CN115678088A - Porous polymer-graphene-based composite shaping phase-change material and preparation and application thereof - Google Patents
Porous polymer-graphene-based composite shaping phase-change material and preparation and application thereof Download PDFInfo
- Publication number
- CN115678088A CN115678088A CN202110836402.5A CN202110836402A CN115678088A CN 115678088 A CN115678088 A CN 115678088A CN 202110836402 A CN202110836402 A CN 202110836402A CN 115678088 A CN115678088 A CN 115678088A
- Authority
- CN
- China
- Prior art keywords
- change material
- phase
- graphene
- polymer
- based composite
- 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.)
- Pending
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/14—Thermal energy storage
Abstract
The invention discloses a porous polymer-graphene-based composite shaped phase-change material and a preparation method thereof, and the preparation method comprises the following specific process steps: (1) Preparing a homogeneous polymer aqueous solution with the mass percentage concentration of 1-10%; (2) Mixing the aqueous polymer solution prepared in the step (1) with graphene oxide aqueous dispersion to obtain black hydrogel; (3) And (3) adding the phase-change material polyethylene glycol into the black hydrogel prepared in the step (2), then continuing stirring, and putting the obtained material into an oven for drying to prepare the porous polymer-graphene-based composite sizing phase-change material. The porous polymer-graphene-based composite shaping phase-change material prepared by the invention is a black blocky substance, wherein the phase-change material has high load and excellent heat storage and shaping capabilities, and can be used for heat energy conversion and storage and temperature management equipment.
Description
Technical Field
The invention belongs to the technical field of phase change energy storage materials and preparation thereof, and relates to a design and preparation technology of a porous polymer-graphene-based composite shaped phase change material.
Background
Heat energy is the most common energy source in our daily life, and is one of the most abundant energy forms. The importance of developing thermal energy storage technologies to effectively increase the efficiency of thermal energy usage is self-evident. Among various thermal energy storage technologies, the latent heat storage technology based on phase change materials has attracted much attention due to its features such as simple operation and high energy storage density. The phase change material can absorb/release energy during its phase change cycle, and the temperature remains substantially constant during the energy transition. The integration of phase change materials into energy storage systems allows for the management of thermal energy and increases the efficiency of its use.
The phase change material is immersed in the internal pore structure of the porous material, so that the shaped phase change material can be obtained. The porous material has large surface area, pore volume and storage capacity, and can well adsorb the phase-change material to store heat energy. By selecting and constructing an ideal porous support material and integrating the porous support material with the phase change material to form the shaped phase change material, the durability, the thermal conductivity, the thermal stability and the chemical stability of the phase change material can be improved. In addition, the pore confinement effect and the interaction between the pore surface and the phase change material molecules can greatly affect the physical properties of the liquid during phase change and prevent leakage.
According to the invention, the polymer solution and the graphene oxide aqueous dispersion are simply mixed to form hydrogel, and then the phase change material polyethylene glycol is added to prepare the porous polymer-graphene-based composite shaping phase change material, wherein the obtained composite phase change material is a black blocky substance, and the phase change material has high load and excellent heat storage and shaping capabilities. Meanwhile, compared with other graphene-based composite phase-change materials, the preparation method disclosed by the invention has the advantages that the complex operations such as freeze drying and vacuum impregnation are avoided, the steps are simple, the operation requirement is low, and the method can be used for heat energy conversion and storage and temperature management equipment.
Disclosure of Invention
The invention provides a simple solution blending method, which is used for preparing a porous polymer-graphene-based composite sizing phase-change material by blending and stirring a polymer solution, a graphene oxide aqueous dispersion and a phase-change material polyethylene glycol.
The technical scheme adopted by the invention is as follows:
(1) Adding a polymer material into water and stirring to prepare a homogeneous polymer aqueous solution with a certain mass percentage concentration;
(2) Mixing the aqueous polymer solution prepared in the step (1) with graphene oxide aqueous dispersion, and stirring to obtain black hydrogel;
(3) And (3) adding a phase-change material polyethylene glycol into the black hydrogel prepared in the step (2), continuously stirring, and then drying the obtained material in an oven to prepare the porous polymer-graphene-based composite shaping phase-change material.
Further, the polymer material used in the step (1) is one or more of polyacrylamide, polyacrylic acid, sodium polyacrylate and polyethyleneimine with the weight-average molecular weight of 1-1000 ten thousand.
Further, the mass percentage concentration of the homogeneous polymer aqueous solution in the step (1) is 1-10%, preferably 1-4%, and is most preferable at 1%.
Further, the graphene oxide content in the graphene oxide aqueous dispersion in the step (2) is 4-13mg/ml, preferably 10-13mg/ml, and most preferably 12.5mg/ml.
Further, the graphene oxide aqueous dispersion and the polymer aqueous solution in the step (2) are mixed and stirred in water for 1 to 6 hours, preferably 1 to 3 hours, and the stirring time is preferably 2 hours.
Further, the mass ratio of the graphene oxide to the polymer in the step (2) is 0.5 to 2:1, preferably 0.5 to 1.5.
Further, the molecular weight of the polyethylene glycol used in the step (3) is 6000 to 20000, preferably 12000 to 20000, and the molecular weight is most preferable at 20000.
Further, the stirring time after the phase change material polyethylene glycol is added in the step (3) is 0.5-4h, preferably 0.5-2h, and is optimal at 1 h.
Further, the drying temperature in the step (3) is 60-120 ℃, the drying temperature is preferably 80-100 ℃, and is optimal at 80 ℃; the drying time is 8-48h, the drying time is preferably 4-24h, and the best drying time is 10 h.
Further, in the step (3), the mass content of the polyethylene glycol in the prepared composite phase-change material is 70-95%, and the mass content of the polyethylene glycol in the phase-change material is preferably 85-95%, and most preferably 90%.
According to the method, a phase-change material polyethylene glycol is used as a heat storage unit, a polymer-graphene matrix is used for preventing the leakage problem caused by polyethylene glycol solid-liquid phase conversion, and the porous polymer-graphene-based composite sizing phase-change material is prepared. The porous polymer-graphene-based composite shape-stabilized phase change material prepared by the method has the advantages of high phase change latent heat, good energy storage stability, good thermal stability, simplicity in operation and low cost, and is easy to apply to the aspects of heat energy conversion and storage, temperature management equipment and the like.
Compared with the prior art, the invention has the following advantages and prominent effects: the porous polymer-graphene-based composite shaping phase-change material prepared by the invention has high load and excellent heat storage and shaping capabilities. Meanwhile, compared with other graphene-based composite phase-change materials, the preparation process of the porous polymer-graphene-based phase-change material does not have complex operations such as freeze drying and vacuum impregnation, the preparation process is simple, the operation is convenient, the requirement is low, the product is non-toxic and pollution-free, large-scale industrial production is easy to realize, and the porous polymer-graphene-based phase-change material can be used for heat energy conversion and storage and temperature management equipment.
Drawings
Fig. 1 is a thermal analysis curve of the porous polymer-graphene-based composite shape-stabilized phase change material (polyethylene glycol 20000-90%) prepared in example 1. Description of the drawings: from the DSC curve, it can be seen that when the temperature increases, the porous polymer-graphene-based composite phase change material starts to melt and absorbs heat; when the temperature drops, the material crystallizes, releasing the stored heat.
Fig. 2 is a thermal analysis curve of the porous polymer-graphene-based composite shape-stabilized phase change material (polyethylene glycol 20000-95%) prepared in example 2.
Fig. 3 is a thermal analysis curve of the porous polymer-graphene-based composite shape-stabilized phase change material (polyethylene glycol 6000-90%) prepared in example 3.
Detailed Description
Example 1
(1) Taking 0.25g of polyacrylamide with the molecular weight of 5000000 at room temperature, adding water into the system to 25g, and stirring for 4 hours to prepare a homogeneous polyacrylamide aqueous solution with the mass percentage concentration of 1%;
(2) Taking 4ml of graphene oxide aqueous dispersion with the graphene oxide content of 12.5mg/ml, dropwise adding 5ml of 1% homogeneous polyacrylamide aqueous solution prepared in the step (1) into the graphene oxide aqueous dispersion, and rapidly stirring for 2 hours to obtain black hydrogel;
(3) And (3) adding 0.9g of phase-change material polyethylene glycol with the molecular weight of 20000 into the black hydrogel prepared in the step (2), then continuing stirring for 1h, putting the obtained black hydrogel into an oven, and drying at 80 ℃ under normal pressure to prepare the porous polymer-graphene-based composite sizing phase-change material with the polyethylene glycol loading capacity of 90%.
The prepared phase-change material capable of storing energy at room temperature for a long time is a black block-shaped material, a thermal analysis curve is shown in figure 1, the melting temperature is 56.50 ℃, and the melting enthalpy is 146.62J/g; the crystallization temperature is 48.27 ℃ and the crystallization enthalpy is 142.96J/g.
Example 2
(1) Taking 0.3g of polyacrylamide with the molecular weight of 5000000 at room temperature, adding water into the system to 30g, and stirring for 4 hours to prepare a homogeneous polyacrylamide aqueous solution with the mass percentage concentration of 1%;
(2) Taking 4ml of graphene oxide aqueous dispersion with the graphene oxide content of 12.5mg/ml, dropwise adding 5ml of 1% homogeneous polyacrylamide aqueous solution prepared in the step (1) into the graphene oxide aqueous dispersion, and rapidly stirring for 2 hours to obtain black hydrogel;
(3) And (3) adding 1.9g of phase-change material polyethylene glycol with the molecular weight of 20000 into the black hydrogel prepared in the step (2), then continuing stirring for 1h, putting the obtained black hydrogel into an oven, and drying at 80 ℃ under normal pressure to prepare the porous polymer-graphene-based composite sizing phase-change material with the polyethylene glycol load of 95%.
The prepared phase-change material capable of storing energy at room temperature for a long time is a black blocky substance, the thermal analysis curve is shown in figure 2, the melting temperature is 46.64 ℃, and the melting enthalpy is 149.37J/g; the crystallization temperature is 38.24 ℃ and the crystallization enthalpy is 144.56J/g.
Example 3
(1) At room temperature, 0.6g of polyacrylamide with the molecular weight of 2000000 is taken, water is added into the system to 30g, and the mixture is stirred for 4 hours to prepare homogeneous polyacrylamide aqueous solution with the mass percentage concentration of 2%;
(2) Taking 4ml of graphene oxide aqueous dispersion with the graphene oxide content of 12.5mg/ml, dropwise adding 2.5ml of 2% homogeneous polyacrylamide aqueous solution prepared in the step (1) into the graphene oxide aqueous dispersion, and rapidly stirring for 2 hours to obtain black hydrogel;
(3) And (3) adding 0.9g of phase change material polyethylene glycol with the molecular weight of 6000 into the black hydrogel prepared in the step (2), then continuing stirring for 1h, putting the obtained black hydrogel into an oven, and drying at 80 ℃ under normal pressure to prepare the porous polymer-graphene-based composite sizing phase change material with the polyethylene glycol load of 90%.
The prepared phase-change material capable of storing energy at room temperature for a long time is a black blocky substance, a thermal analysis curve is shown in figure 3, the melting temperature is 38.98 ℃, and the melting enthalpy is 123.95J/g; the crystallization temperature is 29.35 ℃ and the crystallization enthalpy is 119.31J/g.
Example 4
(1) Taking 0.6g of sodium polyacrylate with molecular weight of 2000000 at room temperature, adding water into the system to 30g, stirring for 4h, and preparing homogeneous sodium polyacrylate water solution with mass percentage concentration of 2%;
(2) Taking 8ml of graphene oxide aqueous dispersion with the graphene oxide content of 6.25mg/ml, dropwise adding 2.5ml of 2% homogeneous sodium polyacrylate aqueous solution prepared in the step (1) into the graphene oxide aqueous dispersion, and rapidly stirring for 3 hours to obtain black hydrogel;
(3) And (3) adding 0.90g of phase change material polyethylene glycol with the molecular weight of 10000 into the black hydrogel prepared in the step (2), then continuing stirring for 1h, putting the obtained black hydrogel into an oven, and drying at 60 ℃ under normal pressure to prepare the porous polymer-graphene-based composite sizing phase change material with the polyethylene glycol load of 90%.
Example 5
(1) Taking 0.3g of sodium polyacrylate with the molecular weight of 10000000 at room temperature, adding water into the system to 30g, and stirring for 6 hours to prepare a homogeneous sodium polyacrylate aqueous solution with the mass percentage concentration of 1%;
(2) Taking 20ml of graphene oxide aqueous dispersion with the graphene oxide content of 2.5mg/ml, dropwise adding 7.5ml of 1% homogeneous sodium polyacrylate aqueous solution prepared in the step (1) into the graphene oxide aqueous dispersion, and rapidly stirring for 1h to obtain black hydrogel;
(3) And (3) adding 2.375g of phase-change material polyethylene glycol with the molecular weight of 6000 into the black hydrogel prepared in the step (2), then continuously stirring for 1h, and then putting the obtained black hydrogel into an oven to dry at the normal pressure and the temperature of 120 ℃ to prepare the porous polymer-graphene-based composite sizing phase-change material with the polyethylene glycol load of 95%.
Claims (7)
1. A preparation method of a porous polymer-graphene-based composite shaped phase-change material is characterized by comprising the following specific process steps:
(1) Adding a polymer material into water and stirring to prepare a homogeneous polymer aqueous solution with a certain mass percentage concentration;
(2) Mixing the aqueous polymer solution prepared in the step (1) with graphene oxide aqueous dispersion, and stirring to obtain black hydrogel;
(3) And (3) adding a phase-change material polyethylene glycol into the black hydrogel prepared in the step (2), continuously stirring, and drying the obtained material in an oven to prepare the porous polymer-graphene-based composite sizing phase-change material.
2. The method of claim 1, wherein:
the polymer material used in the step (1) is one or more than two of polyacrylamide, polyacrylic acid, sodium polyacrylate and polyethyleneimine with the weight-average molecular weight of 1-1000 ten thousand;
the mass percentage concentration of the homogeneous polymer aqueous solution in the step (1) is 1-10%, preferably 1-4%, and is most preferred at 1%.
3. The method of claim 1, wherein:
the content of the graphene oxide in the graphene oxide aqueous dispersion in the step (2) is 4-13mg/ml, preferably 10-13mg/ml, and most preferably 12.5mg/ml;
the mass ratio of the graphene oxide to the polymer in the step (2) is 0.5-2:1, preferably 0.5.
4. The method of claim 1, wherein:
the molecular weight of the polyethylene glycol used in the step (3) is 6000-20000, preferably 12000-20000, and the molecular weight is optimal at 20000;
the drying temperature in the step (3) is 60-120 ℃, the drying temperature is preferably 80-100 ℃, and the best drying temperature is 80 ℃.
5. The method of claim 1, wherein:
in the step (3), the mass content of the polyethylene glycol in the prepared composite phase-change material is 70-95%, and the mass content of the polyethylene glycol in the phase-change material is preferably 85-95%, and is optimally 90%.
6. The porous polymer-graphene-based composite shape-stabilized phase-change material prepared by the preparation method of claims 1-5.
7. The application of the porous polymer-graphene-based composite shape-stabilized phase-change material of claim 6, wherein:
the phase change material product can be used as a phase change material for thermal energy conversion and storage or temperature management.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110836402.5A CN115678088A (en) | 2021-07-23 | 2021-07-23 | Porous polymer-graphene-based composite shaping phase-change material and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110836402.5A CN115678088A (en) | 2021-07-23 | 2021-07-23 | Porous polymer-graphene-based composite shaping phase-change material and preparation and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115678088A true CN115678088A (en) | 2023-02-03 |
Family
ID=85044399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110836402.5A Pending CN115678088A (en) | 2021-07-23 | 2021-07-23 | Porous polymer-graphene-based composite shaping phase-change material and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115678088A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130230496A1 (en) * | 2012-02-23 | 2013-09-05 | Subhra Mohapatra | Graphene hydrogel and method for using the same |
| CN105199675A (en) * | 2015-09-17 | 2015-12-30 | 湖北大学 | Composite phase change material set by oxidized graphene and preparing method thereof |
| CN109385254A (en) * | 2018-11-26 | 2019-02-26 | 同济大学 | A kind of graphene elastomeric polymer phase change composite material and preparation method thereof |
| CN110016323A (en) * | 2019-04-04 | 2019-07-16 | 江南大学 | A kind of selfreparing gel based phase-change material and preparation method thereof |
-
2021
- 2021-07-23 CN CN202110836402.5A patent/CN115678088A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130230496A1 (en) * | 2012-02-23 | 2013-09-05 | Subhra Mohapatra | Graphene hydrogel and method for using the same |
| CN105199675A (en) * | 2015-09-17 | 2015-12-30 | 湖北大学 | Composite phase change material set by oxidized graphene and preparing method thereof |
| CN109385254A (en) * | 2018-11-26 | 2019-02-26 | 同济大学 | A kind of graphene elastomeric polymer phase change composite material and preparation method thereof |
| CN110016323A (en) * | 2019-04-04 | 2019-07-16 | 江南大学 | A kind of selfreparing gel based phase-change material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Tailored phase change behavior of Na2SO4· 10H2O/expanded graphite composite for thermal energy storage | |
| Ren et al. | Ca (NO3) 2-NaNO3/expanded graphite composite as a novel shape-stable phase change material for mid-to high-temperature thermal energy storage | |
| Li et al. | 3D structure fungi-derived carbon stabilized stearic acid as a composite phase change material for thermal energy storage | |
| Liang et al. | Construction and application of biochar-based composite phase change materials | |
| CN101961644B (en) | Chloride-carbonaceous skeleton composite adsorbent and preparation method thereof | |
| CN112094625A (en) | Boron nitride nanotube aerogel/phase change heat conduction composite material and preparation method thereof | |
| CN104559936B (en) | A kind of medium temperature phase change heat storage material and preparation method thereof | |
| CN102432258A (en) | Shape-stabilized phase change energy storage material for building and preparation method thereof | |
| CN108878965A (en) | A kind of gel polymer electrolyte preparation method based on 3D printing technique | |
| CN106242494B (en) | Material for storing heat of phase change in low temperature and preparation method thereof in graphene aerogel complex intensifying | |
| CN102757771B (en) | Composite chemical heat storage material and preparation method thereof | |
| CN105602530A (en) | Preparation method of organic gel composite phase change material | |
| CN102092708B (en) | Method for preparing phenol-formaldehyde carbon aerogel in low alkali | |
| CN109609098B (en) | Composite phase-change heat storage material and preparation thereof | |
| CN109054759B (en) | Phase-change composite material filled with nano graphene sheets and preparation method thereof | |
| CN106967390A (en) | A kind of low-temperature inorganic composite phase-change heat-storage material and preparation method thereof | |
| CN105406027A (en) | Complex formed from aromatic nitrile compound polymerization product and sulfur, preparation method and uses thereof | |
| CN109065851A (en) | A kind of sulphur carbon composite anode material and preparation method thereof | |
| CN103834366B (en) | A kind of industrial medium temperature phase change heat storage material and preparation method thereof | |
| CN106115697B (en) | A kind of preparation method of active carbon of the surface rich in petal-shaped graphene | |
| Yu et al. | Research on thermal properties of novel silica nanoparticle/binary nitrate/expanded graphite composite heat storage blocks | |
| CN106753264A (en) | Standby mesoporous manosil AS alkali sizing phase-change material of a kind of utilization coal ash for manufacturing and preparation method thereof | |
| Wang et al. | Carbon hybrid aerogel-based phase change material with reinforced energy storage and electro-thermal conversion performance for battery thermal management | |
| Mohapatra et al. | Salt in matrix for thermochemical energy storage-A review | |
| CN110127695A (en) | A kind of preparation method of supercapacitor wood sawdust base porous charcoal |
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 |