CN113462367B - Optical energy and magnetic energy dual-drive composite phase change material - Google Patents
Optical energy and magnetic energy dual-drive composite phase change material Download PDFInfo
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Abstract
The application discloses light energy and magnetic energy dual-drive composite phase-change material, which comprises: MXene matrix; magnetic metal oxide doped on the inner surface and the outer surface of the MXene matrix; and a phase change material compounded in the MXene matrix. The composite phase-change material has the performance of high-efficiency light energy and magnetic energy dual-drive energy conversion.
Description
Technical Field
The application relates to the field of composite phase-change materials, in particular to a light energy and magnetic energy dual-drive composite phase-change material.
Background
With the rapid growth of the world population and the economic development, the demand for energy is increasing. However, depletion of fossil energy (e.g., coal, natural gas, oil, etc.) and increasing environmental problems make it important to improve energy use efficiency and develop new energy (e.g., solar energy, magnetic energy, biomass energy, etc.). At present, wind energy, solar energy, ocean energy and the like are widely applied to the related fields of electric power, heat supply and the like. However, the above distribution of energy has problems such as intermittency, randomness, and fluctuation, and it is very difficult to use it. The energy storage and release by using the composite phase-change material is an effective method for solving the problem of mismatching of space and time between heat energy supply and demand, and is one of important means for improving the energy use efficiency.
Chinese patent application CN110126043A discloses a preparation method of heat conduction enhanced phase change energy storage wood based on photo-thermal response, which adopts graphene oxide as heat conduction particles and polyethylene glycol-800 as a phase change energy storage material to improve the energy storage performance of the wood, promote the energy conservation and ensure the stability of the wood in the phase change process. Chinese patent application CN112588214A discloses a phase change material microcapsule with photothermal conversion and energy storage properties and a preparation method thereof, wherein a capsule core of the microcapsule is made of a phase change material, an inner-layer capsule wall is a polydivinylbenzene high polymer shell layer, and an outer-layer capsule wall is an MXene shell layer, so that the multi-wall structure microcapsule has high encapsulation efficiency and higher heat energy storage density and photothermal conversion efficiency. Chinese patent application CN112592698A discloses a shape-stabilized phase change material with photo-thermal conversion property and preparation thereofThe method adopts the technical scheme that: heating the selected solid-liquid phase-change material and the azobenzene side chain type liquid crystal polymer in a closed container to enable the azobenzene side chain type liquid crystal polymer to be completely dissolved in the solid-liquid phase-change material to form a transparent solution, stopping heating, and self-assembling the azobenzene side chain type liquid crystal polymer in the solid-liquid phase-change material in the cooling process to obtain the shape-stabilized phase-change material with the photo-thermal conversion property. Chinese patent application CN110358504A discloses a preparation method of a wood-based functional magneto-thermal composite phase-change heat storage material, which utilizes hydrothermal reaction to carry out magnetic nano Fe 3 O 4 The particles are anchored on the modified poplar wood, and then PEG6000 is loaded to obtain the phase-change heat storage material.
However, the composite phase-change materials can only use a single energy source to store and release energy, and cannot meet the urgent needs of the fields of high-efficiency, rapid and multi-energy-driven energy conversion and thermal energy storage. Therefore, the development of the composite phase change material with the multi-energy-driven energy conversion form has important research significance.
Disclosure of Invention
Aiming at the defects in the prior art, the application provides the optical energy and magnetic energy dual-drive composite phase-change material, different types of magnetic metal oxides can be uniformly embedded into the surface and the interlayer of MXene by adopting an in-situ chemical synthesis method, the magnetic metal oxides can have the size of nanometer level, then the composite carrier is activated in vacuum to activate the composite carrier, then the composite carrier is soaked in a solution of the phase-change material, and the phase-change material is adsorbed and loaded by utilizing physical and chemical acting forces such as capillary pore acting force, hydrogen bond and the like, so that the composite phase-change material with high-efficiency optical energy and magnetic energy dual-drive energy conversion is obtained.
In order to achieve the above object, in a first aspect, the present application provides a light energy and magnetic energy dual-driving composite phase change material, which includes an MXene matrix; magnetic metal oxide doped on the inner surface and the outer surface of the MXene matrix; and phase change material compounded in MXene matrix.
With reference to the first aspect, in one possible embodiment, the composite phase change material is prepared by the following method:
(1) MXene is used as a photon catcher, and a magnetic metal oxide is doped on the surface and between the sheet layers by an in-situ chemical synthesis method to obtain the MXene composite phase change carrier doped with the magnetic metal oxide; and
(2) Compounding the MXene composite phase change carrier doped with the magnetic metal oxide obtained in the step (1) with a phase change core material to obtain the magnetic material.
In a possible embodiment, in combination with the first aspect, the MXene is prepared by etching a precursor MAX phase under acidic conditions with an inorganic fluoride.
Preferably, the MXene is prepared by the following method: adding inorganic fluoride and MAX into an acid solution with the H + concentration of 8M-12M, preferably 10M, under stirring, continuously stirring for 24-48H at 0-70 ℃, preferably normal temperature to 50 ℃, then dispersing the obtained product in water, centrifuging, washing to neutrality, and drying to obtain the MXene.
With reference to the first aspect, in one possible embodiment, the step (1) includes: MXene is dispersed in water, a surfactant is added into the water and stirred, and then a magnetic metal oxide precursor is added and hydrolyzed to obtain the MXene composite phase change carrier doped with the magnetic metal oxide.
Preferably, the magnetic metal oxide precursor is at least one selected from the group consisting of an inorganic acid salt of iron, a complex of iron, an inorganic acid salt of cobalt, a complex of cobalt, an inorganic acid salt of nickel, and a complex of nickel; and the magnetic metal oxide is ferroferric oxide (Fe) 3 O 4 ) Cobaltosic oxide (Co) 3 O 4 ) And/or nickel oxide (NiO).
In one possible embodiment in combination with the first aspect, in step (1), the hydrolysis method of the magnetic metal oxide precursor is to hydrolyze the magnetic metal oxide precursor under basic conditions.
In a possible embodiment in combination with the first aspect, in step (1), the surfactant is at least one selected from the group consisting of octadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide, dioctadecyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, and dodecyl trimethyl ammonium chloride.
With reference to the first aspect, in one possible implementation, the step (2) includes: and activating the MXene composite carrier doped with the magnetic metal oxide in vacuum, dispersing the MXene composite carrier in an aqueous solution/alcoholic solution of the phase-change material, heating and stirring, filtering and drying to obtain the composite phase-change material.
Preferably, the phase change material includes at least one of polyethylene glycol 1000 to 20000, pentaerythritol, neopentyl glycol, stearic acid, myristic acid, palmitic acid, capric acid, lauric acid, pentadecanoic acid, and sebacic acid.
In a possible embodiment in combination with the first aspect, in step (2), the concentration of the aqueous/alcoholic solution of the phase change material is 10mg/mL to 40mg/mL.
In a possible embodiment in combination with the first aspect, in step (2), the vacuum activation condition may be that the MXene composite support doped with the magnetic metal oxide is heated in vacuum at 120 ℃ to 200 ℃ for 3h to 6h, preferably 4h.
In a possible embodiment, in combination with the first aspect, in the step (2), the heating and stirring conditions are heating and stirring at 25 ℃ to 100 ℃ for 1h to 24h.
In a possible embodiment in combination with the first aspect, in the step (2), the drying is performed under the condition of heating and drying at 50 ℃ to 120 ℃ for 2h to 24h.
In a second aspect, the application also provides a preparation method of the above optical energy and magnetic energy dual-drive composite phase-change material, which includes the following steps:
(1) Doping magnetic metal oxide on the surface and between the sheet layers by using MXene as a photon catcher through an in-situ chemical synthesis method to obtain an MXene composite phase change carrier doped with the magnetic metal oxide; and
(2) Compounding the MXene composite phase change carrier doped with the magnetic metal oxide obtained in the step (1) with a phase change core material to obtain the magnetic material.
The technical scheme that this application provided compares prior art and has following beneficial effect at least:
1) Different types of magnetic metal oxides are uniformly embedded into the surface and the interlayer of MXene with excellent light absorption performance by adopting an in-situ chemical synthesis method, so that the problem that the conventionally synthesized magnetic metal oxides are easy to agglomerate is solved;
2) The composite phase-change material which has the double-drive energy conversion form of light energy and magnetic energy can be obtained after being compounded with the phase-change material, meanwhile, the uniformly distributed magnetic metal oxide also realizes the radial transfer of heat from the surface to the inside, shortens a heat transfer path, and further improves the photo-thermal conversion efficiency again, so that the composite phase-change material prepared by the method has higher photo-thermal and magneto-thermal conversion efficiency; and
3) The selection of the magnetic metal oxide and the phase change core material can be diversified, and the economical efficiency is good.
In conclusion, the MXene is used as the photon catcher, and the magnetic oxide is doped on the surface and between the layers of the photon catcher by an in-situ chemical synthesis method, so that the MXene has a light energy and magnetic energy dual-drive energy conversion form, and the problem of single function of the phase change energy storage material is effectively solved. Meanwhile, the in-situ chemical synthesis method adopted by the invention can uniformly disperse the magnetic oxide on the MXene surface and among the sheet layers, effectively solves the problems of non-uniform mechanical, magnetic and heat transfer and the like caused by agglomeration of the magnetic oxide, and simultaneously shortens the heat transfer path by uniformly embedding the magnetic oxide, thereby improving the photo-thermal conversion efficiency again.
Drawings
FIG. 1 shows MXene @ Fe obtained in step (1) of example 1 of the present application 3 O 4 SEM image of the composite support;
FIG. 2 shows MXene @ Fe obtained in step (1) of example 1 of the present application 3 O 4 XRD spectrogram of the composite carrier;
FIG. 3 shows MXene @ Fe obtained in step (1) of example 1 of the present application 3 O 4 A hysteresis loop of the composite carrier;
FIG. 4 shows MXene @ Fe obtained according to example 1 of the present application 3 O 4 DSC profile of MA composite phase change material.
Detailed Description
In order to make the present application more clearly understood by those skilled in the art, the present application is described in further detail below with reference to examples and drawings, but it should be understood that the following examples are only preferred embodiments of the present application, and the scope of the present application is defined by the scope of the claims.
In a first aspect, the application provides a light energy and magnetic energy dual-drive composite phase change material, which comprises an MXene matrix; magnetic metal oxide doped on the inner surface and the outer surface of the MXene matrix; and phase change material compounded in MXene matrix.
In the application, different types of magnetic metal oxides are uniformly embedded into the MXene surface and the MXene layers by adopting an in-situ chemical synthesis method, the magnetic metal oxides can have nanometer-level sizes, then the magnetic metal oxides are activated in vacuum to activate the composite carrier, then the composite carrier is soaked in a solution of a phase-change material, and the phase-change material is adsorbed and loaded by utilizing physical and chemical acting forces such as capillary pore acting force, hydrogen bond and the like, so that the composite phase-change material with high-efficiency light energy and magnetic energy dual-drive energy conversion is obtained. Therefore, the composite phase-change material realizes efficient and rapid energy conversion and storage, has simple preparation process, diversified selection of the magnetic metal oxide and the phase-change material and good economical efficiency.
The MXene is a two-dimensional (2D) layered transition metal carbide/nitride/carbonitride, consisting of several atomic layer thicknesses of transition metal carbides, nitrides or carbonitrides, with a structure similar to graphene. MXene has a high ability to conduct electrons, and thus is excellent in electrical and thermal conductivity, and also has excellent light absorption properties. Compared with the traditional inorganic carbon material, MXene has two obviously enhanced absorption peaks in visible light and near infrared regions, which can be attributed to Local Surface Plasmon Resonance (LSPR) effect, so that MXene has high application value in the field of photothermal conversion. The phase change energy storage material adopts MXene as a photon catcher, and the magnetic metal oxide is doped on the surface and between the layers of the photon catcher by an in-situ chemical synthesis method, so that the phase change energy catcher has a light energy and magnetic energy dual-drive energy conversion form, and the problem of single functionality of the phase change energy storage material is effectively solved.
In addition, because the magnetic force between the magnetic metal oxide particles is large and the magnetic metal oxide particles have a nano-size particle size, the magnetic metal oxide particles are easy to agglomerate, and the mechanical and magnetic properties of the magnetic composite material are affected. Therefore, in order to obtain a magnetic composite material having excellent properties, it is an indispensable prerequisite to avoid agglomeration of magnetic metal oxide particles. In contrast, the method adopts a specific in-situ chemical synthesis method, so that magnetic metal oxide particles can be uniformly dispersed on the outer surface of MXene and between the layers, and a metal source of the magnetic metal oxide is stably anchored on the MXene in the in-situ synthesis process by virtue of a large amount of negative ions existing between the surface of the MXene and the layers, thereby effectively solving the problems of non-uniformity in mechanics, magnetism, heat transfer and the like caused by agglomeration of the magnetic metal oxide. Meanwhile, the uniformly embedded magnetic metal oxide particles can be cooperated with MXene, so that on one hand, the magnetic metal oxide particles realize radial migration of heat from the surface to the inside of the composite phase-change material, the heat transfer path of light-to-heat energy is shortened, the dissipation of heat energy is reduced, and the light-driven energy conversion capability of the composite phase-change material is improved; on the other hand, MXene contributes to rapid conversion and instantaneous effective transfer of magnetic conversion heat energy, so that the photo-thermal and magneto-thermal conversion efficiency is further improved.
In addition, the phase-change material is dispersedly attached to the inner surface and the outer surface of the MXene composite carrier, so that efficient and rapid energy conversion and storage are realized.
Further, the composite phase change material is prepared by the following method:
(1) Doping magnetic metal oxide on the surface and between the sheet layers by using MXene as a photon catcher through an in-situ chemical synthesis method to obtain an MXene composite phase change carrier doped with the magnetic metal oxide; and
(2) Compounding the MXene composite phase change carrier doped with the magnetic metal oxide obtained in the step (1) with a phase change core material to obtain the magnetic material.
In the composite phase change material according to the application, MXene is prepared by etching a MAX phase of a precursor under an acidic condition by using an inorganic fluoride. That is, the MXene can be obtained by selectively etching away some atoms (e.g., A) from a precursor MAX phase ceramic (a metal-based layered ceramic material in which M is a transition metal of the first groups, such as groups IIIB to VI B (e.g., ti, V, mo, etc.), A is a III or lower IV main group element, typically Al or Si, and X is a C and/or N element) to obtain a multilayer structure material MXene having a morphology similar to that of expanded graphite. Correspondingly, MXene may be expressed as M n+1 X n T x Wherein n =1, 2 or 3,Tx represents a surface termination group (-OH, -O, -F).
By way of illustration, in the present application, the MXene can be prepared by: adding inorganic fluoride and MAX to an acidic solution having a H + concentration of 8M to 12M (e.g., 8M, 8.5M, 9M, 9.5M, 10M, 10.5M, 11M, 11.5M, or 12M, or other specific values within the range), preferably 10M, under stirring, and continuing stirring at 0 ℃ to 70 ℃ (e.g., 0 ℃,5 ℃,15 ℃, 20 ℃,25 ℃,30 ℃, 35 ℃, 40 ℃, 45 ℃,50 ℃, 55 ℃, 60 ℃, 65 ℃, or 70 ℃, or other specific values within the range), preferably normal temperature to 50 ℃ (e.g., 24H, 26H, 28H, 30H, 32H, 34H, 36H, 38H, 40H, 42H, 44H, 46H, or 48H, or other specific values within the range), and then dispersing the resultant in water, centrifuging, washing to neutrality, and drying to obtain MX. Wherein the MAX may be Ti 4 AlN 3 、Ti 3 AlC 2 、Mo 2 Ga 2 C、Zr 3 Al 3 C 5 Etc., preferably Ti 3 AlC 2 . Ti as MAX 3 AlC 2 The Al layer can be selectively etched away to obtain Ti 3 C 2 MXene material of (ii); the inorganic fluoride may be selected from HF, and,NH 4 HF 2 LiF, naF, KF, csF and CaF 2 At least one of; the acidic solution may be at least one selected from hydrochloric acid, sulfuric acid, and nitric acid; and the weight ratio of the inorganic fluoride to MAX may be (0.5-5): 1; the acidic solution may be used in an amount of (10 mL-30 mL)/g MAX (e.g., 10mL/g MAX, 12mL/g MAX, 14mL/g MAX, 16mL/g MAX, 18mL/g MAX, 20mL/g MAX, 22mL/g MAX, 24mL/g MAX, 26mL/g MAX, 28mL/g MAX, or 30mL/g MAX, or other specific values within the range). MXene suitable for use in the present application can be prepared by the above method, but the present application is not limited thereto.
In the composite phase change material according to the present application, the step (1) includes: MXene was dispersed in water, a surfactant was added thereto and stirred, and then a magnetic metal oxide precursor was added and hydrolyzed to obtain an MXene composite carrier doped with a magnetic metal oxide.
In the step (1), the magnetic metal oxide precursor may be at least one selected from the group consisting of an inorganic acid salt of iron, a complex of iron, an inorganic acid salt of cobalt, a complex of cobalt, an inorganic acid salt of nickel, and a complex of nickel. Preferably, the magnetic metal oxide precursor may be at least one selected from the group consisting of ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate, cobalt chloride, cobalt sulfate, cobalt nitrate, nickel chloride, nickel sulfate, nickel nitrate, ferric acetylacetonate, cobalt acetylacetonate, and nickel acetylacetonate, and more preferably at least one selected from the group consisting of ferric chloride, ferrous chloride, cobalt chloride, and nickel acetylacetonate. Thus, the magnetic metal oxide may be iron oxide (Fe) 3 O 4 ) Cobaltosic oxide (Co) 3 O 4 ) Or nickel oxide (NiO).
Further, in the step (1), the hydrolysis method of the magnetic metal oxide precursor may be hydrolysis of the magnetic metal oxide precursor under basic conditions. For example, an alkaline solution (e.g., a solution of NaOH or KOH) may be added dropwise to a system in which an inorganic acid salt of iron, an inorganic acid salt of cobalt, or an inorganic acid salt of nickel is dissolved to adjust the pH to 10 or more (e.g., pH =10, 11, or 12), and the reaction and heating may be carried out at room temperatureBy reaction or hydrothermal reaction, to obtain the corresponding magnetic metal oxide, e.g. Fe 3 O 4 、Co 3 O 4 Or NiO; alternatively, oleylamine (cis oleylprimary amine) may be added to a system in which iron acetylacetonate, cobalt acetylacetonate or nickel acetylacetonate is dissolved in the presence of octadecene and oleic acid, and the reaction may be heated to obtain the corresponding magnetic metal oxide, such as Fe 3 O 4 、Co 3 O 4 Or NiO, wherein the molar ratio of the iron acetylacetonate, the cobalt acetylacetonate or the nickel acetylacetonate to the octadecene, the oleic acid and the oleylamine can be 1 (8-11) to (2-4) to (8-10), and is preferably 1. The hydrolysis is carried out on the inner and outer surfaces of MXene, and the generated magnetic metal oxide can be uniformly and stably distributed between the layers and on the surfaces of MXene by using an in-situ synthesis method and electrostatic acting force.
Further, in the step (1), the addition amount of the magnetic metal oxide precursor may be adjusted so that the weight ratio of MXene to the doped magnetic metal oxide is (1-5): 1. Under the doping proportion, the magnetic metal oxide in the composite carrier can be distributed more uniformly.
In step (1), the surfactant may be a quaternary ammonium salt surfactant, for example, at least one selected from the group consisting of octadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide, dioctadecyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, and dodecyl trimethyl ammonium chloride, preferably hexadecyl trimethyl ammonium bromide (CTAB). The weight ratio of MXene to the surfactant may be (1-3): 1, preferably 1.875.
Further, in step (1), in order to promote the dispersion of MXene and the dissolution of the surfactant, the system may be heated to 30 to 50 ℃ (for example, may be, 30 ℃, 32 ℃, 34 ℃, 36 ℃, 38 ℃, 40 ℃, 42 ℃, 44 ℃, 46 ℃, 48 ℃, or 50 ℃, or other specific value within the range) before the addition of the surfactant, and stirred for 15 to 25min (for example, may be, 15min, 16min, 17min, 18min, 19min, 20min, 21min, 22min, 23min, 24min, or 25min, or other specific value within the range) after the addition of the surfactant, preferably for 20min.
In the composite phase change material according to the present application, the step (2) includes: and activating the MXene composite carrier doped with the magnetic metal oxide in vacuum, dispersing the MXene composite carrier in an aqueous solution/alcoholic solution of the phase-change material, heating and stirring, filtering and drying to obtain the composite phase-change material.
In the step (2), the phase change material may be a polyol or a higher fatty acid, wherein the polyol may include polyethylene glycol 1000 to 20000 (for example, polyethylene glycol 1000, polyethylene glycol 2000, polyethylene glycol 3000, polyethylene glycol 4000, polyethylene glycol 5000, polyethylene glycol 6000, polyethylene glycol 7000, polyethylene glycol 8000, polyethylene glycol 9000, polyethylene glycol 10000, polyethylene glycol 11000, polyethylene glycol 12000, polyethylene glycol 13000, polyethylene glycol 14000, polyethylene glycol 15000, polyethylene glycol 16000, polyethylene glycol 17000, polyethylene glycol 18000, polyethylene glycol 19000, or polyethylene glycol 20000), pentaerythritol, neopentyl glycol, or the like, and the fatty acid may include stearic acid, myristic acid, palmitic acid, capric acid, lauric acid, pentadecanoic acid, sebacic acid, or the like.
Further, in step (2), the concentration of the aqueous/alcoholic solution of the phase change material may be 10mg/mL to 40mg/mL (for example, may be 10mg/mL, 15mg/mL, 17.5mg/mL, 20mg/mL, 22.5mg/mL, 25mg/mL, 27.5mg/mL, 30mg/mL, 32.5mg/mL, 35mg/mL, or 40mg/mL, or other specific values within the range), and is preferably 15mg/mL to 35mg/mL.
In the step (2), the vacuum activation condition may be that the MXene composite support doped with the magnetic metal oxide is vacuum-heated at 120-200 ℃ (e.g., 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, or 200 ℃, or other specific value within the range) for 3-6 h (e.g., 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, or 6h, or other specific value within the range), preferably 4h. Through the vacuum activation, small molecular substances in the composite carrier can be effectively removed, and the pore channel of the composite carrier is fully activated, so that the phase change material can be efficiently and stably adsorbed. In addition, in order to further improve the activation efficiency, the vacuum activation may be performed after the composite carrier is freeze-dried to remove most of moisture and other small molecular substances.
In the step (2), the heating and stirring conditions are heating and stirring for 1h to 24h (for example, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h or 24h, or other specific values within the range) at 25 ℃ to 100 ℃ (for example, 25 ℃,30 ℃, 35 ℃, 40 ℃, 45 ℃,50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃, or other specific values within the range). Under the condition, the phase-change material can be fully adsorbed in the pore channels of the composite carrier through capillary action force, hydrogen bond and other physical and chemical action forces.
In the step (2), the drying is performed under a condition of heating and drying for 2h to 24h (for example, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h or 24h, or other specific values within the range) at 50 ℃ to 120 ℃ (for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃, or other specific values within the range).
In a second aspect, the application also provides a preparation method of the above optical energy and magnetic energy dual-drive composite phase-change material, which includes the following steps:
(1) Doping magnetic metal oxide on the surface and between the sheet layers by using MXene as a photon catcher through an in-situ chemical synthesis method to obtain an MXene composite phase change carrier doped with the magnetic metal oxide; and
(2) Compounding the MXene composite phase change carrier doped with the magnetic metal oxide obtained in the step (1) with a phase change core material to obtain the composite phase change material.
The advantages of the optical energy and magnetic energy dual-drive composite phase change material according to the application at least include the following points: 1) Different types of magnetic metal oxides are uniformly embedded on the surface and the interlayer of MXene with excellent light absorption performance by adopting an in-situ chemical synthesis method, so that the problem that the conventionally synthesized magnetic metal oxides are easy to agglomerate is solved; 2) The composite phase-change material which has the double-drive energy conversion form of light energy and magnetic energy can be obtained after being compounded with the phase-change material, meanwhile, the uniformly distributed magnetic metal oxide also realizes the radial transfer of heat from the surface to the inside, shortens a heat transfer path, and further improves the photo-thermal conversion efficiency again, so that the composite phase-change material prepared by the method has higher photo-thermal and magneto-thermal conversion efficiency; and 3) the selection of the magnetic metal oxide and the phase change core material can be diversified and has good economical efficiency.
In summary, the invention takes MXene as a photon catcher, and dopes magnetic oxide on the surface and between layers by an in-situ chemical synthesis method, so that the phase-change energy storage material has a dual-drive energy conversion form of light energy and magnetic energy, and effectively solves the problem of single functionality of the phase-change energy storage material. Meanwhile, the in-situ chemical synthesis method adopted by the invention can uniformly disperse the magnetic oxide on the MXene surface and among the sheet layers, effectively solves the problems of non-uniform mechanical, magnetic and heat transfer and the like caused by agglomeration of the magnetic oxide, and simultaneously shortens the heat transfer path by uniformly embedding the magnetic oxide, thereby improving the photo-thermal conversion efficiency again.
The technical solution of the present application is exemplarily described below by specific embodiments:
sources of materials
Ti 3 AlC 2 The purity is 98 percent, the granularity is 200 meshes, and the product is purchased from Beijing Piweiruike chemical Co.
In addition, other compounds used herein are commercially available or ordered and commercially available to one skilled in the art as desired.
< example >
Preparation of example 1
MXene according to the present application was prepared using the following method:
1g of LiF and 1g of MAX are slowly added to 20mL of HCl (10M) solution with vigorous stirring and stirred for 36h under an oil bath at 35 ℃. The resulting product was dispersed in deionized water and washed by centrifugation at 3600rmp until the supernatant was neutral. The obtained precipitate was freeze-dried to obtain a multilayered MXene powder.
Example 1
(1) 150mg of MXene powder prepared in production example 1 was dispersed in deionized water, heated in an oil bath at 55 ℃ and 80mg of CTAB surfactant was added thereto, and stirred for 20min; thereto was subsequently added 187mg FeCl 3 ·6H 2 O, and stirring for 30min under Ar atmosphere; (ii) a 109mg FeCl was then added to the solution 2 ·4H 2 O, adding NaOH solution to adjust the pH value to be more than 10, stirring for 4h, washing the product to be neutral by deionized water after stirring is finished, and freeze-drying to obtain the MXene composite carrier doped with the magnetic metal oxide, namely MXene @ Fe 3 O 4 And (3) a carrier.
(2) 0.150g of MXene @ Fe prepared in the above step (1) 3 O 4 Activating the carrier at 120 deg.C under vacuum for 4 hr, dispersing in 10mL absolute ethanol solution containing 0.35g Myristic Acid (MA), stirring at 60 deg.C for 2 hr, placing the mixture in 80 deg.C drying oven, maintaining the temperature for 36 hr, and collecting MXene @ Fe 3 O 4 MA-loaded composite phase change materials, i.e. MXene @ Fe 3 O 4 -MA。
FIG. 1 shows MXene @ Fe obtained in step (1) of this example 3 O 4 SEM image of composite Carrier, which shows MXene @ Fe prepared by step (1) of this example 3 O 4 In a composite carrier, magnetic Fe 3 O 4 The particles are uniformly distributed on the surface of MXene without obvious agglomeration.
FIG. 2 shows MXene @ Fe obtained in step (1) of this example 3 O 4 XRD pattern of the composite support, which clearly shows relevanceDiffraction peaks of the elements prove that the magnetic Fe is successfully loaded 3 O 4 And (3) granules.
FIG. 3 shows MXene @ Fe obtained in step (1) of this example 3 O 4 The magnetic hysteresis loop of the composite carrier shows that the saturation magnetization (Ms) of the composite carrier is 15.356emu/g, the coercive force and the remanence are negligible, which indicates that the obtained composite carrier is superparamagnetic at room temperature, and the magnetic characteristic shows that an external magnetic field can attract MXene @ Fe 3 O 4 . Therefore, the composite material has excellent magnetic performance and can be used as a phase change material with great prospect in magnetic-thermal conversion.
FIG. 4 shows MXene @ Fe prepared according to this example 3 O 4 The DSC curve of the composite phase-change material is almost consistent with that of pure MA, and enthalpy values are similar, so that the prepared composite phase-change material has excellent phase-change behavior and phase-change heat storage performance.
Example 2
(1) 150mg of MXene powder prepared in production example 1 was dispersed in deionized water, heated in an oil bath at 40 ℃ and 80mg of CTAB surfactant was added thereto, and stirred for 20min; 165mg of CoCl was then added thereto 2 And stirring for 30min under Ar atmosphere; then adding NaOH solution dropwise to adjust the pH value to be more than 10, stirring for 30min, transferring the mixed system into a reaction kettle, reacting for 5h at 65 ℃, then cooling to room temperature, washing the product to be neutral by deionized water, and freeze-drying to obtain the MXene composite carrier doped with the magnetic metal oxide, namely MXene @ Co 3 O 4 And (3) a carrier.
(2) 0.150g of MXene @ Co prepared in the above step (1) 3 O 4 Activating the carrier at 180 deg.C under vacuum for 4 hr, dispersing in 10mL anhydrous ethanol solution containing 0.225g MA, stirring at 80 deg.C for 2 hr, placing the mixture in 80 deg.C drying oven, maintaining the temperature for 36 hr, and collecting MXene @ Co 3 O 4 MA-loaded composite phase change materials, i.e. MXene @ Co 3 O 4 -MA。
Example 3
(1) 150mg of MXene powder prepared in production example 1 was dispersed in deionized water, heated in an oil bath at 30 ℃ and 80mg of CTAB surfactant was added thereto, and stirred for 20min; 4.70g of octadecene and 1.69g of oleic acid were then added thereto and stirred for 30min, then 0.515g of nickel acetylacetonate was added to the solution at 100 ℃ and stirred for 1.5h. 2.40g of oleylamine was added to the above-obtained pale green mixed system, and stirred at 100 ℃ for 1 hour. And then transferring the obtained product to a reaction kettle, reacting for 6h at 200 ℃, then cooling to room temperature, washing the product with deionized water, and freeze-drying to obtain the MXene composite carrier doped with the magnetic metal oxide, namely the MXene @ NiO carrier.
(2) And (2) activating 0.15g of MXene @ NiO carrier prepared in the step (1) in vacuum at 200 ℃ for 4h, dispersing the MXene @ NiO carrier in 10mL of anhydrous ethanol solution containing 0.15g of MA, stirring the solution at 80 ℃ for 2h, putting the mixed solution in a drying box at 80 ℃, preserving the temperature for 36h, and collecting the MXene @ NiO supported MA composite phase change material, namely MXene @ NiO-MA.
Comparative example 1
(1) 150mg of MXene powder from preparation example 1 were dispersed in deionized water, heated in an oil bath at 30 ℃ and then 125mg of Fe was added directly to the solution 3 O 4 Stirring for 4h, washing the product with deionized water, and freeze drying to obtain MXene-Fe as carrier material 3 O 4 And (3) a carrier.
(2) 0.150g of MXene-Fe prepared in the above step (1) 3 O 4 Activating the carrier at 120 deg.C under vacuum for 4 hr, dispersing in 10mL absolute ethanol solution containing 0.35g Myristic Acid (MA), stirring at 60 deg.C for 2 hr, placing the mixture in 80 deg.C drying oven, maintaining the temperature for 36 hr, and collecting MXene-Fe 3 O 4 MA-loaded composite phase change materials, i.e. MXene-Fe 3 O 4 -MA。
Effects of the embodiment
Test method
1. Latent heat of phase change
N at 50mL/min using Differential Scanning Calorimeter (DSC) 2 The phase change behavior of the pure phase change material and the corresponding composite phase change material was characterized under flow and heating/cooling rate of 10 ℃/min to determine their latent heat of phase change (enthalpy of fusion).
2. Efficiency of photothermal conversion
The photothermal conversion performance of the sample was measured by the following method: a xenon lamp is used as a light source to simulate sunlight for irradiation, and a digital data collector is used for recording a temperature-time curve. In order to reduce the influence of heat exchange between the sample and the external environment on the experiment in the measuring process, a heat-insulating layer is added around the light source and the sample for reducing the heat loss, and a light-transmitting heat-insulating layer is bonded between the light source and the heat-insulating layer for reducing the energy loss from the light source. Further, the photothermal conversion efficiency (%) of the composite phase change materials prepared in examples 1 to 3 was calculated using the following formula:
wherein m is the mass of the sample, Δ H is the melting enthalpy of the sample, P is the light intensity of sunlight simulated by the experiment, T s And T f The phase change starting time and the phase change ending time are respectively set when the temperature is raised by illumination.
Results of the experiment
Using the above test and calculation methods, the prepared products of examples 1-3 and comparative example 1 were subjected to the performance or effect test, and the results are shown in the following Table 1:
[ Table 1]
| Enthalpy of fusion (J/g) | Photothermal conversion efficiency (%) | |
| Example 1 | 138 | 98.0 |
| Example 2 | 112 | 97.6 |
| Example 3 | 103 | 96.7 |
| Comparative example 1 | 98 | 90.2 |
As shown in the above examples 1 to 3 and comparative example 1, the preparation method of the optical energy and magnetic energy dual-drive composite phase change material according to the present application can prepare a composite phase change material having a high enthalpy value and excellent photothermal conversion efficiency.
The above-described embodiments of the present application are only examples of the present application and should not be construed as limiting the present application, and those skilled in the art can make modifications without inventive contribution as required after reading the present specification, however, any modifications, equivalents, improvements, etc. within the spirit and principle of the present application should be included in the scope of the present application.
Claims (6)
1. A composite phase change material driven by both optical energy and magnetic energy comprises: MXene matrix; magnetic metal oxide doped on the inner surface and the outer surface of the MXene matrix; and phase change material compounded in MXene matrix;
the composite phase change material is prepared by the following method:
(1) Dispersing MXene in water, adding a surfactant into the water, stirring, adding a magnetic metal oxide precursor, and hydrolyzing to obtain an MXene composite phase change carrier doped with a magnetic metal oxide;
the magnetic metal oxide precursor is selected from one or more of the following: the magnetic metal oxide is ferroferric oxide, cobaltosic oxide and/or nickel oxide;
the hydrolysis is hydrolysis of the magnetic metal oxide precursor under alkaline conditions;
(2) Activating the MXene composite carrier doped with the magnetic metal oxide in vacuum, dispersing the MXene composite carrier in an aqueous solution/alcoholic solution of the phase-change material, heating and stirring, filtering and drying to obtain the composite phase-change material;
the phase-change material comprises 1000-20000 of polyethylene glycol, pentaerythritol, neopentyl glycol, stearic acid, myristic acid, palmitic acid, capric acid, lauric acid, pentadecanoic acid and sebacic acid.
2. The composite phase change material of claim 1, wherein the MXene is prepared by etching a precursor MAX phase under acidic conditions using an inorganic fluoride;
the MXene is prepared by the following method: adding inorganic fluoride and MAX into an acid solution with the H + concentration of 8M-12M under stirring, continuously stirring for 24H-48H at the temperature of 0-70 ℃, dispersing the obtained product into water, centrifuging, washing to be neutral, and drying to obtain the MXene.
3. The composite phase change material of claim 1, wherein in step (1), the surfactant is at least one selected from the group consisting of octadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide, dioctadecyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, and dodecyl trimethyl ammonium chloride.
4. The composite phase change material of claim 1, wherein in the step (2), the concentration of the aqueous/alcoholic solution of the phase change material is 10mg/mL to 40mg/mL.
5. The composite phase change material of claim 1, wherein in the step (2), the vacuum activation condition is that the MXene composite carrier doped with the magnetic metal oxide is heated in vacuum at 120-200 ℃ for 3-6 h.
6. The composite phase-change material as claimed in claim 1, wherein in the step (2), the heating and stirring conditions are heating and stirring at 25-100 ℃ for 1-24 h; the drying condition is that the mixture is heated and dried for 2 to 24 hours at the temperature of between 50 and 120 ℃.
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