JPS60136180A - Secondary battery - Google Patents

Abstract

PURPOSE:To increase the energy density, the charge-and-discharge efficiency and the cycle life of a secondary battery by using a mixture composed of 1,3-dialkylimidazolium halide and a metal of the IIIa group as the electrolyte. CONSTITUTION:In a secondary battery having electrodes at least one of which is prepared from an acetylene high polymer, the electrolyte consists of a mixture composed of 1,3-dialkylimidazolium halide represented by the general formula (R1 and R2 are alkyl groups containing 4 or less carbon atoms and X is a halogen.) and a metal of the IIIa group. For instance, the above mixture is prepared by mixing 1-methyl-ethylimidazolim bromide and aluminum trichloride in a molar ratio of about 1:2-2:1. This secondary battery has a good voltage flatness and a small self discharge rate. Furthermore, this secondary battery can be easily made light and small.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a secondary battery using an acetylene polymer in at least one electrode. The present invention relates to a secondary battery with good performance, characterized in that it uses a mixture of metal and chloride.

The acetylene polymer obtained by polymerizing acetylene using a so-called Ziegler-Natsuta catalyst, which is composed of a transition metal compound and an organometallic compound, has an electrical conductivity in the semiconductor region, and is suitable for use as an electric/electronic device. It is already known that it is a useful organic semiconductor material.

Methods for producing practical molded products of acetylene high polymers include (a) a method of pressure molding powdered acetylene high polymers;
and (b) a method of obtaining a film-like acetylene polymer having a fibrous microcrystalline (fibril) structure and high mechanical strength by forming it into a film at the same time as polymerization under special polymerization conditions (Tokuko Showa). No. 48-32581) was known.

BF3. BCt, , HCl, CL2
When chemically treated with electron-accepting compounds such as 15o2tNo HCN-, O2, No, etc., the electrical conductivity reaches a maximum of 3.
It is already known that the electrical conductivity increases by an order of magnitude, and conversely, when treated with an electron-donating compound (donor) such as ammonia or methylamine, the electrical conductivity decreases by up to four orders of magnitude.

In addition, I, r C12,Br2* ICL, IBr
+AsF5rSbF5. Electron-accepting compounds such as PF6 and the like are Na.

By chemically doping electron-donating compounds such as K and Li, the electrical conductivity of the acetylene polymer can be increased to 1.
It is already known that it can be freely controlled over a wide range of 0 to 10Ω·α. This do -7°
The idea of using the film-like acetylene polymers produced in this way as materials for positive electrodes in primary batteries has already been proposed.

On the other hand, in addition to the chemical doping method described above, electrochemical doping of Cm4'e PF6- p AsF6-, A
Acetylene polymers are doped with arion such as s'F,,5cF3so,;-,BF4- and cation such as R'4N+ (R/: alkyl group) to form p-type and n-type polymers.
Methods for producing conductive acetylene polymers of the type have also been developed. A rechargeable battery using electrochemical doping using a film-like acetylene polymer obtained by the method (b) has been reported. This battery uses, for example, two 0.1 mm thick acetylene polymer films obtained by the method (b) as positive and negative electrodes, and a tetrahydrofuran solution containing lithium iodide.
When this is soaked and connected to a 9V DC power source, the lithium iodide 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. If this electrolytic doping corresponds to the charging process, then . If a load is connected to the two doped electrodes, the lithium ions and iodine react to generate electricity. In this case, the open circuit voltage (Voc) is 28V, and the short circuit current density is 5 mA/c.
m2, and when a tetrahydrofuran solution of lithium perchlorate is used as the electrolyte, the open circuit voltage is 2.5V.

The short circuit current density was approximately 3 mA/z2.

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.

However, among the electrolytes used in these known documents, alkylammonium salts and lithium salts, which are known as electrolytes with a relatively wide stability range, are all solid, so their own ionic conductivity is low. Therefore, the only way to use it as a battery electrolyte is to dissolve it in an organic solvent.

In addition, propylene carbonate and tetrahydrofuran, which are used as organic solvents for electrolytes in these known documents, have a relatively narrow stable potential range, so they decompose and polymerize during battery charging and discharging, resulting in loss of battery energy. density,
It has the disadvantage of reducing charge/discharge efficiency, voltage flatness during discharge, and number of charge/discharge cycles, and increases the self-discharge rate of the battery.

In general, the stability of an electrolyte is determined by the combination of organic solvent and electrolyte, and in the case of batteries using acetylene polymers as electrodes, it is sufficiently stable during charging or storage storage, and has appropriate conductivity. Not many electrolytes are known that give off dust.

For example, in batteries using acetylene polymers as electrodes, sulfolane compounds, aromatic/logon compounds, nitrile compounds, etc. are known as organic solvents with a relatively wide stable potential range, but sulfolane compounds Generally, aromatic and rogonic compounds have high viscosity,
Even if the electrolyte is dissolved, the conductivity is low, so they are not suitable as organic solvents for batteries, or the solubility of the electrolyte is low.Also, many nitrile compounds are reactive with alkali metals, so There are drawbacks to using alkali metal salts as electrolytes.

Therefore, there has been a desire among those in the industry to establish a battery that is lightweight, easy to downsize, and inexpensive, using an electrolytic solution with a high electrical conductivity and a wide stable potential range.

In view of the above points, the present inventors have discovered that the present invention has high energy density, high charge/discharge efficiency, long cycle life, good voltage flatness, low self-discharge height, light weight, As a result of careful consideration to obtain a battery that is easy to miniaturize and is inexpensive, we found that 1,3-dialkylimidazolium halide and
The present invention has been completed based on the discovery that a secondary battery with good performance can be obtained by using as an electrolyte a mixture of -logonides of all groups of group n+a of the periodic table. be.

That is, the present invention provides a secondary battery in which an acetylene polymer is used for at least one electrode, a 1,3-dialkylimidazolium halide represented by the following general formula as an electrolyte, and a metal in group 1rfa of the periodic table. (However, R4 and R2 in the formula represent an alkyl group having 4 or less carbon atoms, and X represents a halogen.) The battery electrolyte used in the present invention is a mixture of the general formula It is a mixture of a 1,3-dialkylimidazolium-ride represented by the following formula and a halide of a metal of group 1ea of the periodic table.

The halokene of the above 1,3-dialkylimidazolium halide is fluorine, chlorine, bromine or iodine,
Among these heloquines, chlorine or bromine is preferred, and chlorine is particularly preferred.

Specific examples of 1.3-dialkylimidazolium halide include 1-methyl-3-ethylimidazolium chloride, 1-methyl-3-ethylimidazolium bromide, 1-ethyl-3-ethylimidazolium chloride, 1-ethyl -3-ethylimidazolium bromide,
f-methyl-3-propylimidazolium chloride,
■-Methyl-3-butylimidazolium chloride and the like.

On the other hand, the halides of metals in group 111a of the periodic table used in combination with the 1,3-dialkylimidazolium halide are boron, aluminum, indium, and thallium halides; Aluminum halides are particularly preferred, and aluminum halides are particularly preferred. Examples of halogens include fluorine, J-blood, bromine, and iodine.
Chlorine or bromine is preferred, and chlorine is particularly preferred.

Specific examples of halogenides of metals in group 1a of the periodic table include aluminum trichloride, boron trichloride, thallium trichloride, and indium trichloride.

1. Typical combinations of 3-dialkylimidazolium halide and a halide of a metal in group 111a of the periodic table include 1-methyl-3-ethylimidazolium chloride and aluminum trichloride; 1-methyl-3-
Ethylimidazolium chloride and boron trichloride, 1-
Methyl-3-ethylimidazolium bromide and aluminum trichloride, 1-methyl-3-ethylimidazolium chloride and thallium trichloride, ■-Methyl-3-ethylimidazolium bromide and boron trichloride, 1-ethyl:3-ethylimidazo Lium bromide and aluminum trichloride, ■-Ethyl-3-ethylimidazolium chloride and aluminum trichloride, 1-methyl-3-propylimidazolium chloride and aluminum trichloride, ■
Examples include, but are not necessarily limited to, -methyl-3-butylimidazolium chloride and aluminum trichloride.

The mixing ratio of 1,:3-dialkylimidazolium halide and halide of a metal of Group 1IIa of the periodic table is:
In terms of molar ratio, 1=2 to 2:1, preferably 1:1.

(2) The melting point and stable potential range of the 3-noalkylimidazolium halide and the halide of a metal of group 1IIa of the periodic table can be changed by changing the mixing ratio within the above range.

For example, when 1-methyl-3-ethylimidazolium chloride and aluminum trichloride are mixed in equimolar amounts,
The melting point of the mixture is 8°C, and the electrical conductivity at room temperature is 0.
．． 0227Ω-*Cm-.

When 1-methyl-3-ethylimidazolium chloride and aluminum trichloride are heated at a molar ratio of 1:2, the melting point of the mixture is -98°C, and the electrical conductivity at room temperature is 0. 0154Ω-1·dl.

First, the electrolyte of the present invention dissolves well in benzene and toluene, which are inert solvents, and can be used by lowering the melting point of the electrolyte to below -40°C.

(2) An electrolyte consisting of a 3-noalkylimidazolium halide and a halide of a metal in group 1IIa of the periodic table can be used as an electrolyte without being dissolved in an organic solvent; It can also be used by dissolving it in an aprotic organic solvent.

The aprotic organic solvents mentioned here include nonitrile compounds such as acetonitrile, benzonitrile, valeronitrile, α-tolnitrile, and m-tolnitrile; cyclic ethers such as tetrahydrofuran, tetrahydropyran, 1,4-soxane, and dioxolane; , 2-dimethoxyethane, diglyme, etc.; amides such as dinotylformamide, dimethylacetamide, hexamethylphosphoramide, N-methylpyrrolidone; dimethylsulfoxide, sulfolane, N-methylthioe
Examples include sulfur compounds such as propylene carbonate and ethylene carbonate; aromatic halogen compounds such as chlorobenzene and fromobenzene; and inert aromatic compounds such as benzene and toluene. It is not necessarily limited to these.

These organic solvents may be used alone or in combination.

The amount of organic solvent used should be determined to maintain the stable potential range of the electrolyte used, and to increase the electrical conductivity as much as possible for secondary batteries.
In addition, in order to obtain an electrolytic solution with high energy density, it is desirable that the capacity be at most twice the amount of electrolyte.

A preferred example of the electrolyte used in the secondary battery of the present invention is What-1 (1): 1-phthyl. 3-ethylimidazolium chloride and aluminum trichloride in equimolar amounts of 1:1
(2) A method in which the system of (1) is dissolved in an inert aromatic compound such as benzene in an equal volume or more, and used as 1W 711, (3 ): A method of using benzonitrile or acetonitrile in the system of (1), Part 9 is mentioned.

Acetylene polymer used in the present invention ld 4'','
There is no limit to the production method, and products produced by any method can be used, but specific manufacturing methods include Japanese Patent Publication No. 48'-32581, Japanese Patent Publication No. 56-453 (
i5, JP-A-55-129404, JP-A No. 55-129404.
1 2 8 4. 1! No. 1, 55-141201
No. 2, same! No. 56-10428-, 5 61 3 3
1 3 3 +T,. ';, Trans. Fara
dy Soc. +6 4 +823 (1968), J
．． PolymerSci. , A-1.7.3419
('L 9 6 9 ) + Makromol. Ch
emz Rapid Comm-t 1 mm 621 (1.980), J. Chem. Yen〕ys.
．． 6 9 (1), 1 0 G (1978), Syn
thetic metals, c 8 1 (1981
).

In the present invention, a conductive material such as graphite, carbon black, acetylene black, metal powder, carbon fiber, etc. may be mixed with the acetylene polymer, and there is no problem in using a metal net or the like as a current collector. . Furthermore, in the present invention, not only an acetylene polymer but also a conductive acetylene polymer obtained by doping an acetylene polymer with do-gunod in advance can be used as an electrode.

The amount of doping agent doped into the acetylene polymer is 1 to 1 mole of repeating unit of the acetylene polymer.
15 molar ratio, preferably 3 to 10 molar ratio.

Even if the amount of 1ゝ-enoent to be doped is less than 1 molar,
Even if it exceeds 15 molar ratio, a secondary battery with a sufficiently large discharge capacity cannot be obtained.

In the secondary battery of the present invention, as the electrolyte, for example, 1,3
'-Noalkyl imidazolium chlorite):
'8! tJI i'l' Table 111a 75 Metal chlorides (abbreviated as MC16).

However, Mt refers to metals in the periodic Illa group of the P table. ), the mixture B1. : 3-noalkylimigisotrigono and M, Ct 4-anion has an angle completed [1, and the electron/1! 70 Do/p nod B, Mcb4-7=on, and an acetylene polymer is used as the negative electrode of the battery/<-1 If it is doped, do=・Q-on)-f171. 1.1-noargylimidazolium cation.

”＼In the invention, the acetylene polymer is
) :F (i peak, (1)) negative dimension or (1++) positive electrode and knee' peak. &−
,l', (II) 1','1.11 When used in 11Q polymers, conjugated to the main chain as a pair (... 1,
-Len, the moon? (2,5-chenylene), poly+l'
l:J--le,n''? Riimi do, nj? Lif, Niruahitiren, 1? Rialeno, polyacenequinone lanocal tunic combination, quinazoline with one Nuff culture structure, +?
Rimmer, moon? Really Renkinonjite, No.? Reacryl nitrile, I? A thermally decomposed product of liimide or the like can be used.

However, when these highly polarized compounds having a conjugated double bond in the main chain are used for both the 11-electrode and the negative electrode of a battery, when an acetylene polymer is used for the electrode and electrode, the ratio of valence electrons decreases. The bandgap between the band and the conduction band is too large, and during charging, the charge liquid during charging is unstable and tends to cause nllll reactions, and furthermore, the number of minutes per unit of operation increases.
The disadvantage is that the energy density of the battery is too high and the energy density of the battery cannot be increased. Therefore, in this case, it is preferable to use an acetylene polymer for one electrode.

・P for the combination of electrodes that are missing from the invention, as the body side) J
: , 11th grade, q? l'・S raphenylene, using an acetylene high polymer for the negative electrode, 7 for positive and negative electrodes]? Lithiophene, negative% jlτ7 using a high polymer of hytylene, positive (using a high polymer of acetylene for the evening, using high polymer of 7'' for the negative electrode / (: using a high polymer of acetylene for the jE electrode, using graphite for the negative electrode) Examples include those using acetylene polymers for both the positive and negative electrodes.

Among these, the particularly suitable electrode silk combination is rll
Both the electrode and negative electrode are made of acetylene polymer.

The 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. Furthermore, the secondary battery of the present invention is lightweight, compact, and has a high energy density, so it is ideal for use in portable storage systems, electric vehicles, gasoline-powered vehicles, and L-power storage batteries and batteries.

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

Example 1 [Production of film-like acetylene polymer] In a nitrogen atmosphere, 1.7 me of titanium tetrabutoxide was added to a glass reaction vessel with an internal volume of 500 m1 and dissolved in '3Q7 anisole, and then 27 me
of triethylaluminum was added with stirring to prepare a catalyst solution.

This reaction vessel was cooled with liquid nitrogen, and the nitrogen gas in the system was exhausted using a vacuum pump. Next, put this rabbit container into 178 pieces.
It was cooled to 0.degree. C., and while the catalyst solution remained static, 1 atm of anethylene gas made by Ryo Qing was blown into the reactor.

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 acetylene gas in the reaction vessel system was exhausted to stop the polymerization.

After removing the catalyst solution with a syringe under nitrogen atmosphere, -78
The sample kept at ℃ was washed 5 times with 100 mg of purified toluene. The film-like acetylene polymer swollen with toluene was a uniform film-like swollen product in which fibrils were tightly intertwined.

The swollen product was then vacuum-dried to obtain a reddish-purple film with a metallic luster, a thickness of 100 μm, and a film-like acetylene polymer containing 98% of the salt content. In addition, the bulk density of this film-like acetylene polymer is 0.30.9/cc, and its electrical conductivity (DC four-probe method) is 3.2×10 Ω・c at 20°C.
It was m.

[Battery experiment]

Two discs with a diameter of 20 mm were cut out from the film-like acetylene polymer obtained by the above method, and a battery was constructed by using the discs as active materials for a positive electrode and a negative electrode, respectively.

FIG. 1 is a schematic cross-sectional view of a battery cell for measuring the characteristics of a secondary battery, which is a specific example of the present invention, in which 1 is a platinum lead wire for the negative electrode, and 2 is a platinum wire mesh for the negative electrode with a diameter of 20+m++ and 80 meshes. Current collector, 3 is a disc-shaped negative electrode with a diameter of 20 threshold, 4 is a diameter of 20
mm circular porous polypropylene diaphragm thick enough to be sufficiently impregnated with electrolyte, 5 is a disk-shaped positive electrode with a diameter of 20 mm, 6 is a platinum wire mesh current collector for the positive electrode with a diameter of 20 mm, 80 mm, and 2 mm. 7 is a positive electrode lead wire, and 8 is a screw-type 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 poly-00-pyrene diaphragm 4 is placed on top of the positive electrode 5, and after sufficiently impregnated with the electrolyte, the negative electrode 3 is placed on top of the platinum wire mesh current collector 6 for the positive electrode. Overlapping,
Further, a platinum wire mesh current collector 2 for a negative electrode was placed on top of the current collector 2, and a Teflon container 8 was tightened to produce a battery.

As the dielectric substance, a mixture of 1-methyl-3-ethylimidazolium chloride and aluminum trichloride in an equimolar ratio of 1:1 was used, and no organic solvent was used.

1-Methyl-3-ethylimidazolium chloride is
It was synthesized by reacting distilled 1-methylimidazole manufactured by Aldrich Chemical Company with chloroethane manufactured by Tokyo Kasei Kogyo (c), and the product was heated three times in a mixed bath of acetonitrile and ethyl acetate. The crystallized product was dried in vacuum and used.

As aluminum trichloride, crystalline aluminum trichloride manufactured by Kokusan Kagaku Co., Ltd. was purified by sublimation under reduced pressure.

Using the battery thus prepared, charging was performed for 15 minutes at a constant current (1.5 mA/crn2) at 20°C in an argon atmosphere (amount of electricity equivalent to 6 moles of doping), and charging was completed. Immediately after that, under constant current (1.5 m
A/m2), the battery was discharged, and when the battery voltage reached 1V, the battery was charged again under the same conditions as above. When the battery was repeatedly charged and discharged 9 times, the charging and discharging efficiency decreased to 50 cm. Up to now, the number of charge/discharge cycles has been recorded 820 times. The relationship between the discharge time and the voltage after the fifth repetition in this repeated experiment was as shown by the curve (a) in FIG. 2.

Also, the energy density at the 5th repetition is 140W-h
r/kg, and the charge/discharge efficiency was 99.8%.

Comparative Example 1 1-Methyl-3- used as electrolyte for battery in Example 1
The method was exactly the same as in Example 1, except that instead of the liquid electrolyte of ethylimidazolium chloride and aluminum trichloride, a 1 mol/L propylene carbonate solution of lithium barchlorate, which is often used in known literature, was used. We conducted an experiment of repeatedly charging and discharging the battery.

As a result, the highest light/discharge efficiency was 89%, and the number of repetitions until the charge/discharge efficiency decreased to 50% was 45 times. The relationship between the discharge time and voltage for the fifth time in this battery experiment was as shown by curve (b) in FIG.

Also, the energy density at the fifth repetition is 118
W'-hr/kl? The charging/discharging efficiency is 88.5%, which is h.

Comparative example 2 Bult Chem, Soc, Japan+r 51
The positive and negative electrodes were made by molding poly(,i-raphenylene) produced by the method described in 2091 (1978) into a disk shape of 20TMnφ at a pressure of 1 ton/α2, and the doping amount of each of the electrodes was determined by (C6H4
A repeated charging/discharging experiment was carried out in exactly the same manner as in Example 1, except that the repeating unit of ) was set to 36 moles. As a result, the highest light/discharge efficiency was 72%, and the charge/discharge efficiency was 72%.
The number of repetitions of charging and discharging was 28 times until the discharge efficiency decreased to 50%.

The relationship between the discharge time and voltage for the fifth time in this battery experiment was as shown by curve (c) in FIG. 2. Furthermore, the energy density at the fifth repetition was 108% lhr/ky, and the charge/discharge efficiency was 70%.

Example 2 [Battery experiment] A disk having exactly the same dimensions as in Example 1 was prepared from a film-like acetylene polymer having a film thickness of 1 (10 μm and a bulk density of 0.30.97 cc) obtained by the method of Example 1. Two sheets were cut out and used as positive and negative electrode active materials to construct a battery.

゛As the electrolyte, 1-methyl-3- used in Example 1
A mixture of ethylimidazolium chloride and aluminum trichloride in an equimolar ratio of 1:1 was used.

Other battery experiments were conducted in exactly the same manner as in Example 1, with repeated charging and discharging.

As a result, the charging/discharging efficiency decreases to 50%.
The number of repetitions of discharge was recorded as 580 times.

The energy density at the fifth repetition is 139W −
The charging/discharging efficiency was 994 cm at h r /ky.

Comparative Example 3 [Battery Experiment] Instead of the electrolytic solution used in Example 2, tetrabutylammonium tetrafluoroborate, which is an electrolytic solution with a relatively wide stable potential range, was dissolved in acetonitrile at a concentration of 1 mol. A repeated charge/discharge experiment was conducted in exactly the same manner as in Example 2, except that .

As a result, the charging/discharging efficiency decreases to 50%.
The number of repetitions of discharge was recorded as 185 times. The energy density at the fifth repetition is 135 w-hr/kg,
The charging/discharging efficiency was 99.0.

Example 3 [Battery Experiment] In Example 2, a battery experiment was conducted in exactly the same manner as in Example 2, except that the temperature of the battery experiment atmosphere was set to -30°C.

As a result, the charging/discharging efficiency decreases to 50%.
The number of repeated discharges was recorded at 750 times.

The relationship between the discharge time and the voltage after the fifth repetition was as shown in track M(d) in FIG.

The energy density of the fifth repetition is 120.
Comparative Example 4 [Battery Experiment] Tetrabutylammonium tetrafluoroyl” used in Comparative Example 3 was used instead of the electrolyte used in Example 3. -1・
A battery experiment was conducted in exactly the same manner as in Example 3, except that a solution of acetonitrile was used.

As a result, the charging/discharging efficiency decreases to 50%.
The number of repetitions of discharge was recorded as 215 times.

The relationship between discharge time and voltage after the fifth repetition was as shown by curve (e) in Figure 3.

The energy density of the fifth repetition is 1, 0.
At 8 W-hr/kg, charge/discharge efficiency is 992%
Example ・1 [Battery experiment] In place of the battery electrolyte used in Example 1, 1-methyl-
Repeated charging and discharging experiments of the battery were conducted in exactly the same manner as in Example 1, except that a mixture of 3-ethylimidazolium chloride and 3-ethylimidazolium chloride in an equimolar ratio of 1=1 was used.

As a result, the charging/discharging efficiency decreases to 50%.
The number of repetitions of discharge was recorded as 780 times. The energy density at the fifth repetition in this repeated experiment is]
At 28 W-hr 7 kg, the charging/discharging efficiency was 998.

Example 5 [Production of crystalline 2,5-thennylene polymer] Commercially available metallic magnesium 201 El for Grignard reagent
(8 2 7 mm+)mol) using a thermometer, reflux condenser,
The dropping funnel was placed in a Mitsuro flask (No. 1007111), and the inside of the flask was purged with sufficiently dry elementary gas. Add 60 ml of dry purified tetrahydrofuran to this, and while stirring with a magnetic cooler, 20 g (82.
7 mmol) of 2,5-tubromothiophene was added dropwise at room temperature. A reaction started simultaneously with the dropwise addition, and an organomagnesium compound was produced. After the dropwise addition was completed, the mixture was reacted on an oil bath at the reflux temperature of tetrahydrofuran for 9 hours. At this time, the product was decomposed with acid, extracted with ether, and analyzed by gas chromatography. l: Su, 86.4 mol% f2-bromochenyl-5-
It was confirmed that magnesium bromide was produced.

Thereafter, the oil bath temperature was raised to 120° C., and tetrahydrofuran was distilled off under normal pressure and then reduced pressure to obtain a reddish brown oily residue.

This oily residue was mixed with 60 ml of dried purified anisole (2,2'-bivirinone) nickel 80 ml (02
After adding 8 mmol) and reacting at 152° C. for 2 hours, the mixture was poured into 500 ml of hydrochloric acid and acidified methanol and washed.

After repeating this operation twice, it was filtered, and the filtration residue was Soxhlet extracted with hot methanol for 13 hours and then with hot chloroform for 50 hours, and the amount insoluble in hot chloroform was 60.
It was 2 g of blackish brown fine powder and had a heat chloroform soluble area of 0.4'7.

The elemental analysis result of this thermal chloroform insoluble part is carbon 560.
8%, hydrogen 2.61%, ash 109%, Ni 200p
pm, Mg 60 ppm. The average molecular weight calculated from the results of elemental analysis of carbon was 3,880, and the average degree of polymerization was about 45. Furthermore, infrared analysis results (using a JASCOA-31R spectrum photometer manufactured by JASCO Corporation) -, while the absorption based on C-Br stretching vibration near 960 crn-1 is extremely small, the absorption based on the C-Br stretching vibration near 785 cm-1 is The absorption that is thought to be based on the polymer is extremely large, and crystal peaks exist at 20-198°, 232°, and 282° (using an RU-200 model X-ray diffractometer), indicating that the polymer is clearly crystalline. It was shown that

When the crystalline 2,5-chenylene polymer thus obtained was compression molded using a 1-ton press machine, a slightly flexible plate-shaped molded product was obtained. This plate-shaped molded product could be easily cut with a knife without losing its shape.

[Battery experiment]

A battery experiment was conducted in exactly the same manner as in Example 1, except that the crystalline 2,5-chenylene polymer obtained by the above method was used as the positive electrode, and the acetylene polymer obtained by the method of Example 1 was used as the negative electrode. I did this.

However, the doping amount is 24 mol per repeating unit of (C4'H2S) of the crystalline 2.5-thennylene polymer for the positive electrode, and (CH) of the acetylene polymer for the negative electrode.
) was set at 6 moles per repeating unit.

As a result of repeated charge/discharge experiments, the highest light/discharge efficiency was 9.
At 9.9%, the energy density at the fifth repetition was 120 W-hr/kg, and the number of repetitions until the charge/discharge efficiency decreased to 50% was 623.

[Brief explanation of drawings]

FIG. 1 is a schematic cross-sectional view of a battery cell for measuring the characteristics of a secondary battery, which is a specific example of the present invention, and FIGS. FIG. 7 is a diagram showing the relationship between battery discharge time and voltage in Example 3 and Comparative Example 4. DESCRIPTION OF SYMBOLS 1... Platinum lead wire for negative electrode, 2... Platinum edited heavy body for negative electrode, 3... Negative electrode, 4... Porous polypropylene diaphragm, 5... Positive electrode, 6... Platinum mesh for positive electrode Current collector, 7
...Positive electrode lead wire, 8...Teflon container.

Claims (1)

[Scope of Claims] A secondary battery using an acetylene polymer in at least one electrode, a 1,3-dialkylimidazolium-lide represented by the following general formula as an electrolyte, and A secondary battery characterized by using a mixture of a group metal and a halide. - (However, R and R2 in the formula represent an alkyl group having 4 or less carbon atoms, and X represents a halogen.)