US20150303427A1 - Organic/Inorganic Complex Coating Porous Separator And Secondary Battery Using The Same - Google Patents

Organic/Inorganic Complex Coating Porous Separator And Secondary Battery Using The Same Download PDF

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US20150303427A1
US20150303427A1 US14/418,059 US201314418059A US2015303427A1 US 20150303427 A1 US20150303427 A1 US 20150303427A1 US 201314418059 A US201314418059 A US 201314418059A US 2015303427 A1 US2015303427 A1 US 2015303427A1
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Prior art keywords
secondary battery
coating
separator
binder
porous
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Inventor
Jae Yong Hyun
Jin A Yoo
Do Hoon LEE
Chang Hyun CHOI
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Hanwha TotalEnergies Petrochemical Co Ltd
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Samsung Total Petrochemicals Co Ltd
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Assigned to SAMSUNG TOTAL PETROCHEMICALS CO., LTD. reassignment SAMSUNG TOTAL PETROCHEMICALS CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHOI, CHANG HYUN, HYUN, JAE YONG, LEE, DO HOON, YOO, JIN A
Assigned to HANWHA TOTAL PETROCHEMICAL CO., LTD. reassignment HANWHA TOTAL PETROCHEMICAL CO., LTD. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: SAMSUNG ATOFINA CO., LTD., SAMSUNG TOTAL PETROCHEMICALS CO., LTD.
Publication of US20150303427A1 publication Critical patent/US20150303427A1/en
Assigned to HANWHA TOTAL PETROCHEMICAL CO., LTD. reassignment HANWHA TOTAL PETROCHEMICAL CO., LTD. CORRECTIVE ASSIGNMENT TO CORRECT THE RECEIVING PARTY ADDRESS PREVIOUSLY RECORDED AT REEL: 036548 FRAME: 0271. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Assignors: SAMSUNG ATOFINA CO., LTD., SAMSUNG TOTAL PETROCHEMICALS CO., LTD.
Abandoned legal-status Critical Current

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    • H01M2/1686—
    • 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
    • H01M50/446—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
    • 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
    • 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
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • 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
    • 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
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • 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
    • H01M50/44—Fibrous material
    • 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 separator used in a secondary battery and more particularly, to a porous separator in which an organic/inorganic complex coating layer is applied to a porous substrate, and a secondary battery including the same.
  • Lithium ion secondary batteries are basically comprised of an anode, a cathode, a separator, and an electrolyte, and have been widely applied to small-sized electronic devices, for example, mobile phones, notebook computers, and the like, as high energy density energy storage devices which can be charged and discharged by reversible conversion between chemical energy and electric energy.
  • small-sized electronic devices for example, mobile phones, notebook computers, and the like
  • high energy density energy storage devices which can be charged and discharged by reversible conversion between chemical energy and electric energy.
  • application of the lithium ion batteries has been rapidly expanded to hybrid electric vehicles (HEV), plug-in EV, e-bikes, and energy storage systems (ESS).
  • HEV hybrid electric vehicles
  • ESS energy storage systems
  • the lithium ion batteries are stable electrochemical devices insulated by separators, short circuit between an anode and a cathode may be caused by internal or external abnormalities of the batteries or by shocks and there is a possibility of heating and explosion. Therefore, ensuring thermal/chemical stability of the separators as insulators is the most important consideration.
  • a polyolefin-based separator commercially used a lot in lithium secondary batteries is a porous film that prevents short circuit between an anode and a cathode and provides pores serving as a passage of lithium ions.
  • Polyolefin-based separators manufactured by a wet method or a dry method have been widely used commercially.
  • the wet method is a method including mixing, melting, extruding inorganic particles or oil components with polyolefin in an extruder to prepare a sheet, and forming a thin film by simultaneous or successive biaxial orientation using a roller or a tenter, and extracting the inorganic particles or oil components with a solvent to form a porous film.
  • polyethylene (PE) among polyolefins is mainly used to form a film.
  • the dry method is a method of forming a porous film by melting and extruding a resin and then orienting the resultant with a roller or a tenter without using an organic solvent, and generally uses polypropylene (PP) and may use polyethylene as necessary.
  • a polyolefin porous separator in which a porous substrate is generally prepared by a film orientation process, cannot avoid a change in volume such as contraction or fusion of its separator when a temperature of a battery is increased to 100° C. or more due to an internal or external stimulus, and, thus, an electrical short circuit between an anode and a cathode may cause explosion. Further, if the separator is broken due to dendrite growth within the battery, an internal short circuit may induce explosion of the battery.
  • a coating separator in which in order to suppress thermal contraction caused by high temperature and instability of the battery caused by dendrite, inorganic particles together with a binder are coated on one or both surfaces of the substrate of the porous separator, and, thus, the inorganic particles suppresses a contraction rate of the substrate and the separator is more stable due to the inorganic coating layer.
  • an organic/inorganic coating layer applied to the porous substrate is not uniformly coated on the porous substrate, when the coating layer is assembled in a secondary battery or within the battery, a part of the inorganic coating layer can be easily separated due to coating defects on the surface. Such separation can decrease stability of the battery. Therefore, a coating system for more uniform organic/inorganic coating is needed to form a uniform inorganic coating layer and ensure an excellent battery property.
  • an organic solvent dissolves a binder (PVDF-CTFE) to provide an excellent adhesive property between inorganic particles in powder form when it evaporates.
  • Slurry prepared from a binder solution in an organic solvent provides interconnectivity among a porous substrate, an organic/inorganic coating layer, and inorganic particles within the inorganic coating layer.
  • the components connected as such can endure contraction of a porous separator caused by heating and an external physical shock (event) without losing the interconnectivity during a battery is assembled and operated.
  • inorganic particles typically has a certain distribution size, and when a binder is completely dissolved in a solvent and the binder has an excellent compatibility with surfaces of the inorganic particles, as the solvent evaporates, the binder sufficiently covers the surfaces of the inorganic particles.
  • a sufficient adhesive strength between the inorganic particles can be obtained, and even if the binder completely dissolved in the solvent does not have a high wettability with respect to a porous substrate, the binder solution infiltrates into a porous structure and has a sufficient physical adhesive strength with respect to the porous substrate.
  • the binder in a sufficient amount may be needed, or gel is formed as the solvent volatilizes.
  • a solvent-impermeable space is generated, resulting in non-uniformity of an organic/inorganic coating layer, which may cause deterioration in battery property.
  • a concentration of the binder in slurry is increased, a viscosity of the slurry is highly increased, which makes it difficult to prepare an organic/inorganic complex layer of a thin film, and a drying process may require a high temperature.
  • a binder dispersed in a certain size in a solvent has been used in the form of an emulsion or suspension, and a binder dispersed in a certain size in an organic (oil-based) solvent may be used, and particularly, a binder dispersed in a certain size in water-based solvent (water) is preferred since it is eco-friendly and has many processing advantages in coating inorganic particles.
  • a coating method based on a binder composition soluble in an organic solvent has some problems. Firstly, a binder soluble in an organic solvent is formed into gel as the organic solvent volatilizes during a drying process, and, thus, a solvent-impermeable space is generated, resulting in non-uniformity of an organic/inorganic coating layer. Thus, a battery property may be reduced. In order to overcome this problem, the binder needs to undergo a secondary drying process in a vacuum at a glass transition temperature (Tg) or higher. If a residual solvent is present in a product due to insufficient drying, a part of the binder is dissolved and gel may be formed.
  • Tg glass transition temperature
  • a surface of the coating layer becomes sticky, dust from the outside or unnecessary particles may adhere thereto and a defect rate of products may be increased due to adhesion between coating layers or with a substrate when a product is wrapped.
  • a concentration of the binder in the slurry is increased, a viscosity of the slurry is highly increased, which makes it difficult to prepare an organic/inorganic complex layer of a thin film.
  • air permeability is low and a boiling point is high, a drying process requires a high temperature.
  • a low viscosity of the slurry is maintained, an adhesive strength with a porous substrate or between inorganic substances is decreased. Thus, the inorganic particles are easily separated.
  • the organic solvent needs to be specially prepared and managed.
  • the preparation method of the organic/inorganic coating separator using the binder soluble in the organic solvent has limitations in view of characteristics of the battery and characteristics of the process.
  • Korean Patent Laid-open Publication No. 10-2012-0052100 describes a technology of preparing a coating separator having two coating layers, comprising: forming an organic/inorganic complex layer by casting a slurry, in which styrene-butadiene rubber (SBR) and carboxyl methyl cellulose (CMC) are dissolved in acetone as an organic solvent, onto a polyethylene porous film; and performing an electric radiation on a polymer compound solution.
  • SBR styrene-butadiene rubber
  • CMC carboxyl methyl cellulose
  • Korean Patent No. 10-1125013 describes a method for preparing a cross-linked ceramic-coated separator using a water-soluble ionic polymer. This method also uses an ionic polymer which can be dissolved in water, but the ionic polymer is not dispersed in water but completely dissolved in water, and, thus, it cannot avoid confinement of the solvent. Since dimethylacetamide as an organic solvent is used 15 times more than water, it does not provide a fundamental suggestion of a coating method using water.
  • a crosslinking agent and an initiator need to be added together with the organic solvent during a preparation process of slurry, and during a drying process, a heat or UV treatment for 20 hours or more is essentially required.
  • a crosslinking agent and an initiator are added to a slurry solution, before the slurry is applied to the porous substrate, the slurry is partially cross-linked by itself by heat and energy externally applied while a coating solution is stored and transferred, resulting in solidification of the slurry.
  • uniformity of the coating separator is finally decreased.
  • An object of the present invention is to provide a separator capable of improving thermal and chemical stability of a porous substrate by forming an organic/inorganic complex coating porous layer excellent in air permeability and adhesive strength by coating the porous substrate with a coating solution in which a binder and selectively added inorganic particles are dispersed in a specific size, and exhibiting a sufficient adhesive strength between the inorganic particles or between the inorganic particles and the substrate if the inorganic particles are contained, and a secondary battery using the same.
  • An organic/inorganic complex coating porous separator comprises a coating layer coated with a coating solution which contains a binder and selectively inorganic particles dispersed in the form of particle having a certain particle size in a solvent, in a single layer or multiple layers on a single surface or both surfaces of a porous substrate or at least a part of a pore portion of the porous substrate.
  • the binder used in the present invention refers to two types of binders including an oil-based binder dispersed in a certain size in an organic solvent and a water-based binder dispersed in a certain size in water.
  • the expression “dispersed in a certain size” means that binder particles are dispersed with a certain distribution size and are present as an emulsion or a suspension at the time of initial polymerization or by a post-process.
  • An adhesive strength between the inorganic particles or between the inorganic particles and the substrate can be more effectively regulated by regulating a particle size of the dispersed binder by a temperature, a pH, or a concentration of an emulsifier during a preparation process.
  • the term “certain size” of the binder particles means that a mean particle diameter d 50 of the binder is a half or less of a mean diameter of the inorganic particles and also less than one and a half times a mean pore diameter of the porous substrate.
  • a specific surface area of the binder is increased and the binder effectively infiltrate into an inner surface of the porous substrate, thereby effectively improving an adhesive strength between the porous substrate and the binder on an outer surface and an adhesive strength between the substrate and the inorganic particles during a drying process.
  • an adhesive strength between the binder and the substrate is more effectively improved, and if the inorganic particles are contained, a sufficient adhesive strength between the inorganic particles or between the inorganic particles and the substrate can be exhibited.
  • a binder having a specific particle size is used as illustrated in the present invention, it is possible to obtain a higher adhesive strength between a binder and a substrate and a higher adhesive strength between inorganic particles or between the inorganic particles and the substrate, as compared with a case of using a binder which can be chemically crosslinked and ionically crosslinked.
  • the present invention can be applied, without limitation, to a coating separator for secondary battery that does not contain inorganic particles. If a coating solution does not contain inorganic particles, when a mean particle diameter d 50 of a binder is less than one and a half times a mean pore diameter of the porous substrate, an excellent adhesive strength with respect to the substrate can be exhibited.
  • a coating solution uses inorganic particles and a binder
  • an additional binder or a dispersion agent for dispersing the inorganic particles or an antifoaming/defoaming agent, a wetting agent, a leveling agent, a rheology modifier, and the like
  • a dispersion agent low molecular or high molecular dispersion agent
  • for improving a coating property of the coating solutoin may be additinally contained, but preferably, for battery properties, such additives may be added as small as possible.
  • a polyolefin-based porous film having low surface energy has a low wettability, which may cause non-uniformity in coating.
  • a surface treatment technology such as a corona, plasma, or high-energy radiation treatment generally used to increase surface energy and a surface roughness of the porous substrate.
  • a preferable exemplary embodiment of a method for preparing a separator comprises:
  • step (b) a step of preparing a coating solution by mixing a binder in the form of particle with the mixed solution obtained in the step (a);
  • step (c) a step of coating and drying the coating solution obtained in the step (b) on one or more regions selected from the group consisting of a one surface, both surfaces of a porous substrate, and at least a part of a pore portion of the substrate in a single layer or multiple layers.
  • a coating method is not specifically limited, and various coating methods such as typically used dip coating, die coating, Gravure coating, comma coating, may be used.
  • the porous separator of the present invention includes a porous separator in which an organic/inorganic complex coating layer is formed in a single layer or multiple layers on one or more regions selected from the group consisting of a single surface, both surfaces, and at least a part of a pore portion of a porous substrate using the porous substrate and a coating solution containing a binder dispersed in a solvent and selectively added inorganic particles.
  • the porous substrate may employ any porous substrate generally used in an electrochemical device such as a lithium secondary battery.
  • the porous substrate may include, for example, a film or non-woven fabric formed using one or a mixture of two or more polymer compounds such as high-density polyethylene, low-density polyethylene, linear low-density polyethylene, ultra high-molecular weight polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyester, polyacetal, polyamide, polycarbonate, polyimide, polyetherether ketone, polyether sulfone, polyphenylene oxide, polyphenylene sulfide, and polyethylene naphthalene.
  • the porous substrate may be prepared to have a thickness ranging from 1 to 100 ⁇ m, and preferably, 1 to 30 ⁇ m. Along with a recent trend of high power output/high capacity of a battery, it is advantageous to use a thin film as the porous substrate.
  • a pore diameter of the porous substrate is in a range of 0.01 to 50 ⁇ m, and a porosity is 5 to 90% and preferably 20 to 80%. However, these numerical ranges can be easily modified depending on an embodiment or as necessary.
  • a pore of the porous substrate may have various pore structures. If any one of a mean pore diameter measured using a porosimeter or a mean pore diameter observed from an FE-SEM image satisfies the above-described conditions, it can be included in the present invention.
  • a central pore diameter in a TD direction rather than an MD direction in an FE-SEM image becomes a reference (refer to FIG. 1 )
  • a pore diameter measured with a porosimeter typically becomes a reference, but the present invention is not limited thereto.
  • the binder enables adhesion and fixation between the inorganic particles and between the inorganic particles and the surface of the porous substrate, thereby preventing physical deformation and deterioration of properties of the porous substrate.
  • the binder refers to a binder in the form of an emulsion or suspension in which particles of a polymer compound are dispersed in an organic solvent or water, and specifically, the dispersed binder is in an emulsion form or a suspension form of which a mean pore diameter d 50 is a half or less of a mean pore diameter d 50 of the inorganic particles and also less than one and a half times a mean pore diameter d 50 of the porous substrate.
  • the binder may be one or a mixture of two or more selected from the group consisting of latex, emulsions and suspensions formed by dispersing polymer compounds, such as polystyrene-based, styrene butadiene-based, nitrile-based, polyvinyl chloride (PVC)-based, polyolefin-based, acryl-based, acetate-based, polyvinylidene fluoride (PVDF)-based, ethylene-vinyl acetate (EVA)-based, polyvinyl butyral-based, polytetrafluoroethylene (PTFE)-based, polyimide-based, polyethylene oxide-based, cellulose-based, polyvinyl alcohol-based, and starch-based polymers or copolymers, in an organic solvent or a water-based solvent such as water.
  • PVC polyvinyl chloride
  • PVDF polyolefin-based
  • EVA ethylene-vinyl acetate
  • PTFE
  • a particle diameter of the binder As a particle diameter of the binder is decreased, a specific surface area is increased and an amount of the binder passing through the porous substrate is increased. Thus, it is more effective in increasing an adhesive strength between the inorganic particles and between the substrate and the inorganic particles.
  • a mean particle diameter d 50 of the binder is a half or less of a mean diameter of the inorganic particles and also less than one and a half times a mean pore diameter of the porous substrate, an organic/inorganic complex coating separator having an excellent adhesive strength as an object of the present invention can be obtained.
  • a PE separator formed by a wet method and a PP separator formed by a dry method have mean pore diameters of 100 to 700 nm (400 to 700 nm in the case of using a three component system and 100 to 300 nm in the case of using a two component system, and a pore diameter may vary depending on a film forming condition, the pore diameter described herein is not provided to limit a pore diameter) and 50 to 200 nm, respectively.
  • An effective mean particle diameter of the binder for each film may vary.
  • a width of a pore in a TD direction may be in a range of about 50 to about 200 nm, and, thus, a binder having a mean particle diameter of 100 nm or less is preferred.
  • a binder which has a mean particle diameter of 100 nm or less and can be bonded by ions or bonded by a crosslinking agent exhibited a more effective adhesive strength and a thermal property between the inorganic particles and the substrate, but it was found that if a mean particle diameter is great, an adhesive strength is decreased.
  • binders of many kinds having different mean particle diameters may be used as the dispersed binder. In this case, if a mean particle diameter of any one of the binders satisfies the above-described conditions, it is included in the present invention.
  • the coating solution of the present invention besides the binder, in order to more effectively improve an adhesive strength with respect to the substrate and a coating property by inducing an attraction force between the binder and the polymer, as a second organic binder to be dissolved in the solvent, phosphoric ester, phosphoric acryl-based copolymer, modified polyacrylate-based copolymer, modified polyacrylic acid-based copolymer, polyester amine amide-based copolymer, polycarboxylic acid-based copolymer, polyalkylol amino amide-based copolymer, siloxane- and acryl-based copolymer, siloxane- and carboxylic acid-based copolymer, polyalkoxylate-based copolymer, acryl- and ether-based copolymer, and metallic salts thereof may be used, and one or two or more of them may be used.
  • the inorganic particles used in the coating solution of the present invention may employ any inorganic particles typically used in preparing a conventional coating separator for battery.
  • the inorganic particles may include one or a mixture of two or more substances of SnO 2 , BaTiO 2 , Al 2 O 3 , CeO 2 , SiO 2 , TiO 2 , Li 3 PO 4 , NiO, ZnO, MgO, Mg(OH) 2 , CaO, ZrO 2 , Y 2 O 3 , and talc, and the inorganic particles may have a shape such as a sphere shape, a plate shape, or an irregular shape.
  • the inorganic particles are not limited in diameter, but for preparing slurry with good dispersion stability and for forming a coating layer having a uniform thickness, the inorganic particles may have a diameter of preferably 0.001 to 10 ⁇ m, and most preferably 0.1 to 5 ⁇ m. If a mean diameter of the inorganic particles is less than 0.01 ⁇ m, dispersibility of the inorganic particles may be decreased, or the inorganic particles may be distributed within the already-formed pores, and, thus, air permeability may be decreased.
  • a diameter of the inorganic particles is more than 5 ⁇ m, a thickness of the organic/inorganic complex coating layer is increased, resulting in deterioration in mechanical property, or the possibility of an internal short circuit during charge and discharge of the battery is increased due to the excessively large pores. Further, due to an increase in overall thickness of the organic/inorganic complex coating separator, there may be a limitation in manufacturing a middle or large-sized battery cell which is thin and has high capacity.
  • the inorganic particles various inorganic particles having different mean particle diameters may be mixed and used. If a particle distribution of any one kind of inorganic particles satisfies the above-described conditions, it is included in the present invention. Further, a diameter of the inorganic particles can be measured using a device configured to measure a particle diameter and distribution using a laser or a light scattering method.
  • a low-molecular or high-molecular organic compound soluble in the solvent may be further contained in addition to the binder.
  • the coating layer can be formed with a coating solution that contains only particles of the binder but not contains the inorganic particles under the above-described conditions.
  • a coating separator having an excellent adhesive strength can be prepared.
  • a weight ratio of the inorganic particles:the binder is 4:1 to 140:1. If a weight ratio of the inorganic particles to the binder is less than 4:1 an amount of the binder resin with respect to the inorganic particles is great, and, thus, air permeability is reduced and performance of a battery deteriorates. If a weight ratio is more than 140:1 and an amount of the binder is small and an amount of the inorganic particles is too great, an adhesive strength between the inorganic particles or between the porous substrate and the inorganic particles is decreased and separation may occur.
  • the coating layer has a thickness of 0.1 to 50 ⁇ m, a pore diameter of 0.001 to 10 ⁇ m, and a porosity of 30 to 80%.
  • a pore diameter is less than 0.001 ⁇ m, or porosity is less than 30%, pores are filled with a small amount of an electrolyte, and, thus, a lithium ion transfer capability is decreased or performance of a cell deteriorates. If a pore diameter is more than 10 ⁇ m, or porosity is more than 80%, a mechanical property of the porous separator may deteriorate.
  • the method for coating the coating solution on the porous substrate may employ a typical coating method known in the art.
  • various processes such as dip coating, die coating, roll coating, comma coating, Gravure coating, or a combination thereof may be used.
  • the organic/inorganic complex porous separator according to the present invention can be prepared by a typical method known in the art, and a preferable exemplary embodiment of using inorganic particles comprises:
  • step (b) a step of preparing a coating solution by adding and mixing a binder in the form of particle with the mixed solution obtained in the step (a);
  • step (c) a step of coating and drying the coating solution obtained in the step (b) on one or more regions selected from the group consisting of a one surface, both surfaces of a porous substrate, and at least a part of a pore portion of the substrate in a single layer or multiple layers.
  • the inorganic particles may be dispersed using a typical dispersion method known in the art with, for example, an ultrasonic homogenizer, a ball-mill, a disperser, a mixer, and the like, and particularly preferably a ball-mill.
  • a dispersion processing time may vary depending on a capacity, and preferably, it is 1 to 20 hours.
  • a particle diameter of the crushed inorganic particles can be controlled depending on a size of a bead used for the ball-mill and a time for the ball-mill, and preferably, it is about 0.001 to about 10 ⁇ m as described above.
  • a particle dispersion state may deteriorate depending on a size, a shape and a chemical structure of a surface of the inorganic particles. If a polymer dispresion agent is added as necessary, the inorganic particles can be more effectively dispersed. Generally, an amount of the dispresion agent may vary depending on a size, a chemical strucure, and a surface area of inorganic particles, but appropriately, it is 0 to 3 parts by weight with respect to 100 parts by weight of the inorganic particles.
  • the organic/inorganic complex coating solution is prepared by adding the binder to the mixed solution in the form of slurry in which the inorganic particles are dispersed.
  • a wetting agent for improving wettability of the organic/inorganic complex coating solution with respect to the porous substrate a leveling agent for improving surface flatness of the coating layer, an adhesion promoter for improving an adhesive strength between the separator substrate and the coating solution, an antifoaming and defoaming agent, and additives applicable for improving a coating property such as a thickener, a rheology additive, and a UV absorber may be selectivley added in appropriate amounts depending on viscosity or surface energy of the finally obtained coating solution.
  • a kind of the additives can be approprately selected and used depending on a desired coating method and a coating characteristic.
  • the final coating separator according to the present invention can be prepared by coating and drying the coating solution on the porous substrate.
  • the method for coating the coating solution on the porous substrate may employ a typical coating method known in the art. For example, by dip coating, die coating, roll coating, comma coating, Gravure coating, bar coating, or a combination thereof, the coating layer of a single layer or multiple layers may be coated on a single surface or both surfaces, and at least a part of the pore portion of the porous substrate.
  • the organic/inorganic complex coating porous separator according to the present invention may be used as a separator between the anode and the cathode.
  • the electrochemical device includes all devices that make electrochemical reactions.
  • Specific examples of the electrochemical device may include all kinds of primary/secondary batteries, fuel cells, solar cells, or super capacitors.
  • a lithium secondary battery of the secondary batteries is the most preferable.
  • the secondary battery device can be manufactured by a typical method known in the art, and can be manufactured by interposing the separator according to the present invention between the anode and the cathode and injecting the electrolyte.
  • a cathode, an anode, and an electrolyte to be applied as well as the separator of the present invention are not specifically limited and may empoly those typically used in the art.
  • a thus formed organic/inorganic complex coating separator when a binder in a form of particles dispersed in a certain size in an oil-based or water-based solvent is selectively mixed with inorganic particles and then coated and dried on a porous substrate, a thus formed organic/inorganic complex coating separator can exhibit a sufficient adhesive strength without crosslinking by heat or UV, and has a higher adhesive strength with respect to the substrate as compared with the case where crosslinking caused by heat or UV occurs. Further, the organic/inorganic complex coating separator has excellent air permeability, thereby suppressing a thermal contraction rate at a high temperature, and also exhibits excellent processability.
  • organic/inorganic complex coating separator of the present invention is improved in wettability with respect to an electrolyte, and, thus, ionic conductivity of lithium and electrolyte uptake can be improved.
  • the separator of the present invention is applied to a battery and an electrochemical device, it is possible to manufacture an excellent secondary battery device having improved performance of a battery and improved thermal and electrochemical stability.
  • FIG. 1 illustrates a method of measuring a pore diameter of an uniaxially oriented porous separator manufactured by a dry method.
  • FIG. 2 is an FE-SEM image of an organic/inorganic coating porous separator prepared in Example 1.
  • FIG. 3 is a photo illustrating a result of a thermal contraction experiment on separators, and illustrates organic/inorganic complex coating porous separators prepared in Example 1 and Comparative Example 7 after being left at 150° C. for 1 hour.
  • FIG. 4 illustrates a measurement result of a C-rate of organic/inorganic complex coating porous separators prepared in Example 1 and Comparative Example 3.
  • the present invention can be modified and changed in various ways and may include various exemplary embodiments. Although preferred Examples are provided as follows for easy understanding of the present invention, the following Examples are provided just for illustrating the present invention but not for limiting the scope of the present invention.
  • a digimatic thickness gage 547 - 401 ( ⁇ 6.3 mm flat tip type, pressure of 3.5 N or less for measurement) manufactured by Mitutoyo was used for measurement, and a difference between a thickness of a coating separator and a thickness of an original film before coating was calculated.
  • a load of 2 kgf was applied thereto for 10 minutes.
  • an adhesive strength was measured with a LLOYD UTM.
  • a force (gf) applied to pull a tape at a speed of 2 mm/min until the tape was detached was measured using a 180 degree peel test.
  • a sample was cut into a size of 50 mm ⁇ 50 mm, and vertical and horizontal lines (3 cm ⁇ 3 cm) were drawn on a central portion of the sample. Then, the sample was left in an oven at a temperature of 150 ⁇ 5° C. for 1 hour. Thereafter, the sample was taken out of the oven and left at room temperature for 5 minutes or more to be cooled to room temperature. Then, lengths of the lines drawn on the central portion of the sample were measured to calculate a contraction rate with respect to the lengths before contraction.
  • Alumina (Al 2 O 3 ) as inorganic particles was added to water to be solid content 30 weight %, and a modified polyacryl polyether copolymer as a second organic binder was added in amount of 1 weight % with respect to the amount of alumina, and then, the inorganic particles were crushed to a mean particle diameter of 0.5 ⁇ m using the ball-mill for 2 hours or more and dispersed so as to prepare waterborne inorganic slurry.
  • a corona-treated uniaxially oriented polypropylene separator (porosity of 45%) having a mean pore diameter of 100 nm in a TD direction and a thickness of 14 ⁇ m was used.
  • FIG. 1 An FE-SEM image of the prepared separator was as illustrated in FIG. 1 .
  • FIG. 3 illustrates a photo illustrating a result of a thermal contraction experiment on the separator.
  • LiNiCoMnO 2 -based electrode as an anode
  • a graphite electrode as a cathode
  • An organic/inorganic complex coating porous separator and a lithium secondary battery including the same were prepared in the same manner as Example 1 except that a mean pore diameter in a TD direction of a polypropylene separator used as a porous substrate was 130 nm.
  • An organic/inorganic complex coating porous separator and a lithium secondary battery including the same were prepared in the same manner as Example 1 except that a mean pore diameter in a TD direction of a polypropylene separator used as a porous substrate was 80 nm and a mean particle diameter of a binder was 60 nm.
  • An organic/inorganic complex coating porous separator and a lithium secondary battery including the same were prepared in the same manner as Example 1 except that a polyethylene separator having a mean pore diameter of 400 nm in a TD direction was used as a porous substrate.
  • An organic/inorganic complex coating porous separator and a lithium secondary battery including the same were prepared in the same manner as Example 1 except that a polyethylene separator having a mean pore diameter of 400 nm in a TD direction was used as a porous substrate, and a mean particle diameter of crushed alumina was 0.8 ⁇ m and a mean particle diameter of the binder was 100 nm.
  • An organic/inorganic complex coating porous separator and a lithium secondary battery including the same were prepared in the same manner as Example 1 except that a polyethylene separator having a mean pore diameter of 400 nm in a TD direction was used as a porous substrate, and a mean particle diameter of crushed alumina was 1 ⁇ m and a mean particle diameter of the binder was 100 nm.
  • An organic/inorganic complex coating porous separator and a lithium secondary battery including the same were prepared in the same manner as Example 1 except that a mean particle diameter of the binder was 50 nm.
  • An organic/inorganic complex coating porous separator and a lithium secondary battery including the same were prepared in the same manner as Example 1 except that a mean particle diameter of the binder was 100 nm.
  • An organic/inorganic complex coating porous separator and a lithium secondary battery including the same were prepared in the same manner as Example 1 except that a polypropylene separator was used as a porous substrate without a corona treatment.
  • An organic/inorganic complex coating porous separator and a lithium secondary battery including the same were prepared in the same manner as Example 1 except that a polyethylene separator having a mean pore diameter of 100 nm in a TD direction was used as a porous substrate, and a mean particle diameter of the binder was 80 nm.
  • An organic/inorganic complex coating porous separator and a lithium secondary battery including the same were prepared in the same manner as Example 1 except that a polyethylene separator having a mean pore diameter of 400 nm in a TD direction was used as a porous substrate, and an acryl emulsion having a mean particle diameter of dispersed binder of 150 nm was used as binder.
  • An organic/inorganic complex coating porous separator and a lithium secondary battery including the same were prepared in the same manner as Example 1 except that a polyethylene separator having a mean pore diameter of 400 nm in a TD direction was used as a porous substrate, and a PVDF emulsion having a mean particle diameter of dispersed binder of 180 nm was used as binder.
  • An organic/inorganic complex coating porous separator and a lithium secondary battery including the same were prepared in the same manner as Example 1 except that as a binder, SBL (styrene butadiene latex) and CMC (carboxyl methyl cellulose) soluble in a solvent were used together.
  • SBL styrene butadiene latex
  • CMC carboxyl methyl cellulose
  • An organic/inorganic complex coating porous separator and a lithium secondary battery including the same were prepared in the same manner as Example 1 except that a weight ratio of alumina to a binder was 80:1.
  • An organic/inorganic complex coating porous separator and a lithium secondary battery including the same were prepared in the same manner as Example 1 except that a weight ratio of alumina to a binder was 20:1.
  • a lithium secondary battery was prepared in the same manner as Example 1 except that there was used a polypropylene (PP) separator (porosity of 45%) having a thickness of about 14 ⁇ m on which a coating layer was not formed.
  • PP polypropylene
  • a lithium secondary battery was prepared in the same manner as Example 1 except that there was used a polyethylene (PE) separator (porosity of 48%) having a thickness of about 14 ⁇ m on which a coating layer was not formed.
  • PE polyethylene
  • PVDF-HFP was added in an amount of 5 weight % to acetone and then dissolved at 40° C. for about 2 hours or more, thereby preparing a polymer compound solution.
  • Al 2 O 3 powder was added to this polymer compound solution such that a weight ratio (P/B ratio) of Al 2 O 3 powder/PVDF-HFP could be 9/1 to crush and disperse inorganic particles using the ball-mill for 3 hours or more, thereby preparing a coating solution in the form of slurry.
  • a particle diameter of the Al 2 O 3 in the slurry after crushing can be controlled depending on a particle diameter of beads used for the ball-mill and a time for the ball-milling, but in Comparative Example 3, the slurry was prepared by crushing the inorganic particles to have a mean diameter of 0.5 ⁇ m.
  • a corona-treated polypropylene separator (porosity of 45%) having a thickness of 14 ⁇ m was used, and the coating solution was coated on the porous substrate by a dip coating method.
  • the dip coating method was carried out at a line speed of 5 m/min, and a coating separator (PVDF/Al 2 O 3 ) having a thickness of 20 ⁇ m was finally prepared.
  • a lithium secondary battery was prepared using the prepared organic/inorganic complex coating porous separator in the same manner as Example 1.
  • An organic/inorganic complex coating porous separator and a lithium secondary battery including the same were prepared in the same manner as Example 1 except that a weight ratio of Al 2 O 3 powder/SBL was 1/1.
  • An organic/inorganic complex coating porous separator and a lithium secondary battery including the same were prepared in the same manner as Example 1 except that a weight ratio of Al 2 O 3 powder/SBL was 150/1.
  • An organic/inorganic complex coating porous separator and a lithium secondary battery including the same were prepared in the same manner as Example 1 except that a second organic binder was not used.
  • FIG. 3 illustrates a photo illustrating a result of a thermal contraction experiment on the prepared separator.
  • An organic/inorganic complex coating porous separator and a lithium secondary battery including the same were prepared in the same manner as Example 1 except that that a mean pore diameter of a porous substrate was 150 nm, an acryl emulsion having a mean particle diameter of dispersed binder of 250 nm was used as a binder, and a P/B ratio was 20/1.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Porous substrate PP PP PP PE PE PE
  • Substrate 14 14 14 14 14 14 14 14 14 14 14 14 14 thickness ( ⁇ m)
  • Mean pore 100 130 80 400 400 400 diameter (nm) Corona ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ treatment
  • Alumina mean 0.5 0.5 0.5 0.8 1.0 particle diameter ( ⁇ m)
  • Example 2 Example 3 Porous substrate PP PE PP Substrate thickness ( ⁇ m) 14 14 14 Mean pore diameter (nm) 100 400 100 Corona treatment — — ⁇ Alumina mean particle — — 0.5 diameter ( ⁇ m) Binder — — PVDF-HFP Binder mean particle — — — diameter d 50 (nm) P/B ratio — — 9/1 Coated surface — — Both surfaces Coating separator thickness — — 20 ( ⁇ m) Gurley (sec/100 cc) 210 230 300 Adhesive strength (gf) — — 80 MD thermal contraction 40 melted 14 rate (% @ 150° C., 1 hr)
  • Example 1 In order to evaluate performance of lithium secondary batteries prepared in Example 1 and Comparative Example 3, a capacity and a C-rate of each battery were measured.
  • a cycle was carried out five times at a battery discharge speed of 0.2 C, 0.5 C, 1 C, 3 C, and 5 C, and discharge capacities thereof were schematized by C-rate characteristics as illustrated in FIG. 4 .
  • the lithium secondary battery of Example 1 including the coating separator of the present invention exhibited an excellent C-rate characteristic as compared with the battery of Comparative Example 3.
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DE112013003875T5 (de) 2015-04-16
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