WO2021031976A1 - Matériau à changement de phase composite à base de mof façonné, procédé de préparation associé et son utilisation - Google Patents

Matériau à changement de phase composite à base de mof façonné, procédé de préparation associé et son utilisation Download PDF

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Publication number
WO2021031976A1
WO2021031976A1 PCT/CN2020/108939 CN2020108939W WO2021031976A1 WO 2021031976 A1 WO2021031976 A1 WO 2021031976A1 CN 2020108939 W CN2020108939 W CN 2020108939W WO 2021031976 A1 WO2021031976 A1 WO 2021031976A1
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Prior art keywords
mof
phase change
acid
change material
foamed
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PCT/CN2020/108939
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English (en)
Chinese (zh)
Inventor
王戈
唐兆第
高鸿毅
董文钧
高志猛
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苏州阿德旺斯新材料有限公司
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Priority claimed from CN201910762614.6A external-priority patent/CN110484214B/zh
Priority claimed from CN201910762580.0A external-priority patent/CN110484213B/zh
Application filed by 苏州阿德旺斯新材料有限公司 filed Critical 苏州阿德旺斯新材料有限公司
Publication of WO2021031976A1 publication Critical patent/WO2021031976A1/fr

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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

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  • the present invention claims the priority of a Chinese patent application filed in the Chinese Patent Office with the application number 201910762614.6 and the title of the invention "a shaped MOF-based composite phase change material and its preparation method and application”. The entire content of the application is incorporated by reference Incorporated in the present invention.
  • the present invention claims the priority of a Chinese patent application filed in the Chinese Patent Office with the application number 201910762580.0 and the title of the invention "a shaped MOF-based composite phase change material and its preparation method and application”. The entire content of the application is by reference Incorporated in the present invention.
  • the invention relates to the field of composite phase change materials, in particular to a shaped MOF-based composite phase change material and a preparation method and application thereof.
  • Composite phase change materials have attracted more and more attention in solving energy supply and transmission, and energy conversion.
  • composite phase change materials have also been developed in innovative applications such as photothermal conversion, electrothermal conversion, magnetothermal conversion, and hyperthermia. .
  • phase change material has the problem of leakage during the phase change process.
  • phase change carriers such as silica molecular sieve and kaolin are used to prepare shaped composite phase change materials.
  • Metal organic framework (MOF) as a new type of porous organic framework, has a pivotal position in the fields of catalysis, energy storage, gas separation, etc. MOF's three-dimensional ordered interconnected structure, adjustable pore diameter, modifiable pores, and ultra-high Its porosity and large specific surface area make it an ideal carrier to support phase change materials.
  • MOF is easily powdered, difficult to form, and has low thermal conductivity, which greatly limits its application in phase change materials.
  • the thermal conductivity of the composite phase change material can be improved by adding graphene, carbon nanotubes and other thermally conductive materials to the MOF, the powdery structure cannot be changed, and the cost of adding these thermally conductive materials is also high. Therefore, the problem of synthesizing a regular-shaped MOF-based composite phase change material and improving the thermal conductivity of the MOF-based composite phase change material at a low cost is in urgent need of a breakthrough.
  • the purpose of the present invention is to provide a shaped MOF-based composite phase change material and its preparation method and application.
  • the preparation method effectively overcomes the shortcomings of MOF materials that are not easy to form by growing MOF on foamed metal, and at the same time is low cost Ground improves the thermal conductivity of the MOF-based composite phase change material.
  • the shaped MOF-based composite phase change material obtained by using the preparation method has a specified shape and high thermal conductivity.
  • a preparation method of shaped MOF-based composite phase change material includes the following steps:
  • the organic ligand, soluble metal salt and if necessary additives are fully and uniformly dissolved in the solvent to obtain the MOF reaction solution; then the MOF reaction solution is reacted, and the reaction product is separated, washed, and dried to obtain the MOF matrix, and the MOF matrix Dissolve in solvent to obtain MOF mother liquor for later use;
  • the organic phase change core material is dissolved in a solvent to obtain an organic phase change core material solution, the MOF-based carrier is put into the organic phase change core material solution, and then dried to obtain the MOF-based composite phase change material.
  • the foamed metal includes one or more of foamed nickel, foamed aluminum, or foamed copper; optionally, foamed copper.
  • the metal foam substrate is completely covered with MOF before the metal foam matrix is placed in the MOF growth solution for reaction.
  • the organic ligands include: terephthalic acid, phthalic acid, trimesic acid, pyromellitic acid, mellitic acid, 2-sulfonic acid Phthalic acid, 2-nitroterephthalic acid, 2-aminoterephthalic acid, 1,1':4',1"-phenyl-4,4"-dicarboxylic acid, 1,1'-diphenyl One or more of group-4,4'-dicarboxylic acid and 2-methylimidazole.
  • the soluble metal salt includes: chromium nitrate, chromium chloride, chromium sulfate, chromium acetate, zirconium nitrate, zirconium chloride, zirconium sulfate, zirconium acetate, copper nitrate, and chlorine Copper, copper sulfate, copper acetate, zinc nitrate, zinc chloride, zinc sulfate, zinc acetate, nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetate, iron nitrate , Iron chloride, iron sulfate, iron acetate, aluminum nitrate, aluminum chloride, aluminum sulfate, aluminum acetate, manganese nitrate, manganese chloride, manganese sulfate, manganese a
  • the additives include: hydrofluoric acid, sodium hydroxide, formic acid, acetic acid, benzoic acid, polyethylene oxide-polypropylene oxide-polyethylene oxide One or more of triblock copolymer, phloroglucinol/formaldehyde and triblock copolymer, triethylamine, and methanol.
  • the organic phase change core material includes: stearyl alcohol, stearyl alcohol, stearyl acid, paraffin, polyethylene glycol, pentaerythritol, neopentyl glycol, trimethylol One or more of aminomethane and trimethylolpropane.
  • the prepared MOF mother liquid is added dropwise to cover the surface of the foamed metal, then the solvent of the MOF mother liquid is allowed to evaporate, and the weakly bonded MOF is washed away with an organic solvent to obtain the foamed metal matrix.
  • the prepared MOF mother liquor to the MOF mother liquor to completely cover the surface of the foamed metal, then let the solvent of the MOF mother liquor completely evaporate, repeat the process of dropping the MOF mother liquor and the solvent evaporation several times, and then wash away the weak bond with an organic solvent MOF, then repeat the above process of dropping MOF mother liquor, solvent evaporation and organic solvent washing many times until the foam metal surface is completely covered by MOF.
  • the mass ratio of the MOF-based carrier and the organic phase-change core material in the organic phase-change core material solution is 3-10:5; optionally, the mass ratio of the MOF-based carrier and the PEG2000 It is 4:5.
  • the solvent used is water
  • the molar ratio of MOF matrix to water is 1:10-40; optionally 1:20-30; further optional The ground is 1:25.
  • the preheating temperature of the foam metal is 95-105°C.
  • the reaction temperature of the MOF reaction solution is 25-100°C.
  • the temperature at which the obtained foamed metal matrix is placed in the MOF growth solution for reaction is 25-100°C.
  • the metal foam is processed before preheating for use, and the treatment includes the steps of washing and drying the metal foam to obtain a substrate on which MOF can grow; optionally, cleaning is Submerge them in acetone, methanol, and deionized water for ultrasonic cleaning.
  • the invention also provides the shaped MOF-based composite phase change material obtained by the above preparation method.
  • a shaped MOF-based composite phase change material includes a MOF-based carrier and an organic phase-change core material supported on the MOF-based carrier, wherein: the MOF-based carrier includes foamed metal and MOF covering the surface of the foamed metal.
  • the foamed metal includes one or more of foamed nickel, foamed aluminum, or foamed copper; optionally, foamed copper.
  • the organic phase change core material includes: stearyl alcohol, octadecane, octadecanoic acid, paraffin, polyethylene glycol, pentaerythritol, neopentyl glycol, trimethylolaminomethane, tris One or more of hydroxymethyl propane.
  • the MOF includes one or more of Cu-BTC, Cr-MIL-101-NH2, MOF-5, UIO-66, Al-MIL-53, and ZIF-67.
  • the surface of the foamed metal is completely covered by MOF.
  • the mass ratio of the MOF-based carrier and the organic phase-change core material in the organic phase-change core material solution is 3-10:5; optionally the mass of the MOF-based carrier and the organic phase-change core material PEG2000 The ratio is 4:5.
  • a simple preparation method of shaped MOF-based composite phase change material is developed; the preparation method uses the formed MOF substrate as a nucleation site, adds ligands and metal ions, and grows MOF on the foamed metal.
  • the method can overcome the shortcomings that MOF is not easy to shape as a phase change material carrier.
  • the obtained MOF-based composite phase change material has the shape and size of the foam metal; the preparation method uses the foam metal as the shaping
  • a part of the MOF-based composite phase change material is used to enhance the thermal conductivity of the composite phase change material. Because the foam metal itself has high thermal conductivity, it can also enhance the thermal conductivity of the composite phase change material; and the preparation method is applied Wide range, cheap and easily available raw materials, suitable for industrial production.
  • the content of the phase change material encapsulated by the MOF-based carrier is determined so that the encapsulated phase change core material does not leak.
  • the shaped MOF-based composite phase change material of the present invention has a specified shape, high thermal conductivity, and no leakage of the phase change core material.
  • the foam metal is selected as the matrix, the MOF is covered on the surface of the foam metal to obtain a MOF-based carrier, and then the MOF-based carrier is used to support the organic phase change core material, and the resulting shaped MOF-based composite phase change material is controlled by the shape and size of the foam metal.
  • the resulting shaped MOF-based composite phase change material has the shape and size of the foamed metal, and the foamed metal is used as part of the shaped MOF-based composite phase change material. Since the foamed metal itself has high thermal conductivity, it can also enhance the composite phase change material. The thermal conductivity.
  • Figure 1 is the differential scanning calorimetry (DSC) curve of the shaped MOF-based composite phase change material obtained in Example 1 of the present invention, in which: the upper line represents the heat release curve of the composite phase change material, and the lower line represents the composite phase change material The endothermic curve;
  • DSC differential scanning calorimetry
  • Example 2 is a scanning electron microscope (SEM) image of the shaped MOF-based composite phase change material obtained in Example 1 of the present invention at a scale of 2 microns, which shows that the phase change material is successfully supported on the carrier material;
  • Example 3 is a scanning electron microscope (SEM) image of the shaped MOF-based composite phase change material obtained in Example 1 of the present invention at a scale of 20 microns, which indicates that the phase change material is successfully supported on the carrier material.
  • SEM scanning electron microscope
  • the shape and size of the foamed metal are not particularly limited, and those skilled in the art can adjust the shape or corresponding size according to the purpose and application requirements of the present invention.
  • the pore size of the metal foam is not particularly limited, and those skilled in the art can choose the pore size of the metal foam according to the purpose and application requirements of the present invention.
  • the description of the pore size of the foamed copper in the following examples is only an objective description of the selected foamed copper.
  • the 500-mesh copper screen refers to the average pore size of the foamed copper of 500 mesh.
  • the role of specific additives is reflected in the preparation and growth of MOF.
  • the preparation and growth of some MOFs require certain conditions, such as alkaline conditions (for example, by providing sodium hydroxide in Example 1) Or under acidic conditions (for example, by providing the glacial acetic acid in Example 3), but some MOFs are not required.
  • the addition of additives and the amount of additives are determined according to the MOF to be prepared.
  • the addition ratio of the three organic ligands, soluble metal salts and specific additives is determined according to the prepared MOF.
  • the composition of the MOF reaction solution is the same as the composition of the MOF growth solution.
  • the material value includes not only the exact same, but also the reasonable fluctuation range in the understanding of those skilled in the art, including: within ⁇ 3%, ⁇ Within 1% or within ⁇ 0.5%.
  • a simple method can be used to determine whether the MOF growth solution is sufficient, that is, the obtained metal foam substrate is placed in the MOF growth solution for reaction. Not only does MOF grow on the foam metal substrate, but also in the MOF growth solution. There is excess MOF generated.
  • step 1) Preheat the copper sieve in step 1) at 100°C for 10 minutes.
  • step 2) Drop the Cu-BTC mother liquor prepared in step 2) onto the surface of the copper sieve until it completely covers the entire surface, and then continue to Drying at this temperature for 15 minutes to remove the solvent in the Cu-BTC mother liquor, repeat the process of three rounds of mother liquor dropping and solvent removal, and then wash the sample with ethanol and ultrasonic for 1 minute, and repeat four rounds of mother liquor dropping, solvent removal and ultrasonic washing The whole process until the surface of the copper screen is completely covered by Cu-BTC.
  • the copper sieve substrate made above into a mixed solution of 25mL water and 25mL ethanol containing 7.021g copper nitrate and 3.063g trimellitic acid, transfer it into the reaction kettle and put it in an oven to react at 95°C for 15h, then slowly Cooled to room temperature, washed, dried at 80°C for 24 hours to obtain the final Cu-BTC-based carrier for supporting the organic phase change material.
  • the differential scanning calorimetry (DSC) curve, the scanning electron microscope (SEM) image at the 2 micron scale, and the scanning electron microscope (SEM) image at the 2 micron scale of the Cu-BTC-based composite phase change material obtained in Example 1 are shown in the figure respectively.
  • DSC differential scanning calorimetry
  • SEM scanning electron microscope
  • SEM scanning electron microscope
  • step 1) Preheat the copper sieve in step 1) at 100°C for 10 minutes.
  • step 2) Drop the Cr-MIL-101-NH 2 mother liquor prepared in step 2) onto the surface of the copper sieve until it completely covers the entire surface.
  • step 3 Preheat the copper sieve in step 1) at 100°C for 10 minutes.
  • step 2 Drop the Cr-MIL-101-NH 2 mother liquor prepared in step 2) onto the surface of the copper sieve until it completely covers the entire surface.
  • Surface and then continue to dry at this temperature for 15 minutes to remove the solvent in the Cr-MIL-101-NH 2 mother liquor, repeat the process of three rounds of mother liquor dropping and solvent removal, and then wash the sample with ethanol and ultrasound for 1 minute, and repeat four rounds The whole process of mother liquor dropping, solvent removal and ultrasonic washing until the surface of the copper sieve is completely covered by Cr-MIL-101-NH 2 .
  • step 3 Preheat the copper sieve treated in step 1) at 100°C for 10 minutes. At this temperature, drop the UIO-66 mother liquor prepared in step 2) onto the surface of the copper sieve until it completely covers the entire surface. Continue to dry at this temperature for 15 minutes to remove the solvent in the UIO-66 mother liquor, repeat the process of three rounds of mother liquor dropping and solvent removal, and then wash the sample with ethanol and sonicate for 1 minute, and repeat four rounds of mother liquor dropping, solvent removal and ultrasound The whole process of washing until the surface of the copper screen is completely covered by UIO-66.
  • the mesh of the copper-containing substrate formed into 11.4mL of acetic acid, 1.14 g of terephthalic acid and 1.6g ZrCl 100mL of DMF 4 uniformly, into a reaction kettle oven 24h 120 °C placed, then Slowly cooled to room temperature, washed, and dried at 80°C for 24 hours to obtain the final UIO-66-based carrier for supporting organic phase change materials.
  • step 1) Preheat the treated copper sieve in step 1) at 100°C for 10 min.
  • step 2) Drop the Al-MIL-53 mother liquor prepared in step 2) onto the surface of the copper sieve until it completely covers the entire surface , And then continue to dry at this temperature for 15 minutes to remove the solvent in the Al-MIL-53 mother liquor, repeat the process of three rounds of mother liquor dropping and solvent removal, and then wash the sample with ethanol and ultrasound for 1 minute, and repeat four rounds of mother liquor dropping, The entire process of removing the solvent and ultrasonic washing until the surface of the copper screen is completely covered by Al-MIL-53.
  • step 1) Preheat the treated copper sieve in step 1) at 100°C for 10 minutes.
  • step 2) Drop the ZIF-67 mother liquor prepared in step 2) onto the surface of the copper sieve until it completely covers the entire surface.
  • step 3 Preheat the treated copper sieve in step 1) at 100°C for 10 minutes.
  • step 2 Drop the ZIF-67 mother liquor prepared in step 2) onto the surface of the copper sieve until it completely covers the entire surface.
  • step 3 Continue to dry at this temperature for 15 minutes to remove the solvent in the mother liquor of ZIF-67, repeat the process of three rounds of mother liquor dropping and solvent removal, and then wash the sample with ethanol and sonicate for 1 minute, and repeat four rounds of mother liquor dropping, solvent removal and ultrasound The whole process of washing until the surface of the copper screen is completely covered by ZIF-67.
  • the embodiment of the present invention provides a shaped MOF-based composite phase change material and its preparation method and application.
  • the formed MOF substrate is used as a nucleation site, ligands and metal ions are added, and MOF is grown on foam metal. It can overcome the shortcomings that MOF is not easy to form as a phase change material carrier.
  • the obtained MOF-based composite phase change material has the shape and size of the foamed metal; at the same time, the MOF-based composite phase change is improved at low cost.
  • the thermal conductivity of the material is controlled by controlling the shape and size of the foamed metal.

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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

L'invention concerne un matériau à changement de phase composite à base de MOF façonné, un procédé de préparation associé et son utilisation. Le procédé de préparation consiste à utiliser un substrat de MOF formé en tant que site de nucléation, et à ajouter un ligand et des ions métalliques, de façon à surmonter l'inconvénient selon lequel il n'est pas possible de façonner aisément un vecteur quand un MOF est utilisé en tant que matériau à changement de phase, et ce, au moyen de la croissance de MOF sur une mousse métallique. Dans le procédé de préparation, une mousse métallique est utilisée en tant que partie du matériau à changement de phase composite à base de MOF façonné, pour renforcer la conductivité thermique du matériau à changement de phase composite. Le procédé de préparation est largement utilisé, et les matières premières sont économiques et facilement disponibles, et le procédé convient à une production industrielle. Le matériau à changement de phase composite à base de MOF façonné comprend un vecteur à base de MOF et un matériau de cœur à changement de phase organique chargé sur le vecteur à base de MOF, le vecteur à base de MOF comprenant une mousse métallique et un MOF, qui est recouvert sur la surface de la mousse métallique; par régulation de la forme et de la taille de la mousse métallique, le matériau à changement de phase composite à base de MOF façonné a la forme et la taille de la mousse métallique et une grande conductivité thermique.
PCT/CN2020/108939 2019-08-19 2020-08-13 Matériau à changement de phase composite à base de mof façonné, procédé de préparation associé et son utilisation WO2021031976A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201910762614.6A CN110484214B (zh) 2019-08-19 2019-08-19 一种定型mof基复合相变材料及其制备方法和应用
CN201910762614.6 2019-08-19
CN201910762580.0 2019-08-19
CN201910762580.0A CN110484213B (zh) 2019-08-19 2019-08-19 一种定型mof基复合相变材料及其制备方法和应用

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN112981456A (zh) * 2021-03-17 2021-06-18 扬州大学 一种高效制备丙酮的Cu@MIL-101-Cr电催化剂的制备方法
CN114940889A (zh) * 2022-05-25 2022-08-26 大连理工大学 一种具有温敏导电特性的复合相变储能材料及其制备方法与应用
US11555137B1 (en) 2022-05-23 2023-01-17 King Fahd University Of Petroleum And Minerals Method of forming phase change material

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CN110484214A (zh) * 2019-08-19 2019-11-22 苏州阿德旺斯新材料有限公司 一种定型mof基复合相变材料及其制备方法和应用
CN110484213A (zh) * 2019-08-19 2019-11-22 苏州阿德旺斯新材料有限公司 一种定型mof基复合相变材料及其制备方法和应用

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US20100126344A1 (en) * 2007-04-05 2010-05-27 Basf Se Mixture comprising a metal organic framework and also a latent heat store
CN101560377A (zh) * 2009-06-04 2009-10-21 河北科技大学 泡沫金属基高温相变蓄热复合材料及其制备方法
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112981456A (zh) * 2021-03-17 2021-06-18 扬州大学 一种高效制备丙酮的Cu@MIL-101-Cr电催化剂的制备方法
US11555137B1 (en) 2022-05-23 2023-01-17 King Fahd University Of Petroleum And Minerals Method of forming phase change material
US11767456B1 (en) 2022-05-23 2023-09-26 King Fahd University Of Petroleum And Minerals Solution phase method for making phase change materials
CN114940889A (zh) * 2022-05-25 2022-08-26 大连理工大学 一种具有温敏导电特性的复合相变储能材料及其制备方法与应用

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