CN118040232A - Material for positive electrode, dry preparation method and application of material in lithium battery - Google Patents
Material for positive electrode, dry preparation method and application of material in lithium battery Download PDFInfo
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- CN118040232A CN118040232A CN202410314995.2A CN202410314995A CN118040232A CN 118040232 A CN118040232 A CN 118040232A CN 202410314995 A CN202410314995 A CN 202410314995A CN 118040232 A CN118040232 A CN 118040232A
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- polypropylene
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- nitrile rubber
- mica powder
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- 239000000463 material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 10
- 239000004743 Polypropylene Substances 0.000 claims abstract description 165
- 229920001155 polypropylene Polymers 0.000 claims abstract description 165
- -1 polypropylene Polymers 0.000 claims abstract description 162
- 239000010445 mica Substances 0.000 claims abstract description 63
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 63
- 239000000843 powder Substances 0.000 claims abstract description 63
- DEQJNIVTRAWAMD-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)OC(=O)C=C DEQJNIVTRAWAMD-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 59
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 86
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- 238000002156 mixing Methods 0.000 claims description 32
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 25
- 239000000835 fiber Substances 0.000 claims description 24
- 238000009987 spinning Methods 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 23
- 238000000465 moulding Methods 0.000 claims description 23
- 238000007664 blowing Methods 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 14
- 239000007774 positive electrode material Substances 0.000 claims description 14
- 238000005516 engineering process Methods 0.000 claims description 13
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 12
- 238000007731 hot pressing Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000010405 anode material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 31
- 238000009210 therapy by ultrasound Methods 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000001291 vacuum drying Methods 0.000 description 16
- 238000009413 insulation Methods 0.000 description 9
- 239000003779 heat-resistant material Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 2
- 238000000578 dry spinning Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 230000000051 modifying effect Effects 0.000 description 2
- 238000002166 wet spinning Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a material for a positive electrode, a dry preparation method and application of the material in a lithium battery. The polypropylene diaphragm prepared by taking polypropylene as a raw material and adopting a dry process has good insulativity and heat resistance; the polypropylene diaphragm is subjected to finishing modification, and mica powder, organic fluoride and nitrile rubber are introduced, so that the insulativity, heat resistance and mechanical strength of the dry polypropylene diaphragm can be effectively improved; the polypropylene diaphragm is subjected to pre-irradiation treatment, so that grafting reaction of alkenyl modified mica powder containing carbon-carbon double bonds, hexafluorobutyl acrylate and nitrile rubber can be initiated; the mica powder, hexafluorobutyl acrylate and nitrile rubber are connected to the polypropylene diaphragm through a grafting reaction by stable chemical bonds, so that the binding fastness of the effective components in the finishing agent and the polypropylene diaphragm is improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a material for a positive electrode, a dry preparation method and application of the material in a lithium battery.
Background
The lithium battery is an important electric energy storage device because of the advantages of light relative mass, large specific energy, high energy density, small self-discharge effect, stable circularity, no memory effect and the like. The separator is one of key components of the lithium battery, and can separate positive and negative active materials and prevent the two electrodes from being short-circuited due to contact. The separator is generally a porous plastic film, and is prepared by wet spinning or dry spinning, and compared with dry spinning, wet spinning such as electrostatic spinning requires a large amount of solvent, and has poor economical efficiency and environmental protection.
In order to ensure the safety of the lithium battery, the insulating performance and the thermal stability of the diaphragm are required to be high. The diaphragm is used as a material for the positive electrode, chinese patent CN114335410B discloses a dry method positive electrode containing a diaphragm, the dry method positive electrode comprises a current collector, and a dry method ternary film, a dry method lithium iron phosphate film and a diaphragm are sequentially arranged on at least one side surface of the current collector along the direction away from the surface of the current collector, and the diaphragm comprises a PP diaphragm and a PP/PE composite diaphragm. However, polypropylene and PE are poor in heat resistance and easily shrink at high temperature, which may cause contact between positive and negative electrodes and affect safety.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a dry preparation method of a material for a positive electrode, which solves the problem of poor thermal stability and insulation of a lithium battery diaphragm in the prior art.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
The anode material is prepared by the following steps:
Step one, taking polypropylene (PP) as a raw material, preparing a polypropylene fiber web by using a melt-blown spinning technology, and performing hot press molding on the polypropylene fiber web to obtain a dry polypropylene diaphragm;
Mixing gamma- (methacryloyloxy) propyl trimethoxysilane with an ethanol water solution, and hydrolyzing to obtain a hydrolyzed gamma- (methacryloyloxy) propyl trimethoxysilane solution; mixing mica powder with deionized water, performing ultrasonic dispersion, adding the mixture into hydrolyzed gamma- (methacryloyloxy) propyl trimethoxy silane solution, reacting, filtering, washing and drying after the reaction is finished to obtain alkenyl modified mica powder;
Adding liquid nitrile rubber into toluene, stirring and dissolving to obtain a nitrile rubber solution;
dissolving hexafluorobutyl acrylate in ethylene glycol monobutyl ether to obtain hexafluorobutyl acrylate solution;
Mixing hexafluorobutyl acrylate solution, nitrile rubber solution and alkenyl modified mica powder, and performing ultrasonic dispersion to obtain a modified finishing agent;
after the dry polypropylene diaphragm is subjected to pre-irradiation treatment, the diaphragm is immersed in a modified finishing agent for reaction, and after the reaction is finished, the diaphragm is taken out, washed and dried to obtain a product; the product is the modified dry polypropylene diaphragm.
Preferably, in the first step, the process parameters of melt-blown spinning are as follows: the set temperature of the screw extruder is between 175 and 185 ℃ in zone 1, 215 and 225 ℃ in zone 2, 225 and 245 ℃ in zone 3, 235 and 250 ℃ in zone 4 and 230 and 240 ℃ in zone 5; the temperature of the melt-blowing die head is 230-235 ℃; the temperature of the metering pump is 230-250 ℃, and the rotating speed of the metering pump is 230-235r/min; the air temperature of the drafting hot air is 230-250 ℃, and the air pressure of the drafting hot air is 8-15MPa; the moving speed of the net curtain is 1.6-2.5m/min.
Preferably, in the first step, the hot press molding process parameters are as follows: the speed of the net belt is 600m/min, the hot pressing pressure is 102daN/cm, the temperature of the roller is 153.5 ℃, and the temperature of the smooth roller is 142.5 ℃; the dry polypropylene separator has a thickness of 60-110 μm.
Preferably, in the second step, when the alkenyl modified mica powder is prepared, the mass ratio of the mica powder to deionized water to gamma- (methacryloyloxy) propyl trimethoxysilane to ethanol aqueous solution is 25 (125-150): 25-30): 250-300.
Preferably, in the second step, when preparing the alkenyl modified mica powder, the hydrolysis condition is that the reaction is carried out for 20-40min at the temperature of 50-70 ℃, the ultrasonic dispersion condition is that the ultrasonic dispersion is carried out for 30-60min at the frequency of 50-100Hz, and the reaction condition is that the reaction is carried out for 1.5-2.5h at the temperature of 50-70 ℃.
Preferably, the aqueous ethanol solution is a 95wt% aqueous ethanol solution.
Preferably, in the second step, when preparing the nitrile rubber solution, the mass ratio of the liquid nitrile rubber to the toluene is 25 (125-250); when the hexafluorobutyl acrylate solution is prepared, the mass ratio of the hexafluorobutyl acrylate to the ethylene glycol monobutyl ether is (25-30) (200-300).
Preferably, in the second step, when the modified finishing agent is prepared, the mass ratio of the hexafluorobutyl acrylate solution, the nitrile rubber solution and the alkenyl modified mica powder is (225-330): 150-275): 27-28, and the condition of ultrasonic dispersion is ultrasonic at the frequency of 50-100Hz for 30-60min.
Preferably, in the second step, when preparing the modified dry polypropylene membrane, the mass ratio of the dry polypropylene membrane after the pre-irradiation treatment to the modified finishing agent is 1:10.
Preferably, the pre-irradiation treatment of the dry polypropylene separator is: a 60 Co-gamma irradiation source of 3.7X10 14 Bq was used for irradiation for 15-20h.
Preferably, in the second step, when preparing the modified dry polypropylene membrane, the reaction condition is that the modified dry polypropylene membrane is reacted for 2.5 to 3.5 hours at the temperature of 50 to 60 ℃ in a nitrogen environment.
Preferably, the anode material is prepared by adopting the dry preparation method of the anode material.
The invention also discloses a dry preparation method of the anode material, which comprises the following steps:
step one, taking polypropylene as a raw material, preparing a polypropylene fiber net by using a melt-blowing spinning technology, and performing hot press molding on the polypropylene fiber net to obtain a dry polypropylene diaphragm;
Mixing gamma- (methacryloyloxy) propyl trimethoxysilane with an ethanol water solution, and hydrolyzing to obtain a hydrolyzed gamma- (methacryloyloxy) propyl trimethoxysilane solution; mixing mica powder with deionized water, performing ultrasonic dispersion, adding the mixture into hydrolyzed gamma- (methacryloyloxy) propyl trimethoxy silane solution, reacting, filtering, washing and drying after the reaction is finished to obtain alkenyl modified mica powder;
Adding liquid nitrile rubber into toluene, stirring and dissolving to obtain a nitrile rubber solution;
dissolving hexafluorobutyl acrylate in ethylene glycol monobutyl ether to obtain hexafluorobutyl acrylate solution;
Mixing hexafluorobutyl acrylate solution, nitrile rubber solution and alkenyl modified mica powder, and performing ultrasonic dispersion to obtain a modified finishing agent;
after the dry polypropylene diaphragm is subjected to pre-irradiation treatment, the diaphragm is immersed in a modified finishing agent for reaction, and after the reaction is finished, the diaphragm is taken out, washed and dried to obtain a product; the product is the modified dry polypropylene diaphragm.
The invention also discloses application of the anode material in a lithium battery.
Compared with the prior art, the invention has the beneficial effects that:
the material for the positive electrode is specifically a diaphragm, polypropylene is used as a raw material, and the diaphragm is prepared by adopting a dry process, so that the diaphragm is environment-friendly and economical; the dry polypropylene diaphragm prepared by using the melt-blown spinning technology not only has good insulativity and heat resistance of polypropylene, but also has a microporous membrane, so that ions in electrolyte can freely pass through between positive and negative electrodes;
According to the invention, the dry-method polypropylene diaphragm is subjected to finishing modification, and mica powder, organic fluoride and nitrile rubber are introduced, so that the mica powder of the inorganic insulating heat-resistant material and the organic fluoride of the organic insulating heat-resistant material have good insulativity and heat resistance, and the insulativity and heat resistance of the polypropylene diaphragm can be effectively improved; the polypropylene diaphragm is subjected to pre-irradiation treatment to generate polypropylene macromolecule free radicals, so that grafting reaction of alkenyl modified mica powder containing carbon-carbon double bonds, hexafluorobutyl acrylate and nitrile rubber can be initiated; through grafting reaction, mica powder and hexafluorobutyl acrylate can be connected to the polypropylene diaphragm through stable chemical bonds, so that the bonding fastness of inorganic insulating heat-resistant materials, organic insulating heat-resistant materials and the polypropylene diaphragm is improved, and the insulation property and heat resistance stability of the polypropylene diaphragm are improved;
The introduction of the mica powder can not only improve the insulativity and heat resistance of the polypropylene diaphragm, but also effectively improve the mechanical strength of the polypropylene diaphragm; the introduction of the nitrile rubber can introduce a flexible long chain into a polypropylene molecular chain, so that the flexibility of the polypropylene diaphragm is improved, and the puncture resistance of the polypropylene diaphragm can be further enhanced.
Drawings
FIG. 1 is a flow chart of a preparation process of a material for a positive electrode in the present invention;
FIG. 2 is a line graph showing the results of insulation test of the positive electrode materials prepared in examples 1 to 6 and comparative examples 1 to 3 according to the present invention;
FIG. 3 is a line graph showing the heat resistance test results of the positive electrode materials prepared in examples 1 to 6 and comparative examples 1 to 3 according to the present invention;
FIG. 4 is a line graph showing the tensile strength test results of the materials for positive electrodes prepared in examples 1 to 6 and comparative examples 1 to 3 according to the present invention;
FIG. 5 is a line graph showing the results of elongation at break test of the positive electrode materials produced in examples 1 to 6 and comparative examples 1 to 3 in the present invention.
Detailed Description
Example 1
The material for the positive electrode is prepared by the following steps:
step one, taking polypropylene as a raw material, preparing a polypropylene fiber net by using a melt-blowing spinning technology, and performing hot press molding on the polypropylene fiber net to obtain a dry polypropylene diaphragm;
Wherein, the technological parameters of melt-blown spinning are as follows: the set temperature of the screw extruder is 1 zone 175 ℃,2 zone 215 ℃,3 zone 225 ℃,4 zone 235 ℃,5 zone 230 ℃; the temperature of the melt-blowing die head is 230 ℃; the temperature of the metering pump is 230 ℃, and the rotating speed of the metering pump is 230r/min; the air temperature of the drafting hot air is 230 ℃, and the air pressure of the drafting hot air is 8MPa; the moving speed of the net curtain is 1.6m/min;
the technological parameters of hot press molding are as follows: the speed of the net belt is 600m/min, the hot pressing pressure is 102daN/cm, the temperature of the roller is 153.5 ℃, and the temperature of the smooth roller is 142.5 ℃; the thickness of the dry polypropylene diaphragm is 60 mu m;
mixing gamma- (methacryloyloxy) propyl trimethoxysilane with 95wt% ethanol water solution, and reacting at 50 ℃ for 40min to obtain hydrolyzed gamma- (methacryloyloxy) propyl trimethoxysilane solution; mixing mica powder with deionized water, performing ultrasonic treatment at 50Hz for 60min, adding the mixture into hydrolyzed gamma- (methacryloyloxy) propyl trimethoxy silane solution, reacting for 2.5h at 50 ℃, filtering after the reaction is finished, washing with ethanol for 3 times, and drying in a vacuum drying oven at 60 ℃ until the weight is constant to obtain alkenyl modified mica powder;
Wherein, the mass ratio of the mica powder to deionized water to gamma- (methacryloyloxy) propyl trimethoxy silane to 95wt% ethanol aqueous solution is 25:125:25:250;
adding liquid nitrile rubber into toluene, wherein the mass ratio of the liquid nitrile rubber to the toluene is 25:125, and stirring and dissolving to obtain a nitrile rubber solution;
Dissolving hexafluorobutyl acrylate in ethylene glycol monobutyl ether, wherein the mass ratio of the hexafluorobutyl acrylate to the ethylene glycol monobutyl ether is 25:200, so as to obtain hexafluorobutyl acrylate solution;
Mixing a hexafluorobutyl acrylate solution, a nitrile rubber solution and alkenyl modified mica powder according to a mass ratio of 225:150:27, and performing ultrasonic treatment at a frequency of 50Hz for 60min to obtain a modified finishing agent;
After the dry polypropylene diaphragm is subjected to pre-irradiation treatment, the dry polypropylene diaphragm is immersed in a modified finishing agent, the mass ratio of the dry polypropylene diaphragm subjected to the pre-irradiation treatment to the modified finishing agent is 1:10, the dry polypropylene diaphragm reacts for 3.5 hours at 50 ℃ in a nitrogen environment, after the reaction is finished, the dry polypropylene diaphragm is taken out, washed for 3 times by ethanol, and then is placed in a vacuum drying oven at 60 ℃ to be dried to constant weight, so that a product is obtained;
wherein, the pre-irradiation treatment of the dry polypropylene diaphragm is as follows: a 60 Co-gamma irradiation source of 3.7X10 14 Bq was used for 15h.
Example 2
The material for the positive electrode is prepared by the following steps:
step one, taking polypropylene as a raw material, preparing a polypropylene fiber net by using a melt-blowing spinning technology, and performing hot press molding on the polypropylene fiber net to obtain a dry polypropylene diaphragm;
wherein, the technological parameters of melt-blown spinning are as follows: the set temperature of the screw extruder is 1 zone 185 ℃,2 zone 225 ℃,3 zone 245 ℃,4 zone 250 ℃,5 zone 240 ℃; the temperature of the melt-blowing die head is 235 ℃; the temperature of the metering pump is 250 ℃, and the rotating speed of the metering pump is 235r/min; the air temperature of the drafting hot air is 250 ℃, and the air pressure of the drafting hot air is 15MPa; the moving speed of the net curtain is 2.5m/min;
the technological parameters of hot press molding are as follows: the speed of the net belt is 600m/min, the hot pressing pressure is 102daN/cm, the temperature of the roller is 153.5 ℃, and the temperature of the smooth roller is 142.5 ℃; the thickness of the dry polypropylene separator is 110 μm;
Mixing gamma- (methacryloyloxy) propyl trimethoxysilane with 95wt% ethanol water solution, and reacting for 20min at 70 ℃ to obtain hydrolyzed gamma- (methacryloyloxy) propyl trimethoxysilane solution; mixing mica powder with deionized water, performing ultrasonic treatment at 100Hz for 30min, adding into hydrolyzed gamma- (methacryloyloxy) propyl trimethoxy silane solution, reacting at 70 ℃ for 1.5h, filtering after the reaction is finished, washing with ethanol for 3 times, and drying in a vacuum drying oven at 60 ℃ until the weight is constant to obtain alkenyl modified mica powder;
wherein, the mass ratio of the mica powder to deionized water to gamma- (methacryloyloxy) propyl trimethoxy silane to 95wt% ethanol aqueous solution is 25:150:30:300;
adding liquid nitrile rubber into toluene, wherein the mass ratio of the liquid nitrile rubber to the toluene is 25:250, and stirring and dissolving to obtain a nitrile rubber solution;
Dissolving hexafluorobutyl acrylate in ethylene glycol monobutyl ether, wherein the mass ratio of the hexafluorobutyl acrylate to the ethylene glycol monobutyl ether is 30:300, so as to obtain hexafluorobutyl acrylate solution;
Mixing a hexafluorobutyl acrylate solution, a nitrile rubber solution and alkenyl modified mica powder according to the mass ratio of 330:275:28, and performing ultrasonic treatment at the frequency of 100Hz for 30min to obtain a modified finishing agent;
After the dry polypropylene diaphragm is subjected to pre-irradiation treatment, the dry polypropylene diaphragm is immersed in a modified finishing agent, the mass ratio of the dry polypropylene diaphragm subjected to the pre-irradiation treatment to the modified finishing agent is 1:10, the dry polypropylene diaphragm reacts for 2.5 hours at the temperature of 60 ℃ in a nitrogen environment, after the reaction is finished, the dry polypropylene diaphragm is taken out, washed for 3 times by ethanol, and then is placed in a vacuum drying oven at the temperature of 60 ℃ to be dried to constant weight, so that a product is obtained;
Wherein, the pre-irradiation treatment of the dry polypropylene diaphragm is as follows: a 60 Co-gamma irradiation source of 3.7X10 14 Bq was used for irradiation for 20h.
Example 3
The material for the positive electrode is prepared by the following steps:
step one, taking polypropylene as a raw material, preparing a polypropylene fiber net by using a melt-blowing spinning technology, and performing hot press molding on the polypropylene fiber net to obtain a dry polypropylene diaphragm;
Wherein, the technological parameters of melt-blown spinning are as follows: the set temperature of the screw extruder is 180 ℃ in zone 1, 220 ℃ in zone 2, 235 ℃ in zone 3, 240 ℃ in zone 4 and 235 ℃ in zone 5; the temperature of the melt-blowing die head is 235 ℃; the temperature of the metering pump is 240 ℃, and the rotating speed of the metering pump is 235r/min; the air temperature of the drafting hot air is 240 ℃, and the air pressure of the drafting hot air is 10MPa; the moving speed of the net curtain is 2m/min;
the technological parameters of hot press molding are as follows: the speed of the net belt is 600m/min, the hot pressing pressure is 102daN/cm, the temperature of the roller is 153.5 ℃, and the temperature of the smooth roller is 142.5 ℃; the thickness of the dry polypropylene separator is 70 μm;
Mixing gamma- (methacryloyloxy) propyl trimethoxysilane with 95wt% ethanol water solution, and reacting at 60 ℃ for 30min to obtain hydrolyzed gamma- (methacryloyloxy) propyl trimethoxysilane solution; mixing mica powder with deionized water, performing ultrasonic treatment at 80Hz for 45min, adding into hydrolyzed gamma- (methacryloyloxy) propyl trimethoxy silane solution, reacting at 60 ℃ for 2h, filtering after the reaction is finished, washing with ethanol for 3 times, and drying in a vacuum drying oven at 60 ℃ to constant weight to obtain alkenyl modified mica powder;
Wherein, the mass ratio of the mica powder to deionized water to gamma- (methacryloyloxy) propyl trimethoxy silane to 95wt% ethanol aqueous solution is 25:130:26:260;
adding liquid nitrile rubber into toluene, wherein the mass ratio of the liquid nitrile rubber to the toluene is 25:150, and stirring and dissolving to obtain a nitrile rubber solution;
Dissolving hexafluorobutyl acrylate in ethylene glycol monobutyl ether, wherein the mass ratio of the hexafluorobutyl acrylate to the ethylene glycol monobutyl ether is 26:220, so as to obtain a hexafluorobutyl acrylate solution;
mixing hexafluorobutyl acrylate solution, nitrile rubber solution and alkenyl modified mica powder according to the mass ratio of 246:175:27.2, and carrying out ultrasonic treatment at the frequency of 80Hz for 45min to obtain a modified finishing agent;
After the dry polypropylene diaphragm is subjected to pre-irradiation treatment, the dry polypropylene diaphragm is immersed in a modified finishing agent, the mass ratio of the dry polypropylene diaphragm subjected to the pre-irradiation treatment to the modified finishing agent is 1:10, the dry polypropylene diaphragm reacts for 3 hours at 55 ℃ in a nitrogen environment, after the reaction is finished, the dry polypropylene diaphragm is taken out, washed for 3 times by ethanol, and then is placed in a vacuum drying oven at 60 ℃ to be dried to constant weight, so that a product is obtained;
Wherein, the pre-irradiation treatment of the dry polypropylene diaphragm is as follows: a 60 Co-gamma irradiation source of 3.7X10 14 Bq was used for irradiation for 18h.
Example 4
The material for the positive electrode is prepared by the following steps:
step one, taking polypropylene as a raw material, preparing a polypropylene fiber net by using a melt-blowing spinning technology, and performing hot press molding on the polypropylene fiber net to obtain a dry polypropylene diaphragm;
Wherein, the technological parameters of melt-blown spinning are as follows: the set temperature of the screw extruder is 180 ℃ in zone 1, 220 ℃ in zone 2, 235 ℃ in zone 3, 245 ℃ in zone 4 and 235 ℃ in zone 5; the temperature of the melt-blowing die head is 235 ℃; the temperature of the metering pump is 240 ℃, and the rotating speed of the metering pump is 235r/min; the air temperature of the drafting hot air is 240 ℃, and the air pressure of the drafting hot air is 10MPa; the moving speed of the net curtain is 2m/min;
The technological parameters of hot press molding are as follows: the speed of the net belt is 600m/min, the hot pressing pressure is 102daN/cm, the temperature of the roller is 153.5 ℃, and the temperature of the smooth roller is 142.5 ℃; the thickness of the dry polypropylene diaphragm is 80 mu m;
Mixing gamma- (methacryloyloxy) propyl trimethoxysilane with 95wt% ethanol water solution, and reacting at 60 ℃ for 30min to obtain hydrolyzed gamma- (methacryloyloxy) propyl trimethoxysilane solution; mixing mica powder with deionized water, performing ultrasonic treatment at 80Hz for 45min, adding into hydrolyzed gamma- (methacryloyloxy) propyl trimethoxy silane solution, reacting at 60 ℃ for 2h, filtering after the reaction is finished, washing with ethanol for 3 times, and drying in a vacuum drying oven at 60 ℃ to constant weight to obtain alkenyl modified mica powder;
wherein, the mass ratio of the mica powder to the deionized water to the gamma- (methacryloyloxy) propyl trimethoxy silane to the 95wt% ethanol aqueous solution is 25:135:27:270;
adding liquid nitrile rubber into toluene, wherein the mass ratio of the liquid nitrile rubber to the toluene is 25:175, and stirring and dissolving to obtain a nitrile rubber solution;
Dissolving hexafluorobutyl acrylate in ethylene glycol monobutyl ether, wherein the mass ratio of the hexafluorobutyl acrylate to the ethylene glycol monobutyl ether is 27:240, so as to obtain hexafluorobutyl acrylate solution;
Mixing hexafluorobutyl acrylate solution, nitrile rubber solution and alkenyl modified mica powder according to the mass ratio of 267:200:27.4, and carrying out ultrasonic treatment at the frequency of 80Hz for 45min to obtain a modified finishing agent;
After the dry polypropylene diaphragm is subjected to pre-irradiation treatment, the dry polypropylene diaphragm is immersed in a modified finishing agent, the mass ratio of the dry polypropylene diaphragm subjected to the pre-irradiation treatment to the modified finishing agent is 1:10, the dry polypropylene diaphragm reacts for 3 hours at 55 ℃ in a nitrogen environment, after the reaction is finished, the dry polypropylene diaphragm is taken out, washed for 3 times by ethanol, and then is placed in a vacuum drying oven at 60 ℃ to be dried to constant weight, so that a product is obtained;
Wherein, the pre-irradiation treatment of the dry polypropylene diaphragm is as follows: a 60 Co-gamma irradiation source of 3.7X10 14 Bq was used for irradiation for 18h.
Example 5
The material for the positive electrode is prepared by the following steps:
step one, taking polypropylene as a raw material, preparing a polypropylene fiber net by using a melt-blowing spinning technology, and performing hot press molding on the polypropylene fiber net to obtain a dry polypropylene diaphragm;
Wherein, the technological parameters of melt-blown spinning are as follows: the set temperature of the screw extruder is 180 ℃ in zone 1, 220 ℃ in zone 2, 235 ℃ in zone 3, 245 ℃ in zone 4 and 235 ℃ in zone 5; the temperature of the melt-blowing die head is 235 ℃; the temperature of the metering pump is 240 ℃, and the rotating speed of the metering pump is 235r/min; the air temperature of the drafting hot air is 240 ℃, and the air pressure of the drafting hot air is 10MPa; the moving speed of the net curtain is 2m/min;
The technological parameters of hot press molding are as follows: the speed of the net belt is 600m/min, the hot pressing pressure is 102daN/cm, the temperature of the roller is 153.5 ℃, and the temperature of the smooth roller is 142.5 ℃; the thickness of the dry polypropylene separator is 90 μm;
Mixing gamma- (methacryloyloxy) propyl trimethoxysilane with 95wt% ethanol water solution, and reacting at 60 ℃ for 30min to obtain hydrolyzed gamma- (methacryloyloxy) propyl trimethoxysilane solution; mixing mica powder with deionized water, performing ultrasonic treatment at 80Hz for 45min, adding into hydrolyzed gamma- (methacryloyloxy) propyl trimethoxy silane solution, reacting at 60 ℃ for 2h, filtering after the reaction is finished, washing with ethanol for 3 times, and drying in a vacuum drying oven at 60 ℃ to constant weight to obtain alkenyl modified mica powder;
Wherein, the mass ratio of the mica powder to deionized water to gamma- (methacryloyloxy) propyl trimethoxy silane to 95wt% ethanol aqueous solution is 25:140:28:280;
adding liquid nitrile rubber into toluene, wherein the mass ratio of the liquid nitrile rubber to the toluene is 25:200, and stirring and dissolving to obtain a nitrile rubber solution;
Dissolving hexafluorobutyl acrylate in ethylene glycol monobutyl ether, wherein the mass ratio of the hexafluorobutyl acrylate to the ethylene glycol monobutyl ether is 28:260, so as to obtain hexafluorobutyl acrylate solution;
Mixing hexafluorobutyl acrylate solution, nitrile rubber solution and alkenyl modified mica powder according to the mass ratio of 288:225:27.6, and carrying out ultrasonic treatment at the frequency of 80Hz for 45min to obtain a modified finishing agent;
After the dry polypropylene diaphragm is subjected to pre-irradiation treatment, the dry polypropylene diaphragm is immersed in a modified finishing agent, the mass ratio of the dry polypropylene diaphragm subjected to the pre-irradiation treatment to the modified finishing agent is 1:10, the dry polypropylene diaphragm reacts for 3 hours at 55 ℃ in a nitrogen environment, after the reaction is finished, the dry polypropylene diaphragm is taken out, washed for 3 times by ethanol, and then is placed in a vacuum drying oven at 60 ℃ to be dried to constant weight, so that a product is obtained;
Wherein, the pre-irradiation treatment of the dry polypropylene diaphragm is as follows: a 60 Co-gamma irradiation source of 3.7X10 14 Bq was used for irradiation for 18h.
Example 6
The material for the positive electrode is prepared by the following steps:
step one, taking polypropylene as a raw material, preparing a polypropylene fiber net by using a melt-blowing spinning technology, and performing hot press molding on the polypropylene fiber net to obtain a dry polypropylene diaphragm;
Wherein, the technological parameters of melt-blown spinning are as follows: the set temperature of the screw extruder is 180 ℃ in zone 1, 220 ℃ in zone 2, 235 ℃ in zone 3, 245 ℃ in zone 4 and 235 ℃ in zone 5; the temperature of the melt-blowing die head is 235 ℃; the temperature of the metering pump is 240 ℃, and the rotating speed of the metering pump is 235r/min; the air temperature of the drafting hot air is 240 ℃, and the air pressure of the drafting hot air is 10MPa; the moving speed of the net curtain is 2m/min;
The technological parameters of hot press molding are as follows: the speed of the net belt is 600m/min, the hot pressing pressure is 102daN/cm, the temperature of the roller is 153.5 ℃, and the temperature of the smooth roller is 142.5 ℃; the thickness of the dry polypropylene diaphragm is 100 mu m;
Mixing gamma- (methacryloyloxy) propyl trimethoxysilane with 95wt% ethanol water solution, and reacting at 60 ℃ for 30min to obtain hydrolyzed gamma- (methacryloyloxy) propyl trimethoxysilane solution; mixing mica powder with deionized water, performing ultrasonic treatment at 80Hz for 45min, adding into hydrolyzed gamma- (methacryloyloxy) propyl trimethoxy silane solution, reacting at 60 ℃ for 2h, filtering after the reaction is finished, washing with ethanol for 3 times, and drying in a vacuum drying oven at 60 ℃ to constant weight to obtain alkenyl modified mica powder;
wherein, the mass ratio of the mica powder to deionized water to gamma- (methacryloyloxy) propyl trimethoxy silane to 95wt% ethanol aqueous solution is 25:145:29:290;
adding liquid nitrile rubber into toluene, wherein the mass ratio of the liquid nitrile rubber to the toluene is 25:225, and stirring and dissolving to obtain a nitrile rubber solution;
Dissolving hexafluorobutyl acrylate in ethylene glycol monobutyl ether, wherein the mass ratio of the hexafluorobutyl acrylate to the ethylene glycol monobutyl ether is 29:280, so as to obtain hexafluorobutyl acrylate solution;
mixing hexafluorobutyl acrylate solution, nitrile rubber solution and alkenyl modified mica powder according to the mass ratio of 309:250:27.8, and carrying out ultrasonic treatment at the frequency of 80Hz for 45min to obtain a modified finishing agent;
dissolving hexafluorobutyl acrylate in ethylene glycol monobutyl ether, adding alkenyl modified mica powder, and performing ultrasonic treatment at the frequency of 80Hz for 45min to obtain a modified finishing agent;
Wherein the mass ratio of the hexafluorobutyl acrylate to the ethylene glycol monobutyl ether to the alkenyl modified mica powder is 29:280:27.8;
After the dry polypropylene diaphragm is subjected to pre-irradiation treatment, the dry polypropylene diaphragm is immersed in a modified finishing agent, the mass ratio of the dry polypropylene diaphragm subjected to the pre-irradiation treatment to the modified finishing agent is 1:10, the dry polypropylene diaphragm reacts for 3 hours at 55 ℃ in a nitrogen environment, after the reaction is finished, the dry polypropylene diaphragm is taken out, washed for 3 times by ethanol, and then is placed in a vacuum drying oven at 60 ℃ to be dried to constant weight, so that a product is obtained;
Wherein, the pre-irradiation treatment of the dry polypropylene diaphragm is as follows: a 60 Co-gamma irradiation source of 3.7X10 14 Bq was used for irradiation for 18h.
Comparative example 1
The material for the positive electrode is prepared by the following steps:
step one, taking polypropylene as a raw material, preparing a polypropylene fiber net by using a melt-blowing spinning technology, and performing hot press molding on the polypropylene fiber net to obtain a dry polypropylene diaphragm;
Wherein, the technological parameters of melt-blown spinning are as follows: the set temperature of the screw extruder is 1 zone 175 ℃,2 zone 215 ℃,3 zone 225 ℃,4 zone 235 ℃,5 zone 230 ℃; the temperature of the melt-blowing die head is 230 ℃; the temperature of the metering pump is 230 ℃, and the rotating speed of the metering pump is 230r/min; the air temperature of the drafting hot air is 230 ℃, and the air pressure of the drafting hot air is 8MPa; the moving speed of the net curtain is 1.6m/min;
the technological parameters of hot press molding are as follows: the speed of the net belt is 600m/min, the hot pressing pressure is 102daN/cm, the temperature of the roller is 153.5 ℃, and the temperature of the smooth roller is 142.5 ℃; the thickness of the dry polypropylene diaphragm is 60 mu m;
mixing gamma- (methacryloyloxy) propyl trimethoxysilane with 95wt% ethanol water solution, and reacting at 50 ℃ for 40min to obtain hydrolyzed gamma- (methacryloyloxy) propyl trimethoxysilane solution; mixing mica powder with deionized water, performing ultrasonic treatment at 50Hz for 60min, adding the mixture into hydrolyzed gamma- (methacryloyloxy) propyl trimethoxy silane solution, reacting for 2.5h at 50 ℃, filtering after the reaction is finished, washing with ethanol for 3 times, and drying in a vacuum drying oven at 60 ℃ until the weight is constant to obtain alkenyl modified mica powder;
Wherein, the mass ratio of the mica powder to deionized water to gamma- (methacryloyloxy) propyl trimethoxy silane to 95wt% ethanol aqueous solution is 25:125:25:250;
Dissolving hexafluorobutyl acrylate in ethylene glycol monobutyl ether, wherein the mass ratio of the hexafluorobutyl acrylate to the ethylene glycol monobutyl ether is 25:200, so as to obtain hexafluorobutyl acrylate solution;
mixing the hexafluorobutyl acrylate solution and the alkenyl modified mica powder according to the mass ratio of 225:27, and performing ultrasonic treatment at the frequency of 50Hz for 60min to obtain a modified finishing agent;
And (3) dipping the modified finishing agent in a dry polypropylene diaphragm, wherein the mass ratio of the dry polypropylene diaphragm to the modified finishing agent is 1:10, dipping the modified finishing agent at the temperature of 55 ℃ for 3 hours, taking out the dry polypropylene diaphragm, washing the dry polypropylene diaphragm with ethanol for 3 times, and drying the dry polypropylene diaphragm in a vacuum drying oven at the temperature of 60 ℃ to constant weight to obtain the product.
Comparative example 2
The material for the positive electrode is prepared by the following steps:
step one, taking polypropylene as a raw material, preparing a polypropylene fiber net by using a melt-blowing spinning technology, and performing hot press molding on the polypropylene fiber net to obtain a dry polypropylene diaphragm;
Wherein, the technological parameters of melt-blown spinning are as follows: the set temperature of the screw extruder is 1 zone 175 ℃,2 zone 215 ℃,3 zone 225 ℃,4 zone 235 ℃,5 zone 230 ℃; the temperature of the melt-blowing die head is 230 ℃; the temperature of the metering pump is 230 ℃, and the rotating speed of the metering pump is 230r/min; the air temperature of the drafting hot air is 230 ℃, and the air pressure of the drafting hot air is 8MPa; the moving speed of the net curtain is 1.6m/min;
the technological parameters of hot press molding are as follows: the speed of the net belt is 600m/min, the hot pressing pressure is 102daN/cm, the temperature of the roller is 153.5 ℃, and the temperature of the smooth roller is 142.5 ℃; the thickness of the dry polypropylene diaphragm is 60 mu m;
Adding liquid nitrile rubber into toluene, wherein the mass ratio of the liquid nitrile rubber to the toluene is 25:125, and stirring and dissolving to obtain a nitrile rubber solution;
Dissolving hexafluorobutyl acrylate in ethylene glycol monobutyl ether, wherein the mass ratio of the hexafluorobutyl acrylate to the ethylene glycol monobutyl ether is 25:200, so as to obtain hexafluorobutyl acrylate solution;
mixing a hexafluorobutyl acrylate solution and a nitrile rubber solution according to a mass ratio of 225:150, and performing ultrasonic treatment at a frequency of 50Hz for 60min to obtain a modified finishing agent;
After the dry polypropylene diaphragm is subjected to pre-irradiation treatment, the dry polypropylene diaphragm is immersed in a modified finishing agent, the mass ratio of the dry polypropylene diaphragm subjected to the pre-irradiation treatment to the modified finishing agent is 1:10, the dry polypropylene diaphragm reacts for 3.5 hours at 50 ℃ in a nitrogen environment, after the reaction is finished, the dry polypropylene diaphragm is taken out, washed for 3 times by ethanol, and then is placed in a vacuum drying oven at 60 ℃ to be dried to constant weight, so that a product is obtained;
wherein, the pre-irradiation treatment of the dry polypropylene diaphragm is as follows: a 60 Co-gamma irradiation source of 3.7X10 14 Bq was used for 15h.
Comparative example 3
The material for the positive electrode is prepared by the following steps:
step one, taking polypropylene as a raw material, preparing a polypropylene fiber net by using a melt-blowing spinning technology, and performing hot press molding on the polypropylene fiber net to obtain a dry polypropylene diaphragm;
Wherein, the technological parameters of melt-blown spinning are as follows: the set temperature of the screw extruder is 1 zone 175 ℃,2 zone 215 ℃,3 zone 225 ℃,4 zone 235 ℃,5 zone 230 ℃; the temperature of the melt-blowing die head is 230 ℃; the temperature of the metering pump is 230 ℃, and the rotating speed of the metering pump is 230r/min; the air temperature of the drafting hot air is 230 ℃, and the air pressure of the drafting hot air is 8MPa; the moving speed of the net curtain is 1.6m/min;
the technological parameters of hot press molding are as follows: the speed of the net belt is 600m/min, the hot pressing pressure is 102daN/cm, the temperature of the roller is 153.5 ℃, and the temperature of the smooth roller is 142.5 ℃; the thickness of the dry polypropylene diaphragm is 60 mu m;
Adding liquid nitrile rubber into toluene, wherein the mass ratio of the liquid nitrile rubber to the toluene is 25:125, and stirring and dissolving to obtain a nitrile rubber solution;
Dissolving hexafluorobutyl acrylate in ethylene glycol monobutyl ether, wherein the mass ratio of the hexafluorobutyl acrylate to the ethylene glycol monobutyl ether is 25:200, so as to obtain hexafluorobutyl acrylate solution;
mixing a hexafluorobutyl acrylate solution and a nitrile rubber solution according to a mass ratio of 225:150, and performing ultrasonic treatment at a frequency of 50Hz for 60min to obtain a modified finishing agent;
The modified finishing agent is immersed in the dry polypropylene diaphragm, the mass ratio of the dry polypropylene diaphragm to the modified finishing agent is 1:10, the dry polypropylene diaphragm is taken out after being immersed for 3.5 hours at 50 ℃, and the dry polypropylene diaphragm is washed for 3 times by ethanol and is placed in a vacuum drying oven at 60 ℃ to be dried to constant weight, so that the product is obtained.
In the above examples and comparative examples:
polypropylene was purchased from the liandbarsel industries, product model: HP565S B, product categories: natural color homo-polypropylene, melt index (230 ℃/2.16 kg): 38g/10min; mica powder was purchased from the mineral products processing company, product number: chl-ym, particle size/mesh: 1250 mesh; the liquid nitrile rubber is carboxyl-terminated liquid nitrile rubber, and is purchased from Ten-dimensional aviation materials (Yingkou) science and technology Co., ltd., product number: GJB2050A-2020, acrylonitrile content 15% and number average molecular weight 2300-2800.
Test examples
Performance tests were performed on the materials for positive electrodes prepared in examples 1 to 6 and comparative examples 1 to 3:
(1) Insulation properties: the volume resistivity of the positive electrode materials prepared in examples 1 to 6 and comparative examples 1 to 3 was measured, and the measurement results are shown in table 1:
TABLE 1
| Volume resistivity (omega) | Volume resistivity (omega) | ||
| Example 1 | 8.9×1016 | Example 6 | 9.2×1016 |
| Example 2 | 9.2×1016 | Comparative example 1 | 8.8×1016 |
| Example 3 | 9.0×1016 | Comparative example 2 | 5.4×1016 |
| Example 4 | 9.3×1016 | Comparative example 3 | 2.3×1016 |
| Example 5 | 9.1×1016 |
As is clear from Table 1, the positive electrode material obtained by the present invention has excellent insulation properties. The polypropylene has good insulativity, and the insulation property can be effectively improved by introducing the mica powder which is an inorganic insulation material and the organic fluoride which is an organic insulation material. Compared with example 1, the comparative example 1 does not incorporate nitrile rubber, has little influence on the insulation of the polypropylene separator, and has volume resistivity equivalent to that of example 1; in comparative example 2, since the inorganic insulating material mica powder was not introduced, the insulation property was lowered to some extent, and the volume resistivity was lowered; in comparative example 3, not only was the inorganic insulating material mica powder not introduced, but also the polypropylene separator was not subjected to the pre-irradiation treatment, and hexafluorobutyl acrylate was not connected to the polypropylene separator through a chemical bond, and the insulation modifying effect was further weakened and the volume resistivity was lowered as compared with comparative example 2.
(2) Heat resistance: the positive electrode materials prepared in examples 1 to 6 and comparative examples 1 to 3 were measured for heat shrinkage at 200℃for 0.5 hours, and the measurement results are shown in Table 2:
TABLE 2
| Heat shrinkage (%) | Heat shrinkage (%) | ||
| Example 1 | 0.8 | Example 6 | 0.6 |
| Example 2 | 0.6 | Comparative example 1 | 0.9 |
| Example 3 | 0.7 | Comparative example 2 | 1.2 |
| Example 4 | 0.5 | Comparative example 3 | 1.3 |
| Example 5 | 0.7 |
As is clear from Table 2, the positive electrode material obtained by the present invention has excellent heat resistance. The polypropylene has good heat resistance, and the heat resistance can be effectively improved by introducing the inorganic heat-resistant material mica powder and the organic heat-resistant material organic fluoride. Compared with example 1, the comparative example 1 does not incorporate nitrile rubber, has little effect on the heat resistance of the polypropylene separator, and has a heat shrinkage rate equivalent to that of example 1; in comparative example 2, since the inorganic heat-resistant material mica powder was not introduced, heat resistance was lowered and heat shrinkage was increased; in comparative example 3, not only the inorganic heat-resistant material mica powder was not introduced, but also the polypropylene separator was not subjected to the pre-irradiation treatment, and hexafluorobutyl acrylate was not bonded to the polypropylene separator through a chemical bond, and the heat-resistant modifying effect was further weakened and the heat shrinkage rate was increased as compared with comparative example 2.
(3) Mechanical properties: the mechanical properties of the positive electrode materials prepared in examples 1 to 6 and comparative examples 1 to 3 were measured, and the measurement results are shown in Table 3:
TABLE 3 Table 3
As can be seen from Table 3, the positive electrode material prepared by the invention has good mechanical properties. By introducing the inorganic reinforcing material mica powder and the organic toughening material nitrile rubber, the strength and toughness of the polypropylene film can be effectively improved. In comparison with example 1, no nitrile rubber was introduced in comparative example 1, the toughness of the polypropylene separator was reduced, and the elongation at break was reduced; in comparative example 2, since mica powder was not introduced, the tensile strength of the polypropylene separator was lowered; in comparison with comparative example 2, the polypropylene separator of comparative example 3 was not subjected to the pre-irradiation treatment, and hexafluorobutyl acrylate was not connected to the polypropylene separator by chemical bond, and the strength and toughness on the polypropylene separator were not greatly affected, and the tensile strength and elongation at break were comparable to those of comparative example 2.
Although embodiments of the present invention 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 invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The anode material is characterized by comprising the following steps:
step one, taking polypropylene as a raw material, preparing a polypropylene fiber net by using a melt-blowing spinning technology, and performing hot press molding on the polypropylene fiber net to obtain a dry polypropylene diaphragm;
Mixing gamma- (methacryloyloxy) propyl trimethoxysilane with an ethanol water solution, and hydrolyzing to obtain a hydrolyzed gamma- (methacryloyloxy) propyl trimethoxysilane solution; mixing mica powder with deionized water, performing ultrasonic dispersion, adding the mixture into hydrolyzed gamma- (methacryloyloxy) propyl trimethoxy silane solution, reacting, filtering, washing and drying after the reaction is finished to obtain alkenyl modified mica powder;
Adding liquid nitrile rubber into toluene, stirring and dissolving to obtain a nitrile rubber solution;
dissolving hexafluorobutyl acrylate in ethylene glycol monobutyl ether to obtain hexafluorobutyl acrylate solution;
Mixing hexafluorobutyl acrylate solution, nitrile rubber solution and alkenyl modified mica powder, and performing ultrasonic dispersion to obtain a modified finishing agent;
After the dry polypropylene diaphragm is subjected to pre-irradiation treatment, the diaphragm is immersed in a modified finishing agent, reacted, taken out, washed and dried after the reaction is finished, and a product is obtained.
2. A dry process for producing a positive electrode material according to claim 1.
3. The method according to claim 2, wherein in the first step, the process parameters of melt-blown spinning are as follows: the set temperature of the screw extruder is between 175 and 185 ℃ in zone 1, 215 and 225 ℃ in zone 2, 225 and 245 ℃ in zone 3, 235 and 250 ℃ in zone 4 and 230 and 240 ℃ in zone 5; the temperature of the melt-blowing die head is 230-235 ℃; the temperature of the metering pump is 230-250 ℃, and the rotating speed of the metering pump is 230-235r/min; the air temperature of the drafting hot air is 230-250 ℃, and the air pressure of the drafting hot air is 8-15MPa; the moving speed of the net curtain is 1.6-2.5m/min.
4. The method according to claim 2, wherein in the first step, the hot press molding process parameters are as follows: the speed of the net belt is 600m/min, the hot pressing pressure is 102daN/cm, the temperature of the roller is 153.5 ℃, and the temperature of the smooth roller is 142.5 ℃; the dry polypropylene separator has a thickness of 60-110 μm.
5. The dry preparation method of a material for a positive electrode according to claim 2, wherein in the second step, when preparing the alkenyl modified mica powder, the mass ratio of the mica powder to deionized water to gamma- (methacryloyloxy) propyl trimethoxysilane to an ethanol aqueous solution is 25 (125-150): 25-30): 250-300; the hydrolysis condition is that the reaction is carried out for 20-40min at 50-70 ℃, the ultrasonic dispersion condition is that the ultrasonic dispersion is carried out for 30-60min at the frequency of 50-100Hz, and the reaction condition is that the reaction is carried out for 1.5-2.5h at the temperature of 50-70 ℃.
6. The method for dry preparation of a positive electrode material according to claim 2, wherein in the second step, when the nitrile rubber solution is prepared, the mass ratio of the liquid nitrile rubber to toluene is 25 (125-250); when the hexafluorobutyl acrylate solution is prepared, the mass ratio of the hexafluorobutyl acrylate to the ethylene glycol monobutyl ether is (25-30) (200-300).
7. The dry preparation method of the positive electrode material according to claim 2, wherein in the second step, when the modified finishing agent is prepared, the mass ratio of the hexafluorobutyl acrylate solution, the nitrile rubber solution and the alkenyl modified mica powder is (225-330): (150-275): (27-28), and the condition of ultrasonic dispersion is ultrasonic at a frequency of 50-100Hz for 30-60min.
8. The method according to claim 2, wherein in the second step, when preparing the modified dry polypropylene separator, the pre-irradiation treatment of the dry polypropylene separator is: irradiating with 60 Co-gamma irradiation source of 3.7X10 14 Bq for 15-20 hr; the mass ratio of the dry polypropylene diaphragm after the pre-irradiation treatment to the modified finishing agent is 1:10.
9. The method for dry preparation of a material for positive electrode according to claim 2, wherein in the second step, when the modified dry polypropylene separator is prepared, the reaction conditions are that the reaction is carried out in a nitrogen atmosphere at a temperature of 50 to 60 ℃ for 2.5 to 3.5 hours.
10. Use of the positive electrode material according to claim 1 in a lithium battery.
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