JPH0722025B2 - Secondary battery - Google Patents

Description

TECHNICAL FIELD The present invention relates to a secondary battery, and more particularly to a non-aqueous secondary battery using a conductor made of an organic material as an electrode material.

<Prior Art> In recent years, a secondary battery using a conductive polymer made of various organic materials as an electrode material has been proposed.

The conductive polymer used as the electrode material of this type of secondary battery is
Usually, the conductivity is low, but it is possible to dope and undo the dopants such as various anions and cations, and the conductivity is remarkably increased by the doping. Then, a conductive polymer doped with anions is used as a positive electrode material, and a conductive polymer doped with cations is used as a negative electrode material, and a solution containing the above dopant is used as an electrolytic solution. A battery that can be charged and discharged is constructed by performing the chemical reversible process.

As such a conductive polymer, polyacetylene, polythiophene, polypyrrole, etc. have been conventionally known. Taking polyacetylene as an example, polyacetylene is used as an electrode material for at least one of a positive electrode and a negative electrode,
_{^{BF 4 -, ClO 4 -,}} SbF 6 -, PF 6 - , etc. anions or Li, ^+, N
A configuration is adopted in which cations such as a ⁺ , R ₄ -N ⁺ (R represents an alkyl group) and the like are electrochemically reversibly doped and undoped.

By the way, this kind of conductive polymer, for example, polyacetylene, has a drawback that it is very easily oxidized by oxygen in the air in a doped and undoped state. For this reason, when this is used as an electrode material, there is a problem that the management of the electrode manufacturing environment becomes important, the electrode manufacturing work becomes difficult and complicated, and the storage stability of the electrode itself is poor. Furthermore, when it is incorporated into a battery, it may be degraded or decomposed only by the presence of a trace amount of oxygen or water, causing deterioration of the battery characteristics. In addition, if overcharged, the polymer may be degraded or decomposed. However, it is not preferable as an electrode material because it causes a rapid increase in charging voltage, a decrease in charge / discharge efficiency, a decrease in battery cycle life, and the like.

On the other hand, among the above-mentioned various conductive polymers, polypyrrole is characterized in that it has better stability in air, extremely less oxidative deterioration, and is easier to handle than polyacetylene. Therefore, when polypyrrole is used as an electrode material for a battery, it is possible to obtain an electrode that is easy to manufacture and has good storage stability without the drawbacks of polyacetylene.

As such polypyrrole, conventionally known are those in which pyrrole is electrochemically oxidatively polymerized (electrolytically polymerized), those in which pyrrole is chemically oxidatively polymerized using an oxidizing agent, and the like. Then, in the case, polypyrrole is deposited in a film shape on the electrolytic anode, and after the deposition, the film is peeled off from the same electrode to obtain a film-shaped polypyrrole.
In this case, use peroxides such as potassium persulfate or ammonium persulfate as oxidizing agents, acids such as nitric acid, sulfuric acid or chromic acid, and Lewis acids such as ferric chloride, ruthenium chloride, tungsten chloride or molybdenum chloride. Oxidative polymerization, or oxidative polymerization of pyrrole using ferric perchlorate as an oxidant in an organic solvent (Mol. Cryst. Liq. Cryst. 1985 vol 118 vol. 149).
~ 153), powdery polypyrrole is obtained.

<Problems to be Solved by the Invention> However, one of the above-mentioned conventional polypyrroles is obtained because the manufacturing method is complicated and not only causes a high battery cost but also polypyrrole is generated on the electrolytic anode surface. The shape and size of polypyrrole are regulated by the size of the electrode plate, which makes it difficult to form the polypyrrole into a free size according to the battery type. Furthermore, since it is difficult to obtain a uniform thickness and thickness with good reproducibility, only thin thickness materials can be used as industrial battery materials, which limits the battery electrode itself and the charge / discharge capacity of the battery. Therefore, there is also a problem that it is extremely difficult to increase the capacity.

On the other hand, when the polypyrrole obtained above is used, the above problem does not occur. However, since the electric conductivity of polypyrrole is extremely small, when a secondary battery is manufactured by using this as an electrode material, the internal resistance of the battery increases and the charge / discharge reaction becomes nonuniform in each part of the electrode. Therefore, when the charge / discharge cycle is repeated, there is a problem that the charging voltage is likely to increase, and the electrolyte solution is decomposed with the increase of the charging voltage, so that the battery characteristics are likely to be significantly deteriorated.

<Means for Solving Problems> The present inventor has studied to solve the above problems by using a pyrrole-based conductive polymer having no defect such as the conventional pyrrole-based polymer as an electrode material, and specified. The present invention has been completed based on the knowledge that the intended object can be achieved when a powdery organic semiconductor obtained by reacting a ferric compound with a pyrrole compound in the liquid phase is used. That is,
The secondary battery of the present invention is a secondary battery in which a powdery organic semiconductor obtained by reacting a pyrrole compound and an oxidizing agent in a liquid phase is used as at least one electrode of a positive electrode and a negative electrode, agent has the general formula _{Fe m X n ...... (1)} ( wherein, X is ^{_{ClO 4 -, BF 4 -,}} AsF 6 -, PF 6 -, SbF 6 -, CH 3 C 6
^{_{H 4 SO 3 -, CF 3}} SO 3 -, ZrF 6 -, TiF 6 - or SiF ₆ ^- represents, m and n is an integer of 1-3. ) The secondary battery is characterized by being a ferric compound represented by.

The organic semiconductor as described above uses a single or different two or more kinds of pyrrole compounds as described below as starting materials,
This can be obtained by reacting a single or two or more different types of ferric compounds described below.

Examples of the pyrrole compound used in the present invention include those represented by the general formula: (In the formula, R ¹ and R ² represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an allyloxy group, an alkylthio group, an amino group, a halogen atom, a cyano group or a nitro group, and R ³ represents a hydrogen atom, an alkyl group. Or represents an aryl group).

Among the pyrrole compounds represented by the above general formula (2), the pyrrole compounds having no substituent at the 2,5 position of the pyrrole ring skeleton structure are preferable.

Further, in detail, R ^{1 to} R ² are hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, methoxy group, ethoxy group. Group, n-propoxy group, isopropoxy group,
n-butoxy group, phenyl group, toluyl group, naphthyl group,
Phenoxy group, methylphenoxy group, naphthoxy group, methylthio group, ethylthio group, amino group, fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group, R ³ represents a hydrogen atom, a methyl group, an ethyl group , N-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-
Butyl group, tert-butyl group, phenyl group, toluyl group,
Represents a naphthyl group.

As such a pyrrole compound, specifically, pyrrole, N-methylpyrrole, N-ethylpyrrole, N-phenylpyrrole, 3-methylpyrrole, N-methyl-3-methylpyrrole, 3-chloropyrrole, 3,4-dichloropyrrole, 3-
Brompyrrole, N-methyl-3-bromopyrrole, 3-methoxypyrrole, 3-phenoxypyrrole, 3-phenylpyrrole, 3-methylthiopyrrole, 3-ethylthiopyrrole,
3-aminopyrrole, 3-nitropyrrole, N-phenyl-3-
Examples thereof include methylpyrrole and N-naphthyl-3-methylpyrrole.

The ferric iron compound represented by the general formula (1) is specifically Fe (ClO ₄ ) ₃ , Fe (BF ₄ ) ₃ , Fe (AsF ₆ ) ₃ , Fe (PF ₆ ) ₃ , Fe ( _{SbF 6) 3, Fe (CH} 3 C 6 H 4 SO 3) 3, Fe (CF 3 SO 3) 3, Fe 2 (ZrF 6) 3, Fe 2, (TiF 6 -) 3, Fe 2 (SiF 6 ) ₃ , which are usually used as a compound having water of crystallization or as an aqueous solution.

The amount used is 0.01 to 100 times mol, preferably 0.1 to 50 times mol, per mol of the pyrrole compound.

The reaction between the ferric compound represented by the general formula (1) and the pyrrole compound represented by the general formula (2) is
In the liquid phase in the presence of any solvent that dissolves both,
Such a solvent can be appropriately selected as long as it does not directly react with the ferric compound or the pyrrole compound. As a solvent that dissolves both, water, alcohols such as methanol and ethanol, polar organic solvents, specifically acetonitrile, tetrahydrofuran, dioxane,
Nitromethane, acetic acid, propylene carbonate, etc. are used.

When the polar organic solvent is used as the solvent, the polar organic solvent has a very low solubility of the oxidizing agent, for example, ferric perchlorate, as compared with an aqueous solution, and thus the mass production of organic semiconductors. It is disadvantageous due to restrictions on manufacturing in terms of manufacturing property and causes high battery cost, and since the concentration of the doping agent in the solvent decreases by the decrease in solubility, the electrical conductivity of the polypyrrole produced is small. However, there is a drawback that the battery characteristics tend to deteriorate and the degree of deterioration of the battery characteristics is large. This tendency also exists when the above alcohols are used. Therefore, it is preferable to use water that does not have such drawbacks as the solvent.

The reaction temperature is −50 ° C. to 150 ° C., preferably −2
It is 0 ° C to 100 ° C. The reaction time is related to the reaction temperature, but is usually 0.5 to 200 hours, preferably 1.0 to 100 hours.

The reaction product is a dark brown to black powdery substance, and in the reaction in the presence of the above solvent, the solvent may be removed by a usual method after the reaction is completed, or the product may be taken in water, alcohol, etc. it can.

This reaction product is electrically conductive as described in the examples. In the present invention, the reaction product is molded into a desired shape by a known method such as pressure molding and used as an electrode of a secondary battery. At this time, such a reaction product can be used alone, but in order to increase the mechanical strength of the electrode and increase the conductivity to improve the battery characteristics, a thermoplastic resin or an appropriate conductive member is used. Etc. are preferably added. Such a thermoplastic resin can be used without particular limitation as long as it is substantially insoluble in the electrolytic solution of the battery. Usually, those having a molecular weight of 10,000 or more are used. Specific examples include polyethylene, polypropylene,
Ethylene-propylene copolymer, ethylene-tetrafluoroethylene copolymer, polytetrafluoroethylene,
Polytrifluoroethylene, polydifluoroethylene,
Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polytrifluoroethylene chloride, polyvinylidene fluoride, tetrafluoroethylene-ethylene copolymer, chlorotrifluoro Ethylene-ethylene copolymer, polyamide,
Examples thereof include polyester, polycarbonate, and modified polyolefin.

Further, if the conductive member is a material that does not dissolve even after repeated charging and discharging, for example, a member such as stainless steel, metal such as gold, platinum, nickel, copper, molybdenum, titanium, carbon, carbon fiber, etc. There is no particular limitation,
Particularly, a lightweight and highly conductive material is preferable. Specific examples include a metal net made of such a metal, a metal plated fiber, a metal vapor-deposited fiber, a metal-containing synthetic fiber, and a net, a woven fabric and a non-woven fabric made of carbon fiber, carbon composite fiber and the like. .

The amount of such thermoplastic resin and conductive member added is 100 parts by weight of the reaction product (organic semiconductor) based on the thermoplastic resin.
It is preferable to use 0.02 to 1000 parts by weight and 2 to 100 parts by weight of the conductive member.

In the secondary battery of the present invention, an electrode formed by using such a reaction product as an electrode material is used for both positive and negative electrodes, and this electrode is used for only one electrode, and the other electrode is made of metal or metal. In some cases, an oxide or other inorganic compound, or a known conductive polymer other than the reaction product of the present invention, an organic compound, an organometallic compound, or the like is used as an electrode material. Using an electrode using this reaction product only for the positive electrode,
Taking the case of using a metal as the electrode material of the negative electrode, it is preferable to use one having an electronegativity of 1.6 or less as the metal constituting the negative electrode, and examples of such a metal include Li, Na, K, Mg, Al or their alloys, etc.
i and Li alloys are preferred.

On the other hand, as the electrolytic solution used in the secondary battery of the present invention,
For example, a solution in which an electrolyte is dissolved in an organic solvent is used. Examples of such electrolytes include salts with cations such as metal cations having an electronegativity of 1.6 or less, cations such as organic cations, and anions. Examples of onium ions include quaternary ammonium ions, carbonium ions, oxonium ions and the like. As the _{^{anion, BF 4 -, ClO 4 -}} , PF 6 -, AsF 6 -, CF 3 SO 3 -, I -, Br -,
Cl ^-, F ^-, and the like. Then, as a specific example of such an electrolyte, lithium tetrafluoroborate (LiBF
₄ ), Lithium perchlorate (LiClO ₄ ), Lithium hexafluorophosphate (LiPF ₆ ), Lithium tetrachloroaluminate (LiAlCl ₄ ), Tetraethylammonium tetrafluoroborate (Et ₄ NBF ₄ ), Tetra n perchlorate -Butyl ammonium (nBu ₄ NClO ₄ ), lithium trifluoromethanesulfonate (LiCF ₃ SO ₃ ), lithium iodide (LiI),
Examples thereof include lithium bromide (LiBr), but are not limited thereto. Then, using the organic semiconductor of the present invention in the positive and negative electrodes, as an example of a battery configured by using an electrolytic solution obtained by dissolving LiBF ₄ as an electrolyte, during charging, the organic semiconductor in the positive electrode in the electrolytic solution BF ₄ ^{− and} the organic semiconductor in the negative electrode are doped with Li ⁺ in the electrolytic solution, respectively. On the other hand, during discharge, BF ₄ ⁻ and Li ⁺ doped in the positive and negative electrodes are released into the electrolytic solution, respectively.

The organic solvent that dissolves the electrolyte is preferably an aprotic one having a high dielectric constant, such as nitrile, carbonate, ether, nitro compound, amide, sulfur-containing compound,
Chlorinated hydrocarbons, ketones, esters and the like can be used. Further, such solvents may be used as a mixture of two or more kinds. As typical examples of these, acetonitrile, propionitrile, butyronitrile, benzonitrile, propylene carbonate, ethylene carbonate,
Tetrahydrofuran, dioxolane, 1,4-dioxane,
Nitromethane, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, 1,2-dichloroethane, γ-butyrolactone, 1,2-dimethoxyethane, methyl phosphate,
Examples thereof include ethyl phosphate, but are not limited thereto.

And the concentration of the electrolytic solution of the present invention is usually 0.001 ~ 10 mol /
It is used in an amount of 0.1, preferably 0.1 to 3 mol / l.

Such an electrolytic solution can be used not only by pouring but also by preliminarily impregnating the electrode using the organic semiconductor of the present invention.

Further, in the above, the method of forming the electrode as it is without performing the doping treatment on the organic semiconductor has been described, but the organic semiconductor is previously doped with the dopant,
After that, it can be used alone or by molding it into an electrode using the conductive material and / or the thermoplastic resin as described above.

Further, in the present invention, in order to fix the electrode in the electrolyte, the electrode may be covered with glass, Teflon, polyethylene, a plate or the like having a drainboard shape or a hole.

Further, in the battery of the present invention, a porous membrane such as glass filter paper, Teflon, polyethylene, polypropylene, nylon, etc. may be used as the separator.

<Operation> The organic semiconductor as described above is not only excellent in oxidation resistance, but is also easy to manufacture and has high electric conductivity without the problems of the conventional polypyrrole. For this reason, when this organic semiconductor is used as an electrode material, it is very easy to control the electrode production environment, the storage stability of the electrode itself is improved, and the charge / discharge capacity of the battery electrode and the battery is limited. In addition, the degree of deterioration of battery characteristics due to non-uniform charging / discharging reaction of electrode parts is very small, and the cycle characteristics of the battery are significantly improved.

<Examples> The present invention will be specifically described below with reference to Examples.

Production Example 1 1 round bottom flask organic semiconductor _{Fe (ClO 4) 3 · 8H} 2 O and 74.9 g (0.1
(5 mol), add 600 ml of demineralized water, and dissolve with stirring under a nitrogen atmosphere. To this aqueous solution, 10.1 g of pyrrole was added dropwise at room temperature (25 ° C) under a nitrogen stream. The reaction liquid turned black upon dropping, and after stirring for 2 hours and then standing overnight at room temperature, a black powdery precipitate was observed at the bottom of the reaction liquid. After the filtration, the residue was washed 3 times with 200 ml of methanol and then twice with 200 ml of water and 200 ml of toluene.
The washing was repeated twice with 2 times and twice with 200 ml of methanol.
After washing and drying under reduced pressure at 60 ° C., 6.0 g of a black powdery substance was obtained. The elemental analysis of the obtained black material was C50.65%, H
2.83%, N14.45%, a Cl9.29%, assuming carbon 4.0 _{and, C 4.0, H 2.7, N} 1.0, to give the equivalent of Cl _0.25. Separately, as a result of analyzing the iron content, carbon 4.
Iron was 0.001 against 0. This is Fe for pyrrole
It is shown that (ClO ₄ ) ₃ has reacted, and in particular, its anion portion has been added.

As a result of measuring the electric conductivity of this reaction product by the two-terminal method, 7.6 × 10 ^-2 Scm ^-1 was obtained, which was found to be an organic semiconductor having a conductivity in the semiconductor region.

Production Example 2 of Organic Semiconductor As a result of conducting an experiment in the same manner as in Example 1 except that 12.2 g of N-methylpyrrole was used instead of pyrrole, 7.3 g was obtained.
To obtain a black powder substance. The elemental analysis of the obtained black material
C59.58%, H4.77%, N13,90% , a Cl7.75%, assuming 5.0 _{carbon, C 5.0 H 4.8, N 1.0} , to give the equivalent of Cl _0.22.

This indicates that Fe (ClO ₄ ) ₃ was reacted with N-methylpyrrole, and in particular, its anion portion was added. The electrical conductivity of this black material was 3.5 × 10 ^-3 Scm ^-1 .

Production Examples 3 to 14 of Organic Semiconductor Various kinds of pyrrole compounds were used, and the reaction of these with various kinds of ferric compounds was carried out in the same manner as in Example 1. The examination results of the obtained dark brown to black powder are shown in Table 1.

Battery Example Using the organic semiconductor obtained in Production Example 1 as a positive electrode material,
This was mixed with acetylene black (conducting agent) and polytetrafluoroethylene (binder) at a weight ratio of 85: 10: 5, and then pressure-molded into a disk shape to obtain a positive electrode. In addition, lithium was punched into a predetermined size to form a negative electrode.

Next, as shown in FIG. 1, the negative electrode portion is formed by pressing the negative electrode 2 onto the bottom surface of the negative electrode can 7 via the negative electrode current collector 8 and the positive electrode 1 via the positive electrode current collector 6 as shown in FIG. A positive electrode portion that is in close contact with the bottom surface of the positive electrode can 5 is combined through a separator 3 made of polypropylene nonwoven fabric, and an electrolytic solution obtained by dissolving lithium perchlorate (electrolyte) in propylene carbonate (solvent) is prepared. A battery according to the present invention (product A of the present invention) was produced using the above. In FIG. 1, reference numeral 4 is an insulating gasket.

Further, the organic semiconductor obtained in the above Production Example 2 was used as a positive electrode material, which was mixed with acetylene black and polytetrafluoroethylene at a weight ratio of 85: 10: 5 and pressure-molded into a disk shape. Other than the positive electrode, the product A of the present invention
A battery according to the present invention (product B of the present invention) was produced in the same manner as in.

On the other hand, using a polyacetylene powder as the positive electrode material, acetylene black, and polytetrafluoroethylene were mixed at a weight ratio of 85: 10: 5 and pressed into a disk shape to form a positive electrode, and the other embodiments of the present invention A battery for comparison (comparative product C) was prepared in the same manner as product A.

Further, a battery for comparison (Comparative Product D) was produced by the following procedure.

Round bottom flask 500ml FeCl ₃ · 6H ₂ O and 40.6 g (0.15 mol)
Collect, add 300 ml of demineralized water and dissolve under stirring in a nitrogen atmosphere. 10.1 g of pyrrole was added dropwise to this aqueous solution under a nitrogen stream at room temperature (25 ° C). Then, after continuing stirring for 6 hours, the mixture was allowed to stand at room temperature for one day, and black powdery precipitate was observed at the bottom of the reaction solution. After the filtration, the residue was washed with 200 ml of methanol three times, and then with 200 ml of water twice.
The washing was repeated twice with 200 ml of toluene and twice with 200 ml of methanol. After washing, it was dried under reduced pressure at 60 ° C. to obtain a black powdery substance.

In this way, an organic semiconductor (polypyrrole) prepared by chemically polymerizing pyrrole with iron chloride as an oxidant is used as a positive electrode material, and this, acetylene black, and polytetrafluoroethylene are used in a weight ratio of 85: 1.
A comparative battery (comparative product D) was prepared in the same manner as the product A of the present invention, except that the mixture was mixed at a ratio of 0: 5 and pressure-molded into a disk shape to serve as the positive electrode.

The charge and discharge efficiency (%) of the above four batteries was evaluated by repeating a series of charge and discharge cycles of charging the battery at 1 mA for 5 hours and then discharging it at 1 mA until the battery voltage reached 2.5 V. The cycle change was investigated. The results are shown in FIG.

From the figure, the comparative product C has a low charge / discharge efficiency up to 20 cycles, but the products A and B of the present invention maintain a high charge / discharge efficiency from the beginning of the cycle. Thus, the reason why the products A and B of the present invention show high charge / discharge efficiency from the beginning of the cycle is considered to be that the organic semiconductors obtained in the above Production Examples 1 and 2 were previously doped with perchlorate ions. To be The comparative product D also maintains high charge / discharge efficiency from the beginning of the cycle, but is inferior to the products A and B of the invention because the doped ions are not perchlorate ions but chlorine ions. is there.

Further, while the comparative product C shows a sharp decrease in charge / discharge efficiency after about 50 cycles, the products A and B of the present invention not only show higher charge / discharge efficiency than the comparative product C over the entire cycle. It can be seen that the high charge / discharge efficiency of 90% or higher is maintained even after 80 cycles. The charge and discharge efficiencies of the products A and B of the present invention at the 80th cycle were 99% and 95%, respectively.
On the other hand, in the case of the comparative product C and the comparative product D, respectively, 25
% And 55%, which were small. The reason why the cycle characteristic of the comparative product C is such poor is that the positive electrode material is caused by the water and oxygen adsorbed or adhered to the polyacetylene powder without being completely removed, and the dissolved oxygen and trace water in the electrolytic solution. It seems that this is due to the deterioration of the material of a certain polyacetylene powder. In the case of the products A and B of the present invention, since the organic semiconductor that is the positive electrode material has excellent oxidation resistance, there is no material deterioration due to dissolved oxygen or trace moisture in the electrolytic solution, and good cycle characteristics can be obtained. is there. Further, the cycle characteristics of the comparative product D are poor because the conventional polypyrrole obtained by chemically oxidizing and polymerizing the positive electrode material has a low electric conductivity, and chlorine ions are present as a dopant in the positive electrode material. This is probably because chlorine gas is generated during the cycle, and the reaction between the chlorine gas and the negative electrode occurs.
In the case of the products A and B of the present invention, the electrical conductivity of the polypyrrole used as the positive electrode material is excellent, and there is almost no possibility that chlorine ions will be present during the cycle, so that a side reaction occurs in the negative electrode. However, good cycle characteristics can be obtained.

Further, FIG. 3 shows changes with time in the battery voltage during charging and discharging in the 80th cycle. In the figure, the solid line shows the voltage change during charging and the dotted line shows the voltage change during discharging. Third
From the figure, it can be seen that the products A and B of the present invention do not have a sharp rise in voltage during charging, and the discharge voltage is inevitably flatter than the comparative products C and D.

Furthermore, FIG. 4 shows the self-discharge characteristics of the battery during storage. From the figure, it can be seen that the products A and B of the present invention have smaller self-discharge than the comparative products C and D and have good storage stability. Compared with the comparative product C, the products A and B of the present invention have better storage stability than the product of the present invention.
It is considered that this is because the organic semiconductors used as the positive electrode materials in A and B have excellent oxidation resistance, so that there is no material deterioration due to dissolved oxygen or a trace amount of water in the electrolytic solution. Further, in the case of the comparative product D, since the positive electrode material previously doped with chlorine is used, and this dopant and the dopant (perchlorate ion) doped by the battery reaction are different from each other, chlorine ion is not present in the battery system. Will be present,
Therefore, it is considered that the self-discharge is large. In the case of the products A and B of the present invention, this is not the case because impurities such as chlorine ions are unlikely to exist in the battery system, and the shelf life is better than that of the comparative product C.

In the above description, the organic semiconductor is used only as the positive electrode material, but it is clear that the same effect can be obtained when the organic semiconductor according to the present invention is used as the negative electrode material or the positive and negative electrode material.

<Effects of the Invention> According to the secondary battery of the present invention configured as described above,
The management of the electrode production environment is greatly facilitated and the storage stability of the electrode itself is improved, and the charge and discharge capacities of the electrode and the battery are not limited. The effect of improving characteristics such as charge / discharge efficiency and cycle life with a slight deterioration of the characteristics of the battery due to uniformity.

[Brief description of drawings]

FIG. 1 is a sectional view showing a battery structure according to an embodiment of the present invention,
FIG. 2 is a graph showing the cycle characteristics of the product of the present invention and the comparative product, FIG. 3 is a graph showing the change over time of the battery voltage during charging and discharging, and FIG. 4 is a self-discharge characteristic of the product of the present invention and the comparative product. It is a graph showing. 1 ... Positive electrode, 2 ... Negative electrode, 3 ... Separator, 5 ... Positive electrode can, 7 ... Negative electrode can.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Nobuhiro Furukawa 2-18 Keihan Hondori, Moriguchi City, Osaka Prefecture Sanyo Electric Co., Ltd. (72) Koji Nishio 2-18 Keiyo Hondori, Moriguchi City, Osaka Sanyo Electric Incorporated (72) Inventor Masahisa Fujimoto 2-18 Keihan Hondori, Moriguchi City, Osaka Sanyo Electric Co., Ltd. (56) Reference JP-A-62-119860 (JP, A)

Claims (3)

[Claims] 1. A secondary battery comprising a powdery organic semiconductor obtained by reacting a pyrrole compound and an oxidant in a liquid phase as at least one of a positive electrode and a negative electrode, wherein the oxidant is formula _{Fe m X n ...... (1)} ( wherein, X is ^{_{ClO 4 -, BF 4 -,}} AsF 6 -, PF 6 -, SbF 6 -, CH 3 C 6
^{_{H 4 SO 3 -, CF 3}} SO 3 -, ZrF 6 -, TiF 6 - or SiF ₆ ^- represents, m and n is an integer of 1-3. ) A secondary battery which is a ferric compound represented by: 2. A pyrrole compound having a general formula (In the formula, R ¹ and R ² represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an allyloxy group, an alkylthio group, an amino group, a halogen atom, a cyano group or a nitro group, and R ³ represents a hydrogen atom, an alkyl group. Or a compound which represents an aryl group.) The secondary battery according to claim 1, wherein the secondary battery is a compound represented by the formula: 3. The secondary battery according to claim 1 or 2, wherein the reaction between the pyrrole compound and the oxidizing agent is carried out in an aqueous solution.