JPS60180072A - Nonaqueous secondary battery - Google Patents

Abstract

PURPOSE:To provide a high energy density cell and thereby improve charge-and- discharge efficiency by using as an electrolyte an ammonium salt having cation components being specific assymmetrical fourth ammonium ion, and specifying concentration of the electrolyte. CONSTITUTION:A high polymer compound having conjugated double bonds in a main chain or a conductive high polymer compound yielded by doping said high polymer compound with a dopant is employed as a negative electrode or positive and negative electrodes. An ammonium salt is used as an electrolyte, which contains a cation component being assymmetric fourth ammonium ion represented by a general formula shown in the accompanying drawing. In the formula, R1, R2, R3, and R4 are respectively an alkyl group of a 1-16C number and an aryl group, while R1-R4 are not the same group simultaneously. For the electrolyte, an electrolyte of at least 2mol/l is employed. The cell is prolonged in a cycle service life and good in flatness of voltage thereof, and is further reduced in a self-discharge rate, etc.

Description

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

Acetylene polymers obtained by polymerizing acetylene using so-called Ziegler-Tick catalysts, which are composed of transition metal compounds and organometallic compounds, have electrical conductivity in the semiconductor region, making them suitable for electrical and electronic devices. It is already known that it is a useful organic semiconductor material.

Methods for producing practical molded products of acetylene high polymers include (a) a method of pressure molding powdered acetylene high polymers;
and (b) a method of obtaining a film-like acetylene polymer having a fibrous microcrystalline (fibril) structure and high mechanical strength by forming it into a film at the same time as polymerization under special polymerization conditions (Tokuko Showa). 48.-325'81) is known.

BF3. BCl3. HCl, ,C42
, SO2゜No, HCN, 02. When chemically treated with an electron-accepting compound (acceptor) such as No, 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, the electrical conductivity increases to the highest. It is already known that it can drop by four orders of magnitude.

In addition, I2. C12, Br2. ICt, IBr,
AsF5.

Electron accepting compounds such as SbF', PF6, etc. or Na.

By chemically adding electron-donating compounds such as K and Li, the electrical conductivity of the acetylene polymer can be increased to 1.
It is already known that it can be freely controlled over a wide range of 0-8 to 10 3 Ω-1·CrIL-1. The idea of using this dogged 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-mentioned chemical doping method, electrochemical CLO: , PF, ', AsF; ,
Anions such as AsFa 1cF3soH, BF: etc. and cations such as R'4N''- (R/ is an alkyl group and are the same group) are added to an acetylene polymer to form p-type and n-type A method for producing conductive acetylene polymers has also been developed.
A rechargeable battery using electrochemical doping using a film-like acetylene polymer obtained by the method of Naka) has been reported. For example, this battery is made by using two acetylene polymer films with a thickness of 0.01 mm as positive and negative electrodes obtained by the method described in ←), and soaking them in a tetrano-hydrofuran solution containing lithium iodide. When connected to a DC power source, lithium iodide is electrolyzed, the acetylene 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.

(If you connect a load to the two electrodes, lithium ions and iodine ions will react and electricity will be extracted.

In this case, the open circuit voltage (vOC) is 2.8 V, the short circuit current density is 5 m67 cm2, and when the electrolyte is a tetra/\iP rofuran solution of lithium perchlorate, the open circuit voltage is 2. .5 V-, short circuit current density is approximately 3 m corrosion 2
Met.

In addition, two sheets of acetylene high polymer film with a thickness of 0.1 strip obtained by the above method (b) were each wrapped in a platinum mesh with lead wires cut out, and 1 mol/mole was When immersed in an acetonitrile solution containing butylammonium barchlorate and charged at a constant current of 5 mA2 for a certain period of time, tetrabutylammonium ions are doped into the acetylene polymer film at the negative electrode, and -chlorate ions are doped into the acetylene polymer film at the positive electrode. Douged into a high polymer film. In this case, the open circuit voltage of the battery (Voc
) was 2.5 V. This battery is 1 m67cm
2, the battery voltage is 1. If the battery is discharged until it drops to OV, the amount of discharged electricity can be extracted with an efficiency of 81 times compared to the amount of charged electricity.

r 'hI-, tysNm Vr, lightning fii material B J
-1-TES uses an acetylene high polymer that can be easily miniaturized, so it is attracting attention as a battery that has high energy density, is lightweight, easy to miniaturize, and is inexpensive. However, most of the electrolytes used as doxent in these known documents have low solubility in solvents with a relatively wide stable potential range, or have low electrical conductivity as an electrolyte, or However, since the electrolyte itself or its electrolyzed product has reactivity with a solvent having a relatively wide stable potential range, it has the disadvantage that it cannot be used with a solvent having a relatively wide stable potential range.

For example, lithium metal is reactive with nitrile solvents, which are considered to have a relatively wide stable potential range, and there are difficulties in using lithium salts containing lithium metal as a cation component as electrolytes.

In addition, the above-mentioned tetrabutylammonium 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 must be sufficiently satisfied. isn't it.

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 room temperature is 1 mol/l. Therefore, an electrolyte solution in which tetraethylammonium salt is dissolved in penzonitrile is very disadvantageous in terms of energy density, and is difficult to be applied as an electrolyte solution for batteries having a high energy density.

Therefore, when an organic solvent with a relatively wide stable potential range is used, it has high solubility in the organic solvent, has a molar molecular weight as low as possible, provides high electrical conductivity, and has good electrochemical stability. , an electrolyte with low reactivity with a polymer compound having a conjugated double bond in its main chain used as an electrode;
In other words, there is a strong demand among those in the industry to obtain dopants.

In view of the above points, the present inventors have developed a battery that has high energy density, high charge/discharge efficiency, long cycle life, good voltage flatness, low self-discharge rate, light weight, and small size. As a result of various studies to obtain a nonaqueous secondary battery that is easy to produce and inexpensive, we decided to use an ammonium salt whose cation component is an asymmetric quaternary ammonium ion as an electrolyte.
The present invention has been completed based on the discovery that a non-aqueous secondary battery having good performance can be obtained by using an electrolytic solution having an electrolyte concentration of at least 2 mol/l.

That is, the present invention provides a non-conductive polymer that 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, for the negative electrode, or for both the positive and negative electrodes. In a water secondary battery, an ammonium salt whose cation component is an asymmetric quaternary ammonium ion represented by the following general formula is used as an electrolyte, and an electrolytic solution with an electrolyte concentration of at least 2 mol/l is used. The present invention relates to a characteristic non-aqueous secondary battery.

[In the formula, R11R21R3 and R4 have 1 to 1 carbon atoms
6, or an aryl group.

However, all R1+ R2r R5 and R4 are not the same group at the same time. ] The non-aqueous secondary battery of the present invention has a conventionally known R'4N"(R'
are alkyl groups, and are also the same group) (I) Energy high density,
It has the following advantages: (■) good voltage flatness, (III) little self-discharge, and (■) long cycle life.

Specific examples of the polymer compound having a conjugated double bond in the main chain (hereinafter referred to as a conjugated polymer compound) used in the present invention include acetylene polymer metaphenylene, poly(
2,5-f enylene), polypyrrole, polyquinoline,
Examples include phenylacetylene, polyacene, polyacenequinone radical polymers, quinazoline polymers having a Schiff base structure, polyarylene quinones, thermal decomposition products of polyacrylonitrile and polyimide, but are not necessarily limited to these. Any polymer compound having a conjugated double bond in its main chain may be used. Further, there is no problem with either homopolymer or copolymer. Among the above conjugated polymer compounds, preferred are acetylene polymer 1, je lyz47 phenylene, poly(2,5-f enylene), and polypyrrole, and particularly preferred is acetylene. Examples include 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. -142012,
No. 56-10428, No. 56-133133, Tr.
ans, Farady Boa, +64+823
(1968) rJ.

PolymerSci, , Al+7, 341
9 (1969) *Makromo1. Che,m
, + Rapid Comm, r 1 r 621
(1980) +J, Chem, Phys, , 6
9 (1) + 106 (1978), Synth
eticMetals, 4, 81 (1981)
The following methods can be mentioned.

In the present invention, the conjugated polymer compound includes graphite,
Conductive materials such as carden black, acetylene black, metal powder, and carbon fiber may be mixed, and a metal net or the like may be used as a current collector.

In the present invention, instead of a conjugated polymer compound, a conductive polymer compound obtained by adding a dopant to the polymer compound can also 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) iodine, bromine, and bromine iodide; ■) Pentafluoride, arsenic, antimony pentafluoride, silicon tetrafluoride, phosphorus pentachloride,
metals/locides such as phosphorus pentafluoride, ammonium chloride, aluminum bromide and aluminum fluoride;
(■) Norotonic acids such as sulfuric acid, nitric acid, fluorosulfuric acid, trifluoromethanesulfuric acid and chlorosulfuric acid, (■) Oxidizing agents such as sulfur trioxide, nitrogen dioxide, nofluorosulfonyl peroxide, (V) AgCtO4, (Vl ) Tetracyanoethylene, tetracyanoquinodimethane, floranil, 2,3-dichloro-5,6-nocyanopenzoquinone, 2,3-dibromo-5,6-dicyanoquinodipenzoquinone, and the like.

On the other hand, as dogundants for electrochemically doping a conjugated polymer compound, (1) PF; , SbF;
.

/% locanide anion of elements of group Va such as AgF2.5bcz;; halide anions of elements of group 1lJa such as B, ■-(2), Br-r Ct-
(II) Anion dopants such as halogen anions, perchlorate anions such as ct width (Hizure is also effective as a dopant to provide a p-type conductive conjugated polymer compound), and (II) alkalis such as Li+, Na+, K+ Metal ions, cations such as quaternary ammonium ions such as R4N+ (R: hydrocarbon group having 1 to 20 carbon atoms),
(all of which are effective as dopants for providing an n-type conductive conjugated polymer compound), but are not necessarily limited to these.

However, if a conductive polymer compound obtained by doping a conjugated polymer compound with a dopant in advance is used for the electrode, the Dono J? The cation is preferably the same as the asymmetric quaternary ammonium cation used in the electrolyte of the battery in the present invention.

Further, the amount of doping in the battery according to the present invention can be freely controlled by measuring the amount of electricity flowing during electrolysis. Doping may also be carried out using a constant voltage shift method even under constant current. 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, so they are not generally specified. I can't.

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 mole content is preferably from /I to 30 moles, particularly preferably from 5 to 20 moles.

Even if the amount of the doped dopant is less than 2 mol % or more than 40 mol %, a non-aqueous secondary battery with a sufficiently large discharge capacity cannot be obtained.

The electrical conductivity of the conjugated polymer compound before doping is less than 10 Ω. −1·c7rL−” range.

The electrolyte of the battery used in the present invention is an ammonium salt consisting of class ammonium ions.

Specific examples of cationic components of ammonium salts include triethylpropylammonium, trimethylbutylammonium, trimethylhexylammonium, trimethyloxylammonium, trimethylimbutylammonium, trimethyltert-butylammonium, trimethylimbutylammonium, trimethylimbutylammonium, trimethyl Hexadecyl ammonium, trimethyl-anthylammonium, trimethylphenylammonium, triethylbutylammonium, triethylpropylammonium, triethylmethylammonium, triethylhexylammonium, triethylphenylammonium, tripropylditylammonium, triglymethylammonium, tributylethylammonium, digtyl Examples thereof include diethylammonium, digtylddiethylammonium, dibutyldimethylammonium, dimethyldiphenylammonium, diethyldiphenylammonium, subbutylethylmethylammonium, dinolobylethylmethylammonium, butylzorobylethylmethylammonium, and the like.

Specific examples of these cation components and anion components constituting the ammonium salt include HF; and ctoi.

Mcti r BF4 r FeC1; + 5nCA
i, PFM, PCt,, rSiF; +S
Examples include bF6 r AsFg l CF35Oi.

Specific examples of ammonium salts include triethyldithylammonium tetrafluoroborate, triethylbutylammonium verchlorate, triethylbutylammonium hexafluorophosphate, trimethylbutylammonium trifluoromethanesulfonate, trimethylethylammonium tetrafluoroborate,
Trimethylethylammonium hexafluorophosphate, cyphthyldiethylammonium verchlorate, tributylethylammonium tetrafluoro? Examples include, but are not limited to, ester, butylglopylethyl methylammonium hexachloro-7 phosphate, trinotylphenyltetrafluoroporate, triethylphenyltetrafluoroborate, and the like.

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

The ammonium salts of the present invention may also be used as mixed electrolytes with other alkylammonium salts, such as natho-2-butylammonium salts and tetraethylammonium salts, or with alkali metal salts, such as lithium salts, sodium salts and potassium salts. Further, the ammonium salt of the present invention can be used as a mixed electrolyte with a biryllium or pyridium cation represented by the following formula (I): (Ff)n [wherein, / is a hydrogen atom or an alkyl group having 1-15 carbon atoms, or a hydrogen atom or an alkyl group having 6-15 carbon atoms.
aryl group, r is a halodane atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, m is O when X is an oxygen atom, , when X is a nitrogen atom, 6n, which is l, is 0 or 1-5. [In the formula, R' + R2# R' is a hydrogen atom (R',
R21R3 are not hydrogen atoms at the same time), an alkyl group having 1 to 15 carbon atoms, an allyl group,
Aryl group having 6 to 15 carbon atoms or 10R
5 groups, provided that R(/'i represents an alkyl group having ~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. ] may be used in combination with an electrolyte having as a cationic component.

However, when the cation component of the present invention is a mixture of an ammonium salt consisting of an asymmetric quaternary ammonium ion and another electrolyte, it is preferable to use the ammonium salt in a form containing equal moles or more of the ammonium salt.

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

Specific examples of these organic solvents include tetrahydro7rane, 2-methyltetrahydrofuran, 1,4-nooxane, anisole, monoglyme, acetonitrile, propionitrile, butyronitrile, haL/O nitrile, 4-
Methyl-2-pentatuno, benzonitrile, o-tolnitrile, m-tolnitrile, p-tolnitrile
1,2-dichloroethane, γ-butyrolactone, nomethoxyethane, methylformate, globylene carbonate, ethylene carbonate, trimethylformamide 8, trimethylsulfoxide, trimethylthioformamide, sulfolane, 3 -Methyl-sulfolane, trimethyl phosphate, triethyl phosphate, etc. Among these, preferred solvents include acetonitrile, gropionitrile, butyronitrile, valeronitrile, benzonitrile, α-tolnitrile, o-tolnitrile, -Tolnitrile, p-
Particularly preferred solvents include benzonitrile, o-tolnitrile, m-tolnitrile,
Examples include p,-tolnitrile. These solvents may be used as a mixed solvent. The concentration of the electrolyte contained in the non-aqueous secondary battery of the present invention is at least 2 mol/1. Preferably 3 to 10 mol/
It is l. If the electrolyte concentration is less than 2 mol/mol, the non-aqueous secondary battery has the disadvantage that self-discharge is relatively large.

The electrolyte may be either homogeneous or heterogeneous, but it is usually used as a homogeneous electrolyte.

In the present invention, a conjugated polymer compound or a 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 (II) both positive and negative electrodes of a battery. However, in order to maximize the effect f of the present invention, type (U) is preferable.

For example, in the case of a non-aqueous secondary battery using an acetylene polymer as the conjugated polymer compound, as an example of (1), if the acetylene polymer v (cH) x, then graphite (positive electrode) / (M3BuN ) +・(CA04) (electrolyte) /(CH')X (, negative electrode), an example of (II) is C(CH')i, oz4 (Cl-04) 0.024
)X (positive electrode) / (Me3BuN,)”・(czo
4)-, (electrolyte) / ((Me3BuN piece, .2
4(CH)0.024]X(negative electrode), C(CHg, C6
(”F6)o, C6]x (positive electrode)/(Bu3EtN
)+・(,PF6)−(electrolyte)/((” u 3
E t N )S, C6(CI()0.061'X (
negative electrode), C (E ts Bu N) @, 02 (CH)
-□,'02] X (positive electrode) / (EtgBuN
＞+ −(cbo4)−(electrolyte)/((E t 3B
u N ) f, C7 (CH) hair, 07. ]X (negative electrode), etc.

7j? In the case of liparaphenylene, (C6H, 4)
)x is used as (C4H2N)x in the case of polypyrrole in the same type of non-aqueous secondary battery 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 (
CH' )X / gt 5 Bu N-czo4 /
(C6H4)X z(CH)x / MesBuN-
BF4 / (CaH2S) x 1 (C6H4)
/Et2Bu2N-PF6.(C4H2S)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 gradual oxidation reactions due to oxygen, which may reduce the performance of the battery, so the battery must be sealed and substantially oxygen-free. It is necessary that there be.

The non-aqueous secondary battery of the present invention has high energy density, high charge/discharge efficiency, long cycle life, low self-discharge rate, and good voltage flatness during discharge. Furthermore, the non-aqueous secondary battery of the present invention is lightweight, compact, and has a high energy density, so it is suitable for use in portable devices, electric vehicles, gasoline-powered vehicles, and power storage batteries.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Example 1 [Production of film-like acetylene polymer] 1.7 units of titanium tetrasitoxide were added to a glass reaction vessel with an internal volume of 500+nl under a nitrogen atmosphere.
A catalyst solution was prepared by dissolving in 30 ml of anisole and then adding 2.7 ml of triethylaluminum with stirring.

This reaction vessel was cooled with liquid nitrogen, and the nitrogen gas in the system was exhausted using a vacuum pump. Next, this reaction vessel was
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. Thirty minutes after the introduction of acetylene, the acetiine gas in the reaction vessel system was exhausted to stop the polymerization.

After removing the catalyst solution with a syringe under nitrogen atmosphere, -78
It was washed 5 times with 100 ml of purified toluene while keeping the temperature at °C. The film-like acetylene polymer swollen with toluene was a uniform film-like swollen product in which fibrils were tightly intertwined.

The swollen product was then vacuum-dried to obtain a reddish-purple film with a metallic luster, a thickness of 100 μm, and a cis content of 9.8%. Moreover, the bulk density of this film-like acetylene high polymer is 0. , 30. , f/(L), its electrical conductivity (DC four-terminal, 'method) is 3.2X1' at 20°C.
O'Ω-1・cfrL-1〇 [Battery experiment] Two disks with a diameter of 20w1 were cut out from the film-like acetylene polymer obtained by the above method, and each was used as a positive electrode and a negative electrode. A battery was constructed using the active material.

The figure is a schematic cross-sectional view of a battery cell for measuring the characteristics of a non-aqueous secondary battery, which is a specific example of the present invention. Current collector, 3 is a disc-shaped negative electrode with a diameter of 20cm, 4 is a diameter of 20w11
5 is a circular porous polypropylene diaphragm with a thickness that can be sufficiently impregnated with electrolyte, 5 is a disk-shaped positive electrode with a diameter of 20 mm, 6 is a platinum wire mesh current collector for the positive electrode with a diameter of 20 mm, 80 mm, and seam, 7 is a positive electrode lead wire, and 8 is a screw-type Teflon container.

First, the platinum wire mesh current collector 6 for the positive electrode is placed in a Teflon container 8.
The positive electrode 5 is further placed on the positive electrode platinum wire mesh current collector 6, and the porous polypropylene diaphragm 4 is placed on top of the positive electrode platinum wire mesh current collector 6.
After stacking them and sufficiently impregnating them with the electrolytic solution, the negative electrode 3 was stacked, and the platinum wire mesh current collector 2 for the negative electrode was further placed thereon, and the Teflon container 8 was tightened to produce a battery.

As the electrolytic solution, a solution of 3 mol/Et3BuN-BF4 dissolved in distilled and dehydrated benzonitrile according to a conventional method was used.

The thus prepared battery was charged in an argon atmosphere at a constant current (4.0 mA/c) for 15 minutes (the amount of electricity was proportional to the amount of doping of 5 moles). Immediately after charging, apply under constant current (4.0mA/cm)
In 2), a repeated charge/discharge test was performed in which the battery was discharged and the battery voltage became 1V, and then charged again under the same conditions as above.As a result, the charge/discharge efficiency decreased to 50%. The number of repetitions of discharge was recorded as 893 times.

Also, the energy density at the fifth repetition is 14,0
At W-hr 7 kg, the charge/discharge efficiency was 99. When the battery was left charged for 48 hours, its self-discharge rate was 1.2%.

Comparative Example Work In Example 1, Et3 used as the electrolyte of the electrolytic solution
When a battery was repeatedly charged and discharged in the same manner as in Example 2 except that Bu4N-BF4 was used instead of BuNIBF4, the highest light/discharge efficiency was 9.
At the 6th turn, the discharge became impossible after the 479th repetition.

Also, the energy density at the fifth repetition is 1 '30
The charging/discharging efficiency was 96% at W-hr/Kg.

Furthermore, when the battery was left charged for 48 hours, its self-discharge rate was 49%.

Comparative Example 2 A battery was repeatedly charged and discharged in the same manner as in Example 1 except that the electrolyte concentration was changed from 3 mol/l to 1 mol/l. However, the number of repetitions of charging and discharging was 700 times until the charging and discharging efficiency decreased to 50 cm.

Also, the energy density at the fifth repetition is 140
The charging/discharging efficiency was 99% at W-hr/kg. When the battery was left charged for 48 hours, its self-discharge rate was 3.0.

Comparative Example 3 Et3 used as the electrolyte of the electrolytic solution in Example 1
When we tried using equimolar amounts of Et4N-BF4f instead of BuN' BF4, Et4N-BF4 hardly dissolved in benzonitrile, and Ej4N-BF, which did not dissolve,
While '4 remained precipitated, the battery was repeatedly charged and discharged and experiments were conducted in the same manner as in Example 1. the result,
Maximum charging/discharging efficiency is 72%, number of repetitions is 255
The second discharge became impossible.

Comparative Example 4 Et3 used as the electrolyte of the electrolytic solution in Example 1
When an attempt was made to use an equimolar amount of L + BF4 in place of BuN-BF4, LIBF4 was not completely dissolved in benzonitrile, and a portion remained precipitated with insoluble Sakaki. A repeated experiment of charging and discharging the battery was conducted in the same manner as in Example 1. As a result, the highest light/discharge efficiency was 24 cm, making it impossible to avoid repeated discharges for the 122nd time.

Also, the energy density of the fifth repetition is 24W.
The charge/discharge efficiency was 18% in hr/kg.

Example 2 A 1 ton glass reaction vessel completely purged with nitrogen gas,
A 100-mesh stainless steel mesh was inserted, and then 10% of toluene purified according to a conventional method was used as a polymerization solvent.
0m1. Tetrabutoxytitanium 4.41 as a catalyst
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. -7
The reactor was cooled to 8° 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 was completed, unreacted acetylene gas was removed, and the system was washed four times with 200 ml of purified toluene while keeping the temperature at -78°C. A sheet-like swollen acetylene polymer containing a stainless steel mesh was obtained. This swollen acetylene polymer was a swollen product in which fibrous microcrystals (fibrils) with a diameter of 300 to 500× were regularly intertwined, and no powdery or lumpy Qmer was produced.

This sheet-like swollen acetylene polymer containing the stainless steel mesh is sandwiched between chrome-plated ferro plates.
Pre-pressed at room temperature with a pressure of 100 kg/cIrL2,
Then, it was pressed at a pressure of 15 tons/(z2) to form a uniform and flexible film with a reddish-brown metallic luster and a thickness of 280 μm.
The complex was obtained. This composite was vacuum dried for 5 hours at room temperature. The composite contained 43 weight stainless steel mesh.

[Battery experiment]

From the composite obtained by the above method, two disks with a diameter of 20 Tmn were cut out and used as a positive electrode active material and a negative electrode active material.Et dissolved in distilled and dehydrated acetonitrile was used as an electrolyte.
A charging/discharging experiment was conducted in the same cell as in Example 1 using a solution containing 4 mol/3B u N-C2O4. Charging was carried out for 15 minutes at a charging current density of 5.0 mA/cm2 (doping amount equivalent to 5 molti).

Immediately after charging, discharge current density 5. 'OmA/cm
When the battery voltage reached 1■ after discharging at step 2, a repeated charge/discharge test was performed in which the battery was charged again under the same conditions as above. The number of repetitions of discharge was recorded as 663 times.

The energy density at the fifth repetition of this repeated experiment was 152 W-hr'/kg, and the charge/discharge efficiency was 98%. Furthermore, when the battery was left charged for 48 hours, its self-discharge rate was 63%.

Comparative Example 5 In Example 2, the concentration of electrolyte in the electrolytic solution was changed to 1 mol/l.
An experiment of repeatedly charging and discharging the battery was conducted in the same manner as in Example 2, except that the charging and discharging efficiency was 5.
The number of times charging and discharging is repeated until it drops to 0% is 420.
It was times.

The energy density at the fifth repetition is 152 W.
-hr/kg, the charging/discharging efficiency was 98%. When the battery was left charged for 48 hours, its self-discharge rate was 9.5 cm.

Example 3 Bull, Chem, Soa, Japan,
, 51, 2091 (1978).
[Battery experiment] Exactly the same method as in Example 1 except that the positive electrode was formed into a disk shape of 20 mm diameter under a pressure of 20 cm.
As a result, the voltage characteristics were almost the same as the first discharge up to 313 repeated charging/discharging tests.

The number of repetitions until the charging/discharging efficiency drops to 50 is 4.
He recorded 17 times. The energy density of this battery is 166
The W-hr/ was 9, and the charge/discharge efficiency was 93 degrees.Also, when I left it charged for 48 hours, the self-discharge rate was 3.7 degrees.

Example 4 J was substituted for the poly(9) rough enylene) used in Example 3.
, Polym, Sal, * Polym, Leta,
, ed., +18 +9 (1980). [Battery experiment] was carried out in exactly the same manner as in Example 3 except that J (2,5-che2lene) was used. As a result, the number of repetitions until the light/discharge efficiency decreased to 50% was recorded as 505 times. The energy density of this battery is 158 W-hr/kg.
The discharge efficiency was 97 cm. Also, it can be used for 48 hours while it is charged.
When left for a period of time, the self-discharge rate was 4.1%.0 Examples 5 to 11 Charging was carried out in exactly the same manner as in Example 1, except that the combination of electrolyte and solvent was changed as shown in the table. - Conducted repeated discharge experiments. The results are shown in the table. In the table,
The energy density shows the number of repetitions at the fifth time, and the cycle life shows the number of repetitions until the charging/discharging efficiency decreases to 50 cm. Further, the self-discharge amount was shown after being left in an open circuit for 48 hours after completion of charging.

BRIEF DESCRIPTION OF THE DRAWINGS The figure is a schematic cross-sectional view of a battery cell for measuring characteristics of a non-aqueous secondary battery, which is a specific 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 diaphragm 5... Positive electrode 6 - Platinum wire mesh current collector for positive electrode 7... Positive electrode Lead wire 8...Teflon container Patent applicant Showa Denko K.K. Hitachi Ltd. Patent attorney Sei Kikuchi - Diagram

Claims (1)

[Scope of Claims] In a non-aqueous secondary battery using a conductive polymer compound as a negative electrode or both positive and negative electrodes, the cation component as an electrolyte is composed of asymmetric quaternary ammonium ions represented by the following general formula. 1. A non-aqueous secondary battery characterized in that an ammonium salt is used, and an electrolytic solution having an electrolyte concentration of at least 2 mol/L is used. [In the formula, R1, R21R, and R4 have 1 to 1 carbon atoms
6 alkyl group or aryl group. However, all R1, R2, R5 and R4 are not the same group at the same time. ]