CN117210010B - Heat dissipation material for charger baby shell - Google Patents
Heat dissipation material for charger baby shell Download PDFInfo
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- CN117210010B CN117210010B CN202310728643.7A CN202310728643A CN117210010B CN 117210010 B CN117210010 B CN 117210010B CN 202310728643 A CN202310728643 A CN 202310728643A CN 117210010 B CN117210010 B CN 117210010B
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- 239000000463 material Substances 0.000 title claims abstract description 73
- 230000017525 heat dissipation Effects 0.000 title claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 119
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 99
- 239000010455 vermiculite Substances 0.000 claims abstract description 63
- 229910052902 vermiculite Inorganic materials 0.000 claims abstract description 63
- 235000019354 vermiculite Nutrition 0.000 claims abstract description 63
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 46
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910000077 silane Inorganic materials 0.000 claims abstract description 37
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 37
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 35
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 30
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 30
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 19
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 19
- 239000011159 matrix material Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 63
- 239000000203 mixture Substances 0.000 claims description 37
- 239000000835 fiber Substances 0.000 claims description 34
- -1 polydimethylsiloxane Polymers 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 19
- 239000002109 single walled nanotube Substances 0.000 claims description 18
- 238000005507 spraying Methods 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 17
- JKRZOJADNVOXPM-UHFFFAOYSA-N Oxalic acid dibutyl ester Chemical compound CCCCOC(=O)C(=O)OCCCC JKRZOJADNVOXPM-UHFFFAOYSA-N 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 230000003712 anti-aging effect Effects 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000004945 silicone rubber Substances 0.000 claims description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 14
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 14
- 238000004108 freeze drying Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000006467 substitution reaction Methods 0.000 claims description 10
- 230000001112 coagulating effect Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 8
- 229920000459 Nitrile rubber Polymers 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- QWDBCIAVABMJPP-UHFFFAOYSA-N Diisopropyl phthalate Chemical group CC(C)OC(=O)C1=CC=CC=C1C(=O)OC(C)C QWDBCIAVABMJPP-UHFFFAOYSA-N 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 235000019359 magnesium stearate Nutrition 0.000 claims description 4
- MQHNKCZKNAJROC-UHFFFAOYSA-N phthalic acid dipropyl ester Natural products CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004014 plasticizer Substances 0.000 claims description 4
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- WIPVTGFUXLQZEI-UHFFFAOYSA-N titanium(4+);trimethyl(oxido)silane Chemical compound C[Si](C)(C)O[Ti](O[Si](C)(C)C)(O[Si](C)(C)C)O[Si](C)(C)C WIPVTGFUXLQZEI-UHFFFAOYSA-N 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 239000011667 zinc carbonate Substances 0.000 claims description 3
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 3
- 235000004416 zinc carbonate Nutrition 0.000 claims description 3
- AEVMYSJYJJYAFL-UHFFFAOYSA-N CCCC[Sn](CCCC)CCCC.CCCC[Sn](OC)OC Chemical compound CCCC[Sn](CCCC)CCCC.CCCC[Sn](OC)OC AEVMYSJYJJYAFL-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 2
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 claims description 2
- 239000002079 double walled nanotube Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002048 multi walled nanotube Substances 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 claims description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000002604 ultrasonography Methods 0.000 claims 2
- 239000000758 substrate Substances 0.000 claims 1
- 235000010215 titanium dioxide Nutrition 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000011161 development Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 8
- GDESEHSRICGNDP-UHFFFAOYSA-L [Cl-].[Cl-].[Ca+2].CCO Chemical compound [Cl-].[Cl-].[Ca+2].CCO GDESEHSRICGNDP-UHFFFAOYSA-L 0.000 description 7
- 230000004044 response Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 230000035882 stress Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 229920002725 thermoplastic elastomer Polymers 0.000 description 4
- 239000004636 vulcanized rubber Substances 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 3
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- ZXDVQYBUEVYUCG-UHFFFAOYSA-N dibutyltin(2+);methanolate Chemical compound CCCC[Sn](OC)(OC)CCCC ZXDVQYBUEVYUCG-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 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
Abstract
The invention discloses a heat dissipation material for a charger baby shell, which comprises the following raw materials: silicon rubber matrix, graphene oxide, sodium carboxymethyl cellulose, vermiculite powder, carbon nano tube, reinforcing agent, silane crosslinking agent, catalyst, auxiliary agent and lithium chloride aqueous solution; wherein the lithium ion concentration in the lithium chloride aqueous solution is 0.1-1mol/L, and the mass ratio of the silicon rubber matrix, the graphene oxide, the sodium carboxymethyl cellulose, the vermiculite powder, the carbon nano tube, the reinforcing agent, the silane cross-linking agent, the catalyst and the auxiliary agent is 50-100:5-10:1-3:5-15:2-4:2-6:1-2:0.1-1:1-2. The invention also discloses a preparation method of the heat dissipation material for the charger baby shell. The composite silicon rubber obtained by the invention has excellent heat conduction effect, can keep good heat conduction stability especially in the temperature range of 0-250 ℃, can also remarkably improve the mechanical property of the material, and lays a foundation for the further development of the charger housing.
Description
Technical Field
The invention relates to the technical field of heat dissipation materials, in particular to a heat dissipation material for a charger baby shell.
Background
The charger is a portable charger which can be carried by a person and can store electric energy, and is mainly used for charging consumer electronic products such as handheld mobile equipment and the like, and is particularly applied to occasions without external power supply. The treasured that charges is a collection electricity storage, boost voltage, charge management in portable equipment of an organic whole, and the treasured outside of charging is installed the shell and is protected inside not damaged usually.
At present, the charging treasured of the common 18650 lithium battery cell widely used can generate larger heat in the processes of self charging and discharging to external equipment, but the charging treasured is often arranged in a sealing way for attractive purposes, so that heat cannot be timely discharged, the service life of the charging treasured can be greatly reduced for a long time, and accidents such as explosion and the like can be caused due to overhigh heat. Most of the charging devices in the current stage are provided with single heat dissipation holes for dissipating heat of the internal storage battery, so that uneven heat dissipation and local heat accumulation are easily caused, the heat dissipation efficiency is low, and the risk of overheat burning of the storage battery is easily caused.
The room temperature vulcanized silicone rubber can be cured without heating and pressurizing at room temperature, is extremely convenient to use, and has excellent heat resistance and excellent electrical insulation property, so that the room temperature vulcanized silicone rubber has excellent prospect when being applied to the charger housing. However, the silicon rubber is used as a hot bad conductor, heat is accumulated in the silicon rubber at high temperature, so that the temperature in the charger is higher, the temperature required by the charger is increased intangibly, and particularly, the silicon rubber is heated to easily decompose free oxygen free radicals under the high temperature condition to attack the main chain of the silicon rubber molecule, so that the decomposition of the rubber molecule structure is caused, the high temperature aging of the silicon rubber is caused, and the use value is lost.
The prior art basically adopts the method that metal oxides such as magnesium oxide, aluminum oxide and metal nitrides such as silicon nitride and boron nitride are filled in a basic polymer matrix to improve the heat conductivity of a polymer material, but the defects of large filling quantity, unstable glue solution storage and easy aging and yellowing after solidification exist, and the method is not suitable for a charger housing. CN102234427a discloses a silicone rubber composition and a preparation method of silicone rubber, and by adding titanium dioxide coated with zinc hydroxide, the heat conducting property and the stability under high temperature environment are improved, but the composition is nano particle size, and agglomeration phenomenon is very easy to occur.
With the development of scientific technology, the requirements on the thermal conductivity of the charger baby shell are higher and higher, and the requirements on the heat resistance of the silicone rubber are also higher. Graphene is a two-dimensional platelet-like material composed of sp2 hybridized carbon atoms, with a thickness of only 0.335nm. As an emerging two-dimensional material, the material has excellent mechanical flexibility and high thermal stability, and the strength and the heat conducting property of the material can be greatly improved by adding a small amount of graphene into the composite material. Therefore, the graphene and the composite thereof have great application potential in the aspect of heat conduction of the silicon rubber.
CN104327515a discloses a silicon rubber heat-conducting composite material containing graphene and a preparation method thereof, wherein the heat-conducting composite material mainly comprises graphene, inorganic heat-conducting filler and a silicon rubber matrix, and the graphene forms a heat-conducting network in the heat-conducting composite material. However, graphene has poor dispersibility in silicone rubber, low peeling degree and poor heat conduction effect. CN 106674599a discloses a preparation method and application of silicone rubber functionalized graphene, the prepared silicone rubber functionalized graphene can be uniformly dispersed in various organic solvents and silicone rubber resin matrix, and an improved Hummer method is adopted to prepare graphene oxide so as to improve the dispersion effect with the silicone rubber, but the reduced graphene still has the phenomenon that the sheets are easy to stack. At present, due to strong pi-pi interaction and van der Waals force between graphene sheets, aggregation and stacking of the graphene sheets are easy to occur in the practical application process of the graphene sheets added to the charger baby silicon rubber shell, stability of a silicon rubber product is greatly affected, and due to the fact that the number of internal contact points of a heat conduction network formed by the graphene sheets is small, heat conduction efficiency is poor when the addition amount is small, so that the problem needs to be solved.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a heat dissipation material for a charger baby shell, which comprises the following raw materials: silicon rubber matrix, graphene oxide, sodium carboxymethyl cellulose, vermiculite powder, carbon nano tube, reinforcing agent, silane crosslinking agent, catalyst, auxiliary agent and lithium chloride aqueous solution.
The lithium ion concentration in the lithium chloride aqueous solution is 0.1-1mol/L, and the mass ratio of the silicon rubber matrix, the graphene oxide, the sodium carboxymethyl cellulose, the vermiculite powder, the carbon nano tube, the reinforcing agent, the silane cross-linking agent, the catalyst and the auxiliary agent is 50-100:5-10:1-3:5-15:2-4:2-6:1-2:0.1-1:1-2.
Preferably, the weight ratio of the aqueous solution of lithium chloride to the vermiculite powder is 2-10:1.
preferably, the silicone rubber matrix is a hydroxyl-terminated polyorganosiloxane, preferably at least one of a hydroxyl-terminated polydimethylsiloxane, a hydroxyl-terminated polymethylphenylsiloxane, a hydroxyl-terminated polydiphenylsiloxane.
Preferably, the polyorganosiloxane has a number average molecular weight of 10000-100000.
Preferably, the sodium carboxymethylcellulose has a degree of substitution of 0.74 to 0.82 and a degree of polymerization DP of 200 to 300.
Preferably, the reinforcing agent is at least one of carbon black, titanium pigment, nano calcium carbonate and nano aluminum oxide
Preferably, the silane crosslinking agent is at least one selected from methyltriacetonyl silane, methyltributyloximoyl silane, vinyltributylketoxime silane, phenyltributylketoxime silane, tetrabutylketoxime silane and aniline methyltributyloxidoxime silane.
Preferably, the catalyst is at least one of stannous octoate, dibutyl tin dilaurate, dibutyl tin dioctoate, dibutyl tin diacetate, dibutyl tin dimethoxy, dibutyl tin oxide, tetra-n-butyl titanate, tetra-isopropyl titanate, tetra (trimethylsiloxy) titanium.
Preferably, the auxiliary agent comprises: tackifying resin, an active agent, an anti-aging agent and a plasticizer.
More preferably, the tackifying resin is bisphenol a epoxy resin, modified epoxy resin, liquid styrene butadiene rubber, or liquid nitrile butadiene rubber.
More preferably, the active agent is one or two of zinc carbonate, zinc oxide, sodium stearate, magnesium stearate.
More preferably, the antioxidant is an antioxidant RD, an antioxidant DNP, an antioxidant BHT or an antioxidant 4020.
More preferably, the plasticizer is diisopropyl phthalate, dibutyl oxalate, ethyl acrylate or isopropyl acrylate.
The preparation method of the heat dissipation material for the charger baby shell comprises the following steps:
s1, dispersing graphene oxide in water, adding sodium carboxymethylcellulose under stirring, stirring uniformly under normal-temperature ultrasonic assistance, adjusting the temperature to 60-70 ℃, continuing ultrasonic assistance stirring for 30-50min, rapidly cooling to-10 to-20 ℃ at the speed of 5-10 ℃/min, and freeze-drying to obtain the dispersed graphene oxide.
Graphene oxide can be dissolved in water and other solvents in a colloid-like state, and graphene oxide sheets contain a large number of hydroxyl groups, carboxyl groups, epoxy groups, carbonyl groups and the like, and the oxygen-containing functional groups help the graphene oxide sheets to overcome strong pi-pi bond attraction between the graphene oxide sheets, so that the graphene oxide sheets are easy to separate.
According to the method, the graphene sheets and the sodium carboxymethylcellulose macromolecular chains are extruded by the ice crystals which grow directionally in the freeze drying process, self-assembly is induced, and meanwhile, in the rapid cooling process, the ice crystals lack enough growth time, so that the ice crystals are uniform in size, the self-assembled graphene has regular pores, and stress dispersion is facilitated; on the other hand, the surface of the graphene oxide contains rich carboxyl and carbonyl, and the sodium carboxymethyl cellulose molecular chain contains a large amount of oxygen-containing functional groups, so that the graphene oxide has strong water solubility, can be adsorbed on graphene oxide sheets through hydrogen bonding in aqueous solution, can effectively weaken stacking among graphene sheets in the freeze drying process, and can be used as a framework to improve the compression resistance of the graphene.
S2, adding vermiculite powder into lithium chloride aqueous solution, refluxing and stirring at 100-110 ℃ for 1-2 hours, centrifuging to remove supernatant, adding carbon nano tubes into lower gel, carrying out ultrasonic-assisted high-speed grinding in the same direction for 10-16 minutes, spraying the grinding speed into a coagulating bath at a spraying speed of 20-30mm/S, washing with ethanol for 2-4 times, and drying to obtain the thermally-responsive vermiculite fiber.
The vermiculite powder is expanded in lithium chloride aqueous solution under the action of hydrated cations in the ion exchange process to obtain vermiculite gel; adding carbon nano tubes into the heat conducting material, peeling vermiculite sheets by strong grinding and shearing action, arranging the carbon nano tubes in the vermiculite sheet structure regularly under the action force in the same direction, enabling the vermiculite sheets intercalated by the carbon nano tubes to be oriented along the spraying direction under the induction of strong spraying action, forming a shell-like layer-by-layer stacking structure, and connecting the heat conducting network in the horizontal aspect.
And S3, fully stirring the silicon rubber matrix, the dispersed graphene oxide, the thermally responsive vermiculite fiber, the reinforcing agent and the auxiliary agent, maintaining a vacuumizing state in the stirring process to remove bubbles in the mixture, adding the silane cross-linking agent and the catalyst, uniformly mixing, forming, and standing at room temperature to obtain the heat dissipation material for the charger housing.
Preferably, in S2, the carbon nanotubes are at least one of single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes, and preferably are single-walled carbon nanotubes;
preferably, in S2, the coagulating bath is calcium chloride ethanol solution, and the concentration of calcium chloride is 0.8-1.5mol/L.
Preferably, in S2, the thermally responsive vermiculite fibers have a length of 0.1 to 1mm and a diameter of 10 to 100. Mu.m.
The technical effects of the invention are as follows:
the carboxymethyl cellulose sodium molecular chain in the dispersion graphene oxide obtained by the application plays a skeleton role in a graphene three-dimensional network, so that the graphene stacking phenomenon is effectively avoided, the carboxymethyl cellulose sodium molecular skeleton on the carboxymethyl cellulose sodium molecular chain contains a large number of hydroxyl groups and carboxyl groups, the compatibility with hydroxyl-terminated polyorganosiloxane is good, the dispersion graphene oxide is high in bonding degree in a sealing member through curing and crosslinking, the three-dimensional state of the dispersion graphene oxide can be effectively maintained in the system, and the born force can be rapidly transferred to the whole system when the system is subjected to pressure, so that the stability is high.
Although graphene oxide has high heat conductivity coefficient, the addition amount of graphene oxide can effectively construct a heat conduction network only when the addition amount reaches 2% of the system content, and is even higher when the graphene oxide is used in a high-temperature environment. Therefore, the thermal response vermiculite fiber is compounded with the dispersed graphene oxide, and the material obtained by the application has excellent high temperature resistance and heat conduction performance in a high-temperature environment, can prevent the ageing of the shell and improve the use environment. The reason may be that although the surface of the dispersed graphene oxide is coated by the polymer, which hinders the mutual contact effect, the thermally-responsive vermiculite fiber contains regularly arranged carbon nanotubes, the thermally-responsive vermiculite fiber can be directly lapped between the dispersed graphene oxide to form a three-dimensional continuous heat conduction network, the interface thermal resistance is obviously reduced, and along with the rise of the temperature, the thermally-responsive vermiculite fiber begins to expand, extrudes the surrounding environment and exposes more regularly arranged carbon nanotubes, so that the heat is quickly conducted out, the internal heat conduction is accelerated, free oxygen free radicals generated by the heat conduction can be captured in a high-temperature environment, the attack of the free radicals on a silicon rubber main chain is effectively avoided, and the stability of the heat dissipation material in the high-temperature environment is greatly improved.
According to the invention, the dispersed graphene oxide is matched with the thermally-responsive vermiculite fiber, so that the composite silicone rubber has an excellent thermal conduction effect, particularly, the composite silicone rubber can keep good thermal conduction stability at 0-250 ℃, and the mechanical property of the material can be obviously improved, so that the mechanical strength and sealing property of the product are improved, the comprehensive performance is excellent, and a foundation is laid for further development of the charger housing.
The invention can well protect the charger baby, improve the heat dissipation efficiency, avoid heat accumulation, reduce the risk of heating and burning out, effectively prevent explosion accidents caused by high temperature, improve the quality of the charger baby and protect users.
Drawings
FIG. 1 is a graph showing the thermal conductivity of the heat dissipation materials for the battery charger cases obtained in example 5 and comparative examples 1 to 3.
Fig. 2 is a graph showing the thermal conductivity after heat dissipation materials for battery charger cases obtained in example 5 and comparative examples 1 to 3 are subjected to heat and cold cycle impact.
Detailed Description
The invention is further illustrated below in connection with specific embodiments.
Example 1
A heat dissipation material for a charger baby shell comprises the following raw materials: 50kg of hydroxyl-terminated polydiphenylsiloxane with the number average molecular weight of 10000-100000, 5kg of graphene oxide, 1kg of sodium carboxymethyl cellulose with the substitution degree of 0.74-0.82 and the polymerization degree DP of 200-300, 5kg of vermiculite powder, 2kg of single-wall carbon nano tubes, 2kg of carbon black, 1kg of phenylmethyl tributyl ketoxime silane, 0.1kg of stannous octoate, 1kg of auxiliary agent and 0.1mol/L of lithium ion concentration in lithium chloride aqueous solution.
Wherein the auxiliary agent comprises bisphenol A epoxy resin, zinc carbonate, an anti-aging agent RD and diisopropyl phthalate according to the mass ratio of 1:1:1: 1.
The preparation method of the heat dissipation material for the charger baby shell comprises the following steps:
s1, dispersing graphene oxide in 30kg of water, adding sodium carboxymethylcellulose under stirring, uniformly stirring under normal-temperature ultrasonic assistance, adjusting the temperature to 60 ℃, continuing ultrasonic assistance stirring for 30min, rapidly cooling to-10 ℃ at a speed of 5 ℃/min, and freeze-drying to obtain dispersed graphene oxide;
s2, adding vermiculite powder into 25kg of lithium chloride aqueous solution, refluxing and stirring at 100 ℃ for 1h, centrifuging to remove supernatant, adding single-walled carbon nanotubes into lower gel, carrying out ultrasonic-assisted high-speed grinding in the same direction for 10min at a grinding speed of 10000r/min, spraying the powder into a coagulating bath (calcium chloride ethanol solution with concentration of 0.8 mol/L) at a spraying speed of 20mm/S, washing with ethanol for 2 times, and drying to obtain thermally-responsive vermiculite fibers;
s3, mixing hydroxyl-terminated polydiphenylsiloxane, dispersed graphene oxide, thermally-responsive vermiculite fiber, carbon black and an auxiliary agent, adding the mixture into a planetary mixer, fully stirring, maintaining a vacuumizing state in the stirring process to remove bubbles in the mixture, adding phenylmethyl tributyl ketoxime silane and stannous octoate, uniformly mixing, placing the mixture into a forming die, and standing at room temperature for 5 hours to obtain the heat dissipation material for the charger housing.
Example 2
A heat dissipation material for a charger baby shell comprises the following raw materials: 100kg of hydroxyl-terminated polymethylphenylsiloxane with the number average molecular weight of 10000-100000, 10kg of graphene oxide, 3kg of sodium carboxymethyl cellulose with the substitution degree of 0.74-0.82 and the polymerization degree DP of 200-300, 15kg of vermiculite powder, 4kg of single-wall carbon nano tubes, 6kg of nano calcium carbonate, 2kg of methyltriacetone oximido silane, 1kg of dimethoxy dibutyltin, 2kg of auxiliary agent and 1mol/L of lithium ion concentration in lithium chloride aqueous solution.
Wherein the auxiliary agent comprises liquid styrene-butadiene rubber, magnesium stearate, an anti-aging agent DNP and diisopropyl phthalate according to the mass ratio of 2:1:2: 1.
The preparation method of the heat dissipation material for the charger baby shell comprises the following steps:
s1, dispersing graphene oxide in 60kg of water, adding sodium carboxymethylcellulose under stirring, uniformly stirring under normal-temperature ultrasonic assistance, adjusting the temperature to 70 ℃, continuing ultrasonic assistance stirring for 50min, rapidly cooling to-20 ℃ at a speed of 10 ℃/min, and freeze-drying to obtain dispersed graphene oxide;
s2, adding vermiculite powder into 75kg of lithium chloride aqueous solution, refluxing and stirring at 110 ℃ for 2 hours, centrifuging to remove supernatant, adding single-walled carbon nanotubes into lower gel, carrying out ultrasonic-assisted high-speed grinding in the same direction for 16 minutes at a grinding speed of 14000r/min, spraying the mixture into a coagulation bath (calcium chloride ethanol solution with concentration of 1.5 mol/L) at a spraying speed of 30mm/S, washing the mixture for 4 times by adopting ethanol, and drying to obtain thermally-responsive vermiculite fibers;
s3, mixing hydroxyl-terminated polymethylphenylsiloxane, dispersed graphene oxide, thermally-responsive vermiculite fibers, nano calcium carbonate and an auxiliary agent, adding the mixture into a planetary mixer, fully stirring, maintaining a vacuumizing state in the stirring process to remove bubbles in the mixture, adding methyltriacetone oximido silane and dimethoxy dibutyl tin, uniformly mixing, placing the mixture into a forming die, and standing the mixture at room temperature for 10 hours to obtain the heat dissipation material for the charger housing.
Example 3
A heat dissipation material for a charger baby shell comprises the following raw materials: 70kg of hydroxyl-terminated polydimethylsiloxane with the number average molecular weight of 10000-100000, 8kg of graphene oxide, 0.74-0.82 of substitution degree, 1.5kg of sodium carboxymethyl cellulose with the polymerization degree DP of 200-300, 12kg of vermiculite powder, 2.5kg of single-walled carbon nano tubes, 5kg of titanium dioxide, 1.3kg of methyltributylketonoxime silane, 0.8kg of tetra (trimethylsiloxy) titanium, 1.3kg of auxiliary agent and 0.8mol/L of lithium ion concentration in lithium chloride aqueous solution.
Wherein the auxiliary agent comprises bisphenol A epoxy resin, magnesium stearate, an anti-aging agent 4020 and dibutyl oxalate according to the mass ratio of 3:1:2: 1.
The preparation method of the heat dissipation material for the charger baby shell comprises the following steps:
s1, dispersing graphene oxide in 40kg of water, adding sodium carboxymethylcellulose under stirring, uniformly stirring under normal-temperature ultrasonic assistance, adjusting the temperature to 66 ℃, continuing ultrasonic assistance stirring for 35min, rapidly cooling to-12 ℃ at a speed of 8 ℃/min, and freeze-drying to obtain dispersed graphene oxide;
s2, adding vermiculite powder into 60kg of lithium chloride aqueous solution, refluxing and stirring at 108 ℃ for 1.3 hours, centrifuging to remove supernatant, adding single-walled carbon nanotubes into lower gel, carrying out ultrasonic-assisted high-speed grinding in the same direction for 14 minutes at a grinding speed of 11000r/min, spraying the mixture into a coagulating bath (calcium chloride ethanol solution with the concentration of 1 mol/L) at a spraying speed of 28mm/S, washing the mixture for 3 times by adopting ethanol, and drying to obtain thermally-responsive vermiculite fibers with the length of 0.1-1mm and the diameter of 10-100 mu m;
s3, mixing hydroxyl-terminated polydimethylsiloxane, dispersed graphene oxide, thermally-responsive vermiculite fiber, titanium dioxide and an auxiliary agent, adding the mixture into a planetary mixer, fully stirring, maintaining a vacuumizing state in the stirring process to remove bubbles in the mixture, adding methyltributylketon oxime silane and tetra (trimethylsiloxy) titanium, uniformly mixing, placing the mixture into a forming die, and standing at room temperature for 9 hours to obtain the heat dissipation material for the charger housing.
Example 4
A heat dissipation material for a charger baby shell comprises the following raw materials: 90kg of hydroxyl-terminated polydimethylsiloxane with the number average molecular weight of 10000-100000, 6kg of graphene oxide, 2.5kg of sodium carboxymethyl cellulose with the substitution degree of 0.74-0.82 and the polymerization degree DP of 200-300, 8kg of vermiculite powder, 3.5kg of single-walled carbon nano tubes, 3kg of nano alumina, 1.7kg of vinyl tributyl ketoximino silane, 0.2kg of tetra-n-butyl titanate, 1.7kg of auxiliary agent and the concentration of lithium ions in the lithium chloride aqueous solution of 0.2mol/L.
Wherein, the auxiliary agent consists of liquid nitrile rubber, zinc oxide, an anti-aging agent 4020 and dibutyl oxalate according to the mass ratio of 4:1:1: 1.
The preparation method of the heat dissipation material for the charger baby shell comprises the following steps:
s1, dispersing graphene oxide in 50kg of water, adding sodium carboxymethylcellulose under stirring, uniformly stirring under normal-temperature ultrasonic assistance, adjusting the temperature to 64 ℃, continuing ultrasonic assistance stirring for 45min, rapidly cooling to-18 ℃ at a speed of 6 ℃/min, and freeze-drying to obtain dispersed graphene oxide;
s2, adding vermiculite powder into 40kg of lithium chloride aqueous solution, refluxing and stirring at 102 ℃ for 1.7 hours, centrifuging to remove supernatant, adding single-walled carbon nanotubes into lower gel, carrying out ultrasonic-assisted high-speed grinding in the same direction for 12 minutes at a grinding speed of 13000r/min, spraying the mixture into a coagulating bath (calcium chloride ethanol solution with the concentration of 1.4 mol/L) at a spraying speed of 22mm/S, washing the mixture for 3 times by adopting ethanol, and drying to obtain thermally-responsive vermiculite fibers with the length of 0.1-1mm and the diameter of 10-100 mu m;
s3, mixing hydroxyl-terminated polydimethylsiloxane, dispersed graphene oxide, thermally-responsive vermiculite fibers, nano alumina and an auxiliary agent, adding the mixture into a planetary mixer, fully stirring, maintaining a vacuumizing state in the stirring process to remove bubbles in the mixture, adding vinyl tributyl ketoxime silane and tetra-n-butyl titanate, uniformly mixing, placing the mixture into a forming die, and standing at room temperature for 7 hours to obtain the heat dissipation material for the charger housing.
Example 5
A heat dissipation material for a charger baby shell comprises the following raw materials: 80kg of hydroxyl-terminated polydimethylsiloxane with the number average molecular weight of 10000-100000, 7kg of graphene oxide, 2kg of sodium carboxymethyl cellulose with the substitution degree of 0.74-0.82 and the polymerization degree DP of 200-300, 10kg of vermiculite powder, 3kg of single-walled carbon nano tubes, 4kg of nano alumina, 1.5kg of tetrabutyl ketoximino silane, 0.5kg of dibutyltin dilaurate, 1.5kg of auxiliary agent and 0.5mol/L of lithium ion concentration in lithium chloride aqueous solution.
Wherein the auxiliary agent consists of liquid nitrile rubber, zinc oxide, an anti-aging agent BHT and dibutyl oxalate according to the mass ratio of 4:3:2: 1.
The preparation method of the heat dissipation material for the charger baby shell comprises the following steps:
s1, dispersing graphene oxide in 45kg of water, adding sodium carboxymethylcellulose under stirring, uniformly stirring under normal-temperature ultrasonic assistance, adjusting the temperature to 65 ℃, continuing ultrasonic assistance stirring for 40min, rapidly cooling to-15 ℃ at a speed of 7 ℃/min, and freeze-drying to obtain dispersed graphene oxide;
s2, adding vermiculite powder into 50kg of lithium chloride aqueous solution, refluxing and stirring at 105 ℃ for 1.5 hours, centrifuging to remove supernatant, adding single-walled carbon nanotubes into lower gel, carrying out ultrasonic-assisted high-speed grinding in the same direction for 13 minutes at a grinding speed of 12000r/min, spraying the mixture into a coagulating bath (calcium chloride ethanol solution with the concentration of 1.2 mol/L) at a spraying speed of 25mm/S, washing the mixture for 3 times by adopting ethanol, and drying to obtain thermally-responsive vermiculite fibers with the length of 0.1-1mm and the diameter of 10-100 mu m;
s3, mixing hydroxyl-terminated polydimethylsiloxane, dispersed graphene oxide, thermally-responsive vermiculite fibers, nano aluminum oxide and an auxiliary agent, adding the mixture into a planetary mixer, fully stirring, maintaining a vacuumizing state in the stirring process to remove bubbles in the mixture, adding tetrabutyl ketoxime silane and dibutyltin dilaurate, uniformly mixing, placing the mixture into a forming die, and standing at room temperature for 8 hours to obtain the heat dissipation material for the charger housing.
Comparative example 1
A heat dissipation material for a charger baby shell comprises the following raw materials: 80kg of hydroxyl-terminated polydimethylsiloxane with the number average molecular weight of 10000-100000, 7kg of graphene oxide, 2kg of sodium carboxymethyl cellulose with the substitution degree of 0.74-0.82 and the polymerization degree DP of 200-300, 10kg of vermiculite powder, 4kg of nano alumina, 1.5kg of tetrabutyl ketoxime silane, 0.5kg of dibutyltin dilaurate and 1.5kg of auxiliary agent.
Wherein the auxiliary agent consists of liquid nitrile rubber, zinc oxide, an anti-aging agent BHT and dibutyl oxalate according to the mass ratio of 4:3:2: 1.
The preparation method of the heat dissipation material for the charger baby shell comprises the following steps:
i. dispersing graphene oxide in 45kg of water, adding sodium carboxymethylcellulose under stirring, stirring uniformly under normal-temperature ultrasonic assistance, adjusting the temperature to 65 ℃, continuing ultrasonic assistance stirring for 40min, rapidly cooling to-15 ℃ at a speed of 7 ℃/min, and freeze-drying to obtain dispersed graphene oxide;
ii. Mixing hydroxyl-terminated polydimethylsiloxane, dispersed graphene oxide, vermiculite powder, nano aluminum oxide and an auxiliary agent, adding the mixture into a planetary mixer, fully stirring, maintaining a vacuumizing state in the stirring process to remove bubbles in the mixture, adding tetrabutyl ketoxime silane and dibutyltin dilaurate, uniformly mixing, placing the mixture into a forming die, and standing at room temperature for 8 hours to obtain the heat dissipation material for the charger housing.
Comparative example 2
A heat dissipation material for a charger baby shell comprises the following raw materials: 80kg of hydroxyl-terminated polydimethylsiloxane with the number average molecular weight of 10000-100000, 7kg of graphene oxide, 2kg of sodium carboxymethyl cellulose with the substitution degree of 0.74-0.82 and the polymerization degree DP of 200-300, 3kg of single-walled carbon nano-tubes, 4kg of nano-alumina, 1.5kg of tetrabutyl ketoximino silane, 0.5kg of dibutyltin dilaurate and 1.5kg of auxiliary agent.
Wherein the auxiliary agent consists of liquid nitrile rubber, zinc oxide, an anti-aging agent BHT and dibutyl oxalate according to the mass ratio of 4:3:2: 1.
The preparation method of the heat dissipation material for the charger baby shell comprises the following steps:
i. dispersing graphene oxide in 45kg of water, adding sodium carboxymethylcellulose under stirring, stirring uniformly under normal-temperature ultrasonic assistance, adjusting the temperature to 65 ℃, continuing ultrasonic assistance stirring for 40min, rapidly cooling to-15 ℃ at a speed of 7 ℃/min, and freeze-drying to obtain dispersed graphene oxide;
ii. Mixing hydroxyl-terminated polydimethylsiloxane, dispersed graphene oxide, single-walled carbon nanotubes, nano alumina and an auxiliary agent, adding the mixture into a planetary mixer, fully stirring, maintaining a vacuumizing state in the stirring process to remove bubbles in the mixture, adding tetrabutyl ketoxime silane and dibutyl tin dilaurate, uniformly mixing, placing the mixture into a forming die, and standing at room temperature for 8 hours to obtain the heat dissipation material for the charger housing.
Comparative example 3
A heat dissipation material for a charger baby shell comprises the following raw materials: 80kg of hydroxyl-terminated polydimethylsiloxane with the number average molecular weight of 10000-100000, 7kg of graphene oxide, 10kg of vermiculite powder, 3kg of single-walled carbon nanotubes, 4kg of nano alumina, 1.5kg of tetrabutyl ketoximino silane, 0.5kg of dibutyltin dilaurate, 1.5kg of auxiliary agent and 0.5mol/L of lithium ion concentration in lithium chloride aqueous solution.
Wherein the auxiliary agent consists of liquid nitrile rubber, zinc oxide, an anti-aging agent BHT and dibutyl oxalate according to the mass ratio of 4:3:2: 1.
The preparation method of the heat dissipation material for the charger baby shell comprises the following steps:
i. dispersing graphene oxide in 45kg of water, uniformly stirring the graphene oxide under the assistance of normal-temperature ultrasonic waves, adjusting the temperature to 65 ℃, continuing to stir the graphene oxide under the assistance of the ultrasonic waves for 40min, rapidly cooling the graphene oxide to-15 ℃ at the speed of 7 ℃/min, and performing freeze drying to obtain the dispersed graphene oxide;
ii. Adding vermiculite powder into 50kg of lithium chloride aqueous solution, refluxing and stirring at 105 ℃ for 1.5 hours, centrifuging to remove supernatant, adding single-walled carbon nanotubes into lower gel, carrying out ultrasonic-assisted high-speed grinding in the same direction for 13 minutes at a grinding speed of 12000r/min, spraying the mixture into a coagulating bath (calcium chloride ethanol solution with the concentration of 1.2 mol/L) at a spraying speed of 25mm/s, washing with ethanol for 3 times, and drying to obtain thermally-responsive vermiculite fibers with the length of 0.1-1mm and the diameter of 10-100 mu m;
and iii, mixing hydroxyl-terminated polydimethylsiloxane, dispersed graphene oxide, thermally-responsive vermiculite fiber, nano alumina and an auxiliary agent, adding into a planetary mixer, fully stirring, maintaining a vacuumizing state in the stirring process to remove bubbles in the mixture, adding tetrabutyl ketoxime silane and dibutyl tin dilaurate, uniformly mixing, placing into a forming die, and standing at room temperature for 8 hours to obtain the heat dissipation material for the charger housing.
The mechanical properties of the heat dissipation materials for the charger baby cases obtained in example 5 and comparative examples 1 to 3 were tested as follows:
tensile Strength reference GB/T528-2009 "determination of tensile stress Strain Properties of vulcanized rubber or thermoplastic rubber"; peel strength reference HB5249-1993 method for 180℃peel strength test for Room temperature vulcanizing sealants; the high temperature resistance is measured according to GB/T528-2009 'measurement of tensile stress and strain properties of vulcanized rubber or thermoplastic rubber', a test sample strip is prepared, the test sample strip is placed in an aging oven with a set temperature for 7 days, whether the color is yellowing or not is observed, and whether the tensile stress and strain properties of the vulcanized rubber or thermoplastic rubber are attenuated is measured according to GB/T528-2009 'measurement of tensile stress and strain properties of the vulcanized rubber or thermoplastic rubber'.
| Tensile strength, mpa | Peel strength, N/mm | High temperature resistance, DEG C | |
| Example 5 | 3.35 | 6.41 | 360 |
| Comparative example 1 | 2.93 | 3.37 | 210 |
| Comparative example 2 | 2.55 | 3.45 | 190 |
| Comparative example 3 | 1.46 | 2.51 | 230 |
As can be seen from the above table: the heat dissipation material for the charger baby shell is high-temperature resistant, stable in performance, high in mechanical strength and good in sealing effect.
The applicant believes that: on the one hand, the sodium carboxymethyl cellulose molecular chain in the dispersed graphene oxide obtained by the application plays a role of a skeleton in a three-dimensional network of the graphene, so that the graphene stacking phenomenon is effectively avoided, the sodium carboxymethyl cellulose molecular skeleton on the graphene is provided with a large number of hydroxyl groups and carboxyl groups, the compatibility with hydroxyl-terminated polyorganosiloxane is good, the dispersed graphene oxide is high in bonding degree in a sealing member after curing and crosslinking, the three-dimensional state of the dispersed graphene oxide can be effectively maintained in the system, and the born force can be rapidly transmitted to the whole system when the graphene oxide is subjected to pressure, so that the stability is high; on the other hand, the thermal response vermiculite fiber and the dispersed graphene oxide are compounded, and the thermal response vermiculite fiber begins to expand along with the rise of temperature, so that free oxygen free radicals generated can be captured in a high-temperature environment, the attack of the free radicals on a main chain of the silicon rubber is effectively avoided, and the stability of the heat dissipation material in the high-temperature environment is greatly improved.
The mechanical properties of the heat dissipation materials for charger cases obtained in example 5 and comparative examples 1 to 3 were subjected to expansion property tests, specifically as follows:
| initial expansion temperature, DEG C | Maximum expansion temperature, DEG C | Volume expansion rate% | |
| Example 5 | 105 | 130 | 21.3 |
| Comparative example 1 | 90 | 112 | 8.4 |
| Comparative example 2 | 87 | 106 | 5.7 |
| Comparative example 3 | 92 | 121 | 69.3 |
Wherein the expansion temperature is measured by a thermomechanical analyzer TMA-Q400, the temperature is raised within the test temperature interval of 20-300 ℃ and 20 ℃/min, the force of 0.01N is constantly applied above the sample, and the change curve of the sample volume along with the temperature rise is recorded to obtain the initial expansion temperature T s And a maximum expansion temperature T m . Placing the sample in an oven, setting T m Placing at constant temperature for 20min, transferring the expanded sample into a measuring cylinder, and calculating the macroscopic volume expansion rate.
As can be seen from the above table: the heat sink materials for the charger cases obtained in comparative examples 1 and 2 had the smallest volume expansion ratio, since neither thermally responsive vermiculite fiber was used, resulting in difficult sample expansion. The heat dissipation material for the charger housing obtained in comparative example 3 has the highest volume expansion rate, because sodium carboxymethylcellulose is not used in step i in comparative example 3, a three-dimensional state cannot be formed, and when thermally responsive vermiculite fibers expand, restriction cannot be performed.
The heat-dissipating material for the charger baby shell enables the thermally-responsive vermiculite fiber to be directly overlapped between the dispersed graphene oxides to form a three-dimensional continuous heat-conducting network, and the interface thermal resistance is obviously reduced, so that the initial expansion temperature and the maximum expansion temperature are improved.
The heat conductivity of the heat dissipation materials for the charger cases obtained in example 5 and comparative examples 1 to 3 was measured by the astm e1530 test method at 40 ℃.
As shown in fig. 1, the heat dissipation material for the battery pack case obtained in example 5 had the highest heat conductivity and the best heat dissipation performance.
The applicant believes that: the thermal response vermiculite fiber is compounded with the dispersed graphene oxide, the interior of the thermal response vermiculite fiber contains regularly arranged carbon nanotubes, the thermal response vermiculite fiber can be directly overlapped between the dispersed graphene oxide to form a three-dimensional continuous heat conduction network, and the interface thermal resistance is obviously reduced; and as the temperature increases, the thermally responsive vermiculite fibers begin to expand, squeeze the surrounding environment and expose more regularly arranged carbon nanotubes, rapidly conducting heat away, and accelerating internal heat conduction. Thereby improve the thermal conductivity of the heat dissipation material for the treasured shell that charges that this application obtained.
And continuously adopting a cold and hot cycle impact test box to simulate cold and hot cycle impact test under extreme environmental conditions, wherein the hot environment is 150 ℃, the cold environment is-40 ℃, and the residence time of the cold and hot environments is 15min respectively. Each group of samples was simulated in the actual application environment, cycled 600 times for a duration of 4 weeks, and tested for thermal conductivity change every 200 cycles.
As shown in fig. 2, the thermal conductivity of the remaining 3 groups of samples, except for the comparative example 3, was slightly lowered and remained substantially unchanged after a total of 600 cold and hot cycle shocks were applied for a four-week period. The heat conductivity of the heat dissipation material for the charger baby shell obtained in the embodiment 5 is always better than that of the rest groups, which indicates that the heat dissipation material for the charger baby shell obtained in the application has higher heat conductivity, the physical and chemical properties of the heat dissipation material for the charger baby shell are not greatly changed under the long-time extreme environmental conditions, the heat dissipation material has extremely strong environment adaptability, the heat dissipation material is small in chemical change or physical damage to repeated resisting force at high and low temperatures and heat expansion and cold contraction output, and the heat dissipation material has good cold heat cycle impact stability.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (13)
1. The heat dissipation material for the charger baby shell is characterized by comprising the following raw materials: silicon rubber matrix, graphene oxide, sodium carboxymethyl cellulose, vermiculite powder, carbon nano tube, reinforcing agent, silane crosslinking agent, catalyst, auxiliary agent and lithium chloride aqueous solution; the mass ratio of the silicon rubber matrix, the graphene oxide, the sodium carboxymethyl cellulose, the vermiculite powder, the carbon nano tube, the reinforcing agent, the silane crosslinking agent, the catalyst and the auxiliary agent is 50-100:5-10:1-3:5-15:2-4:2-6:1-2:0.1-1:1-2, wherein the concentration of lithium ions in the lithium chloride aqueous solution is 0.1-1mol/L;
the preparation method comprises the following steps:
s1, dispersing graphene oxide in water, adding sodium carboxymethylcellulose under stirring, stirring uniformly under normal-temperature ultrasonic assistance, adjusting the temperature to 60-70 ℃, continuing ultrasonic assistance stirring for 30-50min, cooling rapidly to-10 to-20 ℃, and freeze-drying to obtain dispersed graphene oxide;
s2, adding vermiculite powder into a lithium chloride aqueous solution, refluxing and stirring at 100-110 ℃ for 1-2 hours, centrifuging to remove supernatant, adding carbon nano tubes into lower gel, grinding for 10-16 minutes under the assistance of ultrasound, spraying into a coagulating bath, washing, and drying to obtain thermally-responsive vermiculite fibers;
and S3, fully stirring the silicon rubber matrix, the dispersed graphene oxide, the thermally responsive vermiculite fiber, the reinforcing agent and the auxiliary agent, maintaining a vacuumizing state in the stirring process to remove bubbles in the mixture, adding the silane cross-linking agent and the catalyst, uniformly mixing, forming, and standing at room temperature to obtain the heat dissipation material for the charger housing.
2. The heat dissipating material for a charger baby housing of claim 1, wherein the silicone rubber matrix is a hydroxyl terminated polyorganosiloxane.
3. The heat dissipating material for a charger housing according to claim 1, wherein the silicone rubber substrate is at least one of hydroxyl-terminated polydimethylsiloxane, hydroxyl-terminated polymethylphenylsiloxane, and hydroxyl-terminated polydiphenylsiloxane.
4. The heat dissipating material for a charger baby case according to claim 1, wherein the substitution degree of sodium carboxymethyl cellulose is 0.74 to 0.82 and the polymerization degree DP is 200 to 300.
5. The heat dissipating material for a charger baby case according to claim 1, wherein the reinforcing agent is at least one of carbon black, titanium white, nano calcium carbonate, and nano aluminum oxide.
6. The heat dissipating material for a charger housing of claim 1, wherein the silane cross-linking agent is at least one selected from methyltriacetonyl silane, methyltributylketonyl silane, vinyltributyl ketoxime silane, phenyltributyl ketoxime silane, tetrabutyl ketoxime silane, and phenylmethyltributylketon ketoxime silane.
7. The heat dissipating material for a charger housing according to claim 1, wherein the catalyst is at least one of stannous octoate, dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin diacetate, dibutyltin dimethoxy, dibutyltin oxide, tetra-n-butyl titanate, tetra-isopropyl titanate, tetra (trimethylsiloxy) titanium.
8. The heat dissipating material for a charger baby case according to claim 1, wherein the auxiliary agent comprises: tackifying resin, an active agent, an anti-aging agent and a plasticizer.
9. The heat dissipating material for a charger baby case according to claim 8, wherein the tackifying resin is bisphenol a epoxy resin, modified epoxy resin, liquid styrene-butadiene rubber or liquid nitrile rubber; the active agent is one or two of zinc carbonate, zinc oxide, sodium stearate and magnesium stearate; the anti-aging agent is an anti-aging agent RD, an anti-aging agent DNP, an anti-aging agent BHT or an anti-aging agent 4020; the plasticizer is diisopropyl phthalate, dibutyl oxalate, ethyl acrylate or isopropyl acrylate.
10. A method for preparing the heat dissipation material for a charger baby case according to any one of claims 1 to 9, comprising the steps of:
s1, dispersing graphene oxide in water, adding sodium carboxymethylcellulose under stirring, stirring uniformly under normal-temperature ultrasonic assistance, adjusting the temperature to 60-70 ℃, continuing ultrasonic assistance stirring for 30-50min, cooling rapidly to-10 to-20 ℃, and freeze-drying to obtain dispersed graphene oxide;
s2, adding vermiculite powder into a lithium chloride aqueous solution, refluxing and stirring at 100-110 ℃ for 1-2 hours, centrifuging to remove supernatant, adding carbon nano tubes into lower gel, grinding for 10-16 minutes under the assistance of ultrasound, spraying into a coagulating bath, washing, and drying to obtain thermally-responsive vermiculite fibers;
and S3, fully stirring the silicon rubber matrix, the dispersed graphene oxide, the thermally responsive vermiculite fiber, the reinforcing agent and the auxiliary agent, maintaining a vacuumizing state in the stirring process to remove bubbles in the mixture, adding the silane cross-linking agent and the catalyst, uniformly mixing, forming, and standing at room temperature to obtain the heat dissipation material for the charger housing.
11. The method for manufacturing a heat dissipating material for a charger baby case according to claim 10, wherein in S2, the carbon nanotubes are at least one of single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes.
12. The method for manufacturing a heat dissipating material for a charger baby housing according to claim 10, wherein in S2, the carbon nanotubes are single-walled carbon nanotubes.
13. The method for producing a heat sink for a charger baby case according to claim 10, wherein in S2, the length of the thermally responsive vermiculite fiber is 0.1 to 1mm and the diameter is 10 to 100 μm.
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| CN102234427A (en) * | 2010-04-29 | 2011-11-09 | 比亚迪股份有限公司 | Silicone rubber composition and preparation method of silicone rubber |
| CN104327515A (en) * | 2014-10-20 | 2015-02-04 | 中国科学院金属研究所 | Graphene-containing silicon rubber heat-conducting composite material and preparation method thereof |
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| CN109971123A (en) * | 2019-02-25 | 2019-07-05 | 郭跃 | A kind of preparation method of epoxy-boron nitride composite |
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| US9441076B2 (en) * | 2009-11-12 | 2016-09-13 | The Trustees Of Princeton University | Multifunctional graphene-silicone elastomer nanocomposite, method of making the same, and uses thereof |
| US11641012B2 (en) * | 2019-01-14 | 2023-05-02 | Global Graphene Group, Inc. | Process for producing graphene/silicon nanowire hybrid material for a lithium-ion battery |
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| CN102234427A (en) * | 2010-04-29 | 2011-11-09 | 比亚迪股份有限公司 | Silicone rubber composition and preparation method of silicone rubber |
| CN104327515A (en) * | 2014-10-20 | 2015-02-04 | 中国科学院金属研究所 | Graphene-containing silicon rubber heat-conducting composite material and preparation method thereof |
| CN108395684A (en) * | 2018-03-29 | 2018-08-14 | 合肥佳洋电子科技有限公司 | A kind of preparation method of electronic product casing material |
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