CN102604599A - Inorganic phase change energy storage material - Google Patents
Inorganic phase change energy storage material Download PDFInfo
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- CN102604599A CN102604599A CN2012100377530A CN201210037753A CN102604599A CN 102604599 A CN102604599 A CN 102604599A CN 2012100377530 A CN2012100377530 A CN 2012100377530A CN 201210037753 A CN201210037753 A CN 201210037753A CN 102604599 A CN102604599 A CN 102604599A
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Abstract
The invention relates to the technical field of energy storage material, in particular to inorganic phase change energy storage material. The material comprises the following components by mass: 70 to 99.5 % of energy storage material, 0.25-20 % of nucleating agent, 0.1-15 % of modifying agent and 0.1-15 % of water. The bases hydrate or crystalline hydrous salt, especially the bases hydrate is adopted as energy storage material; the nucleating agent adopts carbonate; and the modifying agent is dispersant. According to the inorganic phase change energy storage material, by selecting proper nucleating agent and the ration of the nucleating agent, material phase separation can be effectively solved, especially the phase change energy storage material prepared by adding the dispersant into a system has good cycling stability, and simultaneously the potential heat value does not change after circulation for thousands of times.
Description
Technical field
The present invention relates to the energy storage material technical field, especially refer to a kind of inorganic-phase variable energy storage material.
Background technology
The research of store energy is energy security and STRATEGIES OF SUSTAINABLE DEVELOPMENT property problem, 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 be the existing energy of rational and efficient use, optimize the important technology that uses renewable energy source and improve efficiency of energy utilization, is the unusual active research direction of one of world's energy-saving field over nearly 20 years.
Utilizing the phase transformation of material to come storage power, realize the storage and the utilization of energy, is to alleviate energy supply and demand both sides unmatched effective means on time, intensity and place.Neither endothermic nor exothermic carries out the storage and the release of energy when promptly utilizing phase transformation, has advantages such as energy storage density height, 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.
The general formula of inorganic salt hydrate is AB " nH
2O, advantage such as it has fusing point fixes, and heat of phase transformation Δ Hf (about 254kJ/kg), thermal conductivity (about 0.5W/m " ℃) and volume energy storage density (about 350MJ/L) are big, and because cost is low, preparation is simple, thereby good prospects for application is arranged; Its thermal energy storage process mainly is that crystal water is deviate from when heating up, and inorganic salt fuse and absorb heat; Inverse process takes place during cooling, absorbs crystal water and heat release.This type phase change material mainly comprises halogenide, nitrate salt, phosphoric acid salt, carbonate of alkali and earth alkali metal etc., like Na
2HPO
4" 12H
2O is as commercial phase change material low-cost, high energy-storage property, and its transformation temperature is 35.4 ℃, and latent heat of phase change is 266kJ/kg; But above-mentioned inorganic salt hydrate material was prone to the cold-peace phenomenon of phase separation; Cause material to be separated out, reduce cycle life, seriously restrict practical application.Producing surfusion is the crystallization nucleation poor-performing owing to inorganic salt hydrate, so needs in the actual application to add prevent cryogen and anti-phase separation agent.Prevented that cryogen mainly plays nucleator and properties-correcting agent, mainly comprised borax, calcium sulfate and atlapulgite etc.; Anti-phase separation agent mainly contains hydroscopic high-molecular resin, CMC 99.5 and surfactant material etc.; Usually also can add excessive water in the actual production,, prevent that fluidized-bed from stopping up, but this method cause also the accumulator system energy storage density to reduce significantly to reduce the formation of anhydrous salt.
We have studied a kind of stable inorganic-phase variable energy storage material based on this; This type material gets up energy with the stores of heat energy; Use during for needs; Solved the unbalance problem of heat energy supply-demand, and all be widely used in the heat fields such as energy-conservation, aerospace and textile industry of heat supply, air-conditioning of " peak load shifting " of the recycling of used heat and waste heat, sun power utilization, electric power, industry and covil construction.Fields such as it can be applied to that solar water heater, floor heating, air-conditioning, automobile are warming, building energy conservation, industrial afterheat recovery and other heating system.Therefore this type of invention has huge using value.
Summary of the invention
The present invention is directed to the deficiency and the defective of prior art, a kind of inorganic-phase variable energy storage material is provided, it is high that it has stability, is not easy to occur cold, phenomenon of phase separation, latent heat energy advantages of higher.
In order to realize the foregoing invention purpose, the present invention provides following technical scheme:
A kind of inorganic-phase variable energy storage material of the present invention, its each composition and degree are following:
Preferably, each composition and degree are following:
Preferably, each composition and degree are following:
Wherein, said energy storage material is bases hydrate or crystalline hydrate salt.Said bases hydrate is a water sodium hydroxide, eight water strontium hydroxides, barium monohydrate, barium hydroxide etc.; Said crystalline hydrate salts substances is ten hydrogen phosphate dihydrate sodium, ten sulfate dihydrate sodium, Sodium acetate trihydrate, MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 etc.
Wherein, said nucleator is a carbonate.Said carbonate is that in lime carbonate, barium carbonate, Strontium carbonate powder or the magnesiumcarbonate one or more are arbitrarily than mixing.
Wherein, said properties-correcting agent is dispersion agent.Said dispersion agent is that in polycarboxylic acid salt, sodium cellulose glycolate, organic phosphate, fatty acid, aliphatic amide type, sulfuric acid and sulfonic acid class tensio-active agent, ester class or the low-molecular-weight wax class one or more are arbitrarily than mixing.Said metal carboxylate is that poly (sodium aspartate), hydrolysis maleic anhydride, ZX-I or gather gone back in the oxydisuccinic acid sodium one or more arbitrarily than mixing.
Beneficial effect of the present invention is:
(1) it is long to recycle the life-span.The invention discloses a kind of inorganic-phase variable energy storage material; Elite with dispersion agent as properties-correcting agent; And non-common thickening material; Dispersion agent can prevent to assemble each other between the filler grain at dispersive simultaneously, because it has suitable consistency and thermostability, can make material have good flowability and effectively overcome the short problem of cycle life that prior art occurs easily.
(2) there is not obvious surfusion.Because of the present invention adopts carbonate as nucleator, it has rudimentary lattice plane, and its crystalline network and energy storage material mate each other; Can effectively influence the energy storage material structure; And with above-mentioned energy storage material chemical reaction does not take place, can effectively promote the crystallization of supercooled liquid, prevented cryogen so need not in component, to add separately; Keep the higher heat enthalpy value of inorganic materials itself effectively, thereby reached the purpose of the little phenomenon generation of condensate depression of the present invention.
(3) has higher enthalpy.Particularly; Energy storage material of the present invention is bases hydrate and crystalline hydrate salt; Characteristics such as this type material has good crystallinity, heat of fusion is big, thermal conductivity is relatively large, the volume storage density is big, thereby it can be as the energy storage material with high enthalpy.
Embodiment
Describe the present invention below in conjunction with accompanying drawing.
Embodiment one
With the barium carbonate (nucleator) of 0.25Kg, the poly (sodium aspartate) of 0.1Kg (properties-correcting agent) and 0.15Kg water, thorough mixing, after heat to more than 60 ℃ the mixture that obtains mixing; About the barium hydroxide that in mixture, adds 99.5Kg again, heated mixt to 80 ℃, barium hydroxide is fully melted, fusing back vigorous stirring to four kind of material blends is even, does not have demixing phenomenon until mixture and produces, and has promptly obtained product A 1.
Above-mentioned products obtained therefrom A1 is carried out dsc analysis, and the result sees table 1, in addition product A 1 is carried out the cooling curve test, and the result sees table 2.
Embodiment two
With the lime carbonate (nucleator) of 2.0Kg, hydrolysis maleic anhydride (properties-correcting agent) and the 4.5Kg water of 1.0Kg, thorough mixing, after heat to more than 60 ℃ the mixture that obtains mixing; About the Sodium acetate trihydrate that in mixture, adds 93Kg again, heated mixt to 80 ℃, Sodium acetate trihydrate is fully melted, fusing back vigorous stirring to four kind of material blends is even, does not have demixing phenomenon until mixture and produces, and has promptly obtained product A 2.
Above-mentioned products obtained therefrom A2 is carried out dsc analysis, and the result sees table 1, in addition product A 2 is carried out the cooling curve test, and the result sees table 2.
Embodiment three
With the Strontium carbonate powder (nucleator) of 1.5Kg, the sodium cellulose glycolate of 2.0Kg (properties-correcting agent) and 3.0Kg water, thorough mixing, after heat to more than 60 ℃ the mixture that obtains mixing; About the ten sulfate dihydrate sodium that in mixture, add 87Kg again, heated mixt to 80 ℃, ten sulfate dihydrate sodium are fully melted, fusing back vigorous stirring to four kind of material blends is even, does not have demixing phenomenon until mixture and produces, and has promptly obtained product A 3.
Above-mentioned products obtained therefrom A3 is carried out dsc analysis, and the result sees table 1, in addition product A 3 is carried out the cooling curve test, and the result sees table 2.
Embodiment four
With the magnesiumcarbonate (nucleator) of 20Kg, the poly (sodium aspartate) of 15Kg (properties-correcting agent) and 15Kg water, thorough mixing, after heat to more than 60 ℃ the mixture that obtains mixing; About the eight water strontium hydroxides that in mixture, add 50Kg again, heated mixt to 80 ℃, eight water strontium hydroxides are fully melted, fusing back vigorous stirring to four kind of material blends is even, does not have demixing phenomenon until mixture and produces, and has promptly obtained product A 4.
Above-mentioned products obtained therefrom A4 is carried out dsc analysis, and the result sees table 1, in addition product A 4 is carried out the cooling curve test, and the result sees table 2.
Table 1: the hot rerum natura table of preparation sample
Table 2: the cooling curve data sheet of preparation sample
Can find out that from table 1 the inorganic-phase variable energy storage material that makes through component of the present invention has high enthalpy, this explains that it has very high calorific potential; Test through DSC is carried out in its circulation after 100 times still demonstrates very high enthalpy, and illustrative material does not recycle its heat release ability is exerted an influence, and this material has extraordinary stability; Can find out that from table 2 the cooling curve platform time is short, shows that its transformation time is shorter, the curve platform does not have variation to explain that it does not have obvious surfusion to produce yet simultaneously.
It below only is preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (11)
1. an inorganic-phase variable energy storage material is characterized in that, its each composition and degree are following:
2. inorganic-phase variable energy storage material according to claim 1 is characterized in that, its each composition and degree are following:
3. inorganic-phase variable energy storage material according to claim 1 is characterized in that, its each composition and degree are following:
4. inorganic-phase variable energy storage material according to claim 1 is characterized in that: said energy storage material is bases hydrate or crystalline hydrate salt.
5. inorganic-phase variable energy storage material according to claim 4 is characterized in that: said bases hydrate is a water sodium hydroxide, eight water strontium hydroxides, barium monohydrate, barium hydroxide etc.
6. inorganic-phase variable energy storage material according to claim 4 is characterized in that: said crystalline hydrate salts substances is ten hydrogen phosphate dihydrate sodium, ten sulfate dihydrate sodium, Sodium acetate trihydrate, MAGNESIUM SULPHATE HEPTAHYDRATE 99.5 etc.
7. inorganic-phase variable energy storage material according to claim 1 is characterized in that: said nucleator is a carbonate.
8. inorganic-phase variable energy storage material according to claim 7 is characterized in that: said carbonate is that in lime carbonate, barium carbonate, Strontium carbonate powder or the magnesiumcarbonate one or more are arbitrarily than mixing.
9. inorganic-phase variable energy storage material according to claim 1 is characterized in that: said properties-correcting agent is dispersion agent.
10. according to right 9 described inorganic-phase variable energy storage materials, it is characterized in that: said dispersion agent in polycarboxylic acid salt, sodium cellulose glycolate, organic phosphate, fatty acid, aliphatic amide type, sulfuric acid and sulfonic acid class tensio-active agent, ester class or the low-molecular-weight wax class one or more arbitrarily than mixing.
11. inorganic-phase variable energy storage material according to claim 10 is characterized in that: said metal carboxylate is that poly (sodium aspartate), hydrolysis maleic anhydride, ZX-I or gather gone back in the oxydisuccinic acid sodium one or more arbitrarily than mixing.
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Application publication date: 20120725 |