WO2015076571A1 - Composition d'agent de revêtement de séparateur, séparateur formé de la composition d'agent de revêtement, et batterie faisant appel à celui-ci - Google Patents

Composition d'agent de revêtement de séparateur, séparateur formé de la composition d'agent de revêtement, et batterie faisant appel à celui-ci Download PDF

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Publication number
WO2015076571A1
WO2015076571A1 PCT/KR2014/011173 KR2014011173W WO2015076571A1 WO 2015076571 A1 WO2015076571 A1 WO 2015076571A1 KR 2014011173 W KR2014011173 W KR 2014011173W WO 2015076571 A1 WO2015076571 A1 WO 2015076571A1
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Prior art keywords
separator
meth
separation membrane
binder
acrylate
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PCT/KR2014/011173
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English (en)
Korean (ko)
Inventor
김남효
박명국
김윤기
김하나
박진규
이병민
Original Assignee
삼성에스디아이 주식회사
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Publication of WO2015076571A1 publication Critical patent/WO2015076571A1/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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/494—Tensile strength
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a membrane coating composition.
  • the present invention also relates to a separator coated with the coating composition and an electrochemical cell using the same.
  • a separator for an electrochemical cell refers to an interlayer membrane which maintains ionic conductivity while separating an anode and a cathode from each other in a cell, thereby allowing the battery to be charged and discharged.
  • a non-woven separator prepared by processing heat-resistant polymer into a fibrous shape, a ceramic separator made by connecting inorganic particles using a small amount of binder, and a coated separator coated with ceramic and binder on existing polyolefin or nonwoven fabrics.
  • Korean Registered Patent No. 10-0775310 Korean Registered Patent No. 10-0775310
  • the present invention is to provide a coating separator that is prevented from shrinking in the battery and improved heat resistance and shape stability.
  • an organic binder comprising an acrylic copolymer comprising a (meth) acrylate-based monomer-derived repeating unit and an acetate group-containing monomer-derived repeating unit; Inorganic particles; And there is provided a membrane coating composition comprising a solvent.
  • a separator comprising an acrylic copolymer comprising a unit and a repeating unit derived from an acetate group-containing monomer.
  • a separator comprising a polyolefin-based substrate film and a coating layer comprising an organic binder and inorganic particles, formed on one or both sides of the substrate film, is placed between the anode and the cathode at 100 °C After pressing for 10 seconds at a pressure of 20kgf / cm 2 to 100kgf / cm 2, the membrane is provided with a separation shrinkage of 10% or less in the MD and TD directions when left at 130 ° C. for 10 minutes.
  • an electrochemical cell particularly a lithium secondary battery, including the separator according to the above example is provided.
  • the separator according to the present invention has the effect of preventing shrinkage in the battery and improving heat resistance.
  • the separator according to the present invention is further excellent in physical properties such as air permeability and mechanical strength.
  • the separator according to an embodiment of the present invention includes a base film, and a coating layer formed on one side or both sides of the base film.
  • the base film may be a polyolefin-based.
  • the polyolefin-based substrate film has an excellent shut down function and may contribute to improvement of safety of the battery.
  • the polyolefin-based substrate film may be selected from the group consisting of, for example, polyethylene monolayer, polypropylene monolayer, polyethylene / polypropylene double membrane, polypropylene / polyethylene / polypropylene triple membrane, and polyethylene / polypropylene / polyethylene triple membrane. .
  • the polyolefin based film may have a thickness of 1 to 40 ⁇ m, specifically 5 ⁇ m to 15 ⁇ m. When using the base film within the thickness range, it is possible to produce a separator having a suitable thickness, thick enough to prevent a short circuit between the positive and negative electrodes of the battery, but not thick enough to increase the internal resistance of the battery.
  • the coating layer may be formed of a coating composition, the coating composition may include an organic binder, inorganic particles, and a solvent.
  • the organic binder may be an acrylic copolymer, and for example, may be an acrylic copolymer including a (meth) acrylate-based monomer-derived repeating unit and an acetate group-containing monomer-derived repeating unit.
  • an acrylic copolymer having a (meth) acrylate-based monomer-derived repeating unit and an acetate group-containing monomer-derived repeating unit as a binder, it is possible to prevent shrinkage of the membrane and improve heat resistance in a battery in which the separator is actually used. have.
  • the heat resistance of the separator is applied to the separator itself under constant conditions, and in each of the longitudinal direction (hereinafter referred to as 'MD direction') and width direction (hereinafter referred to as 'TD direction') of the separator before and after heating.
  • the degree of shrinkage is evaluated.
  • the heat resistance evaluated as described above does not properly reflect the heat shrinkage stability in the environment in which the actual separator is used, and does not match the actual shape stability of the separator in the battery. Therefore, it is necessary to arrange the separator between the electrodes in the battery and to evaluate the heat resistance and shrinkage in the compressed state.
  • the acrylic copolymer improves the adhesion between the electrode and the separator, and the adhesive strength increases the heat resistance. There is an effect to promote and prevent the shrinkage of the separator. That is, the shape stability of the separator in the battery is improved, thereby improving the safety of the battery.
  • the glass transition temperature (Tg) of the acrylic copolymer may be less than 100 °C, for example, 20 to 60 °C. Within this range, the separator may be positioned between the electrodes and formed to have good adhesion at a temperature at which the separator is pressed, thereby improving the shrinkage rate and improving heat resistance.
  • the acrylic copolymer having a (meth) acrylate-based monomer-derived repeating unit and an acetate group-containing monomer-derived repeating unit which can be used herein may be capable of forming a good adhesive force at a temperature compressed between the anode and the cathode as described above.
  • the acrylic copolymer may include at least one selected from the group consisting of butyl (meth) acrylate, propyl (meth) acrylate, ethyl (meth) acrylate and methyl (meth) acrylate ( It may be a copolymer produced by polymerizing a meth) acrylate-based monomer and at least one acetate group-containing monomer selected from the group consisting of vinyl acetate and allyl acetate.
  • the acetate group-containing monomer-derived repeating unit may be a repeating unit of Formula 1:
  • R 1 is a single bond, straight or branched alkyl of 1 to 6 carbon atoms
  • R 2 is hydrogen or methyl
  • l is an integer between 1 and 100, respectively.
  • the acrylic copolymer is a (meth) acrylate monomer and an acetate group-containing monomer, for example, vinyl acetate and / or allyl acetate in a molar ratio of 3: 7 to 7: 3, specifically 4: 6 to 6: 4 More specifically, by polymerization in a ratio of about 5: 5.
  • the acrylic copolymer may include, for example, a butyl (meth) acrylate monomer, a methyl (meth) acrylate monomer, and a vinyl acetate and / or allyl acetate monomer, in a weight ratio of 3 to 5: 0.5 to 1.5: 4 to 6, specifically It may be prepared by a polymerization reaction of 4: 1: 5.
  • the inorganic particles used in the present invention are not particularly limited and may be inorganic particles commonly used in the art.
  • Non-limiting examples of the inorganic particles usable in the present invention include Al 2 O 3 , SiO 2 , B 2 O 3 , Ga 2 O 3 , TiO 2 , SnO 2 , and the like. These can be used individually or in mixture of 2 or more types.
  • Al 2 O 3 (alumina) can be used as the inorganic particles used in the present invention.
  • the size of the inorganic particles used in the present invention is not particularly limited, but the average particle diameter may be 1 nm to 2,000 nm, for example, 100 to 1,000 nm, 300 nm to 500 nm.
  • the inorganic particles in the size range it is possible to prevent the dispersibility and coating processability of the inorganic particles in the coating liquid to be lowered and the thickness of the coating layer is appropriately adjusted to prevent the reduction of mechanical properties and increase of electrical resistance. Can be.
  • the size of the pores generated in the separator is appropriately adjusted, there is an advantage that can lower the probability of the internal short circuit occurs during the charge and discharge of the battery.
  • the inorganic particles may be used in the form of an inorganic dispersion in which it is dispersed in a suitable solvent.
  • the appropriate solvent is not particularly limited and may be a solvent commonly used in the art.
  • Acetone can be used as a suitable solvent for dispersing the inorganic particles, for example.
  • the inorganic dispersion may be prepared by a conventional method without any particular limitation. For example, Al 2 O 3 may be added to acetone in an appropriate amount, and the inorganic dispersion may be milled and dispersed using a bead mill. Dispersions can be prepared.
  • the inorganic particles in the coating layer may be included in 70 to 99% by weight, specifically 75 to 95% by weight, more specifically 80 to 90% by weight based on the total weight of the coating layer.
  • the inorganic particles are contained within the above range, the heat dissipation characteristics of the inorganic particles may be sufficiently exhibited, and when the separator is coated using the inorganic particles, heat shrinkage of the separator may be effectively suppressed.
  • Non-limiting examples of the solvent usable in the present invention include dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), dimethyl carbonate (Dimethyl carbonate, DMC). ) Or N-methylpyrrolidone (N-Methyl pyrrolydone, NMP).
  • the content of the solvent may be 20 to 99% by weight, specifically 50 to 95% by weight, and more specifically 70 to 95% by weight based on the weight of the coating composition. When the solvent is contained in the above range, the coating agent may be easily prepared, and the drying process of the coating layer may be performed smoothly.
  • the coating layer and the coating composition according to the present embodiment is distinguished from the embodiment of the present invention in that another binder is added in addition to the acrylic copolymer.
  • another binder is added in addition to the acrylic copolymer.
  • binders added in addition to the acrylic copolymers include polyvinylidene fluoride (PVdF) homopolymers, polyvinylidene fluoride-Hexafluoropropylene copolymers (PVDF-HFP), and polymethyl Methacrylate (polymethylmethacrylate, PMMA), polyacrylonitrile (PAN), polyvinylpyrrolidone (PVP), polyvinylacetate (PVAc), polyethylene oxide (PEO), cellulose acetate (cellulose acetate, CA), cellulose acetate butyrate (CAB), cellulose acetate propionate (CAP), cyanoethylpullulan (CYEPL), cyanoethylpolyvinyl alcohol ( cyanoethylpolyvinylalcohol (CR-V), cyanoethylcellulose (CEC), Single or a mixture thereof selected from the group consisting of cynoethylsucrose, pullulan, carb
  • the weight ratio of the acrylic copolymer and the added binder may be 9: 1 to 3: 7, specifically 9: 1 to 5: 5, and more specifically 8: 2 to 6: 4. Within this range, the shape stability may be further improved, and thus manufacturing of a battery having high efficiency charge and discharge characteristics may be possible.
  • the PVdF-based binder when the PVdF-based binder is further included, the PVdF-based binder may have a weight average molecular weight (Mw) of 500,000 to 1,500,000 (g / mol).
  • the PVdF-based binder may use, for example, PVdF-HFP or PVdF homopolymer.
  • the PVdF-based binder may use a weight average molecular weight of 1,000,000 g / mol or more.
  • one or more types of weight average molecular weights of 1,000,000 g / mol or less and one or more types of 1,000,000 g / mol or more can be mixed and used.
  • the use of the PVdF-based binder within the above molecular weight range enhances the adhesion between the coating layer and the polyolefin-based substrate film, thereby effectively suppressing shrinkage of the polyolefin-based substrate film, which is weak to heat, and further improving the separation membrane with sufficient electrolyte impregnation. It can be manufactured and by using this has the advantage that can produce a battery with efficient electrical output.
  • Membrane in accordance with embodiments of the present invention is to position the membrane between the anode and the cathode, when On the 100 °C 10 chogan pressure pressed into the 20kgf / cm 2 to 100kgf / cm 2 eseo 130 °C to stand for 10 minutes MD and TD
  • Directional compression shrinkage may be less than 10% each. Specifically, it may be 5% or less, and more specifically 3% or less. Since the compression shrinkage rate is low, heat resistance and shrinkage of the separator are improved in an environment in which the separator is used, thereby improving the safety of the battery. That is, it is possible to provide a separation membrane having excellent shape stability.
  • the method of measuring the compression shrinkage of the separator is as follows:
  • Membrane samples were prepared in 50 mm x 50 mm lengths, and the positive and negative electrodes were cut into 55 mm x 55 mm, respectively, and the aluminum pouches used for cell production were cut into 6 cm x 6 cm. do.
  • the anodes, separators, and cathodes are then placed in order and placed in half folded aluminum pouches.
  • the sample is pressed at 100 ° C. for 10 seconds at a pressure of 20 kgf / cm 2 to 100 kgf / cm 2 , and then left at 130 ° C. for 10 minutes to obtain shrinkage.
  • Separation membrane according to embodiments of the present invention may be less than 500 sec / 100cc, specifically 50 to 400 sec / 100cc, more specifically 50 to 300 sec / 100cc.
  • the tensile strength in the MD direction of the separator according to the embodiments of the present invention may be 1750 kg / cm 2 or more, and the tensile strength in the TD direction may be 1650 kg / cm 2 or more, specifically 1700 kg / cm 2 or more.
  • Separation membrane according to the embodiments of the present invention is excellent in mechanical properties without lowering the air permeability despite excellent compression shrinkage.
  • Method for producing a separator according to an embodiment of the present invention is a repeating unit derived from the (meth) acrylate monomers on one or both sides of the polyolefin-based substrate film, and repeating units derived from an acetate group-containing monomer, such as vinyl acetate or allyl acetate monomer
  • a binder comprising an acrylic copolymer having a; Inorganic particles; And forming a coating layer with a coating composition comprising a solvent.
  • forming the coating composition may include mixing a binder, a solvent, and an inorganic particle including an acrylic copolymer and stirring at 10 to 40 ° C. for 30 minutes to 5 hours.
  • the content of the solid content may be 10 to 20 parts by weight based on the coating composition, the weight ratio of the binder and the inorganic particles in the solid content may be 3: 7 to 0.1: 9.9.
  • a coating composition may be prepared by preparing an inorganic dispersion in which the inorganic particles are dispersed in a dispersion medium, and mixing the mixture with a polymer solution containing a binder and a solvent including an acrylic copolymer.
  • the inorganic dispersion is prepared separately as described above, the dispersibility and crude liquid stability of the inorganic particles and the binder may be improved.
  • the binder component and the inorganic particles may each be prepared and mixed in a dissolved or dispersed state in a suitable solvent.
  • an acrylic copolymer, a polyvinylidene fluoride homopolymer, and / or a polyvinylidene fluoride-hexafluoropropylene copolymer are prepared by dissolving each in an appropriate solvent, and an inorganic dispersion in which inorganic particles are dispersed.
  • the coating composition can then be prepared by mixing them with a suitable solvent.
  • a ball mill, a beads mill, a screw mixer, or the like may be used for the mixing.
  • a coating layer is formed of the coating composition on one or both surfaces of the polyolefin-based substrate film.
  • the method of coating the polyolefin-based substrate film using the coating agent is not particularly limited, and a method commonly used in the art may be used.
  • Non-limiting examples of the coating method may include a dip coating method, a die coating method, a roll coating method, or a comma coating method. These may be applied alone or in combination of two or more methods.
  • the coating layer of the separator of the present invention may be formed by, for example, a dip coating method.
  • the coating layer may have a thickness of 0.01 ⁇ m to 20 ⁇ m, specifically 1 ⁇ m to 10 ⁇ m, and more specifically 1 ⁇ m to 5 ⁇ m. Within the thickness range, it is possible to form a coating layer having a suitable thickness to obtain excellent thermal stability and adhesion, and to prevent the thickness of the entire separator from being too thick to suppress the increase in the internal resistance of the battery.
  • the coating layer may be dried by hot air, hot air, low humidity, vacuum drying, or a method of irradiating far infrared rays or electron beams.
  • the drying temperature is different depending on the type of the solvent, but can be dried at a temperature of approximately 60 °C to 120 °C.
  • the drying time also varies depending on the type of solvent, but may generally be dried for 1 minute to 1 hour. In embodiments, it may be dried for 1 minute to 30 minutes, or 1 minute to 10 minutes at a temperature of 90 °C to 120 °C.
  • an electrochemical cell including a polyolefin-based porous separator including the coating layer and an anode and a cathode and filled with an electrolyte is provided.
  • the kind of the electrochemical cell is not particularly limited, and may be a battery of a kind known in the art.
  • the electrochemical cell of the present invention may be a lithium secondary battery such as a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery or a lithium ion polymer secondary battery.
  • a lithium secondary battery such as a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery or a lithium ion polymer secondary battery.
  • the method for producing the electrochemical cell of the present invention is not particularly limited, and a method commonly used in the art may be used.
  • a non-limiting example of a method of manufacturing the electrochemical cell is as follows: A polyolefin-based separator comprising the coating layer of the present invention is placed between a positive electrode and a negative electrode of the battery, and then the battery is filled in such a manner as to fill an electrolyte solution. It can manufacture.
  • the electrode constituting the electrochemical cell of the present invention can be produced in a form in which the electrode active material is bound to the electrode current collector by a method commonly used in the technical field of the present invention.
  • the cathode active material is not particularly limited, and a cathode active material commonly used in the technical field of the present invention may be used.
  • Non-limiting examples of the positive electrode active material include lithium manganese oxide, lithium cobalt oxide, lithium nickel oxide, lithium iron oxide or a lithium composite oxide in combination thereof.
  • the negative electrode active material of the electrode active material used in one embodiment of the present invention is not particularly limited and may be a negative electrode active material commonly used in the technical field of the present invention.
  • Non-limiting examples of the negative electrode active material include lithium adsorption materials such as lithium metal or lithium alloy, carbon, petroleum coke, activated carbon, graphite (graphite) or other carbons, and the like.
  • the electrode current collector used in one embodiment of the present invention is not particularly limited, and an electrode current collector commonly used in the technical field of the present invention may be used.
  • Non-limiting examples of the positive electrode current collector material of the electrode current collector may be a foil made of aluminum, nickel or a combination thereof.
  • Non-limiting examples of the negative electrode current collector material of the electrode current collector may be a foil produced by copper, gold, nickel, copper alloy or a combination thereof.
  • the electrolyte solution used in the present invention is not particularly limited and may be used an electrochemical cell electrolyte solution commonly used in the technical field of the present invention.
  • the electrolyte solution may be one in which a salt having a structure such as A + B ⁇ is dissolved or dissociated in an organic solvent.
  • a + include a cation consisting of an alkali metal cation such as Li + , Na + or K + , or a combination thereof.
  • the B - Non-limiting examples of the, PF 6 -, BF 4 - , Cl -, Br -, I -, ClO 4 -, AsF 6 -, CH 3 CO 2 -, CF 3 SO 3 -, N (CF 3 SO 2) 2 - or C (CF 2 SO 2) 3 - anions, such as, or may be an anion consisting of a combination thereof.
  • Non-limiting examples of the organic solvent include propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (Dipropyl carbonate, DPC), dimethyl sulfoxide (DMSO), acetonitrile, dimethoxyethane, diethoxyethane, tetrahydrofuran (Tetrahydrofuran, THF), N-methyl- 2-pyrrolidone (N-methyl-2-pyrrolidone, NMP), ethyl methyl carbonate (EMC), gamma-butyrolactone ( ⁇ -Butyrolactone, GBL), etc. are mentioned. These may be used alone or in combination of two or more thereof.
  • PC propylene carbonate
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • DMC dimethyl carbonate
  • Dipropyl carbonate Dipropyl carbonate
  • DMSO dimethyl sulfoxide
  • Acetone is an acrylic copolymer binder in which butyl methacrylate (BMA), methyl methacrylate (MMA), and vinyl acetate (Vinyl Acetate, VAc) are polymerized at a 4/1/5 molar ratio.
  • BMA butyl methacrylate
  • MMA methyl methacrylate
  • VAc vinyl acetate
  • Alumina dispersion was prepared by adding alumina (LS235, Nippon Light Metal) to acetone at 25% by weight and dispersing the beads for 3 hours.
  • the first and second binder solutions and the alumina dispersion were mixed so that the weight ratio of the binder solid content and the alumina solid content was 1/6 so that the weight ratio of the acrylic binder and the PVdF binder was 7/3, and the total solid content was 10 weight.
  • Acetone was added to make the coating solution.
  • 12 ⁇ m thick polyethylene fabric (SK, Inc.) was coated on both sides of the coating solution with a thickness of 2 ⁇ m, respectively, to prepare a coating separator having a total thickness of about 16 ⁇ m.
  • the binder solution and the alumina dispersion were mixed so that the weight ratio of the binder solid content and the alumina solid content was 1/5 such that the weight ratio of the acrylic binder and the KF9300, 21216 binder was 5/3/2, and the total solid content was 10% by weight.
  • Acetone was added to prepare a coating solution.
  • a coating separator of about 16 ⁇ m in total thickness was prepared by coating 2 ⁇ m thick with the coating solution on both sides of a 12 ⁇ m thick polyethylene fabric (SK).
  • Example 1 except that butyl methacrylate (BMA), methyl methacrylate (MMA) and allyl acetate (Allyl Acetate) as the acrylic binder was used in a molar ratio of 4/1/5. In the same manner as in the production of a coating separator having a total thickness of about 16 ⁇ m.
  • BMA butyl methacrylate
  • MMA methyl methacrylate
  • Allyl Acetate allyl acetate
  • Example 1 except that the molar ratio of butyl methacrylate (BMA), acrylonitrile (AN), and vinyl acetate 4/1/5 was used as the acrylic binder in the same manner as in Example 1 A coating separator having a total thickness of about 16 ⁇ m was prepared.
  • BMA butyl methacrylate
  • AN acrylonitrile
  • vinyl acetate 4/1/5 vinyl acetate 4/1/5
  • a separator was manufactured in the same manner as in Example 1, except that the weight ratio of the binder solids to the alumina solids was 1/6 by using only the acrylic copolymer binder without using the PVdF-based binder.
  • Alumina dispersion was prepared by adding alumina (LS235, Nippon Light Metal) to acetone at 25% by weight and dispersing the beads for 3 hours. The binder solution and the alumina dispersion were mixed so that the weight ratio of the binder solid content and the alumina solid content was 1/6 so that the weight ratio of the KF9300 and 21216 binders was 5/5, and acetone was added so that the total solid content was 11% by weight.
  • a coating solution was prepared.
  • a coating separator having a total thickness of about 16 ⁇ m was prepared using a coating solution of polyethylene fabric (SK) having a thickness of 12 ⁇ m.
  • Example 1 except that polybutyl methacrylate (PBMA) was used as the acrylic binder was carried out in the same manner as in Example 1 to prepare a coating separator having a total thickness of about 16 ⁇ m.
  • PBMA polybutyl methacrylate
  • Comparative Example 3 a polyethylene fabric (SK company) having a thickness of 12 um which was the same as that used in Comparative Example 1 was used without coating.
  • Each of the separators prepared in the above Examples and Comparative Examples was prepared to cut 10 samples cut at 10 different points to a size of 1 inch (1 inch) in diameter, and then the air permeability measuring device (Asahi Seiko) G) was used to measure the time for passage of 100 cc of air in each sample. The time was measured five times each, and then the average value was calculated as air permeability.
  • Each of the separators prepared in Examples and Comparative Examples was cut into five pieces in a rectangular shape of 50 mm long by 150 mm long by 150 mm long by MD, and 150 mm long by 50 mm wide by 50 mm TD.
  • Ten samples were prepared, and each sample was mounted on a UTM (tension tester) to bite to a measurement length of 20 mm, and then the sample was pulled to measure average tensile strength in the MD and TD directions.
  • Each of the separators prepared in Examples and Comparative Examples was 50 mm long by 50 mm long by TD.
  • the aluminum pouches used for battery production are cut into 6 cm x 6 cm and prepared.
  • the anodes, separators, and cathodes are then placed in order and placed in half folded aluminum pouches.
  • the compression shrinkage is indicated by 5 points at regular intervals on the membrane, pressurized at 20 kgf / cm 2 for 10 seconds at 100 ° C., left at 130 ° C. for 10 minutes, and then measured by the contracted length between the gaps. The compression shrinkage was obtained.
  • the non-compression shrinkage was measured for 10 minutes after leaving the membrane sample in an oven at 130 °C to measure the shrinkage of the membrane.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Cell Separators (AREA)

Abstract

La présente invention concerne un séparateur qui comprend un film de base en polyoléfine, et une couche de revêtement qui est formée sur une surface ou les deux surfaces du film de base et contient un liant organique et des particules inorganiques, le liant organique comprenant un copolymère à base d'acryle possédant un motif de répétition dérivé d'un monomère de (méth)acrylate et un motif de répétition dérivé d'un monomère contenant un groupe acétate ; une composition d'agent de revêtement de séparateur ; et une batterie électrochimique comprenant le séparateur.
PCT/KR2014/011173 2013-11-21 2014-11-20 Composition d'agent de revêtement de séparateur, séparateur formé de la composition d'agent de revêtement, et batterie faisant appel à celui-ci WO2015076571A1 (fr)

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KR20130142324 2013-11-21

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CN109935755A (zh) * 2018-08-20 2019-06-25 苏州清陶新能源科技有限公司 一种有机-无机复合凝胶隔膜及其制备方法
WO2019156410A1 (fr) * 2018-02-12 2019-08-15 삼성에스디아이주식회사 Séparateur pour une batterie rechargeable au lithium et batterie rechargeable au lithium comprenant ce dernier
CN112640196A (zh) * 2019-05-09 2021-04-09 株式会社Lg化学 用于电化学装置的隔板和包括该隔板的电化学装置
CN112640195A (zh) * 2018-09-18 2021-04-09 三星Sdi株式会社 用于锂二次电池的隔板以及包括该隔板的锂二次电池
CN113471625A (zh) * 2021-06-30 2021-10-01 无锡恩捷新材料科技有限公司 二次电池、电池隔膜以及制备电池隔膜涂层的浆料

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US10637028B2 (en) 2015-07-10 2020-04-28 Lg Chem, Ltd. Separator and electrochemical device comprising same
KR101880237B1 (ko) * 2015-08-28 2018-08-17 삼성에스디아이 주식회사 다공성 내열층 조성물, 상기 다공성 내열층 조성물을 포함하는 분리막, 이를 이용한 이차 전지 및 이들의 제조 방법
KR102546315B1 (ko) * 2015-09-25 2023-06-21 삼성전자주식회사 리튬전지용 전극 복합분리막 어셈블리 및 이를 포함한 리튬전지
US20230163413A1 (en) * 2020-04-06 2023-05-25 Lg Energy Solution, Ltd. Separator for electrochemical device and method for manufacturing same
EP4135113A1 (fr) * 2020-04-14 2023-02-15 LG Energy Solution, Ltd. Séparateur pour dispositif électrochimique et son procédé de fabrication
KR20220021137A (ko) * 2020-08-13 2022-02-22 주식회사 엘지에너지솔루션 PVAc-PMA 공중합체를 포함하는 전지용 고접착 분리막 및 이를 포함하는 이차전지

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WO2019156410A1 (fr) * 2018-02-12 2019-08-15 삼성에스디아이주식회사 Séparateur pour une batterie rechargeable au lithium et batterie rechargeable au lithium comprenant ce dernier
CN111712943A (zh) * 2018-02-12 2020-09-25 三星Sdi株式会社 用于锂二次电池的隔板和包括该隔板的锂二次电池
CN111712943B (zh) * 2018-02-12 2023-08-25 三星Sdi株式会社 用于锂二次电池的隔板和包括该隔板的锂二次电池
CN109935755A (zh) * 2018-08-20 2019-06-25 苏州清陶新能源科技有限公司 一种有机-无机复合凝胶隔膜及其制备方法
CN112640195A (zh) * 2018-09-18 2021-04-09 三星Sdi株式会社 用于锂二次电池的隔板以及包括该隔板的锂二次电池
CN112640195B (zh) * 2018-09-18 2023-04-14 三星Sdi株式会社 用于锂二次电池的隔板以及包括该隔板的锂二次电池
CN112640196A (zh) * 2019-05-09 2021-04-09 株式会社Lg化学 用于电化学装置的隔板和包括该隔板的电化学装置
CN112640196B (zh) * 2019-05-09 2024-02-09 株式会社Lg新能源 用于电化学装置的隔板和包括该隔板的电化学装置
US12100860B2 (en) 2019-05-09 2024-09-24 Lg Energy Solution, Ltd. Separator for electrochemical device and an electrochemical device comprising the same
CN113471625A (zh) * 2021-06-30 2021-10-01 无锡恩捷新材料科技有限公司 二次电池、电池隔膜以及制备电池隔膜涂层的浆料
CN113471625B (zh) * 2021-06-30 2022-08-19 无锡恩捷新材料科技有限公司 二次电池、电池隔膜以及制备电池隔膜涂层的浆料

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