WO2013021443A1 - Batterie rechargeable à électrolyte non aqueux - Google Patents

Batterie rechargeable à électrolyte non aqueux Download PDF

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Publication number
WO2013021443A1
WO2013021443A1 PCT/JP2011/068019 JP2011068019W WO2013021443A1 WO 2013021443 A1 WO2013021443 A1 WO 2013021443A1 JP 2011068019 W JP2011068019 W JP 2011068019W WO 2013021443 A1 WO2013021443 A1 WO 2013021443A1
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Prior art keywords
negative electrode
graphite particles
mass
battery
parts
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PCT/JP2011/068019
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English (en)
Japanese (ja)
Inventor
山田　直毅
博行 戸城
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日立ビークルエナジー株式会社
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Priority to PCT/JP2011/068019 priority Critical patent/WO2013021443A1/fr
Priority to JP2013527766A priority patent/JP5736049B2/ja
Publication of WO2013021443A1 publication Critical patent/WO2013021443A1/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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • 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.
  • lithium ion secondary batteries have been applied to electronic devices such as notebook PCs and digital cameras that are driven at a relatively low voltage of 12 V or less. Under these conditions of use, it is assumed that the battery is used at a lower power than the battery capacity, and the characteristic required for the lithium ion secondary battery is that it has a larger capacity than other systems.
  • lithium-ion secondary batteries for in-vehicle use must have large capacity and high output. To achieve a large capacity, it is necessary to provide a larger amount of active material, and to achieve a high output, it is necessary to improve the input / output performance of the battery.
  • lithium-ion secondary batteries for in-vehicle use are easily assumed to be used for a long period of time, and the number of charge / discharge cycles increases. It is essential to be good.
  • the negative electrode contains a conductive material composed of graphite particles and scaly graphite, and a non-aqueous solution having excellent discharge load characteristics due to the presence of a recess not formed on the surface of the negative electrode.
  • An electrolyte secondary battery has been proposed.
  • Patent Document 2 for the purpose of improving the input / output performance of the battery, that is, reducing the electric resistance of the battery, carboxymethyl cellulose is used as the first binder as the binder component contained in the positive electrode.
  • a structure comprising a polyethylene oxide in a two-binding material has been proposed.
  • the type of binder component is defined as polyethylene oxide
  • the composition is different from that of a conventionally used rubber binder such as styrene butadiene rubber, members constituting other batteries, particularly electrolyte solution
  • a conventionally used rubber binder such as styrene butadiene rubber
  • members constituting other batteries particularly electrolyte solution
  • electrolyte solution there remains a possibility that some constraints will arise on. The reason for this is that, according to the study by the present inventors, low molecular weight components and the like generated during the synthesis of polyethylene oxide may be dissolved in the electrolytic solution, and the solubility of polyethylene oxide in the electrolytic solution needs to be considered. Conceivable.
  • the present invention has been made to solve the above-described problems, and its object is to suppress non-aqueous electrolysis that suppresses battery capacity deterioration with respect to charge / discharge cycles and suppresses an increase in electrical resistance in current input / output. It is to provide a liquid secondary battery.
  • the nonaqueous electrolyte secondary battery of the present invention that solves the above-mentioned problems is characterized in that the negative electrode mixture layer has scaly graphite particles and polyhedral graphite particles whose surfaces are coated with amorphous carbon.
  • the present embodiment is not limited to the following contents and does not depart from the gist thereof. Any change can be made within the range.
  • a nonaqueous electrolyte secondary battery that is, a lithium ion secondary battery
  • the battery according to this embodiment will be described.
  • the battery according to this embodiment is not limited to a non-aqueous electrolyte secondary battery, and the electrode of the battery according to this embodiment can be applied to any battery.
  • FIG. 1 is a schematic perspective view of the internal structure of a non-aqueous electrolyte secondary battery according to an embodiment (first embodiment) of the present invention.
  • the non-aqueous electrolyte secondary battery according to the first embodiment shown in FIG. 2 includes a battery container 1, a gasket 2, an upper lid 3, an upper lid case 4, a positive current collector plate 5, and a negative current collector plate 6.
  • the electrode group 8 and the positive electrode lead 9 are included.
  • the battery container 1 contains a positive electrode current collector plate 5, a negative electrode current collector plate 6, an electrode group 8, a positive electrode lead 9, and a non-aqueous electrolyte (not shown).
  • the battery container 1 has a cylindrical shape, but may have a rectangular shape. Further, as the material of the battery container 1, it is preferable to use a metal that is not corroded by the stored nonaqueous electrolytic solution, and nickel-plated iron or the like is used.
  • the gasket 2 is provided between the battery case 1 and the upper lid case 4.
  • the battery container 1 is sealed by the gasket 2 and the battery container 1 is electrically insulated from the upper lid 3 and the upper lid case 4.
  • a known sealing member such as an elastic resin such as polypropylene (PP) or tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA) can be used.
  • the upper lid 3 is an external terminal for taking out the electric power obtained from the battery, specifically, a positive external terminal.
  • the upper lid case 4 is integrally formed of the same material as the upper lid 3, and the upper lid 3 and the upper lid case 4 are electrically connected. As the material of the upper lid 3 and the upper lid case 4, a conductive metal can be used. The upper lid case 4 and the positive electrode current collector plate 5 are electrically connected via a positive electrode lead 9 made of metal.
  • the positive electrode current collector plate 5 and the negative electrode current collector plate 6 are electrically connected to a positive electrode tab 12 and a negative electrode tab 13 described later, respectively. This electrical connection can be performed by, for example, ultrasonic welding.
  • a hole is provided in the central portion of the positive electrode current collector plate 5 and the negative electrode current collector plate 6, and an axial center 7 (described later) is fitted into the hole, whereby the positive electrode current collector plate 5 and the negative electrode current collector plate.
  • the electric plate 6 is fixed with respect to the shaft center 7.
  • a conductive metal is used as a material for the positive electrode current collector plate 5 and the negative electrode current collector plate 6.
  • the negative electrode current collector plate 6 is electrically connected to the bottom of the battery case 1, and the bottom of the battery case 1 functions as a terminal for taking out the electric power obtained by the battery, specifically, a negative electrode external terminal. ing. Therefore, the bottom part and the side part of the battery container 1 are insulated from each other by an insulator (not shown).
  • the shaft center 7 is located at the center of the electrode group 8, and the positive electrode 14 and the negative electrode 15 are wound with a separator 18 interposed therebetween. Further, the upper and lower end portions of the shaft center 7 penetrate the positive electrode current collector plate 5 and the negative electrode current collector plate 6.
  • the shape of the shaft center is arbitrary, but a hollow cylinder is used in the first embodiment.
  • a resin or the like that does not have conductivity or has extremely low conductivity can be used.
  • the electrode group 8 is configured by winding a separator between the positive electrode 14 and the negative electrode 15 in a cylindrical shape, and the positive electrodes 14 and the negative electrodes 15 are alternately stacked.
  • the positive electrode 14 has a positive electrode current collector and a positive electrode mixture layer 16 provided on both surfaces of the positive electrode current collector, and the negative electrode 15 is formed on both surfaces of the negative electrode current collector and the negative electrode current collector.
  • the negative electrode mixture layer 17 is provided.
  • a separator 18 is provided on the outermost periphery of the electrode group 8.
  • the electrode group 8 is fixed to the separator 18 provided on the outermost periphery by a winding member 19 so that the winding of the electrode group 8 cannot be unwound.
  • a positive electrode tab 12 is provided above the positive electrode 14, and a negative electrode tab 13 is provided below the negative electrode 15.
  • the positive electrode current collector and the positive electrode tab 12 of the positive electrode 14 are made of a metal such as aluminum.
  • the positive electrode mixture layer 16 is formed by applying a slurry-like positive electrode mixture containing a positive electrode active material, a conductive material, and a binder component on both surfaces of the positive electrode current collector, and then drying and pressing the mixture.
  • the negative electrode current collector and the negative electrode tab 13 of the negative electrode 15 are made of a metal such as copper.
  • the negative electrode mixture layer 17 is formed by applying a slurry-like negative electrode mixture containing a negative electrode active material and a binder component on both sides of the negative electrode current collector, followed by drying and pressing.
  • the separator 18 is porous and has an insulating property, and any known separator that can be used for a lithium ion secondary battery can be used.
  • the nonaqueous electrolyte secondary battery according to the present embodiment can be charged from the outside of the battery container 1 or discharged to the outside of the battery container 1 by having the configuration described above and shown in FIG. That is, for example, when the battery is discharged, electrons generated at the negative electrode 15 of the electrode group 8 are taken out through the negative electrode tab 13, the negative electrode current collector plate 6, and the bottom of the battery container 1 in this order. On the other hand, electrons reach the positive electrode 14 of the electrode group 8 from the outside through the upper lid 3, the upper lid case 4, the positive electrode lead 9 and the positive electrode tab 12.
  • Negative electrode [Negative electrode active material]
  • the negative electrode active material is one that occludes and releases lithium ions in the non-aqueous electrolyte that the battery normally has, and also occludes and releases electrons.
  • the negative electrode active material has scaly graphite particles and polyhedral graphite particles whose surfaces are coated with amorphous carbon. According to the present invention, graphite particles having an average particle size of 1 ⁇ m or more and 50 ⁇ m or less can be suitably used.
  • the average particle diameter may be appropriately selected according to the thickness of the negative electrode to be produced.
  • the scaly graphite particles preferably have an average particle diameter of 5 ⁇ m to 50 ⁇ m, and more preferably 10 ⁇ m to 30 ⁇ m.
  • the polyhedral graphite particles preferably have an average particle size of 1 ⁇ m to 50 ⁇ m, and more preferably 5 ⁇ m to 15 ⁇ m.
  • the average particle diameter of the graphite particles exceeds 50 ⁇ m, the size of one particle is large with respect to the thickness of the mixture layer to be produced, and the thickness is likely to fluctuate. Handling becomes complicated and productivity is remarkably inferior.
  • the average particle diameter in this invention is a particle size of the integrated value 50% in the particle size distribution calculated
  • DCR direct current resistance component
  • the scaly graphite particles are a large number of flat graphites and / or aggregates thereof, and have a large surface area per weight. For this reason, there are many sites where lithium ions can be inserted and desorbed, and the resistance during insertion and desorption can be reduced, which can contribute to a reduction in electrical resistance. For this reason, it can be said that the use of scaly graphite particles is essential from the viewpoint of reducing the electric resistance of the battery.
  • the scaly graphite particles are aggregates of fine scaly structures, the contact area between the fine structures is small, and they are relatively brittle with respect to expansion and contraction due to repeated charge and discharge, and the inter-particles Contact is often blocked. That is, the reduction in charge / discharge capacity tends to be quick, and it can be said that there is a problem in the cycle characteristics of a battery using scaly graphite.
  • the polyhedral graphite particles have few voids inside the particles, and the surface area per weight with respect to the average particle diameter, that is, the specific surface area is small.
  • the electrical resistance increases.
  • polyhedral graphite particles are relatively strong in expansion and contraction, and are less likely to block contact between particles, so the charge / discharge capacity tends to decrease slowly and cycle characteristics are low. It can be said that it is relatively good.
  • the positive electrode and the negative electrode for lithium ion secondary batteries it is essential to press the mixture layer on the current collector (metal foil) to a certain density in order to impart desired battery performance.
  • the negative electrode scaly graphite has a relatively brittle structure, and since there are many voids in the particles, it is relatively easy to compress the particles, which is advantageous for adjusting the density.
  • Graphite has a high chemical activity on the surface, and may react with the electrolyte components to gradually change the electrolyte composition.
  • the change in the electrolyte composition is likely to deteriorate the battery performance.
  • the reaction with the electrolyte component can be suppressed by providing a coating layer on the surface of the graphite particles.
  • the method for forming the coating layer include attaching the material of the coating layer to the surface of the graphite powder and sintering it to form an amorphous carbon layer. It is desirable that the graphite powder of the present invention (flaky graphite particles and polyhedral graphite particles) also form a coating layer on the surface.
  • fine plate-like graphite particles which are single particles or those obtained by combining a plurality of particles, are referred to as scaly graphite particles.
  • the fine plate-like graphite particles can be arbitrarily selected in size according to the required performance, and the particle surface may be coated.
  • the surface coating can be realized by, for example, a method of forming an amorphous carbon film on the surface of the graphite particles. Since the basic unit is in the form of a fine plate in this way, the scaly graphite particles have a large number of voids formed between the particles or in the composite particles, and these voids are formed by a scanning electron microscope. (SEM) or the like can be used for easy observation.
  • SEM scanning electron microscope
  • the polyhedral graphite particles of the present invention have a polyhedral shape, almost no voids are observed in the particles, and each takes the form of an independent particle.
  • the shape may be partially spherical due to process conditions or the like, but most of the shape becomes a polyhedral shape due to irregular contact with particles or production equipment. At that time, it is conceivable that a gap is rarely generated due to a crack caused by a contact impact, but it is not intended to positively hold the gap.
  • the shape of the polyhedral graphite particle in this invention differs in a strict meaning from a geometric polyhedron.
  • the polyhedral shape in the present invention indicates a state in which the surface of the particle is flat or has a shape in which one or both of a flat portion having a slight unevenness are mixed. Most of the shape of this plane or planar portion is an irregular polygonal shape.
  • the outline of each particle is basically indefinite, and does not show a uniform shape to a certain extent, such as a spherical particle. It can be easily observed using a scanning electron microscope (SEM) or the like that it is polyhedral and almost no voids are observed inside, like the above-mentioned scaly graphite particles.
  • SEM scanning electron microscope
  • the polyhedral graphite particles are desirably coated on the surface, and polyhedral graphite having an amorphous carbon film is preferable.
  • the negative electrode active material of the negative electrode mixture layer by using a mixture of scaly graphite particles and polyhedral graphite particles, electrical resistance and cycle Achieving compatibility with characteristics.
  • the negative electrode mixture layer contains scaly graphite particles having an average particle diameter of 1 ⁇ m or more and 50 ⁇ m or less and polyhedral graphite particles as a negative electrode active material.
  • the surface of the polyhedral graphite particles is coated with amorphous carbon, and more preferably, the surface of the scaly graphite particles is coated with amorphous carbon.
  • the ratio of the scaly graphite particles and the polyhedral graphite particles to the total amount of the active material is preferably such that the scaly graphite particles are 60 parts by mass or more and 90 parts by mass or less, and the polyhedral graphite particles are 10 parts by mass or more and 40 parts by mass or less, More preferably, the scaly graphite particles are 65 parts by mass or more and 80 parts by mass or less, and the polyhedral graphite particles are 15 parts by mass or more and 20 parts by mass or less, and more preferably, the scaly graphite particles are 65 parts by mass or more and 75 parts by mass or less. And polyhedral graphite particles are 25 mass parts or more and 35 mass parts or less.
  • the number of scale-like graphite particles is less than 60 parts by mass and the number of polyhedral graphite particles is more than 40 parts by mass, the electric resistance of the battery increases and the density adjustment of the negative electrode mixture layer becomes difficult.
  • the scale-like graphite particles are more than 90 parts by mass and the polyhedral graphite particles are less than 10 parts by mass, the cycle characteristics are deteriorated.
  • the mechanism by which the cycle characteristics are improved by setting the scaly graphite particles and polyhedral graphite particles to a preferable mixing ratio is considered as follows.
  • the scaly graphite particles have a relatively low resistance during charging / discharging, but have a characteristic that they are partially broken by the stress of expansion / contraction during charging / discharging. For this reason, when the scaly graphite particles are used alone, the destruction portion due to repeated charge and discharge is expanded. The broken portion is a part of the graphite particles that are not electrically conductive. However, when this ratio is increased, the proportion of the graphite particles that are relatively electrically secured is decreased. This leads to a decrease in the total amount of lithium ions that can be inserted and desorbed, that is, the capacity of the electrode. That is, the cycle characteristics are deteriorated.
  • the polyhedral graphite particles that are relatively resistant to destruction by repeated charge and discharge are arranged so as to contact the scaly graphite particles, the scaly graphite particles themselves are destroyed, but the contacting polyhedrons Electrical conduction is ensured by using the graphite particles as a bypass. That is, the portion where the electrical conductivity is impaired by the scaly graphite particles alone is continuously secured by contact with the polyhedral graphite particles, and can be used for charging and discharging. Accordingly, it is possible to prevent a decrease in the total amount of lithium ions that can be inserted and desorbed, suppress a decrease in electrode capacity, prevent deterioration of cycle characteristics, and extend the life of the battery.
  • polyhedral graphite particles in an amount sufficiently contacting the scaly graphite particles are essential. At the same time, the polyhedral graphite particles are required to be stronger against expansion and contraction due to repeated charge and discharge.
  • the ratio of the graphite particles is preferably 60 parts by mass or more and 90 parts by mass or less of scaly graphite particles and 10 parts by mass or more and 40 parts by mass or less of polyhedral graphite particles, more preferably
  • the scaly graphite particles are 65 parts by mass or more and 80 parts by mass or less
  • the polyhedral graphite particles are 15 parts by mass or more and 20 parts by mass or less
  • the scaly graphite particles are 65 parts by mass or more and 75 parts by mass or less and the polyhedral graphite.
  • the particles are 25 parts by mass or more and 35 parts by mass or less.
  • the surfaces of the polyhedral graphite particles in the present invention are coated with amorphous carbon or the like.
  • Spherical graphite particles tend to have few points of contact with other particles due to their shape. From the viewpoint of ensuring conduction between graphite particles, it is more preferable that there are many contact points with other particles.
  • the polyhedral graphite particles are indefinite, and it can be expected that more contact points can be obtained between the adjacent graphite particles than the spherical graphite particles, and the probability of ensuring conduction between the graphite particles is maintained. Will be higher.
  • the polyhedral graphite particles have a plurality of planar portions and / or planar portions, projecting portions are generated at the borders between them. It can be easily imagined that stronger contact can be obtained in the compression process (described later) when producing a negative electrode when the protrusions are in a positional relationship that penetrates into adjacent graphite particles. From this viewpoint, it can be said that the shape is more preferable.
  • the negative electrode of the non-aqueous electrolyte secondary battery according to the present embodiment includes a binder that holds an active material on the current collector in the mixture layer, that is, a binder component, a rubber binder and carboxymethyl cellulose (hereinafter referred to as CMC). Abbreviated).
  • CMC carboxymethyl cellulose
  • these are essential for securing the binding property between the active materials.
  • a film is formed on the surface of the active material graphite particles, and lithium ions are inserted. Inhibits detachment.
  • the total content of CMC and the rubber binder in the entire negative electrode mixture layer occupies 2.4 parts by mass or more, an increase in electric resistance of the battery due to the presence of an excessive binder component was confirmed. Moreover, when it is less than 2.00 parts by mass, sufficient binding force cannot be obtained, the adhesion of the negative electrode mixture layer to the current collector becomes poor, and charging and discharging may be difficult due to insufficient conduction. Is expensive. Therefore, the total content of CMC and rubber binder with respect to the entire negative electrode mixture layer is preferably 2.05 parts by mass or more and 2.35 parts by mass or less, more preferably 2.10 parts by mass or more and 2.30 parts by mass or less. More preferably, it is 2.15 parts by mass or more and 2.25 parts by mass or less. When the content exceeds 2.35 parts by mass, the DCR of the battery increases.
  • a negative electrode mixture containing both scaly graphite particles and polyhedral graphite particles is particularly applied.
  • Polyhedral graphite particles tend to require a larger amount of binder component than scale-like graphite particles.
  • the detailed cause is unknown, it is presumed that the scaly graphite particles have many irregularities on the surface, and friction between the particles is likely to occur, so that sufficient binding can be secured even with a small amount of binder component.
  • the binder component that is, the rubber binder and the CMC
  • the binder component is not seen when the negative electrode is cut and the mixture layer is not peeled off from the cut portion.
  • the total content is 2.00 parts by mass, the mixture layer is peeled off from the cut portion when the electrode is similarly cut.
  • the tendency of such a mixture layer to peel off is due to a decrease in the binding force between the current collector and the negative electrode mixture layer.
  • the battery is particularly important. Application becomes difficult.
  • the binder component is preferably contained within the above range.
  • the type of rubber binder is arbitrary as long as the effects of the present invention are not significantly impaired, but synthetic rubber is preferred from the viewpoint of easy control of physical properties and few impurities.
  • synthetic rubbers include, for example, styrene-butadiene copolymer rubber (hereinafter abbreviated as SBR) and modified products thereof, acrylonitrile-butadiene copolymer rubber and modified products thereof, acrylic rubber and modified products thereof. And fluororubber.
  • SBR styrene-butadiene copolymer rubber
  • a rubber binder may consist only of 1 type, and may comprise 2 or more types in arbitrary ratios and combinations.
  • the negative electrode binder according to the present embodiment may include a binder other than the rubber binder.
  • a binder other than the rubber binder those having arbitrary physical properties can be used as long as the effects of the present invention are not significantly impaired. Examples thereof include polyvinylidene fluoride (PVDF).
  • PVDF polyvinylidene fluoride
  • 1 type of binders other than a rubber binder may be contained independently, and 2 or more types may be contained by arbitrary ratios and combinations.
  • Positive electrode [Positive electrode active material]
  • the positive electrode active material occludes and releases lithium ions in the non-aqueous electrolyte solution that the non-aqueous electrolyte secondary battery normally has, and takes in electrons.
  • the physical properties and types of the positive electrode active material are arbitrary as long as the effects of the present invention are not significantly impaired. Therefore, a positive electrode active material having any known physical property that is preferably used for a non-aqueous electrolyte secondary battery may be used.
  • lithium oxide or the like can be mentioned as a suitable material.
  • Specific examples of such lithium oxide include lithium cobalt oxide, lithium manganate, lithium nickelate, lithium iron phosphate, and lithium composite oxide (that is, two or more selected from the group consisting of cobalt, nickel, and manganese).
  • Lithium oxide containing the above metal and the like.
  • a positive electrode active material may be used individually by 1 type, and may be used 2 or more types by arbitrary ratios and combinations.
  • binders As the positive electrode according to the present embodiment, those having arbitrary physical properties can be used as long as the effects of the present invention are not significantly impaired. Examples thereof include a rubber binder similar to the negative electrode binder, and polyvinylidene fluoride (PVDF). In addition, 1 type of binders other than a rubber binder may be contained independently, and 2 or more types may be contained by arbitrary ratios and combinations.
  • the electrode according to the present embodiment includes a binder component, but other components that can be included in addition to the binder component are optional as long as the effects of the present invention are not significantly impaired.
  • the electrode according to the present embodiment usually includes a current collector in addition to the above mixture layer, and in particular, the positive electrode further includes a conductive material.
  • the thickness of the current collector is usually 5 ⁇ m or more, preferably 10 ⁇ m or more, and the upper limit is usually 30 ⁇ m or less, preferably 20 ⁇ m or less. If the thickness of the current collector is too thin, the strength of the electrode will decrease, and the electrode may be easily damaged. If it is too thick, the flexibility of the electrode will be impaired, and there will be restrictions on the battery manufacturing method in the subsequent process May occur.
  • the type of the current collector is arbitrary as long as the effect of the present invention is not significantly impaired, but usually a conductive material is used.
  • a conductive material for example, copper is suitably used for the negative electrode, and aluminum or the like is suitably used for the positive electrode.
  • One type of current collector may be used alone, or two or more types may be used in any ratio and combination.
  • the shape of the current collector is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually a foil shape.
  • the conductive material assists the exchange of electrons between the current collector and the active material.
  • the physical properties and types of the conductive material usually included in the electrode according to this embodiment are arbitrary as long as the effects of the present invention are not significantly impaired. Therefore, a conductive material having any known physical property that is suitably used for a non-aqueous electrolyte secondary battery may be used.
  • a conductive material examples include acetylene black and graphite.
  • a conductive material may be used individually by 1 type, and may be used 2 or more types by arbitrary ratios and combinations.
  • Non-aqueous electrolyte The battery according to this embodiment usually has a non-aqueous electrolyte in addition to the binder.
  • a nonaqueous electrolytic solution is not particularly limited as long as it can occlude and release lithium ions with respect to the active material.
  • the non-aqueous electrolyte usually consists of a non-aqueous solvent and a non-aqueous electrolyte.
  • Any nonaqueous solvent may be used as long as the effects of the present invention are not significantly impaired.
  • a carbonate solvent is preferable.
  • Specific examples of the carbonate solvent include cyclic carbonates such as ethylene carbonate (EC) and propylene carbonate (PC), and chain carbonates such as dimethyl carbonate (DMC) and methyl ethyl carbonate (MEC).
  • a non-aqueous solvent may be used individually by 1 type, and may be used 2 or more types by arbitrary ratios and combinations.
  • any nonaqueous electrolyte contained in the nonaqueous electrolytic solution can be used as long as the effects of the present invention are not significantly impaired.
  • a lithium salt is particularly suitable.
  • Specific examples of such a lithium salt include lithium fluorophosphate (LiPF 6 ), lithium fluoroborate (LiBF 4 ), and the like.
  • a non-aqueous electrolyte may also be used individually by 1 type, and may use 2 or more types by arbitrary ratios and combinations.
  • the battery according to the present embodiment can be manufactured by any known method as long as it has the above-described configuration.
  • the manufacturing method of the battery which concerns on this embodiment is given as an example, the manufacturing method of the electric potential which concerns on this embodiment is not limited to the method as described below.
  • the electrode (positive electrode and negative electrode) according to the present embodiment is, for example, applied to a current collector by applying an electrode mixture composed of an active material, a binder, a conductive material, a dispersion medium, and other components as necessary, and then dried. It can produce by doing.
  • the binder used was the one described in “[1-2. Negative electrode binder] of [1-2. Negative electrode]” and “[Positive electrode binder] of [1-3. Positive electrode]”, and a current collector,
  • the active material and the conductive material those described above in “[1-3. Other components]” can be used.
  • the amount of each component in the electrode mixture is the same as the amount of each component contained in the electrode after drying [1-2. Negative electrode] and [1-3. What is necessary is just to adjust suitably so that it may be what was described in the positive electrode].
  • SBR that can be suitably used as a rubber binder contained in the electrode according to the present embodiment can be usually produced by copolymerizing styrene and butadiene.
  • SBR may be synthesized in a system to which a copolymerizable component is appropriately added.
  • Tg glass transition temperature
  • components such as acrylonitrile and 2-vinylpyridine can be used as copolymerizable components.
  • the electrode mixture contains a dispersed liquid.
  • the type of the dispersion medium usually contained in the electrode mixture is arbitrary as long as the effects of the present invention are not significantly impaired.
  • NMP N-methylpyrrolidone
  • a dispersion medium may be used individually by 1 type, and may use 2 or more types by arbitrary ratios and combinations.
  • the amount of the dispersion medium in the electrode mixture is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 20% by weight or more, preferably 30% by weight or more, more preferably 40%, based on the total amount of the electrode mixture.
  • the upper limit is usually 70% by weight or less, preferably 65% by weight or less, more preferably 60% by weight or less. If the amount of the dispersion medium is too small, each component contained in the electrode mixture may not be properly dispersed, and each component may be unevenly distributed on the current collector. It may take too much.
  • Examples of other components included in the electrode mixture as needed include surfactants, antifoaming materials, thickeners, and the like.
  • the electrode mixture contains a surfactant
  • the dispersion stability of the rubber binder contained in the electrode mixture can be improved.
  • coating the electrode mixture containing the said surfactant can be suppressed because an electrode mixture contains an antifoamer.
  • an electrode mixture contains a thickener, the viscosity of an electrode mixture can be made into a desired thing, and application
  • surfactants include sodium n-dodecyl sulfate and the like, and one surfactant may be used alone, or two or more surfactants may be used in any ratio and combination.
  • specific examples of the antifoaming agent include n-octanol, polysiloxane and the like, and one type of antifoaming agent may be used alone, or two or more types may be used in any ratio and combination.
  • specific examples of the thickener include carboxymethyl cellulose (CMC) and the like, and one thickener may be used alone, or two or more thickeners may be used in any ratio and combination.
  • the above-mentioned active material, binder, conductive material, dispersion medium and other components as required can be mixed by any known method to produce an electrode mixture. Any mixing method can be used as long as each component can be uniformly dispersed in the dispersion medium and the effects of the present invention are not significantly impaired.
  • the solid content of the prepared electrode mixture is arbitrary as long as the effects of the present invention are not significantly impaired, but is usually 35% by weight or more, preferably 45% by weight or more, more preferably 50% by weight or more, and the upper limit thereof. Is usually 70% by weight or less, preferably 65% by weight or less, more preferably 60% by weight or less. If the solid content is too small, it may take too much time for the coating and drying process when forming the electrode, and if it is too large, the coating property may be lowered. The solid content can be measured by a method of heating and drying the electrode mixture.
  • the viscosity of the electrode mixture is arbitrary as long as the effects of the present invention are not significantly impaired, but usually 0.5 Pa ⁇ s or more, preferably 1 Pa ⁇ s or more, and the upper limit is usually 100 Pa ⁇ s or less.
  • the pressure is preferably 10 Pa ⁇ s or less. If the viscosity is too small, it may flow in the coating and drying step, and a uniform electrode mixture layer may not be obtained. If it is too large, coating may be difficult.
  • the viscosity can be measured using a measuring device such as a viscometer according to JIS Z 8803.
  • the coating method for applying the prepared electrode mixture to the current collector is arbitrary as long as the effects of the present invention are not significantly impaired.
  • Specific examples of the application method include a roll coating method and a slit die coating method.
  • coating may be performed only by 1 type of methods, and may be performed combining arbitrary 2 or more types of methods.
  • coating may be performed only once, for example, it may dry after apply
  • the application amount when applying the electrode mixture to the electrode is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 10 g / m 2 or more, preferably 20 g / m 2 or more with respect to the one-side surface area of the electrode. More preferably, it is 30 g / m 2 , and the upper limit is usually 500 g / m 2 or less, preferably 350 g / m 2 or less, more preferably 200 g / m 2 or less. If the amount of the electrode mixture is too small, it may be difficult to apply for electrode preparation. If it is too much, the prepared electrode will become more rigid and difficult to handle in the battery assembly process. there is a possibility.
  • drying method after applying the electrode mixture to the current collector is optional as long as the effects of the present invention are not significantly impaired.
  • the drying time is not particularly limited, and it may be dried to such an extent that the active material contained in the electrode mixture can be sufficiently fixed to the current collector.
  • the mixture layer can be brought to a desired density by compressing (pressing) the produced current collector having the electrode mixture layer.
  • compressing pressing
  • the negative electrode active materials contained in the mixture layer come into contact with each other, and current can be input and output, whereby the active material can be used.
  • the compression step is not particularly limited as long as the purpose of the previous period is achieved, but the roll press method is preferable from the viewpoint of productivity. Moreover, you may heat suitably.
  • non-aqueous electrolyte included in the battery according to the present embodiment can also be produced by an arbitrary method as long as the effects of the present invention are not significantly impaired.
  • the nonaqueous electrolyte described in [Nonaqueous Electrolyte] can be dissolved in a nonaqueous solvent so as to have a desired concentration to produce a nonaqueous electrolyte.
  • the large current in the present invention means the amount of current that can be discharged from the upper limit voltage to the lower limit voltage by discharging in less than 1 hour with respect to the initial discharge capacity of the battery to be produced. For example, for a battery with a capacity of 10 Ah, the amount of current that can be discharged in one hour from a fully charged state to a discharged state is 10 A, which is called 1 CA, but a larger amount of current is a large current.
  • the effect of the graphite particle mixing ratio on the discharge capacity retention rate at the 1000th cycle in the charge / discharge cycle was investigated.
  • the negative electrode active material, styrene butadiene rubber (SBR), and carboxymethyl cellulose (CMC, number average polymerization degree 1500, etherification degree 0.7) are mixed so as to be 98: 1: 1.
  • a battery was produced by the method described below. As shown in FIG. 3, it was confirmed that the discharge capacity retention rate tended to improve as the ratio of the polyhedral graphite particles increased as compared with the case where the flaky graphite particles alone were used as the negative electrode active material.
  • the negative electrode mixture layer tends to be exfoliated from the current collector, particularly when the ratio of the polyhedral graphite particles exceeds 40 parts by mass. It was remarkable and it was difficult to produce a battery.
  • Example 1 Scale-like graphite particles having an average particle diameter of 20.5 ⁇ m and a specific surface area of 3.9 ⁇ 10 3 m 2 / kg, and polyhedral graphite particles having an average particle diameter of 5.4 ⁇ m and a specific surface area of 2.5 ⁇ 10 3 m 2 / kg Styrene butadiene rubber (SBR) and carboxymethyl cellulose (CMC, number average polymerization degree 1500, etherification degree 0.7) are 68.46: 29.34: 1.1: 1.1 in weight ratio.
  • SBR Styrene butadiene rubber
  • CMC carboxymethyl cellulose
  • the viscosity was measured using a conical plate viscometer according to JIS Z 8803. Then, the prepared electrode mixture paint is applied to the surface of a copper foil having a thickness of 10 ⁇ m by a roll coating method so that the coating amount is 90 g / m 2, and is sufficiently dried, and further pressed, A negative electrode having a density of 1.5 g / cm 3 was produced.
  • Example 2 A negative electrode was produced in the same manner as in Example 1 except that the content of each component in the electrode mixture was 68.53: 29.37: 1.05: 1.05 by weight.
  • the produced negative electrode mixture paint had a solid content of 50% by weight and a viscosity of 1.7 Pa ⁇ s.
  • Example 3 A negative electrode was produced in the same manner as in Example 1 except that the content of each component in the electrode mixture was 68.53: 29.37: 1: 1.1 by weight.
  • the produced negative electrode mixture paint had a solid content of 50% by weight and a viscosity of 1.7 Pa ⁇ s.
  • Example 4 A negative electrode was produced in the same manner as in Example 1 except that the content of each component in the electrode mixture was 68.53: 29.37: 1.1: 1 by weight.
  • the produced negative electrode mixture paint had a solid content of 50% by weight and a viscosity of 1.6 Pa ⁇ s.
  • Example 5 A negative electrode was produced in the same manner as in Example 1 except that the content of each component in the electrode mixture was 68.53: 29.37: 1.2: 1 by weight.
  • the produced negative electrode mixture paint had a solid content of 50% by weight and a viscosity of 1.7 Pa ⁇ s.
  • Example 1 A negative electrode was produced in the same manner as in Example 1 except that the content of each component in the electrode mixture was 98: 0: 1: 1 by weight, that is, the total amount of graphite particles was scaly graphite particles. did.
  • the produced electrode mixture paint had a solid content of 50% by weight and a viscosity of 2.0 Pa ⁇ s.
  • Example 2 A negative electrode was produced in the same manner as in Example 1 except that the content of each component in the electrode mixture was 68.6: 29.4: 1: 1 by weight.
  • the produced electrode mixture paint had a solid content of 50% by weight and a viscosity of 1.6 Pa ⁇ s.
  • Example 3 A negative electrode was produced in the same manner as in Example 1 except that the content of each component in the electrode mixture was 68.32: 29.28: 1.2: 1.2 by weight ratio.
  • the produced electrode mixture paint had a solid content of 50% by weight and a viscosity of 2.2 Pa ⁇ s.
  • a positive electrode active material lithium manganate
  • a positive electrode conductive agent mixture of graphite and acetylene black
  • a binder polyvinylidene fluoride
  • a slurry of the positive electrode mixture was prepared by dispersing.
  • the produced electrode mixture had a solid content of 60% by weight and a viscosity of 12 Pa ⁇ s. The viscosity was measured by the same method as that for the negative electrode.
  • the prepared electrode mixture was applied to the surface of an aluminum foil having a thickness of 15 ⁇ m by a roll coating method so that the coating amount was 200 g / m 2 , sufficiently dried, further pressed, and the mixture density Produced a positive electrode of 3.0 g / cm 3 .
  • a wound group was produced in which the positive electrode and the negative electrode produced by the above method were wound in a spiral shape through a separator (thickness 25 ⁇ m, width 58 mm) made of a polyethylene porous film. This wound group was inserted into a battery can together with an insulator made of polyethylene. Thereafter, the negative electrode tab was welded to the bottom surface of the battery can, and the positive electrode tab was welded to the positive electrode terminal.
  • FIG. 5 shows a schematic diagram (front view) of the produced nonaqueous electrolyte secondary battery.
  • the left half of FIG. 5 is a schematic view (front view) of a cross section of the nonaqueous electrolyte secondary battery.
  • the positive electrode terminal in FIG. 5 also serves as a sealing lid for the nonaqueous electrolyte secondary battery, and is equipped with a cleavage valve that cleaves to release the pressure inside the battery when the pressure inside the battery rises.
  • the conditions for the charge / discharge evaluation were charging by a constant current-constant voltage method, and termination conditions were an upper limit voltage of 4.1 V and a lower limit current of 20 mA. Further, the discharge was a constant current method, and the termination condition was a lower limit voltage of 2.7V.
  • the initial charge capacity of the batteries averaged 1420 mAh, the initial efficiency averaged 88%, and the battery capacity before evaluation averaged 1249 mAh. Then, the output characteristic in 25 degreeC of the battery charged to SOC (State of Charge) 100% was evaluated.
  • the DCR was calculated from the pre-discharge voltage and the voltage 10 seconds after the start of discharge, assuming that the current value was three conditions of 300 mA, 600 mA, and 1200 mA.
  • the charge / discharge cycle evaluation was performed using two each of the produced batteries. Charging was performed under constant current and constant voltage conditions with a current value of 3A, an upper limit voltage of 4.1V, and a current lower limit of 20mA, and discharging was performed under constant current conditions of a current value of 3A and a lower limit voltage of 2.7V. Furthermore, there was no downtime, that is, a condition was set such that discharging was started immediately at the end of charging, and charging was started immediately at the end of discharging.
  • Table 1 summarizes the composition of the negative electrode mixture, the degree of the mixture layer peeling from the cut surface when the negative electrode was cut, and the DCR and cycle characteristics of the batteries produced in Examples 1 and 2 and Comparative Examples 1 to 3.
  • the cycle characteristics were evaluated by the discharge capacity maintenance rate by inputting and outputting a current of 3 A for both charge and discharge, continuously charging and discharging with an upper limit voltage of 4.1 V and a lower limit voltage of 2.7 V.
  • the discharge capacity retention rate was evaluated in terms of a ratio, with the discharge capacity at 1000 cycles of Comparative Example 1 being 100.
  • Example 1 As shown in Table 1, the negative electrodes produced in Examples and Comparative Examples were each aligned to a width of 56 mm and cut using scissors. The number of cuts was 30 times, the cut length was 1680 mm in total, and peeling of the mixture layer from the cut surface was visually observed. In Examples 1, 2, 4 and 5, no clear peeling was observed. In Comparative Example 1 in which only the scaly graphite particles were used as the active material, no clear peeling was observed. On the other hand, in Comparative Example 2 in which the total amount of binder components was the same as that in Comparative Example 1, many peelings were observed. Moreover, although the tendency which peels off a little also in Example 3 was seen, the remarkable peeling did not arise. In Comparative Example 3 having the largest binder component content, no peeling was observed.
  • the negative electrode which mixed scaly graphite, polyhedral graphite, CMC, and SBR so that it might become 98.0: 0: 1: 1 by weight ratio was used.
  • the total content of the binder components in the mixture layer is 2.1% by mass or more and 2.3% by mass or less.
  • the technique of Comparative Example 1 which is a conventional technique (that is, an electrode containing only scaly graphite as a negative electrode active material), or a binder component content of 2.4% by mass in the mixture layer is compared.
  • the binder component content is an optimal ratio with respect to the active material amount, the durability with respect to the charge / discharge cycle is also improved.
  • the polyhedral graphite particles that are relatively resistant to destruction by repeated charge and discharge are arranged so as to contact the scaly graphite particles. Even if part of the scaly graphite particles is destroyed by the discharge and the fractured part that is not electrically conductive expands, electrical conduction is ensured with the polyhedral graphite particles in contact as a detour, and charging and discharging continue. Be available.
  • the battery having excellent cycle characteristics in the present invention can be suitably used for applications that require large current input / output over a long period of time, particularly for automobiles, railways, and the like.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
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  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
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Abstract

La présente invention vise à proposer une batterie dans laquelle la dégradation de capacité de la batterie a été supprimée par rapport à un cycle de charge/décharge à courant élevé. La batterie rechargeable à électrolyte non aqueux de la présente invention est une batterie rechargeable à électrolyte non aqueux ayant une électrode positive, une électrode négative et un électrolyte non aqueux. Dans cette batterie rechargeable à électrolyte non aqueux, l'électrode négative a une couche de composé d'électrode négative contenant en tant que matières actives d'électrode négative des particules de graphite écailleux et des particules de graphite polyédrique dont la surface a été revêtue de carbone amorphe. De la quantité totale de matières actives contenues dans la couche de composé d'électrode négative, les particules de graphite écailleux sont de préférence de 60 parties en masse ou plus à 90 parties en masse ou moins, les particules de graphite polyédrique sont de préférence de 10 parties en masse ou plus à 40 parties en masse ou moins, et la surface des particules de graphite écailleux est de préférence revêtue de carbone amorphe. Egalement, le composant liant dans la couche de composé d'électrode négative est de préférence de 2,05 parties en masse ou plus à 2,35 parties en masse ou moins de la couche de composé total.
PCT/JP2011/068019 2011-08-08 2011-08-08 Batterie rechargeable à électrolyte non aqueux WO2013021443A1 (fr)

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JP2014175153A (ja) * 2013-03-08 2014-09-22 Toyota Industries Corp 電極及び蓄電装置
JP2014229517A (ja) * 2013-05-23 2014-12-08 日立化成株式会社 リチウムイオン二次電池用負極材、リチウムイオン二次電池用負極及びリチウムイオン二次電池
JP2015052547A (ja) * 2013-09-09 2015-03-19 トヨタ自動車株式会社 計測装置、電極板製造装置及びこれらの方法
KR101605682B1 (ko) * 2013-08-23 2016-03-23 주식회사 엘지화학 분산성이 우수한 도전재를 포함하는 이차전지용 전극 슬러리 및 이를 포함하는 이차전지
US20210002496A1 (en) * 2018-02-28 2021-01-07 Battrion Ag Method for production of a coating
WO2021111931A1 (fr) * 2019-12-06 2021-06-10 三洋電機株式会社 Batterie secondaire à électrolyte non aqueux
WO2021117480A1 (fr) * 2019-12-09 2021-06-17 三洋電機株式会社 Batterie secondaire à électrolyte non aqueux
CN114616708A (zh) * 2019-10-31 2022-06-10 三洋电机株式会社 非水电解质二次电池

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JP2014175153A (ja) * 2013-03-08 2014-09-22 Toyota Industries Corp 電極及び蓄電装置
JP2014229517A (ja) * 2013-05-23 2014-12-08 日立化成株式会社 リチウムイオン二次電池用負極材、リチウムイオン二次電池用負極及びリチウムイオン二次電池
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CN114616708A (zh) * 2019-10-31 2022-06-10 三洋电机株式会社 非水电解质二次电池
WO2021111931A1 (fr) * 2019-12-06 2021-06-10 三洋電機株式会社 Batterie secondaire à électrolyte non aqueux
WO2021117480A1 (fr) * 2019-12-09 2021-06-17 三洋電機株式会社 Batterie secondaire à électrolyte non aqueux

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