CN114539980A - Phase-change material capable of storing energy at room temperature for long time and preparation and application thereof - Google Patents
Phase-change material capable of storing energy at room temperature for long time and preparation and application thereof Download PDFInfo
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- CN114539980A CN114539980A CN202011354658.4A CN202011354658A CN114539980A CN 114539980 A CN114539980 A CN 114539980A CN 202011354658 A CN202011354658 A CN 202011354658A CN 114539980 A CN114539980 A CN 114539980A
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- 239000012782 phase change material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 42
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000004386 Erythritol Substances 0.000 claims abstract description 30
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims abstract description 30
- 229940009714 erythritol Drugs 0.000 claims abstract description 30
- 235000019414 erythritol Nutrition 0.000 claims abstract description 30
- 238000004146 energy storage Methods 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 238000005338 heat storage Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000013526 supercooled liquid Substances 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 239000011232 storage material Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 150000005846 sugar alcohols Chemical class 0.000 claims description 12
- 239000002861 polymer material Substances 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 239000002918 waste heat Substances 0.000 abstract description 7
- 230000007774 longterm Effects 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 2
- 230000008859 change Effects 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000003303 reheating Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004781 supercooling Methods 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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- 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
- Y02E70/00—Other energy conversion or management systems reducing GHG emissions
- Y02E70/30—Systems combining energy storage with energy generation of non-fossil origin
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- Chemical Kinetics & Catalysis (AREA)
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention discloses a preparation method of a phase-change material capable of storing energy at room temperature for a long time. According to the method, the phase-change material erythritol is used as a heat storage unit, the polyacrylamide is used as a material for improving the thermal stability of the supercooled liquid, and the phase-change material which can store heat at room temperature for a long time, can be crystallized and release heat through mechanical modes such as stirring and the like, and realizes heat release controllable long-term energy storage is prepared. The phase-change material capable of storing energy at room temperature for a long time has the advantages of high phase-change latent heat, good energy storage stability, good thermal stability, simplicity in operation, low cost and the like, and is easy to apply to solar heat energy storage, waste heat recycling and the like.
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 phase change material capable of storing energy at room temperature for a long time.
Background
The intermittent nature of solar energy makes it have the mismatch problem between the heat energy supply, needs. For example: solar energy is abundant in summer, and much of the solar energy cannot be utilized, while in winter, the solar energy cannot meet the requirements of people for heat supply. Therefore, the development of a phase change energy storage technology for a long time and the improvement of the energy utilization efficiency have great significance to the energy development of China. The phase-change energy storage material can absorb or release a large amount of phase-change latent heat in the phase-change process, and the heat storage capacity is far higher than that of the traditional sensible heat energy storage material; in addition, the phase change process has reversibility and cycling stability; the efficient long-term phase-change energy storage material can store heat for weeks or months, and is superior to sensible heat storage and chemical heat storage in the aspects of improving the energy utilization rate and solving the problem of unmatched supply and demand in energy space and time.
At present, most of the cross-season phase change energy storage materials are applied to an inorganic hydrated salt system (Chinese patent CN 103712255B), which has high heat storage density and low price, but the inorganic hydrated salt has strong corrosivity to metal and has the phenomena of phase separation and severe supercooling. Organic phase-change materials such as polyols do not corrode metal equipment and have good nucleation property, chemical property and thermal stability; in addition, erythritol which is one of the polyol phase-change materials is a natural product, and the raw materials are cheap and easy to obtain; the phase change energy storage material has the advantages of no toxicity, no flammability, no corrosiveness and the like, is a phase change energy storage material with excellent performance, and has great attention in the fields of waste heat transmission, solar heat storage and automobile waste heat circulation systems. Erythritol has a large number of hydrogen bonds among molecules, has a high supercooling degree, can form hydrogen bonds with erythritol through an additional substance, and is prevented from crystallizing in a cooling process, and is subjected to cold crystallization and subsequent melting in a reheating process. Therefore, the key point of the invention is to prepare the erythritol-based phase-change material capable of storing energy at room temperature for a long time by physical blending, and the material has the advantages of simple preparation process, high heat storage density, controllable heat release and the like, and is suitable for the fields of solar heat energy storage, waste heat transmission and the like.
Disclosure of Invention
The invention mainly solves the technical problems of overcoming the defects and shortcomings in the background technology and providing a preparation method of a phase-change material capable of storing energy at room temperature for a long time, wherein the obtained material can stably and efficiently store heat at room temperature for a long time and has excellent chemical stability, thermal stability and safety; the solar heat energy storage and waste heat transmission device can be used for solar heat energy storage or waste heat transmission and the like.
The technical scheme adopted by the invention is as follows:
(1) stirring polymer polyacrylamide in water for a certain time at room temperature to prepare a homogeneous polyacrylamide aqueous solution with a certain mass percentage concentration;
(2) adding a certain amount of erythritol into the polyacrylamide polymer aqueous solution prepared in the step (1), and stirring for a certain time to obtain a homogeneous sugar alcohol polymer aqueous solution blending system;
(3) and (3) transferring a certain amount of the sugar alcohol polymer aqueous solution prepared in the step (2) into a reagent bottle, drying water at a certain temperature and for a certain time under normal pressure, and preparing the phase-change material capable of storing energy at room temperature for a long time.
Further, the polyacrylamide used in the step (1) is anionic, cationic, nonionic, and is most preferred to be nonionic;
further, the molecular weight of the polyacrylamide polymer material used in the step (1) is between 200 and 1000 ten thousand. Preferably 300-700 ten thousand and the molecular weight is most preferred at 500 ten thousand.
Further, the polymer material polyacrylamide in the step (1) is stirred in water for 2-8h, preferably 4-6h, and is best stirred for 5 h.
Further, the mass fraction of the polyacrylamide in the polyacrylamide aqueous solution in the step (1) is 1-5%, preferably 1-2%, and the mass fraction is most preferably 1%. .
Further, the stirring time after adding erythritol in the step (2) is 0.5-2h, and the stirring time is optimal at 2 h.
Further, in the step (2), the mass content of the phase-change material erythritol in the energy storage material is 85-95%, and the mass content of the polymer material polyacrylamide in the energy storage material is 5-15%. The mass content of the phase-change material erythritol in the energy storage material is preferably 88-92%, and most preferably 90%. The mass of the polymer material polyacrylamide in the energy storage material is preferably 8-12%, most preferably 10%.
Further, the assistant of the energy storage material is water, and the solid content of the phase change material erythritol and the polymer material polyacrylamide in the water is 67-1000mg/ml, preferably 80-150mg/ml, and is optimal when the solid content is 100 mg/ml.
Further, the drying temperature in the step (3) is 80-120 ℃, and the drying time is 8-48 h. The drying temperature is preferably 90-110 deg.C, and is most preferably 110 deg.C. The drying time is preferably 12-24h, and is most preferably 16 h.
According to the method, the phase-change material erythritol is used as a heat storage unit, the polyacrylamide is used as a material for improving the stability of the supercooled liquid, and the phase-change energy storage material capable of storing heat for a long time and controlling heat release is prepared. The phase-change material capable of storing energy at room temperature for a long time 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 solar heat energy storage, waste heat recycling and the like.
Compared with the prior art, the invention has the following advantages and prominent effects: the phase-change material capable of storing energy at room temperature for a long time has excellent heat storage performance, can be stored at room temperature, has the heat release performance of triggering crystallization through external forces such as stirring and the like, and can be suitable for long-term storage of heat energy. The problem of passive storage of the existing heat energy is solved, and meanwhile, the phase-change material capable of storing energy at room temperature for a long time is simple in preparation process, convenient to operate, non-toxic and pollution-free, recyclable and reusable, and easy to realize large-scale industrial production.
Drawings
Fig. 1 is a thermal analysis curve of the phase change material capable of storing energy at room temperature for a long period of time prepared in example 1 (no crystallization occurred on the cooling curve, and cold crystallization occurred during reheating).
FIG. 2 is a graph of the controlled exotherm with stirring for the phase change material prepared in example 1 that can store energy at room temperature for a long period of time (it can be seen that the material initially remains in a transparent liquid state at room temperature, and after stirring with a spatula, a white crystalline region begins to appear in the liquid.
Detailed Description
Example 1
(1) 0.2g of anionic polyacrylamide with the molecular weight of 500W is dissolved in 20ml of water, and the mixture is stirred for 5 hours at normal temperature to obtain a homogeneous polyacrylamide aqueous solution with the mass percentage concentration of 1%.
(2) And (2) adding 1.8g of erythritol into the polyacrylamide aqueous solution obtained in the step (1), and stirring at normal temperature for 2 hours to form a homogeneous sugar alcohol polymer aqueous solution. Wherein the mass ratio of the erythritol to the polyacrylamide is 90: 10.
(3) And transferring the prepared sugar alcohol polymer aqueous solution into a reagent bottle, and drying water at 110 ℃ under normal pressure for 16 hours to obtain the erythritol-loaded phase-change material capable of storing energy at room temperature for a long time.
The prepared phase-change material capable of storing energy at room temperature for a long time is transparent liquid, a thermal analysis curve is shown in figure 1, the melting enthalpy is 209.19J/g, the cold crystallization enthalpy is 182.44J/g, and no crystallization exists in the temperature reduction process. The phase-change material can keep a transparent liquid state at room temperature, has no change after being placed for 180 days, and can be crystallized and emit heat by mechanical means such as stirring. The relevant steps for realizing controllable heat release and the like are shown in figure 2.
Example 2
(1) 0.4g of nonionic polyacrylamide with the molecular weight of 500W is dissolved in 20ml of water, and the mixture is stirred for 5 hours at normal temperature to obtain a homogeneous polyacrylamide aqueous solution with the mass percentage concentration of 2%.
(2) Adding 7.6g of erythritol into the polyacrylamide aqueous solution obtained in the step (1), and stirring at normal temperature for 2 hours to form a homogeneous sugar alcohol polymer aqueous solution. Wherein the mass ratio of the erythritol to the polyacrylamide is 95: 5.
(3) And transferring the prepared sugar alcohol polymer aqueous solution into a reagent bottle, and drying water at the normal pressure of 80 ℃ for 48 hours to obtain the erythritol-loaded phase-change material capable of storing energy at room temperature for a long time.
The prepared phase-change material capable of storing energy at room temperature for a long time is transparent liquid, the melting enthalpy is 238.22J/g, the cold crystallization enthalpy is 179.37J/g, and no crystal exists in the temperature reduction process. Can be kept in a liquid state at room temperature, has no change after being placed for 180 days, and can be crystallized and emit heat by a mechanical mode such as stirring.
Example 3
(1) 0.32g of anionic polyacrylamide with the molecular weight of 500W is dissolved in 16ml of water and stirred for 5 hours at normal temperature to obtain a homogeneous polyacrylamide aqueous solution with the mass percentage concentration of 2%.
(2) Adding 3.68g of erythritol into the polyacrylamide aqueous solution obtained in the step (1), and stirring at normal temperature for 2 hours to form a homogeneous sugar alcohol polymer aqueous solution. Wherein the mass ratio of the erythritol to the polyacrylamide is 92: 8.
(3) And transferring the prepared sugar alcohol polymer aqueous solution into a reagent bottle, and drying water at 110 ℃ under normal pressure for 16 hours to obtain the erythritol-loaded phase-change material capable of storing energy at room temperature for a long time.
Example 4
(1) 0.3g of anionic polyacrylamide with the molecular weight of 500W is dissolved in 30ml of water, and the mixture is stirred for 5 hours at normal temperature to obtain a homogeneous polyacrylamide aqueous solution with the mass percentage concentration of 1%.
(2) And (2) adding 1.7g of erythritol into the polyacrylamide aqueous solution obtained in the step (1), and stirring at normal temperature for 2 hours to form a homogeneous sugar alcohol polymer aqueous solution. Wherein the mass ratio of the erythritol to the polyacrylamide is 85: 15.
(3) And transferring the prepared sugar alcohol polymer aqueous solution into a reagent bottle, and drying water at 110 ℃ under normal pressure for 16 hours to obtain the erythritol-loaded phase-change material capable of storing energy at room temperature for a long time.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (9)
1. A phase-change material capable of storing energy at room temperature for a long time; the method is characterized in that a phase-change material erythritol is used as a heat storage unit, and polyacrylamide is used as a material for improving the thermal stability of the supercooled liquid;
the mass content of the phase-change material erythritol in the energy storage material is 85-95%, and the mass content of the polymer material polyacrylamide in the energy storage material is 5-15%;
the mass content of the phase-change material erythritol in the energy storage material is preferably 88-92%, and the mass content of the polymer material polyacrylamide in the energy storage material is preferably 8-12%;
the mass content of the phase-change material erythritol in the energy storage material is optimally 90%, and the mass content of the polymer material polyacrylamide in the energy storage material is optimally 10%.
2. The method of claim 1, wherein:
the polymer material polyacrylamide used in the step (1) is one or more of anionic, cationic and nonionic, and is preferably nonionic;
the molecular weight of the polymer material polyacrylamide used in the step (1) is between 200 and 1000 ten thousand, preferably 300 and 700 ten thousand, and more preferably the molecular weight is 500 ten thousand.
3. A preparation method of the phase-change material capable of storing energy at room temperature for a long time according to claim 1 or 2 is characterized by comprising the following specific process steps:
(1) stirring polymer polyacrylamide in water at room temperature to prepare homogeneous polyacrylamide aqueous solution;
(2) adding erythritol into the polyacrylamide polymer aqueous solution prepared in the step (1), and stirring to obtain a homogeneous sugar alcohol polymer aqueous solution blending system;
(3) and (3) transferring the aqueous solution of the sugar alcohol polymer prepared in the step (2) into a reagent bottle, and drying water under normal pressure to prepare the phase-change material capable of storing energy at room temperature for a long time.
4. The production method according to claim 3, characterized in that:
the stirring time of the polyacrylamide in the step (1) in water is 2-8h, preferably 4-6h, and more preferably 5 h.
5. The production method according to claim 3, characterized in that:
the mass fraction of the polyacrylamide in the polyacrylamide aqueous solution in the step (1) is 1-5%, preferably 1-2%, and most preferably 1%.
6. The production method according to claim 3, characterized in that:
the stirring time after adding the erythritol in the step (2) is 0.5-2h, and the stirring time is preferably 2 h.
7. The production method according to claim 3, characterized in that:
the auxiliary agent adopted in the preparation process of the energy storage material in the step (2) is water, and the solid content of the phase change material erythritol and the polymer material polyacrylamide in the water is 67-1000mg/ml, preferably 80-150mg/ml, and more preferably is optimal when the solid content is 100 mg/ml.
8. The production method according to claim 1, characterized in that:
in the step (3), the drying temperature is 80-120 ℃, and the drying time is 8-48 h;
the drying temperature is preferably 90-110 ℃, and is more preferably at 110 ℃; the drying time is preferably 12-24h, and more preferably 16 h.
9. Use of a phase change material according to claim 1 or 2, characterized in that: the phase change material product can be used as a phase change material for thermal energy conversion and storage.
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2020
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