CN118700669B - Polypropylene film for lithium battery current collector and preparation method thereof - Google Patents
Polypropylene film for lithium battery current collector and preparation method thereof Download PDFInfo
- Publication number
- CN118700669B CN118700669B CN202411180712.6A CN202411180712A CN118700669B CN 118700669 B CN118700669 B CN 118700669B CN 202411180712 A CN202411180712 A CN 202411180712A CN 118700669 B CN118700669 B CN 118700669B
- Authority
- CN
- China
- Prior art keywords
- modified
- polypropylene film
- current collector
- lithium battery
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- -1 Polypropylene Polymers 0.000 title claims abstract description 111
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 108
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 108
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000004793 Polystyrene Substances 0.000 claims abstract description 43
- 229920002223 polystyrene Polymers 0.000 claims abstract description 43
- 229920001577 copolymer Polymers 0.000 claims abstract description 19
- 238000001125 extrusion Methods 0.000 claims abstract description 6
- 238000005266 casting Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 129
- 239000005543 nano-size silicon particle Substances 0.000 claims description 62
- 235000012239 silicon dioxide Nutrition 0.000 claims description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 56
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000000178 monomer Substances 0.000 claims description 38
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 3
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims 2
- 229920006254 polymer film Polymers 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 89
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 125000004185 ester group Chemical group 0.000 description 7
- 125000006038 hexenyl group Chemical group 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 5
- XUDOZULIAWNMIU-UHFFFAOYSA-N delta-hexenoic acid Chemical compound OC(=O)CCCC=C XUDOZULIAWNMIU-UHFFFAOYSA-N 0.000 description 5
- KSVSZLXDULFGDQ-UHFFFAOYSA-M sodium;4-aminobenzenesulfonate Chemical compound [Na+].NC1=CC=C(S([O-])(=O)=O)C=C1 KSVSZLXDULFGDQ-UHFFFAOYSA-M 0.000 description 5
- 239000002344 surface layer Substances 0.000 description 5
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical group OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229920000128 polypyrrole Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000004075 alteration Effects 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/242—All polymers belonging to those covered by group B32B27/32
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/204—Di-electric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/308—Heat stability
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/10—Batteries
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Laminated Bodies (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention belongs to the technical field of polymer films, and particularly relates to a polypropylene film for a lithium battery current collector and a preparation method thereof. The polypropylene film comprises an upper layer, a middle layer and a lower layer, wherein the components of the upper layer and the lower layer respectively comprise 70-80 parts of isotactic polypropylene and 20-25 parts of modified polystyrene in parts by weight, the components of the middle layer comprise 80-85 parts of isotactic polypropylene and 15-20 parts of cycloolefin copolymer, the components of the upper layer, the middle layer and the lower layer are respectively and uniformly mixed, and then are added into a host machine and an auxiliary machine of a three-layer coextrusion casting machine for melt extrusion to obtain the polypropylene film, and the polypropylene film is subjected to biaxial stretching to obtain the polypropylene film.
Description
Technical Field
The invention belongs to the technical field of polymer films, and particularly relates to a polypropylene film for a lithium battery current collector and a preparation method thereof.
Background
The current collector is an important component of a lithium ion battery, is not only a carrier for carrying battery active materials, but also a medium for transmitting current, has great influence on the performance of the lithium battery, the ideal current collector often needs to have comprehensive performances in multiple aspects such as high conductivity, good stability, good mechanical strength, lower cost and the like, the traditional current collector consisting of pure metal materials (aluminum foil, stainless steel, copper foil and nickel foil) has the defects of high weight, high cost, low safety and the like, and the traditional current collector is difficult to meet the actual use requirement because the composite current collector consisting of partial metal materials is replaced by organic polymers to improve the defects of the traditional current collector, wherein the polypropylene film has the advantages of high breakdown field strength, low dielectric loss, excellent self-healing property, ultrathin property, low cost and the like, is widely applied to the fields of the composite current collector, but has the defects of insufficient mechanical property and high-temperature resistance between polypropylene and metal, and is difficult to meet the actual use requirement.
The Chinese patent with the application number 202210994379.7 discloses a high-tensile-strength polypropylene film for a lithium battery current collector and a preparation method thereof, wherein the polypropylene film is prepared by mixing polypropylene and modified polypyrrole, the modified polypyrrole is utilized to modify the polypropylene, and in the process of preparing the polypropylene film, a carboxylate structure on the modified polypyrrole can induce the polypropylene to crystallize, so that the mechanical property of the polypropylene film is improved to a certain extent, meanwhile, the roughness of the surface of the film can be effectively controlled by adopting a high-pressure air knife method, and the film is subjected to heat treatment and relaxation treatment after being transversely and longitudinally stretched, so that the heat stability of the polypropylene film is ensured.
The Chinese patent application with the application number 202310709758.1 discloses a modified polypropylene film, a preparation method thereof, a composite current collector and a preparation method thereof, wherein the structure of the modified polypropylene film sequentially comprises a first surface layer, a middle layer and a second surface layer, wherein the components of the first surface layer and the second surface layer consist of isotactic polypropylene, atactic polypropylene, a polar additive, conductive particles and a dispersing agent, the components of the middle layer consist of isotactic polypropylene, atactic polypropylene, the polar additive, conductive particles and the dispersing agent, the two surface layers have good adhesion by adjusting the proportion of the isotactic polypropylene and the atactic polypropylene, the added conductive particles enable the polypropylene film to have a conductive effect, a small amount of conductive particles can also serve as heterogeneous nucleation points, the crystallization of the polypropylene is promoted, and the mechanical property of the modified polypropylene film is improved.
Although the mechanical properties of the polypropylene film are improved by different methods in the above patent, the improvement of the heat resistance of the polypropylene film is not involved, and there is room for improvement in the mechanical properties, so that a polypropylene film with excellent comprehensive properties needs to be developed to meet the market demands.
Disclosure of Invention
The invention aims to provide a polypropylene film for a lithium battery current collector and a preparation method thereof, aiming at the defects of the prior art, wherein modified polystyrene and isotactic polypropylene are used as an upper layer and a lower layer of the polypropylene film, and isotactic polypropylene and cycloolefin copolymer are used as an intermediate layer of the polypropylene film, so that the polypropylene film for the lithium battery current collector with excellent mechanical property and heat resistance is obtained.
The technical scheme adopted by the invention for achieving the purpose is as follows:
The polypropylene film for the lithium battery current collector comprises an upper layer, a middle layer and a lower layer, wherein the components of the upper layer and the lower layer comprise 70-80 parts of isotactic polypropylene and 20-25 parts of modified polystyrene in parts by weight, and the components of the middle layer comprise 80-85 parts of isotactic polypropylene and 15-20 parts of cycloolefin copolymer;
Further, the isotacticity of the isotactic polypropylene is more than or equal to 95%, and the melt flow rate is 2.0-5.0g/10min.
Further, the mass fraction of norbornene in the cycloolefin copolymer is 50 to 66%, and the glass transition temperature of the cycloolefin copolymer is 125 to 145 ℃.
Further, the thickness of the upper layer, the middle layer and the lower layer is 3-4 μm.
The preparation method of the modified polystyrene comprises the steps of adding styrene, modified monomers, modified nano silicon dioxide and azodiisobutyronitrile into a polymerization tube, uniformly mixing, replacing nitrogen, sealing, maintaining the reaction temperature at 75-80 ℃ for polymerization for 20-24 hours to obtain the modified polystyrene, wherein the mass ratio of the styrene to the modified monomers to the modified nano silicon dioxide to the azodiisobutyronitrile is 1:0.2-0.3:0.8-1:0.02-0.03. The preparation method of the modified monomer comprises the steps of adding methylene dichloride, sodium sulfanilate and triethylamine into a reaction container, uniformly stirring, slowly dripping epichlorohydrin, maintaining the reaction temperature at 35-40 ℃ after dripping, stirring and reacting for 3-4 hours to obtain an intermediate 1, adding toluene, the intermediate 1, 5-hexenoic acid and p-toluenesulfonic acid into the reaction container, uniformly stirring, maintaining the reaction temperature at 110 ℃, carrying out reflux reaction for 4-5 hours to obtain the modified monomer,
The structural formula is as follows:。
Further, the preparation method of the modified nano silicon dioxide comprises the following steps:
S1, dispersing nano silicon dioxide in a mixed solution of ethanol and water, adding 3-aminopropyl trimethoxy silane, regulating the pH value of the mixed solution to about 6.5, maintaining the reaction temperature to 40-50 ℃, stirring and reacting for 5-6 hours, cooling and filtering after the reaction is finished, repeatedly washing with ethanol, and drying to obtain the aminated nano silicon dioxide, wherein the mass ratio of the nano silicon dioxide to the 3-aminopropyl trimethoxy silane is 1:0.03-0.05, and the volume ratio of the ethanol to the water in the mixed solution is 1-2:1;
S2, dispersing the aminated nano silicon dioxide in ethanol, adding a modified monomer, uniformly stirring, regulating the pH value of the solution to be about 8, maintaining the reaction temperature to be 50-60 ℃, reacting for 6-8 hours, cooling, filtering, repeatedly washing with ethanol, and drying to obtain the modified nano silicon dioxide, wherein the mass ratio of the aminated nano silicon dioxide to the modified monomer is 1:0.2-0.3.
The invention also provides a preparation method of the polypropylene film for the lithium battery current collector, which comprises the following steps of respectively and uniformly mixing the components of the upper layer, the middle layer and the lower layer according to the weight ratio, adding a host machine and an auxiliary machine of a three-layer coextrusion casting machine for melt extrusion to obtain a polypropylene film, and then biaxially stretching the polypropylene film to obtain the polypropylene film.
The invention has the following beneficial effects:
according to the invention, styrene, modified nano silicon dioxide and modified monomers are adopted to prepare the modified polystyrene, both the modified nano silicon dioxide and the modified monomers contain hexenyl ester groups and can participate in styrene polymerization, wherein the modified monomers containing benzenesulfonic acid groups and hexenyl ester groups in the structure are grafted on the surface of the modified nano silicon dioxide, the benzenesulfonic acid groups and the hexenyl ester groups have good high temperature resistance, the heat stability of the film is improved, and the modified monomers are long-chain alkane benzenesulfonic acid sodium compounds, and have a certain dispersing effect, so that the modified nano silicon dioxide is uniformly dispersed in the modified polystyrene, and the modified polystyrene with uniform and stable structure is formed.
According to the invention, the modified nano silicon dioxide is grafted into the modified polystyrene molecule through a chemical bond, so that the modified nano silicon dioxide has better interfacial compatibility with isotactic polypropylene, and can be uniformly dispersed in a film, as the modified nano silicon dioxide surface is grafted with the modified monomer containing benzene sulfonic acid groups, the modified nano silicon dioxide can interact with other benzene ring structures in the modified polystyrene, and the arrangement of isotactic polypropylene chain segments is promoted through the interaction of CH-pi, so that the nucleation crystallization of isotactic polypropylene is effectively promoted, the mechanical property and dielectric property of the film are greatly improved, and meanwhile, the high-temperature resistant benzene sulfonic acid groups and hexenyl ester groups in the modified polystyrene can also promote the thermal stability of the film.
The modified polystyrene and the isotactic polypropylene are used as the upper layer and the lower layer of the polypropylene film, the isotactic polypropylene and the cycloolefin copolymer are used as the middle layer of the polypropylene film, and the prepared composite polypropylene film has good mechanical property and dielectric property and high thermal stability, and is more suitable for lithium battery current collectors.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, but not all embodiments, technical features designed in different embodiments of the present application described below can be combined with each other as long as they do not collide with each other, and all other embodiments obtained by those skilled in the art without making creative efforts on the basis of the embodiments of the present application are all within the scope of protection of the present application.
In the technical scheme of the invention, the chemical reagents are all commonly and commercially available, wherein the isotacticity of isotactic polypropylene is more than or equal to 95%, the melt flow rate is 2.0-5.0g/10min, the isotacticity of isotactic polypropylene is 97%, the melt flow rate is 3.5g/10min, the mass fraction of norbornene in the cycloolefin copolymer is 50-66%, the glass transition temperature of the cycloolefin copolymer is 125-145 ℃, the cycloolefin copolymer is three-well chemical APL5014, the styrene CAS number is 100-42-5, the azodiisobutyronitrile CAS number is 78-67-1, the 3-aminopropyl trimethoxysilane CAS number is 13822-56-5, the epichlorohydrin CAS number is 106-89-8, the sodium sulfanilate CAS number is 515-74-2, the 5-hexenoic acid CAS number is 1577-22-6, and the p-toluenesulfonic acid CAS number is 104-15-4.
In the technical scheme of the invention, the synthetic route of the modified monomer is as follows:
Adding 500mL of dichloromethane, 20.0g of sodium sulfanilate and 15.4g of triethylamine into a reaction vessel, uniformly stirring, slowly dripping 10.3g of epichlorohydrin, maintaining the reaction temperature at 35-40 ℃ after dripping, stirring for 3-4h, filtering after the reaction is finished, taking solid for drying to obtain 30.0g of intermediate 1, adding 500mL of toluene, 30.0g of intermediate 1, 11.6g of 5-hexenoic acid and 0.87g of p-toluenesulfonic acid into the reaction vessel, uniformly stirring, maintaining the reaction temperature at 110 ℃, refluxing for 4-5h, removing toluene after the reaction is finished, extracting with water and dichloromethane, collecting water phase, and concentrating under reduced pressure to obtain 31.6g of modified monomer, wherein the molar ratio of sodium sulfanilate, epichlorohydrin, triethylamine, 5-hexenoic acid and p-toluenesulfonic acid is 1:1.1:1.5:0.05.
Modified monomer ：ESI(m/z)：384.8[M+H]+,1H-NMR(600MHz,DMSO-d6,δppm)：9.53（s,1H）,7.34（d,J=8.6Hz,2H）,7.22（d,J=8.6Hz,2H）,5.56-5.60（m,2H）,4.88-4.93（m,2H）,3.73-3.76（m,1H）,3.43-3.47（m,2H）,3.15-3.17（m,1H）,2.25-2.30（m,4H）,1.76-1.79（m,2H）.
Example 1
The polypropylene film for the lithium battery current collector comprises an upper layer, an intermediate layer and a lower layer, wherein the components of the upper layer and the lower layer comprise 80 parts of isotactic polypropylene and 23 parts of modified polystyrene in parts by weight, the components of the intermediate layer comprise 85 parts of isotactic polypropylene and 20 parts of cycloolefin copolymer, and the thicknesses of the upper layer, the intermediate layer and the lower layer are 4 mu m.
A preparation method of a polypropylene film for a lithium battery current collector comprises the following steps of respectively mixing components of an upper layer, a middle layer and a lower layer uniformly according to weight ratio, adding a main machine and an auxiliary machine of a three-layer coextrusion casting machine for melt extrusion to obtain a polypropylene film, and then biaxially stretching the polypropylene film to obtain the polypropylene film, wherein the melt extrusion temperature is 240 ℃, the longitudinal stretching temperature is 150 ℃, the stretching rate is 5 times when the biaxially stretching is carried out, and the transverse stretching temperature is 160 ℃ and the stretching rate is 6 times.
The preparation method of the modified polystyrene comprises the steps of adding styrene, modified monomers, modified nano silicon dioxide and azodiisobutyronitrile into a polymerization tube, uniformly mixing, replacing nitrogen, sealing, maintaining the reaction temperature at 80 ℃, and carrying out polymerization for 20 hours to obtain the modified polystyrene, wherein the mass ratio of the styrene to the modified monomers to the modified nano silicon dioxide to the azodiisobutyronitrile is 1:0.3:1:0.03.
The preparation method of the modified nano silicon dioxide comprises the following steps:
S1, dispersing nano silicon dioxide in a mixed solution of ethanol and water, adding 3-aminopropyl trimethoxy silane, regulating the pH value of the mixed solution to about 6.5, maintaining the reaction temperature to 50 ℃, stirring for 5 hours, cooling, filtering after the reaction is finished, repeatedly washing with ethanol, and drying to obtain aminated nano silicon dioxide, wherein the mass ratio of the nano silicon dioxide to the 3-aminopropyl trimethoxy silane is 1:0.04, the volume ratio of the ethanol to the water in the mixed solution is 2:1, and the mass ratio of the nano silicon dioxide to the mixed solution is 1:50;
S2, dispersing the aminated nano silicon dioxide in ethanol, adding a modified monomer, uniformly stirring, regulating the pH value of the solution to about 8, maintaining the reaction temperature to be 50 ℃, reacting for 8 hours, cooling, filtering, repeatedly washing with ethanol, and drying to obtain the modified nano silicon dioxide, wherein the mass ratio of the aminated nano silicon dioxide to the modified monomer is 1:0.3, and the use amount of the ethanol is 25 times of the mass of the aminated nano silicon dioxide.
Example 2
The polypropylene film for the lithium battery current collector comprises an upper layer, an intermediate layer and a lower layer, wherein the components of the upper layer and the lower layer comprise 75 parts of isotactic polypropylene and 25 parts of modified polystyrene in parts by weight, the components of the intermediate layer comprise 80 parts of isotactic polypropylene and 18 parts of cycloolefin copolymer, and the thicknesses of the upper layer, the intermediate layer and the lower layer are 3.5 mu m.
A method for preparing a polypropylene film for a lithium battery current collector was the same as in example 1.
The preparation method of the modified polystyrene comprises the steps of adding styrene, modified monomers, modified nano silicon dioxide and azodiisobutyronitrile into a polymerization tube, uniformly mixing, replacing nitrogen, sealing, maintaining the reaction temperature at 75 ℃, and carrying out polymerization for 24 hours to obtain the modified polystyrene, wherein the mass ratio of the styrene to the modified monomers to the modified nano silicon dioxide to the azodiisobutyronitrile is 1:0.25:0.8:0.02.
The preparation method of the modified nano silicon dioxide comprises the following steps:
s1, dispersing nano silicon dioxide in a mixed solution of ethanol and water, adding 3-aminopropyl trimethoxy silane, regulating the pH value of the mixed solution to about 6.5, maintaining the reaction temperature to 40 ℃, stirring for reaction for 6 hours, cooling, filtering, repeatedly washing with ethanol, and drying to obtain aminated nano silicon dioxide, wherein the mass ratio of the nano silicon dioxide to the 3-aminopropyl trimethoxy silane is 1:0.05, the volume ratio of the ethanol to the water in the mixed solution is 1:1, and the mass ratio of the nano silicon dioxide to the mixed solution is 1:50;
S2, dispersing the aminated nano silicon dioxide in ethanol, adding a modified monomer, uniformly stirring, regulating the pH value of the solution to be about 8, maintaining the reaction temperature to be 60 ℃, reacting for 6 hours, cooling after the reaction is finished, filtering, repeatedly washing with ethanol, and drying to obtain the modified nano silicon dioxide, wherein the mass ratio of the aminated nano silicon dioxide to the modified monomer is 1:0.25, and the use amount of the ethanol is 25 times of the mass of the aminated nano silicon dioxide.
Example 3
The polypropylene film for the lithium battery current collector comprises an upper layer, an intermediate layer and a lower layer, wherein the components of the upper layer and the lower layer comprise 70 parts of isotactic polypropylene and 20 parts of modified polystyrene in parts by weight, the components of the intermediate layer comprise 83 parts of isotactic polypropylene and 15 parts of cycloolefin copolymer, and the thicknesses of the upper layer, the intermediate layer and the lower layer are 3 mu m.
A method for preparing a polypropylene film for a lithium battery current collector was the same as in example 1.
The preparation method of the modified polystyrene comprises the steps of adding styrene, modified monomers, modified nano silicon dioxide and azodiisobutyronitrile into a polymerization tube, uniformly mixing, replacing nitrogen, sealing, maintaining the reaction temperature at 80 ℃, and carrying out polymerization for 24 hours to obtain the modified polystyrene, wherein the mass ratio of the styrene to the modified monomers to the modified nano silicon dioxide to the azodiisobutyronitrile is 1:0.2:0.9:0.03.
The preparation method of the modified nano silicon dioxide comprises the following steps:
S1, dispersing nano silicon dioxide in a mixed solution of ethanol and water, adding 3-aminopropyl trimethoxy silane, regulating the pH value of the mixed solution to be about 6.5, maintaining the reaction temperature to be 45 ℃, stirring and reacting for 5.5 hours, cooling and filtering after the reaction is finished, and repeatedly washing with ethanol and drying to obtain the aminated nano silicon dioxide, wherein the mass ratio of the nano silicon dioxide to the 3-aminopropyl trimethoxy silane is 1:0.03, the volume ratio of the ethanol to the water in the mixed solution is 1.5:1, and the mass ratio of the nano silicon dioxide to the mixed solution is 1:50;
S2, dispersing the aminated nano silicon dioxide in ethanol, adding a modified monomer, uniformly stirring, regulating the pH value of the solution to about 8, maintaining the reaction temperature to 55 ℃, reacting for 7 hours, cooling after the reaction is finished, filtering, repeatedly washing with ethanol, and drying to obtain the modified nano silicon dioxide, wherein the mass ratio of the aminated nano silicon dioxide to the modified monomer is 1:0.2, and the use amount of the ethanol is 25 times of the mass of the aminated nano silicon dioxide.
Example 4
The polypropylene film for the lithium battery current collector comprises an upper layer, an intermediate layer and a lower layer, wherein the components of the upper layer comprise 80 parts of isotactic polypropylene and 23 parts of modified polystyrene in parts by weight, the components of the lower layer comprise 75 parts of isotactic polypropylene and 25 parts of modified polystyrene, the components of the intermediate layer comprise 83 parts of isotactic polypropylene and 15 parts of cycloolefin copolymer, the thicknesses of the upper layer and the lower layer are 4 mu m, and the thicknesses of the intermediate layer are 3 mu m.
A method for preparing a polypropylene film for a lithium battery current collector was the same as in example 1.
The preparation method of the modified polystyrene is the same as that of example 1.
The preparation method of the modified nano silicon dioxide comprises the following steps:
s1, the same as the step S1 of the embodiment 2;
s2, the same as in the step S2 of the embodiment 3.
Comparative example 1
In comparison with example 1, this comparative example uses nanosilica in the preparation method of the modified polystyrene.
The polypropylene film for the lithium battery current collector comprises an upper layer, an intermediate layer and a lower layer, wherein the components of the upper layer and the lower layer comprise 80 parts of isotactic polypropylene and 23 parts of modified polystyrene in parts by weight, the components of the intermediate layer comprise 85 parts of isotactic polypropylene and 20 parts of cycloolefin copolymer, and the thicknesses of the upper layer, the intermediate layer and the lower layer are 4 mu m.
A method for preparing a polypropylene film for a lithium battery current collector was the same as in example 1.
The preparation method of the modified polystyrene comprises the steps of adding styrene, modified monomers, nano silicon dioxide and azodiisobutyronitrile into a polymerization tube, uniformly mixing, replacing nitrogen, sealing, maintaining the reaction temperature at 80 ℃, and carrying out polymerization for 20 hours to obtain the modified polystyrene, wherein the mass ratio of the styrene to the modified monomers to the nano silicon dioxide to the azodiisobutyronitrile is 1:0.3:1:0.03.
Comparative example 2
In comparison with example 1, this comparative example does not use a modifying monomer in the preparation method of the modified polystyrene.
The polypropylene film for the lithium battery current collector comprises an upper layer, an intermediate layer and a lower layer, wherein the components of the upper layer and the lower layer comprise 80 parts of isotactic polypropylene and 23 parts of modified polystyrene in parts by weight, the components of the intermediate layer comprise 85 parts of isotactic polypropylene and 20 parts of cycloolefin copolymer, and the thicknesses of the upper layer, the intermediate layer and the lower layer are 4 mu m.
A method for preparing a polypropylene film for a lithium battery current collector was the same as in example 1.
The preparation method of the modified polystyrene comprises the steps of adding styrene, modified nano silicon dioxide and azodiisobutyronitrile into a polymerization tube, uniformly mixing, replacing nitrogen, sealing, maintaining the reaction temperature at 80 ℃ and carrying out polymerization for 20 hours to obtain the modified polystyrene, wherein the mass ratio of the styrene to the modified nano silicon dioxide to the azodiisobutyronitrile is 1:1:0.03.
The preparation method of the modified nano-silica is the same as in example 1.
Comparative example 3
In comparison with example 1, polystyrene was used for both the upper and lower layers of this comparative example.
The polypropylene film for the lithium battery current collector comprises an upper layer, an intermediate layer and a lower layer, wherein the components of the upper layer and the lower layer comprise 80 parts of isotactic polypropylene and 23 parts of polystyrene in parts by weight, the components of the intermediate layer comprise 85 parts of isotactic polypropylene and 20 parts of cycloolefin copolymer, and the thicknesses of the upper layer, the intermediate layer and the lower layer are 4 mu m.
A method for preparing a polypropylene film for a lithium battery current collector was the same as in example 1.
The preparation method of the polystyrene comprises the steps of adding styrene and azodiisobutyronitrile into a polymerization tube, uniformly mixing, replacing nitrogen, sealing, maintaining the reaction temperature at 80 ℃ and carrying out polymerization for 20 hours to obtain the polystyrene, wherein the mass ratio of the styrene to the azodiisobutyronitrile is 1:0.03.
The polypropylene films prepared in examples 1 to 4 and comparative examples 1 to 3 were subjected to performance test, wherein tensile strength and elongation at break were in accordance with GB/T13542.2 standard, heat shrinkage was in accordance with GB/T13542.2 standard, the test conditions were 15 minutes in an oven at 120℃and dielectric properties were in accordance with GB/T1409 standard, and the test results are shown in Table 1.
TABLE 1 Performance test results of Polypropylene films
As shown in Table 1, the polypropylene films prepared in examples 1 to 4 of the present invention have high tensile strength, elongation at break, dielectric loss tangent and breakdown strength, and low heat shrinkage, which means that the polypropylene films have good mechanical properties, dielectric properties and high thermal stability.
Compared with comparative examples 1-3, the preparation method of the modified polystyrene in the embodiment 1 of the invention uses styrene, modified nano silicon dioxide and modified monomers, wherein both the modified nano silicon dioxide and the modified monomers contain hexenyl ester groups and can participate in styrene polymerization, the modified monomers containing the phenylsulfonyl groups and hexenyl ester groups in the structures are grafted on the surfaces of the modified nano silicon dioxide, the phenylsulfonyl groups and the hexenyl ester groups have good high temperature resistance, the heat stability of the film is improved, the modified monomers are long-chain alkane sodium benzenesulfonate compounds and have a certain dispersing effect, the modified nano silicon dioxide is uniformly dispersed in the modified polystyrene, so that the modified polystyrene with uniform and stable structure is formed.
It should be noted that in this document, terms such as "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Although embodiments of the present application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the application, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411180712.6A CN118700669B (en) | 2024-08-27 | 2024-08-27 | Polypropylene film for lithium battery current collector and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411180712.6A CN118700669B (en) | 2024-08-27 | 2024-08-27 | Polypropylene film for lithium battery current collector and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN118700669A CN118700669A (en) | 2024-09-27 |
| CN118700669B true CN118700669B (en) | 2025-01-21 |
Family
ID=92822212
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202411180712.6A Active CN118700669B (en) | 2024-08-27 | 2024-08-27 | Polypropylene film for lithium battery current collector and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118700669B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN120228981B (en) * | 2025-05-29 | 2025-08-22 | 浙江南洋华诚科技股份有限公司 | A method for preparing multi-layer co-extruded composite insulation material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108479631A (en) * | 2018-03-19 | 2018-09-04 | 青岛大学 | A kind of anionic and nonionic type surfactant and preparation method thereof |
| CN118144338A (en) * | 2024-02-29 | 2024-06-07 | 扬州博恒新能源材料科技有限公司 | Flame-retardant and heat-aging-resistant composite current collector base film |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1207739A (en) * | 1968-06-14 | 1970-10-07 | Mallory & Co Inc P R | Electrolytic cells |
| CN115847973A (en) * | 2022-11-15 | 2023-03-28 | 扬州纳力新材料科技有限公司 | Multilayer composite polypropylene material and preparation method and application thereof |
| CN116444728B (en) * | 2023-04-20 | 2025-02-28 | 浙江南洋华诚科技股份有限公司 | A high-voltage and high-temperature resistant film for wind power capacitors and a preparation method thereof |
| CN116922915A (en) * | 2023-07-26 | 2023-10-24 | 厦门长塑实业有限公司 | High-temperature-resistant polypropylene film for film capacitor and preparation method thereof |
| CN118412474B (en) * | 2024-06-27 | 2024-09-27 | 江苏英联复合集流体有限公司 | Modified polypropylene-based film and preparation method thereof, composite current collector and electrode plate |
-
2024
- 2024-08-27 CN CN202411180712.6A patent/CN118700669B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108479631A (en) * | 2018-03-19 | 2018-09-04 | 青岛大学 | A kind of anionic and nonionic type surfactant and preparation method thereof |
| CN118144338A (en) * | 2024-02-29 | 2024-06-07 | 扬州博恒新能源材料科技有限公司 | Flame-retardant and heat-aging-resistant composite current collector base film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN118700669A (en) | 2024-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN117942788B (en) | Modified PET composite film for composite current collector and preparation method thereof | |
| CN118700669B (en) | Polypropylene film for lithium battery current collector and preparation method thereof | |
| CN112952295B (en) | Polyolefin-cellulose composite diaphragm and preparation method thereof | |
| CN119101474B (en) | A solvent-free composite polypropylene matte film with controllable gloss and preparation method thereof | |
| CN118772606A (en) | A tensile-resistant base film for composite current collector and preparation method thereof | |
| CN110229361B (en) | High-filling flexible boron nitride composite film material, high-filling flexible boron nitride copper-clad plate and preparation method thereof | |
| CN112387128B (en) | A kind of polyethylene modified multi-layer composite film for water treatment and preparation method thereof | |
| CN116852833A (en) | A production method of biaxially stretched composite film and biaxially stretched composite film | |
| CN120228981B (en) | A method for preparing multi-layer co-extruded composite insulation material | |
| CN116922915A (en) | High-temperature-resistant polypropylene film for film capacitor and preparation method thereof | |
| CN115831604A (en) | Metallized film for new energy automobile capacitor and preparation method thereof | |
| CN120059423A (en) | Composite current collector base film with high chemical stability and preparation method thereof | |
| CN118791770A (en) | A modified polyester film resistant to electrolyte corrosion and its application in composite current collector | |
| CN115232338B (en) | Cross-linked modified P (VMA-MMA) dielectric film and preparation method and application thereof | |
| CN116780096A (en) | High-affinity polytetrafluoroethylene diaphragm material, preparation method thereof and lithium ion battery | |
| CN117577928A (en) | Double-sided asymmetric quasi-solid composite electrolyte and preparation method and application thereof | |
| CN118693459B (en) | Lithium ion battery diaphragm and modification method | |
| CN114079124B (en) | Organic-inorganic composite lithium-ion battery separator and preparation method thereof | |
| CN116444728A (en) | A wind power capacitor high voltage and high temperature resistant film and its preparation method | |
| CN114421092A (en) | Preparation method of heat-resistant high-breathability composite coating diaphragm | |
| CN119455707B (en) | A large-area continuous MOF membrane and its preparation method and application | |
| CN117410532B (en) | Proton exchange membrane for fuel cell based on metal bipolar plate and preparation method thereof | |
| CN119153891B (en) | A kind of polyacid intercalated hydrotalcite aramid coated lithium battery diaphragm and preparation method thereof | |
| CN120574396B (en) | Preparation method and application of physical cross-linked polyimide dielectric composite material based on supermolecular structure | |
| CN120389206A (en) | A para-aramid composite diaphragm and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |