JP6071819B2 - Secondary battery and method for manufacturing secondary battery - Google Patents

Description

  The present invention relates to a secondary battery and a method for manufacturing a secondary battery, and more particularly, has an electrode active material mainly composed of a multi-electron organic compound, and is charged and discharged using a battery electrode reaction of the electrode active material. The present invention relates to a repetitive secondary battery and a manufacturing method thereof.

  With the expansion of the market for portable electronic devices such as mobile phones, laptop computers, and digital cameras, secondary batteries with high energy density and long life have been actively developed as cordless power sources for these electronic devices.

  Among the constituent elements of the secondary battery, the electrode active material is a substance that directly contributes to a battery electrode reaction such as a charge reaction and a discharge reaction, and has a central role of the secondary battery. That is, the battery electrode reaction is a reaction that occurs with the transfer of electrons by applying a voltage to an electrode active material that is electrically connected to an electrode disposed in the electrolyte, and proceeds during charging and discharging of the battery. To do. Therefore, as described above, the electrode active material has a central role of the secondary battery in terms of system.

  In recent years, organic materials having redox activity have attracted attention as this type of electrode active material. Since organic materials can involve multiple electrons of two or more electrons in an oxidation-reduction reaction, by utilizing such characteristics for battery electrode reactions, two-dimensional materials having a larger capacity density than inorganic materials can be used. It is considered that a secondary battery can be realized.

For example, Patent Document 1 discloses a general formula (1 ′):
-(NH-CS-CS-NH) (1 ')
Or general formula (2 ')
R ¹ — (NH—CS—CS—NH) _n —R ² (2 ′)
A battery electrode containing rubeanic acid or a rubeanic acid polymer capable of binding to lithium ions having a structural unit represented by the above as a positive electrode and an electrode containing an active material capable of occluding and releasing lithium ions as a negative electrode An aqueous battery has been proposed.

In the general formula (2 ′), R ¹ and R ² represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an amino group, a hydroxyl group, or a sulfone group, and n is 1 to 20 Indicates an integer.

  FIG. 4 is a cross-sectional view schematically showing the structure of the non-aqueous battery described in Patent Document 1.

  That is, in this non-aqueous battery, the positive electrode active material layer 102 mainly composed of active material particles 102a made of rubeanic acid or rubeanic acid polymer is formed on the surface of the positive electrode current collector 101 formed of aluminum foil or the like, and the positive electrode current collector is formed. A positive electrode 103 is constituted by the electric conductor 101 and the positive electrode active material layer 102. A negative electrode 104 is disposed on the opposite side of the positive electrode 103. The negative electrode 104 includes a negative electrode current collector 105 made of copper or the like, and a negative electrode active material layer 106 containing metallic lithium formed on the surface of the negative electrode current collector 105 so as to face the positive electrode active material layer 102. have.

  Further, a separator 107 made of a gel or solid electrolyte is interposed between the positive electrode active material layer 102 and the negative electrode active material layer 105, and an electrolyte solution (electrolytic solution) 108 obtained by dissolving an electrolyte salt in a solvent is a battery can. (Not shown).

  And in patent document 1, the rubeanic acid or rubeanic acid polymer containing the dithione structure represented by general formula (1 ') or (2') couple | bonds with the lithium ion at the time of a reduction | restoration, and the said combined lithium ion at the time of oxidation Release. Charging / discharging can be performed by utilizing such a reversible oxidation-reduction reaction of rubeanic acid or rubeanic acid polymer.

  In addition, this Patent Document 1 describes that instead of the electrolyte solution, a solid electrolyte in which an electrolyte salt is contained in a gel or solid (hereinafter referred to as “solid etc.”) may be used. Yes.

  Patent Document 2 discloses a battery including a positive electrode, a negative electrode, and an electrolyte solution containing an electrolyte interposed between the positive electrode and the negative electrode, wherein the positive electrode is rubeanic acid or a rubeanic acid derivative as an active material. And a battery in which the molar concentration of the electrolyte in the electrolytic solution is higher than 1.0 mol / L has been proposed.

  The battery of Patent Document 2 also has the same structure as Patent Document 1.

  In Patent Document 2, the electrolyte salt concentration in the electrolyte solution is increased to increase the molar amount of the anion derived from the electrolyte salt, thereby obtaining a high charge / discharge capacity density.

JP 2008-147015 A (Claim 4, paragraph numbers [0011], [0013], FIG. 3, FIG. 5) JP 2012-164480 A (Claim 1, paragraph numbers [0008], [0028])

  By the way, in the secondary battery described above, since electrons are exchanged between the positive electrode and the negative electrode through lithium ions, lithium ions can freely move to the negative electrode side during charging and freely move to the positive electrode side during discharging. It is important to be able to do it.

  However, in Patent Documents 1 and 2, although the gel 107 or the solid is used for the separator 107, the electrolyte solution 108 is in contact with the surface of the positive electrode active material layer 102. The positive electrode active material may be eluted into the electrolyte solution 108. In particular, in a secondary battery using an organic compound as a positive electrode active material, charge / discharge is performed using the oxidation-reduction reaction of the molecule itself. Therefore, a lithium ion secondary battery that performs charge / discharge while maintaining the crystal system Unlikely, the positive electrode active material is easily dissolved in the electrolyte solution.

  When the positive electrode active material is eluted into the electrolyte solution 108 in this way, the positive electrode active material is eluted into the electrolyte solution 108 and then reaches the negative electrode, thereby causing an unintended redox reaction and taking out a desired current to the outside. There is a risk of disappearing. In addition, as described above, since the positive electrode active material reaches the negative electrode, a negatively active polymer is formed on the surface of the negative electrode, which leads to a decrease in lithium ion and electron transfer efficiency, resulting in charge / discharge efficiency. There is a risk that the battery capacity will deteriorate due to deterioration.

  Further, Patent Document 1 describes that a solid electrolyte may be used in place of the electrolyte solution 108, and it is considered that this can prevent elution of the positive electrode active material. There is no mention of a nuanced technique. Moreover, it is difficult to allow lithium ions to reach the inside of the positive electrode active material only by bringing the solid electrolyte into contact with the positive electrode active material layer 102. That is, the positive electrode active material layer 102 contains a positive electrode active material (active material particles 102a), a conductive additive such as carbon black, and a binder, and the positive electrode active material layer 102 is microscopic. A current collector having a very complicated uneven shape at a level and having a thickness of about several tens of μm is formed. For this reason, if the solid electrolyte is simply brought into contact with the positive electrode active material layer 102, even if the surface area of the positive electrode active material layer 102 is increased, the lithium ions that have moved from the negative electrode 106 are only in contact with the solid electrolyte. Ions cannot be exchanged and it is difficult to reach the inside of the positive electrode active material layer 102, which may cause a significant decrease in ion conduction efficiency.

  Moreover, since the solid electrolyte currently in practical use is inferior in ionic conductivity compared to the liquid electrolyte solution, in order to obtain the desired ionic conductivity, the solid electrolyte is used in combination with the electrolyte solution. It is necessary to reduce the usage rate as much as possible, and there is a risk of complicating the battery configuration.

  This invention is made | formed in view of such a situation, Comprising: It aims at providing the secondary battery which can improve a charging / discharging efficiency, and can obtain desired battery capacity, and the manufacturing method of a secondary battery. And

In order to achieve the above object, a secondary battery according to the present invention includes an electrolyte interposed between a first electrode and a second electrode, and includes the first and second electrodes and the electrolyte. A secondary battery containing lithium in at least one of the first electrode and the second electrode, a multi-electron organic material in which two or more electrons are involved in a battery electrode reaction. In addition to having an electrode active material mainly composed of a compound, the electrode active material is coated with an inorganic active material on at least one of the surface of the active material substrate containing the organic compound and the surface of the particles of the organic compound. And the said inorganic active material is characterized by including lithium iron phosphate .

  Furthermore, in the secondary battery of the present invention, the organic compound has in its constituent unit at least one selected from a dithione compound having a dithione structure, a dione compound having a dione structure, and a diamine compound having a diamine structure. It is preferable.

又は

で表されるのが好ましい。 In the secondary battery of the present invention, the dithione compound has the general formula:

Or

It is preferable to be represented by

Here, in the above general formula, n is an integer of 1 or more, R ₁ to R ₃ and R ₅ is a substituted or unsubstituted amino group, a substituted or unsubstituted imino group, a substituted or unsubstituted alkyl group Substituted or unsubstituted alkylene group, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted alkenyl group, Substituted or unsubstituted aryloxy group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylamino group, substituted or unsubstituted thioaryl group, substituted or unsubstituted thioalkyl group, substituted or unsubstituted heterocyclic ring Group, substituted or unsubstituted formyl group, substituted or unsubstituted silyl group, substituted or unsubstituted A cyano group, a substituted or unsubstituted nitro group, a substituted or unsubstituted nitroso group, a substituted or unsubstituted carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, and a linking group comprising one or more combinations thereof And R _{1 to} R ₃ and R ₅ are the same, and include cases where they are linked to each other to form a saturated or unsaturated ring structure. R ₄ represents at least one of a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, and a substituted or unsubstituted imino group, and the imino groups are linked to each other. Including.

又は、

で表されるのが好ましい。 Further, in the secondary battery of the present invention, the dione compound has the general formula:

Or

It is preferable to be represented by

Here, in the above general formula, n is an integer of 1 or more, R ₆ to R ₈ and R ₁₀ is a substituted or unsubstituted amino group, a substituted or unsubstituted imino group, a substituted or unsubstituted alkyl group Substituted or unsubstituted alkylene group, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted alkenyl group, Substituted or unsubstituted aryloxy group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylamino group, substituted or unsubstituted thioaryl group, substituted or unsubstituted thioalkyl group, substituted or unsubstituted heterocyclic ring Group, substituted or unsubstituted formyl group, substituted or unsubstituted silyl group, substituted or unsubstituted Any one of a cyano group, a substituted or unsubstituted nitro group, a substituted or unsubstituted nitroso group, a substituted or unsubstituted carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, and a linking group comprising one or more combinations thereof R _{6 to} R ₈ and R ₁₀ are the same, and include cases where they are linked to each other to form a saturated or unsaturated ring structure. R ₉ represents at least one of a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, and a substituted or unsubstituted imino group, and the imino groups are linked to each other. Including.

で表されるのが好ましい。 Furthermore, in the secondary battery of the present invention, the diamine compound has the general formula:

It is preferable to be represented by

In the above general formula, R ₁₁ and R ₁₂ are a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted carbonyl group, substituted or unsubstituted Substituted acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted ester group, substituted or unsubstituted ether group, substituted or unsubstituted thioether group, substituted or unsubstituted amino group, substituted or unsubstituted An amide group, a substituted or unsubstituted sulfone group, a substituted or unsubstituted thiosulfonyl group, a substituted or unsubstituted sulfonamido group, a substituted or unsubstituted imino group, a substituted or unsubstituted azo group, and one of these One of the linking groups consisting of the above combinations is shown. X _{1 to} X ₄ are a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, Substituted or unsubstituted aryl group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted aralkyl group, substituted or unsubstituted amino group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy At least one of a group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted acyl group, and a substituted or unsubstituted acyloxy group, and these substituents Includes the case where a substituent forms a ring structure.

  Furthermore, in the secondary battery of the present invention, it is preferable that the electrode active material is included in at least one of a reaction starting material, a product, and an intermediate product in the discharge reaction of the battery electrode reaction.

  In the secondary battery of the present invention, it is preferable that either one of the first and second electrodes forms a positive electrode, and the positive electrode has the electrode active material.

  Also, in the method for manufacturing a secondary battery according to the present invention, an electrode active material mainly composed of a multi-electron organic compound is used as the first and second electrodes, with an electrolyte interposed between the first electrode and the second electrode. A method of manufacturing a secondary battery contained in at least one of the second electrodes, wherein the active material preparation step of preparing the electrode active material includes at least the organic compound and a conductive material. And a coating step of coating the surface of the active material substrate with an inorganic active material.

  Also, in the method for manufacturing a secondary battery according to the present invention, an electrode active material mainly composed of a multi-electron organic compound is used as the first and second electrodes, with an electrolyte interposed between the first electrode and the second electrode. A method of manufacturing a secondary battery contained in at least one of the second electrodes, wherein the active material preparation step of preparing the electrode active material covers the surface of the organic compound particles with an inorganic active material And a forming step of forming the electrode active material by mixing and molding an organic compound coated with the inorganic active material, a conductive material, and a binder.

  According to the secondary battery of the present invention, the electrolyte is interposed between the first electrode and the second electrode, and at least one of the first and second electrodes and the electrolyte is lithium. In which one of the first and second electrodes is an electrode mainly composed of a multi-electron organic compound in which two or more electrons are involved in the battery electrode reaction. Since the electrode active material has an active material, at least one of the surface of the active material substrate containing the organic compound and the particle surface of the organic compound is coated with the inorganic active material. Since the substance has the action of suppressing the elution of the organic compound into the electrolyte, the organic compound, which is the main component of the electrode active material, is supported on the electrode surface or inside the electrode to suppress the elution of the organic compound into the electrolyte. Do Door can be. Since the inorganic active material has electronic conductivity and lithium ion conductivity, the active material substrate can transfer desired electrons within the electrode or on the electrode surface while suppressing the elution of the active material substrate into the electrolyte. Therefore, even if charging / discharging is repeated for a long time, it is possible to suppress a decrease in battery capacity.

  Further, according to the method for manufacturing a secondary battery of the present invention, the electrode active material mainly composed of a multi-electron organic compound is provided with the electrolyte between the first electrode and the second electrode. And a method of manufacturing a secondary battery contained in at least one of the second electrodes, wherein the active material manufacturing step of manufacturing the electrode active material binds at least the organic compound to a conductive material. A substrate preparation step for producing an active material substrate containing an agent and a coating step for coating the surface of the active material substrate with an inorganic active material, so that the surface of the active material substrate is coated with an inorganic active material Thus, it is possible to obtain a secondary battery with good charge and discharge efficiency by suppressing the organic compound from eluting into the electrolyte.

  Further, according to the method for manufacturing a secondary battery of the present invention, the electrode active material mainly composed of a multi-electron organic compound is provided with the electrolyte between the first electrode and the second electrode. And a method of manufacturing a secondary battery contained in at least one of the second electrodes, wherein the active material preparation step of preparing the electrode active material is performed using an inorganic active material on the particle surface of the organic compound. A coating step for coating, and a molding step for preparing the electrode active material by mixing and molding at least the organic compound coated with the inorganic active material, the conductive material, and the binder. The particle surface is coated with an inorganic active material, and in this case as well, it is possible to obtain a secondary battery with good charge and discharge efficiency by suppressing the organic compound from eluting into the electrolyte.

1 is a cross-sectional view schematically showing an embodiment (first embodiment) of a secondary battery according to the present invention. It is sectional drawing which showed typically 2nd Embodiment of the secondary battery which concerns on this invention. It is a figure which shows the charging / discharging characteristic of an Example. It is sectional drawing which showed the conventional example of the secondary battery typically.

  Next, an embodiment of the present invention will be described in detail.

  FIG. 1 is a cross-sectional view schematically showing one embodiment (first embodiment) of a secondary battery according to the present invention.

  In this secondary battery, an active material substrate 2 is formed on the surface of a positive electrode current collector 1 formed of an aluminum foil or the like, and the surface of the active material substrate 2 is covered with an inorganic active material layer 3. The active material substrate 2 and the inorganic active material layer 3 form a positive electrode active material 4, and the positive electrode active material 4 and the positive electrode current collector 1 constitute a positive electrode (first electrode) 5.

  A negative electrode (second electrode) 6 is disposed on the opposite side of the positive electrode 5. The negative electrode 6 includes a negative electrode current collector 7 formed of copper or the like, and a negative electrode active material 8 containing metallic lithium formed on the surface of the negative electrode current collector 6 so as to face the positive electrode active material 4. Have.

  A separator 9 made of a porous resin material or a gel or solid material is interposed between the positive electrode 5 and the negative electrode 6, and an electrolyte solution 10 in which an electrolyte salt is dissolved in a solvent is a battery can (not shown). Have been charged.

  And the active material base | substrate 2 contains the active material particle 11 which consists of a multi-electron type organic compound which becomes a main body of a battery electrode reaction.

  That is, in recent years, electrode active materials mainly composed of organic compounds have attracted attention, and among them, multi-electron organic compounds in which multiple electrons of two or more electrons are involved in battery electrode reactions, such as dithion compounds, dione compounds, and diamine compounds Is promising as an active material capable of realizing a high capacity density with good charge / discharge efficiency.

  Therefore, in the present embodiment, active material particles 11 made of a multi-electron organic compound are contained in the active material substrate 2.

  By the way, when these organic compounds are used mainly for the positive electrode active material, as described in [Problems to be Solved by the Invention], the organic compounds are easily eluted into the electrolyte solution 10, and the positive electrode active material is the electrolyte solution. Since it reaches the negative electrode 6 after elution to 10, an unintended oxidation-reduction reaction occurs, and thus there is a possibility that current cannot be taken out to the outside.

  Furthermore, since a polymer having low electrochemical activity is formed on the surface of the negative electrode 6, there is a possibility that efficient inhibition of the movement of lithium ions and electrons is hindered.

  When a solid electrolyte is used instead of the electrolyte solution, the active material substrate 2 contains a conductive auxiliary agent and a binder in addition to the organic compound particles 11 that are the main components of the battery electrode reaction. Since a current collector having a thickness of several tens of μm having a very complicated uneven shape at a general level is formed, the lithium ion from the negative electrode 6 can be obtained only by bringing the solid electrolyte into contact with the active material substrate 2. The inside of the active material base 2 cannot be reached, and the ion conduction efficiency is low, which may cause a decrease in charge / discharge efficiency.

  Therefore, in the present embodiment, the active material substrate 2 is composed of the inorganic active material layer 3 that has electronic conductivity and lithium ion conductivity, and has an action of suppressing the dissolution of the organic compound contained in the active material substrate 2 into the electrolyte solution 10. Thus, the lithium ion from the negative electrode 6 can effectively reach the surface and the inside of the active material substrate 2 while suppressing elution of the active material substrate 2 into the electrolyte solution 10. The conduction efficiency of ions and electrons is improved. Thus, the charge / discharge efficiency is improved, and it is possible to suppress a decrease in battery capacity even after repeated charge / discharge.

  The inorganic active material layer 3 is sufficient if it can prevent elution of the active material substrate 2 into the electrolyte solution 10. Therefore, the thickness is preferably as thin as possible, and is desirably formed to be about 5 to 20 μm.

As such an inorganic active material layer 3, elution of the organic compound (active material particles 11) contained in the active material substrate 2 into the electrolyte solution 10 can be suppressed, and it has electron conductivity and lithium ion conductivity. is not particularly limited as long, usually cobalt, manganese, and lithium compound containing at least one kind of the nickel, for example, lithium cobalt oxide (LiCoO _2), lithium manganate (LiMn ₂ O ₄₎ Lithium nickelate (LiNiO ₂ ), nickel-manganese-lithium cobaltate (LiNiMnO ₂ ) can be preferably used, or lithium iron phosphate (LiFePO ₄ ) can be preferably used. That is, these lithium compounds can be used alone or in combination of two or more.

  In addition to the active material particles 11, the active material substrate 2 contains a conductive additive and a binder as described above.

  Here, the conductive auxiliary agent is not particularly limited, for example, carbonaceous fine particles such as graphite, carbon black, and acetylene black, vapor grown carbon fibers, carbon nanotubes, carbon fibers such as carbon nanohorns, polyaniline, Conductive polymers such as polypyrrole, polythiophene, polyacetylene, and polyacene can be used. Further, two or more kinds of conductive assistants can be mixed and used. In addition, as for the content rate in the positive electrode active material layer 2 of a conductive support agent, 10 to 80 weight% is preferable.

  Further, the binder is not particularly limited, and various resins such as polyethylene, polyvinylidene fluoride, polyhexafluoropropylene, polytetrafluoroethylene, polyethylene oxide, carboxymethylcellulose, and the like can be used.

The electrolyte solution 10 is interposed between the positive electrode 5 and the negative electrode 6 and transports charge carriers between the two electrodes. As such an electrolyte solution 10, 10 ⁻⁵ to 10 ⁻¹ S / at room temperature. Those having an ionic conductivity of cm can be used, and the electrolyte salt can be used by dissolving in an organic solvent.

Here, as the electrolyte salt, for example, LiPF ₆ , LiClO ₄ , LiBF ₄ , LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiC (CF ₃ SO ₂ ) ₃ , LiC (C ₂ F ₅ SO ₂ ) ₃ or the like can be used.

  As the organic solvent, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, tetrahydrofuran, dioxolane, sulfolane, dimethylformamide, dimethylacetamide, 1-methyl-2-pyrrolidone, etc. are used. be able to.

  As described above, according to the first embodiment, the positive electrode 5 has the active material substrate 2 mainly composed of a multi-electron organic compound in which two or more electrons are involved in the battery electrode reaction, and the active material substrate 2 is active. The surface of the material substrate 2 is covered with the inorganic active material layer 3. And since this inorganic active material layer 3 has an electronic conductivity and lithium ion conductivity, it has the effect | action which suppresses the elution to the electrolyte solution 10 of the active material particle 11 formed with the organic compound, Therefore Lithium ions can easily reach the surface and inside of the active material substrate 2 while suppressing the elution of the material particles 11 into the electrolyte solution 10.

  That is, by supporting the active material substrate 2 in the positive electrode 5, the active material particles 11 are not eluted into the electrolyte solution 10, and desired electrons are effectively exchanged in the positive electrode 5 or on the surface of the positive electrode 5. Since this improves the lithium ion conduction efficiency, it is possible to suppress a decrease in discharge capacity, and to obtain a secondary battery with good charge / discharge efficiency and a desired battery capacity for a long time. Even if charging / discharging is repeated, a decrease in battery capacity can be suppressed.

  Next, among the organic compounds contained in the active material substrate 2, dithion compounds, dione compounds, and diamine compounds that are expected to be put to practical use will be described in detail.

(1) Dithione compound The dithione compound is excellent in stability during charge and discharge (oxidized state and reduced state), and can perform a multi-electron reaction of two or more electrons by an oxidation-reduction reaction. Since the charge / discharge efficiency is improved by covering the surface of the positive electrode active material layer 2 with the ion conductor thin film 3, the charge / discharge of the multi-electron reaction can be stably repeated, and the high capacity density of A secondary battery can be obtained.

  Such a dithione compound is not particularly limited as long as it has a dithione structure in the structural unit, but preferably uses a compound represented by the following general formula (1) or (2). Can do.

Here, in the general formulas (1) and (2), n is an integer of 1 or more, and R _{1 to} R ₃ and R ₅ are a substituted or unsubstituted amino group, a substituted or unsubstituted imino group, Substituted or unsubstituted alkyl group, substituted or unsubstituted alkylene group, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxyl group, substituted Or an unsubstituted alkenyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted thioaryl group, a substituted or unsubstituted thioalkyl group, Substituted or unsubstituted heterocyclic group, substituted or unsubstituted formyl group, substituted or unsubstituted silyl group, substituted Or a linkage composed of an unsubstituted cyano group, a substituted or unsubstituted nitro group, a substituted or unsubstituted nitroso group, a substituted or unsubstituted carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, and one or more combinations thereof Any one of the groups, and R _{1 to} R ₃ and R ₅ are the same, and include cases where they are linked to each other to form a saturated or unsaturated ring structure. R ₄ represents at least one of a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, and a substituted or unsubstituted imino group, including the case where the imino groups are linked to each other. .

  And as a dithione compound which belongs to the category of the said General formula (1), the organic compound shown to following Chemical formula (1a)-(1i) can be mentioned.

  The following chemical reaction formula (I) shows an example of a charge / discharge reaction expected when the dithione compound represented by the chemical formula (1a) is used as the positive electrode active material and Li is used as the cation of the electrolyte salt.

  Examples of the dithione compound belonging to the category of the general formula (2) include organic compounds represented by the following chemical formulas (2a) to (2g).

  The following chemical reaction formula (II) shows an example of a charge / discharge reaction expected when the dithione compound represented by the chemical formula (2a) is used as the positive electrode active material and Li is used as the cation of the electrolyte salt.

  The molecular weight of the organic compound constituting the positive electrode active material is not particularly limited. However, when the portion other than the dithione structure is increased, the molecular weight is increased, so that the storage capacity per unit mass, that is, the capacity density is reduced. Therefore, it is preferable that the molecular weight of the portion other than the dithione structure is small.

(2) Dione Compound Like the dithione compound, the dione compound is excellent in stability during charge and discharge (oxidized state and reduced state), and can perform a multi-electron reaction of two or more electrons by an oxidation-reduction reaction. Since the charge / discharge efficiency is improved by covering the surface of the positive electrode active material layer 2 with the ion conductor thin film 3, the charge / discharge of the multi-electron reaction can be stably repeated, and the high capacity density of A secondary battery can be obtained.

  The dione compound is not particularly limited as long as it has a dione structure in the structural unit, but preferably uses a compound represented by the following general formula (3) or (4). Can do.

Here, in the general formula (3) or (4), n is an integer of 1 or more, and R _{6 to} R ₈ and R ₁₀ are a substituted or unsubstituted amino group, a substituted or unsubstituted imino group, Substituted or unsubstituted alkyl group, substituted or unsubstituted alkylene group, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxyl group, substituted Or an unsubstituted alkenyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted thioaryl group, a substituted or unsubstituted thioalkyl group, Substituted or unsubstituted heterocyclic group, substituted or unsubstituted formyl group, substituted or unsubstituted silyl group, Or a linkage composed of an unsubstituted cyano group, a substituted or unsubstituted nitro group, a substituted or unsubstituted nitroso group, a substituted or unsubstituted carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, and one or more combinations thereof Any of the groups, and R _{6 to} R ₈ and R ₁₀ are the same, and include cases where they are linked to each other to form a saturated or unsaturated ring structure. R ₉ represents at least one of a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, and a substituted or unsubstituted imino group, including the case where the imino groups are linked to each other. .

  And as a dione compound which belongs to the category of the said General formula (3), the organic compound shown to following Chemical formula (3a)-(3e) can be mentioned.

  The following chemical reaction formula (III) shows an example of a charge / discharge reaction expected when the dione compound represented by the chemical formula (3a) is used as the positive electrode active material and Li is used as the cation of the electrolyte salt. .

  Examples of the dione compound belonging to the category of the general formula (4) include organic compounds represented by the following chemical formulas (4a) to (4f).

  The following chemical reaction formula (IV) shows an example of a charge / discharge reaction expected when the dione compound represented by the chemical formula (4a) is used as the positive electrode active material and Li is used as the cation of the electrolyte salt.

  The molecular weight of the organic compound constituting the positive electrode active material is not particularly limited. However, when the portion other than the dione structure is increased, the molecular weight is increased, so that the storage capacity per unit mass, that is, the capacity density is reduced. Therefore, the molecular weight of the portion other than the dione structure is preferably small.

(3) Diamine compound Like the dithione compound and dione compound, the diamine compound is excellent in stability at the time of charge and discharge (oxidized state and reduced state), and a multi-electron reaction of two or more electrons is possible by the oxidation-reduction reaction. . Since the charge / discharge efficiency is improved by covering the surface of the positive electrode active material layer 2 with the ion conductor thin film 3, the charge / discharge of the multi-electron reaction can be stably repeated, and the high capacity density of A secondary battery can be obtained.

  Such a diamine compound is not particularly limited as long as it has a diamine structure in the structural unit, but an organic compound represented by the following general formula (5) can be preferably used.

In the general formula (5), R ₁₁ and R ₁₂ are a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted carbonyl group, Substituted or unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted ester group, substituted or unsubstituted ether group, substituted or unsubstituted thioether group, substituted or unsubstituted amine group, substituted Or an unsubstituted amide group, a substituted or unsubstituted sulfone group, a substituted or unsubstituted thiosulfonyl group, a substituted or unsubstituted sulfonamido group, a substituted or unsubstituted imine group, a substituted or unsubstituted azo group, and Any one of these linking groups consisting of one or more combinations is shown. X _{1 to} X ₄ are a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, Substituted or unsubstituted aryl group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted aralkyl group, substituted or unsubstituted amino group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy At least one of a group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted acyl group, and a substituted or unsubstituted acyloxy group, and these substituents Includes the case where a substituent forms a ring structure.

  And as an organic compound contained in the category of the said General formula (5), the organic compound which contains the phenazine structure which the aryl group couple | bonded across the pyrazine ring in a structural unit is more preferable, for example, chemical formula (5a)-( The organic compounds shown in 5f) can be preferably used.

  The following chemical reaction formula (V) shows an example of a charge / discharge reaction expected when the organic compound shown in the chemical formula (5b) is used as the electrode active material and Li is used as the cation of the electrolyte salt.

  The molecular weight of the diamine compound is not particularly limited. However, when the portion other than the diamine structure is increased, the molecular weight increases, so that the storage capacity per unit mass, that is, the capacity density is reduced. Accordingly, the molecular weight of the portion other than the diamine structure is preferably small.

  The substituents listed in the general formulas (1) to (5) are not limited as long as they belong to the respective categories. However, as the molecular weight increases, the substituents accumulate per unit mass of the positive electrode active material. Since the amount of charge that can be reduced, it is preferable to select a desired substituent so that the molecular weight is about 250.

  Since the positive electrode active material is reversibly oxidized or reduced by charge / discharge, the positive electrode active material takes a different structure and state depending on the charged state, discharged state, or intermediate state. Is contained in at least one of a reaction starting material (a substance that causes a chemical reaction in a battery electrode reaction), a product (a substance resulting from a chemical reaction), and an intermediate product. A secondary battery having a positive electrode active material with good discharge efficiency and high capacity density can be realized.

  Next, an example of a method for manufacturing the secondary battery will be described in detail.

  First, the active material base 2 is formed into an electrode shape. That is, preferably any one of the organic compounds described above is prepared. And the organic compound used as this active material particle 11 is mixed with the conductive support agent and the binder which were mentioned above, a solvent is added, the slurry for active materials is produced, and this slurry for active materials is made on the positive electrode collector 1 The active material substrate 2 is formed on the positive electrode current collector 1 by coating with an arbitrary coating method, forming into an electrode shape, and drying.

  Here, the solvent used for the production of the slurry for active material is not particularly limited. For example, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, propylene carbonate, diethyl carbonate, dimethyl carbonate, γ-butyrolactone, etc. Basic solvents, acetonitrile, tetrahydrofuran, nitrobenzene, non-aqueous solvents such as acetone, and protic solvents such as methanol and ethanol can be used.

  Note that the type of solvent, the compounding ratio of the organic compound and the solvent, the type of conductive agent and binder, and the amount added thereof can be arbitrarily set in consideration of the required characteristics and productivity of the secondary battery. it can.

  Next, an inorganic active material slurry is prepared. That is, an inorganic compound such as a lithium compound is prepared, a predetermined amount of the inorganic compound is weighed and pulverized, and the pulverized product is mixed with a binder and a solvent such as pure water, whereby an inorganic active material slurry is prepared. Is made. And this inorganic active material slurry is apply | coated to the whole surface of the active material base | substrate 2, and it is made to dry, Thereby, the surface of the active material base | substrate 2 is coat | covered with the inorganic active material layer 3 of predetermined thickness (for example, 5-10 micrometers), The positive electrode 5 is formed.

  In addition, the binder similar to the slurry for active material can also be used for the binder for inorganic active material slurry formation.

  Next, the electrolyte solution 10 is prepared. Then, the positive electrode 5 is impregnated with the electrolyte solution 10 so that the positive electrode 5 is impregnated with the electrolyte solution 10, and then the separator 9 impregnated with the electrolyte solution 10 is laminated on the positive electrode 5 and further formed with metal Li or the like. The negative electrode active material 8 and the negative electrode current collector 7 formed of copper foil or the like are sequentially laminated, and then the electrolyte solution 10 is injected into the internal space. Then, the battery is sealed with a battery can (not shown), thereby producing a secondary battery.

  As described above, according to the first embodiment, the active material preparation step for preparing the positive electrode active material 4 includes a substrate for preparing the active material substrate 2 containing at least an organic compound and a conductive additive and a binder. Since the manufacturing process and the coating process of coating the surface of the active material substrate 2 with the inorganic active material layer 3 are included, the surface of the active material substrate 2 is coated with the inorganic active material layer 3. Can be prevented from eluting into the electrolyte solution 10 and a secondary battery with good charge / discharge efficiency can be obtained.

  FIG. 2 is a cross-sectional view schematically showing a second embodiment of the secondary battery according to the present invention.

  In the first embodiment, the surface of the active material substrate 2 is covered with the inorganic active material layer 3, but in the second embodiment, the surface of the active material particles 11 made of an organic compound is inorganic. The active material film 13 is covered.

  That is, in the second embodiment, the positive electrode 13 is formed by the positive electrode active material 12 and the positive electrode current collector 1. The positive electrode active material layer 12 contains active material particles 11 made of an organic compound that is the main component of the battery electrode reaction, and the surface of the active material particles 11 is covered with an inorganic active material film 14.

  The inorganic active material film 14 is sufficient if it can prevent elution of the active material substrate 2 into the electrolyte solution 10. Therefore, the thickness is preferably as thin as possible, and is desirably formed to be about 5 to 20 μm.

  In the second embodiment, the active material particles 11 are suppressed by the inorganic active material film 14 that suppresses the elution of the active material particles 11, which are organic compounds, into the electrolyte solution 11 and has good electron conductivity and ion conductivity. Since the surface of 11 is coated, the active material particles 11 are supported on the inorganic active material film 14. Therefore, the active material particles 11 can be prevented from being eluted into the electrolyte solution 10. A secondary battery with good ion and electron conduction efficiency and good charge / discharge efficiency can be obtained.

  The secondary battery of the second embodiment can be easily manufactured by the following method.

  First, the organic compound and the inorganic active material described above are prepared, and the surface of the active material particles 11 is covered with the inorganic active material film 14 by the following method.

  That is, the inorganic active material is finely pulverized using a pulverizer such as a jet mill until the diameter becomes 1 μm or less. Next, the active material particles which are organic compounds and the finely pulverized inorganic active material are put into a stirrer and stirred. As a result, the finely divided inorganic active material adheres to the surface of the active material 11, and the surface of the active material particles 11 is covered with the inorganic active material film 14.

  Next, an organic compound composed of the active material particles 11 whose surface is coated with the inorganic active material film 14 is mixed with the above-described conductive auxiliary agent and binder, and a solvent is added to prepare a slurry for active material. The material slurry is applied onto the positive electrode current collector 1 by an arbitrary coating method and dried to form the active material substrate 12 into an electrode shape on the positive electrode current collector 1, thereby producing the positive electrode 13. .

  Thereafter, the secondary battery can be manufactured by the same method and procedure as in the first embodiment.

  As described above, in the second embodiment, the active material preparation step for preparing the positive electrode active material 12 includes a coating step for covering the surfaces of the active material particles 11 with the inorganic active material film 14, and at least the inorganic active material film. 14 is formed by mixing the active material particles 11 coated with 14, the conductive auxiliary agent and the binder, and forming the positive electrode active material 12, so that the surface of the active material particles 11 is an inorganic active material film. 14, and in this case as well, it is possible to suppress the organic compound from eluting into the electrolyte and to obtain a secondary battery with good charge / discharge efficiency.

  In addition, this invention is not limited to the said embodiment, A various deformation | transformation is possible in the range which does not deviate from a summary. In the above embodiment, a liquid electrolyte solution in which an electrolyte salt is dissolved in a solvent is used as the electrolyte. However, although the ion conductivity is inferior to that of the electrolyte solution, it is also possible to use a solid electrolyte.

  Here, examples of the polymer compound used for the solid electrolyte include polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-ethylene copolymer, and vinylidene fluoride-monofluoroethylene copolymer. , Vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, and the like, acrylonitrile- Methyl methacrylate copolymer, acrylonitrile-methyl acrylate copolymer, acrylonitrile-ethyl methacrylate copolymer, acrylonitrile-ethyl acrylate copolymer, acrylonitrile-methacrylic acid copolymer, acrylonitrile -Acrylic acid copolymers, acrylonitrile-based polymers such as acrylonitrile-vinyl acetate copolymers, polyethylene oxide, ethylene oxide-propylene oxide copolymers, and polymers of these acrylates and methacrylates. be able to.

  Moreover, it is also possible to use only those polymer compounds containing an electrolyte solution contained in these polymer compounds or a polymer compound containing an electrolyte salt.

  Further, as the electrolyte, a solid electrolyte, an ionic liquid in which a cation and an anion are combined, a symmetrical glycol diether such as glymes, a chain sulfone, or the like can be used.

  Moreover, in the said embodiment, although the organic compound was used as a main body of a positive electrode active material, you may use it for a negative electrode active material.

  Further, the battery shape is not particularly limited, and can be applied to a coin type, a cylindrical type, a square type, a sheet type, and the like. Also, the exterior method is not particularly limited, and a metal case, mold resin, aluminum laminate film, or the like may be used.

  Next, examples of the present invention will be specifically described.

  In addition, the Example shown below is an example and this invention is not limited to the following Example.

[Production of battery cells]
Rubeanic acid represented by the chemical formula (1a) was prepared as an organic compound that is the main component of the active material substrate.

  Then, rubeanic acid: 300 mg, graphite powder as a conductive agent: 600 mg, and polytetrafluoroethylene resin as a binder: 100 mg were weighed and kneaded while mixing so as to obtain a uniform mixture. It was.

  Next, this mixture was coated on an aluminum foil as a positive electrode current collector and pressure-molded to produce a sheet-like member having a thickness of about 150 μm. Next, this sheet-like member was dried in a vacuum at 70 ° C. for 1 hour, and then punched into a circle having a diameter of 12 mm to form an active material substrate mainly composed of rubeanic acid on an aluminum foil.

Next, LiNiMnCoO ₂ was prepared as an inorganic active material. Then, a predetermined amount of this LiNiMnCoO ₂ was weighed and pulverized, and the pulverized product was mixed with pure water together with a binder, thereby preparing an inorganic active material slurry. Here, polyacrylic acid was used as the binder.

  And the inorganic active material slurry was apply | coated to the outer surface of the said active material base | substrate so that a film thickness might be set to 10 micrometers, Then, it vacuum-dried at 100 degreeC, and the positive electrode was obtained by this.

Then, the molar concentration of LiPF ₆ (electrolyte salt) such that 1.0 mol / L, dissolved LiPF ₆ in ethylene carbonate / diethyl carbonate is an organic solvent, thereby to prepare an electrolyte solution. The mixing ratio of ethylene carbonate and diethyl carbonate was ethylene carbonate: diethyl carbonate = 30: 70 in volume%.

  Next, a 20 μm-thick separator made of a polypropylene porous film impregnated with this electrolyte solution is laminated on the positive electrode, and a negative electrode in which lithium is pasted on a negative electrode current collector made of copper foil is laminated on the separator. Formed body.

  And 0.2 mL of this electrolyte solution was dripped at the said laminated body, and it was made to impregnate.

  After that, a metal spring is placed on the negative electrode current collector, and the negative electrode case is joined to the positive electrode case with a gasket disposed on the periphery, and the outer battery is sealed with a caulking machine, thereby Produced.

  Moreover, the battery cell of the comparative example was produced by the method and procedure similar to the said Example except not having coat | covered the active material base | substrate with the inorganic active material layer.

[Battery cell operation check]
The battery cells of Examples and Comparative Examples produced as described above were charged with a constant current of 0.1 mA for 3 hours, and then discharged until the voltage dropped to 1.5 V with a constant current of 0.1 mA. The charge / discharge characteristics were examined.

  FIG. 3 shows the measurement results. The horizontal axis is the capacity density (Ah / kg), the vertical axis is the voltage (V), the solid line shows the charge / discharge curve of the example, and the broken line shows the charge / discharge curve of the comparative example.

  As is clear from FIG. 3, in the comparative example, the voltage flat portion is not formed during charging and discharging, the capacity density is about 70 Ah / kg during charging, and when discharging, the voltage is It decreased rapidly, and the capacity density decreased to 56 Ah / kg.

  On the other hand, in the embodiment, a voltage flat portion is formed at about 2.3 V during charging, the capacity density is about 210 Ah / kg, a voltage flat portion is formed at about 2 V during discharging, and the discharge ends. At a voltage of 5 V, the capacity density was 168 Ah / kg, and a large capacity density could be secured. This is because the surface of the active material substrate mainly composed of rubeanic acid is coated with an inorganic active material, so that rubeanic acid does not dissolve in the electrolyte solution, and lithium ions are generated on the surface of the active material substrate with good ion conduction efficiency. This seems to be because the desired charge / discharge reaction was performed between these lithium ions and rubeanic acid.

  Even when a multi-electron organic compound is used as the main body of the active material substrate, a secondary battery is realized that has good charge / discharge efficiency and can suppress a decrease in battery capacity even after repeated charge / discharge.

2 Active material substrate 3 Inorganic active material layer (inorganic active material)
4 Positive electrode active material (electrode active material)
5 Positive electrode (first electrode)
6 Negative electrode (second electrode)
10 Electrolyte Solution 11 Active Material Particles 12 Positive Electrode Active Material (Electrode Active Material)
13 Positive electrode (first electrode)
14 Inorganic active material film (inorganic active material)

Claims (11)

An electrolyte is interposed between the first electrode and the second electrode, and the secondary battery includes lithium in at least one of the first and second electrodes and the electrolyte,
One of the first and second electrodes has an electrode active material mainly composed of a multi-electron organic compound in which two or more electrons are involved in the battery electrode reaction,
The electrode active material is coated with an inorganic active material on at least one of the surface of the active material substrate containing the organic compound and the particle surface of the organic compound ,
And the said inorganic active material contains a lithium iron phosphate, The secondary battery characterized by the above-mentioned . The organic compound has at least one selected from a dithione compound having a dithione structure, a dione compound having a dione structure, and a diamine compound having a diamine structure in a structural unit. 1 Symbol placement of the secondary battery. The dithione compound has the general formula

Wherein n is an integer of 1 or more, and R ₁ and R ₂ are a substituted or unsubstituted amino group, a substituted or unsubstituted imino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylene Group, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryloxy Group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylamino group, substituted or unsubstituted thioaryl group, substituted or unsubstituted thioalkyl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted Formyl group, substituted or unsubstituted silyl group, substituted or unsubstituted cyano group, substituted or unsubstituted Unsubstituted nitro group, a substituted or unsubstituted nitroso group, a substituted or unsubstituted carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, and indicates one of the linking group comprising a combination of one or more of these, these R ₁ and R ₂ include the same case and the case where they are linked to each other to form a saturated or unsaturated ring structure. ]
The secondary battery according to claim 2 , represented by: The dithione compound has the general formula

Wherein n is an integer of 1 or more, and R ₃ and R ₅ are a substituted or unsubstituted amino group, a substituted or unsubstituted imino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylene, Group, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryloxy Group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylamino group, substituted or unsubstituted thioaryl group, substituted or unsubstituted thioalkyl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted Formyl group, substituted or unsubstituted silyl group, substituted or unsubstituted cyano group, substituted or unsubstituted Unsubstituted nitro group, a substituted or unsubstituted nitroso group, a substituted or unsubstituted carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, and indicates one of the linking group comprising a combination of one or more of these, these R ₃ and R ₅ are the same and include the case where they are linked to each other to form a saturated or unsaturated ring structure, and R ₄ represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, and It represents at least one of substituted or unsubstituted imide groups, and includes cases where the imino groups are linked to each other. ]
The secondary battery according to claim 2 , represented by: The dione compound has the general formula

[Wherein n is an integer of 1 or more, and R ₆ and R ₇ are a substituted or unsubstituted amino group, a substituted or unsubstituted imino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylene, Group, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryloxy Group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylamino group, substituted or unsubstituted thioaryl group, substituted or unsubstituted thioalkyl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted Formyl group, substituted or unsubstituted silyl group, substituted or unsubstituted cyano group, substituted or unsubstituted Unsubstituted nitro group, a substituted or unsubstituted nitroso group, a substituted or unsubstituted carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, and indicates one of the linking group comprising a combination of one or more of these, these R ₆ and R ₇ include the same case and the case where they are linked to each other to form a saturated or unsaturated ring structure. ]
The secondary battery according to claim 2 , represented by: The dione compound has the general formula

Wherein n is an integer of 1 or more, and R ₈ and R ₁₀ are a substituted or unsubstituted amino group, a substituted or unsubstituted imino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylene Group, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryloxy Group, substituted or unsubstituted arylamino group, substituted or unsubstituted alkylamino group, substituted or unsubstituted thioaryl group, substituted or unsubstituted thioalkyl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted Formyl group, substituted or unsubstituted silyl group, substituted or unsubstituted cyano group, substituted or unsubstituted Unsubstituted nitro group, a substituted or unsubstituted nitroso group, a substituted or unsubstituted carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, and indicates one of the linking group comprising a combination of one or more of these, these R ₈ and R ₁₀ are the same and include the case where they are linked to each other to form a saturated or unsaturated ring structure, and R ₉ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, and It represents at least one of substituted or unsubstituted imino groups, and includes cases where the imino groups are linked to each other. ]
The secondary battery according to claim 2 , represented by: The diamine compound has the general formula

[Wherein R ₁₁ and R ₁₂ are a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted acyl group, Substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted ester group, substituted or unsubstituted ether group, substituted or unsubstituted thioether group, substituted or unsubstituted amino group, substituted or unsubstituted amide group, From a substituted or unsubstituted sulfone group, a substituted or unsubstituted thiosulfonyl group, a substituted or unsubstituted sulfonamido group, a substituted or unsubstituted imino group, a substituted or unsubstituted azo group, and combinations of one or more of these Any one of the following linking groups is shown. X _{1 to} X ₄ are a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, Substituted or unsubstituted aryl group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted aralkyl group, substituted or unsubstituted amino group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy At least one of a group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted acyl group, and a substituted or unsubstituted acyloxy group, and these substituents Includes the case where a substituent forms a ring structure. ]
The secondary battery according to claim 2 , represented by: The electrode active material, the reaction starting material in at least the discharge reaction of the battery electrode reaction product and according to any one of claims 1 to 7, characterized in that contained in any of the intermediate product Secondary battery. According to any one of claims 1 to 8 either one of said first and said second electrode forms a positive electrode, wherein the positive electrode has the electrode active material Secondary battery. An electrolyte is interposed between the first electrode and the second electrode, and an electrode active material mainly composed of a multi-electron organic compound is contained in at least one of the first and second electrodes A method for manufacturing a secondary battery, comprising:
The active material preparation step for preparing the electrode active material includes a substrate preparation step for preparing an active material substrate containing at least the organic compound as a conductive material and a binder, and the surface of the active material substrate as an inorganic active material. And a coating step of coating with a secondary battery. An electrolyte is interposed between the first electrode and the second electrode, and an electrode active material mainly composed of a multi-electron organic compound is contained in at least one of the first and second electrodes A method for manufacturing a secondary battery, comprising:
The active material preparation step of preparing the electrode active material includes a coating step of coating the surface of the organic compound particles with an inorganic active material, an organic compound coated with at least the inorganic active material, a conductive material, and a binder. And a forming step of forming the electrode active material by mixing and forming the electrode active material.

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