CN102251307A - 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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- CN102251307A CN102251307A CN201110147725XA CN201110147725A CN102251307A CN 102251307 A CN102251307 A CN 102251307A CN 201110147725X A CN201110147725X A CN 201110147725XA CN 201110147725 A CN201110147725 A CN 201110147725A CN 102251307 A CN102251307 A CN 102251307A
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- polyimide
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- polyamic acid
- spinning
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- 239000012528 membrane Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229920001721 polyimide Polymers 0.000 claims abstract description 68
- 239000004642 Polyimide Substances 0.000 claims abstract description 66
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 10
- 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
- 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
- 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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-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
- 238000001523 electrospinning Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 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
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 4
- 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
- 239000000463 material Substances 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 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
- 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
- 239000002131 composite material Substances 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
- 238000011017 operating method Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 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
- 229920000642 polymer 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
- 239000000126 substance 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
- 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
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 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
- 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
- 229920002521 macromolecule Polymers 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
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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-based nano fibrous membrane.
The invention still further relates to the preparation method of above-mentioned polyimide-based nano fibrous membrane.
The invention still further relates to the application of above-mentioned polyimide-based nano fibrous membrane in lithium rechargeable battery.
Background technology
Lithium rechargeable battery is with its height ratio capacity, high voltage, and volume is little, in light weight, 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 appears in lithium ion battery easily, catches fire, blast, even cause potential safety hazard such as injury to personnel, make high power capacity and power lithium-ion battery also not have extensive use, thereby improve the key that lithium ion battery security can be 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 self-closing temperature again.In addition, behind 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 polyethylene (PE) commonly used now, (the self-closing temperature as the PE barrier film is 135-140 ℃ to polypropylene (PP) because fusion temperature is lower than 200 ℃, the self-closing temperature of PP barrier film is about 170 ℃), in some cases, for example external temperature is too high, excessive or the electrolyte of discharge current is subjected under the situation of the thermal inertia in the thermal process, even electric current is interdicted, the temperature of battery also might continue to raise, therefore barrier film may be destroyed fully 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 also than vertically going up the far short of what is expected of TENSILE STRENGTH, at battery lamination or be subjected to having the hidden danger of film rupture under the situation of 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 address that need, thereby need the better macromolecule diaphragm material of heat resistance.CN101000951A discloses a kind of preparation method of polyimide-based barrier film, it is the polycaprolactone of 1000-50000 that this 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 the preparation method of the polyimide-based barrier film of a kind of high strength, has added inorganic crystal whisker or positive esters of silicon acis in prescription in addition.The whisker that is added 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 the 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 a hydrochloric acid, aqueous sulfuric acid or phosphate aqueous solution etc.The polyamide acid film that forms 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 the preparation method of a kind of lithium rechargeable battery with polyimide-based porous septum, the pore-forming material 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 this method preparation, yield rate height.CN101752540A discloses the polyimide-based porous septum of a kind of lithium rechargeable battery, and this barrier film comprises first surface, second surface, and the 3rd surface, and the duct in three surfaces is tortuous mutually connects.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 the porous polyimide film that polyamic acid solution film and polyolefin porous film lamination composite methods commonly used is obtained the 0.01-10 micron.This polyimide diaphragm is still dangerous when high temperature.
Nearly ten years, because the fast development of nanometer technology, electrostatic spinning technique also causes countries in the world researcher's concern, and becomes gradually and use to such an extent that the most generally produce the method for nanofiber in the world, 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 ℃).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, adopts solvent exchange or the hot perforated membrane that volatilizees the pore-forming material and be prepared into then, and such film is a kind of typical anisotropic membrane, and promptly 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-based nano fibrous membrane.
Another purpose of the present invention is to provide a kind of method for preparing above-mentioned polyimide-based nano fibrous membrane.
For achieving the above object, polyimide-based nano fibrous membrane provided by the invention is that the polyimide nano-fiber of 20-500 nanometer constitutes by diameter, 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-based nano fibrous membrane of preparation provided by the invention, adopt electrostatic spinning that polyamic acid solution is carried out spinning, this spinning with mechanical roll-in compacting after, hot imidization is handled the polyamic acid in the 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 milliliter/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), 4,4 '-diphenyl sulphone (DPS) diamines (SDA), isopropyl diphenyl amine (IPDA), benzidine (BPDA) or 2, two [4-(4-amino-benzene oxygen) phenyl] propane (BAPP) of 2-;
Described solvent is: N,N-dimethylacetamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, 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 gradient increased temperature under nitrogen, argon gas or vacuum condition that hot imidization is handled, 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-based nano fibrous membrane of method of electrostatic spinning preparation to belong to symmetric membrane, pore structure and being evenly distributed, and it is easy to prepare, be suitable for producing in batches, the heat resistance height can be used as lithium ion battery separator, even this barrier film is under 150 ℃ of high temperature simultaneously, battery can not be short-circuited yet, thereby polyimide-based nano fibrous membrane provided by the invention can be used in high power capacity and the electrokinetic cell.
Description of drawings
Fig. 1 is the electron micrograph (before the roll-in) of polyamic acid nano fibrous membrane among the embodiment 1.
Fig. 2 is the electron micrograph (after the 2 MPa roll-ins) of polyimide nanofiber membrane among the embodiment 1.
Fig. 3 is the electron micrograph (after the 5 MPa roll-ins) of polyimide nanofiber membrane among the 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, the TENSILE STRENGTH height, 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 take place at 150 ℃.
The present invention prepares the method for polyimide nanofiber membrane, is to adopt high-voltage electrostatic spinning that polyamic acid is carried out the nanometer spinning earlier, uses mechanical roll-in compacting then, and at high temperature hot imidization prepares polyimide film at last.
Polyimide nanofiber membrane of the present invention can be used in the lithium rechargeable battery, this battery comprises electrode group and nonaqueous electrolytic solution, electrode group and nonaqueous electrolytic solution are sealed in the battery case, the electrode group comprises positive pole, negative pole and barrier film, and wherein used barrier film is a polyimide nanofiber membrane of the present invention.
Battery membranes provided by the invention is owing to adopt 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 invention is heated to 350 ℃ of high temperature and also can break; Battery diaphragm at 150 ℃ percent thermal shrinkage less than 0.5%, all be not more than 1.5% at 300 ℃ percent thermal shrinkages, 3% and 5% percent thermal shrinkage in the prior art, pierce through the pierce through intensity of intensity greater than battery diaphragm in the 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 the electrokinetic cell.
Preferentially adopt binary organic acid acid anhydride and organic diamine to carry out condensation reaction in the 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 N,N-dimethylacetamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, 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 the 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 among the present invention can be the polymer that contains imide group in the various repetitives of this area routine, and under the 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 the 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 milliliter/hour, is controlled at 0.1-1 milliliter/hour more suitable.
The polyamic acid nano fibrous membrane for preparing under the above-mentioned condition is carried out mechanical rod press processing, rod pressure degree 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 the above-mentioned roll-in, at nitrogen, heating is converted into polyimides with polyamic acid under argon gas or the vacuum, to obtain polyimide nano-fiber nonwoven fabric barrier film.The temperature of heating is 100-200 ℃ and kept 0.5-1.5 hour down that 180-250 ℃ kept 0.5-1.5 hour down, keeps 0.5-1.5 hour under the 260-350 ℃ of condition 0.5-1.5 hour under the 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 150 milliliters the four-hole boiling flask, at 0～5 ℃ of following stirring reaction of ice bath, the reaction time is 24 hours then, obtains the polyamic acid solution (mass fraction is 15%) of homogeneous.After having reacted, polyamic acid solution is placed on 4 ℃ of preservations in the refrigerator.Take out 1.6667 gram polyamic acid solutions in 50 milliliters of volumetric flasks, add N,N-dimethylacetamide 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 30 ℃ water-bath is 2.11dL/g.Other takes out 1.0 milliliters of polyamic acid solutions and carries out electrostatic spinning, and 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 electrospinning silk 2 hours obtains thickness and be 98 microns polyamic acid nano fibrous membrane.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 150 ℃ and kept 0.5 hour down that 200 ℃ kept 0.5 hour down, keeps 1.0 hours following 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 150 milliliters the four-hole boiling flask, at 0～5 ℃ of following stirring reaction of ice bath, the reaction time is 24 hours then, obtains the polyamic acid solution (mass fraction is 15%) of homogeneous.After having reacted, polyamic acid solution is placed on 4 ℃ of preservations in the refrigerator.Take out 1.6667 gram polyamic acid solutions in 50 milliliters of volumetric flasks, add N,N-dimethylacetamide 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 30 ℃ water-bath is 1.89dL/g.Other takes out 1.0 milliliters of polyamic acid solutions and carries out electrostatic spinning, and 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 electrospinning silk 2 hours obtains thickness and be 107 microns nano type polyamic acid nano fibrous membrane.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 150 ℃ and kept 0.5 hour down that 200 ℃ kept 0.5 hour down, keeps 1.0 hours following 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 150 milliliters the four-hole boiling flask, at 0～5 ℃ of following stirring reaction of ice bath, the reaction time is 24 hours then, obtains the polyamic acid solution (mass fraction is 15%) of homogeneous.After having reacted, polyamic acid solution is placed on 4 ℃ of preservations in the refrigerator.Take out 1.6667 gram polyamic acid solutions in 50 milliliters of volumetric flasks, add N,N-dimethylacetamide 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 30 ℃ water-bath is 1.49dL/g.Other takes out 1.0 milliliters of polyamic acid solutions and carries out electrostatic spinning, and 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 electrospinning silk 2 hours obtains thickness and be 90 microns nano type polyamic acid nano fibrous membrane.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 150 ℃ and kept 0.5 hour down that 200 ℃ kept 0.5 hour down, keeps 1.0 hours following 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 150 milliliters the four-hole boiling flask, at 0～5 ℃ of following stirring reaction of ice bath, the reaction time is 24 hours then, obtains the polyamic acid solution (mass fraction is 15%) of homogeneous.After having reacted, polyamic acid solution is placed on 4 ℃ of preservations in the refrigerator.Take out 1.6667 gram polyamic acid solutions in 50 milliliters of volumetric flasks, add N,N-dimethylacetamide 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 30 ℃ water-bath is 1.4dL/g.Other takes out 1.0 milliliters of polyamic acid solutions and carries out electrostatic spinning, and 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 electrospinning silk 2 hours obtains thickness and be 107 microns nano type polyamic acid nano fibrous membrane.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 150 ℃ and kept 0.5 hour down that 200 ℃ kept 0.5 hour down, keeps 1.0 hours following 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 150 milliliters the four-hole boiling flask, at 0～5 ℃ of following stirring reaction of ice bath, the reaction time is 24 hours then, obtains the polyamic acid solution (mass fraction is 15%) of homogeneous.After having reacted, polyamic acid solution is placed on 4 ℃ of preservations in the refrigerator.Take out 1.6667 gram polyamic acid solutions in 50 milliliters of volumetric flasks, add N,N-dimethylacetamide 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 30 ℃ water-bath is 1.73dL/g.Other takes out 1.0 milliliters of polyamic acid solutions and carries out electrostatic spinning, and 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 electrospinning silk 2 hours obtains thickness and be 95 microns nano type polyamic acid nano fibrous membrane.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 150 ℃ and kept 0.5 hour down that 200 ℃ kept 0.5 hour down, keeps 1.0 hours following 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 150 milliliters the four-hole boiling flask, at 0～5 ℃ of following stirring reaction of ice bath, the reaction time is 24 hours then, obtains the polyamic acid solution (mass fraction is 15%) of homogeneous.After having reacted, polyamic acid solution is placed on 4 ℃ of preservations in the refrigerator.Take out 1.6667 gram polyamic acid solutions in 50 milliliters of volumetric flasks, add N,N-dimethylacetamide 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 30 ℃ water-bath is 1.32dL/g.Other takes out 1.0 milliliters of polyamic acid solutions and carries out electrostatic spinning, and 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 electrospinning silk 2 hours obtains thickness and be 92 microns nano type polyamic acid nano fibrous membrane.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 150 ℃ and kept 0.5 hour down that 200 ℃ kept 0.5 hour down, keeps 1.0 hours following 1.0 hours of 330 ℃ of conditions under 270 ℃ of conditions.
Embodiment 7
The operating procedure of embodiment 7 and embodiment 1 is identical substantially, and difference is that the polyamic acid spinning solution is kept to 0.5 milliliter, and the electrospinning silk time becomes 1 hour, obtains thickness and be 45 microns nano type polyamic acid nano fibrous membrane.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 identical substantially with embodiment 1, difference is that roll-in intensity is increased to 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 the foregoing description 1-8 and the Comparative Examples 1 is characterized:
Infrared spectrum: the chemical constitution and the imidization degree of coming characterization of membrane with Fourier transformation infrared spectrometer (Nicolet iN10).
ESEM: observe the pattern in the surface and the cross section of film, the size of nanofiber and arrangement, and part pore size with awkward silence at a meeting emission scan electron microscope (S-4800).
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 the n-butanol 2 hours, calculate porosity according to formula then:
Wherein, ρ
aAnd ρ
pBe the density of n-butanol and the dry density of tunica fibrosa, m
aAnd m
pBe the 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 the TENSILE STRENGTH and the percentage elongation of polyimide nanofiber membrane.
Gained the results are shown in table 1.From the result of table 1 as can be seen, 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 the requirement of lithium ion battery separator to the aperture, from the test result of embodiment 1-8 and Comparative Examples 1 as can be seen, anti-shrinkage factor of business-like polyalkene diaphragm and transverse tensile strength are all relatively poor.
The test battery performance
1) Zheng Ji preparation
At first with 5.75 gram positive active material LiCoO
2, 0.31 gram conductive agent acetylene black mixes, and then adds 6.39 gram mass marks again and be 5% Kynoar (PVDF) solution (solvent is the N-N-methyl-2-2-pyrrolidone N-), stirs the uniform anodal slip of formation.
This slip is coated on the aluminium foil uniformly, and it is that 12 millimeters and thickness are 80 microns circular positive plate that 120 ℃ of down oven dry then, 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 add 2.55 gram mass marks again and be 10% Kynoar (PVDF) solution (solvent is the N-N-methyl-2-2-pyrrolidone N-), stir and form uniform negative pole slip.
Cathode size is coated on the Copper Foil equably, and then 120 ℃ of down oven dry, it is that 14 millimeters and thickness are 70 microns circular negative plate that 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 the above-mentioned positive pole that obtains, 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 the polyimide nanofiber membrane and Comparative Examples 1 among the embodiment 1-8.
To contain 1 mole of lithium hexafluoro phosphate (LiPF in the mixed solvent (ethylene carbonate: the volume ratio of Methylethyl carbonic acid ester (EC/EMC) is 1: 1)
6) electrolyte inject above-mentioned batteries for about 150 milligrams, and according to the conventional method ageing, the sealed cell aluminum hull promptly 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 the 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, and the record dump energy, dump energy is high more, and battery life is long more.
To be made into battery with commercialization barrier film in obtained polyimide nanofiber membrane of embodiment 1-8 and the 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 result of table 2 as can be seen, has better security performance and longer service life with polyimide nanofiber membrane of the present invention as the lithium ion battery of battery diaphragm preparation.
Table 1
Table 2
Claims (8)
1. polyimide-based nano fibrous membrane is that the polyimide nano-fiber of 20-500 nanometer constitutes by diameter, 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-based nano fibrous membrane, adopt electrostatic spinning that polyamic acid solution is carried out spinning, this spinning with mechanical roll-in compacting after, hot imidization is handled the polyamic acid in the 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 milliliter/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, to benzene two, m-phenylene diamine (MPD), 3,3 '-diphenyl sulphone (DPS) diamines, 4,4 '-diphenyl sulphone (DPS) diamines, isopropyl diphenyl amine, benzidine or 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-;
Described solvent is: N,N-dimethylacetamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, oxolane, metacresol or dimethyl sulfoxide (DMSO).
5. according to the preparation method described in the 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 heat decomposition temperature is more than 420 ℃.
6. preparation method according to claim 2, wherein, the intensity of mechanical roll-in is the 1-10 MPa, the time of staying was at 5-30 minute.
7. preparation method according to claim 2, wherein, it is gradient increased temperature under nitrogen, argon gas or vacuum condition that hot imidization is handled, 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.
8. the application of the described polyimide-based nano fibrous membrane of claim 1 in lithium rechargeable battery.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030089657A (en) * | 2003-10-06 | 2003-11-22 | 양갑승 | Preparation of activated polyimide-based carbon nanofiber electrode for supercapacitor by electrospinning and its application |
| JP2004308031A (en) * | 2003-04-03 | 2004-11-04 | Teijin Ltd | Polyamic acid nonwoven fabric, polyimide nonwoven fabric obtained from the same and methods for producing those |
| CN101139746A (en) * | 2006-09-04 | 2008-03-12 | 哈尔滨理工大学 | Method for preparing polyimide (PI) non-woven fabric |
| CN101473080A (en) * | 2006-06-22 | 2009-07-01 | 东洋纺织株式会社 | Polyimide nonwoven fabric and process for production thereof |
| CN101603213A (en) * | 2008-11-12 | 2009-12-16 | 苏州大学 | Polyimide nano-fiber and preparation method thereof |
| CN101974828A (en) * | 2010-09-30 | 2011-02-16 | 江西先材纳米纤维科技有限公司 | Copolymerized polyimide nanofiber nonwoven and preparation method and application thereof |
-
2011
- 2011-05-30 CN CN201110147725XA patent/CN102251307B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004308031A (en) * | 2003-04-03 | 2004-11-04 | Teijin Ltd | Polyamic acid nonwoven fabric, polyimide nonwoven fabric obtained from the same and methods for producing those |
| KR20030089657A (en) * | 2003-10-06 | 2003-11-22 | 양갑승 | Preparation of activated polyimide-based carbon nanofiber electrode for supercapacitor by electrospinning and its application |
| CN101473080A (en) * | 2006-06-22 | 2009-07-01 | 东洋纺织株式会社 | Polyimide nonwoven fabric and process for production thereof |
| CN101139746A (en) * | 2006-09-04 | 2008-03-12 | 哈尔滨理工大学 | Method for preparing polyimide (PI) non-woven fabric |
| CN101603213A (en) * | 2008-11-12 | 2009-12-16 | 苏州大学 | Polyimide nano-fiber and preparation method thereof |
| CN101974828A (en) * | 2010-09-30 | 2011-02-16 | 江西先材纳米纤维科技有限公司 | Copolymerized polyimide nanofiber nonwoven and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| 《合成纤维》 20070225 王岩等 静电纺聚酰亚胺非织造布的制备与表征 5-7,11 1-8 , 第02期 * |
| 《弹性体》 20090225 胡建聪 高压静电纺丝法制备聚酰亚胺超细纤维无纺布膜 35-37 1-8 第19卷, 第01期 * |
| 《江西师范大学学报(自然科学版)》 20070715 王素琴等 聚酰亚胺纳米纤维碳化及其储电性能研究 331-335 1-8 第31卷, 第04期 * |
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