CN105585732A - Ultraviolet crosslinking polyaryletherketone porous membrane, preparation method and application of ultraviolet crosslinking polyaryletherketone porous membrane - Google Patents
Ultraviolet crosslinking polyaryletherketone porous membrane, preparation method and application of ultraviolet crosslinking polyaryletherketone porous membrane Download PDFInfo
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Abstract
The invention provides an ultraviolet crosslinking polyaryletherketone porous membrane, a preparation method and an application of the ultraviolet crosslinking polyaryletherketone porous membrane in a lithium ion battery separator material and belongs to the technical field of polymer membrane materials. The membrane has the characteristics of high porosity, good infiltration performance, excellent heat resistance and the like. According to the technical scheme, the preparation method comprises steps as follows: firstly, a patented soluble ultraviolet crosslinking polyaryletherketone polymer (the patent No. 201510991547.7) with excellent comprehensive performance is adopted, and an ultraviolet crosslinking polyaryletherketone microporous membrane with high porosity is prepared with a phase separation method and an auxiliary phase reversal method; then, the electrolyte resistance, the stability of thermal dimension, the chemical stability and the mechanical performance of the microporous membrane are further improved with an ultraviolet crosslinking curing technique on the basis that the pore structure and the membrane thickness are maintained. The material has a great significance in improvement of the high safety of a lithium ion battery and has wide application prospect.
Description
Technical field
The invention belongs to macromolecule member material technical field, be specifically related to a kind of UV-crosslinked PAEK perforated membrane, systemPreparation Method and the application in lithium ion battery separator material thereof.
Background technology
Barrier film is one of interior layer assembly of lithium ion battery key, and the quality of membrane properties directly has influence on the appearance of lithium batteryThe characteristics such as amount, cycle life and security performance, the barrier film of excellent performance has important function to the combination property that improves battery.Barrier film should have good chemical stability, thermal dimensional stability and thermo-chemical stability, ionic conductivity, electrolyte infiltrationProperty, electronic isolation and certain mechanical strength. Current commercial lithium battery diaphragm is mainly with U.S. Celgard and JapanUBE is that polyethylene (PE), polypropylene (PP) microporous barrier and three layers of the polypropylene, polyethylene/polypropylene (PP/PE/PP) of representative is multipleClose microporous barrier, in recent years, the quality of domestic MIcroporous polyolefin film and production capacity have also obtained development rapidly. Although polyalkene diaphragmBe widely applied, but exist porosity lower, the shortcoming that gas permeability and lyophily are poor, cannot meet battery fast completelyThe requirement that speed discharges and recharges, has hindered the raising of battery performance. The more important thing is, the fusing point of polyolefine material is low, and high temperature size is steadyQualitative poor, battery high power discharge, punctured or the situation such as shock under, battery temperature raises and may cause barrier film to melt,Therefore there is serious potential safety hazard. Therefore, exploitation has high porosity, good wetting property, mechanical property, hot sizeThe new types of diaphragm of stability, chemical stability, for improving battery performance, particularly improves the security aspect of battery, has non-Normal important meaning.
PAEK, as class fire resistant special type engineering plastics, has excellent heat resistance, mechanical property, chemistry surelyThe combination properties such as qualitative, fire resistance. Traditional PAEK (as polyether-ether-ketone) is insoluble to most of organic solvents, has limitedIts application. By introduce unsymmetrical monomer, non-coplanar structure and side group structure in PAEK backbone structure, brokenBad segment regularity, improves the dissolubility of this base polymer, improves processing characteristics, thereby expands its range of application. Improve poly-virtueThe stable on heating method of ether ketone mainly contains increases the rigidity of molecular weight, makes the high polymer can crystallization and crosslinked.
At present, the method for preparing lithium battery polymer microporous membrane mainly contains pulling method, phase separation method, phase inversion method and quietElectrical spinning method. In conjunction with barrier film base material and barrier film preparation method, develop excellent heat resistance, mechanical property, electrolysis immersionThe high-safety lithium battery barrier film of the structures such as lubricant nature energy, high porosity and performance advantage, has important using value, is also lithiumThe development trend of battery diaphragm material.
Summary of the invention
The object of the invention is to provide UV-crosslinked PAEK microporous barrier and preparation method thereof for lithium ion battery. This filmHave the features such as high porosity, good wetting property, excellent heat resistance concurrently. For achieving the above object, the skill that the present invention adoptsArt scheme is as follows: first, the solubility with Good All-around Property that adopts patent applied for to protect can UV-crosslinked polyaryletherKetone polymer (number of patent application 201510991547.7), the method combining with auxiliary phase inversion method by phase separation method is prepared highPorosity can UV-crosslinked PAEK microporous barrier; Then, by UV-crosslinked curing technology, at retaining hole structure and thicknessBasis on, further improve electrolyte resistance ability, thermal dimensional stability, chemical stability and the mechanical property of microporous barrier. ShouldMaterial is for the high security that improves lithium ion battery, and tool is of great significance and wide application prospect.
The UV-crosslinked PAEK micro-pore septum of one of the present invention preparation method, its step is as follows:
A) by the solubility of molecular weight ranges 5～80,000 can UV-crosslinked PAEK (structural formula is as follows,Or
Wherein m, n represent the percentage composition of each repeating unit, m+n=1, and 0.6≤m≤0.8), molecular weight ranges 4～60000 polyvinylpyrrolidone, the polyvinyl alcohol of molecular weight ranges 2000～8000, according to certain proportion of composing (polyethyleneThe quality consumption of pyrrolidones and polyvinyl alcohol with solubility can UV-crosslinked PAEK quality consumption identical; And poly-secondIn alkene pyrrolidone and polyvinyl alcohol, the mass content of polyvinylpyrrolidone is 80～90%), be dissolved in N, N-dimethyl secondIn the organic solvents such as acid amides, DMF or 1-METHYLPYRROLIDONE, be made into mass percentage concentration and be 15～The Polymer Solution of 30wt%, filters and removes impurity, standing and defoaming through the filter membrane of 0.3～0.5 μ m;
B) Polymer Solution step a) being obtained after standing and defoaming on the glass plate of level with the scraper of 20～80 μ mEvenly be coated with, leave standstill and on glass plate, obtain polymeric membrane after 10～60 seconds;
C) polymeric membrane that step b) obtains is immersed in ethanol or deionized water solid together with glass plate at ambient temperatureChange, after polymer film solidifies and peels off, by its washing by soaking 2～4 times in 40～60 DEG C of deionized waters, remove organic solvent,Pore creating material polyvinylpyrrolidone and polyvinyl alcohol, then by polymer porous film vacuum drying under 60～80 DEG C of conditions;
D) by dry polymer porous film hardening with radiation 10～30 minutes under 240～280nm UV-irradiation, therebyObtain UV-crosslinked poly aryl ether ketone polymer porous film material of the present invention.
A kind of UV-crosslinked poly aryl ether ketone polymer perforated membrane, it is to be prepared by as above method, perforated membrane thickness is20～80 μ m, porosity 50～70% (according to Archimedes principle, using the porosity of n-butanol measurement and calculation perforated membrane),Pore structure is the spongy hole mutually connecting, and aperture size is between 300nm～800nm.
The useful technique effect that the present invention produces:
Prepared by the technology that 1, the present invention adopts the auxiliary phase inversion method of phase separation method and polymer to combine can UV-crosslinkedly gatherAryl ether ketone polymer porous film there is pore structure evenly and mutually connect, pore-size distribution is narrower, high porosity etc.
2, the use of UV-crosslinked method does not change thickness and the pore structure of polymer porous film material, simultaneously improve andImproved porous film material resistance to elevated temperatures and heat resistanceheat resistant shrinkage, from the angle of lithium battery diaphragm, can ensure lithium electricityThe security performance in pond.
3, UV-crosslinked poly aryl ether ketone polymer perforated membrane has good electrolyte imbibition ability, its electrolyte pick upIt is the twice of commercialization polyethylene barrier film pick up.
The present invention obtain UV-crosslinked poly aryl ether ketone polymer perforated membrane in lithium ion battery field, particularly high safetyProperty lithium ion battery field has huge application prospect. In addition, porous film material prepared by the present invention, filtration, water treatment,The fields such as absorption also have good application potential.
Brief description of the drawings
For crosslinked PAEK perforated membrane SEM shape appearance figure, (Fig. 1 (a) is perforated membrane upper surface topography to Fig. 1, and Fig. 1 (b) is manyPore membrane cross-section morphology, Fig. 1 (c) is perforated membrane lower surface pattern);
Fig. 2 be the crosslinked PAEK perforated membrane prepared of commercial Celgard polyethylene barrier film, the present invention respectively with electricity(Fig. 2 (a) is commercial Celgard polyethylene barrier film, and Fig. 2 (b) is the present invention to separate liquid ethylene carbonate wetting property comparison diagramThe crosslinked PAEK perforated membrane of preparation);
Fig. 3 be before the crosslinked PAEK perforated membrane heat treatment prepared of the present invention (figure a), 180 DEG C of heat treatment 5h (b) heat of figureDimensional stability optical photograph;
Fig. 4 is that crosslinked PAEK perforated membrane prepared by the present invention is assembled into fastening lithium ionic cell first charge-discharge curve(Δ shape curve represents initial charge curve, and Ο shape curve represents discharge curve first).
Detailed description of the invention
Below in conjunction with specific embodiments and the drawings, the present invention is further set forth to explanation.
Embodiment 1
Crosslinked PAEK method for preparing porous film, comprises the following steps: solvable by what synthesize by nucleophilic displacement of fluorine routeCan UV-crosslinked PAEK (structural formula:
Molecular weight 60,000, wherein m, nRepresenting the percentage composition of each repeating unit, m=0.6, n=0.4) room temperature is dissolved in DMA, and magnetic force stirsMix 30min, be mixed with mass fraction and be 20% Polymer Solution, adding mass ratio is the polyvinylpyrrolidone (molecule of 9:1Measure 40,000) and polyvinyl alcohol (molecular weight 2000), both quality consumptions and with solvable can UV-crosslinked poly aryl ether ketone polymerQuality consumption is identical. After dissolving, filter and remove impurity through the filter membrane of aperture 0.3～0.5 μ m, stand-by after standing and defoaming 30mim.
The Polymer Solution that preceding step is obtained scraper with 20 μ m on the glass plate of level carries out even blade coating, quietPut 60 seconds. The polymeric membrane of completing is at the uniform velocity immersed in ethanol and is solidified 10 minutes together with glass plate, treat that polymer film solidifies strippingFrom rear, by curing polymer film washing by soaking 4 times in 40 DEG C of deionized waters, remove organic solvent N, N-dimethyl acetylAmine, pore creating material polyvinylpyrrolidone and polyvinyl alcohol, finally put into polymer porous film 60 DEG C of baking oven vacuum drying 10Hour.
By dry polymer porous film hardening with radiation 10 minutes in the ultraviolet case of wavelength 254nm, obtaining thickness is 20 μThe UV-crosslinked poly aryl ether ketone polymer porous film material of m left and right. Polymer porous film upper and lower surface and section hole consistent appearanceProperty is good. Pore structure is the spongy hole mutually connecting, and aperture size is (Fig. 1) between 300nm～800nm; Survey by n-butanolIt is 70% left and right that examination porosity method records perforated membrane porosity; By contrasting commercial Celgard polyalkene diaphragm with purpleExternal crosslinking PAEK perforated membrane and electrolyte ethylene carbonate (EC) wetting property (Fig. 2), illustrate ultraviolet prepared by the present inventionCrosslinked PAEK perforated membrane electrolyte wetting property is better than commercial Celgard polyalkene diaphragm; UV-crosslinked polyaryletherKetone perforated membrane is under 5 hours conditions of 180 DEG C of heat treatments, and significant change does not occur size, and (b), macro-size percent thermal shrinkage only for Fig. 3It is 0.5% left and right. The electrolyte wetting property of UV-crosslinked PAEK perforated membrane high porosity, excellence and excellent heat resistanceEnergy and thermal dimensional stability energy.
Embodiment 2
As embodiment 1, adding mass ratio is that polyvinylpyrrolidone and the molecular weight that the molecular weight of 9:1 is 60,000 is 8000Polyvinyl alcohol, prepares UV-crosslinked PAEK perforated membrane according to the identical preparation process of embodiment 1. Compare with embodiment 1 and makeStandby perforated membrane, along with the increase of polyvinylpyrrolidone and polyvinyl alcohol molecule amount, the dissolution velocity in ethanol is slack-off, manyThe aperture size of pore membrane slightly reduces, porosity 65% left and right; Perforated membrane is thermal dimensional stability and embodiment 1 under hot conditionsIn the perforated membrane that obtains similar.
Embodiment 3
As embodiment 1, preparation mass fraction to be 25% solvable can UV-crosslinked PAEK Polymer Solution, according to realityExecute the method that example 1 is identical and add polyvinylpyrrolidone and polyvinyl alcohol, and prepare ultraviolet according to identical condition preparation processCrosslinked PAEK perforated membrane. Compare the perforated membrane of preparing with embodiment 1, along with the increase of Polymer Solution concentration, perforated membranePorosity declines to some extent, is 60% left and right; The porous that perforated membrane obtains in thermal dimensional stability and embodiment 1 under hot conditionsFilm is similar.
Embodiment 4
As embodiment 1, preparation mass fraction to be 30% solvable can UV-crosslinked PAEK Polymer Solution, according to realityExecute the method that example 1 is identical and add polyvinylpyrrolidone and polyvinyl alcohol, and prepare ultraviolet according to identical condition preparation processCrosslinked PAEK perforated membrane. Compare the perforated membrane of preparing with embodiment 1, perforated membrane porosity is 55% left and right; Perforated membrane existsUnder hot conditions, thermal dimensional stability is similar to the perforated membrane obtaining in embodiment 1.
Embodiment 5
As embodiment 1, changing dry polymer porous film hardening with radiation time in the ultraviolet case of wavelength 254nm is 20Minute, prepare UV-crosslinked PAEK perforated membrane according to the identical method of embodiment 1 and step. Perforated membrane porosity is not sent outChanging, porosity is still 70% left and right. The porous that its electrolyte wetting property, thermal dimensional stability can be prepared with embodiment 1Film is more approaching.
Embodiment 6
As embodiment 1, scraper gap is adjusted into 40 μ m, prepare ultraviolet according to the identical method of embodiment 1 and step and hand overConnection PAEK perforated membrane. The increase of perforated membrane thickness, perforated membrane porosity slightly declines, porosity 65% left and right. Its electrolysisLiquid wetting property, thermal dimensional stability can be more approaching with perforated membrane prepared by embodiment 1.
Embodiment 7
As embodiment 1, change ethanol into deionized water, prepare UV-crosslinked according to the identical method of embodiment 1 and stepPAEK perforated membrane. Perforated membrane porosity does not have significant change, and porosity is in 70% left and right, with ethanol comparison, make to spend fromPolymer film prepared by sub-water, aperture size reduces to some extent. Its electrolyte wetting property, thermal dimensional stability can with embodiment 1The perforated membrane of preparation is more approaching.
Embodiment 8
As embodiment 7, scraper gap is adjusted into 40 μ m, prepare ultraviolet according to the identical method of embodiment 7 and step and hand overConnection PAEK perforated membrane. Perforated membrane porosity is in 65% left and right, its electrolyte wetting property, thermal dimensional stability can with enforcementPerforated membrane prepared by example 1 is more approaching.
Embodiment 9
As embodiment 7, preparation mass fraction to be 25% solvable can UV-crosslinked PAEK Polymer Solution, according to realityExecute method and the step that example 7 is identical and prepare UV-crosslinked PAEK perforated membrane.
Embodiment 10
As embodiment 7, preparation mass fraction to be 30% solvable can UV-crosslinked PAEK Polymer Solution, according to realityExecute method and the step that example 7 is identical and prepare UV-crosslinked PAEK perforated membrane.
Embodiment 11
As embodiment 1 to embodiment 10, can select respectively DMF or 1-METHYLPYRROLIDONE conductOrganic solvent. Configure according to the method described above variable concentrations Polymer Solution, the crosslinked PAEK porous film material of preparation. Result withAbove-described embodiment is close.
Embodiment 12
As embodiment 1 to embodiment 11, choice structure formula is
Polymer, the crosslinked PAEK porous film material of preparation according to the method described above. Result and above-described embodiment are close.
Embodiment 13
The UV-crosslinked PAEK perforated membrane that adopts embodiment 1 to prepare, is assembled into LiFePO4 according to following stepsCR2025 type button half-cell: mix LiFePO4, acetylene black and Kynoar (1) according to mass ratio 8:1:1, grinding is stirredMix evenly, be coated on aluminium foil, be dried section after 24 hours and make positive plate. (2) the UV-crosslinked polyarylether of being prepared by the present inventionIt is stand-by that ketone perforated membrane cuts into 3cm × 3cm specification. (3) using the made sample of step 1 is positive plate, and lithium sheet is negative plate, usesUV-crosslinked PAEK perforated membrane prepared by the present invention is that barrier film is assembled into CR2025 type button half-cell in glove box. WillThis button cell is put in multichannel cell tester (new prestige, blue electricity) and is tested (Fig. 4). In figure, Δ shape curve represents Ben FaThe UV-crosslinked PAEK perforated membrane assembled battery initial charge curve of bright preparation, Ο shape curve represents purple prepared by the present inventionExternal crosslinking PAEK perforated membrane assembled battery discharge curve first, relatively charge and discharge platform and the capacity of two lines, illustrates thisThe UV-crosslinked PAEK perforated membrane of invention preparation can be used as lithium ion battery separator materials'use, the heat resistance that it is excellentCan be able to improve the security performance of lithium ion battery.
Claims (4)
1. a preparation method for UV-crosslinked PAEK perforated membrane, its step is as follows:
A) by solubility as follows to molecular weight ranges 5～80,000, structural formula can UV-crosslinked PAEK, molecular weight ranges 4～6 ten thousand polyvinylpyrrolidone, the polyvinyl alcohol of molecular weight ranges 2000～8000 are dissolved in organic solvent, are made into qualityPercentage concentration is the Polymer Solution of 15～30wt%, filters and removes impurity, standing and defoaming through the filter membrane of 0.3～0.5 μ m; ItsIn, the quality consumption of polyvinylpyrrolidone and polyvinyl alcohol and with solubility can UV-crosslinked PAEK quality consumption phaseWith, and in polyvinylpyrrolidone and polyvinyl alcohol, the mass content of polyvinylpyrrolidone is 80～90%;
M, n represent the percentage composition of each repeating unit, m+n=1, and 0.6≤m≤0.8;
B) the Polymer Solution scraper with 20～80 μ m on the glass plate of level step a) being obtained after standing and defoaming carries outEvenly coating, leaves standstill and on glass plate, obtains polymeric membrane after 10～60 seconds;
C) polymeric membrane that step b) obtains is immersed at ambient temperature in ethanol or deionized water and solidifies together with glass plate, treatsAfter polymer film solidifies and peels off, by its washing by soaking 2～4 times in 40～60 DEG C of deionized waters, remove organic solvent, pore creating materialPolyvinylpyrrolidone and polyvinyl alcohol, then by polymer porous film vacuum drying under 60～80 DEG C of conditions;
D) by dry polymer porous film hardening with radiation 10～30 minutes under 240～280nm UV-irradiation, thereby obtainUV-crosslinked poly aryl ether ketone polymer porous film material.
2. the preparation method of a kind of UV-crosslinked PAEK perforated membrane as claimed in claim 1, is characterized in that: You JirongAgent is DMA, DMF or 1-METHYLPYRROLIDONE.
3. a UV-crosslinked PAEK perforated membrane, is characterized in that: be to be prepared into by the method described in claim 1 or 2Arrive, and the thickness of this perforated membrane is 20～80 μ m, porosity is 50～70%, and pore structure is the spongy hole mutually connecting, holeFootpath size is between 300nm～800nm.
4. the application of a kind of UV-crosslinked PAEK perforated membrane claimed in claim 3 in lithium ion battery separator material.
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Cited By (12)
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| CN107134556A (en) * | 2017-03-31 | 2017-09-05 | 乐凯胶片股份有限公司 | A kind of lithium ion battery separator |
| CN108063207A (en) * | 2017-12-22 | 2018-05-22 | 深圳市计量质量检测研究院 | A kind of membrane preparation method for lithium sode cell |
| CN108155325A (en) * | 2017-12-22 | 2018-06-12 | 深圳市计量质量检测研究院 | Preparation method of polymer diaphragm based on lithium/sodium ion battery |
| CN108232091A (en) * | 2018-01-10 | 2018-06-29 | 上海恩捷新材料科技股份有限公司 | Battery isolating film preparation method |
| CN108281597A (en) * | 2018-01-10 | 2018-07-13 | 上海恩捷新材料科技股份有限公司 | Mixture of battery isolating film and application thereof |
| CN108565384A (en) * | 2018-05-28 | 2018-09-21 | 中国地质大学（武汉） | A kind of preparation method and application of sulfonated polyether-ether-ketone lighium polymer electrolyte membrance |
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| CN108666502A (en) * | 2018-04-26 | 2018-10-16 | 广东永邦新能源股份有限公司 | A kind of preparation method of hydrophilic heat-resisting lithium battery diaphragm |
| CN110880573A (en) * | 2018-09-05 | 2020-03-13 | 张家港祥成医用材料科技有限公司 | Preparation method of polyether ketone battery diaphragm |
| CN111697190A (en) * | 2020-07-17 | 2020-09-22 | 东北师范大学 | Polyaryletherketone for lithium battery diaphragm |
| WO2020187684A1 (en) * | 2019-03-18 | 2020-09-24 | Solvay Specialty Polymers Usa, Llc | Functionalized poly(aryl ether sulfones) copolymers |
| WO2021123405A1 (en) * | 2019-12-19 | 2021-06-24 | Solvay Specialty Polymers Usa, Llc | Side-chain functionalized poly(aryl ether sulfones) copolymer comprising reactive end-groups |
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| CN111697190A (en) * | 2020-07-17 | 2020-09-22 | 东北师范大学 | Polyaryletherketone for lithium battery diaphragm |
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