CN109486472B - Capsule type phase change energy storage material and preparation method thereof - Google Patents
Capsule type phase change energy storage material and preparation method thereof Download PDFInfo
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- CN109486472B CN109486472B CN201710808853.1A CN201710808853A CN109486472B CN 109486472 B CN109486472 B CN 109486472B CN 201710808853 A CN201710808853 A CN 201710808853A CN 109486472 B CN109486472 B CN 109486472B
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- 238000004146 energy storage Methods 0.000 title claims abstract description 80
- 239000011232 storage material Substances 0.000 title claims abstract description 78
- 239000002775 capsule Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 65
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 44
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000005516 engineering process Methods 0.000 claims abstract description 15
- 238000003466 welding Methods 0.000 claims abstract description 13
- 239000012798 spherical particle Substances 0.000 claims abstract description 12
- 238000003825 pressing Methods 0.000 claims abstract description 6
- 238000004806 packaging method and process Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 239000011162 core material Substances 0.000 claims description 14
- 229920006254 polymer film Polymers 0.000 claims description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims description 13
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000004812 Fluorinated ethylene propylene Substances 0.000 claims description 10
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229920009441 perflouroethylene propylene Polymers 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000007772 electroless plating Methods 0.000 claims description 9
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- 239000001509 sodium citrate Substances 0.000 claims description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 7
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 239000004317 sodium nitrate Substances 0.000 claims description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims description 6
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 5
- 230000004927 fusion Effects 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 238000005234 chemical deposition Methods 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 239000009719 polyimide resin Substances 0.000 claims description 3
- 239000002897 polymer film coating Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 235000011147 magnesium chloride Nutrition 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- QJGLDKKUHNLMCZ-UHFFFAOYSA-N 1,2-difluoropropane;ethene Chemical compound C=C.CC(F)CF QJGLDKKUHNLMCZ-UHFFFAOYSA-N 0.000 claims 1
- 238000005338 heat storage Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 229920001688 coating polymer Polymers 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 65
- 239000000243 solution Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 17
- 239000012782 phase change material Substances 0.000 description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229920000858 Cyclodextrin Polymers 0.000 description 7
- 229920000877 Melamine resin Polymers 0.000 description 7
- 238000005229 chemical vapour deposition Methods 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 7
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 7
- 239000001116 FEMA 4028 Substances 0.000 description 6
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 6
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 6
- 229960004853 betadex Drugs 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000001112 coagulating effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000003094 microcapsule Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000005639 Lauric acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000007966 viscous suspension Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Images
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- 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
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Dispersion Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention relates to a capsule type phase change energy storage material and a preparation method thereof, which comprises the following steps of (1) pressing inorganic metal salt powder into hemispherical particles by adopting a hydraulic forming technology, welding the hemispherical particles into balls, and then coating polymer films on the spherical particles by adopting the hydraulic forming technology to obtain film-coated phase change energy storage material particles; (2) and (2) performing metal packaging on the phase change energy storage material particles coated by the film in the step (1), namely coating a layer of metal on the surface of the film, and drying to obtain the capsule type phase change energy storage material. The capsule phase change energy storage material prepared by the invention has the advantages of larger granularity, high particle strength, good heat conductivity, high heat storage density, good corrosion resistance and longer service cycle.
Description
Technical Field
The invention belongs to the field of phase change energy storage materials, and particularly relates to a capsule type phase change energy storage material and a preparation method thereof.
Background
The phase-change material realizes heat storage by absorbing or emitting heat when a substance undergoes phase change. The capsule phase change energy storage material (encapsulated phase change materials) is a novel composite material with a core-shell structure formed by coating a layer of film with stable performance on the surface of solid-liquid phase change material particles by applying an encapsulation technology, is particles prepared by using a polymer as a capsule wall and a phase change material as a core material, and has the advantages of high heat storage temperature, small equipment volume, high heat efficiency, constant temperature process of heat release and the like. The temperature of the working source or the surrounding environment of the material can be adjusted and controlled by utilizing the heat storage and release effects of the capsule type phase change energy storage material. The substance which has phase change in the capsule phase change energy storage material is sealed in the capsule, thereby effectively solving the problems of leakage, phase separation, corrosivity and the like of the phase change material, being beneficial to improving the application performance of the phase change material and widening the application field of the phase change heat storage technology.
However, the capsule phase-change energy storage materials currently used in commercialization are still limited, and most of the materials are concentrated in microcapsule phase-change energy storage materials (capsule particle size <1000 μm), and the development of large capsule phase-change energy storage materials (capsule particle size >1000 μm) is insufficient. Meanwhile, the existing capsule-type phase-change energy storage material has the defects that the volume of the phase-change material is expanded after being melted, and a phase-change core material and a capsule wall material react to cause liquid leakage and the like.
CN103468223A discloses a phase change energy storage material big capsule and a preparation method thereof, comprising the following steps: 1) uniformly stirring the phase change material, the alkene monomer containing unsaturated double bonds and the initiator at 40-100 ℃ to obtain a uniform oil phase solution; then adding expanded graphite micro powder into the oil phase solution to ensure that the expanded graphite is saturated and adsorbs the oil phase solution, and finally obtaining a mixture; 2) adding the mixture finally obtained in the step 1) into a water-soluble polymer aqueous solution, and fully stirring and emulsifying to obtain a suspension mixed solution; standing and defoaming the suspension mixed solution after reaction to obtain a viscous suspension; 3) and (3) dropwise adding the viscous suspension into a coagulating bath while stirring, coagulating into balls, filtering, washing and drying to obtain the phase change energy storage material macrocapsule. The material has better heat conductivity, but only uses the polymer of unsaturated alkene monomers as the capsule wall material, the particle strength is limited, and the application range is not wide; and the phase-change material is stored by using the expanded graphite micro powder, and after a plurality of cycle periods, the molten phase-change material is easy to seep out from the graphite gap, so that the liquid leakage phenomenon is caused, and the capsule wall is damaged.
CN103194181A discloses a spherical controllable beta-cyclodextrin/melamine resin-TiO2The preparation method of the nanometer phase change energy storage material takes beta-cyclodextrin/melamine resin as the wall material of a phase change nanometer capsule, and simultaneously a certain amount of TiO is added into the wall material2Lauric acid is taken as a core material; under certain conditions, the reaction is carried out by adopting an in-situ polymerization method to prepare the spherical nano phase change energy storage capsule material. The diameter of the spherical phase change energy storage capsule material prepared by the method is about 40nm, the highest content of 52.15% of core materials in 1g of capsule material can be achieved, the enthalpy value can reach 91.70J/g, and the capsule breakage rate is 11.3% at least. The microcapsule has limited coating rate on the phase change material, and lauric acid is taken as a core material, and in the long-term use process, the-COOH functional group contained in the microcapsule is easy to react with beta-ketoneThe cyclodextrin/melamine resin causes acidification, resulting in breakage of the wall material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a capsule type phase change energy storage material and a preparation method thereof. The capsule phase change energy storage material prepared by the invention has the advantages of larger granularity, high particle strength, good heat conductivity, high heat storage density, good corrosion resistance and longer service cycle.
The preparation method of the capsule type phase change energy storage material provided by the invention comprises the following steps:
(1) pressing inorganic metal salt powder into hemispherical particles by adopting a hydraulic forming technology, welding the hemispherical particles into balls, and then coating polymer films on the spherical particles by adopting the hydraulic forming technology to obtain film-coated phase change energy storage material particles;
(2) and (2) performing metal packaging on the phase change energy storage material particles coated by the film in the step (1), namely coating a layer of at least one of IB-VIIB group and VIII group metals on the surface of the film, and drying to obtain the capsule type phase change energy storage material.
In the step (1), the inorganic metal salt is selected from nitrate, chloride and the like of alkali metal or alkaline earth metal, for example, one or more of lithium nitrate, sodium nitrate, potassium nitrate, sodium chloride, magnesium chloride and the like, and the particle diameter of the inorganic metal salt powder is 100 to 200 μm.
In the step (1), pressing inorganic metal salt powder into hemispherical particles by adopting a hydraulic forming technology, wherein the hydraulic pressure is 750N-1200N, and preferably 850N-1000N; the hydraulic temperature is 20-30 ℃, and the molding time is 2.5-5 min. The diameter of the hemispherical grains is 5mm to 35mm, preferably 15mm to 25 mm.
In the step (1), hemispherical particles are welded into spheres by adopting a hot air nozzle welding mode, wherein the flow rate of hot air for welding by the hot air nozzle is 25 mL/min-50 mL/min, preferably 30 mL/min-40 mL/min; the temperature of the hot air is 250-450 ℃, preferably 300-350 ℃.
In the step (1), the polymer film coating the spherical particles is one or more selected from polyvinylidene fluoride films, polyimide resin films, polytetrafluoroethylene films, fluorinated ethylene propylene films and the like, preferably a polytetrafluoroethylene and fluorinated ethylene propylene composite film, and the mass ratio of the two films is 1: 0.5-1: 5, preferably 1: 1-1: 2.5. The polymer composite film is used as the capsule wall material, so that the defect of chemical reaction between the capsule wall material and the phase-change core material is thoroughly overcome, and the composite capsule wall material has the advantages of high elasticity, high temperature resistance (> 500 ℃) and the like, has better expansibility along with melting of the phase-change core material, and can form a reserved phase-change space after primary melting.
In the step (1), the mass ratio of the inorganic metal salt powder to the polymer film is (3-15): 1, preferably (8-12): 1. coating a polymer film on the spherical particles by adopting a hydraulic forming technology, wherein the hydraulic pressure is 750N-1300N, and preferably 900N-1100N; the molding temperature is 250-500 ℃, preferably 300-400 ℃; the molding time is 5min to 30min, preferably 8min to 13 min.
In the step (2), the metal package is to coat a layer of at least one of group IB-VIIB and group VIII metals, such as one or more of nickel, chromium, zinc, and the like, preferably nickel, on the surface of the film. Coating metal on the surface of the film by a chemical deposition technology, wherein the chemical deposition technology belongs to a chemical vapor deposition process, and the specific operation is that the phase change energy storage material particles coated by the film obtained in the step (1) are placed into an electroless plating solution at the temperature of 30-90 ℃, preferably 45-60 ℃, the plating time is 2.5-8.5 min, preferably 4-6 min, and the deposition thickness of the metal is 1-12 μm, preferably 2.5-7.5 μm. The metal salt ions in the plating solution are selected from one or more of metal nickel ions, metal chromium ions, metal zinc ions and the like, preferably metal nickel ions, and the metal salt ions in the plating solution are reduced into simple substance metal under the action of a catalyst to be deposited on the surface of the film. The following formulation of electroless plating bath is preferably employed: the mass ratio of the phase change energy storage material particles coated by the film, metal salt, sodium hypophosphite (reducing agent), sodium citrate (complexing agent), ammonia water (pH regulator), deionized water and sodium tetrachloropalladate (catalyst) is 1: (1.5-3.5): (2-4): (0.6-1.5): (1.7-3.5): (800-1200): (0.005-0.01), wherein the mass concentration of the ammonia water is 20-35 wt%.
In the step (2), the drying temperature is 300-350 ℃, and the drying time is 40-150 min.
The capsule type phase change energy storage material is prepared by the method. The prepared capsule type phase change energy storage material has the particle diameter of 1000-100000 mu m, the coating rate of the phase change core material of 83-93 percent and the particle strength of 92N cm-1～107N·cm-1Latent heat of fusion of 135.6 kJ/kg-1～198.6kJ·kg-1The melting temperature is 299.15-299.33 ℃, and the latent heat of fusion is 135.1 kJ kg after 2000 cycles-1～198kJ·kg-1The melting temperature is 298.01-298.63 ℃, and no liquid leakage exists after 2000 cycles.
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, inorganic metal salt is selected as the phase-change material, and the synergistic effect of polymer coating and metal packaging effectively solves the problem of volume expansion of the phase-change material in the melting process, overcomes the chemical reaction between the inorganic metal salt and the capsule wall material, enhances the particle strength of the capsule type phase-change energy storage material, and improves the application range of the capsule type phase-change energy storage material. The finally prepared capsule type phase change energy storage material has large granularity (not less than 1000 mu m), and overcomes the defects of low coating rate (generally less than 50%) and poor mechanical strength of the microcapsule phase change energy storage material.
(2) The capsule phase-change energy storage material prepared by the invention has better particle strength and corrosion resistance than similar products because the metal film is encapsulated on the outer layer of the polymer film, and the service cycle is longer.
(3) The capsule phase-change energy storage material prepared by the invention has good thermal conductivity, high heat storage density (expressed by phase-change latent heat value), and low consumption, and is convenient for large-scale popularization and application.
Drawings
FIG. 1 is a hydroformed hemispherical grain of inorganic metal salt of example 1;
FIG. 2 is a phase change energy storage material particle coated with a polymer film of example 1;
fig. 3 shows the finally obtained capsule-type phase change energy storage material of example 1.
Detailed Description
The following examples further illustrate the capsule phase change material and the method for preparing the same, but should not be construed as limiting the invention thereto.
Example 1
Weighing 90g of sodium nitrate powder with the particle size of 100 mu m, performing hydraulic forming for 3min under the pressure of 900N and the temperature of 25 ℃ to obtain hemispherical particles with the diameter of 15mm, and welding the hemispherical particles into balls in a hot air nozzle welding mode at the temperature of 300 ℃ and the hot air flow rate of 30 mL/min. Weighing 10g of polytetrafluoroethylene and fluorinated ethylene propylene composite film with the mass ratio of 1:1, coating the spherical particles, and carrying out hydraulic forming at 350 ℃ under 1000N pressure for 8min to obtain the film-coated phase change energy storage material particles.
Adding 10g of film-coated phase-change energy storage material particles, 20g of nickel sulfate hexahydrate, 20g of sodium hypophosphite, 10g of sodium citrate, 20g of ammonia water with the mass concentration of 30wt% and 0.05g of sodium tetrachloropalladate into 10000g of deionized water to prepare an electroless plating solution, and obtaining nickel deposition-coated particles with the thickness of 5 mu m through a chemical vapor deposition process at 45 ℃ for 5 min; drying at 320 ℃ for 50min to obtain the capsule type phase change energy storage material A.
Example 2
120g of sodium nitrate powder with the particle size of 100 mu m is weighed, is hydraulically molded into hemispherical particles with the diameter of 25mm through 3min at the pressure of 1000N and the temperature of 30 ℃, and the hemispherical particles are welded into spheres through a hot air nozzle welding mode under the conditions of 350 ℃ and the hot air flow rate of 40 mL/min. Weighing 10g of a polytetrafluoroethylene and fluorinated ethylene propylene composite film with the mass ratio of 1:2.5, coating the spherical particles, and carrying out hydraulic forming at 350 ℃ under 1000N pressure for 13min to obtain the film-coated phase change energy storage material particles.
Adding 10g of film-coated phase change energy storage material particles, 20g of nickel sulfate hexahydrate, 20g of sodium hypophosphite, 10g of sodium citrate, 20g of ammonia water with the mass concentration of 30wt% and 0.05g of sodium tetrachloropalladate into 10000g of deionized water to prepare an electroless plating solution, and obtaining nickel deposition-coated particles with the thickness of 4.5 mu m through a chemical vapor deposition process at 60 ℃ for 4 min; and drying at 320 ℃ for 50min to obtain the capsule phase change energy storage material B.
Example 3
150g of sodium nitrate powder with the particle size of 100 mu m is weighed, is shaped into hemispherical particles with the diameter of 35mm through hydraulic forming for 5min under the pressure of 1200N and the temperature of 30 ℃, and the hemispherical particles are welded into spheres through a hot air nozzle welding mode under the conditions of 450 ℃ and the hot air flow rate of 50 mL/min. Weighing 10g of a polytetrafluoroethylene and fluorinated ethylene propylene composite film with the mass ratio of 1:0.5, coating the spherical particles, and carrying out hydraulic forming at 500 ℃ under 1200N pressure for 20min to obtain the film-coated phase change energy storage material particles.
Adding 10g of film-coated phase-change energy storage material particles, 20g of nickel sulfate hexahydrate, 20g of sodium hypophosphite, 10g of sodium citrate, 20g of ammonia water with the mass concentration of 30wt% and 0.05g of sodium tetrachloropalladate into 10000g of deionized water to prepare an electroless plating solution, and obtaining nickel deposition-coated particles with the thickness of 10 mu m through a chemical vapor deposition process at 80 ℃ for 5 min; and drying at 320 ℃ for 50min to obtain the capsule phase change energy storage material C.
Example 4
50g of sodium nitrate powder with the particle size of 100 mu m is weighed, is shaped into hemispherical particles with the diameter of 9mm through hydraulic forming for 5min under the pressure of 750N and the temperature of 20 ℃, and the hemispherical particles are welded into spheres through a hot air nozzle welding mode under the conditions of 250 ℃ and the hot air flow rate of 25 mL/min. Weighing 10g of polytetrafluoroethylene and fluorinated ethylene propylene composite film with the mass ratio of 1:5, coating the spherical particles, and carrying out hydraulic forming at 250 ℃ under 750N pressure for 10min to obtain the film-coated phase change energy storage material particles.
Adding 10g of film-coated phase change energy storage material particles, 20g of nickel sulfate hexahydrate, 20g of sodium hypophosphite, 10g of sodium citrate, 20g of ammonia water with the mass concentration of 30wt% and 0.05g of sodium tetrachloropalladate into 10000g of deionized water to prepare an electroless plating solution, and obtaining nickel deposition-coated particles with the thickness of 1.5 mu m through a chemical vapor deposition process at 30 ℃ for 5 min; and drying at 320 ℃ for 50min to obtain the capsule phase change energy storage material D.
Example 5
The preparation method and the operating conditions were the same as in example 1, except that lithium nitrate was used as the inorganic metal salt. And obtaining the capsule type phase change energy storage material E.
Example 6
The preparation method and the operation conditions are the same as example 1, except that the inorganic metal salt is potassium nitrate. And obtaining the capsule type phase change energy storage material F.
Example 7
The preparation method and the operation conditions are the same as those of example 1, except that sodium chloride is used as the inorganic metal salt. And obtaining the capsule type phase change energy storage material G.
Example 8
The preparation method and the operation conditions are the same as those of example 1, except that magnesium chloride is used as the inorganic metal salt. And obtaining the capsule type phase change energy storage material H.
Example 9
The preparation method and the operation conditions were the same as in example 1, except that 10g of polytetrafluoroethylene film was used as the polymer film. And obtaining the capsule type phase change energy storage material I.
Example 10
The preparation method and the operating conditions were the same as in example 1, except that a 10g fluorinated ethylene propylene film was used as the polymer film. And obtaining the capsule type phase change energy storage material J.
Example 11
The preparation method and the operation conditions were the same as those of example 1, except that 10g of polyvinylidene fluoride film was used as the polymer film. And obtaining the capsule type phase change energy storage material K.
Example 12
The preparation method and the operating conditions were the same as in example 1 except that 10g of the polyimide resin film was used as the polymer film. And obtaining the capsule type phase change energy storage material L.
Example 13
The preparation method and the operating conditions were the same as in example 1, except that nickel sulfate hexahydrate was replaced by zinc nitrate hexahydrate. And obtaining the capsule type phase change energy storage material M.
Example 14
The preparation method and the operating conditions were the same as in example 1, except that nickel sulfate hexahydrate was replaced by chromium nitrate nonahydrate. And obtaining the capsule type phase change energy storage material N.
Example 15
The preparation method and the operation conditions are the same as those of the example 1, except that: in the process of preparing the electroless plating solution, the dosage of nickel sulfate hexahydrate is increased to 30g, the dosage of sodium hypophosphite is increased to 30g, the dosage of sodium citrate is increased to 15g, the dosage of ammonia water with the mass concentration of 30wt% is increased to 30g, and the dosage of deionized water is reduced to 8000g, so that the capsule type phase change energy storage material O is obtained.
Example 16
The preparation method and the operation conditions are the same as those of the example 1, except that: and (3) respectively increasing the temperature and the time to 70 ℃ and 8min in the chemical vapor deposition process, respectively increasing the drying temperature and the drying time to 350 ℃ and 100min, respectively increasing the thickness of the nickel deposition film to 11 mu m, and thus obtaining the capsule type phase change energy storage material P.
Comparative example 1
The preparation method and the operation conditions are the same as those of the example 1, except that: the step of coating a polytetrafluoroethylene and fluorinated ethylene propylene composite film is omitted, and nickel plating coating is directly carried out by adopting chemical vapor deposition to obtain the capsule type phase change energy storage material Q.
Comparative example 2
The preparation method and the operation conditions are the same as those of the example 1, except that: and (4) no metal is plated to obtain the capsule type phase change energy storage material R.
Comparative example 3
The preparation method and the operation conditions are the same as those of the example 1, except that: and the phase-change material adopts paraffin to obtain the capsule type phase-change energy storage material S.
Comparative example 4
According to the method described in CN103468223A, 50g of molten n-octadecane, 40g of methyl methacrylate, 10g of 1, 4-butanediol diacrylate and 0.5g of azobisisobutyronitrile are put into a 250mL three-necked flask and stirred uniformly at room temperature to obtain an oil phase solution; then 10g of expanded graphite is poured into the flask under stirring, and the flask is vacuumized to ensure that the oil phase fully enters the graphite pores. And adding the compound of the expanded graphite absorbing the oil phase into 200g of styrene maleic anhydride copolymer salt aqueous solution with the concentration of 10wt%, emulsifying at a high speed of 500rpm for 15min, defoaming in vacuum, dropwise adding into 5wt% of calcium chloride coagulating liquid, and adjusting the pH value of the coagulating bath to 3 to obtain the capsule phase-change energy storage material T.
Comparative example 5
According to the method described in CN103194181A, 2.5g of melamine and 20mL of distilled water are placed in a three-mouth bottle with a stirrer, triethanolamine is added dropwise until the pH value of the solution is 8, then 3.7mL of 37% formaldehyde aqueous solution is added, and a reaction container is closed to obtain a mixed solution of formaldehyde and melamine; dissolving 0.8g of beta-cyclodextrin in a certain amount of distilled water to prepare a beta-cyclodextrin solution, adding the beta-cyclodextrin solution into a mixed solution of formaldehyde and melamine, stirring for 10min in an ice-water bath, adding a titanium dioxide solution, stirring for 20min to obtain a heterogeneous uniform solution of formaldehyde, melamine, beta-cyclodextrin and titanium dioxide, and pouring the heterogeneous uniform solution into a dropping funnel; adding 6g of lauric acid into 10mL of distilled water, heating to melt, taking out, adding 0.3g of emulsifier and 30mL of cyclohexane solution, and dispersing at high speed for 10min to obtain a core material emulsion; and (3) placing the core material emulsion into a three-necked bottle, dropwise adding the multiphase uniform solution into a constant-temperature water bath at 80 ℃, filtering, washing and drying to obtain a white powdery product U.
Test example 1
The physical and chemical properties of the capsule-type phase-change energy storage materials of examples 1 to 16 and comparative examples 1 to 5 were measured, and the specific results are shown in table 1. The phase change latent heat value and the phase change temperature of the capsule phase change energy storage material are measured by a DSC-60 type differential scanning calorimeter of Shimadzu corporation in Japan, and the test conditions are that the temperature is increased at the rate of 5 ℃ per minute under the constant high-purity nitrogen flow rate (20 mL/min), and the temperature is increased from room temperature to 400 ℃ and then the temperature is increased. The particle strength was measured by a KQ-3 particle strength measuring apparatus, a Nanjing Ke-Tou Analyzer Co., Ltd, under conditions of room temperature and relative humidity of 50%. The calculation formula of the coating rate of the phase-change core material is (mass of the phase-change material/phase-change material particles coated by the film) multiplied by 100%.
TABLE 1 physicochemical Properties of Capsule-type phase-Change energy-storage Material
As can be seen from the table 1, the capsule-type phase-change energy storage material prepared by the invention effectively prevents the chemical reaction between the capsule wall material and the phase-change core material due to the double-layer encapsulation mode, and has no liquid leakage phenomenon after 2000 times of heat absorption-heat release cycle tests. The capsule phase change energy storage material has high particle strength which is generally more than 90N cm-1This is not achieved by the current similar products. Meanwhile, the coating rate of the phase change core material is increased to more than 85% by adopting a high molecular polymer film coating mode, so that the application range of the product is expanded, and the durability is improved.
Claims (11)
1. A preparation method of a capsule-type phase-change energy storage material is characterized by comprising the following steps:
(1) pressing inorganic metal salt powder into hemispherical particles by adopting a hydraulic forming technology, welding the hemispherical particles into spheres, and then coating a polymer film on the spherical particles by adopting the hydraulic forming technology, wherein the polymer film is selected from one or more of a polyvinylidene fluoride film, a polyimide resin film, a polytetrafluoroethylene film and an ethylene propylene fluoride film, so as to obtain the film-coated phase change energy storage material particles; the inorganic metal salt is one or more of lithium nitrate, sodium nitrate, potassium nitrate, sodium chloride and magnesium chloride, and the particle size of the inorganic metal salt powder is 100-200 mu m; pressing inorganic metal salt powder into hemispherical particles, wherein the hydraulic pressure is 750N-1200N, the hydraulic temperature is 20-30 ℃, and the molding time is 2.5-5 min; the diameter of the hemispherical grains is 5 mm-35 mm; welding the hemispherical particles into spheres by adopting a hot air nozzle welding mode, wherein the flow rate of hot air for welding by the hot air nozzle is 25 mL/min-50 mL/min, and the temperature of the hot air is 250-450 ℃; the mass ratio of the inorganic metal salt powder to the polymer film is (3-15): 1; coating a polymer film on the spherical particles by adopting a hydraulic forming technology, wherein the hydraulic pressure is 750N-1300N, the forming temperature is 250-500 ℃, and the forming time is 5-30 min;
(2) performing metal packaging on the phase change energy storage material particles coated by the film in the step (1), namely coating a layer of at least one of nickel, chromium and zinc on the surface of the film, and drying to obtain a capsule type phase change energy storage material; coating metal on the surface of the film by a chemical deposition technology, wherein the specific operation is that the phase change energy storage material particles coated by the film obtained in the step (1) are placed into prepared electroless plating solution at the temperature of 30-90 ℃, the plating time is 2.5-8.5 min, and the deposition thickness of the metal is 1-12 mu m; in the electroless plating solution, the mass ratio of the phase change energy storage material particles coated by the film to the metal salt to the sodium hypophosphite to the sodium citrate to the ammonia water to the deionized water to the sodium tetrachloropalladate is 1: (1.5-3.5): (2-4): (0.6-1.5): (1.7-3.5): (800-1200): (0.005-0.01), wherein the mass concentration of the ammonia water is 20-35 wt%.
2. The method of claim 1, wherein: pressing inorganic metal salt powder into hemispherical grains, wherein the hydraulic pressure is 850N-1000N.
3. The method of claim 1, wherein: the diameter of the hemisphere particles is 15 mm-25 mm.
4. The method of claim 1, wherein: in the step (1), the flow rate of hot air welded by the hot air nozzle is 30 mL/min-40 mL/min; the temperature of the hot air is 300-350 ℃.
5. The method of claim 1, wherein: the mass ratio of the inorganic metal salt powder to the polymer film is (8-12): 1.
6. the method according to claim 1 or 5, characterized in that: in the step (1), the polymer film coating the spherical particles is a polytetrafluoroethylene and fluorinated ethylene propylene composite film, and the mass ratio of the polytetrafluoroethylene to the fluorinated ethylene propylene composite film is 1: 0.5-1: 5.
7. The method of claim 6, wherein: the mass ratio of the two films is 1: 1-1: 2.5.
8. The method of claim 1, wherein: the polymer film is coated on the spherical particles by adopting a hydraulic forming technology, the hydraulic pressure is 900N-1100N, the forming temperature is 300-400 ℃, and the forming time is 8-13 min.
9. The method of claim 1, wherein: in step (2), the metal package is formed by coating nickel on the surface of the film.
10. The method of claim 1, wherein: in the step (2), the drying temperature is 300-350 ℃, and the drying time is 40-150 min.
11. A capsule type phase change energy storage material prepared by the method of any one of claims 1 to 10, wherein: the prepared capsule type phase change energy storage material has the particle diameter of 9007-35040 mu m, the coating rate of the phase change core material of 83-93 percent and the particle strength of 92N-cm-1～107N·cm-1Latent heat of fusion of 135.6 kJ/kg-1～198.6kJ·kg-1The melting temperature is 299.15-299.33 ℃, and the latent heat of fusion is 135.1 kJ kg after 2000 cycles-1～198kJ·kg-1The melting temperature is 298.01-298.63 ℃, and no liquid leakage exists after 2000 cycles.
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