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WO2004023590A1 - Pile a combustible secondaire non aqueuse - Google Patents

Pile a combustible secondaire non aqueuse Download PDF

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Publication number
WO2004023590A1
WO2004023590A1 PCT/JP2003/011105 JP0311105W WO2004023590A1 WO 2004023590 A1 WO2004023590 A1 WO 2004023590A1 JP 0311105 W JP0311105 W JP 0311105W WO 2004023590 A1 WO2004023590 A1 WO 2004023590A1
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WO
WIPO (PCT)
Prior art keywords
secondary battery
aqueous electrolyte
electrolyte secondary
ray diffraction
peak
Prior art date
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Ceased
Application number
PCT/JP2003/011105
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English (en)
Japanese (ja)
Inventor
Asako Satoh
Koichi Matsumoto
Hideki Kaido
Masahiro Sekino
Akira Yajima
Minoru Hashimoto
Masayuki Oguchi
Yukio Takahagi
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Toshiba Corp
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Toshiba Corp
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Priority to JP2004534123A priority Critical patent/JP4537851B2/ja
Publication of WO2004023590A1 publication Critical patent/WO2004023590A1/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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • 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
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/0042—Four or more solvents
    • 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 non-aqueous electrolyte secondary battery.
  • Batteries that are widely used as power supplies for these electronic devices include primary batteries such as alkaline manganese batteries, and secondary batteries such as nickel-cadmium batteries and lead-acid batteries. .
  • primary batteries such as alkaline manganese batteries
  • secondary batteries such as nickel-cadmium batteries and lead-acid batteries.
  • non-aqueous electrolyte secondary batteries using lithium composite oxide for the positive electrode and carbonaceous material capable of inserting and extracting lithium ion for the negative electrode are small, lightweight, have high single-cell voltage, and have high energy. The power to obtain the density has been noticed.
  • a lithium-lithium alloy can be used instead of the carbonaceous material.
  • the dissolution and precipitation of lithium are repeated, and it is expected that the lithium will eventually grow into a needle shape.
  • the dendrites may cause an internal short circuit by penetrating through the separator.
  • the negative electrode containing a carbonaceous material forms dendrites 1, as compared with the negative electrode containing lithium or a lithium alloy.
  • the negative electrode capacity can be made closer to the theoretical capacity of 372 mAh / g, and a high-capacity lithium ion secondary battery can be realized. It is possible.
  • the graphite material has high activity with respect to many non-aqueous electrolytes used in lithium ion secondary batteries, and the desorption due to the exfoliation of the material itself. If the initial charge / discharge efficiency, discharge capacity, and cycle characteristics of the secondary battery are reduced because the nonaqueous electrolyte is decomposed, there is a problem.
  • An object of the present invention is to provide a nonaqueous electrolyte secondary battery that simultaneously satisfies initial charge / discharge efficiency, discharge capacity, and cycle characteristics.
  • a non-aqueous electrolyte secondary battery including a positive electrode, a negative electrode containing a carbonaceous substance capable of inserting and extracting lithium ions, and a non-aqueous electrolyte containing a non-aqueous solvent,
  • the non-aqueous solvent includes a sulfonate compound having at least one double bond in a ring.
  • the carbonaceous material has a specific surface area of 0.3 m 2 / g or more and 4 m 2 / g or less according to a BET method, and a plane distance d obtained by powder X-ray diffraction measurement. .
  • the present invention provides a non-aqueous electrolyte secondary battery including a graphite material that does not show a peak at each of 46.6 ° and satisfies the following expressions (1) and (2).
  • I ( ⁇ oi) is the intensity of the diffraction peak on the (101) plane of the X-ray diffraction laser.
  • I (i 00 ) is the intensity of the diffraction peak of the (100) plane of the X-ray diffraction spectrum, and S 0 i) is the diffraction peak of the (101) plane of the X-ray diffraction spectrum.
  • a non-aqueous electrolyte secondary battery comprising a negative electrode containing a carbonaceous substance capable of occluding and releasing ions, and a non-aqueous electrolyte containing a non-aqueous solvent,
  • the non-aqueous solvent contains a sluton compound having at least one double bond in a ring,
  • the carbonaceous material has a specific surface area of 0.3 m 2 / g or more and 4 m 2 / g or less according to a BET method, and a plane distance d obtained by powder X-ray diffraction measurement. . 2 force S 0. In 3 3 6 5 nm or less, wherein (1) and the (2) satisfies the formula, and a non-aqueous electrolyte secondary battery comprising a graphite material having no rhombohedral structure Provided.
  • FIG. 1 is a perspective view showing a thin non-aqueous electrolyte secondary battery which is an example of the non-aqueous electrolyte secondary battery according to the present invention.
  • FIG. 2 is a partial cross-sectional view of the thin nonaqueous electrolyte secondary battery of FIG. 1 taken along the line II-II.
  • FIG. 3 is a partial cross-sectional view showing a cylindrical non-aqueous electrolyte secondary battery which is an example of the non-aqueous electrolyte secondary battery according to the present invention.
  • FIG. 4 is a characteristic diagram showing 1H NMR spectrum of PRS contained in the nonaqueous electrolyte of the nonaqueous electrolyte secondary battery of Example 1.
  • This non-aqueous electrolyte secondary battery includes a container, an electrode group housed in the container and including a positive electrode and a negative electrode, and a non-aqueous electrolyte held by the electrode group and including a non-aqueous solvent. It is.
  • the non-aqueous solvent contains a sulfonate compound having at least one double bond in a ring, and the carbonaceous material has a specific surface area of 0.3 m 2 / g or more according to a BET method. , Containing up to 4 m 2 / g of graphitic material.
  • Sulfon compounds having at least one double bond in the ring can form a protective film on the surface of the carbonaceous material.
  • a carbonaceous material containing a graphite material having a specific surface area of 0.3 m 2 / g or more and 4 m 2 / g or less according to the BET method as in the present invention non-carbonaceous material can be reduced. Since the activity with respect to the aqueous solvent can be reduced, it is possible to suppress the reaction between the lithium ion in the carbonaceous material and the non-aqueous solvent even with a small amount of the sulfur compound. As a result, it is possible to provide a non-aqueous electrolyte secondary battery that simultaneously satisfies the initial charge / discharge efficiency, discharge capacity, and cycle characteristics.
  • the spacing d obtained by powder X-ray diffraction measurement. . 2 is less than 0.337 nm, no rhombohedral structure exists, or the formula (1) (1I ( 101 ) / I (100) ⁇ 2.2) And those satisfying the formula (2) (3.7 ⁇ S ( 101) / S (100) ⁇ 5), the protective film can be formed by the decomposition reaction of the sulfuric acid compound and other solvents. As a result, a protective film having high density and high permeability to lithium ion can be obtained. Therefore, the initial charge / discharge efficiency and discharge capacity of the secondary battery can be further increased. Can be improved.
  • the carbonaceous material has a specific surface area of 0.3 m 2 / g or more and 4 m 2 / g or less, and d-spacing d. . 2 Force S 0.335 nm or less, satisfying the above-mentioned expressions (1) and (2), and having a diffraction angle of 20 force S 4 in X-ray diffraction measurement using Cu C ⁇ ray. 2.8 ° to 44.0 ° and 45.5 ° to 46.6 ° can be obtained by using a graphitic material that does not show a peak or has no rhombohedral structure. As a result, the charge / discharge cycle life of the secondary battery can be further improved.
  • the specific surface area and the spacing d. . 2 is in the above-mentioned range, and the graphite material having no specific diffraction peak or rhombohedral structure reacts with the sulfonate compound and other solvents to form a lithium ion on the negative electrode surface.
  • a protective film can be formed without impairing permeability.
  • this graphite material has a small variation in the overlapping angle of the carbon hexagonal-mesh plane of the graphite structure in order to satisfy the above-mentioned equations (1) and (2). Therefore,- ⁇ , the reaction with the non-aqueous solvent occurs uniformly on the negative electrode surface, and the protective film is formed uniformly on the negative electrode surface. As a result, the charge / discharge cycle life can be further improved.
  • the electrode group the positive electrode, the negative electrode, the separator, the nonaqueous electrolyte, and the container will be described.
  • This electrode group may be formed, for example, by (i) winding a positive electrode and a negative electrode in a flat or spiral shape with a separator interposed therebetween, or (ii) spirally forming a positive electrode and a negative electrode with a separator interposed therebetween. (Iii) bending the positive and negative electrodes one or more times with a separator between them, or (iv) placing the positive electrode and the negative electrode between them. It is manufactured by a method of laminating layers with a separator interposed therebetween.
  • the electrode group may not be pressed, but may be pressed in order to increase the integrated strength of the positive electrode, the negative electrode, and the separator. It is also possible to apply heating during pressing.
  • the positive electrode includes a current collector and a positive electrode layer supported on one or both surfaces of the current collector and containing an active material.
  • the positive electrode layer includes a positive electrode active material, a binder, and a conductive agent.
  • the positive electrode active material include various oxides, for example, manganese dioxide, lithium manganese composite oxide, lithium-containing nickel oxide, lithium-containing cobalt oxide, and lithium.
  • lithium-containing cobalt oxide for example, LiCoO 2
  • lithium-containing nickel cobalt oxide for example, LiNi0.8C 0.
  • Li Ji U Muma down gun composite oxide e.g., L i M n ⁇ 4, L i M n when O 2
  • Ru use Rere and preferred for high voltage can be obtained New
  • one kind of oxide may be used alone, or two or more kinds of oxides may be mixed and used.
  • Examples of the conductive agent include acetylene black and carbohydrate. Black, graphite and the like.
  • the binder has a function of holding the active material on the current collector and connecting the active materials.
  • the binder include polytetrafluoroethylene (PTFE), polyvinylidene polyfluoride (PVdF), polyetherolenosolefone, and polyethylene.
  • PTFE polytetrafluoroethylene
  • PVdF polyvinylidene polyfluoride
  • EPDM ethylene-propylene copolymer
  • SBR styrene-butadiene rubber
  • the mixing ratio of the positive electrode active material, the conductive agent, and the binder was 80 to 95% by weight of the positive electrode active material. /.
  • the conductive agent is contained in the range of 3 to 20% by weight and the binder is contained in the range of 2 to 7% by weight.
  • a conductive substrate having a porous structure or a non-porous conductive substrate can be used as the current collector.
  • These conductive substrates can be formed from, for example, anore miniature, stainless steel, or nickel.
  • a conductive agent and a binder are suspended in a suitable solvent in a positive electrode active material, and this suspension is applied to a current collector, dried, and pressed. It is produced by and.
  • the negative electrode includes a current collector and a negative electrode layer supported on one or both surfaces of the current collector.
  • the negative electrode layer contains a carbonaceous material that stores and releases lithium ion and a binder.
  • the carbonaceous material contains a graphitic material A having a specific surface area of 0.3 m 2 / g or more and 4 m 2 / g or less according to a BET method.
  • a graphitic material having a specific surface area of less than 0.3 m 2 / g Therefore, if only this graphite material is used as the carbonaceous material, the lithium-intercalation reaction rate is reduced, and the discharge capacity is reduced.
  • a graphite material having a specific surface area of more than 4 m 2 / g has a high surface activity. The reaction cannot be suppressed by the protective film, and the discharge capacity or cycle life decreases.
  • a carbonaceous material containing at least 80% by weight of a graphite material A having a specific surface area of 0.3 m 2 / g or more and 4 m 2 / g or less has an appropriate surface activity, and therefore a small amount of a sulfur compound.
  • the reaction between Li + in the carbonaceous material and the non-aqueous solvent can be suppressed, and a secondary battery that simultaneously satisfies the initial charge / discharge efficiency, discharge capacity, and charge / discharge cycle life can be realized. And can be.
  • a more preferable range of the specific surface area of the graphite material A is 0.5 to 4 m 2 / g.
  • Specific surface area of 0 3 m 2 / g or more, ⁇ 4 m 2 / g - than - carbonaceous material comprising one also rather small graphite material A below has a specific surface area of 1 0 m 2 / g or more It is desirable to further contain the graphite material B. According to such a carbonaceous material, the uniformity of distribution of the protective film can be enhanced. A more preferred range of the specific surface area of the graphite material B is 10 to 25 m 2 / g.
  • Graphite material A has a plane spacing d 0 obtained by powder X-ray diffraction measurement. It is preferred that it be less than 2 m S 0.333 11 m. That is, the surface distance d. . If the force exceeds 0.337 nm, the reactivity of the carbonaceous material with respect to the non-aqueous solvent is significantly reduced, so that the There is a possibility that the formation of a protective film by the chemical compound may not occur.
  • Plane spacing d obtained by powder X-ray diffraction measurement. . 2 0.
  • 3 3 7 nm is graphitized material A or less, sulfates tons because decomposition conductive position width can and wide Kusuru
  • This compound is tons compounds during initial charging and other non
  • a protective film can be formed by decomposing water solvent.
  • a protective film having high density and high permeability of lithium ion can be obtained, so that the discharge capacity and charge / discharge cycle life of the secondary battery can be further improved.
  • D-spacing. The more preferred range of 2 is 0.3365 nm or less.
  • the lower limit of the surface spacing d 002 is that you only complete graphite crystal (0 0 2) plane lattice distance d 00 2, i.e. 0. 3 3 5 4 ⁇ arbitrarily favored and the arcs to m.
  • Graphite material A was found to have a diffraction angle of 2 S 42.8 ° to 44.0 ° and 45.5 ° to 46.6 ° in X-ray diffraction measurements using Cu- ⁇ rays. Desirably, no peak is detected. Since such a black lead-material- ⁇ ⁇ does not have a rhombohedral structure, it can increase the decomposition potential width of a smooth-toned compound, and Since the protective film can be formed by the decomposition reaction of the tongue compound and the other solvent, the cycle life of the secondary battery can be further improved.
  • the graphite material A satisfies the following equations (1) and (2).
  • I ( ⁇ 0 ⁇ ) is the number of turns of the (101) plane of the X-ray diffraction spectrum.
  • I ( 00 ) is the intensity of the diffraction peak on the ( 100 ) plane of the X-ray diffraction spectrum
  • S ( 101 ) is the intensity of the diffraction peak on the X-ray diffraction spectrum ( 100 ).
  • the area value of the diffraction peak on the plane, and S (i 00 ) is the area value of the diffraction peak on the (100) plane of the X-ray diffraction spectrum.
  • the hexagonal shape of the carbon crystal structure may be reduced.
  • the regularity of the arrangement between the mesh planes may be impaired, which may hinder in-plane Li ion diffusion.
  • the peak intensity ratio (I (101) / I (100)) exceeds 2.2 or the peak area ratio (S ( 101 ) ZS ( 100 )) is less than 3.7.
  • the structure active to the electrolyte additive is exposed at the crystallite edges and becomes soft.
  • the more preferable range of the peak intensity ratio (I (101) / I (100)) is 1.5 to 2.2, and the more preferable range of the peak area ratio (S ( 101 ) ZS ( 100 )). Is between 3.8 and 4.8.
  • a graphitic material that satisfies the above formulas (1) and (2) and has no rhombohedral structure at a plane spacing force of 0.337 nm or less obtained by powder X-ray diffraction measurement.
  • the carbonaceous material containing A can further improve the initial charge / discharge efficiency, discharge capacity, and cycle life of the secondary battery.
  • the graphite material A used in the present invention a graphite material belonging to artificial graphite, natural graphite, pyrolytic gas-phase carbonaceous material, resin fired body, meso fuse pitch fired body, or the like can be used. You.
  • the graphitic material A may be subjected to a heat treatment at 280 to 300 ° C., for example, for a coat, a pitch, a thermosetting resin, or the like. Alternatively, it can be obtained by adding a coat, pitch, thermosetting resin and the like to natural graphite and subjecting them to a heat treatment.
  • binder examples include polytetrafluoroethylene (PTFE), polyvinylidene vinylidene (PVdF), ethylene propylene, and ethylene propylene.
  • PTFE polytetrafluoroethylene
  • PVdF polyvinylidene vinylidene
  • EPDM styrene-butadiene rubber
  • CMC urenoboximetinoresenorelose
  • a conductive substrate having a porous structure or a non-porous conductive substrate can be used as the current collector.
  • These conductive substrates can be formed from, for example, copper, stainless steel, or nickel.
  • the negative electrode is obtained by, for example, kneading and kneading a carbonaceous substance that occludes and releases lithium ion and a binder in the presence of a solvent, and applies the obtained suspension to a current collector. After drying, it is produced by pressing once or 2 to 5 times at a desired pressure in multiple steps.
  • a microporous membrane, a woven fabric, a nonwoven fabric, a laminate of the same material or a different material, or the like can be used.
  • the material forming the separator include polyethylene, polypropylene, ethylene-propylene copolymer copolymer, and ethylene-butene copolymer polymer. I can list them.
  • the material for forming the separator is selected from the types described above. One or more types can be used.
  • the thickness of the separator is preferably 3 ⁇ or less, and more preferably 2 or less.
  • the lower limit of the thickness is preferably set to 5 ⁇ m, and the more preferable lower limit is 8 m.
  • the separator has a heat shrinkage of 1 hour at 120 ° C.
  • the heat shrinkage is not more than 15%.
  • the porosity is in the range of 30 to 60%.
  • a more preferred range of porosity is between 35 and 50%.
  • the separator has an air permeability of 600 seconds / 100 cm 3 or less.
  • Air permeability refers to the time (seconds) required for 100 cm 3 of air to pass through the separator. It is more preferable to set the upper limit of the air permeability to 500 seconds Z l 0 0 cm 3 . The lower limit of air permeability is 50 seconds Z
  • a value of 100 cm 3 is preferred, and a more preferred lower limit is 80 seconds / 100 cm 3 .
  • the width of the separator be wider than the width of the positive and negative electrodes. With such a configuration, it is possible to prevent the positive electrode and the negative electrode from directly contacting each other without passing through the separator.
  • non-aqueous electrolyte those having a substantially liquid or gel form can be used.
  • the gel-like non-aqueous electrolyte is used to remove the non-aqueous electrolyte when the container is damaged by some external force. The risk of leakage to the part can be reduced.
  • liquid non-aqueous electrolytes can have higher ion conductivity than gelled non-aqueous electrolytes, so that the capacity when discharging non-aqueous electrolyte secondary batteries with a large current and the discharge at low temperatures In this case, the capacity can be improved.
  • the non-aqueous electrolyte is prepared, for example, by the methods described in the following (I) to (VI).
  • a non-aqueous electrolyte is obtained by dissolving an electrolyte (for example, a lithium salt) in the above-mentioned non-aqueous solvent (liquid non-aqueous electrolyte).
  • an electrolyte for example, a lithium salt
  • a cross-linked polymer may be used instead of the organic polymer compound.
  • a prepolymer solution is prepared from a compound having a crosslinkable functional group, a lithium salt and a solvent, and the solution is prepared by using an electrode (at least one of a positive electrode and a negative electrode), a separator, or After coating or impregnating both the electrode and the separator, the compound having a crosslinkable functional group is crosslinked. Next, between the positive and negative electrodes An electrode group is obtained with a separator interposed.
  • the cross-linking step may be performed before or after the solvent is volatilized, or the cross-linking may be performed while the solvent is being volatilized, such as when the cross-linking is performed by heating.
  • the method of cross-linking is not particularly limited, but heat polymerization or photopolymerization by ultraviolet rays is preferred in view of the simplicity of the apparatus and the cost.
  • cross-linking is performed by heating or irradiation with ultraviolet light, it is necessary to add a polymerization initiator suitable for the polymerization method to the prepolymer solution.
  • the polymerization initiator is not limited to one kind, and two or more kinds may be used as a mixture.
  • At least one of the positive electrode and the negative electrode or by applying or impregnating the separator to the electrode or both the electrode and the separator, and then, interposing the separator between the positive electrode and the negative electrode to obtain an electrode group.
  • a secondary battery including the gelled non-aqueous electrolyte is obtained.
  • a cross-linked polymer can be used instead of the organic polymer compound.
  • a pregel solution is prepared from a compound having a bridging functional group, a lithium salt, and an electrolytic solution, and this is used as an electrode (at least one of a positive electrode and a negative electrode) or a separator. , Or electrode and separator After coating or impregnating both, the compound having a crosslinkable functional group is crosslinked. This cross-linking step may be performed before or after the production of the electrode group.
  • the method of crosslinking is not particularly limited, but heat polymerization or photopolymerization by ultraviolet rays is preferred in view of the simplicity of the apparatus and the cost.
  • crosslinking is performed by heating or irradiation with ultraviolet light, it is necessary to add a polymerization initiator suitable for the polymerization method to the pregel solution.
  • the polymerization initiator is not limited to one kind, and two or more kinds may be used as a mixture.
  • Examples of the organic polymer compound in (II) and (IV) described above include, for example, a polymer having a skeleton of an alkylene oxide such as polyethylene oxide, polypropylene oxide or a derivative thereof; Tsidani vinylidene, 6 sutirido propylene, 4 fluorinated polyethylene, perfunoroleanolequinole vinylinoleatenole, or a copolymer thereof; polyacrylonitrile Or a polyacrylate having a polyacrylotrile as a main component and a skeleton of a copolymer of methyl acrylate, butylpyrrolidone, vinyl acetate, etc.
  • a polymer having a skeleton of an alkylene oxide such as polyethylene oxide, polypropylene oxide or a derivative thereof
  • Polymer Polyether polymer; Poly force -Polymeric polymer; Polyacrylonitrile-based polymer-Polyethylene terephthalate, polybutylene terephthalate or derivatives thereof Polyester-based polymers that are copolymers of methyl acrylate, styrene, butyl acetate, etc .; Fluororesin; Polyolefin Resin; a polyether resin; and a copolymer composed of two or more of these.
  • a prepolymer solution (III) and a pregel solution (V) can be prepared from a monomer or an oligomer that is a precursor of these polymers.
  • the present invention is characterized in that the above-mentioned electrolyte contains a sulfon compound having at least one double bond in a ring.
  • the sulfon compound having at least one double bond in the ring may be a sulfon compound A represented by the following general formula (1) or a sulfon compound A: A sulfone compound B in which at least one H of the snorethone compound A is substituted with a hydrocarbon group can be used.
  • the sulfuron compound A or the sulfuron compound B may be used alone, or both the sulfuron compound A and the sulfuron compound B may be used.
  • C m H n is a linear hydrocarbon group, and m and n are integers of 2 or more that satisfy 2 m> 11.
  • Sulfon compounds having a double bond in the ring are reduced with the anode During the reaction, a double bond is opened to cause a polymerization reaction, and a dense protective film can be formed on the negative electrode surface without generating gas. At this time, if EC and PC are present, it is possible to form a dense protective film having excellent lithium ion permeability.
  • 1,3_propene norretone (PRS) is a type of 1,4-butylene sultone (BTS). May be used together.
  • the ratio of the sluton compound is desirably set to 10% by weight or less. This is because when the ratio of the sulfonate tons compound exceeds 1 0 weight 0/0, I ⁇ . Li Chi Umui O emissions permeable protection coating to the negative electrode decreases. Fin impedance increases, sufficient The capacity / charge / discharge efficiency may not be obtained. Furthermore, in order to maintain the design capacity of the electrode and to keep the initial charge / discharge efficiency high, the proportion of the sluton compound is 5% by weight or less (more preferably, 4% by weight or less).
  • the ratio of the slutone compound in order to sufficiently secure the formation amount of the protective film, it is desirable to secure the ratio of the slutone compound to at least 0.01 wt% / 0 . Furthermore, if the ratio of Sunore tons compound 0. 1 wt 0/0 above, Ru can and this to sufficient any protective functions of suppressing the initial charging time of the gas generator that by the protective coating.
  • the non-aqueous solvent preferably contains another solvent in addition to the sulfuric acid compound.
  • cyclic carbonates such as, for example, ethylene carbonate (EC) and propylene carbonate (PC), chain carbonates (eg, methylethylenocarbonate (MEC), Detinocarbonate (DEC), Dimethylcarbonate (DMC) ⁇ , ⁇ — Petit mouth rattan (GBL), vinylene carbonate (VC), vinylenecarbonate (VEC), fu- Noretyrene force component (phEC), ⁇ -norethate ratatone (VL), methyl propionate (MP), ethyl propionate (EP), 2-methylizolefuran 2 Me-F), franc (F), thiophene (TIOP), catechol carbonate (CATC), ethyl phenol olefate (ES), 12—crown 1 4 (C rown), Tetrae Ru can and this include Les packaging Li co-over Norejime Chinoreeteru (E ther) and the like.
  • chain carbonates eg, methyl
  • vinylene carbonate can increase the denseness of the protective film without significantly lowering the lithium ion permeability of the carbonaceous material, so that the initial charge-discharge efficiency and discharge capacity can be improved. The cycle life can be further improved.
  • the weight ratio of vinylene carbonate in the non-aqueous solvent be within the range of 10% by weight or less. This is because if the weight ratio of vinylene carbonate is more than 10% by weight, the lithium-ion permeability of the protective film on the negative electrode surface is reduced, so that the initial charge / discharge efficiency, discharge capacity, or size is reduced. Dramatically shortens the service life This is because they may be A more preferred range of the weight ratio of vinylene carbonate is 5% by weight or less, and the most preferred range is 0.01% to 5% by weight.
  • compositions of the non-aqueous solvent include (I) a non-aqueous solvent containing cyclic carbonate, ⁇ - butyrolataton (GBL) and a snorethone compound, (II) EC, A non-aqueous solvent containing at least a linear carbonate containing MEC, and a sluton compound;
  • the cyclic carbonate of the non-aqueous solvent (I) preferably contains EC, and more preferably contains PC in addition to EC. According to the nonaqueous solvent (I), the high-temperature storage characteristics and cycle life of the secondary battery can be further improved. By adding vinylene carbonate (V C) to the non-aqueous solvent (I), the low-temperature discharge characteristics of the secondary battery can be improved.
  • the chain carbonate of the non-aqueous solvent (II) contains methylethyl carbonate (MEC) as an essential component, and even if MEC alone is used as the chain carbonate, other chain chains are added to the MEC. Carbonate may be used in combination. According to the non-aqueous solvent (II), gas generation during initial charging can be suppressed, and the low-temperature discharge characteristics and cycle life can be improved.
  • MEC methylethyl carbonate
  • chain carbonates used in combination with MEC desirably have a low freezing point and a low viscosity. Furthermore, the molecular weight is relatively small. A solvent is desirable. This is because the discharge characteristics at low temperatures become better. As other chain carbonates, at least one of Jetilka-Polynate (DEC) and Dimethyl-Carbonate (DMC) is preferred. In particular, from the viewpoint of obtaining excellent charge / discharge cycle characteristics, a chain-like carport including MEC and DEC is preferred, while from the viewpoint of obtaining excellent low-temperature discharge characteristics, MEC and DMC are included. Chain carbonate is desirable. By adding vinylene carbonate (VC) to the non-aqueous solvent (II), the cycle life of the secondary battery can be further improved.
  • VC vinylene carbonate
  • II non-aqueous solvent
  • the non-aqueous solvent (III) can reduce the amount of gas generated during the initial charging of the secondary battery, and at the same time, can improve the high-temperature storage characteristics.
  • vinylene carbonate (VC) is further added to the non-aqueous solvent (II)
  • the high-temperature storage characteristics of the secondary battery can be further improved.
  • the non-aqueous solvent (IV) can reduce the amount of gas generated at the time of initial charging, and can also improve the initial charging / discharging efficiency. If vinylene carbonate (VC) is further added to the non-aqueous solvent (IV), the initial charge / discharge efficiency can be further improved.
  • Is the electrolyte to be dissolved in the nonaqueous solvent for example, perchlorate Li Ji U beam (L i C 1 O 4) , six full Tsu reduction-phosphate Li Ji U beam (L i PF 6), four full tree I ⁇ Ho c acid Li Ji U beam (L i BF 4), six full Tsu Lee ⁇ containing Li Ji U beam (L i A s F 6) , Application Benefits off Noreo port meth scan Honoré Ho phosphate Li (Li CF (3 SO 3), bisulfur methyl chloride SO 2). 2] and LiN (C 2 F 5 SO 2 ) 2.
  • the type of electrolyte used can be one, two or more.
  • the amount of the electrolyte dissolved in the non-aqueous solvent is 0.5 to 2.
  • the liquid non-aqueous electrolyte may contain a surfactant such as trioctyl phosphate (TOP) in order to improve the wettability with the separator. Is desirable.
  • TOP trioctyl phosphate
  • the addition amount of the surfactant is preferably 3% or less, and more preferably in the range of 0.1 to 1%.
  • the amount of the liquid non-aqueous electrolyte is 0.2 to 0.6 g per 100 mAh of battery unit capacity.
  • a more preferred range for the mass of the liquid nonaqueous electrolyte is 0.25 to 0.55 g / 100 mAh.
  • Container storage container
  • the shape of the container can be, for example, a cylindrical shape with a bottom, a rectangular tube with a bottom, a bag shape, a cup shape, or the like.
  • This container can be formed, for example, from a sheet including a resin layer, a metal plate, a metal film, or the like.
  • the resin layer contained in the sheet can be composed of, for example, polyolefin and polyamides.
  • the metal plate and the metal film can be formed from, for example, iron, stainless steel, or aluminum.
  • the thickness of the container should be less than 0.3 mm. This is because if the thickness force is larger than S O .3 mm, it becomes difficult to obtain a high weight energy density and a high volume energy density.
  • a preferred range for the thickness of the container is less than 0.25 mm, a more preferred range is less than 0.15 mm, and a most preferred range is less than 0.12 mm.
  • the thickness is smaller than S O .05 mm, the container is liable to be deformed or broken. Therefore, the lower limit of the thickness of the container is preferably set to 0-0.5 mm. ...
  • a thin lithium secondary battery and a cylindrical lithium secondary battery which are examples of the nonaqueous electrolyte secondary battery according to the present invention, will be described in detail with reference to FIGS.
  • FIG. 1 is a perspective view showing a thin lithium ion secondary battery which is an example of the nonaqueous electrolyte secondary battery according to the present invention.
  • FIG. 2 is an enlarged cross-sectional view of a main part of the nonaqueous electrolyte secondary battery shown in FIG.
  • FIG. 3 is a partially cutaway perspective view showing a cylindrical non-aqueous electrolyte secondary battery which is an example of the non-aqueous electrolyte secondary battery according to the present invention.
  • an electrode group 2 is accommodated in a container body 1 having a long box-shaped cup shape.
  • the electrode group 2 has a structure in which a laminate including a positive electrode 3, a negative electrode 4, and a separator 5 disposed between the positive electrode 3 and the negative electrode 4 is wound into a flat shape.
  • the non-aqueous electrolyte is held in electrode group 2.
  • a part of the edge of the container body 1 is wide and functions as a cover plate 6.
  • the container body 1 and the lid plate 6 are each composed of a laminate finolem.
  • This laminated film includes an outer protective layer 7, an inner protective layer 8 containing a thermoplastic resin, and a metal layer 9 disposed between the outer protective layer 7 and the inner protective layer 8. .
  • a lid 6 is fixed to the container body 1 by a heat seal using the thermoplastic resin of the inner protective layer 8, whereby the electrode group 2 is sealed in the container.
  • a positive electrode tab 10 is connected to the positive electrode 3, and a negative electrode tab 11 is connected to the negative electrode 4.
  • the negative electrode tab 11 is drawn out of the container and serves as a positive electrode terminal and a negative electrode terminal.
  • the cylindrical bottomed container 21 made of stainless steel has an insulator 22 disposed at the bottom.
  • the electrode group 23 is housed in the container 21.
  • a band formed by laminating a positive electrode 24, a separator 25, a negative electrode 26, and a separator 25 was spirally wound so that the separator 25 was positioned outside. It is a structure.
  • the container 21 contains a non-aqueous electrolyte. Center The insulating paper 27 having an opening is provided with the electrode group in the container 21.
  • the insulating sealing plate 28 is disposed in the upper opening of the container 21, and the vicinity of the upper opening is caulked inward to fix the sealing plate 28 to the container 21. Have been.
  • the positive electrode terminal 29 is fitted in the center of the insulating sealing plate 28.
  • One end of the positive electrode lead 30 is connected to the positive electrode 24, and the other end is connected to the positive electrode terminal 29.
  • the negative electrode 26 is connected to the container 21 serving as a negative electrode terminal via a negative electrode lead (not shown).
  • the distance ( d002 ) between the (002) planes by powder X-ray diffraction is 0.
  • the plane distance d 002 of the (002) plane is a value determined by the half-width straight-point midpoint method from powder X-ray diffraction spectrum. At this time, scattering correction such as Lorentz scattering was not performed.
  • a product made by Weasa Ionitas Inc. was used as a measuring device.
  • the sample amount was set to around 0.5 g, and the sample was degassed at 1.20 ° C for 15 minutes as a pretreatment.
  • a slurry was prepared. The slurry was applied to both sides of a current collector made of copper foil having a thickness of S12 m, dried, and pressed, whereby the negative electrode layer was supported on the current collector. A negative electrode having a structure was fabricated. The thickness of the negative electrode layer was 55 m per side.
  • a selenium consisting of a microporous polyethylene membrane 25 ⁇ m thick Data was prepared.
  • a positive electrode lead made of a strip of aluminum foil (100 m thick) is ultrasonically welded to the current collector of the positive electrode, and a strip of nickel foil (thickness) is formed on the current collector of the negative electrode.
  • the negative electrode lead made of 100 ⁇ m is ultrasonically welded, the positive electrode and the negative electrode are spirally wound between the positive electrode and the negative electrode via the separator between the positive electrode and the negative electrode. To form an electrode group.
  • a 100 ⁇ m-thick laminating finolem with aluminum foil covered on both sides with polyethylene is formed into a rectangular shape by a press machine.
  • the electrode group was housed in the container thus obtained.
  • the liquid non-aqueous electrolyte was injected into the electrode group in the container so that the amount per 1 Ah of the battery capacity was 4.8 g, and the heat seal was used. After sealing, it has the structure shown in Figures 1 and 2 above, with a thickness of 3.6 mm, a width of 35 mm, a height of 62 mm and a nominal capacity of 0.65 Ah.
  • the thin non-aqueous electrolyte secondary battery was assembled.
  • 1 C is the current required to discharge the nominal capacity (Ah) in one hour.
  • 0.2 C is the current required to discharge the nominal capacity (A h) in 5 hours.
  • a mixed solution of ethylene carbonate (EC) and propylene carbonate (PC) in a volume ratio (EC: PC) force S 50: 50 was applied to a mixed solution of 1,3. -. 2 weight propenyl Nsu Honoré tons (PRS) 0/0 and Application Benefits octene Chirufu O scan off error one preparative (TOP) was added 0 5 wt%, to prepare a non-aqueous solvent.
  • a liquid nonaqueous electrolyte is prepared by dissolving lithium hexafluoride (LiPF6) in the obtained nonaqueous solvent so that the concentration thereof becomes 1 mol ZL. did.
  • a thin non-aqueous electrolyte secondary battery was manufactured in the same manner as described in Example 1 except that the obtained negative electrode and the non-aqueous electrolyte were used.
  • a negative electrode was fabricated in the same manner as described in Example 1.
  • a liquid nonaqueous electrolyte was prepared in the same manner as described in Example 6 described above.
  • a thin non-aqueous electrolyte secondary battery was manufactured in the same manner as described in Example 1 except that the obtained negative electrode and the non-aqueous electrolyte were used.
  • Example 2 Same as described in Example 1 above, except that artificial graphite having the parameters shown in Table 1 below is used as the graphite material and a non-aqueous electrolyte having the composition shown in Table 2 below is used. As a result, a thin nonaqueous electrolyte secondary battery was manufactured.
  • a negative electrode was produced in the same manner as described in Example 1 except that such a carbonaceous material was used.
  • Liquid lithium non-aqueous electrolyte was obtained by dissolving lithium hexafluorophosphate (LiPF6) in the obtained non-aqueous solvent so as to have a concentration of 1 mol / L. Was prepared.
  • a thin non-aqueous electrolyte secondary battery was manufactured in the same manner as described in Example 1 except that the obtained negative electrode and the non-aqueous electrolyte were used.
  • a thin non-aqueous electrolyte secondary battery was manufactured in the same manner as described in Comparative Example 1 except that the composition of the non-aqueous solvent and the type and concentration of the electrolyte were changed as shown in Table 2 below. Manufactured.
  • Example 1 1.4 0.3360 Not detected 1.89 4.57
  • Example 2 1.4 ⁇ 0.3360 Not detected 1.89 4.57
  • Example 3 1.4 0.3360 Not detected 1.89 4.57
  • Example 4 1.4 0.3360 Not detected 1.89 4.57
  • Example 5 1.4 0.3360 Not detected 1.89 4.57
  • Example 6 1.3 0.3375 Not detected 1.28 4.40
  • Example 7 1.6 0.3370 Not detected 0.8 8 7.62
  • Example 8 2.1 0.3358 Not detected 1 47 4.45
  • Example 9 0.9 0.3358 Not detected 1.85 3.78
  • Example 10 3.8 0.3359 Not detected 2.19 4.15 Comparative example 1 0.2 0.3373 Not detected 1.26 4.04 Comparative example 2 0.2 0.3373 Not detected Detection 1.26 4.04 Comparative example 3 0.2 0.3373 Not detected 1.26 4.04 Comparative example 4 6.8 0.3375 Not detected 1.02 5.01 Comparative example 5 4.0 0.3358 Detection 2.17 3.36
  • soTTio / eoozdf / i3d 06sezo / oo ⁇ ; OAV As shown in Tables 1 and 2, the graphite material whose specific surface area by the BET method is in the range of 0.3 m 2 / g or more and 4 m 2 / g or less is used. It can be seen that the secondary batteries of Examples 1 to 10 used are excellent in all of the initial charge / discharge efficiency, the discharge capacity, and the capacity retention rate during 300 cycles. Among them, the interplanar spacing d by powder X-ray diffraction measurement. .
  • the secondary batteries of Comparative Examples 1 to 3 using a carbonaceous material having a specific surface area of less than 0.3 m 2 / g according to the BET method had a discharge capacity and a capacity retention rate of 300 cycles. Both were low.
  • the secondary battery of Comparative Example 4 had a high capacity retention rate during 300 cycles, but a low discharge capacity.
  • the secondary battery of Comparative Example 5 provided with a graphite material having a rhombohedral structure all of the initial efficiency, the discharge capacity, and the capacity retention rate during 300 cycles were as in Example 1. It was low compared to ⁇ 10. It is presumed that this is because the decomposition reaction of the non-aqueous solvent continued from the time of the first charge.
  • the secondary batteries of Examples 6 and 7 were compared with those of Examples 1 to 5 and 8 to 10 by comparing the capacity retention rates of the Examples 1 to 10 during the 500 cycles. It can be understood that the capacity retention rate at the time of 500 cycles is lower than that of the secondary battery. The main causes are explained below.
  • the surface distance d was 0.3 3 7 5 ⁇ m, the protective coating is not formed sufficiently, and if a long cycle of 500 cycles is applied, a sudden capacity deterioration occurs in the middle of the cycle. It is considered that it was.
  • the protective film was formed unevenly on the surface of the negative electrode due to the low integrity of the graphite crystal of the graphite material, and a long cycle cycle of 500 cycles was observed. It is considered that the application caused rapid capacity deterioration during the cycle.
  • the Ar concentration was 99.9 ° /.
  • the electrode group was decomposed in a glove box with a dew point of 150 ° C or less, and the electrode group was taken out. It said pawl electrode group centrifuge tube, dimethyl Chirusu sulfo key sheet de (DMSO) - was sealed by adding d 6, wherein Gurobubo Tsu and exits Ri Installing by click scan was performed centrifugal away. Then, in the glow Bubo click scan, the said centrifugation tube or al the electrolyte DMSO - it was taken mixed solution of d 6.
  • DMSO dimethyl Chirusu sulfo key sheet de
  • the temperature was 25 ° C.
  • a peak corresponding to EC was observed at around 4.5 ppm, and a peak force corresponding to VC at around S7.7 ppm.
  • the peaks corresponding to the PRS peak at around 5.1 lppm ( ⁇ ⁇ 7.05 ppm (P 2 ) and around 7.2 ppm (P 3 )) as shown in the spectrum of Fig. 4. From these results, it was confirmed that VC and PRS were contained in the nonaqueous solvent present in the secondary battery of Example 1 after the first charge / discharge step.
  • the observation frequency was 1 0 0 MH z, dimethyl Chirusuruho key sheet de (DMSO) - d 6 (. 3 9 5 ppm)
  • DMSO dimethyl Chirusuruho key sheet de
  • EC Peak corresponding to S 6 near 6 ppm peak corresponding to VC is -1 -3 3 p-pm
  • peak power corresponding to PRS S 7 near 4 ppm peak power corresponding to PRS S 7 near 4 ppm
  • 1 near 24 ppm and 1 It was observed at around 40 ppm, and this result also indicates that VC and PRS were contained in the non-aqueous solvent present in the secondary battery of Example 1 after the first charge / discharge process. did it.
  • the present invention is not limited to the above-described embodiment, but can be similarly applied to other types of combinations of a positive electrode, a negative electrode, a separator and a container.
  • the present invention is applicable to a secondary battery having a cylindrical or rectangular container. It is possible.

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Abstract

L'invention concerne une pile à combustible secondaire non aqueuse comprenant une électrode positive, une électrode négative à substance carbonée capable d'absorber/de libérer des ions lithium, et un électrolyte non aqueux contenant un solvant non aqueux. Ce solvant renferme un composé de sultone ayant au moins une double liaison dans une chaîne. La surface spécifique de la substance carbonée, évaluée par mesure BET, est comprise entre 0,3 m2/g et 4 m2/g. L'intervalle interplanaire d002 évalué par mesure en diffraction de rayons X sur poudres est inférieur à 0,3365 nm. On n'observe aucune crête entre 42,8° et 44° et entre 45,5° et 46,6° pour l'angle de diffraction 2υ lorsque la substance carbonée est mesurée par diffraction de rayons X reposant sur l'utilisation de la ligne CuKα. La pile secondaire renferme un matériau en graphite qui satisfait les équations (1) et (2) ci-après. 1≤I(101)/I(100)≤2,2 (1) 3,7≤ S(101)/S(100)≤5 (2)
PCT/JP2003/011105 2002-08-29 2003-08-29 Pile a combustible secondaire non aqueuse Ceased WO2004023590A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006004811A (ja) * 2004-06-18 2006-01-05 Toshiba Corp 非水電解質二次電池
JP2007141733A (ja) * 2005-11-21 2007-06-07 Sony Corp 電池
JP2009224221A (ja) * 2008-03-17 2009-10-01 Sony Corp 非水電解質二次電池および負極
JPWO2014050097A1 (ja) * 2012-09-27 2016-08-22 昭和電工株式会社 リチウムイオン二次電池負極用炭素材およびその製造方法並びに用途

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6081339B2 (ja) * 2013-10-11 2017-02-15 オートモーティブエナジーサプライ株式会社 非水電解質二次電池

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000003724A (ja) * 1997-08-22 2000-01-07 Ube Ind Ltd 非水電解液およびそれを用いたリチウム二次電池
JP2001126764A (ja) * 1999-10-26 2001-05-11 Mitsubishi Chemicals Corp 非水系電解液二次電池
JP2002329528A (ja) * 2001-03-01 2002-11-15 Mitsui Chemicals Inc 非水電解液、それを用いた二次電池、および電解液用添加剤
JP2003142152A (ja) * 2001-11-01 2003-05-16 Japan Storage Battery Co Ltd 非水電解質二次電池
JP2003168477A (ja) * 2001-11-29 2003-06-13 Yuasa Corp 非水電解質電池
JP2003308838A (ja) * 2002-04-16 2003-10-31 Mitsubishi Chemicals Corp リチウム二次電池用負極材料及びそれから製造された負極体

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000003724A (ja) * 1997-08-22 2000-01-07 Ube Ind Ltd 非水電解液およびそれを用いたリチウム二次電池
JP2001126764A (ja) * 1999-10-26 2001-05-11 Mitsubishi Chemicals Corp 非水系電解液二次電池
JP2002329528A (ja) * 2001-03-01 2002-11-15 Mitsui Chemicals Inc 非水電解液、それを用いた二次電池、および電解液用添加剤
JP2003142152A (ja) * 2001-11-01 2003-05-16 Japan Storage Battery Co Ltd 非水電解質二次電池
JP2003168477A (ja) * 2001-11-29 2003-06-13 Yuasa Corp 非水電解質電池
JP2003308838A (ja) * 2002-04-16 2003-10-31 Mitsubishi Chemicals Corp リチウム二次電池用負極材料及びそれから製造された負極体

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006004811A (ja) * 2004-06-18 2006-01-05 Toshiba Corp 非水電解質二次電池
JP2007141733A (ja) * 2005-11-21 2007-06-07 Sony Corp 電池
US8980497B2 (en) 2005-11-21 2015-03-17 Sony Corporation Secondary battery including anode with a coating containing a SO3 containing compound
JP2009224221A (ja) * 2008-03-17 2009-10-01 Sony Corp 非水電解質二次電池および負極
JPWO2014050097A1 (ja) * 2012-09-27 2016-08-22 昭和電工株式会社 リチウムイオン二次電池負極用炭素材およびその製造方法並びに用途

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