CN104293305A - Binary organic/inorganic nano-composite phase change energy storage material and preparation method thereof - Google Patents
Binary organic/inorganic nano-composite phase change energy storage material and preparation method thereof Download PDFInfo
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- CN104293305A CN104293305A CN201410503306.9A CN201410503306A CN104293305A CN 104293305 A CN104293305 A CN 104293305A CN 201410503306 A CN201410503306 A CN 201410503306A CN 104293305 A CN104293305 A CN 104293305A
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Abstract
The invention discloses a binary organic/inorganic nano-composite phase change energy storage material and a preparation method thereof. The material is prepared by mixing lauric acid/lauryl alcohol fusion mixture and modified montmorillonite, wherein the weight of the modified montmorillonite is 1-1.8 times that of the lauric acid/lauryl alcohol fusion mixture. The preparation method of the material comprises the following steps: fusing lauric acid and lauryl alcohol in anhydrous ethanol, and drying to obtain a fusing mixture; mixing the fusing mixture with a NaCl solution and triethanolamine modified montmorillonite in water; and mixing, distilling and drying to obtain the binary organic/inorganic nano-composite phase change energy storage material. The composite phase change energy storage material has the advantages of proper phase change temperature, high energy storage density, good stability, low manufacture cost and strong practicality, and can be applied to building energy conservation and other fields.
Description
Technical field
The present invention relates to a kind of phase-changing energy storage material, particularly relate to a kind of organic-inorganic composite phase-change energy-storage material.The invention still further relates to the preparation method of this phase-changing energy storage material.
Background technology
Phase change material (phase change materials) is under a certain specified temp, can from a kind of state-transition to the material of another kind of state, during state-transition, material molecule rapidly by order to unordered or by unordered to ordering transition, simultaneous neither endothermic nor exothermic phenomenon.Utilize this feature of phase change material, can be applied to regulate temperature, alleviate energy supplydemand relationship not mating in time, place and intensity, have a wide range of applications in fields such as Solar use, building energy conservation, waste heat recovery, aerospace.
Phase change material chemically forms can be divided into inorganic, organic and composite phase-change material.
What inorganic phase-changing material use was more is inorganic crystal salt hydrate, mainly comprise alkali and alkaline earth metal halide, nitrate etc., be characterized in that latent heat of phase change is high, with low cost, thermal conductivity is relatively large, but exist condensate depression large, easily separate out, degradation shortcoming under energy storage efficiency after thermal cycling.
Organic phase change material mainly comprises higher aliphatic hydrocarbon, lipid acid and polyvalent alcohol etc., be characterized in that solid state formability is better, not easily be separated and surfusion, stable performance, but there is the shortcomings such as latent heat of phase change is relatively low, thermal conductivity is little, solid-liquid transformation process is easily leaked.
According to existing experimental studies results, transformation temperature and the latent heat of phase change of most unitary organic phase change material are not well positioned to meet concrete application request, and therefore, the organic phase change material that can directly utilize is few in number.According to thermodynamics relevant knowledge, two kinds of organic phase change materials are mixed by a certain percentage, obtains binary eutectic system, suitable transformation temperature and latent heat of phase change can be obtained as requested, the enthalpy of phase change of material can't be reduced simultaneously.In addition, according to the principle that zero pour declines, the phase change material of high transformation temperature can also be applied to low temperature range.Wherein, the advantage of binary of fatty acids phase change material system is that enthalpy of phase change is high, melts and condense can repeat to realize, and has very little condensate depression, but price is the shortcoming of this kind of material.Although dibasic alcohol phase change material system has suitable transformation temperature, Gu also exist larger thermal conversion and reversible solid-change deficiency.
Composite phase-change energy storage material is that scientific research personnel studies more a kind of energy storage material in recent years, specifically form with mineral compound and organic solid-liquid phase change Material cladding, both can overcome the shortcoming of single inorganic phase-changing material or organic phase change material existence, and the effect of phase change material can have been improved again and expand its range of application.The principal element of decision composite phase-change energy storage material performance quality is transformation temperature, energy storage density, stability and economy.From current disclosed relevant report, there is the shortcomings such as energy storage density is low, poor durability, carrier high cost in existing phase-change energy-storage composite material.
Montmorillonite is class natural clay mineral of China's high yield, its frame sheet is in nanoscale, includes three subgrades, two silicon-oxy tetrahedron subgrade therebetween containing an alumina octahedral subgrade, connect with covalent linkage, in conjunction with very firm by sharing Sauerstoffatom between subgrade.Montmorillonite stable chemical nature, specific surface area is large, and absorption property is good, is a kind of natural inorganic nanometer layer structured calcium silicate mineral material.The high-specific surface area of montmorillonite can improve phase change material charge capacity, thus improves latent heat of phase change; Montmorillonite nano Rotating fields can become material molecule by adsorbed stationary phase better, thus improves the weather resistance of composite phase-change material.Montmorillonite wide material sources simultaneously, be easy to exploitation processing, cost is lower.
Summary of the invention
The object of this invention is to provide a kind of binary Organic/inorganic Nanometer Composite Phase Change Materials, and the preparation method of this energy storage material.
Binary Organic/inorganic Nanometer Composite Phase Change Materials of the present invention is made up of with modified montmorillonite used mixing lauric acid/lauryl alcohol melt blended material, and wherein, described modified montmorillonite used weight is 1 ~ 1.8 times of lauric acid/lauryl alcohol melt blended material weight.
In binary Organic/inorganic Nanometer Composite Phase Change Materials of the present invention, described lauric acid/lauryl alcohol melt blended material be by lauric acid and lauryl alcohol according to 1: 1.2 ~ 1.25 the melt blended material that obtains of weight ratio mixed melting.
Further, described lauric acid/lauryl alcohol melt blended material adds in dehydrated alcohol after described lauric acid being mixed with lauryl alcohol, stirs under melted state, the lauric acid/lauryl alcohol melt blended material obtained after removing dehydrated alcohol.
In binary Organic/inorganic Nanometer Composite Phase Change Materials of the present invention, described modified montmorillonite used be by montmorillonite successively with NaCl and trolamine modified obtain modified montmorillonite used.
Wherein, in described NaCl modification, the NaCl solution of 5wt% is preferably used to carry out modification to obtain inorganic modified montmorillonite.More preferably, be use to carry out modification with the equiponderant 5wt%NaCl solution of montmorillonite to montmorillonite.
And then in described trolamine modification, the consumption of trolamine is 1.2 ~ 1.8 times of inorganic modified montmorillonite weight.
The concrete preparation method of binary Organic/inorganic Nanometer Composite Phase Change Materials of the present invention is:
1) by lauric acid and lauryl alcohol according to 1: 1.2 ~ 1.25 weight ratio mix, add 0.8 ~ 2 times of weight in the dehydrated alcohol of mixture, stir 20 ~ 30 minutes under keeping melted state at 50 ~ 60 DEG C, dry lauric acid/lauryl alcohol melt blended material.
2) added in 3 ~ 8 weight parts waters by 1 weight part montmorillonite, add 1 weight part 5wt%NaCl solution, at 50 ~ 60 DEG C, stirring reaction 2 ~ 3 hours, staticly settles 10 ~ 12 hours, and drying precipitate obtains inorganic modified montmorillonite.
3) get that 1 parts by weight of inorganic is modified montmorillonite used to be mixed with the trolamine of 1.2 ~ 1.8 weight parts, add in 1.8 ~ 5 weight parts waters, adjust ph is 6.5 ~ 7.5,50 ~ 60 DEG C of reactions 4 ~ 6 hours, and washing drying obtains modified montmorillonite used.
4) lauric acid/lauryl alcohol melt blended material is mixed with lauric acid/the modified montmorillonite used of lauryl alcohol melt blended material weight 1 ~ 1.8 times, add in the water being equivalent to modified montmorillonite used and lauric acid/lauryl alcohol melt blended material 1 ~ 3 times of weight, 70 ~ 80 DEG C of stirring reactions 6 ~ 8 hours, 80 ~ 90 DEG C of distillations, dry binary Organic/inorganic Nanometer Composite Phase Change Materials.
The invention provides one with alkyd binary organic system for solid-liquid energy storage material, montmorillonite is the binary Organic/inorganic Nanometer Composite Phase Change Materials of immobilization carrier, binary eutectic organic system is made to carry out compound with the inorganic materials with high thermal conductivity, its alkyd binary organic system both can reduce the expensive cost of diprotic acid system, the thermal conversion that dibasic alcohol system is too high can be avoided again, simultaneously, the compound of alkyd binary organic system and montmorillonite, not only can overcome the low shortcoming of organic phase change material thermal conductivity, also can utilize the high-specific surface area of montmorillonite, adsorbed stationary phase becomes material molecule better, organic phase change material is avoided to leak in solid-liquid transformation process, thus improve the weather resistance of composite phase-change material, and improve thermal conductivity.
Binary Organic/inorganic Nanometer Composite Phase Change Materials transformation temperature prepared by the present invention is suitable for, and mates, solve single organic phase change material transformation temperature non-adjustable, limit the problem of its range of application with human body optimal temperature.Meanwhile, composite phase-change energy storage material energy storage density of the present invention is high, good stability, low cost of manufacture, practical, can be applicable to the fields such as building energy conservation, is a kind ofly to have good thermal cycling stability and the composite phase-change material of heat conductivility.
Embodiment
Embodiment 1
Get 15g lauric acid to mix with 20g lauryl alcohol, be dissolved in 65g dehydrated alcohol, stir 20 minutes under keeping melted state at 50 DEG C, suction filtration, natural air drying, obtains lauric acid/lauryl alcohol melt blended material.
Added in 80ml distilled water by 10g montmorillonite, add the 5%NaCl solution of 10g, in 50 DEG C of waters bath with thermostatic control, stirring reaction 2 hours, staticly settles 10 hours, abandons supernatant liquor, and dry, grinding is sieved, and obtains inorganic modified montmorillonite.
Get inorganic modified montmorillonite 15g, after mixing with 20g trolamine, add in 65ml distilled water, adjust ph is 6.5, in 50 DEG C of reactions 4 hours, suction filtration, distilled water wash three times, natural air drying, after pulverizing and sieving, in vacuum drying oven, at 65 DEG C, be dried to constant weight, obtain modified montmorillonite used.
Be dissolved in modified montmorillonite used for 15g in 75ml distilled water, add 10g lauric acid/lauryl alcohol melt blended material, stirring reaction 6 hours at 70 DEG C, 80 DEG C of distillations, after drying, pulverizing, obtain binary Organic/inorganic Nanometer Composite Phase Change Materials.
The product form of composite phase-change energy storage material is Powdered, adopts the resistance to DSC instrument test of speeding of Germany, the transformation temperature of material 26.5 DEG C, latent heat of phase change 102J/g.Adopt the test of Sweden HOTDISK thermal conductivity instrument, material conducts heat performance 0.89W/m.k.Material phase transformation temperature is in the scope of human comfort, and latent heat of phase change is high, can be used for the fields such as building energy conservation.
Embodiment 2
Get 20g lauric acid to mix with 25g lauryl alcohol, be dissolved in 55g dehydrated alcohol, stir 25 minutes under keeping melted state at 55 DEG C, suction filtration, natural air drying, obtains lauric acid/lauryl alcohol melt blended material.
Added in 70ml distilled water by 15g montmorillonite, add the 5%NaCl solution of 15g, in 55 DEG C of waters bath with thermostatic control, stirring reaction 2.5 hours, staticly settles 11 hours, abandons supernatant liquor, and dry, grinding is sieved, and obtains inorganic modified montmorillonite.
Get inorganic modified montmorillonite 15g, after mixing with 25g trolamine, add in 60ml distilled water, adjust ph is 7, in 55 DEG C of reactions 5 hours, suction filtration, distilled water wash three times, natural air drying, after pulverizing and sieving, in vacuum drying oven, at 70 DEG C, be dried to constant weight, obtain modified montmorillonite used.
Be dissolved in modified montmorillonite used for 20g in 65ml distilled water, add 15g lauric acid/lauryl alcohol melt blended material, stirring reaction 7 hours at 75 DEG C, 85 DEG C of distillations, after drying, pulverizing, obtain binary Organic/inorganic Nanometer Composite Phase Change Materials.
The product form of composite phase-change energy storage material is Powdered, adopts the resistance to DSC instrument test of speeding of Germany, the transformation temperature of material 28 DEG C, latent heat of phase change 115J/g.Adopt the test of Sweden HOTDISK thermal conductivity instrument, material conducts heat performance 0.81W/m.k.Material phase transformation temperature is in the scope of human comfort, and latent heat of phase change is high, can be used for the fields such as building energy conservation.
Embodiment 3
Get 25g lauric acid to mix with 30g lauryl alcohol, be dissolved in 45g dehydrated alcohol, stir 30 minutes under keeping melted state at 60 DEG C, suction filtration, natural air drying, obtains lauric acid/lauryl alcohol melt blended material.
Added in 60ml distilled water by 20g montmorillonite, add the 5%NaCl solution of 20g, in 60 DEG C of waters bath with thermostatic control, stirring reaction 3 hours, staticly settles 12 hours, abandons supernatant liquor, and dry, grinding is sieved, and obtains inorganic modified montmorillonite.
Get inorganic modified montmorillonite 2 5g, after mixing with 30g trolamine, add in 45ml distilled water, adjust ph is 7.5, in 60 DEG C of reactions 6 hours, suction filtration, distilled water wash three times, natural air drying, after pulverizing and sieving, in vacuum drying oven, at 75 DEG C, be dried to constant weight, obtain modified montmorillonite used.
Be dissolved in modified montmorillonite used for 25g in 55ml distilled water, add 20g lauric acid/lauryl alcohol melt blended material, stirring reaction 8 hours at 80 DEG C, 90 DEG C of distillations, after drying, pulverizing, obtain binary Organic/inorganic Nanometer Composite Phase Change Materials.
The product form of composite phase-change energy storage material is Powdered, adopts the resistance to DSC instrument test of speeding of Germany, the transformation temperature of material 27.3 DEG C DEG C, latent heat of phase change 120J/g.Adopt the test of Sweden HOTDISK thermal conductivity instrument, material conducts heat performance 0.75W/m.k.Material phase transformation temperature is in the scope of human comfort, and latent heat of phase change is high, can be used for the fields such as building energy conservation.
Claims (8)
1. a binary Organic/inorganic Nanometer Composite Phase Change Materials, is made up of with modified montmorillonite used mixing lauric acid/lauryl alcohol melt blended material, and wherein, described modified montmorillonite used weight is 1 ~ 1.8 times of lauric acid/lauryl alcohol melt blended material weight.
2. binary Organic/inorganic Nanometer Composite Phase Change Materials according to claim 1, it is characterized in that described lauric acid/lauryl alcohol melt blended material be by lauric acid and lauryl alcohol according to 1: 1.2 ~ 1.25 the melt blended material that obtains of weight ratio mixed melting.
3. binary Organic/inorganic Nanometer Composite Phase Change Materials according to claim 1 and 2, it is characterized in that described lauric acid/lauryl alcohol melt blended material adds in dehydrated alcohol after described lauric acid being mixed with lauryl alcohol, stir under melted state, the lauric acid/lauryl alcohol melt blended material obtained after removing dehydrated alcohol.
4. binary Organic/inorganic Nanometer Composite Phase Change Materials according to claim 1, it is characterized in that described modified montmorillonite used be by montmorillonite successively with NaCl and trolamine modified obtain modified montmorillonite used.
5. binary Organic/inorganic Nanometer Composite Phase Change Materials according to claim 4, is characterized in that described NaCl modification uses 5wt% NaCl solution to carry out modification to obtain inorganic modified montmorillonite to montmorillonite.
6. binary Organic/inorganic Nanometer Composite Phase Change Materials according to claim 5, is characterized in that using and carries out modification with the equiponderant 5wt%NaCl solution of montmorillonite to montmorillonite.
7. binary Organic/inorganic Nanometer Composite Phase Change Materials according to claim 4, is characterized in that in described trolamine modification, and the consumption of trolamine is 1.2 ~ 1.8 times of inorganic modified montmorillonite weight.
8. the preparation method of binary Organic/inorganic Nanometer Composite Phase Change Materials described in claim 1, is characterized in that:
1) by lauric acid and lauryl alcohol according to 1: 1.2 ~ 1.25 weight ratio mix, add 0.8 ~ 2 times of weight in the dehydrated alcohol of mixture, stir 20 ~ 30 minutes under keeping melted state at 50 ~ 60 DEG C, dry lauric acid/lauryl alcohol melt blended material;
2) added in 3 ~ 8 weight parts waters by 1 weight part montmorillonite, add 1 weight part 5wt%NaCl solution, at 50 ~ 60 DEG C, stirring reaction 2 ~ 3 hours, staticly settles 10 ~ 12 hours, and drying precipitate obtains inorganic modified montmorillonite;
3) get that 1 parts by weight of inorganic is modified montmorillonite used to be mixed with the trolamine of 1.2 ~ 1.8 weight parts, add in 1.8 ~ 5 weight parts waters, adjust ph is 6.5 ~ 7.5,50 ~ 60 DEG C of reactions 4 ~ 6 hours, and washing drying obtains modified montmorillonite used;
4) lauric acid/lauryl alcohol melt blended material is mixed with lauric acid/the modified montmorillonite used of lauryl alcohol melt blended material weight 1 ~ 1.8 times, add in the water being equivalent to modified montmorillonite used and lauric acid/lauryl alcohol melt blended material 1 ~ 3 times of weight, 70 ~ 80 DEG C of stirring reactions 6 ~ 8 hours, 80 ~ 90 DEG C of distillations, dry binary Organic/inorganic Nanometer Composite Phase Change Materials.
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| CN106010457A (en) * | 2016-06-02 | 2016-10-12 | 上海工程技术大学 | Modified montmorillonite/paraffin composite phase-change energy storage material and preparation method thereof |
| CN108586852A (en) * | 2018-05-23 | 2018-09-28 | 芜湖航天特种电缆厂股份有限公司 | High-tenacity heat-resistant rubber material and preparation method thereof |
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| CN108586852A (en) * | 2018-05-23 | 2018-09-28 | 芜湖航天特种电缆厂股份有限公司 | High-tenacity heat-resistant rubber material and preparation method thereof |
| CN108641144A (en) * | 2018-05-23 | 2018-10-12 | 芜湖航天特种电缆厂股份有限公司 | High strength heat resistant cable and preparation method thereof |
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