CN112495318A - Double-layer microcapsule flame retardant and preparation method thereof - Google Patents
Double-layer microcapsule flame retardant and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 119
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000003094 microcapsule Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002775 capsule Substances 0.000 claims abstract description 81
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 239000012796 inorganic flame retardant Substances 0.000 claims abstract description 11
- 239000002861 polymer material Substances 0.000 claims abstract description 10
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 238000001556 precipitation Methods 0.000 claims abstract description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 106
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 65
- 239000000243 solution Substances 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 32
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 29
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 29
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 20
- 229920002396 Polyurea Polymers 0.000 claims description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 17
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims description 17
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 239000004202 carbamide Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000011888 foil Substances 0.000 claims description 9
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 8
- -1 aluminum ions Chemical class 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- 239000006182 cathode active material Substances 0.000 claims description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical group [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 230000002195 synergetic effect Effects 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000008098 formaldehyde solution Substances 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/18—In situ polymerisation with all reactants being present in the same phase
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
- C08G12/32—Melamines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention provides a double-layer microcapsule flame retardant, which structurally comprises a capsule core, a first layer of capsule wall and a second layer of capsule wall; the preparation method comprises the following steps of selecting an intumescent flame retardant as a capsule core, selecting an inorganic flame retardant as a first layer of capsule wall, selecting a polymeric high polymer material as a second layer of capsule wall, coating the first layer of capsule wall on the surface of the capsule core, and coating the second layer of capsule wall on the outer layer of the first layer of capsule wall. The preparation method of the double-layer microcapsule flame retardant comprises the following steps: selecting an intumescent flame retardant as a capsule core; coating an inorganic flame retardant on the surface of the capsule core by a precipitation method to serve as a first layer of capsule wall; and (III) coating a polymeric high polymer material on the surface of the outer layer of the first layer of the capsule wall by an in-situ polymerization method to form a second layer of the capsule wall. The advantages are that: 1) the double-layer microcapsule flame retardant can achieve the synergistic flame retardant effect of the capsule core and the first layer of capsule wall; 2) the negative effect of the flame retardant on the electrochemical performance of the battery can be reduced.
Description
Technical Field
The invention relates to a double-layer microcapsule flame retardant and a preparation method thereof, belonging to the technical field of battery flame retardance.
Background
Batteries are currently a common type of electrical energy storage and delivery device, but under conditions of abuse of the battery, such as overheating, overcharging, discharging, etc., thermochemical reactions between the internal battery materials occur; for example, a lithium ion battery is a battery commonly used at present, but under the condition of abuse of the lithium ion battery, such as overheating, overcharge, discharge and the like of the battery, a thermochemical reaction occurs between internal battery materials, a large amount of heat and combustible gas are generated, thermal runaway of the battery is caused, and finally, a fire or explosion accident is induced; in order to solve the problem of thermal runaway of the battery, a measure of adding a flame retardant into the battery is often adopted, and the commonly used flame retardants include halogen flame retardants, phosphorus flame retardants and composite flame retardants.
The main working principle of the flame retardant comprises: (1) oxygen is isolated in solid phase and gas phase to inhibit combustion; (2) the flame retardant decomposes to generate free radicals which absorb H ∙ and OH ∙ and block a combustion path; (3) the flame retardant is decomposed to absorb heat, so that the temperature of combustible materials is reduced, and the temperature rise is inhibited; the existing flame retardant applied to the battery is mainly phosphate and phosphazene compounds; although such flame retardants improve the flame retardancy of the battery, they can adversely affect the electrochemical performance of the battery, such as: the safety of the battery can be improved by directly adding the flame retardant into the battery, but the existence of the flame retardant can also cause the impedance of the battery to be increased, so that the capacity of the battery is reduced, and the performance of the battery is influenced; therefore, the research on the battery flame retardant is focused on reducing the negative influence of the flame retardant on the electrochemical performance of the battery while ensuring the flame retardant performance of the flame retardant.
Disclosure of Invention
The invention provides a double-layer microcapsule flame retardant and a preparation method thereof, aiming at ensuring the flame retardant performance of the flame retardant and reducing the negative influence of the flame retardant on the electrochemical performance of a battery.
The technical solution of the invention is as follows: a double-layer microcapsule flame retardant structurally comprises a capsule core, a first layer of capsule wall and a second layer of capsule wall; the preparation method comprises the following steps of selecting an intumescent flame retardant as a capsule core, selecting an inorganic flame retardant as a first layer of capsule wall, selecting a polymeric high polymer material as a second layer of capsule wall, coating the first layer of capsule wall on the surface of the capsule core, and coating the second layer of capsule wall on the outer layer of the first layer of capsule wall.
The preparation method of the double-layer microcapsule flame retardant comprises the following steps:
selecting an intumescent flame retardant as a capsule core;
coating an inorganic flame retardant on the surface of the capsule core by a precipitation method to serve as a first layer of capsule wall;
and (III) coating a polymeric high polymer material on the surface of the outer layer of the first layer of the capsule wall by an in-situ polymerization method to form a second layer of the capsule wall.
The invention has the advantages that:
1) the double-layer microcapsule flame retardant can achieve the synergistic flame retardant effect of the capsule core and the first layer of capsule wall, and has better flame retardant effect than a single flame retardant;
2) the dispersibility of the flame retardant can be improved when the flame retardant is used, so that the impedance of the battery is reduced, the capacity of the battery is increased, and the negative influence of the flame retardant on the electrochemical performance of the battery is reduced.
Drawings
FIG. 1 is a schematic diagram of the theoretical structure of a double-layer microcapsule flame retardant.
FIG. 2 is a schematic representation of APP surface coated with a layer of ATH under weakly alkaline conditions.
FIG. 3 is a schematic representation of the reaction of urea and formaldehyde under mildly alkaline conditions to form a polyureaformaldehyde prepolymer.
FIG. 4 is a schematic representation of the formation of a stable polyureaformaldehyde on the ATH-APP surface under mildly acidic conditions.
Fig. 5 is a schematic of the self-extinguishing time of the battery cathode when different microencapsulated flame retardants are added.
Fig. 6 is a graph showing the discharge capacity of the cathode of a battery when the cathode contains 5% by mass of various flame retardants.
Fig. 7 is a graph showing the discharge capacity of the battery cathode when it contained 10% by mass of various flame retardants.
Detailed Description
A double-layer microcapsule flame retardant structurally comprises a capsule core, a first layer of capsule wall and a second layer of capsule wall; the preparation method comprises the following steps of selecting an intumescent flame retardant as a capsule core, selecting an inorganic flame retardant as a first layer of capsule wall, selecting a polymeric high polymer material as a second layer of capsule wall, coating the first layer of capsule wall on the surface of the capsule core, and coating the second layer of capsule wall on the outer layer of the first layer of capsule wall.
The preparation method of the double-layer microcapsule flame retardant comprises the following steps:
selecting an intumescent flame retardant as a capsule core;
coating an inorganic flame retardant on the surface of the capsule core by a precipitation method to serve as a first layer of capsule wall;
and (III) coating a polymeric high polymer material on the surface of the outer layer of the first layer of the capsule wall by an in-situ polymerization method to form a second layer of the capsule wall.
The intumescent flame retardant serving as the capsule core is preferably ammonium polyphosphate (APP), the inorganic flame retardant serving as the first-layer capsule wall is preferably aluminum hydroxide (ATH), and the polymeric high polymer material serving as the second-layer capsule wall is preferably polyurea formaldehyde (PUF); due to the synergistic flame retardance of the ammonium polyphosphate and the aluminum hydroxide, the double-layer microcapsule flame retardant has better flame retardant performance, and the negative influence of the double-layer microcapsule flame retardant on the battery capacity when in use is reduced due to the existence of the polyurea formaldehyde; the double-layer microcapsule flame retardant with the double-layer capsule wall is prepared by a precipitation method and an in-situ polymerization method, and is applied to the cathode of a lithium ion battery, so that the flame retardant performance can be improved, and the adverse effect of the flame retardant on the battery performance can be reduced.
In the double-layer microcapsule flame retardant, ammonium polyphosphate is an expansive flame retardant which is widely applied and can act under the same conditions of gas phase and condensation to achieve the aim of flame retardance, aluminum hydroxide is used as an inorganic flame retardant and is decomposed into endothermic reaction, and water vapor generated by decomposition can dilute oxygen in air to inhibit combustion; the method takes ammonium polyphosphate as a capsule core, coats a layer of aluminum hydroxide on the surface of the ammonium polyphosphate by a precipitation method, marks the aluminum hydroxide as ATH-APP, and coats a layer of polyurea formaldehyde on the surface of the ATH-APP by an in-situ polymerization method to form en-ATH-APP, so that the synergistic flame-retardant effect of the ammonium polyphosphate and the aluminum hydroxide is achieved; the theoretical structure of the double-layer microcapsule flame retardant is shown in figure 1.
A preparation method of a double-layer microcapsule flame retardant comprises the following steps:
the first step is as follows: adding capsule core ammonium polyphosphate into an organic solution, and adding a dispersing agent into the organic solution to improve the dispersibility of the ammonium polyphosphate; the organic solution is preferably any of ethanol, ethylene glycol, methanol, and the like, and here, an ethanol solution is more preferred.
The second step is that: adding an aluminum chloride solution into an organic solution under the condition of stirring to form a mixed solution, then adding a pH regulator to regulate the mixed solution to be alkalescent, and combining aluminum ions and hydroxide ions under the alkalescent condition to generate aluminum hydroxide precipitates to be coated on the surface of ammonium polyphosphate to form final precipitates;
the third step: filtering and washing the final precipitate obtained in the second step, putting the precipitate into the organic solution again, adding a dispersing agent, and stirring to form a uniformly mixed solution;
the fourth step: mixing urea and formaldehyde, adding a pH regulator to regulate the pH to be alkalescent under the condition of stirring, and stirring for a plurality of hours to generate a prepolymer solution containing a polyureaformaldehyde prepolymer;
the fifth step: and (3) adding the prepolymer solution generated in the fourth step into the uniformly mixed solution formed in the third step, adding a pH regulator, regulating the pH to be weakly acidic, continuously reacting the polyurea formaldehyde prepolymer, coating the generated stable polyurea formaldehyde on the surface of the ATH-APP, and then filtering, washing and drying to obtain the final double-layer microcapsule flame retardant.
In the fourth step, stirring is carried out for several hours, preferably for 1 to 2 hours.
The pH regulator used in the second step and the fourth step is sodium bicarbonate solution with the mass fraction of 10%.
The pH adjusting agent used in the fifth step is acetic acid.
And in the second step, a pH regulator is added to adjust the mixed solution to be alkalescent, specifically to adjust the pH value to be between 7 and 8, and preferably to adjust the pH value to be between 7 and 7.5.
And in the fourth step, urea and formaldehyde are mixed, and a pH regulator is added under stirring to regulate the pH value to be alkalescent, specifically to regulate the pH value to be 7.5-9, preferably to regulate the pH value to be 8-8.5.
And in the fifth step, the prepolymer solution formed in the fourth step is added into the uniformly mixed solution formed in the third step, and a pH regulator is added to regulate the pH to weak acidity, specifically to regulate the pH to 3-4.5, preferably to regulate the pH to 3-4.
The aluminum hydroxide used as the first wall layer can be replaced by magnesium hydroxide, and the magnesium hydroxide is preferably prepared by a precipitation method to form the first wall layer.
The polyurea formaldehyde serving as the second-layer capsule wall can be replaced by melamine formaldehyde resin, and the melamine formaldehyde resin is preferably prepared by an in-situ polymerization method to form the second-layer capsule wall.
A preparation method of a lithium ion battery cathode sheet containing a double-layer microcapsule flame retardant comprises the following steps:
1) mixing and grinding a cathode active material lithium iron phosphate, a conductive agent and a double-layer microcapsule flame retardant, adding the ground mixture into an N-methylpyrrolidone solution containing a binder, and stirring for 1 hour;
2) coating the stirred solution on an aluminum foil, and drying the aluminum foil in a vacuum drying oven for 12 hours;
3) and cutting the dried aluminum foil to obtain the lithium ion battery cathode sheet containing the double-layer microcapsule flame retardant.
The double-layer microcapsule flame retardant is preferably suitable for use in a lithium ion battery cathode sheet.
The lithium ion battery cathode plate comprises a double-layer microcapsule flame retardant, wherein the double-layer microcapsule flame retardant accounts for 5-10% of the mass of the lithium ion battery cathode plate; the total mass of the cathode plate of the lithium ion battery does not contain the mass of the aluminum foil, and is the mass of the cathode plate of the lithium ion battery except the mass of the aluminum foil; the relevant test data of the lithium ion battery cathode plate containing the double-layer microcapsule flame retardant is shown in the attached figures 5, 6 and 7.
The cathode active material is preferably lithium iron phosphate or lithium cobaltate, and the attached figures 5, 6 and 7 are test result data when the cathode active material is lithium iron phosphate.
The synthesis principle of the preparation method of the double-layer microcapsule flame retardant is shown in the accompanying drawings 2-4, and specifically comprises the following steps:
1) as shown in the attached figure 2, Al is added under the weak alkaline condition3+And OH-And (4) reacting, and coating a layer of aluminum hydroxide precipitate on the surface of the ammonium polyphosphate.
2) As shown in FIG. 3, urea and formaldehyde react under slightly alkaline conditions to form a polyurea-formaldehyde prepolymer.
3) As shown in figure 4, under the weak acidic condition, the polyurea-formaldehyde prepolymer further reacts to coat a layer of stable polyurea-formaldehyde on the surface of ATH-APP.
In the invention, the ammonium polyphosphate is insoluble in an organic solvent, so the ammonium polyphosphate is added into an organic solution, preferably an ethanol solution; dispersing agent is added into the obtained organic solution, so that the dispersing rate of the capsule core can be improved during reaction, and the capsule core can be better coated; the aluminum chloride is dissolved in organic solvents such as ethanol, so the aluminum chloride is selected to provide aluminum ions, and then the aluminum ions and hydroxide ions react under alkaline conditions to generate aluminum hydroxide precipitates; urea and formaldehyde generate a polyureaformaldehyde prepolymer under the weakly alkaline condition, the prepolymer is added into a capsule core solution coated with a first layer of capsule wall, then the solution is adjusted to be weakly acidic, and the polyureaformaldehyde prepolymer further reacts to generate stable polyureaformaldehyde.
The invention provides an effective preparation method of a double-layer microcapsule flame retardant, which comprises the steps of generating a layer of aluminum hydroxide marked as ATH-APP on the surface of ammonium polyphosphate by using a precipitation method, and then generating a polyurea formaldehyde capsule wall with good chemical stability on the surface of the ATH-APP by using an in-situ polymerization method to obtain a final microcapsule flame retardant en-ATH-APP; according to the invention, two flame retardants of ammonium polyphosphate and aluminum hydroxide are well combined together, so that the purpose of synergistic flame retardance is achieved, and the flame retardant effect is better than that of a single flame retardant; the double-layer microcapsule flame retardant prepared in the example 3 is added into a battery cathode, and the flame retardant performance and the electrochemical performance of the double-layer microcapsule flame retardant are shown as the self-extinguishing time in the attached figure 5 and the discharge capacity in the attached figures 6 and 7; FIG. 5 shows that due to the synergistic effect of aluminum hydroxide and ammonium polyphosphate, the self-extinguishing time of the cathode of the battery containing ATH-APP is less than that of the cathode of the battery containing APP, and the self-extinguishing time of the cathode containing en-ATH-APP is almost equal to that of the cathode containing ATH-APP, indicating that the outermost layer of polyurea formaldehyde has almost no influence on the flame retardant performance of the flame retardant; FIGS. 6 and 7 show the discharge capacity of the battery cathode when containing different flame retardants, and it can be seen that the discharge capacity when containing the double-layer microcapsule flame retardant (en-ATH-APP) of the present invention is significantly higher than when containing APP and ATH-APP; this is because the outer layer of the polyurea-formaldehyde has a stable chemical property, and can improve the dispersibility of the flame retardant during use, thereby reducing the battery impedance and increasing the battery capacity.
FIG. 5 and FIG. 6 and FIG. 7 show the results of flame retardant performance and electrochemical performance of the microencapsulated flame retardant applied to the cathode of a battery; as shown in figure 5, the self-extinguishing time of the cathode is shortened when APP is added to the cathode, when ATH-APP is added to the cathode, the self-extinguishing time of the cathode is further shortened due to the synergistic flame-retardant effect of ammonium polyphosphate and aluminum hydroxide, and the self-extinguishing time of the cathode containing en-ATH-APP is almost equal compared with the self-extinguishing time containing ATH-APP, which shows that the polyurea formaldehyde has little influence on the flame-retardant performance of ATH-APP; as can be seen from the attached drawings 6 and 7, when the APP and the ATH-APP are added into the cathode, the discharge capacity of the battery is obviously reduced, but when the en-ATH-APP is added into the cathode, the negative influence of the microcapsule flame retardant on the electrochemical performance of the battery is inhibited due to the existence of the polyurea formaldehyde on the surface of the microcapsule, and the battery capacity when the cathode contains the flame retardant additive is improved.
The double-layer microcapsule flame retardant can effectively improve the safety of the battery, can reduce the negative effect of the flame retardant on the battery during use, can be popularized and used in other substances such as rubber, plastic and the like, improves the dispersibility of the double-layer microcapsule flame retardant in the substances due to the existence of the polyurea formaldehyde, reduces the agglomeration phenomenon of the flame retardant, and improves the influence of the flame retardant on the mechanical property of the material.
Example 1
The preparation method of the double-layer microcapsule flame retardant comprises the following steps:
1) weighing 12g of ammonium polyphosphate powder and 0.1g of dispersant triton x-100, and dissolving in 70mL of ethanol to form an ethanol solution; dissolving 4g of anhydrous aluminum chloride in 20mL of distilled water to prepare an aluminum chloride solution, and dropwise adding the aluminum chloride solution into the ethanol solution under the stirring state; slowly adding a sodium bicarbonate solution with the mass fraction of 10% under the stirring condition to adjust the pH value to 7, stirring and reacting for 1h in a constant-temperature water bath kettle at the temperature of 60 ℃, standing and cooling to room temperature, performing suction filtration and washing, and placing in a drying oven to dry for 6h under the condition of 80 ℃ to obtain ATH-APP;
2) adding 2g of urea and 6g of formaldehyde solution into a beaker, stirring the solution until the urea is dissolved to form a formaldehyde mixed solution, adjusting the pH of the formaldehyde mixed solution to 8 by using a sodium bicarbonate solution with the mass fraction of 10%, then heating the formaldehyde mixed solution to 70 ℃, and reacting for 1.5h to obtain a polyurea-formaldehyde prepolymer;
3) weighing 8g of ATH-APP and 0.5g of dispersant triton x-100 in another beaker, adding 65mL of ethanol, stirring and dispersing for 40min to form ATH-APP suspension, adding the ATH-APP suspension into the beaker filled with the polyurea formaldehyde prepolymer, adding 0.3g of resorcinol, 0.4g of formaldehyde solution and 0.3g of ammonium chloride into the beaker, stirring again and reacting for 40min, adjusting the pH value to 3 with acetic acid, reacting for 3h at 60 ℃, and then sequentially cooling, filtering, washing and drying to obtain the double-layer microcapsule flame retardant (en-ATH-APP).
Example 2
The preparation method of the double-layer microcapsule flame retardant comprises the following steps:
1) weighing 8g of ammonium polyphosphate powder and 0.1g of dispersant triton x-100, dissolving in 70mL of ethanol to form an ethanol solution, dissolving 3g of anhydrous aluminum chloride in 20mL of distilled water to prepare an aluminum chloride solution, and dropwise adding the aluminum chloride solution into the ethanol solution under the stirring state; slowly adding 10% sodium bicarbonate solution under stirring to adjust pH value to 7.5, stirring and reacting for 1.5h in a constant-temperature water bath kettle at 65 ℃, standing and cooling to room temperature, performing suction filtration and washing, placing in a drying oven, and drying for 6h at 80 ℃ to obtain ATH-APP;
2) adding 1.5g of urea and 5g of formaldehyde solution into a beaker, stirring the solution until the urea is dissolved to form a formaldehyde mixed solution, adjusting the pH of the formaldehyde mixed solution to 8.5 by using a sodium bicarbonate solution with the mass fraction of 10%, and then heating the formaldehyde mixed solution to 70 ℃ and reacting for 2 hours to obtain a polyurea-formaldehyde prepolymer;
3) weighing 7.5g of ATH-APP and 1g of dispersant triton x-100 in another beaker, adding 60mL of ethanol, stirring and dispersing for 50min to form ATH-APP suspension, adding the ATH-APP suspension into the beaker filled with the polyurea formaldehyde prepolymer, adding 0.4g of resorcinol, 0.5g of formaldehyde solution and 0.4g of ammonium chloride into the beaker, stirring again for 40min, adjusting the pH to 3.5 with acetic acid, reacting for 3.5h at 65 ℃, and then sequentially cooling, filtering, washing and drying to obtain the double-layer microcapsule flame retardant (en-ATH-APP).
Example 3
The preparation method of the double-layer microcapsule flame retardant comprises the following steps:
1) weighing 20g of ammonium polyphosphate powder and 0.3g of dispersant triton x-100, dissolving in 100mL of ethanol to form an ethanol solution, and dissolving 6g of anhydrous aluminum chloride in 20mL of distilled water to prepare an aluminum chloride solution; dropwise adding an aluminum chloride solution into the ethanol solution under the stirring state, slowly adding a sodium bicarbonate solution with the mass fraction of 10% under the stirring condition, adjusting the pH value to 7.5, stirring and reacting for 1.5h at 65 ℃ in a constant-temperature water bath kettle, standing, cooling to room temperature, performing suction filtration and washing, placing in a drying box, and drying for 6h at 80 ℃ to obtain ATH-APP;
2) adding 3g of urea and 8g of formaldehyde solution into a beaker, stirring the solution until the urea is dissolved to form a formaldehyde mixed solution, adjusting the pH of the formaldehyde mixed solution to 8.5 by using a sodium bicarbonate solution with the mass fraction of 10%, then heating the formaldehyde mixed solution to 75 ℃ and reacting for 2 hours to obtain a polyurea-formaldehyde prepolymer;
3) weighing 12g of ATH-APP and 1.2 g of dispersant triton x-100 in another beaker, adding 80mL of ethanol, stirring and dispersing for 1h to form ATH-APP suspension, adding the ATH-APP suspension into the beaker filled with the polyurea formaldehyde prepolymer, adding 0.5g of resorcinol, 0.7g of formaldehyde solution and 0.5g of ammonium chloride into the beaker, stirring for 50min again, adjusting the pH value to 4 with acetic acid, reacting for 3.5h at 65 ℃, cooling, filtering, washing and drying to obtain the double-layer microcapsule flame retardant (en-ATH-APP).
The preparation methods of the two-layer microcapsule flame retardant (en-ATH-APP) provided in examples 1 to 3 can automatically change the quality of various added drugs according to the needs during the actual preparation process.
Claims (10)
1. A double-layer microcapsule flame retardant is characterized by comprising a capsule core, a first layer of capsule wall and a second layer of capsule wall; the preparation method comprises the following steps of selecting an intumescent flame retardant as a capsule core, selecting an inorganic flame retardant as a first layer of capsule wall, selecting a polymeric high polymer material as a second layer of capsule wall, coating the first layer of capsule wall on the surface of the capsule core, and coating the second layer of capsule wall on the outer layer of the first layer of capsule wall.
2. The double-layer microcapsule flame retardant of claim 1, wherein the preparation method of the double-layer microcapsule flame retardant comprises the following steps:
selecting an intumescent flame retardant as a capsule core;
coating an inorganic flame retardant on the surface of the capsule core by a precipitation method to serve as a first layer of capsule wall;
and (III) coating a polymeric high polymer material on the surface of the outer layer of the first layer of the capsule wall by an in-situ polymerization method to form a second layer of the capsule wall.
3. The double-layer microcapsule flame retardant of claim 1 or 2, wherein the intumescent flame retardant serving as the capsule core is ammonium polyphosphate, the inorganic flame retardant serving as the first capsule wall is aluminum hydroxide, and the polymeric high polymer material serving as the second capsule wall is polyurea formaldehyde.
4. A process for preparing a double-layer microencapsulated flame retardant according to claim 3, characterized in that it comprises the following steps:
the first step is as follows: adding capsule core ammonium polyphosphate into an organic solution, and adding a dispersing agent into the organic solution to improve the dispersibility of the ammonium polyphosphate;
the second step is that: adding an aluminum chloride solution into an organic solution under the condition of stirring to form a mixed solution, then adding a pH regulator to regulate the mixed solution to be alkalescent, and combining aluminum ions and hydroxide ions under the alkalescent condition to generate aluminum hydroxide precipitates to be coated on the surface of ammonium polyphosphate to form final precipitates;
the third step: filtering and washing the final precipitate obtained in the second step, putting the precipitate into the organic solution again, adding a dispersing agent, and stirring to form a uniformly mixed solution;
the fourth step: mixing urea and formaldehyde, adding a pH regulator to regulate the pH to be alkalescent under the condition of stirring, and stirring for a plurality of hours to generate a prepolymer solution containing a polyureaformaldehyde prepolymer;
the fifth step: and (3) adding the prepolymer solution generated in the fourth step into the uniformly mixed solution formed in the third step, adding a pH regulator, regulating the pH to be weakly acidic, continuously reacting the polyurea formaldehyde prepolymer to generate stable polyurea formaldehyde to coat the surface of the final precipitate formed in the second step, and then filtering, washing and drying to obtain the final double-layer microcapsule flame retardant.
5. The method for preparing a double-layer microcapsule flame retardant according to claim 3, wherein the aluminum hydroxide as the first layer wall is replaced with magnesium hydroxide, and the polyurea formaldehyde as the second layer wall is replaced with melamine formaldehyde resin.
6. The process for producing a double-layer microcapsule flame retardant according to claim 4, wherein the pH adjustor used in the second and fourth steps is a 10% by mass sodium bicarbonate solution; the pH regulator used in the fifth step is acetic acid; the organic solution is any one of ethanol, glycol and methanol.
7. The method for preparing a double-layer microcapsule flame retardant according to claim 4, wherein the pH-adjusting agent is added in the second step to adjust the mixed solution to be weakly alkaline, specifically to adjust the pH value to between 7 and 8; in the fourth step, urea and formaldehyde are mixed, and a pH regulator is added under the stirring condition to regulate the pH value to be alkalescent, specifically to regulate the pH value to be 7.5-9; in the fifth step, the pH is adjusted to be weakly acidic, specifically, the pH value is adjusted to be 3-4.5; and in the fourth step, stirring for a plurality of hours is 1-2 hours.
8. The double-layer microcapsule flame retardant of claim 1 or 2, which is suitable for use in a lithium ion battery cathode sheet.
9. A method for preparing a cathode sheet for a lithium ion battery comprising the double-layer microcapsule flame retardant of claim 1 or 2, characterized by comprising the steps of:
1) mixing and grinding a cathode active substance, a conductive agent and a double-layer microcapsule flame retardant, adding the ground mixture into an N-methylpyrrolidone solution containing a binder, and stirring for 1 hour;
2) coating the stirred solution on an aluminum foil, and drying the aluminum foil in a vacuum drying oven for 12 hours;
3) and cutting the dried aluminum foil to obtain the lithium ion battery cathode sheet containing the double-layer microcapsule flame retardant.
10. The method for preparing the lithium ion battery cathode sheet containing the double-layer microcapsule flame retardant according to claim 9, wherein the double-layer microcapsule flame retardant accounts for 5-10% of the mass of the lithium ion battery cathode sheet; the total mass of the cathode plate of the lithium ion battery does not contain the mass of aluminum foil; the cathode active material is lithium iron phosphate or lithium cobaltate.
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