CN113969142A - Preparation method of mirabilite-based solid-liquid composite phase-change energy storage material - Google Patents
Preparation method of mirabilite-based solid-liquid composite phase-change energy storage material Download PDFInfo
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- CN113969142A CN113969142A CN202111404137.XA CN202111404137A CN113969142A CN 113969142 A CN113969142 A CN 113969142A CN 202111404137 A CN202111404137 A CN 202111404137A CN 113969142 A CN113969142 A CN 113969142A
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims abstract description 91
- 239000010446 mirabilite Substances 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 239000011232 storage material Substances 0.000 title claims abstract description 40
- 238000004146 energy storage Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000007788 liquid Substances 0.000 title claims abstract description 22
- 239000012782 phase change material Substances 0.000 claims abstract description 61
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 54
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 54
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 46
- 230000008859 change Effects 0.000 claims abstract description 27
- 239000004964 aerogel Substances 0.000 claims abstract description 24
- 239000000017 hydrogel Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 8
- 238000000967 suction filtration Methods 0.000 claims abstract description 7
- 238000005520 cutting process Methods 0.000 claims abstract description 6
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000005516 engineering process Methods 0.000 claims abstract description 4
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 17
- 229960005070 ascorbic acid Drugs 0.000 claims description 12
- 235000010323 ascorbic acid Nutrition 0.000 claims description 12
- 239000011668 ascorbic acid Substances 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- XYQRXRFVKUPBQN-UHFFFAOYSA-L Sodium carbonate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]C([O-])=O XYQRXRFVKUPBQN-UHFFFAOYSA-L 0.000 claims description 10
- 229940018038 sodium carbonate decahydrate Drugs 0.000 claims description 10
- 239000002667 nucleating agent Substances 0.000 claims description 7
- DGLRDKLJZLEJCY-UHFFFAOYSA-L disodium hydrogenphosphate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].OP([O-])([O-])=O DGLRDKLJZLEJCY-UHFFFAOYSA-L 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 229940037003 alum Drugs 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 235000004936 Bromus mango Nutrition 0.000 claims description 2
- 240000007228 Mangifera indica Species 0.000 claims description 2
- 235000014826 Mangifera indica Nutrition 0.000 claims description 2
- 235000009184 Spondias indica Nutrition 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims 1
- 238000007493 shaping process Methods 0.000 claims 1
- 238000004781 supercooling Methods 0.000 abstract description 19
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000012071 phase Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 238000005338 heat storage Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- -1 graphite alkene Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229940123973 Oxygen scavenger Drugs 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- AEDDIBAIWPIIBD-ZJKJAXBQSA-N mangiferin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1C1=C(O)C=C(OC=2C(=CC(O)=C(O)C=2)C2=O)C2=C1O AEDDIBAIWPIIBD-ZJKJAXBQSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 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 2
- 238000013517 stratification Methods 0.000 description 2
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- YWQSXCGKJDUYTL-UHFFFAOYSA-N Mangiferin Natural products CC(CCC=C(C)C)C1CC(C)C2C3CCC4C(C)(C)CCCC45CC35CCC12C YWQSXCGKJDUYTL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229940043357 mangiferin Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The application relates to the technical field of phase change energy storage materials, and particularly discloses a preparation method of a mirabilite-based solid-liquid composite phase change energy storage material, which comprises the following steps: s1, mixing graphene oxide and cuprous oxide powder in a mass ratio of 1-2: 1, uniformly mixing, adjusting the pH value to 10.5, and carrying out hydrothermal reaction to obtain modified nano-graphene composite cuprous oxide hydrogel; s2, washing the modified nano-graphene composite cuprous oxide hydrogel, and freeze-drying to obtain blocky modified nano-graphene composite cuprous oxide aerogel; s3, preparing a mirabilite-based phase change material; and S4, cutting the modified nano-graphene composite cuprous oxide aerogel into a proper size, and then sequentially adopting the dipping and suction filtration technology to adsorb and shape the mirabilite-based phase change material. The preparation method has the advantages of solving the supercooling degree and phase layering phenomenon of the mirabilite phase change energy storage material and prolonging the service life of the phase change energy storage material.
Description
Technical Field
The application relates to the technical field of phase change energy storage materials, in particular to a preparation method of a mirabilite-based solid-liquid composite phase change energy storage material.
Background
With the increasing prominence of the problem of energy shortage and the problem of environmental pollution, the development of renewable energy sources is being promoted. However, renewable energy such as solar energy is usually supplied intermittently, and development and utilization of the renewable energy are severely restricted. The phase-change energy storage material is mainly characterized in that the phase-change property of the material is utilized, heat is absorbed through melting, solidification and heat release so as to store heat energy, and the heat energy is taken as an important means for solving the problem that energy supply is not matched in time and space due to the characteristic that a large amount of heat energy is absorbed or released in the phase-change process, but in practical application, the performance, even the service life and the popularization and utilization of the phase-change energy storage material are influenced undoubtedly by the problems of phase layering, supercooling, leakage and the like.
The supercooling phenomenon is a common problem of a hydrous salt phase change energy storage material, and is mainly caused by the phenomenon that the phase change energy storage material does not generate solidification crystallization phenomenon when reaching the phase change temperature of the phase change energy storage material, but generates solidification crystallization phenomenon again at a certain temperature lower than the phase change temperature point, and simultaneously releases heat while solidifying. However, even if the phase-change material is subjected to a condensation process to release heat, the retardation phenomenon causes the crystallization nucleation degree of the phase-change material to be low, and when the retardation phenomenon is serious, the crystallization is caused to generate an amorphous state, the release energy value is seriously influenced, and the phase-change heat storage density is low; the phase separation phenomenon is that after the hydrous salt phase change energy storage material reaches a certain melting point, the solubility of some salts is not high, so that the insoluble salts are settled at the bottom of the container, and a crystal liquid separation state is formed. When such salts cool, crystals form initially at the settling level of the saturated solution and solids, and finally crystallize upwards in sequence, thus forming a barrier over the unfused salt, preventing the bottom salt from contacting the upper solution, which is the solution, the middle layer of crystalline hydrated salt, and the lower salt, and thus causing delamination.
The mirabilite-based phase change energy storage material is taken as a typical solid-liquid phase change material under the condition of the phase change before and after phase change, the phenomena of phase stratification and supercooling are particularly obvious, so that the service performance of the mirabilite as the phase change energy storage material is obviously reduced, the service life is also obviously shortened, and the popularization and the utilization are not facilitated.
Disclosure of Invention
In order to solve the supercooling degree and the phase stratification phenomenon of the mirabilite phase-change energy storage material, the application provides a preparation method of a mirabilite-based solid-liquid composite phase-change energy storage material.
The preparation method of the mirabilite-based solid-liquid composite phase-change energy storage material adopts the following technical scheme:
a preparation method of a mirabilite-based solid-liquid composite phase-change energy storage material comprises the following steps: s1, mixing graphene oxide and cuprous oxide powder in a mass ratio of 1-2: 1, uniformly mixing, adjusting the pH value to 10.5, and carrying out hydrothermal reaction to obtain modified nano-graphene composite cuprous oxide hydrogel; s2, washing the modified nano-graphene composite cuprous oxide hydrogel, and freeze-drying to obtain blocky modified nano-graphene composite cuprous oxide aerogel; s3, preparing a mirabilite-based phase change material; and S4, cutting the modified nano-graphene composite cuprous oxide aerogel into a proper size, and then sequentially adopting the dipping and suction filtration technology to adsorb and shape the mirabilite-based phase change material.
By adopting the technical scheme, the modified nano-graphene and the cuprous oxide are combined to form the aerogel, so that the carbon aerogel has high adsorbability and high porosity, the adsorption rate is enhanced, and the maximum adsorption capacity can reach 100 times; the cuprous oxide is used as a metal oxide, so that a good anti-corrosion effect can be achieved; the modified nano graphene composite cuprous oxide aerogel has the characteristics of high elasticity, high porosity and high light weight, and the skeleton structure of the aerogel is not lost. This application uses modified nanometer graphite alkene compound cuprous oxide aerogel to adsorb salt cake base phase change material, has realized salt cake base phase change energy storage material's design encapsulation, has solved salt cake phase change material's super-cooled degree and phase layering phenomenon to demonstrate good circulation stability, it is greater than 200J/G to circulate 5000 latent heats of phase transition, has strengthened salt cake base phase change energy storage material's performance, has prolonged life, does benefit to the wide use.
Preferably, in step S1, the hydrothermal reaction temperature is 160 to 200 ℃, and the reaction time is 15 to 18 hours.
By adopting the technical scheme, according to a large amount of experimental data, the compatibility of the modified nano-graphene and the cuprous oxide is better under the reaction temperature and the reaction time, and the obtained modified nano-graphene composite cuprous oxide hydrogel finished product is optimal.
Preferably, in step S1, ascorbic acid is further added to the hydrothermal reaction, and the mass ratio of the ascorbic acid to the cuprous oxide powder is 3-4: 1.
by adopting the technical scheme, the ascorbic acid is added in the hydrothermal reaction of the modified nano-graphene and the cuprous oxide, and the ascorbic acid has good antioxidation, can be combined with oxygen to form an oxygen scavenger, prevents the cuprous oxide from being oxidized to form the cupric oxide, has the action of passivating copper metal ions, and can realize the stable reaction of the cuprous oxide and the modified nano-graphene.
Preferably, in step S3, the mango nitro-phase change material includes a mixture of, by mass, 9: 1 or 7: 3, mirabilite and sodium carbonate decahydrate or the mass ratio of 2: mirabilite 8 and disodium hydrogen phosphate dodecahydrate.
By adopting the technical scheme, compared with the mode that only mirabilite is used as the phase-change heat storage material, sodium carbonate decahydrate or disodium hydrogen phosphate dodecahydrate is added into the mirabilite to form the mirabilite-based phase-change material, the phase-change energy storage effect is better, and the phenomena of phase separation and supercooling of the mirabilite-based phase-change material are not easy to occur.
Preferably, in step S4, the composite phase change energy storage material is prepared by a vacuum impregnation method.
Through adopting above-mentioned technical scheme, utilize the vacuum pump to make the air in the modified nanometer graphite alkene pore be taken out and will modify nanometer graphite alkene and liquid glauber's salt base phase change material mixture, when vacuum environment was destroyed, there was the pressure differential in the modified nanometer graphite alkene pore inside and external environment for liquid awn nitryl phase change material gets into inside the pore. Compared with a direct impregnation method, the vacuum impregnation method can enable the liquid mirabilite-based phase-change material to have larger loading capacity.
Preferably, in step S4, the temperature of the adsorption-forming mirabilite-based phase change material is 40-60 ℃.
By adopting the technical scheme, experiments prove that the modified nano graphene has the best effect of adsorbing the nitro-mango phase change material at the temperature.
Preferably, a nucleating agent is further added into the mirabilite-based phase change material.
By adopting the technical scheme, the extra nucleating agent is added into the mirabilite-based phase-change material, so that the mirabilite-based phase-change material cannot generate solidification and crystallization when reaching the self phase-change temperature, the crystallization nucleation degree of the mirabilite-based phase-change material is improved, the phase-change heat storage density is increased, the supercooling degree of the mirabilite-based phase-change material is reduced, and the energy release value is increased.
Preferably, the nucleating agent is calcium carbonate or alum.
By adopting the technical scheme, calcium carbonate is selected as a nucleating agent, so that the supercooling degree of a mirabilite-based phase change material can be reduced, the porosity of the modified nano-graphene composite cuprous oxide aerogel can be filled, and the rigidity, stability and heat resistance of the aerogel are improved; the alum is selected as the nucleating agent, and has higher latent heat and good thermal conductivity, so that the service life of the mirabilite-based phase change material can be effectively prolonged.
In summary, the present application has the following beneficial effects:
1. according to the method, the modified nano-graphene and the cuprous oxide are combined to form the aerogel, so that the adsorption rate is enhanced, and the maximum adsorption capacity can reach 100 times; the cuprous oxide is used as a metal oxide, so that a good anti-corrosion effect can be achieved; this application uses modified nanometer graphite alkene compound cuprous oxide aerogel to adsorb salt cake base phase change material, has realized salt cake base phase change energy storage material's design encapsulation, has solved salt cake phase change material's super-cooled degree and phase layering phenomenon to demonstrate good circulation stability, it is greater than 200J/G to circulate 5000 latent heats of phase transition, has strengthened salt cake base phase change energy storage material's performance, has prolonged life, does benefit to the wide use.
2. According to the method, the ascorbic acid is added in the hydrothermal reaction of the modified nano-graphene and the cuprous oxide, and the ascorbic acid has a good antioxidation effect, can be combined with oxygen to form an oxygen scavenger, prevents the cuprous oxide from undergoing an oxidation reaction to become the cupric oxide, has the effect of passivating copper metal ions, and can realize a stable reaction of the cuprous oxide and the modified nano-graphene.
3. Compared with the method that only mirabilite is used as the phase-change heat storage material, the sodium carbonate decahydrate or disodium hydrogen phosphate dodecahydrate is added into the mirabilite to form the mirabilite-based phase-change material, the phase-change energy storage effect is better, and the mirabilite-based phase-change material is not easy to generate phase separation and supercooling.
Detailed Description
The present application is further described in detail in connection with the following examples.
Preparation examples of raw materials
Preparation example 1
Preparation of Graphene Oxide (GO)
The preparation method of the graphene oxide suspension (GO) adopts a common Hummers method, and the concentration is 8.4 mg/mL.
Preparation example 2
Preparation of cuprous oxide particles
10mg of copper chloride dihydrate crystals (CuCl) were taken2·2H2O) is dissolved in 15mL of distilled water to form a blue-green solution, 6mL of 2mol/L NaOH solution is added under the stirring state, the solution is precipitated in blue, 12.0mg of ascorbic acid is added after the solution is stirred for 15min, and the stirring is continued for 10min after the solution is completely yellow. And filtering the solution, and drying under a vacuum condition to obtain yellow cuprous oxide particles with the particle diameter of about 30-60 nm.
Examples
Example 1
A preparation method of a mirabilite-based solid-liquid composite phase-change energy storage material comprises the following steps:
s1, taking 4mL of GO solution obtained in preparation example 1, performing ultrasonic treatment for 15min, adding 30mg of cuprous oxide powder and 100mg of ascorbic acid, uniformly stirring, adjusting the pH value to 10.5, transferring the obtained mixed solution into a reaction kettle, and performing hydrothermal reaction for 15h at 160 ℃ to obtain the modified nano-graphene composite cuprous oxide hydrogel.
S2, adding deionized water into the modified nano-graphene cuprous oxide composite hydrogel, cleaning, and freeze-drying to obtain blocky modified nano-graphene cuprous oxide (rGO/Cu)2O) aerogel composite.
S3, weighing 5.4g of mirabilite, 0.6g of sodium carbonate decahydrate and 0.3g of calcium carbonate, putting the materials into a container, adding 5L of water, stirring to fully dissolve the mirabilite and the sodium carbonate decahydrate to obtain the mirabilite-based phase-change material, and heating the mirabilite-based phase-change material to 40 ℃ for later use.
S4, cutting the modified nano-graphene composite cuprous oxide aerogel into square blocks with the side length of 10cm, soaking the square blocks in the mirabilite-based phase change material obtained in the step S3 for 30min, performing suction filtration by using a vacuum pump, so that the modified nano-graphene composite cuprous oxide aerogel adsorbs and shapes the mirabilite-based phase change material, and observing that the mirabilite-based phase change material is completely adsorbed.
Example 2
A preparation method of a mirabilite-based solid-liquid composite phase-change energy storage material comprises the following steps:
s1, taking 4mL of GO solution obtained in preparation example 1, performing ultrasonic treatment for 15min, adding 30mg of cuprous oxide powder and 110mg of ascorbic acid, uniformly stirring, adjusting the pH value to 10.5, transferring the obtained mixed solution into a reaction kettle, and performing hydrothermal reaction for 16h at 180 ℃ to obtain the modified nano-graphene composite cuprous oxide hydrogel.
S2, adding deionized water into the modified nano-graphene cuprous oxide composite hydrogel, cleaning, and freeze-drying to obtain blocky modified nano-graphene cuprous oxide (rGO/Cu)2O) aerogel composite.
S3, weighing 4.2g of mirabilite, 1.8g of sodium carbonate decahydrate and 0.2g of alum, putting the materials into a container, adding 5L of water, stirring to fully dissolve the mirabilite and the sodium carbonate decahydrate to obtain a mirabilite-based phase-change material, and heating the mirabilite-based phase-change material to 50 ℃ for later use.
S4, cutting the modified nano-graphene composite cuprous oxide aerogel into square blocks with the side length of 10cm, soaking the square blocks in the mirabilite-based phase change material obtained in the step S3 for 30min, performing suction filtration by using a vacuum pump, so that the modified nano-graphene composite cuprous oxide aerogel adsorbs and shapes the mirabilite-based phase change material, and observing that the mirabilite-based phase change material is completely adsorbed.
Example 3
A preparation method of a mirabilite-based solid-liquid composite phase-change energy storage material comprises the following steps:
s1, taking 4mL of GO solution obtained in preparation example 1, performing ultrasonic treatment for 15min, adding 30mg of cuprous oxide powder and 120mg of ascorbic acid, uniformly stirring, adjusting the pH value to 10.5, transferring the obtained mixed solution into a reaction kettle, and performing hydrothermal reaction for 18h at 200 ℃ to obtain the modified nano-graphene composite cuprous oxide hydrogel.
S2, adding deionized water into the modified nano-graphene cuprous oxide composite hydrogel, cleaning, and freeze-drying to obtain blocky modified nano-graphene cuprous oxide (rGO/Cu)2O) aerogel composite.
S3, weighing 1.8g of mirabilite, 4.8g of disodium hydrogen phosphate dodecahydrate and 0.3g of calcium carbonate respectively, putting the materials into a container, adding 5L of water, stirring to fully dissolve the mirabilite and the sodium carbonate decahydrate to obtain the mirabilite-based phase change material, and heating the mirabilite-based phase change material to 60 ℃ for later use.
S4, cutting the modified nano-graphene composite cuprous oxide aerogel into square blocks with the side length of 10cm, soaking the square blocks in the mirabilite-based phase change material obtained in the step S3 for 30min, performing suction filtration by using a vacuum pump, so that the modified nano-graphene composite cuprous oxide aerogel adsorbs and shapes the mirabilite-based phase change material, and observing that the mirabilite-based phase change material is completely adsorbed.
Comparative example
Comparative example 1
The difference from example 2 is that only mirabilite is present in the mirabilite-based phase change material.
Comparative example 2
The difference from the embodiment 2 is that the step S1 is omitted, the modified nano-graphene is directly selected as an adsorbent, and the glauber' S salt-based phase-change material is adsorbed and shaped by adopting the impregnation and suction filtration technologies in sequence.
Performance test
1. And detecting the phase change latent heat value of the molded and packaged nitro-mango phase change material after circulation for many times by taking one-time heat absorption and one-time heat release as a one-time phase change process.
2. And detecting the supercooling degree of the nitro-nitro phase change material at a specific temperature.
Test method
1. The solid-liquid phase change latent heat of the formed and packaged Mangiferin phase change material is measured by a temperature difference type heat flux calorimeter method, a German relaxation-resistant NETZSCHDAC 200F3 Differential Scanning Calorimeter (DSC) is adopted to carry out thermal performance test on a phase change material sample, and the phase change latent heat value, nitrogen atmosphere (50mL/min) and temperature rising and falling rate of 1.0 ℃/min of the material are measured; the specific determination method refers to the experimental study of the phase transition temperature and the phase transition latent heat of the square noble silver and the cold storage material [ J ]. the low temperature and the special gas, 2000, 18(5):20-22.
2. Testing the supercooling degree of the mirabilite-based phase change material by adopting a T-history method, performing multiple circulation processes of heat absorption melting and heat release crystallization on the mirabilite-based phase change material to be tested, and controlling the first residence time and the second residence time of the nitrone phase change material in a molten state in the multiple circulation processes, wherein the second residence time is more than 3 hours longer than the first residence time; respectively measuring a first supercooling degree of the first retention time and a second supercooling degree corresponding to the second retention time; and calculating the difference value threshold of the first supercooling degree and the second supercooling degree to obtain the supercooling degree of the mirabilite-based phase change material.
TABLE 1
It can be seen by combining example 2 and comparative example 1 and table 1 that if mirabilite is used as all the mirabilite-based phase change materials, the supercooling degree is obviously high, and the supercooling degree of the mirabilite-based phase change material formed by adding sodium carbonate decahydrate or disodium hydrogen phosphate dodecahydrate into the mirabilite according to a certain proportion is below 1.0 ℃, which shows that the problem of high supercooling degree is well solved.
By combining the example 2 and the comparative example 2 and the table 1, it can be seen that the mirabilite-based phase-change material is shaped and packaged by adopting the modified nano-graphene composite cuprous oxide aerogel, after multiple cycles of heat absorption melting and heat release crystallization, the phase-change latent heat value changes little, the phase-change latent heat value remains more than 200J/G after 2000 cycles, the phase-change latent heat value changes greatly after the mirabilite-based phase-change material is directly shaped and packaged by adopting the modified nano-graphene, and the phase-change latent heat value is reduced to 153J/G after 2000 cycles.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (8)
1. A preparation method of a mirabilite-based solid-liquid composite phase-change energy storage material is characterized by comprising the following steps: the method comprises the following steps:
s1, mixing graphene oxide and cuprous oxide powder in a mass ratio of 1-2: 1, uniformly mixing, adjusting the pH value to 10.5, and carrying out hydrothermal reaction to obtain modified nano-graphene composite cuprous oxide hydrogel;
s2, washing the modified nano-graphene composite cuprous oxide hydrogel, and freeze-drying to obtain blocky modified nano-graphene composite cuprous oxide aerogel;
s3, preparing a mirabilite-based phase change material;
and S4, cutting the modified nano-graphene composite cuprous oxide aerogel into a proper size, and then sequentially adopting the dipping and suction filtration technology to adsorb and shape the mirabilite-based phase change material.
2. The preparation method of the mirabilite-based solid-liquid composite phase-change energy storage material according to claim 1, characterized in that: in step S1, the hydrothermal reaction temperature is 160-200 ℃ and the reaction time is 15-18 h.
3. The preparation method of the mirabilite-based solid-liquid composite phase-change energy storage material according to claim 1, characterized in that: in the step S1, ascorbic acid is further added in the hydrothermal reaction, and the mass ratio of the ascorbic acid to the cuprous oxide powder is (3-4): 1.
4. the preparation method of the mirabilite-based solid-liquid composite phase-change energy storage material according to claim 1, characterized in that: in step S3, the mango nitro phase change material includes, by mass, 9: 1 or 7: 3, mirabilite and sodium carbonate decahydrate or the mass ratio of 2: mirabilite 8 and disodium hydrogen phosphate dodecahydrate.
5. The preparation method of the mirabilite-based solid-liquid composite phase-change energy storage material according to claim 1, characterized in that: in step S4, the composite phase change energy storage material is prepared by a vacuum impregnation method.
6. The preparation method of the mirabilite-based solid-liquid composite phase-change energy storage material according to claim 1, characterized in that: in the step S4, the temperature of the adsorption shaping mirabilite-based phase-change material is 40-60 ℃.
7. The preparation method of the mirabilite-based solid-liquid composite phase-change energy storage material according to claim 4, characterized in that: and a nucleating agent is also added into the mirabilite-based phase change material.
8. The preparation method of the mirabilite-based solid-liquid composite phase-change energy storage material according to claim 7, characterized in that: the nucleating agent is calcium carbonate or alum.
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