CN116144020B - Poly para-aramid lithium battery diaphragm coating polymerization solution and industrial production method thereof - Google Patents
Poly para-aramid lithium battery diaphragm coating polymerization solution and industrial production method thereof Download PDFInfo
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- CN116144020B CN116144020B CN202111382596.2A CN202111382596A CN116144020B CN 116144020 B CN116144020 B CN 116144020B CN 202111382596 A CN202111382596 A CN 202111382596A CN 116144020 B CN116144020 B CN 116144020B
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- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 49
- 238000000576 coating method Methods 0.000 title claims abstract description 35
- 239000011248 coating agent Substances 0.000 title claims abstract description 32
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 19
- 238000009776 industrial production Methods 0.000 title claims abstract description 12
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229920000642 polymer Polymers 0.000 claims abstract description 41
- 239000002121 nanofiber Substances 0.000 claims abstract description 30
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims description 61
- 239000002904 solvent Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 4
- 238000010924 continuous production Methods 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000007711 solidification Methods 0.000 abstract description 2
- 230000008023 solidification Effects 0.000 abstract description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 72
- 238000005086 pumping Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010923 batch production Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 229920001688 coating polymer Polymers 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000010325 electrochemical charging Methods 0.000 description 1
- 238000010326 electrochemical discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000009423 ventilation 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/423—Polyamide resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a poly para-aramid lithium battery diaphragm coating polymerization solution and an industrial production method thereof, wherein a continuous production mode is adopted, p-phenylenediamine/NMP/CaCl 2 solution is prepolymerized with molten terephthaloyl chloride and then reacted with the molten terephthaloyl chloride to prepare the poly para-aramid nanofiber solution, and the poly para-aramid nanofiber solution is defoamed to prepare a polymerization solution with an index system of concentration of <3%, dynamic viscosity of 10000-30000 cp and polymer intrinsic viscosity of 1-2.5, so that the polymerization solution can be used for battery diaphragm coating, pore-forming agents or other fillers are not needed, and nanofibers are naturally accumulated on the surface of a base diaphragm to form pores after solidification, so that the solution has better fluidity and is easier to coat and produce.
Description
Technical Field
The invention relates to a poly para-aramid lithium battery diaphragm coating polymerization solution and an industrial production method thereof, in particular to a poly para-aramid lithium battery diaphragm coating polymerization solution with excellent pore-forming property and film forming property and an industrial production method thereof, belonging to the technical field of lithium battery diaphragm coating materials.
Background
The lithium ion battery has been widely used in mobile electronic devices and power devices with the advantages of high energy density, long cycle life and the like since development, wherein a lithium battery diaphragm is one of key inner layer components of the lithium ion battery, can isolate positive and negative electrodes and prevent electrons in the battery from passing through, and can allow ions to pass through, so that rapid transmission of lithium ions between the positive and negative electrodes in an electrochemical charging and discharging process is completed. Therefore, the quality of the diaphragm performance directly affects the discharge capacity and the cycle life of the battery, and has very important influence on the safety of the lithium battery.
At present, research for improving the safety, usability and manufacturability of lithium ion batteries by improving the performance of separators is receiving increasing attention. However, the existing lithium ion battery diaphragm is made of polypropylene (PP) or Polyethylene (PE) materials, has a low melting point, is easy to shrink when heated, causes contact short circuit of positive and negative electrodes, and reduces the safety of the battery. The current temperature resistance modification of the olefin diaphragm mainly adopts PVDF coating and inorganic particle Al 2O3、ZrO2、SiO2 coating and bonding modification, but the two coatings have the defects of difficult control of the appearance of the coating and poor bonding with the diaphragm. In the fiber field, the polyaramid polymer has the characteristics of high temperature resistance, high strength, high dimensional stability and chemical corrosion resistance, and the thermal decomposition temperature is higher than 450 ℃, so that the polyaramid polymer is used as the lithium battery diaphragm coating, which is beneficial to improving the temperature resistance and puncture resistance of the diaphragm and greatly improving the safety of the lithium battery.
For example: the patent publication No. CN102471518A describes a para-aramid solution prepared by adding phthaloyl dichloride to a solution of N-methyl-2-pyrrolidone (NMP), calcium chloride powder and p-phenylenediamine in portions, stirring and aging to obtain a solution of 6% para-aramid. However, this solution had poor pore-forming property, and therefore, when used, NMP was added to this solution to prepare a solution having a para-aramid concentration of 1.58% by weight, followed by stirring for 60 minutes, mixing again alumina particles, filtering, adding calcium oxide, stirring, neutralizing, and deaerating under reduced pressure to obtain a slurry-like coating solution, which was then applied to a porous membrane to a thickness of 130. Mu.m, and then placed in an oven at 50℃for 15 seconds at 70% RH, and the bonding strength between the para-aramid layer and the porous membrane was measured to reach 9g.
In addition, the invention patent with publication number CN112201903A also describes a poly para-aramid polymerization solution, which is prepared by adding phthaloyl dichloride into NMP/DMAc/DMF, halogenated alkaline earth metal or alkali metal salt and p-phenylenediamine solution in batches, defoaming after reaction to prepare polymer solution with concentration of more than or equal to 3%, coating the polymer solution on the surface of a base film, and then solidifying, cleaning and drying to obtain the polyaramid nanofiber coating, and naturally forming a porous structure. The patent improves the pore-forming property of the polymer solution to a certain extent, but has poorer film forming property in the coating process, which is unfavorable for the mass production of the battery diaphragm coating.
Based on the above situation, in order to solve the problems of pore-forming property and film-forming property of the existing poly-para-aramid polymer solution, and meanwhile, in order to promote the industrialized production of the lithium battery diaphragm coating and improve the industrial efficiency, research and development of an industrialized production method capable of preparing the high-performance poly-para-aramid lithium battery diaphragm coating polymer solution are important points of the current lithium battery diaphragm technology.
Disclosure of Invention
The invention provides an industrial production method for preparing high-performance poly para-aramid lithium battery diaphragm coating polymerization solution, which can accurately control the viscosity of the whole polymer solution so as to realize stable control when a screw replaces an intermittent reaction kettle for continuous production, and simultaneously, the pore-forming property and the film forming property of the polymerization solution are improved. In addition, the invention also provides a poly para-aramid lithium battery diaphragm coating polymerization solution prepared by the industrial production method.
The invention is realized by the following technical scheme: an industrial production method of a poly para-aramid lithium battery diaphragm coating polymerization solution comprises the following steps:
s1, controlling the moisture of an NMP/CaCl 2 solvent system by adopting an online trace moisture instrument, and then heating and dissolving p-phenylenediamine in the solvent system under an N 2 sealing environment to obtain a p-phenylenediamine/NMP/CaCl 2 solution, wherein the content of the p-phenylenediamine in the solution is 0.3-1.2w%, and the moisture content is not less than 200ppm.
S2, cooling the p-phenylenediamine/NMP/CaCl 2 solution obtained in the step S1 to 0-5 ℃, and reacting with molten terephthaloyl chloride in a pre-reaction kettle to obtain a prepolymer;
s3, carrying out contact mixing reaction on the prepolymer obtained in the step S2 and molten terephthaloyl chloride in a premixer, and then entering a screw reactor for stay reaction to obtain a poly para-aramid nanofiber solution;
S4, defoaming the poly para-aramid nanofiber solution obtained in the step S3 to obtain a polymer solution with the concentration of <3%, the dynamic viscosity of 10000-30000 cp and the polymer intrinsic viscosity of 1-2.5.
In the step S2, the p-phenylenediamine/NMP/CaCl 2 solution is continuously introduced into a pre-reaction kettle, the temperature is reduced to 0-5 ℃, and then the melted terephthaloyl chloride is continuously introduced into the pre-reaction kettle, so that the p-phenylenediamine/NMP/CaCl 2 solution and the melted terephthaloyl chloride stay in the pre-reaction kettle for 3-5min and react.
In the step S3, molten terephthaloyl chloride is continuously introduced into a pre-mixer to be mixed with the prepolymer for reaction, and the temperature of the materials after the mixed reaction is controlled to be 0-5 ℃.
In the step S3, the residence time of the materials in the screw reactor is controlled to be 5-25min.
The polymerization solution of the membrane coating of the poly para-aramid lithium battery is prepared by adopting the method, and the indexes of the polymerization solution are as follows: the concentration is less than 3%, the dynamic viscosity is 10000-30000 cp, and the polymer intrinsic viscosity is 1-2.5.
Compared with the prior art, the invention has the following advantages:
(1) The polymerization degree of the polymer in the production process can be accurately and stably controlled by controlling the moisture content in the p-phenylenediamine/NMP/CaCl 2 solution, so that the viscosity of the whole polymer solution can be more accurately controlled, and the polymer solution with the dynamic viscosity of 10000-30000 cp and the intrinsic viscosity of the polymer of 1-2.5 can be obtained by controlling the moisture content in the solution to be more than 200 ppm.
(2) Compared with the conventional intermittent reaction kettle production, the invention realizes high-speed continuous batch production of polymer solution by adopting the screw, ensures stable control of the hydrodynamic viscosity of the polymer, is ready to use, reduces the reduction of the hydrodynamic viscosity of the polymer caused by batch production intervals, solves the problem of difficult stable control of the dynamic viscosity in the production process, improves the film forming property of the product, improves the production efficiency and is suitable for industrialized mass production.
(3) The prepared poly para-aramid polymer solution with the solid content lower than 3 percent has better pore-forming property and fluidity than the prior polymer solution, can be used for battery diaphragm coating without pore-forming agent or other fillers, naturally accumulates nanofibers on the surface of a base diaphragm to form pores after solidification, has better solution fluidity, and is easier to coat and produce.
Drawings
FIG. 1 is a block diagram of a polyaramid nanofiber coating under a microscope (2000 k times) containing the polymerization solution of example 1.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
Example 1:
(1) Preparation of p-phenylenediamine/NMP/CaCl 2 solution:
And controlling the moisture of an NMP/CaCl 2 solvent system by adopting an online micro-moisture instrument, and then heating and dissolving p-phenylenediamine in the solvent system under an N 2 sealing environment to obtain a p-phenylenediamine/NMP/CaCl 2 solution, wherein the p-phenylenediamine content is 0.93 wt%, the CaCl 2 content is 3.6 w%, and the moisture content is 500ppm.
(2) Preparing a prepolymer:
And cooling the p-phenylenediamine/NMP/CaCl 2 solution to 5 ℃, introducing the solution into a pre-reaction kettle according to the flow of 20kg/h, simultaneously introducing molten terephthaloyl chloride into the pre-reaction kettle according to the flow of 0.12kg/h, carrying out reaction, and staying in the pre-reaction kettle for 5min to obtain the prepolymer.
(3) Preparing a poly para-aramid nanofiber solution:
Pumping the prepolymer into a pre-mixer, pumping molten terephthaloyl chloride into the pre-mixer according to the flow of 0.23kg/h, controlling the material temperature at 5 ℃ after the contact and mixing reaction of the molten terephthaloyl chloride and the pre-mixer, and then entering a screw reactor to stay for reaction for 25min to obtain the poly para-aramid nanofiber solution.
(4) Preparing a polymerization solution:
The poly para-aramid nanofiber solution is defoamed for 20min at normal temperature to obtain a polymer solution with the concentration of 2%, the dynamic viscosity of 20000 cp and the polymer intrinsic viscosity of 1.5.
Example 2:
(1) Preparation of p-phenylenediamine/NMP/CaCl 2 solution:
And controlling the moisture of an NMP/CaCl 2 solvent system by adopting an online micro-moisture instrument, and then heating and dissolving p-phenylenediamine in the solvent system under an N 2 sealing environment to obtain a p-phenylenediamine/NMP/CaCl 2 solution, wherein the p-phenylenediamine content is 1.05w%, the CaCl 2 content is 3.6 w%, and the moisture content is 200ppm.
(2) Preparing a prepolymer:
And cooling the p-phenylenediamine/NMP/CaCl 2 solution to 0 ℃, introducing the solution into a pre-reaction kettle according to the flow of 20kg/h, simultaneously introducing molten terephthaloyl chloride into the pre-reaction kettle according to the flow of 0.12kg/h, carrying out reaction, and staying in the pre-reaction kettle for 3min to obtain the prepolymer.
(3) Preparing a poly para-aramid nanofiber solution:
Pumping the prepolymer into a pre-mixer, pumping molten terephthaloyl chloride into the pre-mixer according to the flow of 0.23kg/h, controlling the material temperature at 0 ℃ after the contact and mixing reaction of the molten terephthaloyl chloride and the pre-mixer, and then entering a screw reactor for stay reaction for 15min to obtain the poly para-aramid nanofiber solution.
(4) Preparing a polymerization solution:
the poly para-aramid nanofiber solution is defoamed for 20min at normal temperature to obtain a polymer solution with the concentration of 2.26%, the dynamic viscosity of 10000cp and the polymer intrinsic viscosity of 1.0.
Example 3:
(1) Preparation of p-phenylenediamine/NMP/CaCl 2 solution:
The water content of an NMP/CaCl 2 solvent system is controlled by adopting an online trace water instrument, and then p-phenylenediamine is heated and dissolved in the solvent system under the N 2 sealing environment to obtain a p-phenylenediamine/NMP/CaCl 2 solution, wherein the p-phenylenediamine content is 1.2w percent, the CaCl 2 content is 3.6 w percent, and the water content is 500ppm.
(2) Preparing a prepolymer:
And cooling the p-phenylenediamine/NMP/CaCl 2 solution to 5 ℃, introducing the solution into a pre-reaction kettle according to the flow of 20kg/h, simultaneously introducing molten terephthaloyl chloride into the pre-reaction kettle according to the flow of 0.12kg/h, carrying out reaction, and staying in the pre-reaction kettle for 5min to obtain the prepolymer.
(3) Preparing a poly para-aramid nanofiber solution:
Pumping the prepolymer into a pre-mixer, pumping molten terephthaloyl chloride into the pre-mixer according to the flow of 0.23kg/h, controlling the material temperature at 5 ℃ after the contact and mixing reaction of the molten terephthaloyl chloride and the pre-mixer, and then entering a screw reactor to stay for reaction for 5min to obtain the poly para-aramid nanofiber solution.
(4) Preparing a polymerization solution:
The poly para-aramid nanofiber solution is defoamed for 20min at normal temperature to obtain a polymerization solution with the concentration of 2.6%, the dynamic viscosity of 30000 cp and the polymer intrinsic viscosity of 2.5.
Example 4
(1) Preparation of p-phenylenediamine/NMP/CaCl 2 solution:
The water content of an NMP/CaCl 2 solvent system is controlled by adopting an online trace water instrument, and then p-phenylenediamine is heated and dissolved in the solvent system under the N 2 sealing environment to obtain a p-phenylenediamine/NMP/CaCl 2 solution, wherein the p-phenylenediamine content is 1.07 wt%, the CaCl 2 content is 3.6 w%, and the water content is 480ppm.
(2) Preparing a prepolymer:
And cooling the p-phenylenediamine/NMP/CaCl 2 solution to 5 ℃, introducing the solution into a pre-reaction kettle according to the flow of 20kg/h, simultaneously introducing molten terephthaloyl chloride into the pre-reaction kettle according to the flow of 0.12kg/h, carrying out reaction, and staying in the pre-reaction kettle for 5min to obtain the prepolymer.
(3) Preparing a poly para-aramid nanofiber solution:
Pumping the prepolymer into a pre-mixer, pumping molten terephthaloyl chloride into the pre-mixer according to the flow of 0.23kg/h, controlling the material temperature at 5 ℃ after the contact and mixing reaction of the molten terephthaloyl chloride and the pre-mixer, and then entering a screw reactor to stay for reaction for 20min to obtain the poly para-aramid nanofiber solution.
(4) Preparing a polymerization solution:
The poly para-aramid nanofiber solution is defoamed for 20min at normal temperature to obtain a polymerization solution with the concentration of 2.3%, the dynamic viscosity of 22000 cp and the polymer intrinsic viscosity of 2.1.
Example 5:
(1) Preparation of p-phenylenediamine/NMP/CaCl 2 solution:
the water content of an NMP/CaCl 2 solvent system is controlled by an online micro-water instrument, and then p-phenylenediamine is heated and dissolved in the solvent system under the N 2 sealing environment to obtain a p-phenylenediamine/NMP/CaCl 2 solution, wherein the p-phenylenediamine content is 0.90 wt%, the CaCl 2 content is 3.6 w%, and the water content is 500ppm.
(2) Preparing a prepolymer:
And cooling the p-phenylenediamine/NMP/CaCl 2 solution to 0 ℃, introducing the solution into a pre-reaction kettle according to the flow of 20kg/h, simultaneously introducing molten terephthaloyl chloride into the pre-reaction kettle according to the flow of 0.12kg/h, carrying out reaction, and staying in the pre-reaction kettle for 5min to obtain the prepolymer.
(3) Preparing a poly para-aramid nanofiber solution:
Pumping the prepolymer into a pre-mixer, pumping molten terephthaloyl chloride into the pre-mixer according to the flow of 0.23kg/h, controlling the material temperature at 2 ℃ after the contact and mixing reaction of the molten terephthaloyl chloride and the pre-mixer, and then entering a screw reactor to stay for reaction for 25min to obtain the poly para-aramid nanofiber solution.
(4) Preparing a polymerization solution:
The poly para-aramid nanofiber solution is defoamed for 20min at normal temperature to obtain a polymerization solution with the concentration of 1.9%, the dynamic viscosity of 20000 cp and the polymer intrinsic viscosity of 2.0.
Example 6:
(1) Preparation of p-phenylenediamine/NMP/CaCl 2 solution:
And controlling the moisture of an NMP/CaCl 2 solvent system by adopting an online micro-moisture instrument, and then heating and dissolving p-phenylenediamine in the solvent system under an N 2 sealing environment to obtain a p-phenylenediamine/NMP/CaCl 2 solution, wherein the p-phenylenediamine content is 0.93w percent, the CaCl 2 content is 3.6w percent, and the moisture content is 490ppm.
(2) Preparing a prepolymer:
And cooling the p-phenylenediamine/NMP/CaCl 2 solution to 5 ℃, introducing the solution into a pre-reaction kettle according to the flow of 20kg/h, simultaneously introducing molten terephthaloyl chloride into the pre-reaction kettle according to the flow of 0.12kg/h, carrying out reaction, and staying in the pre-reaction kettle for 4min to obtain the prepolymer.
(3) Preparing a poly para-aramid nanofiber solution:
Pumping the prepolymer into a pre-mixer, pumping molten terephthaloyl chloride into the pre-mixer according to the flow of 0.23kg/h, controlling the material temperature at 0 ℃ after the contact and mixing reaction of the molten terephthaloyl chloride and the pre-mixer, and then entering a screw reactor for stay reaction for 10min to obtain the poly para-aramid nanofiber solution.
(4) Preparing a polymerization solution:
The poly para-aramid nanofiber solution is defoamed for 20min at normal temperature to obtain a polymer solution with the concentration of 2%, the dynamic viscosity of 20000 cp and the polymer intrinsic viscosity of 1.8.
Comparative example 1:
This comparative example uses the same process steps as example 1, except that the water content of the p-phenylenediamine/NMP/CaCl 2 solution is controlled to 150ppm. The thus-prepared polymer solution had a concentration of 2%, a dynamic viscosity of 50000cp and a polymer intrinsic viscosity of 2.7.
In the continuous production process, there is a problem that the viscosity of the polymer solution is too high and the dynamic viscosity is more difficult to control when compared with the process of example 1 due to the reduction of the moisture content.
Comparative example 2:
The present comparative example uses the same process steps as in example 1, except that a batch production process is used, namely: the process of metering and introducing and carrying out reaction is replaced by adding the same amount of materials at one time for carrying out reaction, and the screw reactor is replaced by a reaction kettle for batch production. The thus-prepared polymer solution had a concentration of 2%, a dynamic viscosity of 23000cp and a polymer intrinsic viscosity of 2.1.
By using a batch type production process, problems of longer reaction time, low efficiency, and poor batch stability occur when compared with the process of example 1.
Comparative example 3:
This comparative example used the same process as in example 1, except that the water content of the p-phenylenediamine/NMP/CaCl 2 solution was controlled to 100ppm, and a batch process was used, namely: the process of metering and introducing and carrying out reaction is replaced by adding the same amount of materials at one time for carrying out reaction, and the screw reactor is replaced by a reaction kettle for batch production. The thus-prepared polymer solution had a concentration of 2.3%, an kinetic viscosity of 62000cp and an intrinsic polymer viscosity of 2.8.
Because of the reduction of the moisture content and the intermittent production process, compared with the process of the embodiment 1, the problems of longer reaction time, low efficiency, too high dynamic viscosity and poor fluidity and influence on the stability of the later coating process occur.
The polymerization solutions obtained in examples 1 to 6 and comparative examples 1 to 3 were applied to a PE separator by a doctor blade method, the thickness of the coating was 3. Mu.m, and a polyaramid nanofiber coating was obtained after coagulation, cleaning and drying, and performance test was performed on the coating, and the test data are shown in Table 1 below, and the blank group was a blank PE separator.
The coating prepared in the example 1 is amplified by 2000k times under a microscope, and the structure of the coating is observed, so that the coating has a good porous structure, as shown in figure 1.
TABLE 1
Note that: the tensile strength in Table 1 is carried out according to the standard GB/T21302-2007; puncture strength is carried out according to the standard GB/T21302-2007; the ventilation value is carried out according to the standard GB/T1038-2000; the heat shrinkage was carried out according to the standard GB/T13519-2016.
In summary, the invention provides an industrial continuous production process suitable for a polyaramid nanofiber solution, the polymerization degree of materials can be controlled by controlling the moisture content in a p-phenylenediamine solution, industrial continuous production is realized, and an index system is satisfied: the polymer solution with the concentration of less than 3%, the dynamic viscosity of 10000-30000 cp and the polymer intrinsic viscosity of 1-2.5 is used for battery diaphragm coating, has better pore-forming property and film-forming property, and is easy for coating and industrialized mass production.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent variation, etc. of the above embodiment according to the technical matter of the present invention fall within the scope of the present invention.
Claims (5)
1. An industrial production method of a poly para-aramid lithium battery diaphragm coating polymerization solution is characterized by comprising the following steps: the method comprises the following steps:
s1, controlling the moisture of an NMP/CaCl 2 solvent system by adopting an online trace moisture instrument, heating and dissolving p-phenylenediamine in the solvent system under an N 2 sealing environment to obtain a p-phenylenediamine/NMP/CaCl 2 solution, wherein the content of the p-phenylenediamine in the solution is 0.3-1.2w%, the moisture content is less than or equal to 200ppm and less than or equal to 500ppm,
S2, cooling the p-phenylenediamine/NMP/CaCl 2 solution obtained in the step S1 to 0-5 ℃, and reacting with molten terephthaloyl chloride in a pre-reaction kettle to obtain a prepolymer;
s3, carrying out contact mixing reaction on the prepolymer obtained in the step S2 and molten terephthaloyl chloride in a premixer, and then entering a screw reactor for stay reaction to obtain a poly para-aramid nanofiber solution;
S4, defoaming the poly para-aramid nanofiber solution obtained in the step S3 to obtain a polymer solution with the concentration of <3%, the dynamic viscosity of 10000-30000cp and the polymer intrinsic viscosity of 1-2.5.
2. The industrial production method according to claim 1, wherein: in the step S2, the p-phenylenediamine/NMP/CaCl 2 solution is continuously introduced into a pre-reaction kettle, the temperature is reduced to 0-5 ℃, and then the melted terephthaloyl chloride is continuously introduced into the pre-reaction kettle, so that the p-phenylenediamine/NMP/CaCl 2 solution and the melted terephthaloyl chloride stay in the pre-reaction kettle for 3-5min and react.
3. The industrial production method according to claim 1, wherein: in the step S3, molten terephthaloyl chloride is continuously introduced into a pre-mixer to be mixed with the prepolymer for reaction, and the temperature of the materials after the mixed reaction is controlled to be 0-5 ℃.
4. The industrial production method according to claim 1, wherein: in the step S3, the residence time of the materials in the screw reactor is controlled to be 5-25min.
5. A polymerization solution for a membrane coating of a poly para-aramid lithium battery is characterized in that: the method according to any one of claims 1 to 4, wherein the indexes of the method are as follows: the concentration is less than 3%, the dynamic viscosity is 10000-30000 cp, and the polymer intrinsic viscosity is 1-2.5.
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| CN112201903A (en) * | 2019-11-26 | 2021-01-08 | 中蓝晨光化工研究设计院有限公司 | High-performance polyaramide lithium battery diaphragm coating based polymerization solution and preparation method and application thereof |
| CN112694610A (en) * | 2020-12-16 | 2021-04-23 | 烟台泰和新材料股份有限公司 | Modified para-aramid polymer liquid, coating slurry, lithium battery diaphragm and preparation method thereof |
| CN114388985A (en) * | 2022-01-18 | 2022-04-22 | 烟台泰和新材料股份有限公司 | Para-aramid lithium battery diaphragm and preparation method thereof |
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