JPS6093773A - Secondary battery - Google Patents

Abstract

PURPOSE:To increase energy density and improve charge-discharge efficiency and cycle life by using ammonium salt having a specified quaternary ammonium ion as cation component as electrolyte of electrolyte solution. CONSTITUTION:High molecular compound such as acetylene high polymer having conjugated double bond in its principal chain or electroconductive high molecular compound prepared by doping dopant in the above high molecular compound is used as electrode of a secondary battery. Ammonium salt containing as cation component quaternary ammonium ion indiated by general formular shown in the figure (in the formula, R1-R4 are alkyl group or aryl group having a carbon number of 1-16) is used as electrolyte of electrolyte solution. For example, trimethylpropylammonium is used as cation component of ammonium salt. This secondary battery has small self discharge rate, flat discharge voltage, and is easy to make light and compact.

Description

Detailed Description of the Invention The present invention provides a secondary battery that has high energy density, high charge/discharge efficiency, long cycle life, low self-discharge, and good voltage flatness during discharge. Related to.

Acetylene polymers obtained by polymerizing acetylene using so-called Ziegler-Natsuta catalysts, which are composed of transition metal compounds and organometallic compounds, are useful as electrical and electronic devices because their electrical conductivity is in the semiconductor region. It is well known that the monthly yield of organic semiconductors is

Methods for producing practical molded products of acetylene high polymers include (a) a method of pressure molding a powdered acetylene eight-hand combination, and (LJ) a method of forming a special polymerization strip under a'1 c! Same as ti machine +1
Molded into i5 into NU shape and made into fibrous microcrystals (Neubrill)
A method for obtaining a membranous alebrene high polymer having a structure and mechanical strength (Japanese Patent Publication No. 48-324+8+) is known.

The powdered acetylene polymer molded product obtained by the method (a) above was mixed with BF3, BCl3. H.C.I.

0 sentence 2.802, NO2, 1-IcN, 02, NO
When chemically treated with an electron-accepting compound (acceptor) of 6, the electrical conductivity increases by up to three orders of magnitude, and conversely, when treated with an electron-donating compound (donor) such as ammonia or methylamine, r:
It is well known that electrical conductivity decreases by up to four orders of magnitude when treated.

The film-like acetylene polymer obtained by the method (b) also contains 12, CD-2, Br2. fcffi, 1[3r
By chemically doping an electron-donating compound such as Li into an electron-accepting compound such as , AsF5, SbF5, PFa, etc. or Na, the electrical conductivity of the acetylene polymer can be increased from 10-8 to 103 Ω-. 1・Cm-
It is well known that 1 can be freely controlled over a wide range of areas. The idea of using this doped film-like acetylene polymer as a material for the positive electrode of a primary battery has also been proposed.

On the other hand, in addition to the above-mentioned chemical doping method, electrochemical doping methods such as C04, PI'2, AS F2, As F4
, CF3303, BF4, etc.? nion and R
By doping an acetylene polymer with a cation such as ' 4 N''(R' is an al-I-nyl group, and they are also the same group), p-type and )-type conductive acetylene polymers are prepared. A rechargeable battery using electrochemical doping using the membranous acetylene polymer obtained by the method (b) has been reported. For example, a battery can be made by using two acetylene polymer films obtained by the method (b), with a thickness of 0, imm, as positive and negative electrodes, respectively, and soaking them in a tetrahydrofuran solution containing lithium iodide at 9V.
When connected to a DC power supply, the lithium iodine chloride is electrolyzed, and the aretylene polymer film at the positive electrode is doped with iodine, and the acetylene polymer film at the negative electrode is doped with lithium. This electrolytic doping corresponds to the charging process.

By connecting the negative terminals to two doped electrodes, the boridium ions and iodine ions react, producing electricity. In this case, the open circuit voltage (VOO) is 2.8 V, the yJJ current density is 5 mA/Cl112, and when a tetrahydrofuran solution of lithium perchlorate is used as the electrolyte, the IIH discharge layer edge voltage , 5V, short circuit current density is approximately 3m
7! v/Cll12 Teatsuta.

Further, two acetylene polymer films each having a thickness of 0.1 mm obtained by the method (b) above were individually wrapped in platinum mesh from which lead wires had been taken out.

5 m
When charging at a constant current of A/cm2 for a constant period of 11,), Te1
~ Rubble ammonium ions are doped into the acetylene high polymer film of the negative electrode, and perchloride ions are doped into the acetylene high polymer film of the positive electrode.

In this case, the open circuit voltage (VOC) of the battery is 2.5V.
Tea Tsuta. (7) iJI at 1rnA/c, m2? l! ! The voltage is 1. When discharged until it drops to Ov, the amount of electricity discharged is 4 units with an efficiency of 81% compared to the amount of electricity charged.
υ &q Ll! →Susu These batteries use acetylene polymer as the electrode material, which is easy to reduce weight and size, so they are attracting attention as low-cost batteries that have high energy density and are easy to reduce weight and size. are collecting.

However, most of the electrolytes as dopants used in these known documents have low -C solubility in solvents with a relatively wide stable potential range, and have low electrical conductivity as electrolytes, or Because the electrolyte itself or its electrolyzed product is reactive with solvents that have a relatively wide stable potential range, it cannot be used as a PI medium that has a wide stable potential range.For example, lithium metal cannot be used as a PI medium that has a wide stable potential range. It is reactive with nitrile solvents, which are considered to be solvents with a relatively wide stable potential range, and has a de-U point when a lithium salt containing lithium metal as a cation group is used as an electrolyte.

In addition, the above-mentioned TeI-butylnofun heptanium salt dissolves relatively well in nitrile solvents, and when used as an electrolyte, it is possible to obtain high charge/discharge efficiency, but the energy density is insufficient. It's not something to be satisfied with.

Furthermore, when using tetraethylammonium salt, which is one of the same alkylammonium salts, as an electrolyte, the solubility of tetraethylammonium salt is low in benzonitrile, which has a wide stable potential range, and the saturated solubility at -air temperature is 1 mol. /U, therefore, an electrolytic solution prepared by dissolving a tetraethylammonium salt in benzonitrile is very disadvantageous in terms of energy density, and it is difficult to apply it as an electrolytic solution for batteries with high energy density.

Therefore, when an organic solvent with a relatively wide stable potential range is used, its solubility in the organic solvent is high, the molar molecular weight is as small as possible, and its own electrochemical stability provides high electrical conductivity. There has been a strong demand among those skilled in the art to obtain an electrolyte, that is, a dopant, which has good reactivity and low reactivity with a polymer compound having a conjugated double bond in its main chain used as an electrode.

In view of the above points, the present inventors have developed a battery that has high energy density, high charging/discharging efficiency, long cycle life, good voltage flatness of 9T, low self-discharge rate, and light weight. As a result of various studies to obtain a battery that is easy to miniaturize and is inexpensive, an ammonium salt whose cation component is a quaternary ammonium ion satisfies the above requirements, and by using this as an electrolyte, good performance can be achieved. They discovered that it is possible to obtain a secondary battery that has the same characteristics, and completed the present invention.

That is, the present invention provides a method for using 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, for a negative electrode, or for both a positive electrode and a negative electrode. The present invention relates to a secondary battery characterized in that the cationic component of the electrolyte used in the battery J3 is an ammonium salt consisting of a quaternary ammonium ion represented by the following general formula.

(Left below) [In the formula, R+, R2, R3 and R4 have 1 to 1 carbon atoms.
16 alkyl group or aryl group. However, all R1, R2, R3 and R4 are not the same group at the same time. ] A secondary battery using the present invention's anthinium salt as an electrolyte of an electrolyte is represented by the conventionally known R' 4 N+ (R' is an aruyl group, but at the same time they are the same group). Compared to secondary batteries that use ammonium salts or lithium salts as electrolytes, the cation component of quaternary ammonium ions is
It has the advantages of good voltage flatness, (Ill) little self-discharge, and (IV) long repeated life.

Specific examples of polymer compounds having a conjugated double bond in the main chain (hereinafter referred to as conjugated polymer compounds) used in the present invention include acetylene polymers (polyacetylene),
Polybaraphenylene, polymetaphenylene, poly(2,
5-chenylene), polypyrrole, polyimide, polyphenylacetylene, boriacene, polyacenequinone radical polymer, quinazoline polymer with Schiff base structure, polyarylenequinones, thermal decomposition products of polyacrylonyl-1-lyl and polyimide, etc. Examples include, but are not limited to, any polymer compound having a conjugated double bond in its main chain. Also, there is no problem in some parts of the small polymer 〇 and the drum-shaped combination. Among the above-mentioned polymer compounds, preferred are acetylene high polymer, polyparaphenylene, poly(2,5-chenylene), and polypyrrole, and particularly preferred is acetylene high polymer. be able to.

The method for producing the acetylene polymer preferably used in the present invention is not particularly limited, and any method C can be used. No. 55-129404 1. No. 55-128419, No. 55-142012, No. 56-101128, No. 56-133133,
Trans, Farady 3oc, 64,823
(1968), J.

Polymers ci, A-1, f, 3419
(1969).

Makromol, Cbcm, Rapid Comm
,,1. 621 (1980), J., Chem, P.
hys, 69 (1), 106 (1978), 5
ynthetic Metals, f, 81 (19
81).

In the present invention, the conjugated polymer compound contains graphite,
A mixture of conductive materials such as carbon black, acetylene black, metal powder, and carbon [[1] may also be used, and a metal net or the like may also be added as a part of the material.

In the present invention, not only a conjugated polymer compound but also a conductive polymer compound in which the polymer compound is doped with a dopant can be used as an electrode.

The method of doping a dopant into a conjugated polymer compound is as follows:
Either chemical doping or electrochemical doping may be used.

Dopants to be chemically doped into the conjugated polymer compound include various conventionally known electron-accepting compounds and electron-donating compounds, such as (I) halogens such as iodine, bromine, and bromine iodide; ) arsenic pentafufluoride,
Metal halides such as antifluoride pentafluoride, silicon tetrafluoride, phosphorus pentachloride, phosphorus pentafluoride, ammonium chloride, aluminum bromide and aluminum fluoride, (Il
l) Protic acids such as 1M acid, nitric acid, full AD sulfuric acid, trifluoromethane sulfuric acid and chlorofa acid, (IV
) oxidizing agents such as sulfur trioxide, nitrogen dioxide, difluorosulfonyl bar-A oxidants, (V)AQ CfLO4,
(Vl) Tei~lacyanoethylene, De1~lacyanoquinodimethane, Floranil, 2,3-dichloro-5,6
-dicyanobarabenzoquinone, 2,3-dibrome-5,
Examples include 6,-dicyanobarabenzoquinone.

On the other hand, as dopants to be electrochemically doped into the conjugated polymer compound, (I) pF;, 5bF-2, As
f-s, a halide anion of a Va group element such as SLl Cua, a halide anion of an Ila group element such as BF4, a halide anion such as l(J3), 3r-1C1-, perchloric acid such as cio; Anions and dopants such as anions (effective as dopants to provide conductive conjugated polymers of the ] type) and (n) alkali metal ions such as Li'', Na'', and K+, R4N'' (R: carbon number Examples include anion dopants such as quaternary ammonium ions such as hydrocarbons (M) of 1 to 20 (both are effective as dopants that provide n-hyperactive conjugated polymer compounds), but are not necessarily limited to these. It is not something that will be done.

However, when a conductive polymer compound obtained by doping a conjugated polymer compound with a dopant in advance is used for the electrode, the dopant pre-doped into the negative electrode is a quaternary compound used in the electrolyte of the battery in the present invention. The same one as ammonium cation is preferable.

Furthermore, the doping level of the battery in the present invention can be freely controlled by measuring the amount of electricity flowing during electrolysis. 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 depend on the type of conjugated polymer compound used,
It cannot be specified in part because it varies depending on the height, density, area, type of dopant, type of electrolyte, and required electrical conductivity.

The density of the dopant doped into the conjugated polymer compound is 2 to 40 per mole of the repeating unit of the conjugated polymer compound.
It is mol%, preferably 4 to 30 mol%, particularly preferably 5 to 20 mol%. Even if the density of the doped dopant is less than 2 mol %, it is impossible to obtain a secondary battery with a sufficiently large discharge capacity even if the concentration of the dopant is 401% or more.

The electrically conductive nail of the conjugated polymer compound is 10-6Ω゛1・Cl11-1 or less before doping, and the electrical conductivity of the electrically conductive conjugated polymer compound obtained by doping with a dopant is about 1 to 10”. It is in the range of 1040-1 .Cm-1.

The battery electrolyte used in the present invention is an ammonium salt whose cation component is a quaternary ammonium ion represented by the above general formula.

Specific examples of the cation component of the ammonium salt include trimedelpropylammonium, tributylmethylammonium, trimethylhexylammonium, trimethyl 4:cylammonium, trimedelisobutylammonium, trimethylturn 1-freebutylammonium, and trimethylisopropylammonium. , 1-limethylisobutylammonium, 1-limethylbekyl-1nodecylammonium, trimethylpentyl]non[nium,
Triethylpropylammonium, 1-ethylbutylammonium triethylpropylammonium, tributylmethylammonium, triethylhexylammonium, triethylphenylammonium, tripropylbutylammonium, tributylmethylammonium, i-butylethylammonium, dipropyldiethyl Examples include ammonium, dibutyldiethylammonium, dibutyldimethylammonium, diethyldiphenylammonium, diethyldiphenylammonium, dibutylethylmethylammonium, dipropylethylmethylammonium, butylbropylconidylmethylammonium, and the like.

Specific examples of these cationic components and anionic components constituting the ammonium salt include HF2, C0:, AI
C4, Br;, l”e C:, Sn C1s
, PF6, PC(Lc, St R4, SbF2,
Examples include AsF2, CF3 SOi, etc.

Specific examples of ammonium salts include triedylbutylammonium tetroble A roborate, 1-butylethylammonium bark [ru-1~, hbutylethylammonium hekylyfur A sulfate, and trimethylpenruane trifluoromethane. Sulfone-1., 1~Limethyl 1 f Ammonium Tetroble 71 U Volley 1~. 1-butyl ethyl ammonium to kyriflu A fluorophore-1, dibutyl diethylammonium perchlorate, tributyl ethyl ammonium tetrafluoroborate, butylpropylethyl methyl ammonium niary chlorophosphate, trimederphenyl tetraflumeroborate, triethylphenyl 7 Examples include, but are not limited to, trifluoroborate and the like.

These ammonium salts may be used alone or in combination of two or more.

In addition, the am7-ium Ju of the present invention may be used as a mixed electrolyte with other alkylamn7ium salts, such as tetonozotylammonium salt A5 tetraethylammonium salt, or with alkali metal salts, such as It may be used as a mixed electrolyte with a lithium salt, a lithium salt, and a potassium salt.

Furthermore, the ammonium salt of the present invention is a biryllium or pyridium cation represented by the following formula (I): an elementary atom or an alkyl group having 1 to 15 carbon atoms, or a pyridium cation represented by the following formula (I):
~15 aryl (arVl>base), [di[ma]-logon atom or alkyl group having 1 to 10 carbon atoms, 6 carbon atoms
~15 aryl (ary+) groups 1. is O when X is 1 Kyoko of oxygen, and is 1 when X is a nitrogen atom.

. is O or 1-5T'. 1 or the carbonium cation represented by the following formula (II) bL< is (III') 'r: or R4-C'' (III) 1 [wherein, R1, R2, and R3 are hydrogen atoms (, R1゜1(2
, R3 are hydrogen atoms at the same time 1. IQ&'
), alkyl group having 1 to 15 carbon atoms, allyl
> group, an aryl group having 6 to 15 carbon atoms or an -OR5 group, provided that R5 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, and 1 and 4 are These include a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, and an aryl group having 6 to ↑5 carbon atoms. It is also possible to use C by mixing it with the electrolyte shown on the right as a Kaji A component.

However, when the Kabumen component of the present invention is used in a mixture of an ammonium salt consisting of 11th class ammonium ions and another electrolyte, is it necessary to use the ammonium salt in a form containing equal moles or more of the ammonium salt? Delicious.

The organic solvent of the electrolyte used in the present invention is as follows:
Examples include aliphatic nitrile compounds, aromatic nitrile compounds, ethers, 1.1-alides, amides, carbonates, sulfolane compounds, halogen compounds, etc., but aliphatic nitrile compounds and aromatic compounds are preferred. Examples include aromatic nitrile compounds, particularly aromatic nitrile compounds.
Examples include lyle compounds.

Specific examples of these organic solvents include tetrahydrofuran, 2-methyltetracofuran, 1,4-dioxane, anisole, heptanoglyme, acetonitrile, propionitrile, butyronitrile, valeronitrile,
-Methyl-2-pentanone, benzonitrile, O-tol-1-lyl, m-t-l-dil-lyl, p-tolnitrile, α-1-l-dyl-1-lyl, 1,2-dichloroethane, γ
- lactone, dimethoxyethane, methylformamide, propylene carbonate, ethylene carbonate, dimethylformamide, dimethyl sulfoxide, dimethylthio 7j (lumamide, sulfolane, 3-methyl-sulfolane, trimethyl phosphate, phosphoric acid Among them, preferred solvents include acetonitrile, propyl A-21-lyl, butyronitrile, hare+-+-1-lyl, benzonitrile, α- 1-lunitrile, 0-1-lunitrile, m
Examples include -tolnitrile and []-]1-l-tolnitrile, and particularly preferred solvents include benzonitrile, 0-tolnitrile, m-tolnitrile, and [)-tolnitrile. These solvents may be used as a mixed solvent, and C may also be a part of them.

The degree of m of the electrolyte used in the secondary battery of the present invention varies depending on the type of positive electrode or negative electrode used, the charge/discharge line f'1, the operating hot stone, the type of electrolyte, the type of organic solvent, etc. Although it cannot be specified, it is usually 0.
It is in the range of 5 to 10 mol/1.

The electrolyte may be either homogeneous or heterogeneous.

In the present invention, the conjugated polymer compound or the conductive conjugated polymer compound obtained by doping the conjugated polymer compound with a dopant is used as an active material for the (I) negative electrode or (I [> positive electrode and negative electrode) of the battery. It can be used, but
In order to maximize the effects of the present invention, a battery of type (■) is preferable.

For example, in the case of a secondary battery using an acetylene polymer as a conjugated polymer compound, as an example of (I), if the acetylene polymer is (CI)x, graph 1ite (positive electrode)/
(Et 3 Bu N)" ・(C1O+) - (electrolyte) / (CI-l) x (negative electrode), an example of (n) is [(CH) +ac11(C104)ux]x (positive f
f1)/<MQ3Bu N)"・(C'lOq>-
(Electrolyte) / [(M es B u N ) ” ”
' (Cl-1) -”' ] X (negative electrode), [(C
H) ÷ Sleep (PFe) u Expansion (Positive electrode) / (Bu Et
N) 10・(PFa)−(?ffM￥i)
/[(BU3EtN) +-(pull()-")x(negative electrode), [(Et3BuN)"""(C1l)-"
] x (positive electrode) / (Et 33u N) +・(Cu
O2)-(electrolyte)/[(El3BuN)”
'(CH)-'']x (*1M)W can be given.

In the case of polyparaphenylene, (CaH4)X is substituted for the above (CH)x, and poly(2,6
- Chenylene), instead of (CI-1)χ, (C
4H2S)
N) X is used as a secondary battery of the same type as the 111j described above.

In addition, in the present invention, different conjugated polymer compounds can be used for the positive electrode and the negative electrode, and for the shell side, <
Ctonx/EL3BLIN・CfL O4/ (C6
14)X, (OH)x/Me3BuN-Bf-+
/(C41-12s)x, (CoH4)X/El
2Bu 2 N ・PFs ・(04H2S)x, etc. can be mentioned.

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 with oxygen, which may lower the battery performance. It is necessary that the system be closed and substantially oxygen-free.

The secondary battery of the present invention has an energy density of
The discharge efficiency is high, the cycle XTa is long, the self-discharge rate is low, and the flatness of the electric charge L of the discharge 114 is good. In addition, the secondary battery of the present invention is lightweight, small, and IX'!
Due to its low energy density, it is ideal for portable equipment, electric cars, gasoline car J5, and power storage batteries.

The 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 glass reaction vessel with an internal volume of 500 d under a nitrogen atmosphere
1.7d titanium tetrabutoxide, 30m
Dissolve in 1 liter of anisole, then 2.7 ml! of triethylaluminum was added from If J'l' site to prepare the catalyst solution.

The reaction vessel was cooled with liquid nitrogen for 7JI L'T, and the nitrogen gas in the system was evacuated to 1 to 1 atmosphere using a vacuum pump. The reaction vessel was then cooled to -18 DEG C. II. The solution was brought to a standstill by blowing purified aluminum gas at a pressure of 1 atmosphere.

Immediately, catalyst solution human blood [■] occurred, and a film-like acetylene high polymer was produced. Thirty minutes after the acetylene was added, the acetylene gas in the reaction vessel system was made viscous to stop the polymerization. After removing the catalyst solution with a syringe under nitrogen atmosphere, -γ8℃
Refining 1~run while keeping it 100, +11! Washed repeatedly 5 times. The film-like acetylene polymer swollen with toluene was a uniform film-like swollen product C in which Neubril was tightly entangled. Next, this swollen product was vacuum dried to give a reddish-purple color with a metallic luster and a thickness of 100 μm and a cis content of 98 μm.
% membranous acetylene polymer. In addition, the height density of this film-like acetylene polymer is 0.30 g/cc, and its electrical conductivity (DC four-terminal method) is 7:3 at 20°C.
．． 2x10-9Ω-1. It was I11-1.

[Battery Experiment J] Two disks with a diameter of 20 m Iff were cut out from the film-like acetylene polymer obtained by the above-mentioned method h, and a battery was constructed by using the disks as active materials for a positive electrode and a negative electrode, respectively.

FIG. 1 is a schematic cross-sectional view of a battery rail for measuring characteristics of secondary and rechargeable batteries, which is an integral example of the present invention, in which 1 is a platinum lead wire for the negative electrode, 2 is a collection of platinum wire mesh for the negative electrode with a diameter of 20 mm and 80 meshes. Electric body, 3 is a disc-shaped negative electrode with a diameter of 20IIIll, 4
is a circular porous polypropylene diaphragm with a diameter of 20IIllll.
5 High iii diameter 20mIll) R plate-shaped positive I4i, 6 High ii! We accept platinum wire mesh current collector for positive electrode with diameter 20ml11 and 80 mesh, 7 is positive electrode lead wire, and 8 is screw-type Teflon container.

First, the platinum wire mesh current collector 6 for the positive electrode is placed in a Teflon container 8.
The positive electrode 5 is further placed on the positive electrode platinum wire mesh current collector 6, and a porous poly 1U pyrene partition It
! 4, a bond sufficiently impregnated with an electrolytic solution, a negative electrode 3, and a platinum wire mesh current collector 2 for the negative electrode placed on top of the bond, and a Teflon container 8 closed and sealed to produce a battery. ζ.

As the electrolytic solution, a 1 mol/aqueous solution of Et 3 Bu N-BF4 dissolved in distilled +112 water benzonitrile was used according to a conventional method.

Using the battery prepared in this way, the battery was heated for 15 minutes at a constant current (4.0rnΔ/c+n2) in an argon atmosphere.
Charging was carried out for a minute (amount of electricity corresponding to doping m 5 r nyl %). Immediately after the end of charging, under constant current (4
．． 0mA/cm2), discharge the battery '3:i
When K becomes 1v, repeat the above and Ii 4th article ('l
'('When we conducted a repeated test of charging and discharging, the number of repetitions of charging and discharging until the charging/discharging efficiency decreased to 50% was recorded as 100 @. The relationship between discharge time and voltage after the fifth repetition was as shown by curve (a) in FIG. 2.

The energy density at the fifth repetition is 140W.
- At I+r/kg, the charging/discharging efficiency was 99%.

Furthermore, when the battery was left charged for 48 hours, its self-discharge rate was 3.0%.

Comparative Example 1 In Example 1, E[3
BU 4 N ・8 F instead of Bu N-BF4
A battery charging/discharging experiment was conducted in exactly the same manner as in Example 1, except that the battery was repeatedly charged and discharged.The highest charging/discharging efficiency was 96%, and at the 410th repetition, it became impossible to discharge the battery. became.

The relationship between the discharge time and the electric current L[ in this battery experiment 1-1 was as shown in song M(b) in Figure 2. Also, the energy density at the 5th repetition is +30W・11r/
ko, the charging/discharging efficiency was 96%. Also, when left charged for 48 hours, the self-discharge rate was 5.
．． It was 2%.

Comparative Example 2 In Example 1, Et used as the electrolyte of the electrolytic solution
When I tried using equimolar amounts of Et4N・BF4 instead of 3Bu N-BF4, I found that [Et4N・BF4 hardly/υ dissolves in benzonitrile, and Et4N does not dissolve in benzonitrile.
A repeated experiment of charging and discharging the battery was conducted in the same manner as in Example 1 while -BF< was still precipitated. As a result, the maximum charging/discharging efficiency was 72%, and discharging became impossible after the 25th repetition.

Comparative Example 3 In Example 1, an attempt was made to use equimolar LiBF4 in place of El3BuN-BF4 used as the 'Fi solution v1 of the electrolyte, but Li13F4 was not completely converted to benzonitrile. Repeated charging and discharging experiments of the battery were conducted in the same manner as in Example 1 in a state where the solution was not dissolved and a portion remained undissolved and precipitated. As a result, the maximum charging/discharging efficiency was 24%, and discharging became impossible after 12 repetitions.

5th /15I electric time and electric h-1 in this battery experiment
Section 311 looked like the curve (C) in Figure 2. Also, the energy density at the 5th repetition is 24W・11r/
The charging/discharging efficiency was 18% at k(l).

Example 2 Into 11 glass reaction vessels completely purged with nitrogen gas,
Insert a 100-mesh net of stainless steel,
Then polymerized FFJv1. 1007 ml of toluene purified according to a conventional method, 4.41 ml of rhabdoxytitanium and 11 ml of triethylaluminum as a catalyst.
．． A catalyst solution was prepared by sequentially charging 0T mmol at room temperature. The medium M 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 −18° C., and purified acetylene gas at a pressure of 1 atmosphere was blown into the reactor while the catalyst solution was left standing. 10 while keeping the pressure of acetylene gas at 1 atmosphere n-
After continuing the polymerization reaction for some time, System 1 was agar-like with a reddish-purple color. After the polymerization was completed, unreacted acetylene gas was removed, and the wet melon was heated at 200°C while keeping the temperature at -78°C.
Washing was repeated four times with the purified toluene described in step d to obtain a swollen alledylene polymer in the form of C1-1 containing a toluene-swollen stainless steel mesh having a film thickness of about 0.5 cm. This swollen acetylene polymer has a diameter of 300 to 500 people.
It was a swollen product in which ll-shaped microcrystals (fibrils) were regularly intertwined, and no powder-like or bowl-like polymer was produced.

This sheet-like swollen acetylene polymer containing the stainless steel mesh was sandwiched between chromium-plated ferro plates, pre-pressed at room temperature at a pressure of 100 kg/cm2, and then pressed with a pressure horn of 151011/cm2. A uniform and flexible composite with a reddish-brown metallic luster and a film thickness of 280 μm was obtained by pressing. This composite was vacuum dried for 5 hours at room temperature. This composite contains a stainless steel mesh of 43% by weight and has a diameter of 1° [Battery experiment] From the composite obtained by the above method, two disks with a diameter of 20 mm are cut out and the positive electrode active material is cut out. , the negative electrode active material is Me3 dissolved in distilled and dehydrated acetonitrile as the electrolyte.
A charge/discharge experiment was carried out using a 1 mol/l solution of Bu N-ClO4 using the same hill as in Example 1, and the results were obtained. Charging was carried out for 15 minutes at a charging current density of 5.0 mA/cm2 (the doping amount was equivalent to 5T nyl%). After charging is finished, do you dare to stay? ff ffi el? , density 5.0m
When the battery voltage reached IV, the battery was discharged at A/cm2, and then charged again under the same conditions as described above. When the charge/discharge cycle was repeated, the charge/discharge efficiency was 50%. The number of charging/discharging cycles was recorded 420 times before the battery reached a low point.

The 1st energy honey melon at the 5th repetition of this repeated experiment C is 152W・hr/k (l, and the charging/discharging efficiency is 9
It was 8%. Furthermore, when the battery was left charged for 48M, its self-discharge rate was 9.5%.

Comparative Example 4 In Example 2, Me used as the electrolyte of the electrolytic solution
3Bu N-BF< instead of Et 4N ・r([4
The battery was charged and charged in the same manner as in Example 2 except that
When we conducted a repeated discharge experiment, we found that the number of times charging and discharging was repeated until the charging and discharging efficiency decreased to 50% was 28.
There was a C five times.

The energy density at the fifth repetition is 145W-
The charging/h'l electric efficiency at hr/kQ was 96%. Furthermore, when the battery was left charged for 48 hours, its self-discharge rate was 16.5%.

Comparative Example 5 In Example 2, Me used as the electrolyte of the electrolytic solution
Me 4 N ・BF4 instead of 3Bu N 13F4
When an experiment was attempted using MO<N.13F4, it was hardly dissolved in ace1-nitrile, and charging and discharging were repeated less than 100 times.

Example 3 Bull, Chem, Soc, Japan, 51.
2091 (1978) into a disc shape of 20 m mψ under a pressure of 1 ton 7 cm2 was used as the positive electrode. [Battery experiment] As a result, the voltage characteristics were almost the same as those of the first 7151 telegram up to 250 repeated charging/discharging tests.

The number of repetitions until the charging/discharging efficiency drops to 50% is 3.
He recorded 65 times. The energy density of this battery is 162
W·t+r/kg, and the charging/discharging efficiency was 91%. Furthermore, when the battery was left charged for 48 hours, its self-discharge rate was 4.5%.

Comparative Example 6 In Example 3, E(3
Instead of Bu N-BF4, it is a symmetrical alkyl ammonium salt that dissolves in pentonitrile at nearly 1 mol/a, and the molecular weight is Ej 3 Bu N.13F4.
) Pr4N・BF4 was used as a close b.

Hereinafter, a [battery experiment] was conducted in exactly the same manner as in Example 3. As a result, the repetition of charging and discharging stopped at the 215th time. Also, the energy density of this battery is 145W
- The charging/discharging efficiency was 88% at Il+''/ko.

Roughly speaking, when the battery was left charged for 48 hours, its self-discharge rate was 18%.

Example 4 Example 4 The same cell as that used in Example 1 was used, in which a membranous acetylene polymer was produced in exactly the same manner as in Example 1, and propylene carbonate was used as the solvent for the electrolyte. When a battery experiment was conducted in exactly the same manner as in 1, the number of charging/discharging cycles recorded was 485 before the charging/discharging efficiency decreased to 50%. The energy density at the fifth repetition was 142 W·t+r/ka, and the charge/discharge efficiency was 99%. Also, leave it charged/48 o'clock I! When I stored it, its self-discharge rate was 1.
It was 2%.

Comparative Example 7 In Example 4, Et used as the electrolyte of the electrolytic solution
A battery experiment was conducted in exactly the same manner as in Example 4, except that 3U4N.BF4 was used instead of 3BuN-BF4, and the result was that the battery was repeatedly charged and discharged for the 180th time! ~
It stung. Furthermore, the energy density of this battery at the 15th repetition was 132 W·hr/kg, and the charging/discharging efficiency was 97%. Furthermore, when the battery was left charged for 48 hours, its self-discharge rate was 22%.

Comparative Example 8 Electrolyte used in Example 4 [t 3 Bu N-BI'<
Example 4 except that EL4N-BF4 was used instead of
When I conducted a battery experiment in exactly the same way as
The repetition of 5I Den stopped at the 235th time. Also, the energy density of this battery at the fifth repetition is 1
The charging/discharging efficiency was 98% at 40 W·l+r/kg. Moreover, the self-discharge rate was 15%.

Comparative Example 9 71 yen fi [Tt 3 Bu N-B used in Example 4
A battery experiment was conducted in exactly the same manner as in Example 4 except that l i BF4 was used instead of F4, and the repetition of charging and discharging stopped at the 88th time. Also, the energy density of this battery at the fifth repetition is 121W.
-llr/k (I), the charge/discharge efficiency was 92%, and the self-discharge rate was 4.2%.

Examples 55 to 11 Example '1 is exactly the same as Example '1 except that the combination of electrolyte and solvent was changed as shown in the table.
After repeated charging and discharging experiments, the result was 1j. The results are shown in the table. In the table, energy density 1 good is 55 repetitions]
”, and the recycle life is 50% with charging/discharging efficiency.
The number of repetitions at J: is shown. The self-discharge amount is the amount after being left in an open circuit for 148 hours after charging is completed, and IC6 (the following margins)

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the relationship between voltage and voltage of a secondary battery that is an example of the present invention. 1... Platinum lead wire for negative electrode 2... Platinum wire mesh current collector for negative electrode 3... Negative electrode 4... Porous polypropylene ceramic +1! 5... Positive electrode 6... Platinum wire mesh collection for positive electrode Electrical body 7...Positive lead wire 8...Teflon container Applicant: Showa Denko K.K. Hitachi Ltd. Representative Patent attorney Sei Kikuchi -

Claims (1)

[Claims] A polymer compound having a conjugated double bond in the main chain or a conductive polymer compound obtained by doping the polymer compound with a dopant is used as the negative electrode or both the positive and negative electrodes. As an electrolyte, the cation component is ammonium consisting of a quaternary ammonium ion represented by the following general formula [wherein R+, R2, R: + d3J]
, and 1<4 are an alkyl group having 1 to 16 carbon atoms or an aryl group.However, all R+
, R2, R3 and R4 are never the same group at the same time,]