CN113621349A - Phase-change gel for sunlight photo-thermal conversion and preparation method thereof - Google Patents
Phase-change gel for sunlight photo-thermal conversion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a phase change gel for sunlight photo-thermal conversion and a preparation method thereof, wherein a phase change material is dissolved in an organic solvent, and then a porous support material is added to obtain a phase change solution after complete dissolution; adding a surface-modified photothermal conversion material into the phase change solution, and uniformly dispersing the photothermal conversion material in the phase change solution by a physical means; heating to remove the organic solvent in the phase-change solution to obtain the phase-change gel with the photo-thermal conversion performance. The phase-change gel prepared by the invention is applied to the field of solar photo-thermal conversion, and the energy is directly converted by combining the heat storage of the phase-change gel and thermoelectric generation.
Description
Technical Field
The invention belongs to the technical field of phase-change materials, relates to a phase-change gel, and particularly relates to a phase-change gel for sunlight-thermal conversion and a preparation method thereof.
Background
With the gradual development of society, the demand of people for energy is increasing day by day, fossil energy is non-renewable, and the development is close to saturation, so renewable clean energy becomes the research focus of people. Solar energy, as the most abundant, renewable and environmentally friendly energy source, is the most likely alternative to traditional fossil fuels. However, the intensity of solar energy is limited in time, the energy utilization can only be performed during the day and on sunny days, the utilization is relatively difficult in the evening or on cloudy days, and the utilization of intermittent and discontinuous solar radiation energy is also a serious challenge. The phase-change material has special energy storage characteristics, and the renewable solar energy and the phase-change material are combined to store the solar energy in the phase-change material, so that the intermittent defect of the renewable energy source can be effectively overcome, and the utilization efficiency of the solar energy is improved.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of the phase-change gel for solar photo-thermal conversion.
The second object of the present invention is to provide a phase-change gel for solar photothermal conversion prepared by the above preparation method.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides a method for preparing a phase-change gel for solar photothermal conversion, comprising the steps of:
(1) dissolving an organic phase-change material into an organic solvent, adding a porous support material, and completely dissolving to obtain a phase-change solution, wherein the mass ratio of the organic phase-change material to the porous support material is (80-87): 13-20 parts of;
(2) adding a surface-modified photothermal conversion material into the phase change solution, and uniformly dispersing the photothermal conversion material in the phase change solution by a physical means; the addition amount of the photothermal conversion material accounts for 0.1-11% of the total amount of the organic phase change material and the porous support material;
(3) heating to remove the organic solvent in the phase-change solution to obtain the phase-change gel with the photo-thermal conversion performance.
Preferably, the organic phase change material is selected from one or more of alkanes, alkanols and fatty acids.
Preferably, the porous support material is selected from the group consisting of highly elastic block copolymers, silica, and the like having a porous support.
Preferably, the photothermal conversion material is selected from one or more functional materials having a light absorbing substance, such as multi-walled carbon nanotubes (MWCNTs), graphene, expanded graphite, and carbon fibers.
Preferably, the organic solvent is selected from one or more of tetrahydrofuran, xylene, pentane, hexane, cyclohexane, cyclohexanone, toluene cyclohexanone, chlorobenzene, dichlorobenzene, dichloromethane, methanol, ethanol, isopropanol, diethyl ether, propylene oxide, methyl acetate, ethyl acetate, propyl acetate, acetone, methyl butanone, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile and pyridine.
The invention also provides a preparation method of the phase-change gel for sunlight photo-thermal conversion, which comprises the following steps:
(1) heating, stirring and melting the inorganic phase-change material into colorless and transparent liquid, adding the nucleating agent, heating and stirring until the nucleating agent is uniformly dispersed to obtain a phase-change solution; the addition amount of the nucleating agent accounts for 1% of the mass of the inorganic phase change material;
(2) adding a surface-modified photothermal conversion material into the phase change solution, and uniformly dispersing the photothermal conversion material in the phase change solution by a physical means; the addition amount of the photo-thermal conversion material accounts for 0.1-11% of the mass of the inorganic phase change material;
(3) adding sodium acrylate into the solution obtained in the step (2), stirring at constant temperature for 20-30min, adding a cross-linking agent, continuously stirring at constant temperature for 20-30min, and finally adding an initiator for cross-linking initiation to obtain inorganic phase-change gel with photo-thermal conversion property; the addition amount of the sodium acrylate accounts for 10% of the mass of the inorganic phase-change material, the cross-linking agent accounts for 0.3% -0.5% of the mass of the inorganic phase-change material, and the initiator accounts for 1% -2% of the mass of the inorganic phase-change material.
Preferably, the photothermal conversion material is selected from one or more functional materials having a light absorbing substance, such as multi-walled carbon nanotubes (MWCNTs), graphene, expanded graphite, and carbon fibers.
Preferably, the inorganic phase change material is an inorganic hydrated salt type phase change material.
Preferably, the nucleating agent is selected from one or more of nano-alumina, borax, strontium chloride, magnesium chloride, barium carbonate and disodium hydrogen phosphate dodecahydrate.
Preferably, the cross-linking agent is N, N' -methylene bisacrylamide, and the initiator is ammonium persulfate or potassium persulfate.
In a second aspect, the invention also provides the phase-change gel for solar photothermal conversion prepared by the above preparation method.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention provides a novel idea of combining a phase change material and solar clean energy, which can store sunlight and also can utilize the stored sunlight under the condition of no sunlight.
2) The phase-change material used in the invention can be an organic phase-change material or an inorganic phase-change material.
3) The functional material is added into the phase-change material by a wet method, and a relatively uniform phase-change material solution is obtained.
4) Some physical properties of the phase change material, such as stress strain, temperature tolerance, etc., are indirectly changed after the addition of the functional phase change material.
Drawings
FIG. 1 is a scanning electron micrograph of a phase-change gel having a photothermal conversion property according to example 1.
FIG. 2 is a stress-strain curve of the phase change gel having the light-to-heat conversion property of example 1, which has a high yield strength.
FIG. 3 is a diagram of a finished phase-change gel having a light-to-heat conversion performance in example 1.
Fig. 4 shows the power generation amount of the phase-change gel thermoelectric power generation under different sunlight intensities in example 1.
FIG. 5 is a scanning electron micrograph of a phase change gel having a photothermal conversion property according to example 2.
FIG. 6 is a stress-strain curve of a phase change gel having a light-to-heat conversion property in example 2, which has a high yield strength.
FIG. 7 is a diagram of a finished phase-change gel having light-to-heat conversion properties in example 2.
Fig. 8 shows the power generation amount of the phase-change gel thermoelectric power generation under different sunlight intensities in example 2.
FIG. 9 is a scanning electron micrograph of a phase change gel having a photothermal conversion property according to example 3.
FIG. 10 is a stress-strain curve of a phase change gel having light-to-heat conversion properties of example 3, which has a high yield strength.
FIG. 11 is a diagram of a finished phase-change gel having light-to-heat conversion properties according to example 3.
FIG. 12 shows the power generation amount of the phase-change gel thermoelectric power generation under different sunlight intensities in example 3.
FIG. 13 is a scanning electron micrograph of a phase change gel having a photothermal conversion property according to example 4.
FIG. 14 is a stress-strain curve of a phase change gel having photothermal conversion properties in example 4, which has a high yield strength.
FIG. 15 is a diagram of a finished phase-change gel having light-to-heat conversion properties according to example 4.
Fig. 16 shows the power generation amount of the phase-change gel thermoelectric power generation under different sunlight intensities in example 4.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Example 1
(1) The MWCNT is subjected to chemical surface modification, firstly, the MWCNT is subjected to acidification treatment, and hydroxyl and carboxyl functional groups are introduced to the MWCNT, wherein the modification method comprises the following steps:
10g of MWCNT is placed in 40mL of mixed acid of concentrated nitric acid and concentrated sulfuric acid, and the volume ratio of the concentrated nitric acid to the concentrated sulfuric acid is 1: 3, sonicating at 50 ℃ for 6h to give 10.11g MCNT-COOH.
(2) 87g of 1-octadecanol is taken and added into 50mL of tetrahydrofuran, stirred until the 1-octadecanol is completely dissolved, and then 13g of block copolymer-SEBS is added to completely dissolve the 1-octadecanol in the solution, thus obtaining the phase change solution.
(3) After 10.11g of surface-modified MWCNT was added to the above phase-change solution, ultrasonic oscillation was performed for 5min, so that MWCNT could be dispersed more uniformly in the solution.
(4) And (3) transferring the solution to an open beaker, heating a heating table in a fume hood to 50 ℃, stirring while heating, and separating the solution due to the strong volatility of tetrahydrofuran to completely volatilize to obtain the required phase-change gel.
(5) The obtained phase-change gel is processed at high temperature to obtain a regular rectangle compounded with the thermoelectric generation piece, the prepared functional phase-change gel is bonded with the thermoelectric generation piece through the heat-conducting silicone grease, the lower end of the phase-change gel is provided with a radiating fin, and under sunlight, the voltage at two ends of the thermoelectric generation piece can generate electricity due to different temperature differences. The functional phase-change gel can also store sunlight heat, and can continuously keep the temperature of the high-temperature end under the condition of no sunlight, so that the voltage at the two ends of the thermoelectric generation piece is kept constant in a period of time, and the voltage peak value at the two ends of the thermoelectric generation piece is between 0.3 and 1.5V.
FIG. 1 is a scanning electron micrograph of a phase change material having photothermal conversion properties according to example 1. It can be seen that the material has a regular, layered, stacked structure which helps to increase the tensile strength of the material.
Fig. 2 is a stress-strain curve of the phase change material having the photothermal conversion property of example 1, which has a high yield strength.
Fig. 3 is a diagram of a finished phase change material having a photothermal conversion property in example 1.
Fig. 4 shows the power generation amount of the thermoelectric generation of the phase change material under different sunlight intensities in example 1. It can be seen from the figure that the maximum voltage and the equilibrium voltage of the thermoelectric generation sheet of the material are increased along with the increase of the sunlight intensity.
Example 2
(1) The MWCNT is subjected to chemical surface modification, firstly, the MWCNT is subjected to acidification treatment, and hydroxyl and carboxyl functional groups are introduced to the MWCNT, wherein the modification method comprises the following steps:
placing 5g MWCNT in 40mL mixed acid of concentrated nitric acid and concentrated sulfuric acid, wherein the volume ratio of the concentrated nitric acid to the concentrated sulfuric acid is 1: 3, sonicate at 50 ℃ for 6h to give 5.3g MCNT-COOH.
(2) 87g of n-eicosane is weighed and added into 50mL of tetrahydrofuran, stirred until the n-eicosane is completely dissolved, and then 13g of block copolymer-SEBS is added into the tetrahydrofuran and completely dissolved in the solution, so that a phase-change solution is obtained.
(3) After 5.3g of the surface-modified MWCNT is added into the phase-change solution, ultrasonic oscillation is carried out for 5min, so that the graphene oxide can be dispersed in the solution more uniformly.
(4) And (3) transferring the solution to an open beaker, heating a heating table in a fume hood to 50 ℃, stirring while heating, and separating the solution due to the strong volatility of tetrahydrofuran to completely volatilize to obtain the required phase-change gel.
(5) The obtained phase-change gel is processed at high temperature to obtain a regular rectangle compounded with the thermoelectric generation piece, the prepared functional phase-change material is bonded with the thermoelectric generation piece through heat-conducting silicone grease, a radiating fin is arranged at the lower end of the phase-change material, and under sunlight, voltages at two ends of the thermoelectric generation piece can generate electricity due to different temperature differences to provide electric energy. The functional phase-change material can also store sunlight heat, and can continuously keep the temperature of a high-temperature end under the condition of no sunlight, so that the voltage of the two ends of the thermoelectric generation piece is kept constant within a period of time, and the voltage peak value of the two ends of the thermoelectric generation piece is between 0.3 and 1.5V.
FIG. 5 is a scanning electron micrograph of a phase change material having photothermal conversion properties according to example 2. It can be seen that the material has a regular, layered, stacked structure which helps to increase the tensile strength of the material.
Fig. 6 is a stress-strain curve of the phase change material having the photothermal conversion property of example 2, which has a high yield strength.
FIG. 7 is a diagram of a finished phase change material with photothermal conversion properties according to example 2.
Fig. 8 shows the power generation amount of the phase change material thermoelectric power generation under different sunlight intensities in example 2. It can be seen from the figure that the maximum voltage and the equilibrium voltage of the thermoelectric generation sheet of the material are increased along with the increase of the sunlight intensity.
Example 3
(1) The MWCNT is subjected to chemical surface modification, firstly, the MWCNT is subjected to acidification treatment, and hydroxyl and carboxyl functional groups are introduced to the MWCNT, wherein the modification method comprises the following steps:
1g of MWCNT is placed in 40mL of mixed acid of concentrated nitric acid and concentrated sulfuric acid, and the volume ratio of the concentrated nitric acid to the concentrated sulfuric acid is 1: 3, sonicating at 50 ℃ for 6h to give 1.1g MCNT-COOH.
(2) 80g of 1-tetradecanol is taken and added into 50mL of tetrahydrofuran, stirred until the 1-tetradecanol is completely dissolved, and then 20g of block copolymer-SEBS is added to ensure that the 1-tetradecanol is completely dissolved in the solution, so as to obtain the phase-change solution.
(3) After 1.1g of surface-modified MWCNT was added to the above phase-change solution, ultrasonic oscillation was performed for 5min, so that MWCNT could be dispersed more uniformly in the solution.
(4) And (3) transferring the solution to an open beaker, heating a heating table in a fume hood to 50 ℃, stirring while heating, and separating the solution due to the strong volatility of tetrahydrofuran to completely volatilize to obtain the required phase-change gel.
(5) The obtained phase-change gel is processed at high temperature to obtain a regular rectangle compounded with the thermoelectric generation piece, the prepared functional phase-change material is bonded with the thermoelectric generation piece through heat-conducting silicone grease, a radiating fin is arranged at the lower end of the phase-change material, and under sunlight, voltages at two ends of the thermoelectric generation piece can generate electricity due to different temperature differences to provide electric energy. The functional phase-change material can also store sunlight heat, and can continuously keep the temperature of a high-temperature end under the condition of no sunlight, so that the voltage of the two ends of the thermoelectric generation piece is kept constant within a period of time, and the voltage peak value of the two ends of the thermoelectric generation piece is between 0.3 and 1.5V.
FIG. 9 is a scanning electron micrograph of a phase change material having photothermal conversion properties according to example 3. It can be seen that the material has a regular, layered, stacked structure which helps to increase the tensile strength of the material.
Fig. 10 is a stress-strain curve of the phase change material having the photothermal conversion property of example 3, which has a high yield strength.
FIG. 11 is a diagram of a finished phase change material with photothermal conversion properties according to example 3.
Fig. 12 shows the power generation amount of the phase change material thermoelectric power generation under different sunlight intensities in example 3. It can be seen from the figure that the maximum voltage and the equilibrium voltage of the thermoelectric generation sheet of the material are increased along with the increase of the sunlight intensity.
Example 4
(1) The MWCNT is subjected to chemical surface modification, firstly, the MWCNT is subjected to acidification treatment, and hydroxyl and carboxyl functional groups are introduced to the MWCNT, wherein the modification method comprises the following steps:
1g of MWCNT is placed in 40mL of mixed acid of concentrated nitric acid and concentrated sulfuric acid, and the volume ratio of the concentrated nitric acid to the concentrated sulfuric acid is 1: 3, sonicating at 50 ℃ for 6h to give 1.1g MCNT-COOH.
(2) 100g of inorganic phase-change material sodium acetate trihydrate is heated, stirred and melted at the temperature of 70 ℃ to form colorless and transparent liquid.
(3) And (3) adding 1g of nano alumina nucleating agent into the phase-change material, heating and stirring until the nucleating agent is uniformly dispersed to obtain a phase-change solution.
(4) 1.1g of MWCNT subjected to surface modification is added into the phase-change solution, and ultrasonic oscillation is carried out for 5min, so that the MWCNT can be dispersed in the solution more uniformly.
(5) And adding 10g of sodium acrylate into the solution, stirring at a constant temperature for 30min, adding 0.5g of cross-linking agent N, N' -methylene bisacrylamide, continuously stirring at a constant temperature for 20min, and finally adding 1.5g of initiator ammonium persulfate for cross-linking initiation to obtain the inorganic phase change gel with the photo-thermal conversion property.
(6) The obtained phase-change gel is processed at high temperature to obtain a regular rectangle compounded with the thermoelectric generation piece, the prepared functional phase-change material is bonded with the thermoelectric generation piece through heat-conducting silicone grease, a radiating fin is arranged at the lower end of the phase-change material, and under sunlight, voltages at two ends of the thermoelectric generation piece can generate electricity due to different temperature differences to provide electric energy. The functional phase-change material can also store sunlight heat, and can continuously keep the temperature of a high-temperature end under the condition of no sunlight, so that the voltage of the two ends of the thermoelectric generation piece is kept constant within a period of time, and the voltage peak value of the two ends of the thermoelectric generation piece is between 0.3 and 1.5V.
FIG. 13 is a scanning electron micrograph of a phase change material having photothermal conversion properties of example 4. It can be seen from the figure that such inorganic phase change gels have a very dense structure.
Fig. 14 is a stress-strain curve of the phase change material having the photothermal conversion property of example 4, which has a high yield strength.
FIG. 15 is a diagram of a finished product of the organic phase-change material with photothermal conversion properties of example 4.
Fig. 16 shows the power generation amount of the phase change material thermoelectric power generation under different sunlight intensities in example 4. It can be seen from the figure that the maximum voltage and the equilibrium voltage of the thermoelectric generation sheet of the material are increased along with the increase of the sunlight intensity.
The phase transition temperature and enthalpy of phase transition of the phase transition gel material with photothermal conversion properties prepared in examples 1 to 4 were measured by a DSC differential scanning calorimeter, and the thermal conductivity was measured by Hot disk, and the specific values are shown in table 1:
TABLE 1
| Examples | Phase transition temperature (. degree. C.) | Enthalpy of phase change (J/g) | Coefficient of thermal conductivity (W/mK) |
| Example 1 | 58.67 | 221.36 | 0.31 |
| Example 2 | 58.38 | 225.67 | 0.36 |
| Example 3 | 58.79 | 228.11 | 0.39 |
| Example 4 | 58.59 | 217.45 | 0.86 |
Claims (10)
1. A preparation method of phase-change gel for solar photo-thermal conversion is characterized by comprising the following steps:
(1) dissolving an organic phase-change material into an organic solvent, adding a porous support material, and completely dissolving to obtain a phase-change solution, wherein the mass ratio of the organic phase-change material to the porous support material is (80-87): 13-20 parts of;
(2) adding a surface-modified photothermal conversion material into the phase change solution, and uniformly dispersing the photothermal conversion material in the phase change solution by a physical means; the addition amount of the photothermal conversion material accounts for 0.1-11% of the total amount of the organic phase change material and the porous support material;
(3) heating to remove the organic solvent in the phase-change solution to obtain the organic phase-change gel with the photo-thermal conversion performance.
2. The method of claim 1, wherein the organic phase change material is selected from one or more of alkanes, alkanols and fatty acids.
3. The method of claim 1, wherein the porous support material is selected from a group consisting of a highly elastic block copolymer and silica.
4. The method of claim 1, wherein the organic solvent is one or more selected from tetrahydrofuran, xylene, pentane, hexane, cyclohexane, cyclohexanone, toluene cyclohexanone, chlorobenzene, dichlorobenzene, dichloromethane, methanol, ethanol, isopropanol, diethyl ether, propylene oxide, methyl acetate, ethyl acetate, propyl acetate, acetone, methyl butanone, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, and pyridine.
5. A preparation method of phase-change gel for solar photo-thermal conversion is characterized by comprising the following steps:
(1) heating, stirring and melting the inorganic phase-change material into colorless and transparent liquid, adding the nucleating agent, heating and stirring until the nucleating agent is uniformly dispersed to obtain a phase-change solution; the addition amount of the nucleating agent accounts for 1% of the mass of the inorganic phase change material;
(2) adding a surface-modified photothermal conversion material into the phase change solution, and uniformly dispersing the photothermal conversion material in the phase change solution by a physical means; the addition amount of the photo-thermal conversion material accounts for 0.1-11% of the mass of the inorganic phase change material;
(3) adding sodium acrylate into the solution obtained in the step (2), stirring at constant temperature for 20-30min, adding a cross-linking agent, continuously stirring at constant temperature for 20-30min, and finally adding an initiator for cross-linking initiation to obtain inorganic phase-change gel with photo-thermal conversion property; the addition amount of the sodium acrylate accounts for 10% of the mass of the inorganic phase-change material, the cross-linking agent accounts for 0.3% -0.5% of the mass of the inorganic phase-change material, and the initiator accounts for 1% -2% of the mass of the inorganic phase-change material.
6. The method for preparing the phase-change gel for solar photothermal conversion according to claim 1 or 5, wherein the photothermal conversion material is selected from one or more of multi-walled carbon nanotubes, graphene, expanded graphite and carbon fibers.
7. The method of claim 5, wherein the inorganic phase change material is an inorganic hydrous salt type phase change material.
8. The method for preparing the phase-change gel for the photothermal conversion of sunlight according to claim 5, wherein the nucleating agent is selected from one or more of nano-alumina, borax, strontium chloride hexahydrate, magnesium chloride hexahydrate and barium carbonate.
9. The method for preparing the phase-change gel for solar photothermal conversion according to claim 5, wherein the crosslinking agent is N, N' -methylenebisacrylamide, and the initiator is ammonium persulfate or potassium persulfate.
10. The phase-change gel for solar photothermal conversion prepared by the preparation method of any one of claims 1 to 9.
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