JPS59196571A - Cell - Google Patents

Abstract

PURPOSE:To obtain a cell having high energy density, high charge/discharge efficiency, long cycle life, low self-discharge rate and flat discharge voltage by employing kinason polymer having Schiff base structure for electrode. CONSTITUTION:Kinason polymer having Schiff base structure is produced through reaction between quinone compound and aromatic di-isocyanate compound or tri-isocyanate compound and can be employed as a film, powder, short fiber, etc. Other conductive material such as graphite, carbon black, acetylene black, metal powder, carbon fiber, etc. may be mixed or a metal mesh may be placed as a current collector. Conductive kinason polymer to be produced by doping said kinason polymer can also be employed for the positive or negative electrode.

Description

Detailed Description of the Invention The present invention provides a quinacin polymer t having a Schiff base structure.
+ refers to a battery in which the conductive quinazone polymer obtained by doping the quinacin polymer with a dopant is used for the positive and negative electrodes.

It consists of a transition metal compound and an organometallic compound.

It is already known that the famous acetylene polymer obtained by polymerizing acetylene using the so-called Ziegler-Natsuta catalyst is an organic semiconductor material useful as electrical and electronic devices because its electrical conductivity is in the semiconductor region. I'm laying down. Methods for producing practical molded products of acetylene high polymers include (c) pressure molding of powdered acetylene high polymers, and (b) molding into a film at the same time as polymerization under special polymerization conditions. A method for obtaining a membranous acetylene polymer having a fibrous microcrystalline (fibril) structure and high mechanical strength (Japanese Patent Publication No. 32581/1981).

kO is known.The powdered acetylene polymer molded product that cannot be obtained by the method (a) above is BF3. BCl3. HCl%C12,S02,
Electron-accepting compounds such as NO2, HCN, 02, NO, etc.
It is already known that chemical treatment with an acceptor (acceptor) increases the electrical conductivity by up to three orders of magnitude, and conversely, treatment with an electron-donating compound (donor) such as ammonia or methylamine decreases the electrical conductivity by up to four orders of magnitude. (D, J,
Berets et al., Trans., Far.
ady Soc, , 64°823 (1968)
].

In addition, I2, (J'2, Br2, Icl, IBr, As
Electron-accepting compounds such as F, SbF, P, etc.
It is already known that the electrical conductivity of an acetylene polymer can be freely controlled over a wide range of 10=~103Ω-1・LM-' by chemically doping Na, with an electron-donating compound such as Li. [J, C, S, Chem, Com &, 578 (
(1977), Phys, Rev.

T, ett, 39, 1098 (1977), J
, Am, Soc, , ■曵.

1013 (1975), T. Chem, Ph.
ys, 69.5098 (1978):].

The idea of using this doped membrane acetylene polymer as a positive electrode material for primary batteries has already been proposed.
Teil (Molecular Metals, NA
TOConference 5eries, 5eri
es VI, 471-489 (1978)).

On the other hand, in addition to the above chemical doping method, electrochemical doping methods such as ClO4-, PFfi-1AsF6-, Ag
F2-, CF3-.

Anions such as 503-1BF4- and R', N+
A method for producing P-type and n-type conductive acetylene polymers by doping cations such as (R': alkyl group) into acetylene polymers has already been developed [J, C
, S. Chem, Commu., 1979594. C&
ENJan.

26, 39 (1981), J.C.S., Chem.C.
ommu, 1981.317).

A battery that can be recharged by electrochemical doping using a film-like acetylene polymer obtained by the method (b) has been reported (Paper Present
edat the International C
onference on LowDim! l! n5i
ona+5ynthetic Metals, He
rsinger, Denmark, 10-15
.

August 1980) - This battery is obtained by the method ((b)).

'For example, if two acetylene polymer films with a thickness of 0 and 1 cylinder are used as positive and negative electrodes, respectively, and immersed in a tetrahydrofuran solution containing lithium iodide and connected to a 9-inch DC power source, iodide will be produced. Lithium is electrolyzed, the acetylene polymer film of the positive electrode is doped with iodine, and the acetylene polymer film of the negative electrode is doped with lithium. This electrolytic doping corresponds to the charging process.

When a load is connected to the two doped electrodes, lithium ions and iodine ions react to generate electricity. In this case, the open circuit voltage (Voc) is 2.8 ■, the short circuit current density is 5 mA/al, and when a tetrahydrofuran solution of lithium perchlorate is used as one electrolyte, the open circuit voltage is 2.
．． 5v, short circuit current density approximately 3'mA/c, l
Met.

This battery uses an acetylene polymer as its electrode material, which is easy to reduce weight and size, so it is attracting attention as an inexpensive battery that has high energy density and is easy to reduce weight and size. There is. Also, JP-A-5
6-136469, in addition to acetylene high polymers, poly(CP-phenylene), poly(m-phenylene), poly(phenylene sulfide), poly(phenylacetylene),
Polypyrrole and the like are also disclosed to be useful as electrode materials. However, the cycle life, voltage flatness during discharge, charging/discharging efficiency, etc. of batteries using the above-mentioned polymer compounds having conjugated double bonds in the main chain as active materials of the electrodes have been In view of the above points, the present inventor has developed a battery that has high energy density, good cycle life, good charging/discharging efficiency, and voltage flatness during discharging, and is lightweight. As a result of various studies aimed at obtaining a battery that is easy to miniaturize and is inexpensive, the present invention has been completed.

That is, the present invention provides a quinacin polymer having a Schiff base structure or a conductive quinacin polymer obtained by doping the quinacin polymer with a dopant.A battery obtained by the method of the present invention has a quinacin polymer having a Schiff base structure. (ii) Compared to a secondary battery using, as an electrode, a polymer compound having a conjugated double bond or a conductive polymer compound obtained by doping the polymer compound with a dopant; (ii) Good voltage flatness during discharge. (1) Less self-discharge (ψ long life after repeated charging and discharging.

It has the advantage of

The quinacin polymer having a Schiff base structure used in the present invention is obtained by the reaction of a quinone compound and an aromatic diisocyanate compound or a triisocyanate compound, and an example of the reaction is as follows.

Specific examples of the quinone compound mentioned here include benzoquinone, naphthoquinone, anthraquinone, etc., and specific examples of the aromatic diisocyanate compound include phenylene-1,3-diisocyanate, phenylene-1,4-diisocyanate, etc.
Examples include diisocyanate-1,)I3 diisocyanate and naphthalene diisocyanate. The reaction between a quinone compound and an aromatic diisocyanate compound or a triisocyanate compound is performed by H, A, Pohl and
LT-T.

Englehardt, J. Phys, ch. 6
6, 2085 (1962), but is not necessarily limited to this method.

The quinacin polymer having a Schiff base structure used in the present invention may be in the form of a film, powder, short fibers, or other forms.

1. A quinacin polymer having a Schiff base structure is powdered with other suitable conductive materials, such as graphite, carbon black, acetylene black, and gold.

There is no problem in mixing carbon fiber or the like, or using metal wire as a current collector.

As the positive and negative electrodes of the battery of the present invention, instead of a quinacin polymer having a Schiff base structure, a conductive quinacin polymer obtained by doping the quinacin polymer with a dopant can also be used. As a method for doping a dopant into a quinacin polymer having a Schiff base structure, either chemical doping or electrochemical doping may be employed.

Dopants to be chemically doped include various conventionally known electron-accepting compounds and electron-donating compounds, such as (I) halogens such as iodine, bromine, and bromine iodide, ■ arsenic pentafluoride, pentafluoride; Antimony chloride, silicon tetrafluoride, phosphorus pentachloride, phosphorus pentafluoride, aluminum chloride, aluminum bromide, aluminum fluoride, Nb
F, , TaF, , WF6, FeCl3 and C
Metal halides such as dCl2, protic acids such as sulfurous acid, perchloric acid, -nitric acid, fluorosulfuric acid, trifluoromethanesulfuric acid and chlorosulfuric acid, oxidizing agents such as sulfur trioxide, nitrogen dioxide, difluorosulfonyl peroxide, MAgC104 -(Vl) Tetracyanoethylene, Tetracyanoquinodimethane, Floranil, 2.3
-dichloro-5,6-dicyatsubarabenzoquinone, 2,
3-dibrome-5,6-sinatsubarahenzoquinone, (
vIDCrO2C12,■0C13゜(Vlme NO4-
8I) Normal-, No: 5bF6-, NO”As normal-,
NO"P 几-1NO□'-PIi"6-, NO'-B
F4-1NO+Cll04-1■2,4.6-1linitrophenol, 2,4.6-) IJ nitrophenyl sulfonic acid, 2,4,6-dolinitrophenylcarboxylic acid, (X)T, i, Examples include alkali metals such as Na and K.

On the other hand, as a dopant to be electrochemically doped, (i) PF6-1ST) R6-1AsTi'6-5s
bc4. Halide anions of group elements such as -, halide anions of group elements such as BP'4-, halogen anions such as I-(L-), Br-, C1-, halogen anions such as ClO4-, Anions such as chlorate anions, dopants and (jj) L i +, K+,
Alkali metal ions such as Na+.

4 such as R4N+ (R: hydrocarbon group having 1 to 20 carbon atoms)
Examples include cations and dopants such as class ammonium ions, but are not necessarily limited to stiffness and the like.

Specific examples of compounds providing the above-mentioned anionic dopants and cationic dopants (z) include LiPF6, L
iSbF6. LiAsF, , LiC70,, Na
I, NaPF, , Na5bF,.

KCAQ, [(n −13u)4N)” ・(A
sF6)-1((n-Bu)4N]”-(PFa)-
, [(n-BulN)"-CAO4, LiAfflC4
, LiBF, etc. are not necessarily limited to these. These dopants may be used alone or in combination of two or more.

Anion dopants other than those mentioned above include I-(R'2
- anion, and 1 - a cation dopant other than the above is virylium' represented by the following formula a)! ! R is a pyridinium cation: (wherein, X is an oxygen atom or a nitrogen atom, R' is a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, and
aryl group, R11 is a halogen atom, an alkyl group having 1 to 1 carbon atoms, an aryl group having 6 to 15 carbon atoms, m is @O when X is an oxygen atom, and It is 1 for nitrogen atoms. n is 0 or 1~
It is 5. ) or a carbonium cation represented by the following formula 〇 or σID: T? l and R4-C+ Sub1 [In the above formula, R1, R2, R3 are hydrogen atoms (R1, R2゜R3 are not hydrogen atoms at the same time), carbon number 1-
15 alkyl groups, allyl human disaster prime number 6~
15 aryl groups or -OR5 groups, provided that R6 is an alkyl group having 1 to 10 carbon atoms, and 1 has 6 to 10 carbon atoms.
15 aryl groups, R4 is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms. ] It is.

The T(F2- anion used is usually represented by the following general formula
, Ml has a command: R', N -I-Ip2 ■M-
T(F'2
(V)(R"')n [However, in the above formula, R'4 R" is a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms (a
ryl) group 'fJ, III is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, X is an oxygen atom or a nitrogen atom, and n is a positive integer of 5 or less. It is. M is an alkali metal] It can be obtained by dissolving a compound represented by (hydrogen fluoride) as a supporting electrolyte in a suitable organic solvent. Specific examples of the compounds represented by the above formulas (IV), (g), and
-I-([i'2゜Na-H]F%, K-FIF2.L
The biryllium or pyridinium cation represented by i.HF2 and the above formula (I) is the cation represented by 2a) and c4o4-113min-, AACJ4-, F
eCIQ-1SnC4-PF6-1pcl, ;5bF
It can be obtained by dissolving a salt with an anion such as 6-, AsF6-1CF3so, y, l-lF2- as a supporting electrolyte in an appropriate organic solvent. Specific examples of such salts include I■.

Carbonium cation represented by the above formula 〇 or valence/
Specific examples include (C6I as well), C+, (CH3)3C
+.

The carbonium cation of Kowata et al. can be obtained by dissolving Sowara and an anion (carbonium salt) in a suitable organic solvent as a supporting electrolyte. Typical examples of anions used here are:

BF'4-, l'JcIJ4-, AfflBr3C
A-, FeC4-, 5uC4-, PF6-, PC&-
.

5bcz6-%5bF6-1CJO, -1cF3so;
Specific examples of carbonium salts include:

For example, (QII(6)3C・BF,,((5、C・B
几, HCO・MC4,1-TQ)-BF4. C,H
, Co, SnO&, etc.

The amount of the dopant doped into the quinacin polymer having a Schiff base structure is 2 to 150 mol%, preferably 4 to 130 mol%, particularly preferably 4 to 130 mol%, per 1 mol of V repeating units of the polymer. It is in the range of 5 to 100 moles. Even if the amount of doped dopant is less than 2 mol%, it is 150 mol%'
It is not possible to obtain a battery with a sufficiently large discharge capacity even if the discharge capacity is exceeded.

The amount of doping can be freely controlled by controlling the amount of electricity flowing during electrolysis. Doping may be carried out in a constant manner under constant current, constant voltage, or under conditions of varying current and voltage. Current value during doping.

The voltage value and doping time etc. depend on the type of quinacin polymer having a Schiff base structure used, bulk density, area, etc.
Type of dopant, type of electrolyte.

It cannot be unconditionally defined because it varies depending on the required electrical conductivity. Examples of organic solvents for the electrolytic solution in electrochemical doping include ethers, ketones, nitriles, amines, and amides.

Sulfur compounds, chlorinated hydrocarbons, esters, carbonates, nitro compounds, phosphate ester compounds, sulfolane compounds, etc. can be used, but among these, ethers, ketones, nitriles, chlorinated Hydrocarbons, carbonates, and sulfolane compounds are preferred. Konera's representative f1+ include tetrahydrofuran, 2-methyltetrahydrofuran% 1.4-dioxane, anisole, monoglyme, acetonitrile, propionitrile, 4-methyl-2-pentanone, phthyronitrile, 1.2-dichloroethane, γ-butyrolactone. ,
Examples include dimethoxyethane, methylformate, propylene carbonate, ethylene carbonate, dimethylformamide, dimethyl sulfoxide, dimethylthioformamide, sulfolane, 3-methyl-sulfolane, trimethyl phosphate, triethyl phosphate, etc.
It is not necessarily limited to these.

In the battery of the present invention, when a quinacin polymer having a ship base structure or a conductive quinacin polymer obtained by doping the quinacin polymer with a dopant is used as the positive electrode and the negative electrode, the supporting electrolyte of the electrolyte of the battery is The same method as that used in the electrochemical doping described above is used, and the doping method is also the same as that described above or a conventionally known method (J, C, S, Chem, Commu, 1
931. 317%.

The concentration of the electrolyte used in the battery of the present invention is determined by the type of quinacin polymer having a ship base structure used, charging and
Discharge Conditions 1. Since they vary depending on the operating temperature, type of electrolyte, type of organic solvent, etc., they cannot be defined unconditionally, but 1 are usually in the range of 0001 to 10 mol/l, and can be used even in a supersaturated state.

In the present invention, a quinacin polymer having a Schiff base structure or a conductive quinacin polymer obtained by doping the quinacin polymer with dopane is used as both the positive and negative electrodes of a battery.

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

Also, the battery of the present invention can be a thin battery, even a paper-thin battery, and can have multiple layers stacked on top of each other and coupled together in series or parallel, or can be made into a single long battery by itself. It may be rolled or spirally shaped.

A battery using the quinacin polymer having a Schiff base structure of the present invention or the conductive quinacin polymer obtained by doping the quinacin polymer with a dopant as both positive and negative electrodes has a high energy density, Mitsuru・
It has high discharge efficiency, long cycle life, low self-discharge rate, and good voltage flatness during discharge. Furthermore, the battery of the present invention is lightweight, compact, and has a high energy density, making it ideal for use in portable devices, electric vehicles, gasoline vehicles, and power storage batteries.

EXAMPLES The present invention will be explained in more detail below with reference to Examples and Comparative Examples.

Example 1 [Synthesis of quinacin polymer having a Schiff base structure] Equimolar naphthoquinone and phenylene-1,3-diisocyanate Complete literature T (A, Pohl and EJLE)
nglehardt.

J, Phys, Chem, , 662085 (19
It was synthesized according to the method of 62). The obtained quinacin polymer was pressure-molded at a pressure of 1Qtory to obtain a sheet-like molded product.

[Battery experiment]

The quinacin polymer having a sheet-like Sischiff base structure obtained by the above method has a width of 0.5 cm and a length of 2
．． Two small pieces of 0 cm were cut out to form a fidget positive electrode and a negative electrode, and the distance between the positive electrode and the negative electrode was 3 mm. A sulfolane solution with a concentration of 1.0 mol/l of Et4N・B was used as an electrolyte under a constant current (0.5rr+
A7? (uJ) for 45 minutes. (The amount of electricity corresponds to a doping amount of 7 moles). Immediately after charging, discharge under a constant current (05 ψdan) until the voltage reaches 1.
When we conducted a repeated charge/discharge test in which we charged the battery again under the same conditions as above when the battery reached Ov, we found that the number of repetitions was possible up to 297 times and f? :.

From the results of the 10th repeated test, the energy density (theoretical energy density) for the active material IK9 is 241w
-hr7%? Yes, the charging/discharging efficiency was 95%.

Further, the ratio of the amount of electricity discharged until the voltage decreased to 1.5 μm during discharge to the total amount of electricity discharged was 94 times.

Also, I left it in a charged state for 48 hours.

Its self-discharge rate was 6.

Comparative Example 1 [Production of film-like acetylene polymer] 1 in a glass reaction vessel with an internal volume of 500 m under a nitrogen atmosphere
．． Add 7 liters of titanium tetrabutoxide, 30-
A catalyst solution was prepared by dissolving the mixture in anisole and adding 1 and 2.7-triethylaluminum with stirring.

This reaction vessel was cooled with liquid nitrogen, the nitrogen gas in the system was evacuated using a vacuum pump, the reaction vessel was cooled to 78°C, and the catalyst solution was kept stationary and heated to 1 atm. blown with purified acetylene gas at a pressure of .

Immediately, polymerization occurred on the surface of the catalyst solution, producing a film-like acetylene high polymer. After introducing acetylene.

After 49 minutes, the acetylene gas in the reaction vessel system was exhausted to stop the polymerization. After the catalyst solution was removed with a syringe under a nitrogen atmosphere, it was washed five times with 100 ml of sweet purified toluene while keeping the temperature at -78°C. The film-like acetylene polymer swollen with toluene is a uniform film-like swollen product in which fibrils are tightly intertwined.Then, this swollen product is vacuum-dried to a reddish-purple color with a metallic luster and a thickness of 85 μm. Content 98
A related membranous acetylene polymer was obtained. 1k, the bulk density of this film-like acetylene high polymer is 0.45g, and so on.
Its electrical conductivity (DC four terminal method) is 3.2X1 at 20℃
It was 0-9Ω-"1m-'.

[Battery experiment]

A battery charge/discharge cycle experiment was conducted in exactly the same manner as in Example 1, except that the film-like acetylene polymer obtained by the above method was used for both the positive and negative electrodes.
After the 12,020th repetition of the test, when the eye electrogram became impossible, the film-like acetylene polymer was taken out and found to have been destroyed, and part of it was analyzed by elemental analysis and infrared spectroscopy. , had suffered extensive deterioration. Also,
From the results of the 10th repeated test, in which the electrolyte was also colored brown, the theoretical energy density of this battery was 221 W-hr/Kg, and the charge/discharge efficiency was 87. Also, the ratio of the amount of electricity discharged until the voltage drops to 1.5V during discharge to the total amount of electricity discharged is 87%. I left it charged for 48 hours.

Its self-discharge rate was 12 times.

Patent applicant: Showa Denko Co., Ltd. Hitachi, Ltd. Agent: Patent Attorney Sei Kikuchi

Claims (1)

[Claims] The quinacin polymer 1 having a Schiff base structure is a battery in which a conductive quinacin polymer obtained by doping the quinacin polymer with a dopant is used for the positive and negative electrodes.