CN103205242A - Phase change energy storage material for heat preservation at night and preparation method - Google Patents
Phase change energy storage material for heat preservation at night and preparation method Download PDFInfo
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- CN103205242A CN103205242A CN2013101624012A CN201310162401A CN103205242A CN 103205242 A CN103205242 A CN 103205242A CN 2013101624012 A CN2013101624012 A CN 2013101624012A CN 201310162401 A CN201310162401 A CN 201310162401A CN 103205242 A CN103205242 A CN 103205242A
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Abstract
The invention relates to a phase change energy storage material for heat preservation at night. The medium consists of a CaC12-MgCl2-H2O water salt system and a nucleating agent; the CaC12-MgCl2-H2O water salt system consists of 80-95 % of calcium chloride hexahydrate, 1-7 % of magnesium chloride hexahydrate and 3-15 % of deionized water by mass; and the content of the nucleating agent is 0.5-2.0 % of the total amount of the CaC12-MgCl2-H2O water salt system. The phase change energy storage material has the advantages of high phase change latent heat, relatively low melting temperature and adjustable solidification temperature, can be used for avoiding the phase separation phenomenon, and can be applied to different seasons and different regions.
Description
Technical field
The present invention relates to a kind of phase-changing energy storage material and preparation method, relate in particular to a kind of phase-changing energy storage material and preparation method who can be used for night insulation.
Background technology
A great difficult problem that runs in the development and utilization process for clean energies such as sun power is exactly the storage to energy at present, a kind of energy storage material efficiently can solve this difficult problem to a certain extent, and energy storage material is with a wide range of applications in fields such as the recycling of " peak load shifting " of power supply system, industrial exhaust heat used heat and covil construction energy-saving materials.The transformation temperature of low-temperature phase-change material is near room temperature, be with a wide range of applications in fields such as material of construction, heating plant and agricultural greenhouses, at present the low temperature phase change energy storage material kind that is positioned between 0 ~ 40 ℃ of transformation temperature is few, common organic phase change material (paraffin, the organic solid-liquid phase change material of fatty acid and polyvalent alcohol, high density polyethylene(HDPE) etc.) and the inorganic salt phase change material (Na of being mainly
2SO
410H
2O, CaCl
26H
2O etc.).Na
2SO
410H
2O and CaCl
26H
2O is two kinds of inorganic hydrous salt phase transition energy-storing materials that research is more, and fusing point is respectively about 32.4 ℃ and 29 ℃.
Present stage is more at the research of inorganic hydrous salt phase transition energy-storing material, Kern(Kern.M wherein, R.A.ALDRICH. Phase change energy storage in a greenhouse solar heating system[Z] .Joint ASAE-CSAE Meeting. 1979. Winnipeg.) find because CaCl
26H
2The fusing point of O utilizes CaCl about 29 ℃
26H
2O can reach 33 ℃ as plastic greenhouse temperature in phase transition process of phase change material preparation; For make the inorganic salt phase change material can satisfy specific environment for use temperature range, solve the mistake cold-peace phenomenon of phase separation that occurs in the phase transition process, generally need in inorganic hydrated salt, add certain additive.Nishina(Nishina, H. and Takakura, T.Greenhouse heating by means of latent heat storage units[J]. Acta Hort. (ISHS) 1984,148:751-754.) etc. the people introduced several inorganic salt phase change materials that can be applied to heating at warmhouse booth night, at saltcake (Na
2SO
410H
2O) adding certain additive in can be reduced to fusing point about 20 ℃; And McMullin(McMullin, M., Ben-Abdallah, N.An investigation of low-temperature phase-change materials for short-term energy storage in greenhouses[J]. Canadian Agriculture Engineering. 1988,30:65-68.) wait the people in order to reduce CaCl
26H
2The transformation temperature of O is by adding certain amount of H
2O and reached certain effect-90% CaCl
26H
2O and 10%H
2The system transformation temperature that O forms is near 25 ℃.Relevant patent report is also arranged simultaneously, be CN102268244A(Deng Tian dragon such as publication number. the preparation method of the inorganic salt eutectic phase-change material of a kind of low temperature: China, [201110218313.0 P] .2011-12-07) and CN102268245A(Deng Tian dragon. a kind of preparation method of room temperature inorganic phase-changing material: China, 201110232156.9[P] .2011-12-07) and patent introduced room temperature phase-change energy-storage material and low temperature phase change energy storage material respectively, its transformation temperature scope is respectively 15 ~ 26 ℃ and 13 ~ 26 ℃.Publication number is the CN101289610A(Zeng Dewen. a kind of phase-change and energy-storage medium at room temperature and preparation method: China, 200810044751.8[P] .2008-10-22) and patent of invention introduced a kind of phase-changing energy storage material that can when being higher than 22 ℃, melt, solidify when being lower than 18 ℃.
Existing room temperature phase-change energy-storage material can't satisfy following application demand:
⑴ phase change material melting temperature (Tm) is too high, generally all can't fuse at lesser temps (about 20 ℃);
⑵ phase change material solidification temperature range is narrow, can't be under the nocturnal temperature of Various Seasonal or different regions crystallization and freezing;
⑶ melting temperature (Tm) and the temperature of solidification of the phase-changing energy storage material of reporting in the above-mentioned patent are very approaching, the effect of energy storage low temperature heat release that can't reach a high temperature, thus be difficult to obtain practical application;
⑷ being separated that inorganic-phase variable energy storage material is common can't effectively be solved with surfusion.
A kind of desirable phase-changing energy storage material that can be used for night insulation should have more constant melting temperature (Tm) and adjustable temperature of solidification.Sunshine on daytime abundance, envrionment temperature during greater than melting temperature (Tm) energy storage material begin fusion and then storage power; And night envrionment temperature descend, when temperature drop to temperature of solidification when following phase change material begin crystallization and freezing, and energy stored is discharged.This just requires phase-changing energy storage material to have comparatively stable fusing point, and this melting temperature is lower than room temperature (about 20 ~ 25 ℃); In addition, phase-changing energy storage material should have different temperature of solidification, with satisfy phase-changing energy storage material can be under the nocturnal temperature of Various Seasonal or different regions crystallization and freezing.This desirable energy storage material can be by day stores lot of energy as the energy-accumulating medium of sun power, and releases energy under night or colder weather condition, for environment provides enough heats, thereby reaches energy-conservation effect.
Summary of the invention
Technical problem to be solved by this invention provides a kind of latent heat of phase change height, has low fusion temperature and can regulate temperature of solidification, no phenomenon of phase separation and can be applied to the phase-changing energy storage material that can be used for night insulation of the different regions of Various Seasonal.
Another technical problem to be solved by this invention provides the preparation method of this phase-changing energy storage material.
For addressing the above problem, a kind of phase-changing energy storage material that can be used for night insulation of the present invention, it is characterized in that: this medium is by CaCl
2-MgCl
2-H
2O salt-water system and nucleator are formed; Described CaCl
2-MgCl
2-H
2In the O salt-water system by massfraction by calcium chloride hexahydrate be 80 ~ 95%, magnesium chloride hexahydrate is 1 ~ 7%, deionized water is 3 ~ 15% to form; The content of described nucleator is described CaCl
2-MgCl
2-H
20.5 ~ 2.0% of O salt-water system total amount.
Described nucleator is borax or six water strontium chlorides.
Aforesaid a kind of preparation method who can be used for the phase-changing energy storage material of night insulation may further comprise the steps:
⑴ by each raw material of proportioning weighing;
⑵ the calcium chloride hexahydrate that purified recrystallization is heated to fusion fully in 40 ~ 50 ℃ water bath with thermostatic control, obtain calcium chloride hexahydrate solution;
⑶ put into container with described calcium chloride hexahydrate solution, at rotating speed is to add magnesium chloride hexahydrate and deionized water under the magnetic agitation condition of 500 ~ 800r/min, and heats in the process that stirs, and makes each component fully fuse and mix;
⑷ continue to heat and low whipping speed is under the condition of 800 ~ 1200r/min, sneaks into nucleator, treats that described nucleator fusion is complete, solution stops heating and stirring when being the uniform fluid shape, namely gets mixed solution;
⑸ be cooled to complete crystallization with described mixed solution under 0 ~ 10 ℃ of condition, be to be heated to fusion fully in 40 ~ 50 ℃ of waters bath with thermostatic control in temperature more afterwards, namely gets the inorganic-phase variable energy storage material.
The present invention compared with prior art has the following advantages:
1, since the present invention by CaCl
26H
2O, MgCl
26H
2O and H
2The CaCl of O preparation
2-MgCl
2-H
2O mixed salt system and nucleator are formed, thereby wherein the adding of excessive water can make the system eutectic point reduce the melting temperature (Tm) that reduces phase change material, and therefore, gained phase-changing energy storage material melting temperature (Tm) is low, can fuse fully in 20 ~ 25 ℃ of scopes; Simultaneously, tangible phenomenon of phase separation does not appear in the gained phase-changing energy storage material in phase transition process, improved the stability of energy storage efficiency and use to a certain extent.
2, since the present invention according to CaCl
2-MgCl
2-H
2O mixed salt system phase diagram is by choosing CaCl
26H
2The liquid phase of the different saturation points of O crystallizing field is formed the change material and is formed, thereby can obtain different temperature of solidification, therefore, its temperature of solidification is adjustable, and adjustable extent is wider, and solidification temperature range is 8 ~ 18 ℃, thereby energy storage is carried out in fusion under can be the by day higher temperature, and night during lesser temps the crystallization and freezing heat release replenish the temperature of environment for use, the energy at sunshine on daytime that is fully utilized satisfies the weather condition of different areas, Various Seasonal.Utilize the energy storage material of its preparation.
3, the used starting material of the present invention are inorganic salt, cheap, environmental protection, and have lower production cost.
4, adopt the T-history method that gained phase change material of the present invention is measured its melting temperature (Tm) and temperature of solidification:
Place 40 ℃ thermostatic bath to heat phase change material, phase change material generally all can be kept a constant temp scope in a long time when undergoing phase transition, with the melting temperature (Tm) of this temperature range as phase change material; And in process of cooling, in order to obtain a lower isoperibol, in tank, sneak into ice cube, and keep the tank temperature at 8 ~ 13 ℃, material temperature reduces gradually in the process of cooling, temperature rises rapidly after waiting to solidify, and the back is slow to reduce, and the temperature Schwellenwert before temperature is risen rapidly is as the temperature of solidification of material.
Respectively to of the present invention
Embodiment 2,3,4,7Four kinds of phase change materials with different compositions are measured according to the method described above, obtain four T-history curves (as shown in Figure 1).As can be seen from the figure, the temperature of solidification of four kinds of phase change materials changes in 8.0 ~ 17.3 ℃ of scopes, and melting temperature (Tm) all is lower than 25 ℃.Proof utilizes the temperature of solidification of phase change material of this method preparation adjustable, and adjustable extent is wider, and fuses under can be the by day higher temperature.
5, the phase-changing energy storage material of the present invention's preparation is of very high actual application value, and studies in Application Areass such as farm plastic greenhouses.
Description of drawings
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described in further detail.
Fig. 1 is of the present invention
Embodiment 2,3,4,7T-history curve in cooling and heat-processed.
Embodiment
Embodiment 1A kind of phase-changing energy storage material that can be used for night insulation, this medium is by CaCl
2-MgCl
2-H
2O salt-water system and 1.0g nucleator borax are formed.
Wherein: CaCl
2-MgCl
2-H
2Formed by 95.0g calcium chloride hexahydrate, 1.3g magnesium chloride hexahydrate, 3.7g deionized water in the O salt-water system.
The preparation method of this phase-changing energy storage material may further comprise the steps:
⑴ by each raw material of proportioning weighing;
⑵ the calcium chloride hexahydrate that purified recrystallization is heated to fusion fully in 40 ~ 50 ℃ water bath with thermostatic control, obtain calcium chloride hexahydrate solution;
⑶ put into container with calcium chloride hexahydrate solution, at rotating speed is to add magnesium chloride hexahydrate and deionized water under the magnetic agitation condition of 500 ~ 800r/min, and heats in the process that stirs, and makes each component fully fuse and mix;
⑷ continue to heat and low whipping speed is under the condition of 800 ~ 1200r/min, sneaks into nucleator, treats that the nucleator fusion is complete, solution stops heating when being the uniform fluid shape and stirring, namely gets mixed solution;
⑸ be cooled to complete crystallization with mixed solution under 0 ~ 10 ℃ of condition, be to be heated to fusion fully in 40 ~ 50 ℃ of waters bath with thermostatic control in temperature more afterwards, namely gets the inorganic-phase variable energy storage material.
Adopt the T-history method that the gained phase change material is tested, its melting temperature (Tm) is 24.0 ~ 25.0 ℃, and temperature of solidification is 18.0 ℃.
Embodiment 2A kind of phase-changing energy storage material that can be used for night insulation, this medium is by CaCl
2-MgCl
2-H
2O salt-water system and 1.0g nucleator borax are formed.
Wherein: CaCl
2-MgCl
2-H
2Formed by 92.2g calcium chloride hexahydrate, 2.3g magnesium chloride hexahydrate, 5.5g deionized water in the O salt-water system.
The preparation method of this phase-changing energy storage material together
Embodiment 1
Adopt the T-history method that the gained phase change material is tested, its melting temperature (Tm) is 23.5 ~ 24.5 ℃, and temperature of solidification is 17.3 ℃.
Embodiment 3A kind of phase-changing energy storage material that can be used for night insulation, this medium is by CaCl
2-MgCl
2-H
2O salt-water system and 1.0g nucleator six water strontium chlorides are formed.
Wherein: CaCl
2-MgCl
2-H
2Formed by 90.7g calcium chloride hexahydrate, 2.8g magnesium chloride hexahydrate, 6.5g deionized water in the O salt-water system.
The preparation method of this phase-changing energy storage material together
Embodiment 1
Adopt the T-history method that the gained phase change material is tested, its melting temperature (Tm) is 23.0 ~ 23.5 ℃, and temperature of solidification is 14.4 ℃.
Embodiment 4A kind of phase-changing energy storage material that can be used for night insulation, this medium is by CaCl
2-MgCl
2-H
2O salt-water system and 1.0g nucleator borax are formed.
Wherein: CaCl
2-MgCl
2-H
2Formed by 85.6g calcium chloride hexahydrate, 3.9g magnesium chloride hexahydrate, 10.4g deionized water in the O salt-water system.
The preparation method of this phase-changing energy storage material together
Embodiment 1
Adopt the T-history method that the gained phase change material is tested, its melting temperature (Tm) is 22.5 ~ 23.5 ℃, and temperature of solidification is 10.0 ℃.
Embodiment 5A kind of phase-changing energy storage material that can be used for night insulation, this medium is by CaCl
2-MgCl
2-H
2O salt-water system and 0.5g nucleator borax are formed.
Wherein: CaCl
2-MgCl
2-H
2Formed by 85.6g calcium chloride hexahydrate, 3.9g magnesium chloride hexahydrate, 10.4g deionized water in the O salt-water system.
The preparation method of this phase-changing energy storage material together
Embodiment 1
Adopt the T-history method that the gained phase change material is tested, its melting temperature (Tm) is 22.0 ~ 23.0 ℃, and temperature of solidification is 9.5 ℃.
Embodiment 6A kind of phase-changing energy storage material that can be used for night insulation, this medium is by CaCl
2-MgCl
2-H
2O salt-water system and 2.0g nucleator borax are formed.
Wherein: CaCl
2-MgCl
2-H
2Formed by 83.9g calcium chloride hexahydrate, 4.8g magnesium chloride hexahydrate, 11.3g deionized water in the O salt-water system.
The preparation method of this phase-changing energy storage material together
Embodiment 1
Adopt the T-history method that the gained phase change material is tested, its melting temperature (Tm) is 22.0 ~ 23.5 ℃, and temperature of solidification is 9.0 ℃.
Embodiment 7A kind of phase-changing energy storage material that can be used for night insulation, this medium is by CaCl
2-MgCl
2-H
2O salt-water system and 1.0g nucleator borax are formed.
Wherein: CaCl
2-MgCl
2-H
2Formed by 80.0g calcium chloride hexahydrate, 6.5g magnesium chloride hexahydrate, 13.5g deionized water in the O salt-water system.
The preparation method of this phase-changing energy storage material together
Embodiment 1
Adopt the T-history method that the gained phase change material is tested, its melting temperature (Tm) is 21.0 ~ 22.0 ℃, and temperature of solidification is 8.0 ℃.
Embodiment 8A kind of phase-changing energy storage material that can be used for night insulation, this medium is by CaCl
2-MgCl
2-H
2O salt-water system and 1.5g nucleator six water strontium chlorides are formed.
Wherein: CaCl
2-MgCl
2-H
2Formed by 84g calcium chloride hexahydrate, 1g magnesium chloride hexahydrate, 15g deionized water in the O salt-water system.
The preparation method of this phase-changing energy storage material together
Embodiment 1
Adopt the T-history method that the gained phase change material is tested, its melting temperature (Tm) is 19.0 ~ 21.0 ℃, and temperature of solidification is 6.5 ℃.
Embodiment 9A kind of phase-changing energy storage material that can be used for night insulation, this medium is by CaCl
2-MgCl
2-H
2O salt-water system and 1.2g nucleator six water strontium chlorides are formed.
Wherein: CaCl
2-MgCl
2-H
2Formed by 90g calcium chloride hexahydrate, 7g magnesium chloride hexahydrate, 3g deionized water in the O salt-water system.
The preparation method of this phase-changing energy storage material together
Embodiment 1
Adopt the T-history method that the gained phase change material is tested, its melting temperature (Tm) is 23.5 ~ 24.5 ℃, and temperature of solidification is 15.5 ℃.
Claims (3)
1. phase-changing energy storage material that can be used for night insulation, it is characterized in that: this medium is by CaCl
2-MgCl
2-H
2O salt-water system and nucleator are formed; Described CaCl
2-MgCl
2-H
2In the O salt-water system by massfraction by calcium chloride hexahydrate be 80 ~ 95%, magnesium chloride hexahydrate is 1 ~ 7%, deionized water is 3 ~ 15% to form; The content of described nucleator is described CaCl
2-MgCl
2-H
20.5 ~ 2.0% of O salt-water system total amount.
2. a kind of phase-changing energy storage material that can be used for night insulation as claimed in claim 1, it is characterized in that: described nucleator is borax or six water strontium chlorides.
3. a kind of preparation method who can be used for the phase-changing energy storage material of night insulation as claimed in claim 1 may further comprise the steps:
⑴ by each raw material of proportioning weighing;
⑵ the calcium chloride hexahydrate that purified recrystallization is heated to fusion fully in 40 ~ 50 ℃ water bath with thermostatic control, obtain calcium chloride hexahydrate solution;
⑶ put into container with described calcium chloride hexahydrate solution, at rotating speed is to add magnesium chloride hexahydrate and deionized water under the magnetic agitation condition of 500 ~ 800r/min, and heats in the process that stirs, and makes each component fully fuse and mix;
⑷ continue to heat and low whipping speed is under the condition of 800 ~ 1200r/min, sneaks into nucleator, treats that described nucleator fusion is complete, solution stops heating and stirring when being the uniform fluid shape, namely gets mixed solution;
⑸ be cooled to complete crystallization with described mixed solution under 0 ~ 10 ℃ of condition, be to be heated to fusion fully in 40 ~ 50 ℃ of waters bath with thermostatic control in temperature more afterwards, namely gets the inorganic-phase variable energy storage material.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104232024A (en) * | 2014-08-15 | 2014-12-24 | 北京宇田相变储能科技有限公司 | Energy-storage material for eliminating phase-separating and supercooling |
| CN104419381A (en) * | 2013-09-06 | 2015-03-18 | 广州市香港科大霍英东研究院 | Phase change material and preparation method thereof |
| CN105086947A (en) * | 2014-05-06 | 2015-11-25 | 东北师范大学 | Calcium chloride hexahydrate phase change energy storage material and preparation method therefor |
| CN106047302A (en) * | 2016-06-02 | 2016-10-26 | 中国科学院青海盐湖研究所 | Inorganic phase-change energy-storage material and preparation method thereof |
| CN107384325A (en) * | 2017-07-11 | 2017-11-24 | 江苏理工学院 | A kind of method for extending hydrous salt phase change material service life |
| CN107556972A (en) * | 2017-08-24 | 2018-01-09 | 中国科学院青海盐湖研究所 | Normal low temperature phase change energy-accumulating medium and preparation method thereof |
| CN113136174A (en) * | 2021-04-21 | 2021-07-20 | 贵州国锐鑫节能科技有限公司 | Solar inorganic energy storage material and preparation method and application thereof |
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| CN102268245A (en) * | 2011-08-15 | 2011-12-07 | 天津科技大学 | Preparation method of room temperature inorganic phase-change material |
| CN102876298A (en) * | 2012-10-23 | 2013-01-16 | 中国科学院青海盐湖研究所 | Method for preparing phase change energy storage material in MgCl2*6H2O-CaCl2*6H2O system |
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Patent Citations (2)
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| CN102268245A (en) * | 2011-08-15 | 2011-12-07 | 天津科技大学 | Preparation method of room temperature inorganic phase-change material |
| CN102876298A (en) * | 2012-10-23 | 2013-01-16 | 中国科学院青海盐湖研究所 | Method for preparing phase change energy storage material in MgCl2*6H2O-CaCl2*6H2O system |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104419381A (en) * | 2013-09-06 | 2015-03-18 | 广州市香港科大霍英东研究院 | Phase change material and preparation method thereof |
| CN105086947A (en) * | 2014-05-06 | 2015-11-25 | 东北师范大学 | Calcium chloride hexahydrate phase change energy storage material and preparation method therefor |
| CN104232024A (en) * | 2014-08-15 | 2014-12-24 | 北京宇田相变储能科技有限公司 | Energy-storage material for eliminating phase-separating and supercooling |
| CN106047302A (en) * | 2016-06-02 | 2016-10-26 | 中国科学院青海盐湖研究所 | Inorganic phase-change energy-storage material and preparation method thereof |
| CN107384325A (en) * | 2017-07-11 | 2017-11-24 | 江苏理工学院 | A kind of method for extending hydrous salt phase change material service life |
| CN107556972A (en) * | 2017-08-24 | 2018-01-09 | 中国科学院青海盐湖研究所 | Normal low temperature phase change energy-accumulating medium and preparation method thereof |
| CN107556972B (en) * | 2017-08-24 | 2021-03-02 | 中国科学院青海盐湖研究所 | Normal-low temperature phase change energy storage medium and preparation method thereof |
| CN113136174A (en) * | 2021-04-21 | 2021-07-20 | 贵州国锐鑫节能科技有限公司 | Solar inorganic energy storage material and preparation method and application thereof |
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Application publication date: 20130717 |