CN114686179A - Semi-shaped composite organic phase change material and preparation method thereof - Google Patents
Semi-shaped composite organic phase change material and preparation method thereof Download PDFInfo
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- CN114686179A CN114686179A CN202111614075.5A CN202111614075A CN114686179A CN 114686179 A CN114686179 A CN 114686179A CN 202111614075 A CN202111614075 A CN 202111614075A CN 114686179 A CN114686179 A CN 114686179A
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- 230000008859 change Effects 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 39
- 239000012074 organic phase Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000012071 phase Substances 0.000 claims abstract description 21
- 239000012782 phase change material Substances 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 12
- 239000010439 graphite Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- 235000021360 Myristic acid Nutrition 0.000 claims description 2
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 6
- 239000002562 thickening agent Substances 0.000 abstract description 5
- 238000005338 heat storage Methods 0.000 abstract description 4
- 238000004146 energy storage Methods 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 239000000230 xanthan gum Substances 0.000 abstract description 3
- 229920001285 xanthan gum Polymers 0.000 abstract description 3
- 229940082509 xanthan gum Drugs 0.000 abstract description 3
- 235000010493 xanthan gum Nutrition 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 239000012779 reinforcing material Substances 0.000 abstract 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 9
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229940113116 polyethylene glycol 1000 Drugs 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000011056 performance test Methods 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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- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a semi-shaped composite organic phase-change material and a preparation method thereof, belonging to the field of phase-change energy storage, wherein expanded graphite is used for replacing a conventional thickening agent to be dispersed in an organic phase-change composite material by a one-step hydrothermal method to form the composite material, the obtained composite material can maintain a semi-shaped solid state when solid-liquid phase change occurs, special packaging treatment is not needed during use, the problems of easy leakage and corrosion of the phase-change material are solved, and the phase-change temperature of the composite material is adjustable between 30 and 85 ℃; compared with a conventional composite organic phase change material system using CMC and xanthan gum as thickening agents, the composite material has higher latent heat of phase change, and the heat storage density exceeds 180J/g; the method can synchronously introduce the heat conduction reinforcing material into the system, and the heat conduction coefficient can exceed 1.2W/(m.k); compared with a single organic phase change material main body, the shaped composite organic phase change material system has better stability, and the system is not separated and has no obvious impurities after repeated phase change for 100 times.
Description
Technical Field
The invention belongs to the field of phase change energy storage, and particularly relates to a semi-shaped composite organic phase change material and a preparation method thereof.
Background
In recent years, the economy of China is increasingly developed, and the relationship among the balance of the economy development, the energy supply and the environmental protection is particularly important. Under the large background of carbon peak, carbon neutralization, the problem that how to improve the energy utilization rate and reduce the use of petrochemical energy is difficult to solve by human beings is solved, and the phase change energy storage technology becomes the inevitable trend of the development of science and technology and social progress.
Common phase change materials are classified into two categories, organic phase change materials and inorganic phase change materials. The organic system is not easy to phase separate, the chemical property is stable, the price is relatively low, the solid substance is easy to form, the phase change temperature can be adjusted in a certain range, the cold accumulation temperature range is wide, but the problems of low heat conductivity, low phase change latent heat, easy leakage in the use process and the like exist.
Disclosure of Invention
The invention provides a semi-shaped composite organic phase change material and a preparation method thereof, the prepared composite material still maintains a semi-shaped non-flowing state macroscopically when solid-liquid phase change occurs, and compared with a conventional method of adding a thickening agent, the composite organic phase change material has higher heat conductivity coefficient and latent heat of phase change.
In order to achieve the purpose, the invention adopts the following technical scheme:
a semi-shaped composite organic phase-change material is characterized in that expanded graphite is uniformly dispersed in the organic phase-change material, and the macrostructure of a composite material system is maintained in the phase-change process; the organic phase change material is any one of paraffin, polyethylene glycol, lauric acid, myristic acid and stearic acid, and the content of the organic phase change material exceeds 97% of the total mass.
A preparation method of a semi-shaped composite organic phase change material comprises the following steps:
the method comprises the following steps: heating the organic phase-change material to a phase-change temperature and stirring to completely melt the organic phase-change material into a liquid state;
step two: transferring the liquid organic matter obtained in the step (1) into a reaction kettle, adding a certain amount of expandable graphite into the reaction kettle, setting the reaction temperature to be 230 ℃, starting stirring and sealing for reaction for 6 hours, and expanding and uniformly dispersing the expandable graphite in the organic phase change material;
step three: and (4) transferring the mixed solution obtained after the reaction in the step two to room temperature, cooling and solidifying to obtain the semi-shaped composite organic phase change material.
Has the beneficial effects that: the invention provides a semi-shaped composite organic phase-change material and a preparation method thereof, wherein the semi-shaped composite organic phase-change material is obtained by a one-step hydrothermal method, the obtained semi-shaped composite organic phase-change material can still maintain a stable shaped structure when undergoing phase change in the using process, special packaging treatment is not needed during use, the problems of easy leakage and corrosion of the phase-change material are solved, and the phase-change temperature of the composite phase-change material is adjustable between 30 and 85 ℃; synchronously expanding and uniformly dispersing the expandable graphite in an organic system in the mixing and dispersing process by a simple operation method of a one-step hydrothermal method; compared with a common single phase-change material system or a composite material added with sodium carboxymethyl cellulose (CMC) or xanthan gum with equal proportion, the phase-change material system has higher phase-change enthalpy value and heat conductivity coefficient, the heat storage density exceeds 180J/g, and the heat conductivity coefficient exceeds 1.2W/(m.k); compared with a single organic phase change material, the semi-shaped composite organic phase change material system has better stability, and the system is not separated and has no obvious impurities after repeated phase change for 100 times. According to the invention, the expanded graphite is uniformly dispersed in the organic material by using a one-step hydrothermal method, so that the problem of leakage during phase change of the material is well solved, the heat conductivity and the heat storage density of the material are improved to a certain extent, and the application field of the material is widened.
Drawings
FIG. 1 is a schematic view of polyethylene glycol-1000 after heating in accordance with an embodiment of the present invention;
FIG. 2 shows the DSC test results of composite organic phase change materials using sodium carboxymethyl cellulose (CMC) as a thickener in comparison with examples of the present invention;
FIG. 3 shows DSC results of composite organic phase change material solidified by dispersing expanded graphite by one-step hydrothermal method in an embodiment of the present invention;
FIG. 4 shows the phase change cycling results of the semi-amorphous composite organic phase change material obtained in the example of the present invention.
Detailed Description
The invention is described in detail below with reference to the following figures and specific examples:
a preparation method of a semi-shaped composite organic phase change material comprises the following steps: 97.0 g of polyethylene glycol-1000 was heated to 55 ℃ and stirred rapidly to completely melt the polyethylene glycol-1000. And transferring all the melted polyethylene glycol into a polytetrafluoroethylene reaction kettle, adding 3.0g of expandable graphite into the polytetrafluoroethylene reaction kettle, sealing the reaction kettle, setting the temperature to be 230 ℃, starting stirring for reaction for 6 hours, transferring the reacted dispersion liquid to the room temperature, and cooling and solidifying the dispersion liquid to obtain the semi-shaped composite organic phase change material.
And (3) carrying out performance test on the obtained phase change material:
the experimental results show that:
the viscosity of the obtained semi-shaped composite organic phase change material after phase change by heating exceeds 15000mPa.s, the viscosity is far higher than that of a composite material added with sodium carboxymethyl cellulose (CMC) or xanthan gum in equal proportion, and a semi-shaped structure can still be maintained macroscopically as shown in figure 1. Compared with a material added with sodium carboxymethyl cellulose (CMC), the semi-formed composite organic phase change material prepared by a one-step hydrothermal method has higher phase change latent heat and heat conductivity coefficient as shown in figure 2, figure 3 and table 1, and more proportion of thickener is needed to be added to achieve the same viscosity or forming effect. As shown in FIG. 4, the tested semi-shaped composite organic phase change material has stable performance and long service life in the use process, the phase change temperature deviation is less than 1.5 ℃ after 100 times of circulation, and the attenuation of phase change latent heat is less than 7%.
TABLE 1 thermal conductivity test results
| Serial number | Sample (I) | Status of state | Coefficient of thermal conductivity (W/m. k) |
| 1 | PEG-1000 | Liquid phase (55 ℃ C.) | 0.22 |
| 2 | PEG-1000（CMC） | Liquid phase (55 ℃ C.) | 0.24 |
| 3 | Semi-shaped composite organic phase-change material (PEG-1000-expanded graphite) | Liquid phase (55 ℃ C.) | 1.20 |
The experimental results show that: the phase change temperature of the obtained inorganic substance doped organic phase change composite material system is adjustable between 30 and 85 ℃; the phase change enthalpy value is high, the heat storage density is over 180J/g, and the heat conductivity coefficient is over 1.2W/(m.k); compared with a single organic polymer main body, the inorganic substance doped phase-change composite material system has better stability, and the system is not separated and has no obvious impurities after repeated phase change for 100 times.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and improvements can be made without departing from the principle of the present invention, and these modifications and improvements should also be considered as the protection scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (5)
1. A semi-shaped composite organic phase change material is characterized in that expanded graphite is uniformly dispersed into the organic phase change material, and the macrostructure of a composite material system is maintained in the phase change process; the content of the organic phase change material exceeds 97% of the total mass.
2. The semi-shaped composite organic phase change material as claimed in claim 1, wherein the phase change temperature of the composite material is adjustable between 30 ℃ and 85 ℃.
3. The semi-amorphous composite organic phase change material according to claim 1 or 2, wherein the organic phase change material is any one of paraffin, polyethylene glycol, lauric acid, myristic acid and stearic acid.
4. The semi-amorphous composite organic phase change material according to claim 1, wherein the system viscosity of the semi-amorphous composite organic phase change material after solid-liquid phase change is more than 15000 mPa.s.
5. The preparation method of the semi-shaped composite organic phase change material is characterized by comprising the following steps of:
the method comprises the following steps: heating the organic phase-change material to a phase-change temperature and stirring to completely melt the organic phase-change material into a liquid state;
step two: transferring the liquid organic matter obtained in the step (1) into a reaction kettle, adding a certain amount of expandable graphite, setting the reaction temperature to be 230 ℃, starting stirring and sealing for reaction for 6 hours, and enabling the expandable graphite to expand and uniformly disperse in the organic phase change material;
step three: and (4) transferring the mixed solution obtained after the reaction in the step two to room temperature, cooling and solidifying to obtain the semi-shaped composite organic phase change material.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100999657A (en) * | 2006-12-22 | 2007-07-18 | 华南理工大学 | Organism/expansion graphite composite phase transformation heat storaging material and preparation process and heat storing apparatus thereof |
| CN101239798A (en) * | 2008-01-04 | 2008-08-13 | 华南理工大学 | Organic matter/expandable graphite composite phase change heat-storing building material and preparation method thereof |
| CN102516949A (en) * | 2011-12-06 | 2012-06-27 | 辽宁科隆精细化工股份有限公司 | Compound polyethylene glycol phase change material |
| CN102827584A (en) * | 2012-08-31 | 2012-12-19 | 河南科技大学 | High-phase-change thermoset phase change material and preparation method thereof |
| CN102977858A (en) * | 2011-09-07 | 2013-03-20 | 中国科学院大连化学物理研究所 | Phase change material for thermal energy storage and preparation method thereof. |
| KR20150120586A (en) * | 2014-04-17 | 2015-10-28 | 인하대학교 산학협력단 | Manufacturing method of phase change composites |
| CN105778465A (en) * | 2016-03-29 | 2016-07-20 | 西安理工大学 | Polyethylene glycol-porous expanded graphite material and preparation method thereof |
| US20200095489A1 (en) * | 2017-11-28 | 2020-03-26 | Dalian University Of Technology | Thermal Conduction Enhanced Organic Composite Shape-stabilized Phase Change Material and Preparation Method Thereof |
-
2021
- 2021-12-27 CN CN202111614075.5A patent/CN114686179A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100999657A (en) * | 2006-12-22 | 2007-07-18 | 华南理工大学 | Organism/expansion graphite composite phase transformation heat storaging material and preparation process and heat storing apparatus thereof |
| CN101239798A (en) * | 2008-01-04 | 2008-08-13 | 华南理工大学 | Organic matter/expandable graphite composite phase change heat-storing building material and preparation method thereof |
| CN102977858A (en) * | 2011-09-07 | 2013-03-20 | 中国科学院大连化学物理研究所 | Phase change material for thermal energy storage and preparation method thereof. |
| CN102516949A (en) * | 2011-12-06 | 2012-06-27 | 辽宁科隆精细化工股份有限公司 | Compound polyethylene glycol phase change material |
| CN102827584A (en) * | 2012-08-31 | 2012-12-19 | 河南科技大学 | High-phase-change thermoset phase change material and preparation method thereof |
| KR20150120586A (en) * | 2014-04-17 | 2015-10-28 | 인하대학교 산학협력단 | Manufacturing method of phase change composites |
| CN105778465A (en) * | 2016-03-29 | 2016-07-20 | 西安理工大学 | Polyethylene glycol-porous expanded graphite material and preparation method thereof |
| US20200095489A1 (en) * | 2017-11-28 | 2020-03-26 | Dalian University Of Technology | Thermal Conduction Enhanced Organic Composite Shape-stabilized Phase Change Material and Preparation Method Thereof |
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