CN103184568A - Preparation method for microporous ionic liquid/gel polymer electrolyte fibres - Google Patents
Preparation method for microporous ionic liquid/gel polymer electrolyte fibres Download PDFInfo
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- CN103184568A CN103184568A CN2011104430927A CN201110443092A CN103184568A CN 103184568 A CN103184568 A CN 103184568A CN 2011104430927 A CN2011104430927 A CN 2011104430927A CN 201110443092 A CN201110443092 A CN 201110443092A CN 103184568 A CN103184568 A CN 103184568A
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 54
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title description 9
- 239000012530 fluid Substances 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000009987 spinning Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 9
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 230000008961 swelling Effects 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000000835 fiber Substances 0.000 claims description 20
- 239000000155 melt Substances 0.000 claims description 13
- -1 polyoxyethylene Polymers 0.000 claims description 13
- 239000007921 spray Substances 0.000 claims description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- 230000007613 environmental effect Effects 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000006835 compression Effects 0.000 claims description 6
- 238000007906 compression Methods 0.000 claims description 6
- 230000008030 elimination Effects 0.000 claims description 6
- 238000003379 elimination reaction Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 150000002466 imines Chemical class 0.000 claims description 5
- 230000008676 import Effects 0.000 claims description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical group O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 3
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920005601 base polymer Polymers 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 235000013305 food Nutrition 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000005611 electricity Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 238000011160 research Methods 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
- 239000010977 jade Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- TYOCDPIZUIQUSO-UHFFFAOYSA-N 1-butyl-2,3-dimethyl-2h-imidazole Chemical compound CCCCN1C=CN(C)C1C TYOCDPIZUIQUSO-UHFFFAOYSA-N 0.000 description 1
- REFXEKIEYCQSQN-UHFFFAOYSA-N 1-methyl-2-propylpyrrole Chemical compound CCCC1=CC=CN1C REFXEKIEYCQSQN-UHFFFAOYSA-N 0.000 description 1
- 229910014227 BMIPF6 Inorganic materials 0.000 description 1
- 241000197194 Bulla Species 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 208000002352 blister Diseases 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 239000004744 fabric Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
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- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 238000010791 quenching Methods 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
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- 238000009941 weaving Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a method for preparing microporous ionic liquid/gel polymer electrolyte fibres by applying supercutical fluid melt-blown spinning. The method comprises the following steps of: preparing an ionic liquid, a polymer, lithium salt, a solvent and a nano-additives in a certain ratio, and then leading the ionic liquid, the polymer, the lithium salt, the solvent and the nano-additives in a high-pressure reaction kettle, and obtaining a blend; leading a supercutical fluid in the high-pressure reaction kettle, mixing the supercutical fluid with the blend aforementioned, and reacting; quantitatively feeding the uniformly-mixed materials in a screw to form a homogeneous-phase body, and extruding the homogeneous-phase body from a die-head spinneret orifice via a melt-blown die-head area, an orifice flow area and a swelling area; and naturally cooling to obtain fibres, placing the fibres in drying equipment, drying at a temperature of 80-120 DEG C, and then obtaining the ionic liquid/gel polymer electrolyte ultrafine microporous fibres. The prepared ionic liquid/gel polymer electrolyte ultrafine microporous fibres can meet the needs of the related fields based on lithium batteries, such as spinning, electricity, electronics, machinery, medical treatment, chemical industry, foods, aeronautics and astronautics.
Description
Technical field
The present invention relates to a kind of supercritical fluid of using and melt and spray the preparation method that spinning prepares micropore ionic liquid/gel polymer electrolyte fibrid.
Background technology
At present, lithium-ion battery electrolytes mostly is liquid organic solution, and organic solvent commonly used comprises vinyl carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DEC) etc.But these organic solvents all are combustible materials, and there is the danger of leakage in liquid electrolyte, therefore under abuse conditions, as heat, overcharge, events such as mistake is put, short circuit, vibration, extruding etc. easily cause catching fire, blast and even injury to personnel.And polymer dielectric has advantages such as no leakage, specific energy height, security are good, is significant for exploitation lithium ion battery electrolyte system safe, environmental protection, further develops but lower room-temperature conductivity has restricted it.
Ionic liquid typically refers to by organic cation and inorganic or organic anion and forms the material that at room temperature is in a liquid state.Because non-volatile, plurality of advantages such as steam forces down, good conductivity, electrochemical stability window are wide, Heat stability is good that ionic liquid has, since using as the electrolyte of battery first, late 1970s received increasing concern.Ionic liquid is introduced polymer dielectric, and, electrolytical imagination that room-temperature conductivity high, security good non-volatile in the hope of obtaining caused people's very big interest especially.Fuller etc. at first are applied to this imagination the preparation of ionic liquid/gel polymer electrolyte, are after this launching research widely aspect this electrolyte.According to present bibliographical information, the most employing of ionic liquid/polymer electrolyte polyoxyethylene (PEO), Kynoar (PVDF) and this two big base polymer of copolymer polyvinylidene fluoride-hexafluoropropene [P (VDF-HFP)] thereof are matrix.Be matrix with PEO, introduce ionic liquid N-methyl-N-propyl pyrrole-two (trifluoromethyl sulphonyl) imines (PYR13TFSI), N-methyl-N-propyl pyrrole-two (trifluoromethyl sulphonyl) imines (PYR14TFSI), 1-methyl-4-butyl-pyridinium-two (trifluoromethyl sulphonyl) imines (BMPy-TFSI) respectively, successfully obtained ionic liquid/gel polymer electrolyte.But its room-temperature conductivity is unsatisfactory, does not reach 10
-3Scm
-1The order of magnitude, thus limited the range of application of above-mentioned PEO base ionic liquid/polymer electrolyte; On the other hand, the normal and glyoxaline ion liquid combined preparation ionic liquid/polymer electrolyte of PVDF or P (VDF-HFP) polymeric matrix is because its room-temperature conductivity can reach 10
-3Scm
-1The order of magnitude and attracted numerous researchers' sight.The researcher adopts 1,2-dimethyl-3-N-butyl imidazole (DMBITFSI), 1-methyl-3-ethyl imidazol(e) tetrafluoro boric acid (EMIBF4), 1-methyl-3-butyl imidazole hexafluorophosphoric acid (BMIPF6) glyoxaline ion liquid successfully to prepare PVDF base or P (VDF-HFP) base-ionic liquid/polymer electrolyte respectively.Yet, most researchs only are confined to inquire into the ion transfer of PVDF base or P (VDF-HFP) base-ionic liquid/polymer electrolyte itself, performances such as electrochemical stability window, and to the consistency problem less relevance of this type of electrolyte and electrode material, the successful Application of this type of ionic liquid/gel polymer electrolyte in lithium ion battery be report not especially.
This patent intends adopting the technology of spinning to prepare ionic liquid/gel polymer electrolyte micropore superfine fibre, and improves ion transfer characteristic and electrochemical stability window by adding the EC/PC plasticizer.Solve the consistency problem of electrolyte and electrode material.
The development of meltblown fibers production technology and the expansion of product applications have promoted the use of high-performance polymer, to satisfy the special demands of fabrics for industrial use, little as fibre fineness, high temperature resistant, chemical resistance, good intensity and elasticity, medical product comfort, with the requirements such as security of Food Contact.
Supercritical fluid, refer to that certain material is in the critical point critical-temperature, more than the critical pressure, have a fluid of the unique rerum natura that is different from liquid or gas, not only has the characteristic of gas but also have the characteristic of liquid, therefore we can say that supercritical fluid is to be present in gas, these two kinds of fluid states of liquid the 3rd fluid in addition.Supercritical fluid has the density close with liquid, thereby very strong solvent strength is arranged, and has the viscosity close with gas simultaneously, and mobile more much better than liquid, mass tranfer coefficient is also much bigger than liquid.And performances such as the density of fluid, solvent strength and viscosity all can be regulated easily by the variation of pressure and temperature, thereby have wide practical use.Adopt supercritical CO
2Extract and obtain broad research and commercial Application.In Polymer Processing, adopt supercritical CO
2Though few, obtained suitable attention and research widely, as supercritical CO
2Polymerisation, employing supercritical CO for medium
2In polymer, add additive, supercritical CO
2Swollen-state polymerization obtains blend and composite, polymer classification, extraction oligomer and solvent, microballoon and fento preparation, crystallization etc.
In the microporous polymer preparation, use supercritical fluid to have the following advantages:
(1) mass tranfer coefficient height can reach equilibrium concentration in the short period of time, thereby shorten process time, makes the commercial Application of microporous polymer preparation become possibility.
(2) under uniform temp, use supercritical CO
2Higher equilibrium concentration can be reached, thereby higher cell density and littler cell diameter can be obtained.
(3) can reduce the viscosity of polymer greatly owing to supercritical fluid dissolves in polymer, thereby reduce the flowability that melts and sprays pressure and improve melt.
By changing temperature or the pressure of supercritical fluid, can obtain being in the arbitrary density between gaseous state and the liquid state; Near critical point, the minor variations of pressure and temperature can cause the great variety of density.Because viscosity, dielectric constant, diffusion coefficient are all relevant with density with solvability, therefore can regulate the physicochemical properties that pressure and temperature is controlled supercritical fluid easily.The preparation of microporous polymer is mainly based on gas supersaturation method.Basic process is: at first make gases at high pressure (CO
2And N
2) be dissolved in and form the saturated system of polymer/gas in the polymer; Then by pressure drop and (or) temperature rises sharply and makes it to enter hypersaturated state, thereby a large amount of gas nuclear causes simultaneously and increases; Make the microcellular structure typing by methods such as quenchings at last.The improvement of conventional foam plastics physical blowing is technological parameters such as strict control temperature, pressure, time, makes a large amount of gas nuclear energy cause enough simultaneously, and not merger becomes bulla, thereby obtains microcellular structure.Adopt the supersaturation principle to prepare the process of microporous polymer, according to the continuous degree difference of operation mainly contain the method for fractional steps, semi-continuous process and extrude, continuity methods such as injection moulding, rotational moulding.The method of fractional steps and semi-continuous process are determined by the diffusion velocity of gas to polymeric matrix owing to forming the saturated system required time of polymer/gas, thereby length consuming time, can't satisfy industrial needs, are mainly used in theoretical research.And with the actual appearance that melts and sprays the consistent continuity method of processing, make the practical application of micropore ionic liquid/gel polymer electrolyte fibrid become possibility.The mechanical property of micropore ionic liquid/gel polymer electrolyte fibrid mainly depends on and microcellular structure (comprising: hole dimension, hole density, pore size distribution and hole orientation) and molecular chain orientation.And by optimizing technology, control microcellular structure and molecular chain orientation can obtain the micropore ionic liquid/gel polymer electrolyte fibrid of function admirable.
Summary of the invention
The purpose of this invention is to provide a kind of supercritical fluid of using and melt and spray the method that spinning prepares micropore ionic liquid/gel polymer electrolyte superfine fibre, based on the demand of association areas such as the weaving of satisfying lithium battery, electric, electronics, machinery, medical treatment, chemical industry, food and Aero-Space.
For achieving the above object, the technical solution used in the present invention is as follows:
Application supercritical fluid of the present invention melts and sprays the method that spinning prepares micropore ionic liquid/gel polymer electrolyte fibrid, it is characterized in that: comprise the steps:
(1) takes by weighing ionic liquid 1-12 weight portion, polymer 1-9 weight portion, solvent 80-90 weight portion, nanometer additive 1-3 weight portion respectively, then polymer is dissolved in the part N-methyl pyrrolidone, lithium salts, nanometer additive and ionic liquid are dissolved in the remaining N-methyl pyrrolidone, the concentration of lithium salts is 1mol/L in the control solution, imports simultaneously then evenly to mix in the autoclave that liner is housed to obtain blend;
(2) supercritical fluid is imported to mix and keep pressure with above-mentioned blend in the autoclave be 7-17 MPa, temperature is 50-380 ℃ and stirs down raw material is mixed, synthetic 6-24 hour of reaction in supercritical fluid simultaneously;
(3) above-mentioned even composite material is quantitatively fed screw rod, be transferred and evenly blend in the screw feed section, also become the homogeneous phase body gradually through the compacting of screw compression section then;
(4) in the filter part, the homogeneous phase body is through filter medium, residual catalyst after elimination impurity and the polymerisation;
(5) in the measuring pump part, the homogeneous phase body carries out melt-stoichiometry through gear wheel metering pump, with accurate control fibre fineness and the uniformity;
(6) the homogeneous phase body through the meltblown beam inlet region, orifice flow district and fluffing zone extrude from the die head spinneret orifice;
When (7) the homogeneous phase body body thread of extruding from the die head spinneret orifice because environmental pressure reduces suddenly expanded swelling is taken place, be subjected to the drawing-off of both sides high velocity, hot air stream, be in the melt thread of viscous state by drawing-down rapidly; Simultaneously, the air at room temperature of both sides mixes the drawing-off thermal air current, and melt thread cooling curing is shaped, and forms ultra-fine micropore fibrid.
(8) after cooling off naturally, obtain fiber and put into drying plant, namely get the ultra-fine micropore fibrid of ionic liquid/gel polymer electrolyte in 80-120 ℃ of temperature oven dry.
Described ionic liquid is: imidazoles, pyroles, pyridines etc., but be not limited thereto.
Described polymer is polyoxyethylene, Kynoar class, nano-cellulose etc., but is not limited to this.
Described lithium salts is LiBF4, imines lithium, LiPF6 etc.
,But be not limited to this.
Described solvent is vinyl carbonate, propylene carbonate, dimethyl carbonate etc., but is not limited to this.
Described nanometer additive is nano-cellulose, titanium oxide, aluminium oxide etc., but is not limited to this.
Described supercritical fluid is overcritical N
2,H
2O or supercritical CO
2
Described supercritical fluid is overcritical N
2The time, its temperature is 50 ~ 380 ℃, pressure is 7 ~ 40MPa, overcritical N
2With the mass ratio of blend be 1:400-1:10.
Described supercritical fluid is supercritical CO
2The time, its temperature is 50 ~ 380 ℃, critical pressure is 7 ~ 40MPa, supercritical CO
2With the mass ratio of blend be 1:100 ~ 1:10.
Described homogeneous phase body is 7 ~ 40MPa with the pressure differential in the external world, and melting and spraying speed is 10 ~ 2000cm
3/ s.
Advantage of the present invention is remarkable, adopt of the present inventionly to melt and spray the method that spinning prepares polymer micro ionic liquid/gel polymer electrolyte fibrid with supercritical fluid, can make the micropore ionic liquid/gel polymer electrolyte fibrid of ultra-fine (20-90000nm).
Description of drawings
Fig. 1 uses supercritical fluid to melt and spray the method principle schematic that spinning prepares micropore ionic liquid/gel polymer electrolyte fiber.
The specific embodiment
With ionic liquid: polymer: lithium salts: solvent: nanometer additive is by being 6%: 4%: 1mol/L: 88%: 2% proportional arrangement, respectively P (VDF-HFP) is dissolved in NMP, LiPF6, nano-titanium oxide and EMIPF6 are dissolved in NMP, then both are imported simultaneously in the autoclave that liner is housed evenly to mix.Be 50-380 ℃ with temperature, pressure is the supercritical CO of 7-40MPa
2Import in the autoclave and evenly mix supercritical CO with above-mentioned material
2With the mass ratio of blend be 1:100 ~ 1:10.Stirring mixes raw material under above-mentioned holding temperature, and the reaction generated time is 6 hours in the supercritical fluid.Above-mentioned even composite material is quantitatively fed screw rod, be transferred and evenly blend in the screw feed section, then through the compacting of screw compression section and homogeneous phase body gradually.The homogeneous phase body should pass through filter medium, residual catalyst after elimination impurity and the polymerisation.The homogeneous phase body carries out melt-stoichiometry through gear wheel metering pump, with accurate control fibre fineness and the uniformity.As shown in Figure 1, arrow A is represented the injection direction of homogeneous mixture melt among the figure, and arrow B is represented drawing-off with the hot-air direction that flows, and arrow C is represented the flow of cold air direction.The homogeneous phase body through meltblown beam inlet region 1, orifice flow district 2 and fluffing zone 3 extrude from the die head spinneret orifice, melting and spraying speed is 10-2000 cm
3/ s.When the homogeneous phase body body thread of extruding from the die head spinneret orifice because environmental pressure reduces suddenly expanded swelling is taken place, be subjected to the drawing-off of both sides 70-90 ℃ of high velocity, hot air stream, be in the melt thread of viscous state by drawing-down rapidly.Simultaneously, the air at room temperature of both sides mixes the drawing-off thermal air current, and melt thread cooling curing is shaped, and forms ultra-fine micropore fibrid.Above fiber obtains micropore ionic liquid/gel polymer electrolyte fibrid by oven dry, can directly use this micropore ionic liquid/gel polymer electrolyte fibrid to do the diaphragm material of lithium battery, super capacitor.
Respectively polyoxyethylene, two, trifluoromethyl semi-annular jade pendant acyl-imines lithium and ionic liquid N-methyl-propyl pyrrole two, trifluoromethyl semi-annular jade pendant acyl-imines are dissolved in NMP, import simultaneously then evenly to mix in the autoclave that liner is housed and obtain blend; With 40 ℃, 16 MPa supercritical COs
2Import in the autoclave and evenly mix with above-mentioned material.Stirring mixes raw material under above-mentioned holding temperature, and the reaction generated time is 10 hours in the supercritical fluid.The above-mentioned even composite material of autoclave quantitatively feeds screw rod, is transferred and evenly blend in the screw feed section, then through the compacting of screw compression section and homogeneous phase body gradually; The homogeneous phase body should pass through filter medium, residual catalyst after elimination impurity and the polymerisation; The homogeneous phase body carries out melt-stoichiometry through gear wheel metering pump, with accurate control fibre fineness and the uniformity; The homogeneous phase body through the meltblown beam inlet region, orifice flow district and fluffing zone extrude from the die head spinneret orifice; When the homogeneous phase body body thread of extruding from the die head spinneret orifice because environmental pressure reduces suddenly expanded swelling is taken place, be subjected to the drawing-off of both sides high velocity, hot air stream, be in the melt thread of viscous state by drawing-down rapidly.Simultaneously, the air at room temperature of both sides mixes the drawing-off thermal air current, and melt thread cooling curing is shaped, and forms ultra-fine micropore fibrid; Above fiber obtains micropore ionic liquid/gel polymer electrolyte fibrid by oven dry, can directly use this micropore ionic liquid/gel polymer electrolyte fibrid to do the diaphragm material of lithium battery, super capacitor.
Embodiment 3
With EMIBF4, PVDF-HFP is dissolved in solvent NMP respectively, imports simultaneously then evenly to mix in the autoclave that liner is housed to obtain blend; With 50 ℃, the overcritical N of 7MPa
2Import in the autoclave and evenly mix with above-mentioned material.Stirring mixes raw material under above-mentioned holding temperature, and the reaction generated time is 24 hours in the supercritical fluid.The above-mentioned even composite material of autoclave quantitatively feeds screw rod, is transferred and evenly blend in the screw feed section, then through the compacting of screw compression section and homogeneous phase body gradually.The homogeneous phase body should pass through filter medium, residual catalyst after elimination impurity and the polymerisation.The homogeneous phase body carries out melt-stoichiometry through gear wheel metering pump, with accurate control fibre fineness and the uniformity.The homogeneous phase body through the meltblown beam inlet region, orifice flow district and fluffing zone extrude from the die head spinneret orifice.When the homogeneous phase body body thread of extruding from the die head spinneret orifice because environmental pressure reduces suddenly expanded swelling is taken place, be subjected to the drawing-off of the 90 ℃ of high velocity, hot airs streams in both sides, be in the melt thread of viscous state by drawing-down rapidly.Simultaneously, the air at room temperature of both sides mixes the drawing-off thermal air current, and melt thread cooling curing is shaped, and forms ultra-fine micropore fibrid.Above fiber obtains micropore ionic liquid/gel polymer electrolyte fibrid by oven dry, can directly use this micropore ionic liquid/gel polymer electrolyte fibrid to do the diaphragm material of lithium battery, super capacitor.
Embodiment 4
With EMIPF4, cellulose, alumina nano fiber are dissolved in solvent NMP respectively, in 1-allyl-3-methylimidazole halide and 1-butyl-3-methylimidazole halide, import simultaneously then evenly to mix in the autoclave that liner is housed and obtain blend; With 40 ℃, the overcritical N of 16 MPa
2Import in the autoclave and evenly mix with above-mentioned material.Stirring mixes raw material under above-mentioned holding temperature, and the reaction generated time is 24 hours in the supercritical fluid.The above-mentioned even composite material of autoclave quantitatively feeds screw rod, is transferred and evenly blend in the screw feed section, then through the compacting of screw compression section and homogeneous phase body gradually; The homogeneous phase body should pass through filter medium, residual catalyst after elimination impurity and the polymerisation; The homogeneous phase body carries out melt-stoichiometry through gear wheel metering pump, with accurate control fibre fineness and the uniformity; The homogeneous phase body through the meltblown beam inlet region, orifice flow district and fluffing zone extrude from the die head spinneret orifice; When the homogeneous phase body body thread of extruding from the die head spinneret orifice because environmental pressure reduces suddenly expanded swelling is taken place, be subjected to the drawing-off of both sides high velocity, hot air stream, be in the homogeneous phase body thread of viscous state by drawing-down rapidly.Simultaneously, the air at room temperature of both sides mixes the drawing-off thermal air current, makes homogeneous phase body thread enter cooling curing shaping in the ice bath, forms ultra-fine micropore fibrid; Above fiber obtains micropore ionic liquid/gel polymer electrolyte fibrid by oven dry, can directly use this micropore ionic liquid/gel polymer electrolyte fibrid to do the diaphragm material of lithium battery, super capacitor.
Claims (7)
1. use supercritical fluid and melt and spray the method that spinning prepares micropore ionic liquid/gel polymer electrolyte fiber for one kind, it is characterized in that: comprise the steps:
(1) takes by weighing ionic liquid 1-12 weight portion, polymer 1-9 weight portion, solvent 80-90 weight portion, nanometer additive 1-3 weight portion respectively, then polymer is dissolved in the part N-methyl pyrrolidone, lithium salts, nanometer additive and ionic liquid are dissolved in the remaining N-methyl pyrrolidone, the concentration of lithium salts is 1mol/L in the control solution, imports simultaneously then evenly to mix in the autoclave that liner is housed to obtain blend;
(2) supercritical fluid is imported to mix and keep pressure with above-mentioned blend in the autoclave be 7-17 MPa, temperature is x-x ℃ and stirs down raw material is mixed, synthetic 6-24 hour of reaction in supercritical fluid simultaneously;
(3) above-mentioned even composite material is quantitatively fed screw rod, be transferred and evenly blend in the screw feed section, also become the homogeneous phase body gradually through the compacting of screw compression section then;
(4) in the filter part, the homogeneous phase body is through filter medium, residual catalyst after elimination impurity and the polymerisation;
(5) in the measuring pump part, the homogeneous phase body carries out melt-stoichiometry through gear wheel metering pump, with accurate control fibre fineness and the uniformity;
(6) the homogeneous phase body through the meltblown beam inlet region, orifice flow district and fluffing zone extrude from the die head spinneret orifice;
When (7) the homogeneous phase body body thread of extruding from the die head spinneret orifice because environmental pressure reduces suddenly expanded swelling is taken place, be subjected to the drawing-off of both sides high velocity, hot air stream, be in the melt thread of viscous state by drawing-down rapidly; Simultaneously, the air at room temperature of both sides mixes the drawing-off thermal air current, and melt thread cooling curing is shaped, and forms ultra-fine micropore fibrid.
2.(8) through obtaining fiber and put into drying plant after the cooling naturally, namely get the ultra-fine micropore fibrid of ionic liquid/gel polymer electrolyte in 80-120 ℃ of temperature oven dry.
3. application supercritical fluid according to claim 1 melts and sprays the method that spinning prepares micropore ionic liquid/gel polymer electrolyte fiber, it is characterized in that: described ionic liquid is imidazoles, pyroles or pyridines ionic liquid;
Described polymer is polyoxyethylene, Kynoar class or nano-cellulose base polymer;
Described lithium salts is LiBF4, imines lithium or LiPF6;
Described solvent is vinyl carbonate, propylene carbonate or dimethyl carbonate;
Described nanometer additive is titanium oxide, aluminium oxide or nano-cellulose.
4.3. application supercritical fluid according to claim 1 and 2 melts and sprays the method that spinning prepares micropore ionic liquid/gel polymer electrolyte fibrid, it is characterized in that: described supercritical fluid is overcritical N
2Perhaps supercritical CO
2
5. application supercritical fluid according to claim 3 melts and sprays the method that spinning prepares micropore ionic liquid/gel polymer electrolyte fibrid, it is characterized in that: described supercritical fluid is overcritical N
2The time, its temperature is 50 ~ 380 ℃, pressure is 7 ~ 40MPa, overcritical N
2With the mass ratio of blend be 1:400-1:10.
6. application supercritical fluid according to claim 3 melts and sprays the method that spinning prepares micropore ionic liquid/gel polymer electrolyte fibrid, it is characterized in that: described supercritical fluid is supercritical CO
2The time, its temperature is 50 ~ 380 ℃, critical pressure is 7 ~ 40MPa, supercritical CO
2With the mass ratio of blend be 1:100 ~ 1:10.
7. application supercritical fluid according to claim 3 melts and sprays the method that spinning prepares micropore ionic liquid/gel polymer electrolyte fibrid, it is characterized in that: described homogeneous phase body is 7 ~ 40MPa with the pressure differential in the external world, and melting and spraying speed is 10 ~ 2000cm
3/ s.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104952634A (en) * | 2015-06-05 | 2015-09-30 | 北京大学 | Ionic liquid-lithium salt gel polymer electrolyte and preparation and application thereof |
| CN107546411A (en) * | 2017-08-30 | 2018-01-05 | 清陶（昆山）能源发展有限公司 | A kind of dielectric film and preparation method thereof |
| CN111554971A (en) * | 2020-05-11 | 2020-08-18 | 珠海冠宇电池股份有限公司 | Wire and application thereof |
| CN111554972A (en) * | 2020-05-11 | 2020-08-18 | 珠海冠宇电池股份有限公司 | Wire and application thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003151633A (en) * | 2001-08-17 | 2003-05-23 | Samsung Sdi Co Ltd | Sol state polymer electrolyte and lithium battery adopting the same |
| JP2004111294A (en) * | 2002-09-20 | 2004-04-08 | Nisshinbo Ind Inc | Non-aqueous electrolyte, electric double layer capacitor, and non-aqueous electrolyte secondary battery |
| JP2008257963A (en) * | 2007-04-04 | 2008-10-23 | Central Res Inst Of Electric Power Ind | Non-aqueous electrolyte secondary battery |
| CN102005610A (en) * | 2010-10-21 | 2011-04-06 | 江苏科技大学 | Ionic blended gel polymer electrolyte membrane and preparation method and use thereof |
| CN102244292A (en) * | 2011-06-09 | 2011-11-16 | 华南师范大学 | Lithium ion battery ionic liquid based gel polymer electrolyte as well as preparation and applications thereof |
-
2011
- 2011-12-27 CN CN201110443092.7A patent/CN103184568B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003151633A (en) * | 2001-08-17 | 2003-05-23 | Samsung Sdi Co Ltd | Sol state polymer electrolyte and lithium battery adopting the same |
| JP2004111294A (en) * | 2002-09-20 | 2004-04-08 | Nisshinbo Ind Inc | Non-aqueous electrolyte, electric double layer capacitor, and non-aqueous electrolyte secondary battery |
| JP2008257963A (en) * | 2007-04-04 | 2008-10-23 | Central Res Inst Of Electric Power Ind | Non-aqueous electrolyte secondary battery |
| CN102005610A (en) * | 2010-10-21 | 2011-04-06 | 江苏科技大学 | Ionic blended gel polymer electrolyte membrane and preparation method and use thereof |
| CN102244292A (en) * | 2011-06-09 | 2011-11-16 | 华南师范大学 | Lithium ion battery ionic liquid based gel polymer electrolyte as well as preparation and applications thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104952634A (en) * | 2015-06-05 | 2015-09-30 | 北京大学 | Ionic liquid-lithium salt gel polymer electrolyte and preparation and application thereof |
| CN104952634B (en) * | 2015-06-05 | 2019-07-19 | 北京大学 | A kind of ionic liquid-lithium salts gel polymer electrolyte and its preparation and application |
| CN107546411A (en) * | 2017-08-30 | 2018-01-05 | 清陶（昆山）能源发展有限公司 | A kind of dielectric film and preparation method thereof |
| CN107546411B (en) * | 2017-08-30 | 2020-08-04 | 清陶（昆山）能源发展有限公司 | Electrolyte membrane and preparation method thereof |
| CN111554971A (en) * | 2020-05-11 | 2020-08-18 | 珠海冠宇电池股份有限公司 | Wire and application thereof |
| CN111554972A (en) * | 2020-05-11 | 2020-08-18 | 珠海冠宇电池股份有限公司 | Wire and application thereof |
| CN115559011A (en) * | 2022-09-29 | 2023-01-03 | 武汉纺织大学 | Anisotropic organic-inorganic hybrid ionic liquid gel fiber and preparation method thereof |
| CN115559011B (en) * | 2022-09-29 | 2024-01-26 | 武汉纺织大学 | Anisotropic organic-inorganic hybrid ionic liquid gel fiber and preparation method thereof |
| CN116387612A (en) * | 2023-02-13 | 2023-07-04 | 北京纯锂新能源科技有限公司 | Polymer electrolyte membrane, preparation method and metal lithium battery |
| CN116387612B (en) * | 2023-02-13 | 2023-12-15 | 北京纯锂新能源科技有限公司 | Polymer electrolyte membrane, preparation method and metal lithium battery |
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