KR19990018239A - Cathode material composition and cathode and secondary battery using same - Google Patents

Abstract

The present invention relates to organic disulfide and iron metal, in which an organic thiolate of a metal salt is produced by breaking the bond between sulfur and a sulfur atom during electrolytic reduction, and the reduced organic thiolate is oxidized to form a bond between sulfur and a sulfur atom. A composite cathode material composition composed of a polymer, a cathode prepared by applying the composition to a current collector made of copper metal or copper alloy, a cathode and a polymer electrolyte, and a carbon based lithium metal, lithium alloy or lithium intercalation. A secondary battery consisting of a negative electrode of a material.

The positive electrode manufactured in the present invention has a high discharge capacity, high charge and discharge efficiency, and a small decrease in discharge capacity according to the number of charge / discharge cycles as the positive electrode active material functions not only organic disulfide, but also ferrous metal. When recharging is possible repeatedly and has a high energy density it is possible to reduce the weight. Since the battery prepared in the present invention does not contain a liquid electrolyte, there is no problem due to leakage in use, and it is possible to manufacture small and thin batteries according to the use as a solid type battery.

Description

Cathode material composition and cathode and secondary battery using same

The present invention relates to a composite composition consisting mainly of iron metal, organic disulfide, and a conductive polymer, the cathode material composition having a high energy density and excellent reversible charge and discharge characteristics, and the cathode material composition comprising copper metal material. A solid secondary battery comprising a cathode selected by applying to a current collector and a cathode selected from a cathode, a polymer solid electrolyte, and a carbon-based material capable of lithium intercalation such as lithium metal, lithium alloy, carbon, and graphite. It is about.

Secondary batteries using organic disulfide as a cathode material are known from US Pat. No. 4,833,048. When the organic disulfide is reduced, it forms an organic thiolate, and upon oxidation of the organic thiolate, organic disulfide is reversibly produced. In particular, when two or more thiolate groups are present, organic disulfides in polymer form are formed. The interconversion between the organic disulfide and the organic thiolate by redox can be reversibly repeated and forms a metal-sulfur secondary battery that can be charged and discharged in pairs with redox of the metal constituting the negative electrode. The patent suggests that such secondary batteries have a higher energy density of 150 Wh / kg than typical secondary batteries. However, the type of battery proposed in the above patent has a disadvantage that it is difficult to use at room temperature because it operates at a high temperature up to 100 ℃. In addition, US Patent No. 5,324,599 to Oyama et al. Points out that the electron transfer rate of the above organic disulfide-thiolate redox pair is slow, and therefore, a decrease in output density at room temperature is a disadvantage.

In order to compensate for these disadvantages, U.S. Patent No. 5,324,599 and European Patent 534,407 Al proposed an organic disulfide cathode material containing a pie conjugated organic polymer such as polyaniline, which is electrically conductive. By adding polyaniline to the organic disulfide, the electron transfer rate was increased during the oxidation-reduction of the positive electrode material. When the lithium secondary battery was combined with the negative electrode of the lithium metal and the polymer electrolyte, the energy density increased. Molecular mixing by mixing organic disulfide and polyaniline in an organic solvent, as disclosed by Nature such as U.S. Patent 5,324,599 (N. Oyama, et. Al. Nature, 373, 598, 1995) This is possible and accordingly the energy density is reported to reach 600 Wh / kg. However, in order to obtain such high-density energy, a high voltage of up to 4.75 V must be maintained during charging, and when the battery is charged under a lower voltage, the energy density decreases. This high voltage used during charging affects the stability of battery components including the polymer electrolyte, and thus has the drawback that the reversible stability of the battery is reduced when charging and discharging are repeated.

As described above, batteries using a redox pair positive electrode material of organic disulfide and organic thiolate have been proposed, but much improvement is required to improve capacity and secure charge and discharge stability of a secondary battery using organic disulfide.

In the present invention, a composition of a cathode material having a high difference energy density and reversible redox which has been studied to solve the above disadvantages has been developed.

Accordingly, an object of the present invention is to provide a cathode material composition for a secondary battery whose main components are organic disulfide, ferrous metal and conductive polymer.

Another object of the present invention is to provide a positive electrode for a secondary battery coated with the positive electrode material composition prepared above on a current collector made of copper metal or copper alloy.

Still another object of the present invention is a non-aqueous polymer solid composed of a negative electrode selected from the positive electrode, lithium metal, lithium alloy and lithium intercalation-based carbon material, a polymer capable of dissolving lithium salt and lithium salt, and an organic solvent. It is to provide a secondary battery composed of an electrolyte.

The secondary battery thus made can be reversibly charged and discharged, and has a high energy density, thereby making it possible to reduce the weight of the battery. In addition, since it does not contain a liquid electrolyte, there is no problem due to leakage during use, and it is possible to manufacture small and thin batteries according to the use as a solid type battery.

1 is a battery manufactured by using a cathode material composition and a copper metal current collector produced in Comparative Example 1 to the discharge curve of the battery A produced using a cathode material composition and a copper metal current collector made in Example 1 according to the present invention It is a graph compared with the discharge curve of B.

2 is a charge / discharge graph according to the number of charge and discharge cycles of the battery A fabricated using the cathode material composition and the copper metal current collector made in Example 1 according to the present invention.

3 is a charge / discharge graph according to the number of charge / discharge cycles of the battery C manufactured by using the positive electrode material composition and the SUS 316 current collector made in Comparative Example 2. FIG.

An object of the present invention is an organic disulfide, iron metal or FeX _n form of iron salt which can produce reversible organothiolates when the main component is reduced (where X is a halogen anion or a counterbase anion of an acid, 1 ≦ n ≦ 3, n is an integer) to provide a composite positive electrode material composition for a secondary battery which is at least one iron compound and a conductive polymer.

In addition, the present invention is an iron-organic thiolate complex whose main component is represented by Fe _x (S _y R) _z (where R is an aliphatic or aromatic hydrocarbon, 1≤y≤6, y is an integer, yz / 3≤x ≦ yz) and a conductive positive electrode composition for a secondary battery, which is a conductive polymer.

Another object of the present invention is to provide a cathode for a secondary battery manufactured by applying the cathode material composition to a current collector made of copper metal or copper alloy.

Another object of the present invention is to provide a lithium secondary battery comprising a cathode and a non-aqueous polymer solid electrolyte selected from a cathode and a lithium metal or lithium alloy or a carbon-based material capable of lithium intercalation such as carbon and graphite prepared in the present invention. will be.

Hereinafter, the present invention will be described in detail.

The present invention is an organic disulfide capable of producing an organic thiol reversibly upon reduction; At least one iron compound selected from an iron salt in the form of an iron metal or FeX _n (X is a halogen anion or a counterbase anion of an acid, 1 ≦ n ≦ 3, n is an integer); And a composite positive electrode material composition for a secondary battery having a conductive polymer as a main component. At this time, the organic disulfide breaks the bond between sulfur and sulfur atoms and forms an organic thiolate capable of forming a bond between sulfur and a metal, and when the organic thioleate is oxidized, an organic reversible bond between sulfur and sulfur atoms is formed. Characterized in that it is disulfide. In this case, the metal refers to an iron metal, an alkali metal ion or a hydrogen cation.

On the other hand, the present invention is an iron-organic thiolate complex represented by Fe _x (S _y R) _z (R is an aliphatic or aromatic hydrocarbon, 1≤y≤6, y is an integer, yz / 3≤x≤yz) and conductivity Provided is a composite positive electrode active material composition for a secondary battery having a polymer as a main component. At this time, the iron-organic thiolate complex is an iron-organic thiolate complex in which a bond between sulfur and a sulfur atom is formed upon oxidation and a bond between sulfur and iron ions is formed upon reduction.

The conductive polymer used in the present invention is a material in which elements having a non-covalent electron pair, such as nitrogen or sulfur, are included in the polymer repeating structure and are selected from polyaniline, polypyrrole, and polythiophene. It features.

The positive electrode of the present invention is produced by applying the above composite positive electrode material composition to a current collector made of copper metal or copper alloy.

The present invention provides a lithium secondary battery using a non-aqueous polymer solid electrolyte containing the positive electrode for the secondary battery and a lithium salt, and a material selected from lithium metal, lithium alloy, or a material capable of lithium intercalation such as carbon or graphite as a negative electrode. do. The solid polymer electrolyte contains a lithium salt in the form of LiX (X is a counterbase anion of an acid) so that X ⁻ anion may move from the electrolyte to the anode during charging and may move from the anode to the electrolyte during discharge.

Hereinafter, the operation of the cathode material according to the present invention will be described.

Organic disulfide, which is a main component of the cathode material composition of the present invention, is converted to organic thiolate by a reduction reaction. In the reduction of organic disulfide, the bond between sulfur and sulfur atoms is separated to form an organic thiolate in anionic form. The organic thiolate is in the form of RS-M (M is a metal ion or hydrogen cation) in which sulfur and metal ions or sulfur and hydrogen ions are formed by binding to metal ions present in the electrode or migrated from the electrolyte. The organic thiolate is again formed by the oxidation reaction between the sulfur and sulfur atoms to form an organic disulfide. This redox reaction proceeds reversibly.

Organic disulfides proposed by the present invention are described in US Pat. No. 4,833,048 in the form (R (S) _y ) _n . When these substances are reduced, they can be represented as R (SH) _y or R (SM) _y . R includes an aromatic or aliphatic hydrocarbon group, y is 1 or more, an integer of 6 or less, and n is an integer of 2 or more. Examples of such organic disulfides include 2,5-dimercapto-1,3,4-thiadiazole, trithiocyanuric acid, 1 , 2-ethanedithiol, and the like. Another example is the case where two or more mercaptan groups are present in the molecule itself, as illustrated in US Pat. No. 5,324,599, resulting in the formation of organic disulfides in the molecule reversibly upon oxidation-reduction. An example of such organic disulfide is 1,8-disulfide naphthalene.

Ferrous metal contained in the positive electrode material is an important element of the electrode material of the present invention, which is in an oxidized state when the battery is charged and is converted into a reduced state when discharged. When ferrous metal is oxidized, it will generally be in ionic states, such as Fe (II) and Fe (III). In this case, each iron metal ion is reduced to iron metal at a potential of 2.7 V or more with respect to the lithium negative electrode (-3.05 V vs. NHE). Therefore, it has a range of oxidation-reduction potentials similar to those of organic disulfide electrodes having a potential difference of about 2.7 to 3.8 V for lithium negative electrodes. When the oxidation reaction of ferrous metal proceeds to the oxidation state of Fe (III), the theoretical capacity as a positive electrode is 1,450 mAh / g, and high energy density can be expected when used as an electrode material. Therefore, the cathode material proposed in the present invention can realize weight reduction of the secondary battery by adopting organic disulfide and ferrous metal having high energy density.

In the present invention, the ferrous metal is added to the electrode composition containing the organic disulfide and the conductive polymer in powder form and dispersed in the mixture. Aprotic and polar organic solvents can be used to aid in the dispersion of ferrous metals, and can also be subjected to strong mechanical agitation or sonication. The particle diameter of the powder is preferably 50 μm or less, and the metal surface may be activated by treating the powder surface with a dilute solution of a weak acid such as acetic acid before adding to the electrode mixture. The amount of ferrous metal added has a weight ratio of 0.1 to 10.0 relative to the organic disulfide in the positive electrode mixture. The iron metal may also be added as a salt in the form of FeX _n (1 ≦ _n ≦ 3, where n is an integer, X = halogen anion or an acid base anion).

On the other hand, organic disulfide may be fixed to the electrode by interaction with iron metal or iron ion species. In particular, the organic thiolate having high solubility in organic solvents may decrease the capacity of the battery when charge and discharge are repeated by glass from the conductive material due to dispersion into the electrolyte or movement in the electrode. However, in the present invention, by devising an electrode containing an iron metal, an organic thiolate or organic disulfide is fixed in the electrode by coordinating with or combining with iron metal ions, and thus, dispersion or separation of the electrode material is reduced and reversible charging and discharging is possible. Do.

In addition, the present invention is added as an iron-organic thiolate complex of the form Fe _x (S _y R) _z (R is an aliphatic or aromatic hydrocarbon, y is an integer 1≤y≤6, yz / 3≤x≤yz) The cathode material composition can be prepared. In the case of the iron metal salt or iron-organo thiolate complex soluble in N-methyl-2-pyrrolidone used as the solvent, it is added to the electrode composition in preference to the insoluble component and dissolved therein.

As the conductive polymer added in the present invention, a material in which elements having a non-covalent electron pair such as nitrogen or sulfur are included in the repeating structure of the polymer is preferable. Representative examples of such conductive polymers include polyaniline, polypyrrole, and polythiophene. Conductive polymers can increase the oxidation-reduction rate of organic disulfides, as described in US Pat. No. 5,324,599. In addition, the conductive polymer may be present in the form of an organic thiolate salt in combination with an iron metal or iron ions or in combination with a hydrogen cation contained in an organic disulfide. Conductive polymers have this type of bond with ferrous metals and organic disulfides in the positive electrode mixture, preventing the active material from being released from the electrode and increasing the reversible stability of the cell by immobilizing it in a conductive-network.

The polymer of the polyaniline compound may be prepared by electrochemical oxidation polymerization or chemical oxidation polymerization using an oxidizing agent. As the oxidizing agent used in the chemical oxidation polymerization method of aniline, inorganic and ammonium salts containing peroxydisulfate ions or metal ion salts such as Fe (III) and Cu (I) may be used. The polymerization proceeds in water or in polar organic solvents and may be in acidic conditions if done in water. The polymerized polyaniline is by being doped with a hydrogen cation ^{_{(proton) BF 4 -, PF}} 6 -, ClO 4 -, AsF 6 -, AsCl 6 -, SbCl 6 -, SbF 6 -, H 2 PO 4 -, HSO 4 - , Cl ^-, Br ^- may contain anions such as. These anions may be added in the form of a corresponding acid during polymerization to be doped together with the polymerization, or may be added in the form of an acid to be doped after the polymerization is completed. Doped polyaniline may be neutralized and dedoped when treated with a base such as ammonia water. The polyaniline used according to the invention can be added in doped or undoped form. The amount of conductive polymer added has a weight ratio of 0.1 to 1.5 relative to the organic disulfide in the positive electrode mixture.

As the current collector, a copper metal or a copper alloy is used, and a metal having a potential similar to or higher than that of the copper metal may be used. In addition, an alloy in which a copper metal and a metal satisfying the above conditions are contained in another metal may be used. The current collector made of copper metal or copper alloy used in the present invention fixes the voltage below the oxidation potential of the copper metal during charging of the battery, thereby preventing excessive voltage rise, thereby allowing each element of the battery to maintain stability. When a metal current collector having a lower oxidation potential than an iron metal as an active material is used, the metal constituting the current collector may be ionized before the iron metal during charging, resulting in a decrease in discharge capacity along with current loss. In addition, by using a current collector made of a copper metal or a copper alloy, the organic disulfide is fixed to the electrode so that the capacity of the composite of the organic disulfide and the ferrous metal as a cathode active material can be utilized to the maximum. 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.

In order to complete the cathode material used in the battery, the conductive material may contain a conductive carbon block such as acetylene block, and a binder may be added to prepare a paste. As the polymer material used as the binder of the cathode material, it is preferable to use the same material as the host polymer material used for the polymer electrolyte. However, nonionic conductivity such as EPDM and styrene-butadiene rubber (SBR) is preferable. The use of polymeric materials is also possible. An organic solvent may be used to dissolve the binder. The organic solvent may vary depending on the type of the binder, but aprotic solvents may be generally used. Organic solvents that can be used for this purpose include organic carbonate solvents such as N-methyl-2-pyrrolidone, propylene carbonate, and ethylene carbonate. The positive electrode material mixture prepared by the composition may use strong mechanical stirring or ultrasonic stirring to improve the dispersibility, the well-dispersed positive electrode material mixture can be applied to various metal current collectors in the form of a paste. 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.

The method for producing a positive electrode according to the present invention comprises the first step of dissolving an organic disulfide compound in N-methyl-2-pyrrolidone, which is a non-aqueous solvent, the second step of adding a polyaniline powder to the solution and mixing it completely. A third step of dispersing by adding at least one iron compound selected from an iron metal powder or an iron salt in the form of FeX _n (X is a halogen anion or a strong base anion of strong acid, 1 ≦ n ≦ 3, n is an integer), and The mixed solution is applied on a copper metal conductive electrode plate in an inert gas atmosphere, and dried in a vacuum and compressed. In addition, a method for producing a positive electrode according to the present invention is a first step of adding or dispersing polyaniline powder to N-methyl-2-pyrrolidone, which is a non-aqueous solvent, to completely disperse or dissolve Fe _x (S _y R) _z A second step of fully dispersing by addition of an iron-organic thiolate complex of form (R is an aliphatic or aromatic hydrocarbon, 1 ≦ y ≦ 6, y is an integer, yz / 3 ≦ x ≦ yz), the solution is copper metal conductive After coating in an inert gas atmosphere on the electrode plate, a method of manufacturing a composite positive electrode comprising an iron metal complex, which is characterized by the third step of drying and pressing in a vacuum.

An ion conductive polymer electrolyte is used as the electrolyte of the lithium secondary battery according to the present invention. These ion conductive polymer electrolytes are composed of a lithium salt, a polymer capable of dissolving lithium salt, and an organic solvent used as a plasticizer. 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 a host polymer material 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 polyvinylidene fluoride having a fluorine group [poly (vinylidene fluoride)], poly (vinylidene fluoride-co-hexafluoropropylene), etc. The amount of lithium salt contained in the polymer electrolyte is determined by the ratio of lithium ions per monomer of the polymer. (Li ⁺ / monomer) Adjust to 5-50 mol%.

Organic solvents added as plasticizers contain carbonate groups in highly polar solvents, for example propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and the like. These may be used alone or by any suitable combination of two or more of the above solvents. The amount of plasticizer added is adjusted to be 20-90 wt% of the total polymer electrolyte material.

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 when lithium metal is used, and lithium metal is formed. When carbon-based negative electrodes are used, intercalation of lithium ions occurs. During discharge, lithium ions are produced from the cathode by an oxidation reaction.

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

While the present invention is believed to be useful for lithium secondary batteries at present, it is not limited to certain types of batteries and may be used for primary batteries.

The present invention will be described in more detail with reference to the following Examples. However, the scope of the present invention is not limited to the contents of the following examples.

Example 1

(Manufacture of positive electrode)

1.0 g of trithiocyanuric acid (TTCA, Aldrich), 0.4 g of polyvinylidene fluoride (Aldrich), 1.6 g polyaniline (Vericon), 0.1 g dispersant (Brij 35, Aldrich) N-methyl-2-pyrrolidone (N-methyl-2-prrolidone, Mitsubishi Chemical) dissolved in an organic solvent, iron metal powder (particle diameter ≤ 50㎛) 0.6g, acetylene black (Chetron) 0.7g To this solution. The solution composition is stirred (2 days or more) to mix sufficiently. The positive electrode material mixture thus obtained is coated on a copper metal thin film current collector, then heated to 60 to 80 ° C. in a vacuum, dried, and pressed to prepare a positive electrode. The applied cathode material weighs 0.8 mg per cm 2 of electrode plate. The content of the cathode active material (TTCA) was 22.7% by weight based on the total amount of the cathode composition, and the contents of the iron metal powder and the polyaniline powder were 13.6% and 36.4% by weight, respectively.

(Preparation of negative electrode)

A lithium metal negative electrode having a thickness of 150 to 700 µm is stored and used in an argon gas atmosphere without further purification.

(Production of Polymer Electrolyte)

3.0 g of acrylonitrile-methyl acrylate (poly (acrylonitrile-co-methyl acrylate), 94: 6, Polysciences) and 2.3 g of LiBF ₄ (Merck) were heated (120-140 ° C.) under nitrogen or argon atmosphere. Dissolved in a mixed solvent of propylene carbonate (Misubishi Chemical) and ethylene carbonate (ethylene carbonate, Misubishi Chemical) (1.33: 1.0 weight ratio), cast on a glass plate, and heated in a vacuum (60 ~ 80 ℃) Dry 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. .

Comparative Example 1

An electrode was manufactured in the same manner as in Example 1 using an active material except for ferrous metal. The content of the positive electrode active material (TTCA) was 26.3% and the content of polyaniline powder was 42.1% based on the total positive electrode composition. Using the positive electrode thus obtained, a stacked measurement battery (battery B) was constructed through the same assembly process as in Example 1.

Comparative Example 2

The composite positive electrode composition was prepared in the same manner as in Example 1, but the positive electrode was manufactured using the SUS 316 thin film instead of the copper metal thin film as the current collector for the positive electrode, and the same assembly process as in Example 1 was performed. After rough, the laminated measuring battery (cell C) was comprised.

Example 2

The stacked batteries A, B, and C assembled in Example 1 and Comparative Examples 1 and 2 were stored in an argon gas atmosphere and measured for charge and discharge. All charge and discharge tests were conducted at room temperature. Further, charging and discharging were performed by setting a potential window of 1.5 to 4.2 V under constant current conditions.

The discharge capacities of the battery A prepared in Example 1 and the battery B prepared in Comparative Example 1 are shown in comparison with FIG. 1. As shown in FIG. 1, the battery A shows a significantly improved discharge capacity compared to the battery B in this case. In addition, the discharge capacity of the battery A was found to be 1,000 mWh / g-cathode or more from the continuous charge and discharge results. This is much higher than the theoretical capacity calculated from the trithiocyanuric acid, which is a positive electrode active material. When ferrous metal is added as an active material, not only trithiocyanuric acid but also ferrous metal powder also participates as a positive electrode active material to discharge capacity. Shows increased.

Meanwhile, FIG. 2 shows charge and discharge curves according to the number of charge and discharge cycles of the battery A prepared in Example 1. FIG. Battery A showed a battery efficiency of 95 to 100% even when charging and discharging was repeated 30 or more times in the charging and discharging experiment. That is, the electrode of the present invention shows that the stability is very high during repeated charging and discharging.

3 shows a charge and discharge curve according to the number of charge and discharge cycles of the battery C prepared in Comparative Example 2. However, the battery C shows a rapid decrease in the amount of charge and discharge when charge and discharge are repeated five or more times in the charge and discharge experiment.

As shown in the results of FIGS. 1, 2 and 3, not only trithiocyanuric acid but also iron metal and polyaniline are acting as positive electrode active materials, and by adopting copper metal as a current collector for positive electrode, It can be seen that the discharge capacity and stability during charging and discharging are guaranteed.

The present invention provides a cathode material composition comprising an organic disulfide, an iron metal and a conductive polymer, and a cathode prepared by applying the cathode material composition to a current collector made of copper metal or copper alloy, and the cathode and lithium metal or lithium alloy, carbon, It relates to a secondary battery composed of a negative electrode and a polymer electrolyte of a material capable of lithium intercalation such as graphite.

The secondary battery made as described above has a large discharge capacity, high charging and discharging efficiency, as well as organic disulfide and ferrous metal as a positive electrode active material. Would be possible. In addition, since it does not contain a liquid electrolyte, there is no problem due to leakage in use, and it is possible to manufacture small and thin batteries according to the use as a solid type battery.

Claims (9)

In the cathode material composition for secondary batteries, an organic disulfide whose main component is capable of reversibly producing an organic thiolate: an iron salt of iron metal or FeX _n form, wherein X is a halogen anion or a counterbase anion of an acid, and 1 ≦ n ≦ 3, n is an integer of at least one iron compound selected from; And a cathode material composition made of a conductive polymer. The method of claim 1, wherein the organic disulfide is an organic disulfide which forms an organic thiolate which forms a bond between sulfur and a metal or hydrogen upon reduction, and reversibly forms a bond between sulfur and a sulfur atom upon oxidation of the organic thioleate. A cathode material composition. 3. The cathode material composition according to claim 2, wherein the organic disulfide is 2,5-dimercapto-1,3,4-thiadiazole, tricyanuric acid, 1,2-ethanedithiaol. In the cathode material composition for secondary batteries, an iron-organic compound whose main component is represented by Fe _x (S _y R) _z (R is an aliphatic or aromatic hydrocarbon, 1≤y≤6, y is an integer, yz / 3≤x≤yz) A cathode material composition comprising a thiolate complex and a conductive polymer. The cathode material composition according to claim 4, wherein the iron-organic thiolate complex is a complex of iron-organo thiolate in which a bond between sulfur and a sulfur atom is formed upon oxidation and a bond of sulfur and metal ions is formed upon reduction. . The cathode material composition according to claim 1 or 4, wherein the conductive polymer is a polymer selected from polyaniline, polypyrrole, and polythiophene, which are materials in which elements having lone pairs are included in the polymer repeating structure. The positive electrode for secondary batteries manufactured by apply | coating the positive electrode material composition of Claim 1 or 4 to the electrical power collector which consists of copper metal or a copper alloy. A lithium secondary battery prepared by using a material selected from a non-aqueous polymer solid electrolyte containing a positive electrode for a secondary battery and a lithium salt of claim 7 and a lithium-based metal, lithium alloy, or a carbon-based material capable of lithium intercalation as a negative electrode. 9. The polymer solid electrolyte of claim 8, wherein the polymer solid electrolyte contains a lithium salt in the form of LiX (X is an acidic base anion of acid) in which X ^- anion can move from the electrolyte to the anode at charge and from the anode to the electrolyte at discharge. A lithium secondary battery using a polymer solid electrolyte.