CN103421208B - Irradiation cross-linking lithium-ion battery diaphragm and preparation method thereof - Google Patents
Irradiation cross-linking lithium-ion battery diaphragm and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 21
- 238000004132 cross linking Methods 0.000 title abstract description 16
- -1 polyethylene Polymers 0.000 claims abstract description 31
- 239000012528 membrane Substances 0.000 claims abstract description 23
- 239000004698 Polyethylene Substances 0.000 claims abstract description 22
- 229920000573 polyethylene Polymers 0.000 claims abstract description 22
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 230000004888 barrier function Effects 0.000 claims description 106
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 39
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical group [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 34
- 229910052753 mercury Inorganic materials 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical group C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000002091 cationic group Chemical group 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 6
- 238000010894 electron beam technology Methods 0.000 claims description 6
- 230000005251 gamma ray Effects 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 5
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 5
- 239000012965 benzophenone Substances 0.000 claims description 5
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 5
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 229960001701 chloroform Drugs 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 claims description 3
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 claims description 3
- OKISUZLXOYGIFP-UHFFFAOYSA-N 4,4'-dichlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=C(Cl)C=C1 OKISUZLXOYGIFP-UHFFFAOYSA-N 0.000 claims description 3
- UXJDSNKBYFJNDO-UHFFFAOYSA-N 9-[4-[2-[2-(4-carbazol-9-ylphenyl)phenyl]phenyl]phenyl]carbazole Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C(C=C1)=CC=C1C1=CC=CC=C1C1=CC=CC=C1C1=CC=C(N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 UXJDSNKBYFJNDO-UHFFFAOYSA-N 0.000 claims description 3
- 229920001241 Cyamelide Polymers 0.000 claims description 3
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical group C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 3
- SMEDVXJKKOXLCP-UHFFFAOYSA-N cyamelide Chemical compound N=C1OC(=N)OC(=N)O1 SMEDVXJKKOXLCP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229940059574 pentaerithrityl Drugs 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 9
- 239000003431 cross linking reagent Substances 0.000 abstract 2
- 230000007547 defect Effects 0.000 abstract 1
- 230000010148 water-pollination Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 63
- 239000011148 porous material Substances 0.000 description 23
- 210000004379 membrane Anatomy 0.000 description 20
- 239000008151 electrolyte solution Substances 0.000 description 17
- 229920003020 cross-linked polyethylene Polymers 0.000 description 16
- 239000004703 cross-linked polyethylene Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 13
- 238000011049 filling Methods 0.000 description 11
- 239000004743 Polypropylene Substances 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 238000009736 wetting Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000012982 microporous membrane Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000002352 surface water Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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- 230000000875 corresponding effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
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- 238000004804 winding Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Cell Separators (AREA)
Abstract
The invention discloses a preparation method of an irradiation cross-linking polyethylene porous diaphragm. According to the method, the polyethylene porous diaphragm is soaked in and adsorbs a volatile solvent containing initiator and cross-linking agent to lead initiator and cross-linking agent into the surface and the interior of the polyethylene porous diaphragm, and is then treated with irradiation cross-linking underwater or under the protection of inert gas, and a locally cross-linked diaphragm is obtained by controlling the cross-linking condition. The irradiation cross-linking lithium-ion battery diaphragm has the advantages that the tensile strength and the hydrophily are greatly improved; the high-temperature hot-shrinkage rate is greatly reduced; the defect of low membrane rupture temperature is overcome; the membrane rupture temperature is greatly raised while the normal hole closing of the diaphragm is guaranteed; the hole closing temperature of the diaphragm is 120 to 140 DEG C; the membrane rupture temperature is raised to be higher than 160 DEG C.
Description
Technical field
The present invention relates to field of lithium ion battery, particularly relate to a kind of cross-linking radiation lithium ion battery separator and preparation method thereof.
Background technology
Lithium ion battery is a kind of novel rechargeable battery that grows up on lithium battery basis, to be succeeded in developing and realize commercialization by Sony Corporation in nineteen ninety.There is because of it advantages such as high-energy-density, long circulation life, memory-less effect and become the study hotspot of novel power supply technology in recent years.Portable type electronic product can be widely used in as mobile phone, notebook computer, digital camera, the pick up camera current field such as electric bicycle, electromobile and the energy-storage battery vigorously advocated of the world even.
The primary member of lithium ion battery comprises electrode, barrier film and electrolytic solution three part; wherein barrier film plays the part of critical role in lithium ion battery; it is a kind of insulation porous membrane; in the battery for isolating positive and negative electrode; allow free ion therebetween to pass through, work the provide protection preventing the two poles of the earth short circuit.Thus, battery diaphragm, except needing certain porosity and pore size distribution, allows ion normal through outward, and its most important performance is its security in lithium ion battery use procedure: isolate positive and negative electrode on the one hand, prevents the two directly contact and short circuit; On the other hand at battery because of external fault or internal short-circuit, when causing inside battery runaway reaction and cause inner temperature runaway, barrier film can normal Self-closed hole at a lower temperature, cut off battery plus-negative plate reaction, battery is quit work, and when reacting stopping but internal temperature continues to rise to higher temperature, barrier film still have enough resistances to elevated temperatures, keep the unlikely holes of dimensional stabilizing, namely have higher breaking temperature.So we wish not only barrier film has lower Self-closed hole temperature but also have higher holes temperature.
Current lithium ion battery separator is polyolefins porous membrane mainly, has polyethylene monolayer film, polypropylene unitary film, or polypropylene, polyethylene/polypropylene sandwich diaphragm etc.To polyethylene monolayer film, because of polyethylene about 130 DEG C meltings, fusing point is lower; in lithium ion battery, have lower closed pore temperature, energy available protecting circuit, but its breaking temperature is also very low; less than 140 DEG C with regard to easy melting holes, very unfavorable to the safety performance of lithium ion battery.To polypropylene unitary film, though it has relatively high holes temperature (more than 170 DEG C), but polypropylene fusing point is between 160 ~ 170 DEG C, it only reaches more than 160 DEG C just closed pores at internal temperature of lithium ion battery, this temperature is close to the fusing point of lithium, also higher than battery organic solvent boiling point, solvent evaporates becomes gas that internal pressure can be made to increase; Electrolyte lithium salt also easily decomposes the fluorine-containing sour gas of generation at such a temperature, and makes solvent further decomposition reaction occur.Therefore, its higher closed pore temperature is very unfavorable to lithium ion battery safe handling.To polypropylene, polyethylene/polypropylene sandwich diaphragm, namely this film has the lower closed pore temperature of polyethylene, has again the holes temperature that polypropylene is higher concurrently, can available protecting battery circuit.But its shortcoming is, one, make the normal closed pore of middle polyethylene layer energy, both sides polypropylene layer keeps dimensional stabilizing, its thickness much larger than unitary film, thus will occupy the finite space in lithium ion battery, if trilamellar membrane is accomplished thickness in monolayer, middle polyethylene layer will be very thin, and this thickness will be not enough to complete closed pore to block electric current.Two, this sandwich diaphragm physical strength is lower, and 120 DEG C of thermal contractions are comparatively large, and in use procedure, battery winding short circuit ratio is high, unfavorable production.Three, the holes temperature of this barrier film is still difficult to the field meeting high-power power lithium-ion battery, as power bicycle, power vehicle etc.
The method improving battery safety has a lot: China Patent No. CN101997102A discloses a kind of preparation method of three-layer composite microporous membrane, this film middle layer is multipolymer or the mixture of polyethylene or polyethylene and other alkene, two-layer is outward the multipolymer of polyvinylidene difluoride (PVDF) or R 1216-vinylidene, and this composite membrane has that closed pore temperature is low, breaking temperature is high, physical strength advantages of higher.Patent CN201877484U proposes the sandwich diaphragm sandwiching a microporous teflon membran in the middle of a kind of upper and lower two layers of polypropylene microporous membrane or upper and lower two layers of polyethylene microporous membrane, and this film also brings up to more than 200 DEG C barrier film breaking temperature.Patent CN200580051172 proposes on barrier film, be coated with dystectic poly(isophthaloyl metaphenylene diamine) porous layer and forms combined type barrier film, thus barrier film breaking temperature is increased to more than 250 DEG C.But in this coating process, coating thickness homogeneity difficulty controls on the one hand; On the other hand, coating fluid can blocking portion duct.
In order to solve the shortcoming of aforementioned lithium ion battery separator safety performance deficiency, therefore a kind of lithium ion battery separator to be studied, namely it have low closed pore temperature, have again higher holes temperature concurrently, thickness is unlikely blocked up simultaneously, the barrier film that other performances are more superior, to adapt to more and more harsher market to the requirement of lithium ion battery separator.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of cross-linking radiation lithium ion battery separator and preparation method thereof is provided.
The object of the invention is to be achieved through the following technical solutions: a kind of preparation method of IXPE porous diaphragm, it comprises the following steps: (1) polyethylene porous separator is immersed in containing mass concentration be the light trigger of 0.01-10%, mass concentration is in the easy volatile organic solvent of the linking agent of 0.01-10% more than 5 seconds, drying at room temperature after taking out;
(2) barrier film after step 1 being soaked is placed on below aqueous solution liquid level that mass concentration is the hydrophilic monomer of 0-5% 1-50mm place irradiation source irradiation more than 2 seconds; or use irradiation source irradiation more than 2 seconds under directly the barrier film after immersion being placed in protection of inert gas atmosphere; irradiation temperature is room temperature to 110 DEG C; membrane surface, from irradiation source distance 3-15cm, obtains IXPE porous diaphragm.
Further, described light trigger comprises hydrogen-capture-type light initiator, crack type photoinitiator, cationic initiators; Wherein, described hydrogen-capture-type light initiator is benzophenone, 4-chlorobenzophenone or 4,4 '-dichloro benzophenone; Described crack type photoinitiator is 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-acetone, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio group) phenyl]-1-acetone or 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholine-1-acetone; Described cationic initiators is 261, I-250, NS-1, NS-2, PBCP, CCP, NCP, BCBP, CS-1 or CS-2.
Further, described linking agent is triallyl cyanurate (TAC), cyamelide triallyl (TAIC), Viscoat 295 (TMPTA), triallyl Glycerin ether (TMPTAE), trimethylolpropane trimethacrylate (TMPTMA), tetramethylol methane tetraacrylate (PETA), triallyl pentaerythritol/tetraallyl tetramethylolmethane ether mixture (PETAE) or neopentylglycol diacrylate (NPGDA).
Further, described easy volatile solvent is methyl alcohol, ethanol, methylene dichloride, trichloromethane, ethylene dichloride, trichloroethane, ether, acetone or methyl ethyl ketone.
Further, described hydrophilic monomer is vinylformic acid, methacrylic acid, methacrylic ester, acrylamide or N,N-DMAA.
Further, described irradiation source is mercury lamp, electron beam or gamma ray.
Beneficial effect of the present invention is: IXPE porous diaphragm of the present invention has following characteristics:
1, the security of barrier film is superior to former polyethylene diagrams far away.Barrier film prepared by this kind of method has the lower closed pore temperature (120-140 DEG C) of former polyethylene diagrams, and be different from former polyethylene diagrams 140 DEG C of ruptures of membranes, the porous-film breaking temperature of this research brings up to more than 160 DEG C, reaches as high as 220 DEG C.In other words, even if also fully can cut off cell reaction when lithium ion battery breaks down, prevent on fire and blast, safety performance significantly improves.
2, have the electrolytic solution pick up compared with the better wetting ability of protocnemes and Geng Gao, can significantly improve power cell power, physical strength significantly improves, and high-temperature hot shrinking percentage reduces greatly, has no significant effect barrier film porosity and pore size distribution simultaneously.
3, cheap for manufacturing cost, technique is very simple.
Accompanying drawing explanation
Fig. 1 is the barrier film pre-irradiation rear surface topography scan Electronic Speculum figure that the embodiment of the present invention 1 obtains;
Fig. 2 is porosity and graph of pore diameter distribution after the barrier film pre-irradiation that obtains of the embodiment of the present invention 1;
Fig. 3 is Static water contact angles figure after the barrier film pre-irradiation that obtains of the embodiment of the present invention 1;
Fig. 4 is water contact angle variation diagram in time after the barrier film pre-irradiation that obtains of the embodiment of the present invention 1;
Fig. 5 is Static water contact angles figure after the barrier film pre-irradiation that obtains of the embodiment of the present invention 2;
Fig. 6 is the wetting picture to electrolytic solution after the barrier film pre-irradiation that obtains of the embodiment of the present invention 1;
Fig. 7 is the pick up to electrolytic solution after the barrier film pre-irradiation that obtains of the embodiment of the present invention 1;
Fig. 8 is the morphology change figure of the barrier film high temperature Self-closed hole experiment front and back that the embodiment of the present invention 1 obtains;
Fig. 9 is the barrier film high temperature Self-closed hole experiment front and rear surfaces pattern Electronic Speculum figure that the embodiment of the present invention 1 obtains.
Embodiment
The preparation method of IXPE porous diaphragm of the present invention, comprises the following steps:
The first step: polyethylene porous separator is immersed in containing mass concentration be the light trigger of 0.01-10%, mass concentration is in the easy volatile organic solvent of the linking agent of 0.01-10% more than 5 seconds, drying at room temperature after taking out.
Second step: the barrier film after step 1 being soaked is placed on below aqueous solution liquid level that mass concentration is the hydrophilic monomer of 0-5% 1-50mm place irradiation source irradiation more than 2 seconds; or use irradiation source irradiation more than 2 seconds under directly the barrier film after immersion being placed in protection of inert gas atmosphere; irradiation temperature is room temperature to 110 DEG C, and membrane surface is from irradiation source distance 3-15cm.
Described light trigger comprises hydrogen-capture-type light initiator, crack type photoinitiator, cationic initiators; Wherein, described hydrogen-capture-type light initiator is benzophenone (BP), 4-chlorobenzophenone (4-CBP) or 4,4 '-dichloro benzophenone; Described crack type photoinitiator is 1-hydroxycyclohexyl phenyl ketone (light trigger 184), 2-hydroxy-2-methyl-1-phenyl-acetone (light trigger 1173), 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio group) phenyl]-1-acetone (light trigger 907), 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholine-1-acetone (light trigger 1700); Described cationic initiators 261, I-250, NS-1, NS-2, PBCP, CCP, NCP, BCBP, CS-1 or CS-2.
Described linking agent is triallyl cyanurate (TAC), cyamelide triallyl (TAIC), Viscoat 295 (TMPTA), triallyl Glycerin ether (TMPTAE), trimethylolpropane trimethacrylate (TMPTMA), tetramethylol methane tetraacrylate (PETA), triallyl pentaerythritol/tetraallyl tetramethylolmethane ether mixture (PETAE) or neopentylglycol diacrylate (NPGDA).
Described easy volatile solvent is methyl alcohol, ethanol, methylene dichloride, trichloromethane, ethylene dichloride, trichloroethane, ether, acetone or methyl ethyl ketone.
Described hydrophilic monomer is vinylformic acid (AA), methacrylic acid (MA), methacrylic ester (MMA), acrylamide (AAM) or N,N-DMAA (DMAA).
Described irradiation source is mercury lamp, electron beam or gamma ray.
Describe the present invention in detail according to drawings and embodiments below, object of the present invention and effect will become more obvious.
Have employed three kinds of polyethylene porous separator, barrier film one: thickness 16um, porosity 48%, aperture 10nm; Barrier film two, thickness 10um, porosity 30%, aperture 10nm; Barrier film three: thickness 50um, porosity 70%, aperture 2um.
Performance involved in this patent, detection method is as follows:
1, film thickness: adopt optical thickness measurer to measure
2, porosity and pore size distribution: adopt AutoPoreIV9510 type mercury injection apparatus to detect.
3, Static water contact angles: adopt OCA20 type video optics contact angle measurement, adopt sessile drop method (sessile drop) to measure.
4, electrolytic solution wettability: configuration 1M LiPF
6-EC/DMC(1:1, v/v) electrolytic solution, in the glove box being full of argon gas, the barrier film of drying treatment is placed on a glass, then topple over a certain amount of electrolytic solution thereon, observe the surface wettability of film and take pictures.
5, electrolytic solution pick up: be M by drying treatment quality
0barrier film be immersed in the electrolytic solution of configuration and take out after 24h, wipe the electrolytic solution on film surface away, quality of weighing is M, the pick up by following formulae discovery film:
Pick up %=(M-M
0)/M
0
6, the high-temperature hot shrinking percentage of polyethylene diagrams: barrier film is placed on measures its longitudinal thermal contraction at various temperatures and horizontal thermal contraction after being incubated 60min in the baking oven of 90 DEG C, 100 DEG C, 110 DEG C or 120 DEG C respectively.
7, closed pore temperature and breaking temperature: film sample is whole to be fixed in cylinder shape film device that diameter is 60mm, heat in the baking oven of Hot-blast Heating to preset temp after one minute and take out, cooling sample, to room temperature, detects barrier film air penetrability, judges diaphragm closed pore or rupture of membranes by air penetrability.
Embodiment 1
Barrier film 1 is immersed in 1min in the dichloromethane solution containing 1% mass concentration photoinitiator b P, 1% mass concentration linking agent TAC, drying at room temperature after taking out.Be immersed in by this barrier film in the thermostat water bath filling pure water in irradiator, carry out two-sided irradiation 3min, film position distance water surface 2mm, water temperature 30 DEG C, irradiation source is 2KW high voltage mercury lamp, and mercury lamp distance film 10cm, irradiation obtains crosslinked polyethylene porous diaphragm.
What Fig. 1 provided is membrane surface pattern electron microscopic picture before and after the two-sided irradiation 3min of barrier film 1, (a) pre-irradiation; After (b) irradiation.As seen from the figure, pre-irradiation metacneme aperture pattern is unchanged.The graph of pore diameter distribution that what Fig. 2 provided is before and after the two-sided irradiation 3min of barrier film 1, as seen from the figure, irradiation metacneme pore size distribution is also without impact.From Fig. 1,2, the physical pattern of pre-irradiation metacneme is almost unchanged, namely surface on its in the battery conducting ion without impact.
What Fig. 3 provided is membrane surface water contact angle variation diagram before and after the two-sided irradiation 3min of barrier film 1, (a) pre-irradiation, (b) irradiation 3min.What Fig. 4 provided is corresponding film surface water contact angle trend over time.As seen from the figure, pre-irradiation, barrier film 1 Static water contact angles is 120 °, becomes 34 ° after irradiation, barrier film is stronger hydrophilic after becoming irradiation from pre-irradiation hydrophobic, wetting ability obviously strengthens, and membrane surface drop volume obviously reduces, i.e. a large amount of diffusion in the oriented film of water droplet, only has small part at film surface spreading, and find from aftermentioned embodiment, irradiation time longer barrier film water contact angle reduces more, and water droplet is higher to film internal diffusion degree.
Fig. 6,7 researchs be the change of pre-irradiation metacneme electrolytic solution wettability and pick up.Electrolytic solution is poured over the picture that barrier film obtains by Fig. 6.A () is the barrier film of uncrosslinked process, obviously see that there are a lot of electrolytic solution small droplets and outstanding small bubbles in membrane surface, shows that the hydrophobicity of non-irradiation barrier film makes electrolytic solution can not be fully moistening on film surface.And after (b) septation 1 two-sided cross-linking radiation 3min, making barrier film can be completely moistening in the electrolytic solution, this also proves that irradiation metacneme wetting ability increases greatly further.Fig. 7 is the electrolytic solution pick up trend over time of non-irradiation barrier film and cross linking membrane over time.As seen from the figure, growth in time, the electrolyte content that all barrier films absorb all increases.The barrier film of uncrosslinked process reaches adsorption equilibrium soaking about 3h, and during balance, pick up is about 120wt%.And after irradiation, cross linking membrane reaches time of equilibrium adsorption and extends, pick up also increases sharply, uv irradiation 3min, it is saturated that cross linking membrane reaches absorption through 3.5h, and pick up reaches 200wt% simultaneously, know thus, irradiation energy improves barrier film to the wettability of electrolytic solution and pick up.
The percent thermal shrinkage of barrier film differing temps before and after the two-sided irradiation 3min of barrier film 1 that what table 1 provided is:
From upper table, 90 DEG C, pre-irradiation barrier film insulation 60min is respectively 1.2%/2.4% to percent thermal shrinkage in length and breadth, and is only 0.32%/0.58% respectively after irradiation, much smaller than pre-irradiation.And, all become large with after the rising barrier film percent thermal shrinkage pre-irradiation of temperature, difference is that the barrier film of 120 DEG C of insulation 60min pre-irradiations is increased to 9.25%/17.5% to percent thermal shrinkage in length and breadth, much larger than the safe retracted rate (being all less than 5%) that barrier film requires, but at this temperature of irradiation metacneme only 2.78%/5% percent thermal shrinkage, the high-temperature hot of obvious irradiation metacneme is shunk and is obviously reduced.
After barrier film pre-irradiation, its correlated performance data is summed up in table 2.
From table 2, other performance perameters are found out, after irradiation, barrier film is indulged transverse tensile strength and all improved a lot.Security aspect, diaphragm closed pore temperature is basically identical at 120 DEG C, but 140 DEG C of breaking temperature never irradiation barrier film 1 are brought up to 220 DEG C, and breaking temperature significantly improves, and safety performance obviously strengthens.
In Fig. 8, (a) (b) is the pattern before barrier film 1 and cross linking membrane high temperature Self-closed hole are tested, and (c) (d) is the pattern after closed pore.Obviously, barrier film 120 DEG C of holes of non-radiation treatment, several minutes metacneme completely loses original size.And 220 DEG C of holes after barrier film 1 irradiation 3min, still can keep good dimensional stability after insulation dozens of minutes, film only have a few place is small melts hole.Fig. 9 is the membrane surface scanning electron microscope (SEM) photograph before and after cross linking membrane high temperature Self-closed hole, is known by (b), and after closed pore experiment, film surface region keeps complete closely knit closed pore state.
Embodiment 2
Barrier film 1 is immersed in 1min in the dichloromethane solution containing 1% mass concentration photoinitiator b P, 1% mass concentration linking agent TAC, drying at room temperature after taking out.Be immersed in by this barrier film in the thermostat water bath filling pure water in irradiator, carry out two-sided irradiation 1min, film position distance water surface 2mm, water temperature 30 DEG C, irradiation source is 2KW high voltage mercury lamp, and mercury lamp distance film 10cm, irradiation obtains crosslinked polyethylene porous diaphragm.
As seen from Table 2, irradiation metacneme porosity is also unchanged.What Fig. 5 provided is membrane surface water contact angle variation diagram before and after the two-sided irradiation 1min of barrier film 1, and (a) pre-irradiation, after (b) irradiation.As seen from the figure, after barrier film 1 irradiation 1min, water contact angle is reduced to 82 ° from 120 °, and wetting ability also improves a lot, but does not have irradiation 3min to improve significantly, and as seen from Table 2, after irradiation, barrier film is indulged transverse tensile strength and also improved a lot.Security aspect, diaphragm closed pore temperature does not substantially become at 120 DEG C, but 140 DEG C of breaking temperature never irradiation barrier film 1 increase large 160 DEG C, and breaking temperature also improves a lot, but does not also have irradiation 3min to improve significantly.
Embodiment 3
Barrier film 1 is immersed in 1min in the dichloromethane solution containing 1% mass concentration light trigger Irg.184,1% mass concentration linking agent TAC, drying at room temperature after taking out.Be immersed in by this barrier film in the thermostat water bath filling pure water in irradiator, carry out two-sided irradiation 3min, film position distance water surface 2mm, water temperature 30 DEG C, irradiation source is 2KW high voltage mercury lamp, and mercury lamp distance film 10cm, irradiation obtains crosslinked polyethylene porous diaphragm.
Irradiation metacneme porosity and aperture do not change as seen from Table 2, and wetting ability, tensile strength improve a lot, and closed pore temperature is substantially unaffected, and breaking temperature brings up to 180 DEG C.
Embodiment 4
Barrier film 2 to be immersed in the chloroform soln containing 10% mass concentration light trigger Irg.184,10% mass concentration linking agent TMPTAE 5 seconds, drying at room temperature after taking out.Be immersed in by this barrier film in the thermostat water bath filling pure water in irradiator, carry out two-sided irradiation 3min, film position distance water surface 2mm, water temperature 70 DEG C, irradiation source is 1KW high voltage mercury lamp, and mercury lamp distance film 3cm, irradiation obtains crosslinked polyethylene porous diaphragm.
Embodiment 5
Barrier film 1 to be immersed in the ethanolic soln containing 10% mass concentration light trigger I-250,10% mass concentration linking agent PETA 5 seconds, drying at room temperature after taking out.This barrier film is immersed in the thermostat water bath filling pure water in irradiator, carries out two-sided irradiation 3min, film position distance water surface 2mm, temperature is room temperature, and irradiation source is 1KW high voltage mercury lamp, mercury lamp distance film 3cm, irradiation obtains crosslinked polyethylene porous diaphragm.
The initiator that table 4 is dissimilar and light source are on the impact of barrier film breaking temperature
Initiator type | Hydrogen-abstraction BP | Cracking type Irg.184 | Cationic I-250 |
Breaking temperature (DEG C) | 220 | 180 | 185 |
Irradiation source type | Mercury lamp | Electron beam | Gamma ray |
Breaking temperature (DEG C) | 220 | 185 | 180 |
In table 4, dissimilar light trigger gained barrier film breaking temperature data come from embodiment 1,3,5 respectively and know, obviously find out from data, no matter light trigger is hydrogen-abstraction, cracking type or cationic, there is good cross-linking effect to irradiation reaction, the breaking temperature of barrier film can be significantly improved.
Embodiment 6
Barrier film 2 to be immersed in the dichloromethane solution containing 10% mass concentration light trigger I-250,10% mass concentration linking agent TMPTAE 5 seconds, drying at room temperature after taking out.Be immersed in by this barrier film in the thermostat water bath filling pure water in irradiator, carry out two-sided irradiation 2s, film position distance water surface 1mm, water temperature 70 DEG C, irradiation source is 2KW high voltage mercury lamp, and mercury lamp distance film 3cm, irradiation obtains crosslinked polyethylene porous diaphragm.
Embodiment 7
Barrier film 3 is immersed in 30min in the dichloromethane solution containing 0.01% mass concentration photoinitiator b P and 0.01% mass concentration linking agent TAC, drying at room temperature after taking out.This barrier film is immersed in the thermostat water bath filling pure water in irradiator, carries out two-sided irradiation 15min, film position distance water surface 2mm, water temperature 70 DEG C, irradiation source is 2KW high voltage mercury lamp, mercury lamp distance film 15cm, irradiation obtains crosslinked polyethylene porous diaphragm.
Embodiment 8
Barrier film 3 is immersed in 30min in the dichloromethane solution containing 0.01% mass concentration photoinitiator b P and 0.01% mass concentration linking agent TAC, drying at room temperature after taking out.Be immersed in by this barrier film in the thermostat water bath filling pure water in irradiator, carry out two-sided irradiation 3min, film position distance water surface 2mm, water temperature 30 DEG C, irradiation source is 1KW high voltage mercury lamp, and mercury lamp distance film 3cm, irradiation obtains crosslinked polyethylene porous diaphragm.
Embodiment 9
Barrier film 3 is immersed in 1min in the ethanolic soln containing 10% mass concentration light trigger Irg.184 and 10% mass concentration linking agent TAC, drying at room temperature after taking out.This barrier film is immersed in the thermostat water bath filling pure water in irradiator, carries out two-sided irradiation 3min, film position distance water surface 50mm, water temperature is 10 DEG C, and irradiation source is 1KW high voltage mercury lamp, mercury lamp distance film 3cm, irradiation obtains crosslinked polyethylene porous diaphragm.
Embodiment 10
Barrier film 3 is immersed in 10min in the dichloromethane solution containing 10% mass concentration light trigger Irg.184 and 10% mass concentration linking agent TAC, drying at room temperature after taking out.Being immersed in by this barrier film and being dissolved with mass concentration is in the thermostat water bath of the aqueous solution of 5% acrylamide, two-sided irradiation 3min is carried out in irradiator, film position distance water surface 3mm, water temperature 20 DEG C, irradiation source is 1KW high voltage mercury lamp, mercury lamp distance film 3cm, irradiation obtains crosslinked polyethylene porous diaphragm.
The introducing of table 5 hydrophilic monomer is on the hydrophilic impact of barrier film
Barrier film wetting ability | Comparative example | Embodiment 1 | Embodiment 10 |
Water contact angle (°) | 120 | 34 | 7 |
As seen from Table 5, the introducing of hydrophilic monomer obviously can reduce the water contact angle of barrier film, and barrier film wetting ability can be made greatly to improve.
Embodiment 11
Barrier film 1 is immersed in 1min in the dichloromethane solution containing 1% mass concentration photoinitiator b P, 1% mass concentration linking agent TAIC, drying at room temperature after taking out.Be positioned in nitrogen atmosphere by this barrier film, irradiation source is 1KW high voltage mercury lamp, and mercury lamp distance film 10cm, irradiation temperature 110 degree, irradiation obtains crosslinked polyethylene porous diaphragm.
Embodiment 12
Barrier film 1 is immersed in 1min in the dichloromethane solution containing 1% mass concentration photoinitiator b P, 1% mass concentration linking agent PETA, drying at room temperature after taking out.Be immersed in by this barrier film in the thermostat water bath filling pure water in irradiator, carry out two-sided irradiation 3min, film position distance water surface 2mm, water temperature 30 DEG C, irradiation source is electron beam, and distance film 10cm, irradiation obtains crosslinked polyethylene porous diaphragm.
Embodiment 13
Barrier film 1 is immersed in 1min in the acetone soln containing 1% mass concentration photoinitiator b P, 1% mass concentration linking agent TAC, drying at room temperature after taking out.Be immersed in by this barrier film in the thermostat water bath filling pure water in irradiator, carry out two-sided irradiation 3min, film position distance water surface 2mm, water temperature 30 DEG C, irradiation source is gamma ray, and distance film 10cm, irradiation obtains crosslinked polyethylene porous diaphragm.
In table 4, dissimilar irradiation source gained barrier film breaking temperature data come from embodiment 1,12,13 respectively, obviously find out from data, no matter irradiation source is mercury lamp, electron beam or gamma ray, can significantly improve the breaking temperature of barrier film, namely different irradiation source has good cross-linking effect to irradiation reaction.
Embodiment 14
Barrier film 3 is immersed in 10min in the dichloromethane solution containing 7% mass concentration light trigger Irg.184 and 7% mass concentration linking agent TAC, drying at room temperature after taking out.Being immersed in by this barrier film and being dissolved with mass concentration is in the thermostat water bath of 3% methacrylic aqueous acid, two-sided irradiation 3min is carried out in irradiator, film position distance water surface 3mm, water temperature 50 DEG C, irradiation source is 1KW high voltage mercury lamp, mercury lamp distance film 3cm, irradiation obtains crosslinked polyethylene porous diaphragm.
Embodiment 15
Barrier film 3 is immersed in 1min in the methanol solution containing 1% mass concentration light trigger Irg.184 and 1% mass concentration linking agent TMPTA, drying at room temperature after taking out.Being immersed in by this barrier film and being dissolved with mass concentration is in the thermostat water bath of 1% acrylic acid aqueous solution, two-sided irradiation 3min is carried out in irradiator, film position distance water surface 3mm, water temperature 20 DEG C, irradiation source is 1KW high voltage mercury lamp, mercury lamp distance film 5cm, irradiation obtains crosslinked polyethylene porous diaphragm.
Embodiment 16
Barrier film 1 is immersed in 1min in the dichloromethane solution containing 1% mass concentration photoinitiator b P, 1% mass concentration linking agent TAC, drying at room temperature after taking out.Be positioned in nitrogen atmosphere by this barrier film, irradiation source is 1KW high voltage mercury lamp, and mercury lamp distance film 10cm, irradiation temperature is room temperature, and irradiation obtains crosslinked polyethylene porous diaphragm.
Claims (6)
1. the preparation method of an IXPE porous diaphragm, it is characterized in that, it comprises the following steps: (1) polyethylene porous separator is immersed in containing mass concentration be the light trigger of 0.01-10%, mass concentration is in the easy volatile organic solvent of the linking agent of 0.01-10% more than 5 seconds, drying at room temperature after taking out;
(2) barrier film after step (1) immersion is placed on below the aqueous solution liquid level that mass concentration is the hydrophilic monomer of 0-5% 1-50mm place irradiation source irradiation more than 2 seconds; or use irradiation source irradiation more than 2 seconds under directly the barrier film after immersion being placed in protection of inert gas atmosphere; irradiation temperature is room temperature to 110 DEG C; membrane surface, from irradiation source distance 3-15cm, obtains IXPE porous diaphragm.
2. preparation method according to claim 1, is characterized in that, described light trigger comprises hydrogen-capture-type light initiator, crack type photoinitiator, cationic initiators; Wherein, described hydrogen-capture-type light initiator is benzophenone, 4-chlorobenzophenone or 4,4'-dichloro benzophenone; Described crack type photoinitiator is 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-acetone, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio group) phenyl]-1-acetone or 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholine-1-acetone; Described cationic initiators is 261, I-250, NS-1, NS-2, PBCP, CCP, NCP, BCBP, CS-1 or CS-2.
3. preparation method according to claim 1, it is characterized in that, described linking agent is triallyl cyanurate, cyamelide triallyl, Viscoat 295, triallyl Glycerin ether, trimethylolpropane trimethacrylate, tetramethylol methane tetraacrylate, triallyl pentaerythritol/tetraallyl tetramethylolmethane ether mixture or neopentylglycol diacrylate.
4. preparation method according to claim 1, is characterized in that, described easy volatile solvent is methyl alcohol, ethanol, methylene dichloride, trichloromethane, ethylene dichloride, trichloroethane, ether, acetone or methyl ethyl ketone.
5. preparation method according to claim 1, is characterized in that, described hydrophilic monomer is vinylformic acid, methacrylic acid, methacrylic ester, acrylamide or N,N-DMAA.
6. preparation method according to claim 1, is characterized in that, described irradiation source is mercury lamp, electron beam or gamma ray.
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