CN104953070B - A kind of lithium rechargeable battery barrier film - Google Patents

A kind of lithium rechargeable battery barrier film Download PDF

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Publication number
CN104953070B
CN104953070B CN201510228162.5A CN201510228162A CN104953070B CN 104953070 B CN104953070 B CN 104953070B CN 201510228162 A CN201510228162 A CN 201510228162A CN 104953070 B CN104953070 B CN 104953070B
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barrier film
rechargeable battery
polymer
lithium rechargeable
inorganic particulate
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CN104953070A (en
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蒋中林
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DONGGUAN MOFANG NEW ENERGY TECHNOLOGY Co.,Ltd.
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Kweiyang Odd-Numbered Prescription Science And Technology Ltd
Dongguan City Magic Square New Energy Technology Co Ltd
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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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Cell Separators (AREA)

Abstract

The invention belongs to cell manufacturing techniques field, specifically related to a kind of lithium rechargeable battery barrier film, functional coating is coated with an at least surface for described isolation membrane body, the functional coating is mixed together stirring by inorganic particulate, binding agent and polymer and slurry is made in a solvent, it is then coated with one or two surface of isolation membrane body, functional coating causes inorganic particle layer to be enriched in barrier film body surface by technology controlling and process coating procedure, and polymer rich is on the surface of inorganic particulate.Inorganic particulate in functional coating has excellent heat endurance, inhibit the contraction of barrier film in the case of a high temperature, its heat endurance is improved, while the polymeric layer of surface of inorganic particles enrichment can be bonded together the deformation for suppressing battery in lithium ion battery with its pole piece.

Description

A kind of lithium rechargeable battery barrier film
Technical field
The invention belongs to battery isolating film technical field, and in particular to a kind of lithium rechargeable battery barrier film.
Background technology
The barrier film of lithium rechargeable battery is clipped between both positive and negative polarity as the isolation of both positive and negative polarity, and main function is to prevent Both positive and negative polarity directly contacts generation short circuit.Current barrier film is main by polyethylene, the porous media of the TPO composition such as polypropylene, Polyolefine isolating film has less than 200 DEG C of fusing point, when lithium rechargeable battery because internal or external factor causes generation short Road generate heat and temperature rise when, barrier film easily occur thermal contraction causes both positive and negative polarity it is bigger short circuit generation, cause the heat of battery It is out of control to cause fire accident.Constantly improved with the energy density of lithium rechargeable battery in addition, the graphite of high gram volume is born The ultimate attainment expansion made in its charge and discharge process is very big, result in the torsional deformation of battery.In order to solve the above problems, in industry One layer of porous dielectric layer being made up of inorganic particulate is coated on barrier film surface and coats one layer on the porous dielectric layer again in addition The tack coat of polymer or the mixed coating of coating inorganic particle and Polymer Tie-layer solve safety problem and problem on deformation. The good heat endurance of inorganic particulate ensures its security, and polymer can be bonded together the change for suppressing battery with pole piece Shape.Such as Chinese patent CN102569701A, CN102610773A and CN103441230A and the Chinese patent of LG company CN101326658A.Patent CN102569701A and CN102610773A are the insulating barriers for being initially formed inorganic particulate, are then coated with The tack coat of polymer realizes, it is necessary to repeatedly coating, technical process is more complicated, technique hardly possible control.Chinese patent CN103441230A by inorganic particulate, realize by the technique together with cohesive polymers mixing, but needs heating to be swelled in advance, technique Also it is more complicated.Chinese patent CN101326658A forms binder polymer/inorganic by being repeatedly coated on porous substrate surface Particle content is than graded, and technique is also very complicated.
The content of the invention
It is an object of the invention to：For that can be glued now with the not enough of technology there is provided one kind with electrodes of lithium-ion batteries Knot is good, suppresses lithium ion battery deformation well, while using lithium rechargeable battery of the performance of lithium ion battery without influence Barrier film.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of lithium rechargeable battery barrier film, including isolation membrane body, the described at least table for isolating membrane body Functional coating is coated with face, the functional coating is mixed together and stirred in a solvent by inorganic particulate, binding agent and polymer Mixing is then coated with one or two surface of isolation membrane body into slurry, is formed inorganic particulate and is enriched in barrier film sheet Body surface face, polymer rich is in surface of inorganic particles.
A kind of described lithium rechargeable battery barrier film its preparation method, comprises the following steps：
A) prepared by functional coating slurry：The inorganic particulate, the binding agent and polymer dispersed with stirring is uniform：By nothing Machine particle, binding agent and polymer are dissolved in solvent forming slurry together, and slurry concentration is 1~60wt%, more preferably 5~ 50wt%；
B) it is described isolation membrane body surface on coat the functional coating slurry, be made lithium rechargeable battery with every From film,
Then the barrier film of coating is dried；Segmentation is carried out when drying, and is at least divided to two sections；
First paragraph dries enrichment, is floated by the small polymer of the quick volatile zone dynamic density of solvent, is enriched in inorganic grain Sublist face, first paragraph temperature is selected between 30~130 DEG C, wind speed 0.5m/sec to 20m/sec；It is preferred that between 40~70 DEG C, wind 2~15m/sec of speed；
Second segment is solidification drying stage, and temperature selects 20~70 DEG C, wind speed 0.5m/sec to 15m/sec.
Described drying mode be heated-air drying, infra-red drying, ceramic heat dry or microwave drying any one.
The isolation membrane body is polyethylene micropore film or polypropylene microporous film.
The isolation membrane body is polyimides or non-woven fabrics.
The polymer is Kynoar-hexafluoropropene (PVDF-HFP), polyacrylonitrile (PAN), polyoxyethylene (PEO) At least one of with polymethacrylates (PMMA)；
The binding agent is styrene-butadiene, Kynoar, Kynoar-hexafluoropropene, polypropylene Acid, polymethylacrylic acid, polyacrylate, polymethyl methacrylate, polyacrylonitrile, sodium carboxymethylcellulose, butadiene-the third Any one or more in alkene nitrile polymer, polyvinylpyrrolidone and polyacrylic acid-styrene.
The inorganic particulate is calcium oxide, zinc oxide, magnesia, titanium dioxide, silica, zirconium dioxide, titanium dioxide Any one or more in tin, ceria, alundum (Al2O3), boehmite, calcium carbonate and barium titanate.
The average grain diameter of the inorganic particulate is 0.05~6um, and particle size distribution is 0.01~10 μm；It is preferred that the grain that is averaged Footpath is 0.1~2.0um, and particle size distribution is 0.05~5.0um；The thickness of functional coating be 0.5~10 μm, preferably 2~ 5um。
The mass ratio of the inorganic particulate and binding agent is 80:20~99.9:0.1；Described inorganic particulate and polymer Mass ratio be 50:50~99:1,
Solvent is tetrahydrofuran, MEK, dimethylformamide, dimethyl acetamide, tetramethylurea, tetramethyl phosphoric acid One or more in salt, acetone, dichloromethane, chloroform, dimethylformamide, 1-METHYLPYRROLIDONE, hexamethylene, water, alcohol.
The beneficial effects of the present invention are：The lithium rechargeable battery includes functional coating, functional coating with barrier film Inorganic particle layer is caused to be enriched in barrier film body surface by technology controlling and process coating procedure, polymer rich is in inorganic particulate Surface, because isolation membrane body itself has microcellular structure, and its thermal conductivity coefficient is smaller, when drying, temperature rise, barrier film sheet Temperature can differ larger with Coated Surface Temperature, and the solvent carried secretly in functional coating accelerates upward volatilization, small with dynamic density Polymer floats, and forms polymer rich in surface of inorganic particles.Inorganic particulate in functional coating has excellent thermally-stabilised Property, it is suppressed that the contraction of barrier film in the case of a high temperature, improves its heat endurance, while the polymer of surface of inorganic particles enrichment Layer can be bonded together the deformation for suppressing battery in lithium ion battery with its pole piece.
Embodiment
The present invention and its advantage are described in further detail below in conjunction with embodiment, still, this hair Bright embodiment is not limited thereto.
Comparative example 1
It is prepared by positive plate：By cobalt acid lithium, conductive carbon, binding agent Kynoar in mass ratio 96：2.5：1.5 in N- methyl It is well mixed in pyrrolidones (NMP) solvent and anode sizing agent is made, is then coated on aluminium foil and is carried out after being dried at 110 DEG C Cold pressing, slitting, cutting edge, tab welding, are made 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 in deionized water be well mixed cathode size is made, be then coated on copper foil and at 85 DEG C dry after carry out Cold pressing, slitting, cutting edge, tab welding, are made negative plate.
Barrier film：
The polyethylene micropore film that thickness is 9 μm is taken as barrier film.
The preparation of battery：
The positive plate, barrier film, negative plate of above-mentioned preparation are wound into battery core, the battery core is then placed in aluminium plastic packaging bag In, electrolyte is injected, lithium ion battery is made in the process such as encapsulated, chemical conversion, capacity；It is 1 that wherein electrolyte, which includes mass ratio,: 2:1 ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate, and lithium hexafluoro phosphate, the concentration of lithium hexafluoro phosphate is 1mol/ L。
Comparative example 2
This comparative example is with the difference of comparative example 1：The polyethylene micropore film that thickness is 9 μm is taken as barrier film.
The preparation of inorganic particulate coating：
In deionized water first add 10wt% polyacrylate dispersion (content of polyacrylate is in the aqueous solution 1h 30wt%) is stirred, 90wt% Al is then added2O3After particle, stirring 2h, 1h is ground in ball mill, nothing is prepared Machine particle slurry, the solid content of slurry is 50wt%, Al2O3The average grain diameter of particle be 0.5 μm, particle size distribution be 0.1~ 3μm。
The preparation of barrier film：
Using the mode of intaglio plate coating by slurry uniform fold on barrier film, slurry drying uses heated-air drying, dry It is divided to two sections of progress, 55 DEG C of first paragraph temperature, wind speed 5m/s, second segment temperature is 55 DEG C, wind speed 8m/s, is nothing after slurry drying Then machine particle layer, 5 μm of the thickness of inorganic particle layer, then cut, cut-parts to the barrier film of the coating.Other are identical, Repeat no more.
Comparative example 3
This comparative example is with the difference of comparative example 2, is simply coated on barrier film after the coating of coating inorganic particle The coating of polymer.
Polymer coating is coated with above inorganic particulate coating, barrier film and its preparation are described in detail below：
The inorganic particulate coating in comparative example 2 is taken every barrier film.
The preparation of polymer coating：
Kynoar-hexafluoropropene stirring 4h is added in acetone solvent and is made into polymer solution, concentration is 5%, is led to Inorganic particulate coating barrier film two sides in comparative example 2 is coated the polymer solution by the mode for crossing dip-coating, is then carried out Polymer coating barrier film is dried to obtain, one side coating layer thickness is 3um.Then the barrier film of the coating is cut, cut out Piece.Other are identical, repeat no more.
Embodiment 1
The preparation of the positive plate of the present embodiment, the preparation of negative plate and the preparation of battery are identical with comparative example 1, no longer go to live in the household of one's in-laws on getting married State, barrier film is different from comparative example 1, barrier film and its preparation are described in detail below：
The polyethylene micropore film that thickness is 9 μm is taken as isolation membrane body.
The preparation of functional coating slurry：
1) Al is first added in deionized water2O3Particle is stirred 1h, and solid content is 40wt%, is ground in ball mill 1h is ground, acrylic acid ester emulsion (content of polyacrylate is 25wt% in the aqueous solution) stirring 1h, Al2O3 and propylene is subsequently added into The mass ratio of acid esters is 80:20, then add Kynoar-hexafluoropropene powder and be stirred 2h, Al2O3With polyvinylidene fluoride The mass ratio of alkene-hexafluoropropene is 50:50, the solid content of the slurry is 50wt%, Al2O3The average grain diameter of particle is 0.8 μm, Particle size distribution is 0.1~5 μm；
2) by way of dip-coating, the slurry is respectively coated on 9um polyethylene micropore film two sides, dries and passes through two The heated-air drying of section is carried out, and first paragraph temperature is 60 DEG C, and wind speed is 12m/s, and second segment temperature is 65 DEG C, and wind speed is 8m/s, is done Functional coating barrier film has been obtained after dry, has been 3um per finishing coat thickness, then the barrier film of the coating is cut, cut-parts.
Embodiment 2
The preparation of the positive plate of the present embodiment, the preparation of negative plate and the preparation of battery are identical with comparative example 1, no longer go to live in the household of one's in-laws on getting married State, barrier film is different from comparative example 1, barrier film and its preparation are described in detail below：
The polyimides that thickness is 9 μm is taken as isolation membrane body.
The preparation of functional coating slurry：
1) boehmite particles first being added in deionized water and being stirred 1h, solid content is 30wt%, in ball mill 1h is ground, polyacrylonitrile emulsion (content of polyacrylonitrile is 20wt% in the aqueous solution) stirring 1h is subsequently added into, boehmite is with gathering The mass ratio of acrylonitrile is 90:10, then add polyoxyethylene powder and be stirred 2h, boehmite and polyoxyethylated mass ratio For 80:20, the solid content of the slurry is 33wt%, and the average grain diameter of boehmite particles is 1.5 μm, and particle size distribution is 0.2 ~6 μm；
2) by way of intaglio plate coating, the slurry is respectively coated on 9um polyethylene micropore film two sides, dries logical The heated-air drying for crossing two sections is carried out, and first paragraph temperature is 70 DEG C, and wind speed is 15m/s, and second segment temperature is 70 DEG C, and wind speed is 10m/ S, functional coating barrier film has been obtained after drying, and is 5um per finishing coat thickness, then the barrier film of the coating is cut, Cut-parts.
Embodiment 3
The preparation of the positive plate of the present embodiment, the preparation of negative plate and the preparation of battery are identical with comparative example 1, no longer go to live in the household of one's in-laws on getting married State, barrier film is different from comparative example 1, barrier film and its preparation are described in detail below：
The polypropylene microporous film that thickness is 9 μm is taken as isolation membrane body.
The preparation of functional coating slurry：
1) in ethanol, (quality of ethanol and deionized water is 50 with deionized water mixed solvent:50) TiO is first added in2 Particle is stirred 1h, and solid content is 30wt%, and 1h is ground in ball mill, carboxymethylcellulose sodium solution is subsequently added into (carboxymethylcellulose sodium solution concentration is 1.5wt%) stirring 1h, TiO2Mass ratio with sodium carboxymethylcellulose is 95:5, so Polymethacrylates (PMMA) powder is added afterwards is stirred 2h, TiO2Mass ratio with polymethacrylates powder is 60:40, the solid content of the slurry is 23wt%, TiO2The average grain diameter of particle is 0.5 μm, and particle size distribution is 0.08~2 μ m；
2) by way of dip-coating, the slurry is respectively coated on 9um polyethylene micropore film two sides, dries and passes through two The heated-air drying of section is carried out, and first paragraph temperature is 70 DEG C, and wind speed is 10m/s, and second segment temperature is 65 DEG C, and wind speed is 8m/s, is done Functional coating barrier film has been obtained after dry, has been 2um per finishing coat thickness, then the barrier film of the coating is cut, cut-parts.
Embodiment 4
The present embodiment difference from Example 3 is：The inorganic particulate is calcium oxide and zinc oxide, and its mass ratio is 1:1。
The average grain diameter of the inorganic particulate is 0.8um, and particle size distribution is 0.01~5 μm；The thickness of functional coating For 5 μm.
The mass ratio of the 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 dichloromethane and alcohol.Other are same as Example 3, repeat no more here.
Comparative example and embodiment explanation
Group Description
Comparative example 1 Barrier film is uncoated
Comparative example 2 Barrier film coating inorganic particle coating
Comparative example 3 Polymeric layer is coated with 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
The barrier film in comparative example and embodiment for more than carries out thermal contraction test
Thermal contraction test:Barrier film is punched into 100X100mm square sample, MD and TD directions are indicated, measurement is just 2H is toasted in the MD and TD of beginning length, the baking oven for putting it into 130 degree, the length in MD and TD directions after test is toasted after taking-up Degree, calculates percent thermal shrinkage=[(size after size-baking before baking)/red size before examination] X100%.Acquired results are shown in Table 1
The comparative example of table 1 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, barrier film surface coating functions layer embodiment 1~4 thermal contraction and have coating inorganic particle Barrier film comparative example 2~3 in same level and compared to not having cated barrier film comparative example 1 to improve substantially.
Experimental example 2
The lithium ion battery in comparative example and embodiment for more than carries out discharge-rate test
Discharge-rate is tested:Multiplying power by lithium ion battery first using 0.5C at 25 DEG C is charged, and 0.2C multiplying powers are put Electricity, records discharge capacity；Then 0.5C multiplying power chargings are carried out, 0.5C multiplying power dischargings record discharge capacity；Then 0.5C times is carried out Rate charges, 1.0C multiplying power dischargings, records discharge capacity；Followed by 0.5C multiplying power chargings are carried out, 1.5C multiplying power dischargings, record discharges Capacity；0.5C multiplying power chargings are finally carried out, 2.0C multiplying power dischargings record discharge capacity.Capacity under variant discharge-rate is protected Holdup=(discharge capacity under discharge capacity/0.2C multiplying powers under each multiplying power) X100%.Acquired results are shown in Table 2
Capability retention under the comparative example of table 2 discharge-rate different with 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, coated insulation film surface functional layer embodiment 1~4 high rate performance and do not have cated ratio Compared with the comparative example 2 and inorganic coating of example 1 and inorganic particulate coating and the comparative example 3 of polymer coating in same level.
Experimental example 3
The lithium ion battery in comparative example and embodiment for more than carries out cycle performance test
Cycle performance and thickness test：Lithium ion battery is charged using 0.5C multiplying power at 25 degrees c, 0.5C multiplying power Electric discharge, carries out the battery capacity under 500 circulations, each loop test 0.5C multiplying powers successively, and with circulating under preceding 25 degree of battery Capacity be compared, calculate the capability retention after circulation, capability retention=(capacity after 500 circulations under 0.5C multiplying powers/ Capacity before circulation under 25 degree of battery) X100%.Thickness swelling=(battery completely fills before the thickness/circulation completely filled after 500 circulations Thickness) X100% acquired results are shown in Table 3
The comparative example of table 3 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, cycle performance and the comparative example 1~3 of the embodiment 1~4 of coating functions layer are in same level, but electricity Pond thickness swelling, the embodiment 1~4 of coating functions layer does not have with being coated with the comparative example 3 of polymeric layer in same level, but ratio The comparative example 2 of cated comparative example 1 and non-polymer coating is all obviously improved.
Experimental example 4
The lithium ion battery in comparative example and embodiment for more than carries out drift bolt safety test
Drift bolt is tested：First battery is completely filled, then the standard according to UL1642 is tested, and nail diameter is 2.5mm, drift bolt speed is 100mm/s.Test result is shown in Table 4
Table 4 circulates the drift bolt test result of front and rear battery
As known from Table 4, barrier film surface coating functions layer embodiment 1~4 thermal contraction and have coating inorganic particle Barrier film comparative example 2~3 in same level and compared to not having cated barrier film comparative example 1 to improve substantially.
Experimental example 5
The lithium ion battery in comparative example and embodiment for more than is completely filled visual examination deformation.Proportion of deformation is shown in Table 5
The battery of table 5 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 and the comparative example 3 of polymeric layer is coated with all without electricity Pond is deformed, but does not have all gross distortions of comparative example 2 of cated comparative example 1 and non-polymer coating.
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party Formula is changed and changed.Therefore, the invention is not limited in above-mentioned embodiment, every those skilled in the art exist Made any conspicuously improved, replacement or modification belong to protection scope of the present invention on the basis of the present invention.This Outside, although having used some specific terms in this specification, these terms merely for convenience of description, not to the present invention Constitute any limitation.

Claims (9)

1. a kind of lithium rechargeable battery barrier film, including isolation membrane body, it is characterised in that：Described isolation membrane body It is coated with functional coating on an at least surface, the functional coating passes through inorganic particulate, binding agent and polymer in a solvent one Play mixing and slurry is made, be then coated with one or two surface of isolation membrane body, form inorganic particulate and be enriched in Barrier film body surface, polymer rich is in surface of inorganic particles；The preparation method of the barrier film, comprises the following steps：
A) prepared by functional coating slurry：The inorganic particulate, the binding agent and polymer dispersed with stirring is uniform：By inorganic grain Son, binding agent and polymer are dissolved in solvent to form slurry together, and slurry concentration is 1~60wt%；
B) the functional coating slurry is coated on the surface of the isolation membrane body, lithium rechargeable battery isolation is made Film,
Then the barrier film of coating is dried；Segmentation is carried out when drying, and is at least divided to two sections；
First paragraph dries enrichment, is floated by the small polymer of the quick volatile zone dynamic density of solvent, is enriched in inorganic particulate table Face, first paragraph temperature is selected between 30~130 DEG C, wind speed 0.5m/sec to 20m/sec；
Second segment is solidification drying stage, and temperature selects 20~70 DEG C, wind speed 0.5m/sec to 15m/sec.
2. a kind of lithium rechargeable battery barrier film according to claim 1, it is characterised in that：Described drying mode For heated-air drying, infra-red drying, ceramic heat dry or microwave drying any one.
3. a kind of lithium rechargeable battery barrier film according to claim 1, it is characterised in that：The isolation membrane body For polyethylene micropore film or polypropylene microporous film.
4. a kind of lithium rechargeable battery barrier film according to claim 1, it is characterised in that：The isolation membrane body For polyimides or non-woven fabrics.
5. a kind of lithium rechargeable battery barrier film according to claim 1, it is characterised in that：The polymer is poly- Biasfluoroethylene-hexafluoropropylene (PVDF-HFP), polyacrylonitrile (PAN), polyoxyethylene (PEO) and polymethacrylates (PMMA) At least one of；
The binding agent be styrene-butadiene, Kynoar, Kynoar-hexafluoropropene, polyacrylic acid, Polymethylacrylic acid, polyacrylate, polymethyl methacrylate, polyacrylonitrile, sodium carboxymethylcellulose, butadiene-propylene Any one or more in nitrile polymer, polyvinylpyrrolidone and polyacrylic acid-styrene.
6. a kind of lithium rechargeable battery barrier film according to claim 1, it is characterised in that：The inorganic particulate is Calcium oxide, zinc oxide, magnesia, titanium dioxide, silica, zirconium dioxide, tin ash, ceria, alundum (Al2O3), Any one or more in boehmite, calcium carbonate and barium titanate.
7. a kind of lithium rechargeable battery barrier film according to claim 1, it is characterised in that：The inorganic particulate Average grain diameter is 0.05~6um, and particle size distribution is 0.01~10 μm；The thickness of the functional coating is 0.5~10 μm.
8. a kind of lithium rechargeable battery barrier film according to claim 1, it is characterised in that：The inorganic particulate with The mass ratio of binding agent is 80:20~99.9:0.1；Described inorganic particulate and the mass ratio of polymer are 50:50~99:1.
9. a kind of lithium rechargeable battery barrier film according to claim 1, it is characterised in that：Solvent is tetrahydrochysene furan Mutter, MEK, dimethylformamide, dimethyl acetamide, tetramethylurea, tetramethyl based phosphates, acetone, dichloromethane, chloroform, One or more in dimethylformamide, 1-METHYLPYRROLIDONE, hexamethylene, water, alcohol.
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