CN105552285B - A kind of ceramic-coated separator and preparation method thereof and the application in lithium ion battery - Google Patents
A kind of ceramic-coated separator and preparation method thereof and the application in lithium ion battery Download PDFInfo
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- CN105552285B CN105552285B CN201511030136.8A CN201511030136A CN105552285B CN 105552285 B CN105552285 B CN 105552285B CN 201511030136 A CN201511030136 A CN 201511030136A CN 105552285 B CN105552285 B CN 105552285B
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- 239000000919 ceramic Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title description 12
- 229910001416 lithium ion Inorganic materials 0.000 title description 12
- 239000012528 membrane Substances 0.000 claims abstract description 82
- 238000000576 coating method Methods 0.000 claims abstract description 41
- 238000005524 ceramic coating Methods 0.000 claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 38
- 239000004743 Polypropylene Substances 0.000 claims abstract description 37
- 239000011248 coating agent Substances 0.000 claims abstract description 36
- 229920000098 polyolefin Polymers 0.000 claims abstract description 31
- 239000011159 matrix material Substances 0.000 claims abstract description 29
- -1 polypropylene Polymers 0.000 claims abstract description 23
- 239000006255 coating slurry Substances 0.000 claims abstract description 13
- 238000012986 modification Methods 0.000 claims abstract description 13
- 230000004048 modification Effects 0.000 claims abstract description 13
- 229920001155 polypropylene Polymers 0.000 claims abstract description 13
- 239000004698 Polyethylene Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 238000007756 gravure coating Methods 0.000 claims description 6
- 230000002045 lasting effect Effects 0.000 claims description 6
- 229920005672 polyolefin resin Polymers 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 238000004804 winding Methods 0.000 claims description 6
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 239000013530 defoamer Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- ANJLMAHUPYCFQY-UHFFFAOYSA-N 4-phenyl-1h-benzimidazole-2-sulfonic acid Chemical class C=12NC(S(=O)(=O)O)=NC2=CC=CC=1C1=CC=CC=C1 ANJLMAHUPYCFQY-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 229920005749 polyurethane resin Polymers 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920005990 polystyrene resin Polymers 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 28
- 239000000463 material Substances 0.000 abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 2
- 229920000573 polyethylene Polymers 0.000 abstract description 2
- 210000004379 membrane Anatomy 0.000 description 66
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- 230000009977 dual effect Effects 0.000 description 4
- 238000011017 operating method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 210000002469 basement membrane Anatomy 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- H01M50/431—Inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Cell Separators (AREA)
Abstract
It is symmetrical five laminate the invention discloses a kind of ceramic-coated separator, including two outermost ceramic coatings, twice the chloridized polyolefin coating of outer layer and the matrix membrane in intermediate layer.The preparation method is that ceramic coating slurry will be made after ceramic particle modification, then chloridized polyolefin coating is coated in drying on matrix membrane and forms chloridized polyolefin coating, finally ceramic coating slurry is coated on the chloridized polyolefin coating of matrix membrane and is dried, that is, ceramic-coated separator is made.The ceramic-coated separator of the present invention carries substantial amounts of polar group due to chlorinated polyolefin hydrocarbon layers‑Cl, the adhesion strength of matrix membrane and ceramic coating can not only be improved, and chloridized polyolefin and polypropylene and polyethylene etc. have similar crystal structure and size, thus there is good bond performance to matrix membrane, so as to cohesive force between raising ceramic coating and base material membrane, play the role of being difficult to coming off, not dry linting.
Description
Technical field
The present invention relates to a kind of membrane of lithium ion battery and preparation method thereof, more particularly to a kind of ceramic diaphragm and its system
Preparation Method and the application in lithium ion battery.
Background technology
Lithium ion battery has the advantages that energy density height, long lifespan, power density are big and small, is widely used in
The portable electric appts such as laptop, digital camera, mobile phone, at the same also large-scale application in electric automobile and large-scale
Energy-storage system.But there are the security risk such as battery short circuit, explosion, on fire in use for lithium-ion-power cell.
One of the critical material of membrane as lithium ion battery, directly affects the security and chemical property of battery.
Now widely used commercialized lithium battery diaphragm is all to utilize PE, PP and other polyolefin and their mixture or common
The characteristics of polymers is process, polyolefin is that crystallinity is high, solvent resistance is strong, surface polarity and surface energy are low, so for one
As coating attachment it is difficult, it is necessary to carry out effort in surface treatment and the aspect of modified paint two.Surface treatment can use flame, electricity
Dizzy and chemical treatment, but since membrane thicknesses are typically only several microns to tens microns, to process for treating surface and equipment requirement
It is high, and must paint at once after handling, it is unfavorable for large-scale production.And there are fusing point for this conventional membrane for polymer
The problems such as low, bad mechanical property, overcharge or thermal contraction can occur for (more than 100 DEG C) and easily by lithium branch when temperature raises
Crystalline substance pierces through, so as to cause the safety problem such as battery short circuit, on fire.Further, since the hydrophobic performance of membrane for polymer itself, causes
Its infiltration and retention to electrolyte is poor, limits the big high rate performance of battery, also have impact on lithium ion battery in electronic vapour
Application on car.
By the way that its heat endurance, shrinkage and absorbency can be effectively improved in conventional membrane surface coated ceramic coating,
So as to fulfill the purpose for improving battery security and chemical property.At present, the ceramic coating slurry of document and patent report
Mainly there is two major class of solvent-borne type and water-based system.Solvent-borne type cost of sizing agent is high, and in drying course organic solvent volatilization meeting
Cause environmental pollution.But for water-based system, since traditional lithium ion battery separator is mostly polyolefins non-polar high polymer
Material, it is poor there are wettability with water-based ceramic slurry, cause ceramic particle skewness and ceramic layer and membrane on membrane
The binding agent that matrix is only relied in ceramic coating bonds, and adhesion strength is weaker, thus the membrane is in processing, coiling electrode group and electricity
In the charge and discharge process in pond, it is also easy to produce coating granule and comes off, so as to causes the performance heterogeneities such as the resistance to thermal and electrochemical of membrane, very
To influence battery performance uniformity.This is not mainly due to having polar group, surface energy low in vistanex, for general coating
Be attached with certain difficulty.In addition, the ceramic particle used in ceramic coating is generally nanometer oxide particle, it is easily rolled into a ball
It is poly-, it is difficult in ceramic slurry dispersed.In order to improve the dispersiveness of ceramic powder and improve the cementitiousness of ceramics and membrane,
Chinese patent CN103956450 carries out " grafting " to ceramic particle using anion surfactant and is modified, but the grafting process
Condition it is harsh and cumbersome time-consuming, it is necessary to nitrogen atmosphere protection and be heated to reflux 4~6 it is small when, and be grafted after the completion of, need to centrifuge
Grafting ceramics simultaneously wash repeatedly.Chinese patent CN104466060A disclose a kind of multi-layer co-extruded coating prepare lithium ion it is compound every
The method of film, which is coated with two kinds of functional coatings, although thermal safety and the imbibition of membrane can be improved to a certain extent
Property and environmentally friendly, but do not solve fundamentally water-based bacteria cellulose slurry and aqueous ceramic slurry with it is nonpolar
Polyalkene diaphragm between wettability it is poor, coating is difficult to be evenly distributed, and two kinds of functional coatings and polyalkene diaphragm poor adhesive force
The problems such as.Therefore research fundamentally solve polyolefins basement membrane is Nian Jie with ceramic coating loosely, ceramic coating be easily peeled off it is de-
The problems such as falling has been that situation is compeled.
The content of the invention
The technical problem to be solved in the present invention is overcome the deficiencies of the prior art and provide one kind to improve existing water-based body
Be slurry coating ceramic coating easily come off, the ceramic-coated separator of dusting problems and preparation method thereof.
In order to solve the above technical problems, technical solution proposed by the present invention is：
A kind of ceramic-coated separator, is symmetrical five laminate, including two outermost ceramic coatings, outer layer twice
Chloridized polyolefin coating and intermediate layer matrix membrane.
Above-mentioned ceramic-coated separator, it is preferred that the chloridized polyolefin coating is chlorinated polypropylene coating, chlorination gathers
The mixed coating of vinyl coating or chlorinated polypropylene and haloflex；Described matrix membrane is polyolefins membrane.
Above-mentioned ceramic-coated separator, it is preferred that the polyolefins membrane is PP membranes, PE membranes or PP/PE are compound
Membrane.
Above-mentioned ceramic-coated separator, it is preferred that the thickness of the ceramic coating is 3~15 μm.
The present invention provides a kind of preparation method of above-mentioned ceramic-coated separator, comprises the following steps：
1) 20~40 parts by weight Nano Ceramic Particles are taken, are added in the ethanol and hydrochloric acid solution of pH=3~5, stirring 1~2
Hour, it is then centrifuged for separating, obtains the Nano Ceramic Particles of modification；
2) take 10~20 parts by weight water-soluble resins to add in deionized water to stir evenly, then sequentially add 0.8~1.5
Parts per weight dispersing agent and 0.3~1.0 parts by weight defoamer, it is lasting to stir, add the nanometer of the modification of step 1) preparation
Ceramic particle, ball milling, filtering, vacuum defoamation, obtain ceramic coating slurry；
3) spraying precoating is carried out to matrix membrane using the water-soluble chlorinated polyolefin resin solution of 3wt%~15wt%
Processing, it is then dry at a temperature of 35 DEG C~55 DEG C, form one layer of chloridized polyolefin coating on two surfaces of matrix membrane；
4) chlorination of the ceramic coating slurry coated in matrix membrane prepared by step 2) is gathered using micro- gravure coating technique
On alkene coating, it is 3 μm~15 μm to control thickness of ceramic coating；Coating obtains described after 40 DEG C~55 DEG C drying, winding
Ceramic-coated separator finished product.
Above-mentioned preparation method, it is preferred that in the step 1), Nano Ceramic Particles are nano aluminium oxide, nano-silica
Change one or several kinds of mixtures in titanium, nano zircite, nano-sized iron oxide and nano zine oxide；Nano Ceramic Particles
Particle size is 0.3~1.0 μm.
Above-mentioned preparation method, it is preferred that in the step 2), water-soluble resin is aqueous polyacrylamide acid resin, water-based
One in maleic anhydride modified polyacrylic resin, waterborne polyurethane resin, water-based polystyrene resin and aqueous epoxy resins
Kind is several；Dispersant for amino-organosilanes, carboxyl organosilan, polyvalent alcohol, phenylbenzimidazole sulfonic acid salt, alkyl quaternary ammonium salts,
One or several kinds in alkyl quaternary alkylphosphonium salt and its derivative；Defoamer for polysiloxanes, acrylate copolymer, titanate esters,
One or several kinds in rare-earth coupling agent, soap salt.
Above-mentioned preparation method, it is preferred that in the step 2), when the time of ball milling is 0.5~2 small, the speed of ball milling
For 800~4000rpm/min.
Above-mentioned preparation method, it is preferred that in the step 3), the coated weight of water-soluble chlorinated polyolefin resin solution is
5~50g of water-soluble chlorinated polyolefin resin solution is coated on every square metre of matrix membrane.
The present invention also provides a kind of application of above-mentioned ceramic-coated separator in lithium ion battery.
Compared with prior art, the advantage of the invention is that：
1) ceramic-coated separator of the invention by ceramic coating/chlorinated polyolefin hydrocarbon layers/matrix membrane/chlorinated polyolefin hydrocarbon layers/
The five-layer structure of ceramic coating composition, wherein chlorinated polyolefin hydrocarbon layers play the role of one " forming a connecting link ", since chlorination gathers
Olefin layer carries substantial amounts of polar group-Cl, can not only improve the adhesion strength of base material membrane and ceramic coating, but also chlorination
Polyolefin and polypropylene and polyethylene etc. have similar crystal structure and size, thus have good cohere to base material membrane
Performance, so that cohesive force between raising ceramic coating and base material membrane, plays the role of being difficult to coming off, not dry linting.
2) ceramic-coated separator of the invention by ceramic coating/chlorinated polyolefin hydrocarbon layers/matrix membrane/chlorinated polyolefin hydrocarbon layers/
The five-layer structure of ceramic coating composition, wherein chlorinated polyolefin hydrocarbon layers are due to that containing Cl elements, can play certain fire retardation.
3) Nano Ceramic Particles are carried on a small quantity just through weak acid pretreatment rear surface compensation in preparation method of the invention
Electric charge, due to the like charges effect of repelling each other, thus can effectively prevent Nano Ceramic Particles reunion, playing raising, it is dispersed
Effect.
4) Nano Ceramic Particles are carried on a small quantity by weak acid pretreatment rear surface compensation in the preparation method of the present invention
There is chelating and charge effect between carboxyl, amino and epoxide group in positive charge, with water-soluble resin, can not only promote
Disperseing for modified Nano ceramic particle, also improves the adhesive property of nano ceramic coat.
5) lithium ion battery made of ceramic-coated separator of the invention has extended cycle life, by 200 cycle performances
After test, battery capacity conservation rate is still up to more than 97%.
Brief description of the drawings
Fig. 1 is the structure diagram of the ceramic-coated separator of the present invention.
Fig. 2 is the scanning electron microscopic picture of common PP membranes.
Fig. 3 is the scanning electron microscopic picture of ceramic-coated separator prepared by the embodiment of the present invention 1.
Battery prepared by the ceramic-coated separator and common PP membranes that Fig. 4 is prepared for the embodiment of the present invention 1 is under 3C multiplying powers
Cycle life compare figure.
Marginal data：
1st, ceramic coating；2nd, chloridized polyolefin coating；3rd, matrix membrane.
Embodiment
For the ease of understanding the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face, meticulously describe, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, all technical terms used hereinafter and the normally understood implication of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection domain.
Except there is a special instruction, the various reagents used in the present invention, raw material be can be commercially commodity or
Person can pass through product made from known method.
Embodiment 1：
A kind of ceramic-coated separator, as shown in Figure 1, be symmetrical five laminate, including two outermost ceramics apply
Layer 1, twice the chlorinated polypropylene coating 2 of outer layer and the matrix membrane 3 in intermediate layer；Matrix membrane 3 is PP membranes；Ceramic coating 1
Thickness be 10 μm.
The preparation method of above-mentioned ceramic-coated separator, including operating procedure in detail below：
1) nano alumina particles that 30g particle sizes are 500nm are added to the ethanol and mixed in hydrochloric acid of 150g pH=4
In solution, when stirring 1 is small, it is then centrifuged for separating, obtains the nano alumina particles of modification.
2) the water-soluble maleic anhydride modified polyacrylic resins (solid content 40%) of 20g are taken, 50g deionized waters is added and stirs
Mix uniformly, then sequentially add 0.8g amino-organosilanes and 0.5g acrylate copolymers, lasting stirring, then adds 30g
By the nano alumina particles of modification, using 2000rpm/min speed ball milling 2 it is small when, then filtering, vacuum defoamation,
It can obtain ceramic coating slurry.
3) surface spraying precoating processing is carried out to PP membranes using the water-soluble chlorinated polypropylene solution of 10wt%
(dosage is that the membrane coated weight of unit square metre area is 15g), is then dried with 40 DEG C of hot-airs.
4) the ceramic coating slurry dual coating that step 2) is prepared is being passed through by step 3) place using micro- gravure coating technique
On the PP membranes managed, it is 10 μm to control thickness of ceramic coating；After coating 55 DEG C drying, winding, you can obtain ceramic coating every
Film finished product.
The material property of ceramic-coated separator manufactured in the present embodiment and common PP membranes is tested, as a result such as table 1.From table 1
In as can be seen that ceramic-coated separator manufactured in the present embodiment heat resistance and being folded without breaking intensity obviously higher than common PP
Membrane, its horizontal and vertical hot audience ratings of baking 30min is respectively less than 5% at a high temperature of 140 DEG C, illustrates the ceramic-coated separator
With good high high-temp stability.From table 1 it can also be seen that ceramic-coated separator manufactured in the present embodiment air permeability and
Internal resistance is consistent substantially with common PP membranes.
The comparison of 1 ceramic-coated separator of table and the material property of common PP membranes
Common PP membranes and ceramic-coated separator manufactured in the present embodiment are done into scanning electron microscope respectively, its stereoscan photograph
Respectively as shown in Fig. 2 and Fig. 3.As can be seen that the table of ceramic-coated separator manufactured in the present embodiment from the comparison of Fig. 2 and Fig. 3
Face is smooth, and nano alumina particles are evenly distributed, and is formd between nano alumina particles than more uniform gap structure, carries
The high heat-shrinkable of ceramic-coated separator.
Positive plate is prepared by positive electrode of LiFePO4, Delanium is that negative material prepares negative plate, respectively will this
Ceramic-coated separator and common PP membranes prepared by embodiment is wound with positive and negative electrode pole piece, is added electrolyte, is assembled into
Lithium ion battery, and its relevant chemical property is tested respectively.As shown in figure 4, it is ceramics manufactured in the present embodiment
The cycle life of battery prepared by coated separator and common PP membranes under 3C multiplying powers compares figure.Figure 4, it is seen that passing through
Cross after 100 circulations, battery capacity circulation conservation rate and the ceramic-coated separator system of the present embodiment prepared by common PP membranes
Standby battery capacity circulation conservation rate is not much different.But after 200 circulations, the battery prepared with common PP membranes holds
The conservation rate of amount is 88.74%；And the present embodiment membrane coated separator prepare battery through capacity retention ratio still 97% with
On.It can be seen from the above that nano aluminium oxide ceramic-coated separator manufactured in the present embodiment will to the guarantor's fluidity and wettability of electrolyte
Higher than common PP membranes.In addition, the chlorinated polypropylene coating of ceramic-coated separator manufactured in the present embodiment and answering for nano ceramics
Conjunction sandwich construction improves the interface stability between membrane and positive and negative electrode, so as to improve the cycle life of battery.
Embodiment 2：
A kind of ceramic-coated separator, as shown in Figure 1, be symmetrical five laminate, including two outermost ceramics apply
Layer 1, twice the chlorinated polyethylene ene coatings 2 of outer layer and the matrix membrane 3 in intermediate layer；Matrix membrane 3 is PE membranes；Ceramic coating 1
Thickness be 5 μm.
The preparation method of above-mentioned ceramic-coated separator, including operating procedure in detail below：
1) nano alumina particles that 35g particle sizes are 500nm are taken to add the ethanol and mixed in hydrochloric acid of 140g pH=3
In solution, when stirring 1.5 is small, it is then centrifuged for separating, obtains the nano alumina particles of modification.
2) 20g water-soluble polypropylenes acid resin (solid content 35%) is taken, 35g deionized waters is added and stirs evenly, then
1.2g polyvalent alcohols and 0.8g polysiloxanes are sequentially added, lasting stirring, then adds nano oxygens of the 35g Jing Guo modification
Change aluminum particulate, using 3000rpm/min speed ball milling 2 it is small when, then filtering, vacuum defoamation, you can obtain ceramic coating slurry.
3) surface spraying precoating processing is carried out to PP membranes using the water-soluble chlorinated polyethylene resin solution of 8wt%
(dosage is that the membrane coated weight of unit square metre area is 20g), is then dried with 35 DEG C of hot-airs.
4) the slurry dual coating that step 2) is prepared is being passed through by the processed PP of step 3) using micro- gravure coating technique
On membrane, it is 5 μm to control coating layer thickness；50 DEG C of drying, winding after coating, you can obtain ceramic-coated separator finished product.
The ceramic-coated separator of the present embodiment is assembled into battery together with battery positive and negative plate, measures its service life, is passed through
After 200 cycle performance tests, the conservation rate of battery capacity is still up to 97%.
Embodiment 3：
A kind of ceramic-coated separator, as shown in Figure 1, be symmetrical five laminate, including two outermost ceramics apply
Layer 1, twice the chlorinated polypropylene coating 2 of outer layer and the matrix membrane 3 in intermediate layer；Matrix membrane 3 is PP membranes；Ceramic coating 1
Thickness be 8 μm.
The preparation method of above-mentioned ceramic-coated separator, including operating procedure in detail below：
1) the nano oxidized iron particle that 40g particle sizes are 400nm is added to the ethanol and mixed in hydrochloric acid of 160g pH=3
In solution, when stirring 2 is small, it is then centrifuged for separating, obtains the nano oxidized iron particle of modification.
2) 30g water soluble polyurethane resins (solid content 35%) are taken, 30g deionized waters is added and stirs evenly, Ran Houyi
Secondary addition 1.2g alkyl quaternary ammonium salts and 0.8g rare-earth coupling agents, lasting stirring, then adds nano oxygens of the 40g Jing Guo modification
Change iron particle, using 2500rpm/min speed ball milling 1 it is small when, then filter, vacuum defoamation, you can obtain ceramic coating slurry.
3) surface spraying precoating processing is carried out to PP membranes using the water-soluble chlorinated polypropylene solution of 9wt%
(dosage is that the membrane coated weight of unit square metre area is 18g), is then dried with 40 DEG C of hot-airs.
4) the ceramic coating slurry dual coating that step 2) is prepared is being passed through by step 3) place using micro- gravure coating technique
On the polypropylene diaphragm managed, it is 8 μm to control coating layer thickness；55 DEG C of drying, winding after coating, you can obtain ceramic-coated separator
Finished product.
The ceramic-coated separator of the present embodiment is assembled into battery together with battery positive and negative plate, measures its service life, is passed through
After 200 cycle performance tests, the conservation rate of battery capacity is still up to 97%.
Embodiment 4：
A kind of ceramic-coated separator, as shown in Figure 1, be symmetrical five laminate, including two outermost ceramics apply
Layer 1, twice the chlorinated polyethylene ene coatings 2 of outer layer and the matrix membrane 3 in intermediate layer；Matrix membrane 3 is PE membranes；Ceramic coating 1
Thickness be 10 μm.
The preparation method of above-mentioned ceramic-coated separator, including operating procedure in detail below：
1) nano zirconia particles that 25g particle sizes are 800nm are added to the ethanol and mixed in hydrochloric acid of 100g pH=4
In solution, when stirring 2 is small, it is then centrifuged for separating, obtains the nano zirconia particles of modification.
2) 30g water-soluble polies styrene resin (solid content 35%) is taken, 45g deionized waters is added and stirs evenly, then
1.0g phenylbenzimidazole sulfonic acids salt and 0.8g soap salt are sequentially added, lasting stirring, then adds nano zircites of the 25g Jing Guo modification
Particle, using 3000rpm/min speed ball milling 1 it is small when, then filtering, vacuum defoamation, you can obtain ceramic coating slurry.
3) PE membranes are carried out at surface spraying precoating using the water-soluble chlorinated polyethylene resin solution of 10wt%
Manage (dosage is that the membrane coated weight of unit square metre area is 15g), then dried with 40 DEG C of hot-airs.
4) the slurry dual coating that step 2) is prepared is being passed through by the processed PE of step 3) using micro- gravure coating technique
On membrane, it is 10 μm to control coating layer thickness；45 DEG C of heat drying, windings after coating, you can obtain ceramic-coated separator finished product.
The ceramic-coated separator of the present embodiment is assembled into battery together with battery positive and negative plate, measures its service life, is passed through
After 200 cycle performance tests, the conservation rate of battery capacity is still up to 97%.
Claims (6)
1. a kind of preparation method of ceramic-coated separator, it is characterised in that the ceramic-coated separator is symmetrical five shapes layer by layer
Structure, including two outermost ceramic coatings, twice the chloridized polyolefin coating of outer layer and the matrix membrane in intermediate layer；Described
Chloridized polyolefin coating applies for the mixing of chlorinated polypropylene coating, chlorinated polyethylene ene coatings or chlorinated polypropylene and haloflex
Layer；Described matrix membrane is polyolefins membrane；The preparation method of the ceramic-coated separator comprises the following steps：
1) 20~40 parts by weight Nano Ceramic Particles are taken, are added in the ethanol and hydrochloric acid solution of pH=3~5, when stirring 1~2 is small,
It is then centrifuged for separating, obtains the Nano Ceramic Particles of modification；
2) take 10~20 parts by weight water-soluble resins to add in deionized water to stir evenly, then sequentially add 0.8~1.5 weight
Part dispersant and 0.3~1.0 parts by weight defoamer, it is lasting to stir, add the nano ceramics of the modification of step 1) preparation
Particle, ball milling, filtering, vacuum defoamation, obtain ceramic coating slurry；The water-soluble resin is aqueous polyacrylamide acid resin, water
In property maleic anhydride modified polyacrylic resin, waterborne polyurethane resin, water-based polystyrene resin and aqueous epoxy resins
It is one or several kinds of；
3) matrix membrane is carried out at spraying precoating using the water-soluble chlorinated polyolefin resin solution of 3wt%~15wt%
Reason, it is then dry at a temperature of 35 DEG C~55 DEG C, one layer of chloridized polyolefin coating is respectively formed on two surfaces of matrix membrane；
4) the ceramic coating slurry for being prepared step 2) using micro- gravure coating technique is coated in the chloridized polyolefin of matrix membrane
On coating, it is 3 μm~15 μm to control thickness of ceramic coating；Coating obtains the ceramics after 40 DEG C~55 DEG C drying, winding
Coated separator.
2. preparation method as claimed in claim 1, it is characterised in that the polyolefins membrane for PP membranes, PE membranes or
PP/PE composite diaphragms.
3. preparation method as claimed in claim 1, it is characterised in that in the step 1), Nano Ceramic Particles are nano oxygen
Change one or several kinds of mixtures in aluminium, nano-titanium dioxide, nano zircite, nano-sized iron oxide and nano zine oxide；
The particle size of Nano Ceramic Particles is 0.3~1.0 μm.
4. preparation method as claimed in claim 1, it is characterised in that in the step 2), dispersant for amino-organosilanes,
One or several kinds in carboxyl organosilan, polyvalent alcohol, phenylbenzimidazole sulfonic acid salt, alkyl quaternary ammonium salts, alkyl quaternary alkylphosphonium salt；Defoamer
For the one or several kinds in polysiloxanes, acrylate copolymer, titanate esters, rare-earth coupling agent, soap salt.
5. preparation method as claimed in claim 1, it is characterised in that in the step 2), the time of ball milling is small for 0.5~2
When, the speed of ball milling is 800~4000rpm/min.
6. such as claim 3~5 any one of them preparation method, it is characterised in that in the step 3), water-soluble chlorination gathers
5~50g of the water-soluble chlorinated polyolefin resin solution of coating on the matrix membrane that the coated weight of olefin resin solution is every square metre.
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| CN106519742B (en) * | 2016-11-01 | 2018-11-16 | 旭成（福建）科技股份有限公司 | A kind of fire resistant ceramic modified slurry and the lithium ion battery separator for coating the slurry |
| CN109301136A (en) * | 2018-11-28 | 2019-02-01 | 河北金力新能源科技股份有限公司 | A kind of heat-resisting lithium battery diaphragm and preparation method thereof |
| CN109671894B (en) * | 2018-11-29 | 2021-06-15 | 明基材料（芜湖）有限公司 | Low water content separator and method for producing same |
| CN110086898B (en) * | 2019-03-14 | 2021-04-23 | 潮州三环（集团）股份有限公司 | Mobile terminal component and preparation method thereof |
| CN111725467A (en) * | 2019-03-19 | 2020-09-29 | 河北金力新能源科技股份有限公司 | Lithium-sulfur battery composite coating diaphragm and preparation method and application thereof |
| CN110289381B (en) * | 2019-05-09 | 2021-09-28 | 湖南文理学院 | Diaphragm for lithium ion battery and preparation method |
| CN111205707B (en) * | 2020-01-10 | 2022-04-08 | 武汉中兴创新材料技术有限公司 | Aqueous polyvinylidene fluoride coating slurry, battery diaphragm and preparation method |
| CN112142453B (en) * | 2020-09-29 | 2022-08-16 | 江苏厚生新能源科技有限公司 | Low-moisture alumina ceramic diaphragm, powder, slurry, preparation process and lithium battery |
| CN116073073B (en) * | 2023-03-09 | 2023-06-13 | 合肥长阳新材料科技有限公司 | High-liquid-absorption lithium battery diaphragm and preparation method thereof |
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| CN101872853B (en) * | 2010-04-21 | 2013-03-20 | 东莞新能源电子科技有限公司 | Polymer lithium ion secondary battery and isolating membrane thereof |
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