WO2005078831A1 - 蓄電デバイス - Google Patents
蓄電デバイス Download PDFInfo
- Publication number
- WO2005078831A1 WO2005078831A1 PCT/JP2004/018908 JP2004018908W WO2005078831A1 WO 2005078831 A1 WO2005078831 A1 WO 2005078831A1 JP 2004018908 W JP2004018908 W JP 2004018908W WO 2005078831 A1 WO2005078831 A1 WO 2005078831A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- storage device
- positive electrode
- polymer
- chemical formula
- negative electrode
- Prior art date
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- 238000003860 storage Methods 0.000 title claims abstract description 74
- 229920000642 polymer Polymers 0.000 claims abstract description 73
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000733 Li alloy Inorganic materials 0.000 claims abstract description 15
- 239000001989 lithium alloy Substances 0.000 claims abstract description 15
- 239000007773 negative electrode material Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 49
- -1 nitroxyl cation Chemical class 0.000 claims description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
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- 238000006243 chemical reaction Methods 0.000 claims description 12
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- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
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- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
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- 230000001747 exhibiting effect Effects 0.000 abstract 1
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- 239000000243 solution Substances 0.000 description 11
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- 238000003756 stirring Methods 0.000 description 10
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Classifications
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- 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
- H01M10/052—Li-accumulators
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/137—Electrodes based on electro-active polymers
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/40—Alloys based on alkali metals
- H01M4/405—Alloys based on lithium
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- 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
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- 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
- Y02E60/13—Energy storage using capacitors
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a power storage device having excellent cycle characteristics.
- Patent Document 1 JP 2002-304996 A
- An object of the present invention is to provide a power storage device having excellent cycle characteristics in a power storage device using lithium or a lithium alloy as a negative electrode active material and a nitroxy polymer as a positive electrode active material.
- the electricity storage device of the present invention contains, in a positive electrode, a nitroxynole polymer having a nitroxyl cation partial structure represented by the following chemical formula (I) in an oxidized state and a nitroxyl radical partial structure represented by the following chemical formula (II) in a reduced state:
- a reaction represented by the following reaction formula (B) for transferring electrons between the two states as a positive electrode reaction lithium or a lithium alloy is used as a negative electrode active material, and a power is applied.
- the positive electrode and the negative electrode come into direct contact with each other.
- the nitroxylinole polymer in contact with the lithium or lithium alloy negative electrode exhibits a catalytic effect on the surface of the lithium or lithium alloy negative electrode, thereby suppressing dendrite growth on the negative electrode surface and improving the cycle characteristics of the electric storage device.
- an electric storage device having excellent cycle characteristics can be provided by directly contacting a nitroxylinole polymer with the surface of a lithium or lithium alloy negative electrode.
- FIG. 1 is a schematic diagram showing a configuration of a power storage device described in a first embodiment.
- FIG. 2 is a graph showing the cycle characteristics of the electric storage devices manufactured in Example 1 and Comparative Example 1.
- FIG. 1 there is shown a schematic view of a power storage device as a first embodiment of the present invention.
- a power storage device has, for example, a configuration as shown in FIG.
- the power storage device shown in FIG. 1 is characterized in that a negative electrode 3 made of lithium or a lithium alloy is in direct contact with a positive electrode 4 containing a nitroxynole polymer used as a positive electrode active material.
- the power storage device according to the first embodiment has a coin shape.
- a nitroxynole polymer used as a positive electrode active material poly (2,2,6,6-tetramethylpiperidinoxy methacrylate) (PTMA) represented by the following chemical formula (1) is used. Used.
- a PTMA electrode containing an electrolytic solution is used as the positive electrode 4 containing the nitroxylinole polymer in the first embodiment.
- a current collector auxiliary layer mainly composed of carbon, which is integrally formed on an aluminum electrode is used.
- the negative electrode metal current collector 1 and the positive electrode metal current collector 6 a stainless steel metal current collector is used as the insulating packing 2, a polypropylene insulating packing is used.
- the polymer was precipitated in hexane, separated by filtration, and dried under reduced pressure to obtain 18 g of poly (2,2,6,6-tetramethylpiperidine methacrylate) (yield 90%).
- 10 g of the obtained poly (2,2,6,6-tetramethylpiperidine methacrylate) was dissolved in 100 ml of dry dichloromethane.
- 100 ml of a dichloromethane solution of 15.2 g (0.088 mol) of m-chloroperbenzoic acid was added dropwise over 1 hour while stirring at room temperature.
- the obtained electrode plate was dried in a vacuum at 80 ° C. overnight, punched out into a circular shape having a diameter of 12 mm, and molded as an electrode for a power storage device.
- the obtained electrode was immersed in an electrolytic solution, soaked in the electrolytic solution into a positive electrode containing a nitroxyl polymer, and placed on a metal current collector for the positive electrode.
- a lithium metal plate serving as a negative electrode was directly laminated on the nitroxyl polymer electrode containing the electrolytic solution, and a negative electrode metal current collector covered with an insulating packing was overlaid. A pressure was applied to the laminate thus produced by a force and a tightening machine to obtain a coin-type power storage device.
- the shape of the coin-shaped power storage device can be changed to a conventionally known shape.
- An example of the shape of the electricity storage device is a force S obtained by sealing a laminated body or a wound body of electrodes with a metal case, a resin case, a laminated film, or the like.
- examples of the external appearance include a cylindrical type, a square type, a coin type, and a sheet type.
- a positive electrode current collector using a conductive auxiliary layer mainly composed of carbon and integrally formed on an aluminum electrode is replaced with a conventionally known positive electrode current collector.
- Conventionally known current collectors for positive electrodes include carbon paper and graphite electrodes.
- carbon paper in the present invention is a general term for a material obtained by accumulating fibrous carbon and flattening it, and is roughly classified into a nonwoven fabric structure and a cloth-like structure.
- the thickness of the carbon paper is generally in the range of 0.03 to 0.50 mm. To maintain mechanical strength, 0.05 mm It is preferably equal to or greater than liter. However, from the viewpoint of increasing the energy density of the electricity storage device, it is preferable that the thickness of the carbon paper is 0.25 mm or less, which is better when the carbon paper is thinner.
- the porosity of the carbon paper is generally about 50 to 90%, but is preferably 70% or more from the viewpoint of increasing the contact area with the positive electrode.
- the electrical resistivity of the carbon paper at room temperature is preferably 300 m ⁇ ⁇ cm or less in the thickness direction and 30 m ⁇ ⁇ cm or less in the plane direction from the viewpoint of reducing the internal resistance of the electricity storage device.
- the conductive auxiliary layer formed by coating can be constituted by a conductive auxiliary layer formed by an evaporation method.
- the conductive auxiliary layer mainly composed of a carbon material
- the conductive auxiliary layer can be thinly formed on the aluminum electrode, so that the energy density of the power storage device can be increased. It has a synergistic effect.
- the conductive auxiliary layer in the present invention is a layer for assisting charge transfer between a nitroxyl polymer as a positive electrode active material and aluminum, and contains a carbon material as a main component.
- the main component in the present invention means that the component occupies more than 50% of the total weight of the layer. Examples include activated carbon, graphite, carbon black, furnace black, amorphous carbon, and the like.
- the positive electrode active material PTMA can be composed of a conventionally known nitroxyl polymer.
- the nitroxyle polymer according to the present invention is a generic name of a polymer compound having a nitroxyl structure as represented by the following chemical formula (3), and the nitroxyl structure is represented by the following reaction formula (A).
- reaction formula (A) As shown in the figure, the state of chemical formulas (I) and (III) can be obtained by transferring electrons.
- the power storage device of the present invention uses the reaction between the chemical formulas (I) and (II) as an electrode reaction of a positive electrode, and causes the power storage effect to function by accumulating and discharging electrons.
- the power storage device is a device having at least a positive electrode and a negative electrode, and capable of extracting electrochemically stored energy in the form of electric power.
- the positive electrode refers to an electrode having a high oxidation-reduction potential
- the opposite of the negative electrode means an electrode having a low oxidation-reduction potential.
- the nitroxyl structure in the oxidation state is preferably a cyclic nitroxyl structure represented by the following chemical formula (5).
- the nitroxyl moiety of formula (5) has a nitroxyl radical structure of formula (II).
- an alkyl group particularly preferably a linear alkyl group.
- an alkyl group having 14 to 14 carbon atoms is particularly preferable, and a methyl group is particularly preferable.
- the atoms constituting the ring members in the group are selected from the group consisting of carbon, oxygen, nitrogen and sulfur.
- Adjacent CH, — CH— may be replaced by _ ⁇ —, —NH— or —S—
- Particularly preferable cyclic nitroxynole structures are 2,2,6,6-tetramethylpiperidinoxyl cation represented by chemical formula (6) and 2,2,5,5 represented by chemical formula (7) in an oxidized state. — It is selected from the group consisting of tetramethylpyrrolidinoxyl cation and 2,2,5,5-tetramethylpyrrolinoxyl cation represented by the chemical formula (8).
- the cyclic nitroxynole structure represented by the above chemical formula (5) forms a part of the polymer as a side chain or a part of the main chain.
- the side chain of the polymer is a structure in which at least one hydrogen that binds to the elements that Or it exists in a part of the main chain. It is preferable that it is present in the side chain because of ease of synthesis and the like.
- a residue X ′ obtained by removing hydrogen from CH—, _CH or NH— constituting a ring member in the group X in the chemical formula (5) main
- R R has the same meaning as in the chemical formula (5).
- the main chain polymer used at this time is not particularly limited as long as it has a residue having a cyclic nitroxynole structure represented by the chemical formula (9) in the side chain.
- the following polymers may be obtained by adding a residue of the chemical formula (9) to the polymer, or a polymer in which some atoms or groups of the polymer are substituted by the residues of the chemical formula (9). be able to.
- the residue of the chemical formula (9) may be bonded via an appropriate divalent group instead of directly.
- polyethylene-based polymers such as polyethylene, polypropylene, polybutene, polydecene, polydodecene, polyheptene, polyisobutene, and polyoctadecene; gen-based polymers such as polybutadiene, polychloroprene, polyisoprene, and polyisobutene; poly (meth) acrylic acid; (Meth) acrylonitrile; poly (meth) acrylamide polymers such as poly (meth) acrylamide, polymethyl (meth) acrylamide, polydimethyl (meth) acrylamide, and polyisopropyl (meth) acrylamide; polymethyl (meth) acrylate, Polyalkylene (meth) acrylates such as polyethyl (meth) acrylate and polybutyl (meth) acrylate; fluorine such as polyvinylidene fluoride and polytetrafluoroethylene Polystyrene; Polysty
- Polyamine-based polymers such as hexamethyleneamine and polyethylenetrimethyleneamine; Polyamide-based polymers such as nylon, polyglycine and polyalanine; Polyimine-based polymers such as polyacetylenoleiminoethylene and polybenzoyliminoethylene Polymers: Polyimide-based polymers such as polyesterimide, polyetherimide, polybenzimide, and polypyromerimide; polyarylene, polyarylenealkylene, polyarylenealkenylene, polyphenol, phenolic resin, cellulose, polybenzoimidazole, Polybenzothiazole, polybenzoxazine, polybenzoxazole, olicarborane, polydibenzofuran, polyoxoisoindoline, polyfurantetracarboxylic diimide, polyoxadiazole, polyoxin , Polyphthalazine, polyphthalide, polycyanurate, polyisocyanurate, polypiperazine, polypiperidine, polyvirazinoquinoxan
- polyalkylene polymers poly (meth) acrylic acid, poly (meth) acrylamide polymers, and polyalkyl (meth) atalylates have a main chain having excellent electrochemical resistance.
- a polystyrene-based polymer is preferred.
- the main chain is the most carbon in a polymer compound. A large number of carbon chains.
- the polymer is selected so that it can contain a unit represented by the following chemical formula (10) in an oxidized state.
- R—R has the same meaning as in the aforementioned chemical formula (5).
- R is hydrogen or a methyl group.
- Y is not particularly limited, but has -CO-, -C ⁇ -, -CONR-, - ⁇ , -S-, and a substituent.
- C11-C18 alkylene group C11-C18 arylene group which may have a substituent, and a divalent group obtained by bonding two or more of these groups.
- R represents an alkyl group having 118 carbon atoms.
- Y is a force having the same meaning as in Chemical Formula (10), particularly —COO— and —CONR—.
- the residue of the chemical formula (9) may not be present in all of the side chains.
- all of the units constituting the polymer may be units represented by the chemical formula (10), or some may be units represented by the chemical formula (10).
- the amount contained in the polymer is preferably 1% by weight or more, particularly preferably 10% by weight or more, as long as the presence of even a small amount of force differs depending on the purpose, the structure of the polymer, and the production method. 50% by weight In particular, 80% by weight or more is preferable.
- the residue represented by the chemical formula (9) (or one NH— May be introduced).
- the molecular weight of the nitroxyl polymer in the present invention is not particularly limited, but preferably has a molecular weight that does not dissolve in the electrolyte. This depends on the combination with the type of the organic solvent in the electrolyte. In general, the weight average molecular weight is 1,000 or more, preferably 10,000 or more, especially 100,000 or more. In the present invention, since the power S can be mixed with the positive electrode as a powder, the molecular weight may be very large. Generally, the weight average molecular weight is 5,000 or less. Further, the polymer containing the residue represented by the chemical formula (9) may be crosslinked, thereby improving the durability to the electrolyte.
- a conventionally known polymer electrolyte may be added in order to enhance ionic conductivity.
- conventionally known polymer electrolytes include vinylidene fluoride polymers such as polyvinylidene fluoride and vinylidene fluoride-hexafluoropropylene copolymer, acrylonitrile-methyl methacrylate copolymer, and acrylonitrile-methyl atalylate.
- acrylic nitrile-based polymers such as copolymers, and polyethylene oxide. I can get lost.
- a conventionally known conductivity-imparting agent such as acetylene black is not included in the positive electrode so much.
- the content of the conductivity-imparting agent in the positive electrode is preferably 50% by weight or less, and more preferably 40% by weight or less.
- the positive electrode may contain a conventionally known binder or the like as necessary.
- a negative electrode using lithium metal can be replaced with a conventionally known lithium alloy negative electrode to form a power storage device.
- Conventionally known lithium alloy negative electrodes include, for example, a lithium-aluminum alloy, a lithium tin alloy, and a lithium silicon alloy.
- the material of the negative electrode metal current collector using stainless steel can be replaced with a conventionally known material to form a power storage device.
- Conventionally known materials for a negative electrode metal current collector include, for example, nickel, aluminum, copper, gold, silver, titanium, and aluminum alloy.
- a foil / flat plate or a mesh shape can be used as the shape.
- the power storage device can be configured by replacing the material of the positive electrode metal current collector using stainless steel with a conventionally known material.
- Conventionally known materials for the positive electrode metal current collector include, for example, nickel, aluminum, copper, gold, silver, titanium, and aluminum alloy. Further, as the shape, a foil / flat plate or a mesh shape can be used.
- a current collector for a positive electrode is used in which a conductive auxiliary layer mainly composed of carbon is integrally formed on an aluminum electrode
- a current collector for a positive electrode is used without using a metal current collector for a positive electrode.
- the aluminum used for the positive electrode can be used in place of the metal current collector for the positive electrode.
- the EC / DEC mixed solution containing LiPF electrolyte salt of ImolZl is used.
- the electrolyte transports charge carriers between the negative electrode 3 and the positive electrode 4, and generally has an electrolyte ion conductivity of 10 5 10 cm 2 at room temperature.
- an electrolytic solution obtained by dissolving an electrolyte salt in a solvent can be used.
- Such solvents include, for example, ethylene carbonate, propylene carbonate
- Organic solvents such as dimethinorecarbonate, methinolecarbonate, methinoleethinolecarbonate, ⁇ -butyrolataton, tetrahydrofuran, dioxolane, sulfolane, dimethylformamide, dimethylacetamide, ⁇ ⁇ ⁇ -methyl-2-pyrrolidone, sulfuric acid aqueous solution and water. And so on.
- these solvents can be used alone or in combination of two or more.
- the electrolyte salt include LiPF, LiCIO, LiBF, LiCF SO,
- the polymer was precipitated in hexane, separated by filtration, and dried under reduced pressure to obtain 18 g of poly (2,2,6,6-tetramethylpiperidine methacrylate) (yield 90%).
- 10 g of the obtained poly (2,2,6,6-tetramethylpiperidine methacrylate) was dissolved in 100 ml of dry dichloromethane.
- 100 ml of a dichloromethane solution of 15.2 g (0.088 mol) of m-chloroperbenzoic acid was added dropwise over 1 hour while stirring at room temperature.
- Polymetharate 1 1. Og was added and stirred for 5 minutes to completely dissolve. The obtained solution was thinly applied on a positive electrode current collector in which a conductive auxiliary layer mainly composed of carbon and an aluminum plate were integrated, and dried at 125 ° C. to produce an electrode. The electrode thickness was 50 microns.
- the obtained electrode plate was dried in a vacuum at 80 ° C overnight, and then punched into a circular shape having a diameter of 12 mm. It was molded as an electrode for a power storage device. Next, the obtained electrode was immersed in an electrolytic solution, soaked in the electrolytic solution into a positive electrode containing a nitroxyl polymer, and placed on a metal current collector for a positive electrode (stainless plate).
- electrolytic solution soaked in the electrolytic solution into a positive electrode containing a nitroxyl polymer, and placed on a metal current collector for a positive electrode (stainless plate).
- a lithium metal plate as the negative electrode is directly laminated on the nitroxyl polymer electrode containing the electrolyte, and a negative electrode metal current collector (stainless steel plate) covered with insulating packing (made of polypropylene) is overlaid.
- the pressure was applied to the thus-produced laminate by a press to obtain a coin-type power storage device.
- Example 1 In a small homogenizer container, 20 g of N-methylpyrrolidone was weighed, and the synthesized polyatalylate of the formula (17) 1.Og was added and stirred for 5 minutes to completely dissolve. Thereafter, the same procedure as in Example 1 was performed to obtain a coin-type power storage device.
- Example 2 20 g of N-methylpyrrolidone was weighed and placed in a small homogenizer container, and the synthesized polymethalate of the formula (18) 1.Og was added, and the mixture was stirred for 5 minutes to completely dissolve. Thereafter, the same procedure as in Example 1 was performed to obtain a coin-type power storage device.
- Example 2 20 g of N-methylpyrrolidone was weighed and placed in a small homogenizer container, and 1.0 g of the synthesized polymethalate of the formula (19) was added thereto, followed by stirring for 5 minutes to completely dissolve. Thereafter, the same procedure as in Example 1 was performed to obtain a coin-type power storage device.
- a coin-type power storage device was obtained in the same manner as in Example 1, except that a lithium-suzun alloy negative electrode was used as the negative electrode.
- a coin-type power storage device was obtained in the same manner as in Example 1, except that a lithium-silicon alloy negative electrode was used as the negative electrode.
- the obtained electrode plate was dried in a vacuum at 80 ° C. overnight, punched out into a circular shape having a diameter of 12 mm, and molded as an electrode for a power storage device.
- the obtained electrode was immersed in an electrolytic solution, soaked in the electrolytic solution into a positive electrode containing a nitroxyl polymer, and placed on a metal current collector for a positive electrode (stainless plate).
- EC / D containing lmol / 1 LiPF electrolyte salt
- a porous film separator (made of polypropylene) also impregnated with the electrolytic solution is stacked on the nitroxyl polymer electrode containing the electrolytic solution, and a lithium metal plate serving as a negative electrode is laminated with the separator interposed therebetween.
- a metal current collector for a negative electrode (stainless steel plate) coated with (made of polypropylene) was laminated. Pressure was applied to the laminate thus produced by a press to obtain a coin-type power storage device.
- a coin-type power storage device was obtained in the same manner as in Comparative Example 1, except that a lithium-tin alloy negative electrode was used as the negative electrode.
- a coin-type power storage device was obtained in the same manner as in Comparative Example 1, except that a lithium-silicon alloy negative electrode was used as the negative electrode.
- the open-circuit potential of the electric storage device manufactured in Example 1 was 2.9V.
- the obtained power storage device was charged at a constant current of 0.113 mA, and the charging was terminated when the voltage rose to 4.0 V.
- the storage device after charging was disassembled and the positive electrode was analyzed, a decrease in radical concentration was observed, confirming the formation of the corresponding 2,2,6,6-tetramethylpiperidinoxyl cation. This cation is stabilized by electrolyte anion PF
- Discharge was performed immediately after the voltage rose to 0V. Discharging was performed at the same constant current of 0.113 mA as during charging. Discharging was terminated when the voltage reached 2.5 V. At the time of discharging, a voltage flat portion was observed around 3.4 V. This voltage plateau is due to the reduction reaction that occurs from the nitroxyl cation at the positive electrode to the nitroxyl radical, and the lithium reaction occurring at the negative electrode. It has been found that this corresponds to a potential difference between the ionization reaction of the metal. That is, this is a result indicating that the power storage device according to the first embodiment operates as a chemical battery.
- the average discharge voltage in Example 1 was 3.32V.
- FIG. 2 shows the cycle characteristics of the electric storage devices manufactured in Example 1 and Comparative Example 1.
- the capacity is expressed assuming that the initial discharge capacity is 100%.
- the storage device in which the nitroxy polymer and the lithium negative electrode surface are in direct contact as in Example 1 has better cycle characteristics than the storage device stacked via a separator as in Comparative Example 1. Power, ivy.
- the cycle characteristics of Example 27 and Comparative Example 27 were similarly evaluated, and the capacity retention ratio after 100 cycles is shown in Table 1.
- Example 2-4 Compared Example 2-4 with Comparative Example 2-4, it was found that the nitroxyl polymer and the lithium negative electrode were directly used in any of the positive electrode active materials of Chemical Formulas (17) to (19). By contact, the same tendency as in Example 1 and Comparative Example 1 was observed, and it was found that the cycle characteristics of the electric storage device were improved. Comparing Examples 5 and 6 with Comparative Examples 5 and 6, it was found that even when a lithium tin alloy negative electrode and a lithium-silicon alloy negative electrode were used, the nitroxinole polymer was directly contacted with lithium or the negative electrode. The same tendency as in Comparative Example 1 and Comparative Example 1 was observed, and it was found that the cycle characteristics of the electric storage device were improved.
- the power storage device according to the present invention Since the power storage device according to the present invention has excellent cycle characteristics, it can be used as a power storage device requiring a long life.
- Examples of applications of the present invention include electric double-layer capacitors, lead-acid batteries, nickel-metal hydride batteries, and lithium-ion secondary batteries, which have conventionally been used as backup power supplies for personal computers and servers, auxiliary power supplies for electric vehicles, and portable power supplies. Power supplies for equipment;
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Abstract
Description
Claims
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US10/597,518 US9443661B2 (en) | 2004-02-16 | 2004-12-17 | Power storage device having a nitroxyl polymer in a cathode and a lithium or lithium alloy anode |
JP2005517910A JP4721000B2 (ja) | 2004-02-16 | 2004-12-17 | 蓄電デバイス |
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JP2007157496A (ja) * | 2005-12-05 | 2007-06-21 | Nec Corp | 電極及び二次電池 |
JP2007165054A (ja) * | 2005-12-12 | 2007-06-28 | Nec Corp | 蓄電デバイス |
WO2007141913A1 (ja) * | 2006-06-06 | 2007-12-13 | Nec Corporation | ポリラジカル化合物製造方法及び電池 |
JP2008280401A (ja) * | 2007-05-09 | 2008-11-20 | Nec Corp | ポリラジカル化合物、電極活物質および電池 |
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US20080213669A1 (en) | 2008-09-04 |
JP4721000B2 (ja) | 2011-07-13 |
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