WO2014209021A1 - Procédé pour fabriquer un séparateur poreux pour batterie rechargeable au moyen de nano vapeur, séparateur fabriqué selon ce procédé et batterie rechargeable - Google Patents

Procédé pour fabriquer un séparateur poreux pour batterie rechargeable au moyen de nano vapeur, séparateur fabriqué selon ce procédé et batterie rechargeable Download PDF

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WO2014209021A1
WO2014209021A1 PCT/KR2014/005652 KR2014005652W WO2014209021A1 WO 2014209021 A1 WO2014209021 A1 WO 2014209021A1 KR 2014005652 W KR2014005652 W KR 2014005652W WO 2014209021 A1 WO2014209021 A1 WO 2014209021A1
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drying
separator
nano
vapor
less
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PCT/KR2014/005652
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English (en)
Korean (ko)
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박진규
장우진
박명국
정준호
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제일모직주식회사
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—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
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—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
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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
    • 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 method for producing a porous separator for secondary batteries using nano-steam, a separator prepared by the method, and a secondary battery comprising the separator.
  • the porous separator for a secondary battery refers to an interlayer membrane which maintains ion conductivity while allowing the anode and the cathode to be separated from each other in the battery, thereby allowing the battery to be charged and discharged.
  • the electrode assembly consisting of an anode / separator / cathode may be simply stacked, but may be formed of a structure in which a plurality of electrodes are laminated with a separator interposed therebetween and then bonded to each other by heating / pressurization.
  • bonding of the electrode and the separator is achieved by heating / pressurizing the adhesive layer formed on the separator and the electrode in a state facing each other. Therefore, the separator is generally coated with a polymeric binder in order to improve adhesion and shrinkage with the electrode.
  • a solvent having a high boiling point such as DMF (dimethylformamide) is usually used to dissolve the polymer binder. If the solvent remains in the drying process after coating, an electrochemical side reaction occurs in the secondary battery. This will adversely affect performance. To reduce the solvent content after coating, excessive drying conditions must be imparted. Excessive drying conditions may adversely affect the fabric separator.
  • a lithium secondary battery for example, when the water content in the battery increases, it causes the decomposition of the electrolyte to generate an acid, the acid generated so that the decomposition of the negative electrode solid electrolyte interface (SEI) and dissolution of the positive electrode active material, etc. Promotes side reactions, and ultimately causes problems such as decrease of battery capacity and increase of internal resistance. That is, since the performance of the lithium secondary battery is greatly affected by the moisture content in the battery, it is important to prevent the penetration of moisture in the battery manufacturing process.
  • SEI solid electrolyte interface
  • the present invention is designed to solve the problem that the membrane shrinks or deforms due to heat in the conventional method of heating and drying the solvent and water at a high temperature as described above to provide a separator having excellent heat stability.
  • the present invention effectively removes the moisture in the battery to solve various problems such as decomposition of the negative electrode solid electrolyte interface (SEI), dissolution of the positive electrode active material, reduction of battery capacity and increased internal resistance that can be caused by the moisture It is for.
  • SEI negative electrode solid electrolyte interface
  • At least one side of the substrate is coated with a coating composition comprising a polymer binder and a solvent to prepare a coated separator,
  • It relates to a method for producing a porous separator, comprising first drying the coated separator using nano-vapor.
  • the length change rate L 1 in the vertical direction MD is 1.5% or less and the length change rate L 2 in the horizontal direction TD is 1.0% or less when left at 45 ° C. for 160 hours, and the length change rates L 1 and L
  • a bivalent porous separator for a secondary battery is provided as in Formula 1 below.
  • L 1 ⁇ L m1 -L m0 ⁇ / L m0
  • L m0 and L t0 represent the initial vertical length and the initial horizontal length of the separator, respectively, and L m1 and L t1 are the vertical length and the horizontal length measured after storing the separator for 160 hours at 45 ° C., respectively.
  • Direction length
  • It relates to a secondary battery comprising a positive electrode, a negative electrode and a porous separator for a secondary battery disclosed herein located between the positive electrode and the negative electrode.
  • the method for preparing a separator according to the present invention has the advantage that it is possible to prevent the heat shrink or thermal deformation of the separator due to the high temperature drying by the low-temperature drying through the introduction of nano-vapor.
  • the solvent and / or moisture can be effectively removed through the low temperature heat drying step after the application or before the application of the nano-vapor, there is no restriction in the solvent selection.
  • the method for preparing a separator according to the present invention and the separator prepared by the same may include a solvent and water in a predetermined amount or less, thereby minimizing the progress of side reactions inside the battery due to solvent or moisture.
  • FIG. 1 is a schematic diagram showing the principle of drying the separator using nano-vapor.
  • Figure 1a shows the conventional membrane drying of the hot air method
  • Figure 1b shows the membrane drying using nano-vapor according to the present invention.
  • FIG. 2 is a schematic diagram of a membrane drying process according to an embodiment of the present invention.
  • the present invention can effectively remove the solvent and water of the separator by a drying process at a relatively low temperature by introducing a drying step using nano steam during the drying process of the porous separator for secondary batteries.
  • a substrate is coated with a coating composition comprising a polymer binder and a solvent to prepare a coated separator, and the coated separator is first dried using nano vapor. It may include doing.
  • a coating layer is formed on a substrate.
  • the polymer binder and the solvent are sufficiently stirred using a ball mill, a bead mill, a screw mixer, or the like to form a coating composition in the form of a mixture, and then the coating composition is dip coated or die coated on at least one side of the substrate. It can be coated by a method, a roll coating method, a gravure coating method or a comma coating method.
  • the coating method may be used alone or in combination of two or more methods.
  • the thickness of the coating layer formed by the method may be 0.01 to 10 ⁇ m, for example may be in the range of 1 to 5 ⁇ m.
  • the substrate may be formed of a polyolefin-based composition.
  • the polyolefin-based composition may be a composition including a polyolefin-based resin, and may be used by using one kind of polyolefin or by blending two or more kinds.
  • the polyolefin-based resin is not particularly limited, and for example, high density polyethylene, low density polyethylene, linear low density polyethylene, ultra high molecular weight polyethylene and polypropylene, poly-4-methyl-1-pentene, and the like may be used, and a single film formed of a single layer may be used. It may be a structure or a laminated film structure in which two or more layers are laminated.
  • the substrate may have a thickness of about 1 ⁇ m to about 50 ⁇ m, for example, about 4 ⁇ m to about 25 ⁇ m.
  • the pore size and porosity of the substrate is not particularly limited within a range capable of securing mechanical properties and air permeability.
  • the substrate may be in the form of fibers or membranes.
  • the coated separator is first dried using nano vapor.
  • the nano-vapour refers to a vapor in which the particle size is controlled to 1 ⁇ m or less.
  • the steam generated through the steam generator is passed through a nano steam conversion apparatus equipped with an induction coil heater to control the steam particle size to 1 ⁇ m or less.
  • the 'vapor' means a gas generated by heating water. Therefore, the particle size of water vapor in the nano vapor is 1 ⁇ m or less. Specifically, it may be 500 to 1000 nm.
  • FIG. 1 is a schematic diagram showing the principle of drying the separator using nano-vapor.
  • Figure 1a shows the conventional membrane drying of the hot air method
  • Figure 1b shows the membrane drying using nano-vapor according to the present invention.
  • the separator includes a substrate 1 and a coating layer 2. In the case of the hot air method as shown in FIG.
  • the first drying may be performed while passing through the separator at a rate of 0.5 to 5 m 3 / min, for example 1 to 3 m 3 / min, the dry air containing the nano-vapor. Sufficient drying can be performed without affecting the properties of the separator within the above speed range.
  • the 'dry air' means air passing through to dry the separator of the present invention, for example, a dew point of less than -30 °C air may be used.
  • the first drying may be performed at 50 to 100 ° C., and drying may be performed to secure proper physical properties within the range.
  • the nano-vapor at the time of the first drying it is possible to lower the drying temperature than otherwise to suppress the degradation of physical properties due to high temperature.
  • the first drying may be divided into a plurality of drying sections during drying, the drying temperature in each section may be the same or different.
  • the drying may be partitioned into a first_1 drying zone and a first_2 drying zone, and drying temperatures of the first_1 drying zone and the first_2 drying zone may be 50 to 100 ° C., respectively.
  • the drying temperatures of the 1_1 drying zone and the 1_2 drying zone may be 50 to 90 ° C, respectively. Drying temperatures of the first_1 drying zone and the first_2 drying zone may be different or the same.
  • the drying temperatures of the 1_1 drying zone and the 1_2 drying zone may be 50 ° C, 55 ° C, 60 ° C, 65 ° C, 70 ° C, 75 ° C, 80 ° C, 85 ° C, or 90 ° C, respectively.
  • a 1_3 dry zone, a 1_4 dry zone, a 1_5 dry zone, etc. using nano vapor may be further performed.
  • the method may further include a second drying step of thermally drying at a temperature in a range of 35 to 90 ° C. before or after the drying using the nano vapor.
  • the second drying may be performed after the first drying.
  • the second drying may be performed before the first drying.
  • the second drying step may be performed by differently controlling the drying temperature and time in one drying zone, but may be sequentially performed by dividing the sections into several drying zones and varying the temperature and time for each section.
  • the present invention is not limited thereto, and may be dried by dividing into a 2_1 drying zone and a 2_2 drying zone, and drying temperatures of the 2_1 drying zone and the 2_2 drying zone may be 35 ° C. to 90 ° C., respectively.
  • Drying temperatures of the 2_1 drying zone and the 2_2 drying zone may be different or the same.
  • the drying temperatures of the 2_1 drying zone and the 2_2 drying zone are 35 ° C, 40 ° C, 45 ° C, 50 ° C, 55 ° C, 60 ° C, 65 ° C, 70 ° C, 75 ° C, 80 ° C, 85 ° C, respectively.
  • a 2_3 drying zone, a 2_4 drying zone, etc. using heat drying may be additionally performed.
  • the second drying may be performed in the same temperature range as the first drying.
  • the second drying may be performed while passing through the separator at a rate of 0.5 to 10 m 3 / min, for example, 1 to 5 m 3 / min, in the air heated in the heat drying step. Sufficient drying can be performed without affecting the physical properties of the separator within the above speed range.
  • FIG. 2 is a schematic diagram of a membrane drying process according to an embodiment of the present invention. Referring to FIG. 2, the nano vapor generated in the nano steam generator 3 is sprayed into the first_1 drying zone 5 together with the dry air provided from the dry air provider 4 to dry the separator 10. .
  • the separator may be further dried while passing through the 2_1 drying zone 7 and the 2_2 drying zone 9 of the general hot air dryer.
  • the nano vapor may be injected through the punching plate 6 of the first_1 drying zone 5, and the general hot air vapor may pass through the slit nozzles of the second_1 drying zone 7 and the second_2 drying zone 9, and the like. Can be sprayed through.
  • the second drying may be about 20 to 60 ° C lower than the temperature required when performing heat drying or vacuum drying to make the solvent and water content below a certain amount without undergoing the first drying according to the embodiment of the present invention. Therefore, the low temperature drying is possible through the introduction of the nano-vapor, thereby preventing heat shrinkage or thermal deformation of the separator due to the high temperature drying.
  • a high boiling point solvent eg, boiling point of 200 ° C. or higher, or 250 ° C. or higher
  • heating to the boiling point or higher is required, and heat shrinkage, deformability, and function of the separation membrane by the heating are required.
  • solvents due to damage which also limited the types of polymer binders that could be selected.
  • the method for preparing a separator according to the embodiments of the present invention can be effectively used for high boiling point solvents to effectively remove the solvent and / or water through the nano-vapor process and low temperature heat drying step. Therefore, the solvent to which the nano-vapor drying method of the present invention can be applied is not particularly limited, and in general, the solvent used in the polymer binder of the porous separator for secondary batteries may be the object. For example, acetone, N-methyl-2-pyrollidinone, tetrahydrofuran, dimethylformamide, methylene chloride, chloroform (chloroform), cyclohexane, water or mixtures thereof can be used.
  • the polymer binder that can be used in the coating composition according to the embodiments of the present invention is not particularly limited as long as it has a bonding force with the electrode laminated on the separator and is not easily dissolved by the electrolyte.
  • PVdF polyvinylidene fluoride
  • PVdF-HFP polyvinylidene fluoride-hexafluoropropylene
  • PVdF-TCE polyvinylidene fluoride-trichloroethylene
  • PVdF-CTFE polyvinylidene fluoride-chlorotrifluoroethylene
  • PVdF polymethylmethacrylate, polyacrylonitrile
  • Polyvinylpyrollidone polyvinylacetate, ethylene vinyl acetate copolymer, polyethylene oxide, cellulose acetate, cellulose acetate propionate propionate), cyanoethylpulluran, cyanoethyl polyvin
  • the polymeric binder is selected from the group consisting of PVdF homo or copolymer having a weight average molecular weight (g / mol) of 900,000 or more and PVdF homo or copolymer having a molecular weight of 500,000 to 800,000. May be used, for example, PVdF homopolymer having a weight average molecular weight of 900,000 to 1.1 million and / or PVdF-HFP copolymer having 500,000 to 700,000.
  • the coating composition may further include an inorganic particle.
  • inorganic particles By adding inorganic particles to the polymer binder, the mechanical strength of the separator can be increased to ensure the safety of the battery due to external force and the like, and the heat resistance can be improved.
  • the inorganic particles that can be used in the present invention are not particularly limited so long as they do not cause oxidation and / or reduction reactions, that is, electrochemical reactions, and impair conduction with the positive or negative electrode current collectors in the operating voltage range of the battery.
  • at least one selected from the group consisting of Al 2 O 3 , SiO 2 and TiO 2 are selected from the group consisting of, SnO 2 , Ga 2 O 3 , MgO, NiO, B 2 O 3 , Ga 2 O 3 , SiO 2 and TiO 2 .
  • the solvent residual amount may be 80 ppm or less, and the moisture content may be 500 ppm or less. Specifically, the solvent remaining amount may be 70 ppm or less, and the moisture content may be 400 ppm or less.
  • Another aspect of the present invention is to prepare a first polymer binder solution by (a) adding a first solvent to the first polymer binder and stirring at 15 to 35 °C, (b) inorganic inorganic particles dispersed in a dispersion medium Preparing a dispersion, (c) mixing the first polymer binder solution and the inorganic dispersion prepared in (a) and (b) to prepare a coating composition, (d) the coating on one or both sides of the substrate Coating the composition, and (e) drying the coated separator using nano vapor, there is provided a method for producing a porous separator for secondary batteries.
  • the coating liquid may be prepared by stirring the inorganic particles together with the polymer binder and the first solvent in the step (a) without performing the steps (b) and (c).
  • the (b) and (c) is carried out separately, there is an advantage that can improve the dispersibility and crude liquid stability of the inorganic particles and the binder.
  • another aspect of the present invention provides a method for preparing a coating composition
  • a method for preparing a coating composition comprising (a) preparing a coating composition comprising a polymeric binder, a solvent and inorganic particles; (b) coating the coating composition on one or both sides of the substrate; And (c) there is provided a method for producing a porous separator for secondary batteries, comprising the step of drying the coated separator using nano vapor.
  • a second drying step of thermally drying in a temperature range of 35 to 90 °C before or after the first drying step of drying using the nano-vapor may be further included.
  • the thermal drying step may be performed after the drying step of the nano vapor.
  • the second drying step may be performed by differently controlling the drying temperature and time in one drying zone.
  • the second drying step may be sequentially performed by dividing the partition into several drying zones and varying the temperature and time for each section.
  • the present invention is not limited thereto, and may be dried by dividing into a 2_1 drying zone and a 2_2 drying zone, and drying temperatures of the 2_1 drying zone and the 2_2 drying zone may be 35 ° C. to 90 ° C., respectively.
  • Drying temperatures of the 2_1 drying zone and the 2_2 drying zone may be different or the same.
  • the drying temperatures of the 2_1 drying zone and the 2_2 drying zone are 35 ° C, 40 ° C, 45 ° C, 50 ° C, 55 ° C, 60 ° C, 65 ° C, 70 ° C, 75 ° C, 80 ° C, 85 ° C, respectively.
  • 90 ° C. In addition to the 2_1 drying zone and the 2_2 drying zone, a 2_3 drying zone, a 2_4 drying zone, etc. using heat drying may be further performed.
  • the dispersion medium of the inorganic particles for example, acetone may be used, and the inorganic particles may be dispersed in an appropriate size using a ball mill or a bead mill, preferably in a dispersion medium.
  • the inorganic particles may be used after being dispersed by stirring for preferably 0.5 hours to 4.5 hours using the ball mill or bead mill, and more preferably, may be used after being dispersed by stirring for 1 hour to 3.5 hours.
  • the method may further include adding a second solvent to the second polymer binder after the step (a) and stirring the solution at 15 to 35 ° C. to prepare a second polymer binder solution. It can be used to prepare the coating composition of step (c).
  • the same polymer binder as that mentioned in the present invention may be used for the first polymer binder, the second polymer binder, or the polymer binder.
  • the first solvent, the second solvent, or the solvent may be the same solvent as mentioned in the present invention.
  • the inorganic particles and the substrate may be the same as those mentioned in the present invention.
  • the porous separator for secondary batteries manufactured by the manufacturing method described herein may have a solvent residual amount of 80 ppm or less, and a water content of 500 ppm or less.
  • the solvent residual amount may be 70 ppm or less, and the moisture content may be 400 ppm or less.
  • the solvent residual amount may be 60 ppm or less, and the moisture content may be 300 ppm or less.
  • the length change rate (L 1 ) of the vertical direction (MD) of the following formula ( 1 ) is 1.5% or less and horizontal direction (TD) when stored at 45 ° C. for 160 hours.
  • the rate of change of length L 2 may be 1.0% or less.
  • L 1 ⁇ L m1 -L m0 ⁇ / L m0
  • L m0 and L t0 represent the initial vertical length and the initial horizontal length of the separator prepared in accordance with one embodiment of the present invention, L m1 and L t1 respectively stored the separator at 45 °C for 160 hours The measured vertical length and horizontal length are shown.
  • L m0 and L t0 may each be 50 mm.
  • the present invention minimizes heat shrinkage or thermal deformation of the separator due to conventional high temperature drying by allowing low temperature drying through the introduction of nano-vapor.
  • the length change rate L 1 of the vertical direction MD and the length change rate L 2 of the horizontal direction TD are within the above ranges, short-circuit of the electrode can be effectively prevented, thereby improving battery safety.
  • the method of measuring the length change rate L 1 of the vertical direction MD and the length change rate L 2 of the horizontal direction TD is as follows:
  • Ten specimens cut at ten different points were prepared by separating the membrane 50 mm long by 50 mm long by TD, and each specimen was left in an oven at 45 ° C. for 160 hours.
  • the average length change rate is calculated by measuring the degree of length change in the direction and the TD direction.
  • the residual amount of the solvent of the porous separator for secondary batteries according to the embodiments of the present invention may be 80 ppm or less, and the water content may be 500 ppm or less.
  • the air permeability of the porous separator for secondary batteries may be 300 sec / 100 cc or less.
  • the present invention is a porous separator for a secondary battery prepared according to one embodiment; anode; And a secondary battery comprising a negative electrode is provided.
  • the secondary battery may be a lithium secondary battery. Lithium may be suitable for producing electricity having a small atomic weight of the element itself and a large electric capacity per unit mass.
  • the positive electrode has a positive electrode active material formed in a predetermined region, and examples of the positive electrode active material may include lithium oxide.
  • the negative electrode has a negative electrode active material formed in a predetermined region, and examples of the negative electrode active material may include a carbon material.
  • the porous separator is positioned between the positive electrode and the negative electrode to prevent a short and to allow the movement of lithium ions.
  • the secondary battery includes a liquid electrolyte or a polymer electrolyte, and typical shapes include cylindrical, square and pouch types.
  • PVdF-HFP Polyvinylidene fluoride-hexafluoropropylene copolymer (21216, Solvay) having a weight average molecular weight of 600,000 g / mol was added to acetone at 10% by weight, using a stirrer at 25 ° C. Stirring for 4 hours to prepare a first polymer solution.
  • PVdF-HFP Polyvinylidene fluoride-hexafluoropropylene
  • PVdF Polyvinylidene fluoride
  • DMF dimethylformamide
  • Al 2 O 3 (LS235, Nippon Light Metal) was added to acetone (large gold) at 25% by weight, and milled at 25 ° C. for 3 hours using a beads mill to prepare an inorganic dispersion.
  • the coating was prepared by stirring at 2 ° C. for 2 hours.
  • the prepared coating agent was coated on both sides of a polyethylene single layer base film (Selgard PE) having a thickness of 9 ⁇ m by a dip coating method, and then nano vaporized on the base film (manufacturer: Cheil Industries Co., Ltd., product name: DOYA TEST COATER) Dry air containing 10 vol%) of nano vapor was applied at a rate of 2 m 3 / min and dried in a 1_1 drying zone at 85 ° C. And then dried in a 1_2 dry zone at 85 ° C. using nanosteam under the same conditions and sequentially in a 2_1 dry zone at 85 ° C. and a 2_2 dry zone at 85 ° C. using hot air applied at a rate of 2 m 3 / min. To prepare a porous separator for a secondary battery of Example 1. At this time, the drying air was an air having a dew point of -50 °C.
  • Example 1 The amount of nano vapor used in Example 1 was set to 20 vol%, and then, the separation process of Example 2 was prepared in the same manner as in Example 1 except that the drying process was changed as described in Table 1.
  • Example 1 was prepared in the same manner as in Example 1 except that the amount of the nano vapor used in Example 1 was 30 vol%, and the drying process was changed as described in Table 1 below.
  • Example 1 the amount of nano vapor used was 40 vol%, and then the separation process of Example 4 was prepared in the same manner as in Example 1 except that the drying process was changed as described in Table 1.
  • each of the separators prepared in Examples and Comparative Examples was 50 mm (TD direction) X 100 mm. After the specimens cut in the (MD direction) were produced, a time period for passing 100 cc of air in each of the specimens was measured using an air permeability measuring device (Asahi Seiko: Model EG01-55-1MR). The air was measured by measuring the time five times and then calculating the average value.
  • Each of the separators prepared in Examples and Comparative Examples was prepared with 10 specimens cut at 10 different points with a width of 50 mm ⁇ 50 mm of TD. After the specimens were left in an oven at 45 ° C. for 160 hours, the average length change rate was calculated by measuring the degree of change in the MD direction and the TD direction of each specimen.
  • the method for preparing a separator using nano-steam according to the present invention while maintaining the moisture content and the solvent residual amount of 500ppm or less and 80ppm or less, respectively, has a small TD and MD direction change rate and excellent air permeability characteristics.
  • Comparative Examples 1 and 2 subjected to high temperature heat drying in comparison with the present invention have a large amount of moisture and a solvent remaining amount, and a large heat shrinkage ratio by the high-temperature drying process tends to increase the TD and MD direction length change rates.

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  • Chemical & Material Sciences (AREA)
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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
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Abstract

La présente invention concerne un procédé pour fabriquer un séparateur poreux pour une batterie rechargeable au moyen de nano vapeur, un séparateur fabriqué selon ce procédé et une batterie rechargeable incluant le séparateur.
PCT/KR2014/005652 2013-06-28 2014-06-25 Procédé pour fabriquer un séparateur poreux pour batterie rechargeable au moyen de nano vapeur, séparateur fabriqué selon ce procédé et batterie rechargeable WO2014209021A1 (fr)

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KR1020130075112A KR101661671B1 (ko) 2013-06-28 2013-06-28 나노증기를 이용한 이차 전지용 다공성 분리막의 제조 방법, 이를 이용해 제조된 분리막, 및 이차 전지
KR10-2013-0075112 2013-06-28

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US11239529B2 (en) 2015-09-30 2022-02-01 Sumitomo Chemical Company, Limited Film production method
CN116618262A (zh) * 2023-05-30 2023-08-22 宁夏宝丰昱能科技有限公司 一种电极烘烤装置和电极烘烤方法

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HUE060498T2 (hu) 2017-01-26 2023-03-28 Lg Energy Solution Ltd Eljárás szeparátor elõállítására, az eljárással elõállított szeparátor és a szeparátort tartalmazó elektrokémiai eszköz
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