CN1624952A - Polymer mould method for preparing diaphragm of fluorine-contained polymen lithium ion cell - Google Patents
Polymer mould method for preparing diaphragm of fluorine-contained polymen lithium ion cell Download PDFInfo
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- CN1624952A CN1624952A CNA2004100670086A CN200410067008A CN1624952A CN 1624952 A CN1624952 A CN 1624952A CN A2004100670086 A CNA2004100670086 A CN A2004100670086A CN 200410067008 A CN200410067008 A CN 200410067008A CN 1624952 A CN1624952 A CN 1624952A
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- Prior art keywords
- polymer
- film
- lithium ion
- fluoropolymer
- ion battery
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- 229920000642 polymer Polymers 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 14
- 239000000243 solution Substances 0.000 claims abstract description 38
- 238000002360 preparation method Methods 0.000 claims abstract description 29
- 229920001577 copolymer Polymers 0.000 claims abstract description 15
- 239000011521 glass Substances 0.000 claims abstract description 15
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 7
- 229920006254 polymer film Polymers 0.000 claims abstract description 6
- 238000005266 casting Methods 0.000 claims description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 20
- 230000004888 barrier function Effects 0.000 claims description 19
- 229920002313 fluoropolymer Polymers 0.000 claims description 16
- 239000004811 fluoropolymer Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000013019 agitation Methods 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- -1 carrene Chemical compound 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 159000000002 lithium salts Chemical class 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229960003511 macrogol Drugs 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 abstract description 9
- 239000012528 membrane Substances 0.000 abstract description 9
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000009415 formwork Methods 0.000 abstract 3
- 238000000465 moulding Methods 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000005213 imbibition Methods 0.000 abstract 1
- 238000000935 solvent evaporation Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 239000007789 gas Substances 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 14
- 229910052786 argon Inorganic materials 0.000 description 12
- 238000002386 leaching Methods 0.000 description 12
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- 230000004913 activation Effects 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 229940079593 drug Drugs 0.000 description 10
- 239000003814 drug Substances 0.000 description 10
- 230000008676 import Effects 0.000 description 10
- 238000012856 packing Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 3
- 238000002145 thermally induced phase separation Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 2
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 1
- 241000212978 Amorpha <angiosperm> Species 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229960002715 nicotine Drugs 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Cell Separators (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Secondary Cells (AREA)
Abstract
This invention discloses a polymer formwork method preparing F polymer lithium battery membrane. This invention adopts the low molecular weight as the polymer formwork, metafluoroethylene or its copolymer as the matrix of F polymer, make the thickness solution with different mixture ratio in different solutions under the temperature of 50deg.C--80deg.C; the molding fluid carries out sweep molding on the smooth glass plate, adopt solvent evaporation conversion process to make the polymer film; use extractant to extract polymer formwork under room temperature, then natural dry; activate in the electrolytic solution and get polymer electrolytic film. Using different preparation and extracting conditions to get different apertures and microporous membranes with different structures. This microporou membranes gained by this invention has the regular microporous structure, the porosity ratio is 50-70%, the average aperture is 0.5-3 mum, the imbibitions ration is 250-520%,and the conducting ratio is 10 to the power -3-10 to the power -2 S cm to the power -1 and can be used as the membrane of the secondary battery. This membrane can also be used as compart or supporting membrane.
Description
Technical field
The present invention relates to the preparation method of fluoropolymer lithium ion battery separator, relate in particular to a kind of polymer template method for preparing the fluoropolymer lithium ion battery separator.
Background technology
Along with the energy, information, Development of Materials, secondary lithium battery technology and associated materials thereof are also developed rapidly.Polymer Li-ion battery is compared with the liquid lithium ionic cell of present use, have that volume is little, light weight, the life-span is long, security performance is high and be easy to characteristics such as cell shapes design, can satisfy mobile phone and notebook computer etc. further to the requirement of miniaturization, lightweight development.In secondary lithium battery, micropore polymer diaphragm is the important component part of battery, and it places between the positive and negative electrode, play not only can make two electrodes as far as possible near but also can avoid the effect of both positive and negative polarity active material contact short circuit.The quality of membrane properties affects characteristics such as the internal resistance, charging and discharging currents density, cyclicity of battery, so the barrier film of excellent performance has great significance for the combination property that improves battery.
At present, the microporous barrier that widely used barrier film is produced for the Celgard method in the secondary lithium battery.US4,138,459; 3,801,404; 3,843,761 by melt extruding the thin polymer film that obtains having shish-kebab, and after heat treatment oriented film obtains microporous barrier.But being difficult to obtain the film of aperture homogeneous, this method make distance between electrodes increase the internal resistance that has increased battery.US4, strain rate and processing temperature in 994, the 335 strict control drawing process make it only produce micropore in one direction.The material that is adopted is polypropylene and polyethylene, degree of crystallinity height and polarity are little and be unfavorable for the swelling of electrolyte solution, only depend on the electrolyte conduction of embedding in the micropore, pick up is low, and polypropylene belongs to difficult sticking material, be unfavorable for bonding between positive and negative electrode, the interface combines not closely between barrier film and electrode, influences the energy density and the fail safe of battery.
Polymer dielectric film is often adopted in the following method preparation: (1) polymer, acetone, lithium salts electrolyte solution dissolve casting film behind the solution that obtains thickness together, this film bad mechanical strength, need physics or chemical crosslinking to improve intensity, in addition, because lithium salts is very sensitive to humidity, operation must be carried out under the condition of anhydrous and oxygen-free, has improved running cost.(2) immersion precipitation phase inversion.The homogeneous phase solution that polymer dissolution is obtained in solvent immerses in the non-solvent and is separated and film forming.If adopt organic solvent to do non-solvent, film forming is poor, and the film that obtains is very crisp, bad mechanical strength; The normal non-solvent that adopts is a water, but hydrolysis easily in the environment of lithium salts at water will be removed moisture content through reprocessing.(3) thermally induced phase separation (TIPS).US6,171,723 adopt the TIPS legal systems to be equipped with ultra-high molecular weight polyethylene (UHMWPE) microporous barrier, UHMWPE and diluent mineral oil are dissolved obtain the homogeneous phase melt under the temperature that is higher than more than the fusing point of UHMWPE, the cooling back is separated and film forming, will be microporous barrier after the diluent extraction.Regulate controllable parameters drilling footpath size and structures such as cooldown rate and polymer concentration.But there is cortex in resulting film, is difficult to obtain the film of symmetrical structure, the cost of manufacture height.(4) US5,460,904; 5,296,318; 5,429,891 adopt poly-(biasfluoroethylene-hexafluoropropylene) (PVDF-HFP), DBP and filler SiO
2Mix the back casting film, extractant activates with electrolyte after extracting Plasticizer DBP.But the pore structure that this method obtains is asymmetrical, and the aperture is a nanoscale, thereby has influence on barrier film influences battery to electrolytical liquid absorption electric conductivity.Thereby improving the porosity of barrier film, the aperture that increases barrier film, the symmetric membrane etc. that improves the mechanical strength of barrier film and obtain the pore-size distribution homogeneous is a developing direction of polymer electrolyte diaphragm technology of preparing.
Supercritical fluid is meant that the temperature and pressure when fluid is in its critical pressure and critical temperature when above, claims this fluid to be in supercriticality, distinguishes mutually with common liquids and gases and is called supercritical fluid.The interface of gas-liquid disappears when supercriticality, becomes the system of homogeneous.Supercritical fluid has the density close with liquid, thereby very strong solvent strength is arranged, and it has the viscosity close with gas simultaneously, makes it be easier to spread in polymer, and mass tranfer coefficient is big.In addition, the density of fluid and viscosity can be regulated by the variation of pressure and temperature, thereby supercritical fluid has purposes very widely.Inert gas CO commonly used
2Critical temperature be 31 ℃, 72.9 atmospheric pressure of critical pressure can be operated near normal temperature; It does not react with extract; Nonflammable, nontoxic and do not have the problem of residual gas.Overcritical or near critical CO
2Fluid has been used in and has removed nicotine (US4,675,198) from tobacco, extracted natural products fields such as (US5,009,746) from cellulose.
Summary of the invention
The purpose of this invention is to provide a kind of polymer template method for preparing the fluoropolymer lithium ion battery separator.The step of method is as follows:
1) solvent mechanical agitation in 50-80 ℃ water bath with thermostatic control of the template polymer of the fluorinated copolymer of 10-25wt%, 10-25wt% and 80-50wt% is obtained the casting solution of thickness;
2) solution cool to room temperature, vacuum filtration, deaeration is also removed impurity;
3) adopt scraper with the casting solution blade coating on the bright and clean glass plate, on nonwoven fabrics or the metallic substrates, volatilization is 0.5-8 hour under 25-80 ℃ temperature, obtains thin polymer film;
4) film with drying adopts extraction or direct supercritical CO in the extractant
2Template polymer is fallen in extraction, obtains smooth, white polymer micro barrier film after the drying.
Advantage of the present invention is:
(1) polymeric matrix adopts poly-(biasfluoroethylene-hexafluoropropylene) (PVDF-HFP) etc., not only chemical stability, electrochemical stability is good and mechanical strength is high, and its degree of crystallinity is on the low side, pars amorpha makes the electrolyte solution swelling and improves pick up, and crystalline portion makes after its film forming that intensity is higher not to need physical crosslinking or chemical crosslinking.
(2) polymer template and fluorinated copolymer film forming obtain the polymer micro barrier film after removing template, membrane structure from unsymmetric structure to the symmetrical structure scalable, the big and homogeneous in aperture, the porosity height, mechanical strength is higher.
(3) extraction of template polymer can be adopted extractant, also can adopt supercritical CO
2Extraction, template polymer separates easily and reclaims, and does not have residue, can not destroy the microstructure of polymer, and supercritical CO
2Nontoxic, non-corrosiveness, nonflammable, cheap and easy to get, have hypotoxicity and environment friendly.
Embodiment
Fluoropolymer of the present invention is: Kynoar, poly-(biasfluoroethylene-hexafluoropropylene), poly-(vinylidene-chlorotrifluoroethylene), poly-(vinylidene-ethene) or poly-(vinylidene-propylene).The low-molecular-weight template polymer is: polyethylene glycol oxide, polyvinylpyrrolidone, Macrogol 200, PEG400, Macrogol 600, polymethyl methacrylate or polyacrylonitrile.Organic solvent is: oxolane, acetone, butanone, N-N dimethylacetylamide, N-N dimethyl formamide, N-methyl pyrrolidone, N-N dimethyl sulfoxide (DMSO), triethyl phosphate, trimethyl phosphate or tetramethylurea.Extractant is: absolute methanol, absolute ethyl alcohol, isopropyl alcohol, n-butanol, cyclohexanol, chloroform, carrene, ethylene glycol, glycerol, toluene or butanediol.Lithium salts in the electrolyte solution is: lithium hexafluoro phosphate, hexafluoroarsenate lithium, LiBF4, lithium perchlorate or trifluoromethanesulfonic acid lithium.Organic solvent in the electrolyte solution is: ethylene carbonate, propene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate alkene ester, carbonic acid first propyl ester or 1,4-butyrolactone.
Contain fluorinated copolymer 10-25wt% in the casting solution, the volume ratio of low-molecular-weight template polymer and fluoropolymer 〉=50%.
Following embodiment is done more detailed description to the present invention, but described embodiment is not construed as limiting the invention.Determine performance described herein by following method.
(1) weight average molecular weight (Mw): measure according to the molecular weight of polystyrene by GPC.
GPC instrument: WATERS high performance liquid chromatograph pillar: GMHXL
Solvent: N, N-dimethylacetylamide temperature: 25 ℃
(2) extraction efficiency
Under the room temperature, with certain mass (m
1) and the size polymer film in extractant, extract 24h, be weighed as (m after the air dry
2), extraction efficiency is calculated as follows:
(3) porosity
Densimetry is measured.Cut out the film of certain size size after the microporous barrier drying, measure its length and width and thickness, claim quality, calculate the density (ρ of film thus
m).Density (the ρ of polymeric material
p) be 1.77g
Cm-3Porosity is calculated as follows:
(4) pick up
Under the room temperature, with certain mass (m
1) and the polymer film of size in electrolyte solution, soak 2h, take out the back and between two filter paper, remove the unnecessary electrolyte solution in striping surface gently, be weighed as m
3, be calculated as follows pick up:
Embodiment 1
Preparation 10wt% fluorinated copolymer PVDF-HFP (Aldrich, USA, Mw=4.5 * 10
5, Mn=1.3 * 10
5), the acetone soln of 10wt%PVP (K30, Shanghai chemical reagents corporation of Chinese Medicine group, import packing), mechanical agitation in 50 ℃ water bath with thermostatic control obtains the casting solution of thickness.Vacuum defoamation a few hours, and remove impurity.To bright and clean glass plate, scraper gap 140-500 μ m, sky expose to the sun complete to solvent evaporates in 50 ℃ of vacuumizes behind the 30s with the casting solution blade coating.Under the room temperature, the film of above-mentioned preparation is cut into rectangle, leaching is 24 hours in absolute ethyl alcohol.Adopt gravimetric method to calculate extraction efficiency behind the natural drying at room temperature.It is disconnected that resulting film is quenched in liquid nitrogen, adopts the structure of surface sweeping electron microscopic observation surface and section behind the vacuum metallizing.Cut out the film of certain size size after the microporous barrier drying, calculate the density (ρ of film
m).Density (the ρ of polymeric material
p) be 1.77gcm
-3Calculate porosity by formula (2).
In being full of the glove box of argon gas, moisture＜1ppm, O
2＜1ppm, with the film of known quality at 1MLiPF
6(1: activation is 2 hours 1v/v), film is taken out remove the unnecessary electrolyte in striping surface gently between two filter paper, and pick up is calculated in the back of weighing for/EC-DMC.Resulting film is the microcellular structure of symmetry, the about 3 μ m of average pore size, porosity 70%, pick up 514%.
Embodiment 2
Preparation 25wt% fluorinated copolymer PVDF-HFP (Aldrich, USA, Mw=4.5 * 10
5, Mn=1.3 * 10
5), the acetone soln of 25wt%PVP (K30, Shanghai chemical reagents corporation of Chinese Medicine group, import packing), mechanical agitation in 50 ℃ water bath with thermostatic control obtains the casting solution of thickness.Vacuum defoamation a few hours, and remove impurity.To bright and clean glass plate, scraper gap 140-500 μ m, sky expose to the sun complete to solvent evaporates in 50 ℃ of vacuumizes behind the 30s with the casting solution blade coating.Under the room temperature, the film of above-mentioned preparation is cut into rectangle, leaching is 24 hours in absolute ethyl alcohol.Behind the natural drying at room temperature in being full of the glove box of argon gas, moisture＜1ppm, O
2＜1ppm, with the film of known quality at 1MLiPF
6(1: activation is 2 hours 1v/v), film is taken out remove the unnecessary electrolyte in striping surface gently between two filter paper, and pick up is calculated in the back of weighing for/EC-DMC.
Embodiment 3
Poly-(biasfluoroethylene-hexafluoropropylene-tetrafluoroethene) (Aldrich, USA, Mw=4.5 * 10 of preparation 10wt% fluorinated copolymer
5, Mn=1.3 * 10
5), the acetone soln of 10wt%PVP (K30, Shanghai chemical reagents corporation of Chinese Medicine group, import packing), mechanical agitation in 50 ℃ water bath with thermostatic control obtains the casting solution of thickness.Vacuum defoamation a few hours, and remove impurity.To bright and clean glass plate, scraper gap 140-500 μ m, sky expose to the sun complete to solvent evaporates in 50 ℃ of vacuumizes behind the 30s with the casting solution blade coating.Under the room temperature, the film of above-mentioned preparation is cut into rectangle, leaching is 24 hours in absolute ethyl alcohol, natural drying at room temperature, and in being full of the glove box of argon gas, moisture＜1ppm, O
2＜1ppm, with the film of known quality at 1MLiPF
6(1: activation is 2 hours 1v/v), film is taken out remove the unnecessary electrolyte in striping surface gently between two filter paper, and pick up is calculated in the back of weighing for/EC-DMC.
Embodiment 4
Preparation 10wt%PVDF (Aldrich, USA, Mw=4.5 * 10
5, Mn=1.3 * 10
5), the acetone soln of 10wt%PVP (K30, Shanghai chemical reagents corporation of Chinese Medicine group, import packing), mechanical agitation in 50 ℃ water bath with thermostatic control obtains the casting solution of thickness.Vacuum defoamation a few hours, and remove impurity.To bright and clean glass plate, scraper gap 140-500 μ m, sky expose to the sun complete to solvent evaporates in 50 ℃ of vacuumizes behind the 30s with the casting solution blade coating.Under the room temperature, the film of above-mentioned preparation is cut into rectangle, leaching is 24 hours in absolute ethyl alcohol.Behind the natural drying at room temperature in being full of the glove box of argon gas, moisture＜1ppm, O
2＜1ppm, with the film of known quality at 1MLiPF
6(1: activation is 2 hours 1v/v), film is taken out remove the unnecessary electrolyte in striping surface gently between two filter paper, and pick up is calculated in the back of weighing for/EC-DMC
Embodiment 5
Preparation 10wt%PVDF-HFP (Aldrich, USA, Mw=4.5 * 10
5, Mn=1.3 * 10
5), the acetone soln of 10wt%PEG200, mechanical agitation in 50 ℃ water bath with thermostatic control obtains the casting solution of thickness.Vacuum defoamation a few hours, and remove impurity.To bright and clean glass plate, scraper gap 140-500 μ m, sky expose to the sun complete to solvent evaporates in 50 ℃ of vacuumizes behind the 30s with the casting solution blade coating.Under the room temperature, the film of above-mentioned preparation is cut into rectangle, leaching is 24 hours in absolute ethyl alcohol.In being full of the glove box of argon gas, moisture＜1ppm, O
2＜1ppm, with the film of known quality at 1MLiPF
6(1: activation is 2 hours 1v/v), film is taken out remove the unnecessary electrolyte in striping surface gently between two filter paper, and pick up is calculated in the back of weighing for/EC-DMC.
Embodiment 6
Preparation 10wt%PVDF-HFP (Aldrich, USA, Mw=4.5 * 10
5, Mn=1.3 * 10
5), the acetone soln of 10wt%PEG600, mechanical agitation in 50 ℃ water bath with thermostatic control obtains the casting solution of thickness.Vacuum defoamation a few hours, and remove impurity.To bright and clean glass plate, scraper gap 140-500 μ m, sky expose to the sun complete to solvent evaporates in 50 ℃ of vacuumizes behind the 30s with the casting solution blade coating.Under the room temperature, the film of above-mentioned preparation is cut into rectangle, leaching is 24 hours in absolute ethyl alcohol.In being full of the glove box of argon gas, moisture＜1ppm, O
2＜1ppm, with the film of known quality at 1MLiPF
6(1: activation is 2 hours 1v/v), film is taken out remove the unnecessary electrolyte in striping surface gently between two filter paper, and pick up is calculated in the back of weighing for/EC-DMC.
Embodiment 7
Preparation 10wt% fluorinated copolymer PVDF-HFP (Aldrich, USA, Mw=4.5 * 10
5, Mn=1.3 * 10
5), the tetrahydrofuran solution of 10wt%PVP (K30, Shanghai chemical reagents corporation of Chinese Medicine group, import packing), mechanical agitation in 50 ℃ water bath with thermostatic control obtains the casting solution of thickness.Vacuum defoamation a few hours, and remove impurity.To bright and clean glass plate, scraper gap 140-500 μ m, sky expose to the sun complete to solvent evaporates in 50 ℃ of vacuumizes behind the 30s with the casting solution blade coating.Under the room temperature, the film of above-mentioned preparation is cut into rectangle, leaching is 24 hours in absolute ethyl alcohol.In being full of the glove box of argon gas, moisture＜1ppm, O
2＜1ppm, with the film of known quality at 1MLiPF
6(1: activation is 2 hours 1v/v), film is taken out remove the unnecessary electrolyte in striping surface gently between two filter paper, and pick up is calculated in the back of weighing for/EC-DMC.
Embodiment 8
Preparation 10wt% fluorinated copolymer PVDF-HFP (Aldrich, USA, Mw=4.5 * 10
5, Mn=1.3 * 10
5), the triethyl phosphate solution of 10wt%PVP (K30, Shanghai chemical reagents corporation of Chinese Medicine group, import packing), mechanical agitation in 50 ℃ water bath with thermostatic control obtains the casting solution of thickness.Vacuum defoamation a few hours, and remove impurity.To bright and clean glass plate, scraper gap 140-500 μ m, sky expose to the sun complete to solvent evaporates in 50 ℃ of vacuumizes behind the 30s with the casting solution blade coating.Under the room temperature, the film of above-mentioned preparation is cut into rectangle, leaching is 24 hours in absolute ethyl alcohol.In being full of the glove box of argon gas, moisture＜1ppm, O
2＜1ppm, with the film of known quality at 1MLiPF
6(1: activation is 2 hours 1v/v), film is taken out remove the unnecessary electrolyte in striping surface gently between two filter paper, and pick up is calculated in the back of weighing for/EC-DMC.
Embodiment 9
Preparation 10wt% fluorinated copolymer PVDF-HFP (Aldrich, USA, Mw=4.5 * 10
5, Mn=1.3 * 10
5), the acetone soln of 10wt%PVP (K30, Shanghai chemical reagents corporation of Chinese Medicine group, import packing), mechanical agitation in 50 ℃ water bath with thermostatic control obtains the casting solution of thickness.Vacuum defoamation a few hours, and remove impurity.To bright and clean glass plate, scraper gap 140-500 μ m, sky expose to the sun complete to solvent evaporates in 50 ℃ of vacuumizes behind the 30s with the casting solution blade coating.Under the room temperature, the film of above-mentioned preparation is cut into rectangle, leaching is 24 hours in carrene.Behind the natural drying at room temperature in being full of the glove box of argon gas, moisture＜1ppm, O
2＜1ppm, with the film of known quality at 1MLiPF
6(1: activation is 2 hours 1v/v), film is taken out remove the unnecessary electrolyte in striping surface gently between two filter paper, and pick up is calculated in the back of weighing for/EC-DMC.
Embodiment 10
Preparation 10wt% fluorinated copolymer PVDF-HFP (Aldrich, USA, Mw=4.5 * 10
5, Mn=1.3 * 10
5), the acetone soln of 10wt%PVP (K30, Shanghai chemical reagents corporation of Chinese Medicine group, import packing), mechanical agitation in 50 ℃ water bath with thermostatic control obtains the casting solution of thickness.Vacuum defoamation a few hours, and remove impurity.To bright and clean glass plate, scraper gap 140-500 μ m, sky expose to the sun complete to solvent evaporates in 50 ℃ of vacuumizes behind the 30s with the casting solution blade coating.Under the room temperature, the film of above-mentioned preparation is cut into rectangle, leaching is 24 hours in toluene.After the microporous barrier drying in being full of the glove box of argon gas, moisture＜1ppm, O
2＜1ppm, with the film of known quality at 1MLiPF
6(1: activation is 2 hours 1v/v), film is taken out remove the unnecessary electrolyte in striping surface gently between two filter paper, and pick up is calculated in the back of weighing for/EC-DMC.
Embodiment 11
Preparation 10wt% fluorinated copolymer PVDF-HFP (Aldrich, USA, Mw=4.5 * 10
5, Mn=1.3 * 10
5), the acetone soln of 10wt%PVP (K30, Shanghai chemical reagents corporation of Chinese Medicine group, import packing), mechanical agitation in 50 ℃ water bath with thermostatic control obtains the casting solution of thickness.Vacuum defoamation a few hours, and remove impurity.To bright and clean glass plate, scraper gap 140-500 μ m, sky expose to the sun complete to solvent evaporates in 50 ℃ of vacuumizes behind the 30s with the casting solution blade coating.Under the room temperature, the film of above-mentioned preparation is cut into rectangle, leaching is 24 hours in absolute ethyl alcohol.After the microporous barrier drying in being full of the glove box of argon gas, moisture＜1ppm, O
2＜1ppm, with the film of known quality at 1MLiPF
6Activation is 2 hours among/DMC: DEC: EC (1: 1: the 1) v/v/v=, film is taken out remove the unnecessary electrolyte in striping surface gently between two filter paper, and pick up is calculated in the back of weighing.
Embodiment 12
Preparation 10wt% fluorinated copolymer PVDF-HFP (Aldrich, USA, Mw=4.5 * 10
5, Mn=1.3 * 10
5), the acetone soln of 10wt%PVP (K30, Shanghai chemical reagents corporation of Chinese Medicine group, import packing), mechanical agitation in 50 ℃ water bath with thermostatic control obtains the casting solution of thickness.Vacuum defoamation a few hours, and remove impurity.To bright and clean glass plate, scraper gap 140-500 μ m, sky expose to the sun complete to solvent evaporates in 50 ℃ of vacuumizes behind the 30s with the casting solution blade coating.Under the room temperature, the film of above-mentioned preparation is cut into rectangle, leaching is 24 hours in absolute ethyl alcohol.After the microporous barrier drying in being full of the glove box of argon gas, moisture＜1ppm, O
2＜1ppm exists the film of known quality
1MLiN (CF3SO2) 2,
/(1: activation is 2 hours 1v/v), film is taken out remove the unnecessary electrolyte in striping surface gently between two filter paper, and pick up is calculated in the back of weighing for EC-DMC.
Claims (8)
1. polymer template method for preparing the fluoropolymer lithium ion battery separator is characterized in that the step of method is as follows:
1) solvent mechanical agitation in 50-80 ℃ water bath with thermostatic control of the template polymer of the fluorinated copolymer of 10-25wt%, 10-25wt% and 80-50wt% is obtained the casting solution of thickness;
2) solution cool to room temperature, vacuum filtration, deaeration is also removed impurity;
3) adopt scraper with the casting solution blade coating on the bright and clean glass plate, on nonwoven fabrics or the metallic substrates, volatilization is 0.5-8 hour under 25-80 ℃ temperature, obtains thin polymer film;
4) film with drying adopts extraction or direct supercritical CO in the extractant
2Template polymer is fallen in extraction, obtains smooth, white polymer micro barrier film after the drying.
2. the polymer template method of preparation fluoropolymer lithium ion battery separator according to claim 1, it is characterized in that said fluoropolymer is: Kynoar, poly-(biasfluoroethylene-hexafluoropropylene), poly-(vinylidene-chlorotrifluoroethylene), poly-(vinylidene-ethene) or poly-(vinylidene-propylene).
3. a kind of polymer template method for preparing the fluoropolymer lithium ion battery separator according to claim 1, it is characterized in that said low-molecular-weight template polymer is: polyethylene glycol oxide, polyvinylpyrrolidone, Macrogol 200, PEG400, Macrogol 600, polymethyl methacrylate or polyacrylonitrile.
4. a kind of polymer template method for preparing the fluoropolymer lithium ion battery separator according to claim 1, it is characterized in that said organic solvent is: oxolane, acetone, butanone, N-N dimethylacetylamide, N-N dimethyl formamide, N-methyl pyrrolidone, N-N dimethyl sulfoxide (DMSO), triethyl phosphate, trimethyl phosphate or tetramethylurea.
5. a kind of polymer template method for preparing the fluoropolymer lithium ion battery separator according to claim 1, it is characterized in that said extractant is: absolute methanol, absolute ethyl alcohol, isopropyl alcohol, n-butanol, cyclohexanol, chloroform, carrene, ethylene glycol, glycerol, toluene or butanediol.
6. a kind of polymer template method for preparing the fluoropolymer lithium ion battery separator according to claim 1, it is characterized in that the lithium salts in the said electrolyte solution is: lithium hexafluoro phosphate, hexafluoroarsenate lithium, LiBF4, lithium perchlorate or trifluoromethanesulfonic acid lithium;
7. a kind of polymer template method for preparing the fluoropolymer lithium ion battery separator according to claim 1, it is characterized in that, organic solvent in the said electrolyte solution is: ethylene carbonate, propene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate alkene ester, carbonic acid first propyl ester or 1,4-butyrolactone.
8. a kind of polymer template method for preparing the fluoropolymer lithium ion battery separator according to claim 1, it is characterized in that: contain fluorinated copolymer 10-25wt% in the casting solution of said thickness, the volume ratio of low-molecular-weight template polymer and fluoropolymer 〉=50%.
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| CNB2004100670086A CN1327544C (en) | 2004-09-30 | 2004-09-30 | Polymer mould method for preparing diaphragm of fluorine-contained polymen lithium ion cell |
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|---|---|---|---|
| CNB2004100670086A CN1327544C (en) | 2004-09-30 | 2004-09-30 | Polymer mould method for preparing diaphragm of fluorine-contained polymen lithium ion cell |
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| CN101859046A (en) * | 2010-05-27 | 2010-10-13 | 天津大学 | Preparation method of polyvinylpyrrolidone-based solid electrolyte |
| CN1927921B (en) * | 2006-09-07 | 2011-08-31 | 浙江大学 | Lithium ion conducting gel film containing porous polymer framework and preparation method thereof |
| CN102324481A (en) * | 2011-09-23 | 2012-01-18 | 江苏华富储能新技术发展有限公司 | Composite diaphragm for lithium ion battery and preparation method thereof |
| CN102539516A (en) * | 2011-12-29 | 2012-07-04 | 山东东岳高分子材料有限公司 | Method for detecting metal ions in fluorine-containing polymers |
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| US5418091A (en) * | 1993-03-05 | 1995-05-23 | Bell Communications Research, Inc. | Polymeric electrolytic cell separator membrane |
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