CN103915591A - Water-based ceramic coating lithium ion battery diaphragm and processing method thereof - Google Patents
Water-based ceramic coating lithium ion battery diaphragm and processing method thereof Download PDFInfo
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- CN103915591A CN103915591A CN201410140154.0A CN201410140154A CN103915591A CN 103915591 A CN103915591 A CN 103915591A CN 201410140154 A CN201410140154 A CN 201410140154A CN 103915591 A CN103915591 A CN 103915591A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a water-based ceramic coating lithium ion battery diaphragm. The water-based ceramic coating lithium ion battery diaphragm comprises a polyolefin porous membrane and a coating which coats one or both sides of the polyolefin porous membrane, wherein the coating is 2-8 microns in thickness, and consists of 20-60 percent by weight of base material and 40-80 percent of water; the base material comprises 0.1-5 parts by weight of a water-soluble high polymer thickener, 0.1-5 parts of a water-based dispenser, 0.1-10 parts of a water-based adhesive and 80-99.7 parts of boehmite particles. The invention further discloses a processing method of the ceramic coating lithium ion battery diaphragm. The processing method has the advantages of slight wear to mechanical equipment, uniform and consistent coating thickness and contribution to continuous and stable large-scale production.
Description
Technical field
The present invention relates to barrier film, especially relate to that a kind of wearing and tearing to plant equipment are little, coating layer thickness uniformity, be conducive to the water-based ceramic coating lithium ion battery separator of continous-stable large-scale production.
Background technology
Since the lithium ion battery commercialization nineties in 20th century, because it has that energy density is high, operating voltage is high, memory-less effect and the feature such as have extended cycle life be widely used as the power supply of various mobile devices.Along with the large-scale application of lithium ion battery, its safety problem also highlights day by day.
In lithium ion battery, the Main Function of barrier film is that the positive and negative electrode of battery is separated, and prevents that the two poles of the earth from contacting and short circuit, is one of crucial interior layer assembly.The performance of barrier film has determined interfacial structure, the internal resistance etc. of battery, directly affects the characteristic such as capacity, circulation and security performance of battery, and the barrier film of excellent performance has important effect to the combination property that improves lithium ion battery.
At present, the barrier film that lithium ion battery uses is generally polyolefin-based perforated membrane, because this polyolefin-based perforated membrane fusing point is lower than 200 ℃, therefore there is following defect in them: in the time that battery temperature raises because of inside or external factor, this barrier film can shrink or melting, makes the change in volume of barrier film.The contraction of barrier film or melting can cause again the direct contact between positive pole and negative pole, cause battery short circuit, thereby cause the generation of the contingencies such as battery combustion explosion.Therefore,, in order to guarantee the use safety of battery, must provide a kind of barrier film that can not cause because of battery high-temperature thermal contraction and heat fusing.
In order to improve the thermal stability of polyalkene diaphragm, strengthen the security performance of lithium ion battery, a solution of industry is to adhere at the single or double of polyolefin film the porous active layer being made up of inorganic particle and binding agent, forms organic/inorganic composite film.Because inorganic active layer has higher thermal stability, therefore the thermal contraction of whole laminated film is suppressed greatly, inorganic active layer also has higher mechanical strength simultaneously, this also can reduce that Li dendrite or metal fragment, collector burr etc. in battery punctures barrier film and the probability that causes short circuit, thereby has improved the security performance of battery.But, because the current inorganic material of existing use is in the industry mainly alumina ceramic grain, the hardness of aluminium oxide is high, frictional dissipation to plant equipment is large, in process of production because equipment attrition makes the water-based thickness of ceramic coating of polyalkene diaphragm more and more thinner, the consistent uniformity of coating layer thickness is difficult to control, and is unfavorable for large-scale continuous production.
Given this, be necessary to provide a kind of thermal stability that can effectively improve barrier film, promote battery performance, water-based ceramic coating lithium ion battery separator that again can large-scale continuous steady production.
Summary of the invention
For solving in process of production because equipment attrition makes the water-based thickness of ceramic coating of polyalkene diaphragm more and more thinner; the consistent uniformity of coating layer thickness is difficult to control; be unfavorable for the problem of large-scale continuous production, the object of the present invention is to provide that a kind of wearing and tearing to plant equipment are little, coating layer thickness uniformity, be conducive to the water-based ceramic coating lithium ion battery separator of continous-stable large-scale production.
The present invention realizes by following technical measures, and a kind of water-based ceramic coating lithium ion battery separator comprises polyolefin porous membrane and is coated on the coating of polyolefin porous membrane one or both sides, and coating layer thickness is 2-8 μ m; Described coating is made up of the base-material of the 20-60% calculating according to percentage by weight and the water of 40-80%; Described base-material comprises water soluble polymer thickener 0.1-5 part, aqueous dispersion 0.1-5 part, Aqueous Adhesives 0.1-10 part and the boehmite particle 80-99.7 part of calculating according to weight quota.
As a kind of optimal way, described polyolefin porous membrane is polyethylene porous membrane, polypropylene porous membrane or polypropylene, polyethylene/polypropylene composite materials porous membrane, and film thickness is 5-40 μ m, and porosity is 35-60%.
As a kind of optimal way, described base-material comprises water soluble polymer thickener 0.2-3 part, aqueous dispersion 0.2-3 part, Aqueous Adhesives 2-8 part and the boehmite particle 86-97.6 part of calculating according to weight quota.
As a kind of optimal way, described water soluble polymer thickener is one or more the composition in hydroxyethylcellulose, methyl hydroxyethylcellulose, sodium carboxymethylcellulose (CMC-Na), polyacrylamide (PAM), polyethylene glycol oxide (PEO) or sodium alginate.
As a kind of optimal way, described aqueous dispersion is one or more the composition in polyethylene glycol (PEG), polyacrylic acid (PAA), Sodium Polyacrylate (PAA-Na), polyacrylic acid potassium (PAA-K).
As a kind of optimal way, described Aqueous Adhesives is one or more the composition in butadiene-styrene latex, styrene-acrylic latex, purified petroleum benzin latex, polymethyl methacrylate, polybutyl methacrylate, polyethyl acrylate, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polyvinyl acetate, polyurethane.
As a kind of optimal way, the plate-like particles that described boehmite particle is rhombus, the particle diameter D50 of particle is 0.2-4um, BET is 2-15m2/g.
The processing method that the invention also discloses a kind of ceramic coating lithium ion battery separator, comprises the following steps:
(1), water soluble polymer thickener, aqueous dispersion and the deionized water of formula ratio are first joined in pre-agitator tank, dissolve completely, obtain mixture I;
(2), in said mixture I, add boehmite particle, stir and disperse after 25-50 minute, be dispersed in high speed dispersor and carry out, rotating speed 3000-9000rpm, obtains mixture II;
(3), in said mixture II, add Aqueous Adhesives, low rate mixing evenly after, filter to obtain water-based ceramic size with 300 eye mesh screens;
(4), water-based ceramic size is coated to the one or both sides of polyolefin film, after dry water-based ceramic coating lithium ion battery separator.
As a kind of optimal way, the coating in described step (4) is that dip coating, rolling method, spraying process or die head are coated with.
As a kind of optimal way, the screen cloth in described step (3) is stainless steel mesh.
Compared with prior art, its advantage and beneficial effect are in the present invention:
1, the problem based on current polyalkene diaphragm and the existence of ceramic coated polyalkene diaphragm; water-based ceramic coating lithium ion battery separator prepared by employing the present invention is in improving conventional polyolefins barrier film thermal stability; because the Mohs' hardness of boehmite only has 3-3.5; much smaller than aluminium oxide Mohs' hardness 8.5-9; little to the wearing and tearing of plant equipment in process of production; the control of coating layer thickness uniformity consistency is easy, is conducive to continous-stable large-scale production.
2, the water-based ceramic coating lithium ion battery separator that adopts the present invention to prepare, boehmite particle proportion is less than alumina particle, the weight increasing when coating layer thickness is identical is few, and the lithium ion battery energy density of assembling under the same terms is higher than the polyolefin ceramic diaphragm that adopts aluminium oxide particles to apply.
3, the compatibility that the boehmite that prepared by employing the present invention applies lithium ion battery separator and electrolyte is better than alumina coated lithium ion battery separator, interface impedance is little, the lithium ion battery internal resistance of assembling under the same terms is little, is conducive to promote the performance of lithium ion battery.
4, preparation method of the present invention adopts water to make solvent, therefore has the feature of safety and environmental protection.
Accompanying drawing explanation
Fig. 1 is the Electronic Speculum figure of boehmite particle in the embodiment of the present invention.
Embodiment
Below in conjunction with embodiment and contrast accompanying drawing the present invention is described in further detail.
Embodiment 1
A kind of water-based ceramic coating lithium ion battery separator, comprise polypropylene porous film and the water-based ceramic coating that is coated on polypropylene porous film one side, wherein polypropylene porous film thickness is 16um, porosity is 42%, coating layer thickness is 4um, and coating film slurry used is by the base-material 20% calculating according to percentage by weight and water 80%; Described base-material comprises the water soluble polymer thickener hydroxyethylcellulose 0.1%, the aqueous dispersion polyethylene glycol 0.1% that calculate according to percentage by weight, Aqueous Adhesives butadiene-styrene latex 0.1%, D
50for 0.2um, BET is 15m
2the tabular boehmite particle 99.7% of/g.
Prepare the method for the inorganic lithium ion battery separator of described macromolecule; Comprise and be prepared as follows step:
1, water soluble polymer thickener hydroxyethylcellulose, aqueous dispersion polyethylene glycol and the deionized water of described amount are first joined in pre-agitator tank, dissolve completely, obtain mixture I;
2, toward the tabular boehmite particle that adds described amount in said mixture I, stir and in high speed dispersor, disperse after 25-50 minute, disperse rotating speed 3000rpm, obtain mixture II;
3, toward the Aqueous Adhesives butadiene-styrene latex that adds described amount in said mixture II, low rate mixing evenly after, filter to obtain water-based ceramic size with 300 eye mesh screens (preferred stainless steel mesh);
4, a side of above-mentioned water-based ceramic size being coated to polypropylene porous film with reverse nick version coating machine, obtains water-based ceramic coating lithium ion battery separator after being dried.
Embodiment 2
A kind of water-based ceramic coating lithium ion battery separator, comprise polyethylene porous membrane and the water-based ceramic coating that is coated on polyethylene porous membrane both sides, wherein polyethylene porous membrane thickness is 5um, porosity is 35%, both sides coating layer thickness is 2um, and coating film slurry used is by the base-material 30% calculating according to percentage by weight and water 70%; Described base-material comprises the water soluble polymer thickener sodium carboxymethylcellulose 5%, the aqueous dispersion polyacrylic acid 5% that calculate according to percentage by weight, Aqueous Adhesives polymethyl methacrylate 10%, D
50for 4um, BET is 2m
2the tabular boehmite particle 80% of/g.
Prepare the method for water-based ceramic coating lithium ion battery separator as embodiment 1, vicissitudinous is that dispersion rotating speed is 9000rpm, and coating method is dip-coating.
Embodiment 3
A kind of water-based ceramic coating lithium ion battery separator, comprise polypropylene, polyethylene/polypropylene composite materials porous membrane and the water-based ceramic coating that is coated on polypropylene, polyethylene/polypropylene composite materials porous membrane one side, wherein polypropylene, polyethylene/polypropylene composite materials porous membrane thickness is 20um, porosity is 39%, coating layer thickness is 5um, and coating film slurry used is by the base-material 40% calculating according to percentage by weight and water 60%; Described base-material comprises the water soluble polymer thickener polyacrylamide 0.2%, the aqueous dispersion Sodium Polyacrylate 0.2% that calculate according to percentage by weight, Aqueous Adhesives polyethyl acrylate 2%, D
50for 0.6um, BET is 12m
2the tabular boehmite particle 97.6% of/g.
Prepare the method for water-based ceramic coating lithium ion battery separator as embodiment 1, vicissitudinous is that dispersion rotating speed is 5000rpm, and coating method is crack extrusion coated.
Embodiment 4
A kind of water-based ceramic coating lithium ion battery separator, comprise polypropylene porous membrane and the water-based ceramic coating that is coated on polypropylene porous membrane both sides, wherein polypropylene porous membrane thickness is 40um, porosity is 60%, every side coating layer thickness is 4um, coating layer thickness amounts to 8um, and coating film slurry used is by the base-material 50% calculating according to percentage by weight and water 50%; Described base-material comprises the water soluble polymer thickener sodium alginate 3%, the aqueous dispersion polyacrylic acid potassium 3% that calculate according to percentage by weight, Aqueous Adhesives ethylene-vinyl acetate copolymer 7%, D
50for 1um, BET is 10m
2the tabular boehmite particle 87% of/g.
Prepare the method for water-based ceramic coating lithium ion battery separator as embodiment 1, vicissitudinous is that dispersion rotating speed is 6000rpm, and coating method is spraying.
Embodiment 5
A kind of water-based ceramic coating lithium ion battery separator, comprise polyethylene porous membrane and the water-based ceramic coating that is coated on polyethylene porous membrane one side, wherein polyethylene porous membrane thickness is 12um, porosity is 45%, coating layer thickness is 3um, and coating film slurry used is by the base-material 45% calculating according to percentage by weight and water 55%; Described base-material comprises the water soluble polymer thickener polyethylene glycol oxide 1%, the aqueous dispersion polyethylene glycol 1% that calculate according to percentage by weight, Aqueous Adhesives polyurethane 5%, D
50for 2um, BET is 6m
2the tabular boehmite particle 93% of/g.
Prepare the method for water-based ceramic coating lithium ion battery separator as embodiment 1, vicissitudinous is that dispersion rotating speed is 8000rpm, and coating method is roller transfer coated.
Comparative example 1
This comparative example provides a kind of alumina ceramic coating lithium ion battery separator, comprise polypropylene porous film and the aluminum oxide coating layer that is coated on polypropylene porous film one side, wherein polypropylene porous film thickness is 16um, porosity is 42%, coating layer thickness is 4um, and coating film slurry used is by the composition 20% calculating according to percentage by weight and water 80%; Described composition comprises the water soluble polymer thickener hydroxyethylcellulose 0.1%, the aqueous dispersion polyethylene glycol 0.1% that calculate according to percentage by weight, Aqueous Adhesives butadiene-styrene latex 0.1%, D
50for 1um, BET is 8m
2/ g aluminium oxide particles 99.7%.
Prepare the method for ceramic lithium ion battery separator as traditional coating process.
Comparative example 2
It is 16um that this comparative example adopts thickness, and porosity is 42% polypropylene porous membrane, and does not carry out any coating processing.
The lithium ion battery separator that adopts the method for embodiment 1 to 5 and comparative example 1-2 to prepare is carried out to barrier film thermal contraction test: the lithium ion battery separator that uses the method that adopts embodiment 1 to 5 and comparative example 1-2 to prepare is made sample, test barrier film toasts 2h at 90 ℃, at 135 ℃, toast 1h, at 150 ℃, toast the thermal contraction performance of 30min, same barrier film test 5 times, test result is listed in table 1.
The lithium ion battery separator that adopts the method for embodiment 1-5 and comparative example 1-2 to prepare is carried out to the test of barrier film surface density: from the lithium ion battery separator that embodiment 1-5 and comparative example 1-2 prepare, intercept respectively area (S) for 5 of 100mm × 300mm rectangular areas, weigh its weight (m) with rigorous analysis balance (accuracy 0.0001g), then calculate surface density according to formula ρ=m/S, same barrier film test 5 times, test result is listed in table 1.
The lithium ion battery separator that adopts the method for embodiment 1 to 5 and comparative example 1-2 to prepare is carried out to the test of barrier film surface resistance: the lithium ion battery separator that uses the method that adopts embodiment 1 to 5 and comparative example 1-2 to prepare is made sample, test barrier film surface resistance at room temperature, same barrier film test 5 times, test result is listed in table 1.
Table 1 adopts thermal contraction, surface density and the surface resistance of lithium ion battery separator prepared by the method for embodiment 1-5 and comparative example 1-2.
Table 1
Wherein, MD refers to that longitudinally TD refers to laterally.
As shown in Table 1, under water-based ceramic coating lithium ion battery separator high temperature prepared by employing the present invention, the thermal contraction performance of (135 ℃ and 150 ℃) has clear improvement, can reduce battery in abnormal conditions such as high temperature because barrier film shrinks the both positive and negative polarity short-circuit risks causing, improved the security performance of battery.More known with comparative example 1 by embodiment 1, equal conditions, boehmite applies lithium ion battery separator and have better resistance to elevated temperatures compared with alumina coated lithium ion battery separator, has lower surface density and surface resistance simultaneously, is conducive to the lifting of performance of lithium ion battery.
More than that ceramic coating lithium ion battery separator of the present invention and processing method thereof are set forth; be used for helping to understand the present invention; but embodiments of the present invention are not restricted to the described embodiments; anyly do not deviate from the change done under the principle of the invention, modification, substitute, combination, simplify; all should be equivalent substitute mode, be included in protection scope of the present invention in.
Claims (10)
1. a water-based ceramic coating lithium ion battery separator, is characterized in that: comprise polyolefin porous membrane and be coated on the coating of polyolefin porous membrane one or both sides, coating layer thickness is 2-8 μ m; Described coating is made up of the base-material of the 20-60% calculating according to percentage by weight and the water of 40-80%; Described base-material comprises water soluble polymer thickener 0.1-5 part, aqueous dispersion 0.1-5 part, Aqueous Adhesives 0.1-10 part and the boehmite particle 80-99.7 part of calculating according to weight quota.
2. water-based ceramic coating lithium ion battery separator according to claim 1, it is characterized in that: described polyolefin porous membrane is polyethylene porous membrane, polypropylene porous membrane or polypropylene, polyethylene/polypropylene composite materials porous membrane, film thickness is 5-40 μ m, and porosity is 35-60%.
3. water-based ceramic coating lithium ion battery separator according to claim 1, is characterized in that: described base-material comprises water soluble polymer thickener 0.2-3 part, aqueous dispersion 0.2-3 part, Aqueous Adhesives 2-8 part and the boehmite particle 86-97.6 part of calculating according to weight quota.
4. water-based ceramic coating lithium ion battery separator according to claim 1, is characterized in that: described water soluble polymer thickener is one or more the composition in hydroxyethylcellulose, methyl hydroxyethylcellulose, sodium carboxymethylcellulose, polyacrylamide, polyethylene glycol oxide or sodium alginate.
5. water-based ceramic coating lithium ion battery separator according to claim 1, is characterized in that: described aqueous dispersion is one or more the composition in polyethylene glycol, polyacrylic acid, Sodium Polyacrylate, polyacrylic acid potassium.
6. water-based ceramic coating lithium ion battery separator according to claim 1, is characterized in that: described Aqueous Adhesives is one or more the composition in butadiene-styrene latex, styrene-acrylic latex, purified petroleum benzin latex, polymethyl methacrylate, polybutyl methacrylate, polyethyl acrylate, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polyvinyl acetate, polyurethane.
7. water-based ceramic coating lithium ion battery separator according to claim 1, is characterized in that: the plate-like particles that described boehmite particle is rhombus, and the particle diameter D50 of particle is 0.2-4um, BET is 2-15m2/g.
8. a processing method for ceramic coating lithium ion battery separator, is characterized in that comprising the following steps:
(1), water soluble polymer thickener, aqueous dispersion and the deionized water of formula ratio are first joined in pre-agitator tank, dissolve completely, obtain mixture I;
(2), in said mixture I, add boehmite particle, stir and disperse after 25-50 minute, be dispersed in high speed dispersor and carry out, rotating speed 3000-9000rpm, obtains mixture II;
(3), in said mixture II, add Aqueous Adhesives, low rate mixing evenly after, filter to obtain water-based ceramic size with 300 eye mesh screens;
(4), water-based ceramic size is coated to the one or both sides of polyolefin film, after dry water-based ceramic coating lithium ion battery separator.
9. processing method according to claim 8, is characterized in that: the coating in described step (4) is that dip coating, rolling method, spraying process or die head are coated with.
10. processing method according to claim 8, is characterized in that: the screen cloth in described step (3) is stainless steel mesh.
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