JPS58206078A - Battery - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is characterized by using a polymer compound in which the main chain has no conjugated double bonds or a phosphoric acid ester compound as a doping medium for the polymer compound. This invention relates to a battery with good performance.

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

Acetylene polymers obtained by polymerizing acetylene using catalysts are known to be organic semiconductor materials useful as electrical and electronic devices because their electrical conductivity falls within the semiconductor region. Already known. However, the acetylene polymer obtained in this way does not melt even when heated, and it easily undergoes oxidative deterioration under heating, so it cannot be molded using the usual molding methods used for thermoplastic resins. . Furthermore, no solvent has been found that dissolves this acetylene polymer.

Therefore, the conventional methods for producing practical molded products of acetylene high polymers are (a) pressure molding of powdered acetylene high polymers, and (b) film forming 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 (
% Komei No. 48-32581), K was limited.

However, method (a) only yields a molded product with low mechanical strength, while method (b) produces a molded product with high mechanical strength compared to the molded product obtained by method (a). Although it has advantages, it has the disadvantage that the bulk density of the acetylene polymer molded product obtained is at most 0.60 r/cc (true specific gravity -1,20 r/cc), and only a porous thin film can be obtained. Powdered acetylene polymer molded product obtained by the method (a) above f Br5 , BOls, tiaz , at2
When chemically treated with electron-accepting compounds (acceptors) such as , so2, NO2, HON, 02, and No, the electrical conductivity increases by up to three orders of magnitude, and conversely, electron-donating compounds such as ammonia and methylamine It is already known that the electrical conductivity decreases by up to four orders of magnitude when treated with (donor) (D, J, Berets et al., Tran
s urn FaradySoc,, 64.823 (19
68) ).

In addition, I2, at2, Br2, TOt, TBr,
By chemically doping electron-accepting compounds such as AsF''5, SbF5, pp6, etc. or electron-donating compounds such as Na, K, Li, the electrical conductivity of the acetylene polymer can be increased from 10-8 to 1O-3Q. It is already known that crn-1 can be freely controlled over a wide range [J, O, S, Ohem, Oommu
, 578 (1977), Phys.

Rev. Lett., 39. 1098 (197
7), J. Am, Ohem.

Soc, 100.1013 (1978), J.
Ohem, Phys,, 69°5098 (19
78) ]. The idea of using this doped film-like acetylene polymer as a material for the anode of primary batteries has already been proposed (1'i4o1ccularMe
tals, NATOConference 8eri
es+ 5eries VL471-489 (197
8) ).

On the other hand, in addition to the above-mentioned chemical doping method, C604, PF6LAsF6, AsF4-
Doping an acetylene polymer with an anion such as 1 (jP3So, -1BF4-, etc.) and a cation such as R'4N+ (R1: alkyl group) to produce an n-type and n-type conductive acetylene polymer A method has also already been developed [J, 0.8. Chem, Oommu, .
1979594. O & EN Jan.

26, 39 (1981), J.O.S. Ohem
, Commu, 1981゜317]. and,(
A rechargeable battery using electrochemical doping using a membranous acetylene polymer obtained by method (b) has been reported (Paper Presented at
the Internationalconf
erence onLow Dimensional
5ynthetic Metals+ Hersin
ger+Denmark+ 10~IL August
1980). For example, this battery uses two acetylene polymer films obtained by the method (b), each having a thickness of o-i tm, as positive and negative electrodes, and immersing them in a tetrahydrofuran solution containing lithium iodide. When connected to a 9V DC power supply, lithium iodide is electrolyzed, and the acetylene polymer film at the anode is doped with iodine.
The gruesome acetylene polymer film is doped with lithium. This No. 11 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 28 V, the short circuit current density is s mA/ca, and when a tetrahydrofuran solution of lithium perchlorate is used as the electrolyte, the open circuit voltage is 2.5 ■, short circuit Current density is approximately amA/c
It was 4.

This battery uses high-polymerized acetylene jiI- as its electrode material, which can be easily made into a light lid and downsized, so it is attracting attention as a lightweight, easy-to-downsize, and inexpensive battery with high energy density. are collecting. However, 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 or polymerize during battery charging or discharging, resulting in loss of battery energy. It has the disadvantages of reducing density, light/discharge efficiency, voltage flatness during discharge, and number of charging/waste paper cycles, and also increases the self-discharge rate of the battery, and among those concerned, there is a more stable potential range. There has been a demand for the establishment of a light battery that uses a wide range of organic solvents, is easy to miniaturize, and is inexpensive.

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 rate, light weight, The present invention was completed as a result of various studies aimed at obtaining a battery that is easy to miniaturize and is inexpensive.

That is, the present invention relates to a battery in which at least one electrode uses a polymer compound having a conjugated double bond in its main chain, or a conductive polymer compound obtained by doping the polymer compound with a dopant. The present invention relates to a battery characterized in that a phosphoric acid ester compound represented by the following general formula is used as a liquid organic solvent.

(In the formula, R,,' R2 and R3 each represent a hydrogen atom, an alkyl group having 15 or less carbon atoms, an aryl group, an allyl group, an aralkyl group, and a halogenated alkyl group. However, R1, R2 and IIL3 are (At the same time, it is not a hydrogen atom.) Batteries using the phosphoric acid ester compound of the present invention as an organic solvent of the electrolyte, batteries using conventionally known propylene carbonate or tetrahydrofuran, and batteries using conventionally known propylene carbonate or tetrahydrofuran. Compared to batteries using , in the case of secondary batteries, (1) high energy density, (11) good voltage flatness, (1: low self-discharge, O
v) It has the advantage of long repeat life.

Specific examples of the polymer compounds having a conjugated double bond in the main chain used in the present invention include acetylene polymers such as polyacetylene (polyacetylene), poly(phenylene), polymetaphenylene, poly(2,s-phenylene), and poly(2,s-phenylene). /), polypyrrole,
Examples include polyimide, polyphenylacetylene, thermal decomposition products of polyacrylonitrile, etc., but are not necessarily limited to these, and any polymer compound having a conjugated double bond in the main chain may be used. Among the above-mentioned polymer compounds, preferred are acetylene polymer, polyhalapenylene, and bojJ (2,5-f enylene).
, polypyrrole, and particularly preferred are acetylene high polymers.

The method for producing the acetylene polymer preferably used in the present invention is not particularly limited, and any method can be used. -129404,
No. 55-128419, No. 55-142012, No. 56-10428, No. 56-133133, Tra
ns.

Parady Soc, + 64 + 823 (196
8)+J, Polymer 5ci-+A-1,
7, 3419 (1969), Makromol, O.
hem,, RapidOomm,, 621 (
1980), J. Ohem, Phys., 69
(1).

106 (1978), 5ynthe'tic Me
tals, 4.81 (1981-).

In the present invention, not only a polymer compound having a conjugated double bond in the main chain but also a conductive polymer compound obtained by doping the polymer compound with a dopant can be used as an electrode. When used as a primary battery, it is necessary to use a conductive polymer compound.

As a method for doping a dopant into a polymer compound having a conjugated double bond in its main chain (hereinafter referred to as a conjugated polymer compound), either chemical doping or electrochemical doping may be employed.

In the present invention, the dopants to be chemically doped into the conjugated polymer compound include various conventionally known electron-accepting compounds and electron-donating compounds, namely (I
) halogens such as iodine, bromine and bromine iodide, (2
) Metal halides such as arsenic pentafluoride, antimony pentafluoride, silicon tetrafluoride, phosphorous pentachloride, phosphorous pentafluoride, aluminum chloride, aluminum bromide and aluminum fluoride, (to) sulfuric acid, nitric acid, fluorosulfuric acid , protic acids such as trifluoromethanesulfuric acid and chlorosulfuric acid, (
(i) Oxidizing agents such as sulfur trioxide, nitrogen dioxide, difluorosulfonyl peroxide, (v) Agato4.
(b) Tetracyanoethylene, tetracyanoquinodimethane, floranil, 2,3-dichloro-5,6-dicyazubarapenzoquinone, 2,3-dibromo-5,6-dicyazubarapenzoquinone, etc. I can do it.

On the other hand, dopants to be electrochemically doped into the conjugated polymer compound include (+)PF6-%5bp7, A
s F 6-1 Halide anions of elements of the Va group such as SbO64-, halide anions of elements of the Na group such as BF4-, halogen anions such as Do(Is-), Br, Or, perchlorine such as ClO2- Anion dopants such as acid anions (both are effective as dopants to provide a P-type conductive conjugated polymer compound) and (if) alkali metal ions such as Li", Na", K+, R4N" (R: carbon number (1 to 20 hydrocarbon groups) such as quaternary ammonium ions (all of which are effective as dopants that provide an n-type conductive conjugated polymer compound), but are not necessarily limited to these. It is not something that will be done.

Specific examples of compounds providing the anionic pot dopants and cationic dopants mentioned above include 1iPF6, Li
8 b F 6, Li As F 6, Li04O
4, NaI, NaPF6, NaSbF6, NaAsP
6, N a 0104, KI, KBF4, K8
bF6, KAsF6, KO604, [(n
Bu)4:l''' (AsF3)-, [(n B
u)411"(PF6)-, [(n-Bu)4N"I
+.C6O4, L1AtO44, and LiBF4, but are not necessarily limited to these. These dopants may be used alone or in combination of two or more.

An anion dopant other than the above is HF27 anio/, and a cation dopant other than the above is a biryllium or pyridinium cation represented by the following formula (1): (wherein, X is an oxygen atom or nitrogen atom, R' is a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, and R' is a hydrogen atom or an alkyl group having 6 to 15 carbon atoms.
aryl group 1, R# is a nor\logen atom or an alkyl group having 1 to 10 carbon atoms, and 6 to 1 carbon atoms
In the aryl group of 5, m is 0 when X is an oxygen atom, and 1 when X is a nitrogen atom. n is 0 or 1-5. ) or a carbonium-cation represented by the following formula (6) or (to): and B4-0+ (2) 1 [In the above formula, Bj, B2, B5 are hydrogen atoms (R1,
B2 and R5 are not hydrogen atoms at the same time), alkyl group having 1 to 15 carbon atoms, allyl
group, an aryl group having 6 to 15 carbon atoms or a 10R5 group, where R5 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, R4 is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms,
It is an aryl group having 6 to 15 carbon atoms. ] It is. The above-mentioned HF2'' anion and the pyrylium-cation or pyridinium-cation of formula (I)
The cation and the carbonium cation represented by the formula (10 or (2)) can be doped into the conjugated polymer compound in large amounts, so that the resulting battery has a large discharge capacity and a high energy density.

The HF2-anion used usually has the following general formula %: () () [However, in the above formula, R' and R'' are hydrogen atoms or carbon atoms with 1
~15 alkyl group, aryl having 6 to 15 carbon atoms (ar
yl ) group, all/ is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, and X is an oxygen atom or a nitrogen atom. n is 0 or a positive integer of 5 or less. M is an alkali metal] It can be obtained by dissolving a compound (hydrogen fluoride salt) represented by the following as a supporting electrolyte in an appropriate organic solvent. Specific examples of the compounds represented by the above formulas (IV), (to) and (b) include H4H-HF2, B u 4 N
・HF2, Na'HF2, K' HF2, Li・H
F2 and the biryllium or pyridinium cation represented by the above formula (I) are the cation represented by the formula (I) and cto, -1BF4-1ktO14-1FeO6
4-1S n 0L5-1pH6-1PC16-18b
It can be obtained by dissolving in a suitable organic solvent using a salt with an anion such as F67, As P 6-1OF3SOi1HF2- as a supporting electrolyte. Specific examples of such salts include the following.

Carbonium represented by the above formula (6) or (2)
Specific examples of cations include (0, Hs)sO”, Ccl
ls)s'', from which carbonium cations can be obtained by dissolving salts of them and anions (carbonium salts) in suitable organic solvents as supporting electrolytes. Typical examples of anions used here are: BF4-
lAt014-, ALBr5OL-1FeCL4-
, 5nC15-, PF6-1pat;, 5bct6-
Examples of carbonium salts include (C6'l5)30・BF4, (('Ij3)go・
up4. HCo-htat4, HCO-BF4, C
Examples include 6H3coI+5nct5.

The amount of dopant doped into the conjugated polymer compound is 2 to 40 per mole of repeating unit of the conjugated polymer compound.
The mol% is preferably 4 to 30 mol%, particularly preferably 5 to 20 mol%. Even if the amount of dopant doped is less than 2 mol % or more than 40 mol %, a battery with a sufficiently large discharge capacity cannot be obtained.

The electrical chamber conductivity of a conjugated polymer compound before doping is 10 to 10Ω・α, and the electrical conductivity of a conductive conjugated polymer compound obtained by doping with a dopant is approximately 1
The electrical chamber conductivity of the conductive conjugated polymer compound obtained by doping is generally in the range of 0-10 to 1o4n"'1.il when used as an electrode of a negative battery.
It is preferably larger than 0″Ω-1・dl, and when used as an electrode of a secondary battery, it is about t o ″-1
It may be from 0 to about 10 Ω-1@d1 or greater than about 10 Ω·m.

It can be freely controlled by this. The doping can be carried out either under constant current, constant voltage or under varying conditions of current and voltage. The current value, voltage value, doping time, etc. during doping vary depending on the type of conjugated polymer compound used, bulk density, area, type of dopant, type of electrolyte, and required '-electrical conductivity. cannot be specified.

The electrolytic solution used in the present invention can be either an aqueous solution or a non-aqueous solution, but is preferably one in which the dopant is dissolved in a non-aqueous organic solvent.

The organic solvent used here is preferably aprotic and has a high dielectric constant. For example, ethers, ketones, nitriles, amines, amides, chemical compounds, chlorinated hydrocarbons, esters, carbonates, nitro compounds, etc. can be used, but among these, ethers, ketones, nitriles, chlorinated hydrocarbons, carpone) M is preferred. Representative examples of these include tetrahydrofuran, 2-methyltetrahydrofuran, 1
, 4-dioxane, monoglyme, acetonitrile, propionitrile, 4-methyl-2-pentanone, futiloni F! J Lus 1.2-Dichloroethane, γ-butyrolactone, dimethoxyethane, methylformate, propylene carbonate, ethylene carbonate, dimethylformamide, dimethylsulfoxide, dimethylthioformamide, sulfolane, etc. can be mentioned, but
It is not necessarily limited to these. These organic solvents may be used alone or as a mixed solvent of two or more. Depending on the type of battery used or the type of electrode used, oxygen, water, protic solvents, etc. in these solvents may deteriorate the battery characteristics, so if it is 7 or more, it should be purified according to the usual method. is “preferable”.

The organic solvent of the battery electrolyte used in the present invention is a phosphoric acid ester compound represented by the following general formula.

OR.

/ (In the formula, R1, R2 and R5 each represent a hydrogen atom, an alkyl group having 15 or less carbon atoms, an aryl group, an allyl group, an aralkyl group, and a halogenated alkyl group. However, R4, R2 and R5 are (They cannot be both hydrogen atoms at the same time.)

Specific examples of the phosphate ester compounds used in the present invention include trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, trioctyl phosphate, tris(2-chloroethyl) phosphate, Mention may be made of phosphorus (1,3-dichloro-2-propyl), tris(2,3-dibromopropyl) phosphate, tris(4-tcrt-butylphenyl) phosphate and tritolyl phosphate. .

When a conjugated polymer compound or a cage conductive conjugated simple compound compound obtained by doping the polymer compound with a dopant is used as at least one of the electrodes of the battery, the supporting electrolyte of the electrolyte of the battery is The same materials as those used for chemical doping are used, and the doping conditions are the same as those described above, including the type of anode or cathode used, charge/discharge conditions, operating temperature, type of electrolyte, and type of organic solvent. Since it varies depending on the situation, it cannot be specified unconditionally, but it is usually in the range of 0.001 to 10 mol/l.

In the present invention, a conjugated polymer compound or an electrically conductive conjugated polymer compound obtained by doping the conjugated polymer compound with dopane can be used to activate the (1) positive electrode, (11) debt, or 011) positive and negative electrodes of a battery. Can be used as a substance.

For example, in the case of a secondary battery, as an example of (1), if acetylene polymer 'k (OH)x, (OH)x
(Positive electrode) / Li0604 (Electrolyte) / L seal (Negative electrode)
, [(OH)”□O′(”04) o,C6)x
(Positive electrode) / Li0604 (Electrolyte) / Li (Negative electrode), (For example, ((OH) + 0°024
(ClO4) 0.024” (positive electrode) / (n
Bu4N)"・(cjoO-(electrolyte)/[(n-B
u4N)"0.(124(OH)-'024)X (
negative electrode), [-(all) +0.06(PF6)i,
C6)x (positive electrode) / (n-Bu4N)+・(p
i;'6)-(electrolyte>/[(n-Bu4N) paleo,
. 6(CH)41M 'Jx <negative electrode), [(OH)''
・Opening 50 (0'04)i, oso ) x (positive electrode) /
(n −13u 4N)” ・(0/,04)−C
Electrolyte) / ((OH)”・020(ClO2⇠, 0
20'1lX (negative electrode) -((n-Bu4N)S, C2
(OH)-・02)x (positive electrode)/(Nal (electrolyte)/((OH)-"10(Na)i
5. o+o ) (negative electrode), etc.

In the case of polyparaphenylene, (06H4)X is used instead of (OH)x, in the case of poly(2,5-chenylene), (c4o2s)xk is used instead of (('H)x, and in polypyrrole, In some cases, (04H2N)x is used as a secondary battery of the same type as above.

Furthermore, in the present invention, different conjugated polymer compounds can be used for the positive and negative electrodes, and a specific example thereof is (O
H)x / L10LO4/ (06H4)x, (C1
1) x/Li01O4/ (04H28),
(06H4)X / Li0604/ (C6”4
)x, etc.

In addition, as an example of a secondary battery, a conductive conjugated polymer compound is used as a positive electrode active material, and Pauling's electronegativity is 1.
．． Examples include those in which not more than 6 total islands are used as the negative electrode active material. Examples of metals used as the negative electrode active material include alkali metals such as lithium and sodium, aluminum, and magnesium. Among them, lithium and aluminum are preferred. These metals may be used in the form of a sheet as in a general lithium battery, or the sheet may be crimped onto a nickel or stainless steel mesh.

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 a diaphragm.

In addition, some of the conjugated polymer compounds used in the present invention undergo a gradual oxidation reaction due to oxygen, which deteriorates the performance of the battery. is necessary.

A conjugated polymer compound using a phosphate ester compound as the organic solvent of the electrolytic solution of the present invention or an acid-isotropic conjugated polymer compound obtained by doping the polymer compound with a dopant is used as at least one electrode. The battery has high energy density, high charge/discharge efficiency, long cycle life, low self-release 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 appliances, electric cars, gasoline, automobiles, and power storage batteries.

EXAMPLES 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, a glass reaction vessel with an internal volume of 500 mm was heated.
．． Add 71 nt titanium tetra9 toxide,
A catalyst solution was prepared by dissolving 0- of anisole, and then adding 2.7 ml of triethylaluminum with stirring.

This reaction vessel was completely cooled with liquid nitrogen, and the nitrogen gas in the system was exhausted using a vacuum pump. Next, this reaction vessel wo-78
After cooling to 0.degree. C. and keeping the catalyst solution stationary, purified acetylene gas at a pressure of 1 atmosphere was bubbled through.

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

After 30 minutes, the acetylene gas in the reaction vessel system was exhausted to stop the polymerization. After removing the catalyst solution with a syringe under a nitrogen atmosphere, it was diluted with 100% purified toluene while keeping the temperature at -78°C.
Washed repeatedly. 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 a reddish-purple color with a metallic luster, a thickness of 85 μm, and a cis content of 98%.
A film-like acetylene polymer was obtained. In addition, the bulk density of this film-like acetylene high polymer is 0.29 f/CC,
Its electrical conductivity (DC four terminal method) is 3.2X1 at 20℃
0 Ω・, -1 [Battery experiment] The bulk density was 0.0Ω at the film thickness of 85 μm obtained by the above method.
From a film-like acetylene polymer of 29f/CC, the length force E at width °゛-2. A 1" piece of OBO/J' was mechanically crushed and fixed on a platinum wire to form a positive electrode. On the other hand, lithium metal was used as a negative electrode and lithium metal was used as a reference electrode, and the concentration of Li Oto 4 was is 10 mol/l
A triethyl phosphate solution was used as the electrolyte.

-ffit, iT (.5”A/CI) T 1V
n ra'l ff, '! [k h fx (doping amount: 'electricity 1' corresponding to 9 molti). After charging, immediately discharge under a constant current (o, s mA/crtl), and the acid ratio becomes 2Vil+! : Density When the charge/discharge repetition test 'j-500 was conducted under the same conditions as above, the voltage characteristics at the 500th discharge were exactly the same as those at the first discharge.

The energy density for IKg of the acetylene high polymer used was 710 w-hr/K (7, and the charging and discharging
The efficiency was 93chi. Further, the ratio of the amount of electricity discharged until the voltage decreased to 3cm during discharge to the total discharge 'electricity 1-' was 86cm.

Furthermore, when the battery was discharged for 48 hours in a charged state, the self-discharge rate was 6%.

Comparative Example 1 [Battery Experiment] The bulk density obtained in Example 1 was 0.29 f/a:
,, film thickness is 85 μm, electrical conductivity is 3.2 × 10−
The battery was charged and charged with the same weight as in Example 1, except that a film-like acetylene polymer with a Ω-1 t of 11-' was used, and propylene carbonate was used as the organic solvent for the electrolyte.
When conducting a discharge repetition experiment, the number of repetitions b was 5.
Charging became impossible after the 7th time. After the test, when we took out the film-like acetylene polymer, we found that the film had been destroyed.
When a part of it was analyzed using elemental analysis and infrared spectroscopy, it was found that it had suffered extensive deterioration. The electrolyte was also colored brown.

The energy density with respect to the film-like acetylene high polymer lKf used was 3:10 w-hr/Kl, and the charge/discharge efficiency was 52%. Further, the ratio of the amount of electricity discharged until the voltage decreased to 3V during discharge to the total amount of electricity discharged was 64%.

When the battery was left in a charged state for 48 hours, its self-discharge rate was 35 cm.

Example 2 [Battery experiment] From the acetylene polymer obtained in Example 1, the width was 0.5 mm.
Two pieces of cIn with a length of 20 Crn were cut out and the two pieces were mechanically crimped and fixed to separate platinum wires to form a positive electrode and a negative electrode, respectively. (Bu 4N) ” (P F
6) - A trimethyl phosphate bath solution with a concentration of 0.5 mol/l was used as the electrolyte under constant current (0.5 mA/cr!
) for 2 hours (amount of electricity equivalent to 9 molti doping amount), and immediately after charging, a constant current (0,
When we conducted a repeat charge/discharge test 200 times, we discharged the battery at 5 mA/i) and when the voltage reached IV, we charged it again under the same conditions as above.
The voltage characteristics at the 20,000th time were exactly the same as those at the first time.

The energy density for the used membranous acetylene polymer I Kg is 295 w = hr / Kg,
The charging/discharging efficiency was 87 cm. Furthermore, the ratio of the amount of electricity discharged until the voltage dropped to 15V during discharge to the total number of electric charges was 90%.

Furthermore, when the battery was left in a charged state for 48 hours, its self-discharge rate was 9%.

Comparative Example 2 [Battery Experiment] A repeated charge/discharge experiment was carried out in exactly the same manner as in Example 2, except that tetrahydrofuran was used instead of trimethyl phosphate used as the organic solvent of the electrolyte solution. When I repeated this for the 35th time, charging became impossible. After the experiment, when the film-like acetylene polymer was taken out, it was found to have been destroyed, and part of it was analyzed by elemental analysis and infrared spectroscopy, and it was found that it had suffered significant deterioration.

Further, the electrolyte was colored brown.

Furthermore, the energy density for the acetylene high polymer IKf used was 120 w-hr/Kg, and the charge/discharge efficiency was 46 cm. Furthermore, the ratio of the amount of electricity discharged until the voltage decreased to 1.5 V during discharge to the total amount of electricity discharged was 59. Furthermore, when the battery was left in a charged state for 48 hours, its self-discharge rate was 48 cm.

Example 3 [Doping experiment] From the acetylene polymer obtained in Example 1, the width was 0.
A small piece with a length of -2.0 crn was cut out at 5α, mechanically crimped and fixed to a platinum wire to serve as an anode electrode, and a platinum plate was used as the other electrode to form a dense [ca.0. Using a 3 mol/l propylene carbonate solution as the electrolyte, doping was carried out under constant current (1.0 mA) for 5 hours. After doping, the doped acetylene polymer film was repeatedly washed with propylene carbonate to give it a golden color. A doped acetylene polymer with metallic luster was obtained.

The composition of this doped acetylene polymer film is determined by elemental analysis (0H(BF2) 0.160), and its electrical conductivity (DC four-terminal method) is 470Ω-1・d
[Battery discharge experiment] - BF4' total 4' dove l1 l obtained by the above method
A battery was constructed using a j-conducting acetylene polymer as a positive electrode active material and lithium as a negative electrode active material.

FIG. 1 is a schematic cross-sectional view of a battery cell for measuring the characteristics of a button-type battery, which is a specific example of the present invention, in which 1 is a brass container plated with Ni, 2 is a disc-shaped lithium negative electrode with a diameter of 2011110 mm, and 3 is a A circular porous polypropylene diaphragm with a diameter of 2611 m, 4 a circular carbon fiber felt with a diameter of 261111 m, 5 a positive electrode, and 6 a Teflon sheet with holes with an average diameter of 2 μm (manufactured by Sumitomo Electric Industries, Fluorobore F)
P-200), 7 is a Teflon container with a circular cross section, 8 is a Teflon ring for fixing the positive electrode, and 9 is an N1 lead wire.

The positive electrode (conductive acetylene polymer doped with BF4-i) was placed in the recess at the bottom of the container 1, and a porous circular Teflon sheet 6 was placed over the positive electrode, and then tightened and fixed with a Teflon ring 8. .

Place the felt 4 in the recess at the top of the container L and overlap it with the positive electrode.
After being impregnated with the electrolyte, the lithium negative electrode 2 is inserted through the diaphragm 3.
was placed and tightened with container 7 to produce a battery. The electrolyte was Bu4N dissolved in distilled and dehydrated triethyl phosphate.
A solution of 1 mol/1 fll of 0104 was used.

The open circuit voltage of the battery thus produced was 37 .mu.m.

When this battery was discharged at a constant current of 0.3 mA in an argon atmosphere, the relationship between discharge time and voltage was as shown by curve (a) in FIG. 2.

Comparative Example 3 A battery discharge experiment was conducted in exactly the same manner as in Example 3, except that propylene carbonate was used instead of triethyl phosphate as the organic solvent for the electrolyte of the battery in Example 3. The curve b) was obtained.

Example 4 A 100 mesh mesh of stainless steel was placed in a 1 ton glass reactor which was completely purged with nitrogen gas, and then 100% of toluene purified according to a conventional method was used as a polymerization solvent.
ml, tetrabutquin titanium as catalyst 4.41
A catalyst solution was prepared by sequentially charging mmol and 11.01 mmol of triethylaluminum at room temperature. The catalyst solution was a homogeneous solution.

Next, the reactor was cooled with liquid nitrogen, and the nitrogen gas in the system was exhausted using a vacuum pump. The reactor was cooled to −78° C., and purified acetylene gas at a pressure of 1 atmosphere was blown into the reactor while the catalyst solution was left standing. The polymerization reaction was continued for 10 hours while maintaining the pressure of the acetylene gas at 1 atm. The system was agar-like with a reddish-purple color. After the polymerization, unreacted acetylene gas was removed and the system was washed four times with 200 tnl of purified toluene while keeping the temperature at -78°C.
A sheet-like swollen acetylene polymer containing a steel mesh was obtained. This swollen acetylene high polymer has a molecular weight of 300 to 500
It was a swollen product in which fibrous microcrystals (fibrils) with a diameter of λ were regularly intertwined, and no powder or lump-like polymer was produced.

This sheet-like swollen acetylene polymer containing the stainless steel mesh is sandwiched between chrome-plated ferro plates.
Pre-press at a pressure of 140 K4/- at room temperature and then high-pressure press at a pressure of 15 ton/di to obtain a uniform and flexible film thickness of 2Bθμ with a reddish-brown metallic luster.
A complex of m was obtained. This composite was dried for 5 hours at room temperature under vacuum. The composite contained 43 w+lit'% stainless steel mesh. .

[Battery experiment]

[Battery experiment] was conducted in exactly the same manner as in Example 1 except that the composite obtained by the above method was used.
It was possible to repeat charge and discharge times. In addition, as a result of the first repeated charge/discharge test, the energy density was 750 w'' hr/K9, and the light/discharge efficiency was 9.
It was 8%. Furthermore, when the battery was charged and left for 48 hours, the self-discharge rate was 8%.

Comparative Example 4 [Battery experiment] was carried out in exactly the same manner as in Example 4, except that tetrahytronane was used in place of the tri-ethyl phosphate used as the battery solvent in Example 4. As a result, the repetition of light and discharge stopped at the 180th time. Further, the energy density was 550 w-hr/Kg, and the charge/discharge rate was 72 inches. Furthermore, the self-discharge rate when the battery was charged and left for 48 hours was 38%.

Example 5 Ijull, Chem, Soc, Japan, +
51.2091 (1978).
A battery experiment was carried out in exactly the same manner as in Example 2, except that the positive and negative electrodes were formed into a width of 0.5 c1n x 2.0 crn at a pressure of The voltage characteristics up to the first discharge were exactly the same as those during the first discharge. The energy density of this battery is 320W
-hr/Kg, and the charging/discharging efficiency was 80 cm. Furthermore, when the battery was left charged for 48 hours, its self-discharge rate was 10%.

Comparative Example 5 [Battery experiment] was carried out in exactly the same manner as in Example 5, except that propylene carbonate was used instead of trimethyl phosphate, which was used as a solvent for the battery electrolyte in Example 5.

The octopus stopped repeating light coming and discharging on the 47th time. Also, the energy density of this battery is 270 W −
hr/Ko, and the charging/discharging rate was 67 cm. Furthermore, when the battery was left charged for 48 hours, its self-discharge rate was 52%.

Example 6 J, Polym, Sci, Polym, Lett, E
Example 2 except that the positive and negative electrodes were made of poly(puffed phenylene) produced by the method described in J.D., 18.8 (1980) and molded to a width of 05α×2, OtM under pressure. [Battery experiments] conducted in exactly the same manner as above revealed that the voltage characteristics were exactly the same as the first discharge up to 200 repeated discharge tests.

The energy density of this battery is 260 w @hr /
kg, and the charging/discharging efficiency was 75%. Furthermore, when the battery was left charged for 48 hours, its self-discharge rate was 12%.

Comparative Example 6 [Battery experiment] was carried out in exactly the same manner as in Example 5, except that propylene carbonate was used instead of trimethyl phosphate, which was used as a solvent for the battery electrolyte in Example 6.

As a result, the repetition of light and discharge stopped at the 35th time. Also, the energy density of this battery is 180 w-hr
/ Kg, and the charging/discharging efficiency was 52%. Furthermore, when the battery was left charged for 48 hours, its self-discharge rate was 48%.

[Brief explanation of drawings]

FIG. 1 is a schematic cross-sectional view of a battery cell for measuring the characteristics of a button-type battery, which is a specific example of the present invention, and FIG. 2 is a third embodiment of the present invention.
and FIG. 7 is a diagram showing the relationship between battery discharge time and voltage in Comparative Example 3. l... Container 2... Lithium negative electrode 3... Diaphragm 4... Felt 5... Positive electrode 6... Porous Teflon sheet 7...
Teflon container 8...Teflon ring 9...Ni lead wire Patent applicant Showa Denko Co., Ltd. Hitachi Ltd. representative 1 A Patent attorney Sei Kikuchi - City 1 map Travel time (hours)

Claims (1)

[Scope of Claims] A battery in which at least one electrode uses a polymer compound having a conjugated double bond in its main chain or a conductive polymer compound obtained by doping the polymer compound with a dopant,
A battery characterized in that a phosphoric acid ester compound represented by the following general formula is used as an organic solvent of an electrolytic solution. ＼ J (In the formula, 1, R2 and R5 each represent a hydrogen atom, an alkyl group having 15 or less carbon atoms, an aryl group, an allyl group/aralkyl group, and a halogenated alkyl group. However, 1, R2 and R3 cannot be a hydrogen atom at the same time.)