CN110041895A - A kind of heat accumulation heat-transfer matcrial and preparation method thereof - Google Patents
A kind of heat accumulation heat-transfer matcrial and preparation method thereof Download PDFInfo
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- CN110041895A CN110041895A CN201910376548.9A CN201910376548A CN110041895A CN 110041895 A CN110041895 A CN 110041895A CN 201910376548 A CN201910376548 A CN 201910376548A CN 110041895 A CN110041895 A CN 110041895A
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- 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
Abstract
The present invention provides a kind of hot heat-transfer matcrials and preparation method thereof, are related to physics heat transfer technical field of energy storage, its raw material of heat accumulation heat-transfer matcrial includes the Al of molten salt mixture, molten salt mixture quality 0.06-0.095%2O3/SiO2The dispersing agent of composite nanometer particle and molten salt mixture quality 0.15-0.3%；The raw material of the molten salt mixture includes NaNO3、LiNO3、K NO3、Li2CO3、Sr2CO3；Al is added in the present invention in fused salt mixt2O3/SiO2The heat accumulation heat-transfer matcrial of high specific heat capacity can be prepared in composite nanometer particle, and heat accumulation heat-transfer matcrial storage density is high, has excellent performance.
Description
Technical field
It conducts heat technical field of energy storage the present invention relates to physics, and in particular to a kind of heat accumulation heat-transfer matcrial and preparation method thereof.
Background technique
With scientific and technological progress and human social development, energy demand with environmental pollution is getting worse, and have become system
The about bottleneck of human social development.For this purpose, many countries vigorously advocate energy-saving and emission-reduction, the exploitation benefit of various renewable energy is advocated
With.In numerous energy-saving and emission-reduction and renewable energy utilization system, conversion, transmission and the storing technology of heat can guarantee system
Continuous and steady operation, improve system effectiveness, be one of the key technology of energy-saving and emission-reduction and renewable energy utilization.
The selection of heat transfer heat accumulating is the basis of heat conversion, transmission and storage.Currently used heat transfer heat accumulating
There are water/steam, conduction oil, fuse salt and liquid metal etc..Nitrate is solar heat because having good thermophysical property
The heat transmission medium and heat accumulating of great potential in power generation applications.However, relatively low specific heat capacity makes as heat-storage medium
Obtaining nitrate heat transmission medium has lower storage density.It is a kind of raising heat accumulation that nano particle, which is dispersed in heat-storage medium,
The method of material specific heat capacity.A small amount of nano particle is mixed in a solvent and disperses nanoparticles stable, and resulting liquid can
To be known as " nano-fluid ".It is reported that the ratio of inorganic salts can abnormally be significantly improved by mixing nano particle in inorganic salts
Thermal capacitance.HO etc. has obtained the inorganic salts of specific heat capacity raising by mixing the aluminum oxide nanoparticle of best proportion.BETTS etc. is two
SiO is mixed in first nitrate2After nano particle, specific heat capacity improves 20%.SHIN etc., which has been synthesized, mixes SiO based on fuse salt2It receives
The nano-fluid of rice grain, and observe there is 26% specific heat capacity to increase after the nano-fluid for being added to mass fraction 1%.And
ZHOU etc. is reported mixes Al in water2O3Nano particle formed nano-fluid, be added volume content 21.7% Al2O3
40%~50% specific heat capacity decline is observed after nano particle.
Therefore, suitable Nano-meter SiO_2 is added in heat accumulation heat-transfer matcrial2, nanometer Al2O3Equal particles are passed for improving heat accumulation
Hot material has preferable effect.Therefore, influence of the nano particle in heat accumulation heat-transfer matcrial is studied, and prepared novel
High-performance heat accumulation heat-transfer matcrial has larger effect to the development in the field.
Summary of the invention
The purpose of the present invention is to provide a kind of heat accumulation heat-transfer matcrials and preparation method thereof, are added in fused salt mixt
Al2O3/SiO2The heat accumulation heat-transfer matcrial of high specific heat capacity, heat accumulation heat-transfer matcrial storage density can be prepared in composite nanometer particle
Height is had excellent performance.
In order to achieve the above object, the present invention is achieved by the following technical programs:
A kind of heat accumulation heat-transfer matcrial, raw material include molten salt mixture, molten salt mixture quality 0.06-0.095%
Al2O3/SiO2The dispersing agent of composite nanometer particle and molten salt mixture quality 0.15-0.3%；The original of the molten salt mixture
Material includes NaNO3、LiNO3、K NO3、Li2CO3、Sr2CO3。
Preferably, the molten salt mixture is grouped as by the group of following weight fraction: NaNO3: 40-65 parts, LiNO3: 20-
26 parts, KNO3: 30-40 parts, Li2CO3: 25-32 parts, Sr2CO3: 6-11 parts.
Preferably, the molten salt mixture is grouped as by the group of following weight fraction: NaNO3: 53.5 parts, LiNO3: 22.5
Part, KNO3: 36 parts, Li2CO3: 29 parts, Sr2CO3: 9.5 parts.
Preferably, Al2O3/SiO2Composite nanometer particle is prepared by following methods:
Ethyl alcohol is uniformly mixed with water 4-5:1 in mass ratio, obtains ethanol water, after stirring is warming up to 50-60 DEG C, is added
The ethyl orthosilicate of its quality 20-25%, and appropriate dilute hydrochloric acid is added and promotes to react, after insulation reaction 3-6h, obtain SiO2Colloidal sol；
Then to SiO2Nanometer Al is added in colloidal sol2O3, ultrasonic disperse 2-3h, is then washed 4-5 times using dehydrated alcohol while stirring,
Gained colloidal sol is dried, grinding, which is placed in 450-490 DEG C of Muffle furnace, calcines 2-3h to get the Al2O3/SiO2It is multiple
Close nano particle.
Preferably, the Al2O3The average grain diameter D50 of nano particle is 5-15nm.
Preferably, the Al2O3/SiO2The average grain diameter D50 of composite nanometer particle is 80-110nm.
Preferably, the dispersing agent is polyvinylpyrrolidone.
The preparation method of heat accumulation heat-transfer matcrial in the present invention, comprising the following steps:
(1) each raw material in molten salt mixture is uniformly mixed, and be added in the deionized water of 2-2.5 times of its quality, side
Stirring side is warming up to 45-50 DEG C, the rear Al that molten salt mixture quality 0.06-0.095% is added2O3/SiO2Composite nanometer particle,
And ultrasonic disperse 1-1.5h；Then the dispersing agent of molten salt mixture quality 0.15-0.3% is added, continues ultrasonic disperse 1-1.5h；
(2) it will be placed in crystallizing tank through step (1) resulting material, and be warming up to heated at constant temperature 5-6h at 95 ± 2 DEG C, crystallized
Obtain powder；Powder is dried in vacuo to get the heat accumulation heat-transfer matcrial at 50-55 DEG C.
The beneficial effects of the present invention are:
1, the present invention adds Al in molten salt mixture2O3/SiO2Composite nanometer particle, the Al that the present invention is prepared2O3/
SiO2Composite nanometer particle its compared with same diameter range nanometer Al2O3And Nano-meter SiO_22It is not easy to reunite, therefore in molten salt mixture
In have preferable dispersion effect.Due to substantially reducing for agglomeration, the effect of specific heat capacity enhancing is best.It is added simultaneously
Al2O3/SiO2The comprehensive function of interface resistance and semi-solid layer that composite nanometer particle generates, can effectively improve molten salt mixture
Specific heat capacity.
2, rationally, itself specific heat capacity is big, and thermal conductivity with higher for the fused salt mixt each component cooperation in the present invention,
Latent heat of phase change is high.
3, polyvinylpyrrolidone is added to be dispersed, enhances Al2O3/SiO2Composite nanometer particle is in fused salt mixt
Dispersibility, the reunion of nano particle can be effectively relieved, further improve the specific heat capacity of heat accumulating.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making
Every other embodiment obtained, shall fall within the protection scope of the present invention under the premise of creative work.
Embodiment 1:
A kind of heat accumulation heat-transfer matcrial, raw material include the Al of molten salt mixture, molten salt mixture quality 0.08%2O3/SiO2
The polyvinylpyrrolidone of composite nanometer particle and molten salt mixture quality 0.2%；
Molten salt mixture is grouped as by the group of following weight fraction: NaNO3: 53.5 parts, LiNO3: 22.5 parts, KNO3: 36
Part, Li2CO3: 29 parts, Sr2CO3: 9.5 parts.
Al2O3/SiO2Composite nanometer particle is prepared by following methods:
Ethyl alcohol is uniformly mixed with water 5:1 in mass ratio, ethanol water is obtained and its matter is added after stirring is warming up to 55 DEG C
The ethyl orthosilicate of amount 20%, and appropriate dilute hydrochloric acid is added and promotes to react, after insulation reaction 6h, obtain SiO2Colloidal sol；Then to SiO2
Nanometer Al is added in colloidal sol2O3(average grain diameter D50 is 5nm), ultrasonic disperse 2.5h, is then washed using dehydrated alcohol while stirring
It washs 5 times, gained colloidal sol is dried, grinding, which is placed in 480 DEG C of Muffle furnace, calcines 3h to get the Al2O3/SiO2It is multiple
Nano particle is closed, average grain diameter D50 is 85nm.
The preparation method of heat accumulation heat-transfer matcrial, comprising the following steps:
(1) each raw material in molten salt mixture is uniformly mixed, and be added in the deionized water of 2.5 times of its quality, while stirring
It mixes side and is warming up to 50 DEG C, Al is added afterwards2O3/SiO2Composite nanometer particle, and ultrasonic disperse 1.5h；Then polyvinyl pyrrole is added
Alkanone continues ultrasonic disperse 1.5h；
(2) it will be placed in crystallizing tank through step (1) resulting material, and be warming up to heated at constant temperature 6h at 95 ± 2 DEG C, crystallize
Powder；Powder is dried in vacuo at 50 DEG C to get heat accumulation heat-transfer matcrial.
Embodiment 2:
A kind of heat accumulation heat-transfer matcrial, raw material include the Al of molten salt mixture, molten salt mixture quality 0.06%2O3/SiO2
The polyvinylpyrrolidone of composite nanometer particle and molten salt mixture quality 0.25%；
Molten salt mixture is grouped as by the group of following weight fraction: NaNO3: 53.5 parts, LiNO3: 22.5 parts, KNO3: 36
Part, Li2CO3: 29 parts, Sr2CO3: 9.5 parts.
Al2O3/SiO2Composite nanometer particle is prepared by following methods:
Ethyl alcohol is uniformly mixed with water 4:1 in mass ratio, ethanol water is obtained and its matter is added after stirring is warming up to 50 DEG C
The ethyl orthosilicate of amount 25%, and appropriate dilute hydrochloric acid is added and promotes to react, after insulation reaction 3h, obtain SiO2Colloidal sol；Then to SiO2
Nanometer Al is added in colloidal sol2O3(average grain diameter D50 is 10nm), ultrasonic disperse 3h, is then washed using dehydrated alcohol while stirring
5 times, gained colloidal sol is dried, grinding, which is placed in 490 DEG C of Muffle furnace, calcines 3h to get the Al2O3/SiO2It is compound
Nano particle, average grain diameter D50 are 102nm.
The preparation method of heat accumulation heat-transfer matcrial, comprising the following steps:
(1) each raw material in molten salt mixture is uniformly mixed, and be added in the deionized water of 2.5 times of its quality, while stirring
It mixes side and is warming up to 50 DEG C, Al is added afterwards2O3/SiO2Composite nanometer particle, and ultrasonic disperse 80min；Then polyvinyl pyrrole is added
Alkanone continues ultrasonic disperse 80min；
(2) it will be placed in crystallizing tank through step (1) resulting material, and be warming up to heated at constant temperature 5.5h at 95 ± 2 DEG C, crystallized
Obtain powder；Powder is dried in vacuo at 50 DEG C to get heat accumulation heat-transfer matcrial.
Embodiment 3:
A kind of heat accumulation heat-transfer matcrial, raw material include the Al of molten salt mixture, molten salt mixture quality 0.075%2O3/
SiO2The polyvinylpyrrolidone of composite nanometer particle and molten salt mixture quality 0.2%；
Molten salt mixture is grouped as by the group of following weight fraction: NaNO3: 53.5 parts, LiNO3: 22.5 parts, KNO3: 36
Part, Li2CO3: 29 parts, Sr2CO3: 9.5 parts.
Al2O3/SiO2Composite nanometer particle is prepared by following methods:
Ethyl alcohol is uniformly mixed with water 5:1 in mass ratio, ethanol water is obtained and its matter is added after stirring is warming up to 60 DEG C
The ethyl orthosilicate of amount 20%, and appropriate dilute hydrochloric acid is added and promotes to react, after insulation reaction 4.5h, obtain SiO2Colloidal sol；Then to
SiO2Nanometer Al is added in colloidal sol2O3(average grain diameter D50 is 5nm), ultrasonic disperse 3h, then uses dehydrated alcohol while stirring
Washing 4 times, gained colloidal sol is dried, and grinding, which is placed in 460 DEG C of Muffle furnace, calcines 3h to get Al2O3/SiO2It is compound
Nano particle, average grain diameter D50 are 80nm.
The preparation method of heat accumulation heat-transfer matcrial, comprising the following steps:
(1) each raw material in molten salt mixture is uniformly mixed, and be added in the deionized water of 2.5 times of its quality, while stirring
It mixes side and is warming up to 45 DEG C, Al is added afterwards2O3/SiO2Composite nanometer particle, and ultrasonic disperse 1h；Then polyvinylpyrrolidine is added
Ketone continues ultrasonic disperse 1h；
(2) it will be placed in crystallizing tank through step (1) resulting material, and be warming up to heated at constant temperature 5h at 95 ± 2 DEG C, crystallize
Powder；Powder is dried in vacuo at 55 DEG C to get heat accumulation heat-transfer matcrial.
Embodiment 4:
A kind of heat accumulation heat-transfer matcrial, raw material include the Al of molten salt mixture, molten salt mixture quality 0.095%2O3/
SiO2The polyvinylpyrrolidone of composite nanometer particle and molten salt mixture quality 0.3%.
Molten salt mixture is grouped as by the group of following weight fraction: NaNO3: 53.5 parts, LiNO3: 22.5 parts, KNO3: 36
Part, Li2CO3: 29 parts, Sr2CO3: 9.5 parts.
Al2O3/SiO2The preparation method is the same as that of Example 1 for composite nanometer particle.
The preparation method is the same as that of Example 1 for heat accumulation heat-transfer matcrial.
Embodiment 5:
A kind of heat accumulation heat-transfer matcrial, raw material include the Al of molten salt mixture, molten salt mixture quality 0.085%2O3/
SiO2The polyvinylpyrrolidone of composite nanometer particle and molten salt mixture quality 0.2%.
Molten salt mixture is grouped as by the group of following weight fraction: NaNO3: 53.5 parts, LiNO3: 22.5 parts, KNO3: 36
Part, Li2CO3: 29 parts, Sr2CO3: 9.5 parts.
Al2O3/SiO2The preparation method is the same as that of Example 1 for composite nanometer particle.
The preparation method of heat accumulation heat-transfer matcrial is the same as embodiment 3.
Embodiment 6:
A kind of heat accumulation heat-transfer matcrial, raw material include the Al of molten salt mixture, molten salt mixture quality 0.06%2O3/SiO2
The polyvinylpyrrolidone of composite nanometer particle and molten salt mixture quality 0.15%.
Molten salt mixture is grouped as by the group of following weight fraction: NaNO3: 53.5 parts, LiNO3: 22.5 parts, KNO3: 36
Part, Li2CO3: 29 parts, Sr2CO3: 9.5 parts.
Al2O3/SiO2The preparation method of composite nanometer particle is the same as embodiment 2.
The preparation method is the same as that of Example 1 for heat accumulation heat-transfer matcrial.
Embodiment 7:
A kind of heat accumulation heat-transfer matcrial, raw material include the Al of molten salt mixture, molten salt mixture quality 0.065%2O3/
SiO2The polyvinylpyrrolidone of composite nanometer particle and molten salt mixture quality 0.2%；
Molten salt mixture is grouped as by the group of following weight fraction: NaNO3: 65 parts, LiNO3: 20 parts, KNO3: 40 parts,
Li2CO3: 32 parts, Sr2CO3: 11 parts.
Al2O3/SiO2The preparation method of composite nanometer particle is the same as embodiment 2.
The preparation method of heat accumulation heat-transfer matcrial is the same as embodiment 2.
Embodiment 8:
A kind of heat accumulation heat-transfer matcrial, raw material include molten salt mixture, molten salt mixture quality 0.06-0.095%
Al2O3/SiO2The polyvinylpyrrolidone of composite nanometer particle and molten salt mixture quality 0.15-0.3%；
Molten salt mixture is grouped as by the group of following weight fraction: NaNO3: 40 parts, LiNO3: 26 parts, KNO3: 30 parts,
Li2CO3: 25 parts, Sr2CO3: 6 parts.
Al2O3/SiO2The preparation method is the same as that of Example 1 for composite nanometer particle.
The preparation method is the same as that of Example 1 for heat accumulation heat-transfer matcrial.
Performance test:
The solid-state specific heat capacity and liquid specific heat for measuring the molten salt mixture in embodiment 1-6 are held, then again to embodiment 1-6
In preparation-obtained heat accumulation heat-transfer matcrial solid-state specific heat capacity and liquid specific heat appearance be measured.
The specific heat capacitance of 1 heat accumulation heat-transfer matcrial of table
As shown in Table 1, Al is added2O3/SiO2After composite nanometer particle, resulting heat accumulation heat-transfer matcrial is mixed relative to fused salt
It closes its solid-state specific heat capacity of object and liquid specific heat container improves a lot.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
Invention is explained in detail, those skilled in the art should understand that: it still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these modification or
Replacement, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (8)
1. a kind of heat accumulation heat-transfer matcrial, which is characterized in that its raw material includes molten salt mixture, molten salt mixture quality 0.06-
0.095% Al2O3/SiO2The dispersing agent of composite nanometer particle and molten salt mixture quality 0.15-0.3%；The fused salt is mixed
The raw material for closing object includes NaNO3、LiNO3、K NO3、Li2CO3、Sr2CO3。
2. heat accumulation heat-transfer matcrial according to claim 1, which is characterized in that the molten salt mixture is by following weight fraction
Group be grouped as: NaNO3: 40-65 parts, LiNO3: 20-26 parts, KNO3: 30-40 parts, Li2CO3: 25-32 parts, Sr2CO3: 6-11
Part.
3. heat accumulation heat-transfer matcrial according to claim 2, which is characterized in that the molten salt mixture is by following weight fraction
Group be grouped as: NaNO3: 53.5 parts, LiNO3: 22.5 parts, KNO3: 36 parts, Li2CO3: 29 parts, Sr2CO3: 9.5 parts.
4. heat accumulation heat-transfer matcrial according to claim 1, which is characterized in that Al2O3/SiO2Composite nanometer particle is by following
Method is prepared:
Ethyl alcohol is uniformly mixed with water 4-5:1 in mass ratio, ethanol water is obtained and its matter is added after stirring is warming up to 50-60 DEG C
The ethyl orthosilicate of 20-25% is measured, and appropriate dilute hydrochloric acid is added and promotes to react, after insulation reaction 3-6h, obtains SiO2Colloidal sol；Then
To SiO2Nanometer Al is added in colloidal sol2O3, ultrasonic disperse 2-3h, is then washed 4-5 times using dehydrated alcohol, by institute while stirring
It obtains colloidal sol to be dried, grinding, which is placed in 450-490 DEG C of Muffle furnace, calcines 2-3h to get the Al2O3/SiO2It is compound to receive
Rice grain.
5. heat accumulation heat-transfer matcrial according to claim 5, which is characterized in that the Al2O3The average grain diameter of nano particle
D50 is 5-15nm.
6. heat accumulation heat-transfer matcrial according to claim 5, which is characterized in that the Al2O3/SiO2Composite nanometer particle
Average grain diameter D50 is 80-110nm.
7. heat accumulation heat-transfer matcrial according to claim 1, which is characterized in that the dispersing agent is polyvinylpyrrolidone.
8. the preparation method of heat accumulation heat-transfer matcrial described in any one of -7 according to claim 1, which is characterized in that including following
Step:
(1) each raw material in molten salt mixture is uniformly mixed, and be added in the deionized water of 2-2.5 times of its quality, side stirring
While it is warming up to 45-50 DEG C, the rear Al that molten salt mixture quality 0.06-0.095% is added2O3/SiO2Composite nanometer particle, and surpass
Sound disperses 1-1.5h；Then the dispersing agent of molten salt mixture quality 0.15-0.3% is added, continues ultrasonic disperse 1-1.5h；
(2) it will be placed in crystallizing tank through step (1) resulting material, and be warming up to heated at constant temperature 5-6h at 95 ± 2 DEG C, crystallize to obtain powder
End；Powder is dried in vacuo to get the heat accumulation heat-transfer matcrial at 50-55 DEG C.
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| CN201910376548.9A CN110041895B (en) | 2019-05-07 | 2019-05-07 | Heat storage and transfer material and preparation method thereof |
| 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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| WO2020224080A1 (en) * | 2019-05-07 | 2020-11-12 | 安徽普瑞普勒传热技术有限公司 | Heat storage and heat transfer material and preparation method therefor |
| CN112126208A (en) * | 2020-09-01 | 2020-12-25 | 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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| CN103113854A (en) * | 2013-02-06 | 2013-05-22 | 青岛奥环新能源科技发展有限公司 | Composite phase-change material for mobile heat supply and preparation method thereof |
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| KR101480342B1 (en) * | 2013-11-19 | 2015-01-09 | 한국에너지기술연구원 | Heat storage materials comprising six component system |
| CN109021927A (en) * | 2017-06-09 | 2018-12-18 | 徐辉 | Phase-change heat-storage material composition and preparation method thereof for heat storage type electric heater |
| CN110041895B (en) * | 2019-05-07 | 2020-07-28 | 安徽普瑞普勒传热技术有限公司 | Heat storage and transfer material and preparation method thereof |
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| WO2020224080A1 (en) * | 2019-05-07 | 2020-11-12 | 安徽普瑞普勒传热技术有限公司 | Heat storage and heat transfer material and preparation method therefor |
| CN112126208A (en) * | 2020-09-01 | 2020-12-25 | 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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