CN103992774A - Magnetic microencapsulated phase change energy storage material and preparation method thereof - Google Patents
Magnetic microencapsulated phase change energy storage material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a magnetic microencapsulated phase change energy storage material with magnetic and thermal energy storage functions and a preparation method thereof. A wall material of microcapsules is a magnetic ferrite/silica inorganic hybrid material with the magnetic function and a core material can be paraffin and a higher fatty alcohol, acid and ester type organic phase change energy storage material. The preparation method of the magnetic microencapsulated phase change energy storage material disclosed by the invention comprises the steps of firstly synthesizing magnetic ferrite nanoparticles and further assembling the magnetic ferrite nanoparticles in a solvent to the surfaces of suspended oil droplets of the organic phase change energy storage material through a Pickering emulsion technology; finally forming silica gel on the surface of the phase change energy storage material through an interfacial polymerization technology to fix the magnetic ferrite nanoparticles on the surfaces of the oil droplets of the organic phase change energy storage material so as to form the microcapsules using the magnetic ferrite/silica hybrid wall material to coat the phase change energy storage material.
Description
Technical field
The present invention relates to a kind of micro-encapsulated phase change energy storage material, relate in particular to a kind of wall material and there is microcapsule organic phase change energy storage material of magnetic function and preparation method thereof.
Background technology
The energy is as the power of human society productive life, closely bound up with the development of modern society and economic prosperity.Now, world energy sources oneself step into a new Transformation Period.Energy shortage problem even occurs in global range in most countries, becomes the common issue that countries in the world face.Because the supply and demand of the energy has very strong time-dependent manner under many circumstances, in order reasonably to utilize it, just temporary transient no energy storage need to be got up, in needs, discharge again, this utilising efficiency to save energy and the raising energy is very important beyond doubt.Conflicting the putting forward that the research and development of energy storage material match in time and space in order to solve energy supply and demand just.
Energy storage technology is the new and high technology growing up for 20 end of the centurys, be the effective means that improves energy utilization rate, and energy storage material is the basis of energy storage technology.At present, as the phase-changing energy storage material of the important component part of energy storage material, be subjected to increasing domestic and international corresponding expert's attention, caused association area researchist's very big interest, had development prospect.Phase-changing energy storage material is to utilize the Process of absorption or liberation of heat effect of material in phase transition process to carry out the material of energy storage and temperature adjusting.Such material, because self temperature in phase transition process remains unchanged, can be widely used in building and field of textiles.According to material property classification, phase-changing energy storage material can be divided into inorganic energy storage phase change material and organic energy storage phase change material.Inorganic and organic phase change energy storage material has advantages of respectively separately, but all has some limitations.Inorganic-phase variable energy storage material thermal conductivity is high, good flame resistance and cost low, but there is corrodibility, readily degradable, easy superfusibility, all these shortcomings all have a huge impact its phase transition performance.Organic phase change energy storage material non-corrosiveness, there is chemical stability, there is no surfusion, unit volume latent heat of phase change high, but thermal conductivity is low, volume change is large during phase transformation, and inflammable.According to phase transformation mode, classify, phase-changing energy storage material can be divided into four classes: solid-solid phase-change energy-storage material, solid-liquid phase change energy storage material, solid-gas phase change energy-storage material and liquid-gas phase change energy-storage material.Because latter two phase transformation mode is attended by the existence of a large amount of gases in phase transition process, material volume is changed greatly, although therefore they have very large enthalpy of phase change, but seldom selected in actual applications, so solid-liquid phase change energy storage material and solid-solid phase-change energy-storage material are the emphasis of current this area research.Because the latent heat of phase change of solid-liquid phase change material is larger, its application is also relatively wide.Senior fat hydrocarbon (paraffin) and senior aliphat alcohol, acid, ester class organic phase change energy storage material etc. are all the most frequently used solid-liquid phase change energy storage materials.The transformation temperature of such homology organic phase change energy storage material and enthalpy of phase change can increase along with the growth of carbochain, by mixing, are used and can be realized the controlled of transformation temperature.Although these phase change materials have very high enthalpy of phase change and energy storage density, but in use there is a significant deficiency: latent heat is put in each suction all will experience solid-state-liquid-solid-state physical condition change, this makes it after repeated multiple times phase transformation, very easily reveals, runs off.In order to address the above problem, one preferably method be that phase-changing energy storage material is packaged into microcapsule.In addition, the phase-changing energy storage material yardstick after encapsulation is little, and unit heat exchange area is large, thereby heat exchange efficiency is higher.
The mainstream technology at present phase-changing energy storage material being encapsulated is to take polymkeric substance as wall material.As Chinese patent CN 103170289A, it is that core, melamine formaldehyde resin are wall material that this patent adopts paraffin, utilizes situ aggregation method to prepare microcapsule phase-change energy storage material.The existing major defect of polymer wall material is its poor thermal conductivity, and thermal conductivity is 0.12Wm only
-1k
-1left and right, thus cause the thermal response of microcapsule phase-change energy storage material to slow down, easily produce surfusion.Inorganic materials has the incomparable high strength of macromolecular material, flame retardancy, high thermal stability, (thermal conductivity is conventionally at 1.3Wm for high thermal conductivity
-1k
-1above) and the characteristic such as material is finer and close, formed " shell-core " microcapsule structure is more stable.Gradually ripe for IN-SITU SOL-GEL and the interfacial polymerization synthetic technology of the inorganic wall material microcapsule phase-change energy storage material based on siloxy at present.At present, there is the disclosed patent of invention of preparing silicon dioxde coated phase-change energy-storage material, as Chinese patent CN 101824307A, this patent adopts sol-gel method, has synthesized the microcapsule phase-change energy storage material of the coated with silica paraffin of dimensionally stable under cold condition by surfactant templates method.
Current disclosed data shows, the enhancing at phase change material energy storage simple function is mainly focused in the research and development of relevant phase-changing energy storage material microcapsule, but almost do not relate to the field that utilizes the micro encapsulation of phase-changing energy storage material to expand its function.Along with the continuous developing of phase-changing energy storage material Application Areas, in some special field, the demand having such as the dual-use function microcapsule phase-change energy storage material of the specific physical such as optical, electrical, magnetic or chemical effect is also manifested.This also becomes the important topic that phase-changing energy storage material area research personnel must face.This patent has been opened up a kind of new research field, the magnetic inorganic nano material of tool own is used for to coated phase-change energy storage material, thereby be born, both there is the core of phase-change accumulation energy and temperature adjustment function, there is again the difunctional microcapsule phase-change energy storage material of magnetic function wall material.Because it is very big directly to form the difficulty of magnetic ferrite body wall material, therefore first synthesizing magnetic ferrite nano particles, by pik woods (Pickering) emulsion technology, magnetic ferrite nanoparticle is assembled into phase-changing energy storage material surface again, and is fixed with silicon gel.At present, magnetic ferrite nanoparticle is own in being widely used in biological chemistry, medical science and biotechnology, in order to fixing protein, enzyme and other biological active substance.The magnetic ferrite nanoparticle of single-component can not directly be applied due to easily reunion, poor stability and biological degradation.Magnetic ferrite nanoparticle is introduced and had in the material of special construction, both can overcome the shortcoming of single-component magnetic ferrite nanoparticle, can give magnetism of material energy again.And Pickering emulsion technology provides a kind of method that very easily solid particulate is assembled into water-oil interface.Publication number is that the Chinese patent of CN 1569323A discloses and a kind ofly based on Pickering emulsion technology, solids is assembled into oil-based solvent surface, by controlled chemical reaction, on the nano-solid film at Pickering emulsion interface, successively assemble, obtain composite Nano hollow structure.
The synthetic microcapsule phase-change energy storage material of this patent has soft magnetism feature, is made into functional coat and is applied to integrated circuit (IC) chip, can produce the double effects of cooling and anti-low frequency electromagnetic wave excitation.Meanwhile, this difunctional microcapsule phase-change energy storage material has the decalescence reduction infrared signature of core and the wideband microwave absorbing property of wall material concurrently, can be widely used in military stealthy field.
Summary of the invention
The object of this invention is to provide a kind of not only had magnetic function, but also the microcapsule phase-change energy storage material of tool thermal energy storage and temperature adjustment function and preparation method thereof.Because having adopted high heat conduction inorganic hybridization wall material, this microcapsule phase-change energy storage material is coated, the poor thermal conductivity, the intensity that have not only overcome the coated microcapsule phase-change energy storage material of traditional organic wall material are low, inflammable, easy excessively cold defect during phase transformation, also give its magnetic function simultaneously, make the Application Areas of this microcapsule phase-change energy storage material expand to the fields such as microelectronic material, intelligent fiber and fabric, military stealth material from traditional weaving and building energy saving field.
A kind of magnetic microcapsules phase-changing energy storage material proposed by the invention and preparation method thereof, can realize by following technique means.The synthesis process of magnetic microcapsules phase-changing energy storage material is as follows:
(1) preparation process of modification magnetic ferrite nanoparticle:
Ammoniacal liquor is joined in trivalent iron salt and divalent iron salt mixing solutions and stirred, regulate pH value to alkalescence; Add hydrophobically modified agent, under 55 ℃ and nitrogen protection, stir slaking 20min; The magnetic ferrite nanoparticle of first preparing with deionized water rinsing to be to remove residual ammoniacal liquor, then rinses to remove residual deionized water with non-aqueous solvent, all uses strong magnetic to carry out separated while rinsing with non-aqueous solvent with deionized water.
(2) preparation process of Pickering emulsion:
Phase-changing energy storage material and silicon source are stirred at 45 ℃, meanwhile, the non-aqueous suspension that is mixed with magnetic ferrite nanoparticle is heated to 45 ℃; By above-mentioned two kinds of liquid mixing, and under ultrasonication, form the stable oil-in-water Pickering emulsion of nanoparticle; Add tensio-active agent, stir and form the particle-stabilised Pickering emulsion of small molecules synergic nano.
(3) the magnetic ferrite nanoparticle on silicon gel stationary phase change energy-storage material drop surface form the process of magnetic ferrite/SiO 2 hybrid wall material:
In the Pickering emulsion forming, splash into the hydrochloric acid soln that concentration is greater than 1.26mol/L in process (2), after stirring 3h, close stirring rake, slaking 18～21h; With deionized water rinsing product 2～3 times, filter, natural air drying can obtain magnetic microcapsules phase-changing energy storage material.
In said process (1), magnetic ferrite nanoparticle comprises Fe
3o
4nanoparticle is with γ – Fe
2o
3one or both in nanoparticle, or through the Fe of one or both doping in transition metal Zn, Co, Ni, Mn, Cu, Ba, Cr
3o
4nanoparticle is with γ – Fe
2o
3nanoparticle.
PH value when regulator solution is to alkalescence in said process (1) is 10～11.
In said process (1), the hydrophobically modified agent of magnetic ferrite nanoparticle is cats product.
Phase-changing energy storage material in said process (2) and the mass ratio in silicon source are 80/20～40/60.
Silicon source in said process (2) comprises the organosilicon sources such as the inorganic silicon sources such as water glass, potassium silicate and tetraethyl orthosilicate, methyltrimethoxy silane.
Tensio-active agent in said process (2) can be cats product or nonionogenic tenside, mainly plays the effect of the particle-stabilised Pickering emulsion of synergic nano.
Non-aqueous solvent in said process (1) and process (2) be in methane amide, acetonitrile, methyl alcohol any one.
In said process (3), silicon gel is fixed and forms the process of magnetic ferrite/SiO 2 hybrid wall material to the magnetic ferrite nanoparticle on phase-changing energy storage material drop surface, the synthetic method adopting is interfacial polymerization, using hydrochloric acid as catalyzer, impel tetraethyl orthosilicate to form silicon-dioxide network gel at interface hydrolysis-condensation.
The present invention compared with prior art, there is following high-lighting effect: (1) has broken through the defect of the simple function of traditional microcapsule phase-change energy storage material, realized difunctionalization of microcapsule phase-change energy storage material, the Application Areas of this material is further expanded.This difunctional microcapsule phase-change energy storage material can be applicable to have the fiber of nourishing function and the manufacture of fabric, the cooling of integrated circuit (IC) chip and the exploitation of anti-interference coating, electromagnetism and infrared pair of stealth material.(2) coating efficiency of the magnetic microcapsules phase-changing energy storage material of gained, up to 85%, has good phase transition performance.(3) realized the particle diameter on a large scale of magnetic microcapsules phase-changing energy storage material controlled, the particle diameter of the microcapsule of wherein preparing with cats product is between 3～6 μ m, and particle diameter prepared by nonionogenic tenside is between 30～50 μ m.(4) resulting Microcapsules Size is evenly distributed, and interfacial energy is low, can be combined with most of body materials better.
Accompanying drawing explanation
The electron scanning micrograph of Fig. 1 magnetic microcapsules phase-changing energy storage material;
After breaking, Fig. 2 magnetic microcapsules phase-changing energy storage material shows the electron scanning micrograph of " core-shell " structure;
The means of differential scanning calorimetry spectrogram of Fig. 3 magnetic microcapsules phase-changing energy storage material;
The magnetic hysteresis loop of Fig. 4 magnetic microcapsules phase-changing energy storage material.
Embodiment
Below in conjunction with embodiment and accompanying drawing, further illustrate the present invention.Following embodiment, based on implementing under technical solution of the present invention prerequisite, provides detailed synthetic method and implementation process; But protection scope of the present invention is not limited to following embodiment.
Embodiment 1
First by 0.05mol/L ferric chloride hexahydrate, 0.025mol/L Iron dichloride tetrahydrate is dissolved in 100mL deionized water, and under 55 ℃ and nitrogen protection, mechanical stirring 10min is to obtain uniform solution; With ammoniacal liquor, regulate pH value to 10～11, add 0.08g cetyl trimethylammonium bromide to carry out modification to ferriferrous oxide nano-particle, under 55 ℃ and nitrogen protection, continue stirring 20min; With deionized water and methane amide, rinse ferriferrous oxide nano-particle successively and with strong magnetic, carry out separatedly, to remove respectively residual ammoniacal liquor and deionized water, obtain ferriferrous oxide nano-particle.Then, 4g NSC 62789 and 4g tetraethyl orthosilicate are stirred at 45 ℃, 0.3g ferriferrous oxide nano-particle and 40g methane amide are heated to 45 ℃; By two parts of liquid mixing, ultrasonic 1h at 45 ℃, adds the cetyl trimethylammonium bromide of 0.9109g, with the speed of 300rpm, stirs 1h, obtains stable oil-in-water Pickering emulsion.Finally, splash into the hydrochloric acid soln 60mL of 1.78mol/L; After stirring 3h, close stirring rake, after slaking 18～21h, with deionized water rinsing product 2～3 times, filter, dryly can obtain magnetic microcapsules phase-changing energy storage material.
Embodiment 2
First by 0.05mol/L ferric chloride hexahydrate, 0.025mol/L nickelous nitrate is dissolved in 100mL deionized water, and under 55 ℃ and nitrogen protection, mechanical stirring 10min is to obtain uniform solution; With ammoniacal liquor, regulate pH value to 10～11, add 0.08g cetyl trimethylammonium bromide to carry out modification to Ni ferrite nanoparticle, under 55 ℃ and nitrogen protection, continue stirring 20min; With deionized water and methane amide, rinse Ni ferrite nanoparticle successively and with strong magnetic, carry out separatedly, to remove respectively residual ammoniacal liquor and deionized water, obtain Ni ferrite nanoparticle.Then, 4g NSC 62789 and 4g tetraethyl orthosilicate are stirred at 45 ℃, 0.3g Ni ferrite nanoparticle and 40g methane amide are heated to 45 ℃; By two parts of liquid mixing, ultrasonic 1h at 45 ℃, adds the cetyl trimethylammonium bromide of 0.9109g, with the speed of 300rpm, stirs 1h, obtains stable oil-in-water Pickering emulsion.Finally, splash into the hydrochloric acid soln 60mL of 1.78mol/L; After stirring 3h, close stirring rake, after slaking 18～21h, with deionized water rinsing product 2～3 times, filter, dryly can obtain magnetic microcapsules phase-changing energy storage material.
Embodiment 3
First by 0.05mol/L ferric chloride hexahydrate, 0.025mol/L Iron dichloride tetrahydrate is dissolved in 100mL deionized water, and under 55 ℃ and nitrogen protection, mechanical stirring 10min is to obtain uniform solution; With ammoniacal liquor, regulate pH value to 10～11, add 0.08g cetyl trimethylammonium bromide to carry out modification to ferriferrous oxide nano-particle, under 55 ℃ and nitrogen protection, continue stirring 20min; With deionized water and methane amide, rinse ferriferrous oxide nano-particle successively and with strong magnetic, carry out separatedly, to remove respectively residual ammoniacal liquor and deionized water, obtain ferriferrous oxide nano-particle.Then, 4g NSC 62789 and 4g tetraethyl orthosilicate are stirred at 45 ℃, 0.3g ferriferrous oxide nano-particle and 40g methane amide are heated to 45 ℃; By two parts of liquid mixing, ultrasonic 1h at 45 ℃, adds the cetyl trimethylammonium bromide of 0.9109g, with the speed of 300rpm, stirs 1h, obtains stable oil-in-water Pickering emulsion.Finally, splash into the hydrochloric acid soln 60mL of 1.26mol/L; After stirring 3h, close stirring rake, after slaking 18～21h, with deionized water rinsing product 2～3 times, filter, dryly can obtain magnetic microcapsules phase-changing energy storage material.
Embodiment 4
First by 0.05mol/L ferric chloride hexahydrate, 0.025mol/L Iron dichloride tetrahydrate is dissolved in 100mL deionized water, and under 55 ℃ and nitrogen protection, mechanical stirring 10min is to obtain uniform solution; With ammoniacal liquor, regulate pH value to 10～11, add 0.08g cetyl trimethylammonium bromide to carry out modification to ferriferrous oxide nano-particle, under 55 ℃ and nitrogen protection, continue stirring 20min; With deionized water and methane amide, rinse ferriferrous oxide nano-particle successively and with strong magnetic, carry out separatedly, to remove respectively residual ammoniacal liquor and deionized water, obtain ferriferrous oxide nano-particle.Then, 4g NSC 62789 and 6g tetraethyl orthosilicate are stirred at 45 ℃, 0.3g ferriferrous oxide nano-particle and 40g methane amide are heated to 45 ℃; By two parts of liquid mixing, ultrasonic 1h at 45 ℃, adds the cetyl trimethylammonium bromide of 0.9109g, with the speed of 300rpm, stirs 1h, obtains stable oil-in-water Pickering emulsion.Finally, splash into the hydrochloric acid soln 60mL of 1.78mol/L; After stirring 3h, close stirring rake, after slaking 18～21h, with deionized water rinsing product 2～3 times, filter, dryly can obtain magnetic microcapsules phase-changing energy storage material.
Embodiment 5
First by 0.05mol/L ferric chloride hexahydrate, 0.025mol/L Iron dichloride tetrahydrate is dissolved in 100mL deionized water, and under 55 ℃ and nitrogen protection, mechanical stirring 10min is to obtain uniform solution; With ammoniacal liquor, regulate pH value to 10～11, add 0.08g cetyl trimethylammonium bromide to carry out modification to ferriferrous oxide nano-particle, under 55 ℃ and nitrogen protection, continue stirring 20min; With deionized water and methane amide, rinse ferriferrous oxide nano-particle successively and with strong magnetic, carry out separatedly, to remove respectively residual ammoniacal liquor and deionized water, obtain ferriferrous oxide nano-particle.Then, 4g NSC 62789 and 1g tetraethyl orthosilicate are stirred at 45 ℃, 0.3g ferriferrous oxide nano-particle and 40g methane amide are heated to 45 ℃; By two parts of liquid mixing, ultrasonic 1h at 45 ℃, adds the cetyl trimethylammonium bromide of 0.9109g, with the speed of 300rpm, stirs 1h, obtains stable oil-in-water Pickering emulsion.Finally, splash into the hydrochloric acid soln 60mL of 1.78mol/L; After stirring 3h, close stirring rake, after slaking 18～21h, with deionized water rinsing product 2～3 times, filter, dryly can obtain magnetic microcapsules phase-changing energy storage material.
Embodiment 6
First by 0.05mol/L ferric chloride hexahydrate, 0.025mol/L Iron dichloride tetrahydrate is dissolved in 100mL deionized water, and under 55 ℃ and nitrogen protection, mechanical stirring 10min is to obtain uniform solution; With ammoniacal liquor, regulate pH value to 10～11, add 0.08g cetyl trimethylammonium bromide to carry out modification to ferriferrous oxide nano-particle, under 55 ℃ and nitrogen protection, continue stirring 20min; With deionized water and methane amide, rinse ferriferrous oxide nano-particle successively and with strong magnetic, carry out separatedly, to remove respectively residual ammoniacal liquor and deionized water, obtain ferriferrous oxide nano-particle.Then, 4g NSC 62789 and 4g tetraethyl orthosilicate are stirred at 45 ℃, 0.3g ferriferrous oxide nano-particle and 40g methane amide are heated to 45 ℃; By two parts of liquid mixing, ultrasonic 1h at 45 ℃, adds the mixed surfactant of 0.08g span 80 and 2.00g tween 80, with the speed of 300rpm, stirs 1h, obtains stable oil-in-water Pickering emulsion.Finally, splash into the hydrochloric acid soln 60mL of 1.78mol/L; After stirring 3h, close stirring rake, after slaking 18～21h, with deionized water rinsing product 2～3 times, filter, dryly can obtain magnetic microcapsules phase-changing energy storage material.
The electron scanning micrograph of magnetic microcapsules phase-changing energy storage material prepared by present embodiment (embodiment 1) as shown in Figure 1, can find that the particle diameter of prepared magnetic microcapsules phase-changing energy storage material is between 3～6 μ m, and particle diameter is even.The electron scanning micrograph of magnetic microcapsules phase-changing energy storage material prepared by present embodiment (embodiment 1) single microcapsule after grinding as shown in Figure 2, can find that prepared magnetic microcapsules phase-changing energy storage material has perfectly " core-shell " structure, and wall material is smooth and fine and close.Magnetic microcapsules phase-changing energy storage material prepared by present embodiment (embodiment 1) is after differential scanning calorimeter test, its hot-fluid-temperature curve as shown in Figure 3, curve in Fig. 3 is carried out to melting enthalpy and crystallization enthalpy that integration can obtain this magnetic microcapsules phase-changing energy storage material and be respectively 154.0J/g and 152.4J/g, clad ratio is 64.95%, has good latent heat storage-release performance.Magnetic microcapsules phase-changing energy storage material prepared by present embodiment (embodiment 1) is after vibrating sample magnetometer test, its magnetic hysteresis loop as shown in Figure 4, the saturation magnetization rate that can find this microcapsule phase-change energy storage material is 2.7390emu/g, coercive force and remanent magnetism are almost nil, demonstrate superparamagnetism.
Only for the preferred embodiment of invention, be not used for limiting practical range of the present invention in sum.Be that all equivalences of doing according to the content of the present patent application the scope of the claims change and modify, all should be technology category of the present invention.
Claims (10)
1. a magnetic microcapsules phase-changing energy storage material, it is characterized in that, this magnetic microcapsules phase-changing energy storage material has magnetic and thermal energy storage dual-use function concurrently, and its structure is typical " core-shell " structure, microcapsule wall material is inorganic materials, and core is organic phase change energy storage material; Microcapsules Size is 3～50 μ m, and particle diameter can regulate and control.
2. a kind of magnetic microcapsules phase-changing energy storage material according to claim 1, it is characterized in that, the wall material of described magnetic microcapsules phase-changing energy storage material is the magnetic ferrite/silicon-dioxide inorganic hybrid material with magnetic function, and core is one or more in senior fat hydrocarbon (paraffin) and senior aliphat alcohol, acid, ester class organic phase change energy storage material.
3. a kind of magnetic microcapsules phase-changing energy storage material according to claim 1, it is characterized in that, the organic phase change energy storage material surface of described magnetic microcapsules phase-changing energy storage material capsule-core is covered completely by magnetic ferrite nanoparticle, the space of magnetic ferrite nanoparticle and outer by silica-filled and coated.
4. a kind of magnetic microcapsules phase-changing energy storage material according to claim 1, is characterized in that, the wall material amount percentage composition of described magnetic microcapsules phase-changing energy storage material is 15～55%, and the quality percentage composition of described core is 85～45%.
5. according to the preparation method of a kind of magnetic microcapsules phase-changing energy storage material described in claim 1-4, it is characterized in that, comprise following technological process:
(1) preparation process of modification magnetic ferrite nanoparticle:
Ammoniacal liquor is joined in trivalent iron salt and divalent iron salt mixing solutions and stirred, and regulating pH value is 10～11; Add cats product as hydrophobically modified agent, under 55 ℃ and nitrogen protection, stir slaking 20min; The magnetic ferrite nanoparticle of first preparing with deionized water rinsing to be to remove residual ammoniacal liquor, then rinses to remove residual deionized water with non-aqueous solvent, all uses strong magnetic to carry out separated while rinsing with non-aqueous solvent with deionized water;
(2) preparation process of pik woods (Pickering) emulsion:
By mass ratio, be that 80/20～40/60 phase-changing energy storage material and silicon source stir at 45 ℃, meanwhile, the non-aqueous suspension that is mixed with magnetic ferrite nanoparticle be heated to 45 ℃; By above-mentioned two kinds of liquid mixing, and under ultrasonication, form the stable oil-in-water Pickering emulsion of nanoparticle; Add tensio-active agent, stir and form the particle-stabilised Pickering emulsion of small molecules synergic nano;
(3) the magnetic ferrite nanoparticle on silicon gel stationary phase change energy-storage material drop surface form the process of ferrite/SiO 2 hybrid wall material:
In the Pickering emulsion forming, splash into the hydrochloric acid soln that concentration is greater than 1.26mol/L in process (2), after stirring 3h, close stirring rake, slaking 18～21h; With deionized water rinsing product 2～3 times, filter, natural air drying can obtain magnetic microcapsules phase-changing energy storage material.
6. the preparation method of a kind of magnetic microcapsules phase-changing energy storage material according to claim 5, is characterized in that, in process (1), magnetic ferrite nanoparticle comprises Fe
3o
4nanoparticle is with γ – Fe
2o
3one or both in nanoparticle, or through the Fe of one or both doping in transition metal Zn, Co, Ni, Mn, Cu, Ba, Cr
3o
4nanoparticle is with γ – Fe
2o
3nanoparticle.
7. the preparation method of a kind of magnetic microcapsules phase-changing energy storage material according to claim 5, it is characterized in that, the silicon source in process (2) comprises the organosilicon sources such as the inorganic silicon sources such as water glass, potassium silicate and tetraethyl orthosilicate, methyltrimethoxy silane.
8. the preparation method of a kind of magnetic microcapsules phase-changing energy storage material according to claim 5, it is characterized in that, tensio-active agent in process (2) can be cats product or nonionogenic tenside, mainly plays the effect of the particle-stabilised Pickering emulsion of synergic nano.
9. the preparation method of a kind of magnetic microcapsules phase-changing energy storage material according to claim 5, is characterized in that, the non-aqueous solvent in process (1) and process (2) be in methane amide, acetonitrile, methyl alcohol any one.
10. the preparation method of a kind of magnetic microcapsules phase-changing energy storage material according to claim 5, it is characterized in that, in process (3), silicon gel is fixed and forms the process of magnetic ferrite/SiO 2 hybrid wall material to the magnetic ferrite nanoparticle on phase-changing energy storage material drop surface, the synthetic method adopting is interfacial polymerization, using hydrochloric acid as catalyzer, impel tetraethyl orthosilicate to form silicon-dioxide network gel at interface hydrolysis-condensation.
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