JPS6243065A - Nonaqueous secondary battery - Google Patents

Abstract

PURPOSE:To increase energy density and reduce self discharge by forming a nonaqueous secondary battery with a positive electrode obtained by heat- treating at a specified temperature a polymer prepared by oxidation- polymerization of specified aniline compound. CONSTITUTION:A polymer prepared by oxidation-polymerization of an aniline compound indicated in the general formula shown in the right is heated at 100-500 deg.C, and used in a positive electrode. In the formula, R1, R2, R3, and R4 are hydrogen atom, alkyl group in which the number of carbon is 1-10, or alkoxy group in which the number of carbon is 1-10, and they may have different or the same atoms or groups. The positive electrode is combined with a polyacetylene negative electrode and an electrolyte comprising LiPF8 and organic solvent to form a nonaqueous secondary battery. By removing water, oligomer, and impurities contained in the polymer by heat-treatment, battery performance such as charge-discharge efficiency is increased.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention has high energy density, low self-discharge,
The present invention relates to a non-aqueous secondary battery that has a long cycle life and good charging and lightning efficiency (Coulombic efficiency).

[Prior Art 1 A so-called polymer battery in which a polymer compound having a conjugated double bond in its main chain is used as a Ti electrode is expected to be used as a high energy density secondary battery.

Many reports have already been made regarding polymer batteries, for example, P. G. Nigley et al., Journal of the Chemical Society, Chemical Communication, 1979.

Page 594 (P, J, Nigrey et al., J, C, S,
, ChemCommun, 1979.594)
, Journal Electrochemical Society,
1981, p. 1651 (J, EIectroch
em, Soc, 1981.1651), JP-A-56-136469, JP-A-57-121168, JP-A-59-3870, JP-A-59-3872, JP-A-59-38.
No. 73, No. 59-196566, No. 59-19657
No. 3, No. 59-203368, No. 59-203369
This can be cited as part of the list.

In addition, there have already been proposals to use polyaniline obtained by oxidative polymerization of aniline as an electrode for aqueous or non-aqueous batteries (A.G. Matsuku Diamide et al., Polymer Prebrief, Vol. 25, No. 2.Page 248 (1984)〈＾G, HaCDlar
mid etc., Polymer Preprints, 2
5゜NO, 2, 248 (1984)>, Sasaki et al., Proceedings of the 50th Conference of the Electrochemical Society, 123 (1983)
, Abstracts of the 51st Annual Meeting of the Electrochemical Society, 228 (19
84) ).

[Problem to be Solved by the Invention 1] Oxidized polymers of aniline compounds are obtained by electrolytic polymerization or chemical polymerization in an acidic aqueous solution, so they contain water, and in particular, in chemical 1, It is often obtained in a form containing oligomers that are soluble in the solvent used in the electrolyte solution of non-aqueous solvent secondary batteries. Moreover, there is also a possibility that oxidizing agents, Oj products, etc. remain. However, it is difficult to completely remove water, oligomers, and other impurities contained in oxidized polymers of aniline compounds using normal cleaning methods, making it difficult to obtain pure oxidized polymers of aniline compounds. It's hot.

Therefore, a polymer battery using such an oxidized polymer of an aniline compound as a positive electrode has (1) high energy density, (11) low self-discharge, (iii) high charge/discharge efficiency, and (1v) long cycle life. I haven't been able to find anything that satisfies both.

[Means for Solving the Problems] As a result of intensive study in order to obtain a secondary battery that satisfies the above four battery performances at the same time, the present inventors found that a heat-treated oxidized polymer of an aniline compound can be used for the positive electrode. By,
It was discovered that a secondary battery that satisfies the above four battery performances at the same time can be obtained, and the present invention was achieved.

That is, the present invention provides a non-aqueous secondary product characterized in that a treated product obtained by heat-treating an oxidized polymer of an aniline compound represented by the following general formula at a temperature of 100°C or more and 500°C or less is used as a positive electrode. Regarding batteries.

3 R4 [In the formula, R+, R2, R3J'5 and R4 may be different or the same and are 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.

Representative examples of aniline compounds represented by the above general formula include aniline, 2-methoxy-aniline, 3-methoxy-aniline, 2.3-dimethoxy-aniline, 2.5
-dimethoxy-aniline, 2,6-dime] to 4-cyaniline, 3,5-dimethoxy-aniline, 2-■toxy-3-methoxyaniline, 2,3,5-trimethoxy-
Aniline, 2,3-dimethyl-aniline, 2.3,5.
Examples include 6-titramethyl-aniline, and among these, aniline is most preferred.

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 2~
A current density of 20 mA/a2 is used. Most are 10~
A voltage of 300 volts is applied.

The polymerization is preferably carried out in the presence of an auxiliary liquid in which the aniline compound is soluble. Water or polar organic solvents can be used for this purpose. When using a water-miscible solvent, a small amount of water may be added. Good organic solvents are alcohols, ethers such as dioxane or tetrahydrofuran, at! [-N or acetonitrile, benzonitrile, dimethylformamide or N-methylpyrrolidone.

Polymerization is carried out in the presence of a compounding agent. This includes BFi, ΔS Fi, and ASFii as anions.

5bFi, SbC! J-, PFii, CρOj.

H80i, and a salt containing a 5042- group. The resulting oxidized polymer is a complex compound with the corresponding anion.

These salts contain as cations, for example, quaternary ammonium cations, lithium cations, sodium cations or potassium cations.

The use of compounds of this type is known and is not the subject of the present invention.

When producing an oxidized polymer of an aniline compound by a chemical method, for example, the aniline compound can be polymerized in a strong acid aqueous solution with an inorganic peroxide such as potassium persulfate. According to this method, an oxidized polymer of an aniline compound is obtained in the form of a fine powder. Since an anion is also present in this method, the oxidized polymer of an aniline compound is a complex compound with the corresponding anion.

The oxidized polymer of the aniline compound thus obtained may be heat-treated as it is, but it is preferable to perform the heat treatment after an alkali treatment.

The heat treatment in the present invention means applying heat to the oxidized polymer of the aniline compound to remove water, oligomers, and other impurities contained in the oxidized polymer of the aniline compound.

The heat treatment temperature of the oxidized polymer of the aniline compound is 100
℃ to 500℃, preferably 100℃ to 3
The temperature is below 00℃. The heat treatment temperature of aniline compounds is 1
If the temperature is lower than 00℃, the cycle life will be longer and the self-t
It is not possible to obtain a secondary battery with a low li charge rate. On the other hand, if the heat treatment temperature is higher than 500° C., the oxidized polymer of the aniline compound will deteriorate, making it difficult to obtain a secondary battery with good performance.

Although the heat treatment may be performed in air, it is preferable to perform the treatment under an inert gas atmosphere such as nitrogen or argon, and more preferably in vacuum.

The heat treatment time depends on the type of oxidized polymer of the aniline compound,
Since it varies depending on the processing temperature, etc., it cannot be determined generally, but it is generally preferred that the time is within the range of 5 to 20 hours.

Molded bodies that can be used as positive electrodes can be obtained by various methods. For example, in the case of anodic oxidation of an aniline compound, the compound is complexed with anions to form a polymer that takes the form of the anode used.

If the anode has a flat shape, a flat layer of polymer will be formed. When using the manufacturing method of oxidized polymer fine powder of aniline compound, use this y! The i-powder can be compacted into a shaped body by known methods under pressure and heat. Temperatures from room temperature to 300° C. and pressures from 50 to 150 bar are often used. According to this known method for producing oxidized polymers of anionic complexed aniline compounds, molded bodies of arbitrary shapes can be obtained. For example, moldings in the form of thin films, plates or three-dimensional shapes are used.

The negative electrode used in the 41 water secondary battery of the present invention is not particularly limited, and examples include polypyrrole and polypyrrole derivatives,
Conductive polymers such as polydiophene and polythiophene derivatives, polyquinoline, boriacene, polyvaraphenylene, polyacetylene, granoite, T! 32, alkali metals such as lithium, sodium, lithium aluminum, or alloys thereof, and composites of the above-mentioned conductive polymers and alkali metals or alloys thereof. Among these, preferred are polyacetylene, polyparaphenylene, lithium-aluminum alloy, and a composite of a conductive polymer and an alkali metal or its alloy.

The oxidized polymer of aniline compound and the conductive polymer used as the electrode of the non-aqueous secondary battery of the present invention may include other suitable conductive materials such as carbon black, acetylene, etc. Black, metal powder, gold f1 fiber, carbon fiber, etc. may be mixed.

Further, it may be reinforced with a thermoplastic resin such as polyethylene, modified polyethylene, polypropylene, poly(tetrafluoroethylene), ethylene-propylene dieneter polymer (EPDM), or sulfonated EPDM.

Examples of paid solvents that can be used or mixed as a solvent for the electrolytic solution of the non-aqueous secondary battery of the present invention include the following.

Alkylene nitriles: Examples, crotonitrile (liquid range, -51.1°C to 120°C) two examples of trialkyl borates, trimepuru borate, (CH30) 3 B (liquid range, -29.3°C to 61°C) 1-Laalkyl silic-1 to 2 pieces, tetrametyl silicate, (CH30) 4
Si (boiling point, 121 °C) nitroalkanes: e.g., nitromethane, CH3NO2 (liquid range, -17 °C to 100.8 °C) alkyl nitriles, e.g., acetonitrile, Cl-13CN
<Liquid range, -45°C to 816°C) Dialkylamide:
Example, dimethylformamide, HCON (CH3)2 (liquid range, -60,48°C to 149°C) (liquid range,
-16°C to 202°C) Monocarboxylic varnish resistance: e.g., ethyl acetate (liquid range, -836°C to 7706°C) Orthoester: e.g., trimethyl orthoformate, )
-1c C00 day 3〉3 (boiling point, 103°C) (liquid range, -42 to 206°C) 1 to 1 example of dialkyl carbonate, dimethyl carbonate, QC(OCH3)2 (liquid range, 2-90°C) Alkylene carbonate: Examples, propylene car (liquid range, -48 to 242°C), two monoethers, dieplyether (liquid range, -116 to 34.5°C), two polyethers, 1.1- and 1.2-dimethoxyethane. (liquid range, -1132~64.5℃, respectively)
and -58-83°C) cyclic ethers: e.g., tetrahydrofuran (liquid range, -
65-67°C): 1,3-dioxolane (liquid range, -
95-78°C) 2 nitroaromatics, nitrobenzene (liquid range, 57-2108°C) 2 aromatic carboxylic acid halides, benzoyl chloride (
(liquid range, 0 to 197°C), benzoyl bromide (liquid range, -24 to 218°C), two aromatic sulfonic acid halides, benzenesulfonyl chloride (liquid range, 14.5 to 251°C), diaromatic phosphonic acid Two halides, benzene phosphonyl dichloride (boiling point, 258°C) Aromatic thiophosphonic acid dihalide: Example, benzene thiophosphonyl dichloride boiling point, 124°C at 5I+llll) (melting point, 22°C) 3-methylsulfolane (melting point, - 1℃) 2 alkyl sulfonic acid halides, methane sulfonyl chloride (boiling point, 161℃) Alkyl carboxylic acid halides: Examples, acetyl chloride (liquid range, -112 to 509℃), acetyl bromide (liquid range, -96 ~76°C), propionyl chloride (liquid range, -94 to 80°C), two saturated heterocyclic compounds, tetrahydrothiophene (liquid range, -96 to 121°C): 3-methyl-2-oxazolidone (melting point, 159°C) ) Dialkyl sulfamic acid halides, dimethyl sulfamyl chloride (boiling point, 80°C at 16M) Alkyl halosulfonates, e.g., ethyl chlorosulfonate (boiling point, 151°C) Unsaturated heterocyclic carboxylic acid halides: e.g., 2-chloride Furoyl (liquid range, -2 to 173°C) five-membered unsaturated heterocyclic compound; e.g., 1-methylvinyl (boiling point, 114°C
), 2,4-dimebrubuazole (boiling point, 144°C),
Furan (liquid box! ITI, -85,65~31.36℃
), Methyl and/or halides of dicarboxylic acids: e.g., ethyl oxalyl chloride (boiling point, 135°C) Mixed alkylsulfonic acid halides/carboxylic acid halides: e.g., chlorosulfonylacetyl chloride (boiling point, 10°C) #I at 98°C) 2 dialkyl sulfoxides, dimethyl sulfoxide (liquid range, 184-1
89℃) Dialkyl sulfate: e.g., dimethyl sulfide (liquid range, -3L75~1885℃) 2 dialkyl sulfites, dimethyl sulfide (boiling point, 126℃) 2 alkylene sulfites, ethylene glycol
Sulfide (liquid range, -11~173°C) Halogenated alkanes: e.g., methylene chloride (liquid range, -173°C)
95-40°C>, 1,3-dichloropropane (liquid range, -995-120.4°C) Preferred organic solvents include sulfolane, crotonitrile, nitrobenzene,
Tetrahydrofuran, methyl substituted tetrahydrofuran,
1,3-dioxolane, 3-methyl-2-oxazolidone, propylene or ethylene carbonate, sulfolane, γ-butyrolactone, ethylene glycol sulfide, dimethyl sulfide, dimethyl sulfoxide, and 1,1- and 1,2-dimethoxyethane. This is because they are believed to be the most chemically inert towards battery components and have a wide liquid range, especially since they make the cathode active materials highly advanced and thus available for efficient use. be.

Typical cation components of the supporting electrolyte used in the electrolyte of the nonaqueous secondary battery of the present invention include, for example, metal cations of metals with a Pauling electronegativity value of not exceeding 16, or metal cations with the general formula R4-xMHx.゛ or R3E+ (However, R is an alkyl group having 1 to 10 carbon atoms or an aryl group, M is N, P or As atom, E is 0 or S atom,
X is an integer from O to 4). Further, typical anion components of the supporting electrolyte include, for example, C10: and PFi.

△sF″8. AS Fi, 803 CFi, BF
i, and BR'4 (wherein R is an alkyl group having 1 to 10 carbon atoms or an aryl group).

A specific example of the supporting electrolyte is 1iPFe.

1 i Sb Fa , Li CN 04 , Li
AsFs.

CF3 SOa Li , Li BF4 , Li B
(Bu)4゜Li B (Et)2 (E3u)
2, NaPFe.

NaBF4. NaASFe, NaB (BLI) 4゜KB
Examples include (Bu)4, KA3Fa, etc., but are not necessarily limited to these. These supporting electrolytes may be used alone or in combination of two or more.

The concentration of the supporting electrolyte depends on the type of oxidized polymer of the aniline compound used in the positive electrode, the type of cathode, charging conditions, operating temperature,
Although it cannot be defined unconditionally because it varies depending on the type of supporting electrolyte and the type of organic solvent, it is generally 0.
It is preferably within the range of 5 to 10 mol/liter. The electrolyte may be homogeneous or heterogeneous.

In the non-aqueous secondary battery of the present invention, the amount of the dopant doped into the oxidized polymer of the aniline compound is 20 to 100 mol %, preferably 20 to 100 mol %, based on 1 mol of the oxidized polymer. There is 80 mol% r.

Dope suspension can be freely controlled by measuring the amount of electricity flowing during electrolysis. The doping can 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 made of synthetic resin such as polyethylene or polypropylene or natural fiber paper may be used as the diaphragm.

In addition, some types of [i] used in the non-aqueous secondary battery of the present invention may react with oxygen or water and reduce the performance of the upper reservoir, so the battery should be sealed and substantially Oxygen-free and anhydrous conditions are desirable.

[Effects of the Invention] The non-aqueous secondary battery of the present invention, which uses a heat-treated oxidized polymer of an aniline compound as a positive electrode, has high energy density and high charge/tlil electrodynamics. The nonaqueous secondary battery of the present invention has good cycle life, low self-absorption rate, and good voltage flatness during discharge.Furthermore, the nonaqueous secondary battery of the present invention is light and small, and has high energy density. Ideal for portable equipment, electric automatic vehicles, gasoline automatic vehicles, and power storage batteries.

[Example 1] Hereinafter, the present invention will be explained in further detail by giving Examples and Comparative Examples.

Example 1 (Production and treatment of aniline oxidized polymer) In a glass container, 11121! i! Wooden distilled water, HBF4,
Aniline was added to adjust the concentration of HBF4 to 157 mol and the concentration of aniline to 0.35 mol. Two platinum electrodes of 6 cr each were placed in the aqueous solution at a distance of 2 cm, and then electrolysis was carried out with an electric current of Φ120 ampere-second while stirring. At this time, a dark green oxidized polymer was deposited on the anode plate.

The coated anode was repeatedly washed three times with distilled water, and after drying, the resulting oxidized aniline polymer film was peeled off from the platinum plate. The peeled oxidized polymer was immersed in 28% aqueous ammonia and stirred overnight, washed three times with distilled water, and then vacuum-dried at 250° C. for 15 minutes.

The elemental analysis value of the treated product of the oxidized aniline polymer treated in this way was C: 7938 in weight percent.
, T+: 5.10, N: 15.30, and the composition ratio is C:H:N-605:463:
1.00, which was a fairly high tgA degree.

(It! Production of tertiary acetylene polymer) 1.7 d in a glass reaction vessel with an internal volume of 500 ini under nitrogen atmosphere
A catalyst solution was prepared by adding titanium tetrabutoxide, dissolved in 30-methyl anisole, and then adding 2.7-me 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
℃, and while keeping the catalyst solution stationary, purified acetylene gas at a pressure of 1 atm was blown into the solution.

Immediately, polymerization occurred on the surface of the catalyst solution, producing a film-like acebulene high polymer. Thirty minutes after the introduction of acetylene, the acetylene gas in the reaction vessel system was exhausted to stop the polymerization. Invasion in which the catalyst solution was removed with a syringe under nitrogen atmosphere, -7
It was washed repeatedly with 100 d of purified toluene 5 times while maintaining the temperature at 8°C. The film-like acetylene polymer swollen with toluene was a uniform film-like swollen product in which fibrils were tightly intertwined. Next, this swollen product was vacuum-dried to obtain a membranous acylene high polymer having a metallic luster, a reddish-purple color, a thickness of 180 μm, and a cis content of 98%. In addition, the bulk density of this film-like acetylene polymer is 0.30 g/cc, and its electrical conductivity (DC four-terminal method) is 32 x 10-
It was 90-1.cl-1.

(Battery experiment) Disks with a diameter of 20 IRM were cut out from the treated aniline oxidized polymer film and the membranous acetylene polymer obtained by the above method, and used as active materials for the positive and negative electrodes, respectively. was configured.

The figure is for measuring the characteristics of a non-aqueous secondary battery, which is a specific example of the present invention. This is a new schematic diagram of the S pond cell, in which 1 is a platinum lead wire for the f'4 pole, 2 is a platinum wire mesh current collector for the negative electrode with a diameter of 20 m and 80 meshes, 3 is a disk-shaped negative electrode with a diameter of 20 m, and 4 is diameter 2
0gg circular porous polypropylene diaphragm, thick enough to be sufficiently impregnated with electrolyte, 5 has a diameter of 20J! 1
6 is a positive electrode platinum mesh collection with a diameter of 20 a 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.
The positive electrode 5 is placed in the lower part of the concave part, and the positive electrode 5 is placed on the platinum wire mesh current collector 6 for the positive electrode, and the porous polypropylene diaphragm 4 is placed on top of that, and after sufficiently impregnating with the electrolyte, the negative electrode 3 is placed in a small ,
Furthermore, a platinum wire mesh current collector 2 for a negative wire was placed on top of the current collector 2, and a Teflon container 8 was closed to produce a battery in one step.

The electrolyte was a mixed solvent of propylene carbonate and 1,2-dimethoxyethane (
A 1 mol/exchange solution of Li PFa dissolved in a volume ratio of 1:1) was used.

Using the Ti pond thus prepared, in an argon atmosphere, under a constant current (1.5 mA/a2), an electric current m corresponding to doping m of the positive electrode and negative electrode of 50 mol% and 6 mol%, respectively, was generated. I drained it and charged it. After charging is finished,
When we conducted a repeated charging/discharging test in which we discharged the battery directly under a constant current (2, OmA/c12), and when the battery voltage reached 1.0V, we charged it again under the same conditions as above. The number of repetitions of charging and discharging was recorded as 1210 times until the discharge efficiency decreased to 70%.

The energy density at the fifth repetition is 136W.
-hr/Ky, the highest charge/discharge efficiency was 100%. Also, when I left it charged for 63 hours,
Its self-discharge rate was 18%.

Example 2 [Manufacture and treatment of aniline oxidized polymer] Premer l152w
400 d of 1-element WS distilled water and 100 d of 42% HBF+ aqueous solution were placed in a 3-necked flask, and nitrogen gas was bubbled through the flask 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. Next, add 20 aniline to this
Added 9. To this aniline aqueous solution, 46 g of ammonium persulfate was added to 200 cc of a 1N HBF4 aqueous solution while stirring.
was added dropwise over about 2 hours, and then heated to 40
The mixture was allowed to react for 3 hours.

After the reaction, the dark green reaction solution was filtered, and the obtained llI
Add green aniline oxidized polymer to 28% ammonia water 500%
d and left overnight. After quenching, the aniline oxidized polymer was washed three times with 200 m of distilled water and then vacuum dried at 250°C for 15 hours.

The elemental analysis values of the IS treated aniline oxidized polymer are C: 79.36 and H: respectively in Shigenobu percent.
5.20, N: 15.28, and the composition ratio is C
:H2N= 6.06 : 4.73 : i, o
It was o.

[Battery experiment]

Molded product of the treated aniline oxidized polymer obtained by the above method (100N9/cj+2 pressure vacuum forming for 5 minutes, 10
[Battery experiment] was carried out in exactly the same manner as in Example 1, except that the positive electrode contained % carbon black). As a result, the number of repetitions until the charging/discharging efficiency decreased to 70% was recorded as 1081 times. The energy density of this battery was 132 W-hr/K9, and the maximum charge/discharge efficiency was 100%. Furthermore, when the battery was left charged for 63 hours, its self-discharge rate was 21%.

Example 3 In Example 1, instead of the acetylene high polymer used for the negative electrode, Putin of the Chemical Society of Japan, Vol. 51, p. 2091 (197
8th grade) (Bull. Chem, Soc, Jap
An, 51° 2091 (1978)), it was prepared by the method described in
[Battery experiment] was carried out in exactly the same manner as in Example 1, except that a 20-diameter disk formed under a pressure of on/cm2 was used as the negative electrode. As a result, the charge/discharge efficiency was 7.
The number of repetitions until it decreased to 0% was recorded as 1481 times. The energy density of this battery is 143 W-hr
/ Ks, and the maximum charge/discharge efficiency was 100%. Furthermore, when the battery was left charged for 63 hours, its self-discharge rate was 1.6%.

Example 4 In the same manner as in Example 1, except that instead of the acetylene polymer used in the negative electrode, L1-Al1 alloy (atomic ratio 1:1) was used for the negative electrode. battery experiment) was conducted. 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 is 210W-hr/! I and i
^Charge/discharge efficiency was 100%. Also, when left charged for 63 hours, the self-discharge rate was 1.4%.
Met.

Examples 5 to 6 and Comparative Examples In Example 1, the battery experiment was carried out in exactly the same manner as in Example 1, except that the heat treatment temperature for oxidative polymerization of aniline used in the positive electrode was changed as shown in the table.

As a result, the number of repetitions until the charge/discharge efficiency drops to 70%, energy density, maximum charge/discharge efficiency, charge (1
The self-discharge rate for 63 hours was as shown in the table.

table

[Brief explanation of drawings]

The figure is a schematic cross-sectional view of a battery cell for measuring characteristics of a non-aqueous secondary battery, which is an integral 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 non-aqueous secondary product characterized in that a treated product obtained by heat-treating an oxidized polymer of an aniline compound represented by the following general formula at a temperature of 100°C to 500°C is used as a positive electrode. battery. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2, R_3 and R_4 may be different or the same, and are hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, or hydrogen atoms having 1 to 10 carbon atoms. 10 alkoxy groups. )