CN113105661A - Polyether-ether-ketone diaphragm and preparation method and application thereof - Google Patents
Polyether-ether-ketone diaphragm and preparation method and application thereof Download PDFInfo
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- CN113105661A CN113105661A CN202110343070.7A CN202110343070A CN113105661A CN 113105661 A CN113105661 A CN 113105661A CN 202110343070 A CN202110343070 A CN 202110343070A CN 113105661 A CN113105661 A CN 113105661A
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- 239000004696 Poly ether ether ketone Substances 0.000 title claims abstract description 37
- 229920002530 polyetherether ketone Polymers 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 67
- 238000003756 stirring Methods 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims abstract description 34
- 238000000605 extraction Methods 0.000 claims abstract description 33
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 29
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 18
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 18
- BWQOPMJTQPWHOZ-UHFFFAOYSA-N (2,3-difluorophenyl)-phenylmethanone Chemical compound FC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1F BWQOPMJTQPWHOZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 11
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 11
- 238000005266 casting Methods 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 238000001125 extrusion Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000012528 membrane Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims 1
- 239000010959 steel Substances 0.000 claims 1
- 239000004642 Polyimide Substances 0.000 abstract description 17
- 229920001721 polyimide Polymers 0.000 abstract description 17
- 239000004760 aramid Substances 0.000 abstract description 11
- 229920003235 aromatic polyamide Polymers 0.000 abstract description 10
- 239000000243 solution Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229920005575 poly(amic acid) Polymers 0.000 description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 229940018564 m-phenylenediamine Drugs 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000001360 synchronised effect Effects 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/02—Condensation polymers of aldehydes or ketones with phenols only of ketones
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention discloses a polyether-ether-ketone diaphragm and a preparation method and application thereof, wherein the preparation method comprises the following steps: step 1: under the protection of inert gas, sequentially adding difluorobenzophenone and hydroquinone into diphenyl sulfone to obtain reaction liquid; heating the reaction liquid to 190 ℃ at one time, adding anhydrous potassium carbonate and polyethylene glycol, uniformly stirring, heating to 350 ℃ at 310 ℃ in a stepped manner, and stirring for 2-3h at 350 ℃ at 310 ℃; cooling to 90-180 ℃ and obtaining an extruded body with the viscosity of the reaction solution of 10000-14000 mPa.s; step 2: and (3) carrying out a sheet casting process on the extruded body obtained in the step (1) to obtain a cast sheet, and then carrying out transverse drawing, longitudinal drawing, primary extraction, primary drying, secondary extraction and secondary drying once to obtain the polyether-ether-ketone diaphragm. Compared with the traditional high-temperature-resistant diaphragm, namely a polyimide diaphragm and a meta-aramid diaphragm, the polyether-ether-ketone diaphragm prepared by the preparation method has better high-temperature resistance and mechanical property.
Description
Technical Field
The invention relates to the technical field of battery diaphragms, in particular to a polyether-ether-ketone diaphragm and a preparation method and application thereof.
Background
The battery diaphragm on the market at present generally adopts PE and PP material to make, its advantage with have fine flexibility and intensity, the preparation diaphragm is comparatively simple, its shortcoming lies in not having high temperature resistance. While high temperature resistant membranes generally do not have flexibility and strength. For example, polyimide and meta-aramid fibers are high temperature resistant materials, but they are degraded in various properties after the production of the separator, and are likely to break when subjected to mechanical impact.
Disclosure of Invention
The invention aims to provide a polyether-ether-ketone diaphragm aiming at the technical defect that the common materials in the prior art cannot give consideration to both high temperature resistance and mechanical strength.
The invention also aims to provide a preparation method of the polyether-ether-ketone membrane.
The invention also aims to provide application of the polyether-ether-ketone membrane.
The technical scheme adopted for realizing the purpose of the invention is as follows:
a preparation method of a polyether-ether-ketone diaphragm comprises the following steps:
step 1: preparation of the extrudates
Under the protection of inert gas, sequentially adding difluorobenzophenone and hydroquinone into diphenyl sulfone to obtain reaction liquid; heating the reaction liquid to 190 ℃ at one time, adding anhydrous potassium carbonate and polyethylene glycol, uniformly stirring, heating to 350 ℃ at 310 ℃ in a stepped manner, and stirring for 2-3h at 350 ℃ at 310 ℃; cooling to 90-180 ℃ and obtaining an extruded body with the viscosity of the reaction solution of 10000-14000 mPa.s;
the chemical reaction formula of the process is as follows:
69-51 parts of diphenyl sulfone, 17-23 parts of the sum of difluorobenzophenone and hydroquinone, 2-5 parts of anhydrous potassium carbonate and 12-21 parts of polyethylene glycol; wherein, the molar ratio of the difluorobenzophenone to the hydroquinone is (0.9-1.3): (1-1.5);
step 2: film production
And (3) carrying out a sheet casting process on the extruded body obtained in the step (1) to obtain a cast sheet, and then sequentially carrying out transverse drawing, longitudinal drawing, primary extraction, primary drying, secondary extraction and secondary drying to obtain the polyether-ether-ketone diaphragm.
In the above technical solution, in step 1, the step heating specifically includes: the temperature is raised to 230 ℃ at 200-. The step heating mainly avoids the implosion caused by too fast reaction, and has the advantages of slowing down the reaction, ensuring more sufficient polymerization of molecules, being beneficial to improving the molecular weight of the extruded body and ensuring that the molecular weight of the extruded body is generally between 5 and 8 ten thousand.
In the technical scheme, the heating rate is 3-6 ℃/min when the temperature is raised for one time, two times, three times and four times.
In the technical scheme, in the step 1, the cooling rate is 2-5 ℃/min. The polymer is condensed into small particle blocks when the temperature is reduced too fast, and the small particle blocks are easy to break in the film preparation process in the step 2.
In the technical scheme, in the step 2, the width of an extrusion opening of an extruder in the sheet casting process is 250-350mm, the height of the extrusion opening is 15-25mm, and the extrusion rate is 0.2-0.5 m/s; the temperature of the cooling roller is 110-150 ℃, and the speed of the cooling roller in the sheet casting process is 0.2-0.5 m/s.
In the technical scheme, transverse drawing is carried out through a cooling roller front roller, the speed of the cooling roller front roller is 3-5 times of that of the cooling roller, and the roller distance between the cooling roller front roller and the cooling roller is 0.5 m; the transverse drawing temperature is 90-150 ℃, and the transverse drawing multiplying power is 1.5-3 times.
In the technical scheme, the longitudinal drawing temperature is 90-150 ℃, and the longitudinal drawing multiplying power is 1.5-2 times.
In the technical scheme, the primary extraction temperature is 15-30 ℃, and the extraction liquid is acetone; the temperature of the secondary extraction is 15-30 ℃, and the extraction liquid is water; the primary drying temperature is 50-80 deg.C, the drying time is 0.1-0.3min, the secondary drying temperature is 50-80 deg.C, and the drying time is 0.1-0.3 min.
In another aspect of the invention, the polyether-ether-ketone diaphragm prepared by the preparation method is applied.
In another aspect of the invention, the polyether-ether-ketone diaphragm is applied to a lithium battery diaphragm.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method of the polyether-ether-ketone diaphragm, the phenomenon of implosion caused by too fast reaction is avoided in a stepped heating mode. Meanwhile, the reaction is slowed down, the molecules are more fully polymerized, and the molecular weight of the extruded body reaches between 5 and 8 ten thousand.
2. The polyether-ether-ketone diaphragm provided by the invention has the advantages that the polyether-ether-ketone fibers are uniform in three-dimensional and high in porosity, lithium ions can shuttle among the diaphragms, the surface is smooth, and the toughness and the strength of the diaphragm are high.
3. Compared with the traditional high-temperature-resistant diaphragm, namely a polyimide diaphragm and a meta-aramid diaphragm, the polyether-ether-ketone diaphragm provided by the invention has better high-temperature resistance and mechanical property.
Drawings
FIG. 1 is a scanning electron microscope image of a No. 1 PEEK membrane.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The preparation method of the No. 1 polyetheretherketone diaphragm comprises the following steps:
step 1: preparation of the extrudates
Protecting a reaction kettle with nitrogen, adding diphenyl sulfone, raising the temperature to 30 ℃, then adding difluorobenzophenone, stirring for 20min, then adding hydroquinone, stirring for 20min, heating to 150 ℃ for the first time after stirring, heating at the rate of 3 ℃/min, then adding anhydrous potassium carbonate and polyethylene glycol, stirring for 20min, heating to 200 ℃ for the second time, stirring for 50min, heating to 240 ℃ for the third time, stirring for 10min, heating to 310 ℃ for the last four times, stirring for 2h, then starting cooling, wherein the cooling rate is 2 ℃/min, the cooling process is accompanied with viscosity rise, when the cooling is 180 ℃, the viscosity reaches 10000mPa.s, and the cooling is stopped.
The composition comprises, by mass, 69 parts of diphenyl sulfone, 17 parts of difluorobenzophenone and hydroquinone, 2 parts of anhydrous potassium carbonate and 12 parts of polyethylene glycol; the molar ratio of the difluorobenzophenone to the hydroquinone is 1.2: 1;
step 2: film production
And (2) pressurizing the extruded body obtained in the step (1), opening an extrusion valve at the bottom of the reaction kettle, wherein the width of an extrusion opening is 250mm, the height of the extrusion opening is 15mm, the extrusion rate is 0.2m/s, extruding the extruded body onto a cooling roller, the diameter of the cooling roller is 0.5m, the temperature of the cooling roller is 110 ℃, the linear speed of the cooling roller and the extrusion speed are synchronous to be 0.2m/s, extruding the extruded body onto the cooling roller and then transversely drawing the extruded body by a front roller of the cooling roller, wherein the speed of the front roller of the cooling roller is 3 times that of the cooling roller, and the roller distance between the front roller of the cooling roller and the cooling roller is 0.5 m. The front roller of the cooling roller and the cooling roller are arranged in parallel, and the connecting direction between the front roller and the cooling roller is the transverse direction of the diaphragm. The transverse drawing temperature is 90 ℃, and the transverse drawing multiplying power is 1.5 times. And longitudinally pulling the film after the transverse pulling is finished, wherein the longitudinal pulling method comprises the steps that mechanical force arms for pulling the film outwards are arranged on two sides of the film, the film can be longitudinally pulled by the mechanical force on the two sides when the film moves forwards, the longitudinal pulling temperature is 90 ℃, and the longitudinal pulling multiplying power is 1.5 times.
After transverse drawing and longitudinal drawing are finished, because polyethylene glycol, salt and diphenyl sulfone contained in the film need to be extracted and washed away, the extraction tank is divided into 10 small tanks in a one-time extraction mode, the depth of each tank is 1m, acetone is filled in each tank, a diaphragm penetrates through each tank, and the diphenyl sulfone is extracted through the acetone in sequence. And (3) performing primary extraction, drying in an oven for 0.1min at the drying temperature of 50 ℃ for the first time, performing secondary extraction, and extracting the salt in the polyethylene glycol and the diaphragm by using water, wherein the secondary extraction is realized by dividing an extraction tank into 10 small tanks, the depth of each tank is 1m, the tank is filled with water, the diaphragm penetrates through each tank, and the salt in the polyethylene glycol and the diaphragm is extracted by sequentially using water. And finally, secondary drying is carried out in a drying oven at the drying temperature of 50 ℃ for 0.1min, and then the No. 1 polyetheretherketone diaphragm is obtained.
The scanning electron microscope image of the No. 1 polyetheretherketone diaphragm is shown in figure 1, and it can be seen from the figure that polyetheretherketone fibers are three-dimensionally uniform and have high porosity, so that lithium ions can shuttle between the diaphragms, and the surface of the diaphragm is smooth, so that the diaphragm has high toughness and strength.
Example 2
The preparation method of the No. 2 polyetheretherketone diaphragm comprises the following steps:
step 1: preparation of the extrudates
Protecting a reaction kettle with nitrogen, adding diphenyl sulfone, raising the temperature to 40 ℃, then adding difluorobenzophenone, stirring for 25min, then adding hydroquinone, stirring for 25min, heating to 170 ℃ for the first time after stirring, wherein the heating rate is 5 ℃/min, then adding anhydrous potassium carbonate and polyethylene glycol, stirring for 25min, heating to 220 ℃ for the second time, stirring for 60min, heating to 250 ℃ for the third time, stirring for 20min, heating to 340 ℃ for the last four times, stirring for 2h, then starting cooling, wherein the cooling rate is 4 ℃/min, the cooling process is accompanied with viscosity rise, and when the temperature is reduced to 150 ℃, the viscosity reaches 12000mPa.
Wherein the mass portion of the diphenyl sulfone is 60, the sum of the mass portions of the difluorobenzophenone and the hydroquinone is 20, the anhydrous potassium carbonate is 3, and the polyethylene glycol is 17; the molar ratio of the difluorobenzophenone to the hydroquinone is 1.2: 1;
step 2: film production
And (2) pressurizing the extruded body obtained in the step (1), opening an extrusion valve at the bottom of the reaction kettle, wherein the width of an extrusion opening is 300mm, the height of the extrusion opening is 20mm, the extrusion rate is 0.3m/s, extruding the extruded body onto a cooling roller, the diameter of the cooling roller is 0.5m, the temperature of the cooling roller is 130 ℃, the linear speed of the cooling roller is synchronous to the extrusion speed of 0.3m/s, extruding the extruded body onto the cooling roller, and then transversely drawing the extruded body through a front roller of the cooling roller, wherein the speed of the front roller of the cooling roller is 4 times that of the cooling roller, and the roller distance between the front roller of the cooling roller and the cooling roller is 0.5 m. The transverse drawing temperature is 120 ℃, and the transverse drawing multiplying power is 2 times. And longitudinally pulling the film after the transverse pulling is finished, wherein the longitudinal pulling method comprises the steps that mechanical force arms for pulling the film outwards are arranged on two sides of the film, the film can be longitudinally pulled by the mechanical force on the two sides when the film moves forwards, the longitudinal pulling temperature is 120 ℃, and the longitudinal pulling multiplying power is 1.8 times.
After transverse pulling and longitudinal pulling, the extraction tank is divided into 10 small tanks, the depth of each tank is 1m, acetone is filled in the tank, and the diaphragm penetrates through each tank to extract diphenyl sulfone through the acetone in sequence. And (3) performing primary extraction, drying in an oven for 0.2min at the drying temperature of 60 ℃ for the first time, performing secondary extraction, and extracting the salt in the polyethylene glycol and the diaphragm by using water, wherein the secondary extraction is realized by dividing an extraction tank into 10 small tanks, the depth of each tank is 1m, the tank is filled with water, the diaphragm penetrates through each tank, and the salt in the polyethylene glycol and the diaphragm is extracted by sequentially using water. And finally, secondary drying is carried out in a drying oven at the drying temperature of 60 ℃ for 0.2min, and then the No. 2 polyetheretherketone diaphragm is obtained.
Example 3
The preparation method of the No. 3 polyetheretherketone diaphragm comprises the following steps:
step 1: preparation of the extrudates
Protecting a reaction kettle with nitrogen, adding diphenyl sulfone, raising the temperature to 50 ℃, then adding difluorobenzophenone, stirring for 30min, then adding hydroquinone, stirring for 30min, heating to 190 ℃ for the first time after stirring, heating at the heating rate of 6 ℃/min, then adding anhydrous potassium carbonate and polyethylene glycol, stirring for 30min, heating to 230 ℃ for the second time, stirring for 70min, heating to 260 ℃ for the third time, stirring for 25min, heating to 350 ℃ for the last four times, stirring for 3h, then starting cooling, wherein the cooling rate is 5 ℃/min, the cooling process is accompanied with viscosity rise, and when the temperature is reduced to 130 ℃, the viscosity reaches 14000mPa.
Wherein the mass portion of the diphenyl sulfone is 51, the sum of the mass portions of the difluorobenzophenone and the hydroquinone is 23, the anhydrous potassium carbonate is 5, and the polyethylene glycol is 21; the molar ratio of the difluorobenzophenone to the hydroquinone is 1.2: 1;
step 2: film production
And (2) pressurizing the extruded body obtained in the step (1), opening an extrusion valve at the bottom of the reaction kettle, wherein the width of an extrusion opening is 350mm, the height of the extrusion opening is 25mm, the extrusion rate is 0.5m/s, extruding the extruded body onto a cooling roller, the diameter of the cooling roller is 0.5m, the temperature of the cooling roller is 150 ℃, the linear speed of the cooling roller is synchronous to the extrusion speed of 0.5m/s, extruding the extruded body onto the cooling roller, and then transversely drawing the extruded body through a front roller of the cooling roller, wherein the speed of the front roller of the cooling roller is 5 times that of the cooling roller, and the roller distance between the front roller of the cooling roller and the cooling roller is 0.5 m. The transverse drawing temperature is 150 ℃, and the transverse drawing multiplying power is 3 times. And longitudinally pulling the film after the transverse pulling is finished, wherein the longitudinal pulling method comprises the steps that mechanical force arms for pulling the film outwards are arranged on two sides of the film, the film can be longitudinally pulled by the mechanical force on the two sides when the film moves forwards, the longitudinal pulling temperature is 150 ℃, and the longitudinal pulling multiplying power is 2 times.
After transverse pulling and longitudinal pulling, the extraction tank is divided into 10 small tanks, the depth of each tank is 1m, acetone is filled in the tank, and the diaphragm penetrates through each tank to extract diphenyl sulfone through the acetone in sequence. And (3) drying the primary extract in an oven for 0.3min at the drying temperature of 80 ℃ after the primary extraction, extracting the salt in the polyethylene glycol and the diaphragm by using water after the secondary extraction, wherein the secondary extraction is realized by dividing an extraction tank into 10 small tanks, the depth of each tank is 1m, the tank is filled with water, allowing the diaphragm to pass through each tank, and sequentially extracting the salt in the polyethylene glycol and the diaphragm by using water. And finally, secondary drying is carried out in a drying oven, the drying temperature is 80 ℃, the drying time is 0.3min, and then the No. 3 polyetheretherketone diaphragm is obtained.
Comparative example 1
A preparation method of a polyimide diaphragm comprises the following steps:
step 1, under the protection of nitrogen, adding the N-methylpyrrolidone subjected to water removal into a reaction tank, then adding p-phenylenediamine into the reaction tank, and stirring for 15min at a speed of 30r/min to fully dissolve the p-phenylenediamine to obtain a first mixed solution; introducing chilled water into a jacket of a reaction tank, cooling the first mixed solution in the reaction tank to 7 ℃, adding pyromellitic dianhydride into the first mixed solution to obtain a second mixed solution, gradually heating the second mixed solution to 15 ℃, keeping the temperature, and stirring for 20min at a speed of 30r/min to fully react in the second mixed solution to obtain a polyamic acid solution; wherein, the mass percentage of the N-methyl pyrrolidone is 95 percent, the total mass fraction of the p-phenylenediamine and the pyromellitic dianhydride is 5 percent, and the molar ratio of the p-phenylenediamine to the pyromellitic dianhydride is 1: 2;
step 2, cooling the polyamic acid solution obtained in the step 1 to 5 ℃, adding dimethyl carbonate into the polyamic acid solution, and stirring at 30r/min for 25min to uniformly mix the two to obtain polyamic acid slurry; wherein the mass fraction of the polyamic acid solution obtained in the step 1 is 90 wt%, and the mass fraction of the dimethyl carbonate is 10 wt%;
and 3, preparing the polyamide acid slurry, preparing a polyimide diaphragm precursor by adopting a tape casting method, then preparing the polyimide diaphragm by high-temperature dehydration and conversion, putting the polyimide solution into an extruder, melting and plasticizing the polyimide solution by the extruder, extruding the melted polyamide acid through a die orifice of a slit machine head to enable the melted polyamide acid to be tightly attached to a cooling roller, stretching, trimming and coiling the polyimide, then removing and converting the polyimide by using a high-temperature roller, and finally preparing the polyimide diaphragm.
Comparative example 2
A preparation method of a meta-aramid diaphragm comprises the following steps:
step 1: introducing nitrogen into a reaction tank for protection, adding a dimethylacetamide solution, adding m-phenylenediamine, stirring until the m-phenylenediamine is dissolved for about 20min, introducing chilled water, cooling to 0 ℃, adding isophthaloyl dichloride, stirring for 20min, removing the chilled water, gradually heating and stirring to 80 ℃, wherein the process time is about 80min, then adding calcium hydroxide, and stirring for 30min to obtain a first reaction solution; wherein the mass fraction of the dimethylacetamide solution is 60%, the mass fraction of m-phenylenediamine and isophthaloyl chloride is 35%, the molar mass ratio of m-phenylenediamine to phthaloyl chloride is 1:1, and the mass fraction of calcium hydroxide is 5%;
step 2: adding dimethyl carbonate into the first reaction liquid obtained in the step (1), keeping the temperature at 50 ℃, stirring for 30min to obtain a second reaction liquid, measuring the viscosity of the second reaction liquid, and then adjusting the viscosity of the second reaction liquid to 12000mpa.s by using a dimethylacetamide solution to obtain a precursor; wherein the first reaction liquid accounts for 80 parts by weight, and the dimethyl carbonate accounts for 10 parts by weight.
And step 3: and (3) putting the precursor obtained in the step (2) into a closed stirring tank, stirring for 40min, uniformly extruding the precursor out of the tank through nitrogen high pressure (controlling the thickness of the film through the extrusion speed), and performing transverse drawing, longitudinal drawing, extraction, drying and rolling once to obtain the meta-aramid diaphragm.
When extruding, a receiving roller is arranged below the tank bottom, and the aramid fiber slurry is driven by rotation.
A transverse pulling part: the linear velocity of a receiving roller at the bottom of the tank is 5m/min (the diameter of the receiving roller is 600mm), a buffer roller is arranged in front of the receiving roller, the linear velocity of the buffer roller is 5m/min, two transverse pulling rollers (a transverse pulling roller and a transverse pulling two roller) are arranged in front of the buffer roller, the linear velocity of the transverse pulling roller is 10m/min, and the linear velocity of the transverse pulling roller is 15 m/min;
a longitudinal pulling part: the transversely pulled film is brought to a longitudinal pulling biting wheel through a driving roller, the longitudinal pulling biting wheel is oval, the angle of the longitudinal pulling biting wheel is oblique at 30 degrees, the edge of the oval is provided with dense biting wheels, the edge of the film can be clamped for longitudinal pulling, and the longitudinal pulling is carried out twice in total. So that the corresponding breadth can be reached.
And (3) extraction part: the extraction part is divided into 10 tanks, each tank is separated by a partition board, the first three tanks use dimethylacetamide solutions with the concentration of 60%, 45% and 10%, respectively, and the rest tanks are deionized water.
The following table shows performance data for the polyetheretherketone membranes prepared in examples 1-3, as well as the polyimide membrane prepared in comparative example 1 and the meta-aramid membrane prepared in comparative example 2.
As can be seen from the above table:
1. under the condition of basically same thickness, the air permeability value of the No. 1-3 polyetheretherketone membrane is obviously higher than that of a polyimide membrane and a meta-aramid membrane.
The high-temperature performance of the No. 2.1-3 polyetheretherketone diaphragm is superior to that of polyimide diaphragms and meta-aramid diaphragms.
The tensile strength of No. 3.1-3 polyetheretherketone membranes is 1890-1921kgf/cm2Significantly higher than 235kgf/cm of the polyimide separator2And a m-aramid separator of 133kgf/cm2. The elongation rate of the No. 1-3 polyetheretherketone diaphragm is 102-110%, which is obviously higher than 30% of polyimide diaphragm and 22% of meta-aramid diaphragm. Therefore, the mechanical strength and the toughness of the No. 1-3 polyetheretherketone diaphragm are far better than those of a polyimide diaphragm and a meta-aramid diaphragm.
The polyetheretherketone membranes of the present invention were prepared according to the present disclosure with process parameter adjustments and exhibited substantially the same properties as in example 1.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a polyether-ether-ketone diaphragm is characterized by comprising the following steps: the method comprises the following steps:
step 1: preparation of the extrudates
Under the protection of inert gas, sequentially adding difluorobenzophenone and hydroquinone into diphenyl sulfone to obtain reaction liquid; heating the reaction liquid to 190 ℃ at one time, adding anhydrous potassium carbonate and polyethylene glycol, uniformly stirring, heating to 350 ℃ at 310 ℃ in a stepped manner, and stirring for 2-3h at 350 ℃ at 310 ℃; cooling to 90-180 ℃ and obtaining an extruded body with the viscosity of the reaction solution of 10000-14000 mPa.s;
69-51 parts of diphenyl sulfone, 17-23 parts of the sum of difluorobenzophenone and hydroquinone, 2-5 parts of anhydrous potassium carbonate and 12-21 parts of polyethylene glycol; wherein the molar ratio of the difluorobenzophenone to the hydroquinone is (0.9-1.3); (1-1.5);
step 2: film production
And (3) carrying out a sheet casting process on the extruded body obtained in the step (1) to obtain a cast sheet, and then carrying out transverse drawing, longitudinal drawing, primary extraction, primary drying, secondary extraction and secondary drying once to obtain the polyether-ether-ketone diaphragm.
2. The method of claim 1, wherein: in step 1, the step heating specifically comprises: the temperature is raised to 230 ℃ at 200-.
3. The method of claim 2, wherein: the heating rate of the first heating, the second heating, the third heating and the fourth heating is 3-6 ℃/min.
4. The method of claim 1, wherein: in step 1, the cooling rate is 2-5 ℃/min.
5. The method of claim 1, wherein: in the step 2, the width of an extrusion port of an extruder in the sheet casting process is 250-350mm, the height of the extrusion port is 15-25mm, and the extrusion rate is 0.2-0.5 m/s; the temperature of the cooling roller is 110-150 ℃, and the speed of the cooling roller in the sheet casting process is 0.2-0.5 m/s.
6. The method of claim 5, wherein: transversely drawing the steel wire by a cooling roller front roller, wherein the speed of the cooling roller front roller is 3-5 times of that of the cooling roller, and the roller distance between the cooling roller front roller and the cooling roller is 0.5 m; the transverse drawing temperature is 90-150 ℃, and the transverse drawing multiplying power is 1.5-3 times.
7. The method of claim 6, wherein: the longitudinal drawing temperature is 90-150 ℃, and the longitudinal drawing multiplying power is 1.5-2 times.
8. The method of claim 7, wherein: the primary extraction temperature is 15-30 ℃, and the extraction liquid is acetone; the temperature of the secondary extraction is 15-30 ℃, and the extraction liquid is water; the primary drying temperature is 50-80 ℃, and the secondary drying temperature is 50-80 ℃.
9. The polyetheretherketone membrane prepared by the method of any one of claims 1 to 8.
10. Use of a polyetheretherketone separator according to claim 9 in a lithium battery separator.
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