CN103184568B - 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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- CN103184568B CN103184568B CN201110443092.7A CN201110443092A CN103184568B CN 103184568 B CN103184568 B CN 103184568B CN 201110443092 A CN201110443092 A CN 201110443092A CN 103184568 B CN103184568 B CN 103184568B
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 53
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title description 7
- 239000012530 fluid Substances 0.000 claims abstract description 38
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000009987 spinning Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 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
- 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 23
- 238000003756 stirring Methods 0.000 claims description 11
- -1 polyoxyethylene Polymers 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 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
- 230000000996 additive effect Effects 0.000 claims description 7
- 230000007613 environmental effect Effects 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 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
- 238000003786 synthesis reaction 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
- 239000000155 melt Substances 0.000 claims description 5
- 229910001290 LiPF6 Inorganic materials 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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- 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 10
- 239000002033 PVDF binder Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
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- 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
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
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- 238000009792 diffusion process Methods 0.000 description 2
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- 239000003960 organic solvent Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000243 solution Substances 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
- 241000197194 Bulla Species 0.000 description 1
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- 239000002152 aqueous-organic solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 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
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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
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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 preparation method applying supercritical fluid melt-spraying spinning and prepare micropore ionic liquid/gel polymer electrolyte fibrid.
Background technology
At present, lithium-ion battery electrolytes mostly is aqueous organic solution, and conventional organic solvent comprises vinyl carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DEC) etc.But these organic solvents are all combustible materials, and liquid electrolyte exists the danger of leakage, therefore under abuse conditions, as heated, overcharging, cross put, short circuit, vibration, extruding etc. easily cause catching fire, explode and even the event such as injury to personnel.And polymer dielectric has the advantages such as no leakage, specific energy is high, security is good, exploitation security lithium ion battery electrolyte system that is high, environmental protection is significant, but lower room-temperature conductivity constrains it to be further developed.
Ionic liquid, typically refers to and is made up of organic cation and inorganic or organic anion, the material be at room temperature in a liquid state.There is due to ionic liquid the plurality of advantages such as non-volatile, steam forces down, good conductivity, electrochemical stability window are wide, Heat stability is good, since late 1970s uses as the electrolyte of battery first, received increasing concern.Ionic liquid is introduced polymer dielectric, to obtaining non-volatile, that room-temperature conductivity is high, security is good electrolytical imagination causes people especially great interest.First this imagination is applied to the preparation of ionic liquid/gel polymer electrolyte by Fuller etc., after this expands in this electrolyte and studies widely.According to current bibliographical information, ionic liquid/polymer electrolyte majority adopts polyoxyethylene (PEO), Kynoar (PVDF) and this two large base polymer of copolymer polyvinylidene fluoride-hexafluoropropene [P (VDF-HFP)] thereof to be matrix.Take PEO as matrix, introduce ionic liquid N-Methyl-N-propyl pyrroles-two (trimethyl fluoride sulfonyl) imines (PYR13TFSI), N-Methyl-N-propyl pyrroles-two (trimethyl fluoride sulfonyl) imines (PYR14TFSI), 1-methyl-4-butyl-pyridinium-two (trimethyl fluoride sulfonyl) imines (BMPy-TFSI) respectively, successfully obtain ionic liquid/gel polymer electrolyte.But its room-temperature conductivity is unsatisfactory, does not reach 10
-3scm
-1the order of magnitude, thus the range of application limiting above-mentioned PEO base ionic liquid/polymer electrolyte; On the other hand, the normal and glyoxaline ion liquid of PVDF or P (VDF-HFP) polymeric matrix combines and prepares ionic liquid/polymer electrolyte, because its room-temperature conductivity can reach 10
-3scm
-1the order of magnitude and attracted the sight of numerous researcher.Researcher adopts 1,2-dimethyl-3-N-butyl imidazole (DMBITFSI), 1-methyl-3-ethyl imidazol(e) tetrafluoro boric acid (EMIBF4) respectively, 1-methyl-3-butyl imidazole hexafluorophosphoric acid (BMIPF6) glyoxaline ion liquid has successfully prepared PVDF base or P (VDF-HFP) base-ionic liquid/polymer electrolyte.But, most research is only confined to the ion transmission inquiring into PVDF base or P (VDF-HFP) base-ionic liquid/polymer electrolyte itself, the performances such as electrochemical stability window, and the consistency problem of this type of electrolyte and electrode material is seldom paid close attention to, the successful Application of this type of ionic liquid/gel polymer electrolyte in lithium ion battery is not reported especially.
This patent is intended adopting the technology of spinning to prepare ionic liquid/gel polymer electrolyte micropore superfine fibre, and improves ion transport properties and electrochemical stability window by adding 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 facilitate the use of high-performance polymer, to meet the special demands of fabrics for industrial use, as fibre fineness is little, high temperature resistant, chemical resistance, good intensity and elasticity, medical product comfort, with the requirement such as the security of Food Contact.
Supercritical fluid, refer to that certain material is in critical point critical-temperature, more than critical pressure, there is the fluid of the unique physical property being different from liquid or gas, not only there is the characteristic of gas but also there is the characteristic of liquid, therefore can say, supercritical fluid is present in the 3rd fluid beyond gas, these two kinds of fluid states of liquid.Supercritical fluid has the density close with liquid, thus has very strong solvent strength, and have the viscosity close with gas, mobility is more much better than liquid simultaneously, and mass tranfer coefficient is also much bigger than liquid.And the performances such as the density of fluid, solvent strength and viscosity all regulate easily by the change of pressure and temperature, thus have wide practical use.Adopt supercritical CO
2carry out extracting and extensively studied and commercial Application.Supercritical CO is adopted in Polymer Processing
2although few, obtain suitable attention and studied widely, as supercritical CO
2for polymerisation, the employing supercritical CO of medium
2additive, supercritical CO is added in polymer
2swollen-state polymerization obtains blend and composite, Polymer Fractionation, extraction oligomer and the preparation of solvent, microballoon and fento, crystallization etc.
In microporous polymer preparation, use supercritical fluid to have the following advantages:
(1) mass tranfer coefficient is high, can reach equilibrium concentration in the short period of time, thus shorten process time, and commercial Application prepared by microporous polymer becomes possibility.
(2) at the same temperature, supercritical CO is used
2higher equilibrium concentration can be reached, thus can obtain higher cell density and less cell diameter.
(3) because supercritical fluid dissolves in the viscosity that polymer can reduce polymer greatly, thus decrease melt-blown pressure and improve the mobility of melt.
By changing temperature or the pressure of supercritical fluid, the arbitrary density be between gaseous state and liquid state can be obtained; At Near The Critical Point, the minor variations of pressure and temperature can cause the great variety of density.Because viscosity, dielectric constant, diffusion coefficient and solvability are all relevant with density, pressure and temperature therefore can be regulated easily to control the physicochemical properties of supercritical fluid.The preparation of microporous polymer is mainly based on dissolved gas supersaturation method.Basic process is: first make gases at high pressure (CO
2and N
2) be dissolved in polymer and form the saturated system of polymer/gas; Then risen sharply by pressure drop and (or) temperature and make it to enter hypersaturated state, thus a large amount of gas core causes simultaneously and increases; Finally by methods such as quenchings, microcellular structure is shaped.The improvement of conventional foams physical blowing is the technological parameter such as strict temperature control, pressure, time, a large amount of gas nuclear energy is caused, and not merger becomes bulla enough simultaneously, thus obtains microcellular structure.Adopt supersaturation principle to prepare the process of microporous polymer, mainly contain the method for fractional steps, semi-continuous process according to the continuity degree difference of operation and extrude, injection moulding, the continuity method such as 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, and thus length consuming time, cannot meet industrial needs, be mainly used in theoretical research.And the appearance of the continuity method consistent with the melt-blown processing of reality, 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 Optimization 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 object of this invention is to provide a kind of method applied supercritical fluid melt-spraying spinning and prepare micropore ionic liquid/gel polymer electrolyte superfine fibre, by meet weaving based on lithium battery, electrically, electronics, machinery, medical treatment, chemical industry, the association area such as food and Aero-Space demand.
For achieving the above object, the technical solution used in the present invention is as follows:
The method of micropore ionic liquid/gel polymer electrolyte fibrid is prepared in application supercritical fluid melt-spraying of the present invention spinning, it is characterized in that: comprise the steps:
(1) ionic liquid 1-12 weight portion, polymer 1-9 weight portion, solvent 80-90 weight portion, nanometer additive 1-3 weight portion is taken respectively, then polymer is dissolved in part 1-METHYLPYRROLIDONE, lithium salts, nanometer additive and ionic liquid are dissolved in remaining 1-METHYLPYRROLIDONE, the concentration controlling lithium salts in solution is 1mol/L, then imports uniform stirring in the autoclave that liner is housed simultaneously and is mixed to get blend;
(2) supercritical fluid is imported that to mix with above-mentioned blend and maintain pressure in autoclave be 7-17 MPa, temperature is stir at 50-380 DEG C raw material is mixed, Reactive Synthesis 6-24 hour in supercritical fluid simultaneously;
(3) above-mentioned Homogeneous phase mixing material is quantitatively fed screw rod, be transferred with evenly blended in screw feed section, then also become homogeneous phase body gradually through the compacting of screw compression section;
(4) at filter-portion, homogeneous phase body through filter medium, catalyst residual after elimination impurity and polymerisation;
(5) in measuring pump part, homogeneous phase body carries out melt-stoichiometry through gear wheel metering pump, accurately to control fibre fineness and the uniformity;
(6) homogeneous phase body is extruded from die head spinneret orifice through meltblown beam inlet region, Kong Liuqu and fluffing zone;
(7), while the homogeneous phase body body thread extruded from die head spinneret orifice, because environmental pressure reduces suddenly, expanded swelling occurs, be subject to the drawing-off of both sides high velocity, hot air stream, be in the melt stream of viscous state by rapid drawing-down; Meanwhile, the air at room temperature of both sides mixes drawing-off thermal air current, and melt stream cooling curing is shaped, and forms ultrafine micropore fibrid.
(8) after naturally cooling, obtain fiber and put into drying plant, dry and obtain ionic liquid/gel polymer electrolyte ultrafine micropore fibrid in 80-120 DEG C of temperature.
Described ionic liquid is: imidazoles, pyroles, pyridines etc., but is not limited thereto.
Described polymer is polyoxyethylene, Kynoar class, nano-cellulose etc., but is not limited to this.
Described lithium salts is LiBF4, imine 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
2time, its temperature is 50 ~ 380 DEG C, and pressure is 7 ~ 40MPa, overcritical N
2be 1:400-1:10 with the mass ratio of blend.
Described supercritical fluid is supercritical CO
2time, its temperature is 50 ~ 380 DEG C, and critical pressure is 7 ~ 40MPa, supercritical CO
2be 1:100 ~ 1:10 with the mass ratio of blend.
Described homogeneous phase body is 7 ~ 40MPa with extraneous pressure differential, and melt-blown speed is 10 ~ 2000cm
3/ s.
Advantage of the present invention is remarkable, adopt the method preparing polymer micro ionic liquid/gel polymer electrolyte fibrid with supercritical fluid melt-spraying spinning of the present invention, the micropore ionic liquid/gel polymer electrolyte fibrid of ultra-fine (20-90000nm) can be obtained.
Accompanying drawing explanation
Fig. 1 is the Method And Principle schematic diagram that micropore ionic liquid/gel polymer electrolyte fiber is prepared in the spinning of application supercritical fluid melt-spraying.
Detailed description of the invention
embodiment 1
By ionic liquid: polymer: lithium salts: solvent: nanometer additive by for 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 Homogeneous phase mixing in the autoclave that liner is housed.Be 50-380 DEG C by temperature, pressure is the supercritical CO of 7-40MPa
2import in autoclave and above-mentioned material Homogeneous phase mixing, supercritical CO
2be 1:100 ~ 1:10 with the mass ratio of blend.Stirring under above-mentioned holding temperature makes raw material mix, and in supercritical fluid, the Reactive Synthesis time is 6 hours.Above-mentioned Homogeneous phase mixing material is quantitatively fed screw rod, to be transferred and evenly blended in screw feed section, then through the compacting of screw compression section and gradually homogeneous phase body.Homogeneous phase body should through filter medium, catalyst residual after elimination impurity and polymerisation.Homogeneous phase body carries out melt-stoichiometry through gear wheel metering pump, accurately to control fibre fineness and the uniformity.As shown in Figure 1, in figure, arrow A represents the injection direction of homogeneous mixture melt, and arrow B represents drawing-off hot-air flow direction, and arrow C represents flow of cold air direction.Homogeneous phase body through meltblown beam inlet region 1, Kong Liuqu 2 and fluffing zone 3 extrude from die head spinneret orifice, melt-blown speed is 10-2000 cm
3/ s.The homogeneous phase body body thread extruded from die head spinneret orifice is subject to the drawing-off of both sides 70-90 DEG C of high velocity, hot air stream, is in the melt stream of viscous state by rapid drawing-down while there is expanded swelling because environmental pressure reduces suddenly.Meanwhile, the air at room temperature of both sides mixes drawing-off thermal air current, and melt stream cooling curing is shaped, and forms ultrafine 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 2
Respectively by polyoxyethylene, two, trifluoromethyl semi-annular jade pendant acyl-imine lithium and ionic liquid N-methyI-oropvD pyrroles two, trifluoromethyl semi-annular jade pendant acyl-imines be dissolved in NMP, then import uniform stirring in the autoclave that liner is housed simultaneously and be mixed to get blend; By 40 DEG C, 16 MPa supercritical COs
2import in autoclave and above-mentioned material Homogeneous phase mixing.Stirring under above-mentioned holding temperature makes raw material mix, and in supercritical fluid, the Reactive Synthesis time is 10 hours.The above-mentioned Homogeneous phase mixing material of autoclave quantitatively feeds screw rod, to be transferred and evenly blended in screw feed section, then through the compacting of screw compression section and gradually homogeneous phase body; Homogeneous phase body should through filter medium, catalyst residual after elimination impurity and polymerisation; Homogeneous phase body carries out melt-stoichiometry through gear wheel metering pump, accurately to control fibre fineness and the uniformity; Homogeneous phase body is extruded from die head spinneret orifice through meltblown beam inlet region, Kong Liuqu and fluffing zone; The homogeneous phase body body thread extruded from die head spinneret orifice is subject to the drawing-off of both sides high velocity, hot air stream, is in the melt stream of viscous state by rapid drawing-down while there is expanded swelling because environmental pressure reduces suddenly.Meanwhile, the air at room temperature of both sides mixes drawing-off thermal air current, and melt stream cooling curing is shaped, and forms ultrafine 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
EMIBF4, PVDF-HFP are dissolved in solvent NMP respectively, then import uniform stirring in the autoclave that liner is housed simultaneously and be mixed to get blend; By 50 DEG C, the overcritical N of 7MPa
2import in autoclave and above-mentioned material Homogeneous phase mixing.Stirring under above-mentioned holding temperature makes raw material mix, and in supercritical fluid, the Reactive Synthesis time is 24 hours.The above-mentioned Homogeneous phase mixing material of autoclave quantitatively feeds screw rod, to be transferred and evenly blended in screw feed section, then through the compacting of screw compression section and gradually homogeneous phase body.Homogeneous phase body should through filter medium, catalyst residual after elimination impurity and polymerisation.Homogeneous phase body carries out melt-stoichiometry through gear wheel metering pump, accurately to control fibre fineness and the uniformity.Homogeneous phase body is extruded from die head spinneret orifice through meltblown beam inlet region, Kong Liuqu and fluffing zone.The homogeneous phase body body thread extruded from die head spinneret orifice is subject to the drawing-off of the 90 DEG C of high velocity, hot air streams in both sides, is in the melt stream of viscous state by rapid drawing-down while there is expanded swelling because environmental pressure reduces suddenly.Meanwhile, the air at room temperature of both sides mixes drawing-off thermal air current, and melt stream cooling curing is shaped, and forms ultrafine 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
By EMIPF4, cellulose, alumina nano fiber is dissolved in solvent NMP respectively, in 1-allyl-3-methylimidazolium halides and 1-butyl-3-methylimidazolium halides, then imports uniform stirring in the autoclave that liner is housed simultaneously and is mixed to get blend; By 40 DEG C, the overcritical N of 16 MPa
2import in autoclave and above-mentioned material Homogeneous phase mixing.Stirring under above-mentioned holding temperature makes raw material mix, and in supercritical fluid, the Reactive Synthesis time is 24 hours.The above-mentioned Homogeneous phase mixing material of autoclave quantitatively feeds screw rod, to be transferred and evenly blended in screw feed section, then through the compacting of screw compression section and gradually homogeneous phase body; Homogeneous phase body should through filter medium, catalyst residual after elimination impurity and polymerisation; Homogeneous phase body carries out melt-stoichiometry through gear wheel metering pump, accurately to control fibre fineness and the uniformity; Homogeneous phase body is extruded from die head spinneret orifice through meltblown beam inlet region, Kong Liuqu and fluffing zone; The homogeneous phase body body thread extruded from die head spinneret orifice is subject to the drawing-off of both sides high velocity, hot air stream, is in the homogeneous phase body thread of viscous state by rapid drawing-down while there is expanded swelling because environmental pressure reduces suddenly.Meanwhile, the air at room temperature of both sides mixes drawing-off thermal air current, makes homogeneous phase body thread enter cooling curing in ice bath and is shaped, form ultrafine 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 (5)
1. apply the method that micropore ionic liquid/gel polymer electrolyte fiber is prepared in supercritical fluid melt-spraying spinning, it is characterized in that: comprise the steps:
(1) ionic liquid 1-12 weight portion, polymer 1-9 weight portion, solvent 80-90 weight portion, nanometer additive 1-3 weight portion is taken respectively, then polymer is dissolved in part 1-METHYLPYRROLIDONE, lithium salts, nanometer additive and ionic liquid are dissolved in remaining 1-METHYLPYRROLIDONE, the concentration controlling lithium salts in solution is 1mol/L, then imports uniform stirring in the autoclave that liner is housed simultaneously and is mixed to get blend;
(2) supercritical fluid is imported that to mix with above-mentioned blend and maintain pressure in autoclave be 7-17 MPa, temperature is stir at 50-380 DEG C raw material is mixed, Reactive Synthesis 6-24 hour in supercritical fluid simultaneously;
(3) above-mentioned Homogeneous phase mixing material is quantitatively fed screw rod, be transferred with evenly blended in screw feed section, then also become homogeneous phase body gradually through the compacting of screw compression section;
(4) at filter-portion, homogeneous phase body through filter medium, catalyst residual after elimination impurity and polymerisation;
(5) in measuring pump part, homogeneous phase body carries out melt-stoichiometry through gear wheel metering pump, accurately to control fibre fineness and the uniformity;
(6) homogeneous phase body is extruded from die head spinneret orifice through meltblown beam inlet region, Kong Liuqu and fluffing zone;
(7), while the homogeneous phase body body thread extruded from die head spinneret orifice, because environmental pressure reduces suddenly, expanded swelling occurs, be subject to the drawing-off of both sides high velocity, hot air stream, be in the melt stream of viscous state by rapid drawing-down; Meanwhile, the air at room temperature of both sides mixes drawing-off thermal air current, and melt stream cooling curing is shaped, and forms ultrafine micropore fibrid;
(8) after naturally cooling, obtain fiber and put into drying plant, dry and obtain ionic liquid/gel polymer electrolyte ultrafine micropore fibrid in 80-120 DEG C of temperature;
Described ionic liquid is imidazoles, pyroles or pyridine ionic liquid;
Described polymer is polyoxyethylene, Kynoar class or nano-cellulose base polymer;
Described lithium salts is LiBF4, imine lithium or LiPF6;
Described nanometer additive is titanium oxide, aluminium oxide or nano-cellulose.
2. the method for micropore ionic liquid/gel polymer electrolyte fiber is prepared in application supercritical fluid melt-spraying according to claim 1 spinning, it is characterized in that: described supercritical fluid is overcritical N
2or supercritical CO
2.
3. the method for micropore ionic liquid/gel polymer electrolyte fiber is prepared in application supercritical fluid melt-spraying according to claim 1 spinning, it is characterized in that: described supercritical fluid is overcritical N
2time, its temperature is 50 ~ 380 DEG C, and pressure is 7 ~ 40MPa, overcritical N
2be 1:400-1:10 with the mass ratio of blend.
4. the method for micropore ionic liquid/gel polymer electrolyte fiber is prepared in application supercritical fluid melt-spraying according to claim 1 spinning, it is characterized in that: described supercritical fluid is supercritical CO
2time, its temperature is 50 ~ 380 DEG C, and critical pressure is 7 ~ 40MPa, supercritical CO
2be 1:100 ~ 1:10 with the mass ratio of blend.
5. the method for micropore ionic liquid/gel polymer electrolyte fiber is prepared in application supercritical fluid melt-spraying according to claim 1 spinning, it is characterized in that: described homogeneous phase body is 7 ~ 40MPa with extraneous pressure differential, and melt-blown speed is 10 ~ 2000cm
3/ s.
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| 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 |
| 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 |
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| 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 |
| 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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| JP4298246B2 (en) * | 2002-09-20 | 2009-07-15 | 日清紡ホールディングス株式会社 | Nonaqueous electrolyte, electric double layer capacitor and nonaqueous electrolyte secondary battery |
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