CN117165257A - Graphite pouring sealant for new energy automobile battery and preparation method thereof - Google Patents
Graphite pouring sealant for new energy automobile battery and preparation method thereof Download PDFInfo
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- CN117165257A CN117165257A CN202311259519.7A CN202311259519A CN117165257A CN 117165257 A CN117165257 A CN 117165257A CN 202311259519 A CN202311259519 A CN 202311259519A CN 117165257 A CN117165257 A CN 117165257A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000000565 sealant Substances 0.000 title claims abstract description 92
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 86
- 239000010439 graphite Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 35
- 229920002554 vinyl polymer Polymers 0.000 claims description 35
- 229920005906 polyester polyol Polymers 0.000 claims description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 25
- 150000001282 organosilanes Chemical class 0.000 claims description 25
- 229920002545 silicone oil Polymers 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 229920002050 silicone resin Polymers 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 229910021485 fumed silica Inorganic materials 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229920000728 polyester Polymers 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 239000012948 isocyanate Substances 0.000 claims description 8
- 150000002513 isocyanates Chemical class 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- 150000003077 polyols Chemical class 0.000 claims description 8
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 8
- 238000010008 shearing Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- -1 hydroxyl organosilane Chemical class 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 8
- 239000003607 modifier Substances 0.000 abstract description 2
- 230000005855 radiation Effects 0.000 abstract 1
- 230000017525 heat dissipation Effects 0.000 description 16
- 239000000853 adhesive Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000007531 graphite casting Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000033444 hydroxylation Effects 0.000 description 3
- 238000005805 hydroxylation reaction Methods 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- JTXUAHIMULPXKY-UHFFFAOYSA-N 3-trihydroxysilylpropan-1-amine Chemical compound NCCC[Si](O)(O)O JTXUAHIMULPXKY-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 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
Landscapes
- Sealing Material Composition (AREA)
Abstract
The field relates to the technical field of pouring sealant, in particular to a graphite pouring sealant for a new energy automobile battery and a preparation method thereof, wherein the graphite pouring sealant comprises the following raw materials in parts by weight: the graphite pouring sealant for the new energy automobile battery prepared by the formula has good adhesive property, does not need to treat a base material or add a modifier into the pouring sealant, and can be directly used, and is convenient and quick. Meanwhile, the graphite pouring sealant for the new energy automobile battery has good heat radiation performance, insulating performance, tensile strength and the like after being solidified.
Description
Technical Field
The field relates to the technical field of pouring sealants, in particular to a graphite pouring sealant for a new energy automobile battery and a preparation method thereof.
Background
The new energy automobile battery can generate heat in the use process, and if the heat can not be removed in time, the battery is easily damaged, and even the battery explosion can be caused. In the process of preparing the new energy automobile electronic, the heat dissipation capacity of the battery is improved by adopting the heat dissipation pouring sealant.
The common types of heat-dissipating pouring sealant comprise epoxy resin heat-dissipating pouring sealant, organic silicon heat-dissipating pouring sealant, polyurethane heat-dissipating pouring sealant and the like. The cured organosilicon heat dissipation pouring sealant is soft in material, so that most of mechanical stress can be eliminated, and a shock absorption protection effect is achieved; the physical and chemical properties are stable, the high and low temperature resistance is better, and the high and low temperature resistant composite material can work for a long time within the range of-50 to 200 ℃; meanwhile, the novel energy automobile electric car battery has excellent electrical performance and insulating capability, insulation between internal elements and circuits is effectively improved after encapsulation, and the use stability of the novel energy automobile electric car battery is improved. Therefore, the organic silicon heat dissipation pouring sealant can be used as one of the pouring sealants for the new energy automobile battery.
However, the adhesion of the silicone heat dissipation pouring sealant is inferior to that of the epoxy resin heat dissipation pouring sealant, and in order to improve the adhesion of the silicone heat dissipation pouring sealant, the substrate needs to be subjected to primer treatment or modified by adding a tackifier, so that the use is troublesome.
Disclosure of Invention
The application provides a graphite pouring sealant for a new energy automobile battery and a preparation method thereof, aiming at solving the problem that the adhesive capability of an organosilicon heat-dissipating pouring sealant is poor, and a base material needs to be subjected to primer treatment or modified by adding a tackifier when in use.
In a first aspect, the application provides a graphite pouring sealant for a new energy automobile battery, which adopts the following technical scheme:
the graphite pouring sealant for the new energy automobile battery is prepared from the following raw materials in parts by weight:
vinyl-terminated silicone oil 70-90 parts
10-20 parts of hydroxyl modified organosilicon
20-35 parts of vinyl MQ silicone resin
30-40 parts of modified graphite
10-15 parts of fumed silica
1-2 parts of a first catalyst
0.01-0.03 parts of inhibitor.
By adopting the technical scheme, the graphite pouring sealant for the new energy automobile has good bonding performance, and can be directly used without treating a base material or adding a modifier into the pouring sealant. And a heat conduction and insulation network structure is formed among the vinyl-terminated silicone oil, the modified graphite, the fumed silica and the vinyl MQ silicone resin, so that heat generated in the battery is conducted out. By combining vinyl silicone oil and vinyl MQ silicone resin, a firm chemical bond can be formed on the surface contacted with the battery when the vinyl silicone oil and the vinyl MQ silicone resin are subjected to crosslinking reaction, so that the problem of poor adhesive strength of the organic silicon encapsulation is solved. Meanwhile, the network structure is stable, the bonding performance with the battery is good, and the adhesion between pouring sealant and the battery is reduced and the bonding with the battery is unstable due to external impact, temperature change, water erosion and other reasons.
The modified graphite has good insulating property and thermal conductivity, is used for preparing the pouring sealant of the new energy automobile battery, and can effectively improve the heat dissipation performance and the insulativity of the battery. Graphite is a material with good heat dissipation, but has strong conductivity, and the conductivity of the graphite needs to be blocked when the graphite is used for preparing a new energy automobile battery. By adopting modified graphite, the problem of graphite conduction can be solved.
In the application, more fumed silica and modified graphite are used, and are solid, so that sedimentation phenomenon is easy to occur in a pouring sealant system. According to the application, the hydroxyl modified organic silicon is added, so that the fumed silica and the modified graphite can be uniformly dispersed in the pouring sealant system, the pouring sealant has better fluidity, and the fumed silica and the modified graphite are prevented from sedimentation.
Preferably, the modified graphite is prepared by the following method:
1) Heating graphite at 180-200 deg.c for 1-2 hr, fast heating to 400-450 deg.c, setting heated graphite in quaternary ammonium alkali solution at 40-50 deg.c, stirring for 2-3 hr, adding hydrogen peroxide several times, filtering, leaching with water and filtering to obtain hydroxylated graphite;
2) Dispersing the hydroxylated graphite in a solvent, adding isocyanate and an initiator, heating to 50-60 ℃ for reaction for 3-4 hours, adding a polyester multipolymer and a second catalyst, continuing to react for 4-6 hours, filtering, washing with ethanol, and drying to obtain modified graphite;
the polyester multipolymer comprises polyester polyol and/or polyether polyol.
The graphite has good heat dissipation performance and strong electric conduction performance, and insulating graphite is also available in the market at present, but the graphite is used for pouring sealant, so that the adhesive property of the pouring sealant is reduced. In this regard, the graphite is modified, so that the modified graphite has good insulativity and thermal conductivity, and meanwhile, the adhesive property of the pouring sealant can be improved.
The oily medium and low molecular substances on the surface of the graphite are removed by heating, the chemical stability of the graphite is reduced by rapidly heating to 400-450 ℃, the graphite is added into a quaternary ammonium alkali solution for reaction, so that the surface of the graphite contains a large amount of hydroxyl groups, and hydrogen peroxide is added for multiple times in the reaction process to promote hydroxylation of the surface of the graphite.
And then the hydroxylated graphite reacts with isocyanate and then reacts with polyester polymer continuously, so that the high molecular polymer is grafted on the surface of the graphite, thereby reducing the conductivity of the graphite and improving the heat dissipation performance, the insulativity and the bonding performance of the pouring sealant.
In order to increase the grafting ratio of graphite, it is preferable that the isocyanate used in the present application includes at least one of toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate or lysine diisocyanate.
Preferably, the solvent is at least one of acetone, dichloromethane or toluene.
Preferably, the modified graphite is prepared from the following raw materials in parts by weight:
20-35 parts of graphite
40-60 parts of quaternary ammonium alkali solution
10-15 parts of hydrogen peroxide
40-60 parts of solvent
5-10 parts of isocyanate
1-2 parts of initiator
10-20 parts of polyester multipolymer
And 1-2 parts of a second catalyst.
By adopting the technical scheme, the use amount of the raw materials for preparing the modified graphite is optimized, the hydroxylation of the surface of the graphite is further increased, and the grafting rate of the graphite is improved, so that the insulating property and the adhesive property of the modified graphite are improved.
Preferably, the weight part ratio of the polyester polyol to the polyester polyol ether is (4-7): 5.
the grafting rate of graphite is higher by optimizing the dosage ratio of the polyester polyol to the polyester polyol, and the pouring sealant prepared from the modified graphite has good insulating property, bonding property and stability.
Preferably, the hydroxyl organosilane is hydroxyl modified organosilane, and the hydroxyl modified organosilane is prepared by the following method:
a: mixing polyester polyol and glycerolactone, adding a third catalyst, heating to 90-120 ℃, and reacting for 2-5 hours to obtain a product A, wherein the molar ratio of the polyester polyol to glycidol is (1:4) - (3:8);
b: mixing the obtained product A with organosilane, heating to 80-90 ℃, and reacting for 6-8 hours to obtain the hydroxyl modified organosilane, wherein the molar ratio of the polyester polyol to the organosilane is 1- (1:3).
By adopting the technical scheme, the adhesive property of the battery graphite pouring sealant for the new energy automobile is further improved, and the problem of poor adhesive capability of the organosilicon heat dissipation pouring sealant is solved. The low surface activity of vinyl silicone oil and vinyl MQ silicone resin can lead to the reduced adhesive property of pouring sealant, so that the adhesive is unstable. By adding the hydroxyl modified organosilane prepared in the application, the problem of low surface activity of vinyl silicone oil and vinyl MQ silicone resin is solved, the contact between the pouring sealant and the substrate is promoted, the substrate is fully wetted by the pouring sealant, and the pouring sealant can be directly and stably adhered on the surface of the substrate. Meanwhile, the hydroxyl modified organosilicon can improve the physical and mechanical properties such as tensile strength, impact resistance and the like of the pouring sealant after being cured.
Preferably, the third catalyst is aniline or triethylamine.
Preferably, the organosilane is at least one of aminosiloxane, 3-isocyanatopropyltriethoxysilane or 3-isocyanatopropyltrimethoxysilane.
Preferably, the functionality of the polyester polyol is 2-4 and the molecular weight of the polyester polyol is 500-2000.
By adopting the technical scheme, the functionality and the molecular weight of the polyester polyol are optimized, so that the problem of low surface activity of vinyl silicone oil and vinyl MQ silicone resin at the end of the hydroxyl modified organic silica gel is better improved, and the adhesive property of the pouring sealant is further improved.
Preferably, the viscosity of the vinyl-terminated silicone oil is 1000-2000mPa.s, and the mass percentage of vinyl is 0.4-1.5%.
Preferably, the viscosity of the vinyl MQ silicone resin is 3000-5000 Pa.s, and the mass percentage of vinyl is 1-1.5%.
By adopting the technical scheme, the parameters of vinyl silicone oil and vinyl MQ silicone resin are optimized, so that the cured graphite pouring sealant for the new energy automobile battery has a more stable structure, better tensile strength and better shock resistance.
Preferably, the fumed silica has an average particle size of 100 to 200nm.
By adopting the technical scheme, the particle size of the fumed silica is optimized, the adhesive property of the pouring sealant is further improved, and meanwhile, the shock resistance and strength of the pouring sealant after being cured are also improved.
In a second aspect, the application provides a preparation method of graphite pouring sealant for a new energy automobile battery, which adopts the following technical scheme:
a preparation method of graphite pouring sealant for a new energy automobile battery comprises the following steps:
s1, mixing 1/2 terminal vinyl silicone oil, vinyl MQ silicone resin and a catalyst, and shearing and dispersing at a high speed to obtain a mixture A;
s2, mixing the remaining 1/2 terminal vinyl silicone oil, hydroxyl modified organic silicon, modified graphite, fumed silica and an inhibitor, and shearing and dispersing at a high speed to obtain a mixture B;
and S3, mixing and curing the mixture A and the mixture B to obtain the graphite pouring sealant for the new energy automobile battery.
By adopting the technical scheme, the graphite pouring sealant for the new energy automobile battery has good bonding performance, can be directly used on the surface of the battery, and does not need to be additionally treated. Simultaneously, various raw materials are fully mixed, so that the structural stability, mechanical property, heat dissipation performance, insulativity and high and low temperature resistance after solidification are improved.
In summary, the application has the following beneficial effects:
1. according to the application, the graphite pouring sealant for the new energy automobile is prepared by using vinyl silicone oil, vinyl MQ silicon resin, hydroxyl modified organic silicon, modified graphite, fumed silica, a catalyst and an inhibitor together, so that the problem of poor adhesion of the organic silicon pouring sealant can be effectively solved, and the prepared graphite pouring sealant for the new energy automobile can be directly used without treating a base material, so that the graphite pouring sealant has good adhesion performance; and the graphite pouring sealant for the new energy automobile has the advantages of stable structure, good mechanical property, strong heat dissipation performance, good insulativity and strong high and low temperature resistance after being solidified.
2. According to the method, graphite is heated to remove surface impurities, then rapidly heated to 400-450 ℃, reacted with quaternary ammonium alkali solution, and then added with hydrogen peroxide for multiple times to promote hydroxylation of the graphite; and then the hydroxylated graphite reacts with isocyanate, an initiator and a polyester multipolymer to obtain modified graphite, the insulating property of the modified graphite is greatly reduced, and the modified graphite is used for preparing the graphite pouring sealant for the new energy automobile, so that the heat dissipation performance, the insulating property and the bonding property of the graphite pouring sealant for the new energy automobile can be improved.
3. According to the application, the hydroxyl modified organosilane is obtained by reacting polyester polyol, glycerolactone, a catalyst and organosilane, and the problem of low surface activity of vinyl silicone oil and vinyl MQ silicone resin is improved by adding the hydroxyl modified organosilane, so that the problem of poor adhesive capability of the organosilicon heat dissipation pouring sealant can be effectively solved.
Detailed Description
Examples
Example 1
A graphite pouring sealant for a new energy automobile battery is prepared by the following method:
s1, mixing 300.00g of vinyl-terminated silicone oil, 200.00g of vinyl MQ silicone resin and 10.00g of catalyst (chloroplatinic acid), and shearing and dispersing at a high speed of 1000r/min to obtain a mixture A;
s2, mixing 300.00g of vinyl-terminated silicone oil, 100.00g of hydroxyl organosilicon (3-aminopropyl trihydroxy silane), 300.00g of modified graphite, 100.00g of fumed silica and 0.10g of inhibitor (alkynyl cyclohexanol), and performing high-speed shearing dispersion at a shearing speed of 900r/min to obtain a mixture B;
and S3, mixing and curing the mixture A and the mixture B to obtain the graphite pouring sealant for the new energy automobile battery.
The viscosity of the vinyl-terminated silicone oil is 1000mPa.s, and the mass percentage of vinyl is 0.4%.
The viscosity of the vinyl MQ silicone resin was 3000 Pa.s, and the mass percentage of vinyl was 1%.
The fumed silica has an average particle diameter of 100nm.
Modified graphite is purchased from Beijing New Material science and technology Co., ltd, and is manufactured by the brand of Qiyuan, and is made of carbon.
Examples 2-3 differ from example 1 in the types and amounts of some raw materials used for preparing the graphite casting glue for the new energy automobile battery and the experimental parameters, and the specific differences in examples 1-3 are shown in table 1:
table 1 examples 1-3 kinds and amounts of raw materials and test parameters of graphite casting glue for new energy automobile batteries
Example 4
The graphite pouring sealant for the new energy automobile battery is different from the embodiment 1 in that the modified graphite is prepared by the following method:
1) 200.00g of graphite is heated to 180 ℃ for 1h, then the temperature is quickly raised to 400 ℃, the heated graphite is placed in 400.00g of quaternary ammonium base solution, the temperature is kept at 40 ℃, stirring is carried out for 2h, 100.00g of hydrogen peroxide is added in three times (60.00 g is added in the first two times and 80.00g is added in the third time), filtration is carried out, leaching is carried out with water, and filtration is carried out, thus obtaining hydroxylated graphite;
2) Dispersing the hydroxylated graphite in 400.00g (acetone), adding 50.00g (toluene diisocyanate) of isocyanate and 10.00g (antimony trioxide) of catalyst, heating to 50 ℃ for reaction for 3 hours, adding 100.00g (polyester polyol) of polyester multipolymer and 10.00g (benzoyl peroxide) of initiator, continuing to react for 4 hours, filtering, washing with ethanol, and drying to obtain modified graphite;
the polyester polyol has a functionality of 3 and a molecular weight of 2000.
Examples 5 to 6 differ from example 4 in the amounts of the partial raw materials used for preparing the modified graphite and the experimental parameters, and the specific differences in examples 4 to 6 are shown in Table 2:
table 2 examples 4 to 6 kinds and amounts of modified graphite raw materials and test parameters
The polyether polyol of example 6 has a functionality of 2 and a molecular weight of 1000.
The polyester polyol of example 7 has a functionality of 3 and a molecular weight of 2000; the polyether polyol has a functionality of 2 and a molecular weight of 1000; the weight of both polyester polyol and polyether polyol was 100.00g.
Example 9
The graphite pouring sealant for the new energy automobile battery is different from the embodiment 1 in that hydroxyl organosilane is hydroxyl modified organosilane, and the hydroxyl modified organosilane is prepared by the following method:
a: reacting polyester polyol with glycerolactone at 90 ℃ for 2 hours under the condition of a catalyst to obtain a product A, wherein the molar ratio of the polyester polyol to glycidol is 1:3, a step of;
b: and (3) reacting the obtained product A with organosilane at 80 ℃ for 6 hours to obtain the hydroxyl modified organosilane, wherein the molar ratio of the polyester polyol to the organosilane is 1:3.
Examples 8 to 9 differ from example 7 in the amounts of the partial raw material species used for preparing the hydroxy-modified organosilane and in the experimental parameters, and the specific differences in examples 7 to 9 are shown in Table 3:
TABLE 3 examples 7-9 types and amounts of hydroxyl-modified organosilane raw materials and test parameters
Example 10
The graphite pouring sealant for the new energy automobile battery is different from the graphite pouring sealant in the embodiment 4 in that the hydroxyl modified organosilicon is prepared by the method in the embodiment 7, and the rest experimental steps, raw material types and the dosage are the same as those in the embodiment 4.
Example 11
The graphite pouring sealant for the new energy automobile battery is different from the embodiment 4 in that the polyester multipolymer comprises polyester polyol and polyester polyether with the weight ratio of 4:5 the rest of the experimental procedure, raw material types and amounts were the same as in example 4.
Example 12
The graphite pouring sealant for the new energy automobile battery is different from the embodiment 4 in that the polyester multipolymer comprises polyester polyol and polyester polyether with the weight ratio of 7:5 the rest of the experimental procedure, raw material types and amounts were the same as in example 4.
Example 13
The difference between the embodiment and the embodiment 4 is that in the step 1), the experiment step of directly putting the heated graphite into the quaternary ammonium hydroxide solution without the rapid heating step, and the types and the dosage of the raw materials are the same as those of the embodiment 4.
Example 14
The graphite pouring sealant for the new energy automobile battery is different from the graphite pouring sealant in the embodiment 7 in that the polyether polyol is replaced by the polyol in the step A, and the rest experimental steps, raw material types and the dosage are the same as those in the embodiment 7.
The polyether polyol has a functionality of 3 and a molecular weight of 2000.
Comparative example
Comparative example 1
The graphite pouring sealant for the new energy automobile battery is different from the embodiment 1 in that the graphite which is equivalent to the modified graphite is used for replacing the modified graphite, and the rest experimental steps, raw material types and the dosage are the same as those of the embodiment 1.
Comparative example 2
The graphite pouring sealant for the new energy automobile battery is different from the embodiment 1 in that 3-isocyanatopropyl trimethoxy silane is used for replacing hydroxyl modified organosilane, and the rest experimental steps, raw material types and dosage are the same as those of the embodiment 1.
Performance test
The graphite pouring sealants for the batteries of the new energy automobiles prepared in examples 1 to 14 and comparative examples 1 to 2 were tested for adhesive property, thermal conductivity, volume resistivity, tensile strength and elongation at break.
Detection method/test method
And (3) adhesive property test: the adhesive properties of the potting adhesive were evaluated by measuring the adhesive tensile shear strength of the test sample to aluminum sheet and PPA by using a Z010 type universal material tester from Zwick/Roell, germany, according to GB/T7124-2008.
Thermal conductivity coefficient: the thermal conductivity (W/mk) of the graphite pouring sealant for the new energy automobile battery prepared in examples 1-14 and comparative examples 1-2 after curing was measured according to the standard in GB/T10297-2015.
Volume resistivity: the volume resistivity of the graphite pouring sealant for the new energy automobile battery prepared in examples 1-14 and comparative examples 1-2 was tested according to GB/T1692-2008 pair.
Tensile strength and elongation at break test: and measuring the tensile strength and the elongation at break of the graphite pouring sealant for the new energy automobile battery after curing according to GB/T528-2009. The test data are shown in table 4:
TABLE 4 data on test results for examples 1-14 and comparative examples 1-2
From examples 1 to 14 and comparative examples 1 to 2 in combination with Table 4, it is understood that the graphite casting glue for a battery of a new energy automobile prepared by the present application has good adhesive property, thermal conductivity, insulation property, tensile strength, and the like.
Compared with the comparative example 1, the graphite pouring sealant for the battery of the new energy automobile prepared by adopting the modified graphite has obviously improved bonding strength, insulation property, tensile strength and elongation at break.
Compared with comparative example 2, the graphite pouring sealant for the new energy automobile battery prepared by adopting the hydroxyl modified organosilane has obviously improved adhesive strength, insulativity, tensile strength and elongation at break.
Compared with example 1 and example 4, the graphite pouring sealant for the new energy automobile battery in example 4 has obviously improved bonding strength, insulativity, tensile strength and elongation at break, and in combination with example 4 and example 13, the graphite pouring sealant for the new energy automobile battery prepared by the method provided by the application has improved bonding property, heat conduction property, insulativity and mechanical property.
Example 1 and example 7, and example 7 and example 14, illustrate that the hydroxy-modified organosilane prepared by the present application can improve the adhesive strength, insulation, tensile strength and elongation at break of the graphite pouring sealant for a new energy automobile battery.
Example 4 compared with examples 11 to 12, it was demonstrated that the effect of the modified graphite on the adhesive strength, insulation, tensile strength and elongation at break of the graphite casting glue for a new energy automobile battery can be improved by preparing the modified graphite using the polyester polyol and the polyester polyether in a certain weight ratio.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (10)
1. The graphite pouring sealant for the new energy automobile battery is characterized by comprising the following raw materials in parts by weight:
vinyl-terminated silicone oil 70-90 parts
10-20 parts of hydroxyl organic silicon
20-35 parts of vinyl MQ silicone resin
30-40 parts of modified graphite
10-15 parts of fumed silica
1-2 parts of a first catalyst
0.01-0.03 parts of inhibitor.
2. The graphite pouring sealant for the new energy automobile battery, according to claim 1, is characterized in that the modified graphite is prepared by the following method:
1) Heating graphite at 180-200 deg.c for 1-2 hr, fast heating to 400-450 deg.c, setting heated graphite in quaternary ammonium alkali solution at 40-50 deg.c, stirring for 2-3 hr, adding hydrogen peroxide several times, filtering, leaching with water and filtering to obtain hydroxylated graphite;
2) Dispersing the hydroxylated graphite in a solvent, adding isocyanate and an initiator, heating to 50-60 ℃ for reaction for 3-4 hours, adding a polyester multipolymer and a second catalyst, continuing to react for 4-6 hours, filtering, washing with ethanol, and drying to obtain modified graphite;
the polyester multipolymer comprises polyester polyol and/or polyether polyol.
3. The graphite pouring sealant for the new energy automobile battery, according to claim 2, is characterized by comprising the following raw materials in parts by weight:
20-35 parts of graphite
40-60 parts of quaternary ammonium alkali solution
10-15 parts of hydrogen peroxide
40-60 parts of solvent
5-10 parts of isocyanate
1-2 parts of initiator
10-20 parts of polyester multipolymer
And 1-2 parts of a second catalyst.
4. The graphite pouring sealant for a new energy automobile battery according to claim 3, wherein: the weight part ratio of the polyester polyol to the polyester polyol ether is (4-7): 5.
5. the graphite pouring sealant for the new energy automobile battery, according to claim 1, is characterized in that the hydroxyl organosilane is hydroxyl modified organosilane, and the hydroxyl modified organosilane is prepared by the following method:
a: mixing polyester polyol and glycerolactone, adding a third catalyst, heating to 90-120 ℃, and reacting for 2-5 hours to obtain a product A, wherein the molar ratio of the polyester polyol to glycidol is (1:4) - (3:8);
b: mixing the obtained product A with organosilane, heating to 80-90 ℃, and reacting for 6-8 hours to obtain the hydroxyl modified organosilane, wherein the molar ratio of the polyester polyol to the organosilane is 1- (1:3).
6. The graphite pouring sealant for a new energy automobile battery according to claim 5, wherein: the functionality of the polyester polyol is 2-4, and the molecular weight of the polyester polyol is 500-2000.
7. The graphite pouring sealant for a new energy automobile battery according to claim 1, wherein: the viscosity of the vinyl-terminated silicone oil is 1000-2000mPa.s, and the mass percentage of vinyl is 0.4-1.5%.
8. The graphite pouring sealant for a new energy automobile battery according to claim 1, wherein: the viscosity of the vinyl MQ silicon resin is 3000-5000 Pa.s, and the mass percentage of vinyl is 1-1.5%.
9. The graphite pouring sealant for a new energy automobile battery according to claim 1, wherein: the average particle diameter of the fumed silica is 100-200nm.
10. A method for preparing the graphite pouring sealant for the new energy automobile battery according to any one of claims 1 to 9, which is characterized by comprising the following steps:
s1, mixing 1/2 terminal vinyl silicone oil, vinyl MQ silicone resin and a catalyst, and shearing and dispersing at a high speed to obtain a mixture A;
s2, mixing the remaining 1/2 terminal vinyl silicone oil, hydroxyl modified organic silicon, modified graphite, fumed silica and an inhibitor, and shearing and dispersing at a high speed to obtain a mixture B;
and S3, mixing and curing the mixture A and the mixture B to obtain the graphite pouring sealant for the new energy automobile battery.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311259519.7A CN117165257A (en) | 2023-09-27 | 2023-09-27 | Graphite pouring sealant for new energy automobile battery and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311259519.7A CN117165257A (en) | 2023-09-27 | 2023-09-27 | Graphite pouring sealant for new energy automobile battery and preparation method thereof |
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| CN117165257A true CN117165257A (en) | 2023-12-05 |
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