CN113745757A - Preparation method of lithium battery safety diaphragm material - Google Patents
Preparation method of lithium battery safety diaphragm material Download PDFInfo
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- CN113745757A CN113745757A CN202111047590.XA CN202111047590A CN113745757A CN 113745757 A CN113745757 A CN 113745757A CN 202111047590 A CN202111047590 A CN 202111047590A CN 113745757 A CN113745757 A CN 113745757A
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- imogolite
- diaphragm material
- lithium battery
- battery safety
- density polyethylene
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- 239000000463 material Substances 0.000 title claims abstract description 67
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 42
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 39
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 39
- 239000000126 substance Substances 0.000 claims abstract description 30
- 238000005303 weighing Methods 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 230000004048 modification Effects 0.000 claims abstract description 17
- 238000012986 modification Methods 0.000 claims abstract description 17
- 238000005266 casting Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000005096 rolling process Methods 0.000 claims abstract description 8
- 238000007493 shaping process Methods 0.000 claims abstract description 8
- 239000011858 nanopowder Substances 0.000 claims description 47
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 24
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 claims description 24
- 229920002401 polyacrylamide Polymers 0.000 claims description 23
- GVWYIGSUECJNRM-UHFFFAOYSA-N pyridine-2,5-dicarbaldehyde Chemical compound O=CC1=CC=C(C=O)N=C1 GVWYIGSUECJNRM-UHFFFAOYSA-N 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 abstract description 6
- 230000008018 melting Effects 0.000 abstract description 6
- 230000035699 permeability Effects 0.000 abstract description 6
- 229920000098 polyolefin Polymers 0.000 abstract description 5
- 239000011256 inorganic filler Substances 0.000 description 10
- 229910003475 inorganic filler Inorganic materials 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000012982 microporous membrane Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical group O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- MASNJXDMMSOROP-UHFFFAOYSA-N triethylsilane 2,2,2-trifluoroacetic acid Chemical compound CC[SiH](CC)CC.OC(=O)C(F)(F)F MASNJXDMMSOROP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
- H01M50/417—Polyolefins
-
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a lithium battery safety diaphragm material, which comprises the following steps: step 1, weighing an imogolite modified substance and mixing the imogolite modified substance with white oil to obtain a mixed modified liquid; step 2, weighing high-density polyethylene particles, placing the high-density polyethylene particles in a stirring mixer, and adding a mixed modification solution to obtain a high-density polyethylene mixture; step 3, placing the high-density polyethylene mixture in a double-screw extruder, extruding, casting to the surface of a cooling roller, and obtaining a diaphragm material blank after casting sheet forming; and 4, stretching the diaphragm material blank, and then sequentially drying, shaping and rolling to obtain the lithium battery safety diaphragm material. The invention effectively solves the problems of low melting point and poor size stability of the polyolefin diaphragm by improving the prior process method, the preparation process of the method is simple and convenient, the prepared diaphragm material has high safety, and simultaneously, the wettability and the air permeability of the diaphragm material are increased.
Description
Technical Field
The invention relates to the field of battery diaphragms, in particular to a preparation method of a lithium battery safety diaphragm material.
Background
The lithium battery mainly comprises an anode, a cathode, a diaphragm and electrolyte, wherein the diaphragm provides a channel for lithium ions, and the performance of the diaphragm directly determines the interface structure and the resistance of the battery, so that the diaphragm of the lithium battery is one of the most important materials in the lithium battery, and the preparation of a microporous membrane which is safe, environment-friendly and low in cost is a difficult point in the production process. Lithium battery separators need to be balanced in terms of safety, functionality, cost and the like, which is the development direction and research focus of lithium battery separators in the future. At present, the most widely used battery diaphragm is a polyolefin microporous membrane, but because the polyolefin diaphragm has low melting point and poor dimensional stability, severe thermal shrinkage can be generated when the temperature of the battery is higher than 150 ℃, so that the contact of the positive electrode and the negative electrode of the battery is caused to cause short circuit, and potential safety hazard is caused.
In order to improve the safety of the diaphragm, a plurality of coating diaphragms prepared by coating inorganic filler on the surface of a polyolefin diaphragm have appeared in recent years, and although the inorganic filler has excellent high-temperature resistance and thermal stability, the acting force between the inorganic filler coating and a base film is poor; in addition, the coating modification of the inorganic filler often causes the porosity of the base film to be reduced, and the charge and discharge performance of the battery is influenced.
Disclosure of Invention
Aiming at the problems that the acting force between an inorganic filler coating and a base film is poor frequently and the porosity of the base film is reduced frequently due to the coating modification of the inorganic filler in the prior art, the invention provides a preparation method of a lithium battery safety diaphragm material.
The purpose of the invention is realized by adopting the following technical scheme:
a preparation method of a lithium battery safety diaphragm material comprises the following steps:
step 1, weighing an imogolite modified substance, mixing the imogolite modified substance with white oil, and fully dispersing to obtain a mixed modified liquid;
step 2, weighing high-density polyethylene particles, placing the high-density polyethylene particles in a stirring mixer, heating until the high-density polyethylene particles are completely molten, slowly adding a mixed modification solution, and stirring and dispersing uniformly to obtain a high-density polyethylene mixture;
step 3, placing the high-density polyethylene mixture in a double-screw extruder, extruding, casting to the surface of a cooling roller, and obtaining a diaphragm material blank after casting sheet forming;
step 4, carrying out primary stretching treatment on the diaphragm material blank, then extracting the diaphragm material blank by using dichloromethane, carrying out secondary stretching treatment, and then sequentially carrying out drying, shaping and rolling to obtain the lithium battery safety diaphragm material;
wherein the imogolite modified substance is obtained by crosslinking and modifying imogolite nano powder serving as a base material.
Preferably, the high density polyethylene has a molecular weight of 20 to 50 ten thousand.
Preferably, the preparation method of the imogolite modified product comprises the following steps:
s1, weighing 2, 5-pyridinedicarboxaldehyde, mixing with deionized water, stirring for dissolving, adding activated imogolite nano powder, performing uniform ultrasonic treatment, pouring into a reaction kettle with polytetrafluoroethylene as a lining material, heating to 120-150 ℃, performing heat preservation treatment for 8-12 h, cooling to room temperature, centrifuging to collect lower-layer precipitate, washing for 3-5 times by using pure water, and performing vacuum drying treatment to obtain 2, 5-pyridinedicarboxaldehyde/imogolite; wherein the mass ratio of the 2, 5-pyridinedicarboxaldehyde, the activated imogolite nano powder to the deionized water is 1: 3-6: 10-15;
s2, weighing polyacrylamide and ethylene glycol, mixing, stirring for dissolving, adding 2-pyridylaldehyde/imogolite, uniformly dispersing, sequentially adding triethylsilane and trifluoroacetic acid while stirring, heating to 100-120 ℃ after adding, stirring for reacting for 15-18 h, cooling to room temperature, centrifuging, collecting lower-layer precipitates, washing for 3-5 times by using pure water, and performing vacuum drying treatment to obtain an imogolite modified substance; wherein the mass ratio of the polyacrylamide to the 2-pyridylaldehyde to the imogolite to the ethylene glycol is 1: 3.2-5.6: 8-10; the mass ratio of the triethylsilane to the trifluoroacetic acid to the polyacrylamide is 2: 4-6: 10-15.
Preferably, the preparation process of the activated imogolite nano-powder comprises the following steps: placing the imogolite nano powder into an acid liquor, carrying out ultrasonic treatment for 2-3 h, then washing the imogolite nano powder to be neutral by using pure water, and drying the imogolite nano powder to obtain activated imogolite nano powder; the acid solution comprises 1-2 mol/L sulfuric acid solution or nitric acid solution, and the mass ratio of the imogolite nano powder to the acid solution is 1: 5-10.
More preferably, the particle size of the imogolite nano-powder is 50 to 200 nm.
Preferably, in the step 1, the mass ratio of the imogolite modified product to the white oil is 1: 8-12.
Preferably, in the step 1, the mixing temperature of the imogolite modified product and the white oil is 135-155 ℃, and the dispersion time is 0.5-1 h.
Preferably, in the step 2, the temperature of the stirring mixer is set to be 140-150 ℃.
Preferably, in the step 2, after the mixed modification liquid is completely added, the stirring is continued for 0.2-0.5 h.
Preferably, in the step 3, the temperature of the roll surface is 20-40 ℃.
Preferably, in the step 4, the temperature of the first stretching treatment is 50-70 ℃, and the temperature of the second stretching treatment is 100-120 ℃.
Preferably, in the step 4, the first stretching treatment is transverse stretching and then longitudinal stretching, wherein the transverse stretching magnification is 2-3 times, and the longitudinal stretching magnification is 1.5-2 times.
Preferably, in the step 4, the second stretching treatment is transverse stretching, wherein the transverse stretching magnification is 1.5 to 2 times.
Preferably, in the step 4, the drying condition is vacuum drying, the drying temperature is 45-55 ℃, and the setting temperature is 110-120 ℃.
Preferably, the thickness of the lithium battery safety diaphragm material is 10-50 μm.
The invention has the beneficial effects that:
1. the invention discloses a preparation method of a lithium battery safety diaphragm material, which effectively solves the problems of low melting point and poor size stability of a polyolefin diaphragm by improving the prior process method.
2. According to the safety diaphragm material for the lithium battery, the high-density polyethylene is used as a base material, the imogolite is used as the inorganic filler to improve the high temperature resistance of the safety diaphragm material, the method for coating the inorganic filler layer on the surface of the polyethylene porous membrane in the market is abandoned, the inorganic filler is fused with the polyethylene, the common inorganic material is fused with the polyethylene, the performance cannot be enhanced, and the service life of the polyethylene serving as the diaphragm is shortened. In the process of combining with polyethylene, the pore-forming agent white oil is combined firstly, and then dichloromethane is used for extraction and washing, so that the pore channel is formed.
3. Although high-density polyethylene is excellent in hardness, tensile strength and creep property and improved in heat resistance to a certain extent as compared with ordinary polyethylene, it is still insufficient in shrinkage resistance, and particularly, it is aged by thermal oxidation to significantly reduce the air permeability, so that it is required to be modified. The imogolite modifier prepared by the invention not only enhances the mechanical strength of the high-density polyethylene, but also enhances the high temperature resistance and shrinkage resistance of the high-density polyethylene, so that the finally prepared diaphragm material has better safety.
Detailed Description
For the purpose of more clearly illustrating the present invention and more clearly understanding the technical features, objects and advantages of the present invention, the technical solutions of the present invention will now be described in detail below, but are not to be construed as limiting the implementable scope of the present invention.
The traditional high-temperature-resistant inorganic material cannot meet the market requirement, the prepared inorganic filler coating and the base film have insufficient force, and the inorganic particle coating layer easily blocks micropores of the base film, so that the porosity of the coated diaphragm is reduced, the air permeability of the diaphragm is poor, and the diaphragm needs to be optimized and modified. According to the invention, imogolite which is rare in the market is selected as a high-temperature resistant base material, the imogolite is a natural nano mineral and has a single-wall tubular nano structure, a coiled gibbsite plate forms an outer tube framework, and the inner side of the tube is an orthosilicic acid group.
The process for the preparation of an imogolite modification according to the invention and the principles that may be associated therewith are explained below:
firstly, imogolite is activated by using an acid solution to activate active functional groups on the surface of the imogolite, then, 2, 5-pyridinedicarboxaldehyde containing a dialdehyde is used for surface modification to obtain 2, 5-pyridinedicarboxaldehyde/imogolite with the surface coated with the 2, 5-pyridinedicarboxaldehyde, then, polyacrylamide with excellent thermal stability is used for combining with the 2, 5-pyridinedicarboxaldehyde/imogolite, and under the catalysis of a triethylsilane-trifluoroacetic acid system, aldehyde groups (-CHO) on the 2, 5-pyridinedicarboxaldehyde/imogolite and amide groups (-CO-NH) in the polyacrylamide2) The imide group (-CO-NH-) is generated through the reaction, so that the polyacrylamide is coated outside the 2, 5-pyridinedicarboxaldehyde/imogolite, and the polyacrylamide and the imogolite are crosslinked through the imide group, so that the stability can be improved. The polyacrylamide has strong water solubility, and after reaction treatment, the solubility of the polyacrylamide in water is reduced, but the hydrophilicity is still kept strong, so that the wettability of the diaphragm material on an electrolyte can be ensured, the chemical stability of the 2, 5-pyridinedicarboxaldehyde is strong, and the product obtained after modification of imogolite is more stable. In addition, the invention also finds that the service life of the battery diaphragm is longer and the electrical cycle performance is enhanced after the imogolite modifier is used for modifying the polyethylene.
The invention is further described below with reference to the following examples.
Example 1
A preparation method of a lithium battery safety diaphragm material comprises the following steps:
step 1, weighing an imogolite modified substance, mixing the imogolite modified substance with white oil, wherein the mixing temperature is 145 ℃, and fully dispersing for 0.8h to obtain a mixed modified liquid; wherein the mass ratio of the imogolite modified substance to the white oil is 1: 10;
step 2, weighing high-density polyethylene particles, placing the high-density polyethylene particles into a stirring mixer, heating to 145 ℃ for complete melting, slowly adding the mixed modification solution, and continuously stirring and dispersing for 0.4h to obtain a high-density polyethylene mixture;
step 3, placing the high-density polyethylene mixture in a double-screw extruder, extruding, casting to the roll surface of a cooling roller with the temperature of 30 ℃, and obtaining a diaphragm material blank after casting sheet forming;
step 4, performing primary stretching treatment on the diaphragm material blank at the temperature of 60 ℃, then extracting by using dichloromethane, performing secondary stretching treatment at the temperature of 110 ℃, and then sequentially drying, shaping and rolling to obtain a lithium battery safety diaphragm material with the thickness of 10-50 microns; wherein, the first stretching treatment is transverse stretching and then longitudinal stretching, the transverse stretching multiplying power is 2.5 times, and the longitudinal stretching multiplying power is 1.8 times; the second stretching treatment was transverse stretching with a stretching magnification of 1.8 times.
The preparation method of the imogolite modified product in the step 1 comprises the following steps:
s1, placing imogolite nano powder with the particle size of 50-200 nm into acid liquor, performing ultrasonic treatment for 2.5 hours, then washing the imogolite nano powder to be neutral by using pure water, and drying the imogolite nano powder to obtain activated imogolite nano powder; wherein the acid solution comprises 1.5mol/L sulfuric acid solution or nitric acid solution, and the mass ratio of the imogolite nano powder to the acid solution is 1: 8;
s2, weighing 2, 5-pyridinedicarboxaldehyde, mixing with deionized water, stirring for dissolving, adding activated imogolite nano powder, performing uniform ultrasonic treatment, pouring into a reaction kettle with polytetrafluoroethylene as a lining material, heating to 135 ℃, performing heat preservation treatment for 10 hours, cooling to room temperature, centrifuging to collect lower-layer precipitate, washing for 3-5 times by using pure water, and performing vacuum drying treatment to obtain 2, 5-pyridinedicarboxaldehyde/imogolite; wherein the mass ratio of the 2, 5-pyridine dicarbaldehyde to the activated imogolite nano powder to the deionized water is 1:4: 12;
s3, weighing polyacrylamide and ethylene glycol, mixing, stirring for dissolving, adding 2-pyridylaldehyde/imogolite, uniformly dispersing, sequentially adding triethylsilane and trifluoroacetic acid while stirring, heating to 110 ℃ after adding, stirring for reacting for 16 hours, cooling to room temperature, centrifuging, collecting lower-layer precipitates, washing for 3-5 times by using pure water, and performing vacuum drying treatment to obtain an imogolite modified substance; wherein the mass ratio of the polyacrylamide to the 2-pyridylaldehyde to the imogolite to the ethylene glycol is 1:4.8: 9; the mass ratio of the triethylsilane to the trifluoroacetic acid to the polyacrylamide is 2:5: 13.
Example 2
A preparation method of a lithium battery safety diaphragm material comprises the following steps:
step 1, weighing an imogolite modified substance, mixing the imogolite modified substance with white oil, wherein the mixing temperature is 135 ℃, and fully dispersing for 0.5h to obtain a mixed modified liquid; wherein the mass ratio of the imogolite modified substance to the white oil is 1: 8;
step 2, weighing high-density polyethylene particles, placing the high-density polyethylene particles in a stirring mixer, heating to 140 ℃ to completely melt, slowly adding a mixed modification solution, and continuously stirring and dispersing for 0.2h to obtain a high-density polyethylene mixture;
step 3, placing the high-density polyethylene mixture in a double-screw extruder, extruding, casting to the roll surface of a cooling roller with the temperature of 20 ℃, and obtaining a diaphragm material blank after casting sheet forming;
step 4, performing primary stretching treatment on the diaphragm material blank at the temperature of 50 ℃, extracting by using dichloromethane, performing secondary stretching treatment at the temperature of 100 ℃, and then sequentially drying, shaping and rolling to obtain a lithium battery safety diaphragm material with the thickness of 10-50 microns; wherein, the first stretching treatment is transverse stretching and then longitudinal stretching, the transverse stretching multiplying power is 2 times, and the longitudinal stretching multiplying power is 1.5 times; the second stretching treatment was transverse stretching with a stretching magnification of 1.5 times.
The preparation method of the imogolite modified product in the step 1 comprises the following steps:
s1, placing imogolite nano powder with the particle size of 50-200 nm into acid liquor, performing ultrasonic treatment for 2 hours, washing the imogolite nano powder to be neutral by using pure water, and drying the imogolite nano powder to obtain activated imogolite nano powder; wherein the acid solution comprises 1mol/L sulfuric acid solution or nitric acid solution, and the mass ratio of the imogolite nano powder to the acid solution is 1: 5;
s2, weighing 2, 5-pyridinedicarboxaldehyde, mixing with deionized water, stirring for dissolving, adding activated imogolite nano powder, uniformly performing ultrasonic treatment, pouring into a reaction kettle with polytetrafluoroethylene as a lining material, heating to 120 ℃, performing heat preservation treatment for 8 hours, cooling to room temperature, centrifuging to collect lower-layer precipitate, washing for 3-5 times by using pure water, and performing vacuum drying treatment to obtain 2, 5-pyridinedicarboxaldehyde/imogolite; wherein the mass ratio of the 2, 5-pyridine dicarbaldehyde to the activated imogolite nano powder to the deionized water is 1:3: 10;
s3, weighing polyacrylamide and ethylene glycol, mixing, stirring for dissolving, adding 2-pyridylaldehyde/imogolite, uniformly dispersing, sequentially adding triethylsilane and trifluoroacetic acid while stirring, heating to 100 ℃ after adding, stirring for reacting for 15 hours, cooling to room temperature, centrifuging, collecting lower-layer precipitates, washing for 3-5 times by using pure water, and performing vacuum drying treatment to obtain an imogolite modified substance; wherein the mass ratio of the polyacrylamide to the 2-pyridylaldehyde to the imogolite to the ethylene glycol is 1:3.2: 8; the mass ratio of the triethylsilane to the trifluoroacetic acid to the polyacrylamide is 2:4: 10.
Example 3
A preparation method of a lithium battery safety diaphragm material comprises the following steps:
step 1, weighing an imogolite modified substance, mixing the imogolite modified substance with white oil, wherein the mixing temperature is 155 ℃, and fully dispersing for 1 hour to obtain a mixed modified liquid; wherein the mass ratio of the imogolite modified substance to the white oil is 1: 12;
step 2, weighing high-density polyethylene particles, placing the high-density polyethylene particles in a stirring mixer, heating to 150 ℃ to completely melt, slowly adding a mixed modification solution, and continuously stirring and dispersing for 0.5h to obtain a high-density polyethylene mixture;
step 3, placing the high-density polyethylene mixture in a double-screw extruder, extruding, casting to a roller surface of a cooling roller with the temperature of 40 ℃, and obtaining a diaphragm material blank after casting sheet forming;
step 4, performing primary stretching treatment on the diaphragm material blank at the temperature of 70 ℃, extracting by using dichloromethane, performing secondary stretching treatment at the temperature of 120 ℃, and then sequentially drying, shaping and rolling to obtain a lithium battery safety diaphragm material with the thickness of 10-50 microns; wherein, the first stretching treatment is transverse stretching and then longitudinal stretching, the transverse stretching multiplying power is 3 times, and the longitudinal stretching multiplying power is 2 times; the second stretching treatment was transverse stretching with a stretching magnification of 2.
The preparation method of the imogolite modified product in the step 1 comprises the following steps:
s1, placing imogolite nano powder with the particle size of 50-200 nm into acid liquor, performing ultrasonic treatment for 3 hours, then washing the imogolite nano powder to be neutral by using pure water, and drying the imogolite nano powder to obtain activated imogolite nano powder; wherein the acid solution comprises 2mol/L sulfuric acid solution or nitric acid solution, and the mass ratio of the imogolite nano powder to the acid solution is 1: 10;
s2, weighing 2, 5-pyridinedicarboxaldehyde, mixing with deionized water, stirring for dissolving, adding activated imogolite nano powder, uniformly performing ultrasonic treatment, pouring into a reaction kettle with polytetrafluoroethylene as a lining material, heating to 150 ℃, performing heat preservation treatment for 12 hours, cooling to room temperature, centrifuging to collect lower-layer precipitate, washing for 3-5 times by using pure water, and performing vacuum drying treatment to obtain 2, 5-pyridinedicarboxaldehyde/imogolite; wherein the mass ratio of the 2, 5-pyridine dicarbaldehyde to the activated imogolite nano powder to the deionized water is 1:6: 15;
s3, weighing polyacrylamide and ethylene glycol, mixing, stirring for dissolving, adding 2-pyridylaldehyde/imogolite, uniformly dispersing, sequentially adding triethylsilane and trifluoroacetic acid while stirring, heating to 120 ℃ after adding, stirring for reacting for 18 hours, cooling to room temperature, centrifuging, collecting lower-layer precipitates, washing for 3-5 times by using pure water, and performing vacuum drying treatment to obtain an imogolite modified substance; wherein the mass ratio of the polyacrylamide to the 2-pyridylaldehyde to the imogolite to the ethylene glycol is 1:5.6: 10; the mass ratio of the triethylsilane to the trifluoroacetic acid to the polyacrylamide is 2:6: 15.
Comparative example 1
A preparation method of a lithium battery safety diaphragm material comprises the following steps:
step 1, weighing imogolite and mixing with white oil, wherein the mixing temperature is 145 ℃, and fully dispersing for 0.8h to obtain a mixed modification liquid; wherein the mass ratio of the imogolite to the white oil is 1: 10;
step 2, weighing high-density polyethylene particles, placing the high-density polyethylene particles into a stirring mixer, heating to 145 ℃ for complete melting, slowly adding the mixed modification solution, and continuously stirring and dispersing for 0.4h to obtain a high-density polyethylene mixture;
step 3, placing the high-density polyethylene mixture in a double-screw extruder, extruding, casting to the roll surface of a cooling roller with the temperature of 30 ℃, and obtaining a diaphragm material blank after casting sheet forming;
step 4, performing primary stretching treatment on the diaphragm material blank at the temperature of 60 ℃, then extracting by using dichloromethane, performing secondary stretching treatment at the temperature of 110 ℃, and then sequentially drying, shaping and rolling to obtain a lithium battery safety diaphragm material with the thickness of 10-50 microns; wherein, the first stretching treatment is transverse stretching and then longitudinal stretching, the transverse stretching multiplying power is 2.5 times, and the longitudinal stretching multiplying power is 1.8 times; the second stretching treatment was transverse stretching with a stretching magnification of 1.8 times.
Comparative example 2
A preparation method of a lithium battery safety diaphragm material comprises the following steps:
step 1, weighing an imogolite modified substance, mixing the imogolite modified substance with white oil, wherein the mixing temperature is 145 ℃, and fully dispersing for 0.8h to obtain a mixed modified liquid; wherein the mass ratio of the imogolite modified substance to the white oil is 1: 10;
step 2, weighing high-density polyethylene particles, placing the high-density polyethylene particles into a stirring mixer, heating to 145 ℃ for complete melting, slowly adding the mixed modification solution, and continuously stirring and dispersing for 0.4h to obtain a high-density polyethylene mixture;
step 3, placing the high-density polyethylene mixture in a double-screw extruder, extruding, casting to the roll surface of a cooling roller with the temperature of 30 ℃, and obtaining a diaphragm material blank after casting sheet forming;
step 4, performing primary stretching treatment on the diaphragm material blank at the temperature of 60 ℃, then extracting by using dichloromethane, performing secondary stretching treatment at the temperature of 110 ℃, and then sequentially drying, shaping and rolling to obtain a lithium battery safety diaphragm material with the thickness of 10-50 microns; wherein, the first stretching treatment is transverse stretching and then longitudinal stretching, the transverse stretching multiplying power is 2.5 times, and the longitudinal stretching multiplying power is 1.8 times; the second stretching treatment was transverse stretching with a stretching magnification of 1.8 times.
The preparation method of the imogolite modified product in the step 1 comprises the following steps:
s1, placing imogolite nano powder with the particle size of 50-200 nm into acid liquor, performing ultrasonic treatment for 2.5 hours, then washing the imogolite nano powder to be neutral by using pure water, and drying the imogolite nano powder to obtain activated imogolite nano powder; wherein the acid solution comprises 1.5mol/L sulfuric acid solution or nitric acid solution, and the mass ratio of the imogolite nano powder to the acid solution is 1: 8;
s2, weighing polyacrylamide and ethylene glycol, mixing, stirring for dissolving, adding activated imogolite nano powder, uniformly dispersing, sequentially adding triethylsilane and trifluoroacetic acid while stirring, heating to 110 ℃ after adding, stirring for reacting for 16 hours, cooling to room temperature, centrifuging, collecting lower-layer precipitates, washing for 3-5 times by using pure water, and performing vacuum drying treatment to obtain an imogolite modified substance; wherein the mass ratio of the polyacrylamide to the activated imogolite nano powder to the ethylene glycol is 1:4.8: 9; the mass ratio of the triethylsilane to the trifluoroacetic acid to the polyacrylamide is 2:5: 13.
For more clearly explaining the invention, the membrane materials prepared in examples 1 to 3 and comparative examples 1 to 2 were all prepared to have a thickness of (20 ± 0.1) μm and tested in performance, wherein the tensile strength was tested according to the standard GB/T1040.3-2006, the air permeability, the thermal shrinkage and the ionic conductivity were tested according to the standard GB/T36363-2018, and the thermal shrinkage was the shrinkage after treatment for 1 hour at 150 ℃.
The results are shown in table 1:
table 1 comparison of the properties of different separator materials
As can be seen from Table 1, the film disclosed in the embodiments 1-3 of the invention has better mechanical strength and air permeability, higher film breaking temperature, lower thermal shrinkage and smaller contact angle with water while maintaining the pore closing temperature of 130 ℃, which indicates that the film has better high temperature resistance, air permeability, safety and wettability.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of a lithium battery safety diaphragm material is characterized by comprising the following steps:
step 1, weighing an imogolite modified substance, mixing the imogolite modified substance with white oil, and fully dispersing to obtain a mixed modified liquid;
step 2, weighing high-density polyethylene particles, placing the high-density polyethylene particles in a stirring mixer, heating until the high-density polyethylene particles are completely molten, slowly adding a mixed modification solution, and stirring and dispersing uniformly to obtain a high-density polyethylene mixture;
step 3, placing the high-density polyethylene mixture in a double-screw extruder, extruding, casting to the surface of a cooling roller, and obtaining a diaphragm material blank after casting sheet forming;
step 4, carrying out primary stretching treatment on the diaphragm material blank, then extracting the diaphragm material blank by using dichloromethane, carrying out secondary stretching treatment, and then sequentially carrying out drying, shaping and rolling to obtain the lithium battery safety diaphragm material;
wherein the imogolite modified substance is obtained by crosslinking and modifying imogolite nano powder serving as a base material.
2. The preparation method of the lithium battery safety separator material as claimed in claim 1, wherein the imogolite modified substance is prepared by the following steps:
s1, weighing 2, 5-pyridinedicarboxaldehyde, mixing with deionized water, stirring for dissolving, adding activated imogolite nano powder, performing uniform ultrasonic treatment, pouring into a reaction kettle with polytetrafluoroethylene as a lining material, heating to 120-150 ℃, performing heat preservation treatment for 8-12 h, cooling to room temperature, centrifuging to collect lower-layer precipitate, washing for 3-5 times by using pure water, and performing vacuum drying treatment to obtain 2, 5-pyridinedicarboxaldehyde/imogolite; wherein the mass ratio of the 2, 5-pyridinedicarboxaldehyde, the activated imogolite nano powder to the deionized water is 1: 3-6: 10-15;
s2, weighing polyacrylamide and ethylene glycol, mixing, stirring for dissolving, adding 2-pyridylaldehyde/imogolite, uniformly dispersing, sequentially adding triethylsilane and trifluoroacetic acid while stirring, heating to 100-120 ℃ after adding, stirring for reacting for 15-18 h, cooling to room temperature, centrifuging, collecting lower-layer precipitates, washing for 3-5 times by using pure water, and performing vacuum drying treatment to obtain an imogolite modified substance; wherein the mass ratio of the polyacrylamide to the 2-pyridylaldehyde to the imogolite to the ethylene glycol is 1: 3.2-5.6: 8-10; the mass ratio of the triethylsilane to the trifluoroacetic acid to the polyacrylamide is 2: 4-6: 10-15.
3. The method for preparing a lithium battery safety separator material as claimed in claim 2, wherein the activated imogolite nano-powder is prepared by the following steps: placing the imogolite nano powder into an acid liquor, carrying out ultrasonic treatment for 2-3 h, then washing the imogolite nano powder to be neutral by using pure water, and drying the imogolite nano powder to obtain activated imogolite nano powder; the acid solution comprises 1-2 mol/L sulfuric acid solution or nitric acid solution, and the mass ratio of the imogolite nano powder to the acid solution is 1: 5-10.
4. The preparation method of the lithium battery safety separator material as claimed in claim 1, wherein in the step 1, the mass ratio of the imogolite modified substance to the white oil is 1: 8-12.
5. The preparation method of the lithium battery safety separator material as claimed in claim 1, wherein in the step 1, the mixing temperature of the imogolite modified substance and the white oil is 135-155 ℃, and the dispersion time is 0.5-1 h.
6. The method for preparing a lithium battery safety diaphragm material according to claim 1, wherein in the step 2, the temperature of the stirring mixer is set to be 140-150 ℃.
7. The method for preparing a lithium battery safety diaphragm material according to claim 1, wherein in the step 2, after the mixed modification liquid is completely added, the stirring is continued for 0.2-0.5 h.
8. The method for preparing a lithium battery safety diaphragm material according to claim 1, wherein in the step 4, the temperature of the first stretching treatment is 50-70 ℃, and the temperature of the second stretching treatment is 100-120 ℃.
9. The method for preparing a lithium battery safety diaphragm material according to claim 1, wherein in the step 4, the first stretching treatment is transverse stretching and then longitudinal stretching, wherein the transverse stretching ratio is 2-3 times, and the longitudinal stretching ratio is 1.5-2 times.
10. The method for preparing a lithium battery safety diaphragm material according to claim 1, wherein in the step 4, the second stretching treatment is transverse stretching, wherein the transverse stretching rate is 1.5-2 times.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114032000A (en) * | 2021-12-13 | 2022-02-11 | 安徽漫画树涂料有限公司 | Inorganic aldehyde-removing fireproof water-based paint |
| CN114304824A (en) * | 2022-01-14 | 2022-04-12 | 北京华夏理想证章有限公司 | Lasting wear-resistant souvenir badge and preparation method thereof |
| CN115108817A (en) * | 2022-06-17 | 2022-09-27 | 无锡畾田陶瓷科技有限公司 | Environment-friendly wear-resistant ceramic brick and preparation process thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11130900A (en) * | 1997-10-27 | 1999-05-18 | Asahi Chem Ind Co Ltd | Finely porous polyethylene membrane |
| JP2008088393A (en) * | 2006-09-29 | 2008-04-17 | Toray Saehan Inc | Method for producing polyolefin microporous film |
| CN102064299A (en) * | 2010-12-25 | 2011-05-18 | 佛山塑料集团股份有限公司 | Polyolefin multi-layer porous diaphragm for lithium ion battery and preparation method thereof |
| CN103865093A (en) * | 2012-12-18 | 2014-06-18 | 中国第一汽车股份有限公司 | Pretreatment method for lithium ion battery separator surface |
| CN104272503A (en) * | 2012-05-09 | 2015-01-07 | 日立化成株式会社 | Separator for electrochemical element and manufacturing method thereof |
| CN106784528A (en) * | 2016-12-27 | 2017-05-31 | 深圳市星源材质科技股份有限公司 | A kind of preparation method of lithium battery diaphragm |
| CN109742298A (en) * | 2019-01-08 | 2019-05-10 | 桑顿新能源科技有限公司 | Porous ceramics diaphragm slurry and preparation method thereof, battery diaphragm and battery |
| CN110911617A (en) * | 2019-12-10 | 2020-03-24 | 安徽新衡新材料科技有限公司 | High-toughness polyolefin lithium ion battery diaphragm and preparation method thereof |
| CN112259904A (en) * | 2020-09-28 | 2021-01-22 | 河北金力新能源科技股份有限公司 | High-strength low-shrinkage lithium ion battery diaphragm and preparation method thereof |
| CN112350025A (en) * | 2019-08-09 | 2021-02-09 | 江苏厚生新能源科技有限公司 | Organic/inorganic hybrid microporous diaphragm and application thereof |
-
2021
- 2021-09-07 CN CN202111047590.XA patent/CN113745757B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11130900A (en) * | 1997-10-27 | 1999-05-18 | Asahi Chem Ind Co Ltd | Finely porous polyethylene membrane |
| JP2008088393A (en) * | 2006-09-29 | 2008-04-17 | Toray Saehan Inc | Method for producing polyolefin microporous film |
| CN102064299A (en) * | 2010-12-25 | 2011-05-18 | 佛山塑料集团股份有限公司 | Polyolefin multi-layer porous diaphragm for lithium ion battery and preparation method thereof |
| CN104272503A (en) * | 2012-05-09 | 2015-01-07 | 日立化成株式会社 | Separator for electrochemical element and manufacturing method thereof |
| CN103865093A (en) * | 2012-12-18 | 2014-06-18 | 中国第一汽车股份有限公司 | Pretreatment method for lithium ion battery separator surface |
| CN106784528A (en) * | 2016-12-27 | 2017-05-31 | 深圳市星源材质科技股份有限公司 | A kind of preparation method of lithium battery diaphragm |
| CN109742298A (en) * | 2019-01-08 | 2019-05-10 | 桑顿新能源科技有限公司 | Porous ceramics diaphragm slurry and preparation method thereof, battery diaphragm and battery |
| CN112350025A (en) * | 2019-08-09 | 2021-02-09 | 江苏厚生新能源科技有限公司 | Organic/inorganic hybrid microporous diaphragm and application thereof |
| CN110911617A (en) * | 2019-12-10 | 2020-03-24 | 安徽新衡新材料科技有限公司 | High-toughness polyolefin lithium ion battery diaphragm and preparation method thereof |
| CN112259904A (en) * | 2020-09-28 | 2021-01-22 | 河北金力新能源科技股份有限公司 | High-strength low-shrinkage lithium ion battery diaphragm and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114032000A (en) * | 2021-12-13 | 2022-02-11 | 安徽漫画树涂料有限公司 | Inorganic aldehyde-removing fireproof water-based paint |
| CN114304824A (en) * | 2022-01-14 | 2022-04-12 | 北京华夏理想证章有限公司 | Lasting wear-resistant souvenir badge and preparation method thereof |
| CN114304824B (en) * | 2022-01-14 | 2023-11-17 | 北京华夏理想证章有限公司 | Durable wear-resistant souvenir badge and preparation method thereof |
| CN115108817A (en) * | 2022-06-17 | 2022-09-27 | 无锡畾田陶瓷科技有限公司 | Environment-friendly wear-resistant ceramic brick and preparation process thereof |
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|---|---|
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