CN116574488B - High-heat-conductivity semi-solid phase-change heat-insulation composite material and preparation method and application thereof - Google Patents
High-heat-conductivity semi-solid phase-change heat-insulation composite material and preparation method and application thereof Download PDFInfo
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- CN116574488B CN116574488B CN202310451592.8A CN202310451592A CN116574488B CN 116574488 B CN116574488 B CN 116574488B CN 202310451592 A CN202310451592 A CN 202310451592A CN 116574488 B CN116574488 B CN 116574488B
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- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000009413 insulation Methods 0.000 title claims abstract description 18
- 239000007787 solid Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000012782 phase change material Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000004020 conductor Substances 0.000 claims abstract description 12
- 238000013329 compounding Methods 0.000 claims abstract description 11
- 239000005022 packaging material Substances 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 239000000835 fiber Substances 0.000 claims description 20
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 11
- 239000003063 flame retardant Substances 0.000 claims description 11
- 238000004806 packaging method and process Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- -1 polypropylene Polymers 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- OTRAYOBSWCVTIN-UHFFFAOYSA-N OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N Chemical compound OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N OTRAYOBSWCVTIN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 3
- 239000006012 monoammonium phosphate Substances 0.000 claims description 3
- 239000002985 plastic film Substances 0.000 claims description 3
- 229920006255 plastic film Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 claims description 2
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 229920006284 nylon film Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims 1
- 230000007480 spreading Effects 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 11
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 239000011810 insulating material Substances 0.000 description 11
- 239000004964 aerogel Substances 0.000 description 10
- 230000008859 change Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000002679 ablation Methods 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- 230000002401 inhibitory effect Effects 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012774 insulation material Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910004856 P—O—P Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- ZGUQGPFMMTZGBQ-UHFFFAOYSA-N [Al].[Al].[Zr] Chemical compound [Al].[Al].[Zr] ZGUQGPFMMTZGBQ-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ZUDYPQRUOYEARG-UHFFFAOYSA-L barium(2+);dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Ba+2] ZUDYPQRUOYEARG-UHFFFAOYSA-L 0.000 description 1
- QHFQAJHNDKBRBO-UHFFFAOYSA-L calcium chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ca+2] QHFQAJHNDKBRBO-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- JWEBAGKDUWFYTO-UHFFFAOYSA-L disodium;hydrogen phosphate;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].OP([O-])([O-])=O JWEBAGKDUWFYTO-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 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
- 230000007246 mechanism Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical class [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- UVGLBOPDEUYYCS-UHFFFAOYSA-N silicon zirconium Chemical compound [Si].[Zr] UVGLBOPDEUYYCS-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- 239000008279 sol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
- H01M10/65—Means for temperature control structurally associated with the cells
- H01M10/659—Means for temperature control structurally associated with the cells by heat storage or buffering, e.g. heat capacity or liquid-solid phase changes or transition
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/066—Cooling mixtures; De-icing compositions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- 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 relates to the technical field of battery safety, in particular to a high-heat-conductivity phase-change heat-insulation composite material for heat spreading protection of a battery module and a preparation method thereof. The invention relates to a high-heat-conductivity semi-solid phase-change heat-insulation composite material, which comprises a framework supporting material, a phase-change material, a heat-conducting material and an insulating packaging material; and the phase change material and the heat conduction material are fixed in the framework supporting material to form a composite material to be packaged in the insulating packaging material, and the heat conduction material is added into the composite material through an in-situ compounding method or a doping compounding method. The invention provides a high-heat-conductivity semi-solid phase-change heat-insulation composite material which has good inhibition and delay effects on heat spreading generated by a thermal runaway battery cell in a battery module.
Description
Technical Field
The invention relates to the technical field of battery safety, in particular to a high-heat-conductivity phase-change heat-insulation composite material for heat spreading protection of a battery module and a preparation method thereof.
Background
With the rapid development of electric vehicles, the safety problem of the power battery system of the electric vehicles is receiving more and more attention. In the whole electric automobile safety accident, the single battery cell thermal runaway is generally caused initially. And a large amount of heat is released in a short time after the thermal runaway of the battery cells, and is transferred to the adjacent battery cells to cause temperature rise so as to generate the thermal runaway, and finally the heat spreads to the battery cells in the whole module and even the whole battery pack, thereby causing disastrous accidents. Therefore, when any cell is out of control, inhibiting or delaying the heat generated by the cell from spreading to the adjacent cell is of great importance to ensuring the life and property safety of passengers.
At present, a great number of heat insulation materials for inhibiting heat spreading in a power battery module are available, and various ceramic fibers, ceramic silica gel materials, aerogel and the like are widely applied to inhibiting or delaying the heat spreading of thermal runaway of battery cells in the module. When the battery is in thermal runaway, the material plays a role in delaying heat transfer by the heat released by the battery in thermal runaway by virtue of the excellent heat insulation performance, so that precious time is provided for passengers to escape. However, from the thermal conservation principle, the energy generated by the thermal runaway battery cell is limited in the battery module, the transfer time of the thermal runaway battery cell is delayed by the heat insulation material, and the thermal runaway of other battery cells is caused to cause the thermal spread of the battery pack finally along with the extension of time. In order to further delay the time of heat spreading or to suppress heat spreading on the basis of the existing conventional heat insulating materials, researchers have introduced phase change materials into the heat insulating materials, and when the heat is out of control, energy is consumed through heat insulation of the heat insulating materials and phase change of the phase change materials.
In patent CN114006105a, jintai et al, SK new technology corporation, a heat absorbing fireproof wall heat insulating material is designed, which comprises a heat absorbing layer composed of a phase change material and a heat insulating layer composed of fibers. In the thermal runaway of the battery, a better effect is achieved. But this design adopts sandwich structure, adopts two-layer fibrous layer and one deck phase change material layer, and because the restriction of space in the battery module is very little for the space that prevents the wall, and phase change material volume introduction is restricted, still needs further improvement to the consumption of thermal runaway heat.
To solve this problem, in patent CN113506935A, university of bloom Feng Xuning, et al, proposed a new heat insulating material for preventing heat spreading of a battery module, which was prepared by compounding a silica sol, a flame retardant and a phase change material with a fibrous base material, and then coating with an insulating film. The composite material has a very high phase change enthalpy value, solves the problem of the quantity of the phase change material, and has a good result on heat spreading in the battery module. However, in the design, the phase change material and the base material are soaked together, so that the flowing phase change material brings great trouble in packaging, and meanwhile, in the process of assembling the battery module, after the flowing liquid phase change material is pressed, the insulating film is easily broken and flows into the module, and the battery cell is short-circuited to cause larger accidents. Therefore, a composite material for suppressing the heat spreading of the battery module was developed without affecting the specific energy and safety in the battery module.
Disclosure of Invention
The invention hopefully provides a high-heat-conductivity semi-solid phase-change heat-insulation composite material which has good inhibition and delay effects on heat spreading generated by a thermal runaway battery cell in a battery module, and the specific scheme is as follows:
a high-heat-conductivity semi-solid phase-change heat-insulation composite material comprises a framework supporting material, a phase-change material, a heat-conducting material and an insulating packaging material; and the phase change material and the heat conduction material are fixed in the framework supporting material to form a composite material to be packaged in the insulating packaging material, and the heat conduction material is added into the composite material through an in-situ compounding method or a doping compounding method.
The framework supporting material is a fiber material with the thickness of 1mm-5mm and comprises zirconia fiber, mullite fiber, silica fiber, alumina fiber, rock wool, aluminum silicate fiber or pre-oxidized fiber, and the fiber porosity is 80% -90%.
The phase change material comprises one or more of silicone oil, silica sol, aluminum sol, zirconium sol, silica-alumina sol, silica-zirconia sol, aluminum-zirconium sol, silica-alumina-zirconia sol, paraffin, calcium chloride hexahydrate, sodium sulfate decahydrate, sodium hydrogen phosphate decahydrate, barium hydroxide octahydrate or magnesium chloride hexahydrate. Preferably, a composite hybridization form of sol and inorganic phase-change materials is adopted, and silica sol is a raw material precursor for forming semisolid gel later, and is used for hybridizing various phase-change materials so as to ensure a higher phase-change enthalpy value.
The insulating packaging material is one or more of an aluminum plastic film, a nylon film, a polyimide film, a polypropylene film, a polyethylene film or a polyvinyl chloride film, and the thickness is 0.05-0.25mm.
The heat conducting material used in the in-situ compounding method is one or more of copper powder, silver powder, carbon black, graphene, aluminum nitride, boron nitride, silicon nitride and magnesium oxide, and the particle size of the heat conducting material is 50-100 mu m; the heat conducting material used in the doping compounding method is one or more of iron net, aluminum net, copper net, carbon fiber and carbon nanotube, and has mesh number of 100-200 mesh and thickness of 0.1-0.5mm.
When the heat conducting material is added into the composite material by an in-situ compounding method, the specific steps are as follows: the phase change material, the infrared shielding agent, the flame retardant and the heat conducting material are uniformly stirred to obtain a solution, the pH value is regulated to 4.2-5.8, then the framework supporting material is immersed in the solution, the temperature is kept at 20-70 ℃, the composite material is taken out, and the composite material is packaged by an insulating film for packaging.
When the heat conducting material is added into the composite material by a doping composite method, the specific steps are as follows: uniformly stirring the phase change material, the infrared shielding agent and the flame retardant, regulating the pH to 4.2-5.8 to obtain a solution, immersing the framework supporting material of the composite heat conduction material into the solution, preserving heat at 20-70 ℃, taking out the composite material, and packaging with an insulating film for packaging.
The infrared shielding agent is one or more of titanium dioxide, silicon carbide, carbon powder and potassium hexatitanate whisker.
The flame retardant is one or more of monoammonium phosphate, tri (2, 3-dibromopropyl) phosphate, thiophosphoric acid triisocyanate, urea, ammonium pentaborate, ammonium bicarbonate or melamine cyanurate.
The high-heat-conductivity semi-solid phase-change heat-insulation composite material is applied to a battery module.
Compared with the prior art, the semi-solid phase-change heat-insulating composite material with high heat conductivity is convenient to package and solves the breaking risk. Meanwhile, in order to improve heat conduction between the phase change materials, the heat conducting substance is introduced to ensure that the composite material can rapidly diffuse heat to the phase change materials when the composite material is in thermal runaway, and the heat is transferred out of the battery module through the phase change process of the phase change materials in a short time. Meanwhile, after the phase change material is consumed, the porous heat insulation material can also have a good heat insulation effect. The phase-change heat-insulating material has good effects of inhibiting and delaying the heat spreading generated by the thermal runaway battery cells in the battery module through inhibiting the phase-change heat transfer and the heat transfer.
The invention relates to a semi-solid phase-change heat-insulation composite material, which is formed by fixing a phase-change material in a framework supporting material in a gel form and encapsulating the composite material in an insulating encapsulation material. The method is characterized in that the phase-change material is soaked in the matrix material (framework supporting material) in a spraying or dip-coating mode, the pH value is adjusted to form gel, the gel contains continuous nano or micro holes, and the phase-change material is bound in the holes, so that the method is convenient to process, package and solve the breaking risk. Meanwhile, after the phase change material is consumed, the porous heat insulation material formed between the base material and the gel can also have a good heat insulation effect. In the thermal runaway process, the phase-change material is used for rapidly transferring heat generated by the runaway battery cell into the module, and meanwhile, the porous heat-insulating material formed by the matrix material and the gel after high-temperature drying can effectively prevent the heat generated by the runaway battery cell from being transferred to the adjacent battery cell. The semi-solid phase change heat insulation material can effectively inhibit and delay the heat spreading generated by the thermal runaway battery core in the battery module under the dual functions of heat dissipation and heat insulation.
Drawings
Fig. 1 is a diagram of a high thermal conductivity semi-solid phase change heat insulation composite material package.
FIG. 2 is a graph of thermal ablation of an aerogel of examples and comparative examples.
Detailed Description
Example 1
In the embodiment, aluminum silicate fiber is used as a matrix, 50g of silica sol is dispersed in 100g of water, then 5g of titanium dioxide powder, 3g of monoammonium phosphate, 2g of ammonium bicarbonate and 2g of carbon powder are sequentially added, the mixture is uniformly stirred, and the pH is regulated to 4.5 by dilute sulfuric acid, so that a solution is obtained. Then soaking aluminum silicate fiber in the solution, preserving heat at 60 ℃ for 30min, taking out the composite material, and packaging with an aluminum plastic film with the thickness of 0.15mm to obtain a phase change composite material finished product with the density of 1.2g/cm 3 。
According to the embodiment, the ammonium dihydrogen phosphate and nitrogen-phosphorus synergistic flame-retardant mechanism can realize the comprehensive effects of condensed phase flame retardance and gas phase flame retardance, and the method is characterized in that the flame retardant is heated, decomposed and absorbed to generate inorganic acids such as phosphoric acid and polyphosphoric acid, a layer of non-volatile protective film can be formed on the surface of a flame-retardant substrate, so that air is isolated, ammonia, nitrogen, water vapor, deep nitrogen oxides and other non-combustible gases are easily emitted after being heated, the gases block the supply of oxygen, and most of heat is taken away together with the decomposition and absorption of the flame retardant, so that the surface temperature of the flame-retardant substrate is greatly reduced; most of the phosphorus oxides and nitrogen compounds form P-N-P and P-O-P, a paste with a coked carbon structure is formed through chemical bonds such as P-C and is remained in the residual carbon to generate a covering effect, and the chain reaction of combustion is interrupted, so that the combustion of a base material is effectively inhibited, PO is formed when the base material is combusted, and the PO can be combined with H and HO free radicals in a flame area to play a role in inhibiting flame.
Example 2
In the embodiment, glass fiber is used as a matrix, 50g of silicon-aluminum composite sol is dispersed in 100g of water, then 10g of silicon carbide powder, 8g of ammonium pentaborate and 0.5g of copper powder are sequentially added, uniformly stirred, and the pH is regulated to 5.0 by dilute sulfuric acid to obtain a solution. Then the glass fiber is immersed in the solution, the temperature is kept for 30min at 60 ℃, the composite material is taken out, and is packaged by polyimide with the thickness of 0.15mm, thus obtaining the finished product of the phase-change composite material with the density of 1.1g/cm 3 。
Example 3
In the embodiment, aluminum silicate fiber is used as a matrix, and an iron net with the thickness of 0.15mm is compounded in advance. 50g of silicon-zirconium composite sol is dispersed in 100g of water, then 5g of potassium hexatitanate whisker and 5g of melamine cyanurate are sequentially added, the mixture is stirred uniformly, and the pH is regulated to 4.5 by dilute sulfuric acid, so as to obtain a solution. Then immersing aluminum silicate fibers of the composite iron net into the solution, preserving heat for 30min at 60 ℃, taking out the composite material, and packaging with a polypropylene film with the thickness of 0.15mm to obtain a finished product of the phase-change composite material with the density of 1.15g/cm 3 。
Comparative example 1
The ceramic fiber aerogel, the glass fiber aerogel and the pre-oxidized fiber aerogel with the same thickness in the market are used as comparison samples for carrying out a thermal ablation experiment.
Table 1 list of experimental data for thermal ablation of examples and comparative examples
As can be seen from table 1, the glass fiber aerogel and the pre-oxidized fiber aerogel of the same thickness directly burn through the sample during thermal ablation at around 1100 ℃. The phase-change heat-insulating material and the ceramic fiber aerogel are not burnt through, and compared with the temperature difference of the phase-change heat-insulating material and the ceramic fiber aerogel, the phase-change heat-insulating material has a heat-insulating effect superior to that of the aerogel heat-insulating material with the same thickness.
Examples 4-6 (the following examples are for studying the effect of pH on the present application)
Examples 4-6 are otherwise identical to example 1, except for the pH, as shown in the following table:
table 2 list of experimental data for thermal ablation for examples and comparative examples at different pH
Examples 7-10 (the following examples are for studying the effect of temperature on the present application)
Table 3 list of experimental data for thermal ablation for examples and comparative examples at different temperatures
The foregoing examples are provided for clarity of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (4)
1. A preparation method of a high-heat-conductivity semi-solid phase-change heat-insulation composite material is characterized by comprising the following steps of:
when the heat conducting material is added into the composite material by an in-situ compounding method, the specific steps are as follows: uniformly stirring a phase change material, an infrared shielding agent, a flame retardant and a heat conducting material to obtain a solution, regulating and controlling the pH to 4.2-5.8, then soaking a framework supporting material in the solution, preserving heat at 20-70 ℃, taking out the composite material, and packaging by using an insulating film for packaging;
the high-heat-conductivity semi-solid phase-change heat-insulation composite material comprises a framework supporting material, a phase-change material, a heat-conducting material and an insulating packaging material; the phase change material and the heat conduction material are fixed in the framework supporting material to form a composite material to be packaged in the insulating packaging material, and the heat conduction material is added into the composite material through an in-situ compounding method; the framework supporting material is aluminum silicate fiber with the thickness of 1mm-5mm, and the fiber porosity is 80% -90%; the phase change material is silica sol or silica-alumina sol; the insulating packaging material is one or more of an aluminum plastic film, a nylon film, a polyimide film, a polypropylene film, a polyethylene film or a polyvinyl chloride film, and the thickness is 0.05-0.25mm; the heat conducting material used in the in-situ compounding process is copper powder with the grain size of 50-100 microns.
2. The method for preparing the high-heat-conductivity semi-solid phase-change heat-insulating composite material according to claim 1, which is characterized in that: the infrared shielding agent is one or more of titanium dioxide, silicon carbide, carbon powder and potassium hexatitanate whisker.
3. The method for preparing the high-heat-conductivity semi-solid phase-change heat-insulating composite material according to claim 1, which is characterized in that: the flame retardant is one or more of monoammonium phosphate, tri (2, 3-dibromopropyl) phosphate, thiophosphoric acid triisocyanate, urea, ammonium pentaborate, ammonium bicarbonate or melamine cyanurate.
4. The use of the high-heat-conductivity semi-solid phase-change heat-insulating composite material prepared by the preparation method of the high-heat-conductivity semi-solid phase-change heat-insulating composite material in a battery module.
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