CN107403898A - A kind of lithium ion battery aqueous ceramic slurry and its composite diaphragm preparation method - Google Patents
A kind of lithium ion battery aqueous ceramic slurry and its composite diaphragm preparation method Download PDFInfo
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- CN107403898A CN107403898A CN201710579998.9A CN201710579998A CN107403898A CN 107403898 A CN107403898 A CN 107403898A CN 201710579998 A CN201710579998 A CN 201710579998A CN 107403898 A CN107403898 A CN 107403898A
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- lithium ion
- ion battery
- ceramic slurry
- aqueous ceramic
- aqueous
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- 239000000919 ceramic Substances 0.000 title claims abstract description 66
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 45
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000002002 slurry Substances 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 239000010954 inorganic particle Substances 0.000 claims abstract description 9
- 239000007767 bonding agent Substances 0.000 claims abstract description 6
- 230000004888 barrier function Effects 0.000 claims description 34
- -1 polytetrafluoroethylene Polymers 0.000 claims description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 210000002469 basement membrane Anatomy 0.000 claims description 13
- 239000004743 Polypropylene Substances 0.000 claims description 11
- 210000004379 membrane Anatomy 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 229920001155 polypropylene Polymers 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011247 coating layer Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 230000035699 permeability Effects 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 claims description 5
- IQXJCCZJOIKIAD-UHFFFAOYSA-N 1-(2-methoxyethoxy)hexadecane Chemical compound CCCCCCCCCCCCCCCCOCCOC IQXJCCZJOIKIAD-UHFFFAOYSA-N 0.000 claims description 4
- IEQAICDLOKRSRL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-dodecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO IEQAICDLOKRSRL-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 4
- 229950009789 cetomacrogol 1000 Drugs 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 229960003511 macrogol Drugs 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 229920000459 Nitrile rubber Polymers 0.000 claims description 2
- 239000004677 Nylon Substances 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920003081 Povidone K 30 Polymers 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 claims description 2
- UDHMTPILEWBIQI-UHFFFAOYSA-N butyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(=O)OCCCC)=CC=CC2=C1 UDHMTPILEWBIQI-UHFFFAOYSA-N 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 claims 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- SNRUBQQJIBEYMU-NJFSPNSNSA-N dodecane Chemical group CCCCCCCCCCC[14CH3] SNRUBQQJIBEYMU-NJFSPNSNSA-N 0.000 claims 1
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 229920002239 polyacrylonitrile Polymers 0.000 claims 1
- 229940051841 polyoxyethylene ether Drugs 0.000 claims 1
- 229920000056 polyoxyethylene ether Polymers 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 4
- 238000009736 wetting Methods 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZSCSWNQWTJCZMH-UHFFFAOYSA-N OP(O)(O)=O.CC(C)CCCCCO Chemical compound OP(O)(O)=O.CC(C)CCCCCO ZSCSWNQWTJCZMH-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- PRTVVLKKLCSOAR-UHFFFAOYSA-N [O].OCCO Chemical compound [O].OCCO PRTVVLKKLCSOAR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VCWJPGQFVGJLQJ-UHFFFAOYSA-N methyl octadecanoate;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCCC(=O)OC VCWJPGQFVGJLQJ-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The invention provides a kind of lithium ion battery aqueous ceramic slurry and its composite diaphragm preparation method；The aqueous ceramic slurry is made up of inorganic particle, bonding agent, dispersant, auxiliary agent and deionized water, and present invention also offers the preparation method of the aqueous ceramic composite diaphragm；For oiliness ceramic coated lithium ion battery separator, composite diaphragm disclosed by the invention has good wetting property, heat resistance and adhesive property, coated inorganic diameter of particle is uniform, it is effectively improved the security performance of battery, and environment will not be polluted, have a good application prospect.
Description
Technical field
The invention belongs to cell art, and in particular to a kind of lithium ion battery with aqueous ceramic slurry and its it is compound every
Membrane preparation method.
Background technology
Lithium ion battery is since commercialization, due to operating voltage is high, energy density is high, service life is long, puts certainly
The features such as electric rate is low and green, is widely used in electronic product and electric automobiles.In addition environmental pollution and energy shortage
The problems such as aggravation, in recent years country increase Technique Popularizing and nursery finance to lithium ion battery.
With the large-scale application of lithium ion battery, its safety problem also increasingly highlights.Barrier film is as lithium battery product
One of critical component, it produces and used is paid much attention in field of new materials by country.Barrier film mainly passes through dry method at present
Technique and wet processing are produced.But exist in aperture and uniformity, porosity, heat endurance, puncture resistant etc. certain
Defect, especially seem awkward in terms of applied to high performance lithium ion battery.High performance lithium ion battery requires that barrier film should
There is more preferable heat endurance, higher porosity and intensity.However, the barrier film properties of industrialization at present are not
Can very well take into account, pursue high-energy-density and during high-power charging and discharging capabilities, it is necessary to reduce the thickness of barrier film and improve every
The porosity of film, to reduce the internal resistance of battery.But this will certainly be reduced every the property such as film strength, heat endurance and puncture resistant
Can, the security of lithium ion battery also can drastically decline.Therefore, the same of membrane properties need to improved by developing new diaphragm material
When, lift the security performance of lithium ion battery.
In order to improve the security of battery, domestic and international R＆D institution and manufacturer think to be made pottery on polyalkene diaphragm
Porcelain coating is a kind of more feasible approach.In general, Ceramic Composite barrier film mainly has three big features：(1) barrier film is lifted
Thermal dimensional stability, strengthen the high temperature safety of battery；(2) lifted barrier film wetting characteristics, strengthen barrier film lyophily ability and
Liquid-keeping property, extend the service life of battery；(3) modulate micropore uniformity, improve hot-spot the problem of, while strengthen every
The punctured resistance of film.
The content of the invention
The present invention is in order to overcome the above-mentioned deficiencies of the prior art, there is provided a kind of lithium ion battery aqueous ceramic slurry.
The aqueous ceramic slurry is made up of inorganic particle, bonding agent, dispersant, auxiliary agent and deionized water, and present invention also offers the water
The preparation method of property Ceramic Composite barrier film.It is disclosed by the invention compound for oiliness ceramic coated lithium ion battery separator
Barrier film has good wetting property, heat resistance and adhesive property, and coated inorganic diameter of particle is uniform, is effectively improved electricity
The security performance in pond, and environment will not be polluted, have a good application prospect.
Specifically, the invention provides a kind of lithium ion battery aqueous ceramic slurry, by mass percentage, by 15-
40% inorganic particle, 0.5-5% bonding agent, 0.2-5% dispersant, 0.1-1% auxiliary agent and 50-80% deionization
Water is made.
Inorganic particle described above be boehmite, aluminum oxide, magnesium hydroxide, silica, aluminium hydroxide, titanium dioxide,
One or more combination in zirconium dioxide.
Bonding agent described above is Kynoar, polytetrafluoroethylene (PTFE), fluorubber, nitrile rubber, butadiene rubber, polypropylene
Nitrile, ethylene-vinyl alcohol copolymer, ethylene propylene diene rubber, polyurethane, polyacrylic acid, polyamide, polyvinyl second
In ether, polyimides, butadiene-styrene rubber, propyl benzene rubber, polymethyl methacrylate, polyvinyl acetate, polyvinyl alcohol, polyurethane
One or more combination.
Dispersant described above is polyethylene glycol 200, polyethylene glycol 400, Macrogol 600, cetomacrogol 1000, poly-
Ethylene glycol 2000, Macrogol 6000, PEG20000, PEG 20000, polyethylene glycol 50000, polyvinyl pyrrole
Alkanone K15, PVP K30, polyvinylpyrrolidone k40, polyvinylpyrrolidone K60, polyvinylpyrrolidone
One or more combination in K80, polyvinylpyrrolidone k90.
Auxiliary agent described above is neopelex, fatty alcohol-ether sodium sulfate, sodium butylnaphthalenesulfonate, isooctanol phosphoric acid
It is ester, methyl stearate sodium sulfonate of ethoxylated, Brij30, polyoxyethylene polyoxypropylene pentaerythrite ether, poly-
One or more combination in oxygen Ethylene Glycol ether, polyoxyethylene polyoxy propyl alcohol amidogen ether.
Present invention also offers a kind of preparation method of lithium ion battery Ceramic Composite barrier film, comprise the following steps：
(1) preparation of aqueous ceramic slurry：A) inorganic particle, dispersant and deionized water are added into ball by mass percentage
Ground 1 hour in grinding machine, drum's speed of rotation is set as 2000-4000rpm, obtains dispersion liquid I；B) dispersion liquid I is poured into and divided at a high speed
Dissipate in machine, and add aqueous binders and auxiliary agent, jitter time 2h, speed setting 4000- by mass percentage
6000rpm, vacuum defoamation 12-36h, and filtered in 600 mesh stainless steel mesh, obtain aqueous ceramic slurry；
(2) aqueous ceramic slurry is coated uniformly on micropore basal membrane side using coating machine, lithium ion battery is obtained after drying
Barrier film, 2-6 μm of coating layer thickness.
Further：A kind of preparation method of lithium ion battery Ceramic Composite barrier film, comprises the following steps：
(1) preparation of aqueous ceramic slurry：A) inorganic particle, dispersant and deionized water are added into ball by mass percentage
Ground 1 hour in grinding machine, drum's speed of rotation is set as 2950rpm, obtains dispersion liquid I；B) dispersion liquid I is poured into high speed dispersor
In, and aqueous binders and auxiliary agent, jitter time 2h, speed setting 5000rpm, vacuum defoamation are added by mass percentage
24h, and filtered in 600 mesh stainless steel mesh, obtain aqueous ceramic slurry；
(2) aqueous ceramic slurry is coated uniformly on micropore basal membrane side using coating machine, lithium ion battery is obtained after drying
Barrier film, 2-6 μm of coating layer thickness.
Micropore basal membrane described above is polypropylene microporous basement membrane, polyethylene micropore basement membrane, polypropylene, polyethylene/polypropylene
One kind in three layers of composite microporous basement membrane, cellulose micropore basal membrane, nylon micro porous basement membrane, non-woven fabrics, basement membrane thickness are 5-20 μm,
Air permeability values 100-300s/100ml.
Beneficial effects of the present invention are：
Compared with prior art, lithium ion battery Ceramic Composite barrier film provided by the invention has the following advantages that imitates with technology
Fruit：
(1) slurry prepared is stable, not free settling；
(2) ceramic coating uniform particle sizes, peel strength is high, not dry linting, even if still keeping higher bonding in the electrolytic solution
Power；
(3) thermal dimensional stability of composite diaphragm is obviously improved, and strengthens the high temperature safety of battery.
Brief description of the drawings：
Lithium ion battery Ceramic Composite barrier film coating SEM made from Fig. 1 embodiment of the present invention 2 schemes.
Embodiment
In order to deepen the understanding of the present invention, the present invention is specifically described below by embodiment and accompanying drawing.Having must
Will it is pointed out here that be the present embodiment be served only for invention be described further, it is impossible to be interpreted as the limit to the scope of the present invention
System, if the person skilled in the art in the field makes some nonessential improvement and tune according to the invention described above content to the present invention
It is whole, still fall within the scope of the present invention.
Embodiment 1：The preparation of lithium ion battery Ceramic Composite barrier film
Aqueous ceramic stock quality percentage formula is：
Aqueous ceramic slurry preparation process is：A) by 15% boehmite, 0.2% polyethylene glycol 200 and 79.9% deionization
Water is added in ball mill, speed setting 2950rpm, is ground 1 hour, is obtained dispersion liquid I；B) dispersion liquid I is poured into scattered at a high speed
In machine, and add 4.8% Kynoar and 0.1% neopelex, speed setting 5000rpm.After scattered 2h,
Vacuum defoamation 24h, and filtered in 600 mesh stainless steel mesh, obtain aqueous ceramic slurry；
The preparation process of lithium ion battery Ceramic Composite barrier film is：Aqueous ceramic slurry is coated uniformly on using coating machine
The polyethylene micropore basement membrane side that thickness is 5 μm, air permeability is 100s/100ml, the lithium ion battery of ceramic coated is obtained after drying
Barrier film, 3 μm of coating layer thickness.
Embodiment 2：The preparation of lithium ion battery Ceramic Composite barrier film
Aqueous ceramic percent slurry formula is：
| Formula | Mass percent |
| Aluminum oxide (average grain diameter 400nm) | 40% |
| Cetomacrogol 1000 | 4% |
| Butadiene-styrene rubber | 5% |
| Brij30 | 1% |
| Deionized water | 50% |
Aqueous ceramic slurry preparation process is：A) 40% aluminum oxide, 4% cetomacrogol 1000 and 50% deionized water are added
Enter in ball mill, speed setting 2950rpm, grind 1 hour, obtain dispersion liquid I；B) dispersion liquid I is poured into high speed dispersor,
And add 5% butadiene-styrene rubber and 1% Brij30, speed setting 5000rpm.After scattered 2h, vacuum defoamation
24h, and filtered in 600 mesh stainless steel mesh, obtain aqueous ceramic slurry；
The preparation process of lithium ion battery Ceramic Composite barrier film is：Aqueous ceramic slurry is coated uniformly on using coating machine
The polypropylene, polyethylene that thickness is 16 μm, air permeability is 230s/polypropylene microporous basement membrane side, ceramic coated is obtained after drying
Lithium ion battery separator, 2 μm of coating layer thickness.
Embodiment 3：The preparation of lithium ion battery Ceramic Composite barrier film
Aqueous ceramic percent slurry formula is：
| Formula | Mass percent |
| Silica (average grain diameter 400nm) | 20% |
| Polyvinylpyrrolidone K15 | 5% |
| Polymethyl methacrylate | 0.5% |
| Polyoxyethylene glycerol ether | 0.5% |
| Deionized water | 74% |
Aqueous ceramic slurry preparation process is：A) by 20% silica, polyvinylpyrrolidone K15 and 74% deionization
Water is added in ball mill, speed setting 2950rpm, is ground 1 hour, is obtained dispersion liquid I；B) dispersion liquid I is poured into scattered at a high speed
In machine, and add 0.5% polymethyl methacrylate and 0.5% polyoxyethylene glycerol ether, speed setting 5000rpm.It is scattered
After 2h, vacuum defoamation 24h, and filtered in 600 mesh stainless steel mesh, obtain aqueous ceramic slurry；
The preparation process of lithium ion battery Ceramic Composite barrier film is：Aqueous ceramic slurry is coated uniformly on using coating machine
The polypropylene microporous basement membrane side that thickness is 20 μm, air permeability is 300s/100ml, the lithium-ion electric of ceramic coated is obtained after drying
Pond barrier film, 4 μm of coating layer thickness.
The preparation of the lithium ion battery Ceramic Composite barrier film of embodiment 4
Aqueous ceramic percent slurry formula is：
| Formula | Mass percent |
| Magnesium hydroxide (average grain diameter 400nm) | 18% |
| PEG20000 | 1% |
| Polyurethane | 0.5% |
| Aliphatic acid ether sodium sulfate | 0.5% |
| Deionized water | 80% |
Aqueous ceramic slurry preparation process is：A) 18% magnesium hydroxide, PEG20000 and 80% deionized water are added
Enter in ball mill, speed setting 2950rpm, grind 1 hour, obtain dispersion liquid I；B) dispersion liquid I is poured into high speed dispersor,
And add 0.5% polyurethane and 0.5% aliphatic acid ether sodium sulfate, speed setting 5000rpm.After scattered 2h, vacuum defoamation
24h, and filtered in 600 mesh stainless steel mesh, obtain aqueous ceramic slurry；
The preparation process of lithium ion battery Ceramic Composite barrier film is：Aqueous ceramic slurry is coated uniformly on using coating machine
The polyethylene micropore basement membrane side that thickness is 12 μm, air permeability is 170s/100ml, the lithium-ion electric of ceramic coated is obtained after drying
Pond barrier film, 6 μm of coating layer thickness.
Comparative example 1
Comparative example chooses knob rice tri- layers of composite lithium ion cell barrier films of NM-H16PP/PE/PP.
Embodiment 5：Test result
Test meeting barrier film and comparative example 1 made from embodiment 1-4, as a result such as table 1：
Above-mentioned test data shows：Lithium ion battery Ceramic Composite barrier film produced by the present invention, its thermal dimensional stability is more
It is good, puncture strength increase, and obtained composite diaphragm has good wetting property, heat resistance and an adhesive property, coating without
Machine diameter of particle is uniform, is effectively improved the security performance of battery, and environment will not be polluted, and has good application
Prospect.
Claims (8)
- A kind of 1. lithium ion battery aqueous ceramic slurry, it is characterised in that：By mass percentage, by the inorganic of 15-40% Powder, 0.5-5% bonding agent, 0.2-5% dispersant, 0.1-1% auxiliary agent and 50-80% deionized water are made.
- 2. lithium ion battery according to claim 1 aqueous ceramic slurry, it is characterised in that：The inorganic particle is vigorous One or more combination in nurse stone, aluminum oxide, magnesium hydroxide, silica, aluminium hydroxide, titanium dioxide, zirconium dioxide.
- 3. lithium ion battery according to claim 1 aqueous ceramic slurry, it is characterised in that：Bonding agent described above is Kynoar, polytetrafluoroethylene (PTFE), fluorubber, nitrile rubber, butadiene rubber, polyacrylonitrile, ethylene-vinyl alcohol copolymer, three First EP rubbers, polyurethane, polyacrylic acid, polyamide, polyvinyl ethyl ether, polyimides, butadiene-styrene rubber, propyl benzene One or more combination in rubber, polymethyl methacrylate, polyvinyl acetate, polyvinyl alcohol, polyurethane.
- 4. lithium ion battery according to claim 1 aqueous ceramic slurry, it is characterised in that：The dispersant is poly- second Glycol 200, polyethylene glycol 400, Macrogol 600, cetomacrogol 1000, polyethylene glycol 2000, Macrogol 6000, poly- second two Alcohol 10000, PEG 20000, polyethylene glycol 50000, polyvinylpyrrolidone K15, PVP K30, poly- second Alkene pyrrolidone k40, polyvinylpyrrolidone K60, polyvinylpyrrolidone K80, one kind in polyvinylpyrrolidone k90 or Several combinations.
- 5. lithium ion battery according to claim 1 aqueous ceramic slurry, it is characterised in that：The auxiliary agent is dodecane Base benzene sulfonic acid sodium salt, fatty alcohol-ether sodium sulfate, sodium butylnaphthalenesulfonate, Di-phosphorus pentonide, methyl stearate polyoxyethylene ether sulfonic acid Sodium, Brij30, polyoxyethylene polyoxypropylene pentaerythrite ether, polyoxyethylene glycerol ether, polyoxyethylene polyoxy third One or more combination in alcohol amidogen ether.
- A kind of 6. preparation method of lithium ion battery Ceramic Composite barrier film, it is characterised in that：Comprise the following steps：(1) preparation of aqueous ceramic slurry：A) inorganic particle, dispersant and deionized water are added into ball mill by mass percentage Middle grinding 1 hour, drum's speed of rotation is set as 2000-4000rpm, obtains dispersion liquid I；B) dispersion liquid I is poured into high speed dispersor In, and addition aqueous binders and auxiliary agent by mass percentage, jitter time 2h, speed setting 4000-6000rpm, very Empty deaeration 12-36h, and filtered in 600 mesh stainless steel mesh, obtain aqueous ceramic slurry；(2) aqueous ceramic slurry is coated uniformly on micropore basal membrane side using coating machine, lithium ion battery separator is obtained after drying, 2-6 μm of coating layer thickness.
- 7. the preparation method of lithium ion battery Ceramic Composite barrier film according to claim 6, it is characterised in that：Including as follows Step：(1) preparation of aqueous ceramic slurry：A) inorganic particle, dispersant and deionized water are added into ball mill by mass percentage Middle grinding 1 hour, drum's speed of rotation is set as 2950rpm, obtains dispersion liquid I；B) dispersion liquid I is poured into high speed dispersor, and Addition aqueous binders and auxiliary agent by mass percentage, jitter time 2h, speed setting 5000rpm, vacuum defoamation 24h, And filtered in 600 mesh stainless steel mesh, obtain aqueous ceramic slurry；(2) aqueous ceramic slurry is coated uniformly on micropore basal membrane side using coating machine, lithium ion battery separator is obtained after drying, 2-6 μm of coating layer thickness.
- 8. the preparation method of the lithium ion battery Ceramic Composite barrier film according to claim 6 or 7, it is characterised in that：The micropore basal membrane is that polypropylene microporous basement membrane, polyethylene micropore basement membrane, three layers of polypropylene, polyethylene/polypropylene are compound One kind in micropore basal membrane, cellulose micropore basal membrane, nylon micro porous basement membrane, non-woven fabrics, basement membrane thickness are 5-20 μm, air permeability values 100-300s/100ml。
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| CN108417759A (en) * | 2018-02-06 | 2018-08-17 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of the high wellability diaphragm of cylinder lithium titanate battery |
| CN108807801A (en) * | 2018-08-09 | 2018-11-13 | 珠海恩捷新材料科技有限公司 | A kind of lithium ion battery separator and preparation method thereof |
| CN109167001A (en) * | 2018-08-09 | 2019-01-08 | 上海恩捷新材料科技股份有限公司 | A kind of lithium ion battery separator and preparation method thereof |
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| CN111129397A (en) * | 2019-12-18 | 2020-05-08 | 中国科学院广州能源研究所 | Lithium ion battery diaphragm water-based coating and preparation method thereof |
| CN113497307A (en) * | 2020-04-02 | 2021-10-12 | 时代沃顿科技有限公司 | Method for preparing polyolefin multilayer composite membrane and polyolefin multilayer composite membrane prepared thereby |
| CN111640902A (en) * | 2020-06-08 | 2020-09-08 | 淮北市吉耐新材料科技有限公司 | Preparation process of lithium battery diaphragm |
| CN111668427A (en) * | 2020-06-30 | 2020-09-15 | 沧州明珠锂电隔膜有限公司 | Composite battery diaphragm with excellent temperature resistance and adhesion and preparation method thereof |
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| CN112259911A (en) * | 2020-09-30 | 2021-01-22 | 上海恩捷新材料科技有限公司 | Electrochemical device, novel non-woven fabric ceramic diaphragm and preparation method thereof |
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