WO2014196656A1 - 二次電池用セパレータの製造方法およびリチウム二次電池の製造方法 - Google Patents
二次電池用セパレータの製造方法およびリチウム二次電池の製造方法 Download PDFInfo
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- WO2014196656A1 WO2014196656A1 PCT/JP2014/065395 JP2014065395W WO2014196656A1 WO 2014196656 A1 WO2014196656 A1 WO 2014196656A1 JP 2014065395 W JP2014065395 W JP 2014065395W WO 2014196656 A1 WO2014196656 A1 WO 2014196656A1
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
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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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
- H01M50/406—Moulding; Embossing; Cutting
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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
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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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
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/42—Acrylic resins
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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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/494—Tensile strength
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a method for producing a separator for a secondary battery.
- the present invention relates to a method for manufacturing a separator for a secondary battery comprising a porous heat-resistant resin film having pores arranged in a three-dimensional stereoregular arrangement.
- the present inventors have used a porous resin film having a porosity of 60% or more, a pore having a three-dimensional regular array structure, and a pore communicating with each other through a communication hole.
- a separator for a secondary battery is proposed (Patent Document 1).
- the monodispersed spherical silica particles have a uniform particle size, they are easy to close-pack, and the communication holes formed after dissolving and removing the silica particles have the same size.
- a hydrofluoric acid solution is required, which is disadvantageous in that handling is difficult and manufacturing costs are increased.
- a varnish formed from polyamic acid or polyimide, silica particles and a solvent is formed on a substrate, imidized to obtain a polyimide-silica composite film, and silica is prepared from the polyimide-silica composite film using hydrogen fluoride water.
- a manufacturing method for dissolution and removal has also been proposed (Patent Document 2).
- the hydrofluoric acid solution is also used in the method of Patent Document 2, and there are problems in handling and cost as in Patent Document 1.
- An object of the present invention is to produce a separator for a secondary battery comprising a porous resin film in which pores have a three-dimensional stereoregular arrangement structure, and the pores communicate with each other through communication holes, without using hydrofluoric acid. It is to provide a way to do.
- a method for producing a separator for a secondary battery comprising a porous resin film in which pores have a three-dimensional stereo-regular structure, and the pores communicate with each other by communication holes, A narrow dispersion spherical fine particle dispersion slurry preparation step of uniformly dispersing narrow dispersion spherical fine particles in a dispersion medium to prepare a fine particle dispersion slurry; Narrow dispersion spherical fine particle dispersion film preparation step of drying the fine particle dispersion slurry to obtain a narrow dispersion spherical fine particle dispersion film, A heat treatment of the film to form a fine particle-resin film in which the fine particles are three-dimensionally arranged in a resin matrix; The fine particle-resin film is contacted with an inorganic acid other than hydrofluor
- the narrowly dispersed spherical fine particles are a composite of calcium carbonate, calcium oxide, titanium dioxide, zinc oxide, cerium oxide, polymethyl methacrylate, polystyrene, silica particles, titania particles or ceria particles and carboxymethyl cellulose or polymethyl methacrylate.
- [5] The method according to any one of [2] to [4], wherein the step of inactivating the surface of the narrowly dispersed spherical fine particles includes dispersing the narrowly dispersed spherical fine particles in an aprotic polar solvent.
- the aprotic polar solvent used in the surface-inactivating treatment step of the narrowly dispersed spherical fine particles is selected from N-methyl-2-pyrrolidone, dimethylformamide, tetramethylurea, and hexamethylphosphoric triamide.
- the surface of the narrowly dispersed spherical fine particles is inactivated by modifying the surface of the finely dispersed spherical fine particles with silicon oxide, titanium oxide, aluminum oxide, zinc oxide, tetraethoxysilane, oxalic acid, citric acid or lactic acid.
- the production method according to any one of [2] to [4].
- the alkaline solution is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia, hydroxylamine, ethanolamine, ethylenediamine, phenol, p-cresol, m-cresol, o-cresol, hydroquinone, resorcitol,
- the fine particle dispersion slurry is applied to a substrate selected from polypropylene, aramid, cellulose, and polytetrafluoroethylene and dried to form a narrow dispersion spherical fine particle having a two-layer structure.
- a substrate selected from polypropylene, aramid, cellulose, and polytetrafluoroethylene
- the method according to any one of [1] to [11], wherein a dispersion film is obtained.
- the fine particle dispersion slurry is coated on a film forming substrate and dried, and then the obtained film is peeled off to disperse the narrow dispersion spherical fine particle dispersion having a single layer structure.
- a method for producing a lithium secondary battery comprising positioning the separator for a secondary battery obtained by the production method according to any one of [1] to [13] between a positive electrode and a negative electrode.
- the “three-dimensional stereoregular arrangement structure” means a structure in which pores that are three-dimensionally adjacent to each other are arranged in communication with the entire porous resin film according to the present invention.
- it means a structure in which the porous resin film has a porosity of 70% or more and 90% or less, and three-dimensionally adjacent pores are connected and arranged.
- a secondary resin comprising a porous resin film that does not use hydrofluoric acid, has a three-dimensional stereoregular structure, and the pores communicate with each other through the communicating holes, safely at low cost.
- a battery separator can be manufactured.
- FIG. 10 is a voltage-current curve of a coin cell measured in Example 7.
- FIG. 10 is a graph showing a change with time in voltage measured in Example 7.
- narrow dispersion means that the particle size distribution of fine particles represented by a coefficient of variation (standard deviation of particle size distribution / average value ⁇ 100) is narrow.
- “monodisperse” often means a case where the coefficient of variation is about 10% or less.
- the case where the coefficient of variation is in the range of 0 to 70% is referred to as “narrow dispersion”.
- FIG. 1 shows an example of a flowchart of the manufacturing method of the present invention.
- the present invention is a method for producing a separator for a secondary battery comprising a porous resin film in which holes have a three-dimensional stereoregular arrangement structure including the following steps, and the holes communicate with each other through communication holes.
- Narrowly dispersed spherical fine particle dispersed slurry preparation step Narrowly dispersed spherical fine particles are uniformly dispersed in a dispersion medium to prepare a finely dispersed spherical slurry.
- the dispersion medium is a resin precursor that constitutes the porous resin film.
- the porous resin film may be a resin film normally used for a secondary battery separator, and the dispersion medium may be appropriately selected according to the resin film.
- the dispersion medium is preferably a polyamic acid.
- the narrowly dispersed spherical fine particles are fine particles having a uniform particle size, and have a median diameter of 50 nm to 3000 nm, more preferably 100 nm to 1000 nm, and a coefficient of variation of particle size distribution of 0 to 70%. It is preferably inert.
- Suitable narrowly dispersed spherical fine particles include calcium carbonate, calcium oxide, titanium dioxide, zinc oxide, polymethyl methacrylate, polystyrene, polymethacrylic acid, cerium oxide, and a composite of nano-inorganic particles and a polymer.
- Examples of the composite of nano-inorganic particles and polymer include a composite of silica particles, titania particles or ceria particles and carboxymethyl cellulose or polymethyl methacrylate.
- Inactivation treatment includes (a1) uniformly dispersing the finely dispersed spherical fine particles in an aprotic polar solvent, and (a2) treating the surface of the finely dispersed spherical fine particles with silicon oxide, titanium oxide, aluminum oxide, zinc oxide, tetraethoxy. It can be carried out by coating with silane, oxalic acid, citric acid or lactic acid to modify the surface as a core / shell structure, or by a combination of both (a1) and (a2).
- aprotic polar solvent N-methyl-2-pyrrolidone, dimethylformamide, tetramethylurea, hexamethylphosphoric triamide can be suitably used.
- the aprotic polar solvent is preferably selected in consideration of the interaction with the dispersion medium used for preparing the narrowly dispersed spherical fine particles and the fine particle dispersed slurry. For example, when calcium carbonate is used as the narrowly dispersed spherical fine particles and polyamic acid is used as the dispersion medium, it is preferable to use N-methyl-2-pyrrolidone as the aprotic polar solvent.
- the surface modification of the narrowly dispersed spherical fine particles is carried out by using a method in which the narrowly dispersed spherical fine particles are not dissolved, and the surface of the narrowly dispersed spherical fine particles is dispersed in a solvent in which the modifying agent is dissolved and kept at a predetermined temperature, or a sol-gel method is used. It can be carried out.
- a solvent in which the modifying agent is dissolved and kept at a predetermined temperature
- a sol-gel method is used.
- an alcohol can be preferably used as the solvent.
- calcium carbonate and oxalic acid are dispersed in ethanol and held at room temperature for 2 hours, whereby oxalic acid is adsorbed on the surface of calcium carbonate (CaCO 3 and carboxyl group: —COOH react).
- sol-gel method in which the surface is modified with silica particles, for example, calcium carbonate, alcohol, an aqueous ammonia solution, and tetraethoxysilane are mixed, and -O-Si groups generated by hydrolysis are introduced onto the surface of calcium carbonate.
- silica particles for example, calcium carbonate, alcohol, an aqueous ammonia solution, and tetraethoxysilane are mixed, and -O-Si groups generated by hydrolysis are introduced onto the surface of calcium carbonate.
- the obtained fine particle-dispersed slurry is applied to a film-forming substrate and dried, and the obtained film is peeled off to obtain a single-layer structure film.
- the substrate for film formation can be used without limitation as long as the surface is inactive with respect to the fine particle-dispersed slurry and can be easily peeled off after drying, as long as the surface is flat.
- a metal sheet such as a polymer sheet or stainless steel is preferred.
- a normal coating method can be used without limitation. In particular, a doctor blade method, a spray method, and an injection method can be suitably used.
- the coating thickness can be adjusted according to the desired thickness of the separator, and is, for example, 5 to 100 ⁇ m, preferably 10 to 90 ⁇ m.
- (2-2) Preparation of two-layer structure film The obtained fine particle-dispersed slurry is applied to a substrate selected from polypropylene, aramid, cellulose, and polytetrafluoroethylene and dried to form a two-layered narrow-dispersion spherical fine particle dispersion film.
- a normal coating method can be used without limitation.
- a doctor blade method, a spray method, and an injection method can be suitably used.
- the coating thickness can be adjusted according to the desired thickness of the separator, and is, for example, 5 to 100 ⁇ m, preferably 10 to 90 ⁇ m.
- Fine particle-resin film forming step The obtained narrow dispersion spherical fine particle dispersion film is heat-treated to form a fine particle-resin film in which the fine particles are three-dimensionally arranged in a resin matrix.
- the dispersion medium changes to a resin constituting the resin film. Since the heat treatment conditions affect the physical properties of the resin film, it is preferable to carry out the heat treatment conditions.
- the dispersion medium is a polyamic acid
- polyamic acid thermally imidized, it is preferably heated from room temperature at a heating rate of 10 ° C./min, and preferably heated at a temperature in the range of 280 ° C. to 320 ° C. for 1 hour to 2 hours, preferably at 280 ° C. for 1 hour, Then, it is more preferable to heat at 320 ° C. for 1 hour.
- the heating temperature in the fine particle-resin film forming step is set to a temperature lower than the thermal decomposition temperature of the narrowly dispersed spherical particles.
- imidization is preferably performed in the range of 180 to 320 ° C, more preferably 180 to 250 ° C.
- the obtained fine particle-resin film is brought into contact with an inorganic acid, organic acid, water, or alkali solution excluding hydrofluoric acid to dissolve and remove the fine particles, and communicated with each other through the communication holes. Holes having a three-dimensional stereoregular arrangement structure are formed in the resin matrix.
- the inorganic acid, the organic acid, the alkaline solution, or water may dissolve and remove the fine particles uniformly dispersed in the resin matrix without dissolving the resin matrix. You may select suitably according to it. For example, when the resin matrix is polyimide and the fine particles are calcium carbonate, hydrochloric acid or citric acid is preferable, and when the fine particles are titanium oxide, zinc oxide, aluminum oxide, or the surface is modified by these.
- Sodium hydroxide or sodium carbonate is preferred. Also, it is desirable that it is easy to handle and obtain, for example, hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, boric acid, water, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia, amine Phenol derivatives are preferred. Examples of suitable amines and phenol derivatives are as follows.
- the fine particle-resin film can be heated to remove the fine particles, and pores having a three-dimensional stereoregular arrangement structure can be formed in the resin matrix. If the resin matrix and the fine particles are both dissolved in the same substance and it is not appropriate to use the dissolution removal method, or if the thermal decomposition or melting temperature of the fine particles is higher than the heat treatment temperature for forming the fine particle-resin film, When the temperature is lower than the temperature that induces deterioration, the fine particles are decomposed and melted by heating to be removed.
- the fine particles suitable for removal by heating are polymethyl methacrylate and polystyrene, and disappear from the resin film (polyimide film) by decomposition to monomers, low molecular weight substances, or CO 2 during heating.
- the thermal decomposition temperature of the fine particles to which heat removal is applied is preferably 200 to 320 ° C, more preferably 230 to 260 ° C. If the temperature is too low, setting the conditions for the imidization reaction becomes complicated. If the temperature is too high, the resin film (polyimide film) is likely to be thermally deteriorated by the heat removal treatment.
- the heating condition is preferably maintained at a temperature slightly higher than the thermal decomposition temperature of the selected fine particles, for example, 230 to 350 ° C. for a certain period of time.
- the porous resin Heat removal in the porous resin film forming step for forming the film may be performed in the same step.
- the heat treatment in the fine particle-resin film forming step is preferably performed in a stepwise manner (for example, at a heating rate of 5 to 20 ° C./min) to reach the heat treatment temperature in the porous membrane resin forming step. .
- FIG. 2 shows an example of manufacturing a separator for a porous heat-resistant polyimide secondary battery.
- Calcium carbonate is used as narrow dispersed spherical fine particles
- N-methyl-2-pyrrolidone is used as an aprotic polar solvent for inactivating narrow dispersed spherical fine particles.
- the production method of the present invention when using polyamic acid as the dispersion medium and dimethylacetamide as the solvent for the polyamic acid will be specifically described.
- NMP N-methyl-2-pyrrolidone
- a polyamic acid (PAA) is dissolved in dimethylacetamide (DMAc) and mixed with a dispersion solvent prepared to prepare a calcium carbonate dispersion slurry (CaCO 3 / PAA-NMP-DMAc slurry).
- Narrowly-dispersed spherical fine particle-dispersed film preparation step A calcium carbonate-dispersed slurry (CaCO 3 / PAA-NMP-DMAc slurry) is applied to a glass plate and dried at 60 ° C. for 30 minutes under vacuum to form a membrane (CaCO 3 / PAA The film is peeled off.
- Fine particle-resin film forming step The film (CaCO 3 / PAA film) is heated from room temperature to 280 ° C. at a rate of temperature increase of 10 ° C./min, heat-treated at 280 ° C. for 1 hour, and then increased at 10 ° C./min. Heat to 320 ° C. at a temperature rate and heat treatment at 320 ° C. for 1 hour to cause thermal imidization reaction of the polyamic acid to form a fine particle-resin film (CaCO 3 / PI film).
- Porous resin film forming step The fine particle-resin film (CaCO 3 / PI film) is treated with 10 wt% hydrochloric acid to dissolve and remove calcium carbonate particles, and pores of the same size are formed in the resin matrix (polyimide). Are communicated with each other through the communication holes to form a three-dimensional regular ordered porous polyimide film (PI film) in which the three-dimensional regular ordered array is formed.
- PI film three-dimensional regular ordered porous polyimide film
- the pores of the three-dimensional stereoregular arrangement of the porous resin film are formed by removing fine particles contained in the fine particle dispersed slurry. For this reason, the arrangement of the fine particles in the fine particle dispersed slurry is important.
- the median diameter of the narrowly dispersed spherical fine particles is preferably 50 to 3000 nm, more preferably 100 to 1000 nm.
- the fine particles contained in the fine particle-dispersed slurry must have almost the same particle size, and the coefficient of variation of the fine particles is 0 to 70%. Preferably, it is 0 to 50%, more preferably 0 to 10%.
- the size of the pores after removing the fine particles is somewhat smaller than the average particle size of the fine particles used due to shrinkage of the resin film.
- the average particle diameter of the fine particles can be determined in consideration of the porosity and pore diameter of the porous resin film that are finally required, and the shrinkage ratio of the resin.
- the fine particle-resin film preferably contains 70 to 80 vol% of fine particles.
- the fine particles can be made into a hexagonal close-packed three-dimensional stereoregular arrangement.
- the viscosity of the fine particle dispersed slurry is in the range of 10 to 3000 poise, preferably in the range of 50 to 2000 poise, more preferably in the range of 100 to 1500 poise, and the content of fine particles is 1 It is desirable that the amount be in the range of ⁇ 50 vol%, preferably in the range of 5-30 vol%, more preferably in the range of 10-20 vol%.
- a dispersion medium of polyamic acid containing an acid anhydride component and a diamine component is preferable to use as the fine particle dispersion slurry.
- Acid dianhydrides include ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetra Carboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, pyromellitic dianhydride (1,2,4,5-benzenetetracarboxylic acid-1,2,4,5- Dianhydride), 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane Dianhydride, 3,3 ′, 4,4′-bipheny
- diamine fatty acid diamine, aromatic diamine, etc.
- diamines having about 2 to 15 carbon atoms can be preferably used.
- specific examples include pentamethylene diamine, hexamethylene diamine, heptamethylene diamine and the like.
- aromatic diamine a diamino compound having one phenyl group or about 2 to 10 phenyl groups bonded thereto can be preferably used.
- phenylenediamine and derivatives thereof diaminodiphenyl compounds and derivatives thereof, diaminotriphenyl compounds and derivatives thereof, diaminonaphthalene and derivatives thereof, aminophenylaminoindane and derivatives thereof, diaminotetraphenyl compounds and derivatives thereof, diaminohexaphenyl Compounds and derivatives thereof, cardo type fluorenediamine derivatives.
- Phenylenediamine is m-phenylenediamine, p-phenylenediamine, etc.
- the phenylenediamine derivative is a diamine to which an alkyl group such as methyl group or ethyl group is bonded, such as 2,4-triphenylenediamine.
- the diaminodiphenyl compound is a compound in which two aminophenyl groups are bonded to each other via other groups.
- the bond is an ether bond, a sulfonyl bond, a thioether bond, a bond by alkylene or a derivative group thereof, an imino bond, an azo bond, a phosphine oxide bond, an amide bond, a ureylene bond, or the like.
- the alkylene bond has about 1 to 6 carbon atoms, and the derivative group has one or more hydrogen atoms of the alkylene group substituted with halogen atoms or the like.
- diaminodiphenyl compounds include 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 4 , 4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 2,2-bis (p-aminophenyl) propane, 2,2′-bis (p-aminophenyl) hex
- diaminotriphenyl compound two aminophenyl groups and one phenylene group are both bonded via other groups, and the other groups are the same as the diaminodiphenyl compounds.
- diaminotriphenyl compounds include 1,3-bis (m-aminophenoxy) benzene, 1,3-bis (p-aminophenoxy) benzene, 1,4-bis (p-aminophenoxy) benzene, and the like. be able to.
- diaminonaphthalene include 1,5-diaminonaphthalene and 2,6-diaminonaphthalene.
- aminophenylaminoindane examples include 5 or 6-amino-1- (p-aminophenyl) -1,3,3-trimethylindane.
- diaminotetraphenyl compounds include 4,4′-bis (p-aminophenoxy) biphenyl, 2,2′-bis [p- (p′-aminophenoxy) phenyl] propane, and 2,2′-bis [ p- (p′-aminophenoxy) biphenyl] propane, 2,2′-bis [p- (m-aminophenoxy) phenyl] benzophenone, and the like.
- cardo type fluorene derivative examples include 9,9-bisaniline fluorene.
- the compound in which the hydrogen atom of these aromatic diamines is substituted with at least one substituent selected from the group such as a halogen atom, a methyl group, a methoxy group, a cyano group, and a phenyl group may be used.
- Polyamic acid is a polymer of tetracarboxylic acid and diamine, and is a polyimide precursor obtained by equimolar polymerization of at least one of the above-mentioned tetracarboxylic acid and diamine.
- the dispersion medium constituting the fine particle dispersion slurry is not particularly limited as long as it does not dissolve the fine particles.
- Preferred dispersion media include aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, phenolic solvents such as cresols, and glycolic solvents such as diglyme. Can be mentioned. These dispersion media can be used alone or in admixture of two or more.
- a secondary battery can be manufactured by using the porous resin film as a separator for a secondary battery and positioning it between the positive electrode and the negative electrode in accordance with a normal secondary battery manufacturing method.
- a polyimide film having a porosity of 60 to 90% by volume ratio of calcium carbonate and a film thickness in the range of 5 to 100 ⁇ m can be produced.
- the polyimide film obtained by the production method of the present invention can have an air permeability (air resistance) conforming to JIS P 8117 in the range of 20 to 1700 seconds and a tensile strength in the range of 0.4 to 35 MPa.
- the surface inactivation treatment (NMP treatment) of calcium carbonate was performed as follows.
- a polyamic acid / dimethylacetamide (PAA / DMAc) solution was prepared by mixing with dimethylacetamide so that the total amount was 5 g and a polyamic acid having a concentration of 18 to 20 wt%.
- Calcium carbonate / PAA-NMP-DMAc slurry was applied to a glass plate, dried at 60 ° C. under vacuum for 30 minutes, and the resulting calcium carbonate / PAA film was peeled off (fine particles with a fine particle-resin film of about 75 vol%) including).
- the calcium carbonate / PAA film was heated at a heating rate of 10 ° C./min, heat treated at 280 ° C. for 1 hour, then heat treated at 320 ° C. for 1 hour to thermally imidize the polyamic acid, and calcium carbonate / polyimide (PI ) A film was obtained.
- the calcium carbonate / PI film was treated with 10 wt% hydrochloric acid to dissolve and remove the calcium carbonate to obtain a polyimide (PI) film.
- the surface inactivation treatment (silica modification) of calcium carbonate was performed as follows.
- a polyamic acid / dimethylacetamide (PAA / DMAc) solution was prepared by mixing with dimethylacetamide so that the total amount was 5 g and a polyamic acid having a concentration of 18 to 20 wt%.
- the obtained fine particle-dispersed slurry was coated on a glass plate, dried at 60 ° C. under vacuum for 30 minutes to form a film, and the obtained calcium carbonate / PAA film was peeled off (the fine particle-resin film was about 75 vol. % Fine particles).
- the calcium carbonate / PAA film was heated to 320 ° C. at a rate of temperature increase of 10 ° C./min and heat-treated at 320 ° C. for 1 hour to thermally imidize the polyamic acid to obtain a calcium carbonate / polyimide (PI) film. .
- the calcium carbonate / PI film was treated with 10 wt% hydrochloric acid to dissolve and remove the calcium carbonate to obtain a polyimide (PI) film.
- the surface inactivation treatment (oxalic acid modification) of calcium carbonate was performed as follows.
- oxalic acid 0.2 g was dissolved in 23 g of ethanol to prepare an oxalic acid / ethanol solution.
- the calcium carbonate / ethanol dispersion and the oxalic acid / ethanol solution were stirred at room temperature for 2 hours to obtain an oxalic acid-modified calcium carbonate / ethanol slurry.
- the oxalic acid-modified calcium carbonate / ethanol slurry was vacuum filtered, and the oxalic acid-modified calcium carbonate filtrate obtained by washing was dried at 60 ° C. under vacuum to obtain oxalic acid-modified calcium carbonate.
- An electron microscope (SEM) photograph of the obtained oxalic acid-modified calcium carbonate is shown in FIG.
- a polyamic acid / dimethylacetamide (PAA / DMAc) solution was prepared by mixing with dimethylacetamide so that the total amount was 5 g and a polyamic acid having a concentration of 18 to 20 wt%.
- the obtained fine particle-dispersed slurry was coated on a glass plate, dried at 60 ° C. under vacuum for 30 minutes to form a film, and the obtained calcium carbonate / PAA film was peeled off (the fine particle-resin film was about 75 vol. % Fine particles).
- the calcium carbonate / PAA film was heated at a heating rate of 10 ° C./min, heat-treated at 280 ° C. for 1 hour, and then heat-treated at 320 ° C. for 1 hour to thermally imidize the polyamic acid, and calcium carbonate / polyimide ( PI) membrane was obtained.
- the calcium carbonate / PI film was treated with 10 wt% hydrochloric acid to dissolve and remove the calcium carbonate to obtain a polyimide (PI) film.
- a polyimide film was obtained in the same manner as in Example 1 except that tetramethylurea (TMU) was used in place of NMP in (1a) to perform the calcium carbonate surface inactivation treatment. Manufactured.
- TMD tetramethylurea
- a polyimide film was formed in the same manner as in Example 1 except that the surface deactivation treatment of calcium carbonate was performed in (1a) using dimethylformamide (DEF) instead of NMP. Manufactured.
- DEF dimethylformamide
- polymethyl methacrylate (median diameter: 800 nm, variation coefficient: 40%) is used as narrowly dispersed spherical fine particles, and polyimide (polyamic acid as a dispersion medium) is used as a matrix resin.
- the separator was manufactured as follows.
- Polymethylmethacrylate / PAA-ethanol-DMAc slurry was applied to a glass plate, dried at 60 ° C. for 30 minutes, and the resulting polymethylmethacrylate / PAA film was peeled off (fine particles with a fine particle-resin film of about 75 vol%). Including).
- the peeled polymethylmethacrylate / PAA film was heat-treated from room temperature to 320 ° C. at a rate of temperature increase of 10 ° C./min for a total of 2 hours.
- the imidization of PAA was advanced during the temperature rising process, and complete vacancies and imidization were completed at 320 ° C. while forming vacancies from the thermal decomposition temperature of polymethyl methacrylate at around 280 ° C., thereby producing a polyimide film.
- the separator manufactured in Example 3 was prepared by using Li as a negative electrode active material, a Li-Cu negative electrode using Cu as a current collector, LiCoO 2 as a positive electrode active material, acetylene black as a conductive additive, and polyvinylidene fluoride as a binder.
- a coin cell was manufactured by placing the LiCoO 2 / AB / PVdF positive electrode used (FIG. 15). To the separator, 60 ⁇ L of an electrolytic solution (1 mol / dm 3 LiPF 6 / ethylene carbonate) was dropped.
- FIG. 16 shows the voltage-current curve of the coin cell
- FIG. 17 shows the change over time of the voltage.
- FIG. 16 shows the results of measuring the change in battery voltage when charging and discharging at a constant temperature. It can be seen that a battery having a high charge / discharge reversibility, a small polarization, and an excellent performance could be produced.
- FIG. 17 shows the result of measuring the voltage by sandwiching the separator between two lithium metals and passing a constant positive current and a negative current alternately. It is known that when the lithium metal dendrite passes through the separator, it short-circuits and the voltage does not change, but in the separator of this example, current flows for a long period of time, dendrite generation is suppressed, and short-circuit is prevented. Recognize. [Comparative Example 1]
- Example 2 About the polyimide film (separator) obtained by carrying out similarly to Example 1 and Example 3, the air permeability and the tensile strength were measured by the following method. ⁇ Air permeability (Air resistance) Each polyimide film was cut into a 5 cm square and used as a sample. Using a Gurley type densometer (manufactured by Toyo Seiki), the time required for 100 ml of air to pass through the sample was measured according to JIS P 8117. The results are shown in Table 1. -Tensile strength Each polyimide film was cut into a size of 1 cm x 5 cm to obtain a strip-shaped sample. The stress (MPa) at break of this sample was evaluated using RTC-1210A TENSILON (manufactured by ORIENTEC). The results are shown in Table 1.
- Example 10 Based on the result of Example 10 with the highest air permeability, when the polyimide film thickness is reduced to 5 ⁇ m and the porosity is increased to 90%, the air permeability is 21.5 seconds and the tensile strength is 0.46 MPa. Can be estimated. On the contrary, based on the result of Example 9 having the lowest air permeability, when the film thickness of polyimide is increased to 100 ⁇ m and the porosity is decreased to 60%, the air permeability is 1613.6 seconds and the tensile strength is 33 It can be estimated to be 1 MPa.
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Abstract
Description
[1]空孔が三次元立体規則配列構造を有し、空孔が連通孔により互いに連通された多孔質樹脂膜からなる二次電池用セパレータの製造方法であって、
分散媒に、狭分散球状微粒子を均一に分散させて、微粒子分散スラリを調製する狭分散球状微粒子分散スラリ調製工程と、
当該微粒子分散スラリを乾燥させて、狭分散球状微粒子分散膜を得る狭分散球状微粒子分散膜調製工程と、
当該膜を熱処理して、樹脂マトリクス内に当該微粒子が三次元立体規則配列している微粒子−樹脂膜を形成する微粒子−樹脂膜形成工程と、
当該微粒子−樹脂膜を、フッ酸を除く無機酸、有機酸、水、又はアルカリ溶液と接触させて当該微粒子を溶解除去するか、又は当該微粒子−樹脂膜を加熱して当該微粒子を除去し、連通孔により互いに連通されて三次元立体規則配列構造を有する空孔を当該樹脂マトリクス内に形成させる多孔質樹脂膜形成工程と、を含み、
当該分散媒は、当該樹脂マトリクスを構成する樹脂の前駆体を含み、
当該狭分散球状微粒子の表面は、当該分散媒に対して不活性である
ことを特徴とする、二次電池用セパレータの製造方法。
[2]前記狭分散球状微粒子の表面を前記分散媒に対して不活性化する狭分散球状微粒子表面不活性化処理工程をさらに含む、 [1]に記載の製造方法。
[3]前記狭分散球状微粒子は、50nm~3000nmのメディアン径と、0~70%の粒径分布の変動係数を有する、 [1]又は[2]に記載の製造方法。
[4]前記狭分散球状微粒子は、炭酸カルシウム、酸化カルシウム、二酸化チタン、酸化亜鉛、酸化セリウム、ポリメチルメタクリレート、ポリスチレン、又はシリカ粒子、チタニア粒子あるいはセリア粒子とカルボキシメチルセルロースあるいはポリメチルメタクリレートとの複合体、から選択される、狭分散球状微粒子である、[1]~[3]の何れかに記載の製造方法。
[5]前記狭分散球状微粒子表面不活性化処理工程は、前記狭分散球状微粒子を非プロトン性極性溶媒に分散させることを含む、 [2]~[4]の何れかに記載の製造方法。
[6]前記狭分散球状微粒子表面不活性化処理工程において用いる非プロトン性極性溶媒は、N−メチル−2−ピロリドン、ジメチルホルムアミド、テトラメチルウレア、ヘキサメチルリン酸トリアミドから選択される、 [5]に記載の製造方法。
[7]前記狭分散球状微粒子表面不活化処理工程は、狭分散球状微粒子の表面を酸化ケイ素、酸化チタン、酸化アルミニウム、酸化亜鉛、テトラエトキシシラン、シュウ酸、クエン酸又は乳酸で修飾することを含む、 [2]~[4]の何れかに記載の製造方法。
[8]前記無機酸は、塩酸、硫酸、硝酸、過塩素酸、リン酸、ホウ酸から選択される、 [1]~[7]の何れかに記載の製造方法。
[9]前記有機酸は、クエン酸、酢酸、ギ酸、シュウ酸、乳酸、グルコン酸から選択される、 [1]~[8]の何れかに記載の製造方法。
[10]前記アルカリ溶液は、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、アンモニア、ヒドロキシルアミン、エタノールアミン、エチレンジアミン、フェノール、p−クレゾール、m−クレゾール、o−クレゾール、ヒドロキノン、レゾルシトール、カテコール、フロログルシノールから選択される、[1]~[9]の何れかに記載の製造方法。
[11]前記樹脂マトリクスはポリイミドであり、前記分散媒はポリアミック酸である、 [1]~[10]の何れかに記載の製造方法。
[12]前記狭分散球状微粒子分散膜調製工程において、前記微粒子分散スラリをポリプロピレン、アラミド、セルロース、ポリテトラフルオロエチレンから選択される基体に塗工して乾燥させ、二層構造の狭分散球状微粒子分散膜を得る、 [1]~[11]の何れかに記載の製造方法。
[13]前記狭分散球状微粒子分散膜調製工程において、前記微粒子分散スラリを膜形成用基板に塗工し、乾燥させた後、得られた膜を剥離して、一層構造の狭分散球状微粒子分散膜を得る、 [1]~[11]の何れかに記載の製造方法。
[14] [1]~[13]のいずれかに記載の製造方法により得られた二次電池用セパレータを正極と負極との間に位置づけることを含む、リチウム二次電池の製造方法。
分散媒に、狭分散球状微粒子を均一に分散させて、微粒子分散スラリを調製する。分散媒は、多孔質樹脂膜を構成する樹脂の前駆体である。多孔質樹脂膜は、二次電池用セパレータに通常用いられている樹脂膜でよく、分散媒は樹脂膜に応じて適宜選択すればよい。例えば、多孔質樹脂膜がポリイミド膜である場合には、分散媒はポリアミック酸が好適である。
得られた微粒子分散スラリを膜形成用基板に塗工し、乾燥させて、得られた膜を剥離し、一層構造膜を得る。膜形成用基板としては、微粒子分散スラリに対して不活性であり、乾燥後に容易に剥離することができる表面が平坦な形状であれば制限なく用いることができ、例えば、ガラス板、ポリエチレンテレフタレートなどのポリマーシート、ステンレスなどの金属シートが好適である。微粒子分散スラリの膜形成用基板への塗工は、通常の塗工方法を制限なく用いることができる。特にドクターブレード法、スプレー法、インジェクション法を好適に用いることができる。塗工厚みは、所望のセパレータの厚みに応じて調節することができ、例えば5~100μm、好ましくは10~90μmとすることが望ましい。
得られた微粒子分散スラリをポリプロピレン、アラミド、セルロース、ポリテトラフルオロエチレンから選択される基体に塗工して乾燥させ、二層構造の狭分散球状微粒子分散膜を得る。微粒子分散スラリの基体への塗工は、通常の塗工方法を制限なく用いることができる。特にドクターブレード法、スプレー法、インジェクション法を好適に用いることができる。塗工厚みは、所望のセパレータの厚みに応じて調節することができ、例えば5~100μm、好ましくは10~90μmとすることが望ましい。
得られた狭分散球状微粒子分散膜を熱処理して、樹脂マトリクス内に当該微粒子が三次元立体規則配列している微粒子−樹脂膜を形成する。熱処理により、分散媒が樹脂膜を構成する樹脂に変化する。熱処理条件は、樹脂膜の物性に影響を与えるため、好適な熱処理条件にて行うことが好ましい。例えば、分散媒がポリアミック酸である場合には、熱イミド化反応によりポリイミドになる。ポリアミック酸を熱イミド化する場合、室温から10℃/分の昇温速度で加熱し、280℃~320℃の範囲の温度で1時間~2時間加熱することが好ましく、280℃で1時間、次いで320℃で1時間加熱することがより好ましい。
得られた微粒子−樹脂膜を、フッ酸を除く無機酸、有機酸、水、又はアルカリ溶液と接触させて、微粒子を溶解除去して、連通孔により互いに連通されて三次元立体規則配列構造を有する空孔を当該樹脂マトリクス内に形成させる。無機酸、有機酸、アルカリ溶液又は水は、樹脂マトリクスは溶解させずに、樹脂マトリクス内に均一に分散している微粒子を溶解させて除去することができればよく、樹脂マトリクス及び微粒子の溶解性に応じて適宜選択してよい。例えば、樹脂マトリクスがポリイミドであり、微粒子が炭酸カルシウムの場合には塩酸又はクエン酸が好適であり、微粒子が酸化チタン、酸化亜鉛、酸化アルミニウムであるか又はこれらによって表面修飾されている場合には水酸化ナトリウム又は炭酸ナトリウムが好適である。また、取り扱い及び入手が安易であることが望ましく、例えば、塩酸、硫酸、硝酸、過塩素酸、リン酸、ホウ酸、水、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、アンモニア、アミン類、フェノール誘導体が好適である。好適なアミン類及びフェノール誘導体の例は以下の通りである。
微粒子−樹脂膜を加熱して微粒子を除去して、連通孔により互いに連通されて三次元立体規則配列構造を有する空孔を当該樹脂マトリクス内に形成させることもできる。樹脂マトリクスと微粒子とが共に同じ物質に溶解し、溶解除去法を用いることが適切ではない場合や、微粒子の熱分解や融解温度が微粒子−樹脂膜を形成する熱処理温度よりも高く、樹脂膜の劣化を誘引する温度よりも低い場合は、加熱により微粒子を分解、融解させて除去する。加熱による除去が適する微粒子は、ポリメチルメタクリレート、ポリスチレンであり、加熱時に単量体、低分子量体、あるいは、CO2まで分解することによって、樹脂膜(ポリイミド膜)から消失する。加熱除去を適用する微粒子の熱分解温度は、200~320℃であることが好ましく、230~260℃であることがより好ましい。低温すぎると、イミド化反応の条件設定が煩雑となる。高温すぎると、加熱除去処理による樹脂膜(ポリイミド膜)の熱劣化を招きやすい。加熱条件としては、選択した微粒子の熱分解温度よりもわずかに高い温度、例えば230~350℃に一定時間保持することが好ましい。
図2に、多孔性耐熱性ポリイミド二次電池用セパレータの製造例として、狭分散球状微粒子として炭酸カルシウム、狭分散球状微粒子を不活性化処理する非プロトン性極性溶媒としてN−メチル−2−ピロリドン、分散媒としてポリアミック酸、ポリアミック酸の溶媒としてジメチルアセトアミドを用いる場合の本発明の製造方法を具体的に説明する。
まず、炭酸カルシウム粒子(CaCO3)をN−メチル−2−ピロリドン(NMP)に均一に分散させて、炭酸カルシウム粒子の表面を不活性化する。ポリアミック酸(PAA)をジメチルアセトアミド(DMAc)に溶解させて調製した分散溶媒に混合し、炭酸カルシウム分散スラリ(CaCO3/PAA−NMP−DMAcスラリ)を調製する。
炭酸カルシウム分散スラリ(CaCO3/PAA−NMP−DMAcスラリ)をガラス板に塗工し、60℃真空下で30分間乾燥させ、膜(CaCO3/PAA膜)を剥離する。
膜(CaCO3/PAA膜)を室温から10℃/分の昇温速度で280℃まで加熱して280℃で1時間熱処理し、次いで10℃/分の昇温速度で320℃まで加熱して320℃で1時間加熱処理して、ポリアミック酸を熱イミド化反応させて、微粒子−樹脂膜(CaCO3/PI膜)を形成する。
微粒子−樹脂膜(CaCO3/PI膜)を10wt%塩酸で処理して、炭酸カルシウム粒子を溶解除去して、樹脂マトリクス(ポリイミド)内に同寸法の空孔が連通孔により互いに連通され、三次元立体規則配列している三次元立体規則配列多孔性ポリイミド膜(PI膜)を形成する。
[実施例2]
[実施例3]
[実施例4]
[実施例5]
[実施例6]
[実施例7]
[比較例1]
[実施例8~10]
・透気度(透気抵抗度)
各ポリイミド膜を、5cm角に切り出してサンプルとした。ガーレー式デンソメーター(東洋精機製)を用いて、JIS P 8117に準じて、100mlの空気が上記サンプルを通過する時間を測定した。結果を表1に示す。
・引張強度
各ポリイミド膜を、1cm×5cmの大きさに切り出して短冊状のサンプルを得た。このサンプルの破断時の応力(MPa)を、RTC−1210A TENSILON(ORIENTEC社製)を用いて評価した。結果を表1に示す。
Claims (14)
- 空孔が三次元立体規則配列構造を有し、空孔が連通孔により互いに連通された多孔質樹脂膜からなる二次電池用セパレータの製造方法であって、
分散媒に、狭分散球状微粒子を均一に分散させて、微粒子分散スラリを調製する狭分散球状微粒子分散スラリ調製工程と、
当該微粒子分散スラリを乾燥させて、狭分散球状微粒子分散膜を得る狭分散球状微粒子分散膜調製工程と、
当該膜を熱処理して、樹脂マトリクス内に当該微粒子が三次元立体規則配列している微粒子−樹脂膜を形成する微粒子−樹脂膜形成工程と、
当該微粒子−樹脂膜を、フッ酸を除く無機酸、有機酸、水、又はアルカリ溶液と接触させて当該微粒子を溶解除去するか、又は当該微粒子−樹脂膜を加熱して当該微粒子を除去し、連通孔により互いに連通されて三次元立体規則配列構造を有する空孔を当該樹脂マトリクス内に形成させる多孔質樹脂膜形成工程と、を含み、
当該分散媒は、当該樹脂マトリクスを構成する樹脂の前駆体を含み、
当該狭分散球状微粒子の表面は、当該分散媒に対して不活性である
ことを特徴とする、二次電池用セパレータの製造方法。 - 前記狭分散球状微粒子の表面を前記分散媒に対して不活性化する狭分散球状微粒子表面不活性化処理工程をさらに含む、請求項1に記載の製造方法。
- 前記狭分散球状微粒子は、50nm~3000nmのメディアン径と、0~70%の粒径分布の変動係数を有する、請求項1又は2に記載の製造方法。
- 前記狭分散球状微粒子は、炭酸カルシウム、酸化カルシウム、二酸化チタン、酸化亜鉛、酸化セリウム、ポリメチルメタクリレート、ポリスチレン、又はシリカ粒子、チタニア粒子あるいはセリア粒子とカルボキシメチルセルロースあるいはポリメチルメタクリレートとの複合体、から選択される、狭分散球状微粒子である、請求項1~3の何れかに記載の製造方法。
- 前記狭分散球状微粒子表面不活性化処理工程は、前記狭分散球状微粒子を非プロトン性極性溶媒に分散させることを含む、請求項2~4の何れかに記載の製造方法。
- 前記狭分散球状微粒子表面不活性化処理工程において用いる非プロトン性極性溶媒は、N−メチル−2−ピロリドン、ジメチルホルムアミド、テトラメチルウレア、ヘキサメチルリン酸トリアミドから選択される、請求項5に記載の製造方法。
- 前記狭分散球状微粒子表面不活化処理工程は、狭分散球状微粒子の表面を酸化ケイ素、酸化チタン、酸化アルミニウム、酸化亜鉛、テトラエトキシシラン、シュウ酸、クエン酸又は乳酸で修飾することを含む、請求項2~4の何れかに記載の製造方法。
- 前記無機酸は、塩酸、硫酸、硝酸、過塩素酸、リン酸、ホウ酸から選択される、請求項1~7の何れかに記載の製造方法。
- 前記有機酸は、クエン酸、酢酸、ギ酸、シュウ酸、乳酸、グルコン酸から選択される、請求項1~8の何れかに記載の製造方法。
- 前記アルカリ溶液は、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、アンモニア、ヒドロキシルアミン、エタノールアミン、エチレンジアミン、フェノール、p−クレゾール、m−クレゾール、o−クレゾール、ヒドロキノン、レゾルシトール、カテコール、フロログルシノールから選択される、請求項1~9の何れかに記載の製造方法。
- 前記樹脂マトリクスはポリイミドであり、前記分散媒はポリアミック酸である、請求項1~10の何れかに記載の製造方法。
- 前記狭分散球状微粒子分散膜調製工程において、前記微粒子分散スラリをポリプロピレン、アラミド、セルロース、ポリテトラフルオロエチレンから選択される基体に塗工して乾燥させ、二層構造の狭分散球状微粒子分散膜を得る、請求項1~11の何れかに記載の製造方法。
- 前記狭分散球状微粒子分散膜調製工程において、前記微粒子分散スラリを膜形成用基板に塗工し、乾燥させた後、得られた膜を剥離して、一層構造の狭分散球状微粒子分散膜を得る、請求項1~11の何れかに記載の製造方法。
- 請求項1~13のいずれかに記載の製造方法により得られた二次電池用セパレータを正極と負極との間に位置づけることを含む、リチウム二次電池の製造方法。
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