CN103113854B - A kind of mobile heat supply composite phase-change material and preparation method thereof - Google Patents
A kind of mobile heat supply composite phase-change material and preparation method thereof Download PDFInfo
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- CN103113854B CN103113854B CN201310048088.XA CN201310048088A CN103113854B CN 103113854 B CN103113854 B CN 103113854B CN 201310048088 A CN201310048088 A CN 201310048088A CN 103113854 B CN103113854 B CN 103113854B
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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 kind of mobile heat supply composite phase-change material and preparation method thereof, nonmetal nano material and mixed inorganic are compounded to form by this composite phase-change material; In 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%.Preparation method is as follows: plurality of inorganic salt mixed in mass ratio, stirs, and put into vacuum furnace heating and make it be molten state, the temperature of vacuum furnace controls 40 ~ 50 ° of C more than mixed inorganic transformation temperature; Nonmetal nano material is joined in melting salt, more than magnetic agitation half an hour, prepare uniform and stable molten state composite phase-change material.Compared with prior art, the composite phase-change material that the present invention obtains has that heat conductivility is high, thermal storage density is large and the advantage such as volumetric shrinkage is little, can meet different application demands, be particularly suitable for middle temperature heat recovery.
Description
Technical field
The present invention relates to the preparation method of a kind of mobile heat supply composite phase-change material and this composite phase-change material, belong to phase change heat storage material technical field.
Background technology
Along with the development of society, the demand of the mankind to the energy increases day by day, but the supply and demand of the energy has stronger stage, under many circumstances can't Appropriate application, thus cause a large amount of wastes of the energy, at this moment just need some materials that part energy is stored with the form of heat energy.Along with the enhancing of people's energy saving standard consciousness, energy-saving material more and more receives publicity in waste heat recovery field.Phase change material absorbs in process in phase transformation (solid solid-liquid or solid-) or release amount of heat realizes energy transformation, and its energy storage density is large, efficiency is high, suction exothermic process almost carries out under isothermal conditions.A large amount of heat can be produced in industrial production and life, these heats do not obtain utilizing just being wasted usually, the energy of these wastes or natural energy resources can store as a kind of energy storage material by phase change 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, low price, is also a kind of middle high temperature energy-storage material preferably; Mixing salt melting heat is large, and during fusing, volume change is little, and heat transfer better, has the advantage that melt temperature is adjustable, as required different salt can be configured to the energy storage material of different transformation temperature.In reclaiming for mobile heat supply car, warm waste heat recovery application, selects mixing salt phase change material to have higher economic worth.But in mixing salt, warm phase-changing energy storage material generally has the low shortcoming of heat transfer property, is limited by very large in the application.The effective way improving the thermal conductivity of phase change material own is the nano material of adding high heat conduction in phase change material.Mainly add in phase change material with millimeter, micron order and larger-size nano metal material to improve thermal conductivity at present, owing to there is larger density difference between metal and phase change material, after composite phase-change material fusing, these metal solid particles very easily Precipitation in fused salt mixt, 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, its be by mixed inorganic and nonmetal nano material compounded.
Preferably, the Al of described nonmetal nano material to be particle diameter be below 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 is made up of any two kinds in nitrate, halogenide and carbonate, or is made up 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 that one or both in lithium fluoride and Sodium Fluoride combine; Described carbonate is Quilonum Retard.
Be more preferably, the quaternary mixing salt that described mixed inorganic is made up 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, the fusing point of described composite phase-change material is at 110 ° of more than C, and thermal conductivity is at more than 1.0W/mk.
A preparation method for mobile heat supply composite phase-change material, it comprises the following steps:
(1) plurality of inorganic salt mixed in mass ratio, stir, put into vacuum furnace heating and make it be molten state, the temperature of vacuum furnace controls 40 ~ 50 ° of C more than mixed inorganic transformation temperature, obtained melting salt;
(2) nonmetal nano material is joined in melting salt obtained in step (1), it is constant that the temperature of vacuum furnace controls 40 ~ 50 ° of C more than mixed inorganic transformation temperature, more than magnetic agitation half an hour, prepare uniform and stable molten state composite phase-change material.
Advantageous Effects of the present invention is:
Present invention adds the nonmetal nano material of below 10nm particle diameter in melting mixing inorganic salt, nonmetal nano material and inorganic salt similar density, there will not be the Precipitation of solid particulate, obtained composite phase-change material has and stores that exotherm rate is fast, thermal storage density is high, the advantage of good heat conductivity; Be mainly used in middle temperature waste heat recovery and the utilization of carrying out 110 ° of more than C in mobile heating system.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 the defects such as the heat transfer property that existing mixing salt phase change material exists is poor, volumetric shrinkage is large when solidifying preferably.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described:
Embodiment 1
Be take four kind salt at 38: 20: 12: 30 by the mass ratio of lithium nitrate, SODIUMNITRATE, Sodium Nitrite and lithium fluoride, mechanical stirring is even, and put into vacuum furnace heating and melting, the temperature of vacuum furnace controls 40 ~ 50 ° of C more than mixing salt transformation temperature.Be the Al of 10nm by the particle diameter accounting for total mass 0.5%
2o
3in joining the mixing salt of melting with SiC stuff and other stuff, it is constant that the temperature of vacuum furnace controls 40 ~ 50 ° of C more than 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 by the direct Quick-filling of bottom feed opening in the energy storage tank of mobile heat supply car.Filling complete after, close vacuum furnace and magnetic stirring apparatus.Owing to the addition of nonmetallic nano material, composite phase-change material no matter liquid phase or the capacity of heat transmission of solid phase all improves a lot than mixing salt.After testing, prepared composite phase-change material latent heat is 280KJ/kg, and transformation temperature is 138 ° of C, and solid phase and the liquid phase thermal conductivity ratio mixing salt of composite phase-change material on average improve 13% and 17%.
Embodiment 2
Be take four kind salt at 42: 21: 10: 28 by the mass ratio of lithium nitrate, SODIUMNITRATE, Sodium Nitrite and lithium fluoride, mechanical stirring is even, and put into vacuum furnace heating and melting, the temperature of vacuum furnace controls 40 ~ 50 ° of C more than mixing salt transformation temperature.Be the Al of 10nm by the particle diameter accounting for total mass 0.8%
2o
3in joining the mixing salt of melting with SiC stuff and other stuff, it is constant that the temperature of vacuum furnace controls 40 ~ 50 ° of C more than 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 by the direct Quick-filling of bottom feed opening in the energy storage tank of mobile heat supply car.Filling complete after, close vacuum furnace and magnetic stirring apparatus.Owing to the addition of nonmetallic nano material, composite phase-change material no matter liquid phase or the capacity of heat transmission of solid phase all improves a lot than mixing salt.After testing, prepared composite phase-change material latent heat is 350KJ/kg, and transformation temperature is 125 ° of C, and solid phase and the liquid phase thermal conductivity ratio mixing salt of composite phase-change material on average improve 15% and 19%.
Embodiment 3
Be take four kind salt at 45: 18: 10: 27 by the mass ratio of lithium nitrate, SODIUMNITRATE, Sodium Nitrite and lithium fluoride, mechanical stirring is even, and put into vacuum furnace heating and melting, the temperature of vacuum furnace controls 40 ~ 50 ° of C more than mixing salt transformation temperature.Be the Al of 10nm by the particle diameter accounting for total mass 1.1%
2o
3in joining the mixing salt of melting with SiC stuff and other stuff, it is constant that the temperature of vacuum furnace controls 40 ~ 50 ° of C more than 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 by the direct Quick-filling of bottom feed opening in the energy storage tank of mobile heat supply car.Filling complete after, close vacuum furnace and magnetic stirring apparatus.Owing to the addition of nonmetallic nano material, composite phase-change material no matter liquid phase or the capacity of heat transmission of solid phase all improves a lot than mixing salt.After testing, prepared composite phase-change material latent heat is 390KJ/kg, and transformation temperature is 145 ° of C, and solid phase and the liquid phase thermal conductivity ratio mixing salt of composite phase-change material on average improve 9% and 12%.
Embodiment 4
Be take four kind salt at 35: 15: 12: 30 by the mass ratio of lithium nitrate, SODIUMNITRATE, lithium fluoride and Quilonum Retard, mechanical stirring is even, and put into vacuum furnace heating and melting, the temperature of vacuum furnace controls 40 ~ 50 ° of C more than mixing salt transformation temperature.Be the Al of 8nm by the particle diameter accounting for total mass 2.5%
2o
3in joining the mixing salt of melting with SiC stuff and other stuff, it is constant that the temperature of vacuum furnace controls 40 ~ 50 ° of C more than mixing salt transformation temperature, and this melts of magnetic agitation 100 minutes, prepares uniform and stable nano-composite phase-changing material.
Embodiment 5
Be take four kind salt at 20: 20: 12: 30 by the mass ratio of lithium nitrate, nitrate of baryta, Sodium Nitrite and Sodium Fluoride, mechanical stirring is even, and put into vacuum furnace heating and melting, the temperature of vacuum furnace controls 40 ~ 50 ° of C more than mixing salt transformation temperature.Be the Al of 8nm by the particle diameter accounting for total mass 2.0%
2o
3and Si
3n
4in stuff and other stuff joins the mixing salt of melting, it is constant that the temperature of vacuum furnace controls 40 ~ 50 ° of C more than mixing salt transformation temperature, and this melts of magnetic agitation 120 minutes, prepares uniform and stable nano-composite phase-changing material.
Embodiment 6
Be take three kind salt at 40: 20: 20 by the mass ratio of SODIUMNITRATE, Sodium Nitrite and Quilonum Retard, mechanical stirring is even, and put into vacuum furnace heating and melting, the temperature of vacuum furnace controls 40 ~ 50 ° of C more than mixing salt transformation temperature.Be the Al of 10nm by the particle diameter accounting for total mass 1.8%
2o
3and TiO
2in particle joins the mixing salt of melting, it is constant that the temperature of vacuum furnace controls 40 ~ 50 ° of C more than mixing salt transformation temperature, and this melts of magnetic agitation 80 minutes, prepares uniform and stable nano-composite phase-changing material.
Embodiment 7
Be take two kind salt at 30: 20 by the mass ratio of SODIUMNITRATE and Sodium Fluoride, mechanical stirring is even, and put into vacuum furnace heating and melting, the temperature of vacuum furnace controls 40 ~ 50 ° of C more than mixing salt transformation temperature.Be the TiO of 10nm by the particle diameter accounting for total mass 2.2%
2in joining the mixing salt of melting with SiC stuff and other stuff, it is constant that the temperature of vacuum furnace controls 40 ~ 50 ° of C more than mixing salt transformation temperature, and this melts of magnetic agitation 90 minutes, prepares uniform and stable nano-composite phase-changing material.
Embodiment 8
Be take four kind salt at 35: 15: 12 by the mass ratio of lithium nitrate, lithium fluoride and Quilonum Retard, mechanical stirring is even, and put into vacuum furnace heating and melting, the temperature of vacuum furnace controls 40 ~ 50 ° of C more than mixing salt transformation temperature.Be the Al of 10nm by the particle diameter accounting for total mass 1.2%
2o
3, TiO
2in joining the mixing salt of melting with SiC stuff and other stuff, it is constant that the temperature of vacuum furnace controls 40 ~ 50 ° of C more than mixing salt transformation temperature, and this melts of magnetic agitation 100 minutes, prepares uniform and stable nano-composite phase-changing material.
Claims (2)
1. a mobile heat supply composite phase-change material, is characterized in that: this composite phase-change material be by mixed inorganic and nonmetal nano material compounded; The Al of described nonmetal nano material to be particle diameter be below 10nm
2o
3, SiO
2, SiC, CaCO
3, Si
3n
4with TiO
2in one or more combination; The quaternary mixing salt that described mixed inorganic is made up 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); 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%; The fusing point of described composite phase-change material is more than 110 DEG C, and thermal conductivity is at more than 1.0W/mk.
2. the preparation method of a kind of mobile heat supply composite phase-change material according to claim 1, is characterized in that comprising the following steps:
(1) plurality of inorganic salt mixed in mass ratio, stir, put into vacuum furnace heating and make it be molten state, the temperature of vacuum furnace to control more than mixed inorganic transformation temperature 40 ~ 50 DEG C, obtained melting salt;
(2) nonmetal nano material is joined in melting salt obtained in step (1), the temperature of vacuum furnace to control more than mixed inorganic transformation temperature 40 ~ 50 DEG C constant, more than magnetic agitation half an hour, prepare uniform and stable molten state composite phase-change material.
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| WO2014114220A1 (en) * | 2013-01-25 | 2014-07-31 | 深圳市爱能森科技有限公司 | Nanometer molten salt heat-transfer and heat-storage medium, preparation method and use thereof |
| CN103923619B (en) * | 2013-12-26 | 2017-05-17 | 深圳市爱能森科技有限公司 | Molten nano-carbonate heat transfer and accumulation medium, and preparation method and application thereof |
| CN103911121B (en) * | 2013-12-26 | 2017-05-17 | 深圳市爱能森科技有限公司 | Nanometer molten binary nitrate heat-transfer heat-storage medium and preparation method thereof |
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| CN104559941A (en) * | 2015-01-29 | 2015-04-29 | 哈尔滨工业大学 | Preparation method of nano-composite binary nitrate molten salt material |
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| CN105907379A (en) * | 2016-04-25 | 2016-08-31 | 碧城（上海）新能源科技有限公司 | Low-melting-point nano mixed molten salt heat transfer and storage medium and preparation method thereof |
| CN105838338A (en) * | 2016-04-25 | 2016-08-10 | 碧城（上海）新能源科技有限公司 | Nano mixed molten salt heat transfer and storage medium and preparation method thereof |
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| CN106010468A (en) * | 2016-06-22 | 2016-10-12 | 黄毅 | Low-melting-point mixed molten salt as heat transfer and storage medium |
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| 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 |
| 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 |
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Address after: 266555 20th floor, Hualin building, Qingdao Economic and Technological Development Zone, Shandong Province Patentee after: QINGDAO AOHUAN NEW ENERGY GROUP Co.,Ltd. Address before: 266555 20th floor, Hualin building, Qingdao Economic and Technological Development Zone, Shandong Province Patentee before: QINGDAO AOHUAN NEW ENERGY TECHNOLOGY DEVELOPMENT Co.,Ltd. |