CN108963154A - The preparation method of the coating film of low-inensity radiation - Google Patents
The preparation method of the coating film of low-inensity radiation Download PDFInfo
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- CN108963154A CN108963154A CN201810751800.5A CN201810751800A CN108963154A CN 108963154 A CN108963154 A CN 108963154A CN 201810751800 A CN201810751800 A CN 201810751800A CN 108963154 A CN108963154 A CN 108963154A
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- 239000011248 coating agent Substances 0.000 title claims abstract description 57
- 238000000576 coating method Methods 0.000 title claims abstract description 49
- 230000005855 radiation Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 8
- 239000010452 phosphate Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims description 35
- 239000000725 suspension Substances 0.000 claims description 18
- 230000010355 oscillation Effects 0.000 claims description 17
- -1 ion phosphate Chemical class 0.000 claims description 14
- 210000002469 basement membrane Anatomy 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- 239000004698 Polyethylene Substances 0.000 claims description 11
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 210000004379 membrane Anatomy 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 4
- 239000005955 Ferric phosphate Substances 0.000 claims description 3
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical group O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 3
- 235000011010 calcium phosphates Nutrition 0.000 claims description 3
- GQDHEYWVLBJKBA-UHFFFAOYSA-H copper(ii) phosphate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GQDHEYWVLBJKBA-UHFFFAOYSA-H 0.000 claims description 3
- 229940032958 ferric phosphate Drugs 0.000 claims description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 3
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical group [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 3
- 239000004137 magnesium phosphate Substances 0.000 claims description 3
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 3
- 229960002261 magnesium phosphate Drugs 0.000 claims description 3
- 235000010994 magnesium phosphates Nutrition 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 3
- 229910000164 yttrium(III) phosphate Inorganic materials 0.000 claims description 3
- UXBZSSBXGPYSIL-UHFFFAOYSA-K yttrium(iii) phosphate Chemical compound [Y+3].[O-]P([O-])([O-])=O UXBZSSBXGPYSIL-UHFFFAOYSA-K 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910000154 gallium phosphate Inorganic materials 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims description 2
- DYRWWVFQQONJJK-UHFFFAOYSA-K scandium(3+);phosphate Chemical compound [Sc+3].[O-]P([O-])([O-])=O DYRWWVFQQONJJK-UHFFFAOYSA-K 0.000 claims description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 7
- 150000001768 cations Chemical class 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 27
- 208000028659 discharge Diseases 0.000 description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000003851 corona treatment Methods 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005213 imbibition Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910016722 Ni0.5Co0.2Mn0.3 Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000005495 cold plasma Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PPPGBRSJYRPWKP-UHFFFAOYSA-N fluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical compound FC=C.FC(F)=C(F)C(F)(F)F PPPGBRSJYRPWKP-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000002631 hypothermal effect Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000678 plasma activation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010457 zeolite Substances 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
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/52—Separators
-
- 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
-
- 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
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Paints Or Removers (AREA)
- Cell Separators (AREA)
Abstract
The present invention relates to the preparation methods of the coating film of low-inensity radiation, it is characterized in that as follows in preparation step: mixing acetone and dimethylformamide in a kettle, the coating agent Jing Guo radiation treatment is added, adds Kynoar-hexafluoropropene and polymethyl methacrylate, thick liquid is made.In the coating on base films thick liquid Jing Guo radiation treatment, dry obtained coating film.The coating agent is the phosphate of trivalent (or divalent) cation.The matching of this coating film and anode, cathode, electrolyte etc. is obviously improved, and improves the cycle performance of battery.
Description
Technical field
The present invention relates to the preparation methods of the coating film of low-inensity radiation, and in particular to one kind can be used for lithium battery, lithium from
The preparation method of the coating film of sub- battery, polymer battery and supercapacitor belongs to the technical field of battery diaphragm preparation.
Technical background
Diaphragm is the important component of lithium ion battery.In battery system, diaphragm plays prevention electronics between anode and cathode
The effect of connection and conducting ion.Diaphragm has important role to battery performance and safe handling.According to the difference of production technology,
Diaphragm can be divided into film by dry method, wet process film and composite membrane.The application range of diaphragm based on polyolefine material is most wide.
In abuse conditions, lithium ion battery may be warming up to 100~300 DEG C of high-temperature region.Due to polyethylene (PE), gather
Propylene (PP), polyolefin composite film (e.g., PP/PE/PP, PE/PP) at high temperature can contraction distortion, using polyolefin film lithium from
There are security risks for sub- battery.The coating diaphragm of the preparations such as coating alumina on polyalkene diaphragm, hence it is evident that improve heat resistance
Can, thus, ensure the safety that battery uses.Coating diaphragm is generally made of basement membrane, adhesive and inorganic nano material.
From the point of view of adhesive, coating diaphragm generally use PVDF resin [Hennige V., et al. US 7790321,
2010. 7. 9.], polymethyl methacrylate (PMMA) [Zhao Jinbao etc., Chinese invention patent, 103035866 A of CN,
2013.4.10.], butadiene-styrene rubber (SBR) [Park J. H., et al. J. Power Sources, 2010,195
(24): 8306-8310.], silica solution [Lee J. R., et al. J. Power Sources, 2012,216:42-
47.] and Kynoar-hexafluoropropene (PVDF-HFP) [Jeong H. S., et al. Electrochim. Acta,
The binders such as 2012,86:317-322.].Sohn etc. is by polymethyl methacrylate (PMMA), Kynoar-hexafluoro third
Alkene (PVDF-HFP) and nanometer Al2O3Mixture [Sohn J. Y., et al., J. Solid State
Electrochem., it 2012,16,551-556.] is coated on PE film, is prepared for PVDF-HFP/PMMA coating diaphragm.
Adsorption theory thinks, bonding is between two kinds of material molecules caused by contact and interfacial force.The main source of bonding force
It is intermolecular force (including hydrogen bond and Van der Waals force).Adhesive and continuously contacting with for adherend referred to as soak, and to obtain good
Good bond effect requires the surface tension of binder less than the surface tension of adherend.Untreated polymer (such as poly- second
Alkene, polypropylene) surface inertia it is larger, be difficult to be bonded.
Jeong etc. [Jeong H. S., et al. Electrochim. Acta, 2012,86:317-322.]
Studies have shown that the ratio regular meeting of Kynoar-hexafluoropropene (PVDF-HFP) binder and coated particle to coating diaphragm
Performance generates significant impact.The dosage for increasing binder in coat can reduce falling off for coated particle, and it is mechanical to improve diaphragm
Performance.But, the surface nature of basement membrane can be changed by the coated particle that binder coats, reduce the wetability to electrolyte, it is right
The high rate during charging-discharging of battery is unfavorable.Song etc. [Song J., et al. Electrochim. Acta, 2012,
85:524-530.] it finds, binder can make the particle packing of nanometer coating agent in the duct of basement membrane, reduce the hole of diaphragm
Rate increases the resistance of lithium ion cross-film diffusion.
From the point of view of coat, the inorganic material studied includes nanometer Al2O3、ZrO2、SiO2、TiO2、MgO、CaO、
CaCO3、BaSO4, zeolite, boehmite, clay etc..[Takemura D., the et al. J. Power such as Takemura
Sources, 2005,146 (1/2): 779-783.] investigate Al2O3Influence of the partial size to membrane properties.They have found, apply
Cover Al2O3The high temperature resistance of diaphragm can be improved.Choi etc. [Choi E. S., et al. J. Mater. Chem.,
2011, (38): 14747-14754.] use partial size 40nm SiO2PE microporous barrier is coated, coating diaphragm is prepared for.Special duct
Inorganic material be also used for replace nanometer Al2O3As coating agent, in the battery system using this coating diaphragm, solvent
The lithium ion of change can provide " green channel " along inorganic particle and directly transmit.
From the point of view of basement membrane, since the reactivity of polyolefin-based film surface is little, the coat and basement membrane on diaphragm are coated
Between bond defective tightness.During long-term charge and discharge cycles, the coat for coating diaphragm is easy to fall off.It is existing in order to improve this
As [Chen H., the et al. Plasma activation and atomic layer deposition of such as Chen
TiO2 on polypropylene membranes for improved performances of lithium-ion
Batteries, J. Membr. Sci., 2014,458,217-224.] PP film surface first is handled with plasma technique,
Then it is coated with TiO2, coating diaphragm is made.Studies have shown that corona treatment can generate polar group in PP film surface, have
Conducive to TiO2In the dispersion of membrane surface.The diaphragm of preparation imbibition rate with higher and ionic conductivity, lower thermal contraction
Rate.The lithium ion battery of assembly discharge capacity with higher and preferable multiplying power discharging property.
Although coating diaphragm by above-mentioned study on the modification in battery system and there are some problems.For example, coating diaphragm
It will increase the internal resistance of cell, discharge capacity of the cell made to be difficult to bring into play.Coat the coat and anode, cathode, electrolyte of diaphragm
There are problems that whether matching.
In order to solve the problems, such as coating diaphragm application, the compound of the key containing P-O is added in the present invention in coat,
By the compound of the key containing P-O and reacting for the polyolefin base membrane of corona treatment, the painting with the valuable key connection of basement membrane is formed
Coating significantly improves binding force between coat and basement membrane in coating diaphragm, reduces the internal resistance of cell, promotes the electric discharge of the battery of assembly
Capacity gives full play of, while reducing picking phenomenon.Since the wetability of the compound of the key containing P-O is stronger, to electrolyte
Affinity is strong, and imbibition ability is strong.It is good with the matching of anode, cathode, electrolyte, hence it is evident that improve the performance of coating diaphragm.
Summary of the invention
The technical solution adopted in the present invention comprises the steps of:
In a kettle, according to volume ratio (0.1~10): mixed solution is made in 1 mixing acetone and dimethylformamide.It is added
0.5~2.5% weight of mixed solution weight and coating agent Jing Guo radiation treatment, 1~30 min of supersonic oscillations are made mixed
Close uniform suspension.Kynoar-hexafluoropropene of 1~5% weight of mixed solution weight is added in suspension, then
The polymethyl methacrylate of 0.5~2.5% weight of mixed solution weight is added.10~50min of supersonic oscillations.50~
8~12 h are stirred at 90 DEG C, and solution in reaction kettle is made to be changed into thick liquid.Basement membrane tiling is opened, radiation treatment is carried out.It will glue
Thick liquid is coated in membrane surface Jing Guo radiation treatment, in 50~110 DEG C of temperature ranges the drying of any Temperature Vacuum or
Coating film is made in forced air drying.
The vacuum drying is the heat drying carried out under 0.1~0.00001atm pressure.
The coating agent by radiation treatment be partial size in the μ m of 10nm~5 and trivalent Jing Guo radiation treatment from
Sub- phosphate or divalent ion phosphate.
The trivalent ion phosphate is aluminum phosphate, scandium phosphate, ferric phosphate, phosphoric acid gallium or yttrium phosphate.
The divalent ion phosphate is magnesium phosphate, trbasic zinc phosphate, calcium phosphate, cupric phosphate or barium phosphate.
The radiation be corona discharge, dielectric barrier discharge, RF low-temperature plasma electric discharge, jet stream low temperature etc. from
10 s~10min is handled under conditions of electron discharge, Atomospheric pressure glow discharge or sub-atmospheric pressure glow discharge.
Kynoar-the hexafluoropropene is Kynoar-hexafluoro of the average molecular weight in 20~2,800,000 ranges
Propylene.
The polymethyl methacrylate is polymethyl methacrylate of the average molecular weight in 60~1,600,000 ranges.
The basement membrane is polypropylene or polyethylene monolayer film, or the multilayer film containing polypropylene layer.
The multilayer film is the diaphragm that the number of plies is formed in the monofilm of 2~10 ranges.
Cost of material of the invention is lower, and preparation process is simple, easy to operate, and the coating diaphragm of preparation is used for battery system
In, although the impedance of diaphragm can be made to be increased.But, due to that can be produced between the coat of coating film and battery pole piece and basement membrane
Raw cohesive force, can be obviously reduced the impedance of battery system, improve the discharge performance of battery.During long-term charge and discharge cycles,
The matching of this coating diaphragm and anode, cathode, electrolyte etc. can be significantly improved, thus, improve the circulation of battery
Performance is laid a good foundation for industrialization.
Detailed description of the invention
Fig. 1 is the basement membrane of the coating film of the embodiment of the present invention 1 and the infrared figure of coating bed boundary.
Specific embodiment
The present invention is further detailed below with reference to embodiment.Embodiment is only to further supplement of the invention
And explanation, rather than the limitation to invention.
Embodiment 1
In a kettle, according to volume ratio 4:1 mixing acetone and dimethylformamide, mixed solution is obtained.Mixed solution is added
The aluminum phosphate of 1.25% weight of weight and the partial size 5nm by Atomospheric pressure glow discharge processing 1min, supersonic oscillations 15
Uniformly mixed suspension is made in min.2.5% weight and average molecular weight 150 of mixed solution weight are added in suspension
Ten thousand Kynoar-hexafluoropropene adds 1.25% weight of mixed solution weight and the poly- methyl of average molecular weight 800,000
Methyl acrylate, supersonic oscillations 25min.9 h are stirred at 60 DEG C, and solution in reaction kettle is made to be changed into thick liquid.It will gather
Respectively use Corona discharge Treatment 5min in two surfaces of propylene monofilm (with a thickness of 20 μm).Thick liquid is coated in by processing
Monofilm two surfaces on, make two surfaces coat 12 μm of overall thickness, the vacuum under 60 DEG C and 0.01 atmospheric pressure
It is dry, coating film is made.
Li will be formed1.05Ni0.5Co0.2Mn0.3O2Tertiary cathode material, acetylene black and the PVDF binder of type are according to 85:10:
5 weight ratio weighs, and using N-Methyl pyrrolidone as grinding aid, uniform sizing material is made in ball milling mixing 3h.Uniform sizing material is coated
In aluminum foil current collector, positive plate is made after drying.Lithium metal, the coating film of preparation, positive plate, battery case and electrolyte are set
In the glove box full of argon gas, it is assembled into CR2025 type button cell.To the button of preparation on new Weir battery test system
Formula battery carries out charge and discharge and cycle performance test.Test temperature is room temperature (25 ± 1 DEG C).The section of charge and discharge be 2.5~
4.6V.Charge and discharge cycles experiment carries out under 1C multiplying power electric current.Charge-discharge test shows the electric discharge that the sample the 1st of preparation recycles
Capacity is 180mAh/g.
Embodiment 2
In a kettle, according to volume ratio 0.5:1 mixing acetone and dimethylformamide, mixed solution is obtained.It is molten that mixing is added
0.5% weight of liquid weight and the ferric phosphate for passing through radio-frequency hypothermia plasma discharge treatment 10s and partial size 1nm, supersonic oscillations
Uniformly mixed suspension is made in 1min.1% weight and average molecular weight 200,000 of mixed solution weight are added in suspension
Kynoar-hexafluoropropene, add 0.5% weight of mixed solution weight and the poly- methyl-prop of average molecular weight 600,000
E pioic acid methyl ester, supersonic oscillations 10min.8 h are stirred at 50 DEG C, and solution in reaction kettle is made to be changed into thick liquid.By poly- second
The tiling of alkene monofilm is opened, by the surface RF low-temperature plasma discharge treatment 10s of monofilm, then by thick liquid
On a surface coated in monofilm.It is dried in vacuo under 50 DEG C and 0.1 atmospheric pressure, coating film is made.
Embodiment 3
In a kettle, according to volume ratio 10:1 mixing acetone and dimethylformamide, mixed solution is made.Mixed solution is added
2.5% weight of weight and with Low Temperature Plasma Treating 5min and 5 μm of partial size of yttrium phosphate.Supersonic oscillations 30min is made
Uniformly mixed suspension.5% weight of mixed solution weight and the poly- inclined fluorine of average molecular weight 2,800,000 are added in suspension
Ethylene-hexafluoropropene adds 2.5% weight of mixed solution weight and the poly-methyl methacrylate of average molecular weight 1,600,000
Ester, supersonic oscillations 50min.In 90 DEG C of 12 h of stirring, solution in reaction kettle is made to be changed into thick liquid.By PP/PE/PP multilayer
Film tiling is opened, and handles 10min with jet stream discharge of plasma in low temperature, and thick liquid is coated in the one of treated multilayer film
It on a surface, is dried in vacuo under 110 DEG C and 0.00001 atmospheric pressure, coating film is made.
Embodiment 4
In a kettle, according to volume ratio 1:1 mixing acetone and dimethylformamide, mixed solution is obtained.Mixed solution is added
2% weight of weight and the magnesium phosphate that 10min and 200 nm of partial size are handled by jet stream cold plasma discharge, supersonic oscillations
Uniformly mixed suspension is made in 20 min.1.25% weight and average molecular weight of mixed solution weight are added in suspension
300000 Kynoar-hexafluoropropene adds 1% weight of mixed solution weight and the poly- methyl of average molecular weight 800,000
Methyl acrylate, supersonic oscillations 20min.10 h are stirred at 60 DEG C, and solution in reaction kettle is made to be changed into thick liquid.It will
The tiling of PP/PE multilayer film is opened, and Corona discharge Treatment 1min is respectively used on two surfaces of multilayer film.Thick liquid is coated in multilayer
It on two surfaces of film, is dried in vacuo under 90 DEG C and 0.1 atmospheric pressure, coating film is made.
Embodiment 5
In a kettle, according to volume ratio 2:1 mixing acetone and dimethylformamide, mixed solution is obtained.Mixed solution is added
1% weight of weight and the calcium phosphate that 10s and partial size 100nm are handled by Atomospheric pressure glow discharge, 30 min of supersonic oscillations,
Uniformly mixed suspension is made.The poly- of 2% weight of mixed solution weight and average molecular weight 1,800,000 is added in suspension
Biasfluoroethylene-hexafluoropropylene adds 1.4% weight of mixed solution weight and the polymethylacrylic acid of average molecular weight 1,000,000
Methyl esters, supersonic oscillations 15min.9 h are stirred at 80 DEG C, and solution in reaction kettle is made to be changed into thick liquid.By PP/PP multilayer
Film tiling is opened, and by a surface Corona discharge Treatment 5min of multilayer film, thick liquid is coated in treated multilayer
On two surfaces of film, in 70 DEG C of forced air dryings, coating film is made.
Embodiment 6
In a kettle, according to volume ratio 10:1 mixing acetone and dimethylformamide, mixed solution is obtained.Mixed solution is added
2% weight and process sub-atmospheric pressure glow discharge process 110s and partial size 50nm barium phosphate of weight, supersonic oscillations 10min, system
The suspension that must be uniformly mixed.In suspension be added mixed solution weight 1% weight and average molecular weight 1,000,000 it is poly- partially
Vinyl fluoride-hexafluoropropene adds 2.5% weight of mixed solution weight and the poly-methyl methacrylate of average molecular weight 800,000
Ester, supersonic oscillations 50min.8h is stirred at 50 DEG C, solution in reaction kettle is made to be changed into thick liquid.By polypropylene screen single layer
Film tiling is opened, and 2min is managed with corona discharge in two surfaces of monofilm everywhere, and thick liquid is coated in treated list
It on the surface of tunic, is dried in vacuo under 60 DEG C and 0.0008 atmospheric pressure, coating film is made.
Embodiment 7
In a kettle, according to volume ratio 5:1 mixing acetone and dimethylformamide, mixed solution is obtained.Mixed solution is added
0.67% weight and Low Temperature Plasma Treating 50s and partial size 100nm cupric phosphate of weight, 50 min of supersonic oscillations are made mixed
Close uniform suspension.5% weight of mixed solution weight and the polyvinylidene fluoride of average molecular weight 2,600,000 are added in suspension
Alkene-hexafluoropropene adds 2% weight of mixed solution weight and the polymethyl methacrylate of average molecular weight 900,000, ultrasound
Wave vibrates 20min.12 h are stirred at 70 DEG C, and solution in reaction kettle is made to be changed into thick liquid.PP/PE multilayer film is tiled
It opens, 10min is managed everywhere with corona discharge to two surfaces of multilayer film.Thick liquid is coated in treated multilayer film
On surface, coating film is made in the forced air drying under 110 DEG C and 0.005 atmospheric pressure.
Claims (10)
1. the preparation method of the coating film of low-inensity radiation, it is characterised in that technical solution comprises the steps of:
In a kettle, according to volume ratio (0.1~10): mixed solution is made in 1 mixing acetone and dimethylformamide;It is added
0.5~2.5% weight of mixed solution weight and coating agent Jing Guo radiation treatment, 1~30 min of supersonic oscillations are made mixed
Close uniform suspension;Kynoar-hexafluoropropene of 1~5% weight of mixed solution weight is added in suspension, then
The polymethyl methacrylate of 0.5~2.5% weight of mixed solution weight is added;10~50min of supersonic oscillations;50~
8~12 h are stirred at 90 DEG C, and solution in reaction kettle is made to be changed into thick liquid;Basement membrane tiling is opened, radiation treatment is carried out;It will glue
Thick liquid is coated in membrane surface Jing Guo radiation treatment, in 50~110 DEG C of temperature ranges the drying of any Temperature Vacuum or
Coating film is made in forced air drying.
2. the preparation method of the coating film of low-inensity radiation according to claim 1, it is characterised in that the vacuum is dry
Dry is the heat drying carried out under 0.1~0.00001atm pressure.
3. the preparation of the coating film of low-inensity radiation according to claim 1, it is characterised in that it is described through overshoot at
The coating agent of reason is partial size in the μ m of 10nm~5 and trivalent ion phosphate or divalent ion phosphoric acid Jing Guo radiation treatment
Salt.
4. the preparation method of the coating film of low-inensity radiation according to claim 3, it is characterised in that the trivalent from
Sub- phosphate is aluminum phosphate, scandium phosphate, ferric phosphate, phosphoric acid gallium or yttrium phosphate.
5. the preparation method of the coating film of low-inensity radiation according to claim 3, it is characterised in that the divalent from
Sub- phosphate is magnesium phosphate, trbasic zinc phosphate, calcium phosphate, cupric phosphate or barium phosphate.
6. according to claim 1 or the preparation method of the coating film of low-inensity radiation as claimed in claim 3, it is characterised in that institute
The radiation treatment stated is put in corona discharge, dielectric barrier discharge, RF low-temperature plasma electric discharge, jet stream low-temperature plasma
10 s~10min is handled under conditions of electricity, Atomospheric pressure glow discharge or sub-atmospheric pressure glow discharge.
7. the preparation method of the coating film of low-inensity radiation according to claim 1, it is characterised in that the poly- inclined fluorine
Ethylene-hexafluoropropene is Kynoar-hexafluoropropene of the average molecular weight in 20~2,800,000 ranges.
8. the preparation method of the coating film of low-inensity radiation according to claim 1, it is characterised in that the poly- methyl
Methyl acrylate is polymethyl methacrylate of the average molecular weight in 60~1,600,000 ranges.
9. the preparation method of the coating film of low-inensity radiation according to claim 1, it is characterised in that the basement membrane is
Polypropylene or polyethylene monolayer film, or the multilayer film containing polypropylene layer.
10. the preparation method of the coating film of low-inensity radiation according to claim 9, it is characterised in that the multilayer film
It is the diaphragm that the number of plies is formed in the monofilm of 2~10 ranges.
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