

[Production of film-like acetylene polymer]

A catalyst solution was prepared by adding 1.7 cc of titanium tetrabutoxide to a glass reaction vessel with an internal volume of 500 cc under a nitrogen gas atmosphere, dissolving it in 30 cc of anisole, and then adding 2.7 cc of triedylaluminum 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
Cool to ℃, keep the catalyst solution stationary, and blow purified acetylene gas at a pressure of 1 atm/υ.

Immediately, proper polymerization occurred on the surface of the catalyst solution, and a film-like acetylene high polymer was produced. Thirty minutes after the introduction of acetylene, the acetylene gas in the reaction vessel system was exhausted to stop the polymerization.

After removing the ts 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 membrane-like acetylene polymer polymer treated with toluene was a uniform membrane-like swollen product in which fibrils were tightly intertwined.

Next, this Pf3-hydrated 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%. In addition, the height density of this film-like ethylene polymer is 0.30 y/cc, and its electrical conductivity (DC four-terminal method) is 3.2X 10' at 20°C.
It was S/ctrr.

[Battery experiment]

The reduced oxidized aniline polymer film obtained in the above (Production and Processing of Oxidized Aniline Polymer) 1) was ground into fine powder in an agate mortar under a nitrogen gas atmosphere. For 100 ffl ffi parts of this fine powder, 8. 1 part of O heavy and 1 part of poly(tetrafluoroethylene) were blended and kneaded in the presence of a small amount of acetone. The obtained hydrogen mixture was compressed for 10 minutes at room temperature using a tablet machine with a diameter of 20 mφ under a nitrogen gas atmosphere.
．． A composite was produced by compression molding at a pressure of 000 kg/cm 2 , and then vacuum-dried at 150° C. for 15 hours to obtain a positive electrode active material. The height density of this polymer is 0.55g/cc
Its electrical conductivity (DC four-terminal method) is 6 at 20°C.
．． It was 5X 1O-3S/ctn.

On the other hand, from the film-like acetylene high polymer obtained in the above (manufacturing of film-like acetylene high polymer), a disk having a diameter of 20 ordinarily φ was cut and treated to obtain 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 cell for measuring the characteristics of a non-aqueous solvent secondary battery, which is an example of the present invention, in which 1 is a platinum lead wire for the negative electrode, 2 is a collection of platinum wire mesh for the negative electrode with a diameter of 20 mm and 80 meshes. Electric body, 3 is a disc-shaped negative electrode with a diameter of 20 mm, 4 is a diameter of 2
0. 5 is a circular porous polypropylene diaphragm that is thick enough to be sufficiently impregnated with electrolyte, and 5 has a diameter of 20. 6 is a platinum wire mesh current collector for the positive electrode with a diameter of 20 nra and 80 meshes, 7 is a positive electrode lead wire, and 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, and the porous polypropylene partition g14 is placed on top of the positive electrode 5, and after sufficiently impregnating with the electrolytic solution, the negative electrode 3 is placed in the lower part of the concave part. They were stacked one on top of the other, and the negative electrode platinum wire current collector 2 was further placed thereon, and the Teflon container 8 was tightened to produce a battery.

The electrolyte was dehydrated by distillation according to a conventional method.

1 of LiBF4 dissolved in a mixed solvent of propylene carbonate and 1,2-dimethoxyethane (volume ratio 1:1)
．． A 5 mol/1 solution was used.

Using the battery thus prepared, the battery was charged in an argon gas atmosphere under a constant current (5.0 mA 10 n2) by passing electric current corresponding to doping of the positive and negative electrodes to 60 mol% and 6 mol%, respectively. did. I'm jealous of the end of charging.
Immediately discharge the battery under a constant current (5,017 LA/ctn2>), and when the battery voltage reaches 1.OV, charge again under the same conditions as above.A repeated charge/rIl test was performed. The number of repetitions of charging and discharging was recorded as 1218 times before the efficiency decreased to 70%.

Also, the energy density at the 5th repetition is 158W
-hr/Kg, and the maximum charge/discharge efficiency was 100%. Also, when I left it charged for 60 hours,
Its self-discharge rate was 1.5%.

Comparative Example 1 The same procedure was carried out except that carbon black and poly(tetrafluoroethylene) were not added to the reduced oxidized aniline polymer obtained in Example 1 (manufacture and treatment of aniline oxidized polymer). Compression molding was performed in exactly the same manner as in Example 1 to obtain an aniline oxidation polymerized product. The height density of the obtained aniline oxidation polymerized form was 0.70 g/cc,
Its electrical conductivity (DC four terminal method) is 1O-6 at 20℃.
S/Cm or less.

A battery experiment was conducted in exactly the same manner as in Example 1, except that the molded body obtained by the above method was used as the positive electrode active material.

As a result, the number of repetitions of charging and discharging was recorded as 181 times, and the energy density at the fifth repetition number was 148W -
In hr/Kg, the maximum charge/tlil electrodynamics was 92%. Also, when I left it charged for 60 hours, the self-corrected sentence pattern rate was 21.2%.

Comparative Example 2 Example 1 [Production of oxidized polymer of aniline and! a 浬]
Oxidative polymerization of reduced aniline obtained in 1 water? Except that 8 parts of carbon black were added to 00 parts of W.
A composite was obtained by compression molding in exactly the same manner as in Example 1. The height density of the obtained composite is 0.65 g/CC, and its electrical conductivity (DC four-probe method) is 3.
It was 5X 10'S/on.

A 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 discharging was recorded as 320 times, and the energy density at the fifth repetition number was 150W・h.
r/l (9), the highest light/discharge efficiency was 96%. When the battery was left charged for 60 hours, the self-discharge rate was 21.0%.

Comparative Example 3 A composite was prepared in exactly the same manner as in Example 1, except that the aniline oxidation polymer was used without reduction treatment in the battery experiment of Example 1. 1. Electrical conductivity of the resulting composite The temperature (direct current four terminal method) was 8.1×10'S/ra+ at 20°C. i:F; :, yami training was performed in the same manner as in Example 1 except that this composite was used as the positive electrode active material. As a result, the charging/discharging efficiency was only 78% at Q high, which was 21%.
The charging/discharging efficiency became less than 50% on the second occasion.

Example 2 [Production and treatment of aniline oxidized polymer] 400 cc of distilled water deoxygenated in advance and 42% t-I B F 4 aqueous solution 1
00 cc was placed in a 1 north three-necked flask, and nitrogen gas was bubbled through it for about 1 hour while stirring.・After that, the system was placed under a nitrogen gas atmosphere, a thermometer and a two-inch reddenser were attached, and the solution was heated to 40°C with warm water.

Next, 20 g of aniline was added to this. Add to this aniline aqueous solution, with stirring, over 30 minutes! f-acid amiumium 469
200 cc of a 1N 88 F 4 aqueous solution (200 cc of 1 N 88 F 4 aqueous solution).
Allowed time to react.

After the reaction was completed, the green reaction solution was filtered to obtain 7j s.
Add green anilic acid monopolymer to 28% ammonia water 50%
It was immersed in 0 cc of water and left overnight. ) After rA, the 7-diphosphorylated polymer was repeatedly washed three times with 200 cc of distilled water and then vacuum-dried at 80° C. for 15 hours. The obtained reddish-purple powder was 187. 1.5 J of this reddish-purple powder was added to 50 cc of a solution of 3 g of phenylhydrazine in diethyl ether under a nitrogen gas atmosphere, stirred at room temperature for 1 hour, and then slaked. Next, the solution was washed with diethyl ether until the quenching solution became colorless, washed with 1,2-dimethoxyethane, and dried under vacuum at 80°C for 15 hours. Elemental analysis of the obtained gray-white powder (white indicates that the C+l-ray-N small group percentage is 9
91a%, and its composition ratio is C:H:N=6.00
: 5.01 : 0.98.

[Battery experiment]

[Preparation of aniline oxidized polymer): The composite was molded and dried in exactly the same manner as in Example 1, except that the powder of the reduced aniline oxidized polymer obtained in 1 and treatment) was used. (
It was. The bulk of the obtained composite 11 is 0.56 y/c
e, and its electrical conductivity (DC four-terminal method) was 4.1x 10'3/c 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 70% was recorded as 1018 times. The energy density of this battery was 157 W-hr, /N9, and the highest light/discharge efficiency was 100%. When the battery was left charged for 60 hours, its self-discharge rate was 1.8%.

Comparative Example 4 To 100 parts by weight of the reduced aniline oxidized polymer obtained in Example 2 (Seventh step of manufacturing method and treatment of aniline oxidized polymer), 10 parts of poly(tetrafluoroethylene) was added. A molded product was obtained by compression molding in exactly the same manner as in Example 1 except that part M was added. The height density of the obtained anilinic acid 1-hito synthetic form was 0.787,/CC, and its electrical conductivity (direct current four terminal method) was 10'S/cm at 20'C.

A battery experiment was conducted in the same manner as in Example 1, except that the molded body obtained by the above method was used as a positive electrode active material. As a result, the number of repetitions until the charging/discharging efficiency decreased to 70% was recorded as 211 times. The energy density of this battery is 1
43W・1) ""/KEI, and the maximum charge/discharge efficiency was 91%. When the battery was left charged for 60 hours, its self-discharge rate was 18.3%.

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

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

51, 2091 (1978)).
Except that the negative electrode was formed into a 20 mφ disc shape (containing 10% carbon black) under a pressure of 2.
A battery experiment was conducted in exactly the same manner as in Example 1, and as a result, the number of repetitions until the charging/discharging efficiency decreased to 70% was recorded as 1007 times. The energy density of this battery was 153 W-hr/Kg, and the maximum charge/discharge efficiency was 100%. Also, it can last up to 60 hours while being charged.
When installed, the self-discharge rate was 1. It was G%.

In addition, the bulk density of polyparaphenylene is 0.57 g/C
C, and its electrical conductivity (DC four-terminal method) was 2.3x 1o-3s/cm at 20°C.

Example 4 A battery experiment was carried out in exactly the same manner as in Example 1, except that Li, tAj alloy (atomic ratio 1:1) was used as the negative electrode instead of the acetylene polymer used in Example 1. I did it. As a result, the number of repetitions until the charging/discharging efficiency decreased to 70% was recorded as 881 times. The energy density of this battery was 203 W·hr/K'J, and the maximum charging efficiency was 100%. Furthermore, when the battery was left charged for 60 hours, its self-discharge rate was 1.2%.

Example 5 In Example 1, instead of the acetylene high polymer used for the negative electrode, polyparaphenylene and Li-Al1 alloy used in Examples 3 and 4 were mixed at a weight ratio of 8:2. A battery experiment was conducted in exactly the same manner as in Example 1, except that a composite material (containing 10% carbon black), which was formed by molding this mixture into a disk shape of 20 mm diameter under a pressure of 1 ton/LJ2, was used as the negative electrode. Ta. As a result, the number of repetitions until the charging/discharging efficiency decreased to 70% was recorded as 1118 times.

The energy density of this battery was 178W-117Kg, and the maximum charge/discharge efficiency was 100%. Furthermore, when the battery was left charged for 60 hours, its self-fli power rate was 1.1%.

[Brief Description of the Drawings] The figure shows a non-aqueous solvent secondary ff1tli example of the present invention.
FIG. 2 is a schematic cross-sectional view of a battery cell for measuring the characteristics of q. 1... Platinum lead wire for negative electrode 2... Platinum wire current collector for negative electrode 3... Negative electrode

Claims (1)

[Scope of Claims] An oxidized polymer of an aniline compound represented by the following general formula chemically reduced with a reducing agent, a conductive agent, and a binder, and has an electrical conductivity of 10^-^4S/cm or more. A composite of (i) a light metal, (ii) an alloy of light metals, (iii) a conductive polymer, or (iV) a composite of a light metal or an alloy of light metals and a conductive polymer was used for the negative electrode. A non-aqueous solvent secondary battery characterized by: ▲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 are hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. represents an alkoxy group. ]