CN117844010B - Modified PET film for lithium battery current collector and preparation method thereof - Google Patents
Modified PET film for lithium battery current collector and preparation method thereof Download PDFInfo
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- CN117844010B CN117844010B CN202311769541.6A CN202311769541A CN117844010B CN 117844010 B CN117844010 B CN 117844010B CN 202311769541 A CN202311769541 A CN 202311769541A CN 117844010 B CN117844010 B CN 117844010B
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- 229920002799 BoPET Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 16
- 229920005610 lignin Polymers 0.000 claims abstract description 64
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 55
- 239000005011 phenolic resin Substances 0.000 claims abstract description 55
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 22
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 22
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 20
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 20
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 15
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 55
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 27
- 238000001914 filtration Methods 0.000 claims description 23
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 10
- 229920003023 plastic Polymers 0.000 claims description 10
- 239000004033 plastic Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000004804 winding Methods 0.000 claims description 2
- 239000008098 formaldehyde solution Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 238000007142 ring opening reaction Methods 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The proposal relates to a modified PET film for a lithium battery current collector and a preparation method thereof, wherein lignin is used for replacing part of phenol to prepare lignin-based phenolic resin, butyl acrylate and styrene copolymer are grafted on the surface of the lignin-based phenolic resin, maleic anhydride is subjected to ring opening on styrene to obtain modified lignin-based phenolic resin containing terminal carboxyl, and the modified lignin-based phenolic resin, PET and polyethylene glycol are finally blended, extruded, granulated and stretched to obtain the modified PET film. According to the application, the self-made modified lignin-based phenolic resin is added into the PET base material, so that the heat resistance of the PET film can be well improved, the heat shrinkage rate can be reduced to below 2%, and meanwhile, the good mechanical property of the PET film is ensured, and the tensile strength reaches more than 250 Mpa; meanwhile, the modified PET film has good thickness uniformity and low roughness, and can be used as an organic film layer for a lithium battery composite current collector.
Description
Technical Field
The invention relates to the technical field of polymer films with bases, in particular to a modified PET film for a lithium battery current collector and a preparation method thereof.
Background
The lithium ion battery is the most focused and widely applied material in a plurality of energy storage batteries, and along with the change of the energy strategy layout of China and the rapid development of new energy industry, the requirement on the lithium ion battery is also higher and higher. The composite current collector is used for replacing the traditional anode current collector electrolytic copper foil or the anode current collector calendaring aluminum foil, so that the consumption of metal materials can be effectively reduced, and the material cost can be reduced. The composite current collector is a novel material with a sandwich structure of a metal layer, an organic film layer and a metal layer formed by depositing the metal layer on the surface of the ultrathin organic polymer film, the introduction of the organic film material brings the advantages of light weight and thinning of the battery, and the increase of the active material can effectively improve the energy density of the battery by 5-10%.
The common organic films of the composite current collector are PP (polypropylene), PET (polyethylene terephthalate), PI (polyimide) and the like, wherein the PP film is thin in material and high in chemical stability, and is beneficial to improving the energy density of the battery; and the PET film has excellent mechanical stretching performance, and is the most used base film material at present. However, in practical application, the temperature resistance of the PET film is poor, the long-term operation cannot be performed at high temperature, and the composite current collector is formed by stacking metal atoms on an organic base film layer through coating processes such as evaporation, PVD vacuum sputtering and the like, and the temperature of the production process is high, so that the PET film is easy to deform and the metal layer is fallen.
Disclosure of Invention
Aiming at the defects in the prior art, the invention prepares the modified resin based on lignin, mixes the modified resin with PET, extrudes and granulates the mixture, stretches the mixture into a film, and the prepared modified PET film has obviously improved heat resistance and good mechanical property.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the preparation method of the modified PET film for the lithium battery current collector comprises the following steps:
1) Adding lignin, phenol, polyethylene glycol and 20 wt% sodium hydroxide aqueous solution into a reaction bottle, stirring and mixing uniformly, then adding 37 wt% formaldehyde aqueous solution, heating to 80 ℃ for reaction 60 min, and removing the solvent to obtain lignin-based phenolic resin;
2) Adding lignin-based phenolic resin into a clean reaction bottle, adding dichloromethane, filling inert gas and discharging oxygen, then adding butyl acrylate, styrene and Cu (III), reacting for a certain time at a certain temperature, and cooling and filtering after the reaction is completed;
3) Adding dichloromethane again into the product obtained in the step 2), stirring uniformly, then adding nitrobenzene and maleic anhydride, adding AlCl 3 in the stirring process, continuously stirring at room temperature overnight, filtering after the reaction is finished, washing with water, and drying to obtain the modified lignin-based phenolic resin;
4) Premixing the obtained modified lignin-based phenolic resin, PET and polyethylene glycol in a high-speed mixer, and then carrying out melt extrusion by a double-screw extruder;
5) Filtering the obtained melt by a filter to remove impurities, injecting the melt into a die head after filtering to extrude sheet plastic, cooling the cast sheet plastic by a cooling roller, sequentially stretching the cooled sheet plastic longitudinally and transversely, and finally carrying out traction and corona, and winding to obtain the modified PET film.
Further, in the step 1), the mass ratio of lignin, phenol, polyethylene glycol, sodium hydroxide aqueous solution and formaldehyde aqueous solution is 3-1:7-9:2:2:17.
Further, in the step 2), the molar ratio of butyl acrylate to styrene is 4-6:6-4, and the mass ratio of the total mass of the butyl acrylate to the lignin-based phenolic resin is 2:1.
Further, the reaction condition of the step 2) is 50-60 ℃ for 1.5-2 hours.
Further, in the step 3), the mass-volume ratio of the product, methylene dichloride, nitrobenzene, maleic anhydride and AlCl 3 is 1 g:10 ml:1 ml:1 g:4 g.
Further, the mass ratio of the modified lignin-based phenolic resin to PET to polyethylene glycol is 4-8:91-95:1.
The invention further provides the modified PET film for the lithium battery current collector, which is prepared by the preparation method.
According to the application, lignin is selected as a modified material, contains rich benzene rings, phenolic hydroxyl groups and aldehyde groups, is mixed with phenol and formaldehyde to prepare lignin-based phenolic resin, and can effectively improve the heat resistance of a film when being combined with PET. This is because lignin contains a large amount of benzene rings, and is excessively rigid, resulting in a decrease in tensile strength and elongation at break. Therefore, the vinyl monomer graft copolymerization is continuously initiated on the surface of the lignin-based phenolic resin, butyl acrylate and styrene are selected as monomers, the molar ratio is 6:4 to form a flexible polymer chain, meanwhile, maleic anhydride is continuously grafted on a benzene ring in a ring opening way to form a terminal carboxyl group, the mechanical property of the modified lignin-based phenolic resin is further improved, and when the modified lignin-based phenolic resin is mixed with PET and polyethylene glycol, the terminal carboxyl group plays a crosslinking role, so that the modified lignin-based phenolic resin is fixed in the PET, and the modified PET film has better mechanical property.
Compared with the prior art, the application has the beneficial effects that: according to the application, the self-made modified lignin-based phenolic resin is added into the PET base material, so that the heat resistance of the PET film can be well improved, the heat shrinkage rate can be reduced to below 2%, and meanwhile, the good mechanical property of the PET film is ensured, and the tensile strength reaches more than 250 Mpa; meanwhile, the modified PET film has good thickness uniformity and low roughness, and can be used as an organic film layer for a lithium battery composite current collector.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In addition, the technical features of the different embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Examples
The preparation method of the modified PET film for the lithium battery current collector comprises the following steps:
1) Adding 9 g lignin, 21 g phenol, 6g polyethylene glycol (PEG-200) and 6g of 20wt% sodium hydroxide aqueous solution into a reaction bottle, stirring and mixing uniformly, then adding 51 g of 37 wt% formaldehyde aqueous solution, heating to 80 ℃ for reaction for 60min, and removing the solvent to obtain lignin-based phenolic resin;
2) Adding lignin-based phenolic resin into a clean reaction bottle, adding dichloromethane, filling inert gas and discharging oxygen, then adding butyl acrylate, styrene and Cu (III), reacting for a certain time at a certain temperature, and cooling and filtering after the reaction is completed;
3) Adding dichloromethane again into the product obtained in the step 2), stirring uniformly, then adding nitrobenzene and maleic anhydride, adding AlCl 3 in the stirring process, continuously stirring at room temperature overnight, filtering after the reaction is finished, washing with water, and drying to obtain the modified lignin-based phenolic resin;
4) Premixing the obtained modified lignin-based phenolic resin, PET and polyethylene glycol in a high-speed mixer, and then carrying out melt extrusion by a double-screw extruder;
5) Filtering the obtained melt by a filter to remove impurities, injecting the melt into a die head after filtering to extrude sheet plastic, cooling the cast sheet plastic by a cooling roller, allowing the cooled sheet plastic to enter a longitudinal stretching section, indirectly heating by electrically heating pure water, and simultaneously assisting in far infrared heating to heat the plastic to 70-80 ℃; clamping two sides of a longitudinally stretched film by using clamping chains with the same rotating speed, feeding the film into a tentering furnace for preheating, adopting an electric heating mode in a preheating zone in the process, heating at 100-230 ℃, and transversely stretching the film through wide expansion in a stretching zone;
6) And cooling the film subjected to transverse stretching to 40 ℃ by using air of a fan, and conveying the base film produced by the process into traction equipment. In the traction process, the thickness of the base film is continuously measured by a thickness resolution ratio 0.01 mu m X ray measuring instrument, the measured data is fed back to a computer automatic control system (TEC) and the lip clearance of a die head is timely adjusted to pack the thickness and the precision of the film. And carrying out corona treatment on the surface of the obtained film, and finally rolling to obtain the modified PET film.
Example 1:
1) Obtaining lignin-based phenolic resin by referring to the preparation process;
2) Adding 10 g lignin-based phenolic resin into a clean reaction bottle, adding dichloromethane, charging inert gas and discharging oxygen, then adding 9 g butyl acrylate, 11 g styrene (the molar ratio is 4:6) and Cu (III), reacting for a certain time at a certain temperature, and cooling and filtering after the reaction is completed;
3) Adding 150 ml dichloromethane again into the product 15 g obtained in the step 2), stirring uniformly, then adding 15 ml nitrobenzene and 15 g maleic anhydride, adding 60 g AlCl 3 in the stirring process, continuously stirring at room temperature overnight, filtering after the reaction is finished, washing with water, and drying to obtain modified lignin-based phenolic resin;
4) Premixing the obtained modified lignin-based phenolic resin 4 g, PET 95 g and polyethylene glycol 1g in a high-speed mixer, and then carrying out melt extrusion by a double-screw extruder;
5) According to the preparation process, the modified PET film is obtained.
Example 2:
1) Obtaining lignin-based phenolic resin by referring to the preparation process;
2) Adding 10 g lignin-based phenolic resin into a clean reaction bottle, adding dichloromethane, charging inert gas and discharging oxygen, then adding 11 g butyl acrylate, 9 g styrene (the molar ratio is 5:5) and Cu (III), reacting for a certain time at a certain temperature, and cooling and filtering after the reaction is completed;
3) Adding 150 ml dichloromethane again into the product 15 g obtained in the step 2), stirring uniformly, then adding 15 ml nitrobenzene and 15 g maleic anhydride, adding 60 g AlCl 3 in the stirring process, continuously stirring at room temperature overnight, filtering after the reaction is finished, washing with water, and drying to obtain modified lignin-based phenolic resin;
4) Premixing the obtained modified lignin-based phenolic resin 4 g, PET 95 g and polyethylene glycol 1g in a high-speed mixer, and then carrying out melt extrusion by a double-screw extruder;
5) According to the preparation process, the modified PET film is obtained.
Example 3:
1) Obtaining lignin-based phenolic resin by referring to the preparation process;
2) Adding 10 g lignin-based phenolic resin into a clean reaction bottle, adding dichloromethane, charging inert gas and discharging oxygen, then adding 13 g butyl acrylate, 7 g styrene (the molar ratio is 6:4) and Cu (III), reacting for a certain time at a certain temperature, and cooling and filtering after the reaction is completed;
3) Adding dichloromethane again into the product obtained in the step 2), stirring uniformly, then adding nitrobenzene and maleic anhydride, adding AlCl 3 in the stirring process, continuously stirring at room temperature overnight, filtering after the reaction is finished, washing with water, and drying to obtain the modified lignin-based phenolic resin;
4) Premixing the obtained modified lignin-based phenolic resin 4 g, PET 95 g and polyethylene glycol 1g in a high-speed mixer, and then carrying out melt extrusion by a double-screw extruder;
5) According to the preparation process, the modified PET film is obtained.
Example 4:
1) Obtaining lignin-based phenolic resin by referring to the preparation process;
2) Adding 10g lignin-based phenolic resin into a clean reaction bottle, adding dichloromethane, filling inert gas and discharging oxygen, then adding 13 g butyl acrylate, 7 g styrene and Cu (III), reacting for a certain time at a certain temperature, and cooling and filtering after the reaction is completed;
3) Adding dichloromethane again into the product obtained in the step 2), stirring uniformly, then adding nitrobenzene and maleic anhydride, adding AlCl 3 in the stirring process, continuously stirring at room temperature overnight, filtering after the reaction is finished, washing with water, and drying to obtain the modified lignin-based phenolic resin;
4) Premixing the obtained modified lignin-based phenolic resin 6 g, PET 93 g and polyethylene glycol 1g in a high-speed mixer, and then carrying out melt extrusion by a double-screw extruder;
5) According to the preparation process, the modified PET film is obtained.
Example 5:
1) Obtaining lignin-based phenolic resin by referring to the preparation process;
2) Adding 10g lignin-based phenolic resin into a clean reaction bottle, adding dichloromethane, filling inert gas and discharging oxygen, then adding 13 g butyl acrylate, 7 g styrene and Cu (III), reacting for a certain time at a certain temperature, and cooling and filtering after the reaction is completed;
3) Adding dichloromethane again into the product obtained in the step 2), stirring uniformly, then adding nitrobenzene and maleic anhydride, adding AlCl 3 in the stirring process, continuously stirring at room temperature overnight, filtering after the reaction is finished, washing with water, and drying to obtain the modified lignin-based phenolic resin;
4) Premixing the obtained modified lignin-based phenolic resin 8 g, PET 91 g and polyethylene glycol 1g in a high-speed mixer, and then carrying out melt extrusion by a double-screw extruder;
5) According to the preparation process, the modified PET film is obtained.
Comparative example 1:
1) Obtaining lignin-based phenolic resin by referring to the preparation process;
2) Premixing the obtained lignin-based phenolic resin 4 g, PET 95 g and polyethylene glycol 1g in a high-speed mixer, and then carrying out melt extrusion by a double-screw extruder;
3) According to the preparation process, the modified PET film is obtained.
Comparative example 2:
1) Obtaining lignin-based phenolic resin by referring to the preparation process;
2) Adding 10 g lignin-based phenolic resin into a clean reaction bottle, adding dichloromethane, charging inert gas and discharging oxygen, then adding 13 g butyl acrylate, 7 g styrene and Cu (III), reacting for a certain time at a certain temperature, cooling and filtering after the reaction is finished, and drying to obtain modified lignin-based phenolic resin;
3) Premixing the obtained modified lignin-based phenolic resin 4 g, PET 95 g and polyethylene glycol 1g in a high-speed mixer, and then carrying out melt extrusion by a double-screw extruder;
4) According to the preparation process, the modified PET film is obtained.
Correlation test:
The modified PET films produced in examples 1 to 5 and comparative examples 1 to 2 were subjected to the relevant test, and the relevant data are recorded in Table 1 with reference to GB/T16958-2008 standard.
TABLE 1
As can be seen from the above table, the modified PET films prepared in examples 2-5 of the application are effectively improved in heat shrinkage and mechanical properties, wherein the comprehensive properties of example 4 are optimal, and the data of example 1 are slightly lower than those of examples 2-5. In comparative examples 1-3, the more styrene is used in preparing the modified lignin-based phenolic resin, the greater the rigidity is, which is not beneficial to the improvement of the mechanical properties of the material; in comparative examples 3 to 5, the amount of lignin-based phenolic resin added as a modifier to PET is preferably controlled in the range of 4 to 8 wt%. The longitudinal heat shrinkage of comparative example 1 and comparative example 2 was kept below 5%, the transverse heat shrinkage was kept below 1%, and the heat stability was good, but the tensile strength and elongation at break were poor.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (7)
1. The preparation method of the modified PET film for the lithium battery current collector is characterized by comprising the following steps of:
1) Adding lignin, phenol, polyethylene glycol and 20wt% sodium hydroxide aqueous solution into a reaction bottle, stirring and mixing uniformly, then adding 37wt% formaldehyde aqueous solution, heating to 80 ℃ for reaction for 60min, and removing the solvent to obtain lignin-based phenolic resin;
2) Adding lignin-based phenolic resin into a clean reaction bottle, adding dichloromethane, filling inert gas and discharging oxygen, then adding butyl acrylate, styrene and Cu (III), reacting for a certain time at a certain temperature, and cooling and filtering after the reaction is completed;
3) Adding dichloromethane again into the product obtained in the step 2), stirring uniformly, then adding nitrobenzene and maleic anhydride, adding AlCl 3 in the stirring process, continuously stirring at room temperature overnight, filtering after the reaction is finished, washing with water, and drying to obtain the modified lignin-based phenolic resin;
4) Premixing the obtained modified lignin-based phenolic resin, PET and polyethylene glycol in a high-speed mixer, and then carrying out melt extrusion by a double-screw extruder;
5) Filtering the obtained melt by a filter to remove impurities, injecting the melt into a die head after filtering to extrude sheet plastic, cooling the cast sheet plastic by a cooling roller, sequentially stretching the cooled sheet plastic longitudinally and transversely, and finally carrying out traction and corona, and winding to obtain the modified PET film.
2. The method for preparing a modified PET film for a lithium battery current collector according to claim 1, wherein in the step 1), the mass ratio of lignin, phenol, polyethylene glycol, aqueous sodium hydroxide solution and aqueous formaldehyde solution is 3-1:7-9:2:2:17.
3. The method for preparing a modified PET film for a lithium battery current collector according to claim 1, wherein in the step 2), the molar ratio of butyl acrylate to styrene is 4-6:6-4, and the mass ratio of the total mass of the butyl acrylate to the lignin-based phenolic resin is 2:1.
4. The method for preparing a modified PET film for a lithium battery current collector according to claim 1, wherein the reaction condition of the step 2) is 50-60 ℃ for 1.5-2 hours.
5. The method for preparing a modified PET film for a lithium battery current collector according to claim 1, wherein in the step 3), the mass-volume ratio of the product, methylene dichloride, nitrobenzene, maleic anhydride and AlCl 3 is 1g:10ml:1 g:4g.
6. The method for preparing the modified PET film for the lithium battery current collector, which is disclosed in claim 1, is characterized in that the mass ratio of the modified lignin-based phenolic resin to PET and polyethylene glycol is 4-8:91-95:1.
7. A modified PET film for a lithium battery current collector produced by the production method according to any one of claims 1 to 6.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921387A (en) * | 2010-09-07 | 2010-12-22 | 西南科技大学 | A kind of lignin modified PET (Polyethylene Terephthalate) composite material and preparation method thereof |
| CN105968696A (en) * | 2016-05-26 | 2016-09-28 | 江苏深苏电子科技有限公司 | Preparation method for lithium ion battery electrolyte membrane |
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