WO2016159720A1 - Membrane de séparation composite pour batterie secondaire au lithium et son procédé de fabrication - Google Patents

Membrane de séparation composite pour batterie secondaire au lithium et son procédé de fabrication Download PDF

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Publication number
WO2016159720A1
WO2016159720A1 PCT/KR2016/003420 KR2016003420W WO2016159720A1 WO 2016159720 A1 WO2016159720 A1 WO 2016159720A1 KR 2016003420 W KR2016003420 W KR 2016003420W WO 2016159720 A1 WO2016159720 A1 WO 2016159720A1
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Prior art keywords
heat
layer
resistant layer
lithium secondary
secondary battery
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PCT/KR2016/003420
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English (en)
Korean (ko)
Inventor
주동진
이수지
조규영
김윤봉
김재웅
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에스케이이노베이션 주식회사
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Priority claimed from KR1020160039554A external-priority patent/KR102604599B1/ko
Application filed by 에스케이이노베이션 주식회사 filed Critical 에스케이이노베이션 주식회사
Priority to CN201680020283.3A priority Critical patent/CN107438912B/zh
Priority to US15/562,519 priority patent/US10985356B2/en
Publication of WO2016159720A1 publication Critical patent/WO2016159720A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/02—Details
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—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
    • 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
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/42—Acrylic 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
    • H01M50/443—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
    • H01M50/409—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
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • 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
    • H01M50/489—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a composite separator for a lithium secondary battery that improves the life and safety of the battery and a manufacturing method thereof.
  • Lithium secondary batteries are required for greater quality stability and uniformity in accordance with the trend of high capacity and high output of lithium secondary batteries such as hybrid vehicle batteries. Accordingly, various methods for providing functionality to a porous thin film made of polyethylene or polypropylene, which are separators used in lithium secondary batteries, have been attempted.
  • Pouch-type batteries unlike square or cylindrical batteries, wrap the battery in a soft film-type pouch, and the area of the electrode plate used increases as the battery capacity increases.
  • the positive electrode and the negative electrode plate may not be in close contact with each other, or an excited part may occur, or the battery may be bent, resulting in a decrease in battery life.
  • Japanese Patent Laid-Open No. 5355823 describes a separator having an adhesive layer made of polyvinylidene fluoride resin on at least one surface of a polyolefin separator base material.
  • the above technique attempts to improve both the thermal stability and adhesion of the separator by including an adhesive layer, but there is a problem that it is not suitable for the thinning demand of the battery due to the lack of heat resistance and the thickness of the adhesive layer because the heat resistant layer is not included. It is necessary to improve the adhesion strength with the electrode and to improve the battery life.
  • the present invention has been made to solve the above problems, excellent adhesion to the electrode, excellent flow of ions due to the smooth flow of ions due to charging and discharging, excellent heat resistance so that the separator is not deformed It is to provide a new composite separator for lithium secondary batteries and a method of manufacturing the same that improves the life of the battery.
  • the present invention is a porous substrate layer
  • Inorganic particles are connected and fixed by a binder polymer, the heat-resistant layer formed on the porous base layer;
  • the inorganic particles and the crystalline polymer relates to a composite separator for a lithium secondary battery satisfying the following formula 1.
  • D 1 is the average particle diameter of the heat-resistant layer inorganic particles
  • D 2 is the average particle diameter of the crystalline polymer particles forming a fusion layer.
  • the composite separator of the present invention may further include an interface layer formed between the heat resistant layer and the fusion layer, wherein the inorganic particles and the amorphous polymer particles are mixed.
  • the surface roughness of the composite separator is maintained at 0.3 ⁇ m or less, thereby improving the life of the battery and providing a composite separator having excellent electrical characteristics.
  • the composite separator may be a mixture of the heat-resistant layer and the fusion layer with a predetermined thickness at the interface by the simultaneous coating of the heat-resistant layer coating liquid and then applying the fusion layer coating liquid without drying.
  • the heat-resistant layer comprises 60 to 99% by weight of the inorganic particles and 40 to 1% by weight of the binder polymer with respect to 100% by weight of the total composition
  • the size of the inorganic particles is preferably 0.1 to 2.0 ⁇ m, alumina, be It may include one or more inorganic particles selected from aluminum oxide such as mite, barium titanium oxide, titanium oxide, magnesium oxide, clay glass powder, but are not limited thereto. It is not.
  • examples of the binder of the heat-resistant layer in the present invention are polyvinylidene fluoride-hexafluorofluoropropylene (PVdF-HFP), polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), polyvinyl It may include one or two or more selected from polyvinylpyrrolidone, polyimide, polyethylene oxide (PEO), cellulose acetate, polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), and the like. However, it is not necessarily limited thereto.
  • the crystalline polymer particles having a melting temperature of 100 ° C. or higher in the present invention are not limited as long as they are crystalline polymers having a crystalline temperature above the melting temperature.
  • PVdF polyvinylidene fluoride
  • PS polystyrene
  • the battery life is long, in particular, the adhesion between the electrode and the welding layer is significantly increased, and the battery safety is also increased.
  • the size of the crystalline polymer particles in the present invention is 0.05 to 0.8 ⁇ m is good for achieving the desired effect in the present invention. Moreover, it is preferable that the thickness of the said fusion layer of this invention is 2.0 micrometers or less.
  • the fusion layer additionally adds the inorganic particles used in the heat-resistant layer, it has been confirmed that it gives more excellent adhesiveness and shows excellent results in battery safety and performance.
  • the content of the inorganic particles is preferably 30% by volume or less based on the total content of the particles of the fusion layer.
  • the composite separator when the composite separator is fused with an electrode, fusion in a state containing an electrolyte solution is possible, but fusion in a state without an electrolyte solution is possible, and when fusion is performed with an electrode without an electrolyte solution. It is effective to realize more adhesion.
  • the electrodes and separators which are constituents, enter the hard cylinder or can, but in this case, the electrode cannot be fused by applying temperature and pressure after battery assembly. It is effective when fusion is applied by injecting electrolyte into a cylinder or a can after the separator is fused.
  • the composite separator according to the present invention has excellent lifespan and thermal safety of a lithium secondary battery, is uniformly bonded at the positive electrode and the negative electrode of a wide secondary battery, and smoothly moves ions through uniformly distributed pores of each layer. Therefore, it can have excellent output characteristics.
  • the composite separator according to the present invention may be introduced to improve the performance of large lithium secondary batteries used in electric vehicles.
  • the present invention is a porous substrate layer
  • Inorganic particles are connected and fixed by a binder polymer, the heat-resistant layer formed on the porous base layer;
  • the inorganic particles and the crystalline polymer relates to a composite separator for a lithium secondary battery satisfying the following formula 1.
  • D 1 is the average particle diameter of the heat-resistant layer inorganic particles
  • D 2 is the average particle diameter of the fusion layer polymer particles, it can significantly improve the adhesion to the electrode within the range of 1.5 ⁇ D 1 / D 2 .
  • the permeability of the composite separator can be further increased, and heat resistance and mechanical strength are significantly increased.
  • the present invention may further include an interface layer formed between the heat resistant layer and the fusion layer, wherein the inorganic particles and the amorphous polymer particles are mixed, and the thickness of the interface layer is 40% or less of the thickness of the fusion layer. Can be.
  • the fusion layer may be in the scope of the present invention, either one-sided lamination or two-sided lamination, provided that the fusion layer is laminated on the heat resistant layer.
  • the surface roughness of the composite separator may be maintained at 0.3 ⁇ m or less, thereby manufacturing a composite separator capable of further improving battery life and providing a high energy battery having excellent electrical characteristics. This may be achieved by more uniform adhesion with the electrode to improve the electrical characteristics of the battery.
  • the porous substrate layer may be used as long as it is a polyolefin-based microporous membrane, and may be applied to a battery having pores such as non-woven fabric, paper, and pores in the interior or pores of the microporous membrane thereof.
  • the porous membrane is not particularly limited.
  • the said polyolefin resin is 1 type or more types of polyolefin resins individually or in mixture, and it is especially 1 type or 2 or more types chosen from polyethylene, a polypropylene, and these copolymers.
  • the base layer may be prepared by the polyolefin resin alone or a polyolefin resin as a main component and further comprises an inorganic particle or an organic particle.
  • the base layer may include a polyolefin-based resin in multiple layers, and the base layer composed of the multilayers does not exclude any one layer or all layers including inorganic particles and organic particles in the polyolefin resin.
  • the thickness of the porous substrate layer is not particularly limited, but may be preferably 5 to 30 ⁇ m.
  • the porous base layer is a porous polymer film mainly made through stretching.
  • Method for producing a polyolefin-based porous substrate layer according to an embodiment of the present invention is not limited as long as it is prepared by a person skilled in the art, in one embodiment, can be prepared by a dry method or a wet method.
  • the dry method is a method in which a polyolefin film is formed and then stretched at a low temperature to cause micro cracks between lamellas, which are crystal parts of the polyolefin, to form micro voids.
  • a polyphase resin and diluent are kneaded at a high temperature at which the polyolefin resin is melted to form a single phase, and in the cooling process, the polyolefin and diluent are phase separated, and then the dilution portion is extracted to form voids therein.
  • the wet method is a method of imparting mechanical strength and permeability through the stretching / extraction process after the phase separation process, and may be more preferable than the dry method because the thickness of the film is thin, the pore size is uniform, and the physical properties are excellent.
  • the diluent is not limited as long as it is an organic material forming a single phase with a polyolefin resin, and examples thereof include nonane, decane, decalin, paraffin oil, and paraffin wax.
  • phthalic acid esters such as aliphatic or dibutyl phthalate and dioctyl phthalate, such as wax, and carbon atoms such as palmitic acid, stearic acid, oleic acid, linoleic acid and linolenic acid 20 fatty acids, fatty acid alcohols having 10 to 20 carbon atoms such as palmitic alcohol, stearic acid alcohol, oleic alcohol, and mixtures thereof can be used.
  • the heat-resistant layer is bonded to the base layer by mixing a small amount of binder in the inorganic particles, thereby improving the thermal stability, electrical safety, and electrical properties of the battery, and also serves to suppress the shrinkage of the base layer generated at high temperatures. do.
  • the heat-resistant layer is not largely limited in size of the inorganic particles, but the coating of 1 to 10 ⁇ m thickness on one or both sides of the base layer by mixing the binder polymer in inorganic particles of 0.1 to 2.0 ⁇ m size The effect can be easily achieved.
  • the heat-resistant layer may include 60 to 99% by weight of the inorganic particles and 40 to 1% by weight of the binder polymer with respect to 100% by weight of the total composition. In the above content, the performance of the battery can be effectively achieved.
  • the inorganic particles included in the heat-resistant layer are rigid, so that deformation does not occur due to external impact and force, and thermal deformation and side reactions do not occur even at high temperatures.
  • Alumina, Boehmite, and Aluminum hydroxide (Aluminum Hydroxide), Titanium Oxide, Barium Titanium Oxide, Magnesium Oxide, Magnesium Hydroxide, Silica, Clay, and Glass Powder Glass powder) is preferably one or two or more inorganic particles selected from the group consisting of, but is not limited thereto.
  • the binder polymer included in the heat-resistant layer serves as a binder for stably connecting and stably separating inorganic particles, and may be polyvinylidene fluoride (PVdF) or polyvinylidene fluoride-hexafluoro Propylene (PVdF-HFP), Polymethylmethacrylate (PMMA), Polyacrylonitrile (PAN), Polyvinylpyrrolidone, Polyimide, Polyethylene oxide (PEO), Cellulose acetate acetate), polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC) and one or more binder polymers selected from the group consisting of polybutylacrylate (Polybutylacrylate), but is not limited thereto.
  • the heat resistant layer may further include an acryl-based or butadiene-based polymer in order to improve the adhesive force as necessary.
  • the solvent is not particularly limited.
  • water, methanol, ethanol, 2-propanol, acetone, tetrahydrofuran It may be one kind or two or more kinds selected from methyl ethyl ketone, ethyl acetate, N-methylpyrrolidone, dimethylacetamide, dimethylformamide, dimethylformamide and the like.
  • the thickness of the heat resistant layer may be 1 to 20 ⁇ m, preferably 1 to 10 ⁇ m, on one or both sides of the base layer by mixing the binder polymer with the inorganic particles, thereby ensuring heat resistance and relatively excellent ion permeability. Can be improved.
  • the fusion layer according to an embodiment of the present invention is formed on the outermost layer of the composite separator, and the electrode plate and the separator are bonded to each other to uniformly contact the electrode plate at regular intervals, and the fusion layer is laminated on the heat resistant layer. If so, either single-sided or double-sided stacking may fall within the scope of the present invention.
  • the lamination form of the fusion layer / heat-resistant layer / porous substrate layer / heat-resistant layer / fusion layer and the lamination form of the fusion layer / porous substrate layer / heat-resistant layer / fusion layer and the lamination form of the porous substrate layer / heat-resistant layer / fusion layer It may have, but is not limited thereto.
  • the fusion layer of the present invention contains crystalline polymer particles having a melting temperature of 100 ° C. or more, the fusion polymer layer can be tightly adhered to the fusion layer of the electrode plate and the composite separator, and the adhesion strength is increased in the overall area of the anode and cathode electrode plates.
  • the adhesion between the positive electrode and the negative electrode is strongly and uniformly and uniformly in close contact with each other, thereby achieving an effect of significantly increasing the performance and life of the battery.
  • the fusion layer is formed in the form of crystalline polymer particles having a high melting temperature, so that the characteristics of the battery may be increased by having excellent fusion characteristics and excellent lifespan of the battery, which does not cause local adhesion failure. .
  • the fusion layer of the present invention may be produced using a crystalline polymer in the form of particles, but may not be clearly described, but may exhibit a high degree of swelling during electrolyte impregnation.
  • the crystalline polymer in the form of particles may have a melting temperature of 100 ° C. or more, 100 to 350 ° C., preferably 120 to 350 ° C., and more preferably 150 to 350 ° C. It is preferable that the mobility of ions within the above range is smooth, the gas permeability is excellent, and the life of the battery is improved. This is because most of the conditions for bonding the separator to the electrode is made at a temperature of 70 to 100 °C, in the case of a polymer having a melting temperature of less than 100 °C, the polymer in the form of particles in the adhesion process is present in the heat-resistant layer or the base layer This is because it blocks pores and interferes with the transfer of lithium ions.
  • the adhesive force between the composite separator and the electrode of the present invention shows a remarkable adhesion of the electrode to the electrode at a temperature of 100 ° C. and a pressure of 1 MPa of 10 gf / cm or more.
  • the crystalline polymer in the form of particles included in the fusion layer of the present invention is not particularly limited as long as the melting temperature is 100 ° C. or higher.
  • polyacrylonitrile (PAN), polyvinylidene fluoride (PVdF), and polystyrene Any one or two or more polymers selected from PS) and the like and mixtures thereof are preferred, but are not limited thereto.
  • the thickness of the fusion layer may be coated on both sides of the outermost layer of the composite separator in a thickness of 0.1 to 2.0 ⁇ m, preferably 0.1 to 1.0 ⁇ m. It is possible to smoothly move lithium ions within the above range, it is possible to prevent the increase in the resistance in the separator.
  • the crystalline polymer in the form of particles has a melting temperature of 100 ° C. or more, an inorganic particle of the heat-resistant layer, and a particle size of the crystalline polymer of the fusion layer.
  • the adhesion with the electrode is remarkably increased, the capacity and output can be increased, and the composite separator excellent in heat resistance and mechanical strength can be prepared.
  • D 1 is the average particle diameter of the heat-resistant layer inorganic particles
  • D 2 is the average particle diameter of the fusion layer polymer particles.
  • 1.5 ⁇ D 1 / D as a more specific example 2 satisfies the range of several days, 1.5 ⁇ D 1 / D 2 ⁇ 5.0 , but does not necessarily limited to the upper limit.
  • the surface roughness Ra is 0.3 ⁇ m or less, the adhesion is further increased, and the life of the battery can be improved, which is more preferable.
  • the average particle diameter of the inorganic particles included in the heat resistant layer is not limited, but has a range of 0.1 to 2 ⁇ m, and the average particle diameter of the crystalline polymer particles included in the fusion layer is not limited. , 0.05 to 0.8 mu m, the effect of the present invention can be easily achieved.
  • the method of manufacturing a composite separator according to an embodiment of the present invention may include the following steps.
  • a fusion layer coating liquid including a crystalline polymer in a particle form having a melting temperature of 100 ° C. or more on the coated heat-resistant layer coating liquid
  • the average particle diameter of the inorganic particles may be 1.5 times or more than the average particle diameter of the crystalline polymer particles.
  • the coating layer of the heat-resistant layer coating layer and the fusion layer freely migrates and is mixed by mixing at a predetermined thickness at the interface of the two layers, and thus the surface of the fusion layer is coated very uniformly. This adhesion is done semipermanently.
  • the inorganic layer and the amorphous polymer particles may further include an interfacial layer between the heat-resistant layer and the fusion layer, the thickness of the interfacial layer may be 40% or less of the fusion layer thickness.
  • the long-term life of the battery is not damaged even by long-term use at the laminated interface of each layer of the composite film of the present invention is good because it has an effect that significantly increases.
  • the heat-resistant layer is coated and dried, and then the fusion layer is coated and dried, the long-term life is greatly reduced by 10%, in some cases by more than 30%, due to adhesive deterioration of the interface. It was confirmed that the number of times the battery capacity was significantly lowered.
  • the solvent used as the coating liquid for forming the heat-resistant layer or the fusion layer of the present invention is not limited, but for example, water, methanol, ethanol, 2-propanol, acetone, tetrahydrofuran, methyl ethyl ketone, ethyl acetate, N-methyl It may be one or more selected from pyrrolidone, dimethylacetamide, dimethylformamide, dimethylformamide, and the like, but is not limited thereto.
  • the method of forming the composite separator according to the present invention may be prepared by a conventional method adopted in the art, and is not particularly limited.
  • the bar coating method, the rod coating method, and the die die coating method, wire coating method, comma coating method, micro gravure / gravure method, dip coating method, spray method, ink-jet coating method or a mixture thereof Manner and modified manner can be used.
  • the present invention used a fusion layer and the heat-resistant layer using a multilayer coating method, which is more preferable to increase the productivity of the process.
  • Lithium secondary battery according to an embodiment of the present invention can be prepared including a composite separator, a positive electrode, a negative electrode, and a non-aqueous electrolyte.
  • the positive electrode and the negative electrode may be prepared by mixing and stirring a solvent, a binder, a conductive material, a dispersant, and the like into a positive electrode active material and a negative electrode active material to prepare a mixture, and then applying it to a current collector of a metal material, drying it, and pressing it. .
  • the positive electrode active material can be used as long as it is an active material commonly used for the positive electrode of a secondary battery.
  • Lithium metal oxide particles including one or more metals selected from the group consisting of can be used.
  • the negative electrode active material can be used as long as it is an active material commonly used for the negative electrode of a secondary battery.
  • the negative electrode active material of the lithium secondary battery is preferably a lithium intercalable material.
  • the negative electrode active material is lithium (metal lithium), digraphitizable carbon, non-graphitizable carbon, graphite, silicon, Sn alloy, Si alloy, Sn oxide, Si oxide, Ti oxide, Ni oxide, Fe
  • the oxide (FeO) and lithium-titanium oxide (LiTiO 2 , Li 4 Ti 5 O 12 ) may be one or two or more materials selected from the group of the negative electrode active material.
  • a conventional conductive carbon material can be used without particular limitation.
  • the current collector of the metal material is a metal having high conductivity and which can be easily adhered to the mixture of the positive electrode or the negative electrode active material, and can be used as long as it is not reactive in the voltage range of the battery.
  • Non-limiting examples of the positive electrode current collector is a foil made by aluminum, nickel or a combination thereof
  • non-limiting examples of the negative electrode current collector is made by copper, gold, nickel or copper alloy or a combination thereof Foil and the like.
  • a separator is interposed between the positive electrode and the negative electrode.
  • a method of applying the separator to a battery may include lamination, stacking, and folding of the separator and the electrode, in addition to winding, which is a general method.
  • the nonaqueous electrolyte includes a lithium salt as an electrolyte and an organic solvent, and lithium salts may be used without limitation, those conventionally used in a lithium secondary battery electrolyte, and may be represented by Li + X ⁇ .
  • the lithium salt anion is not particularly limited, F -, Cl -, Br -, I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, PF 6 -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, CF 3 SO 3 -, CF 3 CF 2 SO 3 -, (CF 3 SO 2) 2 N -, (FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, (SF 5) 3 C -, (CF 3 SO 2) 3 C -, CF 3 (CF 2) 7 SO 3 -, CF 3 CO 2 -, CH 3 CO 2 -, SCN - any one of the - and (CF 3 CF 2 SO 2) 2 N Or two or more may be used.
  • Organic solvents include propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate, methylpropyl carbonate, dipropyl carbonate, dimethylsulfuroxide, acetonitrile, dimethoxyethane, diethoxyethane, sulfolane, gamma-buty Rolactone, and tetrahydrofuran, any one selected from the group consisting of, or a mixture of two or more thereof may be used.
  • the nonaqueous electrolyte may be injected into an electrode structure including an anode, a cathode, and a separator interposed between the anode and the cathode.
  • the external shape of the lithium secondary battery is not particularly limited, but may be cylindrical, square, pouch type or coin type using a can.
  • the method of measuring the gas permeability of the separator was in accordance with JIS P8117 standard, and compared by recording the time it takes for 100cc of air to pass through the area of 1inch 2 of the separator in seconds.
  • the separator is cut into a 10 cm square shape to prepare a sample, and then the area of the sample is measured and recorded using a camera. Place five sheets of paper above and below the sample so that the sample is in the center of the sample, and fasten the four sides of the paper with clips. The sample wrapped with paper was left to stand in 130 degreeC hot air drying oven for 1 hour. After leaving the sample, the sample was taken out and the area of the separator was measured by a camera to calculate the shrinkage ratio of the following Equation 1.
  • Shrinkage (%) (area before heating-area after heating) ⁇ 100 / area before heating
  • a sample for measuring the adhesion between the separator and the electrode is placed in a positive electrode and a negative electrode plate, soaked in a separator for 1 hour, and then immersed in an electrolyte solution.
  • the sample is immediately placed in a heat press and fused by applying heat and pressure of 100 ° C. and 1 MPa for 150 seconds. .
  • the specimen thus prepared was immersed in the electrolyte for 1 hour and then taken out, and the peel strength was measured immediately before the electrolyte evaporated.
  • Each battery manufactured through the assembly process was charged and discharged 500 times at a discharge rate of 1C, and then cycle evaluation was performed to measure the degree of reduction compared to the initial capacity by measuring the discharge capacity.
  • the thickness of the battery was measured using a thickness gauge of Mitsutoyo after 500 charging and discharging, and then compared with the thickness before charging and discharging.
  • the battery thickness increase rate of the following Equation 2 was measured.
  • A Battery thickness before charge and discharge (mm)
  • the membrane was prepared in a size of 5 ⁇ 5 ⁇ m, and the Ra value was measured by roughness analysis at the entire size of the sample using AFM (Digital Instruments Nanoscope V MMAFM-8 Multimode).
  • each of the prepared cells were fully charged with 100% SOC (charge rate), and then nail penetration evaluation was performed. At this time, the diameter of the nail was fixed to 3.0mm, the penetration rate of the nail all 80mm / min.
  • L1 no change
  • L2 small heat generation
  • L3 leakage
  • L4 smoke
  • L5 ignition
  • L1 to L3 are Pass
  • L4 to L5 are determined to be Fail.
  • alumina particles having an average particle diameter of 1.0 ⁇ m, 2% by weight of polyvinyl alcohol having a melting temperature of 220 ° C. and a degree of soaping of 99%, and an acrylic latex having a Tg of ⁇ 52 ° C. (solid content of 20% by weight) 4 By weight, added to water as a solvent and stirred to prepare a uniform heat-resistant layer slurry.
  • Melt layer slurry which is composed of polyvinylidene fluoride (PVdF) having a melting temperature of 162 ° C as a main component, and is dispersed in water to maintain a spherical shape with an average particle diameter of 0.3 ⁇ m so as to have a ratio of 20% by weight to water. Used as.
  • PVdF polyvinylidene fluoride
  • the polyolefin microporous membrane (35% porosity) of 7 ⁇ m thick manufactured by SK Innovation was continuously coated with a heat-resistant layer slurry and a melted layer slurry on one side of the substrate without a separate drying process by using a multilayer slot coating die. Thereafter, only the fusion layer slurry was coated on the other side of the substrate using a single layer slot coating die.
  • the separator was wound up in a roll after evaporating the solvent, water.
  • the thickness of the cross-section heat resistant layer was 3 micrometers, and the thickness of the fusion layer was 0.8 micrometer, respectively.
  • Pouch-type batteries were assembled by stacking using the positive electrode, negative electrode, and separator prepared above, and ethylene carbonate (EC) / ethyl in which 1 M lithium hexafluorophosphate (LiPF 6 ) was dissolved in the assembled battery.
  • EMC methyl carbonate
  • DMC dimethyl carbonate
  • Example 1 it carried out similarly to Example 1 except having formed both the heat-resistant layer and the fusion layer on both surfaces of the base material layer.
  • the separation membrane was prepared in the same manner as in Example 1 except that the membrane was prepared as follows.
  • the main component is polyacrylonitrile (PAN), which has a melting temperature of 310 ° C.
  • PAN polyacrylonitrile
  • the polymer particles dispersed in water to maintain a spherical shape with an average particle diameter of 0.15 ⁇ m are diluted to a ratio of 12% by weight with respect to water to form a fused slurry. Used.
  • a polyolefin microporous membrane (35% porosity) having a thickness of 7 ⁇ m manufactured by SK Innovation was used, and a heat resistant layer slurry and a melted layer slurry were simultaneously coated on one side of the substrate using a multilayer slot coating die. After that, only the fusion layer slurry was coated on the other side of the substrate using a single layer slot coating die.
  • the separator was wound up in a roll after evaporating the solvent, water.
  • the thickness of the cross section heat resistant layer was 3 m, and the thickness of the fusion layer was 0.5 m, respectively.
  • Example 3 it carried out similarly to Example 3 except having formed both the heat-resistant layer and the fusion layer on both surfaces of the base material layer.
  • a separator and a battery were manufactured in the same manner as in Example 1, except that alumina particles having an average particle diameter of 0.45 ⁇ m were used as the heat resistant layer of the separator.
  • a separator and a battery were manufactured in the same manner as in Example 1, except that alumina particles having an average particle diameter of 0.6 ⁇ m were used as the heat resistant layer of the separator.
  • a separator and a battery were manufactured in the same manner as in Example 1, except that there was no fusion layer of the separator.
  • a separator and a battery were manufactured in the same manner as in Example 1, except that there was no heat-resistant layer of the separator.
  • the separation membrane was prepared in the same manner as in Example 1 except that the membrane was prepared as follows.
  • PVdF-HFP Polyvinylidene fluoride-hexapullopropylene
  • a coating substrate As a coating substrate, a polyethylene microporous membrane product (SK LiBS) having a thickness of 9 ⁇ m manufactured by SK Innovation was used, and a heat-resistant layer slurry and a melted layer slurry were simultaneously coated on one side of the substrate using a multilayer slot coating die. Thereafter, only the fusion layer slurry was coated on the other side of the substrate using a single layer slot coating die.
  • the separator was wound up in a roll after evaporating the solvent, water.
  • the thickness of the cross-section heat resistant layer was 3 micrometers, and the thickness of the double-sided fusion layer was 0.5 micrometer, respectively.
  • Comparative Example 3 was carried out in the same manner as in Comparative Example 3 except that both the heat resistant layer and the fusion layer were formed on both sides of the substrate layer.
  • a separator and a battery were manufactured in the same manner as in Example 1, except that alumina particles having an average particle diameter of 0.43 ⁇ m were used for the separator.
  • a separator and a battery were manufactured in the same manner as in Example 1, except that alumina particles having an average particle diameter of 0.35 ⁇ m were used as the heat resistant layer of the separator.
  • (D 1 is the average particle diameter of the heat-resistant layer inorganic particles
  • D 2 is the average particle diameter of the fusion polymer particles.

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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)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne : une membrane de séparation composite pour une batterie secondaire au lithium, permettant d'améliorer de façon significative la durée de vie et la sécurité d'une batterie; et une batterie secondaire au lithium la comprenant et, plus particulièrement, une membrane de séparation composite comprenant : une couche de base poreuse; une couche thermorésistante formée sur un côté ou les deux côtés de la couche de base poreuse; et une couche de fusion formée sur une couche la plus à l'extérieur, la couche thermorésistante comprenant des particules inorganiques liées et fixées par des polymères liants, et la couche de fusion comprenant des polymères cristallins sous la forme de particules ayant une température de fusion de 100 °C ou plus.
PCT/KR2016/003420 2015-04-02 2016-04-01 Membrane de séparation composite pour batterie secondaire au lithium et son procédé de fabrication WO2016159720A1 (fr)

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CN201680020283.3A CN107438912B (zh) 2015-04-02 2016-04-01 锂二次电池用复合隔膜及其制造方法
US15/562,519 US10985356B2 (en) 2015-04-02 2016-04-01 Composite separation membrane for lithium secondary battery and manufacturing method therefor

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KR1020160039554A KR102604599B1 (ko) 2015-04-02 2016-03-31 리튬 이차전지용 복합 분리막 및 이의 제조방법

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WO2018145666A1 (fr) * 2017-02-13 2018-08-16 河北金力新能源科技股份有限公司 Séparateur de batterie au lithium-ion résistant aux hautes températures ayant une variété de revêtements et procédé de préparation associé
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EP3675229A4 (fr) * 2018-01-30 2020-12-30 Lg Chem, Ltd. Séparateur pour dispositif électrochimique et procédé de préparation de séparateur
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JP7262283B2 (ja) * 2019-04-16 2023-04-21 住友化学株式会社 非水電解液二次電池用多孔質層
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CN111244362B (zh) * 2020-01-15 2022-09-30 惠州锂威新能源科技有限公司 一种复合隔膜及其制备方法、锂离子电池
CN111640902A (zh) * 2020-06-08 2020-09-08 淮北市吉耐新材料科技有限公司 一种锂电池隔膜的制备工艺
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CN115347321A (zh) * 2022-08-26 2022-11-15 中国长江三峡集团有限公司 一种抑温隔膜及其制备方法

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