CN104087254A - High-heat-conductivity inorganic phase-change energy storage material - Google Patents
High-heat-conductivity inorganic phase-change energy storage material Download PDFInfo
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Abstract
The invention relates to the technical field of energy storage materials, particularly a high-heat-conductivity inorganic phase-change energy storage material. The high-heat-conductivity inorganic phase-change energy storage material is composed of the following components in percentage by mass: 80-99.4% of energy storage material, 0.25-10% of nucleating agent, 0.1-15% of modifier, 0.1-15% of water and 0.15-19% of heat-conducting reinforcing material. The energy storage material is crystalline hydrated salt, the nucleating agent is carbonate or borate, the modifier is a polyacrylic acid emulsion or thickening powder, and the heat-conducting reinforcing material is one or mixture of more of graphite, carbon powder, copper powder, carbon fiber and silicon carbide powder. Compared with the prior art, the energy storage material has the advantages of high stability, low tendency to supercooling, high latent heat energy, high heat conductivity and the like. By selecting the proper modifier and proportion thereof, the heat-conducting reinforcing material and nucleating agent material can be successfully dispersed uniformly in the system, thereby solving the problem of the phenomenon of phase separation of the material due to long-term cycle, further enhancing the heat-conducting property of the material and being worthy of popularization and application.
Description
[technical field]
The present invention relates to energy storage material technical field, specifically a kind of high heat conduction inorganic-phase variable energy storage material.
[background technology]
The research of energy storage is the strategic problem of energy security and Sustainable development, and wherein the storage of heat and application and the international people's livelihood are closely bound up.Energy storage technology, particularly phase change energy storage technology are the existing energy of rational and efficient use, optimize the important technology that uses renewable energy source and improve efficiency of energy utilization, be very active research direction of Jin20Nian Lai world energy-saving field.
Utilizing the phase transformation of material to carry out storage power, realize storage and the utilization of energy, is to alleviate energy supply and demand both sides unmatched effective means on time, intensity and place.While utilizing phase transformation, neither endothermic nor exothermic carries out storage and the release of energy, has the advantages such as energy storage density is high, homo(io)thermism, has become the most rising heat accumulating.Therefore, research and develop high performance phase change material, also enjoy the favor of domestic and international enterprise and correlative study mechanism.Phase-changing energy storage material generally can be divided into inorganic-phase variable energy storage material, organic phase change energy storage material, composite phase-change energy storage material and metal phase change energy-storage material, wherein, common inorganic salt hydrate, buck compound, atlapulgite and the mineral wool etc. of inorganic-phase variable energy storage material.
Wherein, the general formula of inorganic salt hydrate is ABnH2O, it has fusing point and fixes, the advantages such as heat of phase transformation Δ Hf (about 254kJ/kg), thermal conductivity (about 0.5W/m ℃) and volume energy storage density (about 350MJ/L) are large, and because cost is low, preparation simple, thereby there is good application prospect; Its thermal energy storage process is mainly that while heating up, crystal water is deviate from, and inorganic salt melt and absorb heat; During cooling, there is inverse process, absorb crystal water and heat release.This class phase change material mainly comprises halogenide, nitrate, phosphoric acid salt, carbonate of alkali and alkaline-earth metal etc., if Na2HPO412H2O is as commercial phase change material low-cost, high energy-storage property, its transformation temperature is 35.4 ℃, latent heat of phase change is 266kJ/kg, but above-mentioned inorganic salt hydrate material was prone to cold-peace phenomenon of phase separation, cause material to be separated out, reduce cycle life, seriously restrict practical application.Meanwhile, because phase change material self thermal conductivity is on the low side, to product, heat exchange is established and is had higher requirement in actual applications.
Based on this, if can provide a kind of stable mineral-type high heat conduction phase-changing energy storage material, by energy, the form with heat energy stores in realization, during for needs, uses, and finally solves the unbalance problem of heat energy supply-demand, will have huge using value.
[summary of the invention]
Object of the present invention is exactly will solve above-mentioned deficiency and a kind of high heat conduction inorganic-phase variable energy storage material is provided, have stability high, be not prone to the advantages such as surfusion, latent heat energy is high, thermal conductivity is large, solve material because of the phenomenon of phase separation that long-term circulation produces, further improved the heat conductivility of material.
Design for achieving the above object a kind of high heat conduction inorganic-phase variable energy storage material, each composition and mass percentage content are as follows:
As preferably, each composition and mass percentage content are: energy storage material 93%, nucleator 2%, properties-correcting agent 1%, water 2%, enhanced thermal conduction material 2%.
As preferably, each composition and mass percentage content are as follows: energy storage material 93%, nucleator 0.5%, properties-correcting agent 3%, water 2.5%, enhanced thermal conduction material 1%.
Described energy storage material is crystalline hydrate salt.
Described crystalline hydrate salt is one or several the mixture in ten hydrogen phosphate dihydrate sodium, ten sulfate dihydrate sodium, Sodium acetate trihydrate, barium hydroxide, five water Sulfothiorine, calcium chloride hexahydrate, magnesium sulfate heptahydrate, Sodium carbonate decahydrate.
Described nucleator is carbonate or borate.
Described carbonate is one or several the mixture in calcium carbonate, barium carbonate, Strontium carbonate powder, magnesiumcarbonate, and described borate is borax.
Described properties-correcting agent is polyacrylate emulsion or thickening powder.
Described thickening powder is that denseness increases one or several the mixture in times agent, instant all-transparent thickening powder, the transparent thickening powder of instant acid and alkali-resistance, all-transparent thickening powder, translucent thickening powder.
Described enhanced thermal conduction material is one or several the mixture in graphite, carbon dust, copper powder, carbon fiber, carborundum powder.
Compared with the existing technology, tool has the following advantages in the present invention:
(1) service life cycle is long.The invention discloses a kind of inorganic-phase variable energy storage material, select thickening material and dispersion agent as properties-correcting agent, it can improve the fluid volume of mixture itself thickening material, has reduced the space of Particle free activity, thereby improved system viscosity, the effect that has reached its stability and prevented from being separated; And dispersion agent can prevent between filler grain mutually assembling when disperseing, because it has suitable consistency and thermostability, can make material there is good mobility; No matter, as thickening material or the properties-correcting agent of dispersion agent, select suitable proportioning combination, can effectively overcome the short problem of cycle life that prior art easily occurs.
(2) without obvious surfusion.Because the present invention adopts carbonate as nucleator, it has rudimentary lattice plane, its crystalline network is mated mutually with energy storage material, can effectively affect energy storage material structure, and with above-mentioned energy storage material, chemical reaction does not occur, can effectively promote the crystallization of supercooled liquid, therefore without add separately the anti-cryogen of crossing in component, effectively keep the higher heat enthalpy value of inorganic materials itself, thereby reached the object of the phenomenon generation that condensate depression of the present invention is little.
(3) there is higher enthalpy value.Particularly, energy storage material of the present invention is crystalline hydrate salt, and this class material has the features such as good crystallinity, heat of fusion is large, volume storage density is large, thereby it can be as the energy storage material with high enthalpy.
(4) there is high thermal conductivity.Conventional crystalline hydrate salt phase change material, thermal conductivity is between 0.5-1.2.While adding appropriate highly heat-conductive material component in system, the effect of the measurements of the chest, waist and hips grid system forming due to properties-correcting agent, the highly heat-conductive material component of interpolation and nucleator can be distributed in whole system uniformly, and outward appearance has formed a kind of uniform flocculent structure.The interpolation of heat conduction component extremely effectively raises the heat conductivility of material, tool Determination of conductive coefficients, and mean coefficient of heat conductivity improves 2-3 doubly, has further expanded the application space of material.
To sum up, the present invention have stability high, be not prone to the advantages such as surfusion, latent heat energy is high, thermal conductivity is large, according to the present invention, pass through to select applicable properties-correcting agent and ratio thereof, can successfully enhanced thermal conduction material and nucleator material thereof be distributed in system uniformly, both solve material because of the phenomenon of phase separation that long-term circulation produces, further improved again the heat conductivility of material.
[accompanying drawing explanation]
Fig. 1 is preparation method's process flow diagram of the present invention.
[embodiment]
High heat conduction inorganic-phase variable energy storage material of the present invention, can prepare according to following composition and mass percentage content:
(1) energy storage material 93%, nucleator 2%, properties-correcting agent 1%, water 2%, enhanced thermal conduction material 2%;
(2) energy storage material 93%, nucleator 0.5%, properties-correcting agent 3%, water 2.5%, enhanced thermal conduction material 1%;
(3) energy storage material 80%, nucleator 0.25%, properties-correcting agent 0.1%, water 0.65%, enhanced thermal conduction material 19%;
(4) energy storage material 99.4%, nucleator 0.25%, properties-correcting agent 0.1%, water 0.1%, enhanced thermal conduction material 0.15%;
(5) energy storage material 80%, nucleator 10%, properties-correcting agent 4%, water 1%, enhanced thermal conduction material 5%;
(6) energy storage material 81%, nucleator 0.4%, properties-correcting agent 15%, water 3%, enhanced thermal conduction material 0.6%;
(7) energy storage material 80%, nucleator 4%, properties-correcting agent 0.7%, water 15%, enhanced thermal conduction material 0.3%.
Wherein, energy storage material is crystalline hydrate salt, and this crystalline hydrate salt is one or several the mixture in ten hydrogen phosphate dihydrate sodium, ten sulfate dihydrate sodium, Sodium acetate trihydrate, barium hydroxide, five water Sulfothiorine, calcium chloride hexahydrate, magnesium sulfate heptahydrate, Sodium carbonate decahydrate.Nucleator is carbonate or borate, and carbonate is one or several the mixture in calcium carbonate, barium carbonate, Strontium carbonate powder, magnesiumcarbonate, and borate is borax.Properties-correcting agent is polyacrylate emulsion or thickening powder, and thickening powder is that denseness increases one or several the mixture in times agent, instant all-transparent thickening powder, the transparent thickening powder of instant acid and alkali-resistance, all-transparent thickening powder, translucent thickening powder.Enhanced thermal conduction material is one or several the mixture in graphite, carbon dust, copper powder, carbon fiber, carborundum powder.
Below in conjunction with embodiment, the present invention is done to following further illustrating:
Embodiment mono-
By the barium carbonate of 0.25Kg, the sodium polyacrylate emulsion of 0.1Kg and 0.15Kg water, fully mix, after heat to more than 60 ℃, the mixture that obtains mixing; Again to the barium hydroxide that adds 98.5Kg in mixture, add the expanded graphite of 1Kg, heated mixt to 90 ℃ left and right, barium hydroxide is fully melted, after fusing, vigorous stirring to four kind of material blends is even, until mixture produces without demixing phenomenon, obtained high heat conduction inorganic-phase variable energy storage material products A 1.
Above-mentioned products obtained therefrom A1 is carried out to dsc analysis, the results are shown in Table 1.
Embodiment bis-
By the calcium carbonate of 3.0Kg, instant all-transparent thickening powder and the 3.5Kg water of 2.0Kg, fully mix, after heat to more than 60 ℃, the mixture that obtains mixing; Again to the crystallization sodium acetate and the 1.5kg copper powder (100 order) that add 90Kg in mixture, heated mixt to 80 ℃ left and right, crystallization sodium acetate is fully melted, after fusing, vigorous stirring to four kind of material blends is even, until mixture produces without demixing phenomenon, obtained high heat conduction inorganic-phase variable energy storage material products A 2.
Above-mentioned products obtained therefrom A2 is carried out to dsc analysis, the results are shown in Table 1.
Embodiment tri-
By the Strontium carbonate powder of 6Kg (nucleator), the sodium polyacrylate emulsion of 2.0Kg and 3.0Kg water, fully mix, after heat to more than 60 ℃, the mixture that obtains mixing; In mixture, add the sal glauberi of 87Kg and the carbon dust of 2kg again, heated mixt to 80 ℃ left and right, sal glauberi is fully melted, after fusing, vigorous stirring to four kind of material blends is even, until mixture produces without demixing phenomenon, obtained high heat conduction inorganic-phase variable energy storage material products A 3.
Above-mentioned products obtained therefrom A3 is carried out to dsc analysis, the results are shown in Table 1.
Embodiment tetra-
By the barium carbonate of 2.0Kg, the denseness of 3.0Kg increases times agent and 13Kg water, fully mix, after heat to more than 60 ℃, the mixture that obtains mixing; Again to the barium hydroxide and the 2kg chopped carbon fiber that add 80Kg in mixture, heated mixt to 80 ℃ left and right, barium hydroxide is fully melted, after fusing, vigorous stirring to four kind of material blends is even, until mixture produces without demixing phenomenon, obtained high heat conduction inorganic-phase variable energy storage material products A 4.
Above-mentioned products obtained therefrom A4 is carried out to dsc analysis, the results are shown in Table 1.
Table 1 is prepared the hot physical property table of sample for the present invention:
Table 1
As can be seen from Table 1, the inorganic-phase variable energy storage material of preparing by technique of the present invention has high enthalpy, and this illustrates that it has very high calorific potential; By material system after its circulation 5000 times is not observed upper strata and had additional water, there is not obvious layering in the long-term recycled material system of illustrative material, and this material has extraordinary stability.
The present invention is as the high heat conduction phase-changing energy storage material of a kind of stable mineral-type, this material can the form with heat energy store energy, during for needs, use, solved the unbalance problem of heat energy supply-demand, and be all widely used in fields such as energy-conservation, the aerospace of " peak load shifting ", industry and the covil construction heating of used heat and remaining pick up the heat, sun power utilization, electric power, air-conditioning and textile industries.And can be applied to the fields such as solar water heater, floor heating, air-conditioning, automobile heat preservation, building energy conservation, industrial afterheat recovery and other heating system.Therefore, the present invention has huge using value.
The present invention is not subject to the restriction of above-mentioned embodiment, and other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify, and all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. a high heat conduction inorganic-phase variable energy storage material, is characterized in that, each composition and mass percentage content are as follows:
2. energy storage material as claimed in claim 1, is characterized in that, each composition and mass percentage content are as follows:
3. energy storage material as claimed in claim 1, is characterized in that, each composition and mass percentage content are as follows:
4. according to the energy storage material described in claim 1,2 or 3, it is characterized in that: described energy storage material is crystalline hydrate salt.
5. energy storage material according to claim 4, is characterized in that: described crystalline hydrate salt is one or several the mixture in ten hydrogen phosphate dihydrate sodium, ten sulfate dihydrate sodium, Sodium acetate trihydrate, barium hydroxide, five water Sulfothiorine, calcium chloride hexahydrate, magnesium sulfate heptahydrate, Sodium carbonate decahydrate.
6. according to the energy storage material described in claim 1,2 or 3, it is characterized in that: described nucleator is carbonate or borate.
7. energy storage material according to claim 6, is characterized in that: described carbonate is one or several the mixture in calcium carbonate, barium carbonate, Strontium carbonate powder, magnesiumcarbonate, and described borate is borax.
8. according to the energy storage material described in claim 1,2 or 3, it is characterized in that: described properties-correcting agent is polyacrylate emulsion or thickening powder.
9. energy storage material according to claim 8, is characterized in that: described thickening powder is that denseness increases one or several the mixture in times agent, instant all-transparent thickening powder, the transparent thickening powder of instant acid and alkali-resistance, all-transparent thickening powder, translucent thickening powder.
10. according to the energy storage material described in claim 1,2 or 3, it is characterized in that: described enhanced thermal conduction material is one or several the mixture in graphite, carbon dust, copper powder, carbon fiber, carborundum powder.
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