WO2017065399A1 - Film poreux, procédé de fabrication de film poreux et cellule électrochimique le comprenant - Google Patents

Film poreux, procédé de fabrication de film poreux et cellule électrochimique le comprenant Download PDF

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WO2017065399A1
WO2017065399A1 PCT/KR2016/008504 KR2016008504W WO2017065399A1 WO 2017065399 A1 WO2017065399 A1 WO 2017065399A1 KR 2016008504 W KR2016008504 W KR 2016008504W WO 2017065399 A1 WO2017065399 A1 WO 2017065399A1
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porous film
pore
forming particles
microporous layer
volume
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PCT/KR2016/008504
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English (en)
Korean (ko)
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이민정
구영림
라하나
배수학
안성희
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삼성에스디아이 주식회사
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—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
    • 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

  • It relates to a porous film and a method for producing the porous film and an electrochemical cell comprising the same.
  • a separator for an electrochemical cell is an interlayer membrane that allows the battery to be charged and discharged by continuously maintaining ion conductivity while isolating the positive electrode and the negative electrode from each other.
  • the separator consists of a porous film.
  • the method for producing the porous film may be a dry process or a wet process.
  • the dry process is a method of extruding and manufacturing a precursor film, and then adjusting the orientation of the lamellar through heat treatment such as annealing and stretching to form pores.
  • the dry process does not use extraction solvents, so it is environmentally friendly and competitive in price.
  • the dry process has a problem that the stretching speed is slow and the tensile strength in the transverse direction is lowered because the pores are formed by stretching between the crystal and the amorphous of a single material. .
  • the size of the pores is determined by the difference in the strength of the crystal and the amorphous, there is a disadvantage that the size of the pore is determined by the type of material. Therefore, in the case of polyethylene, the pore size is excessively difficult to use as a separator of a secondary battery.
  • the wet process refers to a method of mixing a polymer material with a plasticizer and extruding it to form a sheet, and removing the plasticizer from the sheet to form pores.
  • the size of the pores is determined by controlling the compatibility of the plasticizer, the size of the pores is uniform, but it is difficult to apply the same process to other materials except polyethylene.
  • porous film having a simple manufacturing process and good production efficiency while having excellent pore uniformity, porosity, air permeability and ion permeability. Further, by controlling the porosity and air permeability of the porous film to improve the battery stability and long-term reliability in the electrochemical cell comprising the same.
  • the first microporous layer including the polyethylene-based polymer and the first pore-forming particles, and the porous film including the second microporous layer including the polypropylene-based polymer and the second pore-forming particle are laminated.
  • the average particle diameter of the pore-forming particles and the second pore-forming particles is 300 nm or less, and the first pore-forming particles are included in 5% by volume to 25% by volume based on the total volume of the first microporous layer, and the second fine particles Provided is a porous film comprising from 5% by volume to 25% by volume of second pore-forming particles based on the total volume of the pore layer.
  • preparing a first composition comprising a polyethylene-based polymer and first pore-forming particles
  • preparing a second composition comprising a polypropylene-based polymer and a second pore-forming particle, wherein the first composition and agent 2 the composition is extruded to form a multilayer precursor film
  • the multilayer precursor film is annealed at a temperature of 80 ° C. to 150 ° C.
  • the annealed multilayer film is 50% to 400 at a low temperature of 0 ° C. to 50 ° C.
  • a method of producing a porous film is provided, which comprises% first stretching and 40% to 400% second stretching of the stretched multilayer film at a temperature of 80 ° C to 150 ° C.
  • the first composition and the second composition are respectively extruded to form respective precursor films, and the respective precursor films are laminated at 100 ° C. to 150 ° C. temperature and 0.1 MPa to 5 MPa pressure conditions. Thereafter, the laminated film is first stretched at 50% to 400% at a low temperature of 0 ° C to 50 ° C, and 40% to 400% second stretched at a temperature of 80 ° C to 150 ° C. This is provided.
  • an electrochemical cell that includes the porous film, the positive electrode, the negative electrode, and the electrolyte.
  • the porous film according to one embodiment has uniform pores, excellent porosity, air permeability and ion permeability, and improved shutdown characteristics and tensile strength. Further, by controlling the porosity and air permeability of the porous film has an effect of improving battery stability and long-term reliability in the electrochemical cell including the porous film.
  • the method of manufacturing a porous film according to an embodiment may reduce the manufacturing cost significantly because the manufacturing process is simple and the production efficiency is good.
  • SEM scanning electron microscope
  • SEM scanning electron microscope
  • FIG 3 is an exploded perspective view of an electrochemical cell according to one embodiment.
  • An embodiment is a porous film in which a first microporous layer including a polyethylene-based polymer and first pore-forming particles and a second microporous layer including a polypropylene-based polymer and a second pore-forming particle are laminated.
  • An average particle diameter of the forming particles and the second pore-forming particles is 300 nm or less, and includes 5% by volume to 25% by volume of the first pore-forming particles based on the total volume of the first microporous layer, and the second microporous layer. It relates to a porous film containing 5 to 25% by volume of the second pore-forming particles based on the total volume of.
  • Porous film according to the embodiment may be advantageous in terms of pore uniformity, air permeability and wettability to the electrolyte by including the pore-forming particles in each layer.
  • having a multilayer structure may be advantageous in terms of mechanical properties, shutdown characteristics and heat resistance.
  • the polyethylene-based polymer included in the first microporous layer may be a polyethylene-based polymer capable of crystallization, and may be a polyethylene homopolymer or a polyethylene copolymer. In one example, a polyethylene-based polymer having a Melting Index of 10 or less, or 5 or less, for example, 3 or less may be used.
  • the polyethylene polymer may be high density polyethylene (HDPE), ultra high molecular weight polyethylene (UHMWPE), and the like.
  • HDPE high density polyethylene
  • UHMWPE ultra high molecular weight polyethylene
  • the high density polyethylene may be used alone, two or more types of high density polyethylene may be used in combination
  • the ultra high molecular weight polyethylene may be used alone, or two or more types of ultra high molecular weight polyethylene may be used in combination, or the high density polyethylene may be used.
  • the ultrahigh molecular weight polyethylene can be used in combination.
  • the melt index of the high density polyethylene can be from 0.03 to 3, for example from 0.1 to 3. In one embodiment, it is also possible to use a mixture of two kinds of high-density polyethylene having a different melt index, specifically, a high-density polyethylene having a melt index of 0.5 or less and a high-density polyethylene in the melt index range of 0.5 to 1 can be used.
  • the separator prepared by using the polymer has an advantage of improving long-term reliability.
  • the polypropylene-based polymer that may be used in the second microporous layer may be a polypropylene homopolymer or a polypropylene copolymer as a polypropylene-based polymer capable of crystallization.
  • a polypropylene-based polymer having an isotacticity value of 85% to 99% measured from xylene solubility may be used.
  • the melt index of the polypropylene-based polymer may be 1 to 5 or more, specifically 2 to 4 or more. More specifically, it may be 2 to 10, for example 4 to 10.
  • the polyethylene polymer or the polypropylene polymer may use a compound having a glass transition temperature (Tg) or a melting temperature (Tm) of 100 or more.
  • Tg glass transition temperature
  • Tm melting temperature
  • the strength and thermal stability of the separator are excellent, and oxidation resistance is better than that of the polyethylene-based polymer, thereby achieving high capacity of the battery.
  • the first microporous layer and the second microporous layer may include other resin in addition to the polyethylene polymer or the polypropylene polymer.
  • other resins include poly (4-methylpentene), polyimide, polyester, polyamide, polyetherimide, polyamideimide, polyacetal, or combinations thereof.
  • the polyethylene-based polymer or polypropylene-based polymer and other resins may be blended in an appropriate solvent.
  • the first microporous layer and the second microporous layer may further include a copolymer of an olefin and a non-olefin monomer.
  • the first pore-forming particles and the second pore-forming particles may each independently be inorganic particles or organic particles or composite particles thereof.
  • the inorganic particles include alumina, silica, titania, zirconia, magnesia, ceria, zinc oxide, iron oxide, silicon nitride, titanium nitride, boron nitride, calcium carbonate, barium sulfate, aluminum sulfate, aluminum hydroxide, calcium titanate, barium titanate, talc , Calcium silicate, magnesium silicate and the like.
  • alumina, calcium carbonate or aluminum hydroxide can be used.
  • organic particles may be a polymer of a monomer including a double bond made by emulsion polymerization or suspension polymerization, or a crosslinked polymer, a polymer precipitate made in solution through compatibility control.
  • specific examples include non-crosslinked or crosslinked polystyrene (PS), polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), polyurethane (PU), Polymethylpentene (PMP), Polyethylene terephthalate (PET), Polycarbonate (PC), Polyester (Polyester), Polyvinyl alcohol (PVA), Polyacrylonitrile (PAN), Polymethylene oxide (PMO), Polymethyl Methacrylate (PMMA), polyethylene oxide (PEO), polyamide (PA), silicone acrylic rubber, ethylene-methylacrylate copolymer, polyamideimide (PAI), polysulfone (PSF), polyethylsulfone (PES) , Polyphenylene
  • silicone acrylic rubber More specifically, crosslinked, silicone acrylic rubber, ethylene-methylacrylate copolymer, polystyrene (PS), polyethylene (PE), polypropylene (PP), polysulfone (PSF) and polyimide (PI)
  • PS polystyrene
  • PE polyethylene
  • PP polypropylene
  • PSF polysulfone
  • PI polyimide
  • One or more organic particles selected from may be used, and more specifically, silicone acrylic rubber, ethylene-methylacrylate copolymer, polystyrene (PS) or polyethylene (PE) may be used.
  • the average particle diameter of the first pore-forming particles and the second pore-forming particles may be 300 nm or less, specifically, 30 nm to 300 nm. Specifically, it may be 30 nm to 250 nm, and more specifically 30 nm to 100 nm. Within this range, the dispersibility and processability of the pore-forming particles are not lowered, and the degradation of the mechanical properties of the microporous membrane can be prevented.
  • the use of pore-forming particles having a size in the above range may be advantageous in terms of pore size control, pore uniformity, and air permeability.
  • the pore-forming particles may be treated with a surfactant or the like on the surface of the particles to improve dispersibility in the composition.
  • the average particle diameter may mean a particle size at 50% by volume ratio in a cumulative size-distribution curve.
  • the first pore-forming particles and the second pore-forming particles may be included in each of the first microporous layer and the second microporous layer in 5% by volume to 25% by volume based on the total volume of each layer. Specifically, it may be included in 5% by volume to 20% by volume, and more specifically may be included in 8% by volume to 20% by volume. In the above range, sufficient pore is formed due to the pore-forming particles can improve the air permeability.
  • the porous film may have a thickness of 3 ⁇ m to 30 ⁇ m, specifically 3 ⁇ m to 25 ⁇ m, and more specifically 5 ⁇ m to 25 ⁇ m.
  • the porous film having a thickness in the above range may be a porous film having a suitable thickness that is 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 thickness ratio of the first microporous layer and the second microporous layer may be 1: 9 to 9: 1, specifically 3: 7 to 7: 3, and may be, for example, 4: 6 to 6: 4.
  • the porous film according to the present embodiment in addition to the first microporous layer and the second microporous layer, includes one or more of polyethylene-based polymers, polypropylene-based polymers, and poly (4-methylpentene) and third pore-forming particles. It may further comprise a third microporous layer.
  • the third microporous layer may include a polyethylene-based polymer or a polypropylene-based polymer and third pore-forming particles.
  • polyethylene-based polymer or polypropylene-based polymer the same ones that can be used for the first microporous layer and the second microporous layer can be used.
  • the third pore-forming particles may be the same as the first pore-forming particles and the second pore-forming particles.
  • the average particle diameter of the third pore-forming particles may be 300 nm or less, specifically 30 nm to 300 nm, specifically 30 nm to 250 nm, 30 nm to 200 nm, and more specifically 30 nm to 100 nm Can be.
  • the third pore-forming particles may be included in 5% by volume to 25% by volume based on the total volume of the third microporous layer. Specifically, it may be included in 5% by volume to 20% by volume, and more specifically, may be included in 8% by volume to 20% by volume.
  • the third microporous layer may include a polypropylene-based polymer, and may be laminated on a porous film in which the first microporous layer and the second microporous layer are laminated to form a porous film having a three-layer structure.
  • a porous film having a three-layer structure laminated in the order of the second microporous layer / the first microporous layer / the third microporous layer By having the three-layer structure described above there is an advantage that the mechanical strength, shutdown properties, oxidation resistance and heat resistance of the porous film can be improved.
  • the thickness ratio of (second microporous layer): (first microporous layer): (third microporous layer) is in the range of (1 to 10): (1 to 10): (1 to 10) Can be. Specifically, it may range from (2 to 8) :( 2 to 8) :( 2 to 8), for example, to range from (3 to 7) :( 3 to 7) :( 3 to 7). have. Within the thickness range, the shutdown property, tensile strength, and oxidation resistance of the porous film may be further improved.
  • each microporous layer of the porous film may include a first pore formed by the pore-forming particles and a second pore formed between the lamellae of each of the first microporous layer and the second microporous layer,
  • the volume of the first pore may be larger than the volume of the second pore.
  • the ratio (a / b) of the major axis to the length of the minor axis of the first pore is 1 to 7, for example, 1 to 6 days.
  • a / b of the second pores may be 0.5 or more.
  • a / b of the first pore is 1 to 7, for example, 1 to 6, and a / b of the second pore is greater than 7, or Greater than 9, or greater than 10.
  • a / b of the first pores is 1 to 7, for example, 1 to 6, and a / b of the second pores is greater than 0.5, for example, 0.5 to 5 may be.
  • a porous film according to an embodiment includes fibrils 8 formed between lamellas 7 and lamellas 7, and second pores 6 between neighboring fibrils 8. ) May be formed.
  • the thickness of the lamellar 7 may vary depending on the type of crystalline resin used, but may be 200 nm or less, more specifically 100 nm or less, even more specifically, 80 nm or less.
  • lamellar having a thickness of 100 nm or less for example, 10 nm to 100 nm
  • lamellar having a thickness of 80 nm or less, more specifically, 5 nm to 60 nm can be formed.
  • the first pores have a larger volume than the second pores, the first pores are advantageous in terms of air permeability, electrolyte wettability, and battery capacity. Secondary pores having a relatively small volume and having a rectangular shape are advantageous in terms of heat shrinkage, strength, and pore strain rate.
  • the crystallinity of the porous film according to one embodiment may be 35% to 70%, specifically 40% to 60%, even more specifically 40% to 50% range.
  • a thin lamellar structure can be formed when stretching, so that the air permeability and the ion permeability of the porous film are improved.
  • a non-limiting example of measuring the crystallinity of the porous film is a method of calculating the crystallinity from the heat of fusion (H) of the porous film.
  • the measurement of the heat of fusion can be carried out using TA Instrument's Discovery as a differential scanning calorimeter.
  • an aluminum pan and a reference pan containing about 10 mg of measurement sample are placed in a DSC cell. After stabilizing the equipment in a nitrogen atmosphere, the temperature was raised to 200 ° C. at 10 ° C./min, and then reduced to 30 ° C. after 1 minute of isothermal process. The amount of heat of fusion H is determined from the melting profile at the time of raising the temperature to 200 ° C again, that is, at the time of the second temperature rising.
  • the theoretical heat of fusion of polyethylene resin and polypropylene resin is 293 J / g and 207 J / g, and the crystallinity can be obtained through the following equation.
  • the heat of fusion of the polyethylene polymer is represented by H a
  • the heat of fusion of the polypropylene polymer is represented by H b
  • the content ratio of the polyethylene polymer is represented by ⁇
  • the content ratio of the polypropylene polymer is ⁇ To be displayed.
  • the porosity of the porous film may be 40% to 70%, specifically 45% to 65%.
  • Non-limiting examples of the method for measuring the porosity of the porous film is as follows. The porous film is cut into 10 cm x 10 cm to obtain its volume (cm 3) and mass (g), and the porosity is calculated from the volume and mass and the density (g / cm 3) of the porous film using the following formula.
  • Porosity (%) (volume-mass / density of porous film) / volume ⁇ 100
  • the air permeability of the porous film may be 500 sec / 100cc or less, specifically 450 sec / 100cc or less, and more specifically 400 sec / 100cc or less.
  • Porous film having the air permeability of the above range has the advantage of easy movement between ions in the positive electrode and the negative electrode.
  • Non-limiting examples of how to measure the air permeability of a porous film are as follows. Ten specimens cut at ten different points of the porous film were fabricated, and then 100 cc of air was removed from each specimen using a EG01-55-1MR (Asahi Seiko) model. Measure the average time it takes to penetrate each five times, and then calculate the average value to measure the air permeability.
  • the puncture strength of the porous film may be in the range of 150 gf to 400 gf, specifically, may be in the range of 180 gf to 350 gf.
  • Prick strength can be measured according to methods commonly used in the art as one of the measures of the hardness of a porous film.
  • 10 specimens cut from 10 different points of the porous film (MD) 50 mm x 50 mm (TD) were produced, and then KATO Tech G5 equipment After placing the specimen on the 10 cm hole by using a 1 mm probe can be performed by measuring the punching force three times each and calculating the average value.
  • a method of manufacturing a porous film may include preparing a first composition including a polyethylene-based polymer and first pore-forming particles, preparing a second composition including polypropylene and a second pore-forming particle, and The first composition and the second composition are extruded to form a multilayer precursor film, the multilayer precursor film is annealed at a temperature of 80 ° C. to 150 ° C., and the annealed multilayer film is a low temperature of 0 ° C. to 50 ° C. First stretch at 50% to 400%, and second stretch the stretched multilayer film at a temperature between 80 ° C. and 150 ° C. at a temperature between 40% and 400%.
  • the polyethylene-based polymer, the polypropylene-based polymer, the first pore-forming particles, and the second pore-forming particles are the same as described above in the above embodiments, the following description will mainly focus on a method of manufacturing a porous film using them. .
  • a first composition is prepared by mixing a polyethylene-based polymer and first pore-forming particles.
  • the mixing method is not particularly limited, but in one example, the polyethylene-based polymer and the first pore-forming particles may be melted at a temperature range of 150 ° C. to 220 ° C. using a twin screw extruder, and then pelletized to prepare the first composition. Can be.
  • the second composition is prepared by mixing the polypropylene-based polymer and the second pore-forming particles.
  • the method of mixing is also not particularly limited, and the second composition may be prepared in the same manner as preparing the first composition.
  • each of the first composition and the second composition is extruded to form a multilayer precursor film.
  • the method for forming the multilayer precursor film is not particularly limited, and a method commonly used may be used.
  • each of the first composition and the second composition is extruded to produce polyethylene-based polymer pellets and polypropylene-based polymer pellets, respectively, the polyethylene-based polymer pellets prepared are 200 ° C. to 300 ° C., and the polypropylene-based polymer pellets After melting in an extruder of a single screw or twin screw in the temperature range of 200 ° C to 280 ° C, they may be coextruded using a T die or an annular die to form a multilayer precursor film.
  • the pellets compounding the first composition and the second composition are introduced into a hopper of an extruder with a T die, and the extruder temperature is set at 170 ° C to 280 ° C and extruded.
  • the extrudate may be formed on a casting roll set at 30 ° C. to 120 ° C. to control the extrusion amount so that the draw ratio is 30 to 120, for example, 40 to 100, to form a precursor film. If the stretching ratio is within the above range, uniform pores may be formed, and breakage may not easily occur during the stretching process.
  • the extruder is extruded by setting the extruder temperature at 170 ° C to 220 ° C by a blow method.
  • the thickness of the precursor film may be in the range of 1 ⁇ m to 50 ⁇ m, for example, 3 ⁇ m to 30 ⁇ m, in an embodiment of 5 ⁇ m to 25 ⁇ m.
  • the prepared precursor film may be annealed at a temperature of 80 °C to 150 °C. In one example, it may be annealed at a temperature of (Tm-80) ° C to (Tm-3) ° C.
  • Tm means melting temperature of polyethylene-type resin.
  • Annealing is a heating process that improves the crystal structure and the orientation structure by heat treatment to promote microporous formation upon stretching.
  • the elastic recovery rate of the precursor film may be adjusted to 5% to 80%, specifically 10% to 70%, more specifically, 20% to 60%. When the elastic recovery rate is in the above range, it is easy to form pores and adjust pore size in a subsequent stretching process, and it is easy to implement a morphology including first pores and second pores.
  • annealing is performed by placing a roll of substrate in an oven in which tropical flow occurs, contacting with a heated roll or a heated metal plate, or heating the precursor film through hot air or an IR heater in a tenter or the like. Can be.
  • the annealing may be performed at a temperature range of 100 ° C. to 150 ° C., specifically 120 ° C. to 140 ° C., for 10 minutes to 60 minutes, specifically for 20 minutes to 50 minutes, and for example for 30 minutes.
  • a process of first stretching the annealed film at 50% to 400% at low temperature may be performed.
  • the low temperature stretching process forms pores between the particles and the polymer and induces crazing over the entire area of the film to form uniform pores, for example, using a stretching roll in a single axis (MD direction) or Tentered drawing can be performed.
  • the low temperature stretching temperature may range from 0 ° C. to 50 ° C., in particular 0 ° C. to 40 ° C., 10 ° C. to 35 ° C.
  • the stretching ratio is 50% to 400%, or 50% to 300%, specifically 50% to 200%, more specifically 80% to 100%, can be stretched once in the longitudinal (MD) direction. If the stretching ratio is within the above range, cracks are sufficiently formed in the low temperature stretching process to achieve a desired air permeability or porosity.
  • the low temperature stretched film may be subjected to a second stretching process of 40% to 400% at a temperature of 80 ° C to 150 ° C.
  • the second stretching is a process of stretching in the longitudinal or transverse direction at the temperature of 80 ° C to 150 ° C, respectively or simultaneously using a roll or tenter type apparatus, the magnification of which is 40% in the longitudinal and / or transverse direction. To 400%, for example 50% to 200%.
  • the high temperature stretching may be carried out in a temperature range of 80 ° C to 150 ° C, specifically 90 ° C to 150 ° C, for example, 110 ° C to 135 ° C.
  • heat setting may be further performed as necessary.
  • the heat setting may be left for a certain period of time without stretching under heat.
  • the heat setting may be performed in the longitudinal or transverse direction, respectively or simultaneously, by 110% to 150% in the state of applying heat using a roll or tenter device, and then relaxes to 80% to 100% of the stretched length or width.
  • the heat shrinkage may improve the heat shrinkage of the porous film.
  • the method of preparing the porous film may include extrusion molding a third composition comprising at least one of a polyethylene-based polymer, a polypropylene-based polymer, and poly (4-methylpentene) with third pore-forming particles. It may include. The same materials as described above may be used for the above materials.
  • the method of manufacturing the porous film may be a method of manufacturing a porous film having a three-layer structure of polypropylene / polyethylene / polypropylene.
  • Another embodiment is to prepare a first composition comprising a polyethylene-based polymer and first pore-forming particles, to prepare a second composition comprising a polypropylene-based polymer and second pore-forming particles, wherein the first composition and Each of the second compositions is extruded to form respective precursor films, and the respective precursor films are laminated at 100 ° C. to 150 ° C. temperature and 0.1 MPa to 5 MPa pressure condition, and then the laminated films are 0 ° C. to A method for producing a porous film comprising 50% to 400% first stretching at a low temperature of 50 ° C and 40% to 400% second stretching at a temperature of 80 ° C to 150 ° C.
  • the present embodiment differs in that the first composition and the second composition are extruded to form respective precursor films and then laminated, and the first and second stretches are the same as the above-described examples. Therefore, the following description will focus on the above differences.
  • the polyethylene-based polymer pellets and polypropylene-based polymer pellets are manufactured in the same manner as in the previous embodiment, and the polyethylene-based polymer pellets are 200 ° C to 300 ° C, and the polypropylene-based polymer pellets have a single temperature range of 200 ° C to 280 ° C.
  • a polyethylene-based polymer precursor film or a polypropylene-based polymer precursor film is formed by using a T die or an annular die, respectively.
  • each of the polyethylene-based polymer pellets and the polypropylene-based polymer pellets is introduced into a hopper of an extruder with a T die, and the extruder temperature is set at 170 ° C. to 330 ° C. and extruded.
  • the extrudate may be adjusted to an extrusion ratio of 30 to 120, for example , 40 to 100 , on a casting roll set at 30 ° C. to 120 ° C. to form a polyethylene polymer precursor film and a polypropylene polymer precursor film.
  • Another precursor manufacturing method is extruded by setting the extruder temperature 170 °C to 220 °C by a blow method.
  • Each precursor film prepared above may be laminated at 100 ° C. to 150 ° C. and 0.1 MPa to 5 MPa pressure to prepare a multilayer precursor film.
  • the lamination conditions may be specifically 110 ° C to 140 ° C temperature, 0.1 MPa to 2 MPa.
  • the prepared precursor film may be annealed at a temperature of 80 ° C to 150 ° C. In one example, it may be annealed at a temperature of (Tm-80) ° C to (Tm-3) ° C.
  • Annealing is a heating process that improves the crystal structure and the orientation structure by heat treatment to promote microporous formation upon stretching.
  • the elastic recovery rate of the precursor film may be adjusted to 5% to 80%, specifically 10% to 70%, more specifically, 20% to 60%. When the elastic recovery rate is in the above range, it is easy to form pores and adjust pore size in a subsequent stretching process, and it is easy to implement a morphology including first pores and second pores.
  • annealing is performed by placing a roll of substrate in an oven in which tropical flow occurs, contacting with a heated roll or a heated metal plate, or heating the precursor film through hot air or an IR heater in a tenter or the like. Can be.
  • the annealing may be performed at a temperature range of 100 ° C. to 150 ° C., specifically 120 ° C. to 140 ° C., for 10 minutes to 60 minutes, specifically for 20 minutes to 50 minutes, and for example for 30 minutes.
  • a process of stretching each of the annealed films at a low temperature of 50% to 400% may be performed.
  • the low temperature stretched film may be subjected to a second stretching process of 40% to 400% at a temperature of 80 ° C to 150 ° C.
  • heat setting can be performed further as needed after 2nd extending
  • the method of preparing the porous film may include at least one of a polyethylene-based polymer, a polypropylene-based polymer, and a poly (4-methylpentene) agent in addition to the first composition and the second composition at the time of forming each precursor film. And extruding the third composition comprising the three pore-forming particles. Materials included in the third composition may be the same as described above.
  • the method of manufacturing the porous film may be a method of manufacturing a porous film having a three-layer structure of polypropylene / polyethylene / polypropylene.
  • an antioxidant an antistatic agent, a neutralizing agent, a dispersant, an antiblocking agent, a slip agent, etc. may be appropriately used as necessary.
  • the porous film prepared by the above-described manufacturing methods may include a second pore formed between the first pore 5 formed by the pore-forming particles and the lamellar of the polyethylene-based polymer or the polypropylene-based polymer. And (6) at the same time, wherein the volume of the first pore is larger than the volume of the second pore.
  • the lamellar thickness 7 is very thin compared to the porous film produced by the conventional dry method, and the second pores 6 are formed in the fibril structure between the lamellar and the neighboring lamellar.
  • a separator including the porous film is provided.
  • the separator may be made of only a porous film, or may further include a porous adhesive layer formed on one side or both sides of the porous film.
  • the porous adhesive layer may include binder resin and / or inorganic particles.
  • a separator comprising a porous film disclosed herein, and an electrochemical cell filled with an electrolyte and comprising an anode and a cathode.
  • the kind of the electrochemical cell is not particularly limited, and may be a battery of a kind known in the art.
  • the electrochemical battery 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 manufacturing the electrochemical cell according to one embodiment is not particularly limited, and a method commonly used in the art may be used.
  • FIG. 3 is an exploded perspective view of an electrochemical cell according to one embodiment.
  • an electrochemical cell according to an embodiment is described as an example of being rectangular, the present invention is not limited thereto and may be applied to various types of batteries such as a lithium polymer battery and a cylindrical battery.
  • an electrochemical cell 100 includes an electrode assembly 40 and an electrode assembly 40 which are wound with a separator 30 interposed between the positive electrode 10 and the negative electrode 20. It includes a case 50 to be built.
  • the positive electrode 10, the negative electrode 20, and the separator 30 are impregnated with an electrolyte (not shown).
  • the separator 30 is as described above.
  • the positive electrode 10 may include a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector.
  • the positive electrode active material layer may include a positive electrode active material, a binder, and optionally a conductive material.
  • aluminum (Al), nickel (Ni), or the like may be used, but is not limited thereto.
  • a compound capable of reversible intercalation and deintercalation of lithium may be used. Specifically, at least one of cobalt, manganese, nickel, aluminum, iron, or a combination of metal and lithium composite oxide or phosphoric acid may be used. More specifically, lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium iron phosphate or a combination thereof may be used.
  • the binder not only adheres the positive electrode active material particles to each other but also serves to adhere the positive electrode active material to the positive electrode current collector, and specific examples thereof include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, and polyvinyl chloride.
  • Carboxylated polyvinylchloride polyvinylfluoride, ethylene oxide containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene polymer, polypropylene polymer, styrene Butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon and the like, but is not limited thereto. These may be used alone or in combination of two or more thereof.
  • the conductive material provides conductivity to the electrode, and examples thereof include natural graphite, artificial graphite, carbon black, carbon fiber, metal powder, and metal fiber, but are not limited thereto. These may be used alone or in combination of two or more thereof.
  • metal powder and the metal fiber metals such as copper, nickel, aluminum, and silver may be used.
  • the negative electrode 20 may include a negative electrode current collector and a negative electrode active material layer formed on the negative electrode current collector.
  • the negative electrode current collector may include copper (Cu), gold (Au), nickel (Ni), a copper alloy, or the like, but is not limited thereto.
  • the negative electrode active material layer may include a negative electrode active material, a binder, and optionally a conductive material.
  • the negative electrode active material may be a material capable of reversibly intercalating and deintercalating lithium ions, a lithium metal, an alloy of lithium metal, a material capable of doping and undoping lithium, a transition metal oxide, or a combination thereof. Can be used.
  • Examples of a material capable of reversibly intercalating and deintercalating the lithium ions include carbon-based materials, and examples thereof include crystalline carbon, amorphous carbon, or a combination thereof.
  • Examples of the crystalline carbon include amorphous, plate-shape, flake-shape, spherical or fibrous natural graphite or artificial graphite.
  • Examples of the amorphous carbon include soft carbon or hard carbon, mesophase pitch carbide, calcined coke, and the like.
  • Examples of the alloy of the lithium metal include lithium and Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, and Sn.
  • Alloys of the metals selected may be used.
  • materials capable of doping and undoping lithium include Si, SiO x (0 ⁇ x ⁇ 2), Si-C composites, Si-Y alloys, Sn, SnO 2 , Sn-C composites, Sn-Y, and the like. And at least one of these and SiO 2 may be mixed and used.
  • transition metal oxide examples include vanadium oxide and lithium vanadium oxide.
  • Kinds of the binder and the conductive material used in the negative electrode 20 may be the same as the binder and the conductive material used in the above-described positive electrode.
  • the positive electrode 10 and the negative electrode 20 may be prepared by mixing each active material, a binder, and optionally a conductive material in a solvent to prepare each active material composition, and applying the active material composition to each current collector.
  • N-methylpyrrolidone may be used as the solvent, but is not limited thereto. Since such an electrode manufacturing method is well known in the art, detailed description thereof will be omitted.
  • the electrolyte solution contains an organic solvent and a lithium salt.
  • the organic solvent serves as a medium through which ions involved in the electrochemical reaction of the battery can move.
  • the organic solvent may be selected from a carbonate solvent, an ester solvent, an ether solvent, a ketone solvent, an alcohol solvent, and an aprotic solvent.
  • the carbonate solvent examples include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), ethylmethyl carbonate (EMC), ethylene Carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and the like.
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • DPC dipropyl carbonate
  • MPC methylpropyl carbonate
  • EPC ethylpropyl carbonate
  • EMC ethylmethyl carbonate
  • EMC ethylmethyl carbonate
  • EC ethylene Carbonate
  • PC propylene carbonate
  • BC butylene carbonate
  • ester solvents examples include methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate, ethyl propionate, ⁇ -butyrolactone, decanolide, valerolactone, and meronate. Melononolactone, caprolactone, and the like.
  • ether solvent examples include dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran and the like. Cyclohexanone etc. are mentioned as said ketone solvent, Ethyl alcohol, isopropyl alcohol, etc. are mentioned as said alcohol solvent.
  • the organic solvents may be used alone or in combination of two or more thereof, and the mixing ratio in the case of mixing two or more kinds may be appropriately adjusted according to the desired battery performance.
  • the lithium salt is a substance that dissolves in an organic solvent and acts as a source of lithium ions in the battery to enable operation of a basic electrochemical cell and to promote the movement of lithium ions between the positive electrode and the negative electrode.
  • lithium salt examples include LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiN (SO 3 C 2 F 5 ) 2 , LiN (CF 3 SO 2 ) 2 , LiC 4 F 9 SO 3 , LiClO 4 , LiAlO 2 , LiAlCl 4 , LiN (C x F 2x + 1 SO 2 ) (C y F 2y + 1 SO 2 ) (x and y are natural numbers), LiCl, LiI, LiB (C 2 O 4 ) 2 or a combination thereof Can be mentioned.
  • the concentration of the lithium salt can be used within the range of 0.1M to 2.0M.
  • concentration of the lithium salt is within the above range, since the electrolyte has an appropriate conductivity and viscosity, it can exhibit excellent electrolyte performance, and lithium ions can move effectively.
  • TC oxychloride Calcium Co., Ltd.
  • Polypropylene-based polymer pellets were melt-kneaded and extruded under the same conditions as 80% by volume of polypropylene-based polymer having a melt index of 2.0 (S802, Daehan Chemical Co., Ltd.), and 20% by volume of calcium carbonate (same homology) having an average particle diameter of 60 nm. Was prepared.
  • the prepared polyethylene polymer pellets were melted in a twin screw extruder at 260 ° C. and the polypropylene polymer pellets at 230 ° C., respectively, and co-extruded using a multi-block type T-die to prepare a two-layer precursor film of PP / PE. (Elongation ratio: 40 to 45).
  • the porous film of Example 1 having a two-layer structure of PP / PE having a thickness of 18 ⁇ m was heat-set at 130 ° C. for 2 minutes.
  • Example 1 the polyethylene-based polymer pellets and the polypropylene-based polymer pellets were extruded without co-extrusion to form polyethylene-based polymer precursor films and polypropylene-based polymer precursor films. Further, after stacking each precursor film at 135 ° C. and 0.3 MPa condition, 100% first stretching was performed once in the MD direction at room temperature, 200% second stretched once in the MD direction at 120 ° C. and 2 at 120 ° C. Heat setting was performed for minutes to prepare the porous film of Example 2 having a two-layer structure of PP / PE having a thickness of 18 ⁇ m.
  • Example 1 except that the organic particles having an average particle diameter of 200 nm instead of calcium carbonate was carried out in the same manner as in Example 1 to prepare a porous film of Example 3 having a two-layer structure of PP / PE It was.
  • Example 1 except that the polyethylene-based polymer substrate is an inner layer and co-extruded so that the polypropylene-based polymer substrate on both sides of the polyethylene-based polymer substrate to produce a three-layer precursor film is the same as in Example 1
  • the porous film of Example 4 having a three-layer structure of PP / PE / PP was prepared.
  • Example 1 the porous film of Comparative Example 1 having a two-layer structure was prepared in the same manner as in Example 1 except that calcium carbonate was not included in the production of polyethylene-based polymer pellets.
  • Example 1 the porous film of Comparative Example 2 having a two-layer structure was prepared in the same manner as in Example 1 except that calcium carbonate was not included in the production of polypropylene polymer pellets.
  • Example 1 a porous film of Comparative Example 3 having a two-layer structure was prepared in the same manner as in Example 1 except that calcium carbonate (Chohocalcium Co., Ltd.) having an average particle diameter of 500 nm was used. .
  • Example 1 the same procedure as in Example 1 except that in the manufacture of polyethylene-based polymer pellets and polypropylene-based polymer pellets, calcium carbonate having an average particle diameter of 60 nm is included in each layer by 35% by volume.
  • the porous film of Comparative Example 4 was prepared.
  • the porous film prepared in Examples and Comparative Examples was cut into 10 cm ⁇ 10 cm to obtain its volume (cm 3) and mass (g), and from the volume and mass and the density of the porous film (g / cm 3)
  • the porosity was calculated using the following formula.
  • Porosity (%) (volume-mass / density of porous film) / volume ⁇ 100
  • each of the ten specimens cut from 10 different points to a size that each of the porous film can enter a circle of 1 inch or more in diameter was used to measure the time for 100cc of air to pass through each specimen. The air was measured by measuring the time five times and then calculating the average value.
  • Each of the porous films prepared in Examples and Comparative Examples was cut at ten different points in a rectangular form of transverse (MD) 10 mm ⁇ longitudinal (TD) 50 mm to produce 10 specimens, and then each The specimen was mounted on a UTM (tension tester) and bitten to have a measurement length of 20 mm, and then the specimen was pulled to measure average tensile strength in the MD and TD directions.
  • MD transverse
  • TD longitudinal
  • UTM tension tester
  • Example 1 Example 2 Example 3
  • Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4
  • Sting strength (gf) 193 184 180 209 350 320 175 150
  • Heat shrinkage (%) MD 9 11 15 5 17 13 11 15 TD 0 0 0 0 0 0 0 0 0 0 0 0 0
  • Heat shrinkage (%) MD 9 11 15 5 17 13 11 15 TD 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
  • MD 1100 1020 980 1360 1200 1180 890 840 TD 70 72 76 67 69 70 76 80

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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)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Cell Separators (AREA)

Abstract

La présente invention concerne : un film poreux obtenu par stratification d'une première couche microporeuse contenant un polymère à base de polyéthylène et des premières particules formant des pores et d'une seconde couche microporeuse contenant un polymère à base de polypropylène et des secondes particules formant des pores, lesquelles premières particules formant des pores et lesquelles secondes particules formant des pores ont un diamètre moyen des particules inférieur ou égal à 300 nm, les premières particules formant des pores étant contenues dans 5 à 25 % en volume sur la base du volume total de la première couche microporeuse, les secondes particules formant des pores étant contenues dans 5 à 25 % en volume sur la base du volume total de la seconde couche microporeuse ; un procédé de fabrication du film poreux ; et un séparateur ou une cellule électrochimique comprenant le film poreux.
PCT/KR2016/008504 2015-10-15 2016-08-02 Film poreux, procédé de fabrication de film poreux et cellule électrochimique le comprenant WO2017065399A1 (fr)

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CN110326128A (zh) * 2018-01-31 2019-10-11 株式会社Lg化学 隔膜、包含隔膜的锂二次电池和其制造方法
CN111430643A (zh) * 2019-01-10 2020-07-17 三星Sdi株式会社 隔板及其制备方法以及包括其的可再充电锂电池
EP3920266A4 (fr) * 2019-03-19 2022-03-30 Teijin Limited Séparateur pour cellule secondaire non aqueuse, et cellule secondaire non aqueuse
CN115101893A (zh) * 2022-06-02 2022-09-23 界首市天鸿新材料股份有限公司 利用高熔指和低熔指聚丙烯制备锂电池隔膜的方法

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CN110326128A (zh) * 2018-01-31 2019-10-11 株式会社Lg化学 隔膜、包含隔膜的锂二次电池和其制造方法
CN111430643A (zh) * 2019-01-10 2020-07-17 三星Sdi株式会社 隔板及其制备方法以及包括其的可再充电锂电池
CN111430643B (zh) * 2019-01-10 2022-08-23 三星Sdi株式会社 隔板及其制备方法以及包括其的可再充电锂电池
EP3920266A4 (fr) * 2019-03-19 2022-03-30 Teijin Limited Séparateur pour cellule secondaire non aqueuse, et cellule secondaire non aqueuse
CN115101893A (zh) * 2022-06-02 2022-09-23 界首市天鸿新材料股份有限公司 利用高熔指和低熔指聚丙烯制备锂电池隔膜的方法
CN115101893B (zh) * 2022-06-02 2024-04-12 界首市天鸿新材料股份有限公司 利用高熔指和低熔指聚丙烯制备锂电池隔膜的方法

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