CN104393217A - Composite stacked and coated lithium ion battery diaphragm and preparation method thereof - Google Patents
Composite stacked and coated lithium ion battery diaphragm and preparation method thereof Download PDFInfo
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- CN104393217A CN104393217A CN201410559946.1A CN201410559946A CN104393217A CN 104393217 A CN104393217 A CN 104393217A CN 201410559946 A CN201410559946 A CN 201410559946A CN 104393217 A CN104393217 A CN 104393217A
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
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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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Abstract
The invention relates to a composite stacked and coated lithium ion battery diaphragm and a preparation method thereof. The diaphragm is a porous diaphragm which is prepared by mixing one or many kinds of coating sizing agents and is provided with a layer or multiple layers of structures; the porous diaphragm comprises the following components in parts by weight: 30-100 parts of a polymeric material, 0-70 parts of inorganic powder bodies and a surface treating agent thereof, and 0-50 parts of a compatibilizer; the polymeric material at least selects and uses two kinds of polymeric materials, one kind of the polymeric materials is a thermoplastic material of which the melting point or the viscous flow temperature is 100-150 DEG C, and the other kind of the polymeric materials is a thermoplastic material or a thermosetting material of which the melting point or the viscous flow temperature is higher than or equivalent to that of the thermoplastic material of which the melting point or the viscous flow temperature is 100-150 DEG C. The composite stacked and coated lithium ion battery diaphragm provided by the invention is uniform in bore diameter, good in wettability, favorable in heat resistance and good in hot melting and closing function, and the preparation method for the composite stacked and coated lithium ion battery diaphragm is simple in technology, wide in the material selecting range, and controllable in the micropore forming condition.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly relate to a kind of folded painting compound lithium ion battery separator and preparation method thereof.
Background technology
The free of contamination secondary cell lithium ion battery of environmental type, meets the developing direction of countries nowadays energy environment protection, increases sharply in the use amount of all trades and professions.As the important component part of lithium ion battery, barrier film plays effect battery core positive pole and negative pole separated, and the quality of its performance directly affects the combination property of battery.
Lithium ion battery separator, in the battery for isolating positive and negative electrode, allowing free ion therebetween to pass through, preventing two electrode contacts and short circuit, play protective effect to battery.Thus, battery diaphragm, except needing certain porosity and pore-size distribution, allows ion normal through outward, and its most important performance is its fail safe in lithium ion battery use procedure: on the one hand, isolation both positive and negative polarity, prevents the two directly contact and short circuit; On the other hand, when battery causes inside to be rapidly heated because external fault or internal short-circuit cause inside battery runaway reaction, barrier film can closed pore at a lower temperature, cut off battery plus-negative plate reaction, battery is quit work, and react stop but internal temperature continues to rise to higher temperature time, barrier film still has enough resistances to elevated temperatures, keeps dimensionally stable and not rupture of membranes.
At present, the lithium ion battery separator overwhelming majority is polyolefin, normally polypropylene or polyethylene or both compounds, because the polarity spectrum of polyolefin and battery fluid is larger, the degree of wetting of battery fluid to barrier film is low and cause lithium ion conducting rate low, has had a strong impact on the performance of battery.Along with the development of new energy technology, especially the development of power lithium-ion battery, have higher requirement to the pore size of barrier film and distribution, electrolyte wetability, resistance to elevated temperatures etc., pure polyalkene diaphragm can not meet lithium ion battery and use and the demand of safety.The process of existing production lithium ion battery separator has wet method and dry method two kinds of techniques, due to the restriction of process conditions, is difficult to the poromerics that obtained aperture is homogeneous, is also subject to larger restriction selecting of material simultaneously.Due to needs stretching masking, the barrier film of production has larger shrinkage, and this is also disadvantageous to final usability, and the excellent rate of product of producing is lower.
Summary of the invention
The object of the invention is to propose that a kind of aperture is homogeneous, wetability good, thermal endurance is good, have the folded painting compound lithium ion battery separator that hot melt closes function, there is good fail safe.
Another object of the present invention is to propose a kind of preparation method producing above-mentioned folded painting compound lithium ion battery separator, and technique is simple, and selection range is wide, and micropore pore-forming condition is controlled.
For reaching this object, the present invention by the following technical solutions:
A kind of folded painting compound lithium ion battery separator, it is the porous septum with one or more layers structure be mixed with by one or more coating slurries;
The composition of described porous septum comprises: 30-100 part polymeric material, 0-70 part inorganic particle and surface conditioning agent thereof, 0-50 part bulking agent;
The polymeric material of two classes at least selected by described polymeric material, wherein polymeric material described in a class is fusing point or flow temperature at the thermoplastic of 100-150 DEG C, another kind of described polymeric material be fusing point or flow temperature higher than or be equivalent to described fusing point or flow temperature at the thermoplastic of the thermoplastic of 100-150 DEG C or thermosets.
Barrier film has even and fine and closely woven hole, provides the hole that lithium ion passes through; Described fusing point or flow temperature enable porous septum in use when temperature reaches 100-150 DEG C at the thermoplastic of 100-150 DEG C melting or flowing to occur, realizes closed pore effect; Wherein a base polymer material be fusing point or flow temperature higher than or be equivalent to thermoplastic or the thermosets that described fusing point or flow temperature are the thermoplastic of 100-150 DEG C, can guarantee that porous septum has good intensity and thermal endurance, overcome the problem of current battery barrier film thermal safety deficiency.
Illustrate further, described polymeric material is polyethylene and copolymer thereof and derivative, polypropylene and copolymer thereof and derivative, poly-4-methylpentene and copolymer thereof and derivative, polyolefin and copolymer thereof and derivative, polyvinyl alcohol and copolymer thereof and derivative, polyethylene glycol and copolymer thereof and derivative, PPOX and copolymer thereof and derivative, polyacrylamide and copolymer thereof and derivative, polyacrylonitrile and copolymer thereof and derivative, polyvinylpyrrolidone and copolymer thereof and derivative, acrylic acid (ester) resin and derivative thereof, polymethyl methacrylate and copolymer thereof and derivative, methacrylic acid (ester) resin and derivative thereof, aromatic series or semi-aromatic or aliphatic polyester and copolymer thereof and derivative, aromatic series or semi-aromatic or fatty polyamide and copolymer thereof and derivative, aromatic series or semi-aromatic or aliphatic polyether and copolymer thereof and derivative, aromatic series or semi-aromatic or fatty poly-ester carbonate and copolymer thereof and derivative, polystyrene and copolymer thereof and derivative, epoxy resin and derivative thereof, polyurethane and derivative thereof, phenolic resins and derivative thereof, amino resins and derivative thereof, unsaturated polyester (UP) and derivative thereof, organic siliconresin and derivative thereof, Lauxite and derivative thereof, melamine resin and derivative thereof, melmac and derivative thereof, polyphenylene sulfide and derivative thereof, polyimides and derivative thereof, polysulfones and derivative thereof, polyether-ether-ketone and derivative thereof, fluoropolymer and derivative thereof, Petropols and derivative thereof, one or more in cellulose and its derivates.
Described thermoplastic is polyethylene and copolymer thereof and derivative, polypropylene and copolymer thereof and derivative, polyolefin and copolymer thereof and derivative, poly-4-methylpentene copolymer and derivative, polyvinyl alcohol and copolymer thereof and derivative, polyethylene glycol and copolymer thereof and derivative, polyacrylamide and copolymer thereof and derivative, PPOX and copolymer thereof and derivative, polyacrylonitrile copolymer and derivative thereof, polyvinylpyrrolidone and copolymer thereof and derivative, acrylic acid (ester) resin and derivative thereof, methylmethacrylate copolymer and derivative thereof, methacrylic acid (ester) resin and derivative thereof, aromatic series or semi-aromatic or aliphatic polyester and copolymer thereof and derivative, aromatic series or semi-aromatic or fatty polyamide and copolymer thereof and derivative, aromatic series or semi-aromatic or aliphatic polyether and copolymer thereof and derivative, aromatic series or semi-aromatic or fatty poly-ester carbonate and copolymer thereof and derivative, polystyrene copolymer and derivative thereof, polyurethane and derivative thereof, fluoropolymer and derivative thereof, Petropols and derivative thereof, at least one in cellulose and its derivates.
Illustrate further, described inorganic particle be silicon dioxide, composite granule that aluminium oxide, titanium dioxide, zirconia, zinc oxide, magnesium oxide, tin-antiomony oxide, calcium oxide, tri-iron tetroxide, iron oxide, rare earth, calcium carbonate, barium sulfate, kaolin, imvite, attapulgite, clay, vermiculite, hydroxyapatite, sepiolite, diatomite, mica, graphite oxide, one or more compositions in expanded graphite form or powder mixture.
Illustrate further, described bulking agent is at least one in the polymeric material containing active group, the monomer containing active group or prepolymer, silane coupler, titanate coupling agent, aluminate coupling agent, zirconium ester coupling agent, isocyanates etc.
Illustrate further, described active group comprises at least one in hydroxyl, ammonia (amine/ammonium) base, ester group, carboxyl, carbonyl, ehter bond, acyl group, NCO, sulfydryl, epoxy radicals, double bond, triple bond, anhydride group.
Illustrate further, described inorganic powder surface inorganic agent quality is the 1-500% of inorganic particle quality, and described inorganic powder surface inorganic agent is at least one in silane coupler, titanate coupling agent, aluminate coupling agent, zirconium ester coupling agent, isocyanates, the polymeric material with active group, the monomer with active group or prepolymer.
Produce the preparation method of above-mentioned folded painting compound lithium ion battery separator, comprise the following steps:
Prepared by a, coating: by 30-100 part polymeric material or monomer or prepolymer, 0-70 part inorganic particle and surface conditioning agent thereof and the mixing of 0-50 part bulking agent, add the soluble pore former of 0 to 17/3 times that accounts for said mixture gross mass again, be mixed together processing and be prepared into coating slurry; Above-mentioned processing comprises stirring, grinds, adds one or more modes of hankering; The kind of described coating slurry is no less than a kind;
B, coating are produced:
For the folded painting compound lithium ion battery separator of single layer structure, one or more coating methods in release film adopting scraper, scraper, spraying, cylinder transfer or casting are coated with carry out folded painting;
For the folded painting compound lithium ion battery separator of sandwich construction, one or more coating methods in release film adopting scraper, scraper, spraying, cylinder transfer or casting are coated with carry out folded painting ground floor coating slurry, then after drying or solidification being carried out to ground floor, the folded second layer that is coated with applies slurry again, by that analogy;
C, coating stripping: after folded painting completes after drying or solidification, coating is peeled off from release film;
D, hole formation: hole formed by the pore structure of described inorganic particle self cross-linking reaction or add soluble pore former by dissolved method, the pore of solvent pore method, adopt heating volatilization or with water or solvent, soluble pore former removing is formed hole, hole is formed by above-mentioned one or more methods formed in method, and described solvent is incompatible with described polymeric material;
E, drying, rolling obtain lithium ion battery separator.
The number of plies of described sandwich construction is determined by the number of times folding painting, and the coating slurry prepared with it forms irrelevant, and namely adjacent layer can apply slurry by same and make.
Illustrate further, described soluble pore former is sodium chloride, potassium chloride, calcium chloride, sodium sulphate, sodium carbonate, sodium acid carbonate, boric acid and salt thereof, glucose, sucrose, polyethylene glycol and copolymer thereof and derivative, poly(ethylene oxide) and copolymer thereof and derivative, PPOX and copolymer thereof and derivative, polyvinyl alcohol and derivative thereof, polyvinylpyrrolidone and derivative thereof, polyacrylamide and derivative thereof, polyacrylic acid and salt thereof, polymethylacrylic acid and salt thereof, sodium alginate, Sodium Benzoate, starch, cellulose and its derivates, citric acid and salt thereof, sorbic acid and salt thereof, sorbierite and derivative thereof, aliphatic acid and derivative thereof, fatty alcohol and derivative thereof, organic amine (ammonium) and derivative thereof, organic phosphine (Phosphonium) and derivative, oleic acid and derivative thereof, amino acid and derivative, pentaerythrite and derivative thereof, obtain microcellular structure by dissolved legal system during at least one in glyceride and derivative thereof.
Illustrate further, described soluble pore former is benzene, toluene, dimethylbenzene, pentane, hexane, heptane, octane, cyclohexane, cyclohexanone, toluene cyclohexanone, chlorobenzene, dichloro-benzenes, carrene, chloroform, carbon tetrachloride, trichloroethanes, methyl alcohol, ethanol, propyl alcohol, butanols, isopropyl alcohol, isoamyl alcohol, hexanol, ethylene glycol, propylene glycol, butanediol, hexylene glycol, decanediol, succinic acid, adipic acid, decanedioic acid, glycerol, ether, expoxy propane, benzinum, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, acetone, espeleton, methylisobutylketone, butanone, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, triethanolamine, dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide, pyridine, oxolane, formaldehyde, acetaldehyde, dioxane, naphthane, trimethylbenzene, trichloro-benzenes, metacresol, phenol, formic acid, sulfuric acid, benzenediol, '-biphenyl diphenol, paraffin and atoleine, soybean oil and derivative above-mentioned at least one time be obtain microcellular structure by solvent pore.
Illustrate further, described cross-linking reaction is the reaction that Compound Phase mutual effect containing two and above active group forms cross-linked network, obtains microcellular structure by water or solvent by after the monomer of solubility, colloidal sol removing.Described active group is the compound containing two and above active group, and described active group comprises at least one in hydroxyl, ammonia (amine/ammonium) base, ester group, carboxyl, carbonyl, ehter bond, acyl group, NCO, sulfydryl, epoxy radicals, double bond, triple bond, anhydride group.
Beneficial effect of the present invention: 1, membrane pore size size and aperture rate controlled, make the pore size of barrier film homogeneous; 2, the excellent rate of barrier film finished product is high, and wetability is good, and fail safe is high; 3, the preparation method of barrier film is simple, and selection range is wide.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
Adopt single layer coating to prepare lithium ion battery separator, gross thickness 15 μm, porosity 55%, comprises the following steps:
Prepared by a, coating:
Paste composition comprises: 2 parts of sodium chloride (NaCl), 13 parts of polyvinylpyrrolidones (PVP), 55 parts of dimethylbenzene, 10 parts of atoleines, 10 parts of thermoplastic elastomer (TPE)s (SEBS), 10 parts of HOPPs (i-PP).Described SEBS is the linear butylbenzene triblock copolymer with polybutadiene block hydrotreatment, wherein styrene-content 30wt%, solution viscosity 500mPas.The fusing point Tm=168 DEG C of described i-PP, melt index (MI) MI=10g/min, the soluble pore former wherein added accounts for 4 times of other mixture gross masses.
Slurry preparation method: after NaCl, PVP, dimethylbenzene, atoleine grinding 30min, be heated to 120 DEG C, drop into SEBS and i-PP, obtain after stirring and dissolving applying slurry.
B, coating are produced: on PET release film, adopt scraper coating method to apply;
C, coating stripping: after folded painting completes after hot-air oven drying, peel off coating from PET release film through cooling;
D, hole formation: through 80 DEG C of butanols, 80 DEG C of hot water and normal temperature acetone solvent groove removing soluble pore former;
E, through 80 DEG C of heated-air dryings, rolling after cooling obtains lithium ion battery separator.
Embodiment 2
Adopt single layer coating to prepare lithium ion battery separator, gross thickness 16 μm, porosity 43%, comprises the following steps:
Prepared by a, coating:
Slurry A-1 composition comprises: 1 part of silane coupler (KH570), 20 parts of ethyl acetate, 9 parts of nano silicon (nano-SiO
2), 25 part third oxidation trimethylol propane (TMP3POTA), 10 parts of cetomacrogol 1000s (PEG-1000), 5 parts of Macrogol 200s (PEG-200), 30 parts of pure acrylate resins (DR-A845).
The preparation method of slurry A-1: put into by KH570 in ethyl acetate, drops into nano-SiO after stirring 50min
2, drop into TMP3POTA, PEG-1000 and PEG-200 after stirring 30min, after stirring 30min, drop into DR-A845, after stirring 30min, obtain slurry A-1.
Slurry A-2 composition comprises: 40 parts of Tissuemat Es and 60 parts of dimethylbenzene.Described Tissuemat E average grain diameter is 6 μm, fusing point Tm=129 DEG C.
The preparation method of slurry A-2: Tissuemat E is dropped into dimethylbenzene, stirs 30min and obtains slurry A-2.
Slurry A-3 composition comprises: 50 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone (PI184) and 50 parts of dimethylbenzene.
The preparation method of slurry A-3: PI184 is dropped into dimethylbenzene, stirs 30min and obtains slurry A-3.
The preparation of coating slurry: 40 parts of slurry A-1,58 parts of slurry A-2 and 2 part of slurry A-3 are mixed, stir 30min and obtain applying slurry, the soluble pore former wherein added accounts for 1 times of other mixture gross masses.
B, coating are produced: on PET release film, adopt spraying to carry out coating.
C, coating stripping: after coating completes after ultra-violet curing, peel off coating from PET release film.
D, hole formation: through 80 DEG C of hot water and normal temperature ethyl acetate solvent groove removing soluble pore former, form hole.
E, through 80 DEG C of heated-air dryings, cooling, rolling obtains lithium ion battery separator.
Embodiment 3
Adopt the method for two stacked paintings to prepare lithium ion battery separator, gross thickness 25 μm, ground floor thickness 20 μm, second layer thickness 5 μm, porosity is 43%, comprises the following steps:
Prepared by a, coating:
Slurry B-1 composition comprises: 0.5 part of silane coupler (KH570), 49.5 parts of ethyl acetate, 50 parts of Woelm Aluminas.The average grain diameter of described Woelm Alumina is 18 μm, and average pore size is 8nm.
The preparation method of slurry B-1: put into by KH570 in ethyl acetate, after stirring 5min, drops into Woelm Alumina, stirs 30min, obtain slurry B-1.
Slurry B-2 composition comprises: 5 parts of 1-hydroxy-cyclohexyl-phenyl ketones (PI184), 40 parts of 4-tert-butylcyclohexyl acrylate (TBCHA), 15 parts of ethoxyquin trimethylolpropane triacrylates (TMP3EOTA) and 40 parts of aliphatic urethane acrylates (DR-U218).
The preparation method of slurry B-2: put in the mixed solution of TBCHA and TMP3EOTA by PI 184, stirs 15min, then adds DR-U218, mechanical agitation 30min, obtain slurry B-2.
The preparation of ground floor coating slurry: mixed by 70 parts of slurry B-1 and 30 part slurry B-2, add appropriate defoamer, stir 30min and can obtain ground floor coating slurry, the soluble pore former wherein added accounts for 0.53 times of other total mixture gross masses.
Second layer coating paste composition comprises: 25 parts of thermoplastic elastomer (TPE)s (SEBS), 25 parts of sodium chloride (NaCl), 50 parts of dimethylbenzene.Described SEBS be polybutadiene block through hydrotreated linear butylbenzene triblock copolymer, styrene-content is 30wt%, solution viscosity 500mPas.
The preparation of second layer coating slurry: put into by SEBS and NaCl in dimethylbenzene, grinding 60min, can obtain second layer coating slurry, the soluble pore former wherein added accounts for 3 times of other mixture gross masses.
Slurry is prepared and is deposited and need avoid strong illumination, especially ultraviolet light, and slurry preparation and storage temperature must not higher than 60 DEG C.
B, coating are produced: ground floor is applied slurry and adopt scraper to carry out coating on PP release film, again the second layer is applied slurry and be coated on ground floor after ultra-violet curing.
C, coating stripping: after folded painting completes after heated-air drying, peel off coating from PP release film.
D, hole formation: through 80 DEG C of hot water and normal temperature ethyl acetate solvent groove removing soluble pore former, form hole.
E, through 80 DEG C of heated-air dryings, cooling, rolling obtains the homogeneous lithium ion battery separator in aperture.
Embodiment 4
Adopt the method for two stacked paintings to prepare lithium ion battery separator, thickness 15 μm, ground floor thickness 12 μm, second layer thickness 3 μm, porosity is 37%.
Prepared by a, coating:
Slurry C-1 composition comprises: 5 parts of silane couplers (KH550), 45 parts of ethyl acetate and 50 parts of porous silicas.Described porous silica average grain diameter is 10 μm, and average pore size is 9nm.
The preparation method of slurry C-1: put into by KH550 in ethyl acetate, after stirring 5min, drops into porous silica, stirs 30min, obtain slurry C-1, stand-by.
Slurry C-2 composition comprises: the polypropylene (PP-MAH) of 30 parts of HOPPs (i-PP), 10 parts of modified by maleic acid anhydride graft and 60 parts of dimethylbenzene.The fusing point Tm=168 DEG C of described i-PP, melt index MI=10g/10min.Described PP-MAH percent grafting is 2.6%.
The preparation method of slurry C-2: i-PP and PP-MAH is dissolved in 80 DEG C of dimethylbenzene, obtains slurry C-2, stand-by.
The preparation method of ground floor coating slurry: 60 parts of slurry C-1 and 40 parts of slurry C-2 are mixed, add appropriate defoamer, stir 30min and can obtain ground floor coating slurry, the soluble pore former wherein added accounts for 1.04 times of other total mixture gross masses.
Second layer coating paste composition comprises: 25 parts of COPPs (co-PP), 25 parts of Macrogol 2000s (PEG-2000) and 50 parts of dimethylbenzene.Described co-PP fusing point Tm=130 DEG C, melt index MI=15g/10min.
The preparation method of second layer slurry: put into by co-PP and PEG-2000 in the dimethylbenzene of 80 DEG C, magnetic agitation is dissolved, and can obtain second layer coating slurry, the soluble pore former wherein added accounts for 3 times of other mixture gross masses.
B, coating are produced: ground floor is applied slurry and be coated on PET release film, again the second layer is applied slurry and be coated on ground floor after heated-air drying.
C, coating stripping: after folded painting completes after heated-air drying, peel off coating from PET release film.
D, hole formation: through 80 DEG C of hot water and normal temperature ethyl acetate solvent groove removing soluble pore former, form hole.
E, through 80 DEG C of heated-air dryings, cooling, rolling obtains the homogeneous lithium ion battery separator in aperture.
Embodiment 5
Adopt the method for two stacked paintings to prepare lithium ion battery separator, thickness 25 μm, ground floor thickness 15 μm, second layer thickness 10 μm, porosity is 51%, comprises the following steps:
Prepared by a, coating:
Slurry D-1 composition comprises: 0.6 part of silane coupler (KH550), 35 parts of ethyl acetate, 25 parts of Macrogol 200s (PEG-200), 9.4 parts of nano silicon (nano-SiO
2) and 30 parts of PEPAs (Desmophen1150).Described nano-SiO
2average grain diameter 12 μm, without surface treatment.Hydroxyl value (4.7 ± 0.2) % of described Desmophen1150.
The preparation method of slurry D-1: put into by KH550 in the mixed solution of ethyl acetate and PEG-200, after stirring 15min, drops into nano-SiO
2, add Desmophen1150 after high-speed stirred 30min, after stirring 30min, obtain slurry D-1.
Slurry D-2 composition comprises: 50 parts of vulcabond TDI-HDI tripolymers (Coronate 2604) and 50 parts of butyl acetates.Trimerical-NCO the content of described vulcabond TDI-HDI is 10.6%, Gu containing being 60%.
The preparation method of slurry D-2: be scattered in butyl acetate by Coronate 2604, stirs 15min and obtains slurry D-2.
The preparation of ground floor coating slurry: mixed by 60 parts of slurry D-1 and 40 part slurry D-2, add appropriate defoamer, can obtain ground floor coating slurry after stirring 30min, the soluble pore former wherein added accounts for 1.27 times of other total mixture gross masses.
Slurry E-1 composition comprises: 5 parts of 1-hydroxy-cyclohexyl-phenyl ketones (PI 184), 45 parts of polyethylene wax powder and 50 parts of ethyl acetate.The average grain diameter of described polyethylene wax powder is 5 μm, fusing point Tm=125 DEG C.
The preparation method of slurry E-1: put in ethyl acetate by PI 184, stir 30min, then add polyethylene wax powder, mechanical agitation 30 minutes, obtains slurry E-1.
Slurry E-2 composition comprises: 25 parts of aliphatic urethane acrylates (6185), 25 parts of stearic acid acrylate (SA), 5 part of third oxidation trimethylolpropane triacrylate (TMP4.5POTA) and 45 parts of PEG400s (PEG-400).
The preparation method of slurry E-2: obtain slurry E-2 by 6185, after SA, TMP4.5POTA, PEG-400 mechanical agitation 60min.
The preparation of second layer coating slurry: will obtain second layer coating slurry after 50 parts of slurry E-1 and 50 parts of slurry E-2 mix and blend 30min, the soluble pore former wherein added accounts for 0.9 times of other total mixture gross masses.
The preparation of slurry and deposit and need avoid strong illumination, especially ultraviolet light, slurry preparation and storage temperature must not higher than 60 DEG C.
B, coating are produced: ground floor is applied slurry and be coated on PP release film, again the second layer is applied slurry and be coated on ground floor after hot-air oven drying.
C, coating stripping: after folded painting completes after ultra-violet curing, peel off coating from PP release film.
D, hole formation: through 80 DEG C of hot water and normal temperature ethyl acetate solvent groove removing soluble pore former, form hole.
E, through 80 DEG C of heated-air dryings, cooling, rolling obtains the homogeneous lithium ion battery separator in aperture.
Embodiment 6
Adopt the method for two stacked paintings to prepare lithium ion battery separator, gross thickness 50 μm, ground floor thickness 40 μm, second layer thickness 10 μm, porosity is 50%, comprises following preparation process:
Prepared by a, coating:
Slurry F-1 composition comprises: 1 part of titanate coupling agent (CT115), 39 parts of ethyl acetate, 40 parts of Macrogol 200s (PEG-200), 20 parts of nano titanium oxide (nano-TiO
2).Described nano-TiO
2average grain diameter be 10nm, without surface treatment.
The preparation method of slurry F-1: put into by CT115 in ethyl acetate and PEG-200 mixed solution, after stirring 5min, adds nano-TiO
2, high-speed stirred 60min obtains slurry F-1.
Slurry F-2 composition comprises: 5 part 2; 4,6-trimethylbenzoy-dipheny phosphine oxide (PI TPO), 40 parts of 4-tert-butylcyclohexyl acrylate (TBCHA), 15 parts of ethoxyquin trimethylolpropane triacrylates (TMP3EOTA) and 40 parts of aliphatic urethane acrylates (DR-U312).
The preparation method of slurry F-2: be scattered in the mixed solution of TBCHA and TMP3EOTA by PI TPO, adds DR-U312, mechanical agitation 30min after stirring 15min, obtains slurry F-2.
The preparation of ground floor coating slurry: 70 parts of slurry F-1 and 30 part slurry F-2 is mixed, add appropriate defoamer, stir 30min and can obtain ground floor coating slurry, stand-by, the soluble pore former wherein added accounts for 1.23 times of other total mixture gross masses.
Slurry G-1 composition comprises: 5 parts of 1-hydroxy-cyclohexyl-phenyl ketones (PI 184), 45 parts of polyamide wax powder, 49 parts of ethyl acetate and 1 part of silane coupler (KH560).The average grain diameter of described polyamide wax powder is 4 μm, fusing point Tm=145 DEG C.
The preparation method of slurry G-1: be scattered in ethyl acetate by PI 184 and KH560, add polyamide wax powder after stirring 5min, mechanical agitation 30 minutes, obtains slurry G-1.
The composition of slurry G-2 comprises: 30 parts of aliphatic urethane acrylates (6185), 25 parts of 4-tert-butylcyclohexyl acrylate (TBCHA), 5 part of third oxidation trimethylolpropane triacrylate (TMP4.5POTA) and 40 parts of Macrogol 200s (PEG-200).
The preparation method of slurry G-2: by 6185, TBCHA, TMP4.5POTA and PEG-200 mixing, obtains slurry G-2 after mechanical agitation 60min.
The preparation of second layer coating slurry: will obtain second layer coating slurry after 70 parts of slurry G-1 and 30 parts of slurry G-2 mix and blend 30min, stand-by, the soluble pore former wherein added accounts for 0.86 times of other total mixture gross masses.
The preparation of slurry and deposit and avoid strong illumination, especially ultraviolet light, slurry preparation and storage temperature must not higher than 60 DEG C.
B, coating are produced: ground floor is applied slurry and be coated on PP release film, again the second layer is applied slurry and be coated on ground floor after ultra-violet curing.
C, coating stripping: after folded painting completes after ultra-violet curing, peel off coating from PP release film.
D, hole formation: through 80 DEG C of hot water and normal temperature ethyl acetate solvent groove removing soluble pore former, form hole.
E, through 80 DEG C of heated-air dryings, cooling, rolling obtains the homogeneous lithium ion battery separator in aperture.
Embodiment 7
Adopt the method for three stacked paintings to prepare lithium ion battery separator, thickness 20 μm, ground floor thickness 10 μm, second layer thickness 5 μm, third layer thickness 5 μm, porosity is 54%, comprises following preparation process:
Prepared by a, coating:
Slurry H-1 composition comprises: 1.75 parts of silane couplers (KH550), 40 parts of ethyl acetate, 20 parts of cetomacrogol 1000s (PEG-1000), 20 parts of PEG400s (PEG-400), 18 parts of nano silicon (nano-SiO
2) and 0.25 part of epoxy curing agent (593).Described nano-SiO
2average grain diameter be 10nm, without surface treatment.Described 593 is amine curing agent.
The preparation method of slurry H-1: put into by KH550 in ethyl acetate, PEG-1000 and PEG-400 mixed solution, after stirring 10min, adds nano-SiO
2, add 593 after high-speed stirred 60min, after stirring 30min, obtain slurry H-1.
Slurry H-2 composition comprises: 60 parts of epoxy resin (E44), 20 parts of acetone and 20 parts of ethyl acetate.The epoxide number of described E44 is 0.44mol/100g.
The preparation method of slurry H-2: put into by E44 in the mixed solution of acetoneand ethyl acetate, mechanical agitation 60min, obtains slurry H-2.
The preparation of ground floor coating slurry: 20 parts of slurry H-1 and 80 part slurry H-2 is mixed, add appropriate defoamer, stir 30min and can obtain ground floor coating slurry, stand-by, the soluble pore former wherein added accounts for 0.92 times of other total mixture gross masses.
Slurry I-1 composition comprises: 5 parts of titanate coupling agents (CT115), 45 parts of ethyl acetate, 40 parts of cetomacrogol 1000s (PEG-1000) and 10 parts of nano zircite (nano-ZrO
2).Described nano-ZrO
2average grain diameter 20nm, without surface treatment.
The preparation method of slurry I-1: put into by CT115 in ethyl acetate and PEG-1000 mixed solution, after stirring 5min, adds ZrO
2, high-speed stirred 60min obtains slurry I-1.
The composition of slurry I-2 comprises: 5 part 2; 4,6-trimethylbenzoy-dipheny phosphine oxide (PI TPO), 40 parts of 4-tert-butylcyclohexyl acrylate (TBCHA), 15 parts of ethoxyquin trimethylolpropane triacrylates (TMP3EOTA) and 40 parts of aliphatic urethane acrylates (DR-U312).
The preparation method of slurry I-2: be scattered in the mixed solution of TBCHA and TMP3EOTA by PI TPO, then add DR-U312, mechanical agitation 30min, obtains slurry I-2.
The preparation of second layer coating slurry: 70 parts of slurry I-1 and 30 part slurry I-2 is mixed, add appropriate defoamer, stir 30min and can obtain second layer coating slurry, stand-by, the soluble pore former wherein added accounts for 1.47 times of other total mixture gross masses.
Slurry J-1 composition comprises: 5 parts of 1-hydroxy-cyclohexyl-phenyl ketones (PI 184), 45 parts of polypropylene wax powder and 50 parts of ethyl acetate.The average grain diameter of described polypropylene wax is 5 μm, fusing point Tm=145 DEG C.
The preparation method of slurry J-1: be scattered in ethyl acetate by PI 184, add polypropylene wax powder after stirring 15min, mechanical agitation 30 minutes, obtains slurry J-1.
The composition of slurry J-2 comprises: 30 parts of aliphatic urethane acrylates (6185), 25 parts of 4-tert-butylcyclohexyl acrylate (TBCHA), 5 part of third oxidation trimethylolpropane triacrylate (TMP4.5POTA), 40 parts of butanediols.
The preparation method of slurry J-2: by 6185, TBCHA, TMP4.5POTA and butanediol mixing, mechanical agitation 60min, obtains slurry J-2.
The preparation of third layer coating slurry: will obtain ground floor coating slurry after 50 parts of slurry J-1 and 50 parts of slurry J-2 mix and blend 30min, stand-by, the soluble pore former wherein added accounts for 0.82 times of other total mixture gross masses.
The preparation of slurry and deposit and avoid strong illumination, especially ultraviolet light, slurry preparation and storage temperature must not higher than 60 DEG C.
B, coating are produced: ground floor is applied slurry and be coated on PP release film, the second layer is applied slurry again and be coated on ground floor, after ultra-violet curing, third layer is applied slurry and be coated on the second layer after heated-air drying.
C, coating stripping: after folded painting completes after ultra-violet curing, peel off coating from PP release film.
D, hole formation: through ethyl acetate and alcohol solvent groove removing soluble pore former, form hole.
E, through 80 DEG C of heated-air dryings, cooling, rolling obtains the homogeneous lithium ion battery separator in aperture.
Embodiment 8
Adopt the method for three stacked paintings to prepare lithium ion battery separator, gross thickness 30 μm, ground floor thickness 20 μm, second layer thickness 5 μm, third layer thickness 5 μm, porosity is 42%, comprises following preparation process:
Prepared by a, coating:
Slurry K-1 composition comprises: 5 parts of silane couplers (KH570), 15 parts of tetraethoxysilanes (TEOS), 30 parts of ethyl acetate, 40 parts of ethylene glycol, 5 parts of citric acids and 5 parts of water.
The preparation method of slurry K-1: KH570 and TEOS is put in the mixed solution of ethyl acetate, ethylene glycol, citric acid and water, magnetic agitation 120min obtains silicon dioxide gel solution slurry K-1.
Slurry K-2 composition comprises: 5 parts of 1-hydroxy-cyclohexyl-phenyl ketones (PI 184), 40 parts of 4-tert-butylcyclohexyl acrylate (TBCHA), 15 parts of ethoxyquin trimethylolpropane triacrylates (TMP3EOTA) and 40 parts of aliphatic urethane acrylates (DR-U218).
The preparation method of slurry K-2: put in the mixed solution of TBCHA and TMP3EOTA by PI 184, adds DR-U218, mechanical agitation 30min after stirring 15min, obtains slurry K-2.
The preparation of ground floor coating slurry: 50 parts of slurry K-1 and 50 part slurry K-2 is mixed, add appropriate defoamer, stir 30min and can obtain ground floor coating slurry, stand-by, the soluble pore former wherein added accounts for 0.67 times of other total mixture gross masses.
Slurry L-1 composition comprises: 20 parts of citric acids, 20 parts of ethyl acetate, 40 parts of cetomacrogol 1000s (PEG-1000) and 20 parts of ethylene glycol.
The preparation method of slurry L-1: citric acid and PEG-1000 are put in ethyl acetate and ethylene glycol mixed solution, stirs 30min and obtains slurry L-1.
The composition of slurry L-2 comprises: 3 parts of 1-hydroxy-cyclohexyl-phenyl ketones (PI 184), 2 part 2; 4,6-trimethylbenzoy-dipheny phosphine oxide (PI TPO), 40 parts of 4-tert-butylcyclohexyl acrylate (TBCHA), 15 parts of ethoxyquin trimethylolpropane triacrylates (TMP3EOTA), 40 parts of aliphatic urethane acrylates (DR-U312) and 15 parts of acrylic resins (6536-1).
The preparation method of slurry L-2: put in the mixed solution of TBCHA and TMP3EOTA by PI 184 and PI TPO, adds DR-U312 and 6536-1, mechanical agitation 30min after stirring 15min, obtains slurry L-2.
The preparation of second layer coating slurry: mixed by 40 parts of slurry L-1 and 60 part slurry L-2, add appropriate defoamer, stir 30min and can obtain second layer coating slurry, stand-by, the soluble pore former wherein added accounts for 0.67 times of other mixture gross masses.
Slurry M-1 composition comprises: 5 parts of 1-hydroxy-cyclohexyl-phenyl ketones (PI 184), 40 parts of polyamide wax powder, 30 parts of ethyl acetate, 20 parts of Macrogol 200s (PEG-200) and 5 parts of silane couplers (KH570).The average grain diameter of described polyamide wax powder is 4 μm, and fusing point is 145 DEG C.
The preparation method of slurry M-1: put into by PI 184 and KH570 in the mixed solution of ethyl acetate and PEG-200, add polyamide wax powder after stirring 15min, mechanical agitation 30 minutes, obtains slurry M-1.
Slurry M-2 composition comprises: 30 parts of aliphatic urethane acrylates (6185), 25 parts of 4-tert-butylcyclohexyl acrylate (TBCHA), 5 part of third oxidation trimethylolpropane triacrylate (TMP4.5POTA), 30 parts of butanediols and 10 parts of citric acids.
The preparation method of slurry M-2: by 6185, TBCHA, TMP4.5POTA, butanediol and citric acid mixing, mechanical agitation 60min, obtains slurry M-2.
The preparation of third layer coating slurry: 50 parts of slurry M-1 and 50 parts of slurry M-2 mix and blend 30min can be obtained third layer coating slurry, stand-by, the soluble pore former wherein added accounts for 0.82 times of other total mixture gross masses.
The preparation of slurry and deposit and avoid strong illumination, especially ultraviolet light, slurry preparation and storage temperature must not higher than 60 DEG C.
B, coating are produced: ground floor is applied slurry and be coated on PP release film, the second layer is applied slurry again and be coated on ground floor, after ultra-violet curing, third layer is applied slurry and be coated on the second layer after ultra-violet curing.
C, coating stripping: after folded painting completes after ultra-violet curing, peel off coating from PP release film.
D, hole formation: through 80 DEG C of water-baths and normal temperature alcohol solvent groove removing soluble pore former, form hole.
E, through 80 DEG C of heated-air dryings, cooling, rolling obtains the homogeneous lithium ion battery separator in aperture.
Embodiment 9
Adopt the method for three stacked paintings to prepare lithium ion battery separator, gross thickness 10 μm, ground floor thickness 5 μm, second layer thickness 3 μm, third layer thickness 2 μm, porosity 39%, comprises following preparation process:
Prepared by a, coating:
Slurry N-1 composition comprises: 5 parts of silane couplers (A187), 15 parts of tetraethoxysilanes (TEOS), 25 parts of ethyl acetate, 30 parts of ethylene glycol, 5 parts of citric acids, 10 parts of water and 10 parts of sodium chloride (NaCl).
The preparation method of slurry N-1: put into by A187 and TEOS in the mixed solution of ethyl acetate, ethylene glycol, citric acid, NaCl and water, magnetic agitation 60min obtains silicon dioxide gel solution N-1 slurry.
Slurry N-2 composition comprises: 5 parts of 1-hydroxy-cyclohexyl-phenyl ketones (PI 184), 15 parts of 4-tert-butylcyclohexyl acrylate (TBCHA), 20 parts of ethoxyquin trimethylolpropane triacrylates (TMP3EOTA), 20 parts of polyethylene glycol (400) dimethylacrylates (PEG (400) DMA), 25 parts of aliphatic urethane acrylates (DR-U218) and 15 parts of aliphatic urethane acrylates (6185).
The preparation method of slurry N-2: PI 184 is scattered in the mixed solution of TBCHA, TMP3EOTA and PEG (400) DMA, then adds DR-U218 and 6185, mechanical agitation 60min, obtain slurry N-2.
The preparation of ground floor coating slurry: 50 parts of slurry N-1 and 50 part slurry N-2 is mixed, add appropriate defoamer, stir 30min and can obtain ground floor coating slurry, stand-by, the soluble pore former wherein added accounts for 0.67 times of other total mixture gross masses.
Slurry O-1 composition comprises: 5 parts of tetraethoxysilanes (TEOS), 3 parts of butyl titanates, 2 parts of citric acids, 20 parts of ethyl acetate, 20 parts of ethylene glycol, 5 parts of water, 20 parts of glucose, 5 parts of tertiary amine acrylate (6411) and 20 parts of cetomacrogol 1000s (PEG-1000).
The preparation method of slurry O-1: TEOS, butyl titanate and citric acid are put in ethyl acetate, ethylene glycol and water mixed solution, stir to drop into after 60min glucose, 6411, PEG-1000, stir 30min and obtain slurry O-1.
Slurry O-2 composition comprises: 5 parts of composite photoinitiators (PI 500), 30 parts of 4-tert-butylcyclohexyl acrylate (TBCHA), 15 parts of ethoxyquin trimethylolpropane triacrylates (TMP3EOTA), 15 parts of polyethylene glycol (200) dimethylacrylates (PEG (200) DMA), 25 parts of polyester acrylates (6430) and 10 parts of polyester acrylates (6363).
The preparation method of slurry O-2: PI 500 is scattered in the mixed solution of TBCHA, TMP3EOTA, PEG (200) DMA, then adds 6430 and 6363, mechanical agitation 60min, obtain slurry O-2.
The preparation of second layer coating slurry: 50 parts of slurry O-1 and 50 part slurry O-2 is mixed, add appropriate defoamer, stir 30min and can obtain second layer coating slurry, stand-by, the soluble pore former wherein added accounts for 0.77 times of other total mixture gross masses.
Slurry P-1 composition comprises: 20 parts of polyacrylamides (PAM), 35 parts of calcium chloride (CaCl
2) and 45 parts of dimethylbenzene.
The preparation method of slurry P-1: by PAM and CaCl
2put in dimethylbenzene after grinding 30min, high-speed stirred 60min obtains slurry P-1.
Slurry P-2 composition comprises: 30 parts of thermoplastic elastomer (TPE)s (SEBS), 20 parts of COPPs (co-PP) and 50 parts of dimethylbenzene.Described SEBS is the linear butylbenzene triblock copolymer of polybutadiene block hydrotreatment, and styrene-content is 30%, and solution viscosity is 500mPas.Described co-PP fusing point Tm=135 DEG C, melt index MI=15g/10min.
The preparation method of slurry P-2: SEBS and co-PP is dissolved in 80 DEG C of dimethylbenzene, obtains slurry P-2.
The preparation of third layer coating slurry: 40 parts of slurry P-1 and 60 parts of slurry P-2 mix and blend 30min can be obtained third layer coating slurry, stand-by, the soluble pore former wherein added accounts for 2.33 times of other total mixture gross masses.
The preparation of slurry and deposit and avoid strong illumination, especially ultraviolet light, slurry preparation and storage temperature must not higher than 60 DEG C.
B, coating are produced: ground floor is applied slurry and be coated on PP release film, the second layer is applied slurry again and be coated on ground floor, after ultra-violet curing, third layer is applied slurry and be coated on the second layer after ultra-violet curing.
C, coating stripping: after folded painting completes after heated-air drying, peel off coating from PP release film.
D, hole formation: through 80 DEG C of water-baths and normal temperature alcohol solvent groove removing soluble pore former, form hole.
E, through 80 DEG C of heated-air dryings, cooling, rolling obtains the homogeneous lithium ion battery separator in aperture.
Embodiment 10
Adopt the method for three stacked paintings to prepare lithium ion battery separator, gross thickness 60 μm, ground floor thickness 10 μm, second layer thickness 40 μm, third layer thickness 10 μm, porosity 38%, comprises following preparation process:
Ground floor coating paste composition comprises: 15 parts of thermoplastic elastomer (TPE)s (SEBS), 10 parts of Macrogol 2000s (PEG-2000), 73 parts of dimethylbenzene and 2 parts of ethylene glycol.Described SEBS is the linear butylbenzene triblock copolymer of polybutadiene block hydrotreatment, and styrene-content is 30%, and solution viscosity is 500mPas, and the soluble pore former wherein added accounts for 17/3 times of other mixture gross masses.
The preparation method of ground floor coating slurry: add ethylene glycol after being dissolved in dimethylbenzene by SEBS and PEG-2000, stirs after 30 minutes and obtains ground floor coating slurry.
Slurry Q-1 composition comprises: 5 parts of tetraethoxysilanes (TEOS), 3 parts of butyl titanates, 2 parts of citric acids, 20 parts of ethyl acetate, 20 parts of Macrogol 200s (PEG-200), 5 parts of water, 20 parts of glucose, 5 parts of tertiary amine acrylate (6411) and 20 parts of cetomacrogol 1000s (PEG-1000).
The preparation method of slurry Q-1: TEOS, butyl titanate and citric acid are put in the mixed solution of ethyl acetate, PEG-200 and water, stir to drop into after 60min glucose, 6411, PEG-1000, stir 30min and obtain slurry Q-1.
The composition of slurry Q-2 comprises: 3 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone (PI 1173), 2 parts of 1-hydroxy-cyclohexyl-phenyl ketones (PI 184), 30 parts of 4-tert-butylcyclohexyl acrylate (TBCHA), 15 parts of ethoxyquin trimethylolpropane triacrylates (TMP3EOTA), 15 parts of polyethylene glycol (200) dimethylacrylates (PEG (200) DMA), 25 parts of polyester acrylates (6430) and 10 parts of polyester acrylates (6363).
The preparation method of slurry Q-2: PI 1173 and PI 184 is scattered in the mixed solution of TBCHA, TMP3EOTA, PEG (200) DMA, then adds 6430 and 6363, mechanical agitation 60min, obtain slurry Q-2.
The preparation of second layer coating slurry: 50 parts of slurry Q-1 and 50 part slurry Q-2 is mixed, add appropriate defoamer, stir 30min and can obtain second layer coating slurry, stand-by, the soluble pore former wherein added accounts for 0.77 times of other total mixture gross masses.
The composition of third layer coating slurry comprises: 15 parts of polyethylene (PE), 10 parts of Macrogol 2000s (PEG-2000) and 75 parts of dimethylbenzene.The fusing point Tm=126 DEG C of described PE, melt index MI=7g/10min.
The preparation method of third layer slurry: put into by PE and PEG-2000 in dimethylbenzene, obtain third layer coating slurry after dissolving, stand-by, the soluble pore former wherein added accounts for 17/3 times of other mixture gross masses.
The preparation of slurry and deposit and avoid strong illumination, especially ultraviolet light, slurry preparation and storage temperature must not higher than 60 DEG C.
B, coating are produced: ground floor is applied slurry and be coated on PET release film, the second layer is applied slurry again and be coated on ground floor, after ultra-violet curing, third layer is applied slurry and be coated on the second layer after heated-air drying.
C, coating stripping: after folded painting completes after heated-air drying, peel off coating from PET release film.
D, hole formation: through 80 DEG C of water-baths and normal temperature alcohol solvent groove removing soluble pore former, form hole.
E, through 80 DEG C of heated-air dryings, cooling, rolling obtains the homogeneous lithium ion battery separator in aperture.
Embodiment 11
Adopt the method for two stacked paintings to prepare lithium ion battery separator, gross thickness 40 μm, ground floor thickness 30 μm, second layer thickness 10 μm, porosity is 48%, comprises following preparation process:
The composition of slurry R-1 comprises: 1 part of titanate coupling agent (NDZ-201), 39 parts of ethyl acetate, 40 parts of cetomacrogol 1000s (PEG-1000) and 20 parts of nano titanium oxide (nano-TiO
2).
The preparation method of slurry R-1: put into by NDZ-201 in ethyl acetate and PEG-1000 mixed solution, after stirring 5min, adds nano-TiO
2, high-speed stirred 60min obtains slurry R-1.
The composition of slurry R-2 comprises: by 70 parts of epoxy resin (E-31) and 30 parts of Macrogol 600s (PEG-600).The epoxide number of described E-31 is 0.31mol/100g.
The preparation method of slurry R-2: mixed by E-31 and PEG-600, insulated and stirred 120min at 60 DEG C, obtains slurry R-2.
The composition of slurry R-3 comprises: 20 parts of epoxy hardeners (593), 80 parts of PEG400s (PEG-400).Described 593 is amine curing agent.
The preparation method of slurry R-3: put into 593 in PEG-400, stirs 15min, obtains R-3 slurry.
The preparation of ground floor coating slurry: 40 parts of slurry R-1,56 parts of R-2 and 4 part of R-3 are mixed, add appropriate defoamer, stir 30min and can obtain ground floor coating slurry, stand-by, the soluble pore former wherein added accounts for 1.07 times of other total mixture gross masses.
The composition of slurry S-1 comprises: 5 parts of 1-hydroxy-cyclohexyl-phenyl ketones (PI 184), 1 part of silane coupler (KH560), 49 parts of ethyl acetate and 45 parts of polyamide wax powder.Described amide waxe powder average grain diameter is 4 μm, fusing point Tm=145 DEG C.
The preparation method of slurry S-1: be scattered in ethyl acetate by PI 184 and KH560, add polyamide wax powder after stirring 5min, mechanical agitation 30 minutes, obtains slurry S-1.
The composition of slurry S-2 comprises: the epoxy acrylate (6425) of 20 parts of aliphatic urethane acrylates (6185), 10 parts of amine modifications, 25 parts of 4-tert-butylcyclohexyl acrylate (TBCHA), 5 part of third oxidation trimethylolpropane triacrylate (TMP4.5POTA), 40 parts of cetomacrogol 1000s (PEG-1000).
The preparation method of slurry S-2: by 6185,6425, TBCHA, TMP4.5POTA and PEG-1000 mixing, mechanical agitation 60min, obtains slurry S-2.
The preparation of second layer coating slurry: by 70 parts of slurry S-1 and 30 slurry S-2 mix and blends, can obtain second layer coating slurry, stand-by, the soluble pore former wherein added accounts for 0.86 times of other total mixture gross masses.
Slurry preparation and deposit and avoid strong illumination, especially ultraviolet light, slurry preparation and storage temperature must not higher than 60 DEG C.
B, coating are produced: ground floor is applied slurry and be coated on PP release film, the second layer is applied slurry again and be coated on ground floor, after ultra-violet curing, third layer is applied slurry and be coated on the second layer after ultra-violet curing.
C, coating stripping: after folded painting completes after heated-air drying, peel off coating from PP release film.
D, hole formation: through 80 DEG C of water-baths and normal temperature alcohol solvent groove removing soluble pore former, form hole.
E, through 80 DEG C of heated-air dryings, cooling, rolling obtains the homogeneous lithium ion battery separator in aperture.
Comparative example 12-dry method barrier film manufactures
By PP, PE respectively fusion extrusion casting slab, stretched, the film of obtained 10-25 μm, then PE, PP film is carried out hot compound, heat treatment, heat setting process obtain polyalkene diaphragm, porosity 38%, closed pore temperature is 130 DEG C.Adopt stretching drilling, pore size heterogeneity, size is at 10 ~ 10000nm.
Membrane for polymer of the prior art adopts micropore polyolefin barrier diaphragm mostly, based on the polyolefin of polyethylene (PE) and polypropylene (PP).Film thickness is generally at 10 ~ 40 μm, and pore size is at 50 ~ 10000nm, and porosity is at 35%-50%.But the heatproof of polyalkene diaphragm is limited, and fail safe is lower.In addition, drawing process drilling is all adopted in the dry method that prior art is conventional or wet method, pore size is difficult to control, and size cannot be homogeneous, and have certain shrinkage, barrier film end properties cannot be controlled accurately, the excellent rate of finished product is not high, quality uniformity and poor stability, and polyalkene diaphragm is poor to electrolytical compatibility, pick up is low, does not have good wetability.
In addition, prior art has on polyalkene diaphragm, coats inorganic fine particles to improve the thermal endurance of barrier film, improve limitation, and after stretching masking, carry out coating processing, complex procedures, affect diaphragm quality many factors.The interpolation of pore-foaming agent in the proportioning of Raw of the present invention and coating slurry and folded painting is adopted to process, by the size made for control hole footpath of raw material and corresponding pore-foaming agent, without the need to the drilling that stretches, do not produce contraction problem, pore size is controlled, finished product membrane pore size is homogeneous, the excellent rate of finished product barrier film is improved, has good quality uniformity and stability.
Wherein, the polymeric material that two classes are different at least selected by described polymeric material, wherein polymeric material described in a class is fusing point or flow temperature at the thermoplastic of 100-150 DEG C, another kind of described polymeric material be fusing point or flow temperature higher than or be equivalent to described fusing point or flow temperature at the thermoplastic of the thermoplastic of 100-150 DEG C or thermosets.Barrier film needs to possess thermal stability, having the polymeric material of different melting points, guaranteeing that barrier film is when reaching closed pore temperature, barrier film can keep original integrality and certain mechanical property, rupture of membranes does not occur at a lower temperature, good performance isolation both positive and negative polarity prevents the effect of short circuit.The compatibility of barrier film and electrolyte is improved by the selection of raw material.
It should be noted that, in above-described embodiment the selection of pore-foaming agent be according to the raw material selected of coating slurry in conjunction with pore-foaming agent be used for carry out selecting, different pore-foaming agent has different effects, has respectively: 1, be dispersed in coating slurry, adopt heating volatilization after film forming or with water or solvent removing pore-foaming agent, form loose structure, comprise sodium chloride, potassium chloride, calcium chloride, sodium sulphate, sodium carbonate, sodium acid carbonate, boric acid and salt thereof, glucose, sucrose, polyethylene glycol and copolymer thereof and derivative, poly(ethylene oxide) and copolymer thereof and derivative, PPOX and copolymer thereof and derivative, polyvinyl alcohol and derivative thereof, polyvinylpyrrolidone and derivative thereof, polyacrylamide and derivative thereof, polyacrylic acid and salt thereof, polymethylacrylic acid and salt thereof, sodium alginate, Sodium Benzoate, starch, cellulose and its derivates, citric acid and salt thereof, sorbic acid and salt thereof, sorbierite and derivative thereof, aliphatic acid and derivative thereof, fatty alcohol and derivative thereof, organic amine (ammonium) and derivative thereof, organic phosphine (Phosphonium) and derivative, oleic acid and derivative thereof, amino acid and derivative, pentaerythrite and derivative thereof, at least one in glyceride and derivative thereof, 2, solvent pore, pore-foaming agent is that the state of droplet is present in monomer or prepolymer or polymer, by the pore-foaming agent removing in polymer after monomer or prepolymer polymerization, can select benzene, toluene, dimethylbenzene, pentane, hexane, heptane, octane, cyclohexane, cyclohexanone, toluene cyclohexanone, chlorobenzene, dichloro-benzenes, carrene, chloroform, carbon tetrachloride, trichloroethanes, methyl alcohol, ethanol, propyl alcohol, butanols, isopropyl alcohol, isoamyl alcohol, hexanol, ethylene glycol, propylene glycol, butanediol, hexylene glycol, decanediol, succinic acid, adipic acid, decanedioic acid, glycerol, ether, expoxy propane, benzinum, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, acetone, espeleton, methylisobutylketone, butanone, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, triethanolamine, dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide, pyridine, oxolane, formaldehyde, acetaldehyde, dioxane, naphthane, trimethylbenzene, trichloro-benzenes, metacresol, phenol, formic acid, sulfuric acid, benzenediol, '-biphenyl diphenol, paraffin and atoleine, soybean oil and derivative above-mentioned at least one, 3, cross-linking reaction pore: obtain gel by the density controlling to be cross-linked, then by washing dry removing colloidal sol and unreacted monomer, inside just defines microcellular structure.The pore-foaming agent selected has: the compound containing two and above active group (comprising at least one in hydroxyl, ammonia (amine/ammonium) base, ester group, carboxyl, carbonyl, ehter bond, acyl group, NCO, sulfydryl, epoxy radicals, double bond, triple bond, anhydride group group).Another point needs the hole illustrated can be formed by the pore structure of described inorganic particle self, utilizes the pore structure of inorganic powder itself to make barrier film have pore structure, comprises the hole between the hole of material internal and particle and particle.
Below know-why of the present invention is described in conjunction with specific embodiments.These describe just in order to explain principle of the present invention, and can not be interpreted as limiting the scope of the invention by any way.Based on explanation herein, those skilled in the art does not need to pay performing creative labour can associate other embodiment of the present invention, and these modes all will fall within protection scope of the present invention.
Claims (10)
1. a folded painting compound lithium ion battery separator, is characterized in that: it is the porous septum with one or more layers structure be mixed with by one or more coating slurries;
The composition of described porous septum comprises: 30-100 part polymeric material, 0-70 part inorganic particle and surface conditioning agent thereof, 0-50 part bulking agent;
The polymeric material of two classes at least selected by described polymeric material, wherein polymeric material described in a class is fusing point or flow temperature at the thermoplastic of 100-150 DEG C, another kind of described polymeric material be fusing point or flow temperature higher than or be equivalent to described fusing point or flow temperature at the thermoplastic of the thermoplastic of 100-150 DEG C or thermosets.
2. folded painting compound lithium ion battery separator according to claim 1, is characterized in that: described polymeric material is polyethylene and copolymer thereof and derivative, polypropylene and copolymer thereof and derivative, poly-4-methylpentene and copolymer thereof and derivative, polyolefin and copolymer thereof and derivative, polyvinyl alcohol and copolymer thereof and derivative, polyethylene glycol and copolymer thereof and derivative, PPOX and copolymer thereof and derivative, polyacrylamide and copolymer thereof and derivative, polyacrylonitrile and copolymer thereof and derivative, polyvinylpyrrolidone and copolymer thereof and derivative, acrylic acid (ester) resin and derivative thereof, polymethyl methacrylate and copolymer thereof and derivative, methacrylic acid (ester) resin and derivative thereof, aromatic series or semi-aromatic or aliphatic polyester and copolymer thereof and derivative, aromatic series or semi-aromatic or fatty polyamide and copolymer thereof and derivative, aromatic series or semi-aromatic or aliphatic polyether and copolymer thereof and derivative, aromatic series or semi-aromatic or fatty poly-ester carbonate and copolymer thereof and derivative, polystyrene and copolymer thereof and derivative, epoxy resin and derivative thereof, polyurethane and derivative thereof, phenolic resins and derivative thereof, amino resins and derivative thereof, unsaturated polyester (UP) and derivative thereof, organic siliconresin and derivative thereof, Lauxite and derivative thereof, melamine resin and derivative thereof, melmac and derivative thereof, polyphenylene sulfide and derivative thereof, polyimides and derivative thereof, polysulfones and derivative thereof, polyether-ether-ketone and derivative thereof, fluoropolymer and derivative thereof, Petropols and derivative thereof, one or more in cellulose and its derivates,
Described thermoplastic is polyethylene and copolymer thereof and derivative, polypropylene and copolymer thereof and derivative, polyolefin and copolymer thereof and derivative, poly-4-methylpentene copolymer and derivative, polyvinyl alcohol and copolymer thereof and derivative, polyethylene glycol and copolymer thereof and derivative, polyacrylamide and copolymer thereof and derivative, PPOX and copolymer thereof and derivative, polyacrylonitrile copolymer and derivative thereof, polyvinylpyrrolidone and copolymer thereof and derivative, acrylic acid (ester) resin and derivative thereof, methylmethacrylate copolymer and derivative thereof, methacrylic acid (ester) resin and derivative thereof, aromatic series or semi-aromatic or aliphatic polyester and copolymer thereof and derivative, aromatic series or semi-aromatic or fatty polyamide and copolymer thereof and derivative, aromatic series or semi-aromatic or aliphatic polyether and copolymer thereof and derivative, aromatic series or semi-aromatic or fatty poly-ester carbonate and copolymer thereof and derivative, polystyrene copolymer and derivative thereof, polyurethane and derivative thereof, fluoropolymer and derivative thereof, Petropols and derivative thereof, at least one in cellulose and its derivates.
3. folded painting compound lithium ion battery separator according to claim 2, is characterized in that: the composite granule that described inorganic particle is silicon dioxide, aluminium oxide, titanium dioxide, zirconia, zinc oxide, magnesium oxide, tin-antiomony oxide, calcium oxide, tri-iron tetroxide, iron oxide, rare earth, calcium carbonate, barium sulfate, kaolin, imvite, attapulgite, clay, vermiculite, hydroxyapatite, sepiolite, diatomite, mica, graphite oxide, one or more compositions in expanded graphite form or powder mixture.
4. folded painting compound lithium ion battery separator according to claim 1, is characterized in that: described bulking agent is at least one in the polymeric material containing active group, the monomer containing active group or prepolymer, silane coupler, titanate coupling agent, aluminate coupling agent, zirconium ester coupling agent, isocyanates etc.
5. folded painting compound lithium ion battery separator according to claim 4, is characterized in that: described active group comprises at least one in hydroxyl, amino, amido, ammonium, ester group, carboxyl, carbonyl, ehter bond, acyl group, NCO, sulfydryl, epoxy radicals, double bond, triple bond, anhydride group.
6. folded painting compound lithium ion battery separator according to claim 1, it is characterized in that: described inorganic powder surface inorganic agent quality is the 1-500% of inorganic particle quality, described inorganic powder surface inorganic agent is at least one in silane coupler, titanate coupling agent, aluminate coupling agent, zirconium ester coupling agent, isocyanates, the polymeric material with active group, the monomer with active group or prepolymer.
7. the preparation method of the folded painting compound lithium ion battery separator described in production claim 1, is characterized in that: comprise the following steps:
Prepared by a, coating: by 30-100 part polymeric material or monomer or prepolymer, 0-70 part inorganic particle and surface conditioning agent thereof and the mixing of 0-50 part bulking agent, add the soluble pore former of 0 to 17/3 times that accounts for said mixture gross mass again, be mixed together processing and be prepared into coating slurry; The kind of described coating slurry is no less than a kind;
Above-mentioned processing comprises stirring, grinds, adds one or more modes of hankering;
B, coating are produced:
For the folded painting compound lithium ion battery separator of single layer structure, one or more coating methods in release film adopting scraper, scraper, spraying, cylinder transfer or casting are coated with carry out folded painting;
For the folded painting compound lithium ion battery separator of sandwich construction, one or more coating methods in release film adopting scraper, scraper, spraying, cylinder transfer or casting are coated with carry out folded painting ground floor coating slurry, then after drying or solidification being carried out to ground floor, the folded second layer that is coated with applies slurry again, by that analogy;
C, coating stripping: after folded painting completes after drying, coating is peeled off from release film;
D, hole formation: hole formed by the pore structure of described inorganic particle self cross-linking reaction or add soluble pore former by dissolved method, the pore of solvent pore method, adopt heating volatilization or with water or solvent, soluble pore former removing is formed hole, hole is formed by above-mentioned one or more methods formed in method, and described solvent is incompatible with described polymeric material;
E, drying, rolling obtain lithium ion battery separator.
8. the preparation method of folded painting compound lithium ion battery separator according to claim 7, is characterized in that: described soluble pore former is sodium chloride, potassium chloride, calcium chloride, sodium sulphate, sodium carbonate, sodium acid carbonate, boric acid and salt thereof, glucose, sucrose, polyethylene glycol and copolymer thereof and derivative, poly(ethylene oxide) and copolymer thereof and derivative, PPOX and copolymer thereof and derivative, polyvinyl alcohol and derivative thereof, polyvinylpyrrolidone and derivative thereof, polyacrylamide and derivative thereof, polyacrylic acid and salt thereof, polymethylacrylic acid and salt thereof, sodium alginate, Sodium Benzoate, starch, cellulose and its derivates, citric acid and salt thereof, sorbic acid and salt thereof, sorbierite and derivative thereof, aliphatic acid and derivative thereof, fatty alcohol and derivative thereof, organic amine (ammonium) and derivative thereof, organic phosphine (Phosphonium) and derivative, oleic acid and derivative thereof, amino acid and derivative, pentaerythrite and derivative thereof, obtain microcellular structure by dissolved legal system during at least one in glyceride and derivative thereof.
9. the preparation method of folded painting compound lithium ion battery separator according to claim 7, is characterized in that: described soluble pore former is benzene, toluene, dimethylbenzene, pentane, hexane, heptane, octane, cyclohexane, cyclohexanone, toluene cyclohexanone, chlorobenzene, dichloro-benzenes, carrene, chloroform, carbon tetrachloride, trichloroethanes, methyl alcohol, ethanol, propyl alcohol, butanols, isopropyl alcohol, isoamyl alcohol, hexanol, ethylene glycol, propylene glycol, butanediol, hexylene glycol, decanediol, succinic acid, adipic acid, decanedioic acid, glycerol, ether, expoxy propane, benzinum, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, acetone, espeleton, methylisobutylketone, butanone, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, triethanolamine, dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide, pyridine, oxolane, formaldehyde, acetaldehyde, dioxane, naphthane, trimethylbenzene, trichloro-benzenes, metacresol, phenol, formic acid, sulfuric acid, benzenediol, '-biphenyl diphenol, paraffin and atoleine, soybean oil and derivative above-mentioned at least one time be by solvent pore formed microcellular structure.
10. the preparation method of folded painting compound lithium ion battery separator according to claim 7; it is characterized in that: described cross-linking reaction is the reaction that Compound Phase mutual effect containing two and above active group forms cross-linked network; obtain microcellular structure by water or solvent by after the monomer of solubility, colloidal sol removing, described active group comprises at least one in hydroxyl, ammonia (amine/ammonium) base, ester group, carboxyl, carbonyl, ehter bond, acyl group, NCO, sulfydryl, epoxy radicals, double bond, triple bond, anhydride group.
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Effective date of registration: 20190121 Address after: 528000 First and Second Floors of D2 Industrial Building in the Middle Section of Zhixing Road, Xiqiao Science and Technology Industrial Park, Nanhai District, Foshan City, Guangdong Province Patentee after: FOSHAN HEYUN SPECIAL MATERIALS CO., LTD. Address before: 528211 First Floor, D2 Industrial Building, Middle Section of Zhixing Road, Textile Base, Xiqiao Science and Technology Industrial Park, Nanhai District, Foshan City, Guangdong Province Patentee before: Zheng Shaohua |
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