CN109585757A - A kind of lithium ion battery separator slurry and preparation method thereof and lithium ion battery separator - Google Patents
A kind of lithium ion battery separator slurry and preparation method thereof and lithium ion battery separator Download PDFInfo
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- CN109585757A CN109585757A CN201811203537.2A CN201811203537A CN109585757A CN 109585757 A CN109585757 A CN 109585757A CN 201811203537 A CN201811203537 A CN 201811203537A CN 109585757 A CN109585757 A CN 109585757A
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- ion battery
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- 239000002002 slurry Substances 0.000 title claims abstract description 108
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 73
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000007613 slurry method Methods 0.000 title abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 51
- 239000000945 filler Substances 0.000 claims abstract description 41
- 238000000576 coating method Methods 0.000 claims abstract description 33
- 239000011248 coating agent Substances 0.000 claims abstract description 32
- 239000011230 binding agent Substances 0.000 claims abstract description 30
- 239000002562 thickening agent Substances 0.000 claims abstract description 30
- 238000004078 waterproofing Methods 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims description 24
- 210000002469 basement membrane Anatomy 0.000 claims description 21
- -1 obtains mixed serum Substances 0.000 claims description 12
- 229910001593 boehmite Inorganic materials 0.000 claims description 9
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 8
- 210000002966 serum Anatomy 0.000 claims description 7
- 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 description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 8
- 238000001035 drying Methods 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 14
- 239000004698 Polyethylene Substances 0.000 description 13
- 229920000573 polyethylene Polymers 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000004925 Acrylic resin Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 229920000178 Acrylic resin Polymers 0.000 description 9
- 239000011247 coating layer Substances 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000005457 optimization Methods 0.000 description 6
- 238000000643 oven drying Methods 0.000 description 6
- 238000007761 roller coating Methods 0.000 description 6
- 102220043159 rs587780996 Human genes 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000009938 salting Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000005213 imbibition Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229920006321 anionic cellulose Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 210000004379 membrane Anatomy 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910006636 γ-AlOOH Inorganic materials 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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- 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)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The present invention provides a kind of lithium ion battery separator slurry and preparation method thereof and lithium ion battery separator, it is in terms of 100 parts by the total weight of the slurry, the slurry includes at least the following component of parts by weight: 30 parts~35 parts fillers, 5.5 parts~6.5 parts binders, 0.5 part~1.5 parts waterproofing agents, 0.5 part~1.2 parts thickeners and 55 parts~65 parts water.Being coated the prepared membrane surface coating of drying to slurry provided by the present invention has the characteristics that Ultralow Water, the diaphragm is applied to lithium ion battery, the chemical property of lithium ion battery can be promoted, such as capacity, internal resistance, cycle performance etc., also diaphragm has greatly been saved for client and toasted cost, achieve the purpose that the two-win for reducing cost and high-quality performance.
Description
Technical field
The present invention relates to lithium ion battery preparation technical field, more particularly to a kind of lithium ion battery separator slurry and its
Preparation method and lithium ion battery separator.
Background technique
With the fast development of this several years electric car industries, to lithium ion battery, especially power lithium-ion battery
Quality requirements are obviously improved, and the lithium electricity processing procedure moisture control level requirement having a significant effect to battery performance is tighter
Lattice.Inside lithium ion cell is a more complicated chemical system, the reaction process and result of these chemical systems all with water
Divide closely related.And the out of control or roughening control of moisture, lead to the exceeded presence of moisture in battery, can not only lead to electrolyte lithium
The decomposition of salt, and film forming and stability generation baneful influence to positive and negative pole material, lead to the electrochemistry of lithium ion battery
Energy, such as capacity, internal resistance, cycle performance and product characteristic can all generate more apparent deterioration.Common lithium-ion electricity at this stage
Pond diaphragm moisture value~1200ppm, the moisture value are far from satisfying customer demand.
Lithium ion battery separator Moisture high UCL will lead to battery capacity and become smaller, and discharge time shortens, and internal resistance increases, circulation
Phenomena such as capacity attenuation, cell expansion, because diaphragm is a kind of porous plastic film, the lithium ion battery being commercialized at present
Diaphragm is based on polyethylene (PE), polypropylene (PP) monofilm and polyethylene/polypropylene/polyethylene trilamellar membrane, water imbibition
Very big, so, influence of such as many factors to performance of lithium ion battery, it would be desirable to stringent control lithium ion battery every
The moisture value of film reduces client's diaphragm and toasts cost to promote the chemical property of lithium ion battery.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of lithium ion battery separator slurries
And preparation method thereof and lithium ion battery separator, for solving the problems, such as lithium ion battery separator Moisture high UCL in the prior art.
In order to achieve the above objects and other related objects, the present invention provides a kind of lithium ion battery separator slurry, with described
The total weight of slurry is 100 parts of meters, and the slurry includes at least the following component of parts by weight:
30 parts~35 parts fillers, 5.5 parts~6.5 parts binders, 0.5 part~1.5 parts waterproofing agents, 0.5 part~1.2 parts increasings
Thick dose and 55 parts~65 parts water.
A kind of scheme of optimization as lithium ion battery separator slurry of the present invention, the filler include nano oxidized
One of aluminium, boehmite or a variety of combinations, between 0.6-1.0 μm, purity is greater than the median of the filler
99.99%.
A kind of scheme of optimization as lithium ion battery separator slurry of the present invention, the binder include water soluble acrylic acid
Resin solution, the viscosity of the binder is between 25mPas~55mPas, and pH value is between 5.5~7.5, admittedly contain
Amount is between 38wt%~42wt%, and molecular weight is between 300,000~600,000.
A kind of scheme of optimization as lithium ion battery separator slurry of the present invention, the waterproofing agent include organosilicon coupling
Agent solution.
A kind of scheme of optimization as lithium ion battery separator slurry of the present invention, the thickener include carboxymethyl cellulose
Plain sodium, seed activity object content is greater than or equal to 99.5% in the thickener, and sodium content takes between 6.0%~9.0%
Dai Du is between 0.80~0.95, and partial size is between 160nm~190nm.
A kind of scheme of optimization as lithium ion battery separator slurry of the present invention, the solid content of the slurry is between 34-
Between 38%.
The present invention also provides a kind of preparation method of the lithium ion battery separator slurry of any of the above-described scheme, the preparation sides
Method includes at least:
1) waterproofing agent is uniformly mixed with water, obtains the agent solution that blocks water；
2) filler, the thickener are dispersed in the agent solution that blocks water；
3) binder is added, stirs up to the slurry.
The present invention separately provides a kind of preparation method of the lithium ion battery separator slurry of any of the above-described scheme, the preparation side
Method includes at least:
1) waterproofing agent is uniformly mixed with water, obtains the agent solution that blocks water, in the agent solution that blocks water described in addition
Filler is ground to obtain slurries；
2) thickener is uniformly mixed with water, obtains thickener soln；
3) thickener soln is mixed with the slurries, obtains mixed serum, be added in the mixed serum viscous
Agent is tied, is stirred up to the slurry.
The present invention provides a kind of lithium ion battery separator again, and the lithium ion battery separator includes at least basement membrane and is formed in
Coating at least one surface of the basement membrane, the coating are starched by any one of claim 1~6 lithium ion battery separator
Material is coated on the basement membrane and dries and is made.
A kind of scheme of optimization as lithium ion battery separator of the present invention, the coating layer thickness between 1 μm~4 μm it
Between.
As described above, lithium ion battery separator slurry of the invention and preparation method thereof and lithium ion battery separator, have
Below the utility model has the advantages that
1, in slurry of the invention, by adding waterproofing agent, surface is carried out to the filler and binder and is modified, so that
The filler and binder oleophilic drainage, so that filler and binder be hindered to absorb water.
2, in slurry of the invention, by adding organo-silicon coupling agent solution (silane coupling agent), to filler and bonding
It is modified that agent carries out surface, wherein and silane can replace the water of filler and adhesive surface, coat filler particle and binder,
So that R base (active function groups for having affinity or respond with polymer molecule) is outwardly, filler and binder become parent
It is oily, hydrophobic, facilitate the wetting of filler and basement membrane, so that filler and binder be hindered to absorb water.
3, have the characteristics that Ultralow Water, diaphragm are applied to lithium using diaphragm coating made by slurry provided by the invention
In ion battery, the chemical property of lithium ion battery can be promoted, client's diaphragm is reduced and toasts cost.
Detailed description of the invention
Fig. 1 is the preparation method flow diagram of lithium ion battery separator slurry of the present invention.
Fig. 2 is another flow diagram of preparation method of lithium ion battery separator slurry of the present invention.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
Please refer to attached drawing.It should be noted that only the invention is illustrated in a schematic way for diagram provided in the present embodiment
Basic conception, only shown in schema then with related component in the present invention rather than component count, shape when according to actual implementation
Shape and size are drawn, when actual implementation kenel, quantity and the ratio of each component can arbitrarily change for one kind, and its component cloth
Office's kenel may also be increasingly complex.
The present invention provides a kind of lithium ion battery separator slurry, is the slurry in terms of 100 parts by the total weight of the slurry
Including at least the following component of parts by weight:
30 parts~35 parts fillers, 5.5 parts~6.5 parts binders, 0.5 part~1.5 parts waterproofing agents, 0.5 part~1.2 parts increasings
Thick dose and 55 parts~65 parts water.
As an example, the filler includes one of nano aluminium oxide, boehmite or a variety of combinations.Wherein, institute
Stating nano aluminium oxide is α-Al2O3, the boehmite is γ-AlOOH (hydrated alumina).The filler primarily can be used for
Increase coating layer thickness, and improves substrate high temperature resistant, high security, low self-discharge rate, has extended cycle life, high magnification, good leaching
The performances such as lubricant nature.
Further, for the D50 (median) of the filler between 0.6-1.0 μm, purity is greater than 99.99%,
Apparent density is about 0.48g/cm3, tap density is about 1.10g/cm3.Wherein, apparent density be substance under prescribed conditions from
By full of measured bulk density after volumetric standard, i.e., the quality of unit volume when substance is loosely filled；Tap density refers to
The quality of substance in container unit volume measured after jolt ramming under prescribed conditions.
The parameters adjusting of each component has very the moisture value of the subsequent lithium ion battery separator prepared in the slurry
Big influence, wherein the parts by weight of the filler select within the scope of 30 parts~35 parts, and preferably 32.5 parts.In formula,
Filler ratio increases, it may appear that dispersion is bad, can also affect greatly to coating procedure, uneven thickness occurs in coated product
One, it dries and does not do, loses powder, bonding phenomena such as insecure, so that the quality of coated product is influenced, but, ratio is too low, to the resistance to height of basement membrane
The performance improvements such as temperature are unobvious.
As an example, the binder includes water-based acrylic resin solution, the viscosity of the binder is between 25mPa
Between s~55mPas, pH value between 5.5~7.5, solid content between 38wt%~42wt%, molecular weight between
Between 300000~600,000.
Preferably, the binder is water-based acrylic resin aqueous solution, and the molecular weight of acrylic resin is 30-60 ten thousand.
In slurry provided herein, binder, which is mainly used for filler, bond/adhere to substrate.
The accounting of the binder in the slurry is also very crucial, and content of binder is excessively very few to will affect coated product
Physicochemical property, the parts by weight of the binder select within the scope of 5.5 parts~6.5 parts, preferably 5.7 parts.Additive amount is excessive
Meeting influences the physicochemical property of coated product, the too small meeting of additive amount is so that ceramic particle so that binder particle enters substrate gap
It is deteriorated with the adhesion property of substrate, the phenomenon that loses powder or peel occurs.
In slurry provided herein, the waterproofing agent be mainly used for increasing each component dispersing uniformity in water and
Hinder each component water imbibition.As an example, the waterproofing agent includes organo-silicon coupling agent solution.The organo-silicon coupling agent is also named
Silane coupling agent can preferably improve the dispersion performance of ceramic slurry, the ginseng of silane coupling agent as excellent adhesive accelerant
Number index is as follows: specific gravity (temperature is at 25 DEG C): 0.94, flash-point: and 98 DEG C, refractive index (temperature is at 25 DEG C): 1.42, boiling point:
217 DEG C, molecular weight: 221.4g/mol, the capped area of minimum: 353m2/g。
Silane coupling agent is a kind of low molecule organo-silicon compound with special construction, general formula RSiX3, R in formula
The active function groups for having affinity or respond with polymer molecule are represented, X represents the siloxy that can be hydrolyzed.In water system ring
In border, filler and adhesive surface easily adsorb one layer of water, add silane coupling agent, can be located in advance to filler and binder
Reason (surface modified), silane coupling agent can replace the water of filler and adhesive surface, coated particle (filler and binder),
So that R base is outwardly, become oleophylic, hydrophobic, and be easy to the wetting of filler and basement membrane, plays and hinder filler and binder water suction
Effect.
The content of the waterproofing agent needs in suitable range, because, the waterproofing agent too high levels, dispersion effect meeting
Increase, but the moisture of coated product will not play the role of reduction, play reaction instead, and coating procedure can generate compared with
More foams seriously affect coated product quality；But the agent content that blocks water is very few, and cannot disperse each component well, makes pottery
Phenomena such as porcelain stream of slurry levelling is bad, blocks feeding system.In the present invention, the parts by weight of the waterproofing agent are selected at 0.5 part
Within the scope of~1.5 parts, preferably 1.0 parts.
As an example, the thickener includes sodium carboxymethylcellulose, seed activity object content is greater than in the thickener
Or be equal to 99.5%, sodium content between 6.0%~9.0%, degree of substitution between 0.80~0.95, partial size between
Between 160nm~190nm.The sodium carboxymethylcellulose category anionic cellulose ethers, are generally dissolved easily in cold water or hot water,
Glue can be formed, is formed by solution as neutral or alkalescence.In slurry provided herein, the thickener is main
It is to enable the uniform and stable distribution of each component with then adjusting slurry viscosity.
It is all had certain problems it should be noted that thickener additive amount is excessively very few, the parts by weight of the thickener
Number selection is within the scope of 0.5 part~1.2 parts, and preferably 0.8 part.Amount can excessively make the viscosity of slurry increase, and mobility is deteriorated, and apply
Cloth effect is deteriorated；Measure very few, then (filler in ceramic slurry, i.e. nano aluminium oxide, boehmite of the ceramic powder in slurry
Deng) there is precipitating/lamination, cause coated product performance unstable, in turn result in the internal resistance of cell differ greatly, cycle performance
It is deteriorated
As an example, the solid content of the slurry is between 34-38%.The present invention selects water as solvent, main to use
In providing so that each component environment evenly dispersed in water system.
The present invention also provides a kind of preparation methods of above-mentioned lithium ion battery separator slurry, as shown in Figure 1, the preparation side
Method includes at least:
Step S11 is first carried out, the waterproofing agent is uniformly mixed with water, obtains the agent solution that blocks water；
Then step S12 is executed, the filler, the thickener are dispersed in the agent solution that blocks water；
Then step S13 is executed, the binder is added, is stirred up to the slurry.
The present invention also provides a kind of preparation methods of above-mentioned lithium ion battery separator slurry, as shown in Fig. 2, the preparation side
Method includes at least:
Step S21 is first carried out, the waterproofing agent is uniformly mixed with water, the agent solution that blocks water is obtained, in the waterproofing agent
The filler is added in solution, grinds to obtain slurries；
Then step S22 is executed, the thickener is uniformly mixed with water, obtains thickener soln；
Then step S23 is executed, the thickener soln is mixed with the slurries, obtains mixed serum, described mixed
It closes in slurries and binder is added, stir up to the slurry.
Both the above preparation method can prepare lithium ion battery separator slurry of the invention, using coated by the slurry
The coating of formation has the characteristics that Ultralow Water.
The present invention also provides a kind of lithium ion battery separator, the lithium ion battery separator includes at least basement membrane and is formed in
Coating at least one surface of the basement membrane, the above-mentioned lithium ion battery separator slurry of coating are coated on the basement membrane simultaneously
Drying is made.
As an example, the basement membrane can use polyethylene substrate, polyethylene substrate (PE) average molecular weight is 140
Between ten thousand g/mol-170, ten thousand g/mol.The basement membrane with a thickness of 11 μm -13 μm, can be in the side or two sides of the basement membrane
Surface coating slurry forms the coating, one-sided coatings with a thickness of 1 μm -4 μm.
As an example, the temperature of the drying is 85-90 DEG C.
It can be seen that Ultralow Water coated product is gone for, as long as being not to reduce solvent or reduce aqueous be divided into
The parts by weight divided.The present invention joined waterproofing agent in the slurry, and be used cooperatively each component, to filler, glue
Agent, waterproofing agent, thickener are tied with suitable matching parameter, so that the moisture of coated product substantially reduces.
Further illustrate with reference to embodiments lithium ion battery separator slurry of the invention and preparation method thereof and lithium from
Sub- battery diaphragm.
Embodiment 1
A) 1.0 parts of waterproofing agent (model: KBE-903, supplier: the three limited public affairs of nation's new material science and technology of Dongguan City is weighed
Department), it is added in 60.0 parts of pure water, mixing speed 20HZ, stirring takes 0.8 part to being completely dispersed uniformly as the agent solution that blocks water
Thickener (model: BL-20, supplier: Ashland) is added in the agent solution that blocks water, stirring to transparence liquid, then takes 32.5 parts
Boehmite (D50=0.80 μm of filler) is added in solution, is made into slurries A, slurries A is ground (grinder parameter:
650R/min, 0.25MPa), after the slurries after grinding are cooled to room temperature, 5.7 parts are weighed, molecular weight is 30-60 ten thousand, solid content is
(model: LIB-S101, supplier: the auspicious high molecular material share in Shanghai three is limited for the water-based acrylic resin aqueous solution of 38-42%
Company) it is added in the slurries after dispersing, it is adequately stirred, after stirring evenly, such finished product slurry just prepares completion；
Finished product slurry is coated in polyethylene based film using dimple roller coating method and (supplied by the basement membrane for b) taking 12 μ m thicks
Answer quotient: Co., Ltd., Kpic, similarly hereinafter) unilateral side, coating speed 95m/min carried out into baking oven using Pyatyi baking oven
Drying, oven temperatures at different levels are respectively 85 DEG C, and 88 DEG C, 90 DEG C, 88 DEG C, 85 DEG C, after dry, ultralow moisture content single side can be obtained
The lithium ion battery separator of coating, the lithium ion battery separator of the coating with a thickness of 12 μm, the coating layer thickness of side is 3
μm, overall thickness is 15 μm.
Embodiment 2
A) 1.5 parts of waterproofing agent (model: KBE-903, supplier: the three limited public affairs of nation's new material science and technology of Dongguan City is weighed
Department), it is added in 59.5 parts of pure water, mixing speed 20HZ, stirring takes 0.8 part to being completely dispersed uniformly as the agent solution that blocks water
Thickener (model: BL-20, supplier: Ashland) is added in the agent solution that blocks water, stirring to transparence liquid, then takes 32.5 parts
Boehmite (D50=0.80 μm of filler) is added in solution, is made into slurries A, slurries A is ground (grinder parameter:
650R/min, 0.25MPa), after the slurries after grinding are cooled to room temperature, 5.7 parts are weighed, molecular weight is 30-60 ten thousand, solid content is
(model: LIB-S101, supplier: the auspicious high molecular material share in Shanghai three is limited for the water-based acrylic resin aqueous solution of 38-42%
Company) it is added in the slurries after dispersing, it is adequately stirred, after stirring evenly, such finished product slurry just prepares completion；
Finished product slurry is coated in polyethylene based film using dimple roller coating method and (supplied by the basement membrane for b) taking 12 μ m thicks
Answer quotient: Co., Ltd., Kpic, similarly hereinafter) unilateral side, coating speed 95m/min carried out into baking oven using Pyatyi baking oven
Drying, oven temperatures at different levels are respectively 85 DEG C, and 88 DEG C, 90 DEG C, 88 DEG C, 85 DEG C, after dry, Ultralow Water single side can be obtained
The lithium ion battery separator of coating, the lithium ion battery separator of the coating with a thickness of 12 μm, the coating layer thickness of side is 3
μm, overall thickness is 15 μm.
Embodiment 3
A) 0.5 part of waterproofing agent (model: KBE-903, supplier: the three limited public affairs of nation's new material science and technology of Dongguan City is weighed
Department), it is added in 60.5 parts of pure water, mixing speed 20HZ, stirring takes 0.8 part to being completely dispersed uniformly as the agent solution that blocks water
Thickener (model: BL-20, supplier: Ashland) is added in the agent solution that blocks water, stirring to transparence liquid, then takes 32.5 parts
Boehmite (D50=0.80 μm of filler) is added in solution, is made into slurries A, slurries A is ground (grinder parameter:
650R/min, 0.25MPa), after the slurries after grinding are cooled to room temperature, 5.7 parts are weighed, molecular weight is 30-60 ten thousand, solid content is
(model: LIB-S101, supplier: the auspicious high molecular material share in Shanghai three is limited for the water-based acrylic resin aqueous solution of 38-42%
Company) it is added in the slurries after dispersing, it is adequately stirred, after stirring evenly, such finished product slurry just prepares completion；
Finished product slurry is coated in polyethylene based film using dimple roller coating method and (supplied by the basement membrane for b) taking 12 μ m thicks
Answer quotient: Co., Ltd., Kpic, similarly hereinafter) unilateral side, coating speed 95m/min carried out into baking oven using Pyatyi baking oven
Drying, oven temperatures at different levels are respectively 85 DEG C, and 88 DEG C, 90 DEG C, 88 DEG C, 85 DEG C, after dry, Ultralow Water single side can be obtained
The lithium ion battery separator of coating, the lithium ion battery separator of the coating with a thickness of 12 μm, the coating layer thickness of side is 3
μm, overall thickness is 15 μm.
Embodiment 4
A) 1.0 parts of waterproofing agent (model: KBE-903, supplier: the three limited public affairs of nation's new material science and technology of Dongguan City is weighed
Department), it is added in 42 parts of pure water and stirs to being completely dispersed uniformly as the agent solution that blocks water, take (the filling of 32.5 parts of boehmite powders
D50=0.80 μm of object) it is added in the agent solution that blocks water, it is ground (grinder parameter: 650R/min, 0.25MPa), it is cold after grinding
But to after room temperature, it is made into slurries B, 0.8 part of thickener (model: BL-20, supplier: Ashland) is taken to be added to 18 parts of pure water
In, stirring to transparence liquid is added in the slurries B after grinding, obtains mixed serum C after mixing evenly, weigh 5.7 parts,
Molecular weight is 30-60 ten thousand, water-based acrylic resin aqueous solution that solid content is 38-42% (model: LIB-S101, supplier: on
Hai Sanrui high molecular material limited liability company) it is added in mixed serum C, it is adequately stirred, after stirring evenly, in this way
Finished product slurry just prepares completion；
Finished product slurry is coated in polyethylene based film using dimple roller coating method and (supplied by the basement membrane for b) taking 12 μ m thicks
Answer quotient: Co., Ltd., Kpic, similarly hereinafter) unilateral side, coating speed 95m/min carried out into baking oven using Pyatyi baking oven
Drying, oven temperatures at different levels are respectively 85 DEG C, and 88 DEG C, 90 DEG C, 88 DEG C, 85 DEG C, after dry, Ultralow Water single side can be obtained
The lithium ion battery separator of coating, the lithium ion battery separator of the coating with a thickness of 12 μm, the coating layer thickness of side is 3
μm, overall thickness is 15 μm.
Comparative example 1
A) 1.0 parts of conventional dispersant (ammonium polyacrylate salting liquid, model: PROX B03, supplier: Guangzhou are weighed
This Tu Yuan Chemical Co., Ltd.), it is added in 60.0 parts of pure water, mixing speed 20HZ, stirring is uniformly point to being completely dispersed
Dispersion liquid takes 0.8 part of thickener (model: BL-20, supplier: Ashland) to be added in dispersion liquid, stirring to transparence liquid, then
It takes 32.5 parts of boehmites (D50=0.80 μm of filler) to be added in solution, is made into slurries A, slurries A is ground into (grinder
Parameter: 650R/min, 0.25MPa), after the slurries after grinding are cooled to room temperature, 5.7 parts are weighed, molecular weight is 30-60 ten thousand, admittedly
Content is the water-based acrylic resin aqueous solution (model: LIB-S101, supplier: the auspicious high molecular material stock in Shanghai three of 38-42%
Part Co., Ltd) it is added in the slurries after dispersing, it is adequately stirred, after stirring evenly, such finished product slurry is just prepared
It completes；
Finished product slurry is coated in polyethylene based film using dimple roller coating method and (supplied by the basement membrane for b) taking 12 μ m thicks
Answer quotient: Co., Ltd., Kpic, similarly hereinafter) unilateral side, coating speed 95m/min carried out into baking oven using Pyatyi baking oven
Drying, oven temperatures at different levels are respectively 85 DEG C, and 88 DEG C, 90 DEG C, 88 DEG C, 85 DEG C, after dry, the lithium of single side coating can be obtained
Ion battery diaphragm, the lithium ion battery separator of the coating with a thickness of 12 μm, the coating layer thickness of side is 3 μm, total thickness
Degree is 15 μm.
Comparative example 2
A) 1.0 parts of conventional dispersant (ammonium polyacrylate salting liquid, model: PROX B03, supplier: Guangzhou are weighed
This Tu Yuan Chemical Co., Ltd.), it is added in 42 parts of pure water and stirs to being completely dispersed uniformly as dispersion liquid, take 32.5 parts of vigorous nurses
Stone powder (D50=0.80 μm of filler) is added in solution, is made into slurries B, slurries B is ground (grinder parameter:
650R/min, 0.25MPa), after the slurries after grinding are cooled to room temperature after being cooled to room temperature, take 0.8 part of thickener (model: BL-
20, supplier: Ashland) it is added in 18 parts of pure water, stirring to transparence liquid, in the slurries B after being added to grinding, stir
Slurries C is obtained after mixing uniformly, weighs 5.7 parts, the water-based acrylic resin water that molecular weight is 30-60 ten thousand, solid content is 38-42%
Solution (model: LIB-S101, supplier: the auspicious high molecular material limited liability company in Shanghai three) is added in slurries C, is carried out abundant
Stirring, after stirring evenly, such finished product slurry just prepares completion；
Finished product slurry is coated in polyethylene based film using dimple roller coating method and (supplied by the basement membrane for b) taking 12 μ m thicks
Answer quotient: Co., Ltd., Kpic, similarly hereinafter) unilateral side, coating speed 95m/min carried out into baking oven using Pyatyi baking oven
Drying, oven temperatures at different levels are respectively 85 DEG C, and 88 DEG C, 90 DEG C, 88 DEG C, 85 DEG C, after dry, the lithium of single side coating can be obtained
Ion battery diaphragm, the lithium ion battery separator of the coating with a thickness of 12 μm, the coating layer thickness of side is 3 μm, total thickness
Degree is 15 μm.
The lithium ion battery isolation film properties that above the embodiment of the present invention and comparative example coat are tested, data are shown in
The following table 1:
Table 1
It can be seen that the embodiment of the present invention from the data in upper table 1 to compare with comparative example, the unit coating of coated film
Surface density and thermal contraction data all relatively, but in terms of coated film moisture value, show notable difference.Silane of the present invention is even
The use for joining agent waterproofing agent much improves made using common ammonium polyacrylate salting liquid (cationic) in the prior art
The performance of standby coated film makes it be more in line with our daily production applications, meets customer need.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (10)
1. a kind of lithium ion battery separator slurry, which is characterized in that by the total weight of the slurry be 100 parts in terms of, the slurry
Including at least the following component of parts by weight:
30 parts~35 parts fillers, 5.5 parts~6.5 parts binders, 0.5 part~1.5 parts waterproofing agents, 0.5 part~1.2 parts thickeners
And 55 parts~65 parts water.
2. lithium ion battery separator slurry according to claim 1, it is characterised in that: the filler includes nano oxidized
One of aluminium, boehmite or a variety of combinations, for the median of the filler between 0.6 μm~1.0 μm, purity is big
In 99.99%.
3. lithium ion battery separator slurry according to claim 1, it is characterised in that: the binder includes aqueous acrylamide
Acid resin solution, the viscosity of the binder between 25mPas~55mPas, pH value between 5.5~7.5, Gu
Content is between 38wt%~42wt%, and molecular weight is between 300,000~600,000.
4. lithium ion battery separator slurry according to claim 1, it is characterised in that: the waterproofing agent includes organosilicon idol
Join agent solution.
5. lithium ion battery separator slurry according to claim 1, it is characterised in that: the thickener includes carboxymethyl fibre
Tie up plain sodium, seed activity object content is greater than or equal to 99.5% in the thickener, sodium content between 6.0%~9.0%,
Degree of substitution is between 0.80~0.95, and partial size is between 160nm~190nm.
6. lithium ion battery separator slurry according to claim 1, it is characterised in that: the solid content of the slurry between
Between 34%~38%.
7. a kind of preparation method of lithium ion battery separator slurry as described in any one of claims 1 to 6, which is characterized in that
The preparation method includes at least:
1) waterproofing agent is uniformly mixed with water, obtains the agent solution that blocks water；
2) filler, the thickener are dispersed in the agent solution that blocks water；
3) binder is added, stirs up to the slurry.
8. a kind of preparation method of lithium ion battery separator slurry as described in any one of claims 1 to 6, which is characterized in that
The preparation method includes at least:
1) waterproofing agent is uniformly mixed with water, obtains the agent solution that blocks water, the filling is added in the agent solution that blocks water
Object is ground to obtain slurries；
2) thickener is uniformly mixed with water, obtains thickener soln；
3) thickener soln is mixed with the slurries, obtains mixed serum, binder is added in the mixed serum,
It stirs up to the slurry.
9. a kind of lithium ion battery separator, which is characterized in that the lithium ion battery separator includes at least basement membrane and is formed in institute
The coating at least one surface of basement membrane is stated, the coating is by any one of the claim 1~6 lithium ion battery separator slurry
It is coated on the basement membrane and dries and be made.
10. lithium ion battery separator according to claim 9, it is characterised in that: the thickness of the coating is between 1 μm~4 μ
Between m.
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