JP5365246B2 - Active material, secondary battery - Google Patents

Description

The present invention has a high energy density, chemical and electrically stable, better active material conductivity, and a rechargeable battery.

  Currently, information-related equipment is a social infrastructure that is indispensable for our citizens' lives and economic activities, and sufficient stability and reliability are required. However, these devices are vulnerable to disturbance phenomena from the system such as instantaneous power failure or voltage drop, and the uninterruptible power supply (UPS) ensures reliability. However, UPS has a problem that a large amount of energy is lost due to repeated AC / DC conversion. As a method of improving this loss, a method of connecting a battery inside the device is conceivable, but a high-power battery that can be built in an information-related device that is becoming smaller has not been developed.

  On the other hand, many radical polymers obtained by polymerizing stable radical molecules have been synthesized as one of redox resins since the 1970s. Such a radical polymer is represented by a polymer of an acrylate or a styrene derivative substituted with 2,2,6,6-tetramethylpiperidine-1-oxy (hereinafter abbreviated as “TEMPO”). Catalytic ability to oxidize to aldehydes and ketones.

  The mechanism of action of the radical polymer is in a reversible redox (redox) pair. Taking nitroxide radical as an example, the mechanism of action is shown below. As shown below, the nitroxide radical is oxidized by one electron to become an oxoammonium cation, and when the oxoammonium cation is reduced, the radical is regenerated. In the other redox pair, the nitroxide radical is reduced by one electron and converted into an aminoxy anion, and when this aminoxy anion is oxidized, the redox is brought back to the radical.

  In recent years, active research has been focused on containing this redox pair of radicals in an electricity storage material, that is, an electrode active material of a secondary battery including at least a positive electrode, a negative electrode, and an electrolyte solution. Secondary batteries containing a compound in an electrode active material are disclosed (see Patent Documents 1 to 7). Since the radical redox pair is incorporated into the electrode active material, it is called an organic radical battery (see Non-Patent Documents 1 and 2). The radical compound contained in the electrode active material not only has the moldability and adhesiveness as an electrode, but also has the property of easily penetrating the electrolyte (affinity with the electrolyte) and the property of not eluting into the electrolyte ( Resistant to electrolyte solution), oxidation-reduction characteristics that enable high-speed transfer of electrodes and electrons during charge and discharge, and high energy density that realizes higher battery capacity.

  The advantages of including the polymer having the nitroxide radical in the molecular structure in the electrode active material can be summarized as follows. (1) Chemically very stable. For example, there are polymers whose radical concentration does not decrease over a half year at room temperature. (2) The spin density is localized at N—O, and the molecular weight per radical is small, so the charge capacity per mass is large. (3) Since all monomer units can carry charges, the ultimate heavy doping of nearly 100% becomes possible. (4) Pure organic substance. Incineration, odorlessness, and low toxicity are advantages not found in conventional electrode materials. (5) The redox speed is extremely high, and the battery exhibits high rate characteristics and high output. As such polymers having a nitroxide radical in the molecular structure, acrylate polymers, vinyl polymers, norbornene polymers, etc., in which the TEMPO moiety is substituted with a monomer structural unit have been reported recently (see Patent Documents 1 to 7).

  However, the above polymer is hardly soluble in electrolyte solvents (ethylene carbonates) and is an electrical insulator. Therefore, when an electrode active material layer is formed, a current collector such as carbon graphite and a solvent are added uniformly. After the slurry pulverized and mixed is prepared, the slurry is applied to the electrode substrate, and the solvent is removed by drying. In this method, when the mixing amount of the current collector with respect to the polymer is 50% by mass or less, there is a problem that the smoothness of the electrode surface is lowered and the output is further lowered. (For example, refer nonpatent literature 3) Moreover, the problem that the total amount of the ion in electrolyte solution restrict | limits battery capacity also had a problem (for example, refer nonpatent literature 4). Therefore, the actual battery capacity is 50% or less at most with respect to the theoretical capacity of the radical polymer, and an active material capable of expressing an actual capacity equivalent to the theoretical capacity has been eagerly desired.

  In addition to the above, the nitroxy radical compound and the polymer derived from the compound have a function of a chemical reaction catalyst for oxidizing a primary alcohol to an aldehyde, but it is difficult to control the oxidation rate, It had the disadvantage of being peroxidized to carboxylic acid. In order to remedy this drawback, an oxidizing agent in which p-toluenesulfonate of TEMPO (hereinafter referred to as oxoammonium salt of TEMPO) is supported on a macroporous substrate of poly (styrene-co-divinylbenzene) has recently been developed. It was developed (for example, refer nonpatent literature 5). However, although the peroxidation reaction up to the carboxylic acid was suppressed by this catalyst, the yield of the reaction for oxidizing the aliphatic primary alcohol, which is an inert alcohol, to the corresponding aldehyde was not satisfactory.

JP 2002-151084 A JP 2002-11168 A JP 2002-117853 A JP 2005-209498 A JP 2007-070384 A JP 2007-157696 A JP 2007-184227 A

K. Nakahara et al. , Chem. Phys. Lett. , 359, 351-354 (2002). H. Nishi et al. Electrochim. Acta, 50, 827-831 (2004) NEDO 2004 Research Project Report “Research and Development of High-Power Organic Radical Batteries for Backup” NEC Corporation, pages 11-14 Takeo Suga et al. , Macromolecules 2007, 40, 3167-3173. Homepage: http://www.biotage.co.jp/nl7_tempo Technical Note MP-TsO-TEMPO Biotage Japan Co., Ltd. 2005

The present invention has been made in view of the above problems, and the object of the present invention is (1) high energy density, (2) chemical and electrical stability, (3) excellent conductivity, and electrode activity. can be very small the amount of the current collector, such as carbon graphite in forming the material layer, lies in the difference between the theoretical capacity and the battery actual capacity to provide a very small active material, and rechargeable battery .

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

1. An active material containing an oxoammonium compound, wherein the counter anion of the oxoammonium compound is a sulfonate anion-containing polymer , and the sulfonate anion-containing polymer is a polystyrene sulfonate anion .

2. 2. The active material according to 1 above, wherein the oxoammonium cation structure of the oxoammonium compound is represented by the following general formula 1 or 2.

(In the formula, R _{15 to} R ₁₈ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. X _{1 to} X ₅ each independently represent> CH ₂ ,> N ⁺ = O, or> N. ⁺ H-OH, R ₁₉ represents a hydrogen atom, a halogen atom or a substituent that can be substituted on three carbon atoms of a 6-membered ring, a plurality of R ₁₉ may be the same or different, and n is 0 to 0 Represents an integer of 3.)
3. 2. The active material according to 1 above, wherein the oxoammonium cation structure of the oxoammonium compound is at least one of structures represented by the following general formula 3.

(Wherein R ₂₀ represents a tertiary alkyl group having 4 to ₂₀ carbon atoms, R ₂₁ represents an electron-withdrawing group, and a plurality of R ₂₁ may be the same or different, and m is Represents an integer of 1 to 5.)
4). A secondary battery comprising the active material according to any one of 1 to 3 above.

5. A secondary battery comprising the active material described in 2 above in a positive electrode and the active material described in 3 above in a negative electrode.

According to the present invention, energy density is high, chemically and electrically stable, excellent in electrical conductivity, and the amount of current collector such as carbon graphite can be extremely reduced when forming an electrode active material layer. Thus, an active material and a secondary battery in which the difference between the theoretical capacity and the actual battery capacity is extremely small could be provided .

It is sectional drawing of the secondary battery of this invention. It is sectional drawing of the secondary battery of this invention.

  Hereinafter, although the form for implementing this invention is demonstrated, this invention is not limited to these.

The present invention will be described in more detail.
<Sulfonate anion-containing polymer>
The sulfonate anion-containing polymer of the present invention refers to a polymer in which part or all of the sulfonate group in the sulfonate group-containing polymer is converted to a sulfonate anion. Conventionally known polymers are preferably used as the sulfonic acid group-containing polymer. As a specific example, the polymer unit contains about 50 to about 100% by mass, preferably about 80 to about 100% by mass, of one or more monomers selected from sulfonic acid group-containing monomers and salts thereof. Suitable examples of the sulfonic acid group-containing monomer include vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-acrylamidoethane sulfonic acid, 2-acrylamidopropane sulfonic acid, and 2-methacrylamide. Examples include propanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, and the like. It is done. The preferred weight average molecular weight of the sulfonate anion-containing polymer of the present invention is 10,000 or more and 5 million or less, and the preferred ratio of weight average molecular weight to number average molecular weight (hereinafter abbreviated as molecular weight distribution) is 1.5 or more and 4 0.5 or less, more preferably 100,000 or more and 3 million or less in weight average molecular weight, and 1.5 or more and 3.5 or less in molecular weight distribution, and particularly preferably 300,000 or more in weight average molecular weight. The molecular weight distribution is 1.5 or more and 2.5 or less. The molecular weight was calculated using polystyrene as a standard substance.

<Oxoammonium compound>
The oxoammonium compound of the present invention is a compound having at least one oxoammonium group represented by the following formula (A1) in the molecule.

Formula (A1)> N ⁺ = O
<Polystyrene sulfonate anion>
As the polystyrene sulfonate anion of the present invention, one obtained by converting a part or all of the sulfonate group of a conventionally known polystyrene sulfonate into a sulfonate anion is preferably used. The preferred weight average molecular weight of polystyrene sulfonic acid is 10,000 or more and 50 million or less, and the preferred molecular weight distribution is 1.5 or more and 4.5 or less, more preferably 100,000 or more and 10 million or less in weight average molecular weight. Further, the molecular weight distribution is 1.5 or more and 2.5 or less, particularly preferably, the weight average molecular weight is 500,000 or more and 5 million or less, and the molecular weight distribution is 1.5 or more and 2.0 or less.

<Oxoammonium cation represented by general formula 1>
In General Formula 1, R _{15 to} R ₁₈ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Preferably, it is a hydrogen atom or a methyl group. Particularly preferred is a hydrogen atom. X _{1 to} X ₅ represent> CH ₂ >, N ⁺ ═O or> N ⁺ H—OH, and particularly X ₁ is preferably> N ⁺ ═O or> N ⁺ H—OH.

<Oxoammonium cation represented by general formula 2>
In General Formula 2, R ₁₉ represents a hydrogen atom, a halogen atom, or a substituent that can be substituted with three carbon atoms of a 6-membered ring. A plurality of R ₁₉ may be the same or different, and n represents an integer of 0 to 6, but specific examples of R ₁₉ include a hydrogen atom, a halogen atom (chlorine atom, bromine atom, fluorine atom, iodine atom). And an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, an oxo group, a hydroxyl group, an alkoxy group, an aryloxy group, and an acyloxy group. Preferably, all of R ₁₉ are hydrogen atoms.

<Oxoammonium cation represented by general formula 3>
In the general formula 3, R ₂₀ represents a tertiary alkyl group having 4 to ₂₀ carbon atoms, preferably a tertiary butyl group. R ₂₁ represents an electron-withdrawing group, and a plurality of R ₂₁ may be the same or different, and m represents an integer of 1 to 5, and the electron-withdrawing group may be a Hammett's substituent constant. A group having a value of σp of 0.20 or more is preferable. Specific examples include an aryloxycarbonyl group, an alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, a cyano group, an aryl group, an acyl group, and a trifluoromethyl group. A trifluoromethyl group is preferred, and m = 1 is preferred. The substitution position of the trifluoromethyl group is preferably the ortho position or para position of the oxoammonium group.

  Although the exemplary compound of the oxoammonium compound of this invention is shown below, this invention is not limited to these.

The nitroxide radical is disproportionated into an oxoammonium cation and an aminoxy anion (the aminoxy anion receives two H ⁺ of the sulfonic acid and becomes an aminium cation) in the presence of sulfonic acid. Therefore, the exemplary compound may be described as an energy minimum state (that is, a state where the oxonium cation and the aminium cation are 1: 1).

Since the active material of the present invention uses the sulfonic acid of the sulfonate anion-containing polymer as a counter salt, the nitroxide radical causes disproportionation and becomes a 1: 1 mixture of oxoammonium cation type and aminoxy anion type. Of course, in the case of the oxoammonium cation type, it is a cation type, and even in the case of the aminoxy anion type, the active material of the present invention is converted into a cation type upon receiving two H ⁺ of sulfonic acid. Even in any oxidation-reduction state, the sulfonate anion (-)-containing polymer in the electrode layer can always be used as a counter salt and can be suitably fixed in the electrode layer.

  The synthesis example of the oxoammonium compound of the present invention is shown below.

(Synthesis Example 1: Synthesis of Compound p1-1)
A solution prepared by dissolving 10 g (47 mmol) of polystyrene sulfonic acid (Mw = 1,500,000, Mw / Mn = 2.0) in 30 ml of pure water and 7.9 g (52 mmol) of azaadamantanoxy radical in 15 ml of methanol at room temperature. Slowly added. After stirring for 1 hour as it was, 100 ml of acetonitrile was slowly added dropwise to the reaction solution while stirring, and the produced polymer was filtered off and washed thoroughly with acetonitrile. The solvent was dried at 40 ° C. to obtain 16 g of the desired product p1-1. (Yield 89%, Mw = 15.3 million, Mw / Mn = 2.0)
(Synthesis Example 2: Synthesis of Compound p1-14)
10 g (43 mmol) of polyacrylamide t-butylsulfonic acid (Mw = 1.3 million, Mw / Mn = 3.0) is dissolved in 30 ml of pure water, and 7.9 g (47 mmol) of bisazaadamantanedioxy radical is dissolved in 15 ml of methanol. The dissolved solution was added slowly at room temperature. After stirring for 1 hour as it was, 100 ml of acetonitrile was slowly added dropwise to the reaction solution while stirring, and the produced polymer was filtered off and washed thoroughly with acetonitrile. The solvent was dried at 40 ° C. to obtain 15 g of the desired product p1-14. (Yield 84%, Mw = 13.3 million, Mw / Mn = 2.8)
(Synthesis Example 3: Synthesis of Compound p2-1)
A solution in which 10 g (47 mmol) of polystyrene sulfonic acid (Mw = 800,000, Mw / Mn = 2.0) was dissolved in 30 ml of pure water, and 8.1 g (52 mmol) of tetramethylpiperidineoxy radical was dissolved in 15 ml of methanol at room temperature. Slowly added. After stirring for 1 hour as it was, 80 ml of acetonitrile was slowly added dropwise to the reaction solution while stirring, and the produced polymer was separated by filtration and thoroughly washed with acetonitrile. The solvent was dried at 40 ° C. to obtain 17 g of the desired product p2-14. (Yield 94%, Mw = 779,000, Mw / Mn = 1.8)
(Synthesis Example 4: Synthesis of Compound p2-9)
10 g (39 mmol) of methallyloxybenzenesulfonic acid (Mw = 2.5 million, Mw / Mn = 2.5) was dissolved in 25 ml of pure water, and 6.7 g (43 mmol) of tetramethylpiperidineoxy radical was dissolved in 10 ml of methanol. The solution was added slowly at room temperature. After stirring for 1 hour as it was, 90 ml of acetonitrile was slowly added dropwise to the reaction solution while stirring, and the produced polymer was filtered off and washed thoroughly with acetonitrile. The solvent was dried at 40 ° C. to obtain 14 g of the desired product p2-9. (Yield 84%, Mw = 235.9 million, Mw / Mn = 2.6)
(Synthesis Example 5: Synthesis of Compound p3-1)
10 g (47 mmol) of polystyrene sulfonic acid (Mw = 800,000, Mw / Mn = 2.0) was dissolved in 30 ml of pure water, and 12 g (52 mmol) of Ntbutyl-p-trifluoromethylaniline N-oxy radical was dissolved in 30 ml. Of methanol in methanol was slowly added at room temperature. After stirring for 1 hour as it was, 120 ml of acetonitrile was slowly added dropwise to the reaction solution while stirring, and the produced polymer was filtered off and thoroughly washed with acetonitrile. The solvent was dried at 40 ° C. to obtain 20 g of the desired product p3-1. (Yield 91%, Mw = 768,000, Mw / Mn = 2.8)
(Synthesis Example 6: Synthesis of Compound p3-26)
10 g (61 mmol) of methallylsulfonic acid (Mw = 1 million, Mw / Mn = 2.4) was dissolved in 30 ml of pure water, and 13 g (67 mmol) of Ntbutyl-p-cyanoaniline N-oxy radical was dissolved in 35 ml. A solution dissolved in methanol was added slowly at room temperature. After stirring for 1 hour as it was, 150 ml of acetonitrile was slowly added dropwise to the reaction solution while stirring, and the produced polymer was separated by filtration and thoroughly washed with acetonitrile. The solvent was dried at 40 ° C. to obtain 22 g of the desired product p3-26. (Yield 96%, Mw = 970,000, Mw / Mn = 2.2)
<Active material>
In the present invention, the active material is a composition containing a compound that emits or takes in electrons by a chemical reaction with an electrode and / or an electrolyte. The active material further includes a current collector, a binder, a catalyst, an electrolyte, a solvent, and the like.

(Current collector)
In the present invention, when an electrode layer containing an oxoammonium compound is formed, a current collector such as a conductive auxiliary material or an ion conductive auxiliary material may be mixed for the purpose of reducing impedance. These materials include carbonaceous fine particles such as carbon graphite, carbon black, and acetylene black, or conductive polymers such as PEDOT-PSS, polyaniline, polypyrrole, polythiophene, polyacetylene, and polyacene, and ions as conductive auxiliary materials. Examples of the conductive auxiliary material include a gel electrolyte or a solid electrolyte.

(binder)
In the present invention, a binder may be used to strengthen the connection between the constituent materials. As the binder, resins such as polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, polytetrafluoroethylene, styrene-butadiene copolymer rubber, polypropylene, polyethylene, polyimide, etc. A binder is mentioned.

(catalyst)
In the present invention, a catalyst may be used 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.

<Oxoammonium compound contained in active material>
In the present invention, the oxoammonium compound can be used by being contained in the active material of the positive electrode and the negative electrode or one of the electrodes.

When these materials are used for either the positive electrode or the negative electrode, the following materials can be used for other electrodes. That is, when an oxoammonium 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 , Li _x Mn ₂ O ₄ (0 <x <2) or lithium manganate having a spinel structure, MnO ₂ , LiCoO ₂ , LiNiO ₂ , Alternatively, Li _x V ₂ O ₅ (0 <x <2) and the like are dithioglycol, 2,5-dimercapto-1,3,4-thiadiazole, S-triazine-2,4,6-trithiol as disulfide compounds. In addition, examples of the conductive polymer include polyacetylene, polyphenylene, polyaniline, and polypyrrole. In this invention, these positive electrode layer materials can be used individually by 1 type or in combination of 2 or more types, Furthermore, it is also preferable to mix and use a conventionally well-known active material and these materials.

  On the other hand, when an oxoammonium compound is used for the positive electrode layer, the negative electrode layer includes one or two of carbon graphite, amorphous carbon, lithium metal, lithium alloy, lithium ion storage carbon, and conductive polymer. A combination of species or more is used. 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.

  However, in the present invention, it is preferable to use the active material according to claim 3 of the present invention for the positive electrode and the active material according to claim 4 for the negative electrode.

<Secondary battery>
The secondary battery is also called a storage battery or a rechargeable battery, and is a chemical battery that can be used repeatedly by storing electricity and being used as a battery.

  In the present invention, at least one of the positive electrode and the negative electrode contains the active material of the present invention, but the content is not particularly limited. However, since the capacity of the secondary battery is determined according to the amount of the oxoammonium compound contained, a content of 10% by mass or more is desirable from the viewpoint of the effect of the invention.

(Structure of secondary battery)
The secondary battery of the present invention has a configuration as shown in FIG. 1, for example. FIG. 1 is a cross-sectional view of a stacked secondary battery. The secondary battery shown in the figure has a configuration in which a negative electrode layer 1 and a positive electrode layer 2 are superposed via a separator 5 containing an electrolyte. In the present invention, the active material of the present invention is used for the negative electrode layer 1 or the positive electrode layer 2. The assembled structure is sealed with a sealing material 6.

  FIG. 2 is a cross-sectional view of a stacked secondary battery. The structure is a structure in which the positive electrode current collector 4, the positive electrode layer 2, the separator 5 containing an electrolyte, the negative electrode layer 1, and the negative electrode current collector 3 are sequentially stacked. In the present invention, any method can be used for laminating the positive electrode layer and the negative electrode layer, and a multilayer laminate, a combination of laminates on both sides of a current collector, a wound one, or the like 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, 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 positive electrode and the negative electrode are not in contact with each other.

The electrolyte contained in the separator 5 performs charge carrier transport between both 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 solution in which an electrolyte salt is dissolved in a solvent can be used as the electrolyte. As the electrolyte, for example, an electrolytic solution in which an electrolyte salt is dissolved in a solvent can be used. Examples of such solvents include organic solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, tetrahydrofuran, dioxolane, sulfolane, dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone. A solvent is mentioned. 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 , LiNCF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiC (CF ₃ SO ₂ ) ₃ , LiC. (C ₂ F ₅ SO ₂ ) _{3 and the} like.

  Further, a solid electrolyte may be used as the electrolyte. Polymeric substances used in 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-acrylic Acid copolymers, acrylonitrile - vinyl acetate copolymer, acrylonitrile-based polymer, further polyethylene oxide, ethylene oxide - propylene oxide copolymer, polymer and the like of these acrylates body or methacrylate products thereof. These polymer materials can be used in the form of a gel containing an electrolytic solution, or only the polymer material 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 secondary battery shape include those in which an electrode laminate or a wound body is sealed with a metal film such as a metal case, a resin case or an aluminum foil, and a laminate film made of a synthetic resin film. Examples of the appearance include a cylindrical shape, a square shape, a coin shape, and a sheet shape, but the present invention is not limited to these.

  As a method for producing a secondary battery in the present invention, a conventionally known method can be used. For example, a solvent is added to the active material to form a slurry, which is applied to the electrode current collector, laminated with a counter electrode via a separator, or wrapped around this with an outer package, injected with electrolyte, and sealed. It is a method of stopping.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these. Unless otherwise specified, “%” in the examples represents “mass%”.

Example 1
<< Production of Battery 1 >>
In a dry box equipped with a gas purifier, 50 mg of Comparative Compound (1) and 50 mg of graphite powder as an auxiliary conductive material were mixed in a glass container in an argon gas atmosphere, and this was mixed with vinylidene fluoride-hexafluoropropylene. When 20 mg of copolymer and 1 g of tetrahydrofuran were further added and 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 a positive 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 positive electrode layer is formed, and further, a lithium-bonded negative electrode copper foil (area: 1.5 cm × 1) provided with a lead wire. 5 cm, lithium film thickness 30 μm, copper foil thickness: 20 μm), the whole was sandwiched between 5 mm thick polytetrafluoroethylene sheets, and pressure was applied to produce battery 101.

  In place of the comparative compound (1), the comparative compounds (2) and (3) were used and the addition amount thereof was changed, or the oxoammonium compound of the present invention was used and the addition amount thereof was changed, Batteries 102 to 145 were produced in the same manner as described above except that the amount of carbon graphite as the auxiliary conductive material was changed to the amount shown in Table 1. The results are shown in Table 1.

<Production of battery 2>
In a dry box equipped with a gas purifier, 50 mg of Comparative Compound (4) and 50 mg of graphite powder as an auxiliary conductive material were mixed in a glass container under an argon gas atmosphere, and this was mixed with vinylidene fluoride-hexafluoropropylene. When 20 mg of copolymer and 1 g of tetrahydrofuran were further added and 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 a copper foil (area: 1.5 cm × 1.5 cm, thickness: 20 μm) provided with a lead wire, 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 a negative electrode layer was formed on the copper foil.

  Next, a gel electrolyte film cut out to 2.0 cm × 2.0 cm (same as that prepared in Battery Preparation 1) was laminated on the negative electrode copper foil, and lithium cobaltate-laminated positive electrode aluminum provided with a lead wire. After overlapping the foil (area: 1.5 cm × 1.5 cm, lithium cobalt oxide film thickness 50 μm, aluminum foil thickness: 100 μm), the whole was sandwiched between 5 mm thick polytetrafluoroethylene sheets and the pressure was In addition, a battery 201 was produced.

  Except that the oxoammonium compound of the present invention was used in place of the comparative compound (4), the addition amount was changed, and the amount of carbon graphite of the auxiliary conductive material was changed to the amount shown in Table 2, respectively. Similarly, batteries 202 to 236 were produced. The results are shown in Table 2.

<< Production of Battery 3 >>
In a dry box equipped with a gas purifier, 50 mg of Comparative Compound (1) and 50 mg of graphite powder as an auxiliary conductive material were mixed in a glass container in an argon gas atmosphere, and this was mixed with vinylidene fluoride-hexafluoropropylene. When 20 mg of copolymer and 1 g of tetrahydrofuran were further added and 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 a positive electrode layer was formed on the aluminum foil.

  Similarly, 50 mg of the comparative compound (4) and 50 mg of graphite powder as an auxiliary conductive material were mixed in a glass container in an argon gas atmosphere in a dry box, and 20 mg of vinylidene fluoride-hexafluoropropylene copolymer was mixed with this. When 1 g of tetrahydrofuran was further added and mixed for several more minutes until the whole became uniform, a black slurry was obtained.

  Subsequently, 200 mg of the obtained slurry was dropped on the surface of a copper foil (area: 1.5 cm × 1.5 cm, thickness: 20 μm) provided with a lead wire, 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 a negative electrode layer was formed on the copper foil.

  Next, a gel electrolyte membrane cut out to 2.0 cm × 2.0 cm (same as that prepared in Battery Preparation 1) was laminated on the aluminum foil on which the positive electrode layer was formed, and further a negative electrode layer was formed. After the copper foils were overlaid, the whole was sandwiched between 5 mm thick polytetrafluoroethylene sheets, and pressure was applied to produce a battery 301. The results are shown in Table 3.

  The oxoammonium compound of the present invention was used in place of the comparative compounds (1) and (4), the amount added was changed, and the amount of carbon graphite of the auxiliary conductive material was changed to the amount shown in Table 3, respectively. Batteries 302 to 342 were produced in the same manner as above except that. The results are shown in Table 3.

<Battery evaluation>
About the produced battery, steady operation, discharge duration, and storage stability were evaluated by the following method.

(Evaluation of steady operation)
The produced battery was charged / discharged with a constant current (0.1 mA) and with a cut-off voltage (charge 4.2 V, discharge 2.5 V). Evaluation was made according to the following criteria.
○: A flat voltage portion is recognized near 2.9V and operates as a battery, and charging and discharging is possible over 10 cycles. Δ: A flat voltage portion is recognized near 2.9V and operates as a battery. In addition, when the charge and discharge were repeated for 5 cycles or more, the voltage was clearly reduced. X: A flat voltage portion was not recognized and the battery did not operate.

(Evaluation of discharge duration)
In the evaluation of the steady operation, the battery having an evaluation of ◯ was discharged at a constant current of 0.1 mA, and the time until the voltage became 1 V or less was measured.

(Evaluation of storage stability)
In the evaluation of the steady operation, many batteries with an evaluation of “◯” were produced, and initial charge / discharge was performed for 10 cycles. Subsequently, after charging under the same conditions as described above, each battery was 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 was measured after storage. For each battery, the self-discharge rate was calculated as an index of storage stability according to the following calculation formula.

  In addition, the discharge capacity is discharged at a constant current of 0.1 mA from the fully charged state, and the discharge duration until the battery voltage reaches the discharge end voltage of 2.5 V is measured. “Discharge current value × discharge duration” Calculated as

Self-discharge rate = (discharge capacity before storage + discharge capacity after storage) / discharge capacity before storage × 100 (%)
The results of evaluation are shown in Tables 1 to 3.

  From Tables 1 to 3, since the active material of the present invention and the secondary battery are excellent in conductivity, the amount of current collector such as carbon graphite can be extremely reduced when forming the electrode active material layer. It can be seen that the difference between the theoretical capacity and the actual battery capacity is extremely small.

  Moreover, it turns out that the active material of this invention and a secondary battery have a high energy density.

  Furthermore, it can be seen that the active material and the secondary battery of the present invention are chemically and electrically stable.

Example 2
<Evaluation of reaction rate of oxidation reaction of phenethyl alcohol to phenylacetaldehyde>
About 1 g of each of the comparative compound of Table 2 and the oxoammonium compound of the present invention activated by a known method (described in Non-Patent Document 5), each dispersed in 15 ml of acetonitrile, 0.12 g (0.1 mmol) of phenethyl alcohol ) Were added, and each was stirred at room temperature for 8 hours using a magnetic stirrer. The polymer was separated by filtration, and the reaction rate of the oxidation reaction of phenethyl alcohol to phenylacetaldehyde was quantified by gas chromatography. The reaction rate was calculated by the following formula.

Reaction rate (%) = phenylacetaldehyde production amount (mol / ml) / (phenethyl alcohol remaining amount (mol / ml) + phenylacetaldehyde production amount (mol / ml)) × 100
The results are shown in Table 4.

  Comparative compound 4: An oxidizing agent described in Non-Patent Document 5, that is, an oxidizing agent in which p-toluenesulfonate of TEMPO is supported on a macroporous substrate of poly (styrene-co-divinylbenzene).

  From Table 4, it can be seen that the oxoammonium compound of the present invention can selectively oxidize a less active aliphatic primary alcohol to an aldehyde in a high yield.

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 (5)

An active material containing an oxoammonium compound, wherein the counter anion of the oxoammonium compound is a sulfonate anion-containing polymer , and the sulfonate anion-containing polymer is a polystyrene sulfonate anion . The active material according to claim 1 , wherein the oxoammonium cation structure of the oxoammonium compound is represented by the following general formula 1 or 2.
(In the formula, R _{15 to} R ₁₈ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. X _{1 to} X ₅ each independently represent> CH ₂ ,> N ⁺ = O, or> N. ⁺ H-OH, R ₁₉ represents a hydrogen atom, a halogen atom or a substituent that can be substituted on three carbon atoms of a 6-membered ring, a plurality of R ₁₉ may be the same or different, and n is 0 to 0 Represents an integer of 3.) The active material according to claim 1, wherein the oxoammonium cation structure of the oxoammonium compound is at least one of structures represented by the following general formula 3.

(Wherein R ₂₀ represents a tertiary alkyl group having 4 to ₂₀ carbon atoms, R ₂₁ represents an electron-withdrawing group, and a plurality of R ₂₁ may be the same or different, and m is Represents an integer of 1 to 5.) A secondary battery comprising the active material according to any one of claims 1 to 3 . A secondary battery comprising the active material according to claim 2 in a positive electrode and the active material according to claim 3 in a negative electrode.