CN108346766A - A kind of heat-staple lithium ion battery separator and preparation method thereof - Google Patents
A kind of heat-staple lithium ion battery separator and preparation method thereof Download PDFInfo
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- CN108346766A CN108346766A CN201810066878.3A CN201810066878A CN108346766A CN 108346766 A CN108346766 A CN 108346766A CN 201810066878 A CN201810066878 A CN 201810066878A CN 108346766 A CN108346766 A CN 108346766A
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- Prior art keywords
- bis
- amino
- diamine
- acid
- diamino
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 13
- 239000004642 Polyimide Substances 0.000 claims abstract description 56
- 229920001721 polyimide Polymers 0.000 claims abstract description 56
- 239000000463 material Substances 0.000 claims abstract description 47
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 8
- 230000009477 glass transition Effects 0.000 claims abstract description 8
- 230000003068 static effect Effects 0.000 claims abstract description 8
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 52
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 48
- 229920005575 poly(amic acid) Polymers 0.000 claims description 34
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 33
- 150000004985 diamines Chemical class 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 27
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 26
- -1 propoxyl Chemical group 0.000 claims description 26
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 14
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 238000010041 electrostatic spinning Methods 0.000 claims description 10
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000004305 biphenyl Substances 0.000 claims description 8
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 claims description 8
- 229920002647 polyamide Polymers 0.000 claims description 7
- GWTMTGYTQYLORL-UHFFFAOYSA-N 3-(3-sulfophenyl)benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(C=2C=C(C=CC=2)S(O)(=O)=O)=C1 GWTMTGYTQYLORL-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000012965 benzophenone Substances 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 6
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 6
- 125000006159 dianhydride group Chemical group 0.000 claims description 6
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical class C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 150000002170 ethers Chemical class 0.000 claims description 5
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 claims description 4
- 125000005605 benzo group Chemical group 0.000 claims description 4
- 229940049706 benzodiazepine Drugs 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- YKNMIGJJXKBHJE-UHFFFAOYSA-N (3-aminophenyl)-(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=CC(N)=C1 YKNMIGJJXKBHJE-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- RLXBOUUYEFOFSW-UHFFFAOYSA-N 2,5-diaminobenzene-1,4-diol Chemical compound NC1=CC(O)=C(N)C=C1O RLXBOUUYEFOFSW-UHFFFAOYSA-N 0.000 claims description 2
- 150000005000 2,6-diaminotoluenes Chemical class 0.000 claims description 2
- WTHJTVKLMSJXEV-UHFFFAOYSA-N 2-(4-aminopyridin-2-yl)pyridin-4-amine Chemical group NC1=CC=NC(C=2N=CC=C(N)C=2)=C1 WTHJTVKLMSJXEV-UHFFFAOYSA-N 0.000 claims description 2
- RQGLBHFMSSTAAJ-UHFFFAOYSA-N 2-[5-amino-2-[4-amino-2-(2-sulfophenoxy)phenyl]phenoxy]benzenesulfonic acid Chemical compound C=1C(N)=CC=C(C=2C(=CC(N)=CC=2)OC=2C(=CC=CC=2)S(O)(=O)=O)C=1OC1=CC=CC=C1S(O)(=O)=O RQGLBHFMSSTAAJ-UHFFFAOYSA-N 0.000 claims description 2
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 2
- FGWQCROGAHMWSU-UHFFFAOYSA-N 3-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC(N)=C1 FGWQCROGAHMWSU-UHFFFAOYSA-N 0.000 claims description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 2
- XGGAWFDOIDZRPI-UHFFFAOYSA-N 4,6-Dihydroxy Natural products C1=C2OCOC2=CC(C2OC(C3C(OC(O)C32)C=2C=C3OCOC3=CC=2)O)=C1 XGGAWFDOIDZRPI-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- VVCZPAYWQWDNQO-UHFFFAOYSA-N [2-amino-5-[4-amino-3-(sulfomethyl)phenyl]phenyl]methanesulfonic acid Chemical compound Nc1ccc(cc1CS(O)(=O)=O)-c1ccc(N)c(CS(O)(=O)=O)c1 VVCZPAYWQWDNQO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- XIWMTQIUUWJNRP-UHFFFAOYSA-N amidol Chemical class NC1=CC=C(O)C(N)=C1 XIWMTQIUUWJNRP-UHFFFAOYSA-N 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical compound C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 claims description 2
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-UHFFFAOYSA-N 0.000 claims description 2
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- VILFVXYKHXVYAB-UHFFFAOYSA-N naphthalene-2,7-disulfonic acid Chemical compound C1=CC(S(O)(=O)=O)=CC2=CC(S(=O)(=O)O)=CC=C21 VILFVXYKHXVYAB-UHFFFAOYSA-N 0.000 claims description 2
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 claims description 2
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical class O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- XDGBJDMTNFSTAC-UHFFFAOYSA-N propane-1-sulfonic acid;hydrochloride Chemical compound Cl.CCCS(O)(=O)=O XDGBJDMTNFSTAC-UHFFFAOYSA-N 0.000 claims description 2
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical class NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 claims 2
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 claims 2
- CGMUNRRUYSIWDK-UHFFFAOYSA-N 2-[2-amino-5-[4-amino-3-(2-sulfophenoxy)phenyl]phenoxy]benzenesulfonic acid Chemical compound NC1=CC=C(C=2C=C(OC=3C(=CC=CC=3)S(O)(=O)=O)C(N)=CC=2)C=C1OC1=CC=CC=C1S(O)(=O)=O CGMUNRRUYSIWDK-UHFFFAOYSA-N 0.000 claims 1
- VXLKZBRLFFGAQT-UHFFFAOYSA-N 3h-benzimidazole-5-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=C2N=CNC2=C1 VXLKZBRLFFGAQT-UHFFFAOYSA-N 0.000 claims 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims 1
- YGFZSSUWIRSJQO-UHFFFAOYSA-N NC1=C(C(=CC(=C1)C1=CC=CC=C1)N)O Chemical class NC1=C(C(=CC(=C1)C1=CC=CC=C1)N)O YGFZSSUWIRSJQO-UHFFFAOYSA-N 0.000 claims 1
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- 125000003368 amide group Chemical group 0.000 claims 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- RDRCCJPEJDWSRJ-UHFFFAOYSA-N pyridine;1h-pyrrole Chemical compound C=1C=CNC=1.C1=CC=NC=C1 RDRCCJPEJDWSRJ-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- VACCAVUAMIDAGB-UHFFFAOYSA-N sulfamethizole Chemical compound S1C(C)=NN=C1NS(=O)(=O)C1=CC=C(N)C=C1 VACCAVUAMIDAGB-UHFFFAOYSA-N 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention relates to a kind of heat-staple lithium ion battery separators and preparation method thereof, it is prepared by copolyimide or blending polyimides, its glass transition temperature is more than 260 DEG C, 200 DEG C heating 1 hour after size changing rate be less than 0.2%, decomposition temperature is more than 500 DEG C, 20 50Mpa of mechanical strength, imbibition rate are more than 100%, and static contact angle of the mixed electrolytic solution on diaphragm is 0 15 °.The heat-staple battery diaphragm is a kind of isotropic porous film material with Uniform pore structure, high porosity, there is good dimensional stability, thermal stability, wetability, imbibition rate and solvent resistance simultaneously, small-sized and power lithium-ion battery is can be applied to, the effects that improving battery security, cycle performance of battery and charge-discharge performance is played.
Description
Technical field
The present invention relates to a kind of heat-staple lithium ion battery separators and preparation method thereof, and in particular to polyimide battery
Diaphragm and preparation method thereof.
Technical background
Diaphragm is one of four big critical material of lithium ion battery, and ion is provided in battery charge and discharge process and transports electric channel
Effect, performance directly affects capacity, cycle performance, safety of battery etc..Since polyolefine material diaphragm has height
Tearing toughness, preferable resistance to acid and alkali, the advantages that material is inexpensive, therefore the used diaphragm of lithium ion battery is mostly polyene at present
Hydrocarbon diaphragm includes mainly PP films, PE films, PP/PE bilayers or sandwich diaphragm etc., production technology relative maturity, recent year
Industry development is swift and violent.But the electrolyte wetability of polyalkene diaphragm is poor, thermal stability is poor, even across the methods of coating, compound
It is modified, temperature in use is also no more than 150 DEG C, otherwise will lead to positive and negative anodes contact short circuit because diaphragm is heat-shrinked.
To solve the problems, such as the thermal contraction of diaphragm, numerous studies, the lithium of the material preparations such as PET, PI, PVDF have been carried out both at home and abroad
Ion battery diaphragm is developed in succession.Wherein, polyimides PI materials are because thermal stability is good, polarity is big, high-strength and high-modulus
The advantages that, become the hot spot of battery diaphragm material research.DuPont Corporation announced to have prepared lithium ion battery in 2010
The polyimide nanofiber membrane of diaphragm, this diaphragm make battery capacity improve 15-30%, longer cell life 20%, and
Improve stability of the battery under hot operation state.Patent 201110147715.6 uses fluoropolymer solutions and polyamides
Amino acid solution is compound through coaxial electrostatic spinning, mechanical roll-in and hot imidization obtain composite nano-fiber membrane, has both fluoropolymer
The advantages of both object and polyimides, but the imidization under vacuum or inert conditions is needed when preparation, and need by 4 gradient temperature
Degree heating, complex process, preparation condition are more demanding.A kind of polyimide foraminous is disclosed in patent 201510145561.5 to receive
The preparation method of rice fibre diaphragm, polyamic acid solution is mixed with soluble metallic salt and is made into spinning presoma, then through quiet
Electrospun, imidization, inorganic acid aqueous solution processing are prepared into polyimides and receive um porous tunica fibrosa, BET specific surface area compared with
Common polyimide foraminous tunica fibrosa improves a lot, but a large amount of inorganic acid aqueous solutions, deionized water is needed to be handled, energy consumption
And pollution is larger.
Based on above-mentioned, lithium ion battery separator is prepared using polyimides, though the thermal stability of diaphragm can be improved, improves electricity
Pond stability at high temperature and safety, but there is also complex process, imidization condition is harsh, wellability is poor the problems such as.
Invention content
The object of the present invention is to provide a kind of improved polyimide battery diaphragm materials of structure, go out from molecular structure angle
Hair introduces active group, reduces polyimide material surface tension, and polyimide battery diaphragm is made to have good wellability, from
And improve cycle performance of battery and charge-discharge performance.
It is a further object of the present invention to provide the preparation methods that above structure improves polyimide battery diaphragm material, with solution
Certainly current material preparation process complexity, the problem of imidization condition harshness.
In order to solve the above-mentioned technical problem, technical scheme is as follows：A kind of polyimide battery diaphragm material, packet
It includes copolyimide and/or polyimides is blended；Wherein, the copolyimide contains in sulfonic group, hydroxyl, carboxyl
One or more, the blending polyimides contains one or more in sulfonic group, hydroxyl, carboxyl；Preferably, the diaphragm
The glass transition temperature of material is more than 260 DEG C, and size changing rate is less than 0.2% after 1h is heated at 200 DEG C, and decomposition temperature is more than
500 DEG C, mechanical strength 20-50Mpa, it is further preferred that static contact angle of the mixed electrolytic solution on the diaphragm material is
0-15°.Further, the electrolyte includes LiPF6And ethylene carbonate, dimethyl carbonate, diethyl carbonate, carbon
Two or more in sour methyl ethyl ester.Preferably, the LiPF6A concentration of 1mol/L.
Further, the copolyimide is prepared by hybrid diamine and aromatic dianhydride copolymerization, wherein mixing
The total moles of diamines and aromatic dianhydride ratio is 1：0.95-1.15, the hybrid diamine include first kind diamine monomer and second
Class diamine monomer, first kind diamine monomer contain one or more in sulfonic group, hydroxyl, carboxyl, and first kind diamine monomer accounts for
The 2-30wt% of hybrid diamine total amount.
Further, the aromatic dianhydride include equal benzene dianhydride, even benzene dianhydride, 1,2 ', 3,3 '-benzophenone dianhydrides,
2,2 ', 3,3 '-biphenyl dianhydrides, 3,3 ', 4,4 '-biphenyl dianhydrides, 2,3,3 ', 4 '-biphenyl dianhydrides, mellitic acid dianhydride, 3,6- bis-
The equal benzene dianhydride of hydroxyl, 3,3 ', 4,4 '-para-terpheny dianhydrides, 2,2 ', 3,3 '-para-terpheny dianhydrides, 3,3 ', 4,4 '-benzhydrols
Tetracid dianhydride, 3,3 ', 4,4 '-diphenyl ether dianhydrides, 2,2 ', 3,3 '-diphenyl ether dianhydrides, 3,3 ', 4,4 '-diphenyl sulfone dianhydrides, 2,2 ',
One or more in 3,3 '-diphenyl sulfone dianhydrides.
Further, the first kind diamine monomer includes 2,5-, bis- anilinesulfonic acids, 2,4-, bis- anilinesulfonic acids, 3-
(2 ', 4 '-diamines phenoxyl) propane sulfonic acid hydrochloride, 3,5- diamino -3 '-sulfonic group -4 '-(4- sulfonic benzos oxygroup) two
Benzophenone, 3,5- diamino -3 '-sulfonic group -4 '-(2,4- sulfonic benzos oxygroup) benzophenone, 2- (3,5- diamino-phenyls) benzo
Imidazoles -5- sulfonic acid, benzidine -2,2 '-disulfonic acid, 3,3 '-bis- (sulfomethvl) benzidine, 2,2 '-bis- (3- sulfo groups propoxyl group)
Benzidine, 3,3 '-bis- (3- sulfo groups propoxyl group) benzidine, 2,2 '-bis- (3- sulfo groups butoxy) benzidine, 3,3 '-bis- (3- sulfo groups
Butoxy) benzidine, 2,2 '-bis- (sulfo group phenyl) benzidine, 2,2 '-bis- (4- amino-benzene oxygens) biphenyl -5,5 '-disulfonic acid,
3,3 '-bis- [3- (4- sulfophenoxies) propoxyl group] benzidine, 2,2 '-bis- (sulfophenoxy) benzidine, 3,3 '-bis- (sulfo groups
Phenoxy group) benzidine, 4,4 '-bis- [2- (1- amino -4- naphthalenes sulfo group) azo] biphenyl, 3,3 '-dimethyl -4,4 '-diamino two
Phenylmethane -6,6 '-disulfonic acid, 5- [bis- (4 '-the aminophenyl) -2,2,2- trifluoromethyls of 1,1-] -2- (4 "-sulfonic acid phenoxy group) benzene
Sulfonic acid, 4,4 '-diamino -4 "-methoxyl group -3 "-sulfonic group-triphenylamine, 4,4 '-diaminodiphenyl ethers -2,2 '-disulfonic acid, 1,
Bis- (4- amino-benzene oxygens) naphthalene -2,7- disulfonic acid of 4-, 4,4 '-bis- (4- amino -2- sulfophenoxies) biphenyl, 4,4 '-bis- (4- ammonia
Phenoxyl) biphenyl -3,3 '-disulfonic acid, 4,4 '-bis- (3- amino-benzene oxygens) biphenyl -3,3 '-disulfonic acid, 4,4 '-bis- (4- ammonia
Phenoxyl) -3,3 '-two (sulfonic group phenyl) biphenyl,-two sulphur of 2,2 '-bis- (p- amino-benzene oxygens) -1,1 '-dinaphthalene -6,6 '
Sour, bis- [4- (4- amino-benzene oxygens) phenyl] hexafluoropropane -3,3 '-disulfonic acid, bis- [4- (4- aminobenzene-thios) phenyl] hexichol
Ketone -3,3 '-disulfonic acid, bis- [4- (4- aminobenzene-thios) phenyl] diphenyl sulphone (DPS) -3,3 '-disulfonic acid, bis- [4- (3- amino-benzene oxygens)
Phenyl] diphenyl sulphone (DPS) -3,3 '-disulfonic acid, bis- [4- (4- amino-benzene oxygens) -2- (3- sulfobenzoyls)] diphenyl sulphone (DPS)s, 4,4 ' -
(5- amino -1- naphthoxys) diphenyl sulphone (DPS) disulfonic acid, bis- (3- aminophenyls) -3- sulfonic groups phenyl phosphine oxides, 1,2- dihydros -2-
(3- sulfonic acid -4- aminophenyls) -4- [4- (3- sulfonic acid -4- amino-benzene oxygens)-phenyl]-phthalazone, 2,4- diaminophenols, 2,
Between 6- diamino -4- phenylphenols, 2,5- dihydroxy p-phenylenediamine, 4,6- dihydroxy m-phenylene diamine (MPD), 5- (p- hydroxyphenoxies)
Phenylenediamine, 3,3 '-dihydroxy -2,2- two (4- aminophenyls) hexafluoropropane, bis- (4- the amino-benzene oxygens) -1- methylols of 3,5-
One or more in bis- (4- the amino-benzene oxygens) -1- methylols benzene of benzene, 3,4-, 3,3 '-dicarboxylate biphenyl amine；It is preferred that
Ground, the second class diamine monomer include p-phenylenediamine, m-phenylene diamine (MPD), o-phenylenediamine, 2,6- diaminotoluenes, Isosorbide-5-Nitrae-diamino
Benzotrifluoride, 3,5- diamido-benzotrifluorides, benzidine, 4,4 '-diaminodiphenylmethane, 3,4 '-diaminodiphenylmethane,
4,4 '-diamino benzophenone, 3,4 '-diamino benzophenone, 3,3 '-diamino benzophenone, 4,4 '-bis- (4- amino-benzene oxygens) two
Benzene sulfone, 4,4 '-bis- (3- amino-benzene oxygens) diphenyl sulphone (DPS)s, 4,4 '-bis- (3- amino-benzene oxygens) diphenyl sulfides, 4,4 '-bis- (4- amino
Phenoxy group) diphenyl sulfide, 3,3 '-dimethyl -4,4 '-diaminodiphenylmethane, 3,3 '-diisopropyls -4,4 '-diamino hexichol
Methane, 3,3 ', 5,5 '-tetramethyls -4,4 '-diaminodiphenylmethane, 3,3 ', 5,5 '-tetraethyls -4,4 '-diamino hexichol first
Alkane, 3,3 ', 5,5 '-tetra isopropyls -4,4 '-diaminodiphenylmethane, 2,2- bis- (4- aminophenyls) hexafluoropropane, 2,2- bis-
(3- aminophenyls) hexafluoropropane, 3,3 '-dimethyl -2,2- two (4- aminophenyls) hexafluoropropane, 4,4 '-diamino hexichol
Ether, 3,4 '-diaminodiphenyl ethers, 3,3 '-diaminodiphenyl ethers, octafluoro -4,4- diaminodiphenyl ethers, 4,4 '-diamino hexichol
Thioether, 4,4 '-diamino diphenyl disulfides, 4,4 '-diaminodiphenylsulfones, 3,3 '-diaminodiphenylsulfones, 4,4 '-bis- (p- amino
Phenyl sulfo group) diphenyl sulphone (DPS), 2,6- diamino-pyridines, 2- (4- aminophenyls) -5- aminopyridines, 2,5- bis- (4- aminophenyls) pyrrole
Pyridine, 2,6- bis- (3- amino-benzene oxygens) pyridine, 4,4 '-diamino -2,2 '-bipyridyl, 5,5 '-diamino bipyridyls, hexamethylene diamine,
1,5- diamino -2- methylpentanes, nonamethylene diamine, 3- methyl heptamethylene diamine, 4,4 dimethyl-g diamines, 2,2 '-(ethylene two oxies) two
One or more in ethamine, polyethylene oxide diamine, polyether diamine, fluorine ether diamine, 4- (4- aminobenzyls) cyclohexylamine.
Further, the blending polyimides be blended with the second class polyamic acid by the first kind polyamic acid preparation and
, wherein first kind polyamic acid contains one or more in sulfonic group, hydroxyl, carboxyl, and the first quasi-polyimide can be
The polyimides of single variety, or the mixing of a variety of quasi-polyimides, first kind polyamic acid account for blending polyamic acid
The 2-30wt% of total amount；Second quasi-polyimide is the polyimides without containing sulfonic group, hydroxyl, carboxyl, can be single kind
It is class or mixed species.
Contained using the prepared copolyimide of above-mentioned diamine monomer and dianhydride monomer polymerization or blending polyimides
Sulfonic group, hydroxyl, carboxyl isoreactivity group, these active groups reduce the surface tension of polyimides, increase polyamides Asia
Amine wettability of the surface, thus the polyimide battery diaphragm prepared has good wetability.
Preferably, the structural formula of the polyimides includes following structural unit：
In one kind or more
Kind, wherein m, n, l are positive integer.
The preparation method of polyimide battery diaphragm material as described above, using polyamic acid solution as raw material, in drying
Polyamic acid nano fibrous membrane is obtained by electrostatic spinning in environment, then hot imidization is carried out to the polyamic acid nano fibrous membrane
Processing obtains polyimide battery diaphragm material.
The polyamic acid solution is 1 by molar ratio：The hybrid diamine of 0.95-1.05 gathers in a solvent with aromatic dianhydride
Conjunction obtains, or further dilutes and obtain to the polyamic acid solution that aforementioned polymeric obtains, it is preferable that the polyamic acid solution is special
Property viscosity be 0.4-5.0dL/g, preferably 0.4-2.0dL/g, it is preferable that the dry environment be 15-70 DEG C of environment temperature, humidity
The environment of≤40%RH.
Further, the solvent includes n,N-Dimethylformamide, n,N-dimethylacetamide, N- crassitudes
Ketone, tetrahydrofuran, diacetone alcohol, methanol, ethyl alcohol, isopropanol, ethylene glycol, diethylene glycol, dioxane, glycol dimethyl ether,
Two or more in acetone, toluene, dimethylbenzene.Preferably, the solvent include tetrahydrofuran, diacetone alcohol, methanol,
One or more in ethyl alcohol, isopropanol, dioxane, glycol dimethyl ether, acetone, toluene, dimethylbenzene.
The hot imidization processing procedure is：Since room temperature, 100-150 DEG C is risen to 10-20 DEG C/min heating rates
Interior any temperature keeps 10-60min, and any temperature keeps 1-15min in 200-250 DEG C, is protected in 250-350 DEG C of any temperature
Hold 1-15min.
Hot imidization processing of the present invention need not be under vacuum or inert gas conditions, only need to be in environment temperature 15-
70 DEG C, in the dry environment of humidity≤40%RH.Meanwhile this patent hot imidization time more general hot imidization time has
It is obviously shortened, whole imidization can control the completion in 30min and diaphragm material imidization is complete.
A kind of lithium ion battery, including polyimide battery diaphragm material as described above or preparation method as described above
Obtain polyimide battery diaphragm material.
The improved polyimide battery diaphragm material preparation method of structure of the present invention is used containing low boiling point solvent
Mixed solvent has two aspect advantageous effects.One side low boiling point solvent can be waved quickly in electrostatic spinning and imidization
It sends out, when so that the fiber that electrostatic spinning comes out is kept good pattern, but also improve electrostatic spinning efficiency, and shortening imidization
Between, substantially increase polyimide battery diaphragm material entirety preparation efficiency；On the other hand, by adjusting mixed solvent ratio,
The molecular size range and molecular weight distribution that polyamic acid can be influenced by solvent effect, to prepare different mechanical properties
Polyimide diaphragm material.
The improved polyimide battery diaphragm material of structure provided by the invention is a kind of isotropic with uniform bore
The porous film material of structure, high porosity, while there is good mechanical property, dimensional stability, thermal stability and solvent resistant
Property, size changing rate is less than 0.2% after glass transition temperature heats 1 hour more than 260 DEG C, 200 DEG C, and decomposition temperature is more than
500 DEG C, mechanical strength 20-50Mpa, imbibition rate is more than 100%, and static contact angle of the mixed electrolytic solution on diaphragm is 0-15 °,
Wellability is good.
The improved polyimide battery diaphragm material of structure of the present invention can be used for the mobile digitals such as mobile phone and notebook
Equipment lithium ion battery, it can also be used to power train in vehicle application lithium ion battery etc..
Compared with prior art, the present invention has the advantages that：
(1) diaphragm material of the invention has good mechanical property, dimensional stability, thermal stability and solvent resistance,
It is good with the wetability of electrolyte；
(2) diaphragm material preparation process of the invention is simple, and preparation efficiency is high, and can realize that the performance of diaphragm material is controllable
It prepares.
Specific implementation mode
Following embodiment will be helpful to those skilled in the art and further understand the present invention, but not in any form
The limitation present invention.
Embodiment 1
Polyamic acid solution synthesizes：First 4,4 '-diaminodiphenyl ethers, bis- anilinesulfonic acids of 2,5-, equal benzene dianhydride are massaged
That ratio 0.85：0.15：1.05 weighing.4,4 '-diaminodiphenyl ethers and bis- anilinesulfonic acids of 2,5- are first put into 5-25 DEG C
In dry reaction kettle, about 50% mixed solvent (mass ratio 1 is added：1 ethyl alcohol/N-Methyl pyrrolidone), stirring is molten
Solution, then equal benzene dianhydride is added portionwise, with remaining solvent washing kettle wall residual powder, the reaction was continued 5 hours, obtains mass concentration and is
20% sticky copolyamide acid solution.It is 1.83dL/g to test its inherent viscosity.
It is prepared by polyimide battery diaphragm material：By copolyamide acid solution above electric field strength be 100kv/m
Electrostatic field in carry out electrostatic spinning, and pass through stainless steel drum and receive polyamic acid nano fibrous membrane.Gained nano fibrous membrane
Hot imidization is carried out in high temperature furnace, imidization temperature program is：With 10 DEG C/min heating rates 140 DEG C of holdings are risen to from room temperature
30min keeps 5min at 220 DEG C, and 10min is kept at 300 DEG C, heating is then shut off, is taken out after natural cooling, obtains polyamides Asia
Amine battery diaphragm.
Performance characterization：272 DEG C of glass transition temperature, 200 DEG C heating 1 hour after size changing rate be less than 0.2%, heat point
Solve 514 DEG C, mechanical strength 30Mpa of temperature, imbibition rate 357%, mixed electrolytic solution (1mol/L, LiPF6Ethylene carbonate/carbonic acid
Dimethyl ester) static contact angle on diaphragm is 8 °.Polyimide battery diaphragm material structural formula is as follows：
Embodiment 2
Polyamic acid solution synthesizes：First 4,4 '-diaminodiphenyl ethers, benzidine -2,2 '-disulfonic acid, equal benzene dianhydride are pressed
Molar ratio 0.90：0.10：1.02 weighing.4,4 '-diaminodiphenyl ethers and benzidine -2,2 '-disulfonic acid are first put into 5-25
DEG C dry reaction kettle in, add about 60% mixed solvent (mass ratio 1：1 acetone/n,N-dimethylacetamide),
Stirring and dissolving, then equal benzene dianhydride is added portionwise, with remaining solvent washing kettle wall residual powder, the reaction was continued 5 hours, obtains quality
A concentration of 20% sticky copolyamide acid solution.It is 1.22dL/g to test its inherent viscosity.
It is prepared by polyimide battery diaphragm material：By copolyamide acid solution above electric field strength be 100kv/m
Electrostatic field in carry out electrostatic spinning, and pass through stainless steel drum and receive polyamic acid nano fibrous membrane.Gained nano fibrous membrane
Hot imidization is carried out in high temperature furnace, imidization temperature program is：With 10 DEG C/min heating rates 120 DEG C of holdings are risen to from room temperature
30min keeps 5min at 220 DEG C, and 10min is kept at 300 DEG C, heating is then shut off, is taken out after natural cooling, obtains polyamides Asia
Amine battery diaphragm.
Performance characterization：280 DEG C of glass transition temperature, 200 DEG C heating 1 hour after size changing rate be less than 0.2%, heat point
Solve 520 DEG C, mechanical strength 45Mpa of temperature, imbibition rate 479%, mixed electrolytic solution (1mol/L, LiPF6Ethylene carbonate/carbonic acid
Dimethyl ester/diethyl carbonate) static contact angle on diaphragm is 8 °.Polyimide battery diaphragm material structural formula is as follows：
Embodiment 3
Polyamic acid solution synthesizes：First by 4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulfides,-two sulphur of benzidine -2,2 '
Acid, mellitic acid dianhydride in molar ratio 0.90：0.10：1.05 weighing.First by 4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulfides
It is put into 5-25 DEG C of dry reaction kettle with 2,2 '-disulfonic acid of benzidine-, adding about 50% mixed solvent, (mass ratio is
4：1 tetrahydrofuran/methanol), stirring and dissolving, then mellitic acid dianhydride is added portionwise, remain powder with remaining solvent washing kettle wall
End, the reaction was continued 5 hours, obtains the sticky copolyamide acid solution that mass concentration is 20%.Testing its inherent viscosity is
1.93dL/g。
It is prepared by polyimide battery diaphragm material：By copolyamide acid solution above electric field strength be 100kv/m
Electrostatic field in carry out electrostatic spinning, and pass through stainless steel drum and receive polyamic acid nano fibrous membrane.Gained nano fibrous membrane
Hot imidization is carried out in high temperature furnace, imidization temperature program is：With 10 DEG C/min heating rates 120 DEG C of holdings are risen to from room temperature
30min keeps 5min at 240 DEG C, and 10min is kept at 330 DEG C, heating is then shut off, is taken out after natural cooling, obtains polyamides Asia
Amine battery diaphragm.
Performance characterization：270 DEG C of glass transition temperature, 200 DEG C heating 1 hour after size changing rate be less than 0.2%, heat point
Solve 507 DEG C, mechanical strength 35Mpa of temperature, imbibition rate 485%, mixed electrolytic solution (1mol/L, LiPF6Ethylene carbonate/carbonic acid
Dimethyl ester/diethyl carbonate) static contact angle on diaphragm is 6 °.Polyimide battery diaphragm material structural formula is as follows：
Embodiment 4
Polyamic acid solution synthesizes：First by 4,4 '-diaminodiphenyl ethers, equal benzene dianhydride in molar ratio 1.00：1.05 weighing
It is good.First 4,4 '-diaminodiphenyl ethers are put into 5-25 DEG C of dry reaction kettle, adds about 50% mixed solvent (quality
Than being 4:1 tetrahydrofuran/methanol), stirring and dissolving, then equal benzene dianhydride is added portionwise, remain powder with remaining solvent washing kettle wall
End, the reaction was continued 5 hours, obtains the sticky copolyamide acid solution that mass concentration is 20%.Testing its inherent viscosity is
2.45dL/g.By gained polyamic acid solution and 3 gained polyamic acid solution in mass ratio 1 of embodiment:1 is mixed evenly,
Obtain the blending polyamic acid solution that inherent viscosity is 2.14dL/g.
It is prepared by polyimide battery diaphragm material：By blending polyamic acid solution above electric field strength be 100kv/m
Electrostatic field in carry out electrostatic spinning, and pass through stainless steel drum and receive polyamic acid nano fibrous membrane.Gained nano fibrous membrane
Hot imidization is carried out in high temperature furnace, imidization temperature program is：With 10 DEG C/min heating rates 120 DEG C of holdings are risen to from room temperature
30min keeps 5min at 240 DEG C, and 10min is kept at 330 DEG C, heating is then shut off, is taken out after natural cooling, obtains polyamides Asia
Amine battery diaphragm.
Performance characterization：270 DEG C of glass transition temperature, 200 DEG C heating 1 hour after size changing rate be less than 0.2%, heat point
Solve 512 DEG C, mechanical strength 32Mpa of temperature, imbibition rate 397%, mixed electrolytic solution (1mol/L, LiPF6Ethylene carbonate/carbonic acid
Dimethyl ester/diethyl carbonate/methyl ethyl carbonate) static contact angle on diaphragm is 6 °.Polyimide battery diaphragm material
Structural formula is as follows：
Each technical characteristic of embodiment described above can be combined arbitrarily, to keep description succinct, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, it is all considered to be the range of this specification record.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of polyimide battery diaphragm material, which is characterized in that including copolyimide and/or polyimides is blended；
Wherein, the copolyimide contains one or more in sulfonic group, hydroxyl, carboxyl, and the blending polyimides contains
It is one or more in sulfonic group, hydroxyl, carboxyl；Preferably, the glass transition temperature of the diaphragm material is more than 260 DEG C,
Size changing rate is less than 0.2% after heating 1h at 200 DEG C, and decomposition temperature is more than 500 DEG C, mechanical strength 20-50Mpa, into one
Preferably, static contact angle of the mixed electrolytic solution on the diaphragm material is 0-15 ° to step.
2. polyimide battery diaphragm material according to claim 1, which is characterized in that the copolyimide is by mixing
It closes diamines to be prepared with aromatic dianhydride copolymerization, wherein the total moles of hybrid diamine and aromatic dianhydride ratio is 1：0.95-
1.15, the hybrid diamine includes first kind diamine monomer and the second class diamine monomer, first kind diamine monomer contain sulfonic group,
One or more in hydroxyl, carboxyl, first kind diamine monomer accounts for the 2-30wt% of hybrid diamine total amount.
3. polyimide battery diaphragm material according to claim 2, which is characterized in that the aromatic dianhydride includes equal
Benzene dianhydride, even benzene dianhydride, 1,2 ', 3,3 '-benzophenone dianhydrides, 2,2 ', 3,3 '-biphenyl dianhydrides, 3,3 ', 4,4 '-biphenyl dianhydrides,
2,3,3 ', 4 '-biphenyl dianhydrides, mellitic acid dianhydride, the equal benzene dianhydride of 3,6- dihydroxy, 3,3 ', 4,4 '-para-terpheny dianhydrides, 2,
2 ', 3,3 '-para-terpheny dianhydrides, 3,3 ', 4,4 '-benzhydrol tetracid dianhydrides, 3,3 ', 4,4 '-diphenyl ether dianhydrides, 2,2 ', 3,
One or more in 3 '-diphenyl ether dianhydrides, 3,3 ', 4,4 '-diphenyl sulfone dianhydrides, 2,2 ', 3,3 '-diphenyl sulfone dianhydrides；It is excellent
Selection of land, the first kind diamine monomer include 2,5-, bis- anilinesulfonic acids, 2,4-, bis- anilinesulfonic acids, 3- (2 ', 4 '-two amidos
Phenoxy group) propane sulfonic acid hydrochloride, 3,5- diamino -3 '-sulfonic group -4 '-(4- sulfonic benzos oxygroup) benzophenone, 3,5- diaminos
Base -3 '-sulfonic group -4 '-(2,4- sulfonic benzos oxygroup) benzophenone, 2- (3,5- diamino-phenyls) benzimidazole -5- sulfonic acid, connection
It is aniline -2,2 '-disulfonic acid, 3,3 '-bis- (sulfomethvl) benzidine, 2,2 '-bis- (3- sulfo groups propoxyl group) benzidine, 3,3 '-bis-
(3- sulfo groups propoxyl group) benzidine, 2,2 '-bis- (3- sulfo groups butoxy) benzidine, 3,3 '-bis- (3- sulfo groups butoxy) benzidine,
2,2 '-bis- (sulfo group phenyl) benzidine, 2,2 '-bis- (4- amino-benzene oxygens) biphenyl -5,5 '-disulfonic acid, 3,3 '-bis- [3- (4- sulphurs
Phenoxyl) propoxyl group] benzidine, 2,2 '-bis- (sulfophenoxy) benzidine, 3,3 '-bis- (sulfophenoxy) benzidine, 4,
4 '-bis- [2- (1- amino -4- naphthalenes sulfo group) azo] biphenyl,-two sulphur of 3,3 '-dimethyl -4,4 '-diaminodiphenylmethane -6,6 '
Acid, 5- [bis- (4 '-the aminophenyl) -2,2,2- trifluoromethyls of 1,1-] -2- (4 "-sulfonic acid phenoxy group) benzene sulfonic acid, 4,4 '-diaminos
Bis- (the 4- aminobenzene oxygen of base -4 "-methoxyl group -3 "-sulfonic group-triphenylamine, 4,4 '-diaminodiphenyl ethers -2,2 '-disulfonic acid, 1,4-
Base) naphthalene -2,7- disulfonic acid, 4,4 '-bis- (4- amino -2- sulfophenoxies) biphenyl, 4,4 '-bis- (4- amino-benzene oxygens) biphenyl -
3,3 '-disulfonic acid, 4,4 '-bis- (3- amino-benzene oxygens) biphenyl -3,3 '-disulfonic acid, 4,4 '-bis- (4- amino-benzene oxygens) -3,3 ' -
Two (sulfonic group phenyl) biphenyl, 2,2 '-bis- (p- amino-benzene oxygens) -1,1 '-dinaphthalenes -6,6 '-disulfonic acid, bis- [4- (4- aminobenzenes
Oxygroup) phenyl] hexafluoropropane -3,3 '-disulfonic acid, bis- [4- (4- aminobenzene-thios) phenyl] benzophenone-3, it is 3 '-disulfonic acid, double
[4- (4- aminobenzene-thios) phenyl] diphenyl sulphone (DPS) -3,3 '-disulfonic acid, bis- [4- (3- amino-benzene oxygens) phenyl] diphenyl sulphone (DPS)s -3,3 ' -
Disulfonic acid, bis- [4- (4- amino-benzene oxygens) -2- (3- sulfobenzoyls)] diphenyl sulphone (DPS)s, 4,4 '-(5- amino -1- naphthoxys) two
Benzene sulfone disulfonic acid, bis- (3- aminophenyls) -3- sulfonic groups phenyl phosphine oxides, 1,2- dihydros -2- (3- sulfonic acid -4- aminophenyls) -
4- [4- (3- sulfonic acid -4- amino-benzene oxygens)-phenyl]-phthalazone, 2,4- diaminophenols, 2,6- diamino -4- phenylphenols,
2,5- dihydroxy p-phenylenediamine, 4,6- dihydroxy m-phenylene diamine (MPD), 5- (p- hydroxyphenoxies) m-phenylene diamine (MPD), 3,3 '-dihydroxy -2,
2- bis- (4- aminophenyls) hexafluoropropane, bis- (4- the amino-benzene oxygens) -1- methylols benzene of 3,5-, bis- (the 4- aminobenzene oxygen of 3,4-
Base) -1- methylols benzene, the one or more in 3,3 '-dicarboxylate biphenyl amine；Preferably, the second class diamine monomer
Including p-phenylenediamine, m-phenylene diamine (MPD), o-phenylenediamine, 2,6- diaminotoluenes, 1,4- diamido-benzotrifluorides, 3,5- diamino three
Toluene fluoride, benzidine, 4,4 '-diaminodiphenylmethane, 3,4 '-diaminodiphenylmethane, 4,4 '-diamino benzophenone, 3,
4 '-diamino benzophenone, 3,3 '-diamino benzophenone, 4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulphone (DPS)s, 4,4 '-bis- (3- amino
Phenoxy group) diphenyl sulphone (DPS), 4,4 '-bis- (3- amino-benzene oxygens) diphenyl sulfides, 4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulfides, 3,
3 '-dimethyl -4,4 '-diaminodiphenylmethane, 3,3 '-diisopropyls -4,4 '-diaminodiphenylmethane, 3,3 ', 5,5 '-four
It is methyl -4,4 '-diaminodiphenylmethane, 3,3 ', 5,5 '-tetraethyls -4,4 '-diaminodiphenylmethane, 3,3 ', 5,5 '-four different
Propyl -4,4 '-diaminodiphenylmethane, 2,2- bis- (4- aminophenyls) hexafluoropropane, 2,2- bis- (3- aminophenyls) hexafluoro third
Alkane, 3,3 '-dimethyl -2,2- two (4- aminophenyls) hexafluoropropane, 4,4 '-diaminodiphenyl ethers, 3,4 '-diamino hexichol
Ether, 3,3 '-diaminodiphenyl ethers, octafluoro -4,4- diaminodiphenyl ethers, 4,4 '-diaminodiphenyl sulfides, 4,4 '-diamino two
Diphenyl disulfide ether, 4,4 '-diaminodiphenylsulfones, 3,3 '-diaminodiphenylsulfones, 4,4 '-bis- (p- aminophenyls sulfo group) diphenyl sulphone (DPS)s, 2,
6- diamino-pyridines, 2- (4- aminophenyls) -5- aminopyridines, 2,5- bis- (4- aminophenyls) pyridine, (the 3- aminobenzenes of 2,6- bis-
Oxygroup) pyridine, 4,4 '-diamino -2,2 '-bipyridyl, 5,5 '-diamino bipyridyls, hexamethylene diamine, 1,5- diamino -2- methyl
Pentane, nonamethylene diamine, 3- methyl heptamethylene diamine, 4,4 dimethyl-g diamines, 2,2 '-(ethylene two oxy) diethylamine, polyethylene glycol oxide two
One or more in amine, polyether diamine, fluorine ether diamine, 4- (4- aminobenzyls) cyclohexylamine.
4. polyimide battery diaphragm material according to claim 1, which is characterized in that the blending polyimides is by
A kind of polyamic acid is blended with the second class polyamic acid and is prepared, wherein first kind polyamic acid contain sulfonic group, hydroxyl,
One or more in carboxyl, first kind polyamic acid accounts for the 2-30wt% that polyamic acid total amount is blended.
5. polyimide battery diaphragm material according to claim 1, which is characterized in that the polyimides includes following
Structural unit：
In it is one or more, wherein m, n, l are positive integer.
6. the preparation method of polyimide battery diaphragm material as described in any one in claim 1-5, which is characterized in that with poly-
Amide acid solution is raw material, obtains polyamic acid nano fibrous membrane by electrostatic spinning in dry environment, then to the polyamide
Sour nano fibrous membrane carries out hot imidization processing, obtains polyimide battery diaphragm material.
7. preparation method according to claim 6, which is characterized in that the polyamic acid solution is 1 by molar ratio：
The hybrid diamine of 0.95-1.05 polymerize to obtain in a solvent with aromatic dianhydride, or the polyamic acid obtained to aforementioned polymeric is molten
Further dilution obtains liquid, it is preferable that the polyamic acid solution inherent viscosity is 0.4-5.0dL/g, preferably 0.4-
2.0dL/g, it is preferable that the dry environment be 15-70 DEG C of environment temperature, humidity≤40%RH environment.
8. preparation method according to claim 6, which is characterized in that the solvent includes n,N-Dimethylformamide, N,
N- dimethylacetylamides, N-Methyl pyrrolidone, tetrahydrofuran, diacetone alcohol, methanol, ethyl alcohol, isopropanol, ethylene glycol, diethyl
Two or more in glycol, dioxane, glycol dimethyl ether, acetone, toluene, dimethylbenzene.
9. preparation method according to claim 6, which is characterized in that the hot imidization processing procedure is：It is opened from room temperature
Begin, rising to any temperature in 100-150 DEG C with 10-20 DEG C/min heating rates keeps 10-60min, any in 200-250 DEG C
Temperature keeps 1-15min, and 1-15min is kept in 250-350 DEG C of any temperature.
10. a kind of lithium ion battery, which is characterized in that comprising polyimide battery as described in any one in claim 1-5 every
Membrane material or such as claim 6-9 any one of them preparation methods acquisition polyimide battery diaphragm material.
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| CN111403667A (en) * | 2020-04-13 | 2020-07-10 | 上海极紫科技有限公司 | Composition of high-temperature-resistant lithium battery diaphragm and preparation method thereof |
| CN111534089A (en) * | 2020-05-28 | 2020-08-14 | 苏州梅克兰包装材料有限公司 | Preparation method of antistatic mobile phone battery loading box |
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| CN115579579A (en) * | 2022-10-21 | 2023-01-06 | 天能新能源(湖州)有限公司 | Battery diaphragm with high temperature resistant environment, preparation method thereof and lithium ion battery |
| CN115627000A (en) * | 2022-11-02 | 2023-01-20 | 天能新能源(湖州)有限公司 | High-temperature-resistant polyimide diaphragm, preparation method thereof and application thereof in preparation of lithium ion battery |
| CN115627000B (en) * | 2022-11-02 | 2023-11-10 | 天能新能源(湖州)有限公司 | High-temperature-resistant polyimide diaphragm, preparation method thereof and application thereof in preparation of lithium ion battery |
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