CN110621726A - 氟聚合物杂化复合材料 - Google Patents
氟聚合物杂化复合材料 Download PDFInfo
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- CN110621726A CN110621726A CN201880031416.6A CN201880031416A CN110621726A CN 110621726 A CN110621726 A CN 110621726A CN 201880031416 A CN201880031416 A CN 201880031416A CN 110621726 A CN110621726 A CN 110621726A
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- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 229920002313 fluoropolymer Polymers 0.000 title claims abstract description 28
- 239000004811 fluoropolymer Substances 0.000 title claims abstract description 28
- 239000010409 thin film Substances 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims description 72
- 229920000642 polymer Polymers 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 40
- 239000010408 film Substances 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 239000000155 melt Substances 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 125000000524 functional group Chemical group 0.000 claims description 10
- 239000011256 inorganic filler Substances 0.000 claims description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 229910003471 inorganic composite material Inorganic materials 0.000 claims description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 17
- -1 hydrocarbon radicals Chemical class 0.000 description 14
- 239000002609 medium Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 8
- 238000004898 kneading Methods 0.000 description 8
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 8
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 8
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 7
- 239000003377 acid catalyst Substances 0.000 description 7
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000012736 aqueous medium Substances 0.000 description 6
- 238000007872 degassing Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 4
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229920001002 functional polymer Polymers 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229910017048 AsF6 Inorganic materials 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- 229910005143 FSO2 Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- 235000019801 trisodium phosphate Nutrition 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- WFLOTYSKFUPZQB-OWOJBTEDSA-N (e)-1,2-difluoroethene Chemical group F\C=C\F WFLOTYSKFUPZQB-OWOJBTEDSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 1
- HFNSTEOEZJBXIF-UHFFFAOYSA-N 2,2,4,5-tetrafluoro-1,3-dioxole Chemical class FC1=C(F)OC(F)(F)O1 HFNSTEOEZJBXIF-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 1
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- CUZKCNWZBXLAJX-UHFFFAOYSA-N 2-phenylmethoxyethanol Chemical compound OCCOCC1=CC=CC=C1 CUZKCNWZBXLAJX-UHFFFAOYSA-N 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- MZWXWSVCNSPBLH-UHFFFAOYSA-N 3-(3-aminopropyl-methoxy-methylsilyl)oxypropan-1-amine Chemical compound NCCC[Si](C)(OC)OCCCN MZWXWSVCNSPBLH-UHFFFAOYSA-N 0.000 description 1
- GXDMUOPCQNLBCZ-UHFFFAOYSA-N 3-(3-triethoxysilylpropyl)oxolane-2,5-dione Chemical compound CCO[Si](OCC)(OCC)CCCC1CC(=O)OC1=O GXDMUOPCQNLBCZ-UHFFFAOYSA-N 0.000 description 1
- GBAQKTTVWCCNHH-UHFFFAOYSA-N 3-[dichloro(methyl)silyl]propyl prop-2-enoate Chemical compound C[Si](Cl)(Cl)CCCOC(=O)C=C GBAQKTTVWCCNHH-UHFFFAOYSA-N 0.000 description 1
- MCDBEBOBROAQSH-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C=C MCDBEBOBROAQSH-UHFFFAOYSA-N 0.000 description 1
- ZCRUJAKCJLCJCP-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(C)CCCOC(=O)C=C ZCRUJAKCJLCJCP-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- WYTQXLFLAMZNNZ-UHFFFAOYSA-N 3-trihydroxysilylpropane-1-sulfonic acid Chemical compound O[Si](O)(O)CCCS(O)(=O)=O WYTQXLFLAMZNNZ-UHFFFAOYSA-N 0.000 description 1
- GDCRYMZNGGCWEH-UHFFFAOYSA-N 3-trihydroxysilylpropanoic acid Chemical compound OC(=O)CC[Si](O)(O)O GDCRYMZNGGCWEH-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- JPZOAVGMSDSWSW-UHFFFAOYSA-N 4,6-dichloropyrimidin-2-amine Chemical compound NC1=NC(Cl)=CC(Cl)=N1 JPZOAVGMSDSWSW-UHFFFAOYSA-N 0.000 description 1
- IHBDUARGLPMOND-UHFFFAOYSA-N 4-(2-trichlorosilylethyl)benzenesulfonyl chloride Chemical compound Cl[Si](Cl)(Cl)CCC1=CC=C(S(Cl)(=O)=O)C=C1 IHBDUARGLPMOND-UHFFFAOYSA-N 0.000 description 1
- NYIDSUMRGUILGR-UHFFFAOYSA-N 4-(2-trimethoxysilylethyl)benzenesulfonyl chloride Chemical compound CO[Si](OC)(OC)CCC1=CC=C(S(Cl)(=O)=O)C=C1 NYIDSUMRGUILGR-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- SGVYKUFIHHTIFL-UHFFFAOYSA-N Isobutylhexyl Natural products CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 206010074268 Reproductive toxicity Diseases 0.000 description 1
- 229910007157 Si(OH)3 Inorganic materials 0.000 description 1
- 102100032800 Spermine oxidase Human genes 0.000 description 1
- 101710167338 Spermine oxidase Proteins 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- GTOVGJUKOALMTN-UHFFFAOYSA-N acetic acid;n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CO[Si](OC)(OC)CCCNCCN GTOVGJUKOALMTN-UHFFFAOYSA-N 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 1
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- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
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- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- BCWYYHBWCZYDNB-UHFFFAOYSA-N propan-2-ol;zirconium Chemical compound [Zr].CC(C)O.CC(C)O.CC(C)O.CC(C)O BCWYYHBWCZYDNB-UHFFFAOYSA-N 0.000 description 1
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- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium(IV) ethoxide Substances [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
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- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Abstract
本发明涉及一种氟聚合物杂化的有机/无机复合材料,涉及一种包含所述氟聚合物杂化的有机/无机复合材料的薄膜并且涉及所述薄膜在各种应用中、尤其是在电化学和光电化学应用中的用途。
Description
相关申请的交叉引用
本申请要求于2017年5月12日提交的欧洲申请号17305539.3的优先权,出于所有目的将所述申请的全部内容通过援引方式并入本申请。
技术领域
本发明涉及一种氟聚合物杂化的有机/无机复合材料,涉及一种包含所述氟聚合物杂化的有机/无机复合材料的薄膜并且涉及所述薄膜在各种应用中、尤其是在电化学和光电化学应用中的用途。
背景技术
锂金属聚合物(LMP)电池在本领域中是已知的,其中阳极是Li金属箔并且隔膜是聚(环氧烷)与氟聚合物、优选偏二氟乙烯聚合物的电解质固体聚合物共混物,其结合电解质盐。
这些隔膜典型地通过薄膜挤出获得。不幸的是,此技术的一个缺点是在低于80℃的温度下如此获得的隔膜的低离子电导率。
因此,此领域的挑战是提高这些隔膜的离子电导率以使挤出技术更具吸引力,同时提供安全的隔膜(确保电极的良好分离)。
发明内容
现已发现,本发明的方法代表一种本领域已知的用于制造具有出色的离子电导率的致密薄膜的方法的灵活且容易的替代方案,并且因此适用于电化学和光电化学应用(如电化学装置中的隔膜)。
在第一实例中,本发明涉及一种用于制造氟聚合物杂化的有机/无机复合材料[复合材料(FH)]的方法,所述方法包括:
(i)通过在熔融相中加工,优选地将以下项挤出提供预复合材料[预复合材料(FP)]:
-通过在液体介质的存在下,至少一种具有式(I)的金属化合物[化合物(M)]的至少部分水解和/或缩聚可获得的预凝胶化合物[化合物(MP)]:
X4-mM(OY)m (I)
其中M是选自由Si、Ti和Zr组成的组的金属,X和Y彼此相同或不同并且在每次出现时选自任选地包含一个或多个官能团的烃基,并且m是包括在1与4之间的整数,以及
-至少一种包含至少一个羟基的官能氟聚合物[聚合物(FF)];
(ii)通过将在步骤(i)中提供的该预复合材料(FP)与以下项混配提供组合物:
-至少一种具有式(II)的聚(环氧烷)(PAO):
HO-(CH2CHRAO)n-RB (II)
其中RA是氢原子或C1-C5烷基,RB是氢原子或-CH3烷基并且n是包括在2000与40000之间、优选在4000与35000之间、更优选在11500与30000之间的整数,
-至少一种金属盐[盐(M)],
-任选地,至少一种与该聚合物(FF)相同或不同的氟聚合物[聚合物(F)],以及
-任选地,一种或多种无机填料;以及
(iii)在熔融相中加工,优选地挤出在步骤(ii)中提供的该组合物。
在用于制造本发明的复合材料(FH)的方法的步骤(i)中提供的预复合材料(FP)典型地呈粒料形式。优选地将预复合材料(FP)后处理,优选地在高于100℃且至多170℃的温度下,典型地在包括在10分钟与24小时之间的时间期间。
将在用于制造本发明的复合材料(FH)的方法的步骤(ii)中提供的组合物在熔融相中加工,典型地使用挤出机、优选双螺杆挤出机。
在第二实例中,本发明涉及一种氟聚合物杂化的有机/无机复合材料[复合材料(FH)]。
该复合材料(FH)可有利地通过本发明的方法获得。
该复合材料(FH)典型地呈粒料形式。
该复合材料(FH)典型地包含以下项、优选地由以下项组成:
-至少一种预复合材料[预复合材料(FP)],
-至少一种具有式(II)的聚(环氧烷)(PAO):
HO-(CH2CHRAO)n-RB (II)
其中RA是氢原子或C1-C5烷基,RB是氢原子或-CH3烷基并且n是包括在2000与40000之间、优选在4000与35000之间、更优选在11500与30000之间的整数,
-至少一种金属盐[盐(M)],
-任选地,至少一种与该聚合物(FF)相同或不同的氟聚合物[聚合物(F)],以及
-任选地,一种或多种无机填料。
本发明的复合材料(FH)特别适合在用于制造薄膜的方法中使用。
因此,在第三实例中,本发明涉及一种用于制造薄膜的方法,所述方法包括在熔融相中加工至少一种复合材料(FH)。
根据本发明的用于制造薄膜的方法有利地包括典型地使用挤出机、优选单螺杆挤出机,在熔融相中加工至少一种复合材料(FH)。
该薄膜典型地通过使用薄膜挤出技术如流延薄膜挤出或吹塑薄膜挤出在熔融相中加工至少一种复合材料(FH)来制造。
在第四实例中,本发明涉及通过本发明的方法可获得的薄膜。
本发明的薄膜典型地包含至少一种复合材料(FH)、优选地由其组成。
本发明的薄膜典型地是致密薄膜。
出于本发明的目的,术语“致密”旨在表示没有孔的薄膜。
本发明的薄膜典型地具有包括在2μm与300μm之间、优选在5μm与100μm之间、更优选在10μm与40μm之间的厚度。
在第五实例中,本发明涉及一种包含至少一种本发明的薄膜的电化学装置或光电化学装置。
本发明的薄膜适合在电化学装置或光电化学装置中使用。
合适的电化学装置的非限制性实例包括二次电池,优选锂离子电池。
本发明的薄膜可以有利地用于制造用于电化学装置、优选用于二次电池的部件。
本发明的薄膜特别适合用作用于电化学装置、优选用于二次电池、更优选用于锂离子电池的隔膜。
出于本发明的目的,术语“氟聚合物[聚合物(F)]”旨在表示包含衍生自至少一种氟化单体的重复单元的氟聚合物。
聚合物(F)可进一步包含衍生自至少一种氢化单体的重复单元。
聚合物(FF)典型地是进一步包含衍生自至少一种包含至少一个羟基的官能单体[单体(OH)]的重复单元的聚合物(F)。
聚合物(FF)典型地包含衍生自至少一种氟化单体和至少一种包含至少一个羟基的官能单体[单体(OH)]的重复单元。
术语“氟化单体”在此旨在表示包含至少一个氟原子的烯键式不饱和单体。
术语“氢化单体”在此旨在表示包含至少一个氢原子并且不含氟原子的烯键式不饱和单体。
术语“至少一种氟化单体”应理解为意指氟聚合物可以包含衍生自一种或多于一种氟化单体的重复单元。在本文的其余部分,表述“氟化单体”出于本发明的目的应理解为是复数和单数形式均可,即它们表示一种或多于一种如以上定义的氟化单体二者。
术语“至少一种氢化单体”应理解为意指氟聚合物可以包含衍生自一种或多于一种氢化单体的重复单元。在本文的其余部分,表述“氢化单体”出于本发明的目的应理解为是复数和单数形式均可,即它们表示一种或多于一种如以上定义的氢化单体二者。
术语“至少一种单体(OH)”应理解为意指氟聚合物可以包含衍生自一种或多于一种单体(OH)的重复单元。在本文的其余部分,表述“单体(OH)”出于本发明的目的应理解为是复数和单数形式均可,即它们表示一种或多于一种如以上定义的单体(OH)二者。
聚合物(FF)的单体(OH)可选自由包含至少一个羟基的氟化单体和包含至少一个羟基的氢化单体组成的组。
如果氟化单体包含至少一个氢原子,则将其指定为含氢的氟化单体。
如果氟化单体不含氢原子,则将其指定为全(卤)氟单体。
氟化单体可进一步包含一个或多个其他卤素原子(Cl、Br、I)。
合适的氟化单体的非限制性实例值得注意地包括以下项:
-C3-C8全氟烯烃,如四氟乙烯以及六氟丙烯;
-C2-C8氢化的氟烯烃,如偏二氟乙烯、氟乙烯、1,2-二氟乙烯和三氟乙烯;
-具有式CH2=CH-Rf0的全氟烷基乙烯,其中Rf0是C1-C6全氟烷基;
-氯代-和/或溴代-和/或碘代-C2-C6氟烯烃,如氯三氟乙烯;
-具有式CF2=CFORf1的(全)氟烷基乙烯基醚,其中Rf1是C1-C6氟代-或全氟烷基,例如CF3、C2F5、C3F7;
-CF2=CFOX0(全)氟-氧烷基乙烯基醚,其中X0是C1-C12烷基、或C1-C12氧烷基或包含一个或多个醚基的C1-C12(全)氟氧烷基,如全氟-2-丙氧基-丙基;
-具有式CF2=CFOCF2ORf2的(全)氟烷基乙烯基醚,其中Rf2是C1-C6氟代-或全氟烷基,例如CF3、C2F5、C3F7,或包含一个或多个醚基的C1-C6(全)氟氧烷基,如-C2F5-O-CF3;
-具有式CF2=CFOY0的官能的(全)氟-氧烷基乙烯基醚,其中Y0是C1-C12烷基或(全)氟烷基、或C1-C12氧烷基或包含一个或多个醚基的C1-C12(全)氟氧烷基,并且Y0包含呈其酸、酰基卤或盐的形式的羧酸或磺酸基团;以及
-氟间二氧杂环戊烯,优选全氟间二氧杂环戊烯。
如果氟化单体是含氢的氟化单体,例如像偏二氟乙烯、三氟乙烯、氟乙烯,则氟聚合物包含衍生自所述至少一种含氢的氟化单体和任选地至少一种其他单体的重复单元。
如果氟化单体是全(卤)氟单体,例如像四氟乙烯、氯三氟乙烯、六氟丙烯、(全)氟烷基乙烯基醚,则氟聚合物包含衍生自至少一种全(卤)氟单体和至少一种氢化单体的重复单元。
合适的氢化单体的非限制性实例值得注意地包括乙烯、丙烯、乙烯基单体如乙酸乙烯酯,以及苯乙烯单体如苯乙烯和对-甲基苯乙烯。
聚合物(F)包含优选按摩尔计大于25%、优选按摩尔计大于30%、更优选按摩尔计大于40%的衍生自至少一种氟化单体的重复单元。
聚合物(F)可以包含按摩尔计大于1%、优选按摩尔计大于5%、更优选按摩尔计大于10%的衍生自至少一种氢化单体的重复单元。
聚合物(F)优选包含衍生自至少一种选自由偏二氟乙烯(VDF)、四氟乙烯(TFE)以及氯三氟乙烯(CTFE)组成的组的氟化单体的重复单元。
聚合物(F)更优选选自由包含衍生自偏二氟乙烯(VDF)和任选地至少一种不同于VDF的氟化单体的重复单元的氟聚合物组成的组。
聚合物(F)优选包含衍生自以下项的重复单元:
(a)按摩尔计至少60%、优选按摩尔计至少75%、更优选按摩尔计至少85%的偏二氟乙烯(VDF),以及
(b)任选地,按摩尔计从0.1%至15%、优选按摩尔计从0.1%至12%、更优选按摩尔计从0.1%至10%的氟化单体,该氟化单体选自下组,该组由以下各项组成:氟乙烯、氯三氟乙烯(CTFE)、六氟丙烯(HFP)、四氟乙烯(TFE)、三氟乙烯(TrFE)、全氟甲基乙烯基醚(PMVE)以及其混合物。
聚合物(F)可以是无定形的或半晶质的。
术语“无定形的”在此表示具有如根据ASTM D-3418-08测量的小于5J/g、优选小于3J/g、更优选小于2J/g的熔解热的聚合物(F)。
术语“半晶质的”在此旨在表示具有如根据ASTMD3418-08测量的从10至90J/g、优选从30至60J/g、更优选从35至55J/g的熔解热的聚合物(F)。
聚合物(F)优选地是半晶质的。
聚合物(FF)优选包含按摩尔计至少0.01%、更优选按摩尔计至少0.05%、甚至更优选按摩尔计至少0.1%的衍生自至少一种如以上定义的单体(OH)的重复单元。
聚合物(FF)优选包含按摩尔计至多20%、更优选按摩尔计至多15%、甚至更优选按摩尔计至多10%、最优选按摩尔计至多3%的衍生自至少一种如以上定义的单体(OH)的重复单元。
聚合物(FF)中的单体(OH)重复单元的平均摩尔百分数的确定可以通过任何合适的方法来进行。可以值得注意地提及酸碱滴定方法或NMR方法。
单体(OH)典型地选自由包含至少一个羟基的氢化单体组成的组。
单体(OH)优选地选自由具有式(III)的(甲基)丙烯酸单体和具有式(IV)的乙烯基醚单体组成的组:
其中R1、R2和R3中的每一个,彼此相同或不同,独立地是氢原子或C1-C3烃基,并且ROH是包含至少一个羟基的C1-C5烃基。
单体(OH)优选地具有如以上定义的式(III)。
单体(OH)更优选地具有式(III’):
其中R’1、R’2和R’3是氢原子并且R’OH是包含至少一个羟基的C1-C5烃基。
单体(OH)的非限制性实例值得注意地包括(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯以及(甲基)丙烯酸羟乙基己酯。
单体(OH)最优选选自下组,该组由以下各项组成:
-具有下式的丙烯酸羟乙酯(HEA):
-具有以下任一式的丙烯酸2-羟丙酯(HPA):
-及其混合物。
聚合物(FF)更优选地包含衍生自以下项的重复单元:
(a’)按摩尔计至少60%、优选按摩尔计至少75%、更优选按摩尔计至少85%的偏二氟乙烯(VDF);
(b’)任选地,按摩尔计从0.1%至15%、优选按摩尔计从0.1%至12%、更优选按摩尔计从0.1%至10%的氟化单体,该氟化单体选自下组,该组由以下各项组成:氟乙烯、氯三氟乙烯(CTFE)、六氟丙烯(HFP)、四氟乙烯(TFE)、三氟乙烯(TrFE)、全氟甲基乙烯基醚(PMVE)以及其混合物;以及
(c’)按摩尔计从0.01%至20%、优选按摩尔计从0.05%至15%、更优选按摩尔计从0.1%至10%的至少一种如以上定义的具有式(III)的(甲基)丙烯酸单体。
具有式(I)的化合物(M)可在基团X和Y中的任一个上、优选在至少一个基团X上包含一个或多个官能团。
在如以上定义的具有式(I)的化合物(M)包含至少一个官能团的情况下,它将被指定为官能金属化合物[官能化合物(M)];在基团X和Y均不包含官能团的情况下,如以上定义的具有式(I)的化合物(M)将被指定为非官能金属化合物[非官能化合物(M)]。
一种或多种官能化合物(M)和一种或多种非官能化合物(M)的混合物可以在本发明的方法中使用。另外,一种或多种官能化合物(M)或一种或多种非官能化合物(M)可单独使用。
具有式(I)的化合物(M)优选地具有式(I-A):
R1 4-m’M(OR2)m’ (I-A)
其中M是选自由Si、Ti和Zr组成的组的金属,R1和R2彼此相同或不同并且在每次出现时选自由任选地包含一个或多个官能团的C1-C18烃基组成的组,并且m’是包括在1与4之间的整数。
官能团的非限制性实例包括环氧基团、羧酸基团(以酸、酯、酰胺、酸酐、盐或卤化物形式)、磺酸基团(以酸、酯、盐或卤化物形式)、羟基、磷酸基团(以酸、酯、盐或卤化物形式)、硫醇基团、胺基、季铵基团、烯键式不饱和基团(如乙烯基)、氰基、脲基、有机硅烷基团、芳香族基团。
如果具有式(I)的化合物(M)是官能化合物(M),则它优选地具有式(I-B):
R3 4-m”M(OR4)m” (I-B)
其中M是选自由Si、Ti和Zr组成的组的金属,R3彼此相同或不同并且在每次出现时是包含一个或多个官能团的C1-C12烃基,R4彼此相同或不同并且在每次出现时是C1-C5直链或支链烷基,优选地R4是甲基或乙基,并且m”是包括在2与3之间的整数。
官能化合物(M)的实例值得注意地为乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、具有式CH2=CHSi(OC2H4OCH3)3的乙烯基三甲氧基乙氧基硅烷、具有下式的2-(3,4-环氧环己基乙基三甲氧基硅烷):
具有下式的缩水甘油氧基丙基甲基二乙氧基硅烷:
具有下式的缩水甘油氧基丙基三甲氧基硅烷:
具有下式的甲基丙烯酰氧基丙基三甲氧基硅烷:
具有下式的氨基乙基氨基丙基甲基二甲氧基硅烷:
具有下式的氨基乙基氨基丙基三甲氧基硅烷:
H2NC2H4NHC3H6Si(OCH3)3
3-氨基丙基三乙氧基硅烷、3-苯基氨基丙基三甲氧基硅烷、3-氯异丁基三乙氧基硅烷、3-氯丙基三甲氧基硅烷、3-巯丙基三乙氧基硅烷、3-巯丙基三甲氧基硅烷、正-(3-丙烯酰氧基-2-羟基丙基)-3-氨基丙基三乙氧基硅烷、(3-丙烯酰氧基丙基)二甲基甲氧基硅烷、(3-丙烯酰氧基丙基)甲基二氯硅烷、(3-丙烯酰氧基丙基)甲基二甲氧基硅烷、3-(正-烯丙基氨基)丙基三甲氧基硅烷、2-(4-氯磺酰基苯基)乙基三甲氧基硅烷、2-(4-氯磺酰基苯基)乙基三氯硅烷、羧乙基硅烷三醇及其钠盐、具有下式的三乙氧基甲硅烷基丙基马来酰胺酸:
具有式HOSO2-CH2CH2CH2-Si(OH)3的3-(三羟基甲硅烷基)-1-丙烷-磺酸、N-(三甲氧基甲硅烷基丙基)亚乙基-二胺三乙酸及其钠盐、具有下式的3-(三乙氧基甲硅烷基)丙基琥珀酸酐:
具有式H3C-C(O)NH-CH2CH2CH2-Si(OCH3)3的乙酰胺基丙基三甲氧基硅烷、具有式Ti(A)X(OR)Y的烷醇胺钛酸盐,其中A是胺取代的烷氧基,例如OCH2CH2NH2,R为烷基,并且x和y为使得x+y=4的整数。
非官能化合物(M)的实例值得注意地为三甲氧基硅烷、三乙氧基硅烷、四甲氧基硅烷、四乙氧基硅烷(TEOS)、四甲基钛酸盐、四乙基钛酸盐、四正丙基钛酸盐、四异丙基钛酸盐、四正丁基钛酸盐、四异丁基钛酸盐、四叔丁基钛酸盐、四正戊基钛酸盐、四正己基钛酸盐、四异辛基钛酸盐、四正月桂基钛酸盐、四乙基锆酸盐、四正丙基锆酸盐、四异丙基锆酸盐、四正丁基锆酸盐、四仲丁基锆酸盐、四叔丁基锆酸盐、四正戊基锆酸盐、四叔戊基锆酸盐、四叔己基锆酸盐、四正庚基锆酸盐、四正辛基锆酸盐、四正硬脂基锆酸盐。
术语“液体介质”在此旨在表示在20℃下在大气压下呈液态的介质。
在本发明的用于制造复合材料(FH)的方法的步骤(i)中,具有式(I)化合物(M)在液体介质的存在下部分水解和/或缩聚,所述液体介质典型地包含水,从而提供预凝胶化合物[化合物(MP)]。
该化合物(MP)典型地呈液体组合物的形式,所述液体组合物典型地包含水。
该具有式(I)的化合物(M)与该液体介质的重量比典型地包括在50∶1与1∶50之间、优选在20∶1与1∶20之间、更优选在10∶1与1∶10之间。
该液体介质可进一步包含至少一种酸催化剂。
该液体介质典型地进一步包含按重量计从0.5%至10%、优选从按重量计1%至按重量计5%的至少一种酸催化剂。
该酸催化剂的选择是不受特别限制的。
该酸催化剂典型地选自由有机酸和无机酸组成的组。该酸催化剂优选地选自由有机酸组成的组。
使用柠檬酸已经获得了非常良好的结果。
该液体介质还可以进一步包含一种或多种有机溶剂。
值得注意地,合适的有机溶剂的非限制性实例包括以下各项:
-脂肪族、脂环族或芳香族醚氧化物,更具体地,二乙醚、二丙醚、二异丙醚、二丁醚、甲基叔丁基醚、二戊醚、二异戊醚、乙二醇二甲醚、乙二醇二乙醚、乙二醇二丁醚、苄醚、二噁烷、四氢呋喃(THF),
-乙二醇醚,如乙二醇一甲醚、乙二醇一乙醚、乙二醇一丙醚、乙二醇一异丙醚、乙二醇一丁醚、乙二醇一苯醚、乙二醇一苄醚、二甘醇一甲醚、二甘醇一乙醚、二甘醇一正丁醚,
-乙二醇醚酯,如乙二醇甲醚乙酸酯、乙二醇一乙醚乙酸酯、乙二醇一丁醚乙酸酯,
-醇,如甲醇、乙醇、双丙酮醇,
-酮,如丙酮、甲基乙基酮、甲基异丁基酮、二异丁基酮、环己酮、异佛尔酮,以及
-直链的或环状的酯,如乙酸异丙酯、乙酸正丁酯、乙酰乙酸甲酯、邻苯二甲酸二甲酯、γ-丁内酯。
对于其中该水性介质包含一种或多种另外的有机溶剂的实施例,该水性介质优选不含根据化学品安全分类被定性为致癌、致突变或生殖毒性的溶剂(CMR溶剂);更确切地,该水性介质有利地不含N-甲基-2-吡咯烷酮(NMP)、N,N-二乙基乙酰胺、二甲基甲酰胺(DMF)和N,N-二甲基乙酰胺(DMAC)。
该液体介质优选进一步包含至少一种酸催化剂和一种或多种有机溶剂(S)。
该液体介质更优选进一步包含至少一种酸催化剂和一种或多种醇。
在本发明的用于制造复合材料(FH)的方法的步骤(i)中,通常在室温下或在低于100℃的温度下加热下进行具有式(I)的化合物(M)和聚合物(FF)的水解和/或缩聚。将考虑水性介质的沸点和/或稳定性选择温度。包括在20℃与90℃之间、优选在20℃与50℃之间的温度将是优选的。
应理解的是,在本发明的用于制造复合材料(FH)的方法的步骤(i)中,具有式(I)的化合物(M)的基团Y在聚合物(FF)的存在下在水性介质中部分水解和/或缩聚,以便产生预复合材料[预复合材料(FP)]。
如本领域技术人员将认识到,水解和/或缩聚反应通常产生低分子量的副产物,这些副产物值得注意地可以是水或醇,随如以上定义的具有式(I)的化合物(M)的性质而改变。
因此,在本发明的用于制造复合材料(FH)的方法的步骤(i)中,该水性介质典型地进一步包含一种或多种醇。
化合物(MP)典型地呈包含一个或多个具有式-[O-MX4-m*(OY)m*-2]O-的域的液体组合物形式,其中M是选自由Si、Ti和Zr组成的组的金属,X和Y彼此相同或不同并且在每次出现时是任选地包含一个或多个官能团的烃基,并且m*是包括在2与4之间的整数。
预复合材料(FP)典型地包含一个或多个具有式-[O-M(OZ1)(OZ2)]O-的域,其中M是选自由Si、Ti和Zr组成的组的金属,并且Z1和Z2彼此相同或不同,是任选地包含一个或多个官能团的烃基,所述Z1和Z2中的至少一个是包含衍生自至少一种单体(OH)的重复单元的烃基。
在本发明的用于制造复合材料(FH)的方法中,将在步骤(ii)中提供的组合物在典型地包括在100℃与300℃之间、优选在150℃与250℃之间的温度下在熔融相中加工。
在本发明的用于制造复合材料(FH)的方法的步骤(i)中提供的液体介质典型地包含基于所述液体介质的总重量按重量计从5%至95%、优选按重量计从20%至80%、更优选按重量计从30%至60%的至少一种聚合物(FF)。
在本发明的用于制造复合材料(FH)的方法的步骤(ii)中提供的组合物可以进一步包含至少一种与聚合物(FF)相同或不同的氟聚合物[聚合物(F)],优选非官能氟聚合物[非官能聚合物(F)]。
出于本发明的目的,术语“非官能聚合物(F)”旨在表示不含衍生自至少一种官能单体如包含至少一个羟基的官能单体[单体(OH)]的重复单元的氟聚合物。
对非官能聚合物(F)的选择没有特别限制,前提是它不与预复合材料(FP)和/或具有式(II)的PAO相互作用。
复合材料(FH)优选地包含以下项、更优选由以下项组成:
-按重量计从30%至99%、优选按重量计从50%至95%、更优选按重量计从60%至90%的至少一种预复合材料(FP)和至少一种具有式(II)的PAO,
-按重量计从1%至70%、优选按重量计从5%至50%、更优选按重量计从10%至40%的至少一种盐(M),
-任选地,按重量计从1%至60%、优选按重量计从5%至40%、更优选按重量计从10%至30%的至少一种与聚合物(FF)相同或不同的聚合物(F),以及
-任选地,按重量计从0.1%至90%的一种或多种无机填料,
其中这些量基于所述复合材料(FH)的总重量。
盐(M)典型地以粉末形式或作为包含其的水溶液提供。
盐(M)的性质是不受特别限制的。
盐(M)典型地选自下组,该组由以下各项组成:MeI、Me(PF6)n、Me(BF4)n、Me(ClO4)n、Me(二(草酸)硼酸盐)n(“Me(BOB)n”)、MeCF3SO3、Me[N(CF3SO2)2]n、Me[N(C2F5SO2)2]n、Me[N(CF3SO2)(RFSO2)]n(其中RF是C2F5、C4F9或CF3OCF2CF2)、Me(AsF6)n、Me[C(CF3SO2)3]n和Me2Sn,其中Me是金属,优选过渡金属、碱金属或碱土金属,更优选地Me是Li、Na、K或Cs,甚至更优选地Me是Li,并且n是所述金属的化合价,典型地n是1或2。
盐(M)优选地选自下组,该组由以下各项组成:MeCF3SO3、Me[N(CF3SO2)2]n、Me[N(C2F5SO2)2]n、Me[N(CF3SO2)(RFSO2)]n(其中RF是C2F5、C4F9或CF3OCF2CF2)、Me(AsF6)n、Me[C(CF3SO2)3]n和Me2Sn,其中Me是金属,优选过渡金属、碱金属或碱土金属,更优选地Me是Li、Na、K或Cs,甚至更优选地Me是Li,并且n是所述金属的化合价,典型地n是1或2。
无机填料(如果有的话)典型地以颗粒形式提供。
无机填料典型地具有包括在0.001μm与1000μm之间、优选在0.01μm与800μm之间、更优选在0.03μm与500μm之间的平均粒度。
在适合用于本发明中的无机填料之中,可以提及无机氧化物,包括金属氧化物、金属硫酸盐、金属碳酸盐、金属硫化物等。在金属氧化物之中,可以提及SiO2、TiO2、ZnO和Al2O3。
如果通过援引方式并入本申请的任何专利、专利申请、以及公开物的披露内容与本申请的说明相冲突到了可能导致术语不清楚的程度,则本说明应该优先。
本发明现在将参考以下实例进行说明,这些实例的目的仅仅是说明性的并且不限制本发明的范围。
原材料
聚合物(FF-1):VDF-HEA(按摩尔计0.8%)-HFP(按摩尔计2.4%),具有15g/min的熔体流动指数(MFI)(2.16Kg,230℃)。
聚合物(FF-2):VDF-HEA(按摩尔计0.5%)-HFP(按摩尔计2.2%),具有3.1g/min的熔体流动指数(MFI)(10Kg,230℃)。
PAO-1:具有包括在1000000与1200000之间的平均分子量的聚(环氧乙烷)。
聚合物(1):VDF/HFP(按摩尔计93%/7%),具有15g/min的熔体流动指数(MFI)(2.16Kg,230℃)。
离子电导率的测定
将薄膜放入含有两个不锈钢阻塞电极的电池中。将该电池置于烘箱中并在测量离子电导率之前在每个温度下调节一小时。
在不同温度下测量薄膜的电阻。
使用以下等式计算离子电导率(σ):
离子电导率[σ]=d/(Rbx S)
其中d是薄膜的厚度[cm],Rb是体电阻[Ω]并且S是不锈钢电极的面积[cm2]。
聚合物(FF-1)的制造
在配备有在300rpm的速度下运行的叶轮的80升反应器中,按顺序引入58242g的脱矿质水和11.1g的 K100 GR悬浮剂。在20℃下以真空(30mmHg)和氮气吹扫的顺序吹扫该反应器。然后将21.6g丙烯酸羟乙酯(HEA)和1873g六氟丙烯(HFP)单体引入该反应器中,然后引入149.9g的按重量计75%的过新戊酸叔戊酯引发剂在异十二烷中的溶液。最后,将16597g的偏二氟乙烯(VDF)引入该反应器中。将该反应器逐渐加热直至57℃下的设定值温度,并且将压力固定在110巴。在聚合期间通过进料13kg含有240.6g的HEA的水溶液使压力保持恒定等于110巴。在此进料后,不再引入水溶液并且压力开始下降直至80巴。然后,通过使该反应器脱气直至达到大气压来停止聚合。总体上获得了约75%的单体转化率。然后回收如此获得的聚合物,用脱矿质水洗涤并且在65℃下烘箱干燥。
聚合物(FF-2)的制造
在配备有在650rpm的速度下运行的叶轮的4升反应器中,按顺序引入2438g的脱矿质水、90.74g的浓度为543mmol/kg的磷酸三钠溶液以及59.66g的浓度为14.2g/kg的 K100GR的水溶液。在14℃下以真空(30mmHg)和氮气吹扫的顺序吹扫该反应器。然后将16.42g的5.1wt%的过氧化氢溶液和5.35g的氯甲酸乙酯引入该反应器中。在880rpm的速度下15分钟后,引入25.2g的在水溶液中的丙烯酸羟乙酯(HEA)(其中HEA的浓度为17g/kg)以及107g的六氟丙烯(HFP)共聚单体。最后,将952g的偏二氟乙烯(VDF)引入该反应器中。将该反应器逐渐加热直至45℃下的设定值温度,并且将压力固定在120巴。在聚合期间通过进料605g具有HEA的水溶液使压力保持恒定等于120巴。在此进料后,不再引入水溶液并且压力开始下降。通过使该反应器脱气直至达到大气压来停止聚合。达到了72%的单体转化率。然后回收如此获得的聚合物,用脱矿质水洗涤并且在65℃下干燥整晚。
复合材料(FH)的制造-通用程序
预复合材料(FP)制备
如下形成预凝胶化合物:
a)在配备有以适中的速度运行的磁力搅拌器的500m1烧杯中,按顺序引入以下成分:
-TEOS(原硅酸四乙酯):200g,
-水:69.45g(摩尔比TEOS∶H2O=1∶4),
-乙醇:50g(重量比TEOS∶EtOH=4∶1),
-柠檬酸:2.69g(1wt.%的TEOS+H2O)。
在每个批次中产生的SiO2的理论量是57.68g(起始组分的17.91%);以及
b)使体系在剧烈搅拌下置于室温下约3小时。
将聚合物(FF)从主料斗进料至双螺杆同向旋转相互啮合的挤出机(Leistritz 18ZSE18HP,具有18mm的螺杆直径D和720mm的螺杆长度(40D))。该挤出机配备有主进料器和两个脱气单元。料筒由允许设定所希望的温度曲线的八个温度控制区和一个冷却区(在进料器处)构成。熔融的聚合物从由两个各自具有3mm直径的孔构成的模口离开。随后,将材料在被机器切割成粒料之前同时由拉辊拉动并且在空气中冷却。
同时,预凝胶化合物也通过主料斗进料到挤出机中。预复合材料(FP)的组成将由聚合物(FF)和预凝胶化合物(参见实例)的进料比决定。
此步骤的螺杆外形由以下项构成:输送元件的区域,该区域具有规律地减小的间距(从区0到1),然后是由两个捏合元件构成的捏合块(区2),然后是长的输送区(从区3到4);在这一系列元件之后,定位了两个由三个捏合元件构成并且与两个输送元件交替的捏合块(从区4到6)。最后,四个输送元件和一个脱气单元位于模口出口之前(区6至8)。所使用的温度曲线在下面的表1中报告。曲线A已经被用于聚合物(FF-1)和(FF-2)。挤出机的旋转速度是300rpm。将所获得的粒料在150℃的烘箱中老化40分钟。
表1
区 | 0 | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
曲线A[℃] | 90 | 100 | 100 | 120 | 150 | 150 | 150 | 150 |
复合材料(FH)制备
将预复合材料(FP)、PAO和LiTFSI水溶液(按重量计80%)通过主料斗进料至以下描述的挤出机中。各自用重力进料器装载粒料和PAO并且用蠕动泵装载LiTFSI水溶液。
此步骤的螺杆外形由第一输送区(区0和1)、然后由三个捏合元件形成的捏合块(区2)构成;在这些块之后有一个长的输送区(区3),其中螺杆的间距最大。在此区中存在在大气压下的脱气单元。然后,存在由两个捏合元件和一个回流元件构成的捏合块(区5)。在这个块之后,螺杆由具有最大间距的输送区(区6)构成;在此区中存在-400毫巴下的脱气单元以主要排空LiTFSI溶液中存在的水蒸气。螺杆的最后部分(区7和8)由输送元件构成。
所使用的温度曲线B在下面的表2中报告。挤出机的旋转速度是350rpm。
表2
区 | 0 | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
曲线B[℃] | 150 | 150 | 145 | 140 | 140 | 130 | 120 | 110 |
复合材料(FH)的薄膜挤出
使用单螺杆挤出机(Eurotech,具有25mm的螺杆直径D和75cm的螺杆长度)制备薄膜。该挤出机配备有主进料器。料筒由设定在从140℃至180℃的六个温度控制区构成。熔融的聚合物从具有0.2mm的开口的20cm的扁平模口离开。随后,将材料拉出并且用三压延机系统然后用辊压制。将压延机加热为90℃并且将两个非粘性支撑薄膜进料至前两个压延机之间以引导约30-100μm的挤出薄膜。
实例1
以0.450Kg/h的聚合物(FF-1)的速率以及以0.833Kg/h的预凝胶化合物的速率制造预复合材料(FP)。所获得的标称组成为:FF-1/SiO2:75/25%wt。
复合材料(FH):预复合材料(FP)0.525Kg/h、PAO 0.875Kg/h以及LiTFSI水溶液0.4375Kg/h。
复合材料(FH)的最终组成为:按重量计50%的PAO、按重量计22.5%的聚合物(FF-1)、按重量计20%的LiTFSI以及按重量计7.5%的SiO2。
这种材料的离子电导率在约100μm的压缩模制薄膜上进行测量。结果列于表3中。
实例2
遵循如在实例1中详述的相同的程序,但使用聚合物(FF-2)。
结果列于表3中。
实例3
遵循如在实例1中详述的相同的程序,但使用在0.525Kg/h的聚合物(FF-1)的速率下和在0.417Kg/h的预凝胶化合物的速率下制造的预复合材料。所获得的标称组成为:FF-1/SiO2:87.5/12.5%wt。
复合材料的最终组成为:按重量计50%的PAO、按重量计26.25%的聚合物(FF-1)、按重量计20%的LiTFSI以及按重量计3.75%的SiO2。
结果列于表3中。
实例4
遵循如在实例3中详述的相同的程序,但使用由聚合物(FF-2)获得的预复合材料(FP)。
这种材料被成功地挤出至30μm薄膜厚度,不存在缺陷。
结果列于表3中。
对比实例1
根据用于制造复合材料的通用程序但在不使用预凝胶化合物的情况下,将聚合物(1)、PAO以及LiTFSI按以下比例混配:按重量计50%的PAO+按重量计30%的聚合物(1)以及按重量计20%的LiTFSI。
这种材料的离子电导率在约150μm的挤出薄膜上进行测量。结果列于表3中。
表3
鉴于以上所述,已经出人意料地发现,本发明的方法能够容易地获得产生相较于现有技术的薄膜具有出色的离子电导率的薄膜的复合材料(FH)。
另外,已经出人意料地发现,本发明的复合材料(FH)可以容易地被加工成薄膜隔膜,典型地通过流延挤出。因此,本发明的方法成功地使得能够制造用于电化学装置和光电化学装置二者的隔膜。
Claims (13)
1.一种用于制造氟聚合物杂化的有机/无机复合材料[复合材料(FH)]的方法,所述方法包括:
(i)通过在熔融相中加工,优选地将以下项挤出提供预复合材料[预复合材料(FP)]:
-通过在液体介质的存在下,至少一种具有式(I)的金属化合物[化合物(M)]的至少部分水解和/或缩聚可获得的预凝胶化合物[化合物(MP)]:
X4-mM(OY)m(I)
其中M是选自由Si、Ti和Zr组成的组的金属,X和Y彼此相同或不同并且在每次出现时选自任选地包含一个或多个官能团的烃基,并且m是包括在1与4之间的整数,以及
-至少一种包含至少一个羟基的官能氟聚合物[聚合物(FF)];
(ii)通过将在步骤(i)中提供的该预复合材料(FP)与以下项混配提供组合物:
-至少一种具有式(II)的聚(环氧烷)(PAO):
HO-(CH2CNRAO)n-RB(II)
其中RA是氢原子或C1-C5烷基,RB是氢原子或-CH3烷基并且n是包括在2000与40000之间、优选在4000与35000之间、更优选在11500与30000之间的整数,
-至少一种金属盐[盐(M)],
-任选地,至少一种与该聚合物(FF)相同或不同的氟聚合物[聚合物(F)],以及
-任选地,一种或多种无机填料;以及
(iii)在熔融相中加工,优选地挤出在步骤(ii)中提供的该组合物。
2.根据权利要求1所述的方法,其中,该聚合物(FF)包含按摩尔计至少0.01%、更优选按摩尔计至少0.05%、甚至更优选按摩尔计至少0.1%的衍生自至少一种单体(OH)的重复单元。
3.根据权利要求1或2所述的方法,其中,该聚合物(FF)包含按摩尔计至多20%、更优选按摩尔计至多15%、甚至更优选按摩尔计至多10%、最优选按摩尔计至多3%的衍生自至少一种单体(OH)的重复单元。
4.根据权利要求2或3所述的方法,其中,该单体(OH)选自由具有式(III)的(甲基)丙烯酸单体和具有式(IV)的乙烯基醚单体组成的组:
其中R1、R2和R3中的每一个,彼此相同或不同,独立地是氢原子或C1-C3烃基,并且ROH是包含至少一个羟基的C1-C5烃基。
5.根据权利要求1至4中任一项所述的方法,其中,该化合物(MP)典型地呈包含一个或多个具有式-[O-MX4-m*(OY)m*-2]O-的域的液体组合物的形式,其中M是选自由Si、Ti和Zr组成的组的金属,X和Y彼此相同或不同并且在每次出现时是任选地包含一个或多个官能团的烃基,并且m*是包括在2与4之间的整数。
6.根据权利要求1至5中任一项所述的方法,其中,该预复合材料(FP)包含一个或多个具有式-[O-M(OZ1)(OZ2)]O-的域,其中M是选自由Si、Ti和Zr组成的组的金属,并且Z1和Z2彼此相同或不同,是任选地包含一个或多个官能团的烃基,所述Z1和Z2中的至少一个是包含衍生自至少一种单体(OH)的重复单元的烃基。
7.一种氟聚合物杂化的有机/无机复合材料[复合材料(FH)],其可通过根据权利要求1至6中任一项所述的方法获得。
8.根据权利要求7所述的复合材料(FH),所述复合材料(FH)包含以下项、优选地由以下项组成:
-至少一种预复合材料[预复合材料(FP)],
-至少一种具有式(II)的聚(环氧烷)(PAO):
HO-(CH2CHRAO)n-RB(II)
其中RA是氢原子或C1-C5烷基,RB是氢原子或-CH3烷基并且n是包括在2000与40000之间、优选在4000与35000之间、更优选在11500与30000之间的整数,
-至少一种金属盐[盐(M)],
-任选地,至少一种与该聚合物(FF)相同或不同的氟聚合物[聚合物(F)],以及
-任选地,一种或多种无机填料。
9.一种用于制造薄膜的方法,所述方法包括在熔融相中加工至少一种根据权利要求7或8所述的复合材料(FH)。
10.一种薄膜,其包含至少一种根据权利要求7或8所述的复合材料(FH)。
11.根据权利要求10所述的薄膜,所述薄膜是致密薄膜。
12.一种电化学装置或光电化学装置,其包括至少一种根据权利要求10或11所述的薄膜。
13.根据权利要求10或11所述的薄膜作为用于电化学装置、优选用于二次电池、更优选用于锂离子电池的隔膜的用途。
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