WO2014092128A1 - Dispositif de stockage électrique - Google Patents

Dispositif de stockage électrique Download PDF

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Publication number
WO2014092128A1
WO2014092128A1 PCT/JP2013/083234 JP2013083234W WO2014092128A1 WO 2014092128 A1 WO2014092128 A1 WO 2014092128A1 JP 2013083234 W JP2013083234 W JP 2013083234W WO 2014092128 A1 WO2014092128 A1 WO 2014092128A1
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Prior art keywords
nitroxyl
conductive material
compound
storage device
nitroxyl compound
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PCT/JP2013/083234
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English (en)
Japanese (ja)
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基陽 安井
岩佐　繁之
教徳 西
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日本電気株式会社
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Priority to JP2014552071A priority Critical patent/JPWO2014092128A1/ja
Publication of WO2014092128A1 publication Critical patent/WO2014092128A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
    • 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
    • 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
    • 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 an electricity storage device including a positive electrode including a nitroxyl compound, a negative electrode including a material capable of reversibly inserting and removing lithium ions, and an electrolytic solution including an aprotic organic solvent in which a lithium salt is dissolved. .
  • a power storage device used in such portable electronic devices is required to have high energy density, high output characteristics, high safety, and high cycle stability.
  • a lithium ion capacitor is known as an electricity storage device having high output and high cycle stability. Since electric charges are stored by an electrostatic mechanism using an electric double layer, the energy density is small but the output is high and the cycle stability is also high. Patent Document 1 proposes storing lithium ions in advance by a chemical method for the negative electrode in order to increase the energy density. However, a sufficient energy density is still not obtained.
  • Patent Document 2 proposes a power storage device containing a nitroxyl compound in a positive electrode as a high power power storage device (hereinafter, this power storage device is referred to as an “organic radical battery”).
  • This nitroxyl compound takes an oxoammonium cation partial structure in an oxidized state, takes a nitroxyl radical partial structure in a reduced state, and transfers electrons between the two states, and this reaction is used as an electrode reaction of a positive electrode. . Since this electrode reaction proceeds relatively quickly, a high output battery can be obtained, and the battery is safe without problems such as thermal runaway.
  • Patent Document 3 proposes a method of electrically contacting a negative electrode and a lithium metal foil as a method of storing lithium ions in the negative electrode in advance.
  • Patent Document 4 describes a battery having particles containing, as an active material, an organic compound that generates a radical compound in at least one of an electrochemical oxidation reaction and a reduction reaction. It is described that the particles are integrated with an electron conductive material.
  • Patent Document 5 describes an electricity storage device using a conductive material-containing radical material and containing a nitroxy radical compound in an electrode.
  • the present invention provides a high-power storage device that is inexpensive, safe, and stores a sufficient amount of lithium ions in the negative electrode in advance.
  • One embodiment of the present invention takes a nitroxyl cation partial structure represented by the following formula (1) in the oxidized state and a nitroxyl radical partial structure represented by the following formula (2) in the reduced state, and between the two states It has a positive electrode containing a nitroxyl compound that performs the reaction shown in the following reaction formula (A) for transferring and receiving electrons, an negative electrode, and an electrolytic solution containing an electrolyte salt and an organic solvent, and the positive electrode serves as a lithium ion supply source.
  • the present invention relates to an electricity storage device comprising lithium manganate, lithium iron phosphate or lithium sulfide, wherein the nitroxyl compound forms a conductive material and a nitroxyl compound / conductive material composite.
  • FIG. 1 is a perspective view of a laminate type electricity storage device according to an embodiment of the present invention. It is sectional drawing of the lamination type electrical storage device by embodiment of this invention.
  • An electricity storage device includes a positive electrode including the nitroxyl compound as a positive electrode active material, a negative electrode, and an electrolytic solution including an electrolyte salt and an organic solvent.
  • a lithium compound such as lithium manganate is added to the positive electrode as a lithium ion supply source.
  • the negative electrode can include a material capable of reversibly occluding and releasing lithium ions as a negative electrode active material, a lithium salt can be used as an electrolyte salt, and an aprotic solvent can be used as an organic solvent.
  • an energy storage device can be produced at low cost by adding a lithium compound in the positive electrode instead of using metal lithium in the battery configuration, and the remaining of metal lithium cannot occur. Can be secured.
  • the output characteristics can be improved by incorporating the conductive material into the nitroxyl compound.
  • This is a composite of a nitroxyl compound and a conductive material that suppresses re-doping of lithium ions by lithium manganate, lithium iron phosphate, lithium sulfide, etc., and suppresses the release of lithium ions from the carbon anode. It is thought that there is. Thereby, charging and discharging of the electricity storage device can be performed in a state where a sufficient amount of lithium ions is stored in advance in the negative electrode.
  • the electricity storage device can extract electrochemically stored energy in the form of electric power, and can be applied to an electric capacity device such as a primary battery, a secondary battery, a capacitor and a capacitor.
  • Electrode Material [1-1] Positive Electrode Active Material
  • the nitroxyl cation partial structure N-oxo-ammonium represented by the formula (1) in the oxidized state is used.
  • This nitroxyl compound can perform an oxidation-reduction reaction represented by the reaction formula (A) in which electrons are transferred between these two states.
  • the electricity storage device according to the present embodiment uses this oxidation-reduction reaction as the electrode reaction of the positive electrode.
  • the structure of the nitroxyl compound is not particularly limited, but is preferably a nitroxyl polymer compound from the viewpoint of solubility in the electrolytic solution.
  • the nitroxyl polymer compound is preferably a polymer containing a cyclic nitroxyl structure represented by the following formula (Ia) in the side chain in an oxidized state.
  • R 1 to R 4 each independently represents an alkyl group having 1 to 4 carbon atoms, and X represents a divalent group forming a 5- to 7-membered ring, provided that X represents a side chain of the polymer.
  • X represents a side chain of the polymer.
  • R 1 to R 4 each independently represents an alkyl group having 1 to 4 carbon atoms, preferably an ethyl group or a methyl group, and particularly preferably a methyl group in terms of radical stability.
  • the hydrogen atom bonded to the atoms constituting the ring may be substituted with an alkyl group, a halogen atom, ⁇ O, an ether group, an ester group, a cyano group, an amide group, or the like.
  • Particularly preferred cyclic nitroxyl structures are 2,2,6,6-tetramethylpiperidinoxyl radical (or cation), 2,2,5,5-tetramethylpyrrolidinoxyl radical (or cation), 2,2 , 5,5-tetramethylpyrrolinoxyl radical (cation), 2,2,6,6-tetramethylpiperidinoxyl radical (or cation), 2,2,5,5-tetra A methylpyrrolidinoxyl radical (or cation) is more preferred.
  • the cyclic nitroxyl structure represented by formula (Ia) has a residue X ′ obtained by removing hydrogen from —CH 2 —, —CH ⁇ or —NH— constituting the ring member in X. Can be attached to the polymer.
  • the polymer used as the main chain of the nitroxyl polymer compound is not particularly limited as long as the cyclic nitroxyl structure represented by the formula (Ia) can be present in the side chain.
  • nitroxyl polymer compound examples include those obtained by adding a group of the formula (Ib) to a normal polymer, or those in which some atoms or groups of the polymer are substituted by the group of the formula (Ib).
  • the atoms constituting the cyclic structure of the formula (Ib) may be bonded to the polymer (main chain) via an appropriate divalent group in the middle instead of directly.
  • X ′ and atoms in the main chain of the polymer can be bonded via a divalent group such as an ester bond (—COO—) or an ether bond (—O—).
  • polyalkylene polymers such as polyethylene and polypropylene; poly (meth) acrylic acid; poly (meth) acrylamide polymers are excellent in electrochemical resistance.
  • Poly (meth) acrylate polymers and polystyrene polymers are preferred.
  • nitroxyl polymer compounds those having high stability and those represented by any of the following formulas (3) to (7) are preferable.
  • n is an integer of 1 or more.
  • the nitroxyl polymer compound represented by the formulas (3) to (5) has a 2,2,6,6-tetramethylpiperidinoxyl radical (or cation) in the side chain, and the formulas (6), (7
  • the nitroxyl polymer compound shown in (2) is a polymer compound having a 2,2,5,5-tetramethylpyrrolidinoxyl radical (or cation) in the side chain.
  • These nitroxyl polymer compounds are compounds having a sterically hindered stable radical in the side chain of the polymer.
  • the molecular weight of the nitroxyl polymer compound is preferably 1000 or more, more preferably 10,000 or more, from the viewpoint of solubility in the electrolytic solution. A higher molecular weight is preferred, but one having an average molecular weight of 5 million or less can be used.
  • the skeleton structure of the nitroxyl polymer compound may be any of a chain, a branch, and a network, and may be a structure crosslinked with a crosslinking agent.
  • nitroxyl polymer compound can be used alone, but two or more kinds may be mixed and used.
  • the content of the nitroxyl polymer compound in the positive electrode active material is preferably 50% by mass or more, and more preferably 80% by mass or more.
  • Conductive material examples include carbonaceous fine particles such as graphite, carbon black, and acetylene black, carbon fibers such as carbon nanotubes, and carbon materials such as activated carbon, polyaniline, polypyrrole, polythiophene, polyacetylene, and polyacene.
  • the conductive polymer is mentioned.
  • the nitroxyl compound that is the positive electrode active material and the conductive material form a complex.
  • the manufacturing method of the nitroxyl compound and the electroconductive material composite based on this invention which used the nitroxyl compound and the electroconductive material as main raw materials is demonstrated.
  • the method for producing a nitroxyl compound / conductive material composite according to the present invention includes a raw material solution in which a nitroxyl compound having a radical partial structure in a reduced state is dissolved or swollen and a conductive material is dispersed or dissolved, and the nitroxyl compound
  • a precipitate composed of a nitroxyl compound and a conductive material is generated by dropping or pouring into a solution in which the conductive material does not dissolve or swell. Since the nitroxyl compound and the conductive material are as described above, other configurations will be described below.
  • the solvent constituting the raw material solution needs to be a solvent capable of dissolving or swelling the nitroxyl compound described above. Since many carbon materials and inorganic materials are usually insoluble, the solvent does not necessarily dissolve the conductive material, but it must be dispersed. Specific examples of such a solvent include N-methylpyrrolidone, tetrahydrofuran, toluene, xylene and the like. Of these, N-methylpyrrolidone is preferred.
  • Preparation of the raw material solution involves first dissolving the polymer radical material in a solvent capable of dissolving or swelling the polymer radical material. There, a conductive material is added and stirred. The amount of the conductive material to be added is adjusted in consideration of electronic conductivity and the like. However, when the nitroxyl compound is 100 parts by weight, it is preferably blended in the range of 1 part by weight to 200 parts by weight. Is 1 to 100 parts by weight, more preferably 1 to 40 parts by weight.
  • This blending amount varies depending on the type of nitroxyl compound and the type of conductive material, but when the amount of conductive material is small, the conductivity of the obtained electrode becomes insufficient, and when too large, the nitroxyl compound Since the amount of the battery becomes relatively small, the capacity of the obtained battery becomes small.
  • dissolution of a nitroxyl compound includes not only literally dissolution, but also includes an aspect in which it is compatible with fluidity in a solvent, and “swelling” refers to general dissolution. In other words, it includes a mode in which a so-called swollen state is produced by acting with a solvent, and the conductive material is uniformly dispersed in the nitroxyl compound by mixing with the conductive material.
  • the “dispersion” of the conductive material includes, for example, a mode in which an insoluble material is dispersed in a solvent such as a carbon material, and the “dissolution” of the conductive material is literally dissolved in the solvent. It is intended to include compatible aspects.
  • a stirring / mixing device such as a homogenizer can be used as a device used for mixing the nitroxyl compound and the conductive material.
  • a stirring / mixing device such as a homogenizer.
  • the raw material solution thus obtained is dropped or poured little by little into a solvent (poor solvent) in which the nitroxyl compound and the conductive material do not dissolve or swell.
  • a solvent poor solvent
  • the nitroxyl compound and the conductive material can be precipitated simultaneously.
  • the solvent (poor solvent) in which the nitroxyl compound and the conductive material do not dissolve or swell include methanol, ethanol, dimethyl ether, ethyl methyl ether, diethyl ether, hexane, heptane and the like. Among these, methanol is preferable.
  • the poor solvent is selected mainly in relation to the nitroxyl compound, and methanol or the like is preferably used mainly in the embodiment of the present invention, but other solvents may be used as long as they function as a poor solvent.
  • the conductive material is generally not easily considered because it is difficult to dissolve in an organic solvent, but the conductive material needs to be a solvent that does not dissolve or swell.
  • the raw material solution is dripped little by little into such a poor solvent, or a precipitate is produced by pouring, but the manner of dripping or pouring (the amount of dripping or the dropping speed, etc.) depends on the characteristics and form of the resulting precipitate. Adjusted accordingly.
  • the conductive material is obtained as a precipitate taken in a state of being uniformly dispersed inside the nitroxyl compound, it is desirable to drop or pour in such a manner.
  • the obtained precipitate is collected by filtration or the like, and dried to obtain a nitroxyl compound / conductive material composite.
  • the obtained nitroxyl compound / conductive material composite may be pulverized by pulverization or the like.
  • a conductive material can be uniformly dispersed in a nitroxyl compound, and the nitroxyl compound / conductive material obtained by such a production method can be dispersed. Since the material composite is obtained as a precipitate in which the conductive material is taken into the interior of the nitroxyl compound, the obtained nitroxyl compound / conductive material composite can have good electronic conductivity. As a result, the transfer of electrons accompanying the oxidation / reduction of the nitroxyl compound becomes smooth through the conductive material, and charging / discharging with a large current becomes possible.
  • the resulting nitroxyl compound / conductive material composite also has a high proportion of radical sites that can contribute to the charge / discharge reaction, so that it can be used as an electrode material for power storage devices with little decrease in voltage even when discharged with a large current. It can be preferably used.
  • Lithium ion source can be used to dope the negative electrode with lithium ions.
  • Li X Mn 2 O 4 lithium ion source Li X MnO 2 (x is, 0 ⁇ x ⁇ 1) lithium manganate such as, LiFePO 4 (lithium iron phosphate ), Li 2 S (lithium sulfide), Li X CoO 2 (x is 0 ⁇ x ⁇ 1), Li X NiO 2 (x is 0 ⁇ x ⁇ 1), Li X FeO 2 (x is 0 ⁇ x ⁇ 1), lithium metal oxides such as Li x V 2 O 5 (x is 0 ⁇ x ⁇ 2), etc., and transitions such as Li, Mg, Al, or Co, Ti, Nb, Cr, etc.
  • a material to which a metal is added or substituted may be used. Not only these lithium compounds are used alone, but also a mixture of a plurality of them can be used. Among these, lithium manganate, lithium iron phosphate, and lithium sulfide are preferably used.
  • the weight of the lithium compound used is 0.5% or more and 80% or less, more preferably 1% or more and 40% or less, and further preferably 1% or more and 20% or less of the weight of the positive electrode active material.
  • Negative Electrode Active Material As the negative electrode active material in the electricity storage device according to the present embodiment, a material capable of reversibly occluding and releasing lithium ions (a material capable of occluding and releasing lithium ions during charging and discharging during discharging) is used. Can do. As such a negative electrode active material, carbon materials such as metal oxides and graphite can be used. The shape of these materials is not particularly limited, and examples thereof include a thin film, a powdered product, a fiber, and a flake. Moreover, these negative electrode active materials can be used alone or in combination.
  • Conductivity imparting agent When forming the positive electrode and the negative electrode, a conductivity imparting agent may be further added for the purpose of lowering the impedance.
  • the conductivity-imparting agent include carbonaceous fine particles such as graphite, carbon black and acetylene black, carbon fibers such as carbon nanotubes and carbon materials such as activated carbon, and conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene and polyacene. It is done.
  • Binder A binder can also be used in forming the positive electrode and the negative electrode. By using the binder, it is possible to strengthen the connection between the active materials, between the active material and the conductivity imparting agent, and between the active material or the conductivity imparting agent and the current collector.
  • binder examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer rubber, Examples thereof include resin binders such as polypropylene, polyethylene, polyimide, partially carboxylated cellulose, and various polyurethanes.
  • PTFE polytetrafluoroethylene
  • resin binders such as polypropylene, polyethylene, polyimide, partially carboxylated cellulose, and various polyurethanes.
  • the electrode material containing the positive electrode active material or the negative electrode active material can be provided on the current collector.
  • a foil, sheet, flat plate or the like made of nickel, aluminum, copper, aluminum alloy, stainless steel, carbon, or the like can be used.
  • FIG. 1 is a perspective view of an example of a laminate type power storage device according to the present embodiment, and FIG. As shown in these drawings, the electricity storage device 107 has a laminated structure including a positive electrode 101, a negative electrode 102 facing the positive electrode, and a separator 105 sandwiched between the positive electrode and the negative electrode.
  • the electrode lead 104 is drawn out to the outside of the exterior film 106.
  • An electrolytic solution is injected into the electricity storage device.
  • the positive electrode 101 includes a positive electrode active material and a lithium ion supply source, and further includes a conductivity imparting agent and a binder as necessary, and is formed on one current collector 103.
  • the positive electrode active material of this embodiment is combined with a conductive material.
  • the negative electrode 102 includes a negative electrode active material, and further includes a conductivity imparting agent and a binder as necessary, and is formed on the other current collector 103.
  • An insulating porous separator 105 is provided between the positive electrode 101 and the negative electrode 102 to insulate and separate them.
  • a porous resin film made of polyethylene, polypropylene, or the like, a cellulose film, a non-woven cloth, or the like can be used.
  • Electrolytic Solution transports charge carriers between the positive electrode and the negative electrode, and is impregnated in the positive electrode 101, the negative electrode 102, and the separator 105.
  • the electrolytic solution one having an ion conductivity of 10 ⁇ 5 to 10 ⁇ 1 S / cm at 20 ° C. can be used, and a nonaqueous electrolytic solution in which an electrolyte salt is dissolved in an organic solvent can be used. it can.
  • an aprotic organic solvent can be used as the solvent for the electrolytic solution.
  • electrolyte salt examples include LiPF 6 , LiClO 4 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 (hereinafter “LiTFSI”), LiN (C 2 F 5 SO 2 ) 2 (hereinafter “LiBETI”). ), Li (CF 3 SO 2 ) 3 C, Li (C 2 F 5 SO 2 ) 3 C, or other ordinary electrolyte materials can be used.
  • organic solvent examples include cyclic carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate; chain carbonates such as dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; ⁇ -lactones such as ⁇ -butyrolactone; cyclic rings such as tetrahydrofuran and dioxolane. Ethers; amides such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone and the like.
  • Exterior Film As the exterior film 106, an aluminum laminate film or the like can be used. Examples of the exterior body other than the exterior film include a metal case and a resin case. Examples of the outer shape of the electricity storage device include a cylindrical shape, a square shape, a coin shape, and a sheet shape.
  • the electrode laminate is obtained by placing the positive electrode 101 on the exterior film 106 and superimposing it on the negative electrode 102 with the separator 105 interposed therebetween.
  • the obtained electrode laminate is covered with an exterior film 106, and three sides including the electrode lead portion are heat-sealed.
  • An electrolyte is injected into this and vacuum impregnated. After sufficiently impregnating and filling the gap between the electrode and the separator 105 with the electrolytic solution, the remaining four sides are heat-sealed under reduced pressure, whereby a laminate-type power storage device 107 is obtained.
  • the slurry was applied on a copper mesh as a current collector and then dried at 120 ° C. for 5 minutes. Furthermore, the thickness was adjusted with a roll press. This was cut into a 22 ⁇ 24 mm rectangle, and a nickel electrode lead was ultrasonically bonded. The thickness of the obtained negative electrode was 50 to 60 ⁇ m.
  • Example 1 As a positive electrode active material, 2.1 g of PTMA was dissolved in 12 ml of N-methylpyrrolidone. A carbon material (made by Showa Denko, trade name: VGCF-H / highly crystalline carbon nanofiber synthesized by vapor phase method, fiber diameter 150 nm, fiber length 10 to 20 ⁇ m, aspect ratio 10 to 500 is used here as a conductive material. 0.42 g was added and stirred with a homogenizer to obtain a slurry in which the conductive material was uniformly dispersed in N-methylpyrrolidone in which the positive electrode active material was dissolved.
  • a carbon material made by Showa Denko, trade name: VGCF-H / highly crystalline carbon nanofiber synthesized by vapor phase method, fiber diameter 150 nm, fiber length 10 to 20 ⁇ m, aspect ratio 10 to 500 is used here as a conductive material. 0.42 g was added and stirred with a homogenizer to obtain a slurry in which the conductive material was
  • a nitroxyl compound / carbon material composite 0.2 g of lithium manganate as a lithium ion source, 0.2 g of acetylene black as a conductivity-imparting agent, 0.24 g of carboxymethyl cellulose (CMC) as a binder, and poly 0.03 g of tetrafluoroethylene (PTFE) and 15 ml of water were mixed and stirred with a homogenizer to prepare a uniform slurry.
  • CMC carboxymethyl cellulose
  • PTFE tetrafluoroethylene
  • the slurry was applied on an aluminum foil as a current collector and then dried at 80 ° C. for 5 minutes. Furthermore, the thickness was adjusted with a roll press. This was cut into a 22 ⁇ 24 mm rectangle, and an aluminum electrode lead was ultrasonically bonded. The thickness of the positive electrode obtained was 140 to 150 ⁇ m.
  • a polypropylene porous film separator was sandwiched between the positive electrode and the negative electrode to obtain an electrode laminate.
  • the electrode laminate was covered with aluminum laminate and three sides including the electrode lead portion were heat-sealed.
  • the current is supplied until the voltage reaches 4.6 V at a constant current of 0.1 mA, and then the current is supplied until the voltage reaches 3 V at a constant current of 0.5 mA.
  • Lithium ions were previously stored in the negative electrode.
  • Example 2 An electricity storage device was produced in the same manner as in Example 1 except that 0.2 g of lithium iron phosphate was used as the lithium ion supply source in the slurry.
  • the current is supplied until the voltage reaches 4.0 V at a constant current of 0.1 mA, and then the current is supplied until the voltage reaches 3 V at a constant current of 0.5 mA.
  • Lithium ions were previously stored in the negative electrode.
  • Comparative Example 1 1.75 g of PTMA, 0.2 g of lithium manganate as a lithium ion source, 0.35 g of VGCF-H and 0.2 g of acetylene black as a conductivity-imparting agent, 0.24 g of carboxymethylcellulose (CMC) as a binder and polytetrafluoroethylene (PTFE) 0.03 g and water 15 ml were mixed and stirred with a homogenizer to prepare a uniform slurry.
  • CMC carboxymethylcellulose
  • PTFE polytetrafluoroethylene
  • the slurry was applied on an aluminum foil as a current collector and then dried at 80 ° C. for 5 minutes. Furthermore, the thickness was adjusted with a roll press. This was cut into a 22 ⁇ 24 mm rectangle, and an aluminum electrode lead was ultrasonically bonded. The thickness of the positive electrode obtained was 140 to 150 ⁇ m.
  • a polypropylene porous film separator was sandwiched between the positive electrode and the negative electrode to obtain an electrode laminate.
  • the electrode laminate was covered with aluminum laminate and three sides including the electrode lead portion were heat-sealed.
  • the current is supplied until the voltage reaches 4.6 V at a constant current of 0.1 mA, and then the current is supplied until the voltage reaches 3 V at a constant current of 0.5 mA.
  • Lithium ions were previously stored in the negative electrode.
  • Comparative Example 2 An electricity storage device was produced in the same manner as in Comparative Example 1 except that 0.2 g of lithium iron phosphate was used as a lithium ion supply source in the slurry.
  • the current is supplied until the voltage reaches 4.0 V at a constant current of 0.1 mA, and then the current is supplied until the voltage reaches 3 V at a constant current of 0.5 mA.
  • Lithium ions were previously stored in the negative electrode.
  • Table 1 shows the average voltage results.
  • the average voltages of Example 1, Example 2, Comparative Example 1, and Comparative Example 2 were 3.43V, 3.42V, 3.30V, and 3.34V.
  • This is a composite of a nitroxyl compound and a conductive material, which suppresses re-doping of lithium ions by lithium manganate or lithium iron phosphate and suppresses release of lithium ions from the carbon negative electrode.
  • 1 and 2 are considered to be because charging and discharging were possible in a state where more lithium ions were stored in the negative electrode than in Comparative Examples 1 and 2.
  • Table 2 shows the maximum output results.
  • the maximum outputs of Example 1, Example 2, Comparative Example 1, and Comparative Example 2 were 157 mW / cm 2 , 179 mW / cm 2 , 43 mW / cm 2 , and 78 mW / cm 2 , respectively.
  • the output characteristics were improved by combining the nitroxyl compound with the conductive material.
  • the power storage device is a power storage device for driving or auxiliary such as an electric vehicle or a hybrid electric vehicle, a power source for various portable electronic devices, a power storage device for various energy such as solar energy or wind power generation, or It can be applied to a storage power source for household appliances.

Abstract

L'invention concerne un dispositif de stockage électrique comprenant un électrolyte contenant des sels de lithium et un solvant organique aprotique, une électrode négative contenant un matériau carboné dans lequel des ions de lithium peuvent être introduits et éliminés de manière réversible, et une électrode positive contenant un composé de nitroxyle qui possède une structure partielle de cation de radical nitroxyle représentée par la formule (1) lorsqu'il est dans un état oxydé, et qui possède une structure partielle de radical de nitroxyle représentée par la formule (2) lorsqu'il est dans un état réduit, le dispositif de stockage électrique étant caractérisé en ce que : l'électrode positive contient un composé de lithium ; et le composé de nitroxyle est obtenu par égouttage ou versement d'une solution de matériau brut, dans laquelle un composé de nitroxyle est dissous ou gonflé et un matériau électroconducteur est dispersé ou dissous, dans une solution dans laquelle le composé de nitroxyle et le matériau électroconducteur ne se dissolvent ou ne gonflent pas, ce qui permet d'obtenir un précipité dans lequel le matériau électroconducteur est compris à l'intérieur du composé de nitroxyle, et ainsi le composé de nitroxyle est dans un complexe ayant le matériau électroconducteur. La présente invention fournit un dispositif de stockage électrique ayant un débit élevé.
PCT/JP2013/083234 2012-12-14 2013-12-11 Dispositif de stockage électrique WO2014092128A1 (fr)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
FR3107614A1 (fr) * 2020-02-21 2021-08-27 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procédé de préparation d’un matériau composite particulaire pour électrode organique

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JP2005209498A (ja) * 2004-01-23 2005-08-04 Nec Corp 非水電解液二次電池
JP2007213992A (ja) * 2006-02-09 2007-08-23 Denso Corp 二次電池用電極及び該電極を用いた二次電池
JP2009205918A (ja) * 2008-02-27 2009-09-10 Nec Corp 蓄電デバイス
JP2009238612A (ja) * 2008-03-27 2009-10-15 Nec Corp 蓄電デバイス
JP2010009940A (ja) * 2008-06-26 2010-01-14 Denso Corp 二次電池電極用バインダー、並びに該バインダーを用いた二次電池用電極及び非水電解液二次電池
WO2011034117A1 (fr) * 2009-09-18 2011-03-24 日本電気株式会社 Corps composite de matériau polymère radicalaire - charbon actif - matériau conducteur, procédé de fabrication du corps composite à base de matériau conducteur et dispositif de stockage d'électricité

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005209498A (ja) * 2004-01-23 2005-08-04 Nec Corp 非水電解液二次電池
JP2007213992A (ja) * 2006-02-09 2007-08-23 Denso Corp 二次電池用電極及び該電極を用いた二次電池
JP2009205918A (ja) * 2008-02-27 2009-09-10 Nec Corp 蓄電デバイス
JP2009238612A (ja) * 2008-03-27 2009-10-15 Nec Corp 蓄電デバイス
JP2010009940A (ja) * 2008-06-26 2010-01-14 Denso Corp 二次電池電極用バインダー、並びに該バインダーを用いた二次電池用電極及び非水電解液二次電池
WO2011034117A1 (fr) * 2009-09-18 2011-03-24 日本電気株式会社 Corps composite de matériau polymère radicalaire - charbon actif - matériau conducteur, procédé de fabrication du corps composite à base de matériau conducteur et dispositif de stockage d'électricité

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3107614A1 (fr) * 2020-02-21 2021-08-27 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procédé de préparation d’un matériau composite particulaire pour électrode organique

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