CN102251307B - Polyimide-base nano fibrous membrane, and preparation method and application thereof - Google Patents
Polyimide-base nano fibrous membrane, and preparation method and application thereof Download PDFInfo
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- CN102251307B CN102251307B CN201110147725XA CN201110147725A CN102251307B CN 102251307 B CN102251307 B CN 102251307B CN 201110147725X A CN201110147725X A CN 201110147725XA CN 201110147725 A CN201110147725 A CN 201110147725A CN 102251307 B CN102251307 B CN 102251307B
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- 239000012528 membrane Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229920001721 polyimide Polymers 0.000 claims abstract description 56
- 239000004642 Polyimide Substances 0.000 claims abstract description 54
- 239000002121 nanofiber Substances 0.000 claims abstract description 31
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 229920005575 poly(amic acid) Polymers 0.000 claims description 62
- 150000004985 diamines Chemical class 0.000 claims description 26
- 238000009987 spinning Methods 0.000 claims description 21
- -1 organic acid acid anhydride Chemical class 0.000 claims description 19
- 238000010041 electrostatic spinning Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- FEQIKDBPUQIQKY-UHFFFAOYSA-N n-phenyl-n-propan-2-ylaniline Chemical compound C=1C=CC=CC=1N(C(C)C)C1=CC=CC=C1 FEQIKDBPUQIQKY-UHFFFAOYSA-N 0.000 claims description 7
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 238000006482 condensation reaction Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 6
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 5
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 claims description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 3
- 229940106691 bisphenol a Drugs 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 3
- 229940100630 metacresol Drugs 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 40
- 230000004888 barrier function Effects 0.000 description 30
- 238000010438 heat treatment Methods 0.000 description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 13
- 239000002585 base Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 2
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 2
- 241001502050 Acis Species 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 230000009970 fire resistant effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 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 description 1
- AERQQIJMPSNSAD-UHFFFAOYSA-N CC(C)(c(cc1)ccc1Oc1cc(C)c(C)cc1)c(cc1)ccc1Oc1cc(C)c(C)cc1 Chemical compound CC(C)(c(cc1)ccc1Oc1cc(C)c(C)cc1)c(cc1)ccc1Oc1cc(C)c(C)cc1 AERQQIJMPSNSAD-UHFFFAOYSA-N 0.000 description 1
- BGTZYQSCNQIZER-UHFFFAOYSA-N CC(C)(c1cc(C)c(C)cc1)c1ccc(C)c(C)c1 Chemical compound CC(C)(c1cc(C)c(C)cc1)c1ccc(C)c(C)c1 BGTZYQSCNQIZER-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000005325 alkali earth metal hydroxides Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- AHIHJODVQGBOND-UHFFFAOYSA-N propan-2-yl hydrogen carbonate Chemical compound CC(C)OC(O)=O AHIHJODVQGBOND-UHFFFAOYSA-N 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a polyimide-base nano fibrous membrane which can be used as a lithium ion secondary battery membrane. The polyimide-base nano fibrous membrane is composed of polyimide nano fibers of which the diameters are 20-500 nanometers, the membrane thickness is 15-100 micrometers, and the air penetrability of the membrane is 10-500 seconds; and the pore distribution of the upper and lower surfaces and the inside is symmetrical and uniform, the average pore size is 100 nanometers, and the tensile strength is 100-250mpa. The invention also discloses a preparation method of the polyimide-base nano fibrous membrane. When being used as the lithium ion battery membrane, the polyimide-base nano fibrous membrane has favorable heat resistance, and can not produce the phenomenon of short circuit even at 150 DEG C; and therefore, the battery membrane disclosed by the invention is especially suitable for high-capacity and high-power lithium ion batteries.
Description
Technical field
The present invention relates to a kind of polyimide-base nano fibrous membrane.
The invention still further relates to the preparation method of above-mentioned polyimide-base nano fibrous membrane.
The invention still further relates to the application of above-mentioned polyimide-base nano fibrous membrane in lithium rechargeable battery.
Background technology
Lithium rechargeable battery is with its height ratio capacity, high voltage, and volume is little, lightweight, the advantages such as memoryless property have obtained huge development over past ten years, but for the lithium rechargeable battery that uses liquid electrolyte, some the time, smoldering easily appears in lithium ion battery, catches fire, blast, even cause the potential safety hazards such as injury to personnel, make high power capacity and power lithium-ion battery also there is no extensive use, thereby improve the key that lithium ion battery safety performance is the research and development lithium rechargeable battery.
One of Security Countermeasures of lithium rechargeable battery are to make the electric current blocking, wherein battery diaphragm plays important effect, barrier film with polymer of loose structure melts under higher temperature, thereby cause closing of loose structure, impedance increases sharply and makes the electric current blocking, this temperature is called blocking temperature (shut-down), claims again self-closing temperature.In addition, after the bore closure of barrier film, if battery temperature continues to raise, when surpassing the heat resisting temperature of barrier film, barrier film can melt, and destroys, and causes positive pole, and negative pole directly contacts and short circuit, and this temperature is called film destroy temperature (break-out).Battery diaphragm such as the polyethylene (PE) commonly used now, (the self-closing temperature as the PE barrier film is 135-140 ℃ to polypropylene (PP) lower than 200 ℃ due to fusion temperature, the self-closing temperature of PP barrier film is 170 ℃ of left and right), in some cases, for example external temperature is too high, excessive or the electrolyte of discharge current is subjected in the situation of the thermal inertia in thermal process, even electric current is interdicted, the temperature of battery also might continue to raise, therefore barrier film may be fully destroyed and cause battery short circuit, thereby cause battery explosion or catch fire.In addition, the PE barrier film of simple tension and PP barrier film, TENSILE STRENGTH in the horizontal is far short of what is expected than vertical upper TENSILE STRENGTH also, in the situation that there is the hidden danger of film rupture in battery lamination or be subject to accidental shock.Therefore, adopt the security of PE barrier film and PP barrier film lower.
The factor that high power capacity and high-power battery internal heat increase and temperature raises is a lot, and the resistance to elevated temperatures that therefore improves battery becomes and is even more important.Adopt the security performance of PE barrier film and PP barrier film can not meet the need, thereby need the better polymer separators material of heat resistance.CN101000951A discloses a kind of preparation method of polyimide-based barrier film, it is the polycaprolactone of 1000-50000 that the method adopts weight average molecular weight, expoxy propane, polymethyl-benzene second is rare, and polystyrene is the fire resistant polyimide barrier film that pore former prepares porous.CN101355143A discloses a kind of preparation method of High Strength Polyimide base barrier film, has added in addition inorganic crystal whisker or positive esters of silicon acis in formula.The whisker that adds comprises calcium sulfate crystal whiskers, potassium titanate crystal whisker, and aluminium borate whisker etc., positive esters of silicon acis comprises methyl silicate, ethyl orthosilicate, one or more in positive silicic acid propyl ester and butyl silicate.CN101659753A discloses a kind of preparation method of polyimide-based barrier film of stretching, and the present invention adopts the hydroxide of alkali earth metal, and aluminium hydroxide, alkali-metal phosphate are pore former, and solidification liquid is hydrochloric acid, aqueous sulfuric acid or phosphate aqueous solution etc.The polyamide acid film that forms is stretched and imines after the polyimide-based barrier film that obtains stretching.CN101304082A discloses a kind of preparation method of composite diaphragm, the preparation method comprises: with the presoma of polyimides with become perforated membrane after the solution hybrid reaction becomes oligomer or spinning, and convert polyimides under greater than 200 ℃ or contain the perforated membrane of polyimides composition.CN101665580A has reported that a kind of lithium rechargeable battery is with the preparation method of polyimide-based porous septum, the pore-forming substance that adopts is the benzoic acid polyol ester, the phthalic acid dialkyl, the polyacid Arrcostab, phenyl alkylsulf, chlorinated paraffin wax and epoxy soybean albumen etc., the barrier film of the method preparation, yield rate is high.CN101752540A discloses the polyimide-based porous septum of a kind of lithium rechargeable battery, and this barrier film comprises first surface, second surface, the 3rd surface, and tortuous perforation the mutually of the duct in three surfaces.The pore-forming principle adopts alkali metal salt-acid cure solid-liquid or benzoic acid polyol ester-multiple pore-forming principles such as Re volatilization.JP11310658A2 discloses a kind of polyimide porous membrane and preparation method thereof, comprises that the method that polyamic acid solution film and polyolefin porous film lamination commonly used is compound obtains the porous polyimide film of 0.01-10 micron.This polyimide diaphragm is still dangerous when high temperature.
Nearly ten years, fast development due to nanometer technology, electrostatic spinning technique also causes countries in the world researcher's concern, and becomes gradually and use in the world to such an extent that the most generally produce the method for nanofiber, Kynoar (PVdF) electro spinning nanometer fiber membrane as diaphragm application to lithium battery.The PVdF nano fibrous membrane has the ability (320%-350%) of higher picked-up electrolyte solution and high ionic conductivity (1.7*10
-3S/cm, 0 ℃).The nano non-woven fabrics such as the PAN of same employing method of electrostatic spinning preparation and PVDF-HFP also are widely used in the research of lithium ion battery separator.
Above barrier film preparation method films on substrate, then adopts solvent exchange or the hot perforated membrane that volatilizees pore-forming substance and be prepared into, and such film is a kind of typical anisotropic membrane, and namely the pore size distribution of the upper surface of film and lower surface and pore structure are different.
Summary of the invention
The object of the present invention is to provide a kind of polyimide-base nano fibrous membrane.
Another purpose of the present invention is to provide a kind of method for preparing above-mentioned polyimide-base nano fibrous membrane.
For achieving the above object, polyimide-base nano fibrous membrane provided by the invention, the polyimide nano-fiber that is the 20-500 nanometer by diameter consists of, and the thickness of film is the 15-100 micron, and the air penetrability of film is 10-500 second; Film upper and lower surface and internal holes are distributed symmetrically and even, and average pore size is 100 nanometers, and TENSILE STRENGTH is the 100-250 MPa.
The method of the above-mentioned polyimide-base nano fibrous membrane of preparation provided by the invention, adopt electrostatic spinning to carry out spinning to polyamic acid solution, this spinning with mechanical roll-in compacting after, hot imidization is processed the polyamic acid in spinning is converted into polyimides, obtains polyimide nanofiber membrane;
Polyamic acid solution is to adopt binary organic acid acid anhydride and organic diamine to carry out the condensation reaction preparation in solvent, wherein the mol ratio of binary organic acid acid anhydride and organic diamine is 0.8-1.2, solvent adding amount be binary organic acid acid anhydride and organic diamine gross weight 4.5-10 doubly, the temperature of condensation reaction is 0-25 ℃.
Described preparation method, wherein, the spinning syringe needle internal diameter of electrostatic spinning is the 0.8-2.0 millimeter, and voltage is 100 volts-30 kilovolts, and syringe needle is 10-30 centimetre with the distance of accepting electrode, and the spinning solution flow is greater than 0.1 ml/hour.
Described preparation method, wherein, described binary organic acid acid anhydride is: pyromellitic acid anhydride (PMDA), BPDA (S-BPDA), benzophenone tetracarboxylic dianhydride (BTDA), oxygen bibenzene tetracarboxylic dianhydride (ODPA), bisphenol-A two ether dianhydrides (BPADA) or isopropyl diphenyl acid anhydride (IPDA);
Described organic diamine is: 4,4 '-diaminodiphenyl ether (4,4 '-ODA), 3,4 '-diaminodiphenyl ether (3,4 '-ODA), to benzene two (PDA), m-phenylene diamine (MPD) (MDA), 3,3 '-diphenyl sulphone (DPS) diamines (SDA), 4, two [4-(4-amino-benzene oxygen) phenyl] propane (BAPP) of 4 '-diphenyl sulphone (DPS) diamines (SDA), isopropyl diphenyl amine (IPDA), benzidine (BPDA) or 2,2-;
Described solvent is: DMA, DMA, 1-METHYLPYRROLIDONE, oxolane, metacresol or dimethyl sulfoxide (DMSO).
Described preparation method, wherein, polyimides has following structural formula
Wherein, A
1Aryl for following structure:
Described diamines can be to have NH
2-A
2-NH
2The diamines of the structure of expression, A
2Aryl for following structure;
Polymerization degree n is 50-10000, and the intrinsic viscosity of corresponding polyamic acid is the 1.0-3.0 deciliter/gram, and heat decomposition temperature is more than 420 ℃.
Described preparation method, wherein, the intensity of mechanical roll-in is the 1-10 MPa, the time of staying was at 5-30 minute.
Described preparation method, wherein, it is to heat up at nitrogen, argon gas or vacuum condition Gradient that hot imidization is processed, gradient increased temperature is: 100-200 ℃ kept 0.5-1.5 hour, 180-250 ℃ kept 0.5-1.5 hour, 230-280 ℃ kept 0.5-1.5 hour, and 260-350 ℃ kept 0.5-1.5 hour.
The present invention adopts the polyimide-base nano fibrous membrane of method of electrostatic spinning preparation to belong to symmetric membrane, pore structure and being evenly distributed, and easy to prepare, be suitable for batch production, heat resistance is high simultaneously, can be used as lithium ion battery separator, even this barrier film is under 150 ℃ of high temperature, battery can not be short-circuited yet, thereby polyimide-base nano fibrous membrane provided by the invention can be used in high power capacity and electrokinetic cell.
Description of drawings
Fig. 1 is the electron micrograph (before roll-in) of polyamic acid nano fibrous membrane in embodiment 1.
Fig. 2 is the electron micrograph (after 2 MPa roll-ins) of polyimide nanofiber membrane in embodiment 1.
Fig. 3 is the electron micrograph (after 5 MPa roll-ins) of polyimide nanofiber membrane in embodiment 8.
The specific embodiment
The polyimide nanofiber membrane of symmetry provided by the invention, be characterised in that this film is formed by weaving by nanofiber, film upper and lower surface and internal holes are distributed symmetrically evenly, the aperture is adjustable, TENSILE STRENGTH is high, heat resistance that the more important thing is this film is good, as the barrier film of lithium rechargeable battery, even also the battery short circuit phenomenon can not occur at 150 ℃.
The present invention prepares the method for polyimide nanofiber membrane, is first to adopt high-voltage electrostatic spinning to carry out the nanometer spinning to polyamic acid, then uses mechanical roll-in compacting, and at high temperature hot imidization prepares polyimide film at last.
Polyimide nanofiber membrane of the present invention can be used in lithium rechargeable battery, this battery comprises electrode group and nonaqueous electrolytic solution, electrode group and nonaqueous electrolytic solution are sealed in battery case, the electrode group comprises positive pole, negative pole and barrier film, and wherein barrier film used is polyimide nanofiber membrane of the present invention.
Battery membranes provided by the invention is owing to adopting the fire resistant polyimide nanofiber as base material, thereby has excellent chemical stability, resistance to elevated temperatures, excellent permeability and high TENSILE STRENGTH.The battery diaphragm that obtains in the embodiment of the present invention is heated to 350 ℃ of high temperature and also can break; Battery diaphragm at the percent thermal shrinkage of 150 ℃ less than 0.5%, all be not more than 1.5% at the percent thermal shrinkages of 300 ℃, 3% and 5% percent thermal shrinkage in the prior art, pierce through intensity greater than the intensity that pierces through of battery diaphragm in prior art, film surface and internal holes are evenly distributed, aperture and porosity all satisfy the requirement of conductance, have suitable good air permeability.Use the lithium rechargeable battery of battery diaphragm provided by the invention, even also can not be short-circuited phenomenon under 150 ℃ of high temperature, thereby battery diaphragm provided by the invention can be used in high power capacity and electrokinetic cell.
Preferentially adopt binary organic acid acid anhydride and organic diamine to carry out condensation reaction in embodiment of the present invention in solvent and prepare polyamic acid, the example of binary organic acid acid anhydride includes but not limited to as pyromellitic acid anhydride (PMDA), BPDA (S-BPDA), benzophenone tetracarboxylic dianhydride (BTDA), oxygen bibenzene tetracarboxylic dianhydride (ODPA), bisphenol-A two ether dianhydrides (BPADA), isopropyl diphenyl acid anhydride (IPDA); The example of organic diamine includes but not limited to 4,4 '-diaminodiphenyl ether (4,4 '-ODA), 3,4 '-diaminodiphenyl ether (3,4 '-ODA), to benzene two (PDA), m-phenylene diamine (MPD) (MDA), 3,3 '-diphenyl sulphone (DPS) diamines (SDA), 4,4 '-diphenyl sulphone (DPS) diamines (SDA), isopropyl diphenyl amine (IPDA), benzidine (BPDA), 2, two [4-(4-amino-benzene oxygen) phenyl] propane (BAPP) of 2-; Solvent includes but not limited to DMA, DMA, 1-METHYLPYRROLIDONE, oxolane, metacresol, dimethyl sulfoxide (DMSO).
The mol ratio of binary organic acid acid anhydride and organic diamine is 0.8-1.2, be preferably 1.00-1.02, under preferable case, the addition of solvent be binary organic acid acid anhydride and organic diamine gross weight 4.5-10 doubly, the temperature of condensation reaction is preferably 0-25 ℃, and the time is preferably 18-30 hour.
Polyimides in the present invention can be the polymer that contains imide group in the various repetitives of this area routine, and under preferable case, described polyimides is the polyimides with following structural formula:
Wherein, A
1Be preferably the aryl of following structure:
Described diamines can be to have NH
2-A
2-NH
2The diamines of the structure of expression, A
2It can be the aryl of following structure;
Polymerization degree n can be 50-10000, and the intrinsic viscosity of corresponding polyamic acid can be the 1.0-3.0 deciliter/gram, and heat decomposition temperature is more than 420 ℃.
Get the polyamic acid solution 1.0-5.0 milliliter for preparing under above-mentioned condition, carry out high-voltage electrostatic spinning and prepare the nano fiber non-woven fabric film, spinning syringe needle diameter is less than 5 millimeters, voltage is greater than between 100 volts, syringe needle with accept the distance of electrode greater than 10 centimetres, the spinning solution flow is greater than 0.1 ml/hour, be controlled at 0.1-1 ml/hour more suitable.
The polyamic acid nano fibrous membrane for preparing under above-mentioned condition is carried out mechanical rod press processing, the rod Compressive Strength is between the 1-10 MPa, and the time of staying was at 5-30 minute.
For the hot imidization progressively under the condition of gradient increased temperature of the barrier film after above-mentioned roll-in, at nitrogen, under argon gas or vacuum, heating is converted into polyimides with polyamic acid, to obtain polyimide nano-fiber nonwoven fabric barrier film.The temperature of heating is to keep under 100-200 ℃ 0.5-1.5 hour, keeps 0.5-1.5 hour under 180-250 ℃, keeps 0.5-1.5 hour under 260-350 ℃ of condition 0.5-1.5 hour under 230-280 ℃ of condition.
Embodiment 1
With 4.36 gram pyromellitic acid anhydrides, 4.00 gram diaminodiphenyl ethers, 45.5 milliliters of N, the N-dimethylacetylamide joins in the four-hole boiling flask of 150 milliliters, then at 0～5 ℃ of lower stirring reaction of ice bath, reaction time is 24 hours, obtains the polyamic acid solution (mass fraction is 15%) of homogeneous.After having reacted, polyamic acid solution is placed on 4 ℃ of preservations in refrigerator.Take out 1.6667 gram polyamic acid solutions in 50 milliliters of volumetric flasks, add DMA constant volume to 50 milliliter, be mixed with the solution of 0.0050 grams per milliliter, adopting Ubbelohde viscometer to measure its inherent viscosity in the water-bath of 30 ℃ is 2.11dL/g.Another take out 1.0 milliliters of polyamic acid solutions and carry out electrostatic spinning, the syringe needle diameter is 1.6 millimeters, and spinning voltage is 100 volts, and needle point is 20 centimetres to the height of dash receiver, and Electrospun 2 hours obtains thickness and be the polyamic acid nano fibrous membrane of 98 microns.This film is placed in the roll squeezer that pressure is 2 MPas stopped 10 minutes, obtain the polyamic acid nano fibrous membrane of 30 microns of thickness.Barrier film after roll extrusion hot imidization progressively under the condition of gradient increased temperature, heating is converted into polyimides with polyamic acid under nitrogen atmosphere, to obtain the polyimide nano-fiber non-woven membrane.The temperature of heating is to keep under 150 ℃ 0.5 hour, keeps 0.5 hour under 200 ℃, keeps 1.0 hours lower 1.0 hours of 330 ℃ of conditions under 270 ℃ of conditions.
Embodiment 2
With 5.88 gram bibenzene tetracarboxylic dianhydrides, 4.97 gram diphenyl sulphone (DPS) diamines, 60.3 milliliters of N, the N-dimethylacetylamide joins in the four-hole boiling flask of 150 milliliters, then at 0～5 ℃ of lower stirring reaction of ice bath, reaction time is 24 hours, obtains the polyamic acid solution (mass fraction is 15%) of homogeneous.After having reacted, polyamic acid solution is placed on 4 ℃ of preservations in refrigerator.Take out 1.6667 gram polyamic acid solutions in 50 milliliters of volumetric flasks, add DMA constant volume to 50 milliliter, be mixed with the solution of 0.0050 grams per milliliter, adopting Ubbelohde viscometer to measure its inherent viscosity in the water-bath of 30 ℃ is 1.89dL/g.Another take out 1.0 milliliters of polyamic acid solutions and carry out electrostatic spinning, the syringe needle diameter is 1.6 millimeters, and spinning voltage is 2 kilovolts, and needle point is 20 centimetres to the height of dash receiver, and Electrospun 2 hours obtains thickness and be the nano type polyamic acid nano fibrous membrane of 107 microns.This film is placed in the roll squeezer that pressure is 2 MPas stopped 10 minutes, obtain the polyamic acid nano fibrous membrane of 32 microns of thickness.Film after roll extrusion hot imidization progressively under the condition of gradient increased temperature, heating is converted into polyimides with polyamic acid under nitrogen atmosphere, to obtain the polyimide nano-fiber non-woven membrane.The temperature of heating is to keep under 150 ℃ 0.5 hour, keeps 0.5 hour under 200 ℃, keeps 1.0 hours lower 1.0 hours of 330 ℃ of conditions under 270 ℃ of conditions.
Embodiment 3
With 5.88 gram bibenzene tetracarboxylic dianhydrides, 2.16 gram p-phenylenediamine (PPD), 43.4 milliliters of N, the N-dimethylacetylamide joins in the four-hole boiling flask of 150 milliliters, then at 0～5 ℃ of lower stirring reaction of ice bath, the reaction time is 24 hours, obtains the polyamic acid solution (mass fraction is 15%) of homogeneous.After having reacted, polyamic acid solution is placed on 4 ℃ of preservations in refrigerator.Take out 1.6667 gram polyamic acid solutions in 50 milliliters of volumetric flasks, add DMA constant volume to 50 milliliter, be mixed with the solution of 0.0050 grams per milliliter, adopting Ubbelohde viscometer to measure its inherent viscosity in the water-bath of 30 ℃ is 1.49dL/g.Another take out 1.0 milliliters of polyamic acid solutions and carry out electrostatic spinning, the syringe needle diameter is 1.6 millimeters, and spinning voltage is 25.0 kilovolts, and needle point is 20 centimetres to the height of dash receiver, and Electrospun 2 hours obtains thickness and be the nano type polyamic acid nano fibrous membrane of 90 microns.This film is placed in the roll squeezer that pressure is 2 MPas stopped 10 minutes, obtain the polyamic acid nano fibrous membrane of 27 microns of thickness.Film after roll extrusion hot imidization progressively under the condition of gradient increased temperature, heating is converted into polyimides with polyamic acid under nitrogen atmosphere, to obtain the polyimide nano-fiber non-woven membrane.The temperature of heating is to keep under 150 ℃ 0.5 hour, keeps 0.5 hour under 200 ℃, keeps 1.0 hours lower 1.0 hours of 330 ℃ of conditions under 270 ℃ of conditions.
Embodiment 4
With 5.88 gram bibenzene tetracarboxylic dianhydrides, 4.00 gram diaminodiphenyl ethers, 54.5 milliliters of N, the N-dimethylacetylamide joins in the four-hole boiling flask of 150 milliliters, then at 0～5 ℃ of lower stirring reaction of ice bath, reaction time is 24 hours, obtains the polyamic acid solution (mass fraction is 15%) of homogeneous.After having reacted, polyamic acid solution is placed on 4 ℃ of preservations in refrigerator.Take out 1.6667 gram polyamic acid solutions in 50 milliliters of volumetric flasks, add DMA constant volume to 50 milliliter, be mixed with the solution of 0.0050 grams per milliliter, adopting Ubbelohde viscometer to measure its inherent viscosity in the water-bath of 30 ℃ is 1.4dL/g.Another take out 1.0 milliliters of polyamic acid solutions and carry out electrostatic spinning, the syringe needle diameter is 1.6 millimeters, and spinning voltage is 25.0 kilovolts, and needle point is 20 centimetres to the height of dash receiver, and Electrospun 2 hours obtains thickness and be the nano type polyamic acid nano fibrous membrane of 107 microns.This film is placed in the roll squeezer that pressure is 2 MPas stopped 10 minutes, obtain the polyamic acid nano fibrous membrane of 32 microns of thickness.Film after roll extrusion hot imidization progressively under the condition of gradient increased temperature, heating is converted into polyimides with polyamic acid under nitrogen atmosphere, to obtain the polyimide nano-fiber non-woven membrane.The temperature of heating is to keep under 150 ℃ 0.5 hour, keeps 0.5 hour under 200 ℃, keeps 1.0 hours lower 1.0 hours of 330 ℃ of conditions under 270 ℃ of conditions.
Embodiment 5
With 4.36 gram pyromellitic acid anhydrides, 4.97 diphenyl sulphone (DPS) diamines, 51.1 milliliters of N, the N-dimethylacetylamide joins in the four-hole boiling flask of 150 milliliters, then at 0～5 ℃ of lower stirring reaction of ice bath, the reaction time is 24 hours, obtains the polyamic acid solution (mass fraction is 15%) of homogeneous.After having reacted, polyamic acid solution is placed on 4 ℃ of preservations in refrigerator.Take out 1.6667 gram polyamic acid solutions in 50 milliliters of volumetric flasks, add DMA constant volume to 50 milliliter, be mixed with the solution of 0.0050 grams per milliliter, adopting Ubbelohde viscometer to measure its inherent viscosity in the water-bath of 30 ℃ is 1.73dL/g.Another take out 1.0 milliliters of polyamic acid solutions and carry out electrostatic spinning, the syringe needle diameter is 1.6 millimeters, and spinning voltage is 25.0 kilovolts, and needle point is 20 centimetres to the height of dash receiver, and Electrospun 2 hours obtains thickness and be the nano type polyamic acid nano fibrous membrane of 95 microns.This film is placed in the roll squeezer that pressure is 2 MPas stopped 10 minutes, obtain the polyamic acid nano fibrous membrane of 28 microns of thickness.Film after roll extrusion hot imidization progressively under the condition of gradient increased temperature, heating is converted into polyimides with polyamic acid under nitrogen atmosphere, to obtain the polyimide nano-fiber non-woven membrane.The temperature of heating is to keep under 150 ℃ 0.5 hour, keeps 0.5 hour under 200 ℃, keeps 1.0 hours lower 1.0 hours of 330 ℃ of conditions under 270 ℃ of conditions.
Embodiment 6
With 4.36 gram pyromellitic acid anhydrides, 2.16 gram p-phenylenediamine (PPD), 41.2 milliliters of N, the N-dimethylacetylamide joins in the four-hole boiling flask of 150 milliliters, then at 0～5 ℃ of lower stirring reaction of ice bath, the reaction time is 24 hours, obtains the polyamic acid solution (mass fraction is 15%) of homogeneous.After having reacted, polyamic acid solution is placed on 4 ℃ of preservations in refrigerator.Take out 1.6667 gram polyamic acid solutions in 50 milliliters of volumetric flasks, add DMA constant volume to 50 milliliter, be mixed with the solution of 0.0050 grams per milliliter, adopting Ubbelohde viscometer to measure its inherent viscosity in the water-bath of 30 ℃ is 1.32dL/g.Another take out 1.0 milliliters of polyamic acid solutions and carry out electrostatic spinning, the syringe needle diameter is 1.6 millimeters, and spinning voltage is 30 kilovolts, and needle point is 20 centimetres to the height of dash receiver, and Electrospun 2 hours obtains thickness and be the nano type polyamic acid nano fibrous membrane of 92 microns.This film is placed in the roll squeezer that pressure is 2 MPas stopped 10 minutes, obtain the polyamic acid nano fibrous membrane of 27 microns of thickness.Film after roll extrusion hot imidization progressively under the condition of gradient increased temperature, heating is converted into polyimides with polyamic acid under nitrogen atmosphere, to obtain the polyimide nano-fiber non-woven membrane.The temperature of heating is to keep under 150 ℃ 0.5 hour, keeps 0.5 hour under 200 ℃, keeps 1.0 hours lower 1.0 hours of 330 ℃ of conditions under 270 ℃ of conditions.
Embodiment 7
The operating procedure of embodiment 7 and embodiment 1 is substantially identical, and difference is that the polyamic acid spinning solution is kept to 0.5 milliliter, and the Electrospun time becomes 1 hour, obtains thickness and be the nano type polyamic acid nano fibrous membrane of 45 microns.This film is placed in the roll squeezer that pressure is 2 MPas stopped 10 minutes, obtain the polyamic acid nano fibrous membrane of 15 microns of thickness, other steps are with embodiment 1.
Embodiment 8
The operating procedure of embodiment 8 is substantially identical with embodiment 1, difference is to be the roll-in strength increase 5 MPas, the polyamide acid film of 98 micron thickness is placed in the roll squeezer that pressure is 5 MPas stopped 10 minutes, obtain the polyamic acid nano fibrous membrane of 21 microns of thickness, other steps are with embodiment 1.
Comparative Examples 1
Adopt business-like polyalkene diaphragm Celgard2400 as a comparison, further to illustrate the advantage of the polyimide-based nano fiber diaphragm described in the present invention.
Membrane properties in above-described embodiment 1-8 and Comparative Examples 1 is characterized:
Infrared spectrum: chemical constitution and the imidization degree of coming characterization of membrane with Fourier transformation infrared spectrometer (Nicolet iN10).
ESEM: observe the pattern in surface and the cross section of film with awkward silence at a meeting emission scan electron microscope (S-4800), the size of nanofiber and arrangement, and part pore size.
Gas permeability: adopt Gurley 4110N Permeability gauge (USA) to measure the gas permeability of membrane sample.
Film thickness: adopt the thickness of micrometer (0.01 millimeter of precision) test polyimide nanofiber membrane, 5 points on any sample thief, and average.
Porosity: adopt following method of testing, polyimide nanofiber membrane is immersed in n-butanol 2 hours, then calculate porosity according to formula:
Wherein, ρ
aAnd ρ
pThe density of n-butanol and the dry density of tunica fibrosa, m
aAnd m
pThe quality of the n-butanol that sucks of film and the quality of tunica fibrosa self.
TENSILE STRENGTH: the plastic tensile experimental method of employing GB1040-79 is tested TENSILE STRENGTH and the percentage elongation of polyimide nanofiber membrane.
Acquired results is listed in table 1.From the results shown in Table 1, adopt the polyimide nano-fiber non-woven membrane of method preparation provided by the invention to have high porosity, gas permeability and mechanical strength, meet lithium ion battery separator to the requirement in aperture, can find out from the test result of embodiment 1-8 and Comparative Examples 1, the anti-shrinkage factor of business-like polyalkene diaphragm and transverse tensile strength are all relatively poor.
The test battery performance
1) anodal preparation
At first with 5.75 gram positive active material LiCoO
2, 0.31 gram conductive agent acetylene black mixes, and then adding 6.39 gram mass marks is 5% Kynoar (PVDF) solution (solvent is METHYLPYRROLIDONE) again, stirs to form uniform anodal slip.
This slip is coated on aluminium foil uniformly, and it is that 12 millimeters and thickness are the circular positive plate of 80 microns that then oven dry under 120 ℃, roll-in, punching make radius, wherein contains 17.6 milligrams of active component LiCO
2
2) preparation of negative pole
With 4.74 gram negative electrode active material native graphites, 0.10 gram conductive agent acetylene black mixes, then adding 2.55 gram mass marks is 10% Kynoar (PVDF) solution (solvent is METHYLPYRROLIDONE) again, stirs to form uniform negative pole slip.
Cathode size is coated on Copper Foil equably, and it is that 14 millimeters and thickness are the circular negative plate of 70 microns that then oven dry under 120 ℃, roll-in, punching make radius, wherein contains the native graphite of 11.9 milligrams of active components.
3) with film preparation battery of the present invention
With positive pole obtained above, negative pole and barrier film be (battery size 2032) in lamination and the button cell of packing into successively, and described film is respectively the commercialization polyalkene diaphragm in polyimide nanofiber membrane and Comparative Examples 1 in embodiment 1-8.
To contain 1 mole of lithium hexafluoro phosphate (LiPF in mixed solvent (ethylene carbonate: the volume ratio of Methylethyl carbonic acid ester (EC/EMC) is 1: 1)
6) electrolyte approximately 150 milligrams inject above-mentioned batteries, and according to the conventional method ageing, the sealed cell aluminum hull namely obtains lithium rechargeable battery.
4) battery resistance to elevated temperatures test
Method of testing is as follows: battery is carried out 1C be charged to 100% Charging state, be placed in baking oven, oven temperature was elevated to 150 ℃ and 180 ℃ with 5/ minute from room temperature, and wherein cell voltage falls greater than 0.2 volt and is considered as short circuit.
5) battery life test
Method of testing is as follows: under 25 ± 5 ℃, battery is carried out cycle charge-discharge 250 times, record dump energy, dump energy is higher, and battery life is longer.
To be made into battery with commercialization barrier film in the obtained polyimide nanofiber membrane of embodiment 1-8 and Comparative Examples 1, and carry out battery resistance to elevated temperatures and life test according to above-mentioned method of testing, resulting the results are shown in Table 2.
From the results shown in Table 2, has better security performance and longer service life with polyimide nanofiber membrane of the present invention as the lithium ion battery that battery diaphragm prepares.
Table 1
Table 2
Claims (6)
1. polyimide-base nano fibrous membrane, the polyimide nano-fiber that is the 20-500 nanometer by diameter consists of, and the thickness of film is the 15-100 micron, and the air penetrability of film is 10-500 second; Film upper and lower surface and internal holes are distributed symmetrically and even, and average pore size is 100 nanometers, and TENSILE STRENGTH is the 100-250 MPa.
2. method for preparing polyimide-base nano fibrous membrane, adopt electrostatic spinning to carry out spinning to polyamic acid solution, this spinning uses 1-10 MPa machinery roll-in compacting after 5-30 minute, hot imidization is processed the polyamic acid in spinning is converted into polyimides, obtains polyimide nanofiber membrane;
Polyamic acid solution is to adopt binary organic acid acid anhydride and organic diamine to carry out the condensation reaction preparation in solvent, wherein the mol ratio of binary organic acid acid anhydride and organic diamine is 0.8-1.2, solvent adding amount be binary organic acid acid anhydride and organic diamine gross weight 4.5-10 doubly, the temperature of condensation reaction is 0-25 ℃.
3. preparation method according to claim 2, wherein, the spinning syringe needle internal diameter of electrostatic spinning is the 0.8-2.0 millimeter, and voltage is 100 volts-30 kilovolts, and syringe needle is 10-30 centimetre with the distance of accepting electrode, and the spinning solution flow is greater than 0.1 ml/hour.
4. preparation method according to claim 2, wherein, described binary organic acid acid anhydride is: pyromellitic acid anhydride, BPDA, benzophenone tetracarboxylic dianhydride, oxygen bibenzene tetracarboxylic dianhydride, bisphenol-A two ether dianhydrides or isopropyl diphenyl acid anhydride;
Described organic diamine is: 4,4 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, p-phenylenediamine (PPD), m-phenylene diamine (MPD), 3,3 '-diphenyl sulphone (DPS) diamines, 4, two [4-(4-amino-benzene oxygen) phenyl] propane of 4 '-diphenyl sulphone (DPS) diamines, isopropyl diphenyl amine, benzidine or 2,2-;
Described solvent is: DMA, 1-METHYLPYRROLIDONE, oxolane, metacresol or dimethyl sulfoxide (DMSO).
5. the preparation method described according to claim 2, wherein, polyimides has following structural formula
Wherein, A
1Aryl for following structure:
Described diamines can be to have NH
2-A
2-NH
2The diamines of the structure of expression, A
2Aryl for following structure;
Polymerization degree n is 50-10000, and the intrinsic viscosity of corresponding polyamic acid is the 1.0-3.0 deciliter/gram, and the heat decomposition temperature of polyimides is more than 420 ℃.
6. preparation method according to claim 2, wherein, it is to heat up at nitrogen, argon gas or vacuum condition Gradient that hot imidization is processed, gradient increased temperature is: 100-200 ℃ kept 0.5-1.5 hour, 180-250 ℃ kept 0.5-1.5 hour, 230-280 ℃ kept 0.5-1.5 hour, and 260-350 ℃ kept 0.5-1.5 hour.
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