JPS6293864A - Nonaqueous solvent secondary battery - Google Patents

Abstract

PURPOSE:To make excellent electrode capacity achievable, by using an oxidative polymer of a specific aniline compound as the positive pole. CONSTITUTION:An oxidative polymer of an aniline compound to be secured by polymerizing the aniline compound expressed in a chemical formula (R1, R2 and R3 are a hydrogen atom, an alkyl group of 1-10 in carbon number or an alkoxy group of 1-10 in the carbon number) in a acid aqueous solution of less than pH3 consisting of a peroxide, a ferric ion and proton acid is used as the positive pole. A nonaqueous secondary battery to be formed with this polymer has high energy density, is excellent in charging and discharging efficiencies, long in cycle life, small in a self-discharge rate and, what is more, flatness in voltage at the time of discharging is very good.

Description

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

[Prior Art 1 A so-called polymer battery, in which a polymer compound having a conjugated divalent bond in its main chain is used as an electrode, is expected to be used as a high energy density secondary battery. Many reports have already been made regarding polymer batteries, such as B.G. Nigley et al., General of the Chemical Society, Chemical Communication, p. 594 (
1979) (P., J., Nigrcy et al., J.C.S.
,, Chen+, Con+u+un,, 1979
594); Journal Electrochemical
Society, p. 1651 (1981) (J,
Electrochem.

Soc,, 1981.1651), special fin U
No. 56-136469, No. 57-121168, Book 5
No. 9-3870, No. 59-3872, No. 59-387
No. 3, No. 59-196566, No. 59-196573
No. 59-203368, No. 59-203369, etc. can be mentioned as some of them.

In addition, there has already been a proposal to use polyaniline, which is produced by oxidative polymerization of aniline, which is a type of conjugated polymer, as an i-electrode in aqueous or non-aqueous batteries [A.G. Mido, etc., polymers, etc.
Preblinz, Volume 25, Number 2. Page 248 (H
fB 2nd year) <8, G, HacDiarmid et al., PO
IVmOr Preprints, 25 No. 2
．． 248 (1984)), Sasaki et al., Electrochemical Society Box 5
0th Conference Abstracts, 123 (1983); 51st Conference Abstracts for the Electrochemical Society, 228 <1984>).

Polyaniline can be prepared using electrochemical methods [A.■) Diaz and J.A. Logan et al., Journal Electrochemical Society.

Vol. 111, p. 111 (19130)] and chemical methods [Wilstäter and Droghi, Besozhi I
, Vol. 42, pp. 2147, 4118 (1909)], it is already known that ¥I ffi can be obtained using any of the h methods. It is also already known in chemical methods to polymerize aniline in an acidic aqueous solution using a peroxide.

[Problem to be Solved by the Invention 1] However, polymer batteries using conventionally known polymers as electrodes have problems such as (1) high energy density, (11) low self-discharge, and (iii) g-6 [efficiency d3]. U (iV)ff
It has not been possible to obtain a product that simultaneously satisfies the requirements for l''j cycle life.

Generally, when producing polyaniline industrially, chemical methods are more economically advantageous than electrochemical methods; however, in terms of satisfying the above four battery performance requirements, electrochemical methods are It is more preferable to use polyaniline produced in the above manner as an electrode. Therefore, among the companies concerned,
There has been a strong desire to produce polyaniline with excellent electrode performance by an economically advantageous chemical method. However, when polyaniline obtained by chemically polymerizing aniline with a peroxide and obtained by V,I was used for the electrode, a polymer battery satisfying the above four battery performances could not be obtained.

[Means for Solving the Problems] As a result of intensive studies in view of the above points, the present inventors found that, among chemical methods, aniline-based compounds are treated with an aqueous pro-1-3 acid solution having a pH of 3 or less. In the middle, peroxide contains iron (21Ji
The inventors have discovered that an oxidized polymer of an aniline compound obtained by adding (1q) ions (Fe2+) to T:M-forming tf1 exhibits particularly good electrode performance, and has arrived at the present invention.

That is, the present invention provides 1'1 by polymerizing an aniline compound represented by the following general formula in an acidic aqueous solution containing peroxide, iron (divalent) ions, and protonic acid with a pt of 13 or less.
The present invention relates to a non-aqueous solvent secondary battery characterized by using an oxidized polymer of an aniline compound as a positive electrode.

R2R.

3R4 [In the formula, R+, R2, R3, and R4 are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms] Aniline type used in 1TE14 of the battery in the present invention Oxidized polymers of compounds are made by combining aniline compounds with peroxides, iron (
2 (i! [i) pH 3 consisting of ions and protic acids
Obtained by polymerization in the following acidic aqueous solution.

Any aniline compound may be used as long as it is represented by the above general formula, and representative examples include aniline, 2-methyl-aniline, 2-■thyl-aniline, and 3-methyl-aniline.
Aniline, 3-■derluaniline, 2-methoxy-aniline, 2-ethoxy-aniline, 3-methoxy-aniline, 3-ethoxy-aniline, 2,3-dimethyl-aniline, 2,5-dimethylaniline, 2, 6-dimethoxyaniline, 2,5-dimethoxyaniline, 2゜5-dimethoxyaniline, 2,6-dimethoxyaniline,
3.5-dimethoxy-aniline, 2゜5-jethoxy-
Aniline, 2-Me(hexy-6-methyl-aniline, 2
-Ethoxy-5-medylaniline, 2,3,5-trimethylaniline, 2,3,5,6-titrameth V-cyaniline, and the like. Among these aniline compounds, it is preferable to use aniline from the viewpoint of obtaining a battery with high energy density.

Peroxides are not particularly limited, for example [large]
1! Mei Takayuki, radical polymerization (■), chemical doujinshi.

Any water-soluble material described on page 28 J may be used. Typical examples include inorganic peroxides such as potassium persulfate, am[nium persulfate, monohelium chlorate, potassium chlorate, hydrogen peroxide, etc.; In terms of what you get,
Ammonium persulfate and hydrogen peroxide are preferably used, and ammonium persulfate is particularly preferred.

The peroxide may be used in an amount equal to or more than the number of moles of the aniline compound, but is preferably 1.3 to 2 moles per mole of the aniline compound.

The iron(2(&) ion can be used as a salt. There are no particular restrictions on the salt, and any iron (divalent) ion may be used. For example, ferrous sulfate, ferrous chloride, etc. There is no particular restriction on the use ω of iron (divalent) ions, but it is 0.0001 per mole of the aniline compound.
H-0,1'E is preferred.

The aniline compound is prepared by placing it in an aqueous solution (1), but if necessary, it may be carried out by adding a solvent in which the aniline compound is soluble and miscible with water.
Alcohols, ethers such as dioxane or tetrahydrofuran, 711? +hen, acetonitrile, dimethylformamide, and N-methylpyrrolidone.

There are no particular restrictions on the butonic acid used in the polymerization solution.
Specifically, HC,1)04, HBF4.

HCj, CH30OF (5303t1.tl
2. Examples include SO4. During the use of bu1]tonic acid,
I) I+ of the polymerization solution is 3 or less, and usually it is sufficient that it is equal to or more than the number of moles of the aniline compound, preferably 2 to 3 times the number of moles of the aniline compound.
It is le.

If the IIH of the polymerization solution is 3 or less, there should be no problem, but it is preferably 1 or less. If I)+1 of the polymerization solution is higher than 3, it is not preferable because components soluble in various organic solvents will be produced in the resulting oxidized polymer of the aniline compound.

Polymerization is usually carried out by adding an aniline compound to the above protonic acid aqueous solution, and then adding peroxide and iron (divalent) ions, but is not necessarily limited thereto.

The processing temperature cannot be determined unconditionally since it varies depending on the type of peroxide used, but it is usually within the range of 0°C to 80°C. The polymerization time varies depending on the peroxide used and the polymerization temperature, but in general, after adding the peroxide,
It is sufficient to react for about 24 hours. Although the polymerization may be carried out in air, it is preferable to carry out the polymerization in an atmosphere of an inert gas such as nitrogen because other oxides are less likely to be produced as by-products.

The oxidized polymer of the aniline compound thus obtained by 19 is
411 is made into a powder made of anion-containing compound. A stand using an oxidized polymer as an electrode can be used by compression molding it under pressure and heat using a conventionally known method. Molding is often carried out under vacuum, using temperatures d3 of room temperature to 300° C. and pressures of 50 to 150 bar.

The oxidized polymer of an anionic compound obtained by forming a forceps compound with an anion may be used as it is as the positive electrode of the non-aqueous solvent secondary battery of the present invention, or the complexed anion may be chemically or electrochemically The material removed may be used as a positive electrode.

The negative electrode used in the nonaqueous solvent secondary battery of the present invention is particularly υj
Examples include, but are not limited to, polypyrrol and polypyrrole derivatives, polydiophene and polypyrrole derivatives, conductive polymers such as polyquinoline, boriacene, polyparaphenylene, polyacetylene, graphite, living room compounds such as Ti 82, lithium, sodium, ridium aluminum, etc. an alkali metal or an alloy thereof, the above-mentioned conductor 11a'! Examples include composites of i-molecules and alkali metals or their alloys, among which preferred are polyacetylene, polyparaphenylene, lithium-aluminum alloys, lightning conductive polymers and alkaline metals or alloys thereof, etc. I can give you a complex.

The oxidized polymer of aniline compound and the conductive polymer used as the electrode of the non-aqueous solvent secondary battery of the present invention include:
Other suitable conductive materials, such as carbon black, acetylene black, metal powders, metal fibers, carbon fibers, etc., may be mixed in, as is well known to those skilled in the art.

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

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

Alkylene nitrile: e.g., tri[]tonitrile (liquid range, -51.1°C to 120°C) 2 trialkyl borates, trimethyl borate, (C1-130) 3B (
Liquid range, -29.3°C to 67°C) Tel-La alkyl
Siligu 1-2 cases, silicic acid 11-lamedel, <0 to(:
+0) 4Si (boiling point, 121°C) nitroalkane: e.g.
Nitromethane, CH3NO2 (liquid range, -17℃ to 100.8℃)
Alkyl nitrile: e.g., acetonyl-lyl, Cl-ml
CN (liquid range, -45°C to 8186°C) dialkylamides: e.g., dialkylamides, HCON (CH3
) 2 (Liquid range, -60,48℃~149℃) Two lactams, N-methylpyrrolidone "-1111---- Cl-12-CH2-CH2-GO-N-CH3 (Liquid range, , -16°C to 202°C> Monocarboxylic acid ester: e.g., ethyl acetate (liquid range,
-83, 6 to 77, 06°C) 2 examples of ol-1 to esters, trimethyl orthoformate, I-(C(OCt-h)
3 (TF1 point, 103℃) Two lactones, γ-butyrolactone CH2-CH2-CH2-0-CO (liquid range, -42 to 206℃) Two dialkyl carbonates, dimethyl carbonate, QC(OCH3)2 (liquid range , 2-90°C) Alkylene carbonate: e.g., propylene carbonate, CH(CH3) CH2-0-CO-0 (liquid range, -
48-242°C) Two L-noethers, diethyl ether (liquid range, -116-34.5°C) Polyneedle: e.g., 1,1- and 1,2-dimethoxyethane (liquid range, -113,2-645 respectively) ℃
and -58-83°C) two cyclic ethers, tetrahydrofuran (liquid range, -
65-67°C): 1,3-dioxolane (liquid range, -
95-78°C) 2 examples of nitroaromatics, nitrobenzene (liquid range, 5.7-210.8°C) Aromatic carboxylic acid halides: e.g., benzoyl chloride (
Liquid range, 0-197°C), benzoyl bromide (liquid range, -24-218°C) Aromatic sulfonic acid halide: e.g., benzenesulfonyl chloride (liquid range, 14.5-251°C) Aromatic phosphonic acid 1 halide, benzene phosphonyl dichloride (boiling point, 258°C) Aromatic diophosphonic acid dihalide: e.g., benzene diphosphonyl dichloride (boiling point, 124°C at 5#) cyclic sulfone: e.g., sulfolane, CoCl-12 -CI-Le CH2-CVF6- SO2
(melting point, 22°C) 3-methylsulfolane (melting point, -1°C) Alkyl sulfonic acid halide: e.g., methane sulfonyl chloride (boiling point, 161°C) Two alkyl carboxylic acid halides, acedel chloride (liquid range, - 112-50.9℃), acedel bromide (
Liquid range, -96 to 76°C); Propionyl chloride (Liquid range, -94 to 80°C); Two examples of saturated heterocyclic compounds; Liquid range, -9G to 121°C); -4th: Rizolidone (melting point, 15.9°C) dialkyl sulfamic acid halide; e.g., dimethyl sulfonyl chloride (boiling point, 80°C at 16 zm) two alkyl halosulfonates, ethyl chlorosulfonate (boiling point, 151°C) Two saturated polycyclic carboxyl halides, 2-furoyl chloride (liquid range, -2 to 173°C), five unsaturated heterocyclic compounds: e.g., 1-methylvirol (boiling point, 114°C)
, 2.4-dimey=ludiazole (boiling point, 1.14°C)
, furan (liquid range, -85,65~31.36°C), two examples of esters and/or halides of 2t=i carboxylic acids, oxalyl chloride (boiling point, 135°C), mixed alkylsulfonic acid halides, / Two carboxylic acid halides, chlorosulfonylaredel chloride (boiling point, 10.98°C) dialkyl sulfoxide: e.g., dimethyl sulfoxide (liquid range, 18.4 to 98°C)
189℃) Dialkyl sulfate 1~: Example, dimethyl sulfide (liquid range, -31.75~188.5℃)
Two dialkyl sulfites, dimethyl sulfide (boiling point, 126°C) Alkylene sulfide: e.g., nibrene gellicol
Sulfide (liquid range, -11~173°C) Two halogenated alkanes, methylene chloride (liquid range, -
95 to 40°C), 1,3-dichloropropane (liquid range, -995 to 120.4°C) Preferred organic solvents for t5 above include sulfolane, chloronitrile, nitrobenzene, tetrahydrofuran, methanol-substituted tetrahydrofuran. , 1,3-dioxolane, 3-tablue 2-oxylyzolidone, propylene or ethylene carbonate,
Sulfolane, T-bubrolactone, ethylene glycol sulfide, dimethyl sulfide, dimethyl
sulfoxide, and 1,1-'3 and 1,2-dimethoxyethane τ. This is because these organic solvents appear to be the most chemically inert toward battery components and have a wide liquid range, and in particular they are highly and efficiently capable of dissolving cathode active materials. make available
) + tute・aru.

Typical cationic components of the supporting electrolyte used in the electrolyte of the J[water-solvent secondary battery of the present invention include, for example, metal cations of metals with a Pauling's electric negative value not exceeding 1.6. or the general formula is R4-8MHxl' or R:+
E' (However, 1< is an alkyl group having 1 to 10 carbon atoms, or aryl L1, M is an N, P or AS atom, "(yoO or [maS atom, X is an integer from O to 4)" Typical <ffi anion components of supporting electrolytes include, for example, C, QO
I, PFii.

△sFη, As F, SO3CFi, BF''
4. and BRi (However, [ has a carbon number of 1 to 10
an alkyl group or an aryl group).

A specific example of the supporting electrolyte is 1iPFe.

Li5bFe, 1-icfJOi, LiASFo.

CF33031-i, Li BF4, Li B (
Bu)4゜LiB(Ei)2 (Bu)2. NaPFo
.

NaBF4, NaAsFe, NaB
(Bu) 4.

Examples include, but are not necessarily limited to, KB (3u)4, KA3 [6'; 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 unambiguously expressed because it becomes +N depending on the type of support 'r\i solute and the type of right-eye solvent, etc.
In general, a pronation of 5-410'E/g is preferred.゛The electrolyte may be homogeneous or heterogeneous.

In the nonaqueous solvent secondary battery of the present invention, the concentration of the dopant doped into the sulfurized polymer of the 7-niline compound is 20 to 100% (le%) per mole of the repeating unit of the oxidized polymer.
and preferably 4O-100TJ nyl%.

The dope suspension can be freely controlled by measuring the amount of electricity flowing during electrolysis. Doping may be carried out either under constant current, constant voltage or under conditions of varying current and voltage.

In the present invention, if necessary, a porous membrane made of synthetic resin such as polyethylene or polypropylene or natural fiber Bit 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. Substantially oxygen-free and anhydrous conditions are desirable.

[Effect of the invention 1] The non-aqueous secondary battery using the oxidized polymer of the aniline compound of the present invention as a positive electrode has a high charge/discharge efficiency, a high charge/discharge efficiency, and a lifespan of 1 nil. It is long, has a low self-discharge rate, and has good voltage flatness at all times. Also,
The nonaqueous solvent secondary battery of the present invention is lightweight, compact, and has a high energy density, so it is suitable for use in voltaic devices, electric vehicles, gasoline vehicles, and power storage batteries.

[Example] Hereinafter, the present invention will be explained in more detail by referring to Example J3 and a comparative example.

Example 1 [Manufacture of oxidized polymer] Add aniline 209 and 0.2119 ml of ferrous chloride hydrate to 300 cc of aqueous hydrochloric acid solution, which had been preheated in advance, and place in a 19-sized three-bottle flask. I put it in. The pH of the solution was 1. The inside of the flask is set to a nitrogen atmosphere], and the temperature is set to t1,
The temperature of the solution was brought to 40°C with warm water. To this, 1 g of ammonium persulfate was added under stirring.
A solution dissolved in 200 cc of a specified aqueous hydrochloric acid wI was added dropwise over about 2 hours, and then the reaction was allowed to proceed at 40° C. for 3 hours.

After the reaction, the dark green reaction solution was filtered, and the bright green aniline oxidized polymer was mixed with 500 d of 28% anhydrous
It was left overnight and filtered. This was washed repeatedly three times with 200 ml of distilled water, and then vacuum-dried at 100° C. for 15 hours. The oxidized polymer of 1q aniline is a purple powder, its yield; it +, t 18.2 IJ
Z-There it was.

[Production of membranous adelene high polymer]

1 in a glass-encased reaction vessel with an internal volume of 500 m in a nitrogen atmosphere F.
．． 7nii! Butani 1 Kumtetrabut 4: Reid 7
J11, dissolved in 30d anisole, then r-2,
A catalyst solution was prepared by adding 7d of triethylaluminum with stirring.

This reaction vessel was cooled with liquid nitrogen, and the nitrogen gas in the system was evacuated using a vacuum pump. Next, the reaction vessel was cooled to -78° C., and while the catalyst solution remained stationary, F regigas was blown 4 times per hour into the purification chamber at a pressure of 1 atm.

Immediately, polymerization occurred on the surface of the catalyst solution, producing a film-like acetylene high polymer. Thirty minutes after the introduction of acetylene, the aleben gas in the reaction vessel system was aerated with IJr to stop the polymerization. After removing the catalyst solution with a syringe under nitrogen atmosphere, −
The film-like acetylene polymer swollen with toluene was washed 5 times with 5L of Ii'i (100-100% of toluene) kept at 78°C. Met.

Next, this swollen product was vacuum-dried to obtain a membranous acetylene high polymer having a metallic luster, a reddish-purple color, a thickness of 180 μm'c, and a cis-3 ratio of 98-6. The bulk density of this film-like acetylene polymer is 0.30 g/cc, and its electrical conductivity (direct current four-terminal method) is 32 x 10'Q''・c at 20°C.
It was m-1.

[Battery experiment]

A 4v1 product (i'1tY 20m disk) of an oxidized polymer of aniline prepared by the above-mentioned method 1! '! From l j-D union, diameter 2 (Ig
Cut the disc of
1 and 0 electrode active materials were used to form a pond +i4.

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.
Platinum wire mesh current collector for electrode, 3 is a straight (¥2 omtn disc-shaped negative electrode), 4 is a circular porous polypropylene diaphragm with a diameter of about 20, is a disc-shaped body with a diameter of 20 mm, and 6 is a disc-shaped body with a diameter of 2 (b++ m, 80
Mesh platinum wire mesh current collector for positive electrode, 7 is positive electrode lead wire, 8
indicates a screw-in Teflon container.

First, the positive electrode platinum wire mesh current collector x body 6 is placed in the lower part of the four parts of the Teflon container 8, and the positive electrode 15 is placed on top of the positive electrode platinum wire mesh current collector 6. One made of diaphragms 4 stacked and sufficiently impregnated with electrolyte, and one negative electrode 3
Then, a zero-restriction platinum wire TODEN body 2 was left in the slot, and a Teflon container 8 was tightened to prepare a battery.

The electrolyte is LiBF, which has been distilled and dehydrated according to the usual method.
1 liter/hair solution of 4 was used.

Using the battery prepared in this way, positive I4 was applied under a constant current (1,57 ILA/cm2) in an argon atmosphere.
i! 3 and negative 1 were charged by flowing an amount of electricity corresponding to 50 mol % and 6 mol %, respectively, and then charged again under the same conditions as above. Mitsuru!
When the Il charge repetition test was conducted, the number of charge/111 charge cycles was recorded as 1208 times before the charge/discharge efficiency decreased to 70%.

Also, the energy density at the fifth repetition is 136
W-hr/KgF, maximum charging and power efficiency 'fha 100%
Met. Furthermore, when the battery was left charged for 70 hours, its self-discharge rate was 18%.

Example 2 In place of the acetylene polymer used for the zero pole in J3 in Example 1, Bridge of the Chemical Soliatiy of the °C1 Pan, No. 515. Page 2091 (19
78> (Bull, Chem, Soc, J
apan.

υ, 2091 (1978))! 1 ton/cm of IJ manufactured Boliparaf T nylene
2-1 - [1"
``Battery experiment'' was carried out in exactly the same manner as in Example 1 except that ``It4 was used.
The number of iterations until the rate drops to 7096 is 1.11
He recorded 8 innings.

The second energy of this battery is +43 W-hr y′
Kg, and the maximum charging/flI electric efficiency was 100%. When the battery was left charged for 70 hours, the electric rate was 15%.

Examples 3 to /1J3 and Comparative Example 1 In Example 1, peroxides and Fe2+ ions shown in the table were used in place of the oxidized polymer of aniline used in the positive electrode. [Battery experiment] was carried out in the same manner as in Example 1 (F, except for using the oxidized polymer of aniline which had been prepared by 1). .In addition, please add the solution of water to each individual.
l was 1. As a result, the charging/fJ4i power efficiency is 7Q
The number of repetitions until the battery deteriorated to 9 (,), the energy density of the battery +1 J, the maximum charging/discharging efficiency, and the self-111 electric rate when left charged for 70 hours were as shown in the table.

(Margin below)

[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 an example of the present Bonmei. 1... Platinum lead wire for negative electrode 2... Platinum wire mesh current collector for 0 electrode 3... Negative 4... Porous polypropylene diaphragm 5... Positive electrode 6... Platinum for positive electrode lI!l
Current collector 7...Positive electrode lead wire 8...Teflon container Special If applicant Showa Denko Co., Ltd. Hitachi, Ltd.

Claims (1)

[Scope of Claims] Oxidized polymerization of an aniline compound represented by the following general formula in an acidic aqueous solution of pH 3 or less consisting of peroxide, iron (divalent) ions, and protonic acid. A non-aqueous solvent secondary battery characterized by using a combination as a positive electrode. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2, R_3, R_4 are hydrogen atoms,
Alkyl group having 1 to 10 carbon atoms or 1 to 10 carbon atoms
is an alkoxy group]