JP2010080391A - Secondary battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a secondary battery, having large energy density and superior preservation and cycle characteristics by containing a stabilized radical compound. <P>SOLUTION: The secondary battery has at least a positive electrode, a negative electrode, and an electrolyte as the constituent element, and contains an organic compound having a radical reaction in at least either processes of charging or discharging as an active material (radical compound). The organic compound is a compound as expressed in formula (1). In the formula, X represents a hydrogen bond formation group, R<SB>1</SB>expresses substituted or unsubstituted alkyl group and aryl group, and R<SB>2</SB>-R<SB>5</SB>express at least one selected from among hydrogen atom, alkyl group, cycloalkyl group, aryl group, hydroxyl group, carboxyl group, nitro group, trifluoromethyl group, amide group, ester group, carbonyloxy group, cyano group, halogen atom, alkoxy group, sulfonyl group, alkylthio group, arylthio group, sulfonamide group, sulfamoyl group, amino group, alkylamino group, arylamino group, and polymer chain, or the like. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a secondary battery including a positive electrode, a negative electrode, and an electrolyte as constituent elements, and more particularly to a secondary battery having a large energy density, excellent storage stability, and excellent cycle characteristics.

  Batteries are used to convert chemical energy into electrical energy using the redox reaction that occurs at the positive and negative electrodes, or to store electrical energy converted into chemical energy. It is used as. In recent years, with the rapid market expansion of notebook personal computers and mobile phones, there is an increasing demand for small high-capacity batteries with high energy density. In order to meet this demand, a battery has been developed that uses an alkali metal ion such as lithium ion as a charge carrier and uses an electrochemical reaction associated with charge transfer.

  However, since this lithium ion battery uses a metal oxide having a large specific gravity as the positive electrode active material, there is a problem that the battery capacity per unit mass is not sufficient. Thus, attempts have been made to develop large-capacity batteries using lighter electrode materials. For example, a battery using an organic compound having a disulfide bond as an active material for a positive electrode is disclosed (for example, see Patent Documents 1 and 2). However, since this battery uses an organic compound mainly composed of an element having a small specific gravity such as sulfur or carbon as an electrode material, a certain effect can be obtained in terms of constituting a high-capacity battery having a high energy density. However, there is a problem that the recombination efficiency of the dissociated disulfide bond is small and the stability in the charged state or the discharged state is insufficient.

  Similarly, a battery using a conductive polymer as an electrode material has been proposed as a battery using an organic compound as an active material (see, for example, Patent Document 3). However, in a battery using such a conductive polymer as an electrode material, a certain effect can be obtained in terms of reducing the weight of the battery, but it is still insufficient in terms of increasing the capacity of the battery.

On the other hand, secondary batteries using radical compounds as active materials have been disclosed (see, for example, Patent Documents 4 and 5). This battery has a high capacity density and stable charge / discharge, so the rate characteristics are good. However, the active material shown here has problems such as stability against temperature and a decrease in life, and a solution is desired. ing.
US Pat. No. 4,833,048 Japanese Patent No. 2715778 U.S. Pat. No. 4,442,187 JP 2002-151084 A JP 2004-228008 A

  In order to solve the above-described problems, an object of the present invention is to provide a secondary battery having a large energy density, storage stability and good cycle characteristics by including a stabilized radical compound. And

  The above object of the present invention can be achieved by the following configuration.

  1. In a secondary battery having at least a positive electrode, a negative electrode, and an electrolyte as constituents, and an organic compound accompanied by a radical reaction in at least one of charging and discharging processes as an active material (radical compound), the organic compound has the following general formula ( A secondary battery comprising the compound represented by 1).

[Wherein, X represents a hydrogen bond-forming group, R ₁ represents a substituted or unsubstituted alkyl group or aryl group, and R _{2 to} R ₅ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a hydroxyl group. , Carboxyl group, nitro group, trifluoromethyl group, amide group, ester group, carbonyloxy group, cyano group, halogen atom, alkoxy group, sulfonyl group, alkylthio group, arylthio, sulfonamido group, sulfamoyl group, amino group, alkyl It represents at least one selected from an amino group, an arylamino group, —N (—O ·) R ₁ , and a polymer chain. ]
2. X in the general formula (1) is represented by —OH, —NHRa, —NHC (═O) Rb, —NHC (═O) NHRc, —NHC (═O) ORd or —NHSO ₂ Re. 2. The secondary battery according to 1.
[Ra represents a hydrogen atom, a substituted or unsubstituted alkyl group or an aryl group, and Rb to Re represent a substituted or unsubstituted alkyl group or an aryl group. ]
3. At least one of R _{2 to} R ₅ in the general formula (1) is —N (—O ·) R ₁ ′, and the ortho position of —N (—O ·) R ₁ ′ is —X ′. 3. The secondary battery according to 1 or 2, wherein the secondary battery is replaced.
[X ′ represents a group having the same meaning as X in 2, and R ₁ ′ represents a substituted or unsubstituted alkyl group or aryl group. ]
4). 4. The secondary battery according to any one of 1 to 3, wherein at least one of R _{2 to} R ₅ in the general formula (1) is a polymer chain.

  5. 5. The secondary battery according to any one of 1 to 4, wherein the compound represented by the general formula (1) is the following general formula (2) or (3).

[Wherein X represents a group having the same meaning as X in 2, and X ′ represents a group having the same meaning as X ′ in 3. R _{1, R 2} and _{R 5} represents _R 1, _{R 2} and _{R 5} group having the same meaning as in the general formula (1) represents _{R 1} 'is _{R 1} at the 3' of the same meaning as that group. ]
6). 6. The secondary battery according to 5, wherein at least one of R _{2 and} R ₅ in the compound represented by the general formula (2) or (3) is a polymer chain.

  7). A secondary battery comprising the radical compound according to any one of 1 to 6 in a positive electrode.

  According to the present invention, it is possible to provide a secondary battery including a stabilized radical compound, having a large energy density, storage stability and good cycle characteristics.

  The present invention will be described in more detail. The present invention is a secondary battery that includes at least a positive electrode, a negative electrode, and an electrolyte as constituents and includes an organic compound that undergoes a radical reaction in at least one of a charging reaction and a discharging reaction. The organic compound represented by the general formula (1) can stabilize the nitroxyl radical by introducing a hydrogen bonding group into the organic compound accompanied by the radical reaction, and a more stabilized secondary battery can be obtained. Obtained.

  The embodiment of the secondary battery of the present invention has, for example, a configuration in which a negative electrode layer 1 and a positive electrode layer 2 are superposed via a separator 5 containing an electrolyte, as shown in the front sectional view of FIG. Yes. In the present invention, the active material used for the negative electrode layer 1 or the positive electrode layer 2 is an organic compound that generates a radical compound by a radical reaction, and the generated radical compound is stabilized. In addition, it is considered that the reason why the generated radical is stabilized becomes an active material of the battery is that the stabilized radical can further perform electrochemical oxidation-reduction. The assembled structure is sealed with a sealing material 6.

  FIG. 2 shows a cross-sectional view of the secondary battery. The structure is such that the negative electrode current collector 3, the negative electrode layer 1, the separator 5 containing the electrolyte, the positive electrode layer 2, and the positive electrode current collector 4 are sequentially stacked. It has a structure.

  In the present invention, the method for laminating the positive electrode layer and the negative electrode layer is not particularly limited, and a multi-layered laminate, a combination of laminates on both sides of a current collector, a wound one, or the like can be used.

(1) Active material (compound represented by general formula (1))
In the general formula (1), X represents a hydrogen bond forming group. The hydrogen bond forming group may be any group that forms a hydrogen bond, and preferably —OH, —NHRa, —NHC (═O) Rb, —NHC (═O) NHRc, —NHC (═O) ORd. Or represents the group represented by -NHSO ₂ Re. Examples of the alkyl group represented by Ra to Re and R1, R1 ′ include methyl, ethyl, i-propyl, hydroxyethyl, stearyl, dodecyl, eicosyl, docosyl, oleyl and the like, and aryl groups include phenyl, And naphthyl. The substituent is not particularly limited, and examples thereof include alkyl groups (methyl, ethyl, i-propyl, hydroxyethyl, stearyl, dodecyl, eicosyl, docosyl, oleyl, etc.), cycloalkyl groups (cyclopropyl, cyclohexyl, etc.), aryl Groups (phenyl, p-tetradecanyloxyphenyl, o-octadecanylaminophenyl, naphthyl, hydroxyphenyl, etc.), hydroxyl groups, carboxyl groups, nitro groups, trifluoromethyl groups, amide groups (acetamide, benzamide, etc.), Carbamoyl groups (methylcarbamoyl, butylcarbamoyl, phenylcarbamoyl, etc.), ester groups (ethyloxycarbonyl, i-propyloxycarbonyl, phenyloxycarbonyl, etc.), carbonyloxy groups (methylcarbonyloxy, Pyrcarbonyloxy, phenylcarbonyloxy, etc.), cyano group, halogen atom (chlorine, bromine, iodine, fluorine), alkoxy group (methoxy, ethoxy, butoxy, etc.), aryloxy group (phenoxy, naphthyloxy, etc.), sulfonyl group ( Methanesulfonyl, p-toluenesulfonyl, etc.), alkylthio group (methylthio, ethylthio, butylthio, etc.), arylthio (phenylthio, etc.), sulfonamide group (methanesulfonamide, dodecylsulfonamide, p-toluenesulfonamide, etc.), sulfamoyl group ( Methylsulfamoyl, phenylsulfamoyl etc.), amino group, alkylamino group (ethylamino, dimethylamino, hydroxyamino etc.), arylamino group (phenylamino, naphthylamino etc.).

R _{2 to} R ₅ are a hydrogen atom, an alkyl group (methyl, ethyl, i-propyl, hydroxyethyl, stearyl, dodecyl, eicosyl, docosyl, oleyl, etc.), a cycloalkyl group (cyclopropyl, cyclohexyl, etc.), an aryl group (phenyl). , P-tetradecanyloxyphenyl, o-octadecanylaminophenyl, naphthyl, hydroxyphenyl, etc.), hydroxyl group, carboxyl group, nitro group, trifluoromethyl group, amide group (acetamide, benzamide, etc.), carbamoyl group ( Methylcarbamoyl, butylcarbamoyl, phenylcarbamoyl, etc.), ester groups (ethyloxycarbonyl, i-propyloxycarbonyl, phenyloxycarbonyl, etc.), carbonyloxy groups (methylcarbonyloxy, propylcarbonyl) Xy, phenylcarbonyloxy, etc.), cyano group, halogen atom (chlorine, bromine, iodine, fluorine), alkoxy group (methoxy, ethoxy, butoxy, etc.), aryloxy group (phenoxy, naphthyloxy, etc.), sulfonyl group (methanesulfonyl) , P-toluenesulfonyl etc.), alkylthio group (methylthio, ethylthio, butylthio etc.), arylthio (phenylthio etc.), sulfonamide group (methanesulfonamide, dodecylsulfonamide, p-toluenesulfonamide etc.), sulfamoyl group (methylsulfuramide) Famoiru, phenylsulfamoyl, etc.), an amino group, an alkylamino group (ethylamino, dimethylamino, hydroxyamino, etc.), an arylamino group (phenylamino, naphthylamino, _{etc.), - N (-O ·)} R 1, Polymer chain There is no particular limitation as long as it is a polymer obtained by polymerizing a monomer having a polymerizable group by a known method. For example, the following structure is mentioned.

  In the formula, R represents a hydrogen atom or a methyl group, and R ″ represents an alkylene group or an arylene group.

  Hereinafter, although the compound represented by General formula (1) is described, it is not limited to these.

  The weight average molecular weight when the compound represented by the general formula (1) contains a polymer chain is not particularly limited, but was prepared using standard polystyrene (for example, STK standard polystyrene (manufactured by Tosoh Corporation)). Converted from the calibration curve, it is preferably Mw 3000 or more and 1000000 or less, more preferably 10,000 or more and 500000 or less, and most preferably 30000 or more and 200000 or less.

  In the present invention, a radical compound other than the compound of the present invention can be used in combination, and the type of the radical compound is not particularly limited. Examples of such radical compounds include organic compounds such as oxy radical compounds, nitroxyl radical compounds, nitrogen radical compounds, carbon radical compounds, boron radical compounds, and sulfur radical compounds.

  Specific examples of the radical compound include compounds such as the following general formulas (RA-1) to (RA-14), but are not limited thereto.

  Although the synthesis example of the compound represented by General formula (1) is shown below, it can synthesize | combine by another well-known prescription.

  <Synthesis Example 1 Exemplary Compound (1)>

  Compound (1-a) 10 g (0.024 mol), tetrakis (triphenylphosphine) palladium 0.83 g (0.071 mmol), 2,6-di-t-butyl-4-methylphenol (0.026 g), tri -9.3 g (0.0115 mol) of n-butyl (vinyl) tin was dissolved in 150 ml of toluene and stirred at 100 ° C. for 15 hours. After completion of the reaction, water was added and extracted with ethyl acetate. The solvent of the organic layer was removed under reduced pressure, and the resulting residue was purified by column chromatography to obtain 6.8 g (yield 78%) of compound (1-b). The structure was identified by NMR and MS spectra.

  Compound (1-b) 5.0 g (0.0138 mol) was dissolved in 10 ml of toluene, 6.4 mg of AIBN was added, and the mixture was stirred at 75 ° C. for 15 hours. The reaction solution was allowed to cool and poured into methanol for dispersion. The obtained solid was filtered and dried to obtain 4.3 g of Compound (1-c) (yield 86%).

  4.0 g of compound (1-c) was dissolved in 1000 ml of THF, 10 g of tetrabutylammonium fluoride was added, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, 13.7 g of silver oxide was added, and the mixture was further stirred at room temperature for 12 hours. The precipitate was filtered, and the obtained filtrate was poured into methanol and dispersed. The obtained solid was filtered and dried to obtain 3.2 g of Compound (1). The weight average molecular weight determined by GPC was Mw = 52000, and the degree of dispersion was Mw / Mn = 2.87.

  <Synthesis Example 2 Exemplary Compound (28)>

  6.0 g (9.66 mmol) of the compound (28-a) was dissolved in 12 ml of toluene, 47 mg of AIBN was added, and the mixture was stirred at 75 ° C. for 15 hours. The reaction solution was allowed to cool and poured into methanol for dispersion. The obtained solid was filtered and dried to obtain 4.0 g (yield 67%) of compound (28-b).

  Compound (28-b) (3.0 g) was dissolved in THF (800 ml), tetrabutylammonium fluoride (8.8 g) was added, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, 6.0 g of silver oxide was added, and the mixture was further stirred at room temperature for 12 hours. The precipitate was filtered, and the obtained filtrate was poured into methanol and dispersed. The obtained solid was filtered and dried to obtain 2.6 g of compound (28). The weight average molecular weight determined by GPC was Mw = 47000, and the degree of dispersion was Mw / Mn = 3.86.

(Other than radical compounds)
In the present invention, a material that generates a radical compound in the course of the charge / discharge reaction can be used as an active material for the positive electrode and / or the negative electrode. It is preferable to use as.

In addition, when using these materials as an active material of any one of a positive electrode and a negative electrode, the material listed below can be used as an active material of another electrode. That is, when a material that generates a radical compound is used as the active material of the negative electrode layer, metal oxide particles, a disulfide compound, a conductive polymer, and the like are used as the active material of the positive electrode layer. Here, examples of the metal oxide include lithium manganate such as LiMnO ₂ and Li _x Mn ₂ O ₄ (0 <x <2) or lithium manganate having a spinel structure, MnO ₂ , LiCoO ₂ , LiNiO ₂ , Or Li _x V ₂ O ₅ (0 <x <2) and the like, and disulfide compounds include dithioglycol, 2,5-dimercapto-1,3,4-thiadiazole, S-triazine-2,4,6-trithiol. In addition, examples of the conductive polymer include polyacetylene, polyphenylene, polyaniline, and polypyrrole. In the present invention, these positive electrode layer materials can be used singly or in combination of two or more, and it is also preferable to mix a conventionally known active material and these materials to use as a composite active material.

  On the other hand, when a material that generates a radical compound is used as the active material of the positive electrode layer, graphite, amorphous carbon, lithium metal, lithium alloy, lithium ion storage carbon, and conductive polymer are used as the active material of the negative electrode layer. These are used alone or in combination of two or more. These shapes are not particularly limited. For example, in addition to a thin film of lithium metal, a bulk shape, a powdered shape, a fiber shape, a flake shape, or the like can be used.

(2) Binder In the present invention, a binder can also be used in order to strengthen the bond between the constituent materials. Examples of such binders include polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene / butadiene copolymer rubber, polypropylene, polyethylene, polyimide, and various polyurethanes. And a resin binder.

(3) Catalyst In the present invention, a catalyst that promotes the oxidation-reduction reaction can also be used in order to perform the electrode reaction more smoothly. Examples of such catalysts 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. Is mentioned.

(4) Current collector The current collector in the present invention is formed of a conductor and collects electric charges generated from battery electrodes. In the present invention, as the negative electrode current collector 3 and the positive electrode current collector 4, a metal foil such as nickel, aluminum, copper, gold, silver, aluminum alloy, and stainless steel, a metal flat plate, a mesh electrode, a carbon electrode, or the like is used. be able to. Further, such a current collector may have a catalytic effect, or the active material and the current collector may be chemically bonded.

(5) Separator and Sealing Agent The separator 5 in the present invention prevents the positive electrode layer and the negative electrode layer from contacting each other, and a material such as a porous film or a nonwoven fabric can be used. Further, such a separator is preferably configured to contain an electrolyte. However, when an ion conductive polymer is used as the electrolyte, the separator itself can be omitted. Further, the sealing material 6 in the present invention is not particularly limited, and a conventionally known material used for a battery exterior is used.

(6) Electrolyte In the present invention, the electrolyte performs charge carrier transport between both the negative electrode layer 1 and the positive electrode layer 2, and generally has an ionic conductivity of 10 ⁻⁵ to 10 ⁻¹ S / cm at room temperature. Have. In the present invention, for example, an electrolyte solution in which an electrolyte salt is dissolved in a solvent can be used as the electrolyte. Examples of such an electrolyte salt include LiPF ₆ , LiClO ₄ , LiBF ₄ , LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, Li (C ₂ F ₅ SO ₂ ) ₂ N, and Li (CF ₃ Conventionally known materials such as SO ₂ ) ₃ C and Li (C ₂ F ₅ SO ₂ ) ₃ C can be used.

  Examples of the electrolyte salt solvent include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, tetrahydrofuran, dioxolane, sulfolane, dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone. An organic solvent such as can be used. In the present invention, these solvents can be used alone or as a mixed solvent of two or more.

  Furthermore, in the present invention, a solid electrolyte can be used as the electrolyte. Examples of the polymer compound used in such a solid electrolyte include polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-ethylene copolymer, vinylidene fluoride-monofluoroethylene copolymer, and fluorine. Vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, etc., and 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 - acrylonitrile polymers such as vinyl acetate copolymer, further polyethylene oxide, ethylene oxide - propylene oxide copolymers, and polymers of these acrylates body or methacrylate body thereof. The solid electrolyte may be a gel obtained by adding an electrolytic solution to these polymer compounds, or may be used as it is with only the polymer compound.

(7) Shape In addition, the shape of the battery is not particularly limited, and can be applied to shapes of a cylindrical battery, a coin battery, a square battery, a film battery, a button battery, and the like.

  The present invention will be described more specifically below, but the present invention is not limited to these examples.

Example 1
(1) Production of battery In a dry box equipped with a gas purifier, 50 mg of compound (1) and 60 mg of graphite powder as an auxiliary conductive material were mixed in a glass container under an argon gas atmosphere. When 20 mg of vinylidene-hexafluoropropylene copolymer and 1 g of tetrahydrofuran were further added and further mixed for several minutes until the whole became uniform, a black slurry was obtained.

  Subsequently, 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 lead wires, so that the entire thickness was uniform with a wire bar. When the mixture was allowed to stand at room temperature for 60 minutes, the solvent tetrahydrofuran evaporated, and an electrode layer was formed on the aluminum foil.

Next, 600 mg of vinylidene fluoride-hexafluoropropylene copolymer and 1,400 mg of an electrolyte solution made of a propylene carbonate solution having an acceptor number of 18.9 containing 1 mol / l LiPF ₆ as an electrolyte salt were mixed, To this was further added 11.3 g of tetrahydrofuran, and the mixture was stirred at room temperature. After the vinylidene fluoride-hexafluoropropylene copolymer is dissolved, this solution is applied onto a stepped glass plate, and allowed to stand at room temperature for 1 hour to naturally dry tetrahydrofuran, and a gel electrolyte membrane having a thickness of 1 mm A cast film was obtained.

  Next, a gel electrolyte film cut out to 2.0 cm × 2.0 cm is laminated on the aluminum foil on which the electrode layer is formed, and further a lithium-laminated copper foil (lithium film thickness 30 μm, copper foil film) provided with a lead wire After stacking 20 μm thick), the whole was sandwiched between 5 mm thick polytetrafluoroethylene sheets, and pressure was applied to produce a battery 101.

  Batteries 102 to 112 were produced in the same manner as described above except that the radical compounds listed in Table 1 were used instead of the compound (1).

  The weight average molecular weight Mw of the comparative compound 1 was 89000, and dispersion degree Mw / Mn was 3.3.

(2) Evaluation of Battery The battery 101 manufactured as described above was charged and discharged at a constant current (0.1 mA), with a cut-off voltage of 4.2 V for charging and 2.5 V for discharging. As a result, a flat voltage portion was observed in the vicinity of 2.9 V, and it was confirmed that the device was operating as a battery. Furthermore, when this battery was repeatedly charged / discharged, it was confirmed that it could be charged / discharged over 10 cycles or more and operated as a secondary battery. It was confirmed that the other batteries 102 to 112 also operate as secondary batteries.

(3) Evaluation of preservability A large number of batteries each having the same structure as the obtained batteries 101 to 112 were produced, and initial charge / discharge was performed 10 cycles. Subsequently, after charging under the same conditions as described above, five batteries were stored in a thermostatic chamber having an explosion-proof structure set to 60 ° C. Seven days later, the battery was taken out, discharged under the same conditions as described above, and the “discharge capacity after storage” was measured. For each battery, “self-discharge rate (%)” was calculated according to the following calculation formula.

  Next, charging and discharging were performed under the same conditions. Thus, the obtained discharge capacity was set as “recovery discharge capacity”, and the ratio of each battery to the “discharge capacity before storage” was obtained and set as “recovery capacity ratio (%)”.

  As is clear from Table 2, the secondary battery of the present invention using at least the positive electrode, the negative electrode, and the electrolyte as components and using the compound of the present invention as an active material has good cycleability during charge and discharge, and the storage stability is also good. It turns out that it is improving.

It is front sectional drawing of the secondary battery which concerns on this invention. It is sectional drawing of the secondary battery which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Negative electrode layer 2 Positive electrode layer 3 Negative electrode collector 4 Positive electrode collector 5 Separator 6 Sealing material

Claims (7)

In a secondary battery having at least a positive electrode, a negative electrode, and an electrolyte as constituents, and an organic compound accompanied by a radical reaction in at least one of charging and discharging processes as an active material (radical compound), the organic compound has the following general formula ( A secondary battery comprising the compound represented by 1).

[Wherein, X represents a hydrogen bond-forming group, R ₁ represents a substituted or unsubstituted alkyl group or aryl group, and R _{2 to} R ₅ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a hydroxyl group. , Carboxyl group, nitro group, trifluoromethyl group, amide group, ester group, carbonyloxy group, cyano group, halogen atom, alkoxy group, sulfonyl group, alkylthio group, arylthio, sulfonamido group, sulfamoyl group, amino group, alkyl It represents at least one selected from an amino group, an arylamino group, —N (—O ·) R ₁ , and a polymer chain. ] X in the general formula (1) is represented by —OH, —NHRa, —NHC (═O) Rb, —NHC (═O) NHRc, —NHC (═O) ORd or —NHSO ₂ Re. The secondary battery according to claim 1.
[Ra represents a hydrogen atom, a substituted or unsubstituted alkyl group or an aryl group, and Rb to Re represent a substituted or unsubstituted alkyl group or an aryl group. ] At least one of R _{2 to} R ₅ in the general formula (1) is —N (—O ·) R ₁ ′, and the ortho position of —N (—O ·) R ₁ ′ is —X ′. The secondary battery according to claim 1, wherein the secondary battery is replaced.
[X ′ represents a group having the same meaning as X in claim 2, and R ₁ ′ represents a substituted or unsubstituted alkyl group or aryl group. ] 4. The secondary battery according to claim 1, wherein at least one of R _{2 to} R ₅ in the general formula (1) is a polymer chain. 5. 5. The secondary battery according to claim 1, wherein the compound represented by the general formula (1) is the following general formula (2) or (3).

[Wherein, X represents a group having the same meaning as X in claim 2, and X ′ represents a group having the same meaning as X ′ in claim 3.] R _{1, R 2} and _{R 5} represents _R 1, _{R 2} and _{R 5} group having the same meaning as in the general formula (1), _{R 1} 'is _{R 1} in claim 3' represents a group of the same meaning as. ] The secondary battery according to claim 5, wherein at least one of R _{2 and} R ₅ in the compound represented by the general formula (2) or (3) is a polymer chain. A secondary battery comprising the radical compound according to any one of claims 1 to 6 on a positive electrode.

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