CN106025149A - High-temperature-resistant composite lithium battery diaphragm and preparation method for same - Google Patents
High-temperature-resistant composite lithium battery diaphragm and preparation method for same Download PDFInfo
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- CN106025149A CN106025149A CN201610511146.1A CN201610511146A CN106025149A CN 106025149 A CN106025149 A CN 106025149A CN 201610511146 A CN201610511146 A CN 201610511146A CN 106025149 A CN106025149 A CN 106025149A
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- Prior art keywords
- membrane
- high temperature
- lithium battery
- resistant resin
- fire resistant
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- 239000002131 composite material Substances 0.000 title claims abstract description 84
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000000576 coating method Methods 0.000 claims abstract description 65
- 239000011347 resin Substances 0.000 claims abstract description 64
- 229920005989 resin Polymers 0.000 claims abstract description 64
- 239000011248 coating agent Substances 0.000 claims abstract description 58
- 239000012528 membrane Substances 0.000 claims abstract description 58
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract 2
- 230000009970 fire resistant effect Effects 0.000 claims description 58
- 210000004379 membrane Anatomy 0.000 claims description 54
- 239000002904 solvent Substances 0.000 claims description 47
- 239000010954 inorganic particle Substances 0.000 claims description 34
- 230000004888 barrier function Effects 0.000 claims description 31
- 210000002469 basement membrane Anatomy 0.000 claims description 30
- 239000004760 aramid Substances 0.000 claims description 28
- 229920003235 aromatic polyamide Polymers 0.000 claims description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 27
- 229920001721 polyimide Polymers 0.000 claims description 26
- 239000004642 Polyimide Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- 238000007711 solidification Methods 0.000 claims description 22
- 230000008023 solidification Effects 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229910001868 water Inorganic materials 0.000 claims description 21
- 229920000098 polyolefin Polymers 0.000 claims description 17
- 239000004743 Polypropylene Substances 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 15
- 239000006184 cosolvent Substances 0.000 claims description 14
- 229920006231 aramid fiber Polymers 0.000 claims description 12
- -1 polyethylene Polymers 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001408 amides Chemical class 0.000 claims description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 241001597008 Nomeidae Species 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229950000845 politef Drugs 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 229920002530 polyetherether ketone Polymers 0.000 claims description 3
- 229920006324 polyoxymethylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 150000003568 thioethers Chemical class 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 12
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 230000003064 anti-oxidating effect Effects 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 68
- 238000012360 testing method Methods 0.000 description 31
- 239000000047 product Substances 0.000 description 26
- 239000003795 chemical substances by application Substances 0.000 description 24
- 239000010410 layer Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 239000010409 thin film Substances 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 12
- 238000001514 detection method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000001112 coagulating effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 239000002356 single layer Substances 0.000 description 6
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 5
- 229920000889 poly(m-phenylene isophthalamide) Polymers 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 230000001427 coherent effect Effects 0.000 description 4
- 230000008602 contraction Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 230000003026 anti-oxygenic effect Effects 0.000 description 3
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 description 3
- 238000005524 ceramic coating Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005188 flotation Methods 0.000 description 3
- 238000005213 imbibition Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004531 microgranule Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 206010008190 Cerebrovascular accident Diseases 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 208000006011 Stroke Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000001467 acupuncture Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004306 orthophenyl phenol Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- VACCAVUAMIDAGB-UHFFFAOYSA-N sulfamethizole Chemical compound S1C(C)=NN=C1NS(=O)(=O)C1=CC=C(N)C=C1 VACCAVUAMIDAGB-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a high-temperature-resistant composite lithium battery diaphragm and a preparation method for the same. The diaphragm comprises a base membrane and a high-temperature-resistant resin layer with which at least one surface of the base membrane is coated, wherein the base membrane is a thermoplastic resin porous membrane, and the high-temperature-resistant resin layer is a coating containing high-temperature-resistant resin. The diaphragm has stronger strength, the heat resistance of the diaphragm is greatly improved, and when the diaphragm is used, puncturing of the diaphragm by burrs and short-circuit caused by shrinkage of the diaphragm at high temperature can be reduced, and the using safety of the diaphragm can be improved; the composite diaphragm with high wettability is high in liquid absorption rate and liquid retention rate; the composite diaphragm with high anti-oxidation performance can be adapted to various application environments, and the service life of a corresponding battery is also prolonged.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly relate to a kind of high temperature resistant composite lithium battery membrane and
Its preparation method.
Background technology
Lithium ion battery obtains as the main power source of small size digital electronic product such as mobile phone and notebook computer
To being widely applied, the application in terms of the electrokinetic cells such as electric automobile is also rapidly developed.Along with lithium
The extension of ion battery application, its safety issue have also been obtained to be paid close attention to the most widely.
Battery diaphragm is one of key factor affecting lithium ion battery security, current most widely used electricity
Pond barrier film is microporous polyolefin film, but the dimensional stability of polyolefin film is poor, at battery temperature higher than 150 DEG C
Time can produce serious thermal contraction, cause battery both positive and negative polarity contact and short-circuit, cause potential safety hazard.
For improving barrier film safety, occur in that inorganic filler is coated in polyalkene diaphragm surface by many in recent years
The coated separator of preparation, due to the resistance to elevated temperatures that inorganic filler is excellent, the coated separator of coating inorganic filler
There is good heat stability.But, these coated separator also reduce the infiltration of barrier film and electrolyte simultaneously
Ability；It addition, the most surface treated inorganic filler powder easily produces reunion, and from polyalkene diaphragm table
Emaciated face falls, and affects the performance of separator product.
Summary of the invention
The present invention provides one to have, and intensity is high, safety high, electrolyte wetting capacity is good, good in oxidation resistance,
The preparation method of this high-temperature-resistant membrane can be provided as the high-temperature-resistant membrane of lithium ion battery separator simultaneously.
According to the first aspect of the invention, the present invention provides a kind of high temperature resistant composite lithium battery membrane, this barrier film
Including the fire resistant resin layer of basement membrane He at least one surface being coated on above-mentioned basement membrane, above-mentioned basement membrane is thermoplastic
Property resin perforated membrane, above-mentioned fire resistant resin layer is the coating containing fire resistant resin.
As the preferred version of the present invention, the puncture strength of above-mentioned barrier film is more than or equal to 250gf.
As the preferred version of the present invention, above-mentioned basement membrane is polyolefin single perforated membrane or polyolefin multi-layer porous
Film, preferably polyethylene porous membrane or polypropylene porous film.
As the preferred version of the present invention, possibly together with inorganic particles in above-mentioned fire resistant resin layer；Preferably,
The particle diameter of above-mentioned inorganic particles is 0.01 μm≤D50≤5 μm, more preferably 0.03 μm≤D50≤1 μm.
As the preferred version of the present invention, above-mentioned inorganic particles be aluminium oxide, titanium dioxide, silicon dioxide,
In at least one in zirconium oxide, aluminium hydroxide, magnesium hydroxide, preferably aluminium oxide, aluminium hydroxide extremely
Few one.
As the preferred version of the present invention, above-mentioned fire resistant resin be polysulfones, polyether sulfone, polyphenylene thioether,
Polyether-ether-ketone, Merlon, polyacetals, polyimides, polyamidoimide, meta virtue amide, para-position
At least one in virtue amide, politef and derivant, copolymer or mixture；It is preferably meta
The mixture of aromatic polyamide, para-position aromatic polyamide, meta-aromatic polyamide and polyimides,
Para-position aromatic polyamide and at least one in the mixture of polyimides；More preferably meta-aromatic gathers
Amide and at least in the mixture of polyimides, the para-position aromatic polyamide mixture with polyimides
Kind.
According to the second aspect of the invention, the present invention provides the high temperature resistant complex lithium electricity described in a kind of first aspect
The preparation method of pond barrier film, the method comprises the following steps:
A () will be containing fire resistant resin, inorganic particles, organic solvent, poor solvent, cosolvent, stable
The coating solution of agent and binding agent is at least one surface of basement membrane；
B the product of step (a) is immersed in containing the organic solvent dissolving aramid fiber, can not dissolve aramid fiber by ()
Poor solvent and water mixed liquor in, make above-mentioned fire resistant resin separate out solidification；
C () carries out washing and removes solvent and poor solvent the product of step (b)；
D the product of step (c) is dried by (), i.e. obtain above-mentioned high temperature resistant composite lithium battery membrane.
As the preferred version of the present invention, in above-mentioned steps (b), the water content in mixed liquor is 50～95wt%,
The temperature of above-mentioned mixed liquor is 20～80 DEG C.
As the preferred version of the present invention, the baking temperature in above-mentioned steps (d) is 40-90 DEG C.
According to the second aspect of the invention, the present invention also provides for the high temperature resistant complex lithium described in a kind of first aspect
The preparation method of battery diaphragm, the method comprises the following steps:
A () will be containing fire resistant resin, inorganic particles, organic solvent, poor solvent, cosolvent, stable
The coating solution of agent and binding agent is at least one surface of basement membrane；
(a ') product of step (a) is placed in temperature more than 20 DEG C, relative humidity in the environment of 50-95%,
Above-mentioned fire resistant resin is made to separate out solidification；
B the product of step (a ') is immersed in containing the organic solvent dissolving aramid fiber, can not dissolve aramid fiber by ()
Poor solvent and water mixed liquor in, make above-mentioned fire resistant resin separate out solidification；
C () carries out washing and removes solvent and poor solvent the product of step (b)；
D the product of step (c) is dried by (), i.e. obtain above-mentioned high temperature resistant composite lithium battery membrane.
According to the second aspect of the invention, the present invention also provides for the high temperature resistant complex lithium described in a kind of first aspect
The preparation method of battery diaphragm, the method comprises the following steps:
A () will be containing fire resistant resin, inorganic particles, organic solvent, poor solvent, cosolvent, stable
The coating solution of agent and binding agent is at least one surface of basement membrane；
(a ') product of step (a) is placed in temperature more than 20 DEG C, relative humidity in the environment of 50-95%,
Above-mentioned fire resistant resin is made to separate out solidification；
D the product of step (a ') is dried by (), i.e. obtain above-mentioned high temperature resistant composite lithium battery membrane.
According to the second aspect of the invention, the present invention also provides for the high temperature resistant complex lithium described in a kind of first aspect
The preparation method of battery diaphragm, the method comprises the following steps:
A () will be containing fire resistant resin, inorganic particles, organic solvent, poor solvent, cosolvent, stable
The coating solution of agent and binding agent is at least one surface of basement membrane；
(b ') product of step (a) is placed in thermal environment, evaporate solvent, make above-mentioned fire resistant resin
Separate out solidification while, remove the solvent in above-mentioned coating fluid, i.e. obtain above-mentioned high temperature resistant composite lithium ion battery every
Film.
The high temperature resistant composite lithium battery membrane of the present invention (hereinafter also referred to " high temperature resistant composite separator ", " compound every
Film ", " high-temperature-resistant membrane " or " composite battery separator film " etc.) have higher intensity, its heat resistance also obtains relatively
Big raising, can reduce burr and pierce through and shrink, under barrier film and barrier film high temperature, the short circuit caused in application, improve
The safety in utilization of barrier film；Good wettability makes the composite diaphragm of the present invention have high pick up and guarantor
Liquid rate；Antioxygenic property height makes the composite diaphragm of the present invention can adapt to various use environment, improves corresponding
The service life of battery.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the high temperature resistant composite separator that the embodiment of the present invention 1 prepares；
Fig. 2 is the scanning electron microscope (SEM) photograph of the high temperature resistant composite separator that the embodiment of the present invention 2 prepares；
Fig. 3 is the scanning electron microscope (SEM) photograph of the high temperature resistant composite separator that the embodiment of the present invention 3 prepares；
Fig. 4 is the scanning electron microscope (SEM) photograph of the high temperature resistant composite separator that the embodiment of the present invention 4 prepares.
Detailed description of the invention
Combine accompanying drawing below by detailed description of the invention the present invention is described in further detail.
In order to overcome the deficiencies in the prior art, the invention provides a kind of intensity height, safety height, electrolyte
Wetting capacity is good, good in oxidation resistance, can be as the high-temperature-resistant membrane of lithium ion battery separator；There is provided one simultaneously
Plant the preparation method of this high-temperature-resistant membrane.
One of key of the present invention is, coats one layer of fire resistant resin layer at least one surface of basement membrane,
This fire resistant resin layer is the coating containing fire resistant resin.This layer of fire resistant resin layer can improve barrier film
Resistance to elevated temperatures, the heat stability of barrier film is high, is difficult to thermal contraction, therefore reduces the both positive and negative polarity contact of battery
And the potential safety hazard of short circuit；Meanwhile, the composite diaphragm of the present invention has high pick up and protects the feature of liquid rate；
Additionally, antioxygenic property height makes the composite diaphragm of the present invention can adapt to various use environment, improve corresponding
The service life of battery.
As further improved plan, possibly together with inorganic in the fire resistant resin layer of the composite diaphragm of the present invention
Microgranule, inorganic particles has the resistance to elevated temperatures of excellence, and the composite diaphragm being coated with inorganic particles has well
Heat stability.Meanwhile, in the present invention, inorganic particles together exists with fire resistant resin, the most there is not fall
The problem of the wetting capacity of low barrier film and electrolyte, and inorganic particles will not produce reunion and from membrane surface
Come off and affect the performance of separator product.
In the present invention, fire resistant resin as the skeletal support of coating, have preferable heatproof, insulation,
The performances such as fire-retardant, antioxidation, puncture resistant, remain to play a supporting role when basement membrane high temperature deformation, prevent every
Film both positive and negative polarity contacts.Inorganic particles also has skeletal support effect and excellent resistance to elevated temperatures, make coating every
Film has good heat stability.But inorganic particles itself is poor with the wetting capacity of electrolyte, reduces barrier film
And the wetting capacity between electrolyte；If inorganic particles non-surface treated in addition, be susceptible to reunite and from
Polyalkene diaphragm surface comes off, and affects the serviceability of barrier film.Fire resistant resin, as polymer, not only may be used
To be effectively improved the resistance to elevated temperatures of barrier film, insulating properties, puncture resistance etc., additionally it is possible to effectively improve every
Film and the wellability of electrolyte, be not susceptible to reunion simultaneously and come off.Therefore, fire resistant resin and inorganic particles
Be used in combination, can effectively improve barrier film heat-resisting quantity and with the wellability of electrolyte, coating simultaneously
Difficult drop-off.
The puncture strength of the high-temperature-resistant membrane of the present invention can reach more than or equal to 250gf.Therefore, it is possible to effectively
Ground minimizing burr pierces through and shrinks the short circuit caused under barrier film and barrier film high temperature, improves the safety in utilization of barrier film.
In the present invention, basement membrane can be selected from polyolefin single perforated membrane or polyolefin multi-layer perforated membrane, the most poly-
Ethylene perforated membrane or polypropylene porous film.
Fire resistant resin can select polysulfones, polyether sulfone, polyphenylene thioether, polyether-ether-ketone, Merlon,
Polyacetals, polyimides, polyamidoimide, meta virtue amide, para-position virtue amide, politef and
At least one in its derivant, copolymer or mixture；Particularly preferably meta-aromatic polyamide, para-position
Aromatic polyamide, meta-aromatic polyamide and the mixture of polyimides, para-position aromatic polyamide with
At least one in the mixture of polyimides；More preferably meta-aromatic polyamide and the mixing of polyimides
Thing, para-position aromatic polyamide and at least one in the mixture of polyimides.
It should be noted that above-mentioned several fire resistant resin can meet composite diaphragm resistant to elevated temperatures use demand.
But from the wettability of raising composite diaphragm thus from the standpoint of strengthening its imbibition guarantor's liquid rate, the present invention is preferred
Polyamide-based, polyimide and polyamideimides polymer, polyamide-based and polyimide based resin
Surface can be more than normally used electrolyte, electrolyte is had good wettability, can carry simultaneously
Liquid rate, the therefore preferred meta-aromatic polyamide of the present invention, para-position aromatic polyamide, meta are protected in high imbibition
Aromatic polyamide and the mixture of the mixture of polyimides, para-position aromatic polyamide and polyimides.
Polyimide-based polymer has the environment resistant oxidability of excellence, and polyamide has with polyimide mixture
Ratio is used alone polyimides or is used alone the mechanical performance that polyamide is higher；Therefore, the present invention is more preferably
Meta-aromatic polyamide and the mixing of the mixture of polyimides, para-position aromatic polyamide and polyimides
Thing.
The molecular weight of above-mentioned aromatic polyamide is preferably 20 ten thousand to 100 ten thousand, and the molecular weight of polyimides is preferred
It is 10 ten thousand to 50 ten thousand.Molecular weight polymer within the above range has good heat stability and mobility,
Being prone to processing and forming, easy formation defect is few, the heat-resisting porous layer of uniform film thickness；Simultaneously, it may not be necessary to
Apply additional coating pressure, it is to avoid the blocking of microporous polyolefin film surface holes, prevent heat-resisting porous layer with
The interface breathability of polyolefin micro porous polyolefin membrane reduces.It addition, by coating liquid on polyolefin micro porous polyolefin membrane
After when being immersed in coagulating bath, the polymer in coating layer is readily flowed, can form good micropore.
Meanwhile, the polymer in above-mentioned molecular weight ranges and inorganic particles have the good compatibility, are possible to prevent nothing
Coming off of machine microgranule.If molecular weight is excessive, the viscosity of polymer is big, and the mobility of slurry is bad, is difficult to
Form uniform coat；If molecular weight is the lowest, the intensity of polymer reduces, and heat-resisting quantity declines, and
Mobility is very good, is unfavorable for the carrying out of coating, and is likely to result in plug-hole phenomenon.
Fire resistant resin layer in the present invention contains inorganic particles further；The particle diameter of these inorganic particles is excellent
Elect 0.01 μm≤D50≤5 μm, more preferably 0.03 μm≤D50≤1 μm as.The particle diameter of inorganic particles exists
Time in 0.01 μm≤D50≤5 μ m, the inorganic particles in coating has higher packed density, and coating
It is prone to be bonded in well the surface of microporous polyolefin film, is not susceptible to the obscission of heat-resisting porous layer.
If D50 < 0.01 μm, then inorganic particles is prone to come off from membrane surface thus produces dry linting phenomenon, is unfavorable for
The stability of barrier film and safety in utilization；If D50 > 5 μm, then it is difficult to be formed uniform coating, and coating
Thickness is wayward, therefore the most preferred.These inorganic particles can be selected from aluminium oxide, titanium dioxide, titanium dioxide
In the metal-oxide such as silicon, zirconium oxide, or the metal hydroxides such as aluminium hydroxide, magnesium hydroxide at least
A kind of；Particularly preferably at least one in aluminium oxide, aluminium hydroxide.
The high temperature resistant composite lithium battery membrane of the present invention can be come by several similar but differentiated preparation methoies
Preparation.
The basic skills of the high temperature resistant composite lithium battery membrane of a kind of present invention of preparation comprises the following steps:
A () will be containing fire resistant resin, inorganic particles, organic solvent, poor solvent, cosolvent, stable
The coating solution of agent and binding agent is at least one surface of basement membrane；
B the product of step (a) is immersed in containing the organic solvent dissolving aramid fiber, can not dissolve aramid fiber by ()
Poor solvent and water mixed liquor in, make above-mentioned fire resistant resin separate out solidification；
C () carries out washing and removes solvent and poor solvent the product of step (b)；
D the product of step (c) is dried by (), i.e. obtain above-mentioned high temperature resistant composite lithium battery membrane.
It should be noted that organic solvent preferred solubilized aromatic polyamide and fragrance adoption in step (a)
Imido good solvent, can enumerate: DMF, N,N-dimethylacetamide, N-methyl
Ketopyrrolidine, N, N, N ', N '-tetramethylurea, dimethyl sulfoxide, cresol, o-chlorphenol etc., more preferably N, N-
Dimethyl acetylamide and N-Methyl pyrrolidone.Poor solvent is relative to aromatic polyamide and fragrance adoption
Acid imide is the solvent of lean solvent, can enumerate: methanol, ethanol, propylene glycol, tripropylene glycol, butanol etc.
Alcohols.Cosolvent preferred as alkali or the chloride of alkaline-earth metal, can enumerate: calcium chloride and lithium chloride.
The alcohol such as the preferred Allyl carbonate of stabilizer, sodium cellulosate, butanediol, ethylene glycol, propylene glycol, tripropylene glycol
At least one of apoplexy due to endogenous wind.Binding agent preferred epoxy, polyacrylate, Kynoar, silicone rubber
And at least one in derivant.
There is no particular limitation for coating method in step (a), as long as coating can be made to be uniformly coated on basement membrane table
The method in face is all suitable for, and can enumerate scraper for coating method, Meyer rod coating method, reverse roll coating method, gravure roll
The coating methods such as rubbing method, preferred gravure roll rubbing method in the present invention.
The solidification of step (b) coating, the effect mainly by water makes the fire resistant resin of coating surface separate out
Form semi-solid preparation film and the effect of the solvent in coating, organic solvent and poor solvent of extracting is mainly control hole
Formation and curing rate.The formation of speed of separating out and pore structure in order to control fire resistant resin, mixed liquor
In water content be preferably 50～95wt%, the temperature of mixed liquor is preferably 20～80 DEG C.
The washing of step (c), in the semi-solid preparation film that step (b) obtains, remains organic solvent, alkali
The auxiliary agents such as the chloride of metal or alkaline-earth metal, water and soluble inorganic salt etc., owing to these materials are the most solvable
Yu Shuizhong, by eluting various residue by semi-solid preparation film immersion method in water.
Being dried of step (d), mainly will be attached to the water in coating surface and hole by the effect of temperature
Evaporation removes, and for reaching Drying Rates faster, does not cause the heat shrinkable effect of composite diaphragm simultaneously, excellent
Baking temperature is selected to be 40-90 DEG C.
The method of the high temperature resistant composite lithium battery membrane of the another kind of preparation present invention, in above-mentioned basic skills
Between step (a) and step (b), and addition step (a '): the product of step (a) is placed in temperature and is more than
20 DEG C, relative humidity in the environment of 50-95%, make above-mentioned fire resistant resin separate out solidification.This method has
Body comprises the following steps:
A () will be containing fire resistant resin, inorganic particles, organic solvent, poor solvent, cosolvent, stable
The coating solution of agent and binding agent is at least one surface of basement membrane；
(a ') product of step (a) is placed in temperature more than 20 DEG C, relative humidity in the environment of 50-95%,
Above-mentioned fire resistant resin is made to separate out solidification；
B the product of step (a ') is immersed in containing the organic solvent dissolving aramid fiber, can not dissolve aramid fiber by ()
Poor solvent and water mixed liquor in, make above-mentioned fire resistant resin separate out solidification；
C () carries out washing and removes solvent and poor solvent the product of step (b)；
D the product of step (c) is dried by (), i.e. obtain above-mentioned high temperature resistant composite lithium battery membrane.
Product step (a) obtained in above-mentioned steps (a ') is placed directly within certain temperature and humidity environment
In, make the steam in environment fully contact with film, after coating absorbs a certain amount of steam and heat, coating
In fire resistant resin separate out.
The present invention also has a kind of method of high temperature resistant composite lithium battery membrane preparing the present invention, is with step (a ')
Substitute step (b) and (c) of above-mentioned basic skills.This method specifically includes the following step:
A () will be containing fire resistant resin, inorganic particles, organic solvent, poor solvent, cosolvent, stable
The coating solution of agent and binding agent is at least one surface of basement membrane；
(a ') product of step (a) is placed in temperature more than 20 DEG C, relative humidity in the environment of 50-95%,
Above-mentioned fire resistant resin is made to separate out solidification；
D the product of step (a ') is dried by (), i.e. obtain above-mentioned high temperature resistant composite lithium battery membrane.
The present invention also has a kind of method of high temperature resistant composite lithium battery membrane preparing the present invention, is by above-mentioned base
The step (b) of this method, (c) and (d) are directly reduced to (b '): be placed on by the product of step (a)
In thermal environment, evaporate solvent, while making above-mentioned fire resistant resin separate out solidification, remove in above-mentioned coating fluid
Solvent, i.e. obtain above-mentioned high temperature resistant composite lithium battery membrane.This method specifically includes the following step:
A () will be containing fire resistant resin, inorganic particles, organic solvent, poor solvent, cosolvent, stable
The coating solution of agent and binding agent is at least one surface of basement membrane；
(b ') product of step (a) is placed in thermal environment, evaporate solvent, make above-mentioned fire resistant resin
Separate out solidification while, remove the solvent in above-mentioned coating fluid, i.e. obtain above-mentioned high temperature resistant composite lithium ion battery every
Film.
Step (b ') in, micro-porous film step (a) obtained is placed directly within thermal environment (or hot environment)
In, directly solvent volatilization is removed by being dried, after without the water-washing process of step (c),
Directly obtain composite diaphragm.
It should be noted that wet with through coagulating bath or hot and humid environment of the dry coating method directly dried
Formula rubbing method is compared, and the coated film of formation is comparatively dense, if not adding inorganic filler etc. in coating fluid,
Then it is difficult to be formed more pore structure, and dry linting phenomenon easily occurs in the coating formed.Therefore, from being formed relatively
From the viewpoint of loose structure and stronger cohesive force, in the present invention, wet coating method is preferably used.It is further preferred that
Use the wet coating method processed through coagulating bath.
The high temperature resistant composite lithium battery membrane of the present invention is compared with the battery diaphragm applied in the market, not only
There is the resistance to elevated temperatures of excellence and high physical strength；Meanwhile, the composite diaphragm of the present invention has higher
Wettability is good to imbibition guarantor's liquid rate of electrolyte；Its good antioxygenic property substantially increases it various
Electrochemical stability and the service life of respective battery in environment.
By the following examples and experimental data describes the solution of the present invention, details and effect in detail, it should reason
Solving, embodiment is only exemplary, is not construed as constituting limiting the scope of the invention.
Embodiment 1
The fire resistant resin of the present embodiment is meta-aromatic polyamide (being abbreviated as PMIA), and inorganic particles is adopted
Being the aluminium oxide ceramics powder of 0.6 μm more than 99.99% and D50 by purity, solvent uses N, N-dimethyl second
Amide (DMAc), poor solvent is tripropylene glycol (TPG), and resin cosolvent is lithium chloride (LiCl),
Stabilizer uses Allyl carbonate, and binding agent uses the molecular weight homopolymerization Kynoar more than 600,000.
The preparation of the coating sizing-agent of the high temperature resistant composite lithium battery membrane of the present embodiment: first by tripropylene glycol and
Aluminium oxide ceramics powder is uniformly dispersed with mass ratio for 3:2, is then added to be dissolved in N, N-dimethylacetamide
In PMIA glue in amine, PMIA is 1:3 with the mass ratio of aluminium oxide ceramics powder, adds appropriate afterwards
LiCl, Allyl carbonate and homopolymerization Kynoar, obtain the slurry that viscosity is 150cP after mix homogeneously, slurry
The solid content of material is about 30%, i.e. coating sizing-agent used by the present embodiment.
The thickness that the basement membrane of the present embodiment uses Shenzhen Zhong Xing innovative material Technology Co., Ltd. to prepare is 12 μm
Monolayer PP thin film, after preparing coating sizing-agent, use gravure roll method coating sizing-agent is coated in PP thin film
One of them surface.Then, will after coating thin film dipped containing DMAc, TPG, water composition mixed
Close in coagulating bath so that the fire resistant resin in coating sizing-agent separates out solidification, the quality of water in mixing coagulating bath
Fractional domination is more than 50%, in process of production, by Synchronization Control amount of water, controls containing of water all the time
Amount is between 50-60%；The temperature of mixing coagulating bath controls between 20～80 DEG C.Then, precipitation is solidified
Film be transferred in rinsing bowl carry out multi-stage water wash, use 60m air-flotation type hot-air oven to enter at 70 DEG C afterwards
Row is dried, and the barrier film water residual of outlet is less than 200ppm.Rolling i.e. obtains the high temperature resistant complex lithium of the present embodiment
Battery diaphragm.
Composite battery separator film prepared by the present embodiment carry out thickness, breathability, hot strength, peel strength,
Oxidizing potential, closed pore temperature, broken film temperature etc. detect, and test on composite battery separator film TD/MD direction
The percent thermal shrinkage of 30min at 120 DEG C and 150 DEG C respectively.The most every detection and test all use this area
Conventional test manner, be not specifically limited at this.Test result is as shown in table 1, the resistance to height of the present embodiment
The scanning electron microscope of temperature composite diaphragm is as shown in Figure 1.
Meanwhile, the composite battery separator film prepared by the present embodiment cuts into 44mm width, at full-automatic battery
LP053450 liquid soft-package battery, design capacity 1100mAh, voltage regime 4.35V is made on production line.
Anode uses lithium cobaltate cathode material, actual rolls density 4.15mg/cm3；Negative pole uses Delanium,
Actual roll density 1.71mg/cm3；Electrolyte uses TC-E231, reservoir quantity 2.4g/Ah.
Test battery 1000V insulation impedance when non-fluid injection, and 500V ac leakage electric current；Test electricity
Guarantor's liquid measure in pond, 0.5C discharge capacity, full electricity resistance, full electricity thickness, 60 DEG C of full electricity are from declining K value, routine
In 500 circulation volume retention, 500 circulation volume retention of 60 DEG C of constant temperature, 150 DEG C of hot tank of 60min
Battery maximum temperature, Φ 3mm acupuncture battery maximum temperature.The most every test all uses the routine of this area
Test mode, is not specifically limited at this.Test result is as shown in table 2.
Embodiment 2
Preparing of the coating sizing-agent of the present embodiment and composite battery separator film is same as in Example 1, and basement membrane uses
The monolayer PP thin film that thickness is 12 μm prepared by Shenzhen Zhong Xing innovative material Technology Co., Ltd..
After preparing coating sizing-agent, use gravure roll method that coating sizing-agent is coated in one of them table of PP thin film
Face.Then, the thin film obtained is placed in temperature be 70 DEG C, relative humidity is in the warm and humid environment of 80-90%
Fire resistant resin is made tentatively to separate out solidification.Then, the film tentatively separating out solidification is used same as in Example 1
Coagulating bath, washing and drying condition process, last rolling i.e. obtains the high temperature resistant compound of the present embodiment
Lithium battery diaphragm.
The composite battery separator film prepared the present embodiment afterwards carries out every detection, and is made into battery and carries out
Every coherent detection, preparing of battery is same as in Example 1, test event and concrete grammar and embodiment 1
Identical, not tire out at this and state, test result is as shown in Table 1 and Table 2.The high temperature resistant composite separator of the present embodiment
Scanning electron microscope as shown in Figure 2.
Embodiment 3
Preparing of the coating sizing-agent of the present embodiment and composite battery separator film is same as in Example 1, and basement membrane uses
The monolayer PP thin film that thickness is 12 μm prepared by Shenzhen Zhong Xing innovative material Technology Co., Ltd..
After preparing coating sizing-agent, use gravure roll method that coating sizing-agent is coated in one of them table of PP thin film
Face.Then, the thin film obtained is placed in warm and humid environment same as in Example 2 carry out separate out solidification.
Then, using 60m air-flotation type hot-air oven to be dried at 70 DEG C, the barrier film water residual of outlet is less than
200ppm.Rolling i.e. obtains the high temperature resistant composite lithium battery membrane of the present embodiment.
The composite battery separator film prepared the present embodiment afterwards carries out every detection, and is made into battery and carries out
Every coherent detection, preparing of battery is same as in Example 1, test event and concrete grammar and embodiment 1
Identical, not tire out at this and state, test result is as shown in Table 1 and Table 2.The high temperature resistant composite separator of the present embodiment
Scanning electron microscope as shown in Figure 3.
Embodiment 4
Preparing of the coating sizing-agent of the present embodiment and composite battery separator film is same as in Example 1, and basement membrane uses
The monolayer PP thin film that thickness is 12 μm prepared by Shenzhen Zhong Xing innovative material Technology Co., Ltd..
After preparing coating sizing-agent, use gravure roll method that coating sizing-agent is coated in one of them table of PP thin film
Face.Then, the thin film obtained employing 60m air-flotation type hot-air oven is dried at 70 DEG C.Rolling
I.e. obtain the high temperature resistant composite lithium battery membrane of the present embodiment.
The composite battery separator film prepared the present embodiment afterwards carries out every detection, and is made into battery and carries out
Every coherent detection, preparing of battery is same as in Example 1, test event and concrete grammar and embodiment 1
Identical, not tire out at this and state, test result is as shown in Table 1 and Table 2.The high temperature resistant composite separator of the present embodiment
Scanning electron microscope as shown in Figure 4.
Embodiment 5
In the coating sizing-agent of the present embodiment, fire resistant resin uses meta-aromatic polyamide (PMIA) and polyamides
The mixture of imines (PI), the mass ratio of PMIA Yu PI is 4:1, and polyimides uses biphenyl tetracid two
Acid anhydride and 4,4'-diphenyldiamine system prepare.Other compositions in coating sizing-agent and slurry preparation method with
Embodiment 1 is identical.
Preparation method same as in Example 1 is used to prepare the high temperature resistant composite separator of the present embodiment.
The composite battery separator film prepared the present embodiment afterwards carries out every detection, and is made into battery and carries out
Every coherent detection, preparing of battery is same as in Example 1, test event and concrete grammar and embodiment 1
Identical, not tire out at this and state, test result is as shown in Table 1 and Table 2.
Table 1 embodiment prepares every test result of barrier film
Table 2 embodiment prepares every test result of battery
Comparative example 1
This comparative example directly uses the monolayer of thickness 12 μm of Shenzhen Zhong Xing innovative material Technology Co., Ltd.
PP barrier film carries out every test, is the most also prepared into battery, tests.The test event of PP barrier film
Same as in Example 1, the preparation of battery and the test of battery are the most same as in Example 1.Test result such as table 3
Shown in table 4.
Comparative example 2
This comparative example uses the thickness of Shenzhen Zhong Xing innovative material Technology Co., Ltd. same as in Example 1
The monolayer PP thin film of 12 μm, as basement membrane, carries out ceramic coating coating on a surface of basement membrane, it is thus achieved that this
The composite diaphragm of comparative example.
The ceramic coating of this comparative example, the Al of the 44% of employing suspension gross weight2O3, and appropriate propylene
Esters of gallic acid binding agent, thickening agent, dispersant and dispersing aid, in water dispersed make stable outstanding
Supernatant liquid, uses micro-plate gravure coating method, is evenly applied to a surface of PP thin film, then by a length of 15m,
The temperature multistage oven for drying between 30 DEG C～60 DEG C, forms the ceramic coating that thickness is 2-3 μm, i.e. obtains
Obtain the composite diaphragm of this comparative example.Wherein, the Al that this comparative example uses2O3D50 be that 0.6 μm, purity are big
In 99.99%.
Equally, the composite diaphragm of preparation is carried out every test same as in Example 1, and is prepared into
Battery, the properties of test battery, preparation and the test item of battery are same as in Example 1.Test result
As shown in Table 3 and Table 4.
Table 3 comparative example prepares every test result of barrier film
Table 4 comparative example prepares every test result of battery
By above-mentioned testing result, compared with comparative example 1, embodiments of the invention 1 to 5 are prepared into
To the puncture strength of high temperature resistant composite separator be obtained for raising in various degree；Be coated with ceramic layer
Comparative example 2 is compared, and peel strength and the hot strength of the high temperature resistant composite separator of embodiments of the invention are obvious
It is better than comparative example 2.In terms of thermal contraction performance, the thermal contraction of the high temperature resistant composite separator of embodiments of the invention
Performance is substantially better than comparative example.Meanwhile, in the case of keeping closed pore temperature constant, embodiments of the invention
The broken film temperature of the high temperature resistant composite separator of preparation is greatly increased, and improves the heat-resisting quantity of barrier film
Energy；It addition, guarantor's liquid rate of barrier film also increases.Prepared by the high temperature resistant composite separator using the present invention to prepare
Battery performance test results understand, the cycle performance of battery of composite battery separator film prepared by the present invention is with right
Ratio compares the raising having in various degree, can keep preferable stability, greatly in different high and low temperature environments
Improve greatly the service life of battery.
Fig. 1 to Fig. 4 is the scanning electron microscope (SEM) photograph of embodiments of the invention 1 to 4, it can be seen that not
The surface topography of the composite battery separator film that same post-processing approach prepares is different, through coagulating bath extraction
The composite battery separator film of embodiment 1 and embodiment 2 preparation is with the presence of obvious many and close hole, without solidifying
Gu the hole of the composite battery separator film of the embodiment 3 of bath extraction and embodiment 4 preparation is inconspicuous.Comprehensive barrier film
The performance test results, present invention preferably employs the preparation method of embodiment 1.
Above content is to combine specific embodiment further description made for the present invention, it is impossible to recognize
Determine the present invention be embodied as be confined to these explanations.Ordinary skill for the technical field of the invention
For personnel, without departing from the inventive concept of the premise, it is also possible to make some simple deduction or replace,
All should be considered as belonging to protection scope of the present invention.
Claims (12)
1. a high temperature resistant composite lithium battery membrane, it is characterized in that, described barrier film includes basement membrane and the fire resistant resin layer at least one surface being coated on described basement membrane, and described basement membrane is thermoplastic resin perforated membrane, and described fire resistant resin layer is the coating containing fire resistant resin.
High temperature resistant composite lithium battery membrane the most according to claim 1, it is characterised in that the puncture strength of described barrier film is more than or equal to 250gf.
High temperature resistant composite lithium battery membrane the most according to claim 1 and 2, it is characterised in that described basement membrane is polyolefin single perforated membrane or polyolefin multi-layer perforated membrane, preferably polyethylene porous membrane or polypropylene porous film.
High temperature resistant composite lithium battery membrane the most according to claim 1 and 2, it is characterised in that possibly together with inorganic particles in described fire resistant resin layer；Preferably, the particle diameter of described inorganic particles is 0.01 μm≤D50≤5 μm, more preferably 0.03 μm≤D50≤1 μm.
High temperature resistant composite lithium battery membrane the most according to claim 4, it is characterized in that, described inorganic particles is at least one in aluminium oxide, titanium dioxide, silicon dioxide, zirconium oxide, aluminium hydroxide, magnesium hydroxide, preferably at least one in aluminium oxide, aluminium hydroxide.
High temperature resistant composite lithium battery membrane the most according to claim 1 and 2, it is characterized in that, described fire resistant resin is at least one in polysulfones, polyether sulfone, polyphenylene thioether, polyether-ether-ketone, Merlon, polyacetals, polyimides, polyamidoimide, meta virtue amide, para-position virtue amide, politef and derivant, copolymer or mixture；It is preferably meta-aromatic polyamide, para-position aromatic polyamide, meta-aromatic polyamide and at least one in the mixture of polyimides, the para-position aromatic polyamide mixture with polyimides；More preferably meta-aromatic polyamide and at least one in the mixture of polyimides, the para-position aromatic polyamide mixture with polyimides.
7. the preparation method of the high temperature resistant composite lithium battery membrane described in an any one of claim 1-6, it is characterised in that described method comprises the following steps:
(a) by the coating solution containing fire resistant resin, inorganic particles, organic solvent, poor solvent, cosolvent, stabilizer and binding agent at least one surface of basement membrane；
B the product of step (a) is immersed in containing the organic solvent dissolving aramid fiber, can not dissolve in the poor solvent of aramid fiber and the mixed liquor of water by (), make described fire resistant resin separate out solidification；
C () carries out washing and removes solvent and poor solvent the product of step (b)；
D the product of step (c) is dried by (), i.e. obtain described high temperature resistant composite lithium battery membrane.
Preparation method the most according to claim 7, it is characterised in that in described step (b), the water content in mixed liquor is 50 ~ 95wt%, the temperature of described mixed liquor is 20 ~ 80 DEG C.
9. according to the preparation method described in claim 7 or 8, it is characterised in that the baking temperature in described step (d) is 40-90 DEG C.
10. the preparation method of the high temperature resistant composite lithium battery membrane described in an any one of claim 1-6, it is characterised in that described method comprises the following steps:
(a) by the coating solution containing fire resistant resin, inorganic particles, organic solvent, poor solvent, cosolvent, stabilizer and binding agent at least one surface of basement membrane；
(a ') product of step (a) is placed in temperature more than 20 DEG C, relative humidity in the environment of 50-95%, make described fire resistant resin separate out solidification；
B the product of step (a ') is immersed in containing the organic solvent dissolving aramid fiber, can not dissolve in the poor solvent of aramid fiber and the mixed liquor of water by (), make described fire resistant resin separate out solidification；
C () carries out washing and removes solvent and poor solvent the product of step (b)；
D the product of step (c) is dried by (), i.e. obtain described high temperature resistant composite lithium battery membrane.
The preparation method of the high temperature resistant composite lithium battery membrane described in 11. 1 kinds of any one of claim 1-6, it is characterised in that described method comprises the following steps:
(a) by the coating solution containing fire resistant resin, inorganic particles, organic solvent, poor solvent, cosolvent, stabilizer and binding agent at least one surface of basement membrane；
(a ') product of step (a) is placed in temperature more than 20 DEG C, relative humidity in the environment of 50-95%, make described fire resistant resin separate out solidification；
D the product of step (a ') is dried by (), i.e. obtain described high temperature resistant composite lithium battery membrane.
The preparation method of the high temperature resistant composite lithium battery membrane described in 12. 1 kinds of any one of claim 1-6, it is characterised in that described method comprises the following steps:
(a) by the coating solution containing fire resistant resin, inorganic particles, organic solvent, poor solvent, cosolvent, stabilizer and binding agent at least one surface of basement membrane；
(b ') product of step (a) is placed in thermal environment, evaporate solvent, while making described fire resistant resin separate out solidification, remove the solvent in described coating fluid, i.e. obtain described high temperature resistant composite lithium battery membrane.
Priority Applications (1)
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| CN106654124A (en) * | 2017-01-20 | 2017-05-10 | 东莞市卓高电子科技有限公司 | Method for preparing heat-resistant lithium battery separator |
| CN106876635A (en) * | 2016-11-23 | 2017-06-20 | 德阳九鼎智远知识产权运营有限公司 | A kind of new-energy automobile lithium ion battery strengthens barrier film |
| CN106910858A (en) * | 2017-03-10 | 2017-06-30 | 深圳中兴创新材料技术有限公司 | A kind of polymer composite lithium battery membrane and preparation method thereof |
| CN108807822A (en) * | 2018-06-28 | 2018-11-13 | 桑顿新能源科技有限公司 | A kind of high security lithium ion battery diaphragm |
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| CN106876635A (en) * | 2016-11-23 | 2017-06-20 | 德阳九鼎智远知识产权运营有限公司 | A kind of new-energy automobile lithium ion battery strengthens barrier film |
| CN106876635B (en) * | 2016-11-23 | 2020-07-17 | 深圳市研一新材料有限责任公司 | New energy automobile lithium ion battery reinforcing diaphragm |
| CN106654124A (en) * | 2017-01-20 | 2017-05-10 | 东莞市卓高电子科技有限公司 | Method for preparing heat-resistant lithium battery separator |
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| CN110379984A (en) * | 2018-04-13 | 2019-10-25 | 通用汽车环球科技运作有限责任公司 | Partition for lithium metal base battery group |
| CN108807822A (en) * | 2018-06-28 | 2018-11-13 | 桑顿新能源科技有限公司 | A kind of high security lithium ion battery diaphragm |
| CN108847470A (en) * | 2018-07-03 | 2018-11-20 | 河北金力新能源科技股份有限公司 | A kind of lithium electric separator and preparation method thereof of mixed coating coating |
| CN109181522A (en) * | 2018-07-17 | 2019-01-11 | 河北金力新能源科技股份有限公司 | Aramid fiber coating liquid, lithium ion battery separator and preparation method thereof |
| CN109181522B (en) * | 2018-07-17 | 2020-08-18 | 河北金力新能源科技股份有限公司 | Aramid fiber coating liquid, lithium ion battery diaphragm and preparation method thereof |
| CN110752337A (en) * | 2018-07-24 | 2020-02-04 | 上海凯矜新材料科技有限公司 | Composite diaphragm, preparation method and application thereof |
| CN113875081A (en) * | 2019-04-04 | 2021-12-31 | 赛尔格有限责任公司 | Polyamide-imide coated separator for high energy rechargeable lithium batteries |
| CN112292783A (en) * | 2019-05-09 | 2021-01-29 | 株式会社Lg化学 | Separator for secondary battery including dispersant and method for manufacturing the same |
| US12126047B2 (en) | 2019-05-09 | 2024-10-22 | Lg Energy Solution, Ltd. | Separator for secondary battery comprising dispersant and method of manufacturing the same |
| CN110429229A (en) * | 2019-07-31 | 2019-11-08 | 宁德新能源科技有限公司 | Multi-layer isolation films and the device for using it |
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| CN111916626A (en) * | 2020-07-10 | 2020-11-10 | 东莞东阳光科研发有限公司 | Cross-linked polyimide/aramid fiber composite diaphragm and preparation method thereof |
| CN111916626B (en) * | 2020-07-10 | 2023-04-28 | 东莞东阳光科研发有限公司 | Cross-linked polyimide/aramid composite diaphragm and preparation method thereof |
| CN112038544A (en) * | 2020-09-28 | 2020-12-04 | 合肥国轩高科动力能源有限公司 | A kind of lithium ion battery separator and preparation method thereof |
| CN113161687B (en) * | 2020-09-28 | 2022-05-03 | 蜂巢能源科技有限公司 | High-safety composite reinforced diaphragm, dry preparation method and application thereof |
| CN112038544B (en) * | 2020-09-28 | 2022-03-11 | 合肥国轩高科动力能源有限公司 | A kind of lithium ion battery separator and preparation method thereof |
| CN113161687A (en) * | 2020-09-28 | 2021-07-23 | 蜂巢能源科技有限公司 | High-safety composite reinforced diaphragm, dry preparation method and application thereof |
| CN112670672A (en) * | 2020-12-28 | 2021-04-16 | 横店集团东磁股份有限公司 | Diaphragm for high-temperature storage, preparation method thereof and lithium ion battery |
| EP4175045A1 (en) | 2021-10-28 | 2023-05-03 | Jiangsu Horizon New Energy Tech Co., Ltd | Coated separator with high heat resistance and high peel strength and preparation method thereof |
| CN115207571A (en) * | 2022-06-30 | 2022-10-18 | 合肥国轩高科动力能源有限公司 | A kind of lithium ion battery composite separator and preparation method thereof |
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