CN104868084A - Isolation membrane for lithium ion secondary battery - Google Patents
Isolation membrane for lithium ion secondary battery Download PDFInfo
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- CN104868084A CN104868084A CN201510227999.8A CN201510227999A CN104868084A CN 104868084 A CN104868084 A CN 104868084A CN 201510227999 A CN201510227999 A CN 201510227999A CN 104868084 A CN104868084 A CN 104868084A
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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
- H01M50/44—Fibrous material
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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
- H01M50/411—Organic material
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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 manufacturing of batteries and in particular relates to an isolation membrane for a lithium ion secondary battery. A functional coating is coated on at least one surface of an isolation membrane main body; the functional coating is prepared from coated inorganic particles and an adhesive; with respect to the coated inorganic particles, polymer is dissolved in a solvent and then the inorganic particles are mixed into the solvent and are uniformly stirred; after the mixture is dried, powder is obtained and the inorganic particles coated with the polymer on the surfaces are obtained. The polymer-coated inorganic particles have excellent thermal stability and safety property of batteries is ensured; the polymer coated on the surfaces of the inorganic particles can be well bonded with the positive electrode plate and the negative electrode plate of the lithium ion battery, so that deformation of the battery is restrained; a gap is formed between adjacent polymer-coated inorganic particles and a required function can be realized only by once coating; the inorganic particles slightly block up the isolation membrane and have no influence on the property 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.Chinese patent CN102569701A and Chinese CN102610773A is the insulating barrier first forming inorganic particulate, and then the tack coat of coated polymer realizes.Chinese patent CN101326658A realizes than graded by being repeatedly coated on porous substrate surface formation binder polymer/content of inorganic particles.But multiple coating can block comparatively serious to the hole of barrier film, affect the performance of battery.Together with Chinese patent CN103441230A to be mixed with cohesive polymers by inorganic particulate, technique realizes, but needs to heat swollen polymer in advance, swelling polymer can plug-hole relatively more serious, also can affect battery performance.
Summary of the invention
The object of the invention is to: provide one and there is good thermal stability, ultra-low thermal contraction, excellent security performance, can bond well with electrodes of lithium-ion batteries simultaneously, suppress lithium ion battery distortion, and 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 made up of coated inorganic particulate and bonding agent, described coated inorganic particulate, by first polymer being dissolved in a solvent, then inorganic particulate being mixed into and stirring together, after drying, make the inorganic particulate that powder obtains Surface coating polymer.
Relative to prior art, this functional coating of the present invention forms primarily of inorganic particulate, has good thermostability qualitative; The coated polymeric layer of surface of inorganic particles can have good cementation with the positive/negative plate of lithium ion battery, effectively suppresses the deformation of battery; This functional coating, by coated inorganic particulate and binding agent mixing composition, adopts primary coating technique to realize, forms hole between inorganic particulate coated after coating, minimum to barrier film hole plug, can not have impact to battery performance.Compared to existing coating inorganic coating and the functional coating of polymer coating and the mixed coating of inorganic particulate and polymer, polymer overmold of the present invention is at surface of inorganic particles, can not be filled between inorganic particulate, and carry out primary coating formation, less to the pore plugging of barrier film, on battery performance without impact.
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.
Described barrier film body is polyethylene micropore film or polypropylene microporous film.
Described barrier film body is polyimides or nonwoven fabrics.
Described polymer solvent is one or more in dimethyl carbonate, propene carbonate, ethylene carbonate, oxolane, methylethylketone, dimethyl formamide, dimethylacetylamide, tetramethylurea, tetramethyl phosphate, acetone, carrene, chloroform, dimethylformamide, 1-METHYLPYRROLIDONE, cyclohexane, water, alcohol.
The average grain diameter of described inorganic particulate is 0.05 ~ 6um, and particle size distribution is 0.01 ~ 10 μm, and the average grain diameter of the inorganic particulate after coated is 0.08 ~ 8um, and particle size distribution is 0.01 ~ 12um; The thickness of functional coating is 0.5 ~ 10 μm.
The average grain diameter of described inorganic particulate is 0.1 ~ 2.0um, and particle size distribution is 0.05 ~ 5.0um; The average grain diameter of the inorganic particulate after coated is 0.15 ~ 6um, and particle size distribution is 0.05 ~ 10um; The thickness of functional coating is 1 ~ 8um.
The concentration of described polymer solution is 0.1 ~ 50%, preferably 0.3 ~ 30%;
The mass ratio of described inorganic particulate and binding agent is 80:20 ~ 99.9:0.1.
The preparation method of described a kind of lithium rechargeable battery barrier film, its step comprises as follows:
A) the inorganic particulate preparation of polymer overmold: polymer is dissolved in solvent to form solution, then inorganic particulate is mixed into stir together and forms uniform suspension, the solid content of this suspension is 1 ~ 60%, preferably 5 ~ 45%, then carry out drying and powder preparation, powder preparation method can select physical method also can select chemical method;
B) the slurry preparation of polymer overmold inorganic particulate: stir the inorganic particulate of the polymer overmold of indication in a) together with binding agent obtained slurry in a solvent, described solvent can select oxolane, methylethylketone, dimethyl formamide, dimethylacetylamide, tetramethylurea, tetramethyl phosphate, acetone, carrene, chloroform, dimethylformamide, 1-METHYLPYRROLIDONE, cyclohexane, water, alcohol, described solvent is unrestricted, but this solvent can not be formed the polymer of surface of inorganic particles parcel and destroy, the solid content of described slurry is 10 ~ 60%, preferably 30 ~ 50%,
C) preparation of functional layer: the slurry of preparation in b) is coated in barrier film body one or two on the surface, then drying obtains functional coating; Coating method be dip-coating, die head be coated with, spraying, roller coat, silk screen printing, scraper transfer be coated with and intaglio plate painting in any one or multiple.
Beneficial effect of the present invention is:
The coated inorganic particulate of Inventive polymers has excellent thermal stability, ensure that the security performance of battery; The coated polymer of surface of inorganic particles can bond very well with positive electrode plate and negative electrode plate of lithium ion battery, suppresses the distortion of battery; Form hole between the inorganic particulate of polymer overmold and only carry out the function needed for primary coating realization, having minimum blocking to the hole of barrier film, on the performance of battery without impact.
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:
Above-mentioned positive plate, 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 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: barrier film surface needs the coating of coated polymer again after coating inorganic particle, is described in detail below to barrier film and preparation thereof:
Barrier film:
Getting thickness is that the polyethylene micropore film of 9 μm is as barrier film.
The preparation of inorganic particulate slurry:
The polyacrylate dispersion (in the aqueous solution, the content of polyacrylate is 40wt%) first adding 20wt% in deionized water stirs 1h, then adds Al
2o
3particle, Al
2o
3the mass ratio of particle and polyacrylate is 92:8, and 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 polymer solution:
In acetone solvent, add Kynoar-hexafluoropropylene stirring 4h be made into polymer solution, described solution concentration is 20%
The preparation of barrier film coating:
Use intaglio plate coating mode by inorganic particulate slurry uniform fold on a face of barrier film, thickness is 4um, inorganic coating barrier film is obtained after drying, then by this inorganic coating barrier film dip-coating in a polymer solution, obtain the barrier film of double-sided polymerization thing coating after drying, polymer thickness is one side 2um, and this barrier film has one side inorganic particulate coating and double-sided polymerization thing coating, 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 1 difference are: barrier film needs the mixed coating of coating inorganic particle and polymer, is described in detail below to barrier film and preparation thereof:
Barrier film: getting thickness is that the polyethylene micropore film of 9 μm is as barrier film.
The preparation of inorganic particulate and polymer mixed coating:
In acetone solvent, add Kynoar-hexafluoropropylene and agitating solution 2h, solution concentration is 30wt%, then adds Al
2o
3particle, Al
2o
3the mass ratio of particle and Kynoar-hexafluoropropylene is 80:20, grinds the mixed slurry that 1h obtains inorganic particulate and polymer, then add CMC solution and form last slurry, Al after stirring 2h
2o
3the mass ratio of particle and CMC is 95:5, and the solid content of slurry is 40wt%, Al
2o
3the average grain diameter of particle is 1.2 μm, and particle size distribution is 0.2 ~ 5 μm.
The preparation of barrier film coating:
Use the method for dip-coating by the coating of the mixed coating of inorganic particulate and polymer in barrier film dual coating, obtain the barrier film of two-sided inorganic particulate and polymer coating after drying, thickness is one side 4um, then cuts the barrier film of this coating, 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 bonding polymer coating:
The preparation of polymer overmold inorganic particulate:
In acetone solvent, add Kynoar-hexafluoropropylene stirring 4h be made into polymer solution, described solution concentration is 25%, then by Al
2o
3particle adds, Al
2o
3the weight ratio of powder and polymer solution is 50:50, Al
2o
3the average grain diameter of particle is 0.9um, and distribution is 0.2 ~ 5.0um, grinds, obtain the Al of coated polymer after grinding after stirring 4h after carrying out drying
2o
3particle, the Al after coated
2o
3the average grain diameter of particle is 1.5um, and distribution is 0.2 ~ 6.0um.
The preparation of functional coating
1) preparation of slurry: by above-mentioned coated after Al
2o
3particle adds in the polyacrylate dispersion of 30wt% and deionized water and carries out stirring 5h, the Al after coated
2o
3be 90:10 with the weight ratio of polyacrylate, the slurry solid content after stirring is 45%
2) preparation of functional coating: the slurry of preparation is coated on a face of the polyethylene micropore film of 9um by mode respectively that be coated with by intaglio plate, and thickness is 4um, drying is cut the barrier film of this coating, 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:
Barrier film:
Getting thickness is that the polyimides of 9 μm is as barrier film body.
The preparation of polymer overmold inorganic particulate:
In dimethylacetamide solvent, add polyacrylonitrile dissolving make polymer solution, the concentration of solution is 20wt%, then by TiO
2particle adds, TiO
2the weight ratio of powder and polymer solution is 40:60, TiO
2the average grain diameter of particle is 0.4um, and distribution is 0.08 ~ 3.0um, grinds, obtain the TiO of coated polymer after grinding after stirring 4h after carrying out drying
2particle, the TiO after coated
2the average grain diameter of particle is 0.8um, and distribution is 0.1 ~ 4.0um.
The preparation of functional coating
1) preparation of slurry: by above-mentioned coated after TiO
2particle adds in styrene-butadiene and deionized water and alcohol mixed solvent and carries out stirring 5h, the TiO after coated
2be 97:3 with styrene-butadiene weight ratio, the slurry solid content after stirring is 40%
2) preparation of functional coating: be coated on the polyethylene micropore film two sides of 9um by the mode of dip-coating respectively by the slurry of preparation, one side thickness is 3um, drying is cut the barrier film of this coating, cut-parts.
Embodiment 3
The present embodiment difference from Example 2 is, getting thickness is that the polypropylene microporous film of 9 μm is as barrier film body.
Described polymer adopts polyacrylonitrile (PAN) and polymethacrylates (PMMA), and its mass ratio is 1 ︰ 1, and polymer solvent is 1-METHYLPYRROLIDONE.
Described binding agent adopts polyvinylpyrrolidone.
Described inorganic particulate is silicon dioxide and zirconium dioxide, and mass ratio is 1 ︰ 1.
Described slurry solvent is water.
The average grain diameter of obtained described inorganic particulate is 2.0um, and particle size distribution is 0.9 ~ 3.0um; The average grain diameter of the inorganic particulate after coated is 2.2um, and particle size distribution is 1.0 ~ 5.0um; The thickness of functional coating is 7um.
The mass ratio of described inorganic particulate and binding agent is 80:20.
Other are identical with embodiment 2 has repeated no more here.
Embodiment 4
The present embodiment difference from Example 2 is, get thickness be the nonwoven fabrics of 9 μm as barrier film body, described polymer is Kynoar-hexafluoropropylene (PVDF-HFP); Polymer solvent is propene carbonate
Described binding agent is polyacrylonitrile.
Described inorganic particulate is barium titanate.
Described slurry solvent is cyclohexane and water mixed solvent, and the concentration of described polymer solution is 25%.
The average grain diameter of obtained described inorganic particulate is 6um, and particle size distribution is 3 ~ 10 μm, and the average grain diameter of the inorganic particulate after coated is 8um, and particle size distribution is 5 ~ 12um; The thickness of functional coating is 10 μm.
The mass ratio of described inorganic particulate and binding agent is 90 ︰ 10.
Comparative example and embodiment explanation
| Group | Describe |
| Comparative example 1 | Barrier film is without coating |
| Comparative example 2 | The one side coating of barrier film coated inorganic particle and double-sided polymerization thing coating |
| Comparative example 3 | The two-sided inorganic particulate of barrier film and polymer mixed coating |
| Embodiment 1 | The coating of barrier film one side coated polymer coated inorganic particle |
| Embodiment 2 | The coating of barrier film dual coating polymer overmold inorganic particulate |
| Embodiment 3 | The coating of barrier film dual coating polymer overmold inorganic particulate |
| Embodiment 4 | The coating of barrier film dual coating polymer overmold inorganic particulate |
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 | 21.5％ | 18.9％ |
| Comparative example 2 | 2.9％ | 2.4％ |
| Comparative example 3 | 3.1％ | 2.7％ |
| Embodiment 1 | 3.0％ | 2.5％ |
| Embodiment 2 | 2.9％ | 2.3％ |
| Embodiment 3 | 2.8％ | 2.2％ |
| Embodiment 4 | 2.8％ | 2.4％ |
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
Air permeability test is carried out for the barrier film in above comparative example and embodiment
Air permeability is tested: the gas of 100 milliliters passes through the time of the test area of 1 square inch under the water column pressure of 4.88 inches high.Increase ratio=(respectively organizing test value-comparative example 1 test value)/comparative example 1 test value x100%, acquired results is in table 2
The air permeability test result of table 2 comparative example and embodiment barrier film
| Group | Air permeability (sec/100cc) | Increase ratio |
| Comparative example 1 | 165 | - |
| Comparative example 2 | 258 | 56.4％ |
| Comparative example 3 | 279 | 69.1％ |
| Embodiment 1 | 186 | 12.7％ |
| Embodiment 2 | 192 | 16.4％ |
| Embodiment 3 | 192 | 16.4％ |
| Embodiment 4 | 180 | 12.0％ |
As known from Table 2, increase is had at the comparative example 2 ~ 3 of barrier film surface coating coatings and the air permeability of embodiment 1 ~ 4, but the increase degree of embodiment 1 ~ 4 comparative example 2 ~ 3 is obvious much little, show that the plug-hole of comparative example 2 ~ 3 pairs of barrier films is relatively more serious, the plug-hole of embodiment 1 ~ 4 pair of barrier film is smaller.
Experimental example 3
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 3
Capability retention under table 3 comparative example discharge-rate different from embodiment
| Group | 0.2C | 0.5C | 1.0C | 2.0C |
| Comparative example 1 | 100％ | 97.4％ | 92.5％ | 82.9％ |
| Comparative example 2 | 100％ | 96.1％ | 89.3％ | 78.5％ |
| Comparative example 3 | 100％ | 95.8％ | 88.9％ | 77.8％ |
| Embodiment 1 | 100％ | 97.1％ | 92.3％ | 82.6％ |
| Embodiment 2 | 100％ | 97.3％ | 92.2％ | 82.5％ |
| Embodiment 3 | 100％ | 96.1％ | 91.3％ | 84.6％ |
| Embodiment 4 | 100％ | 97.5％ | 92.7％ | 82.1％ |
As known from Table 3, the high rate performance of comparative example 2 ~ 3 is compared comparative example 1 and is declined a lot, and the higher downward trend of multiplying power is more obvious, and embodiment 1 ~ 4 compares comparative example 1 substantially without decline, in same level.
Experimental example 4
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 4
Table 4 comparative example and embodiment circulation volume conservation rate and thickness swelling
| Group | Capability retention | Thickness swelling |
| Comparative example 1 | 85.5％ | 18.2％ |
| Comparative example 2 | 75.2％ | 8.3％ |
| Comparative example 3 | 73.8％ | 8.1％ |
| Embodiment 1 | 85.1％ | 8.5％ |
| Embodiment 2 | 85.6％ | 8.3％ |
| Embodiment 3 | 85.5％ | 7.9％ |
| Embodiment 4 | 85.8％ | 8.1％ |
As known from Table 4, the circulation volume conservation rate that comparative example 2 ~ 3 compares comparative example 1 declines obviously, the cycle performance of embodiment 1 ~ 4 and comparative example 1 are in same level, but cell thickness expansion rate, comparative example 2 ~ 3 and embodiment 1 ~ 4 are all improved obviously, and embodiment 1 ~ 4 and comparative example 2 ~ 3 are in same level.
Experimental example 5
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 5 circulates
As known from Table 5, in the comparative example 2 ~ 3 of barrier film surface-coated functional layer and fail safe all exhibits excellent of embodiment 1 ~ 4, compare do not have cated barrier film comparative example 1 to improve obviously in same level.
Experimental example 6
Visual examination distortion is completely filled for the lithium ion battery in above comparative example and embodiment.Proportion of deformation is in table 6
Table 6 battery completely fills proportion of deformation
| Group | Cell deformation ratio |
| Comparative example 1 | 80％ |
| Comparative example 2 | 0％ |
| Comparative example 3 | 0％ |
| Embodiment 1 | 0％ |
| Embodiment 2 | 0％ |
| Embodiment 3 | 0％ |
| Embodiment 4 | 0％ |
As can be seen from Table 6, embodiment 1 ~ 4 and the comparative example 2 ~ 3 of coating functions layer all do not have cell deformation, but do not have cated comparative example 1 all gross distortions.
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, comprises barrier film body, it is characterized in that: at least one surface of described barrier film body is coated with functional coating, and described functional coating is made up of coated inorganic particulate and bonding agent,
Described coated inorganic particulate, by first being dissolved in a solvent by polymer, being then mixed into inorganic particulate and stirring together, make the inorganic particulate that powder obtains Surface coating polymer after drying.
2. 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.
3. 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.
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, is characterized in that: described polymer solvent is one or more in dimethyl carbonate, propene carbonate, ethylene carbonate, oxolane, methylethylketone, dimethyl formamide, dimethylacetylamide, tetramethylurea, tetramethyl phosphate, acetone, carrene, chloroform, dimethylformamide, 1-METHYLPYRROLIDONE, cyclohexane, water, alcohol.
7. a kind of lithium rechargeable battery barrier film according to claim 1, it is characterized in that: the average grain diameter of described inorganic particulate is 0.05 ~ 6um, particle size distribution is 0.01 ~ 10 μm, the average grain diameter of the inorganic particulate after coated is 0.08 ~ 8um, and particle size distribution is 0.01 ~ 12um; The thickness of functional coating is 0.5 ~ 10 μm.
8. a kind of lithium rechargeable battery barrier film according to claim 7, is characterized in that: the average grain diameter of described inorganic particulate is 0.1 ~ 2.0um, and particle size distribution is 0.05 ~ 5.0um; The average grain diameter of the inorganic particulate after coated is 0.15 ~ 6um, and particle size distribution is 0.05 ~ 10um; The thickness of functional coating is 1 ~ 8um.
9. a kind of lithium rechargeable battery barrier film according to claim 1, is characterized in that: the concentration of described polymer solution is 0.1 ~ 50%, preferably 0.3 ~ 30%;
The mass ratio of described inorganic particulate and binding agent is 80:20 ~ 99.9:0.1.
10. a kind of lithium rechargeable battery barrier film according to claim 1, it is characterized in that: described preparation method, its step comprises as follows:
A) the inorganic particulate preparation of polymer overmold: polymer is dissolved in solvent to form solution, then inorganic particulate is mixed into stir together and forms uniform suspension, the solid content of this suspension is 1 ~ 60%, preferably 5 ~ 45%, then carry out drying and powder preparation;
B) the slurry preparation of polymer overmold inorganic particulate: stir the inorganic particulate of the polymer overmold of indication in a) together with binding agent obtained slurry in a solvent, and the solid content of described slurry is 10 ~ 60%, preferably 30 ~ 50%;
C) preparation of functional layer: the slurry of preparation in b) is coated in barrier film body one or two on the surface, then drying obtains functional coating; Coating method be dip-coating, die head be coated with, spraying, roller coat, silk screen printing, scraper transfer be coated with and intaglio plate painting in any one or multiple.
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Application publication date: 20150826 |