CN110041895B - Heat storage and transfer material and preparation method thereof - Google Patents
Heat storage and transfer material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a heat storage and transfer material and a preparation method thereof, relating to the technical field of physical heat transfer and energy storage, wherein the heat storage and transfer material comprises a molten salt mixture and Al with the mass of 0.06-0.095% of the molten salt mixture2O3/SiO2Composite nano particles and a dispersant accounting for 0.15 to 0.3 percent of the mass of the fused salt mixture; the raw material of the molten salt mixture comprises NaNO3、LiNO3、K NO3、Li2CO3、Sr2CO3(ii) a The invention adds Al into the mixed molten salt2O3/SiO2The composite nano particles can be used for preparing the heat storage and heat transfer material with high specific heat capacity, and the heat storage and heat transfer material has high heat storage density and excellent performance.
Description
Technical Field
The invention relates to the technical field of physical heat transfer and energy storage, in particular to a heat storage and transfer material and a preparation method thereof.
Background
With the technological progress and the development of human society, the problems of energy demand and environmental pollution become more and more serious, and the problems become bottlenecks restricting the development of human society. Therefore, many countries advocate energy conservation and emission reduction vigorously and various renewable energy sources for development and utilization. In a plurality of energy-saving emission-reducing and renewable energy utilization systems, the heat conversion, transmission and storage technology can ensure the continuous and stable operation of the systems and improve the system efficiency, and is one of the key technologies for energy-saving emission-reducing and renewable energy utilization.
The choice of heat transfer and storage materials is the basis for heat transfer, transfer and storage. The heat transfer and storage materials commonly used at present comprise water/steam, heat transfer oil, molten salt, liquid metal and the like. Nitrate is a heat transfer medium and heat storage material with great potential in solar thermal power generation applications because of its good thermophysical properties. However, as a heat storage medium, the relatively low specific heat capacity results in a nitrate heat transfer medium having a lower heat storage density. Dispersing nanoparticles in a heat storage medium is one method of increasing the specific heat capacity of the heat storage material. The liquid obtained by incorporating a small amount of nanoparticles in a solvent and stably dispersing the nanoparticles may be referred to as "nanofluid". It is reported that the incorporation of nanoparticles into inorganic salts can dramatically increase the specific heat capacity of inorganic salts, which is abnormal. HO, etc. by incorporating optimum proportionsThe alumina nanoparticles give inorganic salts with increased specific heat capacity. BETTS et al incorporate SiO in binary nitrates2After the nano particles, the specific heat capacity is improved by 20 percent. SHIN et al synthesized SiO based on molten salt incorporation2Nanoparticle nanofluids and a 26% increase in specific heat capacity was observed after addition of 1% by mass of nanofluids. While ZHOU et Al report the incorporation of Al in water2O3Nano fluid formed by nano particles, Al with 21.7% of volume content being added2O3A 40% to 50% reduction in specific heat capacity was observed after the nanoparticles.
Therefore, proper amount of nano SiO is added into the heat storage and heat transfer material2Nano Al2O3And the particles have better effect on improving the heat storage and heat transfer materials. Therefore, the influence of the nano particles in the heat storage and heat transfer material is researched, and the novel high-performance heat storage and heat transfer material is prepared, so that the method has a great effect on the development of the field.
Disclosure of Invention
The invention aims to provide a heat storage and transfer material and a preparation method thereof, wherein Al is added into mixed molten salt2O3/SiO2The composite nano particles can be used for preparing the heat storage and heat transfer material with high specific heat capacity, and the heat storage and heat transfer material has high heat storage density and excellent performance.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the heat storing and transferring material consists of molten salt mixture and Al in 0.06-0.095 wt%2O3/SiO2Composite nano particles and a dispersant accounting for 0.15 to 0.3 percent of the mass of the fused salt mixture; the raw material of the molten salt mixture comprises NaNO3、LiNO3、K NO3、Li2CO3、Sr2CO3。
Preferably, the molten salt mixture consists of the following components in parts by weight: NaNO340-65 parts of L iNO3: 20-26 parts of KNO330-40 parts of L i2CO3: 25-32 parts of Sr2CO3: 6-11 parts.
Preferably, the molten salt mixture consists of the following components in parts by weight: NaNO353.5 parts of L iNO3: 22.5 parts of KNO336 parts by weight, L i2CO3: 29 parts of Sr2CO3: 9.5 parts.
Preferably, Al2O3/SiO2The composite nano-particles are prepared by the following method:
mixing ethanol and water according to a mass ratio of 4-5: 1, uniformly mixing to obtain an ethanol water solution, stirring and heating to 50-60 ℃, adding 20-25% by mass of tetraethoxysilane, adding a proper amount of dilute hydrochloric acid to promote reaction, and keeping the temperature to react for 3-6 hours to obtain SiO2Sol; then to SiO2Adding nano Al into the sol2O3Ultrasonically dispersing for 2-3h while stirring, washing for 4-5 times by using absolute ethyl alcohol, drying the obtained sol, grinding, and calcining in a muffle furnace at the temperature of 450-490 ℃ for 2-3h to obtain the Al2O3/SiO2Composite nanoparticles.
Preferably, the Al2O3The average particle diameter D50 of the nano-particles is 5-15 nm.
Preferably, the Al2O3/SiO2The composite nano-particles have an average particle diameter D50 of 80-110 nm.
Preferably, the dispersant is polyvinylpyrrolidone.
The preparation method of the heat storage and heat transfer material comprises the following steps:
(1) uniformly mixing the raw materials in the molten salt mixture, adding the raw materials into deionized water with the mass 2-2.5 times of that of the molten salt mixture, heating to 45-50 ℃ while stirring, and then adding Al with the mass 0.06-0.095% of that of the molten salt mixture2O3/SiO2Compounding nano particles, and ultrasonically dispersing for 1-1.5 h; then adding a dispersant accounting for 0.15 to 0.3 percent of the mass of the molten salt mixture, and continuing to perform ultrasonic dispersion for 1 to 1.5 hours;
(2) placing the material obtained in the step (1) in a crystallizing tank, heating to 95 +/-2 ℃, heating at constant temperature for 5-6h, and crystallizing to obtain powder; and (3) drying the powder at 50-55 ℃ in vacuum to obtain the heat storage and transfer material.
The invention has the beneficial effects that:
1. the invention adds Al into the molten salt mixture2O3/SiO2Composite nano-particles, Al prepared by the invention2O3/SiO2Composite nano-particle and nano Al with same diameter range2O3And nano SiO2Is not easy to agglomerate, thus having better dispersion effect in the molten salt mixture. The effect of the specific heat capacity enhancement is best due to the significant reduction of agglomeration. Al added simultaneously2O3/SiO2The comprehensive effect of the interface thermal resistance generated by the composite nano particles and the semi-solid layer can effectively improve the specific heat capacity of the molten salt mixture.
2. The mixed molten salt has reasonable components, large specific heat capacity, high heat conductivity and high latent heat of phase change.
3. The polyvinylpyrrolidone is added for dispersion, so that Al is enhanced2O3/SiO2The dispersibility of the composite nano particles in the mixed molten salt can effectively relieve the agglomeration of the nano particles, and further improve the specific heat capacity of the heat storage material.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the heat storage and transfer material comprises molten salt mixture, and Al with the mass of 0.08% of the molten salt mixture2O3/SiO2The composite nano particles and polyvinylpyrrolidone with the mass of 0.2% of the fused salt mixture;
the molten salt mixture consists of the following components in parts by weight: NaNO353.5 parts of L iNO3: 22.5 parts of KNO336 parts by weight, L i2CO3: 29 parts of Sr2CO3: 9.5 parts.
Al2O3/SiO2The composite nano-particles are prepared by the following method:
mixing ethanol and water according to a mass ratio of 5: 1, obtaining an ethanol water solution, stirring and heating to 55 ℃, adding 20% of tetraethoxysilane by mass, adding a proper amount of dilute hydrochloric acid to promote reaction, and keeping the temperature for reaction for 6 hours to obtain SiO2Sol; then to SiO2Adding nano Al into the sol2O3(the average grain diameter D50 is 5nm), ultrasonically dispersing for 2.5h while stirring, then washing for 5 times by using absolute ethyl alcohol, drying the obtained sol, grinding, and calcining in a muffle furnace at 480 ℃ for 3h to obtain the Al2O3/SiO2Composite nanoparticles having an average particle diameter D50 of 85 nm.
The preparation method of the heat storage and transfer material comprises the following steps:
(1) uniformly mixing the raw materials in the molten salt mixture, adding the raw materials into deionized water with the mass 2.5 times of that of the molten salt mixture, heating to 50 ℃ while stirring, and then adding Al2O3/SiO2Compounding nano particles, and ultrasonically dispersing for 1.5 h; then adding polyvinylpyrrolidone, and continuing to perform ultrasonic dispersion for 1.5 h;
(2) placing the material obtained in the step (1) in a crystallizing tank, heating to 95 +/-2 ℃, heating at constant temperature for 6 hours, and crystallizing to obtain powder; and (3) drying the powder at 50 ℃ in vacuum to obtain the heat storage and transfer material.
Example 2:
the heat storage and transfer material comprises molten salt mixture, and Al with the mass of 0.06% of the molten salt mixture2O3/SiO2The composite nano particles and polyvinylpyrrolidone with the mass of 0.25 percent of the fused salt mixture;
the molten salt mixture consists of the following components in parts by weight: NaNO353.5 parts of L iNO3: 22.5 parts of KNO336 parts by weight, L i2CO3: 29 parts of Sr2CO3: 9.5 parts.
Al2O3/SiO2The composite nano-particles are prepared by the following method:
mixing ethanol and water according to a mass ratio of 4: 1, obtaining an ethanol water solution, stirring and heating to 50 ℃, adding 25% by mass of tetraethoxysilane, adding a proper amount of dilute hydrochloric acid to promote reaction, and keeping the temperature for reaction for 3 hours to obtain SiO2Sol; then to SiO2Adding nano Al into the sol2O3(the average grain diameter D50 is 10nm), ultrasonically dispersing for 3h while stirring, then washing for 5 times by using absolute ethyl alcohol, drying the obtained sol, grinding, and calcining for 3h in a muffle furnace at 490 ℃ to obtain the Al2O3/SiO2Composite nanoparticles having an average particle diameter D50 of 102 nm.
The preparation method of the heat storage and transfer material comprises the following steps:
(1) uniformly mixing the raw materials in the molten salt mixture, adding the raw materials into deionized water with the mass 2.5 times of that of the molten salt mixture, heating to 50 ℃ while stirring, and then adding Al2O3/SiO2Compounding nano particles, and performing ultrasonic dispersion for 80 min; then adding polyvinylpyrrolidone, and continuing ultrasonic dispersion for 80 min;
(2) placing the material obtained in the step (1) in a crystallizing tank, heating to 95 +/-2 ℃, heating at constant temperature for 5.5h, and crystallizing to obtain powder; and (3) drying the powder at 50 ℃ in vacuum to obtain the heat storage and transfer material.
Example 3:
the heat storage and transfer material comprises molten salt mixture, and Al with the mass of 0.075% of the molten salt mixture2O3/SiO2The composite nano particles and polyvinylpyrrolidone with the mass of 0.2% of the fused salt mixture;
the molten salt mixture consists of the following components in parts by weight: NaNO353.5 parts of L iNO3: 22.5 parts of KNO336 parts by weight, L i2CO3: 29 parts of Sr2CO3: 9.5 parts.
Al2O3/SiO2The composite nano-particles are prepared by the following method：
Mixing ethanol and water according to a mass ratio of 5: 1, obtaining an ethanol water solution, stirring and heating to 60 ℃, adding 20% of tetraethoxysilane by mass, adding a proper amount of dilute hydrochloric acid to promote reaction, and keeping the temperature for reaction for 4.5 hours to obtain SiO2Sol; then to SiO2Adding nano Al into the sol2O3(the average grain diameter D50 is 5nm), ultrasonically dispersing for 3h while stirring, then washing for 4 times by using absolute ethyl alcohol, drying the obtained sol, grinding, and calcining for 3h in a muffle furnace at 460 ℃ to obtain Al2O3/SiO2Composite nanoparticles having an average particle diameter D50 of 80 nm.
The preparation method of the heat storage and transfer material comprises the following steps:
(1) uniformly mixing the raw materials in the molten salt mixture, adding the raw materials into deionized water with the mass 2.5 times of that of the molten salt mixture, heating to 45 ℃ while stirring, and then adding Al2O3/SiO2Compounding nano particles, and ultrasonically dispersing for 1 h; then adding polyvinylpyrrolidone, and continuing to perform ultrasonic dispersion for 1 h;
(2) placing the material obtained in the step (1) in a crystallizing tank, heating to 95 +/-2 ℃, heating at constant temperature for 5 hours, and crystallizing to obtain powder; and (3) drying the powder at 55 ℃ in vacuum to obtain the heat storage and transfer material.
Example 4:
the heat storing and transferring material consists of molten salt mixture and Al in 0.095 wt%2O3/SiO2Composite nano particles and polyvinylpyrrolidone with the mass of 0.3 percent of the fused salt mixture.
The molten salt mixture consists of the following components in parts by weight: NaNO353.5 parts of L iNO3: 22.5 parts of KNO336 parts by weight, L i2CO3: 29 parts of Sr2CO3: 9.5 parts.
Al2O3/SiO2The composite nanoparticles were prepared in the same manner as in example 1.
The preparation method of the heat storage and transfer material is the same as that of example 1.
Example 5:
the heat storage and transfer material comprises molten salt mixture and Al with the mass of 0.085% of the molten salt mixture2O3/SiO2Composite nano particles and polyvinylpyrrolidone with the mass of 0.2 percent of the fused salt mixture.
The molten salt mixture consists of the following components in parts by weight: NaNO353.5 parts of L iNO3: 22.5 parts of KNO336 parts by weight, L i2CO3: 29 parts of Sr2CO3: 9.5 parts.
Al2O3/SiO2The composite nanoparticles were prepared in the same manner as in example 1.
The preparation method of the heat storage and transfer material is the same as that of example 3.
Example 6:
the heat storage and transfer material comprises molten salt mixture, and Al with the mass of 0.06% of the molten salt mixture2O3/SiO2Composite nano particles and polyvinylpyrrolidone with the mass of 0.15 percent of the fused salt mixture.
The molten salt mixture consists of the following components in parts by weight: NaNO353.5 parts of L iNO3: 22.5 parts of KNO336 parts by weight, L i2CO3: 29 parts of Sr2CO3: 9.5 parts.
Al2O3/SiO2The composite nanoparticles were prepared in the same manner as in example 2.
The preparation method of the heat storage and transfer material is the same as that of example 1.
Example 7:
the heat storing and transferring material consists of molten salt mixture and Al in 0.065 wt%2O3/SiO2The composite nano particles and polyvinylpyrrolidone with the mass of 0.2% of the fused salt mixture;
the molten salt mixture consists of the following components in parts by weight: NaNO365 parts by weight of L iNO3: 20 parts of KNO340 portions of L i2CO3: 32 parts of Sr2CO3: 11 parts.
Al2O3/SiO2The composite nanoparticles were prepared in the same manner as in example 2.
The preparation method of the heat storage and transfer material is the same as that of example 2.
Example 8:
the heat storing and transferring material consists of molten salt mixture and Al in 0.06-0.095 wt%2O3/SiO2Polyvinyl pyrrolidone with the mass of the composite nano particles and the molten salt mixture being 0.15-0.3%;
the molten salt mixture consists of the following components in parts by weight: NaNO340 parts of L iNO3: 26 parts of KNO330 parts by weight of L i2CO3: 25 portions of Sr2CO3: 6 parts.
Al2O3/SiO2The composite nanoparticles were prepared in the same manner as in example 1.
The preparation method of the heat storage and transfer material is the same as that of example 1.
And (3) performance testing:
the solid specific heat capacity and the liquid specific heat capacity of the molten salt mixtures in examples 1 to 6 were measured, and then the solid specific heat capacity and the liquid specific heat capacity of the heat storage and transfer materials prepared in examples 1 to 6 were measured.
TABLE 1 specific Heat Capacity values of Heat storage and transfer materials
As can be seen from Table 1, Al was added2O3/SiO2After the nano particles are compounded, the solid specific heat capacity and the liquid specific heat capacity of the obtained heat storage and heat transfer material are greatly improved compared with those of a molten salt mixture.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (6)
1. The heat storage and transfer material is characterized in that the raw materials comprise a molten salt mixture and Al accounting for 0.06-0.095% of the mass of the molten salt mixture2O3/SiO2Composite nano particles and a dispersant accounting for 0.15 to 0.3 percent of the mass of the fused salt mixture; the raw material of the molten salt mixture comprises NaNO3、LiNO3、K NO3、Li2CO3、Sr2CO3；
The molten salt mixture consists of the following components in parts by weight: NaNO340-65 parts of L iNO3: 20-26 parts of KNO330-40 parts of L i2CO3: 25-32 parts of Sr2CO3: 6-11 parts;
the dispersing agent is polyvinylpyrrolidone.
2. The heat storage and transfer material of claim 1 wherein the molten salt mixture consists of the following components in weight fractions: NaNO353.5 parts of L iNO3: 22.5 parts of KNO336 parts by weight, L i2CO3: 29 parts of Sr2CO3: 9.5 parts.
3. The heat storage and transfer material of claim 1 wherein Al is2O3/SiO2The composite nano-particles are prepared by the following method:
mixing ethanol and water according to a mass ratio of 4-5: 1, uniformly mixing to obtain an ethanol water solution, stirring and heating to 50-60 ℃, adding 20-25% by mass of tetraethoxysilane, adding a proper amount of dilute hydrochloric acid to promote reaction, and keeping the temperature to react for 3-6 hours to obtain SiO2Sol; then to SiO2Adding nano Al into the sol2O3Ultrasonic dispersing for 2-3h while stirring, washing for 4-5 times with anhydrous ethanol, drying the obtained sol, grinding, and placing at 450-490 deg.C muffle furnaceCalcining for 2-3h in a furnace to obtain the Al2O3/SiO2Composite nanoparticles.
4. The heat storage and transfer material of claim 3 wherein said Al2O3The average particle diameter D50 of the nano-particles is 5-15 nm.
5. The heat storage and transfer material of claim 4 wherein said Al2O3/SiO2The composite nano-particles have an average particle diameter D50 of 80-110 nm.
6. The method for preparing heat storage and transfer material according to any one of claims 1 to 5, comprising the steps of:
(1) uniformly mixing the raw materials in the molten salt mixture, adding the raw materials into deionized water with the mass 2-2.5 times of that of the molten salt mixture, heating to 45-50 ℃ while stirring, and then adding Al with the mass 0.06-0.095% of that of the molten salt mixture2O3/SiO2Compounding nano particles, and ultrasonically dispersing for 1-1.5 h; then adding a dispersant accounting for 0.15 to 0.3 percent of the mass of the molten salt mixture, and continuing to perform ultrasonic dispersion for 1 to 1.5 hours;
(2) placing the material obtained in the step (1) in a crystallizing tank, heating to 95 +/-2 ℃, heating at constant temperature for 5-6h, and crystallizing to obtain powder; and (3) drying the powder at 50-55 ℃ in vacuum to obtain the heat storage and transfer material.
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| PCT/CN2019/100133 WO2020224080A1 (en) | 2019-05-07 | 2019-08-12 | Heat storage and heat transfer material and preparation method therefor |
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| CN112126208B (en) * | 2020-09-01 | 2022-11-15 | 广州大学 | Phase-change temperature control material and preparation method thereof |
| CN113969141A (en) * | 2021-11-22 | 2022-01-25 | 卓聪（上海）环保科技发展有限公司 | Immersion type cooling liquid for IT communication equipment and preparation method thereof |
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| "Heat capacity of nanofluids for solar energy storage produced by dispersing oxide nanoparticles in nitrate salt mixture directly at high temperature";Manila Chieruzzi等;《Solar Energy Materials and Solar Cells》;20170410;第167卷;第60-69页 * |
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