WO2010098497A1 - Membrane poreuse pour batterie secondaire non aqueuse, séparateur pour batterie secondaire non aqueuse, adsorbant pour batterie secondaire non aqueuse et batterie secondaire non aqueuse - Google Patents

Membrane poreuse pour batterie secondaire non aqueuse, séparateur pour batterie secondaire non aqueuse, adsorbant pour batterie secondaire non aqueuse et batterie secondaire non aqueuse Download PDF

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Publication number
WO2010098497A1
WO2010098497A1 PCT/JP2010/053380 JP2010053380W WO2010098497A1 WO 2010098497 A1 WO2010098497 A1 WO 2010098497A1 JP 2010053380 W JP2010053380 W JP 2010053380W WO 2010098497 A1 WO2010098497 A1 WO 2010098497A1
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Prior art keywords
secondary battery
porous
aqueous secondary
separator
battery
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PCT/JP2010/053380
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English (en)
Japanese (ja)
Inventor
西川聡
大塚淳弘
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帝人株式会社
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Priority to JP2010527268A priority Critical patent/JP4685974B2/ja
Publication of WO2010098497A1 publication Critical patent/WO2010098497A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • 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
    • 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
    • H01M50/44—Fibrous 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
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • 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 non-aqueous secondary battery, a separator for a non-aqueous secondary battery, an adsorbent for a non-aqueous secondary battery, and a non-aqueous secondary battery.
  • Non-aqueous secondary batteries represented by lithium ion secondary batteries are widely used as main power sources for portable electronic devices such as mobile phones and notebook computers.
  • This non-aqueous secondary battery is required to have higher energy density, higher capacity, and higher output, and this demand is expected to increase in the future. From the viewpoint of meeting such demands, ensuring the safety of the battery becomes a more important technical element.
  • a non-aqueous secondary battery has a configuration including a positive electrode, a negative electrode, and a separator disposed between these electrodes.
  • the separator has a function of preventing an internal short circuit between the positive electrode and the negative electrode without hindering the permeation of ions.
  • a polyolefin microporous membrane is generally used as the separator.
  • the separator made of a microporous polyolefin membrane has a shutdown function such that when the battery temperature rises due to overcharge or the like, the polyolefin melts and closes the pores, thereby blocking the current inside the battery. Have. With this function, further heat generation of the battery can be prevented, and the safety of the battery at high temperatures can be improved. However, if the internal temperature of the battery rises even after the holes are closed, there is a risk that the separator will break and an internal short circuit will occur, leading to ignition and the like. Therefore, conventionally, heat-resistant porous membranes have attracted attention in order to improve the safety of non-aqueous secondary batteries.
  • a technique for applying a porous film made of a heat resistant resin to a separator (Patent Document 1), a technique for applying a porous film made of a heat resistant resin and a ceramic powder to a separator (Patent Documents 2 and 3), an inorganic filler and a binder
  • Patent Document 4 a technique for forming a porous film made of resin on the electrode surface
  • Patent Document 5 A technique for dispersing an inorganic filler in a separator made of a polyolefin microporous film is also known (Patent Document 5).
  • the inorganic filler typified by ceramic powder is considered to be effective from the viewpoint of more reliably preventing internal short circuit between the positive and negative electrodes because of high heat resistance and compressive strength.
  • a battery to which such an inorganic filler is applied may cause a decrease in battery durability such as cycle characteristics and storage characteristics.
  • hydrogen fluoride (HF) present in a minute amount in the battery reacts with the inorganic filler, and the surface of the inorganic filler is fluorinated, and at this time, water is generated. It is conceivable that moisture decomposes the SEI (Solid Electrolyte Interface) film formed on the electrolyte solution or electrode surface.
  • SEI Solid Electrolyte Interface
  • the internal resistance of the battery is increased, or lithium necessary for charging / discharging is deactivated, so that the durability of the battery may be reduced.
  • gas is generated, which may also decrease the durability of the battery.
  • a decomposition reaction may cause a decrease in battery safety.
  • a heat resistant resin such as an aromatic polyamide resin
  • the heat resistant resin is generally a substance that easily adsorbs moisture, it can be said that the problem of the decomposition reaction is more likely to occur. .
  • Patent Document 6 proposes a technique for improving gas generation in a battery with an inorganic filler.
  • a gas absorbent made of inorganic powder is mixed in a separator made of polyolefin, and the gas generated in the battery is trapped by the gas absorbent.
  • the inorganic filler which is a gas absorbent is mixed in the polyolefin microporous film having the shutdown function, the shutdown function may be remarkably deteriorated. Therefore, although the gas generation is apparently suppressed, the safety of the battery may be reduced as compared with the case where the conventional polyolefin microporous membrane is applied.
  • a lithium ion secondary battery is composed of a positive electrode such as a lithium transition metal composite oxide, a negative electrode such as a carbon material, an organic electrolytic solution in which a Li salt is dissolved, and a separator such as a polyethylene microporous film.
  • a lithium ion secondary battery is manufactured after strictly managing so that a water
  • the water present in the battery system reacts with a Li salt such as lithium hexafluorophosphate to liberate HF, and the liberated HF reacts as shown in (1) to (3) below. It is known to deteriorate the cycle characteristics of the battery.
  • Patent Documents 7 to 9 disclose a technique in which an inorganic substance having a specific surface area of 15 to 300 m 2 / g is included in a separator, and it is shown that the cycle characteristics are improved by this inorganic substance.
  • Patent Document 8 discloses a technique in which alumina having a specific surface area of 30 to 300 m 2 / g is contained in a negative electrode or a positive electrode, and shows that good cycle characteristics can be obtained.
  • Patent Document 9 discloses a configuration in which activated carbon having a specific surface area of 1000 m 2 / g or more and an inorganic substance are included in the battery system, and it is shown that good cycle characteristics can be obtained by activated carbon or the like.
  • the porous inorganic filler having a specific specific surface area has an effect of improving the cycle characteristics of the battery.
  • a technique for suppressing the reaction with HF and improving the cycle characteristics by factors other than the specific surface area of the inorganic filler is not known.
  • JP 2008-266588 A Japanese Patent No. 3175730 International Publication No. 2008/62727 Pamphlet JP 2008-204788 A Japanese Patent No. 4074116 JP 2008-146963 A Japanese Patent No. 4145762 Japanese Patent No. 3704780 JP 2000-77103 A
  • Lithium-ion secondary battery second edition (Nikkan Kogyo Shimbun, Masayuki Yoshio) Material and application, pages 76-77
  • the first object of the present invention is to provide a technique that can improve both the safety and durability of the non-aqueous secondary battery.
  • a second object is to provide a technique capable of improving cycle characteristics in consideration of reaction with HF and adsorption.
  • a porous membrane for a non-aqueous secondary battery comprising a heat resistant resin and an inorganic filler, wherein the inorganic filler has an average particle diameter of 0.1 to 5.0 ⁇ m and a specific surface area of 40 to A porous membrane for a non-aqueous secondary battery, characterized by being a porous filler of 3000 m 2 / g. 2.
  • a porous film for a non-aqueous secondary battery comprising a heat-resistant resin and an inorganic filler, wherein the inorganic filler is amorphous alumina particles. 4).
  • a nonaqueous secondary battery comprising at least a positive electrode and a negative electrode, wherein the porous film for a nonaqueous secondary battery according to any one of the above 1 to 3 is formed on the surface of at least one of the positive electrode and the negative electrode
  • a separator for a non-aqueous secondary battery comprising a porous substrate and a heat-resistant porous layer containing a heat-resistant resin and an inorganic filler laminated on one or both surfaces of the porous substrate
  • a separator for a non-aqueous secondary battery wherein the inorganic filler is a porous filler having an average particle diameter of 0.1 to 5.0 ⁇ m and a specific surface area of 40 to 3000 m 2 / g. 6). 6.
  • the porous filler is activated alumina having a specific surface area of 300 to 1000 m 2 / g. 7).
  • a separator for a non-aqueous secondary battery comprising a porous substrate and a heat-resistant porous layer containing a heat-resistant resin and an inorganic filler laminated on one or both surfaces of the porous substrate, A separator for a non-aqueous secondary battery, wherein the inorganic filler is amorphous alumina particles. 8).
  • a non-aqueous secondary battery comprising a positive electrode, a negative electrode, and a separator, wherein the non-aqueous secondary battery separator according to any one of 5 to 7 is used as the separator. battery. 9.
  • An adsorbent for hydrogen fluoride mixed in a non-aqueous secondary battery the adsorbent being activated alumina particles having a specific surface area of 300 to 1000 m 2 / g, for a non-aqueous secondary battery Adsorbent.
  • An adsorbent for hydrogen fluoride mixed in a non-aqueous secondary battery wherein the adsorbent is amorphous alumina particles.
  • a porous film for a non-aqueous secondary battery comprising an inorganic filler and a binder resin, wherein the inorganic filler includes the non-aqueous secondary battery adsorbent described in 9 or 10 above.
  • a porous membrane for a non-aqueous secondary battery the adsorbent for hydrogen fluoride mixed in a non-aqueous secondary battery, the adsorbent being activated alumina particles having a specific surface area of 300 to 1000 m 2 / g, for a non-aqueous secondary battery Adsorbent. 10.
  • a separator for a non-aqueous secondary battery comprising a porous base material and a porous layer containing an inorganic filler and a binder resin laminated on one or both sides of the porous base material, the inorganic filler as the inorganic filler
  • a nonaqueous secondary battery separator comprising the adsorbent for a nonaqueous secondary battery as described in 9 or 10 above.
  • a non-aqueous secondary battery comprising a positive electrode, a negative electrode, a non-aqueous electrolyte, and a separator, characterized in that the non-aqueous secondary battery adsorbent described in 9 or 10 is contained in the battery.
  • Non-aqueous secondary battery comprising a positive electrode, a negative electrode, a non-aqueous electrolyte, and a separator, characterized in that the non-aqueous secondary battery adsorbent described in 9 or 10 is contained in the battery.
  • the first aspect of the present invention it is possible to provide a technology capable of improving both safety and durability of a non-aqueous secondary battery.
  • the second aspect of the present invention it is possible to provide a technique capable of improving cycle characteristics in consideration of reaction with HF and adsorption.
  • the porous membrane for a non-aqueous secondary battery according to the first aspect of the present invention is a porous membrane for a non-aqueous secondary battery configured to contain a heat-resistant resin and an inorganic filler, and the inorganic filler has an average particle size The diameter is 0.1 to 5.0 ⁇ m and the specific surface area is 40 to 3000 m. 2 / G porous filler.
  • the inorganic filler has an average particle size of 0.1 to 5.0 ⁇ m and a specific surface area of 40 to 3000 m. 2 Because it is a porous filler of / g, durability such as cycle characteristics and storage characteristics of the battery can be suppressed by suppressing side reactions that reduce durability in the battery and removing gas generated by side reactions. Can be improved.
  • the heat-resistant resin is generally a substance that easily adsorbs moisture
  • the present invention has a configuration in which the side reaction between the HF and the inorganic filler is likely to occur. By applying the filler, the activity of moisture and HF present in a minute amount in the battery can be significantly reduced, and gas generation due to decomposition of the electrolyte and the like can be suppressed.
  • the porous membrane for a battery according to the present invention includes a heat-resistant resin and an inorganic filler, and has a plurality of pores or voids therein, and these pores are connected to each other. Means a quality structure.
  • the heat-resistant resin in the present invention includes a resin having a melting point of 200 ° C. or higher. In addition to a resin having a melting point of 200 ° C. or higher, a resin having a thermal decomposition temperature of 200 ° C. or higher with substantially no melting point. Is also included.
  • Such a heat-resistant resin examples include wholly aromatic polyamides, polyimides, polyamideimides, polysulfones, polyketones, polyether ketones, polyether sulfones, polyether imides, celluloses, combinations of two or more thereof, and the like. .
  • wholly aromatic polyamides are preferable from the viewpoint of durability such as ease of forming a porous structure, binding property with an inorganic filler, strength of the porous film and accompanying oxidation resistance.
  • the wholly aromatic polyamide comparing the para type and the meta type, the meta type wholly aromatic polyamide is preferable from the viewpoint of easy molding, and polymetaphenylene isophthalamide is particularly preferable.
  • the logarithmic viscosity of the following formula (1) is 0.8 to 2.5 dl / g. Those in the range are preferable, and those in the range of 1.0 to 2.2 dl / g are more preferable. Deviating from this range is not preferable because the moldability may be deteriorated.
  • Logarithmic viscosity (unit: dl / g) ln (T / T0) / C (1)
  • T Flow time of capillary viscometer at 30 ° C.
  • Porous fillers applicable to the present invention include zeolite, activated carbon, activated alumina, porous silica, porous fillers obtained by heat treatment of metal hydroxides such as magnesium hydroxide and aluminum hydroxide, synthesized from organic compounds Porous fillers to be used. Of these, activated alumina is particularly preferable.
  • the activated alumina in the present invention has a formula of Al 2 O 3 XH 2 It is a porous filler represented by O (x can take a value of 0 or more and 3 or less).
  • the surface of activated alumina is amorphous Al 2 O 3 , ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 Gibbsite-like Al (OH) 3 Boehmite Al 2 O 3 ⁇ H 2
  • a structure such as O is preferable, and a porous structure formed of these surface structures is particularly preferable from the viewpoint of reducing the activity of moisture and HF.
  • porous filler In addition to the porous filler described above, other non-porous inorganic fillers such as metal oxides such as ⁇ -alumina and metal hydroxides such as aluminum hydroxide may be appropriately added as the inorganic filler.
  • the porous filler is preferably composed of mesopores of 50 nm or less or micropores of 2 nm or less, and particularly preferably has a structure in which micropores of 2 nm or less are developed from the viewpoint of manifestation of the effects of the present invention. .
  • the average particle diameter of the porous filler is preferably in the range of 0.1 to 5.0 ⁇ m.
  • the average particle size of the porous filler is smaller than 0.1 ⁇ m, it is not preferable because it may be difficult to mold the porous film, or the sliding property of the porous film may be deteriorated and handling may be difficult.
  • the average particle diameter of the porous filler is larger than 5.0 ⁇ m, it may be difficult to form the porous film from the viewpoint of surface roughness when it is thinly formed.
  • the specific surface area of the porous filler is 40 to 3000 m. 2 / G is preferable. Specific surface area is 40m 2 If it is less than / g, the activity of moisture and HF cannot be sufficiently reduced, which is not preferable.
  • the specific surface area of the porous filler is 40 to 1000 m. 2 / G is more preferable. Specific surface area is 1000m 2 This is because if it is less than / g, it will be more excellent in terms of mechanical strength and gas generation suppression. More preferably, the specific surface area of the porous filler is 40 to 500 m. 2 / G is preferred.
  • the specific surface area of the porous filler is 150 to 500 m. 2 / G is preferred.
  • Specific surface area is 150m 2 This is because if it is at least / g, it will be more excellent in terms of suppressing gas generation.
  • the specific surface area is obtained by analyzing the adsorption isotherm measured by the nitrogen gas adsorption method using the BET equation.
  • the porous filler has a specific surface area of 300 to 1000 m. 2 / G activated alumina is preferred.
  • Such activated alumina can reduce the activity of HF by adsorbing or reacting with a small amount of HF generated in the battery, and can further improve the cycle characteristics of the non-aqueous secondary battery.
  • the 0 / Al element ratio present on the surface of the activated alumina particles is preferably 1.0 to 2.5 when measured using an X-ray photoelectron spectrometer. More preferably, the 0 / Al element ratio is 1.2 to 1.8. When the surface is formed with such an element ratio, it is preferable from the viewpoint of reducing the activity of HF or the like.
  • the true density of the activated alumina is 2.7 to 3.8 g / cm. 3 And more preferably 2.8 to 3.3 g / cm. 3 Range.
  • True density is 2.7 g / cm 3 If it is less than that, it becomes close to aluminum hydroxide and the like, and it is difficult to obtain the effect of reducing the activity of HF.
  • the true density is 3.8 g / cm. 3 If it is larger, the structure of the filler becomes dense, and the gap through which the electrolytic solution enters becomes small, which may reduce the cycle characteristics of the battery.
  • the specific surface area of the activated alumina is 300 m. 2 / G or more is preferable. Specific surface area is 300m 2 If it is less than / g, the activity of HF or the like may not be sufficiently reduced. On the other hand, the specific surface area of activated alumina is 1000 m.
  • the porous membrane for a non-aqueous secondary battery of the present invention can be applied to any part as long as it is disposed between both the positive electrode and the negative electrode. That is, for example, the porous membrane for a non-aqueous secondary battery of the present invention can be applied as a separator disposed between electrodes. In this case, it is preferable that the puncture strength has a sufficient mechanical strength of 200 g or more. Further, those having a Gurley value of 10 to 300 seconds / 100 cc are preferred.
  • the weight of the porous filler is 10 to 50% by weight with respect to the total weight of the heat resistant resin and the porous filler as the configuration of the porous film for a battery of the present invention. . If the weight of the porous filler exceeds 50% by weight, it may be difficult to obtain sufficient mechanical strength. On the other hand, if the weight of the porous filler is less than 10% by weight, the effect of suppressing side reactions in the battery may be reduced, or the permeability may be lowered. Moreover, when arrange
  • the battery porous membrane of the present invention may be directly formed on the electrode.
  • the electrode becomes a support having sufficient strength, mechanical strength is not required as compared with the case where the porous membrane for a battery is applied alone as a separator.
  • the weight of the porous filler is preferably 10 to 90% by weight, more preferably 50 to 90% by weight, based on the total weight of the heat resistant resin and the porous filler.
  • the weight of the porous filler is less than 10% by weight, the effect of suppressing side reactions in the battery may be reduced, which is not preferable. Moreover, since it may become difficult to shape
  • the battery porous membrane of the present invention when the battery porous membrane of the present invention is directly formed on the electrode, the battery porous membrane can also serve as a separator. Therefore, a separator for preventing a short circuit between the positive and negative electrodes is not disposed. Also good.
  • a battery may be produced by applying only a normal separator such as a polyolefin microporous membrane.
  • the method for producing the porous membrane for a non-aqueous secondary battery of the present invention is not particularly limited, and for example, it can be produced by a production method including the following steps (i) to (iv).
  • the water-soluble organic solvent is not particularly limited as long as it is a good solvent for the heat-resistant resin.
  • polar solvents such as N-methylpyrrolidone, dimethylacetamide, dimethylformamide, and dimethylsulfoxide.
  • the slurry a solvent that becomes a poor solvent for the heat-resistant resin can be partially mixed and used. By applying such a poor solvent, a microphase separation structure is induced and the formation of a heat-resistant porous layer is facilitated.
  • the poor solvent alcohols are preferred, and polyhydric alcohols such as glycol are particularly preferred.
  • the amount of slurry applied to the support is 10 to 60 g / m. 2 The degree is preferred.
  • the coating method include a knife coater method, a gravure coater method, a screen printing method, a Mayer bar method, a die coater method, a reverse roll coater method, an ink jet method, a spray method, and a roll coater method.
  • the reverse roll coater method is preferable from the viewpoint of uniformly applying the coating film.
  • a method for solidifying the heat-resistant resin in the slurry a method in which a coagulating liquid is sprayed on the support after coating, or in a bath (coagulating bath) containing the coagulating liquid. Examples include a method of immersing the substrate.
  • the coagulation liquid is not particularly limited as long as it can coagulate the heat-resistant resin, but water or a mixed liquid in which an appropriate amount of water is contained in a good solvent used in the slurry is preferable.
  • the mixing amount of water is preferably 40 to 80% by weight with respect to the coagulation liquid.
  • the drying method is not particularly limited, but the drying temperature is suitably 50 to 100 ° C. In the case of applying a high drying temperature, it is preferable to apply a method of contacting the roll in order to prevent dimensional change due to heat shrinkage. Moreover, as a 2nd manufacturing method for obtaining the porous film for non-aqueous secondary batteries of this invention, (v) The coated sheet
  • a support is used, and as this support, a glass plate, a film made of polyethylene terephthalate (PET), or the like that exhibits sufficient heat resistance against the drying temperature is suitable. Can be used.
  • PET polyethylene terephthalate
  • the process of peeling the porous film for batteries of this invention from a support body after the drying of said (iv) (v) is included.
  • a porous material such as a polyolefin microporous film or a nonwoven fabric to the support.
  • the non-aqueous secondary battery of the present invention is a non-aqueous secondary battery including at least a positive electrode and a negative electrode, and the porous film for a non-aqueous secondary battery described above is provided on at least one surface of the positive electrode and the negative electrode.
  • the porous film for non-aqueous secondary batteries is used as a separator.
  • the non-aqueous secondary battery of the present invention is improved in battery safety by applying a battery porous film excellent in heat resistance, and the generation of gas is suppressed by the porous filler in the battery porous film. It also has excellent durability such as characteristics and storage characteristics.
  • the battery porous membrane of the present invention may be applied as a separator or may be formed on the electrode surface. When applied as a separator, only the porous film for a battery may be applied alone, or the porous film for a battery may be laminated with a polyolefin microporous film. When the porous membrane for a battery is formed on the electrode surface, it may be formed on either the positive electrode or the negative electrode, or both.
  • a polyolefin microporous membrane or the like may be applied as a separator, or the battery porous membrane of the present invention is formed in advance on the electrode surface, so that no separator is used.
  • the positive electrode and the negative electrode may be joined together.
  • a polyolefin microporous membrane is applied to the separator, a configuration in which the battery porous membrane of the present invention is at least between the polyolefin microporous membrane and the positive electrode is preferable.
  • the oxidation resistance of polyolefin microporous membranes is not necessarily sufficient for application to non-aqueous secondary batteries.
  • Polyolefin microporous membranes may oxidize the surface in contact with the positive electrode, which may deteriorate the battery. By disposing the porous membrane for a battery of the invention as described above, this deterioration can be greatly suppressed.
  • the type and configuration of the non-aqueous secondary battery of the present invention is not limited to the above configuration, but the battery element in which the positive electrode, the separator, and the negative electrode are sequentially laminated is impregnated with the electrolyte, and this is enclosed in the exterior Any structure can be applied as long as the structure is the same. However, as described above, the separator can be omitted.
  • the negative electrode has a structure in which a negative electrode mixture composed of a negative electrode active material, a conductive additive and a binder is formed on a current collector.
  • a current collector for example, copper foil, stainless steel foil, nickel foil or the like is used.
  • the negative electrode active material a material capable of electrochemically doping lithium, for example, a carbon material, silicon, aluminum, tin, or the like is used.
  • the positive electrode has a structure in which a positive electrode mixture composed of a positive electrode active material, a conductive additive and a binder is formed on a current collector.
  • the current collector for example, copper foil, stainless steel foil, nickel foil or the like is used.
  • the positive electrode active material include lithium-containing transition metal oxides such as LiCoO.
  • the electrolytic solution has a structure in which a lithium salt is dissolved in a non-aqueous solvent.
  • the lithium salt include LiPF. 6 , LiBF 4 LiClO 4 Etc.
  • the non-aqueous solvent include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ⁇ -butyrolactone, vinylene carbonate, and the like.
  • the exterior material include a metal can or an aluminum laminate pack.
  • the shape of the battery includes a square shape, a cylindrical shape, a coin shape, and the like, but the separator of the present invention can be suitably applied to any shape.
  • the battery porous membrane of the present invention is formed on an electrode, it is more preferable to apply to a cylindrical battery.
  • the porous membrane for a non-aqueous secondary battery according to the second aspect of the present invention is a porous membrane for a non-aqueous secondary battery configured to contain a heat-resistant resin and an inorganic filler, and the inorganic filler is amorphous.
  • Alumina particles hereinafter referred to as amorphous alumina as appropriate). According to the present invention as described above, the same effects as those of the first embodiment described above can be obtained.
  • amorphous alumina adsorbs a small amount of impurities and by-products such as HF present in the battery, the cycle characteristics of the battery can be further improved.
  • this 2nd form is the same as the 1st form mentioned above except the point which changed the inorganic filler into the amorphous alumina, below, description is abbreviate
  • the “amorphous alumina” in the second form is the same as the “specific surface area of 300 to 1000 m in the first form described above.
  • amorphous alumina particles are those having a formula of Al. 2 O 3 XH 2 It is a filler represented by O (x can take a value of 0 or more and 3 or less), and a clear crystal peak is not confirmed by analysis by X-ray diffraction.
  • amorphous alumina does not have a clear crystal peak completely confirmed by X-ray diffraction analysis, but has a slightly clear crystal peak in a broad peak (amorphous and other compositions).
  • the “other composition” includes a gibbsite-like or bayerite-like Al (OH). 3 Boehmite or diaspore Al 2 O 3 ⁇ H 2 O, ⁇ -Al 2 O 3 Or ⁇ -Al 2 O 3 ⁇ -Al, which is an intermediate alumina such as 2 O 3 Among these, boehmite or gibbsite is preferable in that the effects of the present invention can be satisfactorily obtained.
  • the entire inorganic filler Can be said to be amorphous.
  • the 0 / Al element ratio present on the surface of the amorphous alumina is preferably 1.0 to 2.5 when measured using an X-ray photoelectron spectrometer. More preferably, the 0 / Al element ratio is 1.2 to 1.8. When the surface is formed with such an element ratio, it is preferable from the viewpoint of reducing the activity of hydrogen fluoride (HF) or the like in the battery.
  • the amorphous alumina preferably has a porous structure with a large adsorption area for adsorbing various impurities and by-products mixed in the battery system.
  • the porous structure referred to here means a structure in which a large number of micropores or microvoids are formed inside or on the surface of the particle.
  • the amorphous alumina is preferably configured to include mesopores of 50 nm or less or micropores of 2 nm or less, and in particular, from the viewpoint of manifesting the effects of the present invention, the structure has developed micropores of 2 nm or less. preferable.
  • the specific surface area of the amorphous alumina is 50 m. 2 / G or more is preferable. Specific surface area is 50m 2 If it is less than / g, deterioration of cycle characteristics due to moisture, impurities, etc. cannot be sufficiently suppressed.
  • the specific surface area of amorphous alumina is 1000m. 2 / G or less is preferable, more preferably 500 m 2 / G or less is preferred.
  • the average particle diameter of the amorphous alumina is preferably in the range of 0.1 to 5.0 ⁇ m. If the average particle diameter of the amorphous alumina is smaller than 0.1 ⁇ m, it is not preferable because it may be difficult to mold the porous film, or the sliding property of the porous film may be deteriorated and handling may be difficult. Moreover, when the average particle diameter of amorphous alumina is larger than 5.0 ⁇ m, it may be difficult to form the porous membrane from the viewpoint of surface roughness when it is thinly formed.
  • the separator for a non-aqueous secondary battery according to the third aspect of the present invention is a heat-resistant porous material including a porous substrate and a heat-resistant resin and an inorganic filler laminated on one or both surfaces of the porous substrate.
  • a separator for a non-aqueous secondary battery, wherein the inorganic filler has an average particle diameter of 0.1 to 5.0 ⁇ m and a specific surface area of 40 to 3000 m. 2 / G porous filler.
  • the inorganic filler has an average particle size of 0.1 to 5.0 ⁇ m and a specific surface area of 40 to 3000 m. 2 Because it is a porous filler of / g, durability such as cycle characteristics and storage characteristics of the battery can be suppressed by suppressing side reactions that reduce durability in the battery and removing gas generated by side reactions. Can be improved.
  • this 3rd form is the structure which formed the porous film for batteries in the 1st form mentioned above as a heat resistant porous layer on the porous base material, in the following, the 1st form The description of the same configuration as that of the embodiment is omitted as appropriate.
  • the porous substrate is not particularly limited as long as it has a large number of pores or voids inside and has a porous structure in which these pores are connected to each other. Examples thereof include microporous membranes, nonwoven fabrics, paper-like sheets, and other sheets having a three-dimensional network structure. Among these, a microporous membrane is preferable from the viewpoint of handling properties and strength.
  • thermoplastic resins such as polyolefins are preferable from the viewpoint of obtaining shutdown characteristics. Therefore, if such a polyolefin porous substrate is applied, both heat resistance and a shutdown function can be achieved.
  • the polyolefin resin include polyethylene, polypropylene, polymethylpentene, and the like. Among them, those containing 90% by weight or more of polyethylene are preferable from the viewpoint of obtaining good shutdown characteristics.
  • the polyethylene for example, low density polyethylene, high density polyethylene, ultrahigh molecular weight polyethylene and the like are preferably used, and particularly, high density polyethylene and ultra high molecular weight polyethylene are suitable.
  • polyethylene comprising a mixture of high density polyethylene and ultra high molecular weight polyethylene is preferred from the viewpoint of strength and moldability.
  • the molecular weight of polyethylene is preferably 100,000 to 10,000,000 in terms of weight average molecular weight, and particularly preferably a polyethylene composition containing at least 1% by weight of ultrahigh molecular weight polyethylene having a weight average molecular weight of 1,000,000 or more.
  • the porous substrate in the present invention may be constituted by mixing other polyolefins such as polypropylene and polymethylpentene in addition to polyethylene, or two or more layers of a polyethylene microporous membrane and a polypropylene microporous membrane. You may comprise as a laminated body of.
  • the film thickness of the porous substrate is not necessarily limited, but a range of about 5 to 20 ⁇ m is preferable. If the film thickness is less than 5 ⁇ m, sufficient strength cannot be obtained, handling becomes difficult, and the yield of the battery may be significantly reduced. When the film thickness is larger than 20 ⁇ m, it is not preferable because the movement of ions becomes difficult or the volume occupied by the separator in the battery increases and the energy density of the battery may be lowered.
  • the porosity of the porous substrate is preferably 10 to 60%, more preferably 20 to 50%. When the porosity is lower than 10%, it is difficult to maintain an amount of electrolyte sufficient for battery operation, and the charge / discharge characteristics of the battery may be significantly deteriorated.
  • the puncture strength of the porous substrate is preferably 200 g or more, more preferably 250 g or more, more preferably 300 g or more. If the piercing strength is lower than 200 g, the strength for preventing a short circuit between the positive and negative electrodes of the battery is not sufficient, and there may be a problem that the manufacturing yield does not increase.
  • the Gurley value (JIS P8117) of the porous substrate is preferably in the range of 100 to 500 seconds / 100 cc, more preferably in the range of 100 to 300 seconds / 100 cc.
  • the average pore diameter of the porous substrate is preferably 10 to 100 nm. If the average pore diameter is smaller than 10 nm, it may be difficult to impregnate the electrolytic solution, which is not preferable.
  • the heat-resistant porous layer in the present invention includes a heat-resistant resin and an inorganic filler, and has a porous structure in which a large number of pores or voids are formed inside and these pores are connected to each other. It has become.
  • a heat-resistant porous layer is preferably an embodiment in which the inorganic filler is directly fixed on the porous substrate in a state where the inorganic filler is dispersed and bound in the heat-resistant resin, from the viewpoint of handling properties and the like.
  • a porous layer made of only a heat resistant resin is formed on a porous substrate, and a solution containing an inorganic filler is subsequently applied and immersed in the hole or surface of the heat resistant resin layer.
  • the aspect which the inorganic filler adhered may be sufficient.
  • the heat-resistant porous layer may be configured as an independent porous sheet such as a microporous film, a nonwoven fabric, or a paper-like sheet, and the porous sheet may be adhered to the porous substrate. Good.
  • the separator for a non-aqueous secondary battery of the present invention is characterized in that the above-mentioned inorganic filler is contained in the heat-resistant porous layer, but the inorganic filler is not contained in the porous substrate. Is one of the features.
  • the function of the inorganic filler can be expected to be expressed even if it is not present in the porous layer. For example, even if the inorganic filler is contained in the porous substrate, the effect of suppressing gas generation can be obtained. . However, such a configuration is not preferable because, when a polyolefin porous substrate is applied, the shutdown function may be significantly impaired.
  • an inorganic filler is not contained in a layer that is expected to have a shutdown function but is contained in a porous layer that is expected to have heat resistance.
  • the content of the inorganic filler is less than 20% by weight, it may be difficult to sufficiently obtain the characteristics of the inorganic filler, which is not preferable. If the content of the inorganic filler exceeds 90% by weight, it may be difficult to mold, which is not preferable.
  • the porosity of the heat resistant porous layer is preferably in the range of 30 to 80%. Furthermore, the porosity of the heat resistant porous layer is preferably higher than the porosity of the porous substrate. Such a configuration has advantages in characteristics such as better ion permeability and good shutdown characteristics.
  • the total thickness of the heat resistant porous layer is preferably 2 ⁇ m or more and 12 ⁇ m or less. When the porous porous layer is formed only on one side, it is preferably 2 ⁇ m or more and 12 ⁇ m or less.
  • the nonaqueous secondary battery separator of the present invention preferably has a thickness in the range of 7 to 25 ⁇ m, more preferably 10 to 20 ⁇ m. If the film thickness is thinner than 7 ⁇ m, it is not preferable from the viewpoint of mechanical strength. Further, if it exceeds 25 ⁇ m, it is not preferable from the viewpoint of ion permeability, and it is also not preferable from the viewpoint that the volume occupied by the separator in the battery is increased and the energy density is lowered.
  • the porosity of the non-aqueous secondary battery separator of the present invention is preferably 20 to 70%, more preferably 30 to 60%. If the porosity is lower than 20%, it may be difficult to hold a sufficient amount of electrolyte for battery operation, which is not preferable.
  • the puncture strength of the separator for a non-aqueous secondary battery of the present invention is preferably 200 g or more, more preferably 250 g or more, and further preferably 300 g or more. If the piercing strength is lower than 200 g, the strength for preventing a short circuit between the positive and negative electrodes of the battery is not sufficient, which may cause a problem that the production yield does not increase, which is not preferable.
  • the Gurley value (JIS P8117) in the non-aqueous secondary battery separator of the present invention is preferably in the range of 150 to 600 seconds / 100 cc, more preferably in the range of 150 to 400 seconds / 100 cc.
  • the Gurley value is lower than 150 seconds / 100 cc, although ion permeability is excellent, shutdown characteristics and mechanical strength may be deteriorated, which is not preferable. Further, when forming the porous layer, there is a possibility that a problem such as clogging may occur at the interface between the porous substrate and the heat-resistant porous layer.
  • the Gurley value is larger than 600 seconds / 100 cc, the ion permeability becomes insufficient and the load characteristics of the battery may be deteriorated.
  • the value obtained by subtracting the Gurley value of the porous substrate applied to the Gurley value of the separator for a non-aqueous secondary battery of the present invention is preferably 250 seconds / 100 cc or less, and more preferably 200 seconds / 100 cc or less. .
  • a smaller value is preferable in terms of characteristics such as better shutdown characteristics and improved ion permeability.
  • the heat-resistant porous layer may be formed on at least one surface of the porous substrate, but it is more preferable to form it on both the front and back surfaces of the porous substrate.
  • the method for producing the separator for a non-aqueous secondary battery of the present invention is not particularly limited.
  • the separator can be produced by a production method including the following steps (i) to (iv).
  • a step of producing a coating slurry containing a heat-resistant resin, an inorganic filler, and a water-soluble organic solvent and (ii) coating the obtained coating slurry on one or both surfaces of a porous substrate.
  • a step of coagulating the heat resistant resin in the coated slurry and (iv) a step of washing and drying the sheet after the coagulation step.
  • steps (i) to (iv) are the same as in the case of the first embodiment described above.
  • the method for producing the porous substrate is not particularly limited.
  • a polyolefin microporous film as a porous substrate can be produced as follows.
  • the nonaqueous secondary battery according to the third aspect of the present invention is a nonaqueous secondary battery including a positive electrode, a negative electrode, and a separator, and the separator for a nonaqueous secondary battery described above is used as the separator. It is characterized by.
  • the separator for a non-aqueous secondary battery according to the fourth aspect of the present invention is a heat-resistant porous material including a porous substrate and a heat-resistant resin and an inorganic filler laminated on one or both sides of the porous substrate.
  • the first aspect of the present invention described above is a configuration that solves the problem of compatibility between battery safety and durability in the technical field of separators and the like.
  • the structure using “/ g activated alumina” or “amorphous alumina” significantly lowers the activity of HF and is therefore excellent in the effect of improving the cycle characteristics of the battery. Therefore, in the second aspect of the present invention, focusing on this action effect, “active alumina” and “amorphous alumina” are regarded as hydrogen fluoride adsorbents, and this adsorbent is applied to each part of a non-aqueous secondary battery. explain. (2-1) Fifth form
  • the non-aqueous secondary battery adsorbent according to the fifth aspect of the present invention is an adsorbent of hydrogen fluoride mixed in the non-aqueous secondary battery, and the adsorbent has a specific surface area of 300 to 1000 m.
  • the specific surface area is 300 to 1000 m as the adsorbent for non-aqueous secondary batteries.
  • 2 / G activated alumina this activated alumina adsorbs or reacts with a small amount of HF generated in the battery, thereby reducing the HF activity and improving the cycle characteristics of the non-aqueous secondary battery.
  • the present invention has been made by finding that it exhibits excellent cycle characteristics different from other porous inorganic fillers.
  • alumina is an amphoteric oxide known as a Lewis acid / Lewis base, it can be considered that HF was polarized and HF was trapped efficiently.
  • the specific surface area is 300m 2 It is considered that the surface reaction was smoothly performed and the cycle characteristics were improved by setting the amount to / g or more.
  • Specific surface area is 1000m 2 It is technically difficult to obtain activated alumina exceeding / g at present.
  • the specific surface area is 300 to 1000 m. 2
  • the configuration of the “/ g activated alumina particles” is the same as that in the first embodiment described above, and the description thereof is omitted.
  • Examples of the embodiment containing the activated alumina include the following (A) to (C).
  • a porous membrane for a non-aqueous secondary battery comprising an inorganic filler and a binder resin, wherein the activated alumina is contained as the inorganic filler. film.
  • B A separator for a non-aqueous secondary battery comprising a porous substrate and a porous layer containing an inorganic filler and a binder resin laminated on one or both surfaces of the porous substrate, A separator for a non-aqueous secondary battery, wherein the activated alumina is contained as an inorganic filler.
  • a nonaqueous secondary battery comprising a positive electrode, a negative electrode, a nonaqueous electrolyte, and a separator, wherein the activated alumina is contained in the battery.
  • the activated alumina may be contained in a separator, may be contained in a porous film laminated on a separator or an electrode, or contained in a positive electrode and a negative electrode.
  • the volume of the active material is reduced correspondingly, and the battery capacity is impaired. Therefore, an embodiment in which activated alumina is contained in the separator is preferable.
  • the surface of the porous substrate made of a thermoplastic resin such as polyethylene is coated with a heat resistant porous layer made of a heat resistant resin such as polyamide,
  • a heat resistant porous layer made of a heat resistant resin such as polyamide
  • activated alumina is contained in the heat resistant porous layer.
  • the active alumina is included in the positive electrode, the positive electrode active material, the binder, and the conductive agent in the first embodiment described above and the active alumina are uniformly mixed to produce a positive electrode mixture. Disperse in a solvent to make a positive electrode mixture slurry. Next, the positive electrode mixture is applied to the positive electrode current collector by, for example, a doctor blade method.
  • the positive electrode containing activated alumina is obtained by drying at high temperature to volatilize the solvent and pressurizing.
  • the active alumina is fixed on the positive electrode by coating the active material side of the positive electrode with a coating solution in which the active alumina is dispersed in a solvent such as NMP without containing the active alumina in the positive electrode mixture. Is also effective.
  • the negative electrode contains the activated alumina, the negative electrode active material, the binder, and the conductive agent in the first embodiment described above and the active alumina are uniformly mixed to prepare a negative electrode mixture. Disperse in a solvent to make a negative electrode mixture slurry.
  • the negative electrode containing activated alumina is obtained by drying at high temperature to volatilize and pressurize the solvent.
  • the active alumina is fixed on the negative electrode by coating the active material side of the negative electrode with a coating liquid in which the active alumina is dispersed in a solvent such as NMP without containing the active alumina in the negative electrode mixture. Is also effective.
  • the separator contains the activated alumina
  • a thermoplastic resin such as polyethylene
  • the step of melt-kneading to prepare a thermoplastic resin solution containing the activated alumina, this solution from the die Extruding and cooling to form a gel-like molded product, a primary stretching step and a secondary stretching step, a step of removing the liquid solvent from the gel-shaped molded product, and a step of drying the obtained film A separator can be obtained as a thermoplastic resin microporous film containing activated alumina.
  • a coating solution in which a binder resin such as aromatic polyamide and activated alumina are uniformly dispersed is applied on a base film such as a polypropylene film, solidified, washed and dried, and then the coating film is peeled off. Can also be obtained.
  • activated alumina may be contained in any one of the layers or in all layers.
  • a coating liquid in which a heat-resistant resin such as aromatic polyamide and activated alumina are uniformly dispersed is coated on one or both sides of a porous substrate such as a polyethylene microporous film or nonwoven fabric, a laminated separator containing activated alumina Is obtained.
  • a porous substrate such as a nonwoven fabric is immersed in a coating solution in which a binder resin such as PVdF and activated alumina is uniformly dispersed, taken out, and then washed and dried to obtain a composite separator. It can also be obtained.
  • a binder resin for binding the activated alumina in the separator and the porous film described above in addition to a heat-resistant resin such as aromatic polyamide, thermoplastics such as polyvinylidene fluoride (PVdF), PVdF copolymer, polyethylene, etc. Examples thereof include resins.
  • the non-aqueous secondary battery adsorbent according to the sixth aspect of the present invention is an adsorbent of hydrogen fluoride mixed in the non-aqueous secondary battery, and the adsorbent is amorphous alumina particles. It is characterized by that.
  • amorphous alumina since amorphous alumina is used as the adsorbent for non-aqueous secondary batteries, amorphous alumina adsorbs minute impurities generated in the battery and by-products such as HF. Cycle characteristics can be improved.
  • this 6th form is the same as that of the 5th form mentioned above except the point which changed the adsorbent into amorphous alumina, description is abbreviate
  • “specific surface area is 300 to 1000 m. 2 / G activated alumina "and" amorphous alumina "have functions and effects that are very similar to each other.
  • the activated alumina is obtained from the viewpoint of specific surface area, and the amorphous alumina is obtained from the viewpoint of crystal structure. It is.
  • the embodiment containing the amorphous alumina is the same as the embodiment (A) to (C) in the fifth embodiment described above.
  • the amorphous alumina is preferably contained in any part between the positive electrode and the negative electrode in order to suppress internal short circuit.
  • the BET equation was used for analysis and determination by the nitrogen gas adsorption method.
  • the sample weight during measurement was 0.1 to 0.2 g.
  • the analysis was performed by a three-point method, and the specific surface area was obtained from the BET plot.
  • the XRD diffraction spectrum of the inorganic filler was measured with a powder X-ray diffractometer, and the crystal structure in the bulk structure was analyzed from this spectrum.
  • X-ray diffractometer For the X-ray diffractometer, an X-ray generator ultrax 18 manufactured by Rigaku was used, and Cu-K ⁇ rays were used. The measurement conditions were 45 KV-60 mA, sampling interval 0.020 °, measurement range (2 ⁇ ) 5 ° to 90 °, and scan speed 5 ° / min. As the measurement sample, an agate mortar was used to pulverize the inorganic filler manually and packed into a glass sample plate. The glass sample plate has a groove having a length of 18 mm, a width of 20 mm, and a depth of 0.2 mm, and the thickness of the sample is the depth of the glass sample plate.
  • Example 1-1 Aluminum hydroxide (manufactured by Showa Denko; H-43M) was heat-treated at 280 ° C., average particle diameter 0.8 ⁇ m, specific surface area 400 m 2 / G of activated alumina was obtained.
  • this activated alumina can be said to be amorphous alumina because it mainly has an amorphous bulk structure and a very small amount of boehmite phase is mixed.
  • the 0 / Al element ratio on the surface of the activated alumina was 1.54.
  • Conex registered trademark; manufactured by Teijin Techno Products, which is polymetaphenylene isophthalamide, was used as the meta-type wholly aromatic polyamide.
  • Example 1-2 Activated alumina with an average particle diameter of 4 ⁇ m and a specific surface area of 700 m 2
  • a porous membrane having a film thickness of 10 ⁇ m having sufficient handling properties was obtained in the same manner as in Example 1-1 except that the zeolite was changed to / g zeolite (HSZ-341NHA; manufactured by Tosoh Corporation).
  • Example 1-3 By performing wet pulverization (2-mm diameter zirconia bead mill) using dimethylacetamide (DMAc) as a dispersion solvent on activated carbon (manufactured by Kansai Thermal Chemical Co., Ltd .; MSP-20), an average particle diameter of 0.6 ⁇ m and a specific surface area of 1600 m 2 / G of activated carbon was obtained. A porous film having a thickness of 10 ⁇ m was obtained in the same manner as in Example 1-1 except that the activated alumina was changed to the activated carbon. In addition, this porous film was a little weak compared with the thing of Example 1-1, and was inferior to handleability.
  • DMAc dimethylacetamide
  • Example 1-5 The porous membrane for batteries produced in Example 1-1 was coated with a polyethylene aqueous dispersion (Kemipearl W900: manufactured by Mitsui Chemicals) and dried to obtain a porous membrane having a thickness of 13 ⁇ m.
  • Example 1-1 Activated alumina with an average particle size of 0.8 ⁇ m and a specific surface area of 8 m 2 A porous film with a handleability of 10 ⁇ m in thickness was obtained in the same manner as in Example 1-1, except that / g aluminum hydroxide (made by Showa Denko; H-43M) was used.
  • Comparative Example 1-2 Activated alumina with an average particle diameter of 0.6 ⁇ m and a specific surface area of 6 m 2 A porous film having a film thickness of 10 ⁇ m and a sufficient handling property was obtained in the same manner as in Example 1-1, except that it was changed to / g alumina (manufactured by Showa Denko: AL160SG-3).
  • Conex (registered trademark; manufactured by Teijin Techno Products), which is polymetaphenylene isophthalamide, was used as the meta-type wholly aromatic polyamide.
  • DMAc dimethylacetamide
  • TPG tripropylene glycol
  • a polyethylene solution was prepared by dissolving in a mixed solvent.
  • a slurry in which zeolite (HSZ-500KOA; manufactured by Tosoh Corporation) was dispersed in the polyethylene solution was prepared.
  • the mixing ratio of polyethylene and zeolite was 50:50 by weight.
  • Zeolite has an average particle size of 3 ⁇ m and a specific surface area of 290 m. 2 / G. This slurry was extruded from a die at 148 ° C. and cooled in a water bath to prepare a gel tape (base tape).
  • the base tape was dried at 60 ° C. for 8 minutes and at 95 ° C.
  • the base tape was biaxially stretched by successively performing longitudinal stretching and transverse stretching.
  • the longitudinal stretching was performed at a stretching ratio of 5.5 times and a stretching temperature of 90 ° C.
  • the transverse stretching was performed at a stretching ratio of 11.0 times
  • the stretching temperature was 105 ° C.
  • heat setting was performed at 125 ° C.
  • this was immersed in a methylene chloride bath to extract liquid paraffin and decalin. Thereafter, the film was dried at 50 ° C. and annealed at 120 ° C. to obtain a porous film with sufficient handling property of 10 ⁇ m.
  • Example 1-5 Aluminum hydroxide (manufactured by Showa Denko; H-43M) was heat-treated at 205 ° C., average particle size 0.8 ⁇ m, specific surface area 30 m 2 / G of activated alumina was obtained. In addition, when structural analysis was performed on this activated alumina by XRD, a broad peak derived from the amorphous structure was not confirmed, and a peak derived from the gibbsite was clearly observed. It turned out not to be alumina. A porous membrane having a film thickness of 10 ⁇ m and sufficient handleability was obtained by the same method as in Example 1-1, except that this activated alumina was used in place of the activated alumina of Example 1-1.
  • the measurement cell was stored at 85 ° C. for 3 days, and the volume of the measurement cell before and after storage was measured. A value obtained by subtracting the volume of the measurement cell before storage from the volume of the measurement cell after storage was taken as the gas generation amount.
  • the volume measurement of the measurement cell was performed at 23 ° C., and was performed using an electronic hydrometer (manufactured by Alpha Mirage Co., Ltd .; EW-300SG) according to Archimedes' principle. The results are shown in Table 1.
  • non-aqueous secondary batteries were produced as follows. Lithium cobalt oxide (LiCoO 2 NIPPON CHEMICAL INDUSTRIES CO., LTD.) 89.5 parts by weight of powder, acetylene black (manufactured by Denki Kagaku Kogyo; trade name Denka Black) 4.5 parts by weight, and polyvinylidene fluoride (manufactured by Kureha Chemical Co., Ltd.) 6 parts by weight. These were kneaded using an N-methyl-2pyrrolidone solvent to prepare a slurry.
  • Lithium cobalt oxide LiCoO 2 NIPPON CHEMICAL INDUSTRIES CO., LTD.
  • acetylene black manufactured by Denki Kagaku Kogyo; trade name Denka Black
  • polyvinylidene fluoride manufactured by Kureha Chemical Co., Ltd.
  • the obtained slurry was applied onto an aluminum foil having a thickness of 20 ⁇ m, dried and pressed to obtain a positive electrode having a thickness of 100 ⁇ m.
  • MCMB mesophase carbon microbeads
  • 10 parts by weight of polyvinylidene fluoride manufactured by Kureha Chemical Co., Ltd.
  • the obtained slurry was applied onto a copper foil having a thickness of 18 ⁇ m, dried and pressed to obtain a negative electrode having a thickness of 90 ⁇ m.
  • the positive electrode and the negative electrode were opposed to each other through a separator.
  • This was impregnated with an electrolytic solution and sealed in an exterior made of an aluminum laminate film to produce a non-aqueous secondary battery.
  • the electrolyte is 1M LiPF 6 Ethylene carbonate / ethyl methyl carbonate (3/7 weight ratio) (manufactured by Kishida Chemical Co., Ltd.) was used.
  • the porous membranes of Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-5 were used, and Examples 1-6 to 1-10 and Comparative Example 1 shown in Table 2 were used.
  • Non-aqueous secondary batteries of ⁇ 6 to 1-10 were produced.
  • the porous membranes of Examples 1-3 and 1-4 were used by being laminated with a polyethylene microporous membrane (PE microporous membrane).
  • the PE microporous film used here was produced by the following method. First, as the polyethylene powder, GUR2126 (weight average molecular weight 4150,000, melting point 141 ° C.) and GURX143 (weight average molecular weight 560,000, melting point 135 ° C.) manufactured by Ticona were used.
  • Liquid paraffin manufactured by Matsumura Oil Research Co., Ltd .; Smoyl P-350P; boiling point 480 ° C.
  • decalin so that GUR2126 and GURX143 are 1: 9 (weight ratio) and the polyethylene concentration is 30% by weight.
  • This polyethylene solution was extruded from a die at 148 ° C. and cooled in a water bath to prepare a gel tape (base tape). The base tape was dried at 60 ° C. for 8 minutes and at 95 ° C.
  • the base tape was biaxially stretched by successively performing longitudinal stretching and transverse stretching.
  • the longitudinal stretching was performed at a stretching ratio of 5.5 times and a stretching temperature of 90 ° C.
  • the transverse stretching was performed at a stretching ratio of 11.0 times
  • the stretching temperature was 105 ° C.
  • heat setting was performed at 125 ° C.
  • this was immersed in a methylene chloride bath to extract liquid paraffin and decalin. Then, it dried at 50 degreeC and annealed at 120 degreeC, and obtained the polyethylene microporous film
  • the capacity retention rate was calculated by multiplying the value obtained by dividing the remaining capacity by the initial capacity by 100. This capacity maintenance rate was used as an index for evaluating the storage test. The results are shown in Table 2. [Battery swelling] Each battery after the above storage test was visually confirmed. If the battery was clearly swollen, it was judged as x, and if the battery was not swollen in appearance, it was judged as ⁇ . In this case, the swelling of the battery is due to the generation of gas in the battery. The results are shown in Table 2.
  • Lithium cobalt oxide LiCoO 2 NIPPON CHEMICAL INDUSTRIES CO., LTD. 89.5 parts by weight of powder, acetylene black (manufactured by Denki Kagaku Kogyo; trade name Denka Black) 4.5 parts by weight, and polyvinylidene fluoride (manufactured by Kureha Chemical Co., Ltd.) 6 parts by weight. These were kneaded using an N-methyl-2pyrrolidone solvent to prepare a slurry. The obtained slurry was applied onto an aluminum foil having a thickness of 20 ⁇ m, dried and pressed to obtain a positive electrode having a thickness of 100 ⁇ m.
  • MCMB mesophase carbon microbeads
  • acetylene black manufactured by Denki Kagaku Kogyo; trade name Denka Black
  • polyvinylidene fluoride manufactured by Kureha Chemical Co., Ltd.
  • Example 1-11 was also evaluated for the oven test, cycle characteristics, storage test, and battery blistering described above. The results are shown in Table 3.
  • Lithium cobalt oxide LiCoO 2 NIPPON CHEMICAL INDUSTRIES CO., LTD. 89.5 parts by weight of powder, acetylene black (manufactured by Denki Kagaku Kogyo; trade name Denka Black) 4.5 parts by weight, and polyvinylidene fluoride (manufactured by Kureha Chemical Co., Ltd.) 6 parts by weight. These were kneaded using an N-methyl-2pyrrolidone solvent to prepare a slurry. The obtained slurry was applied onto an aluminum foil having a thickness of 20 ⁇ m, dried and pressed to obtain a positive electrode having a thickness of 100 ⁇ m.
  • MCMB mesophase carbon microbeads
  • acetylene black manufactured by Denki Kagaku Kogyo; trade name Denka Black
  • polyvinylidene fluoride manufactured by Kureha Chemical Co., Ltd.
  • the positive electrode and the negative electrode were opposed to each other through a separator. This was impregnated with an electrolytic solution and sealed in an exterior made of an aluminum laminate film to produce a non-aqueous secondary battery.
  • the electrolyte is 1M LiPF 6 Ethylene carbonate / ethyl methyl carbonate (3/7 weight ratio) (manufactured by Kishida Chemical Co., Ltd.) was used.
  • the separator used was the PE microporous membrane in Examples 1-8 and 1-9 described above.
  • the battery of Example 1-12 was also evaluated for the above-described oven test cycle characteristics, storage test, and battery blistering. The results are shown in Table 3.
  • Example 1-13 Lithium cobalt oxide (LiCoO 2 NIPPON CHEMICAL INDUSTRIES CO., LTD.) 89.5 parts by weight of powder, acetylene black (manufactured by Denki Kagaku Kogyo; trade name Denka Black) 4.5 parts by weight, and polyvinylidene fluoride (manufactured by Kureha Chemical Co., Ltd.) 6 parts by weight. These were kneaded using an N-methyl-2pyrrolidone solvent to prepare a slurry. The obtained slurry was applied onto an aluminum foil having a thickness of 20 ⁇ m, dried and pressed to obtain a positive electrode having a thickness of 100 ⁇ m.
  • Lithium cobalt oxide LiCoO 2 NIPPON CHEMICAL INDUSTRIES CO., LTD.
  • acetylene black manufactured by Denki Kagaku Kogyo; trade name Denka Black
  • polyvinylidene fluoride manufactured by Kureha Chemical Co., Ltd.
  • MCMB mesophase carbon microbeads
  • acetylene black manufactured by Denki Kagaku Kogyo; trade name Denka Black
  • polyvinylidene fluoride manufactured by Kureha Chemical Co., Ltd.
  • the electrolyte is 1M LiPF 6 Ethylene carbonate / ethyl methyl carbonate (3/7 weight ratio) (manufactured by Kishida Chemical Co., Ltd.) was used.
  • the separator used was the PE microporous membrane in Examples 1-8 and 1-9 described above.
  • the battery of Example 1-13 was also evaluated for the oven test, cycle characteristics, storage test, and battery blistering described above. The results are shown in Table 3. (2) Examples according to the third and fourth aspects Examples according to the third and fourth aspects of the present invention will be described below.
  • the measurement method applied in this example is as follows.
  • the cell resistance was measured by increasing the temperature at a rate of temperature increase of 1.6 ° C./min and simultaneously applying alternating current with an amplitude of 10 mV and a frequency of 1 kHz.
  • the resistance value is 10 in the range of 135 to 150 ° C. in the above measurement. 3 ohm-cm 2
  • the SD characteristic was evaluated as “good”, and when it was not, the SD characteristic was evaluated as “poor”.
  • Lithium cobalt oxide LiCoO 2 NIPPON CHEMICAL INDUSTRIES CO., LTD. 89.5 parts by weight of powder, acetylene black (manufactured by Denki Kagaku Kogyo; trade name Denka Black) 4.5 parts by weight, and polyvinylidene fluoride (manufactured by Kureha Chemical Co., Ltd.) 6 parts by weight. These were kneaded using an N-methyl-2pyrrolidone solvent to prepare a slurry. The obtained slurry was applied onto an aluminum foil having a thickness of 20 ⁇ m, dried and pressed to obtain a positive electrode having a thickness of 100 ⁇ m.
  • MCMB mesophase carbon microbeads
  • acetylene black manufactured by Denki Kagaku Kogyo; trade name Denka Black
  • polyvinylidene fluoride manufactured by Kureha Chemical Co., Ltd.
  • the positive electrode and the negative electrode were opposed to each other through the separators prepared in the following examples and comparative examples. This was impregnated with an electrolytic solution and sealed in an exterior made of an aluminum laminate film to produce a non-aqueous secondary battery.
  • the electrolyte is 1M LiPF 6 Ethylene carbonate / ethyl methyl carbonate (3/7 weight ratio) (manufactured by Kishida Chemical Co., Ltd.) was used.
  • the non-aqueous secondary battery was subjected to constant current / constant voltage charging at 0.2 C 4.2 V for 8 hours and constant current discharge at 0.2 C, 2.75 V cutoff. The discharge capacity obtained at the fifth cycle was defined as the initial capacity of this cell.
  • Example 2-1 As polyethylene powder, GUR2126 (weight average molecular weight 41.50 million, melting point 141 ° C.) and GRX143 (weight average molecular weight 560,000, melting point 135 ° C.) manufactured by Ticona were used. Liquid paraffin (manufactured by Matsumura Oil Research Co., Ltd .; Smoyl P-350P; boiling point 480 ° C.) and decalin so that GUR2126 and GURX143 are 1: 9 (weight ratio) and the polyethylene concentration is 30% by weight. A polyethylene solution was prepared by dissolving in a mixed solvent.
  • This polyethylene solution was extruded from a die at 148 ° C. and cooled in a water bath to prepare a gel tape (base tape).
  • the base tape was dried at 60 ° C. for 8 minutes and at 95 ° C. for 15 minutes, and the base tape was biaxially stretched by successively performing longitudinal stretching and transverse stretching.
  • the longitudinal stretching was performed at a stretching ratio of 5.5 times and a stretching temperature of 90 ° C.
  • the transverse stretching was performed at a stretching ratio of 11.0 times
  • the stretching temperature was 105 ° C.
  • heat setting was performed at 125 ° C.
  • DMAc dimethylacetamide
  • TPG tripropylene glycol
  • As a porous filler an average particle diameter of 3 ⁇ m and a specific surface area of 290 m 2 / G of zeolite (HSZ-500KOA; manufactured by Tosoh Corporation) was used.
  • the polyethylene microporous membrane was passed between Mayer bars carrying the dispersion, and the dispersion was applied to both sides of the polyethylene microporous membrane.
  • the clearance between the Mayer bars was 30 ⁇ m, and the number of the Mayer bars was 2 and # 6.
  • This was immersed in a coagulating liquid having a weight ratio of water: DMAc: TPG 70: 18: 12 (weight ratio) of 30 ° C., then washed with water and dried.
  • a heat-resistant porous layer made of Conex was formed to obtain a separator for a non-aqueous secondary battery of the present invention. The characteristics of the obtained non-aqueous secondary battery separator are shown in Tables 4 and 5.
  • Example 2-2 As a porous filler, the average particle diameter is 2 ⁇ m and the specific surface area is 400 m. 2 / G of zeolite (HSZ-980HOA; manufactured by Tosoh Corporation) was used in the same manner as Example 2-1 to obtain a non-aqueous secondary battery separator.
  • Porous filler has an average particle size of 4 ⁇ m and a specific surface area of 700 m 2 / G of zeolite (HSZ-341NHA; manufactured by Tosoh Corporation) was used in the same manner as in Example 2-1, to obtain a nonaqueous secondary battery separator.
  • Example 2-4 Activated carbon (manufactured by Kansai Thermal Chemical Co., Ltd .; MSP-20) is wet pulverized (2 mm zirconia bead mill) using dimethylacetamide (DMAc) as a dispersion solvent to obtain an average particle diameter of 0.6 ⁇ m and a specific surface area of 1600 m. 2 / G of activated carbon was obtained.
  • DMAc dimethylacetamide
  • the separator for non-aqueous secondary batteries of this invention was obtained like Example 2-1, except the point which used this activated carbon as a porous filler.
  • Example 2-5 Porous filler has an average particle size of 1.4 ⁇ m and a specific surface area of 190 m 2
  • a separator for a non-aqueous secondary battery of the present invention was obtained in the same manner as in Example 2-1, except that / g of activated alumina (manufactured by Sumitomo Chemical Co., Ltd .; KC-501) was used.
  • Example 2-6 Aluminum hydroxide (made by Showa Denko; H-43M) was heat-treated at 220 ° C., average particle size 0.8 ⁇ m, specific surface area 60 m 2 / G of activated alumina was obtained.
  • this activated alumina can be said to be amorphous alumina because it mainly has an amorphous bulk structure and a very small amount of boehmite phase is mixed.
  • the 0 / Al element ratio on the surface of the activated alumina was 1.54.
  • the separator for non-aqueous secondary batteries of this invention was obtained like Example 2-1, except the point which used this activated alumina as a porous filler.
  • Example 2-8 A separator for a non-aqueous secondary battery of the present invention was obtained in the same manner as in Example 2-7, except that the dispersion was applied to only one surface of a polyethylene microporous membrane to form a porous layer.
  • Example 2-1 instead of the porous filler used in Example 2-1, the average particle diameter was 0.6 ⁇ m and the specific surface area was 6 m as an inorganic filler. 2 A non-aqueous secondary battery separator was produced in the same manner as in Example 2-1, except that / g of ⁇ -alumina (manufactured by Showa Denko: AL160SG-3) was applied.
  • Example 2-2 instead of the porous filler used in Example 1, an inorganic filler has an average particle diameter of 0.6 ⁇ m and a specific surface area of 15 m.
  • Example 2 A non-aqueous secondary battery separator was produced in the same manner as in Example 2-1, except that / g boehmite (manufactured by Daimei Chemical Co., Ltd .: C06) was applied.
  • this activated alumina was analyzed by XRD, a broad peak derived from the amorphous structure was not confirmed, and a peak derived from the gibbsite was clearly observed.
  • the bulk structure was mainly gibbsite, and the amorphous structure was amorphous. It turned out not to be alumina.
  • a separator for a non-aqueous secondary battery was obtained in the same manner as in Example 2-1, except that the porous filler was changed to this activated alumina.
  • Comparative Example 2-4 As polyethylene powder, GUR2126 (weight average molecular weight 41.50 million, melting point 141 ° C.) and GRX143 (weight average molecular weight 560,000, melting point 135 ° C.) manufactured by Ticona were used.
  • GUR2126 and GURX143 are in a ratio of 1: 9 (weight ratio), and liquid paraffin (manufactured by Matsumura Oil Research Co., Ltd .; Smoyl P-350P; boiling point 480 ° C.) and decalin are added so that the polyethylene concentration is 15% by weight.
  • this zeolite has an average particle diameter of 3 ⁇ m and a specific surface area of 290 m. 2 / G.
  • This slurry was extruded from a die at 148 ° C. and cooled in a water bath to prepare a gel tape (base tape).
  • the base tape was dried at 60 ° C. for 8 minutes and at 95 ° C. for 15 minutes, and the base tape was biaxially stretched by successively performing longitudinal stretching and transverse stretching.
  • the longitudinal stretching was performed at a stretching ratio of 5.5 times and a stretching temperature of 90 ° C.
  • the transverse stretching was performed at a stretching ratio of 11.0 times
  • the stretching temperature was 105 ° C.
  • heat setting was performed at 125 ° C.
  • Lithium cobalt oxide LiCoO 2 NIPPON CHEMICAL INDUSTRIES CO., LTD. 89.5 parts by weight of powder, acetylene black (manufactured by Denki Kagaku Kogyo; trade name Denka Black) 4.5 parts by weight, and polyvinylidene fluoride (manufactured by Kureha Chemical Co., Ltd.) 6 parts by weight. These were kneaded using an N-methyl-2pyrrolidone solvent to prepare a slurry. The obtained slurry was applied onto an aluminum foil having a thickness of 20 ⁇ m, dried and pressed to obtain a positive electrode having a thickness of 100 ⁇ m.
  • MCMB mesophase carbon microbeads
  • acetylene black manufactured by Denki Kagaku Kogyo; trade name Denka Black
  • polyvinylidene fluoride manufactured by Kureha Chemical Co., Ltd.
  • the electrolyte is 1M LiPF 6 Ethylene carbonate / ethyl methyl carbonate (3/7 weight ratio) (manufactured by Kishida Chemical Co., Ltd.) was used.
  • separators of Example 2-7 and Example 2-8 were used, and batteries of Examples 2-9 to 2-11 shown in Table 6 were produced.
  • Evaluation of cycle characteristics is 1C 4.2V 2 hours constant current / constant voltage charge, 1C, charge / discharge with constant current discharge of 2.75V cutoff, 300 cycles when the first cycle capacity is used as a reference The eye capacity retention rate was used as an index of cycle characteristics.
  • the temperature at the time of measurement was 30 ° C.
  • the results are shown in Table 6. From the results of Table 6, it was found that the configuration in which the heat-resistant porous layer was formed on both sides of the porous substrate was superior in capacity retention rate than the configuration on one side. It was also found that the capacity retention rate was higher when the polyethylene microporous membrane was arranged on the negative electrode side even with a single-sided configuration.
  • the specific surface area is 300 to 1000 m. 2
  • the structure using activated alumina of / g is examined. The measurement methods applied in the following examples are as follows.
  • Example 3-1 (I) Production of PE microporous membrane As polyethylene powder, GUR2126 (weight average molecular weight 41.50 million, melting point 141 ° C.) and GRX143 (weight average molecular weight 560,000, melting point 135 ° C.) manufactured by Ticona were used. GUR2126 and GURX143 are made to have a ratio of 1: 9 (weight ratio) and liquid paraffin (manufactured by Matsumura Oil Research Co., Ltd .; Smoyl P-350P; boiling point 480 ° C.) and decalin so that the polyethylene concentration becomes 30% by weight. A polyethylene solution was prepared by dissolving in a mixed solvent.
  • This polyethylene solution was extruded from a die at 148 ° C. and cooled in a water bath to prepare a gel tape (base tape).
  • the base tape was dried at 60 ° C. for 8 minutes and at 95 ° C. for 15 minutes, and then the base tape was stretched by biaxial stretching that was performed in the order of longitudinal stretching and lateral stretching.
  • the longitudinal stretching was 5.5 times
  • the stretching temperature was 90 ° C.
  • the transverse stretching was 11.0 times the stretching ratio
  • the stretching temperature was 105 ° C.
  • heat setting was performed at 125 ° C.
  • this activated alumina can be said to be amorphous alumina because it mainly has an amorphous bulk structure and a very small amount of boehmite phase is mixed.
  • the obtained paste was applied onto an aluminum foil having a thickness of 20 ⁇ m, dried and pressed to obtain a positive electrode having a thickness of 97 ⁇ m.
  • Vi Manufacture of negative electrode
  • a negative electrode active material 87 parts by weight of mesophase carbon microbeads (MCMB, manufactured by Osaka Gas Chemical Co., Ltd.), 3 parts by weight of acetylene black and 6 parts by weight of polyfluorinated so that the dry weight of polyvinylidene fluoride is 10 parts by weight.
  • a negative electrode paste was prepared using an NMP solution of vinylidene.
  • the obtained paste was applied onto a copper foil having a thickness of 18 ⁇ m, dried and pressed to prepare a negative electrode having a thickness of 90 ⁇ m.
  • the base tape was stretched by biaxial stretching that was performed in the order of longitudinal stretching and lateral stretching.
  • the longitudinal stretching was 5.5 times
  • the stretching temperature was 90 ° C.
  • the transverse stretching was 11.0 times the stretching ratio
  • the stretching temperature was 105 ° C.
  • heat setting was performed at 125 ° C.
  • this was immersed in a methylene chloride bath to extract liquid paraffin and decalin. Then, it dried at 50 degreeC and annealed at 120 degreeC, and obtained the separator which consists of PE microporous films.
  • a nonaqueous secondary battery was produced in the same manner as in Example 3-1, except that this separator was used.
  • this activated alumina was mainly gibbsite.
  • a nonaqueous secondary battery was obtained in the same manner as in Comparative Example 3-1, except that this activated alumina was used as an inorganic filler.
  • As an inorganic filler an average particle diameter of 2 ⁇ m and a specific surface area of 400 m 2
  • a nonaqueous secondary battery was obtained in the same manner as Comparative Example 3-1, except that / g of zeolite (HSZ-980HOA; manufactured by Tosoh Corporation) was used.
  • Comparative Example 3-5 As an inorganic filler, an average particle diameter of 2 ⁇ m and a specific surface area of 300 m 2 A nonaqueous secondary battery was obtained in the same manner as Comparative Example 3-1, except that / g of silica (manufactured by Tokai Chemical Industry Co., Ltd .; ML-384) was used.
  • Activated carbon manufactured by Kansai Thermal Chemical Co., Ltd .; MSP-20
  • DMAc dimethylacetamide
  • Example 4-1 A nonaqueous secondary battery of Example 4-1 was produced in the same manner as Example 3-1 described above.
  • Comparative Example 4-1 As polyethylene powder, GUR2126 (weight average molecular weight 41.50 million, melting point 141 ° C.) and GRX143 (weight average molecular weight 560,000, melting point 135 ° C.) manufactured by Ticona were used. GUR2126 and GURX143 are made to have a ratio of 1: 9 (weight ratio) and liquid paraffin (manufactured by Matsumura Oil Research Co., Ltd .; Smoyl P-350P; boiling point 480 ° C.) and decalin so that the polyethylene concentration becomes 30% by weight.
  • the base tape was stretched by biaxial stretching that was performed in the order of longitudinal stretching and lateral stretching.
  • the longitudinal stretching was 5.5 times
  • the stretching temperature was 90 ° C.
  • the transverse stretching was 11.0 times the stretching ratio
  • the stretching temperature was 105 ° C.
  • heat setting was performed at 125 ° C.
  • this was immersed in a methylene chloride bath to extract liquid paraffin and decalin. Then, it dried at 50 degreeC and annealed at 120 degreeC, and obtained the separator which consists of PE microporous films.
  • a nonaqueous secondary battery was produced in the same manner as in Example 3-1 described above except that this separator was used.
  • Comparative Example 4-2 As an inorganic filler, average particle diameter 0.6 ⁇ m, specific surface area 15 m 2 A nonaqueous secondary battery was obtained in the same manner as Comparative Example 4-1, except that / g nonporous alumina (manufactured by Daimei Chemical Co., Ltd .; C06) was used. When this alumina was subjected to XRD analysis, a clear peak derived from boehmite was observed.
  • Comparative Example 4-3 As an inorganic filler, average particle diameter 0.8 ⁇ m, specific surface area 7m 2 A nonaqueous secondary battery was obtained in the same manner as Comparative Example 4-1, except that / g nonporous aluminum hydroxide (manufactured by Showa Denko; H-43M) was used. When this aluminum hydroxide was subjected to XRD analysis, a clear peak derived from gibbsite was observed.
  • / g nonporous aluminum hydroxide manufactured by Showa Denko; H-43M
  • Example 4-1 using amorphous alumina includes ⁇ -alumina (Comparative Example 4-1), boehmite (Comparative Example 4-2), gibbsite (Comparative Example 4-3) and the like. Compared to the alumina-based filler, the capacity retention rate after 400 cycle characteristic tests is remarkably superior. This is presumably because amorphous alumina lowered the activity of HF in the battery. (5) Example according to the fifth embodiment Examples according to the fifth aspect of the present invention will be described below. The average particle diameter, specific surface area, true density, crystal structure and element ratio, and film thickness measuring method of the inorganic filler are as described above.
  • Example 5-1 (I) Production of activated alumina Activated alumina A was produced in the same manner as in Example 3-1. (Ii) Production of positive electrode, negative electrode and non-aqueous electrolyte A positive electrode, a negative electrode, and a nonaqueous electrolyte were also produced in the same manner as in Example 3-1. (Iii) Manufacture of separators As polyethylene powder, GUR2126 (weight average molecular weight 41.50 million, melting point 141 ° C.) and GRX143 (weight average molecular weight 560,000, melting point 135 ° C.) manufactured by Ticona were used.
  • the base tape was dried at 60 ° C. for 8 minutes and at 95 ° C. for 15 minutes, and then the base tape was stretched by biaxial stretching that was performed in the order of longitudinal stretching and lateral stretching.
  • the longitudinal stretching was 5.5 times
  • the stretching temperature was 90 ° C.
  • the transverse stretching was 11.0 times the stretching ratio
  • the stretching temperature was 105 ° C.
  • heat setting was performed at 125 ° C. Next, this was immersed in a methylene chloride bath to extract liquid paraffin and decalin. Then, it dried at 50 degreeC and annealed at 120 degreeC, and obtained the PE separator which consists of a polyethylene microporous film.
  • Non-aqueous secondary battery The positive electrode and negative electrode obtained as described above were opposed to each other through a separator. This was impregnated with a non-aqueous electrolyte and sealed in an outer package made of an aluminum laminate film to produce a non-aqueous secondary battery of an example of the present invention.
  • Example 5-2 Aluminum hydroxide (Showa Denko; H-43M) was heat-treated at 260 ° C., average particle size 0.8 ⁇ m, specific surface area 350 m 2 / G, true density 3.0 g / cm 3 Activated alumina B was obtained.
  • this activated alumina mainly has an amorphous bulk structure and a very small amount of boehmite phase was mixed.
  • a nonaqueous secondary battery of the present invention was obtained in the same manner as in Example 5-1, except that this activated alumina B was used as an inorganic filler.
  • TPG propylene glycol
  • Example 5-4 A coating solution was prepared by mixing 5 parts by weight of polyvinylidene fluoride, 1 part by weight of activated alumina A, and 94 parts by weight of DMAc and stirring sufficiently to obtain a uniform solution.
  • Example 5-5 A nonaqueous secondary battery of the present invention was obtained in the same manner as in Example 5-4 except that the PVdF / PP separator obtained in Example 5-4 was used so that the coating layer was in contact with the negative electrode.
  • Example 5-6 Lithium manganate (LiMn 2 O 4 89.5 parts by weight of powder (manufactured by JGC Chemical Co., Ltd.), 4.5 parts by weight of acetylene black (DENKA BLACK, manufactured by Denki Kagaku Kogyo Co., Ltd.) and 6 parts by weight of dry weight of polyvinylidene fluoride (manufactured by CLEA Chemical Industries, Ltd.)
  • a positive electrode paste was prepared using an NMP solution of 6% by weight of polyvinylidene fluoride.
  • a nonaqueous secondary battery of the present invention was obtained in the same manner as in Example 5-1, except that this positive electrode was used.
  • Example 5-7 Lithium cobalt oxide (LiCoO 2 , Manufactured by Nippon Chemical Industry Co., Ltd.) 89.5 parts by weight of powder, 4.5 parts by weight of acetylene black (Denka Black, manufactured by Denki Kagaku Kogyo Co., Ltd.), 3 parts by weight of activated alumina A and polyvinylidene fluoride (manufactured by Claire Chemical Industries, Ltd.) A positive electrode paste was prepared using 6 wt% of an NMP solution of polyvinylidene fluoride so that the dry weight of 6) was 6 parts by weight.
  • the obtained paste was applied onto an aluminum foil having a thickness of 20 ⁇ m, dried and pressed to obtain a positive electrode having a thickness of 97 ⁇ m.
  • polyethylene powder GUR2126 (weight average molecular weight 41.50 million, melting point 141 ° C.) and GRX143 (weight average molecular weight 560,000, melting point 135 ° C.) manufactured by Ticona were used.
  • GUR2126 and GURX143 are made to have a ratio of 1: 9 (weight ratio) and liquid paraffin (manufactured by Matsumura Oil Research Co., Ltd .; Smoyl P-350P; boiling point 480 ° C.) and decalin so that the polyethylene concentration becomes 30% by weight.
  • a polyethylene solution was prepared by dissolving in a mixed solvent.
  • This polyethylene solution was extruded from a die at 148 ° C. and cooled in a water bath to prepare a gel tape (base tape).
  • the base tape was dried at 60 ° C. for 8 minutes and at 95 ° C. for 15 minutes, and then the base tape was stretched by biaxial stretching that was performed in the order of longitudinal stretching and lateral stretching.
  • the longitudinal stretching was 5.5 times
  • the stretching temperature was 90 ° C.
  • the transverse stretching was 11.0 times the stretching ratio
  • the stretching temperature was 105 ° C.
  • heat setting was performed at 125 ° C.
  • Example 5-1 A nonaqueous secondary battery of the present invention was obtained in the same manner as in Example 5-1, except that the positive electrode and PE separator produced as described above were used.
  • Example 5-8 As negative electrode active material, 87 parts by weight of mesophase carbon microbeads (MCMB, manufactured by Osaka Gas Chemical Co., Ltd.), 3 parts by weight of acetylene black, 3 parts by weight of activated alumina A, and 10 parts by weight of dry weight of polyvinylidene fluoride As described above, a negative electrode agent paste was prepared using an NMP solution of 6% by weight of polyvinylidene fluoride. The obtained paste was applied onto a copper foil having a thickness of 18 ⁇ m, dried and pressed to produce a negative electrode having a thickness of 91 ⁇ m.
  • MCMB mesophase carbon microbeads
  • a nonaqueous secondary battery of the present invention was obtained in the same manner as in Example 5-1, except that this negative electrode was used and the PE separator in Example 5-7 was used.
  • Example 5-9 The coating liquid prepared in Example 5-4 was applied to the active material side of the positive electrode manufactured in Example 5-1 using a bar coater, and then dried at 60 ° C. As a result, a positive electrode having a coating layer (positive electrode surface layer) having a thickness of 4 ⁇ m was obtained.
  • a nonaqueous secondary battery of the present invention was obtained in the same manner as in Example 5-1, except that this positive electrode was used and the PE separator in Example 5-7 was used.
  • Example 5-10 The coating liquid prepared in Example 5-4 was applied to the active material side of the negative electrode manufactured in Example 5-1 using a bar coater, and then dried at 60 ° C. As a result, a negative electrode having a coating layer (negative electrode surface layer) having a thickness of 4 ⁇ m was obtained.
  • a nonaqueous secondary battery of the present invention was obtained in the same manner as in Example 5-1, except that this negative electrode was used and the PE separator in Example 5-7 was used.
  • Comparative Example 5-1 A non-aqueous secondary battery was obtained in the same manner as in Example 5-1, except that the PE separator in Example 5-7 was used.
  • a separator in which polyvinylidene fluoride was combined with a nonwoven fabric was obtained.
  • a nonaqueous secondary battery was obtained in the same manner as in Example 5-1, except that this PVdF / nonwoven fabric separator was used.
  • a polypropylene separator (Celguard # 2400) was used instead of the PE separator.
  • Example 5-4 As an inorganic filler, average particle size 0.5 ⁇ m, specific surface area 7 m 2 A non-aqueous secondary battery was obtained in the same manner as in Example 5-1, except that / g of ⁇ -alumina (AL-160SG-3; manufactured by Showa Denko) was used.
  • / g of ⁇ -alumina AL-160SG-3; manufactured by Showa Denko
  • Aluminum hydroxide made by Showa Denko; H-43M
  • Example 5-6 Aluminum hydroxide (Showa Denko; H-43M) was heat-treated at 240 ° C., average particle diameter 0.8 ⁇ m, specific surface area 200 m 2 / G, true density 2.6 g / cm 3 Of activated alumina D was obtained.
  • Example 5-7 As an inorganic filler, an average particle diameter of 2 ⁇ m and a specific surface area of 400 m 2 / G zeolite (HSZ-980HOA; manufactured by Tosoh Corporation) was used in the same manner as in Example 5-1, to obtain a non-aqueous secondary battery.
  • Example 5-8 Without using activated alumina as an inorganic filler, the average particle size is 2 ⁇ m and the specific surface area is 300 m. 2 A non-aqueous secondary battery was obtained in the same manner as in Example 1 except that / g of silica (manufactured by Tokai Chemical Industry; ML-384) was used.
  • Activated carbon manufactured by Kansai Thermal Chemical Co., Ltd .; MSP-20
  • DMAc dimethylacetamide
  • a nonaqueous secondary battery was obtained in the same manner as in Example 5-1, except that this activated carbon was used as an inorganic filler.
  • a nonaqueous secondary battery was obtained in the same manner as in Comparative Example 5-1, except that the positive electrode produced in Example 5-6 was used.
  • the specific surface area is 1600m 2 In Comparative Example 5-9 using activated carbon of / g, the capacity retention rate was as low as 62% compared to Examples 5-1 and 5-2. From this, the specific surface area is 1000m 2 / G or less, more preferably 500 m 2 / G or less is suitable. On the other hand, the true density is 2.7 g / cm. 3 Below and 3.9 g / cm 3 Then, the capacity retention rate is low, and 2.8 to 3.3 g / cm 3 It was found that better results could be obtained within this range.
  • the location of the activated alumina was effective even if contained in the electrode or laminated on the electrode surface.
  • the specific surface area is 300 to 1000 m. 2
  • the location of the activated alumina is not particularly limited.
  • HF content is measured by disassembling the non-aqueous secondary battery after measuring the capacity retention rate, and then in a predetermined amount of solution in which ethylene carbonate and ethyl methyl carbonate are mixed at a weight ratio of 3: 7. And left for 1 week to extract HF present in the battery with a solution. Then, titration was performed with an aqueous sodium hydroxide solution using bromothymol blue as an indicator, and the acid concentration in the extracted solution was determined. Finally, the value obtained by converting the obtained acid concentration per weight of the electrolyte used in the non-aqueous secondary battery was defined as the HF content (ppm). The measurement results for each sample are shown in Table 10 below.
  • Example 5-1 A non-aqueous secondary battery was produced in the same manner as in Example 5-1.
  • Example 6-2 A non-aqueous secondary battery was produced in the same manner as in Example 5-2 described above.
  • Example 6-3 A non-aqueous secondary battery was produced in the same manner as Example 5-3 described above.
  • Example 6-4 A non-aqueous secondary battery was produced in the same manner as in Example 5-4 described above.
  • Example 6-5 A non-aqueous secondary battery was produced in the same manner as in Example 5-5 described above.
  • Example 6-6 A non-aqueous secondary battery was produced in the same manner as in Example 5-9 described above.
  • Example 6-7 A nonaqueous secondary battery was produced in the same manner as in Example 5-10 described above.
  • Example 6-1 A non-aqueous secondary battery was produced in the same manner as Comparative Example 5-1 described above.
  • Comparative Example 6-2 A non-aqueous secondary battery was produced in the same manner as Comparative Example 5-2 described above.
  • Comparative Example 6-3 A non-aqueous secondary battery was produced in the same manner as Comparative Example 5-3 described above.
  • Comparative Example 6-4 Without using alumina A as an inorganic filler, the average particle size is 0.5 ⁇ m and the specific surface area is 7 m. 2 / G nonporous alumina E (manufactured by Showa Denko; AL-160SG-3) was used in the same manner as in Example 6-1 to obtain a nonaqueous secondary battery.
  • Example 6-5 Without using alumina A as an inorganic filler, the average particle diameter is 0.6 ⁇ m and the specific surface area is 15 m. 2 A nonaqueous secondary battery was obtained in the same manner as in Example 6-1, except that / g nonporous alumina F (Daimei Chemical Industries; C06) was used. When this alumina F was subjected to XRD analysis, a clear peak derived from boehmite was observed.
  • / g nonporous alumina F Daimei Chemical Industries; C06
  • Example 6-1 A nonaqueous secondary battery was obtained in the same manner as in Example 6-1 except that / g of silica (manufactured by Tokai Chemical Industry Co., Ltd .; ML-644) was used.
  • Comparative Example 6-9 A non-aqueous secondary battery was produced in the same manner as Comparative Example 5-9 described above.
  • Comparative Examples 6-4 to 6-6 having a structure other than amorphous had a capacity retention rate as low as 60% or less, and further, ignition was confirmed in a 140 ° C. oven test. This indicates that amorphous alumina is excellent in both cycle characteristics and safety in internal short circuit. Further, as other inorganic fillers, zeolite, silica, and activated carbon were evaluated in Comparative Examples 6-7 to 6-9, but the capacity retention rate was slightly over 60% as compared with Examples 6-1 to 6-2. Low and ignition was confirmed in the 140 ° C. oven test. This also shows that amorphous alumina is excellent as the inorganic filler to be added.
  • MD direction thermal shrinkage (length between AB before heat treatment ⁇ length between AB after heat treatment) / (length between AB before heat treatment) ⁇ 100
  • TD direction thermal shrinkage (length between CDs before heat treatment ⁇ length between CDs after heat treatment) / (length between CDs before heat treatment) ⁇ 100 From Table 12, Examples 6-1 to 6-2, which did not ignite in the 140 ° C. oven test, had a heat shrinkage ratio of 15% or less in the MD direction and 2% in the TD direction.
  • the thermal shrinkage rate in the MD direction was 20% or more
  • the thermal shrinkage rate in the TD direction was 3% or more, which was higher than those in Examples 6-1 to 6-2. From this, when the thermal shrinkage rate is 20% or more in the MD direction and 3% or more in the TD direction, the separator in the non-aqueous secondary battery breaks in the 140 ° C. oven test and causes ignition due to an internal short circuit. I can guess.
  • amorphous alumina is contained between the negative electrode and the positive electrode. The knowledge that it was good to be able to be made was able to be acquired.

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Abstract

L'invention concerne, d'une part, une technique visant à améliorer la sûreté et la durabilité d'une batterie secondaire non aqueuse et, d'autre part, une technique visant à améliorer les caractéristiques de cycle eu égard à la réaction avec le fluorure d'hydrogène ou à l'adsorption. L'invention concerne en particulier une membrane poreuse pour une batterie secondaire non aqueuse, conçue de manière à contenir une résine thermorésistante et une charge inorganique. La membrane poreuse pour une batterie secondaire non aqueuse est caractérisée en ce que la charge inorganique est composée d'une charge poreuse dont le diamètre moyen des particules est compris entre 0,1 et 5,0 μm et dont la surface spécifique est comprise entre 40 et 3000 m2/g, ou de particules d'alumine amorphe. L'invention concerne également en particulier un séparateur obtenu par mise en place de la membrane poreuse, servant de couche poreuse thermorésistante, sur une base poreuse. L'invention concerne aussi un adsorbant du fluorure d'hydrogène qui a pénétré dans une batterie secondaire non aqueuse, caractérisé en ce qu'il est composé de particules d'alumine active dont la surface spécifique est comprise entre 300 et 1000 m2/g, ou d'alumine amorphe.
PCT/JP2010/053380 2009-02-24 2010-02-24 Membrane poreuse pour batterie secondaire non aqueuse, séparateur pour batterie secondaire non aqueuse, adsorbant pour batterie secondaire non aqueuse et batterie secondaire non aqueuse WO2010098497A1 (fr)

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