CN114921232B - Diatomite/Cu nanowire phase-change energy storage composite matrix material and preparation method thereof - Google Patents
Diatomite/Cu nanowire phase-change energy storage composite matrix material and preparation method thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 238000004146 energy storage Methods 0.000 title claims abstract description 69
- 239000002070 nanowire Substances 0.000 title claims abstract description 57
- 239000011159 matrix material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011232 storage material Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 21
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 19
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 9
- 229960003280 cupric chloride Drugs 0.000 claims abstract description 9
- 229960001031 glucose Drugs 0.000 claims abstract description 9
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims description 54
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 24
- 239000005639 Lauric acid Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000012188 paraffin wax Substances 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- XQSBLCWFZRTIEO-UHFFFAOYSA-N hexadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH3+] XQSBLCWFZRTIEO-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000005909 Kieselgur Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 2
- 239000012071 phase Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 6
- 239000012074 organic phase Substances 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 5
- 239000002981 blocking agent Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005338 heat storage Methods 0.000 description 2
- 239000012782 phase change material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229940089206 anhydrous dextrose Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
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- 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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- 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
- Y02E60/14—Thermal energy storage
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Abstract
The invention discloses a diatomite/Cu nanowire phase-change energy-storage composite matrix material and a preparation method thereof, wherein the method comprises the following steps: adding water into cupric chloride dihydrate, stirring, adding tetramethyl ethylenediamine, stirring, adding anhydrous glucose, stirring, adding end capping agent until the solution is stirred to form uniform bright blue turbid solution, and adding diatomite; and (3) after fully stirring, reacting the solution at 120-160 ℃ for 6-12 hours to obtain the diatomite/Cu nanowire phase-change energy storage composite matrix material. The method can grow and wrap the Cu nanowire on the surface of the diatomite particles. After the organic phase is loaded on the diatomite/Cu nanowire composite matrix material, the thermal conductivity of the formed composite phase change energy storage material is greatly improved.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a diatomite/Cu nanowire phase-change energy storage composite matrix material and a preparation method thereof.
Background
The diatomite has good adsorption performance and structural stability, and can be used as a matrix of the phase change energy storage material. At present, the composite phase change heat storage material with diatomite as a matrix and organic matters as phase change materials is gradually paid attention to, and has good application prospect.
At present, the research on diatomite-based phase change energy storage materials is mainly focused on improving the comprehensive performance of the organic phase change energy storage materials by compounding the diatomite with the organic phase change materials. However, at present, diatomite-based composite organic phase change heat storage materials still have some defects: such as low thermal conductivity and significant supercooling of the phase change material due to the low thermal conductivity.
Disclosure of Invention
In order to solve the problems in the prior art, the embodiment of the invention provides a diatomite/Cu nanowire phase-change energy storage composite matrix material and a preparation method thereof. The technical scheme is as follows:
In a first aspect, a preparation method of a diatomite/Cu nanowire phase-change energy storage composite matrix material is provided, which comprises the following steps:
Adding water into cupric chloride dihydrate, stirring, adding tetramethyl ethylenediamine, stirring, adding anhydrous glucose, stirring, adding end capping agent until the solution is stirred to form uniform bright blue turbid solution, and adding diatomite; and (3) after fully stirring, reacting the solution at 120-160 ℃ for 6-12 hours to obtain the diatomite/Cu nanowire phase-change energy storage composite matrix material.
Further, the capping agent includes any one of cetyl ammonium bromide, adipic acid, terephthalic acid, or maleic anhydride.
Further, the mass ratio of the anhydrous dextrose to the anhydrous cupric chloride is 1:2.6-2.7.
Further, copper chloride dihydrate: diatomaceous earth=1:20 in mass ratio.
Further, the solution was reacted at 160℃for 6 hours after the sufficient stirring.
Further, after adding the end-capping reagent, stirring was carried out at 800r/min for 30min.
The second method provides a diatomite/Cu nanowire phase-change energy storage composite matrix material, which is prepared by adopting the method in the first aspect.
The technical scheme provided by the embodiment of the invention has the beneficial effects that: in the embodiment of the invention, cupric chloride dihydrate is taken to be stirred after being added with water, tetramethyl ethylenediamine is added to be continuously stirred after being completely dissolved, anhydrous glucose is added to be stirred, and finally a blocking agent is added until the solution is stirred to form a uniform bright blue turbid solution, and diatomite is added; and (3) after fully stirring, reacting the solution at 120-160 ℃ for 6-12 hours to obtain the diatomite/Cu nanowire phase-change energy storage composite matrix material. The method can grow and wrap the Cu nanowire on the surface of the diatomite particles. After the organic phase is loaded on the diatomite/Cu nanowire composite matrix material, the thermal conductivity of the formed composite phase change energy storage material is greatly improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern of the diatomite/Cu nanowire phase change energy storage composite matrix material prepared in example 1 of the present invention;
Fig. 2 is an SEM image of the diatomite/Cu nanowire phase-change energy storage composite matrix material prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below.
Example 1 preparation of diatomite/Cu nanowire phase-change energy storage composite matrix Material
1.078G of cupric chloride dihydrate and 40ml of deionized water are taken and added into a beaker, the beaker is placed on a magnetic stirrer and stirred for 5min, then 4.8ml of tetramethyl ethylenediamine is added and stirred for 5min, then 2.88g of anhydrous glucose is added and stirred for 5min, finally 3.23g of cetyl ammonium bromide is added as a blocking agent until the solution is stirred to form a bright blue turbid solution with uniform components, and then 20g of diatomite is added. And (3) fully stirring at the rotating speed of 800r/min for 30min, taking out the magnetic rotor, putting the solution into a hydrothermal reaction kettle, and reacting at 160 ℃ in a constant temperature box for 6h to obtain the diatomite/Cu nanowire phase-change energy-storage composite matrix material.
Example 2 preparation of diatomite/Cu nanowire phase-change energy storage composite matrix Material
1.235G of cupric chloride dihydrate and 40ml of deionized water are taken and added into a beaker, the beaker is placed on a magnetic stirrer and stirred for 5min, then 5.5ml of tetramethyl ethylenediamine is added and stirred for 5min, then 3.29g of anhydrous glucose is added and stirred for 5min, finally 1.03g of oxalic acid is added as a blocking agent until the solution is stirred to form a bright blue turbid solution with uniform components, and then 25g of diatomite is added. And (3) fully stirring at the rotating speed of 800r/min for 30min, taking out the magnetic rotor, putting the solution into a hydrothermal reaction kettle, and reacting at 140 ℃ for 8h in a constant temperature box to obtain the diatomite/Cu nanowire phase-change energy storage composite matrix material.
Example 3 preparation of diatomite/Cu nanowire phase-change energy storage composite matrix Material
1.168G of cupric chloride dihydrate and 40ml of deionized water are taken and added into a beaker, the beaker is placed on a magnetic stirrer and stirred for 5min, then 5.2ml of tetramethyl ethylenediamine is added and stirred for 5min, then 3.11g of anhydrous glucose is added and stirred for 5min, finally 1.80g of terephthalic acid is added as a blocking agent until the solution is stirred to form a bright blue turbid solution with uniform components, and then 25g of diatomite is added. And (3) fully stirring at the rotating speed of 800r/min for 30min, taking out the magnetic rotor, putting the solution into a hydrothermal reaction kettle, and reacting at the temperature of 140 ℃ for 10h in a constant temperature box to obtain the diatomite/Cu nanowire phase-change energy-storage composite matrix material.
Example 4 preparation of diatomite/Cu nanowire phase-change energy storage composite matrix Material
1.415G of cupric chloride dihydrate and 40ml of deionized water are taken and added into a beaker, the beaker is placed on a magnetic stirrer and stirred for 5min, then 6.3ml of tetramethyl ethylenediamine is added and stirred for 5min, then 3.76g of anhydrous glucose is added and stirred for 5min, finally 1.29g of maleic anhydride is added as a blocking agent until the solution is stirred to form a bright blue turbid solution with uniform components, and then 28g of diatomite is added. And (3) fully stirring at the rotating speed of 800r/min for 30min, taking out the magnetic rotor, putting the solution into a hydrothermal reaction kettle, and reacting at 120 ℃ for 12h in a constant temperature box to obtain the diatomite/Cu nanowire phase-change energy storage composite matrix material.
Example 5 diatomite/Cu nanowire phase-change energy storage composite matrix composite lauric acid phase-change energy storage material
Respectively weighing lauric acid and diatomite/Cu nanowire phase-change energy storage composite matrix material according to a mass ratio of 3:1, mixing the lauric acid and the diatomite/Cu nanowire phase-change energy storage composite matrix material, placing the mixture into an oven for vacuumizing, heating to 90 ℃, and preserving heat for 1h; and (3) reducing the temperature to 40 ℃ and preserving heat for 30min, then heating to 80 ℃ and preserving heat for 30min, and finally naturally cooling to room temperature.
Example 6 diatomite/Cu nanowire phase-change energy storage composite matrix composite Paraffin phase-change energy storage Material
Respectively weighing paraffin wax and diatomite/Cu nanowire phase-change energy storage composite matrix material according to a mass ratio of 3:1, mixing the paraffin wax and the diatomite/Cu nanowire phase-change energy storage composite matrix material, placing the mixture into an oven for vacuumizing, heating to 90 ℃, and preserving heat for 1h; and (3) reducing the temperature to 45 ℃ and preserving heat for 30min, then heating to 80 ℃ and preserving heat for 30min, and finally naturally cooling to room temperature.
Example 7 diatomite/Cu nanowire phase-change energy storage composite matrix composite polyethylene glycol phase-change energy storage material
Respectively weighing polyethylene glycol and diatomite/Cu nanowire phase-change energy storage composite matrix material according to a mass ratio of 3:1, mixing the polyethylene glycol and the diatomite/Cu nanowire phase-change energy storage composite matrix material, placing the mixture into an oven for vacuumizing, heating to 90 ℃, and preserving heat for 1h; and (3) reducing the temperature to 50 ℃ and preserving heat for 30min, then heating to 80 ℃ and preserving heat for 30min, and finally naturally cooling to room temperature.
The diatomite/Cu nanowire phase-change energy-storage composite matrix material prepared in the example 1 is taken and detected by X-ray diffraction, and the result is shown in figure 1. The diatomite/Cu nanowire phase-change energy storage composite matrix material is arranged at the upper part of the figure, and the Cu nanowire is arranged at the lower part of the figure. It can be seen that the material prepared in example 1 perfectly exhibited phase data of Cu and was perfectly matched to the standard data. The prepared composite matrix material is provided with Cu.
Fig. 2 is an SEM image of the diatomite/Cu nanowire phase-change energy storage composite matrix material prepared in example 1, in which diatomite particles are completely wrapped by Cu nanowires interwoven together, and a large number of pore structures are formed, and in the case of retaining diatomite particles, such a microscopic morphology is very favorable for storage of organic phase-change energy storage materials.
The loading rate of pure diatomite to lauric acid is 54% -58%, and compared with the loading rate of diatomite/Cu nanowire phase change energy storage composite matrix to lauric acid is about 66%, the loading rate of copper nanowire to diatomite is proved to have a certain lifting effect, and the loading rate corresponds to the result of SEM.
The method can grow and wrap the Cu nanowire on the surface of the diatomite particles, and has good effect. The thermal conductivity of pure lauric acid is 0.2326W/(m.K), and the thermal conductivity of the diatomite/Cu nanowire phase-change energy storage composite matrix after loading lauric acid is 0.56543W/(m.K), compared with pure lauric acid, the thermal conductivity of the composite phase-change energy storage material is greatly improved. After diatomite/Cu nanowire phase-change energy storage composite matrix composite paraffin (example 6) or polyethylene glycol (example 7), the heat conductivity of the composite matrix composite paraffin is improved by 123% and 155% respectively compared with pure paraffin and polyethylene glycol.
The foregoing is only illustrative of the present invention and is not to be construed as limiting thereof, but rather as various modifications, equivalent arrangements, improvements, etc., within the spirit and principles of the present invention.
Claims (4)
1. The phase-change energy-storage material is characterized by being diatomite/Cu nanowire phase-change energy-storage composite matrix composite lauric acid phase-change energy-storage material, diatomite/Cu nanowire phase-change energy-storage composite matrix composite paraffin phase-change energy-storage material or diatomite/Cu nanowire phase-change energy-storage composite matrix composite polyethylene glycol phase-change energy-storage material;
the preparation method of the diatomite/Cu nanowire phase-change energy storage composite matrix composite lauric acid phase-change energy storage material comprises the following steps: respectively weighing lauric acid and diatomite/Cu nanowire phase-change energy storage composite matrix material according to a mass ratio of 3:1, mixing the lauric acid and the diatomite/Cu nanowire phase-change energy storage composite matrix material, placing the mixture into an oven for vacuumizing, heating to 90 ℃, and preserving heat for 1h; reducing the temperature to 40 ℃ and preserving heat for 30min, then heating to 80 ℃ and preserving heat for 30min, and finally naturally cooling to room temperature;
the preparation method of the diatomite/Cu nanowire phase-change energy storage composite matrix composite paraffin phase-change energy storage material comprises the following steps: respectively weighing paraffin wax and diatomite/Cu nanowire phase-change energy storage composite matrix material according to a mass ratio of 3:1, mixing the paraffin wax and the diatomite/Cu nanowire phase-change energy storage composite matrix material, placing the mixture into an oven for vacuumizing, heating to 90 ℃, and preserving heat for 1h; reducing the temperature to 45 ℃ and preserving heat for 30min, then heating to 80 ℃ and preserving heat for 30min, and finally naturally cooling to room temperature;
The preparation method of the diatomite/Cu nanowire phase-change energy storage composite matrix composite polyethylene glycol phase-change energy storage material comprises the following steps: respectively weighing polyethylene glycol and diatomite/Cu nanowire phase-change energy storage composite matrix material according to a mass ratio of 3:1, mixing the polyethylene glycol and the diatomite/Cu nanowire phase-change energy storage composite matrix material, placing the mixture into an oven for vacuumizing, heating to 90 ℃, and preserving heat for 1h; reducing the temperature to 50 ℃ and preserving heat for 30min, then heating to 80 ℃ and preserving heat for 30min, and finally naturally cooling to room temperature;
The preparation method of the diatomite/Cu nanowire phase-change energy storage composite matrix material comprises the following steps:
Adding water into cupric chloride dihydrate, stirring, adding tetramethyl ethylenediamine, stirring, adding anhydrous glucose, stirring, adding end capping agent until the solution is stirred to form uniform bright blue turbid solution, and adding diatomite; after fully stirring, reacting the solution at 120-160 ℃ for 6-12 hours to obtain the diatomite/Cu nanowire phase-change energy storage composite matrix material;
The end-capping agent comprises any one of hexadecyl ammonium bromide, adipic acid, terephthalic acid or maleic anhydride;
Copper chloride dihydrate, diatomaceous earth=1:20 by mass.
2. The phase-change energy storage material according to claim 1, wherein the ratio of anhydrous glucose to anhydrous copper chloride is 1:2.6-2.7.
3. The phase change energy storage material of claim 1, wherein said solution is reacted at 160 ℃ for 6 hours after said thoroughly stirring.
4. The phase change energy storage material of claim 1, wherein after adding the capping agent, stirring is carried out at 800r/min for 30min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109622986A (en) * | 2018-12-26 | 2019-04-16 | 天津理工大学 | A kind of preparation method of copper-based modification infusorial earth |
| CN109652022A (en) * | 2018-12-28 | 2019-04-19 | 青海大学 | A kind of preparation method of NEW TYPE OF COMPOSITE diatomite phase-changing energy storage material carrier |
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| US10626238B2 (en) * | 2018-07-27 | 2020-04-21 | King Fahd University Of Petroleum And Minerals | Calcium-doped magnesium carbonate-polymer-based synergistic phase change composite |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109622986A (en) * | 2018-12-26 | 2019-04-16 | 天津理工大学 | A kind of preparation method of copper-based modification infusorial earth |
| CN109652022A (en) * | 2018-12-28 | 2019-04-19 | 青海大学 | A kind of preparation method of NEW TYPE OF COMPOSITE diatomite phase-changing energy storage material carrier |
Non-Patent Citations (2)
| Title |
|---|
| Thermal conductivity enhancement of diatomite-based composite phase change materials by interfacial reduction deposition of Cu nanoparticles;Wu D, Gu X, Sun Q, et al.;Journal of Energy Storage(第61期);1-8 * |
| 硅藻土基相变储能材料研究进展;彭立华等;硅酸盐学报;第49卷(第5期);1006-1016 * |
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