WO2010067410A1 - Batterie lithium-ion et son procédé de fabrication - Google Patents

Batterie lithium-ion et son procédé de fabrication Download PDF

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Publication number
WO2010067410A1
WO2010067410A1 PCT/JP2008/072267 JP2008072267W WO2010067410A1 WO 2010067410 A1 WO2010067410 A1 WO 2010067410A1 JP 2008072267 W JP2008072267 W JP 2008072267W WO 2010067410 A1 WO2010067410 A1 WO 2010067410A1
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Prior art keywords
negative electrode
active material
material layer
electrode active
current collector
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PCT/JP2008/072267
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English (en)
Japanese (ja)
Inventor
龍太 森島
仁 酒井
博昭 池田
宏之 秋田
秀仁 松尾
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トヨタ自動車株式会社
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Priority to PCT/JP2008/072267 priority Critical patent/WO2010067410A1/fr
Publication of WO2010067410A1 publication Critical patent/WO2010067410A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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 lithium ion battery and a manufacturing method thereof.
  • a typical configuration of a lithium ion battery includes a configuration including positive and negative electrodes including an electrode active material capable of occluding and releasing lithium ions, a separator disposed therebetween, and a non-aqueous electrolyte.
  • a positive and negative electrode sheet in which a layer mainly composed of an electrode active material (electrode active material layer) is held on the surface of a long sheet-shaped current collector is stacked with a separator between both electrode sheets.
  • a lithium ion battery having a configuration in which an electrode body (rolled electrode body) obtained by winding these in the longitudinal direction is housed in a container together with a nonaqueous electrolyte is known.
  • Patent Document 1 describes a technique for extending the charge storage period at a high temperature by providing a porous film having a predetermined thickness and porosity on the negative electrode surface.
  • Patent Documents 2 and 3 can be cited as other prior art documents relating to lithium ion batteries.
  • an electrode sheet in which the electrode active material layer is provided in a strip shape with one edge along the longitudinal direction of the current collector is used, and the strip portion is a counter electrode.
  • both electrode sheets are overlapped so as to protrude from the sheet.
  • An object of the present invention is to provide a lithium ion battery including such an electrode body, which has a higher performance (for example, excellent capacity maintenance) and a method for manufacturing the lithium ion battery.
  • the inventor conducted various studies on the behavior of the lithium ion battery including the electrode body of the above form.
  • a minute internal short circuit may occur due to a mechanism different from that of a wound electrode body using an electrode sheet that does not have a strip-shaped active material layer non-forming portion along the longitudinal direction.
  • the present invention was completed by finding a structure capable of effectively preventing the occurrence of the internal short circuit and a method for producing a battery having the structure.
  • a negative electrode sheet having a negative electrode active material layer on the surface of a long sheet-shaped negative electrode current collector, and a positive electrode sheet having a positive electrode active material layer on the surface of a long sheet-shaped positive electrode current collector there is provided a lithium ion battery including an electrode body formed by being rolled up with a long sheet-shaped separator.
  • the negative electrode active material layer is provided leaving at least one edge along the longitudinal direction of the negative electrode current collector in a strip shape.
  • the negative electrode sheet is overlapped with the positive electrode sheet such that the belt-like portion protrudes from one end portion along the longitudinal direction of the positive electrode sheet.
  • a porous inorganic layer is formed on the outer surface of the negative electrode active material layer so as to reach the surface of the negative electrode current collector from the flat portion of the active material layer to the end on the belt-like portion side.
  • the mass ratio Wa / Wb between the basis weight Wa of the inorganic layer at the end on the belt-like portion side and the basis weight Wb of the inorganic layer at the center of the width of the negative electrode active material layer is 0.5 or more and 1.2. It is in the following range.
  • the belt-shaped portion of the negative electrode sheet (that is, the strip-shaped negative electrode active material layer non-forming portion along the longitudinal direction) is provided with an electrode body wound out of one end along the longitudinal direction of the positive electrode sheet.
  • the end 32c of the positive electrode sheet 32 is located behind the end of the electrode body 30 in the winding axis direction (left end in FIG. 2).
  • a gap is formed at a position indicated by a symbol S in FIG.
  • the gap S is a place where foreign matter is likely to accumulate when foreign matter is present in the battery.
  • foreign matter may be trapped in the gap S due to movement of the electrolytic solution accompanying charge / discharge, movement of the electrolytic solution accompanying fluctuations in the posture of the battery, or vibration.
  • a minute short-circuit portion may be formed between the positive electrode sheet 32 and the negative electrode sheet 34.
  • the metal contained in the foreign material elutes electrochemically with charging / discharging of the battery and precipitates on the surface of the negative electrode sheet 34 or in the vicinity thereof, the deposit fills the pores of the separator 35 and forms both electrode sheets. It is possible to form a conductive path between 32 and 34.
  • Such a short-circuit can cause Joule heat locally at the short-circuit location, thereby damaging the separator (typically made of thermoplastic resin) and causing a larger internal short-circuit (self-discharge). Further, the micro short-circuit causes a voltage drop with time, and may be a factor for reducing fuel consumption when used as a power source for a hybrid vehicle, for example.
  • the negative electrode active material layer is a porous inorganic layer that extends from the flat surface to the current collector surface around the edge. Covered. In this way, not only the flat portion of the negative electrode active material layer but also the end portion of the negative electrode active material layer (the portion close to the portion where the foreign matter tends to accumulate) is completely covered by the inorganic layer (that is, the insulating protective layer). By setting it as the covered structure, the micro short circuit resulting from the said foreign material can be prevented highly. Therefore, the lithium ion battery according to the present invention can be excellent in internal short circuit prevention.
  • the bad effect for example, battery performances, such as a capacity
  • the bad effect which may arise by providing the inorganic layer completely covering the said edge part. Can be prevented or alleviated.
  • the negative electrode sheet has an end portion on the strip-like portion side (negative electrode active material layer non-formation portion side) of the negative electrode active material layer formed from the positive electrode active material layer.
  • the positive electrode sheet is overlaid so as to protrude.
  • the configuration in which the negative electrode active material layer is arranged in a range extending to the band-shaped part side from the positive electrode active material layer is such that lithium ions that have moved from the positive electrode active material layer to the negative electrode side are on the surface of the negative electrode current collector. This is advantageous in preventing an event that precipitates (that is, where the negative electrode current collector is exposed).
  • the surface of the negative electrode active material layer is provided with the inorganic layer that extends from the planar portion to the end of the current collector surface. Even in a configuration in which foreign matter tends to accumulate, the above-described minute short circuit can be prevented appropriately. By setting Wa / Wb of the inorganic layer in the above range, particularly good results can be realized.
  • a lithium ion battery comprising an electrode body formed by winding a positive and negative electrode sheet having an active material layer formed on the surface of a long sheet-shaped current collector and a long sheet-shaped separator.
  • a method of manufacturing includes a step of forming a negative electrode active material layer on the surface of the negative electrode current collector, leaving at least one edge along the longitudinal direction of the current collector in a strip shape.
  • a slurry containing inorganic particles and a binder is applied to the negative electrode current collector on which the negative electrode active material layer is formed, and the negative electrode passes through the flat part of the negative electrode active material layer and the end on the band-like part side.
  • a step of forming a porous inorganic layer reaching the surface of the current collector has a mass ratio Wa / Wb of the basis weight Wa of the inorganic layer at the end on the belt-like portion side to the basis weight Wb of the inorganic layer at the center of the width of the negative electrode active material layer is 0.00. It is applied so as to be 5 or more and 1.2 or less.
  • the manufacturing method also includes a step of forming a negative electrode sheet in which the negative electrode active material layer and the porous inorganic layer are formed on the surface of the negative electrode current collector through the separator and along the longitudinal direction of the positive electrode sheet.
  • the method includes a step of superposing the positive electrode sheet so that the band-shaped portion protrudes from the other end, and winding them (that is, the superimposed positive electrode sheet, negative electrode sheet, and separator) to form an electrode body. Further, the method includes a step of housing the electrode body together with a nonaqueous electrolyte in a container to construct a lithium ion battery.
  • a preferable aspect of the method for producing a lithium ion battery disclosed herein is that Wa / Wb is 0.5 or more and 1.2 or less based on a result of fluorescent X-ray analysis of the inorganic particles contained in the porous inorganic layer.
  • the method further includes the step of selecting the composition of the slurry and / or the application conditions of the slurry so as to be.
  • the inorganic layer is formed according to the selected conditions. According to such a method, an inorganic layer satisfying a predetermined Wa / Wb can be efficiently formed. Therefore, the productivity of the lithium ion battery according to the present invention can be increased.
  • the lithium ion battery disclosed here is suitable as a lithium ion battery mounted on a vehicle because it has excellent self-discharge prevention properties as described above.
  • it can be suitably used as a power source for a motor (electric motor) of a vehicle such as an automobile, in the form of an assembled battery in which a plurality of the lithium ion batteries are connected in series.
  • a vehicle comprising any of the lithium ion batteries disclosed herein (which may be lithium ion batteries manufactured by any of the methods disclosed herein).
  • FIG. 1 is a schematic cross-sectional view showing a structure of a lithium ion battery according to an embodiment.
  • FIG. 2 is a schematic cross-sectional view showing a positive and negative electrode sheet and a separator constituting a lithium ion battery according to an embodiment.
  • FIG. 3 is a schematic plan view showing a negative electrode sheet constituting a lithium ion battery according to an embodiment.
  • FIG. 4 is a schematic diagram showing a part of FIG. 2 in an enlarged manner.
  • FIG. 5 is a graph showing the relationship between Wa / Wb and the capacity retention rate of the porous inorganic layer.
  • FIG. 6 is a side view schematically showing a vehicle (automobile) provided with the lithium ion battery of the present invention.
  • the invention disclosed herein includes a negative electrode sheet having a negative electrode active material layer on the surface of a long sheet-like negative electrode current collector, and a positive electrode sheet having a positive electrode active material layer on the surface of a long sheet-like positive electrode current collector
  • a lithium-on battery comprising a porous inorganic layer on the outer surface of the negative electrode active material layer, and the lithium ion battery It can be widely applied to negative electrodes for manufacturing as well as their production.
  • the outer shape of the lithium ion battery is not particularly limited, and may be, for example, a rectangular parallelepiped shape, a flat rectangular shape, a cylindrical shape, or the like.
  • the negative electrode current collector a sheet-like member made of a metal having good conductivity can be preferably used.
  • the size of the negative electrode current collector is not particularly limited, and can be appropriately selected according to the shape of the target lithium ion battery.
  • a metal foil having a thickness of about 5 ⁇ m to 30 ⁇ m can be preferably used as the negative electrode current collector.
  • the width of the negative electrode current collector can be, for example, about 2 cm to 15 cm, and the length can be, for example, about 5 cm to 1000 cm.
  • the negative electrode sheet in the technology disclosed herein has a layer (negative electrode active material layer) containing a negative electrode active material as a main component on the surface of the negative electrode current collector.
  • the negative electrode active material layer is typically formed on the surfaces (both sides) of both sides of the negative electrode current collector, leaving at least one edge along the longitudinal direction of the negative electrode current collector in a strip shape.
  • the band-like portion (the portion where the negative electrode active material layer is not formed on the negative electrode current collector, that is, the portion where the negative electrode active material layer is not formed) is electrically connected to the negative electrode terminal for external connection as described later. It can be used as a part (current collector) connected to.
  • the negative electrode active material layer non-forming portion is preferably provided at a position where both surfaces of the negative electrode current collector overlap (preferably, substantially the same position on both surfaces). From the viewpoint of the energy density of the lithium ion battery, a negative electrode active material layer non-forming portion is provided at one edge along the longitudinal direction of the negative electrode current collector at substantially the same position on both surfaces, and the longitudinal direction of the current collector.
  • a negative electrode sheet in a form in which a negative electrode active material layer is formed on the other edge along the both sides almost to the end that is, a form in which an active material layer non-forming portion is provided only on one edge along the longitudinal direction
  • the negative electrode active material layer non-forming portion is continuously formed in a wound electrode body using the negative electrode sheet so as to have a length extending over at least two rounds of the winding.
  • the negative electrode active material layer non-forming portion is formed over the entire length of the negative electrode sheet.
  • the width of the negative electrode active material layer non-forming portion can be appropriately set according to the shape of the electrode body, the connection structure of the current collector portion, and the like. Usually, a width of about 5 mm to 50 mm (for example, 10 mm to 30 mm) is appropriate.
  • the negative electrode active material a material capable of reversibly occluding and releasing lithium ions is used, and various negative electrode active materials known to be able to function as a negative electrode active material of a general lithium ion battery are used. Things can be adopted.
  • a carbon material is illustrated as a suitable negative electrode active material in the technique disclosed here. It is preferable to use a particulate carbon material (carbon particles) containing a graphite structure (layered structure) at least partially. Any carbon material of a so-called graphitic material (graphite), a non-graphitizable carbonaceous material (hard carbon), a graphitizable carbonaceous material (soft carbon), or a material having a combination of these is suitable. For example, natural graphite, mesocarbon microbeads (MCMB), highly oriented graphite (HOPG), etc. can be used.
  • MCMB mesocarbon microbeads
  • HOPG highly oriented graphite
  • the properties of the negative electrode active material for example, particles having an average particle diameter of about 5 ⁇ m to 50 ⁇ m are preferable. Among them, it is preferable to use carbon particles having an average particle diameter of about 5 ⁇ m to 15 ⁇ m (for example, about 8 ⁇ m to 12 ⁇ m). Thus, carbon particles having a relatively small particle size have a large surface area per unit volume, and thus can be a negative electrode active material suitable for more rapid charge / discharge (for example, high power discharge). Therefore, a lithium ion battery having such a negative electrode active material can be suitably used, for example, as a lithium ion battery for mounting on a vehicle.
  • the carbon particle having a relatively small particle size has a smaller volume variation of the individual carbon particles due to charge / discharge compared to the case of using a larger particle. Can be better buffered (absorbed). This is advantageous from the viewpoint of durability (prevention of peeling and the like) of the porous inorganic layer formed on the negative electrode active material layer.
  • the negative electrode active material layer includes, for example, a liquid composition (typically a paste or slurry negative electrode active material composition) in which a negative electrode active material (preferably particulate, for example, carbon particles) is dispersed in an appropriate solvent. It can preferably be produced by applying to a negative electrode current collector and drying the composition.
  • a solvent dispersion medium of the negative electrode active material
  • any of water, an organic solvent, and a mixed solvent thereof can be used.
  • an aqueous solvent water or a mixed solvent containing water as a main component
  • the negative electrode active material composition may be used alone or in combination of two or more liquid compositions used for forming a negative electrode active material layer in the production of a general negative electrode for a lithium ion battery.
  • these materials can be contained as required.
  • examples of such materials include polymers that can function as binders and / or fluidity modifiers.
  • polymers such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC), etc.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PVDF-HFP polyvinylidene fluoride-hexafluoropropylene copolymer
  • SBR styrene butadiene rubber
  • CMC carboxymethyl cellulose
  • the solid content concentration of the negative electrode active material composition is, for example, about 40% to 60%. Is appropriate.
  • the mass ratio of the negative electrode active material to the solid content (negative electrode active material layer forming component) can be, for example, about 85% or more (typically about 85% to 99.9%), and about 90%. It is preferable to set it to ⁇ 99%, and more preferably about 95% to 99%.
  • a technique similar to a conventionally known method can be appropriately employed.
  • a predetermined amount of the negative electrode active material composition may be applied to the surface of the current collector using a suitable coating device (such as a gravure coater, slit coater, die coater, or comma coater).
  • the negative electrode active material layer can be formed in a predetermined range by applying the composition leaving a portion corresponding to the negative electrode active material layer non-forming portion.
  • the coating amount of the negative electrode active material composition is not particularly limited, and may be appropriately varied depending on the shape and target performance of the negative electrode sheet and the battery.
  • the composition is applied to both sides of a foil-like current collector (for example, a metal foil (copper foil, etc.) having a thickness of about 5 ⁇ m to 30 ⁇ m can be preferably used). That is, it is preferable to apply so that the mass after drying) is approximately 5 to 20 mg / cm 2 on both sides.
  • the coated material is dried by an appropriate drying means, and pressed as necessary, whereby a negative electrode active material layer can be formed on the surface of the negative electrode current collector.
  • the density of the negative electrode active material layer may be about 1.1 to 1.5 g / cm 3, for example.
  • the density of the negative electrode active material layer may be about 1.1 to 1.3 g / cm 3 .
  • the press conditions may be set so that a negative electrode active material layer having such a density is formed.
  • the edge of the active material layer non-formation part side is turned around from the flat part of the active material layer to the outer surface of the negative electrode active material layer to the negative electrode current collector surface.
  • a porous inorganic layer is provided.
  • the “planar portion” of the negative electrode active material layer refers to a portion where the active material layer spreads in a planar shape, preferably with a substantially uniform thickness.
  • a portion where the negative electrode active material layer and the positive electrode active material are arranged so as to overlap each other is included in the flat portion of the negative electrode active material layer.
  • the porous inorganic layer is continuously provided over the entire range of the planar portion.
  • the “end on the active material layer non-formation part side” of the negative electrode active material layer refers to an end along the boundary with the active material layer non-formation part of the negative electrode active material layer. It is the part that follows the flat part of the material layer.
  • This active material layer non-formation part side edge part can be the range of width 2mm which goes to the inner side of this negative electrode active material layer from the boundary of a negative electrode active material layer and an active material layer non-formation part, for example. It is preferable that this active material layer non-formation part side edge part protrudes from a positive electrode active material layer, and is arrange
  • the porous inorganic layer 346 is formed from the flat portion 344a of the negative electrode active material layer 344 to the negative electrode active material layer non-formation portion.
  • the end portion 344b is continuously provided until reaching the surface of the negative electrode current collector 342 through the end portion 344b along the thickness of the negative electrode active material layer 344. That is, the end 344 b of the negative electrode active material layer 344 is completely covered with the insulating porous inorganic layer 346.
  • FIG. 2 is a schematic cross-sectional view showing an enlarged part of a cross section obtained by cutting the wound electrode body 30 in the radial direction (stacking direction of the positive and negative electrode sheets and the separator).
  • the negative electrode sheet disclosed here includes a weight per unit area Wa of the inorganic layer formed at an end of the negative electrode active material layer on the side where the active material layer is not formed, and an inorganic layer at the center of the width of the negative electrode active material layer.
  • the mass ratio Wa / Wb with the basis weight Wb is in the range of 0.5 to 1.2.
  • the basis weight of the inorganic layer (for example, an inorganic layer containing alumina particles as a main component) in each part can be grasped by, for example, general fluorescent X-ray analysis.
  • the basis weight of the porous inorganic layer can be obtained by conducting a preliminary experiment for examining the correlation between the basis weight and the fluorescent X-ray intensity according to the material of the inorganic particles to be used, and applying the result.
  • the inorganic layer covering the negative electrode active material layer provides resistance to the entry and exit of Li ions into the active material layer. For this reason, if Wa / Wb is too smaller than 0.5, the resistance of the end portion is locally reduced, and current concentration at the end portion (reaction unevenness in charge / discharge) occurs. Such current concentration (that is, current density bias) can be a factor for promoting deterioration of the battery. In particular, in a usage pattern involving high-rate charging, such as a lithium ion battery used as a power source for vehicles, the current density bias tends to increase, so that side reactions such as decomposition of the electrolytic solution are easily promoted. If charging with a large current density is repeated as described above, the capacity of the battery decreases.
  • the end of the negative electrode active material is completely covered with the porous inorganic layer, while highly preventing the occurrence of micro short circuits.
  • the durability of the battery (for example, the decrease in capacity even when charging and discharging are repeated) can be maintained at a high level.
  • the preferred Wb range may vary depending on the composition of the porous inorganic layer, the configuration of the battery, and the like, but is usually about 0.3 to 3 mg / cm 2 (eg, 0.5 to 1 mg / cm 2 ). is there. If Wb is too small, it may be difficult to obtain a sufficient effect of preventing a short circuit. If Wb is too large, the internal resistance of the battery tends to increase.
  • the weight per unit area Wb of the inorganic layer at the center of the width of the negative electrode active material layer is represented by the basis weight at the exact center of the width of the negative electrode active material layer (that is, the value of the basis weight is defined as Wb). Can be adopted).
  • the basis weight Wa of the inorganic layer formed at the end portion on the side where the active material layer is not formed can be represented by the basis weight inside 2 mm from the boundary between the negative electrode active material layer and the active material layer non-formed portion. it can.
  • the porous inorganic layer extends from the boundary between the negative electrode active material layer and the active material layer non-formation part to the outside (the active material layer non-formation part side).
  • the size of the spread can be, for example, in a range of 3 mm or less (for example, 1 mm to 2 mm) from the boundary to the side where the active material layer is not formed. According to this aspect, the occurrence of a micro short circuit can be prevented to a higher degree.
  • the thickness of the porous inorganic layer provided on the active material layer non-forming part is not particularly limited, but is usually 0.5 ⁇ m or more (preferably 1 ⁇ m or more) and less than the thickness of the negative electrode active material layer. It is. Although not particularly limited, it is usually appropriate that the thickness of the inorganic layer at the central portion of the width of the negative electrode active material layer is about 0.5 ⁇ m to 10 ⁇ m (for example, 1 ⁇ m to 6 ⁇ m).
  • the end face of the negative electrode active material layer is porous at the end opposite to the one edge. It may be covered with an inorganic layer or may not be covered.
  • an end surface 344c opposite to the active material layer non-forming portion 342a is used. Is preferably provided with the negative electrode sheet 34 in a mode in which the porous inorganic layer 346 is not provided (in other words, the end surface along the thickness of the negative electrode active material layer 344 is exposed).
  • the negative electrode sheet of this embodiment is formed, for example, by forming a negative electrode active material layer on a negative electrode current collector having a width twice that of the intended negative electrode sheet, leaving both edges along the longitudinal direction of the current collector in a strip shape. Furthermore, the negative electrode sheet of the lithium ion battery according to the present invention can be efficiently produced by forming a porous inorganic layer from above the active material layer and then cutting (slit) at the center of the width.
  • the porous inorganic layer typically contains non-conductive (insulating) inorganic compound particles (inorganic particles) as a main component.
  • the inorganic compound that is a constituent material of the inorganic particles can be an oxide, carbide, silicide, nitride, or the like of a metal element or a nonmetal element.
  • oxide particles such as alumina (Al 2 O 3 ), silica (SiO 2 ), zirconia (ZrO 2 ), magnesia (MgO) can be preferably used.
  • silicide particles such as silicon carbide (SiC) and nitride particles such as aluminum nitride (AlN) can also be used.
  • ⁇ -alumina particles similar to the inorganic oxide filler in the technique described in JP-A-2005-327680 can be preferably used as the inorganic particles constituting the porous inorganic layer of the present invention.
  • the ⁇ -alumina particles can be particles having a plurality of (for example, about 2 to 10) primary particles connected (connected particles).
  • Such connecting particles can be produced based on the contents described in JP-A No. 2005-327680 and / or other publicly known documents and technical common sense in the field, or obtain appropriate commercial products. Can do.
  • the average particle diameter of the inorganic particles can be, for example, about 0.1 ⁇ m to 15 ⁇ m.
  • the average particle size referred to here can be employed common commercial granulometer an average particle size of the measured volume basis using a (laser diffraction particle size distribution measuring apparatus or the like) (D 50). It is preferable to use inorganic particles having an average particle diameter of about 0.2 ⁇ m to 1.5 ⁇ m. According to the porous inorganic layer formed using ceramic particles having such an average particle size, the application effect of the present invention can be better exhibited.
  • a negative electrode having a structure in which such an inorganic layer is provided on a negative electrode active material may be suitable for the construction of a lithium ion battery that exhibits better battery performance.
  • the porous inorganic layer can contain a binder (polymer component) for binding the inorganic particles in addition to the inorganic particles.
  • a binder for example, one or two or more materials appropriately selected from the polymers exemplified as the binder that can be blended in the negative electrode active material composition can be suitably used as the binder.
  • binders that can be preferably used include acrylonitrile-butadiene copolymer rubber (NBR), acrylonitrile-isoprene copolymer rubber (NIR), and acrylonitrile-butadiene-isoprene copolymer rubber.
  • NBIR acrylonitrile
  • acrylic polymer containing acrylic acid, methacrylic acid, acrylic acid ester or methacrylic acid ester (eg alkyl ester) as the main copolymerization component acrylic polymer containing acrylic acid, methacrylic acid, acrylic acid ester or methacrylic acid ester (eg alkyl ester) as the main copolymerization component
  • polyvinyl acetate, ethylene -Vinyl acetate resin such as vinyl acetate copolymer (EVA);
  • the binder used for forming the negative electrode active material layer and the binder used for forming the porous inorganic layer may be the same or different.
  • the invention disclosed herein can be preferably implemented in a mode in which the binders used in both layers are different types of binders.
  • a water-soluble (CMC or the like) binder and / or a water-dispersible binder (SBR or the like) is used for one of the negative electrode active material layer and the inorganic layer, and the other is a binder that dissolves in an organic solvent ( PVDF, organic solvent-soluble acrylic polymer, etc.) can be used.
  • the mass ratio (inorganic particles: binder) between the inorganic particles and the binder contained in the inorganic layer can be, for example, about 80:20 to 99.5: 0.5.
  • the mass ratio may be about 95: 5 to 99: 1.
  • a method for forming a porous inorganic layer on the surface of the negative electrode active material layer for example, a method of preparing a coating agent containing inorganic powder and a binder and applying the coating agent from above the negative electrode active material layer is preferably employed. can do.
  • a liquid coating agent in which the inorganic powder and the binder are dispersed or dissolved in an appropriate solvent is applied (typically applied) to the surface of the negative electrode active material layer, and the applied liquid coating agent is dried.
  • the method is simple and preferable.
  • the solvent dispersion medium such as inorganic particles
  • any of water for example, ion-exchanged water
  • an organic solvent for example, N-methylpyrrolidone
  • a mixed solvent of water and an organic solvent can be used.
  • the solid content concentration of the liquid coating agent ratio of the inorganic layer forming component in the coating agent
  • the solvent used for the negative electrode active material composition and the solvent used for the liquid coating agent may be the same or different.
  • a solvent different from the solvent of the negative electrode active material composition can be preferably employed as the solvent for the liquid coating agent.
  • the solvent of the negative electrode active material composition is an aqueous solvent (for example, water)
  • a liquid coating agent containing an organic solvent such as N-methylpyrrolidone (NMP) can be preferably used.
  • NMP N-methylpyrrolidone
  • an organic solvent system is formed on the negative electrode active material layer formed using the aqueous negative electrode active material composition (typically containing a water-soluble binder and / or a water-dispersible binder).
  • liquid coating agent solvent type, typically containing a binder that dissolves in an organic solvent
  • the applied liquid coating agent is brought into the state of the negative electrode active material layer.
  • events that affect eg cause swelling
  • Such an effect can also be realized by a combination of a solvent-based negative electrode active material composition and an aqueous liquid coating agent.
  • thermoplastic resin particles for example, polyolefin particles, EVA particles, etc.
  • binders By applying a powdery coating agent (coating agent powder) containing inorganic particles in layers on the negative electrode active material layer and heating, the inorganic particles are fused via the thermoplastic resin particles to make the porous material porous.
  • the method of forming an inorganic layer is mentioned.
  • the average pore diameter of pores (voids) contained in the porous inorganic layer the ratio of the total volume of the pores to the volume of the entire inorganic layer (porosity), etc.
  • the preferable range of the average pore diameter is about 0.01 ⁇ m to 10 ⁇ m (preferably about 0.1 ⁇ m to 4 ⁇ m)
  • the preferable range of the porosity is about 20 to 75% by volume (preferably about 35 to 70% by volume).
  • the average pore diameter and porosity can be measured using a commercially available mercury porosimeter or the like.
  • the lithium ion battery that can be provided by the present invention includes the above-described negative electrode sheet (including the negative electrode sheet produced by the above-described method) and a positive electrode active material layer on the surface of a long sheet-like positive electrode current collector.
  • An electrode body is formed by stacking and winding a positive electrode sheet via a long sheet-like separator, and typically has a configuration in which the electrode body is housed in a suitable outer container together with a non-aqueous electrolyte. .
  • a lithium ion battery 10 includes a container 11 made of metal (a resin or a laminate film is also suitable).
  • a wound electrode body 30 configured by laminating a positive electrode sheet 32, a negative electrode sheet 34, and two separators 35 in this container 11 and then winding (in this embodiment, winding in a flat shape) Contained.
  • the positive electrode sheet 32 includes a long sheet positive electrode current collector 322 and a positive electrode active material layer 324 formed on the surface thereof.
  • a sheet material typically, a metal foil having a thickness of about 5 to 30 ⁇ m, such as an aluminum foil
  • the positive electrode active material layer 324 is mainly composed of a positive electrode active material capable of inserting and extracting lithium ions.
  • an oxide-based positive electrode active material having a layered structure used for a general lithium ion battery, an oxide-based positive electrode active material having a spinel structure, or the like can be preferably used.
  • the main component is lithium cobalt complex oxide (typically LiCoO 2 ), lithium nickel complex oxide (typically LiNiO 2 ), lithium manganese complex oxide (LiMn 2 O 4 ), or the like.
  • a positive electrode active material can be used.
  • the positive electrode active material layer 324 can contain a binder and a conductive material in addition to the positive electrode active material.
  • a binder the thing similar to the binder for negative electrode active material compositions mentioned above etc. can be used.
  • the conductive material various carbon blacks (acetylene black, furnace black, ketjen black, etc.), carbon powder such as graphite powder, metal powder such as nickel powder, and the like can be used.
  • the amount of the conductive material used with respect to 100 parts by mass of the positive electrode active material can be, for example, in the range of 1 to 20 parts by mass (preferably 5 to 15 parts by mass).
  • the amount of the binder used with respect to 100 parts by mass of the positive electrode active material can be, for example, in the range of 0.5 to 10 parts by mass.
  • the positive electrode active material layer 324 typically, a positive electrode active material layer formed by mixing a suitable positive electrode active material as described above with a suitable conductive material and binder and water (for example, ion exchange water) is formed. A material (here, a water-kneaded paste-type positive electrode mixture) is applied to the surfaces of both sides of the positive electrode current collector 322 so that the active material is not denatured (typically 70 to 150 ° C.). ) To dry the coated material. Thereby, the positive electrode active material layer 324 can be formed in a desired part (part corresponding to the application range of the positive electrode active material composition) on the surfaces of both sides of the positive electrode current collector 32 (FIG. 2). The thickness and density of the positive electrode active material layer 324 can be appropriately adjusted by performing an appropriate press process (for example, a roll press process) as necessary.
  • an appropriate press process for example, a roll press process
  • a positive electrode active material layer non-forming part 322a is provided at one edge along the longitudinal direction of the positive electrode current collector 322 at the same position on both surfaces.
  • the width of the active material layer non-forming portion 322a can be, for example, about 10 mm to 30 mm, and is 17 mm in this embodiment.
  • the positive electrode active material layer 324 is formed up to the end of the current collector 322 on both sides.
  • the negative electrode sheet 34 includes a long sheet-like negative electrode current collector 342, a negative electrode active material layer 344 formed on the surface thereof, and a porous inorganic layer 346 that covers the negative electrode active material layer. ( Figures 2-4).
  • the negative electrode active material layer 344 is coated with a suitable negative electrode active material composition as described above on the surfaces of both sides of the negative electrode current collector 342 and dried at an appropriate temperature. It is obtained by performing a density adjustment process (for example, a roll press process).
  • a strip-shaped negative electrode active material layer non-forming portion 342a is provided at substantially the same position on both sides.
  • the width of the active material layer non-forming portion 342a can be, for example, about 10 mm to 30 mm, and is 15 mm in this embodiment.
  • the negative electrode active material layer 344 is formed up to the end of the current collector 342 on both sides.
  • the porous inorganic layer 346 is formed by applying a suitable coating agent (typically a liquid coating agent) as described above from above the negative electrode active material layer 344 and drying it at an appropriate temperature.
  • a suitable coating agent typically a liquid coating agent
  • the negative electrode active material layer 344 extends from the flat portion 344a to the end portion 344b along the thickness to reach the surface of the negative electrode current collector 342, and further on the negative electrode active material layer non-formation portion 342a of the current collector 342.
  • An inorganic layer 346 is formed in a range extending approximately 2 mm. In FIG.
  • a part of the inorganic layer 346 is removed at one end in the longitudinal direction of the negative electrode sheet 34 (lower left portion in the figure), and the negative electrode active material layer 344 below it can be seen. I am doing so.
  • porous sheets that are known to be usable as a separator for a lithium ion battery including a nonaqueous electrolytic solution are used.
  • a porous resin sheet (film) made of a polyolefin resin such as polyethylene or polypropylene can be preferably used.
  • the preferable porous sheet (typically a porous resin sheet) has an average pore diameter of about 0.0005 ⁇ m to 30 ⁇ m (more preferably 0.001 ⁇ m to 15 ⁇ m) and a thickness of Examples thereof include a porous resin sheet having a size of about 5 ⁇ m to 100 ⁇ m (more preferably 10 ⁇ m to 30 ⁇ m).
  • the porosity of the porous sheet can be, for example, about 20 to 90% by volume (preferably 30 to 80% by volume).
  • both the active material layers 324 and 344 are overlapped and the active material layer non-forming portion 322a of the positive electrode sheet and the negative electrode sheet are overlapped.
  • the positive and negative electrode sheets 32 and 34 are overlapped with each other so that the active material layer non-forming portion 342a is separately disposed at one end and the other end along the longitudinal direction.
  • the position of the end of the positive electrode active material layer 324 and the position of the end surface 344c of the negative electrode active material layer 344 are substantially matched on the active material layer non-forming part 322a side of the positive electrode sheet.
  • the position of the end of the negative electrode active material layer 344 coincides with the position of the end of the positive electrode active material layer 324 (in this embodiment, the end of the positive electrode sheet 32). A little overhanging.
  • the width of the negative electrode active material layer 344 protruding from the positive electrode active material layer 324 can be, for example, about 0.1 mm to 5 mm, and is about 1 mm in this embodiment.
  • One end of the two separators 35 along the longitudinal direction protrudes from the end of the negative electrode active material layer 344 toward the active material layer non-forming portion 342a with a width of, for example, about 2 mm.
  • the other end portion along the longitudinal direction protrudes from the end of the positive electrode active material layer 324 to the active material layer non-forming portion 322a side, for example, with a width of about 12 to 17 mm.
  • the protruding width of the separator 35 is preferably smaller than the width of the active material layer non-forming portions 322a and 342a.
  • the obtained wound electrode body 30 is electrically connected to each of the positive terminal 14 and the negative terminal 16 for external connection.
  • the portions of the positive electrode active material layer non-forming portion 322a and the negative electrode active material layer non-forming portion 342a that protrude from the separator 35 are gathered together in the radial direction of the wound electrode body 30, respectively. It can be suitably performed by connecting (for example, welding) the terminal 14 and the negative electrode terminal 16 respectively.
  • the active material layer is not formed at a part of the circumferential direction of the wound electrode body 30 used for connection with the terminals 14 and 16 in order to facilitate the penetration of the electrolyte into the electrode body 30.
  • the parts 322a and 342a are gathered in the radial direction.
  • the active material layer non-forming portions 322a and 342a are opened to the outside at both ends of the wound electrode body 30 in the winding axis direction.
  • FIG. 2 shows a cross section of the portion opened to the outside.
  • the electrode body 30 to which the terminals 14 and 16 are connected is accommodated in the container 11, and an appropriate nonaqueous electrolytic solution is disposed (injected) therein to seal the container 11.
  • an appropriate nonaqueous electrolytic solution is disposed (injected) therein to seal the container 11.
  • a non-aqueous electrolyte the same thing as a general lithium ion battery can be used.
  • a lithium salt such as LiPF 6 in a mixed solvent in which carbonates such as ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) are appropriately combined.
  • a nonaqueous electrolytic solution containing (supporting salt) at a concentration of about 0.1 mol / L to 5 mol / L (for example, about 0.8 mol / L to 1.5 mol / L) can be preferably used.
  • the end 344 b (see FIG. 4) of the negative electrode active material layer 344 is completely covered with the porous inorganic layer 346.
  • the porous inorganic layer 346 prevents direct contact between the metallic deposit caused by the foreign matter and the negative electrode sheet 34. The occurrence of minute short circuits can be highly prevented.
  • the porous inorganic layer 346 is formed so that Wa / Wb is 0.5 or more and 1.2 or less, the adverse effect of providing the inorganic layer by completely covering the end portion is avoided. Can do.
  • the lithium ion battery according to the present invention can highly prevent a minute short circuit, and thus has high reliability and excellent cycle characteristics.
  • the battery may be less deteriorated (for example, a decrease in battery capacity, that is, capacity deterioration) due to repeated charge / discharge (especially repeated use in a mode including high-rate charge of about 5 A).
  • the lithium ion battery according to the present invention can be suitably used as a power source for a motor (electric motor) mounted on a vehicle such as an automobile. Therefore, as schematically shown in FIG. 6, the present invention is in the form of one of the lithium ion batteries 10 disclosed herein (a battery pack formed by connecting a plurality of lithium ion batteries 10 in series. 1 is provided as a power source (typically, an automobile, in particular, an automobile including an electric motor such as a hybrid vehicle, an electric vehicle, and a fuel cell vehicle).
  • a power source typically, an automobile, in particular, an automobile including an electric motor such as a hybrid vehicle, an electric vehicle, and a
  • a slurry-like negative electrode active material composition is prepared by mixing natural graphite (negative electrode active material) having an average particle size of 10 ⁇ m, SBR, and CMC with ion-exchanged water so that the mass ratio of these materials is 98: 1: 1.
  • This composition was applied to both sides of a long copper foil having a thickness of 10 ⁇ m, a width of 160 mm, and a length of 5000 mm for a negative electrode current collector, and dried to form a negative electrode active material layer.
  • the application range of the negative electrode active material composition was a range in which both edges along the longitudinal direction of the copper foil were left in a strip shape of 15 mm on both sides.
  • a slurry coating agent for forming a porous inorganic layer is prepared by mixing alumina particles having an average particle size of 0.7 ⁇ m and PVDF as a binder with NMP so that the mass ratio of these materials is 95: 5. did.
  • This coating agent was applied so as to cover the whole of the negative electrode active material layer formed as described above, and further protruded by 2 mm on both sides from the formation width of the active material layer, and dried to form a porous inorganic layer.
  • two long negative electrode sheets were produced by cutting the copper foil provided with the negative electrode active material layer and the porous inorganic layer along the width center.
  • This negative electrode sheet was provided with a strip-like negative electrode active material layer non-formation part having a width of 15 mm on both sides over the entire length of one edge along the longitudinal direction of a negative electrode current collector (copper foil) having a width of 80 mm. It has a configuration. At the other edge along the longitudinal direction of the negative electrode current collector, the negative electrode active material layer is formed almost to the ends on both sides.
  • the coating agent was applied using a general gravure coater.
  • the coating amount of the coating agent was adjusted so that the target value of the basis weight in the flat portion of the negative electrode active material layer was 0.65 to 0.75 ⁇ m / cm 2 . This adjustment was performed at positions where the distance from one end of the formation width of the negative electrode active material layer before the cutting was 1/4, 2/4, and 3/4.
  • the gravure coater is adjusted so that the target value of the coating weight per unit area is larger than that of the plane portion, or the plane portion and After forming a porous inorganic layer by applying a coating agent with an equivalent basis weight, the above inorganic layer is scraped with sandpaper in a range of 2 mm from both ends along the longitudinal direction of the negative electrode active material layer toward the center of the width. The basis weight was reduced. In this manner, nine types of negative electrode sheet samples having different mass ratios Wa / Wb between the inorganic layer basis weight Wa at the end of the negative electrode active material layer and the inorganic layer basis weight Wb at the planar portion were prepared.
  • a lithium ion battery 10 having the schematic configuration shown in FIGS. 1 to 4 was produced by the following procedure.
  • the following was used as the positive electrode sheet. That is, lithium nickelate (LiNiO 2 ) powder, acetylene black, CMC and PTFE were mixed with ion-exchanged water so that the mass ratio of these materials was 94: 1: 5 and the solid content concentration was 45% by mass. Thus, a slurry-like positive electrode active material composition was prepared. This composition was applied to both sides of a long aluminum foil having a thickness of 10 ⁇ m, a width of 160 mm, and a length of 5000 mm for a positive electrode current collector, and dried to form a positive electrode active material layer.
  • lithium nickelate (LiNiO 2 ) powder, acetylene black, CMC and PTFE were mixed with ion-exchanged water so that the mass ratio of these materials was 94: 1: 5 and the solid content concentration was 45% by mass.
  • a slurry-like positive electrode active material composition was prepared. This composition was applied to both sides of a long aluminum foil having a thickness
  • the application range of the positive electrode active material composition was set to a range in which both edges along the longitudinal direction of the aluminum foil were left in a strip shape of 17 mm on both sides.
  • the coating amount of the positive electrode active material composition in the coating range was adjusted so that the total coating amount (solid content conversion) on both surfaces was 10 mg / cm 2 .
  • two long positive electrode sheets were produced by cutting the aluminum foil provided with the positive electrode active material layer along the width center.
  • This positive electrode sheet was provided with a strip-shaped positive electrode active material layer non-formation part having a width of 17 mm on both sides over the entire length at one edge along the longitudinal direction of a positive electrode current collector (aluminum foil) having a width of 80 mm. It has a configuration. On the other edge along the longitudinal direction of the positive electrode current collector, the positive electrode active material layer is formed almost to the ends on both sides.
  • the negative electrode sheet sample and the positive electrode sheet prepared above were superposed via two separators (here, a porous polypropylene sheet having a thickness of 30 ⁇ m, a width of 80 mm, and a length of 5000 mm was used).
  • the positive electrode active material layer non-formation part and the negative electrode active material layer non-formation part are arranged on the opposite side, and the negative electrode active material layer non-formation part side of the negative electrode sheet protrudes from the positive electrode sheet with a width of 1 mm from the end ( That is, both the electrode sheets were shifted and overlapped so that the entire negative electrode active material layer non-forming portion and a range of 1 mm from the end of the negative electrode active material layer adjacent thereto protruded from the positive electrode active material layer (see FIG. 2). ).
  • the laminated sheet was wound about 30 times in the longitudinal direction, and the wound body was crushed from the side to form a flat electrode body.
  • the positive electrode terminal made of aluminum and the negative electrode terminal made of copper were welded to the positive electrode active material layer non-formed part and negative electrode active material layer non-formed part protruding from the separator at both ends of the electrode body, respectively.
  • This was housed in a flat rectangular container together with a non-aqueous electrolyte, and the opening of the container was sealed to construct a lithium ion battery.
  • a non-aqueous electrolyte a non-aqueous electrolyte having a composition in which a supporting salt (here, LiPF 6 ) is dissolved in a mixed solvent of EC, DMC, and EMC at a volume ratio of 1: 1: 1 at a concentration of 1 mol / L. , 50 mL was used for each battery.
  • a total of nine types of lithium ion batteries corresponding to each negative electrode sheet sample were obtained.
  • the battery was discharged at a constant current of 5 A from 4.1 V to 3.0 V at 25 ° C., and then discharged at a constant voltage until the total discharge time was 2 hours. Capacity).
  • the operation of charging each battery with a constant current of 5 A from 3.0 V to 4.1 V and the operation of discharging with a constant current of 5 A from 4.1 V to 3.0 V are alternately repeated 1000 cycles. It was.
  • the battery after the charge / discharge cycle was discharged at a constant current of 5 A from 4.1 V to 3.0 V, and then discharged at a constant voltage until the total discharge time was 2 hours. Capacity).
  • the lithium ion battery constructed using the negative electrode sheet sample in which Wa / Wb is in the range of 0.5 to 1.2 shows a high capacity maintenance rate of around 92%. Met. In addition, it was confirmed that the capacity maintenance rate dropped sharply for batteries with Wa / Wb below 0.5 or above 1.2.

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  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention porte sur une batterie lithium-ion qui comprend un corps d'électrode (30) formé par stratification d'une feuille d'électrode positive longue (32) et d'une feuille d'électrode négative longue (34) par l’intermédiaire d’un séparateur (35) puis enroulement du stratifié. La feuille d'électrode négative (34) comprend une couche de matériau actif (344) formée sur un collecteur de courant (342) tout en laissant un bord du collecteur non revêtu sous la forme d'une bande selon la direction longitudinale, et la feuille d'électrode négative (34) est stratifiée de telle manière que la partie (342a), dans laquelle la couche de matériau actif en forme de bande n'est pas formée, fait saillie au-delà de la feuille d'électrode positive (32). Sur la surface extérieure de la couche de matériau actif d'électrode négative (344), une couche inorganique poreuse (346) est formée de façon à s'étendre depuis une partie plane (344a) de la couche de matériau actif jusqu'à la surface du collecteur de courant (342) par l'intermédiaire d'une partie d'extrémité (344b). Le rapport de masse par unité d'aire Wa/Wb entre la partie d'extrémité (344b) et la partie plane (344a) de la couche inorganique (346) se situe dans la plage de 0,5 à 1,2.
PCT/JP2008/072267 2008-12-08 2008-12-08 Batterie lithium-ion et son procédé de fabrication WO2010067410A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8658305B2 (en) 2009-04-10 2014-02-25 Toyota Jidosha Kabushiki Kaisha Lithium-ion battery and use thereof
RU2539264C1 (ru) * 2011-04-07 2015-01-20 Ниссан Мотор Ко., Лтд. Укладочное устройство и способ укладки

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07220759A (ja) * 1994-01-31 1995-08-18 Sony Corp 非水電解液二次電池
JPH09147916A (ja) * 1995-11-20 1997-06-06 Fuji Photo Film Co Ltd 非水二次電池
JP2006228544A (ja) * 2005-02-17 2006-08-31 Matsushita Electric Ind Co Ltd リチウムイオン二次電池
JP2006310010A (ja) * 2005-04-27 2006-11-09 Matsushita Electric Ind Co Ltd リチウムイオン二次電池
JP2007273123A (ja) * 2006-03-30 2007-10-18 Matsushita Electric Ind Co Ltd 非水電解質二次電池とその製造方法
JP2008103310A (ja) * 2006-09-19 2008-05-01 Matsushita Electric Ind Co Ltd 二次電池用電極の製造方法及び二次電池

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07220759A (ja) * 1994-01-31 1995-08-18 Sony Corp 非水電解液二次電池
JPH09147916A (ja) * 1995-11-20 1997-06-06 Fuji Photo Film Co Ltd 非水二次電池
JP2006228544A (ja) * 2005-02-17 2006-08-31 Matsushita Electric Ind Co Ltd リチウムイオン二次電池
JP2006310010A (ja) * 2005-04-27 2006-11-09 Matsushita Electric Ind Co Ltd リチウムイオン二次電池
JP2007273123A (ja) * 2006-03-30 2007-10-18 Matsushita Electric Ind Co Ltd 非水電解質二次電池とその製造方法
JP2008103310A (ja) * 2006-09-19 2008-05-01 Matsushita Electric Ind Co Ltd 二次電池用電極の製造方法及び二次電池

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8658305B2 (en) 2009-04-10 2014-02-25 Toyota Jidosha Kabushiki Kaisha Lithium-ion battery and use thereof
RU2539264C1 (ru) * 2011-04-07 2015-01-20 Ниссан Мотор Ко., Лтд. Укладочное устройство и способ укладки

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