CN101552327A - Preparing of composite polymer modified diaphragm containing shape selectivity molecular sieve filling agent - Google Patents
Preparing of composite polymer modified diaphragm containing shape selectivity molecular sieve filling agent Download PDFInfo
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- CN101552327A CN101552327A CNA2009100433685A CN200910043368A CN101552327A CN 101552327 A CN101552327 A CN 101552327A CN A2009100433685 A CNA2009100433685 A CN A2009100433685A CN 200910043368 A CN200910043368 A CN 200910043368A CN 101552327 A CN101552327 A CN 101552327A
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- composition polymer
- diaphragm
- polymer modified
- modified diaphragm
- molecular sieve
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Polymer modified diaphragm preparation, using polyolefin as principle material to prepare modified matrix membrane, the polyolefin material is added with 20-80% hydroscopicity resin, using the T-shape membrane method single screw rod of the melting express method to expressing shape and getting the polyolefin modified membrane. Then coating the composite polymer material containing shape selectivity molecular sieve filling agent onto the polyolefin modified matrix membrane wo prepare composite polymer modified membrane. The hydroscopicity resin used not only improves pore size distribution in diaphragm and the hydrophilic group improves diaphragm wettability and interface property, the shape selectivity molecular sieve used can not only make acid-base reaction with O via louis acid site on the surface, reducing the force between them and the L1 [+], and make the anion with relative larger radius difficult to transmit via pipes because of regulartwo-dimension cross pore, and improving migration volume of the L1 [+]. The method assures mechanical property of the diaphragm and improves interface property of the diaphragm, and at the moment of strengthening membrane fluid absorption capacity and improving electric conductivity, avoiding the extraction step.
Description
Technical field
The present invention relates to a kind of preparation method of polymer Li-ion battery composition polymer modified diaphragm
Background technology
Characteristics such as green secondary lithium battery is with its excellent electric performance and nuisanceless, and security performance is good, development is exceedingly fast, and becomes the focus of novel power supply technical research in recent years.Common lithium rechargeable battery by just/negative material, electrolyte, barrier film and battery case packaging material form.Barrier film is the important component part of liquid lithium ion secondary cell, in battery, play and just preventing/the negative pole short circuit, the effect of ion transportation electric channel is provided in charge and discharge process simultaneously, its performance has determined interfacial structure, internal resistance of battery etc., directly influence the characteristics such as capacity, cycle performance and security performance of battery, the barrier film of excellent performance has important effect to the combination property that improves battery.The lithium ion battery separator of existing marketization still based on the polyalkene diaphragm of polyethylene, polypropylene, comprises individual layer PE, individual layer PP, three layers of PP/PE/PP composite membrane.Because polyethylene, microporous polypropylene membrane have higher porosity, lower resistance, high tear resistance, antiacid alkali ability, better elastic and to the maintenance performance of aprotic solvent preferably.Patent US in 1970 Patent3426754 of U.S. Celanse company is used to produce the polypropylene porous film of individual layer.This technology is very ripe in the U.S., Japan through the development of decades, and U.S. Celgard company, Japanese UBE company adopt this kind explained hereafter individual layer PP, PE and three layers of PP/PE/PP composite membrane now.In the existing widely used Celgard method, patent US4138459,3801404,3843761 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 interelectrode distance increase the internal resistance that has increased battery.Generally speaking, polyethylene, polypropylene diaphragm are relatively poor to the electrolyte compatibility, and imbibition ability is low, causes the battery conductance rate low.The appearance of polymer dielectric makes poly-lithium battery have high-energy-density and long circulation life, self discharge is low, no leakage, characteristics such as fail safe is good, U.S. Bellcore Communication Studies institute has announced patent US5460904 in 1994,5296318, the preparation method of membrane for polymer in 5429891: the PVDF-HFP copolymer is dissolved in acetone or N-methyl pyrrolidone or both mixed liquors, add a certain amount of plasticizer, the gas phase inorganic powder, the furnishing pasty state is coated with to substrate or coating machine with the scraper blade coating then, extract plasticizer behind the evaporating solvent, drying makes the Bellcore barrier film.Compare polyalkene diaphragm, good imbibition liquid-keeping property is arranged, the higher and better mechanical property of conductivity, this makes poly-lithium battery have good prospect.But,, can introduce impurity and cause film mechanical performance variation owing to need the extraction plasticizer.Complicated step makes that again production cost improves greatly.
Summary of the invention
The object of the present invention is to provide a kind of mechanical strength height, the wetting property composition polymer modified diaphragm that is compounded to form of modified matrix film and the composite polymeric materials with high conductivity preferably.
1, the said composition polymer modified diaphragm of the present invention is made up of modified matrix film and composition polymer.Modification basement membrane component is polyolefine material and water-absorbing resins material; The composition polymer component is polymeric material and " selecting shape " molecular sieve filling.
Said polyolefine material is optional from polyethylene powder, polypropylene powder, ethane-acetic acid ethyenyl copolymer or both mixtures wherein.
Said water-absorbing resins material can be selected from Aqua keep 4S, Aqua keep 10SH, PVAB-I, PVAB-II, PVACMA-I, SGP5025 etc.
Said polymeric material is optional from polyethylene glycol oxide (PEO), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), poly-inclined to one side fluorine vinyl chloride (PVDF), biasfluoroethylene-hexafluoropropylene (VF2-HFP) etc.
Said " selecting shape " molecular sieve filling can be selected from ZSM-5, ZSM-35, ZSM-57, silicon zeolite etc.
2, the said composition polymer modified diaphragm of the present invention preparation method is:
1), be that 20% ~ 80% water-absorbing resins mixed material adds in the extruder with polyolefine material and consumption, through melt extruding, the cooling back is rolled into flat film in the T pattern, make the modified matrix film through simple tension.
2) molecular sieve filling is scattered in the solvent will " to select shape ", is stirred to be uniformly dispersed, and adds polymeric material again and makes its dissolving, gets the gel composition polymer.
3) composition polymer is coated with, floods or is sprayed at modified matrix film surface.
4) solvent final vacuum drying is removed in thermal evaporation, obtains the composition polymer modified diaphragm.
Said to melt extrude temperature be 150 ℃～300 ℃ as step 1.
As the said T pattern of step 1 roll-in temperature is 50 ℃～150 ℃.
As the said simple tension speed of step 1 is 0.3 meter～8 meters/minute, and diaphragm thickness is 15～45 microns.
As the said solvent of step 2 is one or both and above mixed liquor among acetone, oxolane, ethyl acetate, NMP or the DMP.
As step 2 said " selecting shape " molecular sieve is ZSM-5, ZSM-35, ZSM-57, silicon zeolite etc.
As step 2 said " selecting shape " molecular sieve filling consumption is 1%～50%.
Description of drawings
With ZSM-5 is example, and the ZSM-5 molecular sieve is the synthetic novel crystallization Si-Al zeolite of template by containing organic ammonium cation, and structure cell consists of NanAlnSi98-nO19216H2O.N is the former in number of aluminium in the structure cell in the formula, can be typically about 3 from 0～27.Lewis acid position and the O generation acid-base function on surface weakens the active force between they and the LI+, thereby discharges more LI
+The ZSM-5 structure is by a large amount of five-membered rings be connected (Fig. 1,2).Have rule two dimension intersection duct straight channel 0.53*0.56nm, Z-shaped passage 0.51*0.55nm (Fig. 3) can make the less lithium ion of diameter freely pass through, and make the relatively large anion of radius be difficult to pass through pipeline transmission.The more important thing is that its two-dimentional duct has increased the approach of ion transfer, inorganic fillers such as relative SiO2, the adding of ZSM-5 molecular sieve is less to the porosity influence of film.Wherein:
Fig. 1 is the feature structure of ZSM-5.
Fig. 2 is the skeleton structure of ZSM-5.
Fig. 3 is the connection diagram of ZSM-5, contains two groups of channel system of intersecting: one group is the sinusoidal duct that trend is parallel to (001) crystal face, and another group is the linear duct that is parallel to (010) crystal face.The aperture is a ten-ring, and ovalize, major axis are 0.6nm-0.9nm, and minor axis is 0.55nm.
Embodiment
Embodiment 1
With polyethylene and amount ratio is that 20%, model is in the water-absorbing resins mixed material adding extruder of Aqua keep 4S, melt extrude through 150 ℃, cooling back temperature in T pattern roll-in form flat film, is delivered to one-way stretcher to flat film with 0.3 meter/minute drawing and forming under 60 ℃.ZSM-5 molecular sieve filling with 5% is scattered in the 5ml acetone solvent, and the polyethylene oxide polymer of adding 95% is dissolved into the gel composition polymer.Composition polymer is coated modified matrix film surface.Vacuumize in drying box behind 80 ℃ of thermal evaporations removal solvents obtains the composition polymer modified diaphragm.
Embodiment 2～4
By the method preparation identical with embodiment 1, just polyethylene is different with Aqua keep 4 water-absorbing resins amount ratios, and water-absorbing resins accounts for 30%, 40%, 50% respectively, obtains the composition polymer modified diaphragm under the same terms.
Embodiment 5
Fixedly polyethylene and water-absorbing resins amount ratio get the modified matrix film with 5 meters/minute drawing and formings.ZSM-5 molecular sieve filling with 10% is scattered in the 5ml acetone solvent, and the polyethylene oxide polymer of adding 90% is dissolved into the gel composition polymer.Composition polymer is coated modified matrix film surface.Vacuumize in drying box behind 100 ℃ of thermal evaporations removal solvents obtains the composition polymer modified diaphragm.
Embodiment 6
By the method preparation identical with embodiment 5, just polymer is poly-inclined to one side fluorine vinyl chloride.The same terms is preparation composition polymer modified diaphragm down.
Embodiment 7～10
With polyethylene and amount ratio is that 30%, model is in the water-absorbing resins mixed material adding extruder of Aqua keep 4S, through melt extruding, cooling back temperature in T pattern roll-in form flat film, is delivered to the one-way stretcher drawing and forming to flat film under 60 ℃ ~ 120 ℃.Respectively 20%, 30%, 40%, 50% ZSM-5 molecular sieve filling is scattered in the DMP solvent, add corresponding ratio: 50%, 40%, 30%, 30% poly-inclined to one side fluorine vinyl chloride-base polymer is dissolved into the gel composition polymer.Composition polymer is coated modified matrix film surface.Vacuumize in drying box behind the thermal evaporation removal solvent obtains the composition polymer modified diaphragm.
Claims (10)
1, a kind of composition polymer modified diaphragm is characterized in that the composition polymer modified diaphragm is made up of modified matrix film and composition polymer.Composition polymer is present in the surface and hole of matrix barrier film through coating, dipping or spraying, is combined into an integral body with the matrix barrier film, becomes the composition polymer modified diaphragm.
2, composition polymer modified diaphragm as claimed in claim 1 is characterized in that said modified matrix film is that main material doping water-absorbing resins is prepared from through melt extruding by polyolefin.
3, composition polymer modified diaphragm as claimed in claim 2 is characterized in that said polyolefine material is polyethylene powders, polypropylene powder, ethane-acetic acid ethyenyl copolymer or both mixtures wherein.
4, composition polymer modified diaphragm as claimed in claim 2, it is characterized in that said water-absorbing resins is Powdered, consist of crosslinked salt polyacrylate, sex change PVA, vinyl alcohol acrylates block copolymer, starch-grafted acrylonitrile saponification hydrolysate, its model is one or more of Aqua keep 4S, Aqua keep 10SH, PVAB-I, PVAB-II, PVACMA-I, SGP5025 etc.
5, modified matrix film as claimed in claim 2, it is characterized in that said preparation method is: with polyolefine material and amount ratio is that 20%～80% water-absorbing resins mixed material adds in the extruder, through melt extruding, cooling back temperature in T pattern roll-in form flat film, is delivered to the one-way stretcher drawing and forming to flat film under 50 ℃～150 ℃.
6, the preparation of composition polymer modified diaphragm as claimed in claim 1 is characterized in that said composition polymer is by mix " selecting shape " molecular sieve filling and making of polymeric material.
7, the preparation of composition polymer modified diaphragm as claimed in claim 5 is characterized in that the said polymer material is polyethylene glycol oxide (PEO), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), poly-inclined to one side fluorine vinyl chloride (PVDF), biasfluoroethylene-hexafluoropropylene (VF2-HFP).
8, the preparation of composition polymer modified diaphragm as claimed in claim 5 is characterized in that said " selecting shape " molecular sieve filling is ZSM-5, ZSM-35, ZSM-57, silicon zeolite etc.
9, the preparation of composition polymer modified diaphragm as claimed in claim 1 is characterized in that step is:
1), preparation modified matrix film;
2), molecular sieve filling is scattered in the solvent will " to select shape ", is stirred to be uniformly dispersed, and adds polymeric matrix again and makes its dissolving, gets the gel composition polymer;
3), composition polymer is coated with, floods or is sprayed at modified matrix film surface;
4), thermal evaporation removes solvent final vacuum drying, obtains the composition polymer modified diaphragm.
10, the preparation of composition polymer modified diaphragm as claimed in claim 9 is characterized in that said solvent is one or both and the above mixed liquor among acetone, oxolane, ethyl acetate, NMP or the DMP.The temperature that solvent is removed in thermal evaporation is controlled at 40 ℃～180 ℃.Vacuumize is no less than 24 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106876638A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of flow battery molecular sieve composite porous film and its preparation and application |
| CN114292552A (en) * | 2021-12-31 | 2022-04-08 | 蜂巢能源科技(无锡)有限公司 | Polyolefin diaphragm modification liquid, modified polyolefin diaphragm and preparation method and application thereof |
| CN114709561A (en) * | 2016-04-08 | 2022-07-05 | 达拉米克有限责任公司 | Lead-acid battery separator, enhanced flooded battery, vehicle, and related methods |
-
2009
- 2009-05-12 CN CNA2009100433685A patent/CN101552327A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106876638A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of flow battery molecular sieve composite porous film and its preparation and application |
| CN114709561A (en) * | 2016-04-08 | 2022-07-05 | 达拉米克有限责任公司 | Lead-acid battery separator, enhanced flooded battery, vehicle, and related methods |
| CN114292552A (en) * | 2021-12-31 | 2022-04-08 | 蜂巢能源科技(无锡)有限公司 | Polyolefin diaphragm modification liquid, modified polyolefin diaphragm and preparation method and application thereof |
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Application publication date: 20091007 |