CN104953070A - Isolating membrane for lithium ion secondary battery - Google Patents
Isolating membrane for lithium ion secondary battery Download PDFInfo
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- CN104953070A CN104953070A CN201510228162.5A CN201510228162A CN104953070A CN 104953070 A CN104953070 A CN 104953070A CN 201510228162 A CN201510228162 A CN 201510228162A CN 104953070 A CN104953070 A CN 104953070A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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 belongs to the technical field of battery manufacture and in particular relates to an isolating membrane for a lithium ion secondary battery. According to the isolating membrane, at least one surface of an isolating membrane body is coated with a functional coating layer; the functional coating layer is formed in a manner that inorganic particles, a binder and a polymer are mixed and stirred in a solvent to form slurry, and at least one surface or two surfaces of the isolating membrane body is/are coated with the slurry; and the coating process of the functional coating layer is controlled by adopting a process, so as to enable an inorganic particle layer to be enriched on the surface of the isolating membrane body, and the polymer to be enriched on the surfaces of the inorganic particles. The inorganic particles in the functional coating layer have the excellent heat stability, so that the shrinking of the isolating membrane under a high temperature condition is inhibited, and the heat stability of the isolating membrane is improved; and simultaneously a polymer layer enriched on the surfaces of the inorganic particles can be bonded together with electrode pieces of the lithium ion secondary battery in the lithium ion secondary battery so as to inhibit the deformation of the battery.
Description
Technical field
The invention belongs to battery isolating film technical field, be specifically related to a kind of lithium rechargeable battery barrier film.
Background technology
The barrier film of lithium rechargeable battery, as the isolation of both positive and negative polarity, is clipped between both positive and negative polarity, and Main Function prevents from both positive and negative polarity from directly contacting to be short-circuited.Current barrier film is primarily of polyethylene, the porous media of the TPO compositions such as polypropylene, polyolefine isolating film has the fusing point of less than 200 DEG C, when lithium rechargeable battery generates heat and temperature raises because inner or external factor cause being short-circuited, very easily there is the short circuit generation that thermal contraction causes both positive and negative polarity larger in barrier film, causes the thermal runaway of battery to cause fire accident.In addition along with the energy density of lithium rechargeable battery constantly improves, the graphite cathode of high gram volume causes the expansion in its charge and discharge process very large, result in the torsional deformation of battery.In order to solve the problem, the mixed coating of tack coat or coating inorganic particle and Polymer Tie-layer that the porous dielectric layer that industry inherent barrier film surface-coated one deck is made up of inorganic particulate applies one layer of polymeric in addition again on this porous dielectric layer solves safety problem and problem on deformation.The good thermal stability of inorganic particulate ensures its fail safe, and polymer can be bonded together with pole piece the distortion suppressing battery.As the Chinese patent CN101326658A of Chinese patent CN102569701A, CN102610773A and CN103441230A and LG company.Patent CN102569701A and CN102610773A is the insulating barrier first forming inorganic particulate, and then the tack coat of coated polymer realizes, and needs repeatedly to apply, technical process more complicated, and technique difficulty controls.Together with Chinese patent CN103441230A to be mixed with cohesive polymers by inorganic particulate, technique realizes, but needs heating swelling in advance, and technique is also more complicated.Chinese patent CN101326658A forms binder polymer/content of inorganic particles than graded by being repeatedly coated on porous substrate surface, and technique is also very complicated.
Summary of the invention
The object of the invention is to: for the deficiency having now technology, provide one can bond well with electrodes of lithium-ion batteries, suppress lithium ion battery distortion well, simultaneously on the lithium rechargeable battery barrier film of performance of lithium ion battery without impact.
To achieve these goals, the present invention adopts following technical scheme:
A kind of lithium rechargeable battery barrier film, comprise barrier film body, at least one surface of described barrier film body is coated with functional coating, described functional coating is mixed together stirring in a solvent by inorganic particulate, binding agent and polymer and makes slurry, then be coated in barrier film body one or two on the surface, form inorganic particulate and be enriched in barrier film body surface, polymer rich is at surface of inorganic particles.
Described a kind of lithium rechargeable battery barrier film its preparation method, comprises the steps:
A) functional coating slurry preparation: by even to described inorganic particulate, described binding agent and polymer dispersed with stirring: inorganic particulate, binding agent are dissolved in together with polymer in solvent to form slurry, slurry concentration is 1 ~ 60wt%, is more preferably 5 ~ 50wt%;
B) on the surface of described barrier film body, described functional coating slurry is applied, obtained lithium rechargeable battery barrier film,
Then drying is carried out to the barrier film of coating; Time dry, segmentation is carried out, and at least divides two sections;
The dry enrichment of first paragraph, the polymer little by the quick volatile zone dynamic density of solvent floats, and is enriched in surface of inorganic particles, between first paragraph thermal creep stress 30 ~ 130 DEG C, wind speed 0.5m/sec to 20m/sec; Preferably between 40 ~ 70 DEG C, wind speed 2 ~ 15m/sec;
Second segment is solidification drying stage, thermal creep stress 20 ~ 70 DEG C, wind speed 0.5m/sec to 15m/sec.
Described drying mode is heated-air drying, infra-red drying, any one of the dry or microwave drying of ceramic heat.
Described barrier film body is polyethylene micropore film or polypropylene microporous film.
Described barrier film body is polyimides or nonwoven fabrics.
Described polymer is Kynoar-hexafluoropropylene (PVDF-HFP), polyacrylonitrile (PAN), at least one in polyoxyethylene (PEO) and polymethacrylates (PMMA);
Described binding agent be in styrene-butadiene, Kynoar, Kynoar-hexafluoropropylene, polyacrylic acid, polymethylacrylic acid, polyacrylate, polymethyl methacrylate, polyacrylonitrile, sodium carboxymethylcellulose, butadiene-acrylonitrile polymer, polyvinylpyrrolidone and polyacrylic acid-styrene any one or multiple.
Described inorganic particulate be in calcium oxide, zinc oxide, magnesium oxide, titanium dioxide, silicon dioxide, zirconium dioxide, tin ash, ceria, alundum (Al2O3), boehmite, calcium carbonate and barium titanate any one or multiple.
The average grain diameter of described inorganic particulate is 0.05 ~ 6um, and particle size distribution is 0.01 ~ 10 μm; Preferred average grain diameter is 0.1 ~ 2.0um, and particle size distribution is 0.05 ~ 5.0um; The thickness of functional coating is 0.5 ~ 10 μm, preferably 2 ~ 5um.
The mass ratio of described inorganic particulate and binding agent is 80:20 ~ 99.9:0.1; Described inorganic particulate and the mass ratio of polymer are 50:50 ~ 99:1,
Solvent is one or more in oxolane, methylethylketone, dimethyl formamide, dimethylacetylamide, tetramethylurea, tetramethyl phosphate, acetone, carrene, chloroform, dimethylformamide, 1-METHYLPYRROLIDONE, cyclohexane, water, alcohol.
Beneficial effect of the present invention is: described lithium rechargeable battery barrier film comprises functional coating, functional coating causes inorganic particle layer to be enriched in barrier film body surface by technology controlling and process coating procedure, polymer rich is on the surface of inorganic particulate, because barrier film body itself has microcellular structure, and its thermal conductivity coefficient is less, time dry, temperature raises, septum body temperature and Coated Surface Temperature can differ larger, the solvent carried secretly in functional coating accelerates upwards to volatilize, the polymer little with dynamic density floats, form polymer rich at surface of inorganic particles.Inorganic particulate in functional coating has excellent thermal stability, inhibit barrier film contraction in the case of a high temperature, improve its thermal stability, the polymeric layer of surface of inorganic particles enrichment simultaneously can be bonded together with its pole piece the distortion suppressing battery in lithium ion battery.
Embodiment
Below in conjunction with embodiment, the present invention and beneficial effect thereof are described in further detail, but the specific embodiment of the present invention is not limited thereto.
Comparative example 1
Prepared by positive plate: by cobalt acid lithium, conductive carbon, binding agent Kynoar in mass ratio 96:2.5:1.5 mix in 1-METHYLPYRROLIDONE (NMP) solvent and make anode sizing agent, then to be coated on aluminium foil and carry out after drying at 110 DEG C colding pressing, itemize, cutting edge, tab welding, make positive plate.
The preparation of negative plate:
By graphite, conductive carbon, thickener sodium carboxymethylcellulose, binding agent butadiene-styrene rubber in mass ratio 96.5:1.5:1.0:1.5 mix in deionized water and make cathode size, then to be coated on Copper Foil and carry out after drying at 85 DEG C colding pressing, itemize, cutting edge, tab welding, make negative plate.
Barrier film:
Getting thickness is that the polyethylene micropore film of 9 μm is as barrier film.
The preparation of battery:
The positive plate of above-mentioned preparation, barrier film, negative plate are wound into battery core, then this battery core are placed in aluminium plastic packaging bag, inject electrolyte, through encapsulating, changing into, the operation such as capacity, make lithium ion battery; Wherein electrolyte comprises ethylene carbonate, dimethyl carbonate and the methyl ethyl carbonate that mass ratio is 1:2:1, and lithium hexafluoro phosphate, and the concentration of lithium hexafluoro phosphate is 1mol/L.
Comparative example 2
This comparative example and comparative example 1 difference are: getting thickness is that the polyethylene micropore film of 9 μm is as barrier film.
The preparation of inorganic particulate coating:
The polyacrylate dispersion (in the aqueous solution, the content of polyacrylate is 30wt%) first adding 10wt% in deionized water stirs 1h, then adds the Al of 90wt%
2o
3particle, after stirring 2h, then in grinding in ball grinder 1h, prepare inorganic particulate slurry, the solid content of slurry is 50wt%, Al
2o
3the average grain diameter of particle is 0.5 μm, and particle size distribution is 0.1 ~ 3 μm.
The preparation of barrier film:
Use intaglio plate coating mode by slurry uniform fold on barrier film, slurry drying uses heated-air drying, and dry point two sections are carried out, first paragraph temperature 55 DEG C, wind speed 5m/s, second segment temperature is 55 DEG C, and wind speed 8m/s, is inorganic particle layer after slurry drying, the thickness of inorganic particle layer 5 μm, then, then the barrier film of this coating is cut, cut-parts.Other are identical, repeat no more.
Comparative example 3
This comparative example and comparative example 2 difference are, are the coating of coated polymeric again after the coating of coating inorganic particle on barrier film.
Coated polymer coating again above inorganic particulate coating, is described in detail to barrier film and preparation thereof below:
Get inorganic particulate coating in comparative example 2 every barrier film.
The preparation of polymer coating:
In acetone solvent, add Kynoar-hexafluoropropylene stirring 4h be made into polymer solution, concentration is 5%, by the mode of dip-coating, the inorganic particulate coating barrier film two sides in comparative example 2 is coated with this polymer solution again, then carry out drying and obtain polymer coating barrier film, one side coating layer thickness is 3um.Then the barrier film of this coating is cut, cut-parts.Other are identical, repeat no more.
Embodiment 1
The preparation of the positive plate of the present embodiment, the preparation of negative plate are identical with comparative example 1 with the preparation of battery, and repeat no more, barrier film is different from comparative example 1, is described in detail below to barrier film and preparation thereof:
Getting thickness is that the polyethylene micropore film of 9 μm is as barrier film body.
The preparation of functional coating slurry:
1) first Al is added in deionized water
2o
3particle carries out stirring 1h, solid content is 40wt%, again in grinding in ball grinder 1h, then add acrylic acid ester emulsion (in the aqueous solution, the content of polyacrylate is 25wt%) and stir 1h, the mass ratio of Al2O3 and acrylate is 80:20, then add Kynoar-hexafluoropropylene powder and carry out stirring 2h, Al
2o
3be 50:50 with the mass ratio of Kynoar-hexafluoropropylene, the solid content of this slurry is 50wt%, Al
2o
3the average grain diameter of particle is 0.8 μm, and particle size distribution is 0.1 ~ 5 μm;
2) by the mode of dip-coating, be coated with respectively on the polyethylene micropore film two sides of 9um and be covered with this slurry, the dry heated-air drying by two sections is carried out, and first paragraph temperature is 60 DEG C, and wind speed is 12m/s, second segment temperature is 65 DEG C, wind speed is 8m/s, obtains functional coating barrier film after drying, and every finishing coat thickness is 3um, then the barrier film of this coating is cut, cut-parts.
Embodiment 2
The preparation of the positive plate of the present embodiment, the preparation of negative plate are identical with comparative example 1 with the preparation of battery, and repeat no more, barrier film is different from comparative example 1, is described in detail below to barrier film and preparation thereof:
Getting thickness is that the polyimides of 9 μm is as barrier film body.
The preparation of functional coating slurry:
1) first add boehmite particles in deionized water and carry out stirring 1h, solid content is 30wt%, again in grinding in ball grinder 1h, then add polyacrylonitrile emulsion (in the aqueous solution, the content of polyacrylonitrile is 20wt%) and stir 1h, the mass ratio of boehmite and polyacrylonitrile is 90:10, then add polyoxyethylene powder and carry out stirring 2h, boehmite and polyoxyethylated mass ratio are 80:20, the solid content of this slurry is 33wt%, the average grain diameter of boehmite particles is 1.5 μm, and particle size distribution is 0.2 ~ 6 μm;
2) by mode that intaglio plate is coated with, be coated with respectively on the polyethylene micropore film two sides of 9um and be covered with this slurry, the dry heated-air drying by two sections is carried out, and first paragraph temperature is 70 DEG C, and wind speed is 15m/s, second segment temperature is 70 DEG C, wind speed is 10m/s, obtains functional coating barrier film after drying, and every finishing coat thickness is 5um, then the barrier film of this coating is cut, cut-parts.
Embodiment 3
The preparation of the positive plate of the present embodiment, the preparation of negative plate are identical with comparative example 1 with the preparation of battery, and repeat no more, barrier film is different from comparative example 1, is described in detail below to barrier film and preparation thereof:
Getting thickness is that the polypropylene microporous film of 9 μm is as barrier film body.
The preparation of functional coating slurry:
1) in ethanol and deionized water mixed solvent (quality of ethanol and deionized water is for being 50:50), first TiO is added
2particle carries out stirring 1h, and solid content is 30wt%, then in grinding in ball grinder 1h, then adds carboxymethylcellulose sodium solution (carboxymethylcellulose sodium solution concentration is 1.5wt%) and stir 1h, TiO
2be 95:5 with the mass ratio of sodium carboxymethylcellulose, then add polymethacrylates (PMMA) powder and carry out stirring 2h, TiO
2be 60:40 with the mass ratio of polymethacrylates powder, the solid content of this slurry is 23wt%, TiO
2the average grain diameter of particle is 0.5 μm, and particle size distribution is 0.08 ~ 2 μm;
2) by the mode of dip-coating, be coated with respectively on the polyethylene micropore film two sides of 9um and be covered with this slurry, the dry heated-air drying by two sections is carried out, and first paragraph temperature is 70 DEG C, and wind speed is 10m/s, second segment temperature is 65 DEG C, wind speed is 8m/s, obtains functional coating barrier film after drying, and every finishing coat thickness is 2um, then the barrier film of this coating is cut, cut-parts.
Embodiment 4
The present embodiment difference from Example 3 is: described inorganic particulate is calcium oxide and zinc oxide, and its mass ratio is 1:1.
The average grain diameter of described inorganic particulate is 0.8um, and particle size distribution is 0.01 ~ 5 μm; The thickness of functional coating is 5 μm.
The mass ratio of described inorganic particulate and binding agent is 85:15; Described inorganic particulate and the mass ratio of polymer are 80:20,
Solvent is the mixed liquor of carrene and alcohol.Other are identical with embodiment 3, repeat no more here.
Comparative example and embodiment explanation
| Group | Describe |
| Comparative example 1 | Barrier film is without coating |
| Comparative example 2 | Barrier film coating inorganic particle coating |
| Comparative example 3 | Coated polymer layer again after barrier film coating inorganic particle coating |
| Embodiment 1 | Embodiments of the invention 1 |
| Embodiment 2 | Embodiments of the invention 2 |
| Embodiment 3 | Embodiments of the invention 3 |
| Embodiment 4 | Embodiments of the invention 4 |
Experimental example 1
Thermal contraction test is carried out for the barrier film in above comparative example and embodiment
Thermal contraction is tested: square sample barrier film being die-cut into 100X100mm, indicate MD and TD direction, measure the length of initial MD and TD, put it in the baking oven of 130 degree and toast 2H, after taking out, the length in rear MD and the TD direction of test baking, calculates percent thermal shrinkage=[(size after the size-baking before baking)/red size before examination] X100%.Acquired results is in table 1
Table 1 comparative example and embodiment barrier film percent thermal shrinkage
| Group | MD | TD |
| Comparative example 1 | 18.5％ | 15.3％ |
| Comparative example 2 | 2.5％ | 2.2％ |
| Comparative example 3 | 2.4％ | 2.2％ |
| Embodiment 1 | 2.4％ | 2.3％ |
| Embodiment 2 | 2.2％ | 1.9％ |
| Embodiment 3 | 2.3％ | 2.0％ |
| Embodiment 4 | 2.2％ | 1.85％ |
As known from Table 1, the embodiment 1 ~ 4 of barrier film surface-coated functional layer thermal contraction with have the barrier film comparative example 2 ~ 3 of coating inorganic particle in same level and compared with do not have cated barrier film comparative example 1 to improve obviously.
Experimental example 2
Discharge-rate test is carried out for the lithium ion battery in above comparative example and embodiment
Discharge-rate is tested: at 25 DEG C, first adopted by lithium ion battery the multiplying power of 0.5C to charge, 0.2C multiplying power discharging, record discharge capacity; Then the charging of 0.5C multiplying power is carried out, 0.5C multiplying power discharging, record discharge capacity; Then the charging of 0.5C multiplying power is carried out, 1.0C multiplying power discharging, record discharge capacity; Then the charging of 0.5C multiplying power is carried out again, 1.5C multiplying power discharging, record discharge capacity; Finally carry out the charging of 0.5C multiplying power, 2.0C multiplying power discharging, record discharge capacity.Capability retention under variant discharge-rate=(discharge capacity under the discharge capacity under each multiplying power/0.2C multiplying power) X100%.Acquired results is in table 2
Capability retention under table 2 comparative example discharge-rate different from embodiment
| Group | 0.2C | 0.5C | 1.0C | 2.0C |
| Comparative example 1 | 100％ | 98.5％ | 95.6％ | 85.3％ |
| Comparative example 2 | 100％ | 98.2％ | 95.3％ | 85.5％ |
| Comparative example 3 | 100％ | 98.5％ | 95.3％ | 84.8％ |
| Embodiment 1 | 100％ | 98.7％ | 95.5％ | 85.6％ |
| Embodiment 2 | 100％ | 98.1％ | 95.0％ | 85.2％ |
| Embodiment 3 | 100％ | 98.6％ | 95.3％ | 85.3％ |
| Embodiment 4 | 100％ | 98.7％ | 94.3％ | 84.9％ |
As known from Table 2, the embodiment 1 ~ 4 of coated insulation film surface functional layer high rate performance with do not have the comparative example 3 of the comparative example 2 of cated comparative example 1 and inorganic particulate coating and inorganic coating and polymer coating in same level.
Experimental example 3
Cycle performance test is carried out for the lithium ion battery in above comparative example and embodiment
Cycle performance and thickness measuring: adopted by lithium ion battery the multiplying power of 0.5C to charge at 25 degrees c, the multiplying power discharging of 0.5C, carry out 500 circulations successively, battery capacity under each loop test 0.5C multiplying power, and compare with the capacity under front 25 degree, the battery of circulation, capability retention after computation cycles, capability retention=(capacity before the capacity/circulation after 500 circulations under 0.5C multiplying power under 25 degree, battery) X100%.Thickness swelling=(thickness that before the thickness/circulation of completely filling after 500 circulations, battery completely fills) X100% acquired results is in table 3
Table 3 comparative example and embodiment circulation volume conservation rate and thickness swelling
| Group | Capability retention | Thickness swelling |
| Comparative example 1 | 86.3％ | 16.3％ |
| Comparative example 2 | 87.1％ | 15.8％ |
| Comparative example 3 | 86.9％ | 7.5％ |
| Embodiment 1 | 87.3％ | 7.8％ |
| Embodiment 2 | 86.8％ | 6.9％ |
| Embodiment 3 | 87.5％ | 7.2％ |
| Embodiment 4 | 87.7％ | 6.8％ |
As known from Table 3, the cycle performance of the embodiment 1 ~ 4 of coating functions layer and comparative example 1 ~ 3 are in same level, but cell thickness expansion rate, the embodiment 1 ~ 4 of coating functions layer be coated with the comparative example 3 of polymeric layer in same level, but than not having the comparative example 2 of cated comparative example 1 and non-polymer coating all obviously to improve.
Experimental example 4
Drift bolt safety test is carried out for the lithium ion battery in above comparative example and embodiment
Drift bolt is tested: first completely fill battery, and the standard then according to UL1642 is tested, and nail diameter is 2.5mm, and drift bolt speed is 100mm/s.Test result is in table 4
The drift bolt test result of battery before and after table 4 circulates
As known from Table 4, the embodiment 1 ~ 4 of barrier film surface-coated functional layer thermal contraction with have the barrier film comparative example 2 ~ 3 of coating inorganic particle in same level and compared with do not have cated barrier film comparative example 1 to improve obviously.
Experimental example 5
Visual examination distortion is completely filled for the lithium ion battery in above comparative example and embodiment.Proportion of deformation is in table 5
Table 5 battery completely fills proportion of deformation
| Group | Cell deformation ratio |
| Comparative example 1 | 75％ |
| Comparative example 2 | 80％ |
| Comparative example 3 | 0％ |
| Embodiment 1 | 0％ |
| Embodiment 2 | 0％ |
| Embodiment 3 | 0％ |
| Embodiment 4 | 0％ |
As can be seen from Table 5, the embodiment 1 ~ 4 of coating functions layer does not all have cell deformation with the comparative example 3 being coated with polymeric layer, but does not have comparative example 2 all gross distortions of cated comparative example 1 and non-polymer coating.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also change above-mentioned execution mode and revise.Therefore, the present invention is not limited to above-mentioned embodiment, and any apparent improvement of every those skilled in the art done by basis of the present invention, replacement or modification all belong to protection scope of the present invention.In addition, although employ some specific terms in this specification, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (10)
1. a lithium rechargeable battery barrier film, comprise barrier film body, it is characterized in that: at least one surface of described barrier film body is coated with functional coating, described functional coating is mixed together stirring in a solvent by inorganic particulate, binding agent and polymer and makes slurry, then be coated in barrier film body one or two on the surface, form inorganic particulate and be enriched in barrier film body surface, polymer rich is at surface of inorganic particles.
2. a kind of lithium rechargeable battery barrier film according to claim 1, is characterized in that: preparation method, comprises the steps:
A) functional coating slurry preparation: by even to described inorganic particulate, described binding agent and polymer dispersed with stirring: inorganic particulate, binding agent are dissolved in together with polymer in solvent to form slurry, slurry concentration is 1 ~ 60wt%, is more preferably 5 ~ 50wt%;
B) on the surface of described barrier film body, described functional coating slurry is applied, obtained lithium rechargeable battery barrier film,
Then drying is carried out to the barrier film of coating; Time dry, segmentation is carried out, and at least divides two sections;
The dry enrichment of first paragraph, the polymer little by the quick volatile zone dynamic density of solvent floats, and is enriched in surface of inorganic particles, between first paragraph thermal creep stress 30 ~ 130 DEG C, wind speed 0.5m/sec to 20m/sec; Preferably between 40 ~ 70 DEG C, wind speed 2 ~ 15m/sec;
Second segment is solidification drying stage, thermal creep stress 20 ~ 70 DEG C, wind speed 0.5m/sec to 15m/sec.
3. a kind of lithium rechargeable battery barrier film according to claim 2, is characterized in that: described drying mode is heated-air drying, infra-red drying, any one of the dry or microwave drying of ceramic heat.
4. a kind of lithium rechargeable battery barrier film according to claim 1, is characterized in that: described barrier film body is polyethylene micropore film or polypropylene microporous film.
5. a kind of lithium rechargeable battery barrier film according to claim 1, is characterized in that: described barrier film body is polyimides or nonwoven fabrics.
6. a kind of lithium rechargeable battery barrier film according to claim 1, it is characterized in that: described polymer is Kynoar-hexafluoropropylene (PVDF-HFP), polyacrylonitrile (PAN), at least one in polyoxyethylene (PEO) and polymethacrylates (PMMA);
Described binding agent be in styrene-butadiene, Kynoar, Kynoar-hexafluoropropylene, polyacrylic acid, polymethylacrylic acid, polyacrylate, polymethyl methacrylate, polyacrylonitrile, sodium carboxymethylcellulose, butadiene-acrylonitrile polymer, polyvinylpyrrolidone and polyacrylic acid-styrene any one or multiple.
7. a kind of lithium rechargeable battery barrier film according to claim 1, is characterized in that: described inorganic particulate be in calcium oxide, zinc oxide, magnesium oxide, titanium dioxide, silicon dioxide, zirconium dioxide, tin ash, ceria, alundum (Al2O3), boehmite, calcium carbonate and barium titanate any one or multiple.
8. a kind of lithium rechargeable battery barrier film according to claim 1, is characterized in that: the average grain diameter of described inorganic particulate is 0.05 ~ 6um, and particle size distribution is 0.01 ~ 10 μm; Preferred average grain diameter is 0.1 ~ 2.0um, and particle size distribution is 0.05 ~ 5.0um; The thickness of described functional coating is 0.5 ~ 10 μm, preferably 2 ~ 5um.
9. a kind of lithium rechargeable battery barrier film according to claim 1, is characterized in that: the mass ratio of described inorganic particulate and binding agent is 80:20 ~ 99.9:0.1; Described inorganic particulate and the mass ratio of polymer are 50:50 ~ 99:1.
10. a kind of lithium rechargeable battery barrier film according to claim 1, is characterized in that: solvent is one or more in oxolane, methylethylketone, dimethyl formamide, dimethylacetylamide, tetramethylurea, tetramethyl phosphate, acetone, carrene, chloroform, dimethylformamide, 1-METHYLPYRROLIDONE, cyclohexane, water, alcohol.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105762319A (en) * | 2016-03-02 | 2016-07-13 | 南京国轩电池有限公司 | Composite lithium ion battery diaphragm with high cohesion and preparation method thereof |
| CN105958000A (en) * | 2016-07-11 | 2016-09-21 | 东莞市魔方新能源科技有限公司 | Lithium ion battery composite membrane and preparation method thereof |
| CN106374136A (en) * | 2016-08-26 | 2017-02-01 | 浙江长兴金太阳电源有限公司 | Overheat-proof diaphragm used for lithium ion batteries and preparation method thereof |
| CN106898721A (en) * | 2017-02-28 | 2017-06-27 | 沧州明珠隔膜科技有限公司 | A kind of lithium ion battery separator for being suitable to hot dry-pressing and preparation method thereof |
| CN107513196A (en) * | 2016-06-17 | 2017-12-26 | 常州百思通复合材料有限公司 | A kind of method using microwave high-efficiency heating high molecular polymer |
| CN107955468A (en) * | 2017-11-16 | 2018-04-24 | 珠海恩捷新材料科技有限公司 | A kind of lithium ion battery separator of polyacrylonitrile coating |
| CN108011067A (en) * | 2018-01-04 | 2018-05-08 | 东莞市魔方新能源科技有限公司 | A kind of membrane configuration |
| CN109860488A (en) * | 2019-01-23 | 2019-06-07 | 东莞市魔方新能源科技有限公司 | Lithium battery diaphragm coating paste and preparation method thereof and diaphragm containing the slurry |
| CN111987273A (en) * | 2019-05-23 | 2020-11-24 | 河北金力新能源科技股份有限公司 | PVDF&Al2O3Mixed coating slurry, preparation method thereof, lithium ion battery diaphragm and lithium ion battery |
| CN112194936A (en) * | 2020-09-18 | 2021-01-08 | 河北金力新能源科技股份有限公司 | Ultra-high dispersion type PVDF slurry, diaphragm and preparation method thereof |
| CN112701420A (en) * | 2021-01-23 | 2021-04-23 | 山东天瀚新能源科技有限公司 | Multifunctional diaphragm for lithium battery, preparation method and application |
| CN113258208A (en) * | 2021-05-10 | 2021-08-13 | 江苏厚生新能源科技有限公司 | Preparation method of high-nickel ternary special ceramic coating diaphragm |
| CN114006048A (en) * | 2021-10-25 | 2022-02-01 | 珠海冠宇电池股份有限公司 | Battery with a battery cell |
| CN114024098A (en) * | 2021-10-25 | 2022-02-08 | 珠海冠宇电池股份有限公司 | Battery with a battery cell |
| CN115820064A (en) * | 2022-01-27 | 2023-03-21 | 宁德时代新能源科技股份有限公司 | Coating composition, separator, secondary battery, battery module, battery pack, and electric device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105762319A (en) * | 2016-03-02 | 2016-07-13 | 南京国轩电池有限公司 | Composite lithium ion battery diaphragm with high cohesion and preparation method thereof |
| CN107513196A (en) * | 2016-06-17 | 2017-12-26 | 常州百思通复合材料有限公司 | A kind of method using microwave high-efficiency heating high molecular polymer |
| CN105958000A (en) * | 2016-07-11 | 2016-09-21 | 东莞市魔方新能源科技有限公司 | Lithium ion battery composite membrane and preparation method thereof |
| CN106374136A (en) * | 2016-08-26 | 2017-02-01 | 浙江长兴金太阳电源有限公司 | Overheat-proof diaphragm used for lithium ion batteries and preparation method thereof |
| CN106898721A (en) * | 2017-02-28 | 2017-06-27 | 沧州明珠隔膜科技有限公司 | A kind of lithium ion battery separator for being suitable to hot dry-pressing and preparation method thereof |
| CN107955468B (en) * | 2017-11-16 | 2021-03-12 | 珠海恩捷新材料科技有限公司 | Polyacrylonitrile coated lithium ion battery diaphragm |
| CN107955468A (en) * | 2017-11-16 | 2018-04-24 | 珠海恩捷新材料科技有限公司 | A kind of lithium ion battery separator of polyacrylonitrile coating |
| CN108011067A (en) * | 2018-01-04 | 2018-05-08 | 东莞市魔方新能源科技有限公司 | A kind of membrane configuration |
| CN109860488A (en) * | 2019-01-23 | 2019-06-07 | 东莞市魔方新能源科技有限公司 | Lithium battery diaphragm coating paste and preparation method thereof and diaphragm containing the slurry |
| CN111987273A (en) * | 2019-05-23 | 2020-11-24 | 河北金力新能源科技股份有限公司 | PVDF&Al2O3Mixed coating slurry, preparation method thereof, lithium ion battery diaphragm and lithium ion battery |
| CN112194936A (en) * | 2020-09-18 | 2021-01-08 | 河北金力新能源科技股份有限公司 | Ultra-high dispersion type PVDF slurry, diaphragm and preparation method thereof |
| CN112701420A (en) * | 2021-01-23 | 2021-04-23 | 山东天瀚新能源科技有限公司 | Multifunctional diaphragm for lithium battery, preparation method and application |
| CN113258208A (en) * | 2021-05-10 | 2021-08-13 | 江苏厚生新能源科技有限公司 | Preparation method of high-nickel ternary special ceramic coating diaphragm |
| CN113258208B (en) * | 2021-05-10 | 2022-06-17 | 江苏厚生新能源科技有限公司 | Preparation method of high-nickel ternary special ceramic coating diaphragm |
| CN114006048A (en) * | 2021-10-25 | 2022-02-01 | 珠海冠宇电池股份有限公司 | Battery with a battery cell |
| CN114024098A (en) * | 2021-10-25 | 2022-02-08 | 珠海冠宇电池股份有限公司 | Battery with a battery cell |
| CN114006048B (en) * | 2021-10-25 | 2023-12-26 | 珠海冠宇电池股份有限公司 | Battery cell |
| CN114024098B (en) * | 2021-10-25 | 2024-05-17 | 珠海冠宇电池股份有限公司 | Battery cell |
| CN115820064A (en) * | 2022-01-27 | 2023-03-21 | 宁德时代新能源科技股份有限公司 | Coating composition, separator, secondary battery, battery module, battery pack, and electric device |
| CN115820064B (en) * | 2022-01-27 | 2024-03-22 | 宁德时代新能源科技股份有限公司 | Coating composition, separator, secondary battery, battery module, battery pack, and electric device |
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