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WO2009151054A1 - Film poreux pour séparateur, séparateur de batterie, électrode de batterie et leurs procédés de fabrication, et batterie secondaire au lithium - Google Patents

Film poreux pour séparateur, séparateur de batterie, électrode de batterie et leurs procédés de fabrication, et batterie secondaire au lithium Download PDF

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Publication number
WO2009151054A1
WO2009151054A1 PCT/JP2009/060538 JP2009060538W WO2009151054A1 WO 2009151054 A1 WO2009151054 A1 WO 2009151054A1 JP 2009060538 W JP2009060538 W JP 2009060538W WO 2009151054 A1 WO2009151054 A1 WO 2009151054A1
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Prior art keywords
separator
inorganic oxide
oxide particles
battery
porous membrane
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Ceased
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PCT/JP2009/060538
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English (en)
Japanese (ja)
Inventor
阿部浩史
阿部敏浩
松本修明
片山秀昭
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Maxell Ltd
Original Assignee
Hitachi Maxell Ltd
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Filing date
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Priority claimed from JP2008150186A external-priority patent/JP2009032677A/ja
Application filed by Hitachi Maxell Ltd filed Critical Hitachi Maxell Ltd
Priority to KR1020107026558A priority Critical patent/KR101229902B1/ko
Priority to US12/989,897 priority patent/US8920960B2/en
Priority to CN200980121546XA priority patent/CN102057518A/zh
Priority to JP2010516860A priority patent/JP5530353B2/ja
Publication of WO2009151054A1 publication Critical patent/WO2009151054A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a porous membrane for a separator for forming a lithium secondary battery having excellent dimensional stability at high temperatures and little deterioration in properties during long-term use and long-term storage, a method for producing the same, and the porous membrane for a separator
  • the present invention relates to a battery separator provided with a separator, a manufacturing method thereof, a battery electrode provided with the separator porous membrane and a manufacturing method thereof, and a lithium secondary battery using the battery separator or the battery electrode.
  • a lithium secondary battery which is a typical battery using a non-aqueous electrolyte, is widely used as a power source for portable devices such as mobile phones and notebook personal computers because of its high energy density.
  • Lithium secondary batteries use chemically highly active lithium ions and electrolytes containing non-flammable organic solvents (non-aqueous electrolytes) to prevent ignition and smoke during abnormal conditions. Safety mechanisms are in place. As the performance of portable devices and the like increases, the capacity of lithium secondary batteries tends to increase further, and it is important to ensure further safety and reliability.
  • a polyolefin microporous film having a thickness of about 20 to 30 ⁇ m is used as a separator interposed between a positive electrode and a negative electrode.
  • the above-mentioned separator that is currently widely used tends to shrink when the inside of the battery becomes very hot, and there is a risk of short circuit. Therefore, studies have been made to further improve the safety and reliability of lithium secondary batteries by improving the separator.
  • Patent Documents 1 to 4 propose that an electrochemical element such as a lithium secondary battery is formed by a separator having filler particles having good heat resistance and a resin component for ensuring a shutdown function. Yes.
  • JP 2000-30686 A International Publication No. 2006/62153 JP 2007-273443 A JP 2007-280911 A
  • Patent Documents 1 to 4 by using a porous substrate with good heat resistance and a separator formed using filler particles, thermal runaway is unlikely to occur even in the event of abnormal overheating, and excellent safety A lithium secondary battery can be provided.
  • the present invention has been made in view of the above circumstances, and has a high reliability and a porous membrane for a separator for forming a lithium secondary battery with less characteristic deterioration during long-term use and long-term storage;
  • a battery separator and an electrode provided with the porous membrane for a separator are provided, and a lithium secondary battery using the battery separator or the electrode is provided.
  • the separator porous membrane of the present invention is a porous membrane containing inorganic oxide particles and a binder for binding the inorganic oxide particles, the inorganic oxide particles containing boehmite, and the porous
  • the amount of Na contained in the film is 1000 ppm or less.
  • the battery separator of the present invention is characterized by including the separator porous film of the present invention and a microporous film having a heat-meltable resin layer having a melting point of 80 to 140 ° C.
  • the battery electrode of the present invention is a battery electrode including an active material-containing layer and the separator porous membrane of the present invention, and the active material layer and the separator porous membrane are integrated with each other. It is characterized by that.
  • the lithium secondary battery of the present invention is a lithium secondary battery including a positive electrode, a negative electrode, a separator and a non-aqueous electrolyte, wherein the separator is the battery separator of the present invention.
  • another aspect of the lithium secondary battery of the present invention is a lithium secondary battery including a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte, wherein at least one of the positive electrode and the negative electrode is the book. It is the battery electrode of the invention.
  • the method for producing a porous membrane for a separator according to the present invention includes a step of washing inorganic oxide particles with water to reduce the amount of alkali metal element contained in the inorganic oxide particles to 1000 ppm or less, and the inorganic oxide particles And a step of forming a porous film containing the inorganic oxide particles by binding with a binder.
  • the method for producing a battery separator of the present invention includes a step of washing the inorganic oxide particles with water to reduce the amount of alkali metal element contained in the inorganic oxide particles to 1000 ppm or less, and the inorganic oxide particles as a binder. And forming a porous film containing the inorganic oxide particles on a microporous film having a heat-meltable resin layer having a melting point of 80 to 140 ° C.
  • the method for producing a battery electrode of the present invention includes a step of washing the inorganic oxide particles with water to reduce the amount of alkali metal element contained in the inorganic oxide particles to 1000 ppm or less, and the inorganic oxide particles as a binder. And forming a porous film including the inorganic oxide particles on the electrode including the active material-containing layer.
  • the present invention it is possible to provide a lithium secondary battery having high reliability and having little characteristic deterioration during long-term use and long-term storage.
  • FIG. 1A is a schematic plan view of a lithium secondary battery of the present invention
  • FIG. 1B is a schematic cross-sectional view of the lithium secondary battery of the present invention
  • FIG. 2 is a schematic external view of the lithium secondary battery of the present invention.
  • the porous membrane forming the battery separator of the present invention is a porous membrane formed by containing inorganic oxide particles and binding the inorganic oxide particles with a binder.
  • the inorganic oxide particles include boehmite, and the amount of alkali metal element, particularly Na, contained in the porous film is 1000 ppm or less (mass basis, the same applies hereinafter).
  • alkali metal elements contained in the separator alkali metal elements that exist in a state that can be eluted in water, particularly Na, were repeatedly charged and discharged for a long time or stored for a long time.
  • cause deterioration of characteristics That is, it is considered that the side reaction of the organic solvent in the nonaqueous electrolytic solution occurs in the battery due to the alkali metal element in the separator. Due to this side reaction, gas is generated particularly when the battery is stored for a long time in a charged state, and the battery capacity decreases due to battery swelling, etc., and the irreversible capacity increases due to the side reaction. It seems that the battery capacity decreases when charging and discharging are repeated.
  • the separator porous membrane of the present invention by setting the amount of alkali metal element in the separator, particularly Na, to 1000 ppm or less, side reactions of the organic solvent that occur when the separator is configured can be suppressed, and the battery can be stored for a long time. It suppresses the capacity drop at the time and the capacity drop when it is used over a long period of time and is repeatedly charged and discharged.
  • the alkali metal element contains the above-mentioned elements such as hydroxides, oxides, carbonates, etc., in addition to metals composed of these elements and alloys containing these elements.
  • the “amount of alkali metal element” and “amount of Na” referred to in the present specification are intended samples (porous membrane for separator, separator, and inorganic oxide particles described later).
  • 0.5 g is immersed in 25 cm 3 of ion exchange water at 25 ° C. for 12 hours, the ion exchange water after immersion is diluted 10 times, and the amount of the alkali metal element eluted in the ion exchange water is inductively coupled. It is a value determined by high-frequency plasma spectroscopic analysis (ICP spectroscopic analysis) and obtained as a ratio to the weight of the original sample (weight including the alkali metal element).
  • ICP spectroscopic analysis high-frequency plasma spectroscopic analysis
  • the amount of the alkali metal element in the separator is preferably as small as possible, and is most preferably 0 ppm.
  • boehmite is used as the inorganic oxide particles, it is possible to produce a separator that does not contain any alkali metal element. It is difficult, and the normal lower limit value seems to be about 10 ppm.
  • the porous membrane for a separator of the present invention contains inorganic oxide particles, and the inorganic oxide particles contain boehmite.
  • the separator of the present invention by providing the separator porous membrane, in the temperature range where the battery is normally used, the positive electrode and the negative electrode are pressed through the separator to form an electrode body. Can be prevented from being short-circuited by penetrating the separator and coming into contact with the negative electrode.
  • the presence of the inorganic oxide particles suppresses the thermal shrinkage of the separator and maintains its shape. A short circuit due to contact can also be prevented. Therefore, batteries using the separator of the present invention (batteries such as the lithium secondary battery and non-aqueous electrolyte primary battery of the present invention) are excellent in safety and reliability.
  • the porous membrane for a separator of the present invention has a configuration mainly composed of inorganic oxide particles, that is, a constituent of the porous membrane (however, it is constituted by a fibrous material described later). It is desirable to employ a configuration in which the inorganic oxide particles are 50% by volume or more in the entire volume of the sheet.
  • boehmite represented by the composition formula such as AlOOH or Al 2 O 3 ⁇ H 2 O is contained a lot of their preparation on an alkali metal element, of commercially available, the amount of generally alkali metal element It exceeds 1000ppm. Also, in other inorganic oxide particles, the amount of alkali metal element may exceed 1000 ppm depending on the production method.
  • the amount of alkali metal element, particularly the amount of Na is preferably 1000 ppm or less, more preferably 600 ppm or less. Preferably, 0 ppm is most preferable.
  • alkali metal elements Na has a particularly strong effect of lowering the long-term storage characteristics and charge / discharge cycle characteristics of the battery. Therefore, by reducing the amount of Na in the inorganic oxide particles as described above, the effect of the present invention is further improved. Prominently played.
  • the method for removing the alkali metal element from the inorganic oxide particles is not particularly limited as long as other impurities are not mixed in.
  • the method of washing the inorganic oxide particles with water is simple and advantageous in terms of cost. Because it is, it is recommended.
  • the washing of the inorganic oxide particles with water may be repeated, for example, batchwise until the amount of alkali metal element is 1000 ppm or less (preferably until the amount of Na is 600 ppm or less), or may be performed continuously. Also good.
  • the treatment should be performed until the amount of the alkali metal element, particularly Na, is about 10 to 500 ppm.
  • the alkali metal element is present as a water-soluble compound exhibiting alkalinity such as hydroxide or carbonate, the alkali metal element is washed with an aqueous solution in which an inorganic acid such as hydrochloric acid or an organic acid such as citric acid is dissolved. Can be removed faster or more.
  • the inorganic oxide particles have heat resistance and electrical insulation, are stable with respect to the electrolyte, and are electrochemically stable that are not easily oxidized or reduced in the operating voltage range of the battery.
  • the heat resistance for example, it is desired that the material does not deform to a temperature of 150 ° C. or higher, preferably 180 ° C. or higher.
  • boehmite is particularly preferably used.
  • boehmite generally contains a large amount of alkali metal elements derived from the production method thereof, so that the effect of the present invention is particularly remarkable when boehmite is contained in the separator.
  • the present invention is also preferably used for inorganic oxide particles containing a large amount of eluted alkali metal elements.
  • the average particle size of the inorganic oxide particles is 0.01 ⁇ m or more, since the battery characteristics can be improved by increasing the gap between the particles to some extent and shortening the ion conduction path. Is more preferable, and it is more preferably 0.1 ⁇ m or more. On the other hand, when the particle size of the inorganic oxide particles is too large, the gap between the particles becomes too large, and a short circuit due to lithium dendrite may easily occur. Therefore, the average particle diameter of the inorganic oxide particles is preferably 10 ⁇ m or less, and more preferably 5 ⁇ m or less.
  • the average particle size of the particles in the present specification is measured by dispersing the particles in a medium that does not swell or dissolve the particles (for example, water) using a laser scattering particle size distribution analyzer (for example, “LA-920” manufactured by HORIBA).
  • the particle diameter at 50% (D50%) in the integrated volume-based fraction is measured by dispersing the particles in a medium that does not swell or dissolve the particles (for example, water) using a laser scattering particle size distribution analyzer (for example, “LA-920” manufactured by HORIBA).
  • the shape of the inorganic oxide particles may be any of amorphous, granular, plate-like, cubic, etc., and may be primary particles or secondary particles may be formed.
  • the path between the positive electrode and the negative electrode in the separator that is, the so-called curvature can be increased, and even when dendrite is generated in the battery, Since it becomes difficult for the dendrite to reach the positive electrode from the negative electrode, the reliability of the dendrite short circuit can be further increased.
  • secondary particles it is possible to improve the load characteristics of the battery while effectively suppressing a short circuit due to the dendrite.
  • the aspect ratio (ratio between the maximum length of the plate-like particles and the thickness of the plate-like particles) can increase the reliability improvement effect against dendritic shorts by orienting the particles. It is preferably 2 or more, more preferably 5 or more, and still more preferably 10 or more.
  • the aspect ratio of the plate-like inorganic oxide particles is preferably 100 or less, and 50 or less. More preferably.
  • the aspect ratio can be obtained by analyzing an image of particles photographed by a scanning electron microscope (SEM).
  • the presence form in the separator is preferably such that the flat plate surface is parallel or substantially parallel to the separator surface, more specifically, the plate shape in the vicinity of the separator surface.
  • the average angle between the flat plate surface and the separator surface is preferably 30 ° or less. Most preferably, the average angle is 0 °, that is, a plate-like flat plate surface in the vicinity of the surface of the separator is parallel to the separator surface.
  • Near the surface refers to a range of about 10% from the surface of the separator to the entire thickness.
  • the ratio of the inorganic oxide particles in the porous membrane constituting the separator is a component of the porous membrane (however, described later) from the viewpoint of ensuring the function (particularly the short-circuit preventing function) by the inorganic oxide particles.
  • the sheet-like material is not included in the constituent components. Is more preferable.
  • the ratio of the inorganic oxide particles is preferably 99.5% by volume or less, and 99% by volume or less. Is more preferable.
  • the thickness of the porous film is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more from the viewpoint of ensuring a short-circuit prevention function, and on the other hand, improvement of battery energy density and impedance reduction. In view of the above, it is preferably 15 ⁇ m or less, and more preferably 10 ⁇ m or less.
  • the porous membrane can be used alone as a separator, but it is desirable to constitute the separator together with a microporous membrane having a heat-meltable resin layer having a melting point of 80 to 140 ° C. Since the separator has the microporous membrane, when the separator receives heat due to abnormal overheating or the like in the battery, the heat-melting resin is melted to cause a so-called shutdown that closes the separator gap. Can increase the sex. In this case, it is preferable to form the porous film on the microporous film because the shrinkage of the hot-melt resin layer when the temperature of the separator further increases after shutdown occurs can be suppressed.
  • the heat-meltable resin has the melting point described above, has electrical insulation, is stable with respect to the electrolyte, and is electrochemically stable that is not easily oxidized or reduced in the operating voltage range of the battery.
  • PE polyethylene
  • copolymerized polyolefin for example, a copolymer having a structural unit derived from ethylene of 85 mol% or more
  • polyolefin derivative such as chlorinated polyethylene
  • polyolefin wax such as chlorinated polyethylene
  • petroleum wax such as carnauba Wax etc.
  • copolymer polyolefin examples include an ethylene-propylene copolymer, an ethylene-vinyl monomer copolymer, more specifically, an ethylene-vinyl acetate copolymer (EVA), an ethylene-methyl acrylate copolymer, or an ethylene- An ethyl acrylate copolymer can be illustrated.
  • EVA ethylene-vinyl acetate copolymer
  • polycycloolefin etc. can also be used.
  • the melting point of the heat-meltable resin is more preferably 130 ° C. or lower in order to keep the temperature at which shutdown occurs low.
  • the melting point of the heat-meltable resin can be defined by the melting temperature measured using a differential scanning calorimeter (DSC) according to the Japanese Industrial Standard (JIS) K 7121.
  • DSC differential scanning calorimeter
  • JIS Japanese Industrial Standard
  • a hot-melt resin having a temperature of 80 to 140 ° C. may be used.
  • the heat-meltable resin may be only one kind of the above-mentioned constituent materials, or may be composed of two or more kinds.
  • PE ethylene-propylene copolymer, polyolefin wax, or EVA having a structural unit derived from ethylene of 85 mol% or more is preferable.
  • the microporous film having a heat-meltable resin layer having a melting point of 80 to 140 ° C. may be composed of only a porous resin layer made of a heat-meltable resin of 80 to 140 ° C.
  • a laminated film in which a heat-meltable resin layer at 0 ° C. and a porous resin layer having higher heat resistance are laminated may be used.
  • the heat-meltable resin layer having a melting point of 80 to 140 ° C. may contain a resin or filler having higher heat resistance.
  • microporous film a commercially available microporous film made of a hot-melt resin such as a polyethylene microporous film or a laminated film of a polyethylene microporous film and a polypropylene microporous film can be preferably used.
  • the particles formed of the heat-meltable resin may be integrated with a binder or the like to form a microporous film.
  • the thickness of the microporous membrane is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more.
  • 30 ⁇ m It is preferable to set it as follows, and it is more preferable to set it as 15 micrometers or less.
  • the ratio of the inorganic oxide particles in the separator is 10% by volume or more in the total volume of the constituent components of the separator from the viewpoint of ensuring the function of the inorganic oxide particles (particularly the function of preventing short circuit). Preferably, it is more preferably 30% by volume or more, and particularly preferably 40% by volume or more. On the other hand, the ratio of the inorganic oxide particles in the separator is preferably 80% by volume or less.
  • the separator contains a sheet-like material composed of a fibrous material described later, the volume ratio of the inorganic oxide particles is shown as a ratio in the total volume of the constituent components of the separator excluding the sheet-like material. It is.
  • the thickness (total thickness) of the porous membrane is 10% or more of the thickness (total thickness) of the microporous membrane. Is preferable, and is more preferably 20% or more. This is because it becomes easy to suppress thermal shrinkage of the microporous film at a high temperature.
  • the porous membrane for a separator of the present invention or the separator of the present invention may contain a fibrous material as a reinforcing material for increasing the strength.
  • the fibrous material is not particularly limited as long as it has electrical insulating properties, is electrochemically stable, and is stable to a nonaqueous electrolytic solution described in detail later. Those that do not deform (those that are not visually observed even when heated to 150 ° C.) are desirable.
  • the fibrous material When the fibrous material is contained in the separator porous membrane, the fibrous material can be bound together with inorganic oxide particles with a binder to form a porous membrane, and the sheet formed of the fibrous material A porous film can also be formed by holding inorganic oxide particles in the voids of the material and fixing them with a binder.
  • the fibrous material when the fibrous material is included in the microporous membrane, the fibrous material can be bound with a heat-melting resin particle having a melting point of 80 to 140 ° C. with a binder to form a porous resin layer.
  • the porous resin layer can be formed by holding the heat-meltable resin particles in the voids of the sheet-like material formed by the fibrous material and fixing them with a binder.
  • the strength of the separator can be improved without impairing the heat resistance of the separator, and when the separator is wound together with an electrode, it is inorganic. It is more preferable because the oxide particles can be prevented from falling off.
  • fibrous material refers to those having an aspect ratio [length in the long direction / width in the direction perpendicular to the long direction (diameter)] of 4 or more.
  • the aspect ratio of the fibrous material is preferably 10 or more.
  • the constituent material of the fibrous material examples include, for example, cellulose, modified cellulose (such as carboxymethyl cellulose), polypropylene (PP), polyester [polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), etc.] , Resins such as polyacrylonitrile (PAN), polyvinyl alcohol (PVA), aramid, polyamideimide, and polyimide; inorganic materials (inorganic oxides) such as glass, alumina, and silica; and the like.
  • the fibrous material may contain one kind of these constituent materials, or may contain two or more kinds. Further, the fibrous material may contain various additives (for example, an antioxidant in the case of a resin) as a constituent component, if necessary, in addition to the constituent materials described above.
  • the diameter of the fibrous material may be not more than the thickness of the separator, but is preferably 0.01 to 5 ⁇ m, for example. If the diameter is too large, when using a sheet-like material formed by gathering a large number of fibers described later, the entanglement between the fibrous materials is insufficient, the strength of the sheet-like material formed with these, The effect of improving the strength of the separator by using a fibrous material may be reduced. On the other hand, if the diameter of the fibrous material is too small, the gap of the separator becomes too small and the ion permeability tends to decrease, and the load characteristics may be deteriorated in a battery using this.
  • a material in which a large number of fibrous materials are aggregated to form a sheet material for example, a material such as a woven fabric, a nonwoven fabric, or paper is preferably used. It can be set as the separator of the structure which hold
  • the inorganic oxide particles and the like can be fixed with a binder or the like as necessary.
  • the basis weight (basis weight) is used to ensure the preferred volume ratio of the inorganic oxide particles or to ensure the mechanical strength such as the tensile strength of the sheet-like material.
  • the thickness is preferably 3 to 30 g / m 2, and the thickness is preferably 7 to 20 ⁇ m.
  • the amount of the fibrous material in the separator is preferably 10 to 50% by volume in the total volume of the constituent components of the separator including the fibrous material.
  • the separator of the present invention may contain fillers other than the inorganic oxide particles, particles composed of the above-described hot-melt resin, and the like.
  • the filler may be any material that has electrical insulation, is stable to the non-aqueous electrolyte of the battery, and does not cause side reactions such as oxidation / reduction in the operating voltage range of the battery.
  • Inorganic nitrides such as silicon nitride; poorly soluble ion-binding compounds such as calcium fluoride, barium fluoride, and barium sulfate; covalent bonding compounds such as silicon and diamond; clays such as montmorillonite;
  • the surface of a conductive material exemplified by a metal, a conductive oxide such as SnO 2 and tin-indium oxide (ITO), a carbonaceous material such as carbon black and graphite, etc. is coated with a material having electrical insulation.
  • grains which gave electrical insulation by this may be sufficient.
  • fillers include various cross-linking polymers such as cross-linked polymethyl methacrylate, cross-linked polystyrene, cross-linked polydivinylbenzene, styrene-divinylbenzene copolymer cross-linked product, polyimide, melamine resin, phenol resin, and benzoguanamine-formaldehyde condensate. Resins such as molecules; heat-resistant polymers such as PP, polysulfone, polyethersulfone, polyphenylene sulfide, polytetrafluoroethylene, PAN, aramid, polyacetal, and thermoplastic polyimide can also be exemplified.
  • cross-linking polymers such as cross-linked polymethyl methacrylate, cross-linked polystyrene, cross-linked polydivinylbenzene, styrene-divinylbenzene copolymer cross-linked product, polyimide, melamine resin, phenol resin, and benzo
  • These resins include mixtures of the above-mentioned materials, modified products, derivatives, copolymers (random copolymers, alternating copolymers, block copolymers, graft copolymers), and cross-linked products of the heat-resistant polymers. It may be.
  • the average particle diameter of the filler and the heat-meltable resin particles is preferably 0.001 ⁇ m or more, more preferably 0.1 ⁇ m or more, and preferably 15 ⁇ m or less, as D50% obtained by the measurement method. Preferably it is 1 micrometer or less.
  • porous membrane for a separator of the present invention or the separator of the present invention binds inorganic oxide particles to each other, or combines with inorganic oxide particles and a fibrous material used as necessary (and its A binder may be contained for the purpose of binding sheet-like materials), fillers, hot-melt resin particles and the like.
  • any binder may be used as long as it is electrochemically stable and stable with respect to the non-aqueous electrolyte, and can adhere well to inorganic oxide particles, fibrous materials, fillers, hot-melt resin particles, and the like.
  • EVA with a structural unit derived from vinyl acetate of 20 to 35 mol%
  • ethylene-acrylic acid copolymer such as ethylene-ethyl acrylate copolymer, fluorine-based rubber, styrene butadiene rubber (SBR), carboxy
  • SBR styrene butadiene rubber
  • carboxy Examples include methyl cellulose (CMC), hydroxyethyl cellulose (HEC), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinyl pyrrolidone (PVP), polyurethane, and epoxy resin, and these may be used alone. More than one species may be used in combination.
  • the binder is preferably a material that does not melt or de
  • the hot-melt resin when the above-described hot-melt resin functions also as a binder, the hot-melt resin can also be used as a binder.
  • these binders When these binders are used, they can be used in the form of an emulsion or plastisol dissolved or dispersed in a solvent of a composition for forming a separator described later.
  • some binders have a form of an alkali metal salt such as Na, and alkali metal elements such as Na are mixed into the binder solution or emulsion due to the surfactant.
  • these alkali metal elements may increase the amount of alkali metal elements in the separator. Therefore, in the separator of the present invention, it is desirable to use a material with a small amount of the alkali metal element (particularly an alkali metal element present in a state that can be eluted in water) for the constituent materials other than the inorganic oxide particles. .
  • the thickness of the separator is preferably 3 ⁇ m or more, and more preferably 5 ⁇ m or more.
  • the thickness of the separator is preferably 50 ⁇ m or less, and more preferably 30 ⁇ m or less.
  • the porosity of the separator is preferably 20% or more, and preferably 30% or more in a dried state, in order to secure the liquid retention amount of the non-aqueous electrolyte and to improve the ion permeability. It is more preferable.
  • the porosity of the separator is preferably 70% or less, and more preferably 60% or less, in a dry state.
  • the porosity of the separator: P (%) can be calculated by obtaining the sum for each component i from the thickness of the separator, the mass per unit area, and the density of the constituent components using the following formula (1).
  • a i ratio of component i expressed by mass%
  • ⁇ i density of component i (g / cm 3 )
  • m mass per unit area of separator (g / cm 2 )
  • t The thickness (cm) of the separator.
  • the separator of the present invention is measured by a method according to JIS P 8117, and has a Gurley value (air permeability) indicated by the number of seconds that 100 ml of air passes through the membrane under a pressure of 0.879 g / mm 2. 10 to 300 sec is desirable. If the air permeability is too high, the ion permeability is reduced, whereas if it is too low, the strength of the separator may be reduced. Further, the strength of the separator is desirably 50 g or more in terms of piercing strength using a needle having a diameter of 1 mm. If the piercing strength is too low, a short circuit may occur due to the breakthrough of the separator when lithium dendrite crystals are generated.
  • ⁇ Manufacturing method (I)> In the production method (I), a separator-forming composition (slurry or the like) containing inorganic oxide particles and a solvent is added to an ion-permeable sheet-like material (various woven fabrics, nonwoven fabrics, etc.) composed of fibrous materials. In this method, coating is performed with a blade coater, a roll coater, a die coater or the like, and then dried at a predetermined temperature.
  • the “sheet-like material” as used in the present production method includes a porous sheet such as a non-woven fabric composed of at least one of the fibrous materials and having a structure in which these fibrous materials are entangled with each other. More specifically, nonwoven fabrics such as paper, PP nonwoven fabric, polyester nonwoven fabric (PET nonwoven fabric, PEN nonwoven fabric, PBT nonwoven fabric, etc.) and PAN nonwoven fabric are preferably used.
  • the composition for forming a separator contains inorganic oxide particles and, if necessary, other fillers, hot-melt resin particles, a binder, and the like, and these are dispersed in a solvent (including a dispersion medium, the same applies hereinafter). It is a thing. However, the binder may be dissolved in a solvent.
  • the solvent used in the composition for forming a separator may be any solvent that can uniformly disperse inorganic oxide particles, fillers, hot-melt resin particles, and the like, and can dissolve or disperse the binder uniformly.
  • organic solvents such as aromatic hydrocarbons such as tetrahydrofuran, furans such as tetrahydrofuran, and ketones such as methyl ethyl ketone and methyl isobutyl ketone are preferably used.
  • alcohols ethylene glycol, propylene glycol, etc.
  • various propylene oxide glycol ethers such as monomethyl acetate may be appropriately added to these solvents.
  • water may be used as a solvent.
  • alcohols methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, etc.
  • the interfacial tension can be controlled.
  • the solid content containing inorganic oxide particles, fillers, hot-melt resin particles and binder is preferably set to 30 to 70% by mass, for example.
  • the composition for forming a separator may not be a single composition containing all of inorganic oxide particles, heat-meltable resin particles, a binder, and the like.
  • plural types of compositions having different compositions are used, such as using two types of compositions, ie, a composition (1) containing inorganic oxide particles and a binder and a composition (2) containing hot-melt resin particles.
  • the composition (1) is first applied to a sheet and dried to form a support layer (porous separator membrane). After that, the composition (2) is applied and dried to form a shutdown layer, whereby a separator having a plurality of layers can be produced.
  • the support layer (the separator porous membrane) may be used alone as a separator, and is combined with the above-mentioned microporous membrane having a heat-meltable resin layer having a melting point of 80 to 140 ° C. It can also be.
  • the support layer (porous separator film) and the shutdown layer (heat-meltable resin layer) may have at least one of a plurality.
  • the sheet-like material is composed of a fibrous material such as paper, PP nonwoven fabric, polyester nonwoven fabric or the like, and the opening diameter of the gap is relatively large (for example, the opening diameter of the gap). This is likely to cause a short circuit of the battery. Therefore, in such a case, it is preferable to have a structure in which some or all of the inorganic oxide particles are present in the voids of the sheet-like material. Further, it is more preferable that the filler other than the inorganic oxide particles and the heat-meltable resin particles have a structure in which part or all of them are present in the voids of the sheet-like material. The effect of use can be exhibited more effectively.
  • a separator-forming composition containing these is applied to the sheet-like material and then passed through a certain gap.
  • a method such as drying after removing the excess composition may be used.
  • a separator-forming composition containing inorganic oxide particles is applied and impregnated on a sheet-like material in order to enhance its orientation and to exert its action more effectively. Thereafter, a method of applying a shear or a magnetic field to the composition may be used. For example, as described above, after the separator-forming composition is applied to a sheet-like material, the composition can be shared by passing through a certain gap.
  • the separator-forming composition shown in the production method (I) further contains a fibrous material as necessary, and this is applied onto a substrate such as a film or metal foil, In this method, the substrate is peeled from the substrate after being dried at a temperature of 1.
  • the composition for forming a separator used in the production method is the same as the composition for forming a separator according to the production method (I) except that a fibrous material is contained as necessary.
  • two or more kinds of compositions are used as a separator forming composition as necessary, and a separator having a plurality of layers is obtained by applying each composition separately. It can also be formed.
  • a support layer (a porous membrane for a separator) formed by a composition containing a fibrous material in the composition (1) may be used alone as a separator, as described above.
  • the separator may be combined with a microporous film having a heat-meltable resin layer having a melting point of 80 to 140 ° C.
  • the composition containing the fibrous material in the composition (1) is applied on the microporous membrane, dried at a predetermined temperature to form a separator, and formed. It is not necessary to peel the separator porous membrane from the microporous membrane.
  • a separator having a plurality of at least one of a support layer (a separator porous membrane) and a shutdown layer (a heat-meltable resin layer) can be formed.
  • a support layer a separator porous membrane
  • a shutdown layer a heat-meltable resin layer
  • the separator tends to warp toward the coating surface in the drying step of removing the solvent of the composition to make it porous, In the winding process of the separator, the slit, or the winding with the electrode, there is a risk that the defect occurrence rate is increased. In such a case, warpage of the separator can be suppressed by using plate-like particles as inorganic oxide particles, fillers, and the like.
  • the thickness (total thickness) of the porous membrane is preferably 10% or more of the thickness (total thickness) of the microporous membrane. 20% or more is more preferable. This is because it becomes easy to suppress thermal shrinkage of the microporous film at a high temperature.
  • the thickness (total thickness) of the porous membrane is preferably 50% or less, more preferably 40% or less of the thickness (total thickness) of the microporous membrane. preferable.
  • the separator obtained by the production method (II) when a fibrous material is used to form a sheet-like material, inorganic oxide particles, fillers, and hot-melt resin particles are formed in the voids of the sheet-like material. It is preferable to have a structure in which a part or all of is present, and when plate-like inorganic oxide particles are used, the inorganic oxide particles are preferably oriented.
  • the separator obtained by this production method in order to make some or all of the various particles exist in the voids of the sheet-like material, the separator is formed using the fibrous material and the composition for forming a separator containing these particles. do it.
  • the same method as described in the production method (I) can be used.
  • the composition for forming a separator according to the production method (I) or the production method (II) is applied to the surface of a battery electrode (positive electrode or negative electrode described later), for example, the surface of an active material-containing layer.
  • coating is performed with a coater, roll coater, die coater or the like and then dried at a predetermined temperature.
  • the porous membrane for a separator of the present invention or an electrode integrated with the separator of the present invention can be produced.
  • porous membrane for a separator and the separator of the present invention are not limited to those having the above structure.
  • the inorganic oxide particles may be present independently of each other, and some of them may be fused to each other or to a fibrous material.
  • the battery separator and the electrode of the present invention can be used for both a primary battery and a secondary battery as long as the battery uses a non-aqueous electrolyte. (Especially, prevention of characteristic deterioration during long-term use) is particularly remarkable.
  • the lithium secondary battery of the present invention only needs to use the battery separator of the present invention, and there are no particular restrictions on the other configurations and structures, and the configurations and structures employed in conventional lithium secondary batteries are the same. Can be applied.
  • Examples of the form of the lithium secondary battery include a cylindrical shape (such as a rectangular tube shape or a cylindrical shape) using a steel can or an aluminum can as an outer can. Moreover, it can also be set as the soft package battery which used the laminated film which vapor-deposited the metal as an exterior body.
  • the positive electrode is not particularly limited as long as it is a positive electrode used in a conventional lithium secondary battery, that is, a positive electrode containing an active material capable of occluding and releasing Li ions.
  • a positive electrode active material a lithium-containing transition metal oxide having a layered structure represented by Li 1 + x MO 2 ( ⁇ 0.1 ⁇ x ⁇ 0.1, M: Co, Ni, Mn, Al, Mg, etc.), It is possible to use LiMn 2 O 4 , a spinel-structure lithium manganese oxide obtained by substituting some of its elements with other elements, or an olivine type compound represented by LiMPO 4 (M: Co, Ni, Mn, Fe, etc.). Is possible.
  • lithium-containing transition metal oxide having a layered structure examples include LiCoO 2 and LiNi 1-x Co xy Al y O 2 (0.1 ⁇ x ⁇ 0.3, 0 ⁇ y ⁇ 0.2).
  • an oxide containing at least Co, Ni, and Mn LiMn 1/3 Ni 1/3 Co 1/3 O 2 , LiMn 5/12 Ni 5/12 Co 1/6 O 2 , LiNi 3/5 Mn 1/5 Co 1/5 O 2 etc.).
  • a positive electrode active material-containing layer can be formed, for example, on a current collector by using a positive electrode mixture in which a positive electrode active material is mixed, thereby forming a positive electrode.
  • a metal foil such as aluminum, a punching metal, a net, an expanded metal, or the like can be used.
  • an aluminum foil having a thickness of 10 to 30 ⁇ m is preferably used.
  • the lead portion on the positive electrode side is usually provided by leaving the exposed portion of the current collector without forming the positive electrode active material-containing layer on a part of the current collector and forming the lead portion at the time of producing the positive electrode.
  • the lead portion is not necessarily integrated with the current collector from the beginning, and may be provided by connecting an aluminum foil or the like to the current collector later.
  • the negative electrode is not particularly limited as long as it is a negative electrode used in a conventional lithium secondary battery, that is, a negative electrode containing an active material capable of occluding and releasing Li ions.
  • a negative electrode active material lithium, such as graphite, pyrolytic carbons, cokes, glassy carbons, fired organic polymer compounds, mesocarbon microbeads (MCMB), and carbon fibers, can be occluded and released.
  • MCMB mesocarbon microbeads
  • One type or a mixture of two or more types of carbon-based materials are used.
  • elements such as Si, Sn, Ge, Bi, Sb, In and their alloys or oxides thereof, compounds that can be charged and discharged at a low voltage close to lithium metal such as lithium-containing nitrides, and lithium-containing composites such as lithium titanate An oxide, or a lithium metal or a lithium / aluminum alloy can also be used as the negative electrode active material.
  • a negative electrode mixture obtained by appropriately adding a conductive additive (carbon material such as carbon black) or a binder such as PVDF to these negative electrode active materials is formed into a molded body (negative electrode active material-containing layer) using a current collector as a core material.
  • a finished product, or the above-described various alloys or lithium metal foils are used as a negative electrode active material-containing layer, which is used alone or laminated on a current collector.
  • the current collector When a current collector is used for the negative electrode, the current collector may be copper, nickel, aluminum foil, punching metal, net, expanded metal, etc., but copper foil is usually used.
  • the upper limit of the thickness is preferably 30 ⁇ m, and the lower limit is preferably 5 ⁇ m.
  • the lead portion on the negative electrode side may be formed in the same manner as the lead portion on the positive electrode side.
  • the electrode can be used in the form of a laminate obtained by laminating the positive electrode and the negative electrode via the separator of the present invention, or a wound electrode body obtained by winding the laminate.
  • the non-aqueous electrolyte a solution in which a lithium salt is dissolved in an organic solvent is used.
  • the lithium salt is not particularly limited as long as it dissociates in a solvent to form Li + ions and hardly causes side reactions such as decomposition in a voltage range used as a battery.
  • LiClO 4 , LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 and other inorganic lithium salts LiCF 3 SO 3 , LiCF 3 CO 2 , Li 2 C 2 F 4 (SO 3 ) 2 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiC n F 2n + 1 SO 3 (n ⁇ 2), LiN (RfOSO 2 ) 2 [where Rf is a fluoroalkyl group] and the like can be used. .
  • the organic solvent used in the non-aqueous electrolyte is not particularly limited as long as it dissolves the lithium salt and does not cause side reactions such as decomposition in the voltage range used as a battery.
  • cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate and vinylene carbonate
  • chain carbonates such as dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate
  • chain esters such as methyl propionate
  • cyclic esters such as ⁇ -butyrolactone
  • Chain ethers such as dimethoxyethane, diethyl ether, 1,3-dioxolane, diglyme, triglyme and tetraglyme
  • cyclic ethers such as dioxane, tetrahydrofuran and 2-methyltetrahydrofuran
  • nitriles such as acetonitrile, propionitrile and methoxypropionitrile Sulfites such as
  • a combination that can obtain high conductivity such as a mixed solvent of ethylene carbonate and chain carbonate.
  • vinylene carbonates, 1,3-propane sultone, diphenyl disulfide, cyclohexyl benzene, biphenyl, and fluoro are used for the purpose of further improving the safety, charge / discharge cycleability, and high-temperature storage properties of these non-aqueous electrolytes.
  • Additives such as benzene and t-butylbenzene may be added as appropriate.
  • the concentration of this lithium salt in the non-aqueous electrolyte is preferably 0.5 to 1.5 mol / l, more preferably 0.9 to 1.25 mol / l.
  • the positive electrode having the positive electrode active material-containing layer and the negative electrode having the negative electrode active material-containing layer are, for example, a positive electrode active material obtained by dispersing a positive electrode mixture in a solvent such as N-methyl-2-pyrrolidone (NMP).
  • NMP N-methyl-2-pyrrolidone
  • a composition for forming a material-containing layer (slurry, etc.) or a composition for forming a negative electrode active material-containing layer (slurry, etc.) in which a negative electrode mixture is dispersed in a solvent such as NMP is applied onto a current collector and dried. It is produced by this.
  • a positive electrode active material-containing layer forming composition is applied on a current collector, and the separator and the separator are formed before the composition is dried.
  • a negative electrode active material-containing layer forming composition is applied onto a current collector, and the separator and the negative electrode and separator are integrated before the composition is dried.
  • a lithium secondary battery can also be configured.
  • FIG. 1A is a schematic plan view of a lithium secondary battery of the present invention
  • FIG. 1B is a schematic cross-sectional view of the lithium secondary battery of the present invention
  • FIG. 2 is a schematic external view of the lithium secondary battery of the present invention.
  • the battery shown in FIGS. 1A, 1B and 2 will be described.
  • the negative electrode 1 and the positive electrode 2 are spirally wound through the separator 3 of the present invention, and further pressed so as to be flattened. 6 is accommodated in a rectangular tube-shaped outer can 20 together with a non-aqueous electrolyte.
  • FIG. 1B in order to avoid complication, the metal foil and the nonaqueous electrolyte that are the current collectors of the negative electrode 1 and the positive electrode 2 are not illustrated, and the central portion of the spirally wound electrode body 6 and the separator 3 are not illustrated. Does not show hatching indicating the cross section.
  • the outer can 20 is made of an aluminum alloy and constitutes a battery outer body.
  • the outer can 20 also serves as a positive electrode terminal.
  • the insulator 5 which consists of a polyethylene sheet is arrange
  • the negative electrode lead portion 8 and the positive electrode lead portion 7 are drawn out.
  • a stainless steel terminal 11 is attached to a sealing lid plate 9 made of aluminum alloy for sealing the opening of the outer can 20 via a polypropylene insulating packing 10.
  • a stainless steel lead plate 13 is attached via 12.
  • the cover plate 9 is inserted into the opening of the outer can 20 and welded to join the opening of the outer can 20 so that the inside of the battery is sealed. Further, the lid plate 9 is provided with a non-aqueous electrolyte inlet 14, and the non-aqueous electrolyte inlet 14 is welded and sealed by, for example, laser welding with a sealing member inserted. Thus, the battery is sealed. In FIG. 1A, B, and FIG. 2, the nonaqueous electrolyte inlet 14 is displayed including the nonaqueous electrolyte inlet itself and the sealing member for convenience. Further, the lid plate 9 is provided with a cleavage vent 15 as a mechanism for discharging the internal gas to the outside when the internal pressure rises due to the temperature rise of the battery or the like.
  • the outer can 20 and the cover plate 9 function as a positive electrode terminal by directly welding the positive electrode lead portion 7 to the cover plate 9.
  • the terminal 11 functions as a negative electrode terminal by welding to the lead plate 13 and conducting the negative electrode lead portion 8 and the terminal 11 through the lead plate 13, but depending on the material of the outer can 20, etc. The sign may be reversed.
  • the lithium secondary battery of the present invention can be applied to the same uses as various uses in which conventional lithium secondary batteries are used.
  • the volume content of each component in the separator shown in each example is the volume content in all components except the nonwoven fabric.
  • the melting point (melting temperature) of the heat-meltable resin particles shown in each example is a value measured using DSC in accordance with the provisions of JIS K7121.
  • Example 1 Preparation of separator> Plate-like boehmite (aspect ratio 10) was repeatedly washed with water as inorganic oxide particles, and dried at 120 ° C. Plated boehmite after drying: 0.5 g of alkali metal element immersed in 25 cm 3 of ion exchange water at 25 ° C. for 12 hours, diluted ion exchange water 10 times, and eluted in ion exchange water The amount of was measured by ICP spectroscopy. As a result, the alkali metal element was almost composed only of Na, and the amount was found to be 500 ppm based on the weight of the plate boehmite.
  • the dispersion was prepared by adding 500 g of ion-exchanged water and 5 g of a 40 mass% ammonium polycarboxylate dispersant to 500 g of the plate-like boehmite that had been washed with water, and performing a dispersion treatment with a ball mill.
  • the particle size of the plate boehmite in the dispersion was measured with a laser scattering particle size distribution meter, the average particle size (D50%) in the volume-based integrated fraction was 0.8 ⁇ m.
  • the separator-forming composition (1) had a solid content of 55% by mass.
  • a PET nonwoven fabric (width 200 mm, thickness 17 ⁇ m, basis weight 10 g / m 2 ) was used as the fibrous sheet, and this was dipped and pulled into the separator-forming composition (1) at a rate of 1 m / min.
  • the separator-forming composition (1) was applied to a PET nonwoven fabric and dried to obtain a separator.
  • the obtained separator had a thickness of 25 ⁇ m, a porosity of 50%, and a Gurley value of 200 sec.
  • the volume content of the plate-like boehmite in the separator calculated with the specific gravity of boehmite being 3.0 g / cm 3 and the specific gravity of the binder being 1.0 g / cm 3 was 75%.
  • the positive electrode active material LiCoO 2 85 parts by mass, the conductive auxiliary agent acetylene black: 10 parts by mass, and the binder PVDF: 5 parts by mass are mixed uniformly using NMP as a solvent.
  • An agent-containing paste was prepared. This paste was intermittently applied to both sides of an aluminum foil having a thickness of 15 ⁇ m as a current collector so that the active material application length was 280 mm on the front surface and 210 mm on the back surface, dried, and then subjected to a calendar treatment to obtain a total thickness.
  • the thickness of the positive electrode active material-containing layer was adjusted to 150 ⁇ m and cut to a width of 43 mm to prepare a positive electrode having a length of 280 mm and a width of 43 mm. Further, a tab was welded to the exposed portion of the aluminum foil of the positive electrode to form a lead portion.
  • a negative electrode mixture-containing paste was prepared by mixing 90 parts by mass of graphite as a negative electrode active material and 10 parts by mass of PVDF as a binder so as to be uniform using NMP as a solvent.
  • This negative electrode mixture-containing paste was intermittently applied on both sides of a 10 ⁇ m-thick current collector made of copper foil so that the active material application length was 290 mm on the front surface and 230 mm on the back surface, dried, and then subjected to calendar treatment.
  • the thickness of the negative electrode active material-containing layer was adjusted so that the total thickness was 142 ⁇ m, and the negative electrode having a length of 290 mm and a width of 45 mm was prepared by cutting to a width of 45 mm. Further, a tab was welded to the exposed portion of the copper foil of the negative electrode to form a lead portion.
  • the positive electrode and the negative electrode were spirally wound through the separator to form a wound electrode body.
  • the wound electrode body is crushed into a flat shape and loaded into a rectangular outer can (height 48 mm, width 33 mm, thickness 4 mm), and a non-aqueous electrolyte (ethylene carbonate and methyl ethyl carbonate in a volume of 1: 2).
  • a solution in which LiPF 6 was dissolved at a concentration of 1.2 mol / l) was injected into the solvent mixed at a ratio, and then the outer can was vacuum sealed to obtain a lithium secondary battery.
  • Example 2 Except for using granular boehmite as inorganic oxide particles and adding 12.5 g of the dispersant, the thickness was 20 ⁇ m, the porosity was 40%, the Gurley value was 100 sec, and the boehmite A separator having a volume content of 75% was prepared.
  • the elution amount of the alkali metal element of the granular boehmite after washing with water was measured in the same manner as in Example 1, it was 40 ppm based on the weight of the granular boehmite, and the total amount was Na.
  • the average particle diameter (D50%) of the granular boehmite measured in the same manner as in Example 1 was 0.4 ⁇ m.
  • a lithium secondary battery was produced in the same manner as in Example 1 except that the separator was used.
  • Example 3 In the same plate-like boehmite dispersion used in Example 1, 500 g of dispersion of self-crosslinkable polybutyl acrylate (solid content 45% by mass) and PE emulsion (of PE) as heat-meltable resin particles 5 g of melting point 130 ° C., solid content 45% by mass) were added and stirred for 3 hours with a three-one motor to obtain a separator-forming composition (2).
  • the separator-forming composition (2) had a solid content of 55% by mass.
  • a separator was produced in the same manner as in Example 1 except that the separator-forming composition (2) was used.
  • the obtained separator had a thickness of 20 ⁇ m, a porosity of 40%, and a Gurley value of 100 sec.
  • the volume content of the plate-like boehmite in the separator calculated by setting the specific gravity of boehmite to 3.0 g / cm 3 , the specific gravity of the binder to 1.0 g / cm 3 , and the specific gravity of PE to 1.0 g / cm 3 is 50 %Met.
  • a lithium secondary battery was produced in the same manner as in Example 1 except that the separator was used.
  • Example 4 A separator was produced in the same manner as in Example 3 except that the same granular boehmite as that used in Example 2 was used instead of plate-like boehmite.
  • the obtained separator had a thickness of 20 ⁇ m, a porosity of 40%, and a Gurley value of 100 sec. Further, the volume content of the granular boehmite in the separator calculated in the same manner as in Example 3 was 50%.
  • a lithium secondary battery was produced in the same manner as in Example 1 except that the separator was used.
  • Example 1 A separator was produced in the same manner as in Example 1 except that the same plate-like boehmite used in Example 1 was used without being washed with water.
  • the obtained separator had a thickness of 25 ⁇ m, a porosity of 40%, and a Gurley value of 100 sec.
  • the elution amount of the alkali metal element of the plate-like boehmite that was not washed with water was measured in the same manner as in Example 1, it was 2400 ppm based on the weight of the plate-like boehmite, and almost the whole amount was Na. there were.
  • a lithium secondary battery was produced in the same manner as in Example 1 except that the separator was used.
  • Example 2 A separator was produced in the same manner as in Example 1 except that the same plate-like boehmite used in Example 1 was used after being washed once with water.
  • the obtained separator had a thickness of 20 ⁇ m, a porosity of 40%, and a Gurley value of 100 sec.
  • the elution amount of the alkali metal element of the plate-like boehmite after washing with water was measured in the same manner as in Example 1, it was 1200 ppm based on the weight of the plate-like boehmite, and the total amount was the amount of Na.
  • a lithium secondary battery was produced in the same manner as in Example 1 except that the separator was used.
  • each separator sample 0.5 g was immersed in 25 cm 3 of ion exchange water at 25 ° C. for 12 hours, The ion-exchanged water after immersion was diluted 10 times, and the amount of the alkali metal element eluted in the ion-exchanged water was measured by ICP spectroscopic analysis, and the ratio to the weight of the original separator was obtained.
  • the results are shown in Table 1 together with the amount of alkali metal element eluted from the inorganic oxide particles used in each separator. Almost all of the alkali metal element eluted from the separator was Na.
  • Charging is a constant current-constant voltage charging (total charging time) that combines constant current charging until the battery voltage reaches 4.2 V at a current value of 850 mA (equivalent to 1 C) and constant voltage charging at 4.2 V. 3 hours), and the discharge was a constant current discharge at a current value of 850 mA until the battery voltage reached 2.75 V.
  • This charging / discharging operation was defined as one cycle, and charging / discharging was repeated up to 500 cycles.
  • the lithium secondary batteries of Examples 1 to 4 can maintain a high capacity even after 500 cycles of charge and discharge, and constitute a highly reliable battery with little characteristic deterioration during long-term use. did it.
  • the lithium secondary batteries of Examples 1 to 4 are less likely to have a decrease in discharge capacity due to a storage test at a high temperature and have excellent storage characteristics (long-term storage characteristics). Recognize.
  • Example 5 For separator formation, the same separator-forming composition (1) as used in Example 1 and the same PE emulsion as used in Example 3 were used on both sides of the same negative electrode used in Example 1.
  • the thickness of the support layer in the separator was 20 ⁇ m (per side of the negative electrode), the thickness of the shutdown layer was 5 ⁇ m (per side of the negative electrode), and the porosity of the separator was 40%.
  • the volume content of the plate-like boehmite in the separator calculated by setting the specific gravity of boehmite to 3.0 g / cm 3 , the specific gravity of the binder to 1.0 g / cm 3 , and the specific gravity of PE to 1.0 g / cm 3 is 50 %Met.
  • a lithium secondary battery was produced in the same manner as in Example 1 except that the negative electrode and the separator were changed to an integrated product of the negative electrode and the separator.
  • Example 6 The same composition for forming a separator (1) as used in Example 1 was applied to one side of a commercially available polyethylene microporous film (melting point: 135 ° C., thickness: 15 ⁇ m) with a die coater and dried to form a separator. Obtained. The obtained separator had a thickness of 18 ⁇ m, a porosity of 50%, and a Gurley value of 200 sec. Thereafter, a lithium secondary battery was produced in the same manner as in Example 1. Almost no warpage or the like was observed in the produced separator.
  • Comparative Example 3 The same composition for forming a separator as that used in Comparative Example 1 and the same PE emulsion as that used in Example 3 are formed on both sides of the same negative electrode as used in Example 1, and the composition for forming a separator is Multilayer coating was applied so as to be on the negative electrode side, followed by drying to prepare a negative electrode (integrated product of negative electrode active material-containing layer and separator) having a separator having a two-layer structure comprising a support layer and a shutdown layer on both surfaces.
  • the thickness of the support layer in the separator was 20 ⁇ m (per side of the negative electrode), the thickness of the shutdown layer was 5 ⁇ m (per side of the negative electrode), and the porosity of the separator was 40%.
  • a lithium secondary battery was produced in the same manner as in Example 1 except that the negative electrode and the separator were changed to an integrated product of the negative electrode and the separator.
  • Table 4 shows the elution amount of alkali metal elements obtained in the same manner as the separator of Example 1 for the separator peeled from the integrated negative electrode and separator of Example 5 and Comparative Example 3 and the separator of Example 6. Show. Almost all of the alkali metal element eluted from the separator was Na.
  • Example 5 shows the results of the charge / discharge cycle test
  • Table 6 shows the results of the storage test.
  • the lithium secondary batteries of Examples 5 and 6 have characteristics in long-term use.
  • the battery had little deterioration, excellent long-term storage characteristics, and excellent reliability.
  • the present invention it is possible to provide a lithium secondary battery having high reliability and having little characteristic deterioration during long-term use and long-term storage.

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  • Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention porte sur une batterie secondaire au lithium, dans laquelle des particules d'oxyde inorganique, dans lesquelles la quantité d'élution d'éléments de métaux alcalins durant l'immersion dans une eau échangeuse d'ions est inférieure à moins de 1 000 ppm, sont liées par un liant pour former une membrane poreuse, et un séparateur comprenant la membrane poreuse est utilisé pour construire la batterie secondaire au lithium. Ainsi, une batterie secondaire au lithium qui présente une fiabilité élevée et peu de dégradation dans les caractéristiques de celle-ci durant une utilisation prolongée et un stockage prolongé peut être fournie.
PCT/JP2009/060538 2007-07-04 2009-06-09 Film poreux pour séparateur, séparateur de batterie, électrode de batterie et leurs procédés de fabrication, et batterie secondaire au lithium Ceased WO2009151054A1 (fr)

Priority Applications (4)

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KR1020107026558A KR101229902B1 (ko) 2008-06-09 2009-06-09 세퍼레이터용 다공질막, 전지용 세퍼레이터, 전지용 전극 및 그것들의 제조방법, 및 리튬 2차전지
US12/989,897 US8920960B2 (en) 2007-07-04 2009-06-09 Porous film for separator, battery separator, battery electrode, and manufacturing methods therefor, and lithium secondary battery
CN200980121546XA CN102057518A (zh) 2008-06-09 2009-06-09 隔膜用多孔质膜、电池用隔膜、电池用电极及这些的制造方法及二次锂电池
JP2010516860A JP5530353B2 (ja) 2008-06-09 2009-06-09 セパレータ用多孔質膜、電池用セパレータ、電池用電極およびそれらの製造方法、ならびにリチウム二次電池

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JP2008150186A JP2009032677A (ja) 2007-07-04 2008-06-09 セパレータ用多孔質膜およびその製造方法、電池用セパレータおよびその製造方法、電池用電極およびその製造方法、ならびにリチウム二次電池

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JPWO2012002359A1 (ja) * 2010-06-28 2013-08-22 株式会社村田製作所 蓄電デバイスとその製造方法
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WO2019049937A1 (fr) * 2017-09-07 2019-03-14 Ｎｅｃエナジーデバイス株式会社 Électrode et pile rechargeable
US10283747B2 (en) 2014-03-17 2019-05-07 Kabushiki Kaisha Toshiba Nonaqueous electrolyte secondary battery and battery pack
CN110364661A (zh) * 2018-04-11 2019-10-22 宁德新能源科技有限公司 隔离膜及储能装置
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JP2013073678A (ja) * 2011-09-26 2013-04-22 Toyota Motor Corp 非水系二次電池
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WO2013187458A1 (fr) * 2012-06-12 2013-12-19 三菱製紙株式会社 Séparateur pour pile lithium-ion
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JPWO2020261742A1 (fr) * 2019-06-26 2020-12-30
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