CN110157387A - High extinction, fatty acid/nano-complex PERFORMANCE OF MODIFIED VERMICULITE composite phase-change energy storage material of high thermal conductivity and preparation method thereof - Google Patents

High extinction, fatty acid/nano-complex PERFORMANCE OF MODIFIED VERMICULITE composite phase-change energy storage material of high thermal conductivity and preparation method thereof Download PDF

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CN110157387A
CN110157387A CN201910525504.8A CN201910525504A CN110157387A CN 110157387 A CN110157387 A CN 110157387A CN 201910525504 A CN201910525504 A CN 201910525504A CN 110157387 A CN110157387 A CN 110157387A
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acid
nano
fatty acid
vermiculite
modified vermiculite
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CN110157387B (en
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李湘祁
张嘉胜
王宗明
吴茜
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Fuzhou University
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Abstract

The invention discloses a kind of high extinctions, fatty acid/nano-complex PERFORMANCE OF MODIFIED VERMICULITE composite phase-change energy storage material of high thermal conductivity and preparation method thereof, to have loaded TiO2- TiC-C or SiO2PERFORMANCE OF MODIFIED VERMICULITE after-SiC-C nano-complex is as supporting matrix, the unary fatty acid or polyhydric aliphatic acid eutectic mixture of fusing is added, fatty acid/nano-complex PERFORMANCE OF MODIFIED VERMICULITE composite phase-change energy storage material of the high extinction, high thermal conductivity is made by vacuum impregnation absorption method.Preparation method proposed by the present invention solves the problems, such as that current phase-changing energy storage material phase transformation enthalpy is low and thermal coefficient is low, obtained composite phase-change energy storage material can fast implement photothermal conversion under sunlight irradiation, it can be used as heat source, its phase transition temperature can be adjusted control by the type and mass ratio of fatty acid, therefore the material has preferable application value in thermal energy storage and field of solar energy conversion.

Description

Fatty acid/nano-complex PERFORMANCE OF MODIFIED VERMICULITE composite phase change energy-storing of high extinction, high thermal conductivity Material and preparation method thereof
Technical field
The invention belongs to energy saving energy storage material technical fields, and in particular to fatty acid/nanometer of a kind of high extinction, high thermal conductivity Compound PERFORMANCE OF MODIFIED VERMICULITE composite phase-change energy storage material and preparation method thereof.
Background technique
So far, the measure to tap a new source of energy is not able to satisfy the demand developed to the energy.For the energy, supply falls short of demand The problem of, the exploitation in addition to seeking new energy should also improve the utilization efficiency to the existing energy, change the knot that the energy uses Structure, reduces unnecessary energy loss, and efficient thermal energy storage is one of implementation of this thinking.Various novel building materials Material comes into being, and among these just includes phase-changing energy storage material.Have benefited from the thermal energy storage property of phase-change material, many plus hot and cold But application development is rapid.Phase-change material is obvious advantage is that their constant temperature property and high heat storage density.
Fatty acid phase-change material is a kind of solid-liquid phase change material, and raw material sources are extensive, most of fatty acid phase transformation Material can be extracted from animals and plants, and raw material has the characteristics that renewable and environmentally friendly and more Recent study have Machine class phase transformation energy storage material.Meanwhile suitable transition temperature range, high heat capacity, nontoxic, non-corrosive, chemical stability is good, The advantages that at low cost, nonflammable, volume change is small, answers so that it becomes one of the phase-changing energy storage material with application potential Cover the multiple fields such as building, weaving, battery thermal management with range.Although fatty acid phase-change material latent heat of phase change is high, chemistry Stability is good, transition temperature range is wider, but easily undergoes phase transition that volume change, heating conduction be poor, solid-state in actual use Thermal conductivity is low, liquid leakage, is not easy the problems such as storage transport, and to overcome these disadvantages, composite phase-change energy storage material comes into being. Composite phase-change energy storage material can effectively solve the problems, such as single phase-changing energy storage material using when exist, while possessed high energy storage The suction exothermic process of density and intimate constant temperature can be effectively improved the application effect of phase-change material and expand its application range.Using Suitable carrier matrix, which carries out cladding sizing to fatty acid phase-change material, can solve the leakage problem of phase-change material, due to carrying The capillary force and surface tension of micropore, make liquid phase phase-change material be difficult to happen leakage in body matrix.For thermal coefficient Low this problem, the method that people generally use are that appropriate high heat conductive material such as graphite, metal oxygen are added in fatty acid Compound, carbon fiber etc., thus come improve heat reservoir storage, exothermic rate.Although thermal conductivity increases, usually also result in The problem of reduction of latent heat of phase change, the stored energy capacitance decline of composite energy-storage material.Chinese patent CN106701033A discloses one Kind is using porous support materials such as active carbon, expanded graphite or carbon aerogels as carrier, the composite phase-change materials such as Lai Tigao paraffin Thermal coefficient.The packaging effect of the composite phase-change materials such as paraffin made from this method is higher, but since support carrier is to stone The adsorbance of the phase-change materials such as wax is less and causes the latent heat of phase change of composite phase-change material low, therefore limits its extensive use.In State patent CN 102531506A is phase-changing energy storage material by absorption carrier, paraffin of porous matrix, mixes by stirring and is answered Phase-change material is closed, this method avoids macroscopical container or microcapsules from encapsulating, and preparation process is simple, lower cost for material, but low thermally conductive Coefficient still limits the extensive use of the material.Chinese patent CN106854456A is using ternary aliphatic acid eutectic mixture as phase transformation Material, expanded graphite are Supporting Media, are prepared into composite phase-change material.This method efficiently solves solid-liquid phase change material in phase The flow field problem of liquid when change, but the thermal coefficient of composite phase-change material is lower, therefore limits its extensive use.
Chinese patent CN103131395A reports a kind of paraffin-graphite foam composite material, adsorption rate with higher And thermal conductivity, but graphite higher cost.Chinese patent CN107163590A with polyvinyl chloride, polyethylene etc. for backing material, it is swollen Swollen perlite, expanded graphite etc. are porous material, and paraffin, fatty acid etc. are phase-change material, and add some function additives, are prepared Functionalization composite phase-change material, has preferable photothermal conversion efficiency and a higher thermal conductivity, but raw material type and prepares Journey is excessively complicated, brings certain difficulty to practical application.
Vermiculite because its with large specific surface area, strong adsorption, good thermal stability, have with organic phase change material it is good Chemical compatibility, the excellent properties such as cheap and easy to get, therefore can be used as the carrier matrix of organic phase change energy storage material.It is with vermiculite Carrier matrix is packaged the encapsulation be formed and may be implemented to phase-change material to phase-change material, is effectively prevented liquid phase leakage.Draw Enter new heat transfer carrier, that is, add suitable high heat conductive material into vermiculite, increases the surface tension and capillary of vermiculite Guan Li improves the latent heat of phase change of composite phase-change material and the heating conduction of vermiculite, substantially improves vermiculite base composite phase-change material The energy storage of material and temperature adjusting performance.Meanwhile high absorbing ability can carry out photothermal conversion well, improve energy utilization rate.
Summary of the invention
The purpose of the present invention is to provide fatty acid/nano-complex PERFORMANCE OF MODIFIED VERMICULITE of a kind of high extinction, high thermal conductivity is compound Phase-changing energy storage material and preparation method thereof, for existing phase-changing energy storage material latent heat of phase change is low, photothermal conversion ability difference and low The defect of thermal coefficient provides one kind to load nano-TiO2- TiC-C or SiO2The PERFORMANCE OF MODIFIED VERMICULITE of-SiC-C nano-complex For the novel high extinction of supporting matrix, fatty acid/nano-complex PERFORMANCE OF MODIFIED VERMICULITE composite phase-change energy storage material of high thermal conductivity, the material The thermal coefficient and latent heat of phase change of material are increased dramatically, and especially its phase transition temperature can pass through the type and quality of fatty acid Than being adjusted control in a certain range, therefore the material has preferable application in thermal energy storage and field of solar energy conversion Value, has further widened the application field of the composite phase-change energy storage material.
To achieve the above object, the present invention adopts the following technical scheme:
Fatty acid/nano-complex PERFORMANCE OF MODIFIED VERMICULITE composite phase-change energy storage material of a kind of high extinction, high thermal conductivity, is by unitary rouge Fat acid or polyhydric aliphatic acid eutectic mixture and PERFORMANCE OF MODIFIED VERMICULITE are combined, and wherein unary fatty acid or polyhydric aliphatic acid eutectic are mixed Closing weight percent shared by object is 42 ~ 72%.
The unary fatty acid is capric acid, lauric acid, myristic acid, palmitinic acid, any one in stearic acid.
The polyhydric aliphatic acid eutectic mixture is lauric acid, any 2 ~ 3 kinds of eutectic mixes in myristic acid, stearic acid Object;Preferably mass ratio is respectively lauric acid: myristic acid=67:33, lauric acid: stearic acid=83:17, myristic acid: stearic Acid=75:25, lauric acid: myristic acid: stearic acid=60.7: the eutectic mixture of 29.9:9.4.
The preparation method of the polyhydric aliphatic acid eutectic mixture is to be selected according to required phase transition temperature for mixing Raw material of fatty acid and clear raw material proportioning, then selected raw material is put into heating stirring in 85 DEG C of thermostat water bath in proportion The polyhydric aliphatic acid eutectic mixture is obtained after 10 ~ 20min, then 2 ~ 5min of ultrasound.
Phase transition temperature is determined according to use environment temperature, and comprehensively considers the size of phase transformation enthalpy, preferably lauric acid/cardamom Acid/stearic acid ternary eutectic mixture or lauric acid/myristic acid or the binary such as lauric acid/stearic acid or myristic acid/stearic acid Eutectic mixture;
The PERFORMANCE OF MODIFIED VERMICULITE is TiO2- TiC-C nano-complex PERFORMANCE OF MODIFIED VERMICULITE or SiO2- SiC-C nano-complex PERFORMANCE OF MODIFIED VERMICULITE;
Wherein TiO2The preparation method of-TiC-C nano-complex PERFORMANCE OF MODIFIED VERMICULITE the following steps are included: by butyl titanate and its 9 15min is mixed in the dehydrated alcohol of times volume, the glacial acetic acid of 1/3 volume, and expanded vermiculite is then added, 90 are added dropwise while stirring The ethanol solution of ~ 95wt% stirs ultrasound 30min after 1 ~ 2h, and adding nitric acid to keep solution ph is 1 ~ 2, after being vigorously stirred 1 ~ 2h It is slowly added dropwise the sucrose solution of 0.31g/ml, the mass ratio of sucrose and vermiculite is 4: 5, continues 1 ~ 2h of stirring, then solution is fallen Enter water heating kettle, 22 ~ 25h is reacted at 180 ~ 200 DEG C, then be placed in 75 ~ 85 DEG C of dryings, finely ground, at 1000 DEG C of carbon thermal reduction atmosphere 2h is calcined, load nano-TiO is obtained2The vermiculite of-TiC-C;Wherein the additional amount of butyl titanate is to assume the TiC generated completely It is 5% meter with vermiculite mass ratio.
SiO2- SiC-C nano-complex PERFORMANCE OF MODIFIED VERMICULITE preparation method is the following steps are included: by the sucrose solution of 0.2g/ml It is mixed with the glacial acetic acid of its 1/15 volume or ammonium hydroxide, expanded vermiculite is added, ultrasound 3min forms dispersion after stirring 20min at room temperature Uniform solution system, being then added dropwise is the tetraethyl orthosilicate of 1/10 volume of sucrose solution and the mixed liquor of ethyl alcohol, And it is vigorously stirred 2 ~ 3h in 60 DEG C of water-baths, then solution is poured into water heating kettle, 10 ~ 13h is reacted at 160 ~ 190 DEG C, then set 2h is calcined at 60 ~ 80 DEG C of dryings, grinding, 900 ~ 1000 DEG C of carbon thermal reduction atmosphere, obtains load Nano-meter SiO_22The leech of-SiC-C Stone;Wherein the additional amount of tetraethyl orthosilicate is in terms of 5% by the SiC and vermiculite mass ratio that assume to generate completely.
The fatty acid/PERFORMANCE OF MODIFIED VERMICULITE composite phase-change energy storage material preparation method the following steps are included:
1) PERFORMANCE OF MODIFIED VERMICULITE is mixed with unary fatty acid or polyhydric aliphatic acid eutectic mixture 1:3 in mass ratio and is placed on bottle,suction In, 5 ~ 10min of forvacuum, makes 0.01 ~ 0.05MPa of vacuum degree at room temperature;
2) bottle,suction is placed in 85 DEG C of temperature, is adsorbed while stirring with the revolving speed of 200 ~ 600rpm;
3) it under agitation, is vacuumized again again after 60min closes vacuum, opens bottleneck 1-2min, so repeatedly 2 ~ 3 It is secondary, vacuum is finally closed, stirs 20min under normal pressure;
4) sample is placed in temperature filtration 12 in 90 DEG C of baking oven ~ for 24 hours, then takes out and is cooled to room temperature, is ground, then be placed in 90 DEG C Baking oven in constant temperature place 12 ~ for 24 hours, until no fatty acids leakage and take out after reaching constant weight, be cooled to room temperature and high inhaled to get described Fatty acid/nano-complex PERFORMANCE OF MODIFIED VERMICULITE composite phase-change energy storage material of light, high thermal conductivity.
Compared with existing product and technology, present invention has an advantage that
1, the present invention with PERFORMANCE OF MODIFIED VERMICULITE be porous supporting matrix, using unitary or polyhydric aliphatic acid eutectic mixture as phase-change accumulation energy master Body prepares composite phase-change energy storage material, and obtained composite phase-change energy storage material not only has high thermal coefficient and enthalpy of phase change Value, but also there is excellent absorbing ability, photothermal conversion can be fast implemented under sunlight irradiation, can be used as heat source, gained The phase transition temperature of composite phase-change energy storage material is 25 ~ 66 DEG C, therefore is led in battery thermal management, Solar use, building energy conservation etc. Domain all has broad application prospects.
2, the present invention loads TiO on nonmetallic mineral vermiculite2- TiC-C or SiO2- SiC-C nano-complex, these are received Rice compound provides new heat transfer carrier and light absorption carrier not only for composite phase-change energy storage material, to improve its heating conduction With photo absorption performance;And the specific surface area of vermiculite is increased, the cellular structure of vermiculite is improved, so that vermiculite is to fatty acid phase transformation The adsorption rate of material improves 171%, solves in current porous mineral base energy storage material and leads since phase-change material adsorbance is low The problem for causing the phase transformation enthalpy of composite phase-change energy storage material low.Therefore, TiO is loaded with vermiculite2- TiC-C or SiO2- SiC-C receives The new support substrate that rice compound is formed, can cooperate with and promote fatty acid/nano-complex PERFORMANCE OF MODIFIED VERMICULITE composite phase-change energy storage material Thermal coefficient, heat storage capacity and optical and thermal convert three big performances.
3, high extinction provided by the invention, high thermal conductivity fatty acid/nano-complex PERFORMANCE OF MODIFIED VERMICULITE composite phase change energy-storing material The preparation process of material is simple, low in cost, meanwhile, the composite phase-change energy storage material be also equipped with do not leak, that thermal stability is good etc. is excellent Point is a kind of novel environment-protective energy-saving functional material.
Detailed description of the invention
Fig. 1 is TiO2- TiC-C PERFORMANCE OF MODIFIED VERMICULITE (EVTa) and pure vermiculite (EV) and its composite phase-change energy storage material (LA-MA- SA/EVTa, LA-MA-SA/EV) photothermal conversion temperature changing curve diagram.
Fig. 2 is TiO2The X-ray diffracting spectrum of-TiC-C PERFORMANCE OF MODIFIED VERMICULITE (EVTa) and pure vermiculite (EV).It can from Fig. 2 Out, the XRD diffracting spectrum of EVTa is relative to EV, and in 2 θ=35.8 °, the diffraction that TiC occurs in 41.8 ° and 60.4 ° of position is special Peak is levied, TiO occurs in the position of 2 θ=25.9 °2The diffractive features peak of (rutile), and TiO2- TiC-C PERFORMANCE OF MODIFIED VERMICULITE (EVTa) appearance is black, shows the presence for having C.To sum up, it was demonstrated that TiO2- TiC-C is successfully supported on vermiculite.
Fig. 3 is SiO2The X-ray diffracting spectrum of-SiC-C PERFORMANCE OF MODIFIED VERMICULITE (EVSC) and burnt vermiculite (EVS).By scheming 3 can be seen that the XRD diffracting spectrum of EVSC relative to EVS, the diffractive features peak of SiC occur in the position of 2 θ=35.6 °, There is Si in the position of 2 θ=44.8 °5C3Diffractive features peak, XRD spectrum has SiO in 2 θ=20 ~ 35 °2Armorphous peak, and The appearance of PERFORMANCE OF MODIFIED VERMICULITE is black, shows the presence for having C.To sum up, it was demonstrated that SiO2- SiC-C is successfully supported on vermiculite.
Fig. 4 is TiO2The scanning electron microscope (SEM) photograph of-TiC-C PERFORMANCE OF MODIFIED VERMICULITE (EVTa), can be seen from the chart vermiculite interlayer and table Face has loaded TiO2- TiC-C nano-complex.
Fig. 5 is TiO2The scanning of the composite phase-change energy storage material (LA-MA-SA/EVTa) of-TiC-C PERFORMANCE OF MODIFIED VERMICULITE (EVTa) Electron microscope.As can be seen from Figure 5 ternary aliphatic acid fills out the interlayer for being filled with PERFORMANCE OF MODIFIED VERMICULITE.
Fig. 6 is SiO2The scanning electron microscope (SEM) photograph of-SiC-C PERFORMANCE OF MODIFIED VERMICULITE (EVSC), can be seen from the chart vermiculite interlayer and table Face has loaded SiO2- SiC-C nano-complex.
Fig. 7 is SiO2The scanning electron microscope (SEM) photograph of the composite phase-change energy storage material (MA/EVSC) of-SiC-C PERFORMANCE OF MODIFIED VERMICULITE.By Fig. 7 As can be seen that PERFORMANCE OF MODIFIED VERMICULITE not only filled by fatty acid by interlayer, surface is also covered by fatty acid.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention Technical solution is described further, but the present invention is not limited only to this.
Embodiment 1
(1) it weighs 15g myristic acid and is placed in beaker, then put it into heating stirring 10min in 90 DEG C of thermostat water bath, ultrasound It takes out and is cooled to room temperature after 3min;It is 54.6 DEG C with differential scanning calorimetry measurement myristic acid fusing point, freezing point is 51.8 DEG C, phase Change latent heat is 189.4J/g.
(2) by 3g sucrose and 15mL water, 1mL glacial acetic acid wiring solution-forming after, 5g expanded vermiculite is added, is stirred at room temperature Ultrasound 3min forms finely dispersed solution system after 20min, be then added dropwise 1.5mL tetraethyl orthosilicate and 1.5mL without The mixed solution of water-ethanol is warming up at 60 DEG C after being added dropwise and continues to stir 2h, then solution is poured into water heating kettle, at 180 DEG C Lower reaction 12h, then be placed in 70 DEG C of baking ovens and dry and grind, the carbon thermal reduction at 1000 DEG C of obtained presoma is calcined 2 hours Afterwards, SiO is obtained2- SiC-C PERFORMANCE OF MODIFIED VERMICULITE.
(3) by SiO2- SiC-C PERFORMANCE OF MODIFIED VERMICULITE is mixed with myristic acid 1:3 in mass ratio and is placed on equipped with magnetic stir bar In bottle,suction, forvacuum 10min, vacuum degree 0.01MPa at room temperature.Bottle,suction is placed in 85 DEG C of water-baths again In, it is adsorbed while stirring with the revolving speed of 500rpm;Under agitation, vacuum is closed every 60min, open bottleneck 2min, weight It is 2 times multiple;Vacuum is closed, stirs 20min under normal pressure.Sample is placed in 90 DEG C of baking oven temperature filtrations for 24 hours, then takes out and is cooled to room Temperature, grinding, then be placed in 90 DEG C of baking oven temperature filtrations and take out afterwards for 24 hours, it is cooled to room temperature to get myristic acid/SiO2- SiC-C is modified Vermiculite composite phase-change energy storage material.It is 54.2 DEG C with the fusing point that differential scanning calorimetry measures gained composite phase-change energy storage material, Freezing point is 52.1 DEG C, latent heat of phase change 135.8J/g.The thermal coefficient for measuring the composite phase-change energy storage material is 0.726W/ MK, compared to myristic acid (0.241 W/mK), vermiculite (0.396 W/mK) and myristic acid/vermiculite composite phase-change material (0.497 W/mK thermal conductivity) is obviously improved.
Embodiment 2
(1) lauric acid, myristic acid, stearic acid in mass ratio 60.7: 29.9:9.4 is uniformly mixed, is placed in 80 DEG C of constant temperature It takes out and is cooled to room temperature after heating stirring 20min in water-bath, ultrasonic 2min;Lauric acid/meat is measured with differential scanning calorimetry Myristic acid/stearic acid ternary eutectic mixture fusing point is 31.0 DEG C, and freezing point is 27.6 DEG C, latent heat of phase change 164.0J/g.
(2) 1.42mL butyl titanate is measured, 12.78mL dehydrated alcohol is added, 0.48mL is added after magnetic agitation 15min Glacial acetic acid, be vigorously agitated again 15min, 5g expanded vermiculite (EV) then be added, stir 1h, after ultrasonic vibration 30min, continue to stir It mixes, then the mixed liquor of 3mL dehydrated alcohol Yu 0.3mL distilled water is added dropwise, drop rate is about 1 drop/5s, with 0.01mL nitric acid It adjusts pH value of solution and is maintained at 1 ~ 2 or so, room temperature is vigorously stirred 2h, and body then is added dropwise in 4g sucrose and 13mL water wiring solution-forming In system, continue to stir 1h, then solution is poured into water heating kettle, be reacted for 24 hours at 200 DEG C, then is placed in 85 DEG C of dryings, finely ground, carbon heat 2h is calcined at 1000 DEG C of reducing atmosphere, obtains load 5wt% nano-TiO2The vermiculite of-TiC-C;By nano-TiO2- TiC-C is modified leech Stone composite material is that 1:6 is mixed with the nitric acid solution of 6mol/L in mass ratio, is placed in 90 DEG C of thermostat water bath and is activated 2h is reacted, resulting slurries are filtered, are washed to neutrality, dries, crush and be sieved, obtain TiO2- TiC-C is modified leech Stone.
(3) by TiO2- TiC-C PERFORMANCE OF MODIFIED VERMICULITE and lauric acid/myristic acid/stearic acid ternary eutectic mixture in mass ratio 1: 3 mixing are placed in the bottle,suction equipped with magnetic stir bar, and forvacuum 20min at room temperature, vacuum degree are 0.03MPa;Bottle,suction is placed in 85 DEG C of water-baths again, is adsorbed while stirring with the revolving speed of 300rpm;Under agitation, often Vacuum is closed every 60min, opens bottleneck 1min, is repeated 2 times;Vacuum is closed, stirs 20min under normal pressure.Sample is placed in 90 DEG C Baking oven temperature filtration 12h, then takes out and is cooled to room temperature, grinding, then takes out after being placed in 90 DEG C of baking oven temperature filtration 12h, cooling To room temperature to get ternary aliphatic acid/TiO2- TiC-C PERFORMANCE OF MODIFIED VERMICULITE composite phase-change energy storage material.It is measured with differential scanning calorimetry Ternary aliphatic acid/PERFORMANCE OF MODIFIED VERMICULITE composite phase-change energy storage material fusing point is 30.4 DEG C, and freezing point is 28.0 DEG C, and latent heat of phase change is 115.7J/g.The thermal coefficient for measuring the composite phase-change energy storage material is 0.676W/mK.
Fig. 1 is by the TiO in the present embodiment2- TiC-C PERFORMANCE OF MODIFIED VERMICULITE (EVTa), pure vermiculite (EV), composite phase change energy-storing material Material (LA-MA-SA/EVTa, LA-MA-SA/EV) is pressed into disk (1. EV, 2. EVTa, the 3. LA- of same size and thickness respectively MA-SA/EV, 4. LA-MA-SA/EVTa), under equal conditions, irradiated with 300W xenon lamp simulated solar irradiation, temperature is more than phase transformation material Light source is closed after the fusion temperature of material, stops thermometric after temperature drops to room temperature, measures the temperature variation curve of photothermal conversion. It can be seen from the figure that TiO2- TiC-C PERFORMANCE OF MODIFIED VERMICULITE (EVTa) reaches with pure vermiculite (unmodified) (EV) in light application time 1040s(closes light source) when, temperature has respectively reached 48.1 DEG C and 39.7 DEG C, illustrates the TiO under same illumination condition2-TiC-C PERFORMANCE OF MODIFIED VERMICULITE (EVTa) has better photothermal conversion ability.TiO2- TiC-C PERFORMANCE OF MODIFIED VERMICULITE (EVTa) is answered with pure vermiculite (EV's) Phase-changing energy storage material (LA-MA-SA/EVTa, LA-MA-SA/EV) heating curve is closed to occur turning in the fusion temperature of phase-change material Point shows that luminous energy is converted to thermal energy and melts phase-change material;Reach 3340s(in light application time and close light source) when, the two temperature 52.4 DEG C and 47.4 DEG C are respectively reached, show TiO2The composite phase-change energy storage material of-TiC-C PERFORMANCE OF MODIFIED VERMICULITE (EVTa) has stronger Absorbing ability, convert light energy into thermal energy.
Embodiment 3
(1) lauric acid, myristic acid, stearic acid in mass ratio 60.7: 29.9:9.4 is uniformly mixed, is placed in 80 DEG C of constant temperature It takes out and is cooled to room temperature after heating stirring 30min in water-bath, ultrasonic 2min;Lauric acid/meat is measured with differential scanning calorimetry Myristic acid/stearic acid ternary eutectic mixture fusing point is 31.0 DEG C, and freezing point is 27.6 DEG C, latent heat of phase change 164.0J/g.
(2) by 3g sucrose and 15mL water, 1mL ammonium hydroxide wiring solution-forming after, 5g expanded vermiculite is added, is stirred at room temperature Ultrasound 3min forms finely dispersed solution system after 20min, be then added dropwise 1.5mL tetraethyl orthosilicate and 1.5mL without The mixed solution of water-ethanol is warming up at 60 DEG C after being added dropwise and continues to stir 2h, then solution is poured into water heating kettle, at 180 DEG C Lower reaction 11h, then be placed in 70 DEG C of baking ovens and dry and grind, the carbon thermal reduction at 900 DEG C of obtained presoma is calcined 2 hours Afterwards, SiO is obtained2- SiC-C PERFORMANCE OF MODIFIED VERMICULITE.
(3) by SiO2- SiC-C PERFORMANCE OF MODIFIED VERMICULITE and lauric acid/myristic acid/stearic acid ternary eutectic mixture in mass ratio 1: 3 mixing are placed in the bottle,suction equipped with magnetic stir bar, and forvacuum 10min at room temperature, vacuum degree are 0.05MPa;Bottle,suction is placed in 85 DEG C of water-baths again, is adsorbed while stirring with the revolving speed of 200rpm;Under agitation, often Vacuum is closed every 60min, opens bottleneck 1min, is repeated 2 times;Vacuum is closed, sample is placed in 90 DEG C of baking oven temperature filtrations for 24 hours, It then takes out and is cooled to room temperature, grind, then be placed in 90 DEG C of baking oven temperature filtrations and take out afterwards for 24 hours, be cooled to room temperature to get ternary rouge Fat acid/SiO2- SiC-C PERFORMANCE OF MODIFIED VERMICULITE composite phase-change energy storage material.It is sour/modified that the ternary aliphatic is measured with differential scanning calorimetry The fusing point of vermiculite composite phase-change energy storage material is 30.2 DEG C, and freezing point is 27.9 DEG C, latent heat of phase change 69.3J/g.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification, is all covered by the present invention.

Claims (8)

1. a kind of fatty acid of high extinction, high thermal conductivity/nano-complex PERFORMANCE OF MODIFIED VERMICULITE composite phase-change energy storage material, feature exist In: it is combined by unary fatty acid or polyhydric aliphatic acid eutectic mixture and PERFORMANCE OF MODIFIED VERMICULITE, wherein unary fatty acid or polynary Weight percent shared by fatty acid eutectic mixture is 42 ~ 72%.
2. the fatty acid of high extinction according to claim 1, high thermal conductivity/nano-complex PERFORMANCE OF MODIFIED VERMICULITE composite phase change energy-storing Material, it is characterised in that: the unary fatty acid is capric acid, lauric acid, myristic acid, palmitinic acid, any one in stearic acid.
3. the fatty acid of high extinction according to claim 1, high thermal conductivity/nano-complex PERFORMANCE OF MODIFIED VERMICULITE composite phase change energy-storing Material, it is characterised in that: the polyhydric aliphatic acid eutectic mixture be lauric acid, myristic acid, in stearic acid any 2 ~ 3 kinds be total to Brilliant mixture;Preparation method is 10 ~ 20min of heating stirring in the thermostat water bath for be put into selected raw material in proportion 85 DEG C, The polyhydric aliphatic acid eutectic mixture is obtained after 2 ~ 5min of ultrasound again.
4. the fatty acid of high extinction according to claim 3, high thermal conductivity/nano-complex PERFORMANCE OF MODIFIED VERMICULITE composite phase-change storage Energy material, it is characterised in that: the polyhydric aliphatic acid eutectic mixture is that mass ratio is respectively lauric acid: myristic acid=67: 33, lauric acid: stearic acid=83:17, myristic acid: stearic acid=75:25, lauric acid: myristic acid: stearic acid=60.7: 29.9:9.4 eutectic mixture.
5. the fatty acid of high extinction according to claim 1, high thermal conductivity/nano-complex PERFORMANCE OF MODIFIED VERMICULITE composite phase change energy-storing Material, it is characterised in that: the PERFORMANCE OF MODIFIED VERMICULITE is TiO2- TiC-C nano-complex PERFORMANCE OF MODIFIED VERMICULITE or SiO2- SiC-C is nano combined Object PERFORMANCE OF MODIFIED VERMICULITE.
6. the fatty acid of high extinction according to claim 5, high thermal conductivity/nano-complex PERFORMANCE OF MODIFIED VERMICULITE composite phase-change storage Energy material, it is characterised in that: TiO2- TiC-C nano-complex PERFORMANCE OF MODIFIED VERMICULITE preparation method is the following steps are included: by four fourth of metatitanic acid 15min is mixed in the glacial acetic acid of ester and the dehydrated alcohol of its 9 times of volumes, 1/3 volume, and expanded vermiculite, side stirring is then added The ethanol solution of 90 ~ 95wt% is added dropwise in side, stirs ultrasound 30min after 1 ~ 2h, and adding nitric acid to adjust solution ph is 1 ~ 2, is acutely stirred Mix the sucrose solution that 0.31g/ml is slowly added dropwise after 1 ~ 2h, the mass ratio of sucrose and vermiculite is 4: 5, continue 1 ~ 2h of stirring, then Solution is poured into water heating kettle, 22 ~ 25h is reacted at 180 ~ 200 DEG C, then be placed in 75 ~ 85 DEG C of dryings, finely ground, carbon thermal reduction atmosphere 2h is calcined at 1000 DEG C, obtains load nano-TiO2The vermiculite of-TiC-C;Wherein the additional amount of butyl titanate is to assume completely The TiC and vermiculite mass ratio of generation are 5% meter.
7. the fatty acid of high extinction according to claim 5, high thermal conductivity/nano-complex PERFORMANCE OF MODIFIED VERMICULITE composite phase change energy-storing Material, it is characterised in that: SiO2- SiC-C nano-complex PERFORMANCE OF MODIFIED VERMICULITE preparation method is the following steps are included: by 0.2g/ml's Sucrose solution is mixed with the glacial acetic acid of its 1/15 volume or ammonium hydroxide, and expanded vermiculite is added, and stirs ultrasound 3min after 20min at room temperature Form finely dispersed solution system, be then added dropwise be 1/10 volume of sucrose solution tetraethyl orthosilicate and ethyl alcohol Mixed liquor, and be vigorously stirred 2 ~ 3h in 60 DEG C of water-baths, then solution is poured into water heating kettle, react 10 at 160 ~ 190 DEG C ~ 13h, then 60 ~ 80 DEG C of dryings, grinding are placed in, 2h is calcined at 900 ~ 1000 DEG C of carbon thermal reduction atmosphere, obtains load Nano-meter SiO_22- The vermiculite of SiC-C;Wherein the additional amount of tetraethyl orthosilicate is in terms of 5% by the SiC and vermiculite mass ratio that assume to generate completely.
8. the fatty acid of high extinction according to claim 1, high thermal conductivity/nano-complex PERFORMANCE OF MODIFIED VERMICULITE composite phase change energy-storing The preparation method of material, it is characterised in that: the following steps are included:
1) PERFORMANCE OF MODIFIED VERMICULITE is mixed with unary fatty acid or polyhydric aliphatic acid eutectic mixture 1:3 in mass ratio and is placed on bottle,suction In, 5 ~ 10min of forvacuum, makes 0.01 ~ 0.05MPa of vacuum degree at room temperature;
2) bottle,suction is placed in 85 DEG C of water-baths, is adsorbed while stirring with the revolving speed of 200 ~ 600rpm;
3) it under agitation, is vacuumized again again after 60min closes vacuum, opens bottleneck 1-2min, so repeatedly 2 ~ 3 It is secondary, vacuum is finally closed, stirs 20min under normal pressure;
4) sample is placed in temperature filtration 12 in 90 DEG C of baking oven ~ for 24 hours, then takes out and is cooled to room temperature, is ground, then be placed in 90 DEG C Baking oven in constant temperature place 12 ~ for 24 hours, until no fatty acids leakage and take out after reaching constant weight, be cooled to room temperature and high inhaled to get described Fatty acid/nano-complex PERFORMANCE OF MODIFIED VERMICULITE composite phase-change energy storage material of light, high thermal conductivity.
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