JPS6293863A - Nonaqueous system secondary battery - Google Patents

Abstract

PURPOSE:To make three capacities of high energy density, a low self-discharge rate and high coulomb efficiency satisfiable at the same time, by treating a pyrrole polymer with alkali, in case of the nonaqueous system secondary batter constituted of the positive pole of the pyrrole polymer, the negative pole of a lithium system, and non-aqueous electrolysis consisting of an alkali metallic salt electrolyte and an organic solvent. CONSTITUTION:A pyrrole compound polymer to be expressed with a chemical formula (R1-R3 are a hydrogen atom, an alkyl group 1-10 in carbon number, an alkoxy group, an allyl group or a substitution allyl group of 1-10 in carbon number) is treated with alkali. In general, a polymer electrode is better in charge and discharge efficiency than that its bulk density is made smaller, and it is easy to operate with high current density, but even in case such a pyrrole polymer as being low in the bulk density might be, it is subjected to reduction treatment with alkali, whereby the low mobility anion contained is neutralized and remove, and simultaneously other impurities are eliminable, thus a utilization factor in the anion capable of charging and discharging the pyrrole polymer is sharply improved, and a battery characteristic is improvable even in respect of energy density.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a high-performance nonaqueous secondary battery that has high energy density, low self-discharge rate, and good coulombic efficiency.

[Prior art] Currently, commonly used secondary batteries include lead acid batteries, Ni/Ni/
There are CDZ ponds etc. These secondary batteries have a high single cell battery voltage.2. It is about OV, and is generally an aqueous battery. BACKGROUND ART In recent years, research has been actively conducted on the development of secondary batteries that use lithium as a negative electrode as a secondary battery that can provide a high battery voltage.

When l i is used for the negative electrode, it is necessary to use a non-aqueous electrolyte because of the high reactivity of 11 with water.

However, when performing a secondary battery reaction using Ll as a negative electrode active material, dendrites are generated when [i+ is reduced during charging, resulting in problems such as a decrease in charge/discharge efficiency and a short circuit between the positive and negative electrodes. Therefore, many technological developments have been reported to prevent dendrites and improve the charge/discharge efficiency and cycle life of negative electrodes. M. Abraham et al. Palitium Batchries'', edited by G.B. Calbuff 1, published by Academic Press,
London (1983) (K, H, Abraham e
tal, in “LithiulBatter”
ies”, J.P., Gabano, editor.
, Academicpress, London (1
983)))), a method of preventing l-i dendrites by incorporating additives into the electrolyte system, or alloying the electrode itself with A hair [Japanese Patent Application Laid-open No. 59-108281] has been proposed. ing.

In addition to alkali metals and Li/Hachijo Hegotoki alkali metal alloys, it is also known to use conductive polymers having conjugated double bonds in their main chains as negative electrode active materials [G.H. Curfman, J.A.・W. Kaufer, nee J. Heeger, Earl Karner, nee.
G. McDiarmid, Physics Review,.

Volume 826, page 2321 (1982) (J, 11
．． Kaul'man.

J, W, niawt'er, A, J, Heeger,
Kaner, R.

A, G, HacDiarmid, phys, Rev,
, 826 2327 (1982)>) Well-known conductive polymers used in this method include polyacetylene, polythiophene, polyparaphenylene, polypyrrole, and the like.

On the other hand, as a positive electrode active material, it is also known to use a conductive polymer as well as a negative electrode active material, and T i S
It is also known to use compounds that form intercalation compounds with alkali metals such as No. 2, other chalcogenide compounds, inorganic oxides, and the like.

1j conductive polymers used as positive electrode active materials include:
Including polyacetylene similar to that used for negative electrodes,
Examples include polythiophene, polyaniline derivatives, polyparaphenylene, polyparaphenylene derivatives, polypyrrole, polypyrrole derivatives, and other well-known examples include polyaniline and polyaniline derivatives.

Specific examples of chalcogenide compounds and inorganic oxides used as positive electrode active materials include TiS, Nb3S4. Mo3S4゜CoS, FeS
2. V2O5, Cr2O.

MnO,5i02. CoO2, 5n02, etc. are known.

Among these positive electrode active materials, those having particularly low self-discharge rates when used in batteries include polypyrrole-based polymers such as polypyrrole and polypyrrole derivatives. The following methods are well known as methods for producing pyrrole polymers. For example, pyrrole is oxidized (
Pyrrole black, a powdered polymeric material produced by, for example, hydrogen peroxide), has been known for many years [Gardini, Advanced Heterocyclic Chemistry, (Adv, Heterocy.
cl.

Chem, ) 15.67 (1973)], an electrochemical method for producing polypyrrole as a powder film on an electrode has been reported (A. Doll'Olio et al., Camp, Rend.
) 433°267C (1968)]. It has been reported that a polymer film can be produced from pyrrole by electropolymerization [Diaz et al., Journal of
The Chemical Society Chemical Communication (J, Chem, Soc, Chem, Co
mm,,) 635. (1979) (hereinafter referred to as Diaz (
I)), Diaz et al., General of the Chemical Society, Chemical ψ Communication (J
, Chem, Soc, Chem.

Co1n, ) 397 (1980) (hereinafter referred to as Diaz (■)), Diaz, Chemi-Riki Scribta (Che
m i ca Scripta, ) 17.45. (19
81) (hereinafter referred to as Diaz (■)), and Kananawa et al., Journal of the Chemical Society.
Chemical Communication (J, Chem, So
c, Chem Comm,) 954 (1979
) (hereinafter referred to as Kanazawa (engineering))]. Electropolymerized polypyrroles made from substituted pyrroles have been reported (Diaz (■), Diaz et al., Journal of Electroanalytical Chemistry (J, Elect).
roanal Chet, ) 129.115. (19
81) Kuko, Diaz (■)), Diaz et al., Journal of Electroanalytical Chemistry (J, [l1roanal Chem,,) 130.1
811. (1981) (hereinafter referred to as Diaz (V)). Copolymer films made by electrocoating mixtures of pyrrole and substituted pyrrole have also been reported.

Mixtures of pyrrole and N-mebrupyrrole have also been polymerized, and it is believed that these monomers are contained in the polymer (Díaz (■), Dip,
Proceedings of the International Conference 7th Lens On Raw Dimensional Synthetic Metals Chemiriki Scribta (Proc,
Int, Cant.

on Low Dimensional 5ynthe
tic Hetals Chemical Scripta
) 17,0000. (1981) (hereinafter referred to as Deip (Vl)), and Kanazawa et al., Synthetic Metals (Synth Hetals) 4.119. (
1981) (see Kanazawa (■) below)].

Polypyrrole is electrically conductive in its charged or oxidized state (black) and is produced by electropolymerization in this state. This is the neutralized state or discharged state (yellow)
When completely reduced to , it becomes an insulator. Electrolytically polymerized polypyrrole is produced in an oxidized, ie, conductive state, and unlike other conductive polymers such as polyacetylene, its conductivity is greater than 1/ohm·an. During electropolymerization, counteranions are introduced to balance the positive charges on the polymer main chain (see dip<m>).

Polypyrrole can be produced as a powder (see Gardini above), and polypyrrole can be electrolytically polymerized to form a continuous film with an electric current. It has been reported that the highest conductivity for this continuous film is on the order of about 100/ohm cm [Deip (■), Kanazawa et al., Synthetic Metals (Syn, Metals) 1.329.
(1980) (see Kanazawa (■) below)]. This conductivity value can be lower depending on the type of counteranion introduced.

CM O; , H80i, C
F3 SO:i.

CH3Ce　H4SOi　, CF3　COO-.

HCl2, and FQ (ON)6 [Deip (■), Deip (■), Kanazawa (■), and Nowfi et al., Journal of the Electrochemical
Society (J, IEI (ICtrOChemSo
c,) 128,2596. (1981)].

N-substituted virols have also been polymerized. Examples are medylpyrrole, ethylpyrrole, n-propylpyrrole, n-butylpyrrole, isobutylpyrrole, phenylpyrrole, and substituted phenylpyrrole.
Dip (■), Dip I, Electrochemical
Society Extended Abstracts, 8
Volume 2-1 Abstract A, 617. (1982)
(See Deip (■) below)]. The conductivity values of these polymers have been reported to be of an order of magnitude lower than that of polypyrrole itself (see Kanadjiwa (II) and Deip (■)).In addition, beta-substituted pyrroles such as 3,4-dimethylpyrrole It has also been polymerized [see Gardini, supra].

To date, the above polymers have been produced using non-aqueous solvents, typically acetonitrile (see Dip (T), Dip (II) and Dip (Vl)) containing salts that supply the counter-anion. It is known that the physical properties of the 1q film differ depending on the conditions under which it was produced. For example, the presence of trace amounts of water in acetonitrile results in films with smoother surfaces than those produced in anhydrous acetonitrile.
See VT)]. The polypyrrole tetrafluoroborate film produced by Diaz et al.
It is continuous, bulky, and has very poor crystallinity with a density of cIII [see Kanazawa (I)].

Polypyrrole films are thermally stable at room temperature and insoluble in common solvents (Fias (■), Kanazawa <■), and Tourilon (11 Electrochemical Society Extended Abstracts,
82-1%, abstract 618. (1982)
reference〕. Polypyrrole in the oxidized state is reported to be chemically stable for several months in an oxygen and moisture atmosphere [Diaz et al., Journal of Electrical Chemistry (J,
1. Chem, ) 121°355, (1981
) (hereinafter referred to as Dayp (■)), Watanabe et al., Bulletin of the Chemical Society of Japan (Bull, Chcm, Soc,, Jpn,...
54゜227g, (refer to 198).Polyvirol fluo mouth Volley-1 ~ film is +0.6 volts (vs. 5C
E) J'3 has been shown to be unstable under oxidizing conditions such as at potentials above or in the presence of [Pul et al.
Sosiadi (J, [electroehem, So
c. Heat 129, 1009 (1982)).

Polypyrrole can be repeatedly driven between a conductive state and a non-conductive state [Pul et al., Diaz et al. [Conducting Polymers], Polymer Science and Technology (PolymerSci, &
Technology, pp. 149 et seq. (Courtesy of Blenheim Press) (see Diaz (rX) below). Rapid and complete switching requires the use of thin films (i.e., about 0.1 micrometers or less); It is said that switching is difficult at a thickness exceeding micrometer (see fias (n) and Dias (rX)). The pyrrole polymer film can contain BF ions when it is formed (i.e., in a charged state), but when it is in a neutralized state (i.e., in a reduced or discharged state), BF ions are no longer present in the neurium. It has been shown that this is not the case [see Dias (IV)]. Also, both anions and cations of electrolyte salts have been shown to influence ion diffusion during reduction, 33 and oxidation of polypyrrole films [see Yias (IV)].

Virole polymers have been prepared with various degrees of oxidation, depending on the type of anion and/or substituent.

That is, since the virol polymer is produced by the above method or a method similar to the above method, most of the virol polymers obtained have an oxidation degree of 0.20 to 0.40, that is, a repeating virol polymer. per unit, 175-21
5 is obtained in an oxidized state. The E, virol-based polymer is often obtained in a form containing electrolyte, oxidizing agent, additives, impurities in the electrolytic solution, side reaction products during polymerization, oligomers, etc. .

When the virol polymer obtained by the above method is used as a positive electrode, when electrochemically discharging the anion already doped during polymerization, the dopant inevitably remains in the virol polymer, causing reversible damage. The amount of dopant that can be charged is limited, the energy density is small,
Furthermore, the maximum electrical capacity ω that can be accommodated by the positive electrode wheel was not sufficient, and a secondary battery with good performance could not be obtained. Further, even if the virol polymer obtained by the above method is vacuum-dried for, for example, 3 to 48 hours and heat-treated at 200° C. or lower, a battery with good performance cannot be obtained.

[Problems to be Solved by the Invention] An object of the present invention is to solve the above-mentioned drawbacks of the prior art, and to solve the problems (
I) high energy density, (II) low self-discharge rate and (I
ll) To provide a non-aqueous secondary battery that simultaneously satisfies the three performance requirements of high coulombic efficiency.

[Means for Solving the Problems] According to the present invention, a positive electrode made of a virol polymer, and a negative electrode made of lithium, a lithium alloy, a conductive polymer, or a composite of a lithium alloy and a conductive polymer. , a non-aqueous secondary battery mainly composed of an alkali metal salt electrolyte and a non-aqueous electrolyte consisting of a different solvent, characterized in that the pyrrole polymer is treated with an alkali. The following batteries are provided.

The pyrrole-based polymer used in the positive electrode of the non-aqueous secondary battery of the present invention is a polymer of pyrrole-based compounds represented by the following general formula.

[In the formula, R1-R3 may be different or the same, and may be a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms.
10 alkoxy groups, aryl groups or substituted aryl groups. ] Typical examples of virol compounds represented by the above general formula include virol, 3-methyl-pyrrole, 3,4-dimedyruvirol, 3-methyl-4-edyruvirol,
3-Methoxy-pyrrole, N-Mediruby [Cole, N
-ethyl-virol, N-n-propyl-virol, N
-n-butyruvirol, N-isobutylupyryl, N-ph]-nyl-virol, and the like. These virol compounds may be used alone or in a mixture of two or more.

As mentioned above, the virole polymer can be produced by either the electrochemical polymerization method or the chemical polymerization method.

Next, the method for alkali treatment of a pyrrole polymer according to the present invention will be explained.

As mentioned above, the pyrrole-based polymer polymerized by electrochemical polymerization method or chemical polymerization method is in an oxidized state, and the electrolyte, oxidizing agent, additives,
1q is often produced in a form containing impurities in the electrolyte, side reaction products during polymerization, oligomers, etc.

As a method of treating virol polymer with alkali,
A method in which a virol polymer is washed with water or a linear alkaline aqueous solution, a method in which a virol polymer is washed with an alkali, then washed with water, and this is repeated alternately; a method in which a virol polymer is washed with an alkali, then washed with water, and then this is repeated alternately. Examples of the method include repeating the process repeatedly, and finally washing with water again until the [)11 of the washing liquid becomes 5 or more, preferably pl+ of the washing liquid becomes within the range of 6 to 8.

As the alkaline aqueous solution used here, any aqueous solution can be used, but in order to increase treatment efficiency, an aqueous solution with pl+ of 12 or more is preferable.

As the alkali species, either a non-I alkali or an organic alkali may be used as long as it is water-soluble, but from a loss point of view, it is preferable to use a general-purpose alkali species. Specific examples of such alkali species include alkali metal hydroxides such as KOH and NaOH, M! J(OH):+,C
a (0)-1>2! ! Examples include aqueous solutions of alkaline earth hydroxides, ammonia, amines, etc. Preferred among these alkaline species are KOH, NaOH and aqueous ammonia.

In particular, aqueous ammonia is an alkaline species from which residual alkali or neutralized salts can be easily removed during washing with water after neutralization and drying under reduced pressure of the virol polymer.

The number of times a pyrrole polymer is treated with alkali varies depending on the size or shape of the polymer to be treated, the process in which the polymer is packaged, the size or shape of the treatment liquid, the amount of water used, and the treatment container, but usually Wash once or several times.

When treating virol-based polymers with alkali,
Simply immersing the polymer in an alkaline aqueous solution is sufficiently effective, but for even more rapid and effective cleaning, it is necessary to circulate the alkaline aqueous solution or immerse the polymer in the alkaline aqueous solution. Alternatively, external energy such as ultrasonic waves may be applied.

The alkali treatment time, like the number of alkali treatments, depends on the fabric and shape of the virol polymer, the electrical production of the treatment liquid, the size and shape of the hanging and treatment container, and cannot be unconditionally defined.

It goes without saying that the shape of the pyrrole polymer to be washed with alkali may be in the form of a film, particles, or powder.

As mentioned above, the virol polymer used in the present invention may be produced by electrochemical polymerization or chemical polymerization, but the virol polymer with a low bulk density may be From the point of view of obtaining, for example, JP-A-59-
It is preferable to use a pyrrole polymer produced according to the method described in Japanese Patent No. 166529.

In general, polymer electrodes have better charge/discharge efficiency when their bulk density is lower, and are easier to operate at high current densities.
(below) and used for electrodes. In order to lower the bulk density of the polymer, it is necessary to add halogen or B to the dopant.
It is more desirable to carry out electrolytic polymerization using a relatively high-molecular, low-mobility anion as a dopant than to carry out electrolytic polymerization using a low-molecular-weight anion such as F. However, this type of low-mobility anion doped with -kame cannot be electrochemically undoped, and it tends to remain inside the electrode if the post-treatment method consists of vacuum drying and heat treatment at 200°C or less. . Therefore, when this type of polymer containing low-mobility anions is used as an electrode in a battery, anions (dopants) or salts that cannot be electrochemically charged and discharged remain, and a corresponding amount of the anions (dopants) or salts are used as electrodes to reduce the actual energy density. becomes smaller.

However, in the present invention, by reducing even a virol-based polymer with a low bulk density with an alkali, it is possible to neutralize and remove the low-mobility anions contained therein, and at the same time, remove impurities, etc. As a result, the utilization rate of the chargeable and dischargeable anions of the virol polymer can be significantly increased, and the battery characteristics can also be improved in terms of energy density.

The alkali-treated virol-based polymer may include a suitable binder material and/or a high surface area carbon material >31a.
The species may also contain other redox species. Suitable binder materials are inert polymeric binders that do not interfere with the electrochemical performance of the resulting electrode. Examples are halogenated polymers such as bolite-1-lafluoro-1 dylene, which are preferably introduced from an aqueous dispersion. Such a dispersion is commercially available, for example, from J″]-Pon under the trade name Teflon T30B.

It is possible to use polytetraflu-3-brene, which is introduced in the form of a powder. , other polymers may be used, such as boria-1-cobylene, under conditions that are not strongly oxidizing. The high surface area carbon material is about 1 to about 2000 m
2/! 7, preferably about 60 to about 1200 m
There is something with a surface area of 2/l. Examples of commercially available high surface area carbon materials include RB carbon, which has a surface area of about 1200 m2/9;
Shawinigan black with a surface area of 7.

A virol-based polymer electrode is prepared by first injecting the virol-based polymer into water or a liquid (optional), optionally with a binder material, a high surface area carbon material, and/or other redox species.
(e.g., mineral spirits) to form a pasty mixture. The pasty mixture is cold pressed or rolled into the desired shape of the electrode by standard techniques, preferably at a pressure of about 500 to 12,000 PSI and a temperature from room temperature to the decomposition temperature of the pyrolytic polymer. The pyrrole polymer of the present invention is preferably heat-treated in step 11a or after forming the paste-like mixture in order to increase its electrochemical storage capacity.

BACKGROUND ART A virol-based polymer electrode, either as a film on an anode or press-molded from a powder, is used as a positive electrode in a secondary battery. This electrode can be formed into a size and shape depending on the shape and shape of the secondary battery in which it is incorporated.

The negative electrode active material used in the present invention is lithium, a lithium alloy, a conductive polymer, or a composite of a lithium alloy and a conductive polymer.

For Li-18 alloy, Li/1-(c
+.

1i/Zn, li/Cd, Li/Sn
, Li/Pb, and three or more types of alloys containing lithium used in these alloys. Examples of conductive polymers include polygorole and polypyrrole derivatives, polythionone and polypyrrole derivatives, polyquinoline, boriacene, borivaraf-1-nylene, boria (?thylene), etc.Furthermore, composites of lithium alloys and conductive polymers Examples of the body include a composite of an L1/A further alloy and various conductive polymers.The composite here refers to a homogeneous mixture of a lithium alloy and a conductive polymer, an FI layer body, and a substrate. It means a modified product in which one component is modified with another component.

The INfi solvent of the electrolyte used in the non-aqueous secondary battery of the present invention is preferably one that is non-bucodonic and has a high dielectric chamber. For example, ethers, ketones, amides, sulfur compounds, phosphate ester compounds, chlorinated hydrocarbons, esters, carbonates, nitro compounds, sulfolanes, etc. can be used, but among these, ethers , ketones, phosphoric acid ester compounds, chlorinated hydrocarbons, h-bonnets 1 to 1, and sulfolanes are preferred.

Representative examples of these solvents include tetrahydrofuran, 2-methylna-1-lahydrofuran, 1,4-dioxane, monoglyme, 4-methyl-2-pentanone, 1.
2-dichloroethane, γ-butyrolactone, valerolactone, dimethoxyethane, methylforme-1-, propylene carbonate, ebulene carbonate, dimethylformamide, dimethyl sulfoxide, dimethylthioformamide, ethyl phosphate, methyl phosphate, chlorobenzene, sulfolane, 3- Examples include methylsulfolane. Two or more of these organic solvents may be used in combination.

Further, a specific example of the alkali metal salt electrolyte used in the non-aqueous secondary battery of the present invention is 1ipFa.

Li5bFe, LiCJO+, LiASFe.

CF35○3 Li, Li BF4, Li B
(Bll)4.

Li B (Ej)2(811)2 , Na PFa
.

NaBF4, NaAsFe, NaB
(BLI)4.

Examples include KB (BL114), KAsFe, etc., but are not necessarily limited to these.These alkali metal salt types may be used alone or in combination of two or more types.

The production of electricity using alkali metal salt electrolytes varies depending on the type of pyrrole polymer used for the positive electrode, the type of cathode, charging conditions, operating temperature, type of alkali metal salt electrolyte, type of solvent, etc., so there are no general regulations. However, it is generally preferable that the amount is within the range of 05 to 10 mol/G. The electrolyte may be homogeneous or heterogeneous. In the non-aqueous secondary battery of the present invention, the total amount of dopant doped into the virol polymer is 10 to 60 mol %, preferably 20 to 50 mol %, based on 1 mol of repeating medium of the virol polymer. %. The doped skewer can be freely controlled by measuring the amount of electricity that flows during electrolysis. The doping may be carried out either under constant current, under constant voltage, or under varying current and voltage.

[Effect of the invention] The non-aqueous secondary battery of the present invention has a high energy density,
It has high charge/discharge efficiency, good cycle life, low self-discharge rate, and good voltage flatness during discharge. In addition, the nonaqueous secondary battery of the present invention is lightweight, compact, and has high energy density, so it can be used in portable devices, electric vehicles, etc.
Ideal for gasoline-powered vehicles and power storage batteries.

[Example] Hereinafter, the present invention will be explained in further detail by giving Examples and Comparative Examples.

Example 1 Pyrrole 40g Sodium lauryl sulfate 40g Polyethylene glycol]-
Le 20g distilled water 1600
g Hebutane 200 g The above four ingredients were mixed in a container and made homogeneous, and 375-cm of this mixture was charged into a 10.8 x 8.9 x 5.7 cm reaction vessel. Two platinum electrodes were installed.

Heptane 50m! ! , and stirring was performed using a Vibrow mixer.

Two separate films were obtained with a reaction time of 30 minutes at 2Δ. The temperature was controlled with a water bath and was 21°C initially and rose to about 34-37°C during the reaction. The current was maintained at 2Δ, but the voltage was varied from about 60V to about 40V during the course of the reaction. There were slight irregularities in the form of dendrites (approximately 1 mm) on the bath side of each film, which were removed by light sanding before peeling the films from the electrodes. Each film was thoroughly rinsed in distilled water and heptane.

One film was thoroughly dried in a vacuum oven at 50°C for 2 hours. Thus, the 11-layer film consisted of three layers. The first layer closest to the steel electrode was smooth and continuous. The second layer following this first layer was uniformly porous, and the third layer following it was denser and less porous than the second layer. Another result obtained in this example
The film should be peeled off from its backing layer or smooth layer.
It was cut into strips of /4 in 7-. The film strips were washed in a Soxhlet extractor with distilled water for 15 hours.

After drying at ¥ temperature, it was further dried in a vacuum oven at 50° C. for 24 hours.

Next, this film was immersed in a 1a container containing 500 m of a 28% by weight aqueous ammonia solution for 3 hours.

During this time, neutralization was promoted by ultrahigh waves for 15 minutes. After repeating this operation twice, each sample was washed three times with 11 distilled water. At this time, the pH of the third washing solution was 7.6. The alkali-treated electrode was preliminarily dried at 50° C. for 1 hour, and then dried in a vacuum oven at 80° C. for 12 hours.

A disk with a diameter of 20M was cut out from the alkali-treated polypyrrole film obtained in the above-mentioned process and used as a positive electrode, and six lithium plates with a thickness of 200μm were stacked together to form a disk with a diameter of 20I.
A battery was constructed by punching out a disk shape of un and using it as a negative electrode.

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, in which 1 is a nickel lead wire for the negative electrode, 2 is a nickel mesh for the negative electrode with a diameter of 20 m, and 80 meshes. Electric body, 3 is a disc-shaped negative electrode with a diameter of 20 mts, 4 is a circular porous polypropylene diaphragm with a diameter of 20 m, and is thick enough to be sufficiently impregnated with the electrolyte, 5 is a diameter of 20 m
m, a disc-shaped positive electrode; 6, a platinum wire mesh current collector for the positive electrode with a diameter of 20 m and 180 mesh; 7, a positive electrode lead wire; and 8, a screw-in type container made of [].

First, the platinum wire mesh current collector 6 for the positive electrode is placed in the lower part of the concave portion of the Teflon container 8, and the square wire 5 is placed on top of the platinum wire mesh current collector 6 for the positive electrode. After stacking the partitions 4 made of polypropylene and fully impregnating them with electrolyte, the negative electrode 3 is stacked, and the nickel mesh current collector 2 for the negative electrode is placed on the space 1-, and the Teflon container 8 is tightened to complete the battery. was created.

As the electrolytic solution, a 0.8 mol/l solution of Li.PFo dissolved in 2-methyl-tetrahydrofuran was used which had been distilled and dehydrated according to a conventional method.

Using the battery prepared in this manner, it was filled by flowing an amount of electricity corresponding to 45 mol% of doping to 1TEt (i) under a constant current (1.0 mA/c2) in an argon atmosphere. Charging completed. After that, immediately under a constant current (1.5mA
/α2), and when the battery voltage reached 1.5V, a repeated charge/discharge test was performed in which the battery was charged again under the same conditions as above, and the charge/discharge efficiency was 50.
%, the number of times the light/discharge was repeated was 368 times. The highest value of Coulombic efficiency was 100%. The energy density of this battery is 452 fathoms/hr, 'Kg
Met. When the battery was left charged for 48 hours, its self-discharge rate was 3.8%. Here, the energy density was calculated using the following formula.

Energy = l! - Density [W - hr/Ky ] = Comparative Example 1 A battery experiment was conducted in exactly the same manner as in Example 1 except that a polypyrrole film that was not subjected to alkali treatment was used as the positive electrode. As a result, the number of charge/discharge cycles was 220, and the energy density was 388-hr.
/Kff. Moreover, the self-discharge rate was 68%.

Example 2 In Example 1, a sodium hydroxide aqueous solution (sodium hydroxide concentration 40j'fffHt%) was used instead of the ammonia aqueous solution.
A battery experiment was conducted in the same manner as in Example 1, except that a polypyrrole film treated with ) was used. the result,
The number of repetitions of charging and discharging was recorded as 308 times. The highest value of Coulombic efficiency was 100%. The energy density of this battery was 43814-hr/Kg and the self-discharge rate was 4,0%.

Example 3 Example 1 except that polypyrrole produced under the following polymerization conditions was used instead of the polypyrrole used in Example 1.
Ammonia aqueous solution treatment and battery experiments were conducted in the same manner as above.

A mixture consisting of 5 g of virol, 1 g of sodium ethanedisulfonate, 2 g of polyethylene glycol, and 2009 g of water was prepared and charged into an 8X7X4.5 (J) reaction vessel. Sim Platinum (NID 8/to ID^1
613D A[) and the anode is 10x 5 xo
, Kkel 2 on a platinum 200 panel with a size of 0.5 cm.
00 was made by Inco, high purity nickel).

The surface area of each electrode (electrode side, smooth portion) immersed in the electrolytic bath was approximately 40 cm2. Toluene 20mf! was added, and the mixture was stirred using a blow mixer. The electropolymerization reaction was carried out at a constant current of 0.5 A for 15 minutes at a voltage of about 17 V. The film formed on the electrode was peeled off. This was a relatively porous, uniform film with a thickness of about 0.3-0411 IIl.

As a result of the battery experiment, the number of repeated charging and discharging times was recorded as 304 times. The highest value of Coulombic efficiency was 100%.

The energy density of this battery was 425 h/Kg, and the self-fliction rate was 41%.

Comparative Example 2 Except for using polypyrrole, which was not treated with an ammonia aqueous solution, as the positive electrode in Example 3, the actual product was 7 il! A battery experiment was conducted in exactly the same manner as in Example 3. As a result, the number of charge/discharge cycles was 195, and the energy density was 382.
-・hr/ It was Kbi. Also, the self-discharge rate is 6.9
%Met.

Example 4 Example 1 except that Polypyrrole, which was produced under the following polymerization conditions, was used instead of the polypyrrole used in Example 1.
Antonia aqueous solution treatment and battery experiments were conducted in the same manner as above. Virol 209, 1-4% tetrahydrogenbentaerythritol, 4g polyethylene glycol, and 80% water
0! ? A more tli mixture was prepared and stirred to homogeneity. This 375d is 5゜7x 8.9x10.8c
1, and 50 ml of dichloromethane was added thereto. The cathode is a platinum panel (Nl5I No, 10/10) with a size of 15X 7.5x005,
7 nodes is 14.2X 7. It was a platinum 200 sheet with a size of OX O,025c. For electrolytic polymerization, the current is 2A.
The test was carried out in a standard manner for 15 minutes while maintaining the temperature. Thus, it is approximately 1 cyr thick and has a low density (0,17/cm3
) A porous material was obtained. It was electrically conductive.

As a result of the battery experiment, the number of repeated charging and discharging times was recorded as 364 times. The highest value of Coulombic efficiency was 100%.

The energy density of this battery was 450 W·hr/Kg, and the self-tIi electric rate was 3.9%.

Comparative Example 3 A battery experiment was conducted in exactly the same manner as in Example 4, except that polypyrrole, which was not treated with an ammonia aqueous solution, was used as the positive electrode.As a result, the number of charge/discharge cycles was 212. The energy density was 3821 J-hr/K9, and the self-discharge rate was 7.
It was 0%.

Example 5 Example 1 except that polypyrrole produced under the following polymerization conditions was used instead of the polypyrrole used in Example 1.
Ammonia aqueous solution treatment and battery experiments were conducted in the same manner as above.

Pentaerythritol tetrasulfate ammonium salt was prepared from pentaerythritol and sulfamic acid in N,N-dimethylformamide. Pyrrole 5 in 200 d of water!
? and a mixture of 5 of the above ammonium salts, 8X
Electropolymerization was carried out in a 7 x 4.5 cm reaction vessel. In this electropolymerization, 15× 5 X O,
Using a platinum sheet of 0.25 cm, the anode was connected to 'C6,
A platinum sheet measuring 4 x 5 x 0.025 cm was used.

The surface area of the platinum sheet immersed in the electrolytic bath was approximately 40 cm2. Further, the electrode spacing was 4.5 crn. Electrolytic polymerization was carried out for 10 minutes at a current of 0.3 A, and 1 q of black conductive film with a somewhat rough surface was formed on the electrolytic bath side.

As a result of the battery experiment, the number of repeated charging and discharging times was recorded as 358 times. The highest value of Coulombic efficiency was 100%.

The energy density of this battery was 446-hr/KLJ, and the self-discharge rate was 41%.

Example 6 In Example 5, Ll-hep alloy (50
:50 atomic ratio) was used as the negative electrode, a battery experiment was conducted in the same manner as in Example 5. As a result, Mitsuru・tl
The number of repetitions of i-den was recorded as 628 times. Moreover, the maximum coulomb efficiency was 100%. The energy density of this battery was 447 hr/Ky, and the self-discharge rate was 4.2%.

Comparative Example 4 A battery experiment was conducted in exactly the same manner as in Example 6, except that polypyrrole, which was not treated with an ammonia aqueous solution, was used as the positive electrode. As a result, the number of repetitions of charging and discharging was recorded as 458 times. Also, the energy density is 3
75k・hr/Kg, self tIj, electric rate is 71%
Met.

Example 7 Example 1 except that polypyrrole produced under the following polymerization conditions was used instead of the polypyrrole used in Example 1.
Ammonia aqueous solution 98 and battery experiments were conducted in the same manner as described above.

Five steps were carried out as in Example 5 except that 2 g of polyethylene glycol was added to the mixture in the reaction vessel. The resulting black conductive film was 6 more uniform and smooth on the electrolytic bath side than the film of Example PA5.

As a result of the battery experiment, the number of repeated charging and discharging times was recorded as 356 times. The highest value of Coulombic efficiency was 100%.

The energy density of this battery was 449 hours/KFJ, and the self-release rate was 4.0%.

Comparative Example 5 A battery experiment was conducted in exactly the same manner as in Example 7, except that polypyrrole, which was not treated with an ammonia aqueous solution, was used as the positive electrode. As a result, the number of repetitions of charging and discharging was recorded as 208 times. Also, the energy density is 3
77W-hr, 'K9''C: Yes, self full electric rate was 69%.

Example 8 Example 1 except that polypyrrole produced under the following polymerization conditions was used instead of the polypyrrole used in Example 1.
Ammonia aqueous solution treatment and battery experiments were conducted in the same manner as above.

A mixture of 15 g of virol and 500 g of water was prepared, while a mixture of 10 g of potassium ferricyanide and 5 J of polyethylene glycol was prepared in 400 d of water. These 2
The two solutions were mixed and shaken. This mixture of 450m is 10. It was charged into a reaction vessel of ax 8.9 x 5.7 cm. Both electrodes used in this example were platinum panels. Electrolytic polymerization was carried out at 5△. The temperature at the start of the reaction was 23°C, and the voltage was 22V. During the electropolymerization reaction, the temperature was maintained at 31-32°C with a water bath. At this temperature, a voltage of 20V was required to maintain a current of 5A. The electrode spacing was 5.5 m. Electrolytic polymerization was carried out for 40 minutes. The resulting film was peeled off from the anode.

This film has a thickness of 0.8. It was a black conductive film. Also, this film was smooth on both sides.

As a result of the battery experiment, the number of repeated charging and discharging times was recorded as 359 times. The highest value of Coulombic efficiency was 100%.

The energy density of this battery was 452.A battery experiment was conducted in exactly the same manner as in Example 8, except that polypyrrole, which was not treated with an ammonia aqueous solution, was used as the positive electrode. As a result, the number of charging/discharging cycles μ216 was recorded. Also, the energy density is 37914・hr/4
．． y, and the self-discharge rate was 7.0%.

Example 9 Example 1 except that polypyrrole produced under the following polymerization conditions was used instead of the polypyrrole used in Example 1.
Ammonia aqueous solution treatment and battery experiments were conducted in the same manner.

A mixture consisting of 04 g of a 50% aqueous solution of the sodium salt of pyrrole 2q12-acrylamido-2-mebrubrobanesulfonic acid and 100 d of water was prepared 2 and mixed to homogenize. In this example, the cathode is a platinum platelet (0,5x 3
cm >, and the anode (over the whole surface (approximately 4CI112
was immersed in an electrolytic bath). The electrodes were rinsed with distilled water before use. Electropolymerization was carried out using a Hea-7-Let Barracard power supply/amplifier model 6824A. The electrolytic polymerization reaction was carried out at a current of 24 mA and a voltage of 15 V for 2 minutes. A thin black conductive film was thus deposited on the gold-filled surface.

As a result of the battery experiment, the number of repeated charging/discharging times was recorded as 346 times. The highest value of Coulombic efficiency was 100%. The energy density of this battery was 448 W-hr/Ky, and the self-discharge rate was 4.3%.

Comparative Example 7 A battery experiment was conducted in exactly the same manner as in Example 9, except that polypyrrole, which was not treated with an ammonia aqueous solution, was used as the positive electrode. As a result, the number of repetitions of charging and discharging was recorded as 211 times. Also, the energy density is 3
76W-hr/K9, self-discharge rate is 7.3%
Met.

Example 10 Example 1 except that polypyrrole produced under the following polymerization conditions was used instead of the polypyrrole used in Example 1.
Ammonia aqueous solution treatment and battery experiments were conducted in the same manner as above.

1 g of phenylphosphonic acid and 2 g of virol in 100 g of water
An electrolytic bath was prepared. Electrolytic polymerization was carried out on a small gold plate with a size of 3 x 0.5 cm without stirring the electrolytic bath. All platelets were immersed to a depth of 10. A platinum electrode was used as a counter electrode, and a current of 1 mA was maintained for 300 seconds. 1!1
The resulting product was a black conductive film.

As a result of the battery experiment, the number of repeated charging/discharging times was recorded as 365 times. The highest value of Coulombic efficiency was 100%. The energy density of this battery was 445 W-hr/'J, and the self-discharge rate was 3.9%.

Comparative Example 8 A battery experiment was conducted in exactly the same manner as in Example 10, except that polypyrrole, which was not treated with an ammonia aqueous solution, was used as the positive electrode. As a result, the number of repetitions of charging and discharging was recorded as 228 times. Also, the energy density is 374 hr/N! IF, and the self-discharge rate is 6.
It was 7%.

Example 11 Ammonia aqueous solution treatment and battery experiment were carried out in the same manner as in Example 1, except that a copolymer of pyrrole and N-methyl pyrrole produced under the following polymerization conditions was used instead of the polypyrrole used in Example 1. I did it.

Virol 209, N-methylvirol 20g, 1゜6-
A mixture consisting of 15% sodium hexane disulfate, 0.67% C-C alpha olefin sulfonate and 1400% water was stirred to homogenize and was heated to 8°25x14x19C.
It was charged into a reaction vessel of I11. The cathode is 14x 19x O, 'Icm Al5f N degreased with toluene.
o, 10/10 platinum panel, anode 14x
It was a platinum 200 panel of 19 x O, In. 150 d of heptane was added, and the mixture was stirred using a Vibro Miki.

The anode surface area covered by the produced polymer is approximately 250 cm
It was 2. Electrolytic polymerization was carried out for 1 hour at a current of about 5 A (direct current).

The resulting polymer film was peeled off from the anode and partially ground by hand while being washed with distilled water. The polymer was further washed by Soxhlet extraction with distilled water, dried in a vacuum oven at 85° C. for 20 hours, and then further ground with a motorized pestle. In this way, a fine black inductive powder was obtained.

As a result of the battery experiment, the number of charging/discharging cycles was recorded as 315 times. The highest value of Coulombic efficiency was 100%. The energy density of this battery was 435 W·hr/'J, and the self-discharge rate was 4.2%.

Comparative Example 9 A battery experiment was carried out in exactly the same manner as in Example 11, except that a copolymer of pyrrole and N-methyl pyrrole, which was not treated with an aqueous ammonia solution, was used as the positive electrode. As a result, the number of repetitions of charging and discharging was recorded as 201 times. Further, the energy density was 365 hours/sg, and the self-discharge rate was 7.0%.

Example 12 Ammonia aqueous solution treatment was carried out in the same manner as in Example 1, except that a copolymer of Gorole and N-methyl Gorole produced under the following polymerization conditions was used instead of the polypyrrole used in Example 1. A battery experiment was conducted in the same manner as in Example 11.

Virol 20g, N-methylvirol 207, sodium lauryl sulfate 40g, polyethylene glycol 20g
, and 1400 (j) of water was stirred to homogenize and charged into an 8.25 x 14 x 19 c IR reaction vessel. Both electrodes used were 14 x 19 x o, 1 c
m, 1~Al5I degreased with toluene No, 10/
10 steel panels. 150 d of heptane was added and stirred with a Vibrow mixer. The anode surface area covered by the resulting polymer was approximately 250 c.2. Electrolytic polymerization was carried out for 1 hour at a current of about 5 A (direct current). The resulting polymer film was peeled off from 7 nodes and partially ground by hand while being washed with distilled water. The polymer was further washed by Soxhlet extraction with distilled water and then placed in a vacuum oven for 85 min.
After drying at ℃ for 20 hours, it was further crushed using a pestle with a top. In this way, 411 fine black conductive powder is produced.

As a result of battery experiments, the number of times of charging/IIIi charging is 340.
recorded times. The maximum Coulombic efficiency was 100%. The energy density of this battery is 438 m/h "Example 1
A battery experiment was conducted in exactly the same manner as in Example 12, except that in Example 2, a copolymer of pyrrole and N-methylpyrrole that was not treated with an ammonia aqueous solution was used as the positive electrode. As a result, the number of repetitions of charging and discharging was recorded as 208 times. In addition, the energy density is 368 stomach・hr//(g,
The self-discharge rate was 6.9%.

[Brief explanation of drawings]

The figure is a schematic cross-sectional view of a battery cell for measuring characteristics of a non-aqueous secondary battery, which is an integral example of the present invention. 1... Nickel lead wire for negative electrode 2... Nickel mesh current collector for 08i 3... Negative electrode 4... Porous bolibu I] Pyrene diaphragm 5... Positive electrode 6... For positive electrode Platinum mesh current collector 7...Positive electrode lead wire 8...Teflon container Patent applicant Showa Denko Co., Ltd. 1 Hitachi, Ltd.

Claims (1)

[Claims] A positive electrode made of a pyrrole polymer, a negative electrode made of lithium, a lithium alloy, a conductive polymer, or a composite of a lithium alloy and a conductive polymer, and a non-aqueous electrolyte made of an alkali metal salt electrolyte and an organic solvent. A non-aqueous secondary battery configured as a main component, wherein the pyrrole polymer is treated with an alkali.