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WO2006082708A1 - Electrode positive d'element secondaire, procede de fabrication de celle-ci et element secondaire - Google Patents

Electrode positive d'element secondaire, procede de fabrication de celle-ci et element secondaire Download PDF

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Publication number
WO2006082708A1
WO2006082708A1 PCT/JP2006/300695 JP2006300695W WO2006082708A1 WO 2006082708 A1 WO2006082708 A1 WO 2006082708A1 JP 2006300695 W JP2006300695 W JP 2006300695W WO 2006082708 A1 WO2006082708 A1 WO 2006082708A1
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WO
WIPO (PCT)
Prior art keywords
positive electrode
secondary battery
carbon fiber
active material
material layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2006/300695
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English (en)
Japanese (ja)
Inventor
Jiro Iriyama
Kentaro Nakahara
Shigeyuki Iwasa
Masahiro Suguro
Masaharu Satoh
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NEC Corp
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NEC Corp
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Publication date
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Priority to JP2007501525A priority Critical patent/JPWO2006082708A1/ja
Publication of WO2006082708A1 publication Critical patent/WO2006082708A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 positive electrode for a secondary battery, a method for producing the same, and a secondary battery. More specifically, in a positive electrode for a secondary battery containing a radical compound, the electrical resistance of the positive electrode is reduced and the machine The present invention relates to a positive electrode for a secondary battery with improved mechanical strength, a method for producing the same, and a secondary battery.
  • Patent Document 1 As a secondary battery having a high energy density and a high capacity and excellent stability, a nitroxyl radical compound, an oxy radical compound, Lithium secondary batteries using radical compounds such as oxy radical compounds and polymer compounds having an aminotriazine structure have been proposed.
  • Patent Document 2 As a secondary battery that can be used at a large current with a high energy density, a -troxyl cation partial structure is formed in an acid state and a -troxyl radical portion is formed in a reduced state.
  • a lithium secondary battery has been proposed in which a structure-troxyl compound is contained in the active material layer of the positive electrode, and the electron transfer reaction between the acid state and the reduced state is used as the positive electrode reaction. .
  • Patent Document 3 as a secondary battery having a high energy density and a large capacity and stable, at least a positive electrode, a negative electrode, and an electrolyte are used as constituent elements, and at least an electrochemical oxidation reaction and a reduction reaction are performed.
  • a lithium secondary battery having particles containing an organic compound that generates a radical compound in one process as an active material, and in which the active material layer for the positive electrode is formed of a composite having at least two compositional regions. Secondary batteries have been proposed.
  • Patent Document 4 discloses a secondary battery that improves the conductivity and mechanical strength of an electrode.
  • As an active material layer containing a disulfide group the S—S bond of the disulfide group is cleaved by electrochemical reduction and regenerated by electrochemical oxidation.
  • the lithium secondary battery used has been proposed.
  • carbon nanotubes are dispersed in a conductive matrix.
  • Patent Document 1 Japanese Patent Laid-Open No. 2002-151084
  • Patent Document 2 JP-A-2002-304996
  • Patent Document 3 Japanese Patent Laid-Open No. 2002-298850
  • Patent Document 4 Japanese Patent Laid-Open No. 11-329414
  • the lithium secondary batteries described in Patent Documents 1 to 3 have low mechanical strength, the current collector active material layer may fall off during storage without charge / discharge of the lithium secondary battery. Therefore, the charge / discharge capacity of the active material layer during storage (referred to as storage characteristics) may be reduced.
  • the lithium secondary battery described in Patent Document 4 since the regeneration efficiency of the cleaved S—S bond is small during the electrochemical reaction during charge and discharge, it is described in Patent Documents 1 to 3. Compared to a lithium secondary battery using an active material layer of the above radical compound, stability during charging and discharging is poor. For this reason, the lithium secondary battery described in Patent Document 4 has a problem that it is difficult to use as a large-capacity secondary battery capable of charging and discharging using a large current, and there is a need for a solution to the problem. It was.
  • the present invention has been made to solve the above-mentioned problems, and its first object is to The object is to provide a positive electrode for a secondary battery with low electrode resistance and high mechanical strength, and a method for producing the same.
  • a second object of the present invention is to provide a secondary battery having a large capacity and excellent storage characteristics that can be charged and discharged using a large current.
  • a positive electrode for a secondary battery according to the present invention for solving the above-described problems is a carbon fiber having an average value of a radical compound and an interlayer distance d of a graphite structure in a range of 0.335 nm or more and 0.340 nm or less.
  • an active material layer including at least a fiber.
  • the radical compound and the carbon fiber are included, it is considered that the interface resistance between the two is remarkably reduced, and the conductivity of the active material layer containing them can be increased. As a result, a positive electrode for a secondary battery having a low electric resistance can be configured. Also, the average value of the interlayer distance d of the graphite structure of the carbon fiber contained in the active material layer is 0.335 nm or more.
  • the carbon fiber within the range of 340 nm or less has high mechanical strength, the mechanical strength of the active material layer containing such carbon fiber can be increased. As a result, a positive electrode for a secondary battery having an active material layer with high conductivity that does not crack or fall off can be configured. Moreover, since the active material layer of the positive electrode for secondary battery of the present invention contains a radical compound, a secondary battery using the positive electrode for secondary battery can have a large capacity.
  • the tensile elastic modulus of the carbon fiber is in a range of 200 GPa to 800 GPa.
  • the average value of the interlayer distance d of the above-mentioned graphite structure is in the range of 0.335 nm or more and 0.340 nm or less.
  • the carbon fiber in the enclosure usually has a large value with a tensile elastic modulus in the range of 200 GPa to 800 GPa. According to the present invention, it is possible to increase the mechanical strength of the active material layer containing such carbon fibers and the positive electrode for a secondary battery including the active material layer.
  • the volume resistivity of the carbon fiber is in a range of 200 ⁇ ⁇ cm to 2000 ⁇ ′cm.
  • the volume resistivity of the carbon fibers contained in the active material layer is in the range of 200 ⁇ -cm to 2000 / ⁇ ⁇ ′cm, the active material layer containing such carbon fibers.
  • the conductivity becomes higher.
  • the electrode resistance of the positive electrode for a secondary battery provided with such an active material layer The resistance can be lowered.
  • the carbon fiber is preferably a vapor-grown carbon fiber.
  • the carbon fiber is a vapor-grown carbon fiber having excellent dispersibility
  • the dispersibility of the carbon fiber in the radical compound when producing the active material layer can be improved. wear.
  • an active material layer having uniform characteristics in each part and a secondary battery positive electrode including the active material layer can be easily obtained.
  • the carbon fiber is a graphitized carbon fiber having a mesophase pitch as a precursor.
  • Mesophase pitch is a polycyclic aromatic compound contained in coal tar or petroleum pitch that undergoes a polycondensation reaction by heating or the like and has uniform optical anisotropy.
  • carbon fibers having a mesophase pitch as a precursor By firing carbon fibers having a mesophase pitch as a precursor at a temperature of 2600 ° C to 3000 ° C, carbon fibers having an extremely high graphitization degree can be obtained. Since carbon fiber has such a high degree of graphite and excellent electrical conductivity and mechanical strength, when it is used for a positive electrode, a positive electrode for a secondary battery with low resistance and excellent mechanical strength can be obtained. Can be easily obtained.
  • the carbon fiber content in the active material layer is preferably in the range of 10 wt% to 50 wt%.
  • the mechanical strength of the active material layer can be increased.
  • the mechanical strength of the positive electrode for the secondary battery can be increased.
  • the content ratio of the carbon fiber in the active material layer is 50% by weight or less, the content ratio of the radical compound in the active material layer can be relatively increased, and as a result, the secondary content of the present invention can be increased.
  • a secondary battery using a positive electrode for a battery can have a large capacity.
  • the positive electrode for a secondary battery of the present invention preferably contains at least one of the radical compound power nitroxyl radical compound, oxy radical compound and nitrogen radical compound, in particular, Among the troxyl radical compounds, poly (4-methacryloyloxy 1, 2, 6, 6-tetramethylpiperidine 1-1-oxyl), poly (4-ataryloxyoxy 2, 2, 6, 6-tetramethylpiperidine) 1-oxyl) or poly (4-bi) -Luoxy-1,2,6,6-tetramethylpiperidine1-1-oxyl).
  • the method for producing a positive electrode for a secondary battery of the present invention for solving the above-mentioned problem is a method for producing a positive electrode for a secondary battery having an active material layer containing at least a radical compound and carbon fiber.
  • the average value of the interlayer distance d of the graphite structure is
  • It has a step of dispersing the carbon fiber in the range of not less than 0.335 nm and not more than 0.340 nm.
  • the carbon fiber in the active material layer it is preferable to disperse the carbon fiber in the active material layer so that the carbon fiber content is in the range of 10 wt% to 50 wt%. That's right.
  • the carbon fiber content in the active material layer is dispersed so as to be within the above range, an active material layer in which the electrical resistance and mechanical properties are uniform in each part can be formed. As a result, a positive electrode for a secondary battery having a low electrical resistance and a high mechanical strength can be produced.
  • the secondary battery of the present invention for solving the above problems is a secondary battery comprising at least a positive electrode, a negative electrode, and an electrolyte solution, wherein the positive electrode is the positive electrode for a secondary battery according to the present invention described above. It is characterized by being.
  • the positive electrode for a secondary battery including a radical compound and having an active material layer having a low electrode resistance and a large mechanical strength is provided, a large current V is charged and discharged.
  • a secondary battery having a large capacity and excellent storage characteristics can be obtained.
  • the positive electrode for a secondary battery of the present invention since the conductivity of the active material layer is increased and neither cracking nor dropping occurs, the electrical resistance is low and the mechanical strength is high.
  • a positive electrode for a secondary battery can be configured.
  • the active material layer of the positive electrode for secondary battery of the present invention contains a radical compound, a secondary battery using the positive electrode for secondary battery can have a large capacity.
  • an active material layer having uniform electric resistance and mechanical characteristics in each part can be formed, so that the electric resistance is low and the mechanical strength is large.
  • a positive electrode for a secondary battery can be manufactured.
  • the secondary battery of the present invention since the positive electrode for a secondary battery having high mechanical strength is provided, the electrode resistance is increased due to cracks in the active material layer, or the active material layer is dropped off. It is possible to suppress deterioration of storage characteristics.
  • the secondary battery of the present invention includes a positive electrode for a secondary battery that includes a radical compound and has an active material layer that has low, electrode resistance, and high mechanical strength, charging and discharging using a large current is possible. A secondary battery having a large capacity and excellent storage characteristics can be obtained.
  • FIG. 1 is a schematic cross-sectional view showing an example of a secondary battery of the present invention.
  • the positive electrode for secondary battery of the present invention is an average of the radical compound and the interlayer distance d of the graphite structure
  • the 002 has an active material layer containing at least carbon fibers within a range of 0.335 nm or more and 0.340 nm or less. Such an active material layer is usually formed on a current collector and forms a part of a positive electrode for a secondary battery.
  • the current collector is preferably a general material and shape that is not particularly limited. Examples of the current collector material include various materials such as aluminum, nickel, aluminum alloy, nickel alloy, and carbon. Examples of the shape thereof include foil, flat plate, and mesh. The one that also has shape power can be mentioned.
  • a radical compound is a compound which comprises an active material layer as an active material.
  • the radical compound, free radical having an unpaired electron i.e., radical
  • the radical compound, free radical having an unpaired electron is a compound having, Rajikarui ⁇ composing this onset Ming, spin concentration force S l0 21 radical density in the high instrument equilibrium A state where spinZg or higher continues for 1 second or longer.
  • the charged state of the radical compound constituting the present invention is preferably electrically neutral from the viewpoint of easy charge / discharge reaction.
  • the radical density (density of unpaired electrons) is equal to the spin concentration.
  • the spin concentration is a value obtained by, for example, the following method from the absorption area intensity of an electron spin resonance spectrum (hereinafter referred to as ESR spectrum).
  • ESR spectrum an electron spin resonance spectrum
  • the ESR ⁇ vector can be measured using, for example, the EOL-JES-FR30 ESR ⁇ spectrometer.
  • the spin concentration can be calculated by integrating the obtained ESR signal twice and comparing it with the calibration curve. In the present invention, any measuring instrument and measurement condition are applicable as long as the spin concentration can be measured correctly.
  • radical compound examples include polymer-troxyl radical compound, polymer oxydica Examples thereof include a Louis compound and a polymer hydrazyl radical compound.
  • radical compound examples include polymer-troxyl radical compound, polymer oxydica Examples thereof include a Louis compound and a polymer hydrazyl radical compound.
  • At least one or two or more of these radical compounds can be used.
  • a polymer-troxyl radical compound that is, a polymer having -toxyl is most preferably used.
  • Nitroxyl is particularly preferable as an active material because of its extremely high stability due to nonlocality of radicals.
  • Typical examples of the polymer-troxyl radical compound include A-1 to A-8 of the following chemical structural formulas.
  • each radical is further stabilized by steric hindrance due to a bulky substituent in the vicinity and a resonance structure.
  • the polymer main chain includes poly (meth) acrylic acid, polyalkyl (meth) acrylates, polybutyl ethers, poly (meth) acrylamides, polymer strength, high oxidation resistance and reduction resistance, and electrochemical properties. Is particularly preferable.
  • R to R are poly (meth) acrylic acid, polyalkyl (meth) acrylates, polybutyl ethers, poly (meth) acrylamides, polymer strength, high oxidation resistance and reduction resistance, and electrochemical properties. Is particularly preferable.
  • R to R are examples of the formula, R to R are
  • the A-7 A-8 polymer oxyradical compound is a polymer having an oxyradical, and typical examples thereof include A-9 to A-11 of the following chemical structural formula.
  • the high molecular hydrazyl radical compound is a polymer having a hydrazyl radical, and examples thereof include A-12 and A-13 of the following chemical structural formula. In the formula, R to R are respectively
  • the carbon fiber of the present invention has a graphite structure interlayer distance d
  • the average value of 002 is 0.335 nm or more 0.34
  • the average value of the interlayer distance d of the carbon fiber graphite structure is, for example, an X-ray rotation
  • the graphite structure of carbon fiber it can be represented by the analysis result of the X-ray diffraction peak that appears as the average value of the inter-layer distance d.
  • the carbon fiber having an interlayer distance within the above range has a large mechanical strength (for example, tensile elastic modulus), the mechanical strength of the active material layer can be increased. The result is an active material layer that does not fall off if cracked, and has a highly conductive active material layer. Can be configured.
  • tensile elastic modulus for example, tensile elastic modulus
  • the mechanical strength of the active material layer containing carbon fibers may be insufficient due to a lack of mechanical strength (for example, tensile modulus).
  • 002 is 0.335 nm, and there is no carbon fiber with an interlayer distance less than 0.335 nm.
  • the tensile elastic modulus of the carbon fiber is preferably in the range of 200 GPa to 800 GPa.
  • the average value of the interlayer distance d of the above graphite structure is 0.335 nm or more and 0.340 nm or less.
  • Such an active material layer containing carbon fibers can increase the mechanical strength of the positive electrode for a secondary battery having a high mechanical strength. If the tensile modulus of the carbon fiber is less than 200 GPa, the mechanical strength of the active material layer containing the carbon fiber may be insufficient because the mechanical strength is insufficient.
  • the upper limit of the tensile modulus of carbon fiber was set to 800 GPa from the viewpoint of carbon fiber production cost.
  • the definition and measurement method of the tensile modulus of carbon fiber are based on JIS R7601-1986 (carbon fiber test method).
  • the active material layer containing carbon fiber described above has a feature that mechanical strength is increased.
  • the volume resistivity of the carbon fiber is 200 ⁇ 'cm or more and 2000 ⁇ 'cm or less. It is preferable to be within the range.
  • carbon fibers having a volume resistivity in such a range are included in the active material layer, the conductivity of the active material layer is increased. As a result, the electrode resistance of the positive electrode for secondary batteries provided with the active material layer can be lowered.
  • the lower limit of the volume resistivity of the carbon fiber was set to 200 ⁇ ′ cm from the viewpoint of the production cost of the carbon fiber.
  • the electrode resistance of the positive electrode may not be sufficiently lowered.
  • the definition and measurement method of the volume resistivity of carbon fiber are also in accordance with JIS R7601-1986 (carbon fiber test method), similar to the above-mentioned tensile elastic modulus.
  • the types of carbon fibers are classified according to the production method, but the carbon fibers applicable to the present invention are not particularly limited, and various types of carbon fibers that satisfy the above characteristics can be used.
  • PAN carbon fibers obtained by carbonizing polyacryl-tolyl (PolyAcryloNitrile: PAN) precursors, pitches obtained when refining petroleum and coal are used as precursors Pitch carbon fiber obtained by carbonizing and graphitizing this, and vapor grown carbon fiber (Vapor-) obtained by growing fiber on a substrate in a reaction furnace using hydrocarbon vapor.
  • Grown Carbon F3 ⁇ 4ers (VGCF), carbon nanotubes (CNT) obtained by an arc discharge method using an arc discharge between graphite electrodes, and the like can be used. These may be used alone or in combination of two or more.
  • VGCF vapor-grown carbon fibers
  • mesophase pitch carbon fiber obtained by carbonizing and graphitizing mesophase pitch having optical anisotropy among pitches obtained when refining petroleum or coal is used as a precursor.
  • mesophase pitch carbon fiber obtained by carbonizing and graphitizing mesophase pitch having optical anisotropy among pitches obtained when refining petroleum or coal is used as a precursor.
  • mesophase pitch carbon fiber obtained by carbonizing and graphitizing mesophase pitch having optical anisotropy among pitches obtained when refining petroleum or coal is used as a precursor.
  • boron in the range of 10 to 50 ppm is added to the mesophase pitch for easier progress of graphite.
  • the size of the carbon fiber is not particularly limited, but in the present invention, the average length is usually from 10 ⁇ m to 200 ⁇ m and the average diameter is from 0.4 ⁇ m to 4 ⁇ m.
  • a fibrous material is preferably used for the reason of good dispersibility.
  • the average length and the average diameter are the average length and the average diameter when 1000 or more carbon fibers are observed with an electron microscope or the like.
  • the active material layer is formed on the current collector to constitute the positive electrode for a secondary battery of the present invention, and includes at least the radical compound and the carbon fiber.
  • the active material layer contains carbon fiber in a proportion within the range of 10 wt% to 50 wt%.
  • carbon fiber in this ratio in the active material layer, the mechanical strength of the active material layer can be increased and the electrical resistance can be decreased. If the carbon fiber content in the active material layer is less than 10% by weight, the active material layer may be cracked or dropped, resulting in insufficient mechanical strength. On the other hand, if the carbon fiber content in the active material layer exceeds 50% by weight, the proportion of the radical compound that functions as the active material is relatively lowered. The capacity
  • Such a phenomenon is a remarkable effect obtained by a combination of a radical compound and carbon fiber, and the present inventor has used other conductors such as gold, silver, copper, etc. instead of carbon fiber. In some cases, it has been confirmed that the conductivity of the active material layer does not increase.
  • the active material layer described in Patent Document 4 (the active material layer in which carbon nanotubes are dispersed in a conductive matrix containing a disulfide group) has conductivity equivalent to that of carbon nanotubes.
  • the active material layer used in the present invention in that even when silver, gold, copper, etc. are dispersed instead of carbon nanotubes to form an active material layer, the conductivity of the active material layer is similarly increased? Differently.
  • the method for producing a positive electrode for a secondary battery of the present invention is a method for producing a positive electrode for a secondary battery having an active material layer containing at least a radical compound and carbon fiber, and more specifically, in a solvent containing a radical compound.
  • the average value of the interlaminar distance d of the black lead structure is not less than 0.335 nm and not more than 0.340 nm.
  • a solution in which the radical compound is dissolved in a solvent is prepared, the carbon fiber and a binder (also referred to as a binder) are mixed with the solution, and ultrasonic waves are radiated to the mixed solution. Then, a slurry is obtained by dispersing the carbon fibers in the mixed solution. Next, after applying this slurry on the current collector to a predetermined thickness, the solvent is evaporated, whereby a positive electrode for a secondary battery having an active material layer can be produced.
  • n-methylpyrrolidone (NMP), tetrahydrofuran (THF), toluene and the like can be used. These may be used alone or in combination of two or more.
  • NMP n-methylpyrrolidone
  • THF tetrahydrofuran
  • toluene and the like can be used. These may be used alone or in combination of two or more.
  • binder poly (vinylidene fluoride), bi-lidene fluoride monohexafluoropropylene copolymer, bi-lidene fluoride-tetrafluoroethylene copolymer, and the like can be used. These may be used alone or in combination of two or more.
  • the ratio of the binder contained in the active material layer is preferably in the range of 1% by weight to 10% by weight.
  • the ratio of the binder in the active material layer is less than 1% by weight, there is a risk of peeling due to poor adhesion between the formed active material layer and the current collector.
  • the proportion of the binder in the active material layer exceeds 10% by weight, the proportion of the radical compound or carbon fiber in the active material layer is relatively lowered, so that the positive electrode according to the present invention is used.
  • the capacity of the secondary battery may be reduced, and the mechanical strength of the active material layer may be insufficient.
  • the radical compound is dissolved in a solvent, the solution is impregnated in the carbon fiber-strength sheet, and the solvent is evaporated.
  • a positive electrode for a secondary battery having a material layer can be manufactured. In this case, since the function as the current collector is borne by the sheet in which the carbon fibers are intertwined, the binder as described above is not included.
  • the secondary battery of the present invention is composed of a positive electrode, a negative electrode and an electrolytic solution, and the positive electrode for a secondary battery is used as the positive electrode.
  • the positive electrode for a secondary battery according to the present invention described above since the positive electrode for a secondary battery according to the present invention described above is used, an increase in electrode resistance due to cracks in the active material layer and a deterioration in storage characteristics due to dropout of the active material layer. Can be suppressed.
  • the active material layer of the positive electrode contains a radical compound that functions as an active material and has low electrode resistance, so that the charge / discharge capacity at a large current can be increased. Therefore, this secondary battery can be charged and discharged using a large current, has a large capacity and excellent storage characteristics.
  • any laminated form is not particularly limited as to the laminated form of the positive electrode and the negative electrode.
  • it may be a multilayer laminate, a form in which the current collectors are laminated on both sides, or a form in which these are wound.
  • the shape of the secondary battery of the present invention is not particularly limited, and a conventionally known one can be used.
  • a coin type, a cylindrical type, a square type, a sheet type, or the like can be used. wear.
  • FIG. 1 is a schematic cross-sectional view of a coin-type secondary battery showing an example of the secondary battery of the present invention.
  • a coin-type secondary battery 10 shown in FIG. 1 has a positive electrode 11 composed of an active material layer 1 and a current collector 3, and a negative electrode 12 also composed of an active material layer 2 and a current collector 4.
  • the positive electrode 11 and the negative electrode A porous separator 13 is sandwiched between the two to prevent electrical connection between them.
  • the positive electrode 11, the negative electrode 12 and the separator 13 are immersed in the electrolyte solution 5, and these are configured to be sealed in the positive electrode outer can 6 and the negative electrode outer can 7 by the insulating packing portion 8!,
  • the positive electrode 11, the negative electrode 12 and the separator 13 are immersed in the electrolyte solution 5, and these are configured to be sealed in the positive electrode outer can 6 and the negative electrode outer can 7 by the insulating packing portion 8!,
  • the insulating packing portion 8! The
  • the negative electrode is obtained by forming an active material layer for a negative electrode on a current collector, and the active material layer includes an active material for the negative electrode.
  • the active material for the negative electrode is not particularly limited, and any conventionally known material can be used as long as the acid reduction potential is lower than that of the positive electrode.
  • carbon materials such as polyacrylonitrile-based carbon fiber, fullerene, and carbon nanotube can be used.
  • Li-based material such as _M N (where X is 0 ⁇ x ⁇ 1 and M is at least one element selected from Co, Ni, and Cu). These materials can be used alone or in combination of two or more.
  • the current collector one made of any material of copper, silver, copper alloy, silver alloy, and carbon can be used.
  • the shape of the current collector include foil, flat plate, and mesh.
  • Examples of a method for forming an active material layer including an active material for a negative electrode on a current collector include a method in which a mixture of a negative active material and a binder is applied to the current collector. be able to.
  • the binder is not particularly limited, and any conventionally known binder can be used.
  • any conventionally known binder can be used.
  • the current collector is also made of the same material, so that the entire negative electrode can be made of the same material.
  • electrolytic solution an electrolytic solution in which an electrolyte salt is dissolved is used.
  • the materials used for these are not particularly limited, and conventionally known materials can be used.
  • electrolyte salts examples include LiPF, LiAsF, LiAlCl, LiCIO, LiBF, LiSbF, LiCF S
  • lithium salts such as O, LiCF CO, Li (CF SO), LiN (CF SO), etc.
  • electrolyte salts include quaternary ammonium salts such as tetraammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate, and tetraethylphosphonium tetrafluoroborate.
  • quaternary phosphonium salts imidazolium salts such as tetramethylborate tetramethylborate, and salts that are selected for isotropic force. These materials can be used alone or in combination of two or more.
  • the electrolyte solution solvent is capable of dissolving the above electrolyte salt, and is arbitrarily selected depending on the electrolyte salt used.
  • the electrolyte solvent include cyclic carbonates such as propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), and beylene carbonate (VC), dimethyl carbonate (DMC), jetyl carbonate (DEC), A mixture of two or more chain carbonates such as ethino-retinoyl carbonate (EMC) and dipropyl carbonate (DPC) can be used.
  • the separator is not particularly limited, and a conventionally known separator can be used.
  • a material for the separator for example, polyolefin such as polypropylene and polyethylene, fluorine resin, and the like can be used.
  • a porous thin film is preferably used.
  • Poly (4-methacryloyloxy) which is a cyclic-toxyl structure-containing polymer represented by -2, 2, 6, 6-tetramethylpiperidine 1-oxyl) (PTME) was synthesized.
  • AIBN azobisisobutyric-tolyl
  • the polymer was precipitated in hexane, filtered, and dried under reduced pressure to obtain 18 g (yield 90%) of poly (2, 2, 6, 6-tetramethylpiperidine metatalylate).
  • 10 g of the obtained poly (2, 2, 6, 6-tetramethylpiperidine metatalylate) was dissolved in 100 ml of dry-treated dichloromethane.
  • 100 ml of a dichloromethane solution of 15.2 g (0. 088 mol) of m-chloroperbenzoic acid was added dropwise over 1 hour with stirring at room temperature.
  • a weight ratio of 4: 1: 5 was measured and mixed in n-methylpyrrolidone as a solvent to prepare a slurry.
  • This slurry was irradiated with 40 kilohertz ultrasonic waves for 30 minutes, and then applied onto a positive electrode current collector 20 / zm thick aluminum foil using a doctor blade and dried at 125 ° C.
  • a positive electrode was obtained by evaporating n-methylpyrrolidone.
  • the positive electrode active material layer thus obtained had a thickness of 150 m.
  • the active material layer after drying has Cracks and current collectors were not seen.
  • the volume resistivity of the above vapor-grown carbon fiber was 300 ⁇ ′cm, the average length was 10 ⁇ m, and the average diameter was 0.5 ⁇ m.
  • a negative electrode was produced.
  • artificial graphite manufactured by Osaka Gas: MCMB25-28
  • rubber binder manufactured by ZEON: BM-400B
  • a doctor blade it was applied onto a copper foil having a thickness of 10 m, dried at 80 ° C., and then compressed with a roller.
  • the negative electrode active material layer thus obtained had a thickness of 20 m. The active material layer after drying did not crack or fall off from the current collector.
  • electrolyte salt containing 0.9 molZl of LiPF is used as the electrolyte.
  • the salt was prepared by dissolving it in an electrolyte solvent consisting of ethylene carbonate Z jetyl carbonate mixed solution (volume mixing ratio 3: 7).
  • the positive electrode and the negative electrode produced as described above were cut into a circular shape having a size of 12 mm and overlapped with a 25- ⁇ m-thick porous polypropylene used as a separator.
  • Example 1 The same radical compound as in Example 1, the same polyvinylidene fluoride as in Example 1, the same vapor-grown carbon fiber as in Example 1, and acetylene black (Denka Black manufactured by Denki Kagaku Kogyo Co., Ltd.). 4: 1: 3: 2 were weighed and mixed in n-methylpyrrolidone as a solvent to prepare a slurry. The slurry was irradiated with ultrasonic waves of 40 kilohertz for 30 minutes, and then applied onto a 20 m thick aluminum foil as a positive electrode current collector using a doctor blade, and dried at 125 ° C. A positive electrode was obtained by evaporating n-methylpyrrolidone.
  • the positive electrode active material layer thus obtained had a thickness of 150 m.
  • the active material layer after drying did not crack or fall off from the current collector.
  • a coin-type secondary battery of Example 2 was fabricated in the same manner as in Example 1 except for the negative electrode other than the positive electrode, the electrolyte, the cell router, and the like.
  • Example 2 The same radical compound as in Example 1, the same polyvinylidene fluoride as in Example 1, and benzene Vapor-grown carbon fibers obtained by pyrolyzing gas and firing carbon fibers grown on a substrate sprayed with iron fine particles at 3000 ° C (the average value of the interlayer distance d of the graphite structure is 0.335 ⁇ )
  • Example 2 the tensile modulus is 800 GPa
  • the same acetylene black as in Example 2 is weighed in a weight ratio of 4: 1: 1: 4 and mixed in n-methylpyrrolidone as a solvent to form a slurry.
  • the slurry was irradiated with ultrasonic waves of 40 kilohertz for 30 minutes, and then applied onto a 20 m thick aluminum foil as a positive electrode current collector using a doctor blade and dried at 125 ° C.
  • a positive electrode was obtained by evaporating n-methylpyrrolidone.
  • the positive electrode active material layer thus obtained was 150 m thick.
  • the dried active material layer was strong enough to show no cracks or falling off the current collector.
  • the volume resistivity of the above vapor grown carbon fiber was 200 ⁇ ′cm, the average length was 10 ⁇ m, and the average diameter was 0.5 ⁇ m.
  • a coin-type secondary battery of Example 3 was produced in the same manner as Example 1 except for the negative electrode other than the positive electrode, the electrolyte, the separator, and the like.
  • This slurry was irradiated with ultrasonic waves of 40 kilohertz for 30 minutes, and then applied onto a 20 m thick aluminum foil as a positive electrode current collector using a doctor blade, and dried at 125 ° C.
  • a positive electrode was obtained by evaporating n-methylpyrrolidone.
  • the positive electrode active material layer thus obtained had a thickness of 150 / zm.
  • the dried active material layer was strong enough to show no cracks or falling off the current collector.
  • the volume resistivity of the above vapor-grown carbon fiber was 800 ⁇ ′cm, the average length was 20 ⁇ m, and the average diameter was 0.5 ⁇ m.
  • a coin-type secondary battery of Example 4 was produced in the same manner as Example 1 except for the negative electrode other than the positive electrode, the electrolyte, the separator, and the like.
  • Carbon fibers are weighed in a weight ratio of 4: 1: 5, and they are in the solvent n-methylpyrrolidone.
  • the positive electrode active material layer thus obtained had a thickness of 150 m. In the active material layer after drying, the cracks and current collector force did not fall off.
  • the volume resistivity of the above vapor-grown carbon fiber was 2000 ⁇ ′cm, the average length was 20 ⁇ m, and the average diameter was 0.5 ⁇ m.
  • a coin-type secondary battery of Example 5 was fabricated in the same manner as Example 1 except for the negative electrode other than the positive electrode, the electrolyte, the separator, and the like.
  • Graphitized PTVE synthesized in the same manner as in Example 5, polyvinylidene fluoride as in Example 1, and carbon fiber with a mesophase pitch as a precursor (Petoriki Co., Ltd., interlayer distance d of graphite structure)
  • the average value is 0.333 nm
  • the tensile modulus is 550 GPa
  • the volume resistivity is 400 ⁇
  • Example 6 A coin-type secondary battery of Example 6 was fabricated in the same manner as Example 1 except for the negative electrode other than the positive electrode, the electrolyte, the separator, and the like.
  • Example 1 The same radical compound as in Example 1, the same polyvinylidene fluoride as in Example 1, and the same acetylene black as in Example 2 are weighed in a weight ratio of 4: 1: 5 and used as a solvent.
  • a slurry was prepared by mixing with n-methylpyrrolidone. This slurry was irradiated with 40 kilohertz ultrasonic waves for 30 minutes, and then applied onto a 20 m thick aluminum foil as a positive electrode current collector using a doctor blade, and dried at 125 ° C.
  • a positive electrode was obtained by evaporating n-methylpyrrolidone.
  • the positive electrode active material layer thus obtained had a thickness of 150 m.
  • the active material layer after drying was cracked and dropped from the current collector.
  • Negative electrode other than positive electrode, electrolyte And the separator and the like were made in the same manner as in Example 1 to produce a coin-type secondary battery of Comparative Example 1.
  • Example 2 The same radical compound as in Example 1, the same polyvinylidene fluoride as in Example 1, and gold powder (average particle size 3 m) were weighed to a weight ratio of 4: 1: 5, and they were used as solvents.
  • a slurry was prepared by mixing with n-methylpyrrolidone. This slurry was irradiated with 40 kilohertz ultrasonic waves for 30 minutes, and then applied onto a 20 m thick aluminum foil, which is a positive electrode current collector, using a doctor blade, and dried at 125 ° C. A positive electrode was obtained by evaporating n-methylpyrrolidone. The active material layer of the positive electrode thus obtained was 150 m thick. The dried active material layer was cracked and detached from the current collector.
  • a coin-type secondary battery of Comparative Example 2 was produced in the same manner as Example 1 except for the negative electrode other than the positive electrode, the electrolyte, the separator, and the like.
  • the coin-type secondary batteries of Examples 1 to 6 and Comparative Examples 1 and 2 were charged and discharged at a constant current in a voltage range of 2V force and 4V. Charging / discharging was performed in a thermostatic chamber set at 20 ° C. The charge current was 1C and the discharge current was 1C and 50C. The discharge capacity in each case was measured. The 1C current is a current value at which discharge is completed in one hour, and the 50C current is a current 50 times the 1C current. As a measure of the capacity characteristics of the secondary battery during large current discharge, the ratio of the discharge capacity at 50C current to the discharge capacity at 1C current was investigated.
  • the positive electrodes of Examples 1 to 6 did not crack or fall off, whereas the positive electrodes of Comparative Examples 1 and 2 were cracked or dropped.
  • the positive electrodes of Examples 1 to 6 were free from cracking or falling off because the active material layer contained carbon fibers having an average value of the interlayer distance d of the graphite structure in the range of 0.335 nm to 0.340 nm. This is because the mechanical strength of the active material layer of the positive electrode is improved.
  • the secondary batteries of Examples 1 to 6 were all stronger than the secondary battery of Comparative Example 1. This is because, in the secondary batteries of Examples 1 to 6, the active material layer of the positive electrode is not cracked, the conductivity of the active material layer is high, and the electrode resistance of the positive electrode is low. This shows an improvement over the comparative example.
  • the secondary battery of Comparative Example 2 has no capacity at 1C discharge, and the ratio of 50C to the 1C discharge capacity and the ratio of the discharge capacity after one week storage to the discharge capacity before storage should be obtained. I didn't do it. This is probably because the charge transfer resistance at the interface between the radical compound and the gold particles was significantly higher than that of carbon fiber, and the charge / discharge reaction did not proceed. Therefore, even if the same conductor is used, a positive electrode with low electrode resistance cannot be obtained when an active material layer containing gold is used instead of carbon fiber.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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Abstract

Il est possible de fournir une électrode positive d'élément secondaire présentant une faible résistance électrique et une grande résistance mécanique, ainsi qu'un élément secondaire pouvant effectuer une charge/décharge en utilisant un courant important et présentant une grande capacité et d'excellentes caractéristiques de stockage. L'électrode positive de l'élément secondaire comporte une couche de matériau actif contenant au moins un composé de radical et une fibre de carbone présentant une valeur moyenne de distance inter couches d002 de la structure de graphite dans une plage allant de 0,335 nm à 0,340 nm. La fibre de carbone présentant une telle distance inter couches possède un module d'élasticité dans la plage allant de 200 GPa à 800 GPa et elle possède de préférence une résistivité volumique dans la plage allant de 200 µΩ•cm à 2000 µΩ•cm. La fibre de carbone est de préférence une fibre de carbone épitaxiée en phase vapeur ou bien une fibre de carbone formée par un résidu de mésophase qui a été graphité.
PCT/JP2006/300695 2005-02-04 2006-01-19 Electrode positive d'element secondaire, procede de fabrication de celle-ci et element secondaire Ceased WO2006082708A1 (fr)

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JP2006257250A (ja) * 2005-03-17 2006-09-28 Mitsubishi Gas Chem Co Inc 安定ラジカルを持つ高分子化合物の製造方法
FR2912554A1 (fr) * 2007-02-12 2008-08-15 Arkema France Electrode comprenant au moins un nitroxyde et des nanotubes de carbone
JP2009140647A (ja) * 2007-12-04 2009-06-25 Nec Tokin Corp 非水電解液二次電池
WO2010002002A1 (fr) * 2008-07-03 2010-01-07 Dic株式会社 Batterie secondaire et encre au carbone pour une couche auxiliaire conductrice de la batterie secondaire
JP2010114042A (ja) * 2008-11-10 2010-05-20 Nec Corp 二次電池及びその製造方法
JP2011074317A (ja) * 2009-10-01 2011-04-14 Waseda Univ ポリラジカル化合物の製造方法
KR20170113250A (ko) * 2016-03-24 2017-10-12 주식회사 엘지화학 도전재 분산액 및 이를 이용하여 제조한 이차전지
US10844145B2 (en) 2016-06-02 2020-11-24 Evonik Operations Gmbh Method for producing an electrode material
US11001659B1 (en) 2016-09-06 2021-05-11 Evonik Operations Gmbh Method for the improved oxidation of secondary amine groups

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KR102288293B1 (ko) 2018-06-20 2021-08-10 주식회사 엘지화학 리튬 이차 전지용 양극 활물질 및 리튬 이차 전지

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JP2002083601A (ja) * 2000-09-06 2002-03-22 Toshiba Corp 正極及び非水電解質二次電池
JP2002304996A (ja) * 2001-04-03 2002-10-18 Nec Corp 蓄電デバイス
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006257250A (ja) * 2005-03-17 2006-09-28 Mitsubishi Gas Chem Co Inc 安定ラジカルを持つ高分子化合物の製造方法
FR2912554A1 (fr) * 2007-02-12 2008-08-15 Arkema France Electrode comprenant au moins un nitroxyde et des nanotubes de carbone
WO2008104683A1 (fr) * 2007-02-12 2008-09-04 Arkema France Electrode comprenant au moins un nitroxyde et des nanotubes de carbone
JP2009140647A (ja) * 2007-12-04 2009-06-25 Nec Tokin Corp 非水電解液二次電池
JP4637293B2 (ja) * 2008-07-03 2011-02-23 Ｄｉｃ株式会社 二次電池およびその導電補助層用カーボンインキ
WO2010002002A1 (fr) * 2008-07-03 2010-01-07 Dic株式会社 Batterie secondaire et encre au carbone pour une couche auxiliaire conductrice de la batterie secondaire
JP2010114042A (ja) * 2008-11-10 2010-05-20 Nec Corp 二次電池及びその製造方法
JP2011074317A (ja) * 2009-10-01 2011-04-14 Waseda Univ ポリラジカル化合物の製造方法
KR20170113250A (ko) * 2016-03-24 2017-10-12 주식회사 엘지화학 도전재 분산액 및 이를 이용하여 제조한 이차전지
JP2018533175A (ja) * 2016-03-24 2018-11-08 エルジー・ケム・リミテッド 導電材分散液およびこれを用いて製造した二次電池
US11108050B2 (en) 2016-03-24 2021-08-31 Lg Chem, Ltd. Conductive material dispersed liquid and secondary battery manufactured using the same
KR102320010B1 (ko) * 2016-03-24 2021-11-02 주식회사 엘지에너지솔루션 도전재 분산액 및 이를 이용하여 제조한 이차전지
US10844145B2 (en) 2016-06-02 2020-11-24 Evonik Operations Gmbh Method for producing an electrode material
US11001659B1 (en) 2016-09-06 2021-05-11 Evonik Operations Gmbh Method for the improved oxidation of secondary amine groups

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