CN101067077A - Room temperature phase change energy storing medium - Google Patents
Room temperature phase change energy storing medium Download PDFInfo
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- CN101067077A CN101067077A CN 200710034840 CN200710034840A CN101067077A CN 101067077 A CN101067077 A CN 101067077A CN 200710034840 CN200710034840 CN 200710034840 CN 200710034840 A CN200710034840 A CN 200710034840A CN 101067077 A CN101067077 A CN 101067077A
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Abstract
The room temperature phase change energy-storing medium consists of ammonium nitrate 30-40 wt% and lithium nitrate trihydrate 60-70 wt%. The energy-storing medium has stable phase change temperature, low toxicity, less corrosion, no supercooling property, identical solid phase composition and liquid composition, high temperature sensitivity and other advantages.
Description
Technical field:
The present invention relates to a kind of phase change material with phase deformation type heat energy storage.
Background technology
Phase-change and energy-storage medium at room temperature is a kind of undergoing phase transition in narrow room temperature region and storing or the material of release of heat.Its mechanism of action is, when room temperature rises to 15 ℃-25 ℃, phase-change and energy-storage medium at room temperature absorbs a large amount of heats and melts from environment, energy storage is got up, when temperature is lower than said temperature, the phase-change and energy-storage medium at room temperature that has melted is condensed into solid and discharges a large amount of heats to indoor environment, thereby keeps the constant relatively of room temperature.In temperature difference per day or the very big area of week (per week) temperature difference, phase-change and energy-storage medium at room temperature has important use and is worth, and it can be used as the absorption agent of sun power in the high temperature period, and gives indoor heating at night or colder period, thereby reaches purpose of energy saving.
Material as phase-change and energy-storage medium can be anhydrous salt, salt water chemical compound and composition thereof, organism etc.Wherein have as the organism of room temperature phase-change energy-storage material dangerous inflammable, shortcoming such as price is more expensive, and thermal conductivity is bad; Anhydrous fused salt is applicable to high-temperature heat-storage; Salt water chemical compound and composition thereof is suitable for storing low-temperature heat source, and these materials are in sun power and city UTILIZATION OF VESIDUAL HEAT IN, and many-sides such as the peak load shifting of electrical network have a wide range of applications.
Usually a kind of energy-accumulating medium with industrial application value should have: phase transformation temperature points is suitable, characteristics such as toxicity is little, corrodibility is weak, little, the no layering of superfusibility energy, cheapness.At present, satisfy above-mentioned all requirements simultaneously, particularly transformation temperature is actually rare at 15 ℃～25 ℃ phase change material.Transformation temperature is then especially rare at the nonflammable inorganic phase-changing material of above-mentioned scope.
Summary of the invention
Purpose of the present invention aims to provide a kind of transformation temperature near room temperature, comparatively environmental protection, the relatively poor low inorganic-phase variable energy-accumulating medium of cost.
The contriver after ammonium nitrate, lithium nitrate and water composition according to a certain percentage mixes, can obtain the energy-accumulating medium of a temperature of fusion about 15 ℃ by discovering.
The objective of the invention is to realize by following manner:
The energy-accumulating medium of the tertiary mixture that ammonium nitrate of the present invention and nitrate trihydrate lithium constitute, the compositing range of this medium is: ammonium nitrate: 30-40wt.%, nitrate trihydrate lithium: 60-70wt.%.
The best group of described energy-accumulating medium becomes ammonium nitrate: 34.7wt.%, nitrate trihydrate lithium: 65.3wt.%.
The nitrate trihydrate lithium can make by the condensing crystal lithium nitrate solution, and also can be by water and anhydrous nitric acid lithium by 3 ± 0.2: 1 mol ratio mixed makes.The mol ratio of water and lithium nitrate is 3+0.2.
Its mechanism of action is, has an eutectic point of being made up of nitrate trihydrate lithium and anhydrous nitric acid ammonium in ammonium nitrate-lithium nitrate-water ternary system, and the eutectic temperature of this point is about 15 ℃.
This energy-accumulating medium is packaged in metal or transparent glass (or synthetic glass) container, places the indoor or body of wall of buildings, can be applicable to absorb daytime sun power, evening, release of heat was to heat to the room; Perhaps the energy that absorbs high temperature heat source (greater than 16 degree) some of one day is stored period, in low temperature period release of heat to heat to the room.
The inventor has determined that by experimental study repeatedly this ternary system is as the room temperature energy-accumulating medium, found the corresponding content of each component composition of this system, this material has that phase transformation temperature points is stable, toxicity is little, corrodibility is little, solid phase is formed, phase transformation consistent with the liquid phase composition and varied with temperature plurality of advantages such as sensitivity when no superfusibility energy, phase transformation.
Description of drawings
Fig. 1 energy storage material and the pure water temperature lowering curve in 10 ℃ air ambient relatively.Experiment condition: is internal diameter that 33 millimeters and test tubes that 50 gram pure water or 50 gram energy storage materials (containing ammonium nitrate 34.7wt.%, nitrate trihydrate lithium 65.3wt.%) are housed place 10 ℃ air ambient, measures in vitro medium temperature curve over time.
Fig. 2 energy storage material and the pure water heating curve in 20 ℃ air ambient relatively.Experiment condition: is internal diameter that 33 millimeters and test tubes that 50 gram energy storage materials (containing ammonium nitrate 34.7wt.%, nitrate trihydrate lithium 65.3wt.%) are housed place 20 ℃ air ambient, measures in vitro medium temperature curve over time.
Fig. 3 energy storage material and the pure water temperature lowering curve in 10 ℃ air ambient relatively.(the same Fig. 1 of experiment condition).
Fig. 4 energy storage material and the pure water heating curve in 20 ℃ air ambient relatively.(the same Fig. 2 of experiment condition).
Fig. 5 energy storage material and the pure water temperature lowering curve in 10 ℃ air ambient relatively.(the same Fig. 1 of experiment condition).
Fig. 6 energy storage material and the pure water heating curve in 20 ℃ air ambient relatively.(the same Fig. 2 of experiment condition).
Fig. 7 energy storage material and the pure water temperature lowering curve in 10 ℃ air ambient relatively.(the same Fig. 1 of experiment condition).
Fig. 8 energy storage material and the pure water heating curve in 20 ℃ air ambient relatively.(the same Fig. 2 of experiment condition).
Fig. 9 energy storage material and the pure water temperature lowering curve in 10 ℃ air ambient relatively.(the same Fig. 1 of experiment condition).
Figure 10 energy storage material and the pure water heating curve in 20 ℃ air ambient relatively.(the same Fig. 2 of experiment condition).
Embodiment:
Following examples are in order to explain the present invention in more detail, but are not limitations of the present invention.
Embodiment 1:
34.7 gram ammonium nitrate and 65.3 gram nitrate trihydrate lithiums are mixed, be heated to 25 ℃ and keep for some time, find that solid is fused into liquid fully, be loaded in the encloses container, this container is placed 10 ℃ air ambient, record medium temperature and change shown in Fig. 1 solid line, as seen, a tangible temperature platform occurs at 14.7 ℃, this is to discharge a large amount of heats because medium solidifies under this temperature to environment, thereby keeps the stable of self temperature.The crystallization behavior of observing medium as seen, in the time of 16 ℃, medium is entirely liquid state, and in the time of 14 ℃, medium almost completely changes into solid-state.Pure water with same weight repeats said process, records its temperature lowering curve shown in Fig. 1 dotted line, and visible water temperature promptly drops to envrionment temperature in very short time.Compare both as seen, energy-accumulating medium of the present invention can be lower than 15 ° of environment to temperature and discharge a large amount of heats, thereby keeps the constant of medium itself and envrionment temperature.
Embodiment 2:
To be positioned over room temperature for a long time be 20 ℃ environment the container of completely crued energy-accumulating medium 10 ℃ time the by embodiment 1 preparation is housed, observe and find, the medium heating curve as shown in Figure 2, as seen, a tangible temperature platform is arranged about 15 ℃, and this is this medium a large amount of causes that absorb heat from environment, is higher than 16 ℃, medium melts fully, thereby heat-up rate is accelerated.This shows that energy-accumulating medium of the present invention can absorb from the low temperature environment about 20 ℃ and store a large amount of heats, thermal storage performance is superior.
30 gram ammonium nitrate and 70 gram nitrate trihydrate lithiums are mixed, be heated to 25 ℃ and keep for some time, solid all is melted into liquid, this mixture is loaded in the encloses container, this container is placed 10 ℃ air ambient, record medium temperature and change shown in Fig. 3 dotted line, as seen, a temperature platform also appears in this mixture about 14 ℃, but platform is held time and is slightly less than the material that makes by embodiment one.
Embodiment 4
To be positioned over room temperature for a long time be 20 ℃ environment the container of completely crued energy-accumulating medium 10 ℃ time the by embodiment 3 preparation is housed, measure this medium heating curve shown in Fig. 4 dotted line, as seen, significantly temperature platform is arranged, but heat-up rate is slightly faster than the material (shown in Fig. 4 solid line) of pressing embodiment 1 preparation between 15 ℃-16 ℃.This shows that the material energy-storage property by the present embodiment proportioning slightly is worse than embodiment 1.
Embodiment 5
40 gram ammonium nitrate and 60 gram nitrate trihydrate lithiums are mixed, be heated to 25 ℃ and keep for some time, most solids are melted into liquid, and this mixture is loaded in the encloses container, this container is placed 10 ℃ air ambient, record medium temperature and change shown in Fig. 5 dotted line.As seen, a temperature platform also appears in this mixture about 14 ℃, but platform is held time and is slightly less than the material that makes by embodiment 1.
To be positioned over room temperature for a long time be 20 ℃ environment the container of completely crued energy-accumulating medium 10 ℃ time the by embodiment 5 preparation is housed, measure this medium heating curve shown in Fig. 6 dotted line, a temperature platform also appears at 15 ℃-16 ℃, faster than the material of pressing embodiment 1 preparation, this shows that the material energy-storage property by this routine proportioning slightly is worse than embodiment 1 to heat-up rate slightly.
Comparative Examples 1
52 gram ammonium nitrate and 48 gram nitrate trihydrate lithiums are mixed, be heated to 25 ℃ and keep for some time, discovery still has the part solid not to be fused into liquid, this mixture is loaded in the encloses container, this container is placed 10 ℃ air ambient, record medium temperature and change shown in Fig. 7 dotted line, as seen, also occur a temperature platform at this mixture at 14.7 ℃, but platform is held time and is significantly less than the material that makes by embodiment one.As seen, the material exothermicity that makes by this routine proportioning is inferior to example 1.
Comparative Examples 2
To be positioned over room temperature for a long time be 20 ℃ environment the container of completely crued energy-accumulating medium 10 ℃ time the by embodiment 7 preparation is housed, recording medium temperature changes shown in Fig. 8 dotted line, as seen, a tangible temperature platform is arranged about 15 ℃, but heat-up rate shows by the material energy-storage property of this routine proportioning relatively poor faster than the material by example 1 preparation.Observe and find,, still have the considerable part energy-accumulating medium not melt even if be warming up to 20 ℃.
Comparative Examples 3
14 gram ammonium nitrate and 86 gram nitrate trihydrate lithiums are mixed, be heated to 25 ℃ and keep for some time, solid all is melted into liquid, and this mixture is loaded in the encloses container, this container is placed 10 ℃ air ambient, record medium temperature and change shown in Fig. 9 dotted line.Be cooled to 11 ℃ from 25 ℃, temperature platform does not appear in the material of preparing by present embodiment always, and the cooling required time is in 500 minutes, only for pressing half of 1 its preparing materials of embodiment (shown in Fig. 9 solid line) temperature fall time.As seen, the material exothermicity that makes by this routine proportioning is inferior to example 1.
Comparative Examples 4
To be positioned over room temperature for a long time be 20 ℃ environment the container of completely crued energy-accumulating medium 10 ℃ time the by embodiment 9 preparation is housed, recording medium temperature changes shown in Figure 10 dotted line, as seen, about 15 ℃, do not see tangible temperature platform, heat-up rate is obviously faster than the material by example 1 preparation, observe and find,, still have the part solid not melt in this medium even if be warming up to 20 ℃.This shows by the material energy-storage property of this routine proportioning relatively poor.
By above examples of implementation as seen, 30-40wt.% ammonium nitrate and 60-70wt.% nitrate trihydrate lithium are mixed, particularly by the best proportioning (ammonium nitrate: 34.7wt.% of forming, nitrate trihydrate lithium: the energy storage material that 65.3wt.%) makes, can from the environment that is higher than 16 ℃ (as 20 ℃), absorb heat in a large number, and a large amount of heat releases in the environment that is lower than 14 ℃ (as 10 ℃), has good low temperature storage, exothermicity, and exceed this scope (ammonium nitrate: 30-40wt.%, the nitrate trihydrate lithium: 60-70wt.%) by ammonium nitrate and nitrate trihydrate lithium mix and other medium, shown in Comparative Examples 1-4, store the obvious variation of thermal effect.
Claims (3)
1, a kind of phase-change and energy-storage medium at room temperature is characterized in that: energy-accumulating medium is made up of ammonium nitrate, nitrate trihydrate lithium, and wherein the mass range of each component is ammonium nitrate 30-40wt.%, nitrate trihydrate lithium: 60-70wt.%.
2, a kind of phase-change and energy-storage medium at room temperature according to claim 1, it is characterized in that: the mol ratio of water and lithium nitrate is 3 ± 0.2, the nitrate trihydrate lithium is the nitrate trihydrate crystalline lithium that directly crystallization generates from solution, or water and anhydrous nitric acid the lithium crystal or the liquid that get by the preparation of 3 ± 0.2: 1 mol ratio.
3 a kind of phase-change and energy-storage medium at room temperature according to claim 1 is characterized in that: described energy-accumulating medium consist of ammonium nitrate: 34.7wt.%, nitrate trihydrate lithium: 65.3wt.%.
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| CN107418520A (en) * | 2017-05-24 | 2017-12-01 | 中南大学 | A kind of phase-change and energy-storage medium and preparation method and application |
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| GB358844A (en) * | 1930-02-18 | 1931-10-15 | Electrolux Ltd | Improvements in or relating to absorption refrigerating apparatus |
| DE10220516A1 (en) * | 2002-05-08 | 2003-11-27 | Merck Patent Gmbh | Means for storing heat II |
| CN2631248Y (en) * | 2003-06-03 | 2004-08-11 | 清华大学 | Regenerative warming clothing with phase transforming material |
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| CN107418520A (en) * | 2017-05-24 | 2017-12-01 | 中南大学 | A kind of phase-change and energy-storage medium and preparation method and application |
| CN107418520B (en) * | 2017-05-24 | 2020-06-09 | 中南大学 | Phase-change energy storage medium and preparation method and application thereof |
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