WO2016003094A1 - Membrane de separation poreuse a base de polyolefine et procede de preparation de cette membrane - Google Patents

Membrane de separation poreuse a base de polyolefine et procede de preparation de cette membrane Download PDF

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Publication number
WO2016003094A1
WO2016003094A1 PCT/KR2015/006201 KR2015006201W WO2016003094A1 WO 2016003094 A1 WO2016003094 A1 WO 2016003094A1 KR 2015006201 W KR2015006201 W KR 2015006201W WO 2016003094 A1 WO2016003094 A1 WO 2016003094A1
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polyolefin
separator
stretching
mol
molecular weight
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PCT/KR2015/006201
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English (en)
Korean (ko)
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김기욱
이상호
이용배
이정승
장정수
조재현
홍대현
Original Assignee
삼성에스디아이 주식회사
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Priority to CN201580035489.9A priority Critical patent/CN106489215A/zh
Priority to JP2016575432A priority patent/JP6818557B2/ja
Publication of WO2016003094A1 publication Critical patent/WO2016003094A1/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
    • H01M50/489—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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
    • B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H01M50/406—Moulding; Embossing; Cutting
    • 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
    • H01M50/417—Polyolefins
    • 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
    • H01M50/409—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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/068—Ultra high molecular weight polyethylene
    • 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 polyolefin-based separator and a method for producing the same.
  • a separator for an electrochemical cell refers to an interlayer membrane which maintains ion conductivity while allowing the cathode and the cathode to be separated from each other in the cell, thereby allowing the battery to be charged and discharged.
  • the present invention is to provide a separator having excellent air permeability and porosity while having a strong strength and a low strain rate of the shape or size of the pores of the separator.
  • a composition comprising a polyolefin resin and a plasticizer is melt-kneaded and extruded to form a sheet, and the sheet is elongated at a temperature T 1 in the longitudinal direction by an E 1 times and at a temperature T 2 in the width direction.
  • a method for producing a separator is provided.
  • a polyolefin containing a polyolefin-based resin, the average point pressure (psi) / bubble point pressure (psi) in the wet and dry curve of the separator measured by capillary flow porosimeter is 1.8 to 2.4
  • a system separator is provided.
  • Separation membrane according to an embodiment of the present invention has a higher electrolyte hygroscopicity by the form of pores of the membrane.
  • the separator according to an embodiment of the present invention also has a strong mechanical strength while having excellent air permeability and porosity by controlling the size distribution of the pores of the separator.
  • FIG. 1 is a graph of capillary flow porometer (Pillary flow porometer) of PMI measured for the separator according to an embodiment of the present invention.
  • the pressure at the starting point at which the curve is drawn in the wet graph is called bubble point pressure (psi), and the pressure at the point where the wet curve meets the virtual straight line where the slope of the straight line is 1/2 in the dry graph This is called the mean point pressure (psi).
  • the bubble point pressure and the average point pressure reflect the maximum pore size and the average pore size of the separator, respectively.
  • a melt-kneaded and extruded composition comprising a polyolefin-based resin and a plasticizer to form a sheet
  • the sheet is stretched E 1 times at a temperature T 1 in the longitudinal direction
  • a first stretching of E 2 times in the width direction at a temperature of T 2 extracting a plasticizer from the stretched sheet, and making the final stretch ratio in the width direction of the sheet from which the plasticizer is extracted to be 1.25 times to 1.5 times.
  • First, forming the sheet includes melt-kneading and extruding a composition containing a polyolefin resin and a plasticizer to form a cooled solidified sheet.
  • the polyolefin-based resin is a resin containing a polyolefin, for example, a group consisting of ultra high molecular weight polyethylene, high molecular weight polyethylene, high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, high crystalline polypropylene and polyethylene-propylene copolymer It may include one or two or more selected from.
  • the polyolefin resin may include other resin in addition to the polyolefin. Examples of other resins include polyimide, polyester, polyamide, polyetherimide, polyamideimide, polyacetal, and the like.
  • the polyolefin resin composition may be prepared by blending the polyolefin resin and the other resin in an appropriate solvent.
  • the viscosity average molecular weight (Mv) of the high density polyethylene may be 1 ⁇ 10 5 g / mol to 9 ⁇ 10 5 g / mol, for example, 3 ⁇ 10 5 g / mol to 6 ⁇ 10 5 g / mol have.
  • the viscosity average molecular weight of the ultrahigh molecular weight polyethylene may be 9 ⁇ 10 5 g / mol or more, specifically 9 ⁇ 10 5 g / mol to 5 ⁇ 10 6 g / mol.
  • the high density polyethylene may be used alone or the ultra high molecular weight polyethylene may be used alone, or both the high density polyethylene and the ultra high molecular weight polyethylene may be used.
  • the ultrahigh molecular weight polyethylene may be used in an amount of 30% by weight or less based on the weight of the polyolefin resin, and for example, a viscosity average molecular weight of 1 ⁇ 10 5 g / mol to 9 ⁇ 10 5 g / Polyolefin resins containing 70% by weight or more of high density polyethylene, which is mol, and 30% by weight or less of ultra high molecular weight polyethylene having a viscosity average molecular weight of 9 ⁇ 10 5 g / mol or more can be used.
  • the polyolefin resin is advantageous because it can produce a high strength separator. In addition, when it contains two or more types of said polyolefin resin, it is good to mix using 1 or more types chosen from the group which consists of a Henschel mixer, a Bambari mixer, and a French mixer.
  • the plasticizer may be an organic compound that forms a single phase with the polyolefin-based resin at an extrusion temperature.
  • plasticizers usable in the present invention include aliphatic or cyclic hydrocarbons such as nonane, decane, decalin, liquid paraffin (or paraffin oil), paraffin wax; Phthalic acid esters such as dibutyl phthalate and dioctyl phthalate; Fatty acids having 10 to 20 carbon atoms, such as palmitic acid, stearic acid, oleic acid, linoleic acid, and linolenic acid; C10-C20 fatty acid alcohols, such as a palmitic alcohol, a stearic acid alcohol, and an oleic acid alcohol, etc.
  • liquid paraffin can be preferably used. Liquid paraffin is harmless to the human body, has a high boiling point and low volatile components, making it suitable for use as a plasticizer in the wet process.
  • Melting and kneading the composition comprising the polyolefin-based resin and the plasticizer herein may use a method known to those skilled in the art, and may be melt-kneading the polyolefin-based resin and the plasticizer at a temperature of 150 ° C to 250 ° C.
  • the melt-kneaded composition may be injected into a twin screw extruder to extrude at 150 ° C to 250 ° C. Thereafter, the extruded polyolefin resin is cooled using a casting roll of 20 ° C. to 80 ° C. or forcedly cooled by cold air injected from an air knife to crystallize the film to form a solidified sheet.
  • the temperature of the cool air injected from the air knife may be -20 °C to 40 °C.
  • the sheet in the longitudinal direction is carried out first stretch of E 2 times longer in the temperature T 2 to the E 1 times and then stretched widthwise at a temperature T 1.
  • the stretching temperature conditions at the time of stretching are 100 ° C ⁇ T 1 ⁇ 115 ° C, 100 ° C ⁇ T 2 ⁇ 115 ° C, and T 2 ⁇ T 1 .
  • the same stretching may cause a difference in the length of stretching for each part, and after stretching in the TD direction can be formed in the separation membrane of two or more different pore size.
  • relatively small pores are advantageous in terms of heat shrinkage, strength, and pore strain, and relatively large pores are advantageous in terms of air permeability, electrolyte wettability, and battery capacity.
  • the MD direction draw ratio (E 1 ) and the TD direction draw ratio (E 2 ) are 7.5 times and 8 times or more, respectively, and the draw surface ratio (E 1 ⁇ E 2 ) is 60 to 80, which is high. Due to the stretched surface magnification, it is possible to minimize the strain of the shape and size of the pores due to the external pressure of the separator to improve battery stability.
  • the present invention can minimize the strain of the shape and size of the pores by the external pressure while ensuring the porosity required for the separation membrane by stretching under the conditions of the stretching temperature and the draw ratio as described above.
  • the MD stretching temperature T 1 may be 2 ° C. or more lower than the TD stretching temperature T 2 . For example, it may be lower than 3 ° C, or higher than 5 ° C.
  • MD direction draw ratio E 1 is 7.5 times, TD direction draw ratio E 2 is 8 times; MD direction draw ratio E 1 is 8 times, TD direction draw ratio E 2 is 8 times; MD direction draw ratio E 1 is 8 times, TD direction draw ratio E 2 is 8.5 times; Alternatively, the MD direction draw ratio E 1 may be 8.5 times, and the TD direction draw ratio E 2 may be 8.5 times.
  • the draw ratios in the width direction and the longitudinal direction may be the same or different. Specifically, the ratio of E 1 / E 2 may be 0.85 to 1. If it is the range of the said extending
  • the plasticizer may be extracted after the first stretching.
  • the plasticizer extraction may be performed using an organic solvent, and in particular, the longitudinally stretched and the widthwise stretched separator may be immersed in an organic solvent in the plasticizer extracting apparatus to extract a plasticizer.
  • the organic solvent used for the plasticizer extraction is not particularly limited, and any solvent may be used as long as it can extract the plasticizer.
  • Non-limiting examples of the organic solvent may be methyl ethyl ketone, methylene chloride, hexane, etc., which has high extraction efficiency and easy drying, and methylene chloride is preferably used as the organic solvent when liquid paraffin is used as a plasticizer. .
  • the second drawing may be performed such that the sheet from which the plasticizer has been extracted is stretched in the width direction such that the final draw ratio is 1.25 to 1.5 times.
  • the stretching in the width direction is a heat setting step for removing the residual stress of the film to reduce the shrinkage of the final film, and can adjust the heat shrinkage rate, transmittance, etc. of the film according to the temperature and fixation ratio during the heat setting.
  • the heat setting may be performed in the width direction of the drawing in a range of 1.25 times to 2 times of the 2-1 stretching, and relaxed to 70% to 100% of the stretched width direction so that the final drawing ratio is 1.25 times to 1.5 times. Can be.
  • the heat setting in the arrangement has the effect of improving the air permeability by adjusting the deviation of the pores generated during the biaxial stretching.
  • the heat setting may be performed at 100 to 150 ° C., for example, may be performed at 120 to 135 ° C. It is effective in removing residual stress of the film in the above range, and can improve physical properties.
  • the present invention provides a polyolefin-based separator prepared by the method for producing a polyolefin-based separator according to the above examples.
  • the polyolefin separator may have an average point pressure (psi) / bubble point pressure (psi) of about 1.8 to about 2.4 in a wet curve of the separator measured by a capillary flow porosimeter.
  • the pore size is varied so that the porosity required for the membrane, eg, 40% or more It is possible to provide a separator having excellent air permeability and excellent electrolyte wettability and strength while achieving.
  • the bubble point pressure refers to the pressure of the starting point at which the wet curve is drawn in the capillary flow pore meter. Specifically, when the membrane sample is soaked in the solution, the pore is filled with the solution, and the air is increased while the air is blown while increasing the pressure. The solution filled inside moves under pressure first, and the pressure at this time is called bubble point pressure. Referring to FIG. 1, the bubble point pressure refers to the pressure at the time when the flow velocity is maintained at 0 and starts to increase in the graph of the flow rate change with increasing pressure of the capillary flow pore meter.
  • the average point pressure refers to the pressure at the point where the wet straight line meets the imaginary straight line and the wet curve in which the slope is 1/2 in the dry straight line in the capillary flow pore meter. Specifically, when the air is blown while increasing the pressure while the membrane sample is not wetted with the solution, a graph having a linear shape in which the flow rate increases in proportion to the pressure increase is obtained. Referring to FIG. 1, when a virtual straight line (half dry graph in FIG. 1) having a slope is 1/2 in the straight graph (dry graph in FIG. 1), the virtual straight line and the wet curve are The pressure at the point of meeting is called the average point pressure.
  • the polyolefin-based separator according to an embodiment of the present invention may have a porosity of 40% to 50% and a permeability of 50 sec / 100 cc to 200 sec / 100 cc.
  • air permeability refers to the time at which 100 cc of air passes through the separator.
  • the air permeability may be 60 sec / 100cc to 150 sec / 100cc.
  • the ratio of tensile strength (kg / cm 2 ) / elongation (%) in the longitudinal and width directions of the separator is 15 to 28 ⁇ (kg / cm 2 ) /% ⁇ , respectively.
  • the polyolefin-based separator according to an embodiment of the present invention may have a tensile strength of 1700 kg / cm 2 or more in the longitudinal direction of the membrane, a tensile strength of 1800 kg / cm 2 or more in the width direction, elongation and Elongation in the width direction may be 100% or less, more specifically 98% or less.
  • a separation membrane having improved stability against deformation of the pore size and shape may be provided.
  • the polyolefin-based separator according to an embodiment of the present invention may have a water droplet contact angle of the separator 107 ° or less, for example, 95 ° to 107 °, specifically, 100 ° to 106 °. When the contact angle is in the above range, the electrolyte wettability is good, and thus battery performance may be improved.
  • the separator according to the present embodiment may include a coating layer on one side or both sides of the separator manufactured according to the example of the present invention, the coating layer may include an organic binder, and may further include inorganic particles.
  • the organic binder may include, for example, a polyvinylidene fluoride polymer having a weight average molecular weight of 1,000,000 g / mol or more, a polyvinylidene fluoride polymer having a weight average molecular weight of 800,000 g / mol or less, or a mixture thereof. have.
  • PVdF polyvinylidene fluoride homopolymer
  • PVdF-HFP polyvinylidene fluoride-hexapropylene copolymer
  • the inorganic particles there may be mentioned Al 2 O 3, SiO 2, B 2 O 3, Ga 2 O 3, TiO 2, and SnO 2 and the like.
  • the coating layer may be formed by a dip coating method.
  • the separator having the coating layer may be left in an oven at 105 ° C. for 1 hour, and the heat shrinkage may be 3% or less in the MD and TD directions, respectively. More specifically, it may be 2% or less.
  • the porous polyolefin-based separator according to embodiments of the present invention may have an average thickness of 7 ⁇ m to 20 ⁇ m and a variation in thickness may be less than 4% of the average thickness.
  • the porous polyolefin-based separator according to the embodiments of the present invention may have an average puncture strength of 300 gf or more, and specifically 400 gf or more.
  • the porous polyolefin-based separator or coating separator according to the embodiments of the present invention is cut to 50 ⁇ 50 mm in size of the separator prepared in a 120 °C oven after shrinking for 1 hour, after which the size of the contracted separator
  • the shrinkage in the longitudinal direction may be 5% or less
  • the shrinkage in the width direction may be 3% or less
  • the shrinkage in the longitudinal direction is 4% or less
  • the shrinkage in the width direction is 2% or less.
  • the present invention also provides a battery chemical cell comprising the porous polyolefin-based separator, positive electrode, negative electrode and electrolyte disclosed in the present invention.
  • the type of electrochemical cell is not particularly limited and may be a kind of electricity known in the art.
  • the electrochemical cell of the present invention may preferably be a lithium secondary battery such as a lithium metal secondary battery, a lithium ion 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:
  • the cell can be prepared by placing the separator or coated separator of the present invention between the positive and negative electrodes of the cell and then filling the electrolyte therewith. have.
  • 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.
  • the positive electrode includes a positive electrode active material capable of reversibly inserting and detaching lithium ions
  • the positive electrode active material may be at least one selected from cobalt, manganese, nickel, and a composite metal oxide with lithium.
  • the solid solution ratio between the metals may be various, and in addition to these metals, Mg, Al, Co, Ni, K, Na, Ca, Si, Ti, Sn, V, Ge, Ga, B, As, Zr, Mn, Cr, An element selected from the group consisting of Fe, Sr, V, and rare earth elements may be further included.
  • the anode may be, for example, a composite metal oxide of a metal selected from the group consisting of lithium and Co, Ni, Mn, Al, Si, Ti, and Fe, and specifically, lithium cobalt oxide (LCO.)
  • LiCoO 2 lithium nickel manganese cobalt oxide, NCM.
  • Li [Ni (x) Co (y) Mn (z)] O 2 lithium manganese oxide
  • Lithium manganese oxide, LMO for example LiMn 2 O 4, LiMnO 2
  • LiFePO 4 lithium nickel oxide
  • LiNO for example LiNiO 2
  • the negative electrode includes a negative electrode active material capable of inserting and desorbing lithium ions, and the negative electrode active material includes crystalline or amorphous carbon, or a carbon-based negative electrode active material (thermally decomposed carbon, coke, graphite) and combustion of a carbon composite.
  • Organic polymer compounds, carbon fibers, tin oxide compounds, lithium metal or alloys of lithium and other elements can be used.
  • amorphous carbon includes hard carbon, coke, mesocarbon microbeads (MCMB) fired at 1,500 ° C or lower, and mesophase pitch-based carbon fibers (MPCF).
  • the crystalline carbon includes a graphite material, and specific examples thereof include natural graphite, graphitized coke, graphitized MCMB, graphitized MPCF, and the like.
  • the negative electrode may include, for example, crystalline or amorphous carbon.
  • the positive electrode or the negative electrode may be prepared by dispersing a binder, a conductive material, and, if necessary, a thickener in a solvent in addition to an electrode active material to prepare an electrode slurry composition, and applying the slurry composition to an electrode current collector.
  • the binder, the conductive material and the thickener may be used as commonly used in the art.
  • the binder polyvinylidene-fluoride (PVdF), styrene-butadiene rubber (SBR), and the like, carbon black as a conductive material, and carbonate methyl cellulose as a thickener (Carbonate methyl cellulose, CMC) can be used.
  • the electrode current collector used in 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, a copper alloy or a combination thereof.
  • the positive electrode current collector and the negative electrode current collector may be in the form of a foil or a mesh.
  • 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.
  • Non-limiting examples of the organic solvent include propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dimethylformamide (Dimethylformamide, DMF), Dipropyl carbonate (DPC), Dimethyl sulfoxide (DMSO), Acetonitrile, Dimethoxyethane, Diethoxyethane, Tetrahydrofuran ( Tetrahydrofuran), N-methyl-2-pyrrolidone (NMP), ethyl methyl carbonate (EMC), or gamma-butyrolactone (-Butyrolactone). 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
  • DMF dimethylformamide
  • DMF dimethylformamide
  • DPC Dipropyl carbonate
  • DMSO Dimethyl sulfoxide
  • Acetonitrile Dimeth
  • High-density polyethylene (HDPE; manufactured by Mitsui Chemical) having a viscosity average molecular weight of 600,000 g / mol was fed to a twin screw extruder, and then liquid paraffin (Far East Emulsification) was weighted to polyethylene 30 to liquid paraffin.
  • the extruder was injected into the twin screw extruder in an amount of 70.
  • the gel phase obtained through the T-die was manufactured as a sheet-type separator using a cooling roll.
  • the membrane was stretched in the longitudinal direction (Machine Direction, MD) at 110 ° C and in the transverse direction (TD) at 113 ° C (stretch ratio: 8.0 (MD) x 8.0 (TD)).
  • the stretched polyolefin-based separator was immersed in methylene chloride (Samsung Fine Chemical) to extract liquid paraffin, and then transferred to a drying roll to dry.
  • methylene chloride Sudsung Fine Chemical
  • the dried film was heat-set in the width direction of the secondary stretching (width direction draw ratio: 1.0 ⁇ 1.6 ⁇ 1.4, stretching temperature 128 ° C.) to prepare a porous polyolefin separator having a thickness of 12.5 ⁇ m.
  • Example 1 the stretching was performed in the machine direction (Machine Direction, MD) at 103 ° C and transverse direction (TD) at 105 ° C (stretch ratio: 8.5 (MD) x 8.5 (TD)) In the same manner as in Example 1, a separator having a thickness of 12.3 ⁇ m was prepared.
  • Example 1 the stretching was performed in the machine direction (Machine Direction, MD) at 120 ° C and in the transverse direction (TD) at 123 ° C (stretch ratio: 8 (MD) x 8 (TD)). Then, a membrane having a thickness of 12.2 ⁇ m was prepared in the same manner as in Example 1.
  • Example 2 the same method as in Example 2, except that the stretching direction in the longitudinal direction (MD) and the stretching direction in the transverse direction (TD) were set to 7 (MD) x 7 (TD). 12.3 ⁇ m thick membrane was prepared.
  • Table 1 shows the production conditions of the separators according to Examples 1 and 2 and Comparative Examples 1 and 2.
  • Example 1 Example 2 Comparative Example 1 Comparative Example 2 Drawing method rotor rotor rotor rotor rotor Stretch ratio (MD x TD) 8 ⁇ 8 8.5 ⁇ 8.5 8 ⁇ 8 7 ⁇ 7 MD drawing temperature 110 °C 103 °C 120 °C 103 °C TD drawing temperature 113 °C 105 °C 123 °C 105 °C 2nd TD drawing temperature 128 °C 128 °C 128 °C 128 °C 2nd TD final draw ratio 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4
  • Example 1 Example 2 Comparative Example 1 Comparative Example 2 Average point pressure (psi) 258.856 272.12 201.34 282.24 Bubble Point Pressure (psi) 121.675 113.31 121.54 113.35 Average Point Pressure / Bubble Point Pressure 2.13 2.40 1.66 2.49 Porosity (%) 44.5 43 53.1 38.5 Breathability (sec / 100cc) 122 115 95 223 Tensile Strength (kg / cm 2 ) (MD, TD) 2120, 2214 2250, 2305 1653,1622 1742,1783 Elongation (%) (MD, TD) 89, 92 86, 88 95, 110 93, 98 Tensile Strength / Elongation (MD, TD) 23.8, 24.1 26.2, 26.2 17.4, 14.7 18.7, 18.2 Droplet contact angle (°) 102 103 111 111 Shrinkage (%) (MD, TD) 2,0 2,0 8,3 2,0
  • each of the separators prepared in Examples and Comparative Examples was sampled into a circle having a diameter of 26 mm.
  • the membrane itself is mounted on a PMI capillary flow pore meter and thoroughly wetted with Galwick TM solution (surface tension of 15.9 dyne / cm). Wet up Calc. After setting the mode, draw the wet curve by measuring the flow rate of N 2 for each pressure. The pressure at which the first bubble is detected in the wet curve is recorded as the bubble point pressure (psi).
  • each of the separators prepared in Examples and Comparative Examples was sampled in a circle having a diameter of 26 mm and the separator itself was mounted on the device, and then the device was dried.
  • the mode was set, and the flow rate of N 2 for each pressure was measured and shown as a dry curve graph.
  • a straight line extends from the origin to a point having linearity, draws an imaginary straight line that is half of the slope of the straight line, and the pressure at the point where the imaginary straight line and the wet curve meet the average point pressure ( psi).
  • Porosity (%) (volume-mass / density of sample) / volume x 100
  • Density of sample density of polyethylene
  • Each of the separators prepared in the above Examples and Comparative Examples was prepared to cut 10 samples cut from 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.
  • Each of the membranes prepared in Examples and Comparative Examples was made of 10 samples cut at 10 different points (MD) 10 mm ⁇ length (TD) 50 mm, and 20 mm portions were bitten in the UTM. After pulling up and down the strength was measured. The tensile strength of each sample was measured three times, and then the average value was calculated.
  • Each of the separators prepared in Examples and Comparative Examples was prepared with 10 samples cut at 10 different points with a width of 50 mm and a length of 50 mm of TD. The samples were left in an oven at 105 ° C. for 1 hour, and then the average thermal shrinkage (%) was calculated by measuring the shrinkage in the MD and TD directions of each sample.
  • Each of the separators prepared in Examples and Comparative Examples was cut to 20 mm long by 20 mm wide by 20 mm long by TD to prepare five samples.
  • the sample was placed on a contact angle measuring device (DSA-100, Matek Trading Co., Ltd.), and water was dropped by dropper, and then contact angle was measured. The contact angles (°) of the five samples were averaged and calculated.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Cell Separators (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention concerne un procédé de préparation d'une membrane de séparation à base de polyoléfine et une membrane de séparation à base de polyoléfine préparée par le procédé. Le procédé consiste à : former une feuille par mélange à l'état fondu d'une composition comprenant une résine à base de polyoléfine et un plastifiant, et extruder celle-ci ; mettre en oeuvre un premier étirage dans laquelle la feuille est étirée E1 fois à une température T1 dans la direction longitudinale, et étirée E2 fois à une température T2 dans la direction de la largeur ; extraire le plastifiant de la feuille étirée ; et mettre en oeuvre un deuxième étirage de la feuille dont le plastifiant a été extrait, jusqu'à un allongement final égal à 1,25-1,5 fois l'étirage dans la direction de la largeur ; dans le premier étirage, les conditions de température sont 100 °C < T1 < 115°C, 100°C < T2 < 115°C et T2 ≥ T1, et l'état d'agrandissement est de E1×E2 = 60-80.
PCT/KR2015/006201 2014-06-30 2015-06-18 Membrane de separation poreuse a base de polyolefine et procede de preparation de cette membrane WO2016003094A1 (fr)

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CN111801811B (zh) 2018-06-22 2022-11-01 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
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WO2020213741A1 (fr) * 2019-04-18 2020-10-22 マクセルホールディングス株式会社 Cellule à électrolyte liquide aqueux et timbre
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