JP2004179169A - Secondary battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new lithium secondary battery having high energy density, high capacity and excellent stability. <P>SOLUTION: The active material of a positive electrode layer contains the radical compound. As this radical compound, a compound having a radical on a trivalent verdazyl group or a tetravalent verdazyl group, which respectively has a radical on a nitrogen atom, or a compound having a triphenyl-verdazyl group is used. <P>COPYRIGHT: (C)2004,JPO

Description

  The present invention relates to a secondary battery having high energy density and excellent stability, and an active material used for the secondary battery.

  With the rapid market expansion of notebook personal computers, mobile phones, and the like, there is an increasing demand for small-capacity, large-capacity secondary batteries with high energy density used for these. In order to meet this demand, secondary batteries have been developed which use an alkali metal ion such as lithium ion as a charge carrier and utilize an electrochemical reaction accompanying the charge transfer. Above all, lithium ion secondary batteries are used in various electronic devices as high-capacity secondary batteries with excellent stability and high energy density.

  Such a lithium ion secondary battery uses a lithium-containing transition metal oxide for the positive electrode and carbon for the negative electrode as active materials, and performs charge / discharge using insertion and desorption reactions of lithium ions into and from these active materials. It is carried out.

  However, since this lithium ion secondary battery uses a metal oxide having a large specific gravity especially for the positive electrode, the secondary battery capacity per unit mass cannot be said to be sufficient. Attempts to develop a secondary battery have been considered. For example, US Pat. No. 4,833,048 (Patent Document 1) and Patent No. 2715778 (Patent Document 2) disclose a secondary battery using an organic compound having a disulfide bond for a positive electrode. This utilizes an electrochemical redox reaction involving the formation and dissociation of disulfide bonds as the principle of a secondary battery. Since this secondary battery is composed of an electrode material mainly composed of elements having a low specific gravity such as sulfur and carbon, it has a certain effect in terms of a high-capacity secondary battery with a high energy density, but has been dissociated. The efficiency of the recombination is low, and the stability in the charged state or the discharged state is also insufficient.

  On the other hand, as a secondary battery using an organic compound, a secondary battery using a conductive polymer as an electrode material has been proposed. This is a secondary battery based on the principle of doping and undoping of electrolyte ions with respect to a conductive polymer. The doping reaction described here is a reaction in which excitons such as charged solitons and polarons generated by oxidation or reduction of a conductive polymer are stabilized by counter ions. On the other hand, the undoping reaction corresponds to the reverse reaction, and indicates a reaction of electrochemically oxidizing or reducing exciton stabilized by a counter ion. U.S. Pat. No. 4,442,187 (Patent Document 3) discloses a secondary battery using such a conductive polymer as a material for a positive electrode or a negative electrode. This secondary battery is composed only of elements having a low specific gravity, such as carbon and nitrogen, and was expected to be developed as a high-capacity secondary battery. However, conductive polymers have the property that excitons generated by oxidation-reduction are delocalized over a wide range of π-electron conjugated systems and interact with each other. This limits the concentration of the generated excitons and limits the capacity of the secondary battery. For this reason, a secondary battery using a conductive polymer as an electrode material has a certain effect in terms of weight reduction, but is insufficient in terms of large capacity.

As described above, various secondary batteries that do not use a transition metal-containing active material have been proposed in order to realize a high-capacity secondary battery. However, a secondary battery having high energy density, high capacity and excellent stability has not yet been obtained.
U.S. Pat.No. 4,833,048 Patent No. 2715778 U.S. Pat.No. 4,442,187

  As described above, in a lithium ion secondary battery using a transition metal oxide for the positive electrode, the specific gravity of the elements is large, and thus, it has been difficult in principle to manufacture a high-capacity secondary battery that exceeds the current state. Therefore, an object of the present invention is to provide a novel secondary battery having high energy density, high capacity, and excellent stability.

  According to the present invention for solving the above problems, at least a positive electrode, a negative electrode, and a secondary battery comprising an electrolyte as a constituent element, wherein at least one active material of the positive electrode and the negative electrode contains a radical compound Wherein the radical compound is a compound having a radical on the trivalent ferdazyl group represented by the chemical formula (C1) or the tetravalent ferdazyl group represented by the chemical formula (C2), or the chemical formula (C3) or the chemical formula (C4) ), Or a compound having an aminotriazine structure represented by the general formula (C7).

(Wherein R ₆ represents a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group , An aryloxycarbonyl group, an acyl group, a carboxyl group, and an oxo radical.)
Note that the secondary battery is characterized in that the compound having an aminotriazine structure is a polymer compound having the aminotriazine structure represented by the general formula (C7) as a repeating unit.

  An object of the present invention is to provide a secondary battery using a radical compound as an electrode active material and using a novel mechanism that has not existed before. When the radical compound is composed only of a substance having a small mass such as carbon, hydrogen, or oxygen, a secondary battery having a large energy density per mass is expected to be obtained. Moreover, in the secondary battery of the present invention, since only the radical site contributes to the reaction, a secondary battery having excellent stability whose cycle characteristics do not depend on diffusion of the active material can be obtained. In the radical compound, the unreacted unreacted electrons are localized and present in the radical atom, so that the concentration of the reaction site can be increased and a high capacity secondary battery can be expected. INDUSTRIAL APPLICABILITY The present invention can be suitably applied to a secondary battery that performs charging and discharging and an active material for a secondary battery.

  The electrode active material is a material that directly contributes to an electrode reaction such as a charge reaction and a discharge reaction, and plays a central role in a secondary battery system. The active material in the present invention can be used as either a positive electrode active material or a negative electrode active material, but has a feature that its mass is smaller than that of a metal oxide-based active material. It is more preferable to use it as a positive electrode active material because of its superior energy density as compared with

  Further, from the viewpoint of stability, it is particularly preferable that, of the electrode reactions at the positive electrode, the electrode reaction at the time of discharge is an electrode reaction using a radical compound as a reactant. Moreover, if the product of this reaction is a reaction that forms a bond with the electrolyte cation, further improvement in stability is expected. Although any electrolyte cation can be used, lithium ions are particularly preferable from the viewpoint of capacity.

  The reactant in the present invention is a substance that causes a chemical reaction and is a substance that exists stably for a long time. On the other hand, a product is a substance produced as a result of a chemical reaction, and is a substance that exists stably for a long time. The present invention does not include, in the scope of the present invention, a product in which a reactant or a product is a radical compound and generates a radical only for a moment as a reaction intermediate generated in a reaction process of an electrode reaction.

By the way, from the viewpoint of statistical mechanics, it is considered that any chemical substance has an atomic species in a radical state at room temperature. However, in the present invention, it is important to have a radical concentration that can function as an active material of a secondary battery. For example, in the above-mentioned Japanese Patent No. 2715778, organic compounds such as polyaniline, polypyrrole, polyacene, polythiophene, and disulfide compounds are disclosed as electrode active materials. It is about ¹⁸ spins / g.

On the other hand, the radical compound of the present invention preferably has a radical concentration of 10 ¹⁹ spins / g or more, more preferably 10 ²¹ spins / g or more, from the viewpoint of the capacity of the secondary battery. Is more preferable.

Generally, the radical concentration can be represented by a spin concentration. That is, the spin concentration means the number of unpaired electrons (radicals) per unit weight, and is a value determined by the following method from the absorption area intensity of an electron spin resonance spectrum (hereinafter referred to as an ESR spectrum). First, a sample to be subjected to ESR spectrum measurement is ground and crushed in a mortar or the like. By this treatment, it is possible to pulverize the particles into particles having such a size that the skin effect (a phenomenon that the microwave does not pass through the inside) can be ignored. A fixed amount of the pulverized sample is filled in a quartz glass capillary having an inner diameter of 2 mm or less, desirably 1-0.5 mm, deaerated to 10 ^-5 mmHg or less, sealed, and an ESR spectrum is measured. The ESR spectrum is measured using, for example, a JEOL-JES-FR30 type ESR spectrometer. The spin concentration can be determined by integrating the obtained ESR signal twice and comparing with a calibration curve. However, in the present invention, a measuring instrument and measuring conditions are not limited as long as the method can correctly measure the spin concentration. As described above, the spin concentration of the radical compound can be evaluated by, for example, an electron spin resonance spectrum or the like. The charge state of the radical compound is preferably neutral from the viewpoint of the ease of the charge / discharge reaction. Further, considering the stability of the secondary battery, the radical compound is desired to be a stable radical compound. Here, the stable radical compound is a compound having a long radical lifetime. The longer the lifetime of the radical, the better, but this is affected by the reactivity of the radical itself and the surrounding environment such as a solvent.

  A radical is a chemical species having an unpaired electron, and a compound having this chemical species is a radical compound. Radicals are generally reactive chemical species, and are often unstable as intermediates of various reactions. These unstable radicals form bonds with peripheral substances present in the reaction system and disappear after a certain lifetime.

However, some stable radical compounds do not form a bond with surrounding substances and exist stably for a relatively long time. These compounds stabilize radicals, for example, by steric hindrance by an organic protecting group or delocalization of π electrons. The electrode active material of the present invention utilizes such a compound, and has a spin concentration measured by electron spin resonance analysis for a long time, for example, 1 second or more, usually in the range of 10 ¹⁹ to 10 ²³ spins / g. Is within.

In particular, in the present invention, a compound in which the state in which the spin concentration in the equilibrium state is 10 ²¹ spins / g or more continues for 1 second or more is called a stable radical compound.

  The radical compound in the present invention is a compound having an unpaired electron in the sense of a dangling bond, and does not include a transition metal compound having a stable unpaired electron in the inner shell.

  Generally, an electrode active material of a secondary battery takes two states, a starting state and a state oxidized or reduced by an electrode reaction. In the present invention, the active material is in either a starting state or an oxidized or reduced state. And is characterized by containing a radical compound. As a mechanism of charge and discharge, a mechanism in which a radical group in the active material is reversibly changed to a radical state and an ionic state by an electrode reaction to accumulate charges is considered, but the details are not clear. Further, the present invention is characterized in that the radical compound directly contributes to the electrode reaction at the positive electrode or the negative electrode, and thus the electrode used as the active material is not limited to either the positive electrode or the negative electrode. However, from the viewpoint of energy density, it is particularly preferable to use a radical compound as the electrode active material of the positive electrode. Further, from the viewpoint of stability, it is particularly preferable that, of the electrode reactions at the positive electrode, the electrode reaction at the time of discharge is an electrode reaction using a radical compound as a reactant. Moreover, if the reaction product forms a bond with the cation of the electrolyte salt, further improvement in stability is expected. In the present patent, these electrolyte cations are not particularly limited, but lithium ions are particularly preferable in terms of capacity.

  Examples of the radical compound in the present invention include compounds having a radical on a nitrogen atom.

The compound having a radical on a nitrogen atom is a compound containing a substituent consisting of a nitrogen atom having an unpaired electron. In general, radicals are highly reactive chemical species and often disappear with a certain lifetime due to interaction with surrounding substances.However, depending on resonance effects, steric hindrance, and solvation conditions, radicals are considered to be stable. Become. Some of these compounds having a radical on a stable nitrogen atom have a spin concentration measured by electron spin resonance analysis within a range of 10 ¹⁹ to 10 ²³ spins / g for a long time.

  As described above, according to the present invention, since a radical compound is used as a substance involved in an electrode reaction, a secondary battery having high energy density, high capacity, and excellent stability can be realized.

(Constituent material of electrode)
The following configuration is adopted in the secondary battery according to the present invention.
(i) A configuration in which a material containing a radical compound is used as an active material.
(ii) A configuration utilizing an electrode reaction using a radical compound as a reactant or product.

  The electrode reaction in the above (ii) can be a discharge reaction using a radical compound as a reactant or a discharge reaction using a radical compound as a product. An example of a discharge reaction using a radical compound as a reactant is a discharge reaction that generates a bond between a radical compound and an electrolyte cation. An example of a discharge reaction using a radical compound as a product is a discharge reaction that cleaves a bond between a radical compound and an electrolyte anion.

  Examples of the radical compound used in the present invention include a hydrazyl radical compound represented by the following chemical formula 1, a high molecular weight hydrazyl radical compound represented by the following chemical formula 2, and the like. And a polymer compound in which these compounds are present in the structure. Further, two or more radical compounds may be used in combination.

  In the present invention, a polymer compound is a collection of macromolecules, which are molecules having a large molecular weight, and has a feature that it is hardly soluble in various solvents due to a large interaction between the molecules as compared with a low molecule. I have. For this reason, when a secondary battery is formed using a polymer radical compound, elution from the electrode is suppressed and the stability is excellent. In the present invention, the radical compound as the active material needs to be on the electrode during the charge / discharge process. Therefore, it is preferable that the radical compound is hardly soluble in the basic solvent constituting the electrolytic solution. However, when a high-capacity secondary battery is formed, since the amount of the electrolyte or the electrolyte solution with respect to the active material is small, the solubility (the amount of the solute (gram) with respect to 100 g of the solvent) is almost 1 g or less. If it exists, it can be stably present on the electrode.

In the present invention, an active material comprising a radical compound is used for both the positive electrode layer and the negative electrode layer, or one of them, and when used for either one of them, the active material of the secondary battery is used for the other electrode layer. A conventionally known substance can be used. As such a material, for example, when a radical compound is used for the negative electrode layer, metal oxide particles, a disulfide compound, a conductive polymer, and the like are used for the positive electrode layer. Here, as the metal oxide, for example, lithium manganate such as LiMnO ₂ or LixMn ₂ O ₄ (0 <x <2) or lithium manganate having a spinel structure, MnO ₂ , LiCoO ₂ , LiNiO ₂ , or LixV ₂ O ₅ (0 <x <2), and the conductive polymer includes polyacetylene, polyphenylene, polyaniline, polypyrrole, and the like.

  In the present invention, these positive electrode layer materials can be used alone or in combination. Further, a conventionally known active material and a radical compound may be mixed and used as a composite active material.

  On the other hand, when a radical compound is used for the positive electrode, examples of the negative electrode layer include carbon materials such as graphite and amorphous carbon, lithium metals and lithium alloys, lithium ion storage carbon, and conductive polymers. As these shapes, for example, lithium metal is not limited to a thin film shape, and any shape such as a bulk shape, a solidified powder, a fiber shape, and a flake shape can be used.

  In the present invention, when forming an electrode layer containing a radical compound, a conductive auxiliary material or an ion conductive auxiliary material may be mixed for the purpose of reducing impedance. As these materials, as a conductive auxiliary material, graphite, carbon black, carbonaceous fine particles such as acetylene black, or a conductive polymer such as polyaniline, polypyrrole, polythiophene, polyacetylene, polyacene, and as an ion conductive auxiliary material, A gel electrolyte or a solid electrolyte is mentioned.

  In the present invention, a binder may be used to strengthen the connection between the constituent materials. As the binder, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, polytetrafluoroethylene, styrene-butadiene copolymer rubber, polypropylene, polyethylene, polyimide, etc. Resin binder.

  In the present invention, a catalyst may be used in order to perform the electrode reaction more smoothly. Examples of the catalyst include conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polyacene; basic compounds such as pyridine derivatives, pyrrolidone derivatives, benzimidazole derivatives, benzothiazole derivatives, and acridine derivatives; and metal ion complexes.

  The present invention is characterized in that at least one active material of the positive electrode and the negative electrode contains a radical compound, but the content is not particularly limited. However, since the capacity of the secondary battery is determined according to the amount of the contained radical compound, the content is preferably 1% by mass or more from the viewpoint of the effect of the invention. If the content is less than that, the effect of the present invention that the energy density is high and the capacity is high becomes unclear.

(Structure of secondary battery)
The secondary battery according to the present invention has, for example, a configuration as shown in FIG. The secondary battery shown in the figure has a configuration in which a negative electrode layer 1 and a positive electrode layer 2 are stacked via a separator 5 containing an electrolyte. In the present invention, the active material used for the negative electrode layer 1 or the positive electrode layer 2 is a radical compound.

  FIG. 2 shows a cross-sectional view of the stacked secondary battery. The structure is such that a positive electrode current collector 4, a positive electrode layer 2, a separator 5 containing an electrolyte, a negative electrode layer 1, and a negative electrode current collector 3 are sequentially stacked. In the present invention, any method of laminating the positive electrode layer and the negative electrode layer can be used, and a multilayer laminate, a combination of those laminated on both sides of a current collector, or a wound one can be used.

  As the negative electrode current collector 3 and the positive electrode current collector 4, a metal foil such as nickel, aluminum, copper, gold, silver, an aluminum alloy, stainless steel, a metal flat plate, a mesh electrode, a carbon electrode, or the like can be used. Further, the current collector may have a catalytic effect, or the active material and the current collector may be chemically bonded. On the other hand, a separator or a nonwoven fabric made of a porous film can be used so that the above-described positive electrode and negative electrode do not come into contact with each other.

The electrolyte contained in the separator 5 transports charge carriers between the two electrodes of the negative electrode layer 1 and the positive electrode layer 2 and generally has an electrolyte ion conductivity of 10 ^-5 to 10 ^-1 S / cm at room temperature. ing. In the present invention, for example, an electrolyte in which an electrolyte salt is dissolved in a solvent can be used as the electrolyte. Examples of such a solvent include organic solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, tetrahydrofuran, dioxolan, sulfolane, dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone. Solvents. In the present invention, these solvents may be used alone or in combination of two or more. Examples of the electrolyte salt include LiPF ₆ , LiClO ₄ , LiBF ₄ , LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , and LiC (CF ₃ SO ₂ ) _3. , LiC (C ₂ F ₅ SO ₂ ) _{3 and the} like.

  Further, a solid electrolyte may be used as the electrolyte. Examples of the polymer substance used for these solid electrolytes include polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-ethylene copolymer, vinylidene fluoride-monofluoroethylene copolymer, and vinylidene fluoride. -Vinylidene fluoride polymers such as trifluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, and acrylonitrile-methyl methacrylate copolymer. Polymer, acrylonitrile-methyl acrylate copolymer, acrylonitrile-ethyl methacrylate copolymer, acrylonitrile-ethyl acrylate copolymer, acrylonitrile-methacrylic acid copolymer, acrylonitrile-acryl Acid copolymers, acrylonitrile - vinyl acetate copolymer, acrylonitrile-based polymer, further polyethylene oxide, ethylene oxide - propylene oxide copolymers, and polymers of these acrylates body or methacrylate body thereof. A gel obtained by adding an electrolytic solution to such a polymer substance can be used, or only the polymer substance may be used as it is.

  A conventionally known method can be used for the shape of the secondary battery in the present invention. Examples of the shape of the secondary battery include those in which an electrode laminate or a wound body is sealed with a metal case, a resin case, or a laminate film made of a metal foil such as an aluminum foil and a synthetic resin film. Examples of the external appearance include a cylindrical type, a square type, a coin type, and a sheet type, but the present invention is not limited to these.

  A conventionally known method can be used as a method for manufacturing a secondary battery in the present invention. For example, a slurry is prepared by adding a solvent to the active material, and the slurry is applied to the electrode current collector. It is a method of stopping. When manufacturing a secondary battery, there are a case where a secondary battery is manufactured using a radical compound itself and a case where a secondary battery is manufactured using a compound which is converted into a radical compound by a secondary battery reaction. Examples of the compound which is converted into a radical compound by the secondary battery reaction include a lithium salt and a sodium salt of an anion obtained by reducing the radical compound. In the present invention, a secondary battery may be manufactured using a compound that changes to a radical compound as a result of the secondary battery reaction as described above.

(Compound having a radical on a nitrogen atom)
The compound having a radical on a nitrogen atom used as the active material of the present invention has a radical on a nitrogen atom in the molecular structure. For example, a compound having a radical on an amino group described in Osamu Shimamura et al., "Free Radical Reaction", pp. 24-34 (Tokyo Kagaku Dojin, 1964), ferdazil represented by the chemical formula (C8) A compound having a radical on the group,

  Polymer compounds described in Shin Ogawara, "Chemical Reaction of Polymers", pp. 340-346 (Kagaku Dojin, 1972).

  More specifically, a lophine derivative represented by the chemical formula (C10), a tetraphenylpyrrole derivative represented by the chemical formula (C11), a phenothiazine derivative represented by the chemical formula (C12), and a 2 represented by the chemical formula (C13) , 2-Diphenyl-1-picrylhydrazyl, 1,1,5,5-tetraphenyl-1,2,4,5-tetraaza-2-pentene derivative represented by the chemical formula (C14), chemical formula (C15) And a compound having a triphenylferdazyl group represented by chemical formulas (C16) and (17), and a compound represented by chemical formulas (C18) to (25). Examples include a polymer compound having a phenylferdazyl group and a polymer compound having an aminotriazine structure represented by chemical formulas (C26) to (28).

(In each of the above formulas, n represents 1 to 8.)
In the present invention, the molecular weight of the compound having a radical on a nitrogen atom is not particularly limited, and a low molecular compound to a high molecular compound can be used as needed. Since a polymer compound generally has lower solubility in an electrolytic solution than a low molecular compound, a decrease in capacity due to dissolution in the electrolytic solution is small. Examples of the high molecular compound include compounds having the structures shown in Chemical Formulas C18 to C28, and C31 and C32. In addition, a high molecular compound having a polyolefin structure, polyacetylene, polyphenylene structure, or aromatic five-membered heterocyclic structure can be used. Further, the polymer compound may have a three-dimensional network structure. In the secondary battery of the present invention, the compound having a radical on a nitrogen atom, which is an active material, may be in a solid state, or may be in a state of being dissolved or dispersed in an electrolyte. However, when it is used in a solid state, it is preferably insoluble or lowly soluble in the electrolytic solution, since the capacity is less reduced by dissolution in the electrolytic solution. In the secondary battery of the present invention, the compound having a radical on a nitrogen atom, which is an active material, is usually used alone, but two or more kinds may be used in combination. Further, it may be used in combination with another active material.

Hereinafter, the present invention will be described specifically with reference to examples.
First, the compounds used in Experimental Examples 1 to 5 are shown below.

Experimental example 1
An ethylene carbonate / propylene carbonate mixed solution containing 1 mol / l of LiPF ₆ electrolyte salt in 60 mg of vinylidene fluoride-hexafluoropropylene copolymer in a dry box equipped with a gas purifier under an argon gas atmosphere (mixing ratio 1: 1) ) Was mixed, and 1130 mg of tetrahydrofuran was added and dissolved at room temperature to prepare a gel electrolyte tetrahydrofuran solution.

  Then, in a glass container, 30 mg of 2,2,6,6-tetramethylpiperidoxyl radical (TEMPO radical) having one of the nitroxyl radical compounds having the molecular structure represented by the above-mentioned chemical formula 1 as a radical compound is placed in a glass container. Then, 60 mg of graphite powder was mixed as a conductive auxiliary material, and 200 mg of the above-mentioned gel electrolyte tetrahydrofuran solution was added and mixed as an ion conductive auxiliary material. Thereafter, 1000 mg of tetrahydrofuran was added and further mixed until the whole became uniform, whereby a black slurry was obtained. 200 mg of the obtained slurry was dropped on the surface of an aluminum foil (area: 1.5 cm × 1.5 cm, thickness: 100 μm) provided with a lead wire, and the whole was developed with a wire bar so as to have a uniform thickness. After standing at room temperature for 60 minutes, the solvent, tetrahydrofuran, vaporized, and a layer of an organic compound containing TEMPO radicals was formed on the aluminum foil.

A part of the coating film was taken and pulverized, and an electron spin resonance spectrum was measured. The spin concentration was measured using a JEOL-JES-FR30 type ESR spectrometer in the range of 335.9 mT ± 5 mT under the conditions of a microwave output of 4 mW, a modulation frequency of 100 kHz, and a modulation width of 79 μT. The absorption area intensity was determined by integrating the first-order differential ESR spectrum obtained by the above method twice, and the spin concentration was measured by comparing with the absorption area intensity of a known sample measured under the same conditions. As a result, the spin concentration was 10 ²¹ spins / g or more, and it was found that radicals were formed in the initial state.

Next, 600 mg of a vinylidene fluoride-hexafluoropropylene copolymer was mixed with 1400 mg of an electrolytic solution composed of a mixed solution of ethylene carbonate and propylene carbonate containing 1 mol / l of LiPF ₆ (mixing ratio 1: 1), and 11.3 g of tetrahydrofuran was added. In addition, the mixture was stirred at room temperature. After the vinylidene fluoride-hexafluoropropylene copolymer was dissolved, it was applied on a stepped glass plate so as to have a thickness of 1 mm. The mixture was allowed to stand for 1 hour, and the solvent tetrahydrofuran was air-dried, whereby a gel electrolyte membrane having a thickness of 150 μm was obtained on a glass plate.

  Next, a gel electrolyte membrane cut into 2.0 cm × 2.0 cm was laminated on the aluminum foil on which the layer of the organic compound containing the TEMPO radical was formed, and a lithium-bonded copper foil (lithium film thickness) provided with a lead wire was further provided. 30 μm and a copper foil thickness of 20 μm) were overlaid. The whole was sandwiched between polytetrafluoroethylene sheets having a thickness of 5 mm, and pressure was applied to produce a secondary battery.

The secondary battery prepared as described above was discharged at a constant current of 0.1 mA using an aluminum foil on which an organic compound layer containing a TEMPO radical was formed as a positive electrode and a lithium-bonded copper foil as a negative electrode. The results are shown in FIG. 3, where a voltage flat portion was observed at around 2.3 V, indicating that the battery operated as a secondary battery. A part of the layer of the compound containing the TEMPO radical was cut out from the sample after the discharge, and the electron spin resonance spectrum was measured by the method described above. As a result, the spin concentration was 10 ¹⁹ spins / g or less. From this, it was considered that the TEMPO radical formed a bond with lithium ions in the state where the discharge was completed, and the radical effective for the secondary battery reaction disappeared.

  Further, a secondary battery was manufactured in the same manner, and a change in voltage due to charge and discharge was measured. FIG. 4 shows the result of repeating the charge / discharge cycle 10 times. Even after repeated charge and discharge, a flat portion was observed in the discharge curve, indicating that the secondary battery also operated.

  Among the nitroxyl radical compounds, a secondary battery was prepared using a compound represented by Chemical Formulas 2 and 3 and a polymer compound represented by Chemical Formulas 4 to 6 instead of the TEMPO radical used in Experimental Example 1. However, the operation as a secondary battery was confirmed as in Experimental Example 1.

Comparative Example 1
Except that the TEMPO radical was not contained in the glass container of Experimental Example 1, a conductive auxiliary material, an ion conductive auxiliary material, a mixed solution of ethylene carbonate / propylene carbonate, and tetrahydrofuran were added and mixed. A slurry was obtained. Thereafter, a layer of a compound containing no TEMPO radical was formed on the aluminum foil in the same manner as in Experimental Example 1. An electron spin resonance spectrum of a portion of this layer was measured by the method of Experimental Example 1, and it was found that the spin concentration was 10 ¹⁹ spins / g or less and the radical concentration was low.

  Next, the gel electrolyte membrane of Experimental Example 1 was laminated on the aluminum foil on which the layer of the compound containing no TEMPO radical was formed, and the lithium-bonded copper foil of Experimental Example 1 was further laminated. Finally, as in Experimental Example 1, the whole was sandwiched between polytetrafluoroethylene sheets, and pressure was applied to complete the secondary battery.

  The secondary battery prepared as described above was discharged at a constant current of 0.1 mA using an aluminum foil having a compound layer containing no TEMPO radical as a positive electrode and a lithium-bonded copper foil as a negative electrode. The results are shown in FIG. 3, but did not show the behavior as a secondary battery. When charging was performed with a constant current of 0.1 mA, the voltage instantaneously increased to exceed 3.0 V, and no flat portion was observed in the voltage curve even when the battery was discharged again. From this, it was found that this battery configuration did not operate as a secondary battery.

Experimental example 2
In the glass container of Experimental Example 1, a phenoxyl radical compound was used instead of the TEMPO radical, and a galvinoxyl radical having a molecular structure represented by Chemical Formula 7 was used. An auxiliary material, an ion conductive auxiliary material, a mixed solution of ethylene carbonate / propylene carbonate, and tetrahydrofuran were added and mixed to obtain a black slurry. Thereafter, a layer of a compound containing a galvinoxyl radical was formed on the aluminum foil in the same manner as in Experimental Example 1. A part of this layer was cut out, and the electron spin resonance spectrum was measured by the method of Experimental Example 1. The spin concentration was 10 ²¹ spins / g or more, and it was found that radicals were formed in the initial state.

  Next, the gel electrolyte membrane of Experimental Example 1 and a lithium-bonded copper foil were sequentially laminated on the aluminum foil on which the layer of the compound containing a galvinoxyl radical was formed. Finally, the whole was sandwiched between polytetrafluoroethylene sheets as in Experimental Example 1, and pressure was applied to form a secondary battery.

The secondary battery prepared as described above was discharged at a constant current of 0.1 mA using an aluminum foil on which a layer of a compound containing a galvinoxyl radical was formed as a positive electrode and a lithium-bonded copper foil as a negative electrode. The results are shown in FIG. 3, where flat portions were observed at around 2.3 V, 2.0 V, and 1.5 V, indicating that the secondary battery was operating. A layer of a compound containing a galvinoxyl radical was partially cut from the sample after the discharge, and the electron spin resonance spectrum was measured by the method of Experimental Example 1. The spin concentration was 10 ¹⁹ spins / g or less. From this, it is considered that the galvinoxyl radical forms a bond with lithium ion in a state where the discharge is completed, and the radical effective for the secondary battery reaction has disappeared.

  Further, a change in battery voltage due to charging and discharging was measured in the same manner as in Experimental Example 1. As a result, it was found that the battery can be repeatedly charged and discharged and also operates as a secondary battery.

  Among the phenoxyl radical compounds, a secondary battery was manufactured using a compound represented by Formula 8 and a polymer compound represented by Formula 9 and Formula 10 in place of the galvinoxyl radical used in Experimental Example 2. However, the operation as a secondary battery was confirmed as in Experimental Example 2.

Experimental Example 3 [including Example 1 (example using the compound represented by Chemical Formula 12) and Example 2 (example using the compound represented by Chemical Formula 14)]
Instead of the TEMPO radical in the glass container of Experimental Example 1, one of the hydrazyl radical compounds, 2,2-diphenyl-1-picrylhydrazyl radical (DPPH radical) having the molecular structure represented by the above-mentioned chemical formula 11 Was used in the same manner as in Experimental Example 1 except that a conductive auxiliary material, an ion conductive auxiliary material, a mixed solution of ethylene carbonate / propylene carbonate, and tetrahydrofuran were added and mixed to obtain a black slurry.

Thereafter, a layer of a compound containing DPPH radicals was formed on the aluminum foil in the same manner as in Experimental Example 1. A part of this layer was cut out, and the electron spin resonance spectrum was measured by the method of Experimental Example 1. The spin concentration was 10 ²¹ spins / g or more, and it was found that radicals were formed in the initial state.

  Next, the gel electrolyte of Experimental Example 1 and a lithium-bonded copper foil were sequentially laminated on the aluminum foil on which the layer of the compound containing the DPPH radical was formed. Finally, the whole was sandwiched between polytetrafluoroethylene sheets as in Experimental Example 1, and pressure was applied to form a secondary battery.

The secondary battery prepared as described above was discharged at a constant current of 0.1 mA using a copper foil on which a layer of a compound containing DPPH radicals was formed as a positive electrode and a lithium-bonded copper foil as a negative electrode. The results are shown in FIG. 3, where flat portions were observed at around 3.1 V and 2.5 V, indicating that the secondary battery was operating. A part of the compound layer containing the DPPH radical was cut out from the sample after the discharge, and the electron spin resonance spectrum was measured by the method of Experimental Example 1. As a result, the spin concentration was 10 ¹⁹ spins / g or less. From this, it is considered that the DPPH radical forms a bond with lithium ion after the discharge is completed, and the radical effective for the secondary battery reaction has disappeared.

  Further, a change in battery voltage due to charging and discharging was measured in the same manner as in Experimental Example 1. As a result, it was found that the battery can be repeatedly charged and discharged and also operates as a secondary battery.

  Among the hydrazyl radical compounds, instead of the DPPH radical used in Experimental Example 3, a compound represented by Chemical Formula 12 (Example 1) and Chemical Formula 13 and a compound represented by Chemical Formula 14 (Example 2) and Chemical Formula 15 are used. Even when a secondary battery was manufactured using a molecular compound, the operation as a secondary battery was confirmed as in Experimental Example 3.

Experimental example 4
In the same manner as in Experimental Example 1, except that lithium-2,4,6-tritert-butylphenoxide having a molecular structure represented by the above-mentioned chemical formula 16 was used in the glass container of Experimental Example 1 instead of the TEMPO radical, An auxiliary material, an ion conductive auxiliary material, a mixed solution of ethylene carbonate / propylene carbonate, and tetrahydrofuran were added and mixed to obtain a black slurry. Thereafter, a layer of a compound containing lithium-2,4,6-tri-tert-butylphenoxide was formed on the aluminum foil in the same manner as in Experimental Example 1. A part of this layer was cut out, and the electron spin resonance spectrum was measured by the method of Experimental Example 1. As a result, it was found that the spin concentration was 10 ¹⁹ spins / g or less, and no radical was present in the initial state.

  Next, the gel electrolyte of Experimental Example 1 and a lithium-bonded copper foil were sequentially laminated on the aluminum foil on which the layer of the compound containing lithium-2,4,6-tritertiarybutylphenoxide was formed. Finally, the whole was sandwiched between polytetrafluoroethylene sheets as in Experimental Example 1, and pressure was applied to form a secondary battery.

For the secondary battery prepared as described above, a copper foil having a compound layer containing lithium-2,4,6-tritertiarybutylphenoxide formed thereon was used as a positive electrode, and a lithium-bonded copper foil was used as a negative electrode. The battery was charged at a constant current. When the battery voltage reached 3 V, the voltage was kept constant, and charging was terminated when the current value reached 0.01 mA. After an interval of 5 minutes, discharge was started again, and a discharge curve was obtained. As a result, a flat portion was observed around 2.3 V, indicating that the battery was operating as a secondary battery. Further, a layer of the compound containing lithium-2,4,6-tritertiarybutylphenoxide was partly cut from the sample immediately after charging, and the electron spin resonance spectrum was measured by the method of Experimental Example 1. Was 10 ²¹ spins / g or more. From this, it was considered that lithium-2,4,6-tri-tert-butylphenoxide changed to a state of 2,4,6-tri-tert-butylphenoxyl radical after charging was completed.

  Further, a change in battery voltage due to charging and discharging was measured in the same manner as in Experimental Example 1. As a result, it was found that the battery can be repeatedly charged and discharged and also operates as a secondary battery.

Experimental example 5
A compound layer containing lithium-2,4,6-tritertiarybutylphenoxide was formed on an aluminum foil in the same manner as in Experimental Example 4. A part of this layer was cut out and the electron spin resonance spectrum was measured by the method of Experimental Example 1. As a result, it was found that the spin concentration was 10 ¹⁹ spins / g or less, and the radical concentration was small in the initial state.

  Next, a slurry in which polyvinylidene fluoride, N-methyl-2-pyrrolidone, petroleum petroleum coke, and acetylene black were mixed at a weight ratio of 1: 30: 20: 1 was cast on a copper foil having a thickness of 20 μm, and a wire was cast. It was molded uniformly using a bar. After vacuum drying at 100 ° C. for 2 hours, it was cut into a size of 1.5 cm × 1.5 cm to obtain an electrode layer containing powdered petroleum coke.

  The gel electrolyte of Experimental Example 4 and the electrode layer containing powdered petroleum coke were sequentially laminated on the aluminum foil on which the layer of the compound containing lithium-2,4,6-tritertiarybutylphenoxide was formed. Finally, the whole was sandwiched between polytetrafluoroethylene sheets as in Experimental Example 1, and pressure was applied to form a secondary battery.

For the secondary battery prepared as described above, a copper foil on which a layer of a compound containing lithium-2,4,6-tritertiarybutylphenoxide was formed was used as a positive electrode, and a copper foil on which a layer of powdered petroleum coke was formed. The negative electrode was charged at a constant current of 0.1 mA. When the battery voltage reached 3 V, the voltage was kept constant, and charging was terminated when the current value reached 0.01 mA. After an interval of 5 minutes, discharge was started and a discharge curve was obtained. As a result, a flat portion was observed at around 2.0 V, indicating that the battery was operating as a secondary battery. Further, a layer of the compound containing lithium-2,4,6-tritertiarybutylphenoxide was partly cut from the sample immediately after charging, and the electron spin resonance spectrum was measured by the method of Experimental Example 1. Was 10 ²¹ spins / g or more. From this, it was considered that lithium-2,4,6-tri-tert-butylphenoxide changed to a state of 2,4,6-tri-tert-butylphenoxyl radical after charging was completed. Further, a change in battery voltage due to charging and discharging was measured in the same manner as in Experimental Example 1. As a result, it was found that the battery can be repeatedly charged and discharged and also operates as a secondary battery.

Experimental example 6
2,2,6,6-tetramethylpiperidinoxyl radical (TEMPOα radical) having the molecular structure represented by the chemical formula (A26) in a glass container under an argon gas atmosphere in a dry box equipped with a gas purification device. The mixture was mixed with 60 mg of graphite powder as an auxiliary conductive material, 20 mg of vinylidene fluoride-hexafluoropropylene copolymer and 1 g of tetrahydrofuran were added, and the mixture was further mixed for several minutes until the whole became uniform. Was obtained. When the electron spin resonance spectrum was measured by the method of Experimental Example 1 using the TEMPOα radical used as a sample, the spin concentration was 10 ²¹ spins / g or more.

  200 mg of the slurry obtained as described above is dropped onto the surface of an aluminum foil (area: 1.5 cm × 1.5 cm, thickness: 100 μm) provided with a lead wire, and the entire thickness is made uniform with a wire bar. Expanded to. When this was allowed to stand at room temperature for 60 minutes, the solvent, tetrahydrofuran, evaporated, and a layer containing TEMPOα radical was formed on the aluminum foil.

Next, 600 mg of a vinylidene fluoride-hexafluoropropylene copolymer was mixed with 1400 mg of an electrolytic solution composed of an ethylene carbonate / propylene carbonate mixed solution (mixing ratio 1: 1) containing 1 mol / l of LiPF ₆ as an electrolyte salt. Then, 11.3 g of tetrahydrofuran was added, and the mixture was stirred at room temperature. After the vinylidene fluoride-hexafluoropropylene copolymer was dissolved, it was coated on a stepped glass plate, allowed to stand at room temperature for 1 hour, and tetrahydrofuran was naturally dried to obtain a cast film having a thickness of 1 mm. .

  Next, a gel electrolyte membrane cut into 2.0 cm × 2.0 cm was laminated on the aluminum foil on which the electrode layer containing the TEMPOα radical was formed, and a lithium-bonded copper foil with a lead wire (lithium film thickness) 30 μm and a copper foil thickness of 20 μm) were overlaid. Thereafter, the whole was sandwiched between polytetrafluoroethylene sheets having a thickness of 5 mm, and pressure was applied to form a secondary battery.

  When the secondary battery prepared as described above was used as a sample and the electrode layer containing TEMPOα radical was used as a positive electrode and the lithium-bonded copper foil was used as a negative electrode and discharged at a constant current of 0.1 mA, operation as a secondary battery was confirmed. Was. Further, when the secondary battery was repeatedly charged and discharged, it was found that the secondary battery operated as a rechargeable battery capable of charging and discharging over 10 cycles or more.

Experimental example 7
Under an argon gas atmosphere in a dry box equipped with a gas purification device, 50 mg of dibutyl nitroxyl radical (DBNO radical) having the molecular structure represented by the chemical formula (A12) was placed in a glass container, and graphite powder 60 was used as an auxiliary conductive material. Then, 20 mg of the vinylidene fluoride-hexafluoropropylene copolymer and 1 g of tetrahydrofuran were added, and the mixture was further mixed for several minutes until the whole became uniform, whereby a black slurry was obtained. When the electron spin resonance spectrum was measured by the method of Experimental Example 1 using the used DBNO radical as a sample, the spin concentration was 10 ²¹ spins / g or more.

  200 mg of the slurry obtained as described above was dropped on the surface of an aluminum foil (area: 1.5 cm × 1.5 cm, thickness: 100 μm) provided with a lead wire, and a uniform thickness was obtained using a wire bar. Expanded to. When this was allowed to stand at room temperature for 60 minutes, tetrahydrofuran as a solvent was evaporated, and a layer containing DBNO radical radicals was formed on the aluminum foil.

Next, 600 mg of a vinylidene fluoride-hexafluoropropylene copolymer was mixed with 1400 mg of an electrolytic solution composed of an ethylene carbonate / propylene carbonate mixed solution (mixing ratio 1: 1) containing 1 mol / l of LiPF ₆ as an electrolyte salt. Then, 11.3 g of tetrahydrofuran was added, and the mixture was stirred at room temperature. After the vinylidene fluoride-hexafluoropropylene copolymer was dissolved, it was coated on a stepped glass plate, allowed to stand at room temperature for 1 hour, and tetrahydrofuran was naturally dried to obtain a cast film having a thickness of 1 mm. .

  Next, a gel electrolyte membrane cut into 2.0 cm × 2.0 cm was laminated on the aluminum foil on which the electrode layer containing DBNO radicals was formed, and a lithium-bonded copper foil (lithium film thickness) with a lead wire was further provided. 30 μm and a copper foil thickness of 20 μm) were overlaid. Thereafter, the whole was sandwiched between polytetrafluoroethylene sheets having a thickness of 5 mm, and pressure was applied to form a secondary battery.

  Using the secondary battery prepared as described above as a sample, discharging with a constant current of 0.1 mA using the electrode layer containing DBNO radicals as a positive electrode and the lithium-bonded copper foil as a negative electrode, the operation as a secondary battery was confirmed. Was. Further, when the secondary battery was repeatedly charged and discharged, it was found that the secondary battery operated as a rechargeable battery capable of charging and discharging over 10 cycles or more.

Experimental example 8
Under an argon gas atmosphere in a dry box equipped with a gas purification device, 50 mg of diphenylnitroxyl radical (DPNO radical) having a molecular structure represented by the chemical formula (A21) was placed in a glass container, and graphite powder 60 was used as an auxiliary conductive material. Then, 20 mg of the vinylidene fluoride-hexafluoropropylene copolymer and 1 g of tetrahydrofuran were added, and the mixture was further mixed for several minutes until the whole became uniform, whereby a black slurry was obtained. When the electron spin resonance spectrum was measured by the method of Experimental Example 1 using the DPNO radical used as a sample, the spin concentration was 10 ²¹ spins / g or more.

  200 mg of the slurry obtained as described above was dropped on the surface of an aluminum foil (area: 1.5 cm × 1.5 cm, thickness: 100 μm) provided with a lead wire, and a uniform thickness was obtained using a wire bar. Expanded to. When this was left as it was at room temperature for 60 minutes, the solvent, tetrahydrofuran, was evaporated, and a layer containing BPNO radicals was formed on the aluminum foil.

Next, 600 mg of a vinylidene fluoride-hexafluoropropylene copolymer was mixed with 1400 mg of an electrolytic solution composed of an ethylene carbonate / propylene carbonate mixed solution (mixing ratio 1: 1) containing 1 mol / l of LiPF ₆ as an electrolyte salt. Then, 11.3 g of tetrahydrofuran was added, and the mixture was stirred at room temperature. After the vinylidene fluoride-hexafluoropropylene copolymer was dissolved, it was coated on a stepped glass plate, allowed to stand at room temperature for 1 hour, and tetrahydrofuran was naturally dried to obtain a cast film having a thickness of 1 mm. .

  Next, a gel electrolyte membrane cut to 2.0 cm × 2.0 cm was laminated on the aluminum foil on which the electrode layer containing DPNO radicals was formed, and a lithium-bonded copper foil (lithium film thickness) with lead wires was further provided. 30 μm and a copper foil thickness of 20 μm) were overlaid. Thereafter, the whole was sandwiched between polytetrafluoroethylene sheets having a thickness of 5 mm, and pressure was applied to form a secondary battery.

  When the secondary battery prepared as described above was used as a sample and the electrode layer containing DPNO radicals was used as a positive electrode and the lithium-bonded copper foil was used as a negative electrode and discharged at a constant current of 0.1 mA, operation as a secondary battery was confirmed. Was. Further, when the secondary battery was repeatedly charged and discharged, it was found that the secondary battery operated as a rechargeable battery capable of charging and discharging over 10 cycles or more.

Experimental example 9
In a dry box equipped with a gas purifier, a 3-amino-2,2,6,6-tetramethylpyrrolidinoxyl radical (TEMPOβ) having a molecular structure represented by the chemical formula (A33) is placed in a glass container under an argon gas atmosphere. 50 mg of radical), 60 mg of graphite powder as an auxiliary conductive material was mixed, 20 mg of vinylidene fluoride-hexafluoropropylene copolymer and 1 g of tetrahydrofuran were added, and the mixture was further mixed for several minutes until the whole became uniform. However, a black slurry was obtained. When the electron spin resonance spectrum was measured by the method of Experimental Example 1 using the used radical as a sample, the spin concentration was 10 ²¹ spins / g or more.

  200 mg of the slurry obtained as described above was dropped on the surface of an aluminum foil (area: 1.5 cm × 1.5 cm, thickness: 100 μm) provided with a lead wire, and a uniform thickness was obtained using a wire bar. Expanded to. When this was allowed to stand at room temperature for 60 minutes, the solvent tetrahydrofuran was evaporated, and a layer containing TEMPOβ radical radical was formed on the aluminum foil.

Next, 600 mg of a vinylidene fluoride-hexafluoropropylene copolymer was mixed with 1400 mg of an electrolytic solution composed of an ethylene carbonate / propylene carbonate mixed solution (mixing ratio 1: 1) containing 1 mol / l of LiPF ₆ as an electrolyte salt. Then, 11.3 g of tetrahydrofuran was added, and the mixture was stirred at room temperature. After the vinylidene fluoride-hexafluoropropylene copolymer was dissolved, it was coated on a stepped glass plate, allowed to stand at room temperature for 1 hour, and tetrahydrofuran was naturally dried to obtain a cast film having a thickness of 1 mm. .

  Next, a gel electrolyte membrane cut into 2.0 cm × 2.0 cm was laminated on the aluminum foil on which the electrode layer containing the TEMPOβ radical was formed, and a lithium-bonded copper foil with a lead wire (lithium film thickness) 30 μm and a copper foil thickness of 20 μm) were overlaid. Thereafter, the whole was sandwiched between polytetrafluoroethylene sheets having a thickness of 5 mm, and pressure was applied to form a secondary battery.

  When the secondary battery prepared as described above was used as a sample and the electrode layer containing the TEMPOβ radical was used as a positive electrode and the lithium-bonded copper foil was used as a negative electrode and discharged at a constant current of 0.1 mA, the operation as a secondary battery was confirmed. Was. Further, when the secondary battery was repeatedly charged and discharged, it was found that the secondary battery operated as a rechargeable battery capable of charging and discharging over 10 cycles or more.

Experimental example 10
Under a argon atmosphere in a dry box equipped with a gas purifier, a 3-amino-2,2,6,6-tetramethylpyrrolinoxyl radical (TEMPOγ) having a molecular structure represented by the chemical formula (A39) is placed in a glass container. 50 mg of radical), 60 mg of graphite powder as an auxiliary conductive material was mixed, 20 mg of vinylidene fluoride-hexafluoropropylene copolymer and 1 g of tetrahydrofuran were added, and the mixture was further mixed for several minutes until the whole became uniform. However, a black slurry was obtained. When the electron spin resonance spectrum was measured by the method of Experimental Example 1 using the used TEMPOγ radical as a sample, the spin concentration was 10 ²¹ spins / g or more.

  200 mg of the slurry obtained as described above was dropped on the surface of an aluminum foil (area: 1.5 cm × 1.5 cm, thickness: 100 μm) provided with a lead wire, and a uniform thickness was obtained using a wire bar. Expanded to. When this was allowed to stand at room temperature for 60 minutes, tetrahydrofuran as a solvent was evaporated, and a layer containing a TEMPOγ radical was formed on the aluminum foil.

Next, 600 mg of a vinylidene fluoride-hexafluoropropylene copolymer was mixed with 1400 mg of an electrolytic solution composed of an ethylene carbonate / propylene carbonate mixed solution (mixing ratio 1: 1) containing 1 mol / l of LiPF ₆ as an electrolyte salt. Then, 11.3 g of tetrahydrofuran was added, and the mixture was stirred at room temperature. After the vinylidene fluoride-hexafluoropropylene copolymer was dissolved, it was coated on a stepped glass plate, allowed to stand at room temperature for 1 hour, and tetrahydrofuran was naturally dried to obtain a cast film having a thickness of 1 mm. .

  Next, a gel electrolyte membrane cut into 2.0 cm × 2.0 cm was laminated on the aluminum foil on which the electrode layer containing the TEMPOγ radical was formed, and a lithium-bonded copper foil (lead film) having a lead wire was further laminated. 30 μm and a copper foil thickness of 20 μm) were overlaid. Thereafter, the whole was sandwiched between polytetrafluoroethylene sheets having a thickness of 5 mm, and pressure was applied to form a secondary battery.

  When the secondary battery prepared as described above was used as a sample and the electrode layer containing the TEMPOγ radical was used as a positive electrode and the lithium-bonded copper foil was used as a negative electrode and discharged at a constant current of 0.1 mA, operation as a secondary battery was confirmed. Was. Further, when the secondary battery was repeatedly charged and discharged, it was found that the secondary battery operated as a rechargeable battery capable of charging and discharging over 10 cycles or more.

Experimental Example 11
Under a argon atmosphere in a dry box equipped with a gas purifier, a glass container was charged with 50 mg of a nitronyl nitroxide compound (NONO) having a molecular structure represented by the chemical formula (A43), and 60 mg of graphite powder was used as an auxiliary conductive material. Were added, 20 mg of vinylidene fluoride-hexafluoropropylene copolymer and 1 g of tetrahydrofuran were added, and the mixture was further mixed for several minutes until the whole became uniform, whereby a black slurry was obtained. When the electron spin resonance spectrum was measured by the method of Experimental Example 1 using the NONO used as a sample, the spin concentration was 10 ²¹ spins / g or more.

  200 mg of the slurry obtained as described above was dropped on the surface of an aluminum foil (area: 1.5 cm × 1.5 cm, thickness: 100 μm) provided with a lead wire, and a uniform thickness was obtained using a wire bar. Expanded to. When this was left as it was at room temperature for 60 minutes, the solvent tetrahydrofuran was evaporated, and a layer containing NONO was formed on the aluminum foil.

Next, 600 mg of a vinylidene fluoride-hexafluoropropylene copolymer was mixed with 1400 mg of an electrolytic solution composed of an ethylene carbonate / propylene carbonate mixed solution (mixing ratio 1: 1) containing 1 mol / l of LiPF ₆ as an electrolyte salt. Then, 11.3 g of tetrahydrofuran was added, and the mixture was stirred at room temperature. After the vinylidene fluoride-hexafluoropropylene copolymer was dissolved, it was coated on a stepped glass plate, allowed to stand at room temperature for 1 hour, and tetrahydrofuran was naturally dried to obtain a cast film having a thickness of 1 mm. .

  Next, a gel electrolyte membrane cut to 2.0 cm × 2.0 cm was laminated on the aluminum foil on which the electrode layer containing NONO was formed, and a lithium-bonded copper foil with a lead wire (lithium film thickness: 30 μm) , A copper foil thickness of 20 μm). Thereafter, the whole was sandwiched between polytetrafluoroethylene sheets having a thickness of 5 mm, and pressure was applied to form a secondary battery.

  When the secondary battery prepared as described above was used as a sample and the electrode layer containing NONO was used as a positive electrode and the lithium-bonded copper foil was used as a negative electrode and discharged at a constant current of 0.1 mA, operation as a secondary battery was confirmed. . Further, when the secondary battery was repeatedly charged and discharged, it was found that the secondary battery operated as a rechargeable battery capable of charging and discharging over 10 cycles or more.

Experimental Example 12
In a dry box equipped with a gas purifier, 50 mg of galvinoxyl having a molecular structure represented by the chemical formula B5 was placed in a glass container under an argon gas atmosphere, and 60 mg of graphite powder was mixed as an auxiliary conductive material. When 20 mg of hexafluoropropylene copolymer and 1 g of tetrahydrofuran were added and mixed for several minutes until the whole became uniform, a black slurry was obtained. When the electron spin resonance spectrum was measured using the galvinoxyl used as a sample by the method of Experimental Example 1, the spin concentration was 10 ²¹ spins / g or more, and it was found that the structure had an oxy radical shown in Chemical Formula 5 in the initial state. all right.

  200 mg of the slurry obtained as described above was dropped on the surface of an aluminum foil (area: 1.5 cm × 1.5 cm, thickness: 100 μm) provided with a lead wire, and the whole was made to have a uniform thickness with a wire bar. Expanded to. When this was left as it was at room temperature for 60 minutes, tetrahydrofuran as a solvent was evaporated, and a layer containing galvinoxyl radical was formed on the aluminum foil.

Next, 600 mg of a vinylidene fluoride-hexafluoropropylene copolymer was mixed with 1400 mg of an electrolytic solution composed of an ethylene carbonate / propylene carbonate mixed solution (mixing ratio 1: 1) containing 1 mol / l of LiPF ₆ as an electrolyte salt. Then, 11.3 g of tetrahydrofuran was added, and the mixture was stirred at room temperature. After the vinylidene fluoride-hexafluoropropylene copolymer was dissolved, it was coated on a stepped glass plate, allowed to stand at room temperature for 1 hour, and tetrahydrofuran was naturally dried to obtain a cast film having a thickness of 1 mm. .

  Next, a gel electrolyte membrane cut into 2.0 cm × 2.0 cm was laminated on the aluminum foil on which the galvinoxyl radical-containing electrode layer was formed, and a lithium-bonded copper foil (lithium A film thickness of 30 μm and a copper foil thickness of 20 μm) were overlaid. Thereafter, the whole was sandwiched between polytetrafluoroethylene sheets having a thickness of 5 mm, and pressure was applied to form a secondary battery.

Using the secondary battery prepared as described above as a sample, discharging was performed at a constant current of 0.1 mA using an electrode layer containing galvinoxyl radical as a positive electrode and a lithium-bonded copper foil as a negative electrode. As a result, a voltage flat portion was observed around 2.3 V, indicating that the battery was operating as a secondary battery. Further, when the secondary battery was repeatedly charged and discharged, it was found that the secondary battery operated as a rechargeable battery capable of charging and discharging over 10 cycles or more. Further, a part of the positive electrode layer was cut out from the sample after discharging, and the electron spin resonance spectrum was measured by the method of Experimental Example 1. As a result, the spin concentration was 10 ¹⁹ spins / g or less. From this, it was considered that the galvinoxyl radical formed a bond with lithium ions and lost the radical after the discharge was completed.

Experimental Example 13
Equimolar potassium ferricyanide and sodium hydroxide were allowed to act on 50 mg of poly (vinyl-di-tert-butylphenol) to obtain poly (vinyl-di-tert-butylphenoxy radical). When this was used as a sample and the electron spin resonance spectrum was measured by the method of Experimental Example 1, it was found that the spin concentration was 10 ²¹ spins / g or more, and the structure had an oxy radical represented by the chemical formula B10 in the initial state. .

  Next, an auxiliary conductive material, a vinylidene fluoride-hexafluoroethylene copolymer, were prepared in the same manner as in Example 12 except that poly (vinyl-di-tert-butylphenoxy radical) was used instead of galvinoxyl in Example 12. Tetrahydrofuran was added and mixed to obtain a black slurry. Thereafter, a layer of a compound containing poly (vinyl-di-tert-butylphenoxy radical) was formed on the aluminum foil in the same manner as in Experimental Example 12.

An ethylene carbonate / propylene carbonate mixed solution containing 1 mol / l LiPF ₆ as an electrolyte salt prepared in Experimental Example 12 on an aluminum foil on which the obtained poly (vinyl-di-tert-butylphenoxy radical) was formed, and vinylidene fluoride -A cast film made of a hexafluoropropylene copolymer electrolyte was cut into 2.0 cm x 2.0 cm, laminated, and laminated with a lithium-bonded foil in the same manner as in Experimental Example 12 to form a secondary battery.

Using the secondary battery prepared as described above as a sample, discharging was performed at a constant current of 0.1 mA using an electrode layer containing poly (vinyl-di-tert-butylphenoxy radical) as a positive electrode and a lithium-bonded copper foil as a negative electrode. . As a result, a flat portion of the voltage was observed around 2.4 V, indicating that the battery was operating as a secondary battery. Further, when the change in voltage accompanying the charging and discharging of the secondary battery was measured, it was found that the secondary battery operated. Further, a part of the positive electrode layer was cut out from the sample after the discharge, and the electron spin resonance spectrum was measured by the method of Experimental Example 1. As a result, the spin concentration was 10 ¹⁹ spins / g or less. From this, it was considered that the poly (vinyl-di-tert-butylphenoxy radical) of the positive electrode formed a bond with lithium ions and the like in the discharged state, and the radical disappeared.

Experimental Example 14
Acetyl-di-tert-butylphenol was reacted in benzene with molybdenum pentachloride at 40 ° C. to synthesize poly (3,5-di-tert-butyl-4-hydroxyphenylacetylene). This was reacted with potassium ferricyanide and sodium hydroxide in the same manner as in Experimental Example 13 to obtain poly (acetyl-di-tert-butylphenoxy radical). Using this as a sample and measuring the electron spin resonance spectrum by the method of Experimental Example 1, it was found that the spin concentration was 10 ²¹ spins / g or more, and the structure had an oxy radical shown in Chemical Formula 12 in the initial state. .

  Next, an auxiliary conductive material, a vinylidene fluoride-hexafluoroethylene copolymer, were prepared in the same manner as in Experimental Example 12, except that poly (acetyl-di-tert-butylphenoxy radical) was used instead of galvinoxyl in Experimental Example 12. Tetrahydrofuran was added and mixed to obtain a black slurry. Thereafter, a layer of a compound containing poly (acetyl-tert-butylphenoxy radical) was formed on the aluminum foil in the same manner as in Experimental Example 12.

An ethylene carbonate / propylene carbonate mixed solution containing 1 mol / l of LiPF ₆ prepared in Experimental Example 12 as an electrolyte salt and vinylidene fluoride-hexaene were formed on the obtained aluminum foil on which poly (acetyl-di-tert-butylphenoxy radical) was formed. A cast film made of a fluoropropylene copolymer electrolyte was cut into 2.0 cm × 2.0 cm, laminated, and laminated with a lithium bonding foil in the same manner as in Experimental Example 12 to form a secondary battery.

Using the secondary battery prepared as described above as a sample, discharging was performed at a constant current of 0.1 mA using an electrode layer containing poly (vinyl-di-tert-butylphenoxy radical) as a positive electrode and a lithium-bonded copper foil as a negative electrode. . As a result, a flat portion of the voltage was observed around 3.3 V, indicating that the secondary battery was operating. Further, when the change in voltage accompanying the charging and discharging of the secondary battery was measured, it was found that the secondary battery operated. Further, a part of the positive electrode layer was cut out from the sample after discharging, and the electron spin resonance spectrum was measured by the method of Experimental Example 1. As a result, the spin concentration was 10 ¹⁹ spins / g or less. From this, it was considered that the poly (acetyl-di-tert-butylphenoxy radical) of the positive electrode formed a bond with lithium ions and the like in the discharged state, and the radical disappeared.

Experimental example 15
A nitrobenzene solution in which 0.25 M LiAsF ₆ , 0.25 M CuCl ₂ , and 0.5 M benzene were dissolved or dispersed was placed in an electrolytic reaction cell, and two platinum plates were inserted to perform an electrolytic reaction at a voltage of 10 V. . As a result, a conductive polyparaphenylene film having a thickness of 10 μm was formed on the anode surface. After the reaction was completed, the electrode was short-circuited and peeled off from the electrode. Thereafter, the obtained polyparaphenylene film was placed in a vacuum vessel, heated to 450 ° C. together with 0.1 mol of oxygen with respect to the monomer unit, and heat-treated for 2 hours. This was cooled to room temperature and used as a sample. When the NMR spectrum and IR spectrum of this sample were measured, the molecular structure was presumed to be semiquinone in which a part of polyparaphenylene was substituted with oxygen as shown by the chemical formula B9. In addition, the measurement result of the ESR spectrum showed that the spin concentration of the obtained sample was 2 × 10 ²¹ spins / g.

Next, the sample having a semiquinone structure was directly laminated on an aluminum foil, and pressed and pressed. A cast film made of an ethylene carbonate / propylene carbonate mixed solution containing 1 mol / l LiPF ₆ as an electrolyte salt and a vinylidene fluoride-hexafluoropropylene copolymer electrolyte prepared in Experimental Example 12 was 2.0 cm × It was cut out to a thickness of 2.0 cm, laminated, and laminated with a lithium-bonded foil in the same manner as in Experimental Example 12 to form a secondary battery.

Using the secondary battery prepared as described above as a sample, discharging was performed at a constant current of 0.1 mA using an electrode obtained by laminating a compound having a semiquinone structure as a positive electrode and a lithium-bonded copper foil as a negative electrode. As a result, a flat portion of the voltage was observed around 3.1 V, indicating that the battery was operating as a secondary battery. Further, when the change in voltage accompanying the charging and discharging of the secondary battery was measured, it was found that the secondary battery operated. Further, a part of the positive electrode layer was cut out from the sample after the discharge, and the electron spin resonance spectrum was measured. As a result, the spin concentration was 10 ¹⁹ spins / g or less. From this, it was considered that the compound having a semiquinone structure of the positive electrode formed bonds with lithium ions and the like in the discharged state, and the radicals disappeared.

Experimental Example 16
A powder of 1,3,5-trisdiazo-cyclohexane-2,4,6-trione was put in a vacuum vessel, heated to 600 ° C. under vacuum, and kept for 20 hours. This was cooled to room temperature and used as a sample. When the NMR spectrum and IR spectrum of this sample were measured, the molecular structure was presumed to be a network-like polyoxy radical having the basic structure represented by the chemical formula B4. In addition, from the measurement results of the ESR spectrum, it was found that the spin concentration of the obtained sample was 8 × 10 ²¹ spins / g.

  Next, an auxiliary conductive material, a vinylidene fluoride-hexafluoroethylene copolymer, and tetrahydrofuran were prepared in the same manner as in Experimental Example 12 except that a compound presumed to be a network-like polyoxy radical was used instead of galvinoxyl in Experimental Example 12. Was added and mixed to obtain a black slurry. Thereafter, a layer of a network-like compound assumed to be a polyoxy radical was formed on the aluminum foil in the same manner as in Experimental Example 12.

An ethylene carbonate / propylene carbonate mixed solution containing 1 mol / l of LiPF ₆ as an electrolyte salt prepared in Experimental Example 12 was formed on the obtained aluminum foil on which a layer of a compound assumed to be a polyoxy radical was formed. A cast film made of a vinylidene fluoride-hexafluoropropylene copolymer electrolyte was cut into 2.0 cm × 2.0 cm, laminated, and laminated with a lithium-bonded foil in the same manner as in Experimental Example 12 to form a secondary battery.

Using the secondary battery prepared as described above as a sample, discharging was performed at a constant current of 0.1 mA using an electrode layer containing a network-like compound estimated to be a polyoxy radical as a positive electrode and a lithium-bonded copper foil as a negative electrode. As a result, a flat portion of the voltage was observed around 3.3 V, indicating that the secondary battery was operating. Further, when the change in voltage accompanying the charging and discharging of the secondary battery was measured, it was found that the secondary battery operated. Further, a part of the positive electrode layer was cut out from the sample after discharging, and the electron spin resonance spectrum was measured by the method of Experimental Example 1. As a result, the spin concentration was 10 ¹⁹ spins / g or less. From this, it was considered that the compound presumed to be a mesh-like polyoxy radical of the positive electrode formed a bond with lithium ions and the like in the discharged state, and the radical was lost.

Experimental Example 17
A method for manufacturing a secondary battery using diphenylpicrylhydrazyl represented by the chemical formula (C29) as an active material is described below. The electron spin resonance spectrum of diphenylpicrylhydrazyl was measured in advance, and it was confirmed that the spin concentration was 10 ²¹ spins / g or more.

An ethylene carbonate / propylene carbonate mixed solution containing 1 mol / l of LiPF ₆ electrolyte salt in 60 mg of vinylidene fluoride-hexafluoropropylene copolymer in a dry box equipped with a gas purifier under an argon gas atmosphere (mixing ratio 1: 1) ) Was mixed, and 1130 mg of tetrahydrofuran was added and dissolved at room temperature to prepare a gel electrolyte solution of tetrahydrofuran. Next, 30 mg of diphenylpicrylhydrazyl was placed in a glass container, 60 mg of graphite powder was mixed as a conductive auxiliary material, and 200 mg of the above-described gel electrolyte in tetrahydrofuran was added and mixed as an ion conductive auxiliary material. 1000 mg of tetrahydrofuran was added thereto, and the mixture was stirred for 3 hours to obtain a black slurry. 200 mg of the slurry obtained as described above was dropped on the surface of an aluminum foil (area: 1.5 cm × 1.5 cm, thickness: 100 μm) provided with a lead wire, and the whole was made to have a uniform thickness with a wire bar. Expanded. When this was allowed to stand at room temperature for 3 hours, the solvent, tetrahydrofuran, was substantially volatilized, and an electrode layer containing diphenylpicrylhydrazyl was formed on the aluminum foil.

Next, 600 mg of a vinylidene fluoride-hexafluoropropylene copolymer was mixed with 1400 mg of an electrolytic solution composed of an ethylene carbonate / propylene carbonate mixed solution (mixing ratio 1: 1) containing 1 mol / l of LiPF ₆ as an electrolyte salt. Then, 11.3 g of tetrahydrofuran was added, and the mixture was stirred at room temperature. After the vinylidene fluoride-hexafluoropropylene copolymer was dissolved, it was applied on a glass plate provided with a glass frame, and allowed to stand at room temperature for 1 hour to dry naturally tetrahydrofuran. As a result, a cast film having a thickness of 300 μm was obtained on a glass plate.

  Next, a gel electrolyte membrane cut into 2.0 cm × 2.0 cm was laminated on the aluminum foil on which the electrode layer containing diphenylpicrylhydrazyl prepared above was formed, and further, a lithium-bonded copper having a lead wire was provided. Foil (lithium film thickness 30 μm, copper foil film thickness 20 μm) were overlaid. Thereafter, the whole was sandwiched between sheets of polytetrafluoroethylene having a thickness of 5 mm, and pressure was applied to form a secondary battery.

Using the secondary battery prepared as described above as a sample, discharging was performed at a constant current of 0.1 mA using an electrode layer containing diphenylpicrylhydrazyl as a positive electrode and a lithium-bonded copper foil as a negative electrode. As a result, the voltage became constant around 2.5 V for about 5 hours, and it took 12 hours until the voltage became 1 V or less. Further, it was confirmed that the voltage became constant at around 2.5 V even when charging and discharging were repeated 10 times. From this, it was found that this secondary battery was operating as a secondary battery. Further, a part of the positive electrode layer was cut out from the sample after the discharge, and the electron spin resonance spectrum was measured. As a result, the spin concentration was 10 ¹⁹ spins / g or less. This is considered to be because diphenylpicrylhydrazyl was changed to a compound having no radical in the electrode reaction at the time of discharge. It is considered that diphenylpicrylhydrazyl became an active material in the positive electrode, and this secondary battery operated.

Experimental Example 18 [Example 3]
A secondary battery was fabricated in the same manner as in Experimental Example 17, except that diphenylpicrylhydrazyl was used instead of triphenylferdazyl having a molecular structure represented by the following chemical formula (C30), and discharge was performed. . Note that the electron spin resonance spectrum of triphenylferdazyl was measured in advance, and it was confirmed that the spin concentration was 10 ²¹ spins / g or more.

The secondary battery prepared as described above was discharged at a constant current of 0.1 mA using an aluminum foil on which a layer of a compound containing triphenylfeldadyl was formed as a positive electrode and a lithium-bonded copper foil as a negative electrode. As a result, a flat portion was observed around 2.3 V, and it took 8 hours until the voltage became 1 V or less. Further, a part of the positive electrode layer was cut out from the sample after the discharge, and the electron spin resonance spectrum was measured by the method of Experimental Example 1. As a result, the spin concentration was 10 ¹⁹ spins / g or less. This is considered to be because triphenylferdazyl was changed to a compound having no radical in the electrode reaction at the time of discharge. It is considered that this secondary battery operated, with triphenylferdazyl as the active material in the positive electrode.

Experimental Example 19 [Example 4]
A secondary battery was manufactured in the same manner as in Experimental Example 17, except that a polymer compound represented by the following chemical formula (C31) having a ferdazyl structure was used instead of diphenylpicrylhydrazyl, and discharged. Was. Note that an electron spin resonance spectrum of a polymer compound having a molecular structure represented by the chemical formula (C31) was measured in advance, and it was confirmed that the spin concentration was 10 ²¹ spins / g or more.

  With respect to the secondary battery fabricated as described above, a constant current of 0.1 mA was determined using an aluminum foil having a layer of a polymer compound having a molecular structure represented by the chemical formula (C31) as a positive electrode and a lithium-bonded copper foil as a negative electrode. Discharge was performed with current. As a result, a flat portion was observed at around 2.3 V, and it took 12 hours to reach 1 V or less.

Experimental Example 20 [Example 5]
A secondary battery was prepared in the same manner as in Experimental Example 17, except that a polymer compound represented by the following chemical formula (C32) having an aminotriazine structure was used instead of diphenylpicrylhydrazyl, and discharge was performed. went. Note that an electron spin resonance spectrum of a polymer compound having a molecular structure represented by the chemical formula (C32) was measured in advance, and it was confirmed that the spin concentration was 10 ²¹ spins / g or more.

  With respect to the secondary battery fabricated as described above, an aluminum foil on which a layer of a polymer compound having a molecular structure represented by the chemical formula (C32) was formed as a positive electrode, and a lithium-bonded copper foil as a negative electrode, with a constant current of 0.1 mA. Discharge was performed with current. As a result, a flat portion was observed around 2.3 V, and it took 10 hours to reach 1 V or less.

Comparative Example 2
A secondary battery was fabricated in the same manner as in Experimental Example 17, except that a compound having a radical on a nitrogen atom was not used as an active material. When discharging was performed at a constant current of 0.1 mA, the voltage rapidly dropped to 0.8 V in about 50 minutes. In addition, when charging was attempted by flowing a constant current of 0.1 mA, the voltage instantaneously rose to exceed 3.0 V, and even when the battery was discharged again, the voltage rapidly dropped to 0.8 V in about 50 minutes. From this, it was found that this battery configuration did not operate as a secondary battery.

Experimental Example 21
The gel electrolyte membrane of the method of Experimental Example 1 was laminated on the aluminum foil on which the organic compound layer containing a TEMPO radical prepared in Experimental Example 1 was formed, and further, a lithium-bonded copper foil provided with a lead wire was laminated, and the entire thickness was increased. The sheet was sandwiched between polytetrafluoroethylene sheets each having a thickness of 5 mm, and pressure was applied to produce a secondary battery.

The secondary battery prepared as described above was charged at a constant current of 0.1 mA using an aluminum foil on which an organic compound layer containing a TEMPO radical was formed as a positive electrode and a lithium-bonded copper foil as a negative electrode. As a result, a voltage flat portion was observed at around 3.5 V, indicating that the battery operated as a secondary battery. Further, a layer of the compound containing a TEMPO radical was cut out from the charged sample, and the electron spin resonance spectrum was measured by the method of Experimental Example 1. The spin concentration was 10 ¹⁹ spins / g or less. From this, it is considered that the TEMPO radical forms a bond with the electrolyte anion when the charging is completed, and the radical has disappeared. This secondary battery was discharged at a constant current of 0.1 mA, and the electron spin resonance spectrum was measured by the method of Experimental Example 1. The spin concentration was 10 ²¹ spins / g or more. It was considered that the bond was cleaved to generate a radical compound.

  Further, a secondary battery was manufactured in the same manner, and a change in voltage due to charge and discharge was measured. Even after repeated charge and discharge, a flat portion was observed in the discharge curve, indicating that the secondary battery also operated.

1 is a top view illustrating an example of a configuration of a secondary battery of the present invention. FIG. 1 is a cross-sectional view illustrating an example of a configuration of a secondary battery of the present invention. FIG. 3 is a discharge curve diagram of the secondary batteries measured in Experimental Examples 1 to 3 and Comparative Example 1 of the present invention. FIG. 3 is a charge / discharge curve diagram of a secondary battery measured in Experimental Example 1 of the present invention.

Explanation of reference numerals

REFERENCE SIGNS LIST 1 negative electrode layer 2 positive electrode layer 3 negative electrode current collector 4 positive electrode current collector 5 separator 6 negative electrode terminal 7 positive electrode terminal 8 outer layer film

Claims (4)

In a secondary battery including at least a positive electrode, a negative electrode, and an electrolyte as constituent elements, at least one active material of the positive electrode and the negative electrode contains a radical compound, and the radical compound is a trivalent ferdazyl group or a chemical formula represented by the chemical formula (C1). A secondary battery, which is a compound having a radical on a tetravalent ferdazyl group represented by (C2).

In a secondary battery including at least a positive electrode, a negative electrode, and an electrolyte, at least one of the active materials of the positive electrode and the negative electrode contains a radical compound, and the radical compound is a triphenylfelder represented by a chemical formula (C3) or a chemical formula (C4). A secondary battery having a jill group.

In a secondary battery including at least a positive electrode, a negative electrode, and an electrolyte, at least one of the positive electrode and the negative electrode contains a radical compound, and the radical compound has an aminotriazine structure represented by the general formula (C7). A secondary battery, which is a compound.

(Wherein R ₆ represents a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group , An aryloxycarbonyl group, an acyl group, a carboxyl group, and an oxo radical.) The secondary battery according to claim 3, wherein the compound having an aminotriazine structure is a polymer compound having the aminotriazine structure represented by the general formula (C7) as a repeating unit.

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