KR100302191B1 - Metal-Polymer Composite Electrode Material and Its Use - Google Patents

Abstract

The present invention relates to a composite electrode material composed of a transition metal species and polyaniline, a cathode prepared by applying the same to a conductive current collector, and a secondary battery including the cathode, and a compound selected from aniline, aniline derivatives and dimers. By adding an oxidizing transition metal salt to the oxidized polymer in a solvent to obtain a composite electrode material, and applying it directly to a conductive current collector to complete the electrode, the mixing of the electrode material is effective, it is possible to produce an electrode of uniform composition Good dispersibility to polyaniline serving as a matrix polymer of transition metal species, which is an electrode active material; The electrode thus prepared has a high fixing effect due to chemical affinity with the nitrogen atom contained in the polyaniline as the active metal transition metal species, so that the capacity decreases according to the number of charge and discharge cycles, and the high capacity of the transition metal as the electrode material can be effectively utilized. Not only; As a result, the secondary battery using the same can be repeatedly recharged, has a high energy density, can be lightened, and does not contain a liquid electrolyte, so there is no problem due to leakage when used. Thin battery production is possible.

Description

Metal-polymer composite electrode materials and uses thereof

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal-polymer composite electrode material and its use. More particularly, the present invention relates to a composite cathode material comprising a polymer compound containing a transition metal and polyaniline, and an electrode prepared from the cathode material as a cathode. And a lithium secondary battery having a high energy density and excellent reversible charge / discharge characteristics, which is composed of a material selected from lithium-based metals such as lithium metal, lithium alloy, or carbon-based materials capable of lithium intercalation, such as carbon and graphite. will be.

Batteries have become an important component of electronic devices used in various ways in modern life. The development of electronic communication and computer equipment has led to the rapid dissemination of portable devices, and as an essential factor for the convenience of portable devices, high capacity, long life, miniaturization and light weight of small secondary batteries are required.

Many studies have been conducted to manufacture secondary batteries using a transition metal, which is a high capacity cathode material, as an active material.

For example, US Pat. Nos. 4,546,055, 4,795,685, 4,992,345, 4,288,506, 4,797,333, and 4,945,012 use alkali metals as cathodes, and molten salts of NaAlX _n type. It is disclosed that a molten salt electrolyte and a beta-alumina separator are used. As the anode, a halogen compound of transition metals such as iron (Fe), copper (Cu), nickel (Ni), cobalt (Co), and chromium (Cr), or a compound form with an inorganic material was used. Such a battery operates at a high temperature of 200 ° C. or higher, which is higher than the melting point of NaAlX _n type of molten salt, and is highly corrosive to chlorides generated during charging and discharging. On the other hand, it is pointed out in US Pat. No. 5,283,135 that the capacity of the electrode is reduced and the life is shortened due to the low conductivity of the metal chloride layered on the surface of the electrode, and the capacity due to the agglomeration of the metal particles forming the electrode is indicated. A method of adding sulfur to nickel electrodes to prevent degradation is also disclosed in US Pat. No. 5,573,873.

In addition, US Pat. No. 4,844,993 and Electrochemical Society (J. Electrochem. Soc. 134, 2383, 1987) and the like use copper (II) chloride as a cathode material for a lithium secondary battery, and a battery using a liquid electrolyte. Is disclosed. Here, a mixture of lithium aluminum chloride (LiAlCl ₄ ) and sulfur dioxide was used as the liquid electrolyte. Such a liquid electrolyte has an advantage of providing high electrical conductivity, but such a solvent system may be solidified according to a change in the component ratio, thereby deteriorating conductivity or volatilization to generate pressure. In order to compensate for this disadvantage, US Patent No. 5,024,906 proposes a method of adding an organic solvent such as ethyl chloroformate or sulfolane to the mixed electrolyte. Since the copper salt used as the ash is dissolved and dispersed in the electrolyte, the capacity may gradually decrease and thus the life of the secondary battery may decrease. In addition, there is a need for a rigid battery structure for cell internal pressure control, which may inevitably be caused by leakage prevention or volatilization of a solvent.

Meanwhile, the chemical preparation of polyaniline and various polyaniline derivatives, which are electrically conductive materials, is disclosed in US Pat. No. 4,940,517, Polymer (1989, Vol. 30, pp2305-2311) and the like, respectively.

As the oxidizing agent used in the chemical oxidation polymerization method of aniline and aniline derivatives, peroxydisulfate or peroxides and strong oxidizing metal ion salts are used.

Polyaniline polymers in emeraldine salt form have been reported to be insoluble in almost all solvents.

In addition, polyaniline doped with an acid such as CSA or DBSA or chemically polymerized from aniline derivatives during chemical oxidation polymerization is known to show improved solubility in some polar organic solvents, but solvents showing low solubility and solubility are limited. (See Synth. Metals, 48 (1992) pp91-97).

In addition, it was observed that the emeraldine base form obtained by the base treatment of the chemically oxidized polyaniline polymer showed solubility in some organic solvents, but the solubility was low as 5 to 10 wt% and easily gelled over time. Is reported. Therefore, such insolubility in using polyaniline as an electrode material has a limitation in electrode workability.

Lithium secondary batteries using polyaniline, an electrically conductive polymer material, as a cathode active material are described in US Pat. Nos. 5,202,202, 4,940,640, and the like, respectively. Specifically, U. S. Patent No. 5,202, 202 discloses a battery in which an electrode prepared in pellet form by mixing chemically oxidized polyaniline with a carbon block is used as a positive electrode, and is combined with a non-aqueous electrolyte solution and a lithium negative electrode. In addition, US Pat. No. 4,940,640 discloses a battery using a positive electrode obtained by electrochemically polymerizing polyaniline in the form of a film. However, this type of electrode is difficult to manufacture in large areas, and since polyaniline is used as the anode, the cycle life is long, the average discharge capacity (theoretical capacity = 150mAh / g) is low, and the charging and discharging speed is still small. In the type and button type secondary battery, the situation is looking for the applicability.

A method of adding polyaniline to improve the efficiency of the electrode material is disclosed in US Pat. No. 5,324,599. In this case, a doping process in which an ionic salt is formed by mixing an organic disulfide electrode material and a polyaniline in an organic solvent to bond protons of the organic disulfide anode material to a nitrogen atom of the polyaniline is used. The polyaniline mixed at the molecular level in the electrode material by this method has a catalytic effect of improving the electron transfer rate of the organic disulfide material.

As described above, many secondary batteries using a transition metal or polyaniline as a cathode material have been proposed. However, many improvements are required for proper mixing and dispersing of these electrode materials, and accordingly to manufacture an effective electrode.

The improvement of these problems is indispensable for realizing high capacity and charging / discharging stability in batteries using transition metal or polyaniline as a cathode material.

In the present invention, while developing to solve the above disadvantages, a composite electrode material having a good dispersibility, high energy density, and reversible redox was developed.

An object of the present invention is to provide an electrode material whose main component is polyaniline and at least one transition metal species selected from transition metals or transition metal salts.

It is another object of the present invention to provide an electrode material which is prepared in a single process from a reaction mixture of an oxidizing transition metal species and a monomer or dimer of an aniline or an aniline derivative, and has a good dispersibility and can be easily produced. have.

Another object of the present invention is to provide a positive electrode for a secondary battery manufactured by applying the electrode material prepared above to a conductive current collector.

It is still another object of the present invention to provide a secondary battery comprising the positive electrode and a negative electrode selected from lithium metal, lithium alloy and lithium intercalation-based carbon material, and a polymer electrolyte prepared from lithium salt and a polymer and an organic solvent. To provide.

1 is a graph showing the results of measuring charge and discharge capacity for each of the batteries A and B prepared according to Examples 1 and 2 of the present invention.

Figure 2 is a graph showing the result of measuring the discharge capacity according to the number of charge and discharge when the battery A prepared according to Example 1 of the present invention at 100% utilization.

The metal-polymer composite electrode material of the present invention for achieving the above object is prepared by oxidative polymerization by adding an oxidative transition metal salt to one compound selected from aniline, aniline derivatives and dimers in a solvent. It is done.

In addition, the present invention is characterized in that the metal-polymer composite electrode material is applied to a current collector and used as a positive electrode for a secondary battery.

The present invention will be described in more detail as follows.

The present invention relates to an electrode material prepared from a mixture of transition metal species and polyaniline, which is prepared in a single process by reaction of an oxidizing transition metal salt with an aniline monomer, dimer, or aniline derivative.

According to the present invention, the monomers of the transition metal salt and the aniline or aniline derivative are mixed in the organic solvent, so that the oxidative polymerization of the aniline or the aniline derivative is induced directly in the positive electrode composition. This electrode composition is used directly. The positive electrode for secondary batteries is manufactured by apply | coating said electrode composition to an electroconductive collector.

Here, MX _n is a transition metal salt with the oxidizing power (here, M is copper or iron, X is a halogen ^{_{anion, ClO 4 -, PF 6 -}} , BF 4 -, NO 3 -, CH 3 COO - , n is In the form of an integer of 1 to 3), and preferred transition metals constituting the same are iron (Fe), copper (Cu), vanadium (V), molybdenum (Mo), chromium (Cr), Tungsten (W). The most preferable transition metal is iron (Fe) and copper (Cu) which are excellent electrode materials among metals with strong oxidation power.

In the present invention, the aniline derivative used in the cathode material mixture is ortho toluidine (o-toluidine), metatoluidine (m-toluidine), 2-ethylaniline (2-ethylaniline), 3-ethylaniline (3- ethylaniline, 2-aminothiophenol, 3-aminothiophenol, 2-aminophenyl disulfide, N-methylaniline, N-ethyl N-ethylaniline, ortho-anisidine, m-anisidine, 2-ethoxyaniline, 3-ethoxyaniline, 3-ethoxyaniline, 2-anilinoethanol and diphenylamine. In addition, N-phenyl-1,4-phenylenediamine may be used as the aniline dimer.

On the other hand, the positive electrode of this invention is manufactured by apply | coating said composite positive electrode active material to a conductive electrical power collector. At this time, as a preferable electrical power collector, the electrical power collector which consists of a copper metal or a copper alloy is used, and the said positive electrode material is apply | coated here, and an electrode is manufactured.

In addition, the present invention is a lithium lithium secondary battery comprising a cathode selected from a positive electrode for a secondary battery, a non-aqueous polymer solid electrolyte containing a lithium salt, and a material capable of lithium intercalation such as lithium metal, lithium alloy, carbon, or graphite. It provides a secondary battery. The solid polymer electrolyte is an ion conductive polymer electrolyte and contains a lithium salt in the form of LiY (Y is a counterbase anion of an acid) so that Li ⁺ cations can be precipitated as metal on the cathode or intercalated on the anode material during charging. do. In addition, charge and discharge of the anode is achieved by supplying or absorbing ions depending on the oxidation state of the anode during charge and discharge.

The transition metal species used as the cathode active material of the present invention may be present in the electrode composition in the form of transition metal or transition metal cation. When the battery is charged, the transition metal is oxidized to metal ions, and when discharged, the transition metal is reduced to produce a transition metal or a metal ion of a low oxidation state. The potentials at which Cu (I) is reduced to copper metal and Cu (II) to copper metal are 3.57 V and 3.39 V for the lithium electrode, respectively, so that copper metal species is used as the positive electrode active material and lithium metal species is used as the negative electrode material. In this case, a 3.0 V battery can be constructed. In addition, when the oxidation reaction of copper metal proceeds to Cu (II), the theoretical capacity is 843 mAh / g, and in the case of vanadium, iron, and molybdenum, the theoretical capacity is 2,630 mAh / g, 1,440 mAh / g, and 1,670 mAh, respectively. Expect high capacity at / g. (D. Linden Ed., Handbook of Batteries and Fuel Cells, McGraw-Hill, C-3, 1984). Therefore, the positive electrode material proposed in the present invention can realize the weight reduction of a lithium secondary battery by adopting a transition metal having a high energy density as an active material.

In the present invention, polyaniline, which is one of the main components constituting the electrode, not only contains transition metal species, which is an active material, but also has a function of a matrix polymer for forming a thin film electrode. In addition, the use of polyaniline, an electronic conductive polymer, can improve the conductivity of the electrode and minimize the additional use of the conductive material. In addition, since the polyaniline contains nitrogen atoms capable of bonding with the transition metal species in the repeating structure, when the transition metal species are dispersed in the polyaniline, the affinity between the transition metal species active material and the polyaniline matrix polymer may be enhanced. .

The affinity between polyaniline and transition metal species offers the following advantages; First, the capacity of the cell is maintained by immobilizing the transition metal species on the electrode. The transition metal cations produced by the oxidation of the transition metal species during charging may be dissolved in an organic solvent in the electrode or the electrolyte and thus dispersed or migrate in the electrolyte. As a result, the transition metal cation may be released from the conductive material, and thus the capacity of the battery may be reduced when charging and discharging are repeated. However, in the present invention, the use of polyaniline allows the transition metal ions to be fixed to the polyaniline chain, which forms the matrix of the electrode, thereby reducing the dispersion and dissociation of the active material, thereby enabling reversible charging and discharging.

The second advantage is that the affinity between the transition metal species and polyaniline is connected to the conductive network formed by the polyaniline, thereby increasing the electron transfer efficiency of the electrode and enabling fast charge and discharge.

In addition, by using a polyaniline matrix having a basic functional group having affinity with transition metal species, the electrode active material may be contained in the electrode material to maximize the capacity of the electrode, and the metal active material may be uniformly dispersed in the electrode material. To make sure.

Hereinafter, the manufacturing method of the composite electrode material will be described in detail.

<Metal-Polymer Composite Electrode Material and Anode>

Polyaniline conductive polymers generally have a disadvantage in that processing is difficult due to low solubility in organic solvents. When the electrode mixture is prepared in a state in which it is not dissolved in an organic solvent, nonuniformity of the electrode material due to insufficient dispersion is inevitable. In order to overcome this disadvantage, in the method of manufacturing the electrode according to the present invention, instead of polyaniline, which is difficult to dissolve, monomers or dimers of aniline or aniline derivatives having high solubility in organic solvents are first dissolved in organic solvents and then oxidized. The transition metal salt is added to simply prepare an integrated positive electrode mixture of polyaniline and transition metal species by chemical oxidative polymerization. Transition metal ion salts such as Fe (III), Cu (I), Cu (II), Ce (IV), Cr (VI), Mn (Ⅶ), and V (V) are used as oxidants for the oxidative polymerization of aniline. A method for preparing polyaniline is presented in US Pat. No. 4,940,517, Polymer, 1993, Vol. 34, No. 1, pp158-162, and Polymer, 1989, Vol. 30, pp2305-2311, and the like.

In the composite electrode material of the present invention, aniline derivatives and dimers which can be oxidized by transition metal ion salts are as described above.

These aniline derivatives or dimers are oxidatively polymerized together with a transition metal salt in a solvent, wherein the solvent is aniline, aniline derivatives, or N-phenyl-1,4-phenylene diamine (N-phenyl-1, Non-aqueous organic solvents can be selected from various solvents capable of dissolving 4-phenlyenediamine). It is preferably an aprotic solvent with a high polarity. Specific examples thereof include acetonitrile, sulfolane, dimethyl sulfoxide, and the like. In addition, there are propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and the like containing carbonate groups. In addition, dichloromethane (dichlorometane), dichloroethane (dicholoethane), 1,4-dioxane (1,4-dioxane) and the like can also be used. If necessary, these solvents may be selected and used alone or in combination of two or more. It is preferable that the usage-amount of a solvent is 20-2000 weight% by weight with respect to an aniline derivative.

On the other hand, since the oxidation polymerization of polyaniline requires two equivalents of oxidizing agent per aniline monomer, two equivalents of metal ions are required when aniline is used as a starting material of the electrode mixture. In addition, 2 equivalents of Cu (I) ions are required also when starting from dimer, N-phenyl-1,4-phenylene diamine. In order to increase the polymer conversion rate of the added monomer, the amount of added Cu (I) ions may be used in excess of 20% by weight.

In addition, a transition metal or an ionic salt of the transition metal may be further added to the electrode mixture prepared by oxidative polymerization in order to improve electrode capacity.

In addition, in order to increase the conductivity of the electrode, a conductive material and a binder material may be added to improve the processability of the electrode. As the conductive material, a conductive carbon material such as acetylene block and graphite may be used. The conductive material or other additives may be added early in the preparation of the electrode composition, or may be added after chemical oxidation polymerization of monomers or dimers of aniline, aniline derivatives. In the case of preparing the electrode composition by adding such a conductive material additive, strong mechanical agitation or ultrasonic agitation may be used to improve the dispersibility of the positive electrode material mixture.

Through such stirring, the well-dispersed cathode material mixture can be applied onto various metal current collectors. For coating, a simple painting or a mechanical coating method such as spin coating or bar coating may be used. It is preferable to maintain an inert gas atmosphere when the positive electrode material is applied on the current collector.

As the current collector of the positive electrode, a conductive support of metal or carbon material may be used. The shape of the current collector may be used in the form of a thin film, a gauze, a mesh, or the like depending on the battery structure. As a preferable conductive current collector, an electrode is manufactured using a current collector made of copper metal or a copper alloy.

<Polymer Electrolyte>

When preparing a secondary battery including the positive electrode as described above, a polymer electrolyte is used. As the electrolyte of the lithium secondary battery according to the present invention, an ion conductive polymer electrolyte is used.

According to the present invention, the polymer electrolyte receives Li ⁺ from the negative electrode and the negative electrode from the positive electrode when the battery is discharged to form a LiY-type lithium salt, and when charged, Li ⁺ moves to the negative electrode and the Y ⁻ anion is positive. It must contain LiY type lithium salt to be able to move.

These ion conductive polymer electrolytes are composed of lithium salts, polymer compounds, and organic solvents used as plasticizers. Lithium salts used include LiBF ₄ , LiPF ₆ , LiClO ₄ , LiAsF ₆ , LiAsCl ₆ . LiSbCl ₆ , LiSbF ₆ , LiN (SO ₂ CH ₃ ) _2, and the like. As the host polymer constituting the polymer electrolyte, polyethylene (poly (ethylene oxide)) and polypropylene oxide (poly (ethylene oxide)) having a functional group containing oxygen, nitrogen and sulfur to have a chemical affinity for lithium ions )), Polyacrylate, polyacrylonitrile, acrylonitrile-methyl acrylate copolymer (poly (acrylonitrile-co-methyl acrylate)) and the like; Polyvinylidene fluoride (poly (vinylidene fluoride)) having a fluorine group, polyvinylidene fluoride-hexafluoropropylene (poly (vinylidene fluoride-co-hexafluoropropylene)) and the like. The amount of lithium salt contained in the polymer electrolyte is controlled so that the ratio (Li ⁺ / monomer) of lithium ions per monomer of the polymer is 5 to 50 mol%.

The organic solvent added as a plasticizer contains a carbonate group in a highly polar solvent, and examples thereof include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate. And the like, and may be used alone or in combination of two or more. The amount of plasticizer added is adjusted to be 20-90 wt% of the total polymer electrolyte material.

<Cathode>

As the negative electrode according to the present invention, a metal material of lithium metal or lithium alloy may be used. In addition, carbon-based materials such as carbon and graphite capable of intercalating lithium ions may be used. When the secondary battery is charged, lithium ions supplied from the electrolyte are reduced to form lithium metal when lithium metal is used, and intercalation of lithium ions occurs when a carbon-based negative electrode is used. During discharge, lithium ions are generated from the cathode by an oxidation reaction.

Lithium secondary battery according to the present invention has no problem due to leakage due to the solid state of the battery content, and can be used for portable electronic devices used for mobile use because it is light and easy to select an external form according to the use because a simple sealed packaging is possible. It is advantageous to

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.

Example 1

(Manufacture of positive electrode)

40 g of propylene carbonate solvent 4.0 g of N-phenyl-1,4-phenylenediamine (hereinafter referred to as PPDA), 5.0 g of CuCl (copper salt) and 2.0 g of acetylene block It was put in a sufficiently stirred to prepare a composite cathode slurry. At this time, the mixture is first obtained by completely dissolving the component (PPDA) in the propylene carbonate solvent, then adding the insoluble component (CuCl, acetylene block) later, and then stirring (2 days or more) to obtain sufficient mixing and viscosity.

The cathode material mixture thus obtained was thinly coated on a copper metal thin film current collector in an argon gas atmosphere, and dried in a vacuum at 60 to 80 ° C., and pressed to prepare a composite positive electrode for experiments. The content of CuCl, which is a positive electrode active material, was 45.4% with respect to the positive electrode composition.

(Preparation of negative electrode)

A lithium metal plate (battery grade) having a thickness of 150 to 700 μm was used as a negative electrode and stored under an argon gas atmosphere without further purification.

(Production of Polymer Electrolyte)

3.0 g of acrylonitrile-methyl acrylate copolymer (94: 6) and 2.3 g of LiBF ₄ were heated (120-140 ° C.) under nitrogen or argon gas atmosphere, After dissolving in a mixed solvent of ethylene carbonate (10.5: 7.9 weight ratio), cast on a glass plate, heated in vacuum (60 ~ 80 ℃) and dried to prepare a film. The ionic electrical conductivity of the prepared polymer electrolyte membrane was 10 ^-3 to 10 ^-4 S / cm as a result of impedance measurement.

(Assembly of measurement battery)

Using the positive electrode material, the polymer electrolyte membrane, the negative electrode made of a lithium thin film, the current collector for a positive electrode of a copper metal thin film, and the current collector for a nickel metal mesh negative electrode, a stacked measurement battery (cell A) without a liquid electrolyte was constructed. .

Example 2

2.5 g of ortho toluidine, 5.0 g of CuCl (copper salt, oxidizing agent) and 1.0 g of acetylene block were added to a propylene carbonate solvent and sufficiently stirred to prepare a composite cathode slurry. In this case, the mixture is obtained by first adding a completely soluble component (ortho toluidine) in a propylene carbonate solvent, then adding an insoluble component (CuCl, acetylene block) and then stirring (2 days or more) to obtain sufficient mixing and viscosity. .

The cathode material mixture thus obtained was thinly coated on a copper metal thin film current collector in an argon gas atmosphere, and dried in a vacuum at 60 to 80 ° C., and pressed to prepare a composite positive electrode for experiments. The content of CuCl, which is a positive electrode active material, was 58.8% with respect to the positive electrode composition.

Using the positive electrode thus obtained, a stacked measurement battery (cell B) was constructed through the same assembly process as in Example 1.

Experimental Example 1

The stacked batteries A and B assembled according to Examples 1 and 2 were stored in an argon gas atmosphere and charged and discharged by setting a potential window of 1.8 to 4.5 V (for Li / Li ⁺ ) at a constant current / voltage condition at room temperature. The measurement was made.

The charge and discharge curves of the battery A prepared in Example 1 and the battery B prepared in Example 2 are shown in FIG. 1.

Specifically, FIG. 1 shows respective discharge curves shown after the transition metal cathode active materials included in the composite cathode material compositions of the batteries A and B manufactured through the examples were charged at a utilization rate of 75% with respect to the theoretical capacity.

It can be seen from FIGS. 1A and BB that the batteries A and B all have similar discharge curve shapes, discharge capacities, and discharge voltages.

In FIG. 2, the charge / discharge curves generated when the battery A prepared according to Example 1 is charged at 100% of the utilization rate with respect to the theoretical capacity of the positive electrode active material (CuCl) are determined by the number of charge and discharge cycles (1, 20, 40 times). Represented by.

Even when the utilization rate for the copper metal active material is 100%, the charge and discharge efficiency reaches 90% or more, and shows a stable charge and discharge curve without significant change even after repeated charge and discharge.

The average discharge potential was 2.7 V, and the discharge capacity and the energy density were 250 mAh / g-cathode and 675 mWh / g-cathode, respectively.

When the aniline derivative is included in the cathode material together with the copper salt (CuCl) from the results of FIGS. 1 and 2, the electrode manufactured by using the same has a high reversibility and reproducibility during repeated charging and discharging, and has a high density of the active material. It can be seen that the discharge capacity is guaranteed.

In addition, by adopting the copper metal as the current collector for the positive electrode to fix the voltage below the oxidation potential of the copper metal during the charging of the battery to prevent excessive voltage rise, each element of the battery can maintain the stability.

As described in detail above, when aniline, aniline derivatives or dimers are oxidatively polymerized with transition metal salts in a solvent and used directly as a positive electrode without using polyaniline directly as a cathode material composition according to the present invention, the transition metal species is well suited to polyaniline. It is possible to develop a secondary battery which is dispersed and composed of a negative electrode of lithium metal or lithium alloy and a polymer electrolyte using this positive electrode; The secondary battery thus made is reversible during charging and discharging, and has a high energy density, thereby making it possible to reduce the weight of the battery; Since it does not contain a liquid electrolyte there is no problem due to leakage during use; As solid cells, small and thin batteries can be produced depending on the application.

Claims (7)

Aniline, MX _n form the one kind of compound selected from aniline derivatives and dimerization body (here, M is copper or iron, X is a halogen ^{_{anion, ClO 4 -, PF 6 -}} , BF 4 -, NO 3 -, CH ₃ COO ^-, n is a metal produced by transformation with the oxidizing power of an integer from 1 to 3) was added to the metal salt oxidation polymerization in a solvent-polymer composite electrode material. The metal-polymer composite electrode material according to claim 1, wherein the content of the transition metal salt is at least twice the molar ratio with respect to the amount of the aniline or aniline derivative added. The aniline derivative according to claim 1, wherein the aniline derivative is ortho toluidine, meta toluidine, 2-ethylaniline, 3-ethylaniline, 3-ethylaniline, N-methylaniline, N-ethylaniline, 2-aminothiophenol ), 3-aminothiophenol, 2-aminophenyl disulfide, meta-anasidine, ortho-anasidine, 2-ethoxyaniline, 3-ethoxyaniline, 2- Metal-polymer composite electrode material, characterized in that at least one selected from aniline ethanol and diphenylamine. The metal-polymer composite electrode material according to claim 1, wherein the aniline dimer is N-phenyl-1,4-phenylenediamine. The solvent of claim 1, wherein the solvent is acetonitrile, sulfolane, dimethyl sulfoxide, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl A metal-polymer composite electrode material, characterized in that it is a single or a mixture selected from methyl methyl carbonate, dichlorometane, dicholoethane and 1,4-dioxane. A secondary battery positive electrode comprising the composite electrode material of claim 1. A lithium secondary battery comprising a positive electrode made of the composite electrode material of claim 1.