JPS6093771A - Secondary battery - Google Patents

Abstract

PURPOSE:To increase cycle life and energy density of a secondary battery by using high molecular compound having conjugated double bond as active material and using carbon as positive current collector and metal as negative current collector. CONSTITUTION:A high molecular compound such as acetyene high polymer having conjugated double bond in its principal chain is used as positive and negative active materials. In this secondary battery, carbon such as graphite is used as a positive current collector and metal such as nickel, stainless steel is as a negative current collector. This secondary battery has high energy density, long discharge time, and flat discharge voltage. It is easy to make light and compact.

Description

[Detailed description of the invention] The present invention relates to a secondary battery with a good cycle life.

The acetylene polymer obtained by polymerizing acetylene using a so-called Ziegler-Natsuta catalyst consisting of a transition metal compound and an organometallic compound is suitable as an electric/electronic device because its electric element 4 degrees is in the semiconductor region. It is already known that it is a useful organic semiconductor material. However, the acetylene polymer obtained in this way does not melt even when heated, and the product undergoes oxidative deterioration under heating, so it cannot be molded using the usual molding methods used for thermoplastic resins. Can not. Furthermore, no solvent has been found that dissolves this acetylene polymer. Therefore, conventional methods for producing practical molded products of acetylene high polymers include (a) a method of pressure molding powdered acetylene high polymers;
and ←) Formed into a film at the same time as polymerization under special polymerization conditions,
Method for obtaining a membranous acetylene high-11 polymer having a fibrous microcrystalline (fizuril) structure (Japanese Patent Publication No. 32581/1983)
, was known.

The powdered acetylene polymer molded product obtained by the method (a) above was converted into BF3, BC115HHCII + CI.
J2 t 802 +NO2r HCN + 02 t
When chemically treated with an electron-accepting compound (acceptor) such as No, the electrical conductivity increases by up to three orders of magnitude;
It is already known that treatment with electron-donating compounds (donors) such as monium or methylamine can reduce electrical conductivity by up to four orders of magnitude.

Furthermore, I2 + C112+ Br2 + IC1l IB is added to the film-like acetylene polymer obtained by the method (0).
r + AsF5°SbF5. 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 by IQ.
It is already known that it can be freely controlled over a wide range of ~IO'Ω-1·cnr-'. The idea of using this doped film-like acetylene polymer as a material for the positive electrode of a primary battery has already been proposed.

On the other hand, in addition to the above chemical doping method, electrochemical ClO4+PF6-+AsF6-+AsF4-
+CF35o3rBF; anion such as 'J and R'
, Ni (R': alkyl group) and other cations have been doped into acetylene polymers to produce p-type and n-type conductive acetylene polymers. A rechargeable battery using electrochemical doping using a film-like acetylene polymer obtained by the method (b) has been reported. This battery uses two acetylene polymer films obtained by the method (b), for example, with a thickness of O, l tan, as positive and negative electrodes, respectively, and immerses them in a tetranohydrofuran solution containing lithium iodide. When connected to a 9V DC power source, 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. This electrolytic doping corresponds to the charging process. If a load is connected to the two doped electrodes, the lithium ions and iodine ions will react and generate electricity. In this case, the open circuit voltage ("oc") is 28 V, the short circuit current density is 5 mA/2, and when a tetranohydrofuran solution of lithium perchlorate is used as the p1 electrolyte, the open circuit voltage is 2.5 V.
1 short circuit current density was approximately 3 mA/cm2.

In addition to acetylene copolymer, it is already known that polymeric compounds having a conjugated double bond in the main chain, such as polyno('raphenyle/) and polythiophene, can also be used as electrode materials for batteries.

These batteries use polymeric compounds with conjugated double bonds in their main chains, such as acetylene polymers, which are easy to reduce weight and size as electrode materials, so they are lightweight and have high energy density. It is attracting attention as a battery that is easy to miniaturize and is inexpensive. However, this battery uses a system consisting of an organic solvent and a supporting electrolyte as the electrolyte, and because the voltage of the battery is high, it uses commonly used austenitic stainless steel such as SUS 304 or Ni for both the positive and negative electrodes. When used as a current collector (current collector), a reaction between the current collector and the electrolytic solution occurs during repeated charging and discharging, and a sufficient cycle life cannot be obtained.

In view of the above points, the present inventors have developed a system that has a high energy density, has a sufficient cycle life, and is easy to reduce weight and size.
The present invention has been completed as a result of various studies aimed at obtaining a battery that is also inexpensive.

That is, the present invention describes the use of carbon as the current collector of the positive electrode and the metal as the current collector of the negative electrode in a secondary battery using a polymer compound having a conjugated double bond as the active material of the positive electrode and the negative electrode. Regarding the characteristics of secondary batteries.

Specific examples of polymer compounds having a conjugated double bond in the main chain used in the present invention include acetylene polymer (polyacetylene), polyphenylacetylene, polyparaphenylene/, polymekuphenylene, and moon? (2,5-chenylene), poly(3-methyl-2,5-chenylene), polyphenylene sulfide, polypyrrole, polyimide,
Thermal decomposition products of polyacrylonitrile and poly-α-noanoacryl, polymer compounds having a polyacene structure, polyacequinone radical polymers, quinacin having a n, f base structure, I? Polymer polyarylene quinone M, EP
-Heat-treated phenolic novolak resin disclosed in No. 67,444 and French Patent No. 2,505,8
Examples thereof include the polymers disclosed in No. 54, but are not necessarily limited thereto, and any polymer compound having a conjugated double bond in the main chain may be used.

Among the above polymer compounds, preferred are:
Acetylene high polymer 49 lino-e rough phenylene, poly(
215 thienylene), polypyrrole, and preferred examples include acetylene polymers, particularly preferably highly crystalline acetylene polymers.

The method for producing the acetylene polymer used in the present invention is not particularly limited, and any method can be used.
No. 45365, JP-A-55-129404, JP-A No. 55-
No. 128419, No. 55-142012, No. 56-1
No. 0428, No. 56-115305, No. 56-133
No. 133, No. 57-53324, No. 57-70114
No., Trans, Farady'SOc, +64
+823 (1968), J. Polymer Sci, +
A-L7 r 3419 (1969) + Makr
omol,Chem,,RapidComm,+1+
6.21 (1980), J.Chem.Phy.
s.

69 (1) + 106 (1978) + 5ynth
etic Metals.

4.8] and (1,981).

The polymer compound having a conjugated double bond in its main chain used in the present invention can be in any form such as film, powder, short fibers, etc.

In addition, polymer compounds having conjugated double bonds in their main chains can be made using reinforcing materials such as expanded lattice bodies or continuous cast lattice bodies.
It is also possible to use ember which is reinforced by methods known to those skilled in the art to increase its mechanical strength. Furthermore, it is also possible to mix other suitable conductive materials such as graphite, carponsic, acetylene black, metal powder, carbon fiber, etc. with the polymer compound having a conjugated double bond in the main chain. .

As electrodes for the battery of the present invention, not only polymer compounds having a conjugated double bond in the It can be used as

Dono to a polymer compound having a conjugated double bond in its main chain (hereinafter abbreviated as a conjugated polymer compound)? The doping method may be either chemical doping or vapor chemical doping.

Chemically doping compounds include various conventionally known electron-accepting compounds and electron-donating compounds, including (I) halogens such as iodine, bromine, and bromine iodide, (■) Metal halides such as arsenic pentafluoride, antimony pentafluoride, silicon tetrafluoride, phosphorus pentachloride, phosphorus pentafluoride, aluminum chloride, aluminum bromide and aluminum fluoride, (to) sulfuric acid, nitric acid, fluorosulfuric acid , triflu, 71-o protic acids such as meta/sulfuric acid and chlorosulfuric acid, oxidizing agents such as sulfur dioxide, nitrogen dioxide, nofluorosulfonyl nitrogen, (v) AgC104, (to) tetracyano ethylene,
Examples include tetro/anoquinodimethane, floranil, 2,3-dichloro-5,6-ran anoparabenzoquinone, and 2,3 nobromo-5,6-ran anoparabenzoquinone.

On the other hand, as a doping agent for electrochemically doping a conjugated polymer compound, (1 pF; , 5bp7 +
AsFxi, halide anions of group Va elements such as 5bcxy, halide anions of group A elements such as BF7, halogen anions such as Br-+ Cl'-, Anionic dopants such as perchlorate anions and (II) Ll
++ Alkali metal ions such as Na+, K'', R4
Examples include cation dopants such as quaternary ammonium ions such as N+ (R2 hydrocarbon group having 1 to 20 carbon atoms), but are not necessarily limited to these.

Specific examples of compounds providing the above-mentioned anionic dopants and cationic dopants include LiPF + L.
iAsF6+ LiSbF6+ Li(JO4, NaI
rNaPF, Na5bF + NaAsF,
NaC10+KI+KPF6+6 6 6 4 KSbF6. KAsF61 KClO41[:(n-
Bu)4N)”(AsF6)-.

[:(n-Bu)4N]'(PF6)-((n-Bu)
4N)' ClO4-+LiA/C/ + LiBF
, N()AsF, No IAsT, No-BF
Examples include 4°4 4 6 26 NO.BF and No-PF6, but 4 is not necessarily limited to these. These dopants may be used singly or in combination of two or more.

Anions other than the above, such as dopa/1, are HF; - anions, and cations and dopants other than the above, are biryllium or bilinonium cations represented by the following formula (1): (wherein, X is an oxygen atom or a nitrogen atom Hl is a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, 6 to 15 carbon atoms
aryl group, R'' is a halodane atom or
'c-position alkyl group having 1 to 10 carbon atoms, 6 to 15 carbon atoms
aryl! Sm is O when X is an oxygen atom
It is 1 when X is a nitrogen atom. n is 0 or 1
~5. ) or Cal expressed by the following formula (If) or (to)?
or R'-C" (Ill) 1 [In the above formula, R'+ R2, R3 are hydrogen atoms (R1+ R
21R3 is not a hydrogen atom at the same time], an alkyl group having 1 to 15 carbon atoms, an allyl group, an aryl group having 6 to 15 carbon atoms, or an -OR group,
However, R5 represents an alkyl group having 1 to JO carbon atoms or an aryl group having 6 to 15 carbon atoms, and R4 represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an alkyl group having 6 to 15 carbon atoms.
5 is an aryl group. ] It is.

The above-mentioned HFi anion, the pyrylium cation or pyridinium cation represented by formula (1), and the calcium d? The conjugated polymer compound can be heavily doped with nium cations, so that the resulting battery has a large discharge capacity and a high energy density.

The HFi anion used typically has the following general formula % formula %
(: ) () () [However, in the above formula, R'tR" is a hydrogen atom or a carbon number of 1
~15 alkyl group, aryl having 6 to 15 carbon atoms (ar
yl) group, RII' is an alkyl group having 1-10 carbon atoms,
An aryl group having 6 to 15 carbon atoms, X is an oxygen atom or a crab atom, and n is 0 or a positive integer of 5 or less. M is an alkali metal]
, hydrogenide salt) as a supporting electrolyte and dissolved in a suitable organic solvent. Specific examples of compounds represented by the above formulas (g), (to) and (to) are H4N"
HFz + Bu2N”HF2 *Na”fir,
K'HF, Li''HF2 and 2 The pyrylium or pyridinium cation represented by the above formula (1) is the cation represented by the formula (1) and CnoQ, -, BF2 + AlCl; *FsCJa I
5nCJi + PF6 *PCI6 * BbF;
t AsFi t It can be obtained by dissolving in a suitable organic solvent using a salt with an anion such as CF, So, " + HF2 as a supporting electrolyte. Specific examples of such a salt include the following.

Carbonium represented by the above formula (n) or (to)
Force f: 4-n cQ Specific examples are (C6H,), C++
(C) f3), C+.

OO These carbonium cations can be obtained by dissolving a salt of them and an anion (carbonium salt) in a suitable organic solvent as a supporting electrolyte. Representative examples of anions used here include BF4' t AlC1a
p AjBJCI-r FeCl2 t 5nCjs
# PF6 eP% SbC/; l SbF; i
I can list CJo71 cr, so; etc.
In addition, specific examples of carbonium salts include -cu, example jt(
c6n5), c-up, p (CH3)3C-BF4
, HCO"AICJ, HCO"BF4. C, H5
Examples include CO'5nCj5.

In the present invention, the carbon used as a current collector for the positive electrode of a battery refers to a material consisting essentially only of carbon, such as graphite, artificial graphite, and the like. The shape of the carbon current collector is not particularly limited, and it may be in the form of a sheet, or it may be coated with carbon on a base material such as metal by a method such as vacuum deposition or suctioning. . Furthermore, it may be coated with carbon paste. The electrical conductivity of these carbon current collectors is 1Ω
-1·crn'-' or more is preferable.

Specific examples of metals used as the current collector of the negative electrode of the battery of the present invention include nickle, titanium, austenitic stainless steel, aluminum, platinum, and high-chromium, high-purity ferritic stainless steel.

The contact between the conjugated polymer compound and the current collector may be simply pressed, but the conjugated polymer compound and the current collector may be
Although the bonding is performed by pressing or rolling at a pressure of 7 cm2 or more, it is also possible to directly polymerize a monomer on the surface of the current collector to form a composite of the conjugated polymer compound and the current collector.

The electrolytic solution used in the secondary battery of the present invention can be either an aqueous solution or a non-aqueous solution, but is preferably one in which the above dopant is dissolved in a non-aqueous organic solvent. The organic solvent mentioned here is preferably one that is aprotic and has a high dielectric constant. For example, ethers, ketones, nitriles, pyridines, amides, sulfur compounds,
Chlorinated hydrocarbons, esters, phosphate ester compounds, phosphite ester compounds, carbonates, nitro compounds, etc. can be used, but among these, ethers, ketones, nitriles, chlorinated Hydrocarbons and carbonates are preferred. Representative examples of these organic solvents include tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-nooxa/, monoglyme, acetonitrile, propionitrile, valeronitrile, 4-methyl-2,-o-onthanone, butyronitrile, benzonitrile, .2-nochloroethane, γ-butyrolactone, valerolactone, dimethoxyethane, methylformate, globylene carbonate, ethylene carbonate, dimethylformamide, trimethylsulfoxide, dimethylthiolumamide, pyrinone, sulfolane, 3-methylsulfora, and ethyl phosphate. , methyl phosphate, ethyl phosphite, methyl phosphite, etc., but are not necessarily limited to these. These organic solvents are the same as those used in vapor chemical doping as one type or a mixed solvent of two or more types, and the doping conditions are conventionally known methods (J, C, S, +
Chem+Commu, + 1981 + J 17
).

゛ The amount of doping can be determined freely by determining the electricity flowing during electrolysis (d11)! 1jlJ can be controlled.

Doping may be carried out either under constant current, constant voltage, or under varying current and voltage conditions. The current value, voltage value, doping time, etc. during doping depend on the bulk, degree, area, and doping of the electrode used.
The amount of dopant doped into a conjugated polymer compound cannot be specified because it varies depending on the type of cent, the type of electrolyte, and the required electrical conductivity of the conjugated polymer compound. repeating unit of a compound (
The amount is 2 to 200 mol, preferably 3 to 100 mol, particularly preferably 4 to 80 mol, per mol of the monomer. Even if the amount of the doped dopant is less than 2 molar or more than 200 molar, a battery with a sufficiently large discharge capacity cannot be obtained.

However, the concentration of the electrolyte used in the secondary battery of the present invention cannot be specified in part because it varies depending on the type of positive electrode or negative electrode used, charge/discharge conditions, operating temperature, type of electrolyte, type of organic solvent, etc. . The electrolyte can be either a homogeneously dissolved system or a heterogeneous system, but it is usually 0.
．． The range is from 0.001 to 10 mol/l.

In addition to the electrolyte described above, the secondary battery of the present invention may also contain a highly ionic conductive organic solid electrolyte made of polyethylene oxide and Nal or Na5CN, or a mixture of an electrolyte with a saturation solubility or higher (do-cent) and an organic solvent. A paste-like product can be used.

In the secondary battery of the present invention, the conductive conjugated polymer compound obtained by doping the conjugated polymer compound with Do-Gund can be used as an active material for the positive electrode and negative electrode of the battery. .

As a specific example of a secondary battery, for example, if acetylene polymer is (CH)x, (CH)x (IE electrode)/
L 1C1104 (supporting electrolyte)/(CH)X (negative electrode)
, [(CH)+0・024(ClO4)io24]X(
positive electrode) / (n Bu4N)' (C104) - (supporting electrolyte) / C (n - Bu4N), 024 (
CH)'・024]X (negative electrode), C(CH)+0・0
6 (PF6),. 6]X (positive electrode)/(Et4N)+・
(PF6)-(Support 1E solute)/[(Li)Kichi,. 6(
CH]0.06]X (negative electrode), [(CH)-0.050
(“0a) o oso ]X (positive electrode)/, (Li)+・
(ClO4)-(supporting electrolyte)/[(CH)+0.02
0(C104)Ko2o]X (negative electrode), [(n −B
H4S) =, o2! (CH)-・02]x (positive electrode)
/ (n-Bu4N)”-(C104)-(
supporting electrolyte) / ((Bl14N)3..

(CH)-”)x (negative electrode), ((CH)0.010(
H3) 0.01°]X (positive electrode)/LiI (supporting electrolyte)
/((CH)-0-”'(Li) left, olo-] <
negative electrode), etc. In the case of poly-phenylene, (C6H4)X is substituted for the above (CH)x, in the case of poly2.5-chenylene, (C4H2S)X is substituted for (cH)x, and polypyrrole is used. In the case of (C4
H5N)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 electrode and the negative electrode, and specific examples thereof include (
CFI)x/LiCN4/ (C6114)x, (CH
)x /Li(JO4/(C4H2S), (C6H
4) X/LiClO4/(C4H2S)X, etc. can be mentioned.

7J if necessary in the present invention? A porous membrane made of synthetic resin such as polyethylene or polypropylene or natural fiber paper may be used as the diaphragm in some cases.

Moreover, the conjugated polymer compound used in the present invention is
Some batteries undergo a gradual oxidation reaction due to oxygen, reducing the performance of the battery, so it is necessary that the battery be sealed and substantially oxygen-free.

The secondary battery of the present invention has a high energy density, is capable of long-time discharge, and has good voltage flatness. However, the secondary battery of the present invention is lightweight, small, and
And because it has high energy density? - tuple equipment,
Ideal for electric vehicles, ganolin 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 [Preparation of composite] 200 ml of toluene was added to a 1 liter glass autoclave equipped with a blade-type mechanical stirrer under a nitrogen atmosphere. 2 ml of tetrabutoxytitanium (5,9 m mol) and 2 ml of triethylaluminum (14,6 m mol)
mol) and acetylene partial pressure 0.9 kg/an
2+ Polymerization was carried out at a combination temperature of -20°C with stirring for 2 hours.

Simultaneously with the introduction of acetylene gas, short fibrous acetylene polymers of reddish-purple color and approximately one cylinder in length began to be produced.

After the polymerization was completed, the produced short fibrous acetylene polymer was placed on a glass filter and thoroughly washed with about 11 toluene solvents to remove the catalyst. After catalyst removal, the short fibrous acetylene polymer contained 52% by weight of toluene. This toluene-containing short fibrous acetylene polymer 157 and 4 g of carbon black powder (electrical conductivity -2.1x]o3Ω-1/Kushi-1) were mixed in a ball mill. Next, the heated mixture with high chromium high purity ferritic stainless steel (collector) [Showa Denko (
Co., Ltd.'R1 [SHOMAC3O-2J, film thickness 50μ
m] and pressed at a pressure of J OOO kg/crn2, and then degassed under vacuum to form a negative electrode. Similarly, graphite foil (collector, "Graphoil" manufactured by U, C, C, film thickness), 30/'m + electrical conductivity -3.2X103
The above mixture was pressure-bonded to Ω-1.cfn-') to serve as a positive electrode.

The yield of the short fibrous acetylene polymer obtained by this polymerization method was 5.7 g, the cis content was 76%, and the electrical conductivity at room temperature (DC two terminal method) was 5.7 g. I X 10'Ω-1・O
It was n'-'. Further, when the obtained short fibrous acetylene high polymer was observed with a scanning electron microscope, it was found that the acetylene high polymer had a structure consisting of fibrous microcrystals (fibrils) with a diameter of 300 to 400X.

[Battery experiment]

The composite of the mixture of acetylene polymer and carbon black obtained by the above method and the current collector was cut out into small pieces of a predetermined size, and a battery was constructed by using them as a positive electrode and a negative electrode, respectively.

The figure 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. A circular porous polypropylene diaphragm with a diameter of 26 mm, 4 a circular carbon fiber felt with a diameter of 26 mm, and 5 a "S"
A negative electrode with HOMAC30-2J as a current collector, 6 is a Teflon sheet (manufactured by Sumitomo Kekko,
Fluoropore FP-200), 7 is a Teflon container with a circular cross section, 8 is a Teflon H') ring for fixing the positive electrode, and 9 is a Ni lead wire.

The negative electrode (composite of acetylene high polymer, KaryJe black, and l'-SHOMAC30-2J) was placed in the lower four parts of the container 1, and a porous circular Teflon sheet 6 was placed over the negative electrode, and then Teflon was placed. It was fixed by tightening it with a ring 8. The felt 4 is placed in the recess at the top of the container 1 and overlapped with the negative electrode, and after being impregnated with electrolyte, the positive electrode (a composite of a mixture of acetylene high polymer and carbon black and graphite foil) 2 is inserted through the diaphragm 3. It was placed and tightened with container 7 to create a battery. As the electrolyte, a 1 mol/l solution of Bu4N''BF40 dissolved in distilled and dehydrated benzonitrile was used.

Charging was performed under a constant current (2.0 mA 7 cm2) (
amount of electricity equivalent to a doping amount of 5 molti). Immediately after charging, discharge is performed at a constant current (2.0 m1% Arn2) until the voltage reaches 1. When the battery reached Ov, a repeated charging/discharging test was performed in which charging was performed again under the same conditions as above, and the charging/discharging efficiency fell below 50% at the 633rd time.

Comparative Example 1 A battery experiment was carried out in exactly the same manner as in Example 1, except that the electrodes manufactured using graphite foil as the current collector were used for both the positive and negative electrodes. Using this electrode, a battery charging/discharging edge reversal experiment was conducted in exactly the same manner as in Example 1, and the charging/discharging efficiency fell below 50 at the 424th repetition.

Comparative Example 2 A battery experiment was conducted in exactly the same manner as in Example 1, except that nickel foil was used instead of the graphite foil used as the current collector of the positive electrode in Example 1. As a result of repeated charging and discharging tests, 4
At the 39th time, the charging/discharging efficiency fell below 50 units.

Comparative Example 3 A battery experiment was conducted in exactly the same manner as in Example 1, except that titanium foil was used in place of the graphite foil used as the positive electrode current collector in Example 1.

As a result of repeated charging/discharging tests, the charging/discharging efficiency fell below 50 cm at the 407th test.

Example 2 An ri/
Glass autoclave nitoluene 500ml,
l) and triethylaluminum 2m1 (14,6m
mol), acetylene partial pressure i, 6kg/
cm 2 and polymerization temperature of 30° C. while stirring for 1 hour. Simultaneously with the introduction of acetylene gas, a black powdery acetylene polymer having a particle size of about 0.1 ran was produced, and the catalyst was removed by washing with a toluene solvent. After catalyst removal, the powdered acetylene polymer contained 47% by weight toluene.

The powdered acetylene polymer obtained by the above method was used as a substitute for the mixture of acetylene polymer and carbon black used in Example 1. A battery experiment was conducted in exactly the same manner as in Example 1, except that titanium foil was used instead of -2J.

- When repeated charging/discharging tests were conducted, the charging/discharging efficiency fell below 50% at the 652nd time.

Comparative Example 4 “SUS 316 J (film thickness 50 ttm) was used instead of the graphite foil and titanium foil used as current collectors in Example 2.
) was used for both electrodes, and an electrode was formed in exactly the same manner as in Example R, and a battery experiment was conducted in exactly the same manner as in Example 1 using this electrode.

When repeated charging/discharging tests were conducted, the charging/discharging efficiency fell below 50% at the 297th time.

Example 3 Instead of the acetylene high polymer used in Example 2, Bul
l, Chem, Soc, Japan, -yu l 2091
(1978)
An electrode was manufactured in exactly the same manner as in Example 2, except that GRAphenylene was used, and then a battery experiment was conducted in the same manner as in Example 2. As a result, the repeated charge/discharge test was 60
The charging/discharging efficiency fell below 50% on the first try.

Example 4 The acetylene high J used in Example 2 “J instead of coalescence,
Polym, Sci, +Polym, Lets, FD,
18, 9 (1980). , l(2,5-thennylene) was used, but an electrode was manufactured in exactly the same manner as in Example 2, and then a [battery experiment] was conducted in the same manner as in Example 2. As a result, the repeated charge/discharge cycle was At the 588th repetition test, the charging/discharging efficiency fell below 50%.

[Brief explanation of drawings]

The figure shows a schematic cross-sectional view of a battery cell for measuring time of a button type battery, which is a specific example of the present invention. 1... Container, 2... Positive electrode, 3... Diaphragm, 4...
Felt, 5... Negative electrode, 6... Porous Teflon notebook, 7... Teflon container, 8... Teflon ring, 9... N1 lead wire. Patent applicant Showa Denko Co., Ltd. Hitachi Ltd. Representative Patent attorney Sei Kikuchi - Figure

Claims (1)

[Claims] A secondary battery using a polymer compound having a conjugated double bond in its main chain as an active material for the positive and negative electrodes, characterized in that carbine is used as the current collector of the positive electrode and metal is used as the current collector of the negative electrode. Secondary battery.