CN113527825B - Graphene-based flexible composite shaped phase-change material film and preparation and application thereof - Google Patents
Graphene-based flexible composite shaped phase-change material film and preparation and application thereof Download PDFInfo
- Publication number
- CN113527825B CN113527825B CN202010285705.8A CN202010285705A CN113527825B CN 113527825 B CN113527825 B CN 113527825B CN 202010285705 A CN202010285705 A CN 202010285705A CN 113527825 B CN113527825 B CN 113527825B
- Authority
- CN
- China
- Prior art keywords
- graphene
- change material
- film
- aerogel
- phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
- C08J2491/06—Waxes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a graphene-based flexible composite shaped phase-change material film and preparation and application thereof, and the preparation method specifically comprises the following process steps: (1) carrying out ultrasonic treatment on the graphene oxide dispersion liquid to form a uniform suspension; then preparing graphene oxide aerogel by freeze drying; then reducing the graphene oxide aerogel into graphene aerogel at high temperature; then mixing the graphene aerogel and the polyvinylidene fluoride solution into a uniform mixed solution; then, carrying out blade coating on the mixed solution and replacing the solvent in water to obtain a graphene film, and carrying out cold freeze-drying on the graphene film to obtain the graphene composite film carrier. (2) And (3) mixing the phase change material with the carrier obtained in the step (1), and putting the mixture into a carrier structure to obtain the graphene-based flexible composite sizing phase change material film. The graphene-based flexible composite shaped phase-change material film prepared by the invention is a black film, and meanwhile, the system has strong light absorption, can convert light energy into heat energy for storage, and can be used in the field of wearable heat energy conversion and storage.
Description
Technical Field
The invention belongs to the field of composite sizing phase-change materials, and particularly relates to a preparation method for synthesizing a graphene-based flexible composite sizing phase-change material film capable of being used for wearable flexible heat energy conversion and storage by methods such as freeze drying, high-temperature reduction, blade coating, vacuum impregnation and the like.
Background
The energy crisis is an important problem to be solved urgently along with the development of the human society, and improving the energy utilization rate and exploring new energy are important ways to solve the problem. The heat energy is an important branch of the energy field, and the improvement of the storage and the utilization rate of the heat energy is beneficial to reducing the consumption of energy and promoting the reasonable distribution of the energy.
The phase-change material is used as a core unit of thermal energy storage, and research and development of the phase-change material are crucial to improvement of heat storage capacity of a thermal energy storage system. At present, solid-liquid phase change materials are widely studied by researchers due to the advantages of large phase change enthalpy, small volume change in the phase change process, wide temperature zone range and the like. However, the materials have the problem of leakage during phase change, so that the phase change materials are often loaded into a carrier material to prepare a composite shaped phase change material so that the composite shaped phase change material is still stable in the phase change process. However, the prepared composite shape-stabilized phase change material tends to have rigidity, so that the operability thereof is reduced, and it is difficult to satisfy applications in many practical scenarios. Therefore, the preparation of the flexible composite shape-stabilized phase-change material has important practical value.
According to the method, graphene oxide is used as a raw material, graphene aerogel is prepared through freeze drying and high-temperature reduction, polyvinylidene fluoride is introduced, a graphene composite film is prepared through a blade coating method, and then a phase-change material is immersed in the graphene composite film through vacuum impregnation to finally prepare the graphene-based flexible composite sizing phase-change material film. In the product, the phase-change material has excellent heat storage performance, flexibility and shape stability, meanwhile, the system can respond to light energy and convert the light energy into heat energy for storage, the excellent heat energy conversion and storage capacity is shown, and the system can be used in the field of heat energy conversion and storage and wearable heat energy management equipment.
Disclosure of Invention
The invention provides a graphene-based flexible composite shaped phase-change material film which is prepared by taking graphene oxide as a raw material, obtaining a composite graphene film by freeze drying, high-temperature reduction, blade coating and other methods, and then immersing a phase-change material in the composite graphene film through vacuum impregnation.
The synthesized graphene-based flexible composite sizing phase-change material film comprises the following steps:
(1) carrying out ultrasonic treatment on graphene oxide aqueous dispersion with a certain concentration for a certain time to form uniform turbid liquid; then, preparing the graphene oxide aerogel by freeze drying for a certain time at a certain temperature; then reducing the graphene oxide aerogel at a high temperature for a certain time under a nitrogen atmosphere to prepare graphene aerogel; then magnetically stirring the graphene aerogel and the polyvinylidene fluoride solution according to a certain proportion for a certain time to uniformly mix; then preparing a graphene composite membrane with a certain thickness by blade coating the mixed solution, placing the graphene composite membrane in distilled water for replacement for a certain time; and then, freeze-drying the membrane at a certain temperature for a certain time to prepare the graphene composite membrane carrier.
(2) Mixing the phase-change material with the membrane carrier obtained in the step (1), and putting the mixture in a vacuum oven to enable the phase-change material to fully enter a carrier structure to obtain the graphene-based flexible composite sizing phase-change material membrane.
Further, the concentration of the graphene oxide dispersion liquid in the step (1) is 2-10 g/L.
Further, the ultrasonic time required for forming the graphene oxide dispersion liquid in the step (1) is 2-4 h.
Further, the freeze-drying temperature in the step (1) is-20 ℃ to-5 ℃, and the time is 48-72 h.
Further, the temperature of the high-temperature reduction in the step (1) is 700-900 ℃, and the time is 2-4 h.
Further, in the step (1), the mass ratio of the graphene aerogel to the polyvinylidene fluoride is 1: 2-1: 20.
further, the solvent of the polyvinylidene fluoride solution in the step (1) is methyl pyrrolidone.
Further, the mass fraction of polyvinylidene fluoride in the polyvinylidene fluoride solution in the step (1) is 3% -10%.
Further, in the step (1), magnetically stirring the graphene aerogel and the polyvinylidene fluoride solution for 5-8 hours.
Further, the thickness of the graphene composite membrane obtained by blade coating in the step (1) is 50-500 um.
Further, the time for placing in distilled water for replacement in the step (1) is 1h-3 h.
Further, the phase change material in the step (2) is one or more than two of paraffin, polyethylene glycol, fatty alcohol and fatty acid.
Further, the set temperature of the vacuum oven in the step (2) is 80-100 ℃, and the vacuum degree is-0.1 MPa.
Further, the vacuum impregnation time in the step (2) is 2-4h, and the effect is best when the vacuum impregnation time is 4 h.
The design reaction conditions of the invention have low requirements on preparation conditions, the operation is simple and convenient, the prepared composite shaped phase-change material film has excellent heat storage performance, flexibility and shape stability, meanwhile, the system can respond to light energy and convert the light energy into heat energy for storage, the excellent heat energy conversion and storage capacity is shown, and the system can be used in the field of heat energy conversion and storage and wearable heat energy management equipment.
Drawings
FIG. 1 is a differential scanning calorimetry curve of a graphene-based composite shape-stabilized phase-change material film.
FIG. 2 is an absorbance curve of a graphene-based composite shape-fixed phase-change material film.
FIG. 3 is a view showing a graphene-based composite shape-fixed phase-change material film (irradiation intensity 300 mW/cm)2) Photothermal conversion curve of
Detailed Description
Example 1
(1) Taking 0.12g of graphene oxide in 20mL of distilled water, performing ultrasonic treatment for 2 hours to form a uniform suspension, and then placing the suspension in a freeze dryer, setting the temperature to be-10 ℃, and performing freeze drying for 48 hours to obtain graphene oxide aerogel; then placing the graphene oxide aerogel in a tubular furnace, and reducing for 2 hours at 800 ℃ under the condition of nitrogen to obtain graphene aerogel; then, mixing the graphene aerogel and a polyvinylidene fluoride solution (5 wt%, wherein the solvent of the polyvinylidene fluoride solution is methyl pyrrolidone) according to a mass ratio of the graphene aerogel to the polyvinylidene fluoride of 1: 10, stirring by magnetic force for 6 hours and mixing uniformly; and then, blade-coating the mixed solution into a graphene film with the thickness of about 100 micrometers, placing the graphene film in distilled water for replacement for 1 hour, finally placing the film in a freeze dryer, setting the temperature to be-10 ℃, and freeze-drying for 48 hours to obtain the graphene composite film carrier.
(2) Adding a proper amount of paraffin into the carrier in the step (1), and placing the carrier in a vacuum oven, wherein the vacuum degree is-0.1 MPa, and the temperature is 80 ℃ for dipping for 3 hours. And removing redundant paraffin on the surface to finally obtain the graphene-based flexible composite sizing phase-change material film.
The graphene-based flexible composite shaped phase-change material film is a black film, the size of the film is 10cm x 5cm, the thickness of the film is about 100 mu m, and the phase-change enthalpy of the film is about 150J/g, so that the material has excellent phase-change heat storage capacity; the material can be bent by 360 degrees and then can recover the initial shape without fracture, which shows that the material has excellent flexibility and shape stability; the absorbance of the material is 1-1.6 at the wavelength of a test light source of 200nm-800nm, which shows that the material has excellent light absorption capacity; the differential scanning calorimetry curve is shown in figure 1,
Example 2
(1) Taking 0.10g of graphene oxide in 20mL of distilled water, carrying out ultrasonic treatment for 3h to form a uniform suspension, then placing the suspension in a freeze dryer, setting the temperature to be-10 ℃, and carrying out freeze drying for 48h to obtain graphene oxide aerogel; then placing the graphene oxide aerogel in a tubular furnace to be reduced for 2 hours at 800 ℃ under the condition of nitrogen to obtain graphene aerogel; then, mixing the graphene aerogel with a polyvinylidene fluoride solution (6 wt%, wherein the solvent of the polyvinylidene fluoride solution is methyl pyrrolidone) according to the mass ratio of the graphene aerogel to the polyvinylidene fluoride of 1: stirring for 5h by magnetic force for 10 hours and mixing uniformly; and then, blade-coating the mixed solution into a graphene film of about 200um, placing the graphene film in distilled water for replacement for 1h, finally placing the graphene film in a freeze dryer, setting the temperature to be-10 ℃, and freeze-drying for 48h to obtain the graphene composite film carrier.
(2) Adding a proper amount of paraffin into the carrier in the step (1), and placing the carrier in a vacuum oven, wherein the vacuum degree is-0.1 MPa, and the temperature is 80 ℃ for dipping for 3 hours. And removing redundant paraffin on the surface to finally obtain the graphene-based flexible composite sizing phase-change material film.
The graphene-based flexible composite shaped phase-change material film is a black film, the size of the film is 10cm x 4cm, the thickness of the film is about 200 mu m, and the phase-change enthalpy of the film is about 140J/g, so that the material has excellent phase-change heat storage capacity; the material can be bent by 180 degrees and then can be recovered to the initial state without fracture, which shows that the material has excellent flexibility and shape stability; and the absorbance of the test light source at the wavelength of 200nm-800nm is 1.0-1.7, and the result shows that the material has excellent light absorption capacity; the absorbance curve is shown in FIG. 2.
Example 3
(1) Taking 0.16g of graphene oxide in 20mL of distilled water, carrying out ultrasonic treatment for 4 hours to form a uniform suspension, then placing the suspension in a freeze dryer, setting the temperature to be-10 ℃, and carrying out freeze drying for 48 hours to obtain graphene oxide aerogel; then placing the graphene oxide aerogel in a tubular furnace, and reducing for 2 hours at 900 ℃ under the condition of nitrogen to obtain graphene aerogel; then, mixing the graphene aerogel with a polyvinylidene fluoride solution (10 wt%, wherein the solvent of the polyvinylidene fluoride solution is methyl pyrrolidone) according to the mass ratio of the graphene aerogel to the polyvinylidene fluoride of 1: stirring by magnetic force for 7h for 20 h, and uniformly mixing; and then, blade-coating the mixed solution into a graphene film of about 100um, placing the graphene film in distilled water for replacement for 1h, finally placing the graphene film in a freeze dryer, setting the temperature to be-10 ℃, and freeze-drying for 48h to obtain the graphene composite film carrier.
(2) Adding a proper amount of octadecanoic acid into the carrier in the step (1), and placing the carrier in a vacuum oven, wherein the vacuum degree is-0.1 MPa, and the temperature is 80 ℃ for soaking for 3 hours. And removing redundant paraffin on the surface to finally obtain the graphene-based flexible composite sizing phase-change material film.
The graphene-based flexible composite shaped phase-change material film is a black film, the size of the film is 12cm x 5cm, the thickness of the film is about 100um, and the phase-change enthalpy of the film is 170J/g, so that the material has excellent phase-change heat storage capacity; the material can be bent by 180 degrees and then can be recovered to the initial state without being damaged, which shows that the material has excellent flexibility and shape stability; and the absorbance of the test light source at the wavelength of 200nm-800nm is 1-1.6, and the result shows that the material has excellent light absorption capacity.
Example 4
(1) Taking 0.12g of graphene oxide in 20mL of distilled water, performing ultrasonic treatment for 3 hours to form a uniform suspension, and then placing the suspension in a freeze dryer, setting the temperature to be-10 ℃, and performing freeze drying for 48 hours to obtain graphene oxide aerogel; then placing the graphene oxide aerogel in a tubular furnace, and reducing for 2 hours at 900 ℃ under the nitrogen condition to obtain graphene aerogel; then, mixing the graphene aerogel with a polyvinylidene fluoride solution (5 wt%, wherein the solvent of the polyvinylidene fluoride solution is methyl pyrrolidone) according to the mass ratio of the graphene aerogel to the polyvinylidene fluoride of 1: 5, stirring by magnetic force for 8 hours and mixing uniformly; and then, blade-coating the mixed solution into a graphene film of about 100um, placing the graphene film in distilled water for replacement for 1h, finally placing the graphene film in a freeze dryer, setting the temperature to be-10 ℃, and freeze-drying for 48h to obtain the graphene composite film carrier.
(2) Adding a proper amount of octadecanol into the carrier in the step (1), and placing the carrier in a vacuum oven, wherein the vacuum degree is-0.1 MPa, and the temperature is 80 ℃ for soaking for 2 hours. And removing redundant paraffin on the surface to finally obtain the graphene-based flexible composite sizing phase-change material film.
The graphene-based flexible composite shaped phase-change material film is a black film, the size of the film is 10cm x 4cm, the thickness of the film is about 100 mu m, and the phase-change enthalpy of the film is about 160J/g, so that the material has excellent phase-change heat storage capacity; and the material can be bent by 270 degrees and then returns to the initial state and is kept undamaged, which indicates that the material has excellent flexibility and shape stability; and the absorbance of the test light source at the wavelength of 200nm-800nm is 1-1.5, which shows that the material has excellent light absorption capacity.
Example 5
(1) Taking 0.13g of graphene oxide in 20mL of distilled water, carrying out ultrasonic treatment for 2h to form a uniform suspension, then placing the suspension in a freeze dryer, setting the temperature to be-10 ℃, and carrying out freeze drying for 48h to obtain graphene oxide aerogel; then placing the graphene oxide aerogel in a tubular furnace, and reducing for 2 hours at 900 ℃ under the condition of nitrogen to obtain graphene aerogel; then, mixing the graphene aerogel with a polyvinylidene fluoride solution (5 wt%, wherein the solvent of the polyvinylidene fluoride solution is methyl pyrrolidone) according to the mass ratio of the graphene aerogel to the polyvinylidene fluoride of 1: stirring for 5h by magnetic force for 10 hours and mixing uniformly; and then, blade-coating the mixed solution into a graphene film of about 100um, placing the graphene film in distilled water for replacement for 1h, finally placing the graphene film in a freeze dryer, setting the temperature to be-10 ℃, and freeze-drying for 48h to obtain the graphene composite film carrier.
(2) Adding a proper amount of eicosane into the carrier in the step (1), and placing the carrier in a vacuum oven for soaking for 2 hours at the temperature of 80 ℃ and the vacuum degree of-0.1 MPa. And removing redundant paraffin on the surface to finally obtain the graphene-based flexible composite shaping phase-change material film.
The graphene-based flexible composite shaped phase-change material film is a black film, the size of the film is 12cm x 5cm, the thickness of the film is about 100 mu m, and the phase-change enthalpy of the film is about 180J/g, so that the material has excellent phase-change heat storage capacity; the material can be bent by 180 degrees and then returns to the initial state and keeps the shape from being damaged, which shows that the material has excellent flexibility and shape stability; and the absorbance of the test light source at the wavelength of 200nm-800nm is 1-1.6, and the result shows that the material has excellent light absorption capacity.
Example 6
(1) Taking 0.14g of graphene oxide in 20mL of distilled water, performing ultrasonic treatment for 3 hours to form a uniform suspension, and then placing the suspension in a freeze dryer, setting the temperature to be-10 ℃, and performing freeze drying for 72 hours to obtain graphene oxide aerogel; then placing the graphene oxide aerogel in a tubular furnace, and reducing for 2 hours at 800 ℃ under the condition of nitrogen to obtain graphene aerogel; then, mixing the graphene aerogel with a polyvinylidene fluoride solution (5 wt%, wherein the solvent of the polyvinylidene fluoride solution is methyl pyrrolidone) according to the mass ratio of the graphene aerogel to the polyvinylidene fluoride of 1: 10, stirring by magnetic force for 6 hours and mixing uniformly; and then, blade-coating the mixed solution into a graphene film of about 100um, placing the graphene film in distilled water for replacement for 1h, finally placing the graphene film in a freeze dryer, setting the temperature to be-10 ℃, and freeze-drying for 72h to obtain the graphene composite film carrier.
(2) Adding a proper amount of paraffin into the carrier in the step (1), and placing the carrier in a vacuum oven, wherein the vacuum degree is-0.1 MPa, and the temperature is 80 ℃ for soaking for 2 hours. And removing redundant paraffin on the surface to finally obtain the graphene-based flexible composite sizing phase-change material film.
The graphene-based flexible composite shaped phase-change material film is a black film, the size of the film is 10cm x 5cm, the thickness of the film is about 100 mu m, and the phase-change enthalpy of the film is about 145J/g, so that the material has excellent phase-change heat storage capacity; the material can be bent by 360 degrees and then returns to the initial state and keeps the shape from being damaged, which shows that the material has excellent flexibility and shape stability; and the absorbance of the test light source at the wavelength of 200nm-800nm is 1-1.7, and the result shows that the material has excellent light absorption capacity.
Product application example
Placing the obtained graphene-based flexible composite shaping phase-change material film with the size of 3cm x 3cm and the thickness of about 200um (the filling phase-change material is paraffin, and the phase-change enthalpy is about 150J/g) under a xenon lamp light source simulating sunlight irradiation, wherein the distance between the material and the lamp light is 20cm,the irradiation power was adjusted to 100mW/cm2，200mW/cm2,300mW/cm2Detecting the temperature change curve of the material along with time, wherein the photothermal conversion curve is shown in figure 3; the result shows that the temperature of the material is rapidly increased under the illumination condition, and the light energy is converted into heat energy and stored in a material system, so that the material has excellent photo-thermal conversion capability.
Claims (19)
1. A preparation method of a graphene-based flexible composite sizing phase-change material film is characterized by comprising the following process steps:
(1) ultrasonically treating the graphene oxide aqueous dispersion to form a uniform turbid liquid; then preparing graphene oxide aerogel by cooling, freeze-drying and drying; reducing the graphene oxide aerogel at high temperature in a nitrogen atmosphere to prepare graphene aerogel; uniformly stirring and mixing graphene aerogel with a polyvinylidene fluoride solution by magnetic force to obtain a mixed solution; preparing a graphene composite membrane from the mixed solution by blade coating, placing the graphene composite membrane in water for replacement, and then preparing a graphene composite membrane carrier by cooling, freeze-drying and drying; the mass ratio of the graphene aerogel and the polyvinylidene fluoride in the step (1) is 1: 2-1: 20;
(2) Mixing the phase change material with the membrane carrier obtained in the step (1), and putting the mixture in a vacuum oven to enable the phase change material to fully enter a carrier structure to obtain a graphene-based flexible composite sizing phase change material membrane; the phase-change material in the step (2) is one or more than two of paraffin, polyethylene glycol, fatty alcohol and fatty acid.
2. The method of claim 1, wherein: the concentration of the graphene oxide dispersion liquid in the step (1) is 2-10 g/L.
3. The method of claim 2, wherein: the concentration of the graphene oxide dispersion liquid in the step (1) is 5-7 g/L.
4. The method of claim 1, wherein: the ultrasonic time required for forming the graphene oxide dispersion liquid in the step (1) is 2-4 h;
and (2) magnetically stirring the graphene aerogel and the polyvinylidene fluoride solution in the step (1) for 5-8 hours.
5. The method of claim 4, wherein: the ultrasonic time required for forming the graphene oxide dispersion liquid in the step (1) is 3-4 h;
and (2) magnetically stirring the graphene aerogel and the polyvinylidene fluoride solution in the step (1) for 7-8 h.
6. The production method according to claim 1, characterized in that: the freeze-drying temperature in the step (1) is-20 ℃ to-5 ℃, and the time is 48-72 hours.
7. The method of manufacturing according to claim 6, characterized in that: the freeze-drying temperature in the step (1) is-15 ℃ to-10 ℃, and the time is 48-60 hours.
8. The production method according to claim 1, characterized in that: the temperature of the high-temperature reduction in the step (1) is 700-900 ℃, and the time is 2-4 h.
9. The method of claim 1, wherein: the mass ratio of the graphene aerogel and the polyvinylidene fluoride in the step (1) is 1: 9-1: 15.
10. the method of claim 1, wherein: the solvent of the polyvinylidene fluoride solution in the step (1) is methyl pyrrolidone;
the mass fraction of the polyvinylidene fluoride in the polyvinylidene fluoride solution in the step (1) is 3-10%.
11. The method of manufacturing according to claim 10, wherein:
the mass fraction of the polyvinylidene fluoride in the polyvinylidene fluoride solution in the step (1) is 3-8%.
12. The method of claim 1, wherein: the thickness of the graphene composite membrane obtained by blade coating in the step (1) is 50-500 um.
13. The method of manufacturing according to claim 12, wherein: the thickness of the graphene composite membrane obtained by blade coating in the step (1) is 100-200 um.
14. The method of claim 1, wherein: the time for replacing in water in the step (1) is 1-3 h, and the adopted water is distilled water.
15. The method of claim 14, wherein: the time for placing in water for replacement in the step (1) is 2-3 h.
16. The method of claim 1, wherein: the set temperature of the vacuum oven in the step (2) is 80-100 ℃, and the vacuum degree is-0.1 MPa;
the vacuum impregnation time in the step (2) is 2-4 h.
17. The method of manufacturing according to claim 16, wherein: the set temperature of the vacuum oven in the step (2) is 80-90 ℃;
the vacuum impregnation time in the step (2) is 3-4 h.
18. The graphene-based flexible composite shape-stabilized phase-change material film prepared by the preparation method of any one of claims 1 to 17, wherein: the finally prepared graphene-based composite shape-fixed phase-change material film is a black film; absorbance of 1-1.8, and bending to 180 oThe above still maintains the shape without breaking.
19. The use of the graphene-based flexible composite shaped phase change material film according to claim 18, wherein: the finally prepared graphene-based composite shape-fixed phase-change material film can convert light energy into heat energy for storage;
or, as a phase change material for thermal energy conversion and storage;
or as a wearable functional material for flexible thermal energy conversion and storage and photothermal conversion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010285705.8A CN113527825B (en) | 2020-04-13 | 2020-04-13 | Graphene-based flexible composite shaped phase-change material film and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010285705.8A CN113527825B (en) | 2020-04-13 | 2020-04-13 | Graphene-based flexible composite shaped phase-change material film and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113527825A CN113527825A (en) | 2021-10-22 |
| CN113527825B true CN113527825B (en) | 2022-06-07 |
Family
ID=78087886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010285705.8A Active CN113527825B (en) | 2020-04-13 | 2020-04-13 | Graphene-based flexible composite shaped phase-change material film and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113527825B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117720767A (en) * | 2022-09-09 | 2024-03-19 | 中国石油化工股份有限公司 | Composite aerogel, recyclable heat storage phase change composite material with photo-thermal conversion function, preparation method and application |
| CN117447737B (en) * | 2023-10-25 | 2024-05-31 | 江西省科学院应用化学研究所 | Phase-change energy-storage flexible film based on green building materials and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107053817A (en) * | 2016-12-28 | 2017-08-18 | 镇江博昊科技有限公司 | A kind of continuous coiled preparation method of flexible multi-layered graphene |
| CN107254297A (en) * | 2017-06-13 | 2017-10-17 | 中国科学技术大学 | A kind of flexible phase-change material for electronic equipment thermal control |
| CN108000845A (en) * | 2017-12-06 | 2018-05-08 | 航天特种材料及工艺技术研究所 | The phase change thermal management component that a kind of forming method of phase change thermal management component and shaping obtain |
| CN108394155A (en) * | 2018-03-09 | 2018-08-14 | 武汉纺织大学 | A kind of energy saving sunlight membrane material |
| CN110204751A (en) * | 2019-05-23 | 2019-09-06 | 北京工商大学 | A kind of preparation method of phase-change material flexible membrane |
| CN110655910A (en) * | 2019-11-13 | 2020-01-07 | 南京工业大学 | Preparation method of graphene aerogel phase-change energy storage material |
| CN110804420A (en) * | 2019-10-09 | 2020-02-18 | 北京化工大学 | Phase-change composite material based on high-thermal-conductivity anisotropic graphene framework and preparation method thereof |
| CN110845828A (en) * | 2019-11-27 | 2020-02-28 | 福建师范大学 | Modified heat-conducting filler for polymer and preparation method of composite material of modified heat-conducting filler |
-
2020
- 2020-04-13 CN CN202010285705.8A patent/CN113527825B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107053817A (en) * | 2016-12-28 | 2017-08-18 | 镇江博昊科技有限公司 | A kind of continuous coiled preparation method of flexible multi-layered graphene |
| CN107254297A (en) * | 2017-06-13 | 2017-10-17 | 中国科学技术大学 | A kind of flexible phase-change material for electronic equipment thermal control |
| CN108000845A (en) * | 2017-12-06 | 2018-05-08 | 航天特种材料及工艺技术研究所 | The phase change thermal management component that a kind of forming method of phase change thermal management component and shaping obtain |
| CN108394155A (en) * | 2018-03-09 | 2018-08-14 | 武汉纺织大学 | A kind of energy saving sunlight membrane material |
| CN110204751A (en) * | 2019-05-23 | 2019-09-06 | 北京工商大学 | A kind of preparation method of phase-change material flexible membrane |
| CN110804420A (en) * | 2019-10-09 | 2020-02-18 | 北京化工大学 | Phase-change composite material based on high-thermal-conductivity anisotropic graphene framework and preparation method thereof |
| CN110655910A (en) * | 2019-11-13 | 2020-01-07 | 南京工业大学 | Preparation method of graphene aerogel phase-change energy storage material |
| CN110845828A (en) * | 2019-11-27 | 2020-02-28 | 福建师范大学 | Modified heat-conducting filler for polymer and preparation method of composite material of modified heat-conducting filler |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113527825A (en) | 2021-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113527825B (en) | Graphene-based flexible composite shaped phase-change material film and preparation and application thereof | |
| CN106315695A (en) | Strawberry like Ni-Co nano material and preparing method thereof | |
| CN109621988B (en) | Sea urchin-shaped hollow-structure nickel-copper-selenium ternary nano catalytic material and preparation method and application thereof | |
| CN108686697A (en) | A kind of alginic acid alkali composite nitride carbon photocatalysis aerogel material and the preparation method and application thereof | |
| CN108807878A (en) | A method of preparing molybdenum disulfide/vulcanization tin composite material of hollow structure | |
| CN107195908B (en) | A kind of foamed material composite cathode of microorganism electrolysis cell and preparation method thereof | |
| CN111394833A (en) | Carbon nanotube/graphene composite fiber and preparation method thereof | |
| CN110156003A (en) | A kind of graphene oxide dispersion and preparation method thereof | |
| CN112246272A (en) | Has a defect g-C3N4Preparation method of nanosheet photocatalyst | |
| CN113117709A (en) | High-efficiency zinc-air battery catalyst prepared based on MXene and sodium alginate | |
| CN102502775A (en) | Preparation method of spherical copper sulphide (CuS) particles | |
| CN102441395B (en) | Application of macroporous oxide oxygen carrier in circular hydrogen production of chemical chain and preparation method | |
| CN113629245A (en) | Novel compounding method of carbon material and transition metal compound, composite material and application | |
| CN105990560A (en) | Iron oxide porous nanorod array electrode material and preparation method thereof | |
| CN109926086B (en) | Nitrogen-doped carbon foam @ WS2Preparation method of nanosheet three-dimensional network composite structure | |
| CN115260995A (en) | Double-network heat-conducting porous aerogel energy storage material and preparation method and application thereof | |
| CN113698915A (en) | Graphene-based multi-response shaped composite phase change material and preparation and application thereof | |
| CN110492114B (en) | Nitrogen-doped porous carbon-oxygen reduction catalyst and preparation method and application thereof | |
| CN114835163B (en) | Novel tungsten sulfide photo-thermal material for water purification and preparation and application thereof | |
| CN109590478A (en) | The method of iridium nano particle of the ps pulsed laser and ns pulsed laser ablation synthesis rich in atomic steps is utilized in liquid phase | |
| CN111533121B (en) | Preparation method of porous graphite hollow hemisphere with high specific surface area | |
| CN113903911A (en) | Preparation method and application of bowl-shaped carbon/molybdenum disulfide composite material derived from natural agar | |
| CN106927513A (en) | A kind of method that nano bar-shape electrode material is prepared based on tin oxide nickel molybdate | |
| CN113808856A (en) | Honeycomb-shaped LaMnO3Preparation method of super capacitor | |
| CN108615615B (en) | The preparation method and its usage of the compound porous nanofiber of NiO/TiC/C |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |