WO2012133204A1 - Batterie - Google Patents

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Publication number
WO2012133204A1
WO2012133204A1 PCT/JP2012/057551 JP2012057551W WO2012133204A1 WO 2012133204 A1 WO2012133204 A1 WO 2012133204A1 JP 2012057551 W JP2012057551 W JP 2012057551W WO 2012133204 A1 WO2012133204 A1 WO 2012133204A1
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WIPO (PCT)
Prior art keywords
pyrroline
electrode
polymer
nitroxide
battery
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PCT/JP2012/057551
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English (en)
Japanese (ja)
Inventor
西出　宏之
研一 小柳津
壮介 山口
信貴 藤本
祐治 金原
瞬 橋本
岩佐　繁之
中原　謙太郎
Original Assignee
学校法人早稲田大学
住友精化株式会社
日本電気株式会社
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Priority to JP2013507524A priority Critical patent/JPWO2012133204A1/ja
Publication of WO2012133204A1 publication Critical patent/WO2012133204A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a battery capable of suppressing elution of electrode components into an electrolyte solution.
  • lithium ion secondary batteries using a lithium-containing transition metal compound as a positive electrode and a lithium storage compound such as a carbon material as a negative electrode are widely used as power sources for such portable electronic devices.
  • the energy density of the lithium ion secondary battery is approaching the theoretical limit, and development of a new secondary battery capable of realizing a high capacity is demanded.
  • the reaction rate of an electrode reaction is small in a lithium ion secondary battery, the battery performance is remarkably lowered when a large current is passed.
  • the capacity and output are often much lower than expected, and charging needs to be performed for a long time.
  • a secondary battery using an organic radical compound as an electrode active material charges and discharges using a radical oxidation-reduction reaction, and thus has a high reaction rate. Therefore, it has the characteristics that it has high output and charging is completed in a relatively short time.
  • An object of this invention is to provide the battery which can suppress the elution to the electrolyte solution of an electrode component.
  • the present invention Item 1. A battery having an electrode containing a pyrroline-based nitroxide polymer and an electrolytic solution, wherein the electrolytic solution contains a polyethylene glycol, Item 2.
  • Item 2. The battery according to Item 1, wherein the pyrroline nitroxide polymer is a polymer obtained by polymerizing a pyrroline nitroxide compound represented by the following general formula (1). In formula (1), n represents 0 or 1.
  • Item 3. The battery according to Item 1, wherein the pyrroline nitroxide polymer is a polymer obtained by polymerizing a pyrroline nitroxide compound represented by the following general formula (2).
  • Item 4. Item 2. The battery according to Item 1, wherein the amount of polyethylene glycol used is 0.05 to 30 parts by mass with respect to 100 parts by mass of the electrolyte. About. The present invention is described in detail below.
  • the battery according to the present invention has an electrode containing a pyrroline-based nitroxide polymer.
  • the pyrroline nitroxide polymer is obtained by polymerizing a pyrroline nitroxide compound.
  • the pyrroline nitroxide polymer is preferably a polymer obtained by polymerizing a pyrroline nitroxide compound represented by the following general formula (1).
  • n 0 or 1.
  • Examples of the pyrroline nitroxide compound represented by the general formula (1) include 3-oxiranyl-2,2,5,5-tetramethylpyrrolin-1-oxyl where n is 0, and pyrroline nitroxide where n is 1. Examples thereof include substituted glycidyl ethers.
  • the 3-oxiranyl-2,2,5,5-tetramethylpyrroline-1-oxyl is, for example, as shown in the following formula (3), 3-carbamoyl-2,2,5,5-tetramethylpyrroline- It can be produced by a method using 1-oxyl (Tetrahedron Letters, 43 (4), 553-555 (2002)).
  • 3-carbamoyl-2,2,5,5-tetramethylpyrrolin-1-oxyl is hydrolyzed using an aqueous sodium hydroxide solution or the like to produce 3-carboxy-2,2,5,5-tetra Methylpyrrolin-1-oxyl is then reduced using 3-aluminum-2,2,2, and the like using lithium aluminum hydride-tert-butoxide in an inert gas atmosphere such as argon gas or nitrogen gas.
  • 5-Oxylanyl-2,2,5,5-tetramethylpyrroline-1-oxyl is produced by cyclizing 5,5-tetramethylpyrroline-1-oxyl with trimethylsulfonium iodide. can do.
  • the pyrroline-based nitroxide-substituted glycidyl ether is, for example, a method of reacting epichlorohydrin with 4-hydroxyproxyl in the presence of sodium hydroxide using tetrabutylammonium sodium hydrogensulfate as a catalyst (Macromolecules, 26, 3227-3229 (1993)).
  • Examples of a method for polymerizing the pyrroline nitroxide compound represented by the general formula (1) to obtain a pyrroline nitroxide polymer include a polymerization method using a bulk polymerization method, a solution polymerization method, and the like.
  • a method of polymerizing using the bulk polymerization method for example, using a reactor equipped with a stirrer, a thermometer, a gas introduction pipe for introducing an inert gas such as argon gas or nitrogen gas, and a cooling pipe.
  • Examples thereof include a method in which a predetermined amount of a nitroxide compound is charged, deoxygenated with an inert gas, and then a polymerization initiator is added while stirring.
  • an inert solvent is charged together with a predetermined amount of nitroxide compound, deoxygenated with an inert gas, and then stirred.
  • examples of the method include adding a polymerization initiator.
  • the pyrroline nitroxide polymer is preferably a polymer obtained by polymerizing a pyrroline nitroxide compound represented by the following general formula (2).
  • the pyrroline-based nitroxide compound represented by the general formula (2) is, for example, a method using 3-carbamoyl-2,2,5,5-tetramethylpyrrolin-1-oxyl as shown in the following formula (4) (CAN. J. CHEM., 64, 1482-1490 (1986)).
  • 3-carbamoyl-2,2,5,5-tetramethylpyrrolin-1-oxyl is hydrolyzed using an aqueous sodium hydroxide solution or the like to produce 3-carboxy-2,2,5,5-tetra Methylpyrrolin-1-oxyl is then reduced using 3-aluminum-2,2,2, and the like using lithium aluminum hydride-tert-butoxide in an inert gas atmosphere such as argon gas or nitrogen gas.
  • 5-vinyl-2,2,5,5-tetramethylpyrrolin-1-oxyl is produced by converting it to 5,5-tetramethylpyrroline-1-oxyl and then vinylating it with methyltriphosphonium bromide can do.
  • Examples of a method for polymerizing the pyrroline nitroxide compound represented by the general formula (2) to obtain a pyrroline nitroxide polymer include a polymerization method using a bulk polymerization method, a solution polymerization method, and the like.
  • a method of polymerizing using the bulk polymerization method for example, using a reactor equipped with a stirrer, a thermometer, a gas introduction pipe for introducing an inert gas such as argon gas or nitrogen gas, and a cooling pipe.
  • Examples thereof include a method in which a predetermined amount of a nitroxide compound is charged, deoxygenated with an inert gas, and then a polymerization initiator is added while stirring.
  • an inert solvent is charged together with a predetermined amount of nitroxide compound, deoxygenated with an inert gas, and then stirred.
  • examples of the method include adding a polymerization initiator.
  • the number average molecular weight of the pyrroline-based nitroxide polymer is preferably 500 to 5,000,000, and more preferably 1,000 to 1,000,000.
  • the number average molecular weight is less than 500, the pyrroline-based nitroxide polymer is dissolved in the electrolytic solution, and the capacity may be reduced when the battery is used repeatedly.
  • the number average molecular weight exceeds 5,000,000, the solubility in the electrolytic solution is lowered, and the capacity may be lowered when the battery is repeatedly used.
  • the number average molecular weight in this invention means the value measured by the high performance liquid chromatography and converted into polystyrene of the molecular weight existing value.
  • the pyrroline nitroxide polymer may be used alone or in combination of two or more.
  • the electrode preferably comprises an electrode active material, a conductivity-imparting agent (auxiliary conductive material), an ion conduction auxiliary material, a binder, a thickener, and a catalyst in addition to the pyrroline-based nitroxide polymer.
  • auxiliary conductive material auxiliary conductive material
  • ion conduction auxiliary material a binder, a thickener, and a catalyst in addition to the pyrroline-based nitroxide polymer.
  • Electrode Active Material refers to a material that directly contributes to electrode reactions such as charge reaction and discharge reaction, and plays a central role in the battery system.
  • the electrode active material contains the pyrroline nitroxide polymer, and the pyrroline nitroxide polymer may be used alone or in combination of two or more as the positive electrode and / or negative electrode active material. Alternatively, the electrode active material may be combined with other electrode active materials.
  • examples of other electrode active materials include metal oxides, disulfide compounds, other stable radical compounds, and conductive polymers.
  • the metal oxide examples include lithium manganate such as LiMnO 2 and Li x Mn 2 O 4 (0 ⁇ x ⁇ 2), lithium manganate having a spinel structure, MnO 2 , LiCoO 2 , LiNiO 2 , or Li y V 2 O 5 (0 ⁇ y ⁇ 2), olivine-based material LiFePO 4 , materials obtained by substituting a part of Mn in the spinel structure with other transition metals, LiNi 0.5 Mn 1.5 O 4 , LiCr 0.
  • lithium manganate such as LiMnO 2 and Li x Mn 2 O 4 (0 ⁇ x ⁇ 2)
  • lithium manganate having a spinel structure MnO 2 , LiCoO 2 , LiNiO 2 , or Li y V 2 O 5 (0 ⁇ y ⁇ 2)
  • olivine-based material LiFePO 4 materials obtained by substituting a part of Mn in the spinel structure with other transition metals, LiNi 0.5 Mn 1.5 O 4 , LiC
  • disulfide compound examples include dithioglycol, 2,5-dimercapto-1,3,4-thiadiazole, S-triazine-2,4,6-trithiol and the like.
  • Examples of the other stable radical compound include poly (2,2,6,6-tetramethyl-4-piperidinoxymethacrylate).
  • Examples of the conductive polymer include polyacetylene, polyphenylene, polyaniline, and polypyrrole.
  • lithium manganate and LiCoO 2 are preferably used.
  • These other electrode active materials may be used alone or in combination with the pyrroline nitroxide polymer, or may be used in combination of two or more.
  • electrode active material when used as an electrode active material for a negative electrode, other electrode active materials include graphite, amorphous carbon, metallic lithium and lithium alloy, lithium ion storage carbon, metallic sodium, and other stable radical compounds. And conductive polymers.
  • stable radical compounds include poly (2,2,6,6-tetramethyl-4-piperidinoxymethacrylate) and the like.
  • metallic lithium or graphite it is preferable to combine with metallic lithium or graphite.
  • metallic lithium or graphite it does not specifically limit as these shapes, A thin-film thing, a bulk thing, the thing which hardened the powder, a fibrous thing, a flake-like thing, etc. may be sufficient.
  • These other electrode active materials may be used alone or in combination with the pyrroline nitroxide polymer, or may be used in combination of two or more.
  • the electrode active material containing the pyrroline nitroxide polymer is preferably used as a positive electrode active material, and the pyrroline nitroxide polymer is combined with the other electrode active material. More preferably, it is used alone. Moreover, it is preferable to use metallic lithium or graphite as the electrode active material of the negative electrode at this time.
  • Conductivity imparting agent (auxiliary conductive material) and ion conductivity assisting material
  • the conductivity imparting agent is used for the purpose of reducing impedance and improving energy density and output characteristics.
  • auxiliary conductive material or ion conduction auxiliary material may be mixed.
  • auxiliary conductive material examples include carbonaceous fine particles such as graphite, carbon black, and acetylene black, carbon fibers such as vapor grown carbon fiber (VGCF) and carbon nanotube, polyaniline, polypyrrole, polythiophene, polyacetylene, and polyacene. Molecule.
  • ion conduction auxiliary material examples include polymer gel electrolytes and polymer solid electrolytes. Among these, carbon fibers are preferably used, and vapor-grown carbon fibers are more preferably used. By using carbon fiber, the tensile strength of the electrode is increased, and the electrode is less likely to crack or peel off.
  • These auxiliary conductive materials and ion conductive auxiliary materials may be used alone or in combination of two or more. When the auxiliary conductive material or the ion conductive auxiliary material is used, the mixing ratio in the electrode is preferably 10 to 80% by mass.
  • Binder in the electrode active material a binder may be mixed in order to strengthen the bond between the constituent materials.
  • the binder include polytetrafluoroethylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer rubber, polypropylene, polyethylene, and polyimide.
  • resin binders such as various polyurethanes. These binders may be used individually by 1 type, or may use 2 or more types together. When the binder is used, the mixing ratio in the electrode is preferably 5 to 30% by mass.
  • a thickener may be mixed.
  • the thickener include carboxymethyl cellulose, polypropylene oxide, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl hydroxyethyl cellulose, polyvinyl alcohol, polyacrylamide, hydroxyethyl polyacrylate, ammonium polyacrylate, and sodium polyacrylate. .
  • These thickeners may be used individually by 1 type, or may use 2 or more types together. When the thickener is used, the mixing ratio in the electrode is preferably 0.1 to 5% by mass.
  • Catalyst In the electrode active material in order to perform the electrode reaction more smoothly, a catalyst that assists the oxidation-reduction reaction may be mixed.
  • 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. . These catalysts may be used individually by 1 type, or may use 2 or more types together. When the catalyst is used, the mixing ratio in the electrode is preferably 10% by mass or less.
  • the battery according to the present invention has an electrolytic solution.
  • the electrolytic solution performs charge carrier transport between the negative electrode and the positive electrode, and generally has an ionic conductivity of 10 ⁇ 5 to 10 ⁇ 1 S / cm at 20 ° C. Preferably it is.
  • the electrolytic solution for example, an electrolytic solution in which an electrolyte salt is dissolved in a solvent can be used.
  • electrolyte salt examples 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, Li (CF 3 SO 2 ) Conventionally known materials such as 3 C and Li (C 2 F 5 SO 2 ) 3 C can be mentioned. These electrolyte salts may be used individually by 1 type, or may use 2 or more types together.
  • solvent examples include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ⁇ -butyrolactone, tetrahydrofuran, dioxolane, sulfolane, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl.
  • organic solvents such as -2-pyrrolidone. These solvents may be used alone or in combination of two or more.
  • the electrolytic solution contains polyethylene glycols.
  • the polyethylene glycols are electrochemically stable resins.
  • polyethylene glycols examples include polyethylene glycol and derivatives thereof, such as polyethylene glycol, sodium polyoxyethylene alkylphenyl ether alkylbenzene sulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl ether methylcarboxylate.
  • polyethylene glycols polyethylene glycol and polyethylene oxide are preferable, and polyethylene glycol is more preferable from the viewpoint of being easily available industrially, inexpensive, and obtaining a high effect.
  • the polyethylene glycols may be used alone or in combination of two or more.
  • the number average molecular weight of the polyethylene glycol is usually preferably 500 to 500,000, more preferably 1,000 to 50,000, still more preferably 2,000 to 40,000, and particularly preferably 5,000. ⁇ 20,000.
  • the number average molecular weight is less than 500, the affinity with the pyrroline nitroxide polymer is inferior and the solubility of the pyrroline nitroxide polymer in the electrolytic solution is increased, so that a sufficient effect may not be obtained.
  • the number average molecular weight exceeds 500,000, the solubility in the electrolytic solution is decreased, the viscosity of the electrolytic solution is increased, and the oxidation-reduction wave of the obtained battery may be reduced, or it may be used repeatedly. When doing so, the capacity may be reduced.
  • the number average molecular weight in this invention means the value measured by the high performance liquid chromatography and converted into polystyrene of the molecular weight existing value.
  • the amount of the polyethylene glycol used can be appropriately adjusted depending on the molecular weight of the polyethylene glycol, but is preferably 0.05 to 30 parts by mass, and 0.5 to 10 parts by mass with respect to 100 parts by mass of the electrolytic solution. More preferred.
  • the amount of the polyethylene glycol used is less than 0.05 parts by mass, the effect of suppressing elution of the pyrroline nitroxide polymer into the electrolytic solution may be reduced.
  • the usage-amount of the said polyethyleneglycol exceeds 30 mass parts, there is no effect corresponding to a usage-amount and it is not economical.
  • a battery characteristic may fall because electrolyte solution viscosity increases.
  • a polymer compound may be added to the electrolytic solution.
  • the polymer compound include polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-ethylene copolymer, vinylidene fluoride-monofluoroethylene copolymer, and vinylidene fluoride-trifluoroethylene copolymer.
  • Polymers vinylidene fluoride-tetrafluoroethylene copolymers, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymers and other vinylidene fluoride polymers; acrylonitrile-methyl methacrylate copolymers, acrylonitrile-methyl Acrylate copolymer, acrylonitrile-ethyl methacrylate copolymer, acrylonitrile-ethyl acrylate copolymer, acrylonitrile-methacrylic acid copolymer, acrylonitrile-acrylic acid copolymer, acryloni Lil - acrylonitrile polymers such as vinyl acetate copolymer; and polyethylene oxide, ethylene oxide - propylene oxide copolymer, polymer and the like of these acrylates body or methacrylate products thereof.
  • the battery according to the present invention preferably includes a current collector and a separator in addition to the electrode and the electrolytic solution.
  • the current collector and the separator are preferably used in contact with an electrode active material.
  • the current collector used in contact with the electrode active material include nickel, aluminum, copper, gold, silver, aluminum alloy, stainless steel, carbon, etc., and those having a shape such as a foil, a metal flat plate, and a mesh shape. Can be used.
  • the current collector may have a catalytic effect, or the electrode active material and the current collector may be chemically bonded.
  • examples of the separator include porous films and nonwoven fabrics made of polyethylene, polypropylene, and the like.
  • the shape of the battery according to the present invention is not particularly limited, and a conventionally known battery can be used.
  • a metal case a resin case, or a laminate film composed of a metal foil such as an aluminum foil and a synthetic resin film, etc.
  • Examples include molds and sheet molds.
  • FIG. 1 shows an example of an embodiment of a battery according to the present invention.
  • the battery shown in FIG. 1 has a configuration in which a positive electrode 5 and a negative electrode 3 are stacked so as to face each other with a separator 4 containing an electrolytic solution, and a positive electrode current collector 6 is further stacked on the positive electrode 5.
  • These are externally covered with a stainless steel exterior 1 on the negative electrode side and a stainless steel exterior 1 on the positive electrode side, and an insulating packing 2 made of an insulating material such as a plastic resin is disposed between them for the purpose of preventing electrical contact therebetween. .
  • the battery manufacturing method according to the present invention is not particularly limited, and a method appropriately selected according to the material can be used.
  • an electrode is prepared by adding a solvent to the electrode active material containing the pyrroline-based nitroxide polymer, a conductivity-imparting agent, etc., and applying it to the electrode current collector, and volatilizing the solvent at room temperature or heating. Further, this electrode is laminated or wound with a counter electrode and a separator in between, wrapped in an outer package, and sealed by injecting an electrolytic solution.
  • Solvents for slurrying include ether solvents such as tetrahydrofuran, diethyl ether, ethylene glycol dimethyl ether and dioxane; amine solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone; benzene, toluene and xylene Aromatic hydrocarbon solvents such as hexane, heptane, etc .; Halogenated hydrocarbon solvents such as chloroform, dichloromethane, dichloroethane, trichloroethane, carbon tetrachloride; Alkyl ketone solvents such as acetone and methyl ethyl ketone Alcoholic solvents such as methanol, ethanol and isopropyl alcohol; dimethyl sulfoxide, water and the like.
  • ether solvents such as tetrahydrofuran, diethyl ether, ethylene glycol dimethyl ether and dioxane
  • the present invention by adding polyethylene glycols to the electrolytic solution, the elution of the pyrroline nitroxide polymer into the electrolytic solution is suppressed, and as a result, the battery characteristics can be maintained over a long period of time. Can be provided. Although the mechanism is not clear, it is considered that polyethylene glycols having excellent affinity with the pyrroline nitroxide polymer protect the surface of the electrode.
  • a 3 mL 4-neck flask equipped with a stirrer, an argon gas introduction tube, a thermometer, and a reflux condenser and previously substituted with argon gas was obtained in the same manner as in the production of the pyrroline nitroxide compound.
  • -0.18 g (1 mmol) of oxiranyl-2,2,5,5-tetramethylpyrroline-1-oxyl was added, 0.2 mL of the diethylzinc / water-based initiator was added, and the mixture was brought to room temperature under an argon gas atmosphere. For 48 hours.
  • the resulting 3-carboxy-2,2,5,5-tetramethylpyrrolin-1-oxyl (1 g) was equipped with a stirrer, an argon gas inlet tube, and a thermometer, and was previously replaced with argon gas in a 4-mL volume of 4 necks.
  • the flask was charged and dissolved by adding a mixed solvent of 12 mL of benzene / 0.44 mL of pyridine. Next, it was cooled to 5 ° C. in an argon atmosphere, 0.44 mL of thionyl chloride / 2 mL of benzene was added and stirred for 1 hour, and then the solvent was distilled off, and 10 mL of THF was added and dissolved.
  • the obtained film-forming electrode was subjected to polyethylene glycol (Sigma Aldrich Japan Co., Ltd., number average molecular weight ⁇ 8,500-11) in advance using an electrochemical analyzer (BAS Co., Ltd., trade name: ALS model 600B electrochemical analyzer). 500) in acetonitrile (concentration of 5% by mass), tetrabutylammonium perchlorate as an electrolytic substrate (0.1 mol / L), a reference electrode as Ag / AgCl, and a scanning speed of 20 mV / s at 25 ° C. CV curve was measured. As a result, a redox wave derived from the pyrroline-based nitroxide polymer appeared at 0.88 V, and no change was observed in the redox wave even after 1000 sweeps.
  • Reference Example 2 In Reference Example 1, in place of acetonitrile in which polyethylene glycol (manufactured by Sigma-Aldrich Japan Co., Ltd., number average molecular weight ⁇ 8,500 to 11,500) was dissolved (5 mass% concentration), acetonitrile (no addition of polyethylene glycol) was used. A CV curve was measured in the same manner as in Reference Example 1 except that was used. As a result, the curve attenuated with the sweep.
  • polyethylene glycol manufactured by Sigma-Aldrich Japan Co., Ltd., number average molecular weight ⁇ 8,500 to 11,500
  • Example 1 Battery using electrode active material containing pyrroline nitroxide polymer
  • a pyrroline nitroxide polymer obtained in the same manner as in Production Example 1 0.08 g of graphite powder as an auxiliary conductive material, and 0.01 g of polytetrafluoroethylene as a binder, and prepare an agate mortar. And kneaded. The mixture obtained by dry-mixing for about 10 minutes was subjected to roller stretching under pressure to obtain a thin film having a thickness of about 150 ⁇ m. This was dried overnight at 100 ° C. in a vacuum and then punched into a circle having a diameter of 12 mm to form a coin battery electrode. The mass of this electrode was 13.1 mg.
  • polyethylene glycol manufactured by Sigma Aldrich Japan Co., Ltd.
  • an ethylene carbonate / diethyl carbonate mixed solution (mixing volume ratio 1: 1) containing 1.0 mol / L LiPF 6 electrolyte salt as an electrolytic solution.
  • 0.10 parts by mass of a number average molecular weight ⁇ 8,500 to 11,500 was added to prepare an electrolyte solution containing polyethylene glycol.
  • the electrode obtained as described above was immersed in the electrolytic solution containing polyethylene glycol, and the voids in the electrode were impregnated with the electrolytic solution.
  • the electrode impregnated with the electrolytic solution is placed on a stainless steel sheath (manufactured by Kagatsu Co., Ltd.) that also serves as a positive electrode current collector, and a polypropylene porous film separator impregnated with the electrolytic solution is laminated thereon. did. Furthermore, the lithium disk used as a negative electrode was laminated
  • Example 2 A sealed coin-type battery was produced in the same manner as in Example 1 except that 0.02 part by mass of polyethylene glycol was used instead of 0.10 part by mass of polyethylene glycol.
  • Example 3 A sealed coin-type battery was produced in the same manner as in Example 1 except that 0.19 parts by mass of polyethylene glycol was used instead of 0.10 parts by mass of polyethylene glycol.
  • Example 4 Instead of 0.10 parts by mass of polyethylene glycol (manufactured by Sigma-Aldrich Japan Co., Ltd., number average molecular weight ⁇ 8,500 to 11,500), 0.10 parts by mass of polyethylene glycol (manufactured by Sigma Aldrich Japan Co., Ltd., number average molecular weight ⁇ A sealed coin-type battery was manufactured in the same manner as in Example 1 except that 570 to 630) were used.
  • Example 5 Instead of 0.10 parts by mass of polyethylene glycol (manufactured by Sigma-Aldrich Japan Co., Ltd., number average molecular weight ⁇ 8,500 to 11,500), 0.10 parts by mass of polyethylene glycol (manufactured by Sigma Aldrich Japan Co., Ltd., number average molecular weight ⁇ A sealed coin-type battery was manufactured in the same manner as in Example 1 except that 400,000) was used.
  • Example 6 Instead of 0.10 parts by mass of polyethylene glycol (manufactured by Sigma-Aldrich Japan Co., Ltd., number average molecular weight ⁇ 8,500 to 11,500), 0.10 parts by mass of polyethylene glycol (manufactured by Sigma Aldrich Japan Co., Ltd., number average molecular weight ⁇ A sealed coin-type battery was produced in the same manner as in Example 1 except that 285 to 315) were used.
  • Example 7 Instead of 0.10 parts by mass of polyethylene glycol (manufactured by Sigma-Aldrich Japan Co., Ltd., number average molecular weight ⁇ 8,500 to 11,500), 0.10 parts by mass of polyethylene glycol (manufactured by Sigma Aldrich Japan Co., Ltd., number average molecular weight ⁇ A sealed coin-type battery was manufactured in the same manner as in Example 1 except that 900,000) was used.
  • Example 8 Example 1 except that 0.10 g of the pyrroline nitroxide polymer obtained in the same manner as in Production Example 2 was used instead of 0.10 g of the pyrroline nitroxide polymer obtained in the same manner as in Production Example 1. Similarly, a radical composition and a sealed coin-type battery were produced.
  • Example 1 A coin-type battery was produced in the same manner as in Example 1, except that an electrolyte not containing polyethylene glycol (manufactured by Sigma Aldrich Japan Co., Ltd., number average molecular weight ⁇ 8,500 to 11,500) was used. did.
  • the battery which can suppress the elution to the electrolyte solution of an electrode component can be provided.

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Abstract

La présente invention concerne une batterie capable de minimiser l'élution des composants d'électrode vers un électrolyte. La présente invention vise une batterie qui possède un électrolyte et des électrodes contenant un polymère de nitroxyde de pyrroline, ledit électrolyte contenant un polyéthylène glycol.
PCT/JP2012/057551 2011-03-31 2012-03-23 Batterie WO2012133204A1 (fr)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014073560A1 (fr) * 2012-11-09 2014-05-15 株式会社村田製作所 Batterie secondaire et procédé de charge et de décharge de batterie secondaire
DE102014003300A1 (de) 2014-03-07 2015-09-10 Evonik Degussa Gmbh Neue Tetracyanoanthrachinondimethanpolymere und deren Verwendung
DE102014004760A1 (de) 2014-03-28 2015-10-01 Evonik Degussa Gmbh Neue 9,10-Bis(1,3-dithiol-2-yliden)-9,10-dihydroanthracenpolymere und deren Verwendung
JP5969981B2 (ja) * 2011-03-31 2016-08-17 住友精化株式会社 ラジカル組成物およびそれを用いた電池
JP2016534521A (ja) * 2013-09-09 2016-11-04 ユニヴェルシテ・カトリック・ドゥ・ルーヴァン 非水電解質二次電池用ハイブリッド電極
EP3135704A1 (fr) 2015-08-26 2017-03-01 Evonik Degussa GmbH Utilisation de certains polymeres en tant qu'accumulateurs de charge
EP3136410A1 (fr) 2015-08-26 2017-03-01 Evonik Degussa GmbH Utilisation de certains polymeres en tant qu'accumulateurs de charge
EP3279223A1 (fr) 2016-08-05 2018-02-07 Evonik Degussa GmbH Utilisation de polymères contenant du thianthrène en tant qu'accumulateurs de charge
WO2018024901A1 (fr) 2016-08-05 2018-02-08 Evonik Degussa Gmbh Utilisation de polymères contenant du thianthrène comme accumulateurs de charges
WO2018046387A1 (fr) 2016-09-06 2018-03-15 Evonik Degussa Gmbh Procédé d'oxydation améliorée de groupes aminés secondaires
DE102017005924A1 (de) 2017-06-23 2018-12-27 Friedrich-Schiller-Universität Jena Verwendung benzotriazinyl-haltiger Polymere als Ladungsspeicher
US10756348B2 (en) 2015-08-26 2020-08-25 Evonik Operations Gmbh Use of certain polymers as a charge store
US10844145B2 (en) 2016-06-02 2020-11-24 Evonik Operations Gmbh Method for producing an electrode material
US10957907B2 (en) 2015-08-26 2021-03-23 Evonik Operations Gmbh Use of certain polymers as a charge store

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002304996A (ja) * 2001-04-03 2002-10-18 Nec Corp 蓄電デバイス
JP2008078063A (ja) * 2006-09-25 2008-04-03 Toyota Central R&D Labs Inc 蓄電デバイスおよび蓄電デバイスに用いられる電極
WO2009038125A1 (fr) * 2007-09-21 2009-03-26 Waseda University Polymère de nitroxyde de pyrroline et batterie l'utilisant
WO2010104002A1 (fr) * 2009-03-12 2010-09-16 学校法人早稲田大学 Polymère nitroxyde à base de pyrroline et pile utilisant celui-ci
JP2010285408A (ja) * 2009-06-15 2010-12-24 Sumitomo Seika Chem Co Ltd ３−オキシラニル−２，２，５，５−テトラメチルピロリン−１−オキシルの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002304996A (ja) * 2001-04-03 2002-10-18 Nec Corp 蓄電デバイス
JP2008078063A (ja) * 2006-09-25 2008-04-03 Toyota Central R&D Labs Inc 蓄電デバイスおよび蓄電デバイスに用いられる電極
WO2009038125A1 (fr) * 2007-09-21 2009-03-26 Waseda University Polymère de nitroxyde de pyrroline et batterie l'utilisant
WO2010104002A1 (fr) * 2009-03-12 2010-09-16 学校法人早稲田大学 Polymère nitroxyde à base de pyrroline et pile utilisant celui-ci
JP2010285408A (ja) * 2009-06-15 2010-12-24 Sumitomo Seika Chem Co Ltd ３−オキシラニル−２，２，５，５−テトラメチルピロリン−１−オキシルの製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
OYAIZU K ET AL.: "Synthesis and Characterization of Radical-Bearing Polyethers as an Electrode- Active Material for Org", MACROMOLECULES, vol. 41, 21 June 2008 (2008-06-21), pages 6646 - 6652 *
OYAIZU K ET AL.: "Synthesis and Charge Transport Properties of Redox-Active Nitroxide Polyethers with Large Site Densi", MACROMOLECULES, vol. 43, 16 November 2010 (2010-11-16), pages 10382 - 10389 *

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5969981B2 (ja) * 2011-03-31 2016-08-17 住友精化株式会社 ラジカル組成物およびそれを用いた電池
US9711824B2 (en) 2012-11-09 2017-07-18 Murata Manufacturing Co., Ltd. Secondary battery and method for charging and discharging secondary battery
WO2014073560A1 (fr) * 2012-11-09 2014-05-15 株式会社村田製作所 Batterie secondaire et procédé de charge et de décharge de batterie secondaire
JP5800443B2 (ja) * 2012-11-09 2015-10-28 株式会社村田製作所 二次電池、及び二次電池の充放電方法
JPWO2014073560A1 (ja) * 2012-11-09 2016-09-08 株式会社村田製作所 二次電池、及び二次電池の充放電方法
JP2016534521A (ja) * 2013-09-09 2016-11-04 ユニヴェルシテ・カトリック・ドゥ・ルーヴァン 非水電解質二次電池用ハイブリッド電極
DE102014003300A1 (de) 2014-03-07 2015-09-10 Evonik Degussa Gmbh Neue Tetracyanoanthrachinondimethanpolymere und deren Verwendung
US9890230B2 (en) 2014-03-07 2018-02-13 Evonik Degussa Gmbh Tetracyanoanthraquinodimethane polymers and use thereof
US10263280B2 (en) 2014-03-28 2019-04-16 Evonik Degussa Gmbh 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene polymers and use thereof
DE102014004760A1 (de) 2014-03-28 2015-10-01 Evonik Degussa Gmbh Neue 9,10-Bis(1,3-dithiol-2-yliden)-9,10-dihydroanthracenpolymere und deren Verwendung
EP3136410A1 (fr) 2015-08-26 2017-03-01 Evonik Degussa GmbH Utilisation de certains polymeres en tant qu'accumulateurs de charge
EP3135704A1 (fr) 2015-08-26 2017-03-01 Evonik Degussa GmbH Utilisation de certains polymeres en tant qu'accumulateurs de charge
US10756348B2 (en) 2015-08-26 2020-08-25 Evonik Operations Gmbh Use of certain polymers as a charge store
US10957907B2 (en) 2015-08-26 2021-03-23 Evonik Operations Gmbh Use of certain polymers as a charge store
US10844145B2 (en) 2016-06-02 2020-11-24 Evonik Operations Gmbh Method for producing an electrode material
EP3279223A1 (fr) 2016-08-05 2018-02-07 Evonik Degussa GmbH Utilisation de polymères contenant du thianthrène en tant qu'accumulateurs de charge
WO2018024901A1 (fr) 2016-08-05 2018-02-08 Evonik Degussa Gmbh Utilisation de polymères contenant du thianthrène comme accumulateurs de charges
US10608255B2 (en) 2016-08-05 2020-03-31 Evonik Operations Gmbh Use of thianthrene-containing polymers as a charge store
WO2018046387A1 (fr) 2016-09-06 2018-03-15 Evonik Degussa Gmbh Procédé d'oxydation améliorée de groupes aminés secondaires
US11001659B1 (en) 2016-09-06 2021-05-11 Evonik Operations Gmbh Method for the improved oxidation of secondary amine groups
DE102017005924A1 (de) 2017-06-23 2018-12-27 Friedrich-Schiller-Universität Jena Verwendung benzotriazinyl-haltiger Polymere als Ladungsspeicher

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