CN103113854A - Composite phase-change material for mobile heat supply and preparation method thereof - Google Patents
Composite phase-change material for mobile heat supply and preparation method thereof Download PDFInfo
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- CN103113854A CN103113854A CN201310048088XA CN201310048088A CN103113854A CN 103113854 A CN103113854 A CN 103113854A CN 201310048088X A CN201310048088X A CN 201310048088XA CN 201310048088 A CN201310048088 A CN 201310048088A CN 103113854 A CN103113854 A CN 103113854A
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a composite phase-change material for mobile heat supply and a preparation method thereof. The composite phase-change material is formed by compounding 97.5-99.5 wt% of mixed inorganic salts and 0.5-2.5 wt% of non-metal nano material. The preparation method comprises the following steps: mixing a plurality of inorganic salts according to mass ratio, stirring, adding into a vacuum heating furnace, and heating into a molten state, wherein the temperature of the vacuum heating furnace is controlled at 40-50 DEG C higher than the phase-change temperature of the mixed inorganic salts; and adding the non-metal nano material into the molten salts, and magnetically stirring for more than half an hour to prepare the uniform and stable molten-state composite phase-change material. Compared with the prior art, the composite phase-change material disclosed by the invention has the advantages of high heat-conducting property, high heat accumulation density, small volume shrinkage and the like, can satisfy different application requirements, and is especially suitable for moderate-temperature waste heat recovery.
Description
Technical field
The present invention relates to a kind of mobile heat supply with the preparation method of composite phase-change material and this composite phase-change material, belong to the phase change heat storage material technical field.
Background technology
Development along with society, the mankind increase day by day to the demand of the energy, but the supply and demand of the energy has stronger stage, can't rationally utilize under many circumstances, thereby cause a large amount of wastes of the energy, at this moment just need some materials that the form of part energy with heat energy stored.The enhancing of and environmental consciousness energy-conservation along with people, energy-saving material more and more receives publicity in the waste heat recovery field.Phase change material absorbs in process or discharges amount of heat in phase transformation (solid solid-liquid or solid-) realizes energy transformation, and its energy storage density is large, efficient is high, the suction exothermic process almost carries out under isothermal condition.Can produce a large amount of heat in industrial production and life, these heats do not obtain just utilizing being wasted usually, phase change material can store the energy or the natural energy resources of these wastes as a kind of energy storage material, discharge according to different needs, the energy is reasonably utilized, and its Application Areas mainly comprises sun power, industrial thermal utilization and waste heat recovery, power peak regulation, building energy conservation, agricultural greenhouse, aerospace equipment etc.At present, in solid-liquid phase change, high temperature phase change material (pcm) is mainly high-temperature fusion salt, alkali, mixing salt.High-temperature fusion salt mainly contains halogenide, oxide compound, nitrate, vitriol, carbonate etc., and they have higher transformation temperature and latent heat of phase change; The specific heat capacity of alkali is high, and melting heat is large, good stability, and low price is also a kind of middle high temperature energy-storage material preferably; The mixing salt melting heat is large, and during fusing, volume change is little, conducts heat better, has advantages of that melt temperature is adjustable, can be configured to different salt as required the energy storage material of different transformation temperatures.In reclaiming for mobile heat supply car, warm waste heat recovery is used, and selects the mixing salt phase change material to have higher economic worth.Yet in the mixing salt, warm phase-changing energy storage material generally has the low shortcoming of heat transfer property, is limited by very large in application.The effective way that improves the thermal conductivity of phase change material own is to add the nano material of high heat conduction in phase change material.Mainly to add to improve thermal conductivity with millimeter, micron order and larger-size nano metal material in phase change material at present, owing to there being larger density difference between metal and phase change material, after the composite phase-change material fusing, these metal solid particles are Precipitation in fused salt mixt very easily, greatly reduces the enhanced heat exchange effect of composite phase-change material.
Summary of the invention
Based on above-mentioned technical problem, the invention provides a kind of mobile heat supply composite phase-change material and preparation method thereof.
Its technical solution is:
A kind of mobile heat supply composite phase-change material, it is compounded by mixed inorganic and nonmetal nano material.
Preferably, described nonmetal nano material is that particle diameter is the following Al of 10nm
2O
3, SiO
2, SiC, CaCO
3, Si
3N
4With TiO
2In one or more combination.
Be more preferably, described nonmetal nano material is by Al
2O
3Form with SiC.
Preferably, described mixed inorganic forms by any two kinds in nitrate, halogenide and carbonate, or is comprised of nitrate, halogenide and carbonate.
Preferably, described nitrate is the one or more combination in lithium nitrate, Sodium Nitrite, nitrate of baryta, SODIUMNITRATE and saltpetre; Described halogenide is one or both combinations in lithium fluoride and Sodium Fluoride; Described carbonate is Quilonum Retard.
Be more preferably, the quaternary mixing salt that described mixed inorganic is comprised of lithium nitrate, SODIUMNITRATE, Sodium Nitrite and lithium fluoride, wherein the mass ratio of lithium nitrate, SODIUMNITRATE, Sodium Nitrite and lithium fluoride is (15～45): (5～15): (5～10): (20～55).
Preferably, in described composite phase-change material, mixed inorganic accounts for total mass 97.5～99.5%, and nonmetal nano material accounts for total mass 0.5～2.5%.
Be more preferably, more than C, thermal conductivity is more than 1.0W/mk at 110 ° for the fusing point of described composite phase-change material.
A kind of mobile heat supply preparation method of composite phase-change material, it comprises the following steps:
(1) plurality of inorganic salt is mixed in mass ratio, stir, put into the vacuum furnace heating and make it be molten state, the temperature of vacuum furnace is controlled at above 40～50 ° of C of mixed inorganic transformation temperature, makes melting salt;
(2) nonmetal nano material is joined in the melting salt that makes in step (1), it is constant that the temperature of vacuum furnace is controlled at above 40～50 ° of C of mixed inorganic transformation temperature, magnetic agitation is prepared uniform and stable molten state composite phase-change material more than half an hour.
Useful technique effect of the present invention is:
The present invention has added the nonmetal nano material of the following particle diameter of 10nm in the melting mixing inorganic salt, nonmetal nano material is close with inorganic salt density, the Precipitation of solid particulate can not occur, prepared composite phase-change material has advantages of that the heat release of holding speed is fast, thermal storage density is high, good heat conductivity; Be mainly used in carrying out in mobile heating system 110 ° of C above middle temperature waste heat recovery and utilization.Compare with existing mixing salt phase change material, composite phase-change material of the present invention can reduce volumetric shrinkage and reach more than 25%, improve thermal conductivity and reach more than 40%, increase latent heat and reach more than 13%, overcome preferably the defectives such as the heat transfer property that existing mixing salt phase change material exists is poor, when solidifying volumetric shrinkage is large.
Embodiment
The invention will be further described below in conjunction with specific embodiment:
Embodiment 1
Mass ratio by lithium nitrate, SODIUMNITRATE, Sodium Nitrite and lithium fluoride is 38: 20: 12: 30 take four kinds of salt, and mechanical stirring is even, puts into the vacuum furnace heating and melting, and the temperature of vacuum furnace is controlled at above 40～50 ° of C of mixing salt transformation temperature.Be the Al of 10nm with the particle diameter that accounts for total mass 0.5%
2O
3Join in the mixing salt of melting with the SiC stuff and other stuff, it is constant that the temperature of vacuum furnace is controlled at above 40～50 ° of C of mixing salt transformation temperature, and this melts of magnetic agitation 40 minutes prepares uniform and stable nano-composite phase-changing material.The nano-composite phase-changing material of molten state can be by the direct Quick-filling of bottom feed opening in the energy storage tank of mobile heat supply car.After can is completed, close vacuum furnace and magnetic stirring apparatus.Owing to having added nonmetallic nano material, composite phase-change material is liquid phase or the capacity of heat transmission of solid phase all improves a lot than mixing salt no matter.After testing, prepared composite phase-change material latent heat is 280KJ/kg, and transformation temperature is 138 ° of C, and the solid phase of composite phase-change material and liquid phase thermal conductivity ratio mixing salt have on average improved 13% and 17%.
Embodiment 2
Mass ratio by lithium nitrate, SODIUMNITRATE, Sodium Nitrite and lithium fluoride is 42: 21: 10: 28 take four kinds of salt, and mechanical stirring is even, puts into the vacuum furnace heating and melting, and the temperature of vacuum furnace is controlled at above 40～50 ° of C of mixing salt transformation temperature.Be the Al of 10nm with the particle diameter that accounts for total mass 0.8%
2O
3Join in the mixing salt of melting with the SiC stuff and other stuff, it is constant that the temperature of vacuum furnace is controlled at above 40～50 ° of C of mixing salt transformation temperature, and this melts of magnetic agitation 80 minutes prepares uniform and stable nano-composite phase-changing material.The nano-composite phase-changing material of molten state can be by the direct Quick-filling of bottom feed opening in the energy storage tank of mobile heat supply car.After can is completed, close vacuum furnace and magnetic stirring apparatus.Owing to having added nonmetallic nano material, composite phase-change material is liquid phase or the capacity of heat transmission of solid phase all improves a lot than mixing salt no matter.After testing, prepared composite phase-change material latent heat is 350KJ/kg, and transformation temperature is 125 ° of C, and the solid phase of composite phase-change material and liquid phase thermal conductivity ratio mixing salt have on average improved 15% and 19%.
Embodiment 3
Mass ratio by lithium nitrate, SODIUMNITRATE, Sodium Nitrite and lithium fluoride is 45: 18: 10: 27 take four kinds of salt, and mechanical stirring is even, puts into the vacuum furnace heating and melting, and the temperature of vacuum furnace is controlled at above 40～50 ° of C of mixing salt transformation temperature.Be the Al of 10nm with the particle diameter that accounts for total mass 1.1%
2O
3Join in the mixing salt of melting with the SiC stuff and other stuff, it is constant that the temperature of vacuum furnace is controlled at above 40～50 ° of C of mixing salt transformation temperature, and this melts of magnetic agitation 150 minutes prepares uniform and stable nano-composite phase-changing material.The nano-composite phase-changing material of molten state can be by the direct Quick-filling of bottom feed opening in the energy storage tank of mobile heat supply car.After can is completed, close vacuum furnace and magnetic stirring apparatus.Owing to having added nonmetallic nano material, composite phase-change material is liquid phase or the capacity of heat transmission of solid phase all improves a lot than mixing salt no matter.After testing, prepared composite phase-change material latent heat is 390KJ/kg, and transformation temperature is 145 ° of C, and the solid phase of composite phase-change material and liquid phase thermal conductivity ratio mixing salt have on average improved 9% and 12%.
Embodiment 4
Mass ratio by lithium nitrate, SODIUMNITRATE, lithium fluoride and Quilonum Retard is 35: 15: 12: 30 take four kinds of salt, and mechanical stirring is even, puts into the vacuum furnace heating and melting, and the temperature of vacuum furnace is controlled at above 40～50 ° of C of mixing salt transformation temperature.Be the Al of 8nm with the particle diameter that accounts for total mass 2.5%
2O
3Join in the mixing salt of melting with the SiC stuff and other stuff, it is constant that the temperature of vacuum furnace is controlled at above 40～50 ° of C of mixing salt transformation temperature, and this melts of magnetic agitation 100 minutes prepares uniform and stable nano-composite phase-changing material.
Embodiment 5
Mass ratio by lithium nitrate, nitrate of baryta, Sodium Nitrite and Sodium Fluoride is 20: 20: 12: 30 take four kinds of salt, and mechanical stirring is even, puts into the vacuum furnace heating and melting, and the temperature of vacuum furnace is controlled at above 40～50 ° of C of mixing salt transformation temperature.Be the Al of 8nm with the particle diameter that accounts for total mass 2.0%
2O
3And Si
3N
4Stuff and other stuff joins in the mixing salt of melting, and it is constant that the temperature of vacuum furnace is controlled at above 40～50 ° of C of mixing salt transformation temperature, and this melts of magnetic agitation 120 minutes prepares uniform and stable nano-composite phase-changing material.
Embodiment 6
Be to take three kind salt at 40: 20: 20 by the mass ratio of SODIUMNITRATE, Sodium Nitrite and Quilonum Retard, mechanical stirring is even, puts into the vacuum furnace heating and melting, and the temperature of vacuum furnace is controlled at above 40～50 ° of C of mixing salt transformation temperature.Be the Al of 10nm with the particle diameter that accounts for total mass 1.8%
2O
3And TiO
2Particle joins in the mixing salt of melting, and it is constant that the temperature of vacuum furnace is controlled at above 40～50 ° of C of mixing salt transformation temperature, and this melts of magnetic agitation 80 minutes prepares uniform and stable nano-composite phase-changing material.
Embodiment 7
Be to take two kind salt at 30: 20 by the mass ratio of SODIUMNITRATE and Sodium Fluoride, mechanical stirring is even, puts into the vacuum furnace heating and melting, and the temperature of vacuum furnace is controlled at above 40～50 ° of C of mixing salt transformation temperature.Be the TiO of 10nm with the particle diameter that accounts for total mass 2.2%
2Join in the mixing salt of melting with the SiC stuff and other stuff, it is constant that the temperature of vacuum furnace is controlled at above 40～50 ° of C of mixing salt transformation temperature, and this melts of magnetic agitation 90 minutes prepares uniform and stable nano-composite phase-changing material.
Embodiment 8
Be to take four kind salt at 35: 15: 12 by the mass ratio of lithium nitrate, lithium fluoride and Quilonum Retard, mechanical stirring is even, puts into the vacuum furnace heating and melting, and the temperature of vacuum furnace is controlled at above 40～50 ° of C of mixing salt transformation temperature.Be the Al of 10nm with the particle diameter that accounts for total mass 1.2%
2O
3, TiO
2Join in the mixing salt of melting with the SiC stuff and other stuff, it is constant that the temperature of vacuum furnace is controlled at above 40～50 ° of C of mixing salt transformation temperature, and this melts of magnetic agitation 100 minutes prepares uniform and stable nano-composite phase-changing material.
Claims (9)
1. mobile heat supply composite phase-change material, it is characterized in that: this composite phase-change material is compounded by mixed inorganic and nonmetal nano material.
2. a kind of mobile heat supply composite phase-change material according to claim 1 is characterized in that: described nonmetal nano material is that particle diameter is the following Al of 10nm
2O
3, SiO
2, SiC, CaCO
3, Si
3N
4With TiO
2In one or more combination.
3. a kind of mobile heat supply composite phase-change material according to claim 2, it is characterized in that: described nonmetal nano material is by Al
2O
3Form with SiC.
4. a kind of mobile heat supply composite phase-change material according to claim 1, it is characterized in that: described mixed inorganic forms by any two kinds in nitrate, halogenide and carbonate, or is comprised of nitrate, halogenide and carbonate.
5. a kind of mobile heat supply composite phase-change material according to claim 4, it is characterized in that: described nitrate is the one or more combination in lithium nitrate, Sodium Nitrite, nitrate of baryta, SODIUMNITRATE and saltpetre; Described halogenide is one or both combinations in lithium fluoride and Sodium Fluoride; Described carbonate is Quilonum Retard.
6. a kind of mobile heat supply composite phase-change material according to claim 5, it is characterized in that: the quaternary mixing salt that described mixed inorganic is comprised of lithium nitrate, SODIUMNITRATE, Sodium Nitrite and lithium fluoride, wherein the mass ratio of lithium nitrate, SODIUMNITRATE, Sodium Nitrite and lithium fluoride is (15～45): (5～15): (5～10): (20～55).
7. a kind of mobile heat supply composite phase-change material according to claim 1, it is characterized in that: in described composite phase-change material, mixed inorganic accounts for total mass 97.5～99.5%, and nonmetal nano material accounts for total mass 0.5～2.5%.
8. a kind of mobile heat supply composite phase-change material according to claim 1, it is characterized in that: more than C, thermal conductivity is more than 1.0W/mk at 110 ° for the fusing point of described composite phase-change material.
9. the described a kind of mobile heat supply of arbitrary claim with the preparation method of composite phase-change material, is characterized in that comprising the following steps according to claim 1～8:
(1) plurality of inorganic salt is mixed in mass ratio, stir, put into the vacuum furnace heating and make it be molten state, the temperature of vacuum furnace is controlled at above 40～50 ° of C of mixed inorganic transformation temperature, makes melting salt;
(2) nonmetal nano material is joined in the melting salt that makes in step (1), it is constant that the temperature of vacuum furnace is controlled at above 40～50 ° of C of mixed inorganic transformation temperature, magnetic agitation is prepared uniform and stable molten state composite phase-change material more than half an hour.
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| CN109233751B (en) * | 2018-11-09 | 2020-11-10 | 中国建筑材料科学研究总院有限公司 | Carbon-based composite phase change energy storage material and preparation method thereof |
| CN110041895A (en) * | 2019-05-07 | 2019-07-23 | 安徽普瑞普勒传热技术有限公司 | A kind of heat accumulation heat-transfer matcrial and preparation method thereof |
| 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 |
| 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 |
| CN111560235A (en) * | 2020-05-20 | 2020-08-21 | 贵州梅岭电源有限公司 | High-viscosity high-heat-storage type phase-change material for thermal battery and preparation method and application thereof |
| CN111560235B (en) * | 2020-05-20 | 2021-08-03 | 贵州梅岭电源有限公司 | High-viscosity high-heat-storage type phase-change material for thermal battery and preparation method and application thereof |
| CN114806511A (en) * | 2022-04-28 | 2022-07-29 | 四川大学 | Movable semi-packaged solid-liquid phase change heat storage material and preparation method and application thereof |
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