CN107603570A - Phase-changing energy storage material with photothermal deformation performance and preparation method thereof - Google Patents
Phase-changing energy storage material with photothermal deformation performance and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of phase-changing energy storage material with photothermal deformation performance and preparation method thereof, should include two types with the phase-changing energy storage material of photothermal deformation performance：Inner core and/or shell contain the phase-changing energy storage material I of optical-thermal conversion material；Composite setting phase-changing energy storage material II containing optical-thermal conversion material.Phase-changing energy storage material provided by the invention has good photothermal deformation performance, thermal energy storage can be converted solar energy into phase-changing energy storage material, can be applied to the fields such as Solar use, industrial afterheat recovery, building energy conservation, heating air-conditioner, Aero-Space and textile fabric.
Description
Technical field
The invention belongs to technical field of phase-change energy storage, and in particular to a kind of phase-change accumulation energy with photothermal deformation performance
Material and preparation method thereof.
Background technology
Today's society energy shortage problem getting worse, unmatched contradiction gradually swashs energy supply and demand over time and space
Change, while a large amount of consumption of fossil fuel cause global warming and ecological environment constantly to deteriorate, and save and develop renewable
The energy turns into current focus of concern.
Energy storage technology (Thermal Energy Storage) is that to solve energy shortage and time, spatial distribution unequal
One effective method of problem, it is the effective means for improving energy utilization rate and environmental protection.The mode of energy storage
Including mechanical energy, electromagnetic energy, chemical energy and thermal energy storage etc..After from the 1970s oil crisis, thermal energy storage technology exists
The application of industrial energy saving and new energy field is increasingly subject to pay attention to.Thermal energy storage includes sensible heat storage and latent heat (heat of transformation) storage again
Deposit.Wherein, sensible heat storage is carried out using the intrinsic thermal capacitance of material, latent heat storage, or phase-change accumulation energy, is to utilize to be claimed
For phase-change material material states of matter change (solid-liquid, solid-solid or solution-air) when, absorb or release a large amount of latent heat and carry out.
It is right because phase-change material (Phase Change Material, PCM) has the advantages of green, cheap, recyclable
Most attention of the research of its thermal storage performance by each industrially developed country.Research of the industry to phase-change material is mostly based on heat conduction
The raising of performance.Traditional phase-change material is difficult to control with volume in actual applications, and thermal conductivity factor is low, easy leakage, perishable
The shortcomings of erosion, its application in practice has been fettered significantly.Therefore, the study hotspot of current people is to carry out phase-change material
Encapsulation, and improve the thermal conductivity factor of phase-change material.Current encapsulating material has organic material and inorganic material, and organic material has poly-
Ethene, polystyrene, polyureas, polyamide, epoxy resin, Lauxite, melamine formaldehyde resin etc., inorganic material has two
Silica, expanded graphite, gypsum, expanded clay, expanded perlite, celluar concrete etc..Compared to organic material, inorganic material tool
Have that thermal conductivity factor is high, nonflammable advantage, in actual applications more advantage.
It is in recent years, right except to traditional inorganic salts, inorganic hydrated salt, in addition to organic and phase change materials are studied
The development of new phase-changing energy storage material, exist from inorganic to organic, from single component to composite, from macroscopic view to nanometer/micro- glue
The trend of encapsulated.Shaping phase-change material, the microencapsulation of phase-change material, function energy storage fluid etc. and its in building, solar energy etc.
The application in field turns into the focus of research.
Based on currently prominent energy critical shortage and problem of environmental pollution, solar energy as it is a kind of it is inexhaustible with it not
The regenerative resource of the clean environment firendly exhausted, there is huge potential value, increasingly cause the extensive concern in the world.However,
There is the shortcomings that low energy density and climate and big seasonal effect in solar radiation, make it directly using being restricted.Profit
The efficient utilization of solar energy can be realized by absorbing solar energy with optical-thermal conversion material.Using solar energy heating phase-change material, make it
Absorb energy to undergo phase transition, solar energy storage is got up, when there is no the sun, discharge heat energy further through phase transition process and carry out profit
With can solve the problems, such as that solar radiation climate and seasonal effect are big.Therefore, by optical-thermal conversion material and phase-change material phase
With reference to the technology for making solar energy be converted into heat energy and storing is undoubtedly a kind of current energy shortage of solution and wasted effective
Means, to efficiently utilizing solar energy and solving the problems, such as that energy shortage is significant.
The content of the invention
(1) technical problems to be solved
In view of this, it is a primary object of the present invention to provide phase-changing energy storage material and its system with photothermal deformation performance
Preparation Method, to solve at least one of above-described technical problem.
(2) technical scheme
To achieve the above object, the invention provides the phase-changing energy storage material with photothermal deformation performance, there should be photo-thermal
Optical-thermal conversion material is combined in phase-change material by the phase-changing energy storage material of conversion performance, includes phase-changing energy storage material I and phase transformation
Energy storage material II two types.
In the technical scheme, the phase-changing energy storage material I with photothermal deformation performance includes inner core material and outer shell material
Material：The inner core material includes phase-change material；The sheathing material includes organic sheathing material, inorganic shell material, outside metal
Shell material or composite skin material；Optical-thermal conversion material is included in the inner core material and/or sheathing material, institute turns comprising photo-thermal
The mass fraction of conversion materials is 0.01~90wt%, it is preferable that 0.01~50wt%.
In the technical scheme, the phase-changing energy storage material II with photothermal deformation performance includes optical-thermal conversion material, phase
Become material and backing material, each component content are：10~90wt% of phase-change material；10~90wt% of backing material；Photo-thermal turns
0.01~80wt% of conversion materials, it is preferable that be 0.01~50wt%.
It is described it is a further object to provide the preparation method of the phase-changing energy storage material with photothermal deformation performance
Method is as follows：
1. in the technical scheme, the phase-changing energy storage material I with photothermal deformation performance, its preparation method is as follows：
(1) preparation of inner core material：Phase-change material is mixed with emulsifying agent, obtains breast in 20~100 DEG C of conditions are emulsified
Liquid, or directly using phase-change material as inner core material.
(2) preparation of sheathing material and its encapsulation to inner core material are using any one side in following (a), (b), (c)
Method：
(a) sheathing material is organic material, using situ aggregation method, interfacial polymerization, suspension polymerization, multiple cohesion
Any one method synthesis organic shell material in legal, and inner core material obtained by step (1) is packaged.
(b) sheathing material is inorganic material, and inorganic shell material, step (1) gained are synthesized using sol-gel process
Inner core material is packaged.
(c) by organic material, inorganic material, metal material, or its composite is prepared into the container with hollow cavity,
Such as straight tube-like, bent tube form, mono-/bis-helix, spherical, ellipsoid, hemispherical, dome shape, ring-type, and profile is square
Tabular of the random geometries such as shape, sector, hexagon, circle, semicircle, ellipse etc., afterwards by inner core obtained by step (1)
Material is fitted into above-mentioned outer casing container.
(3) addition of optical-thermal conversion material, there are following three kinds of modes：
(a) optical-thermal conversion material is only added in inner core material, (a), (b), (c) are any in above-mentioned steps (2)
A kind of method realizes encapsulation of the sheathing material to inner core material, and obtaining inner core material has the phase-change accumulation energy material of photothermal deformation performance
Expect I.
(b) optical-thermal conversion material is only added in organic shell material/inorganic shell material, passed through above-mentioned steps (2)
Middle method (a)/(b) realizes encapsulation of the sheathing material to inner core material, and obtaining sheathing material has the phase transformation of photothermal deformation performance
Energy storage material I；
Optical-thermal conversion material is only added in composite skin material or coated in metal shell material surface, by above-mentioned
Method (c) realizes encapsulation of the sheathing material to inner core material in step (2), and obtaining sheathing material has the phase of photothermal deformation performance
Change energy-storage material I.
(c) optical-thermal conversion material is added in inner core material and organic shell material/inorganic shell material simultaneously, passed through
Method (a)/(b) realizes encapsulation of the sheathing material to inner core material in above-mentioned steps (2), obtains inner core material and sheathing material all
Phase-changing energy storage material I with photothermal deformation performance.
(d) optical-thermal conversion material is added in inner core material and coated in metal shell material surface simultaneously, by upper
State in step (2) (c) and realize encapsulation of the sheathing material to inner core material, obtain inner core material and sheathing material and all turn with photo-thermal
The phase-changing energy storage material I of transsexual energy.
Optical-thermal conversion material is added in inner core material and composite skin material simultaneously, passes through side in above-mentioned steps (2)
Method (c) realizes encapsulation of the sheathing material to inner core material, and obtaining inner core material and sheathing material all has photothermal deformation performance
Phase-changing energy storage material I.
2. in the technical scheme, the described phase-changing energy storage material II with photothermal deformation performance, its preparation method includes
Three kinds below：
(1) sol-gel process is used by the sol precursor of inorganic material, water, cosolvent, catalyst, photothermal deformation material
Material, and phase-change material are added in flask, and 0.5~24h is stirred at 20~100 DEG C, is put into afterwards in baking oven in 20~100 DEG C
0.5~48h of lower ageing, obtains the phase-changing energy storage material II with photothermal deformation performance.
(2) phase-change material is mixed with emulsifying agent, obtains emulsion 20~100 DEG C of conditions are emulsified；Using sol-gel
The sol precursor of inorganic material, water, cosolvent, catalyst, optical-thermal conversion material, and above-mentioned emulsion are added flask by method
In, 0.5~24h is stirred at 20~100 DEG C, 0.5~48h of ageing at 20~100 DEG C is put into baking oven afterwards, is had
The phase-changing energy storage material II of photothermal deformation performance.
(3) phase-change material is mixed with emulsifying agent, obtains emulsion 20~100 DEG C of conditions are emulsified；Photo-thermal is turned afterwards
Conversion materials, stratiform or porous material are well mixed with above-mentioned emulsion, be then placed in 15~60 DEG C of vacuum tanks and vacuumize 5~
120min, obtain the phase-changing energy storage material II with photothermal deformation performance.
The optimum condition of technical scheme provided by the present invention is as follows：
Preferably, the organic shell material of phase-changing energy storage material I described in the technical scheme includes：Polyacrylate, polyureas
Resin, polyurethane, polyvinyl alcohol, epoxy resin, phenolic resin, melamine formaldehyde resin, Lauxite, polyethylene, poly- third
One kind or at least two combination in alkene, polyvinyl chloride, polystyrene, polyamide, polycarbonate resin, acetal resin.
It is highly preferred that the typical but non-limiting examples of above-mentioned organic shell combination of materials include：Polyacrylate and poly-
The combination of carbamide resin；The combination of the combination of polyurethane and polyvinyl alcohol, epoxy resin and phenolic resin；Carbamide tree
The combination of fat and Lauxite；Polyethylene and polyacrylic combination；The combination of polyvinyl chloride and polystyrene；Polycarbonate resin and
The combination of acetal resin；The combination of polyacrylate, carbamide resin and polyurethane；Polyvinyl alcohol, epoxy resin and phenolic aldehyde tree
The combination of fat；The combination of polyethylene, polypropylene and polyvinyl chloride；Phenolic resin, melamine formaldehyde resin and Lauxite
Combination；The combination etc. of polyethylene, polypropylene, polyvinyl chloride and polystyrene.
Preferably, the technical scheme prepares the metal shell material of the phase-changing energy storage material I and included：Copper, iron, aluminium, zinc,
In gold, silver, tin, platinum, titanium, tungsten and its alloy any one or at least two combination.
It is highly preferred that the typical but non-limiting examples of above-mentioned metal shell combination of materials include：Copper and iron and its alloy
Combination；The combination of aluminum and zinc and its alloy；The combination of gold and silver and its alloy；The combination of platinum and tin and its alloy；Copper, iron and
The combination of zinc and its alloy；The combination of copper, iron and tungsten and its alloy；Combination of iron, tin and titanium and its alloy etc..
Preferably, the composite skin material that the technical scheme prepares the phase-changing energy storage material I is organic material, inorganic material
At least two combination in material, metal material.
It is highly preferred that the typical but non-limiting examples of above-mentioned composite skin material combination include：Organic material and inorganic
The combination of material；The combination of inorganic material and metal material；The combination etc. of organic material, inorganic material, metal material.
Preferably, the technical scheme is layered or porous material includes expanded graphite, graphene, graphite flake, graphite bubble
Foam, activated carbon, kaolin, bentonite, diatomite, Woelm Alumina, gypsum, expanded clay, expanded perlite, bloating shale,
It is any one in celluar concrete, zeolite, molecular sieve, metal porous skeleton, organic porous polymer, metal-organic framework
Kind or at least two combination.
It is highly preferred that above-mentioned stratiform or the typical but non-limiting examples of porous material combination include：Expanded graphite and stone
The combination of black alkene；The combination of graphite flake and graphite foam；Kaolin and bentonitic combination；The group of diatomite and expanded clay
Close；The combination of gypsum and Woelm Alumina；The combination of expanded perlite and celluar concrete；The combination of zeolite and molecular sieve；Gold
Combination of genus polyporus skeleton, organic porous polymer and metal-organic framework etc..
Preferably, inorganic material described in the technical scheme includes：Silica, titanium dioxide, zinc oxide, zirconium oxide or oxygen
Change tin in any one or at least two combination.
It is highly preferred that the typical but non-limiting examples of above-mentioned inorganic material combination include：Silica and titanium dioxide
Combination；The combination of titanium dioxide and zinc oxide；The combination of zinc oxide and zirconium oxide；The combination of zirconium oxide and tin oxide；Dioxy
The combination of SiClx, titanium dioxide and zinc oxide；Combination of zinc oxide, zirconium oxide and tin oxide etc..
Preferably, sol-gel process described in the technical scheme, which prepares the sol precursor of silica, includes positive silicic acid first
Ester, tetraethyl orthosilicate, butyl silicate, positive isopropyl silicate, tetramethoxy titanate ester, tetraethyl titanate, butyl titanate, metatitanic acid four
Isopropyl ester, zinc acetate, the methyl esters of zirconic acid four, zirconic acid tetra-ethyl ester, tetrabutyl zirconate, the isopropyl ester of zirconic acid four, the methyl esters of stannic acid four, stannic acid four
Ethyl ester, the butyl ester of stannic acid four, positive stannic acid isopropyl ester etc..
Preferably, the cosolvent of sol-gel process described in the technical scheme includes methanol, ethanol, ethylene glycol, propyl alcohol, different
In propyl alcohol, acetone, formic acid or acetic acid any one or at least two combination.
It is highly preferred that the typical but non-limiting examples of above-mentioned cosolvent combination include：The combination of methanol and ethanol；Ethanol
With the combination of ethylene glycol；The combination of propyl alcohol and isopropanol；The combination of isopropanol and acetone；The combination of isopropanol and acetone；Acetone
With the combination of formic acid；The combination of formic acid and acetic acid；The combination of methanol, ethanol and ethylene glycol；The group of ethylene glycol, propyl alcohol and isopropanol
Close；The combination etc. of isopropanol, acetone, formic acid and acetic acid.
Preferably, the catalyst of sol-gel process described in the technical scheme includes acid catalyst or base catalyst.
Preferably, acid catalyst described in the technical scheme includes hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, glacial acetic acid, citric acid
In formic acid any one or at least two combination.
It is highly preferred that the typical but non-limiting examples of above-mentioned acid catalyst combination include：The combination of hydrochloric acid and sulfuric acid；It is sub-
The combination of sulfuric acid and hydrochloric acid；The combination of glacial acetic acid and citric acid；The combination of citric acid and formic acid；Hydrochloric acid, sulfuric acid and sulfurous acid
Combination；Combination of glacial acetic acid, citric acid and formic acid etc..
Preferably, base catalyst described in the technical scheme includes any one in sodium hydroxide, potassium hydroxide or ammoniacal liquor
Or at least two combination.
The typical but non-limiting examples of the combination include：The combination of sodium hydroxide and potassium hydroxide；Potassium hydroxide and
The combination of ammoniacal liquor；Combination of sodium hydroxide, potassium hydroxide and ammoniacal liquor etc..
Preferably, organic phase-change material includes described in the technical scheme：Higher aliphatic hydrocarbon, higher fatty acids, advanced fat
One kind or at least two combination in fat alcohol, high-grade aliphatic ester.
It is highly preferred that the typical but non-limiting examples of above-mentioned organic phase-change material combination include：Higher aliphatic hydrocarbon and
The combination of higher fatty acids；The combination of higher fatty acids and high-grade aliphatic ester；The group of high-grade aliphatic ester and higher aliphatic
Close；The combination of higher aliphatic hydrocarbon, higher fatty acids and high-grade aliphatic ester；Higher aliphatic hydrocarbon, higher fatty acids, higher fatty acids
Combination of ester and higher aliphatic etc..
It is highly preferred that the halogenated alkane that the higher aliphatic hydrocarbon includes the alkane that carbon number is 10~42, carbon number is 10~42
In paraffin any one or at least two combination.The typical but non-limiting examples of the combination include：Carbon number is 10
~42 alkane and carbon number is the combination of 10~42 halogenated alkane；Carbon number is the combination of 10~42 halogenated alkane and paraffin；
Combination of halogenated alkane and paraffin that alkane that carbon number is 10~42, carbon number are 10~42 etc..
It is highly preferred that the paraffin includes atoleine and/or solid paraffin.
It is highly preferred that the higher fatty acids includes the aliphatic acid that carbon number is 6~24, now effect is optimal.
It is highly preferred that the higher aliphatic includes the alphanol that carbon number is 8~22, now effect is optimal.
It is highly preferred that the high-grade aliphatic ester is butyl stearate and/or diglycol stearate, now effect is most
It is excellent.
Preferably, hydrated salt class phase transformation material includes CaCl described in the technical scheme2·6H2O、CaBr2·6H2O、
Na2HPO4·12H2O、Na2CO3·10H2O、Na2SO4·10H2O、NaCH3COO·3H2O、Mg(NO3)2·6H2O、Ba(OH)2·
8H2O、MgCl2·6H2O、Na2S2O3·5H2O、Na3PO4·12H2O and MgSO4·7H2Any one in O or at least two
Combination.
It is highly preferred that the typical but non-limiting examples of above-mentioned hydrated salt class phase transformation combination of materials include：CaCl2·6H2O
And Na2HPO4·12H2O combination；Na2CO3·10H2O and Na2SO4·10H2O combination；Ba(OH)2·8H2O and
NaCH3COO·3H2O combination；Mg(NO3)2·6H2O, and MgCl2·6H2O combination；Na2SO3·5H2O and Na3PO4·
12H2O combination；Na3PO4·12H2O and MgSO4·7H2O combination；CaCl2·6H2O、Na2HPO4·12H2O and NaCO3·
10H2O combination；Na2SO4·10H2O、Ba(OH)2·8H2O and NaCH3COO·3H2O combination；Mg(NO3)2·6H2O、
MgCl2·6H2O and Na2SO3·5H2O combination；MgCl2·6H2O、Na2SO3·5H2O、Na3PO4·12H2O and MgSO4·
7H2O combination etc..
Preferably, the emulsifying agent of phase-change material described in the technical scheme includes styrene-maleic anhydride copolymer, benzene second
Sodium salt, OP emulsifying agents, NPE, lauryl sodium sulfate, the detergent alkylate sulphur of alkene-copolymer-maleic anhydride
Sour sodium, dodecyl sodium sulfate salt, hexadecyltrimethylammonium chloride, DTAC, dodecyl front three
Appoint in base ammonium bromide, span 20, span 40, sorbester p18, sorbester p17, sorbester p37, polysorbas20, polysorbate40, polysorbate60 or Tween 80
Anticipate a kind of or at least two combinations.
It is highly preferred that the typical but non-limiting examples of mentioned emulsifier combination include：Styrene-maleic anhydride copolymer
With the combination of the sodium salt of styrene-maleic anhydride copolymer；Styrene-maleic anhydride copolymer, OP emulsifying agents and nonyl phenol gather
The combination of oxygen vinethene；The combination of NPE, lauryl sodium sulfate and neopelex；Dodecane
The combination of base sodium sulphate, neopelex and dodecyl sodium sulfate salt；Span 20, span 40, sorbester p18 and sapn
80 combination；The combination etc. of polysorbas20, polysorbate40, polysorbate60 and Tween 80.
It is highly preferred that the emulsifying agent is styrene-maleic anhydride copolymer, lauryl sodium sulfate, cetyl three
Any one in ammonio methacrylate, DTAC, DTAB, sorbester p18 or polysorbate60
Or at least two combination.
Preferably, optical-thermal conversion material described in the technical scheme includes inorganic non-metallic, the metal in addition to carbon material
Base or its compound optical-thermal conversion material.
Preferably, optical-thermal conversion material described in the technical scheme includes：Black titanium oxide, black alumina, black oxygen
Change zinc, black zirconia, black ferroferric oxide, black oxidation cerium, nanoscale molybdenum oxide, micro-/ nano cuprous sulfide, micro-/ nano
It is any one in zinc sulphide, the metal nano optical-thermal conversion material selected from Cu, Fe, Ni, Pt, Au and/or Ag, Si based micro-nano materials
Kind or at least two combination.
It is highly preferred that the typical but non-limiting examples of above-mentioned optical-thermal conversion material combination include：Black titanium oxide and
The combination of black alumina；The combination of black oxidation zinc and black zirconia；The group of black zirconia and black ferroferric oxide
Close；The combination of black oxidation cerium and nanoscale molybdenum oxide；The combination of micro-/ nano cuprous oxide and micro-/ nano zinc sulphide；Selected from Cu,
Any at least two combination in Fe, Ni, Pt, Au and/or Ag metal nano optical-thermal conversion material；Black oxidation titanium, black
The combination of sub- titanium oxide and black alumina；The combination of black oxidation zinc, black zirconia and ferroso-ferric oxide；Black oxidation
The combination etc. of cerium, nanoscale molybdenum oxide, micro-/ nano cuprous oxide and micro-/ nano zinc sulphide.
It is highly preferred that the black titanium oxide includes TiO, TiO2、TinO2n-1(n≥4)、Ti2O3、Ti3O5、Ti2O、
TiO2- R (R=H, S, I, N, As etc.), Ti3+-TiO2-xOne kind or at least two combination in (0 ＜ x ＜ 2).
It is highly preferred that the typical but non-limiting examples of above-mentioned black titanium combination of oxides have：TiO and TiO2Combination；
TiO2And TinO2n-1The combination of (n >=4)；TinO2n-1(n >=4) and Ti2O3Combination；Ti3O5And Ti2O combination；TiO2- R (R=
H, S, I, N, As etc.) and Ti3+-TiO2-xThe combination of (0 ＜ x ＜ 2)；TiO2、TinO2n-1(n >=4) and Ti2O3Combination；Ti2O3、
Ti3O5And Ti2O combination；Ti2O、TiO2- R (R=H, S, I, N, As etc.) and Ti3+-TiO2-xThe combination of (0 ＜ x ＜ 2) etc..
Preferably, the mass percent of emulsifying agent described in the technical scheme is 0.01~10%.
Preferably, the volume ratio of phase-changing energy storage material and emulsifying agent described in the technical scheme is 1: 1~1: 30.
It is highly preferred that the volume ratio of the phase-changing energy storage material and emulsifying agent is 1: 5~1: 15.
Preferably, the mass ratio of emulsifying agent and phase-changing energy storage material described in the technical scheme is 1: 2.5~1: 100.
It is highly preferred that the mass ratio of the emulsifying agent and phase-changing energy storage material is 1: 5~1: 50.
Preferably, the sol precursor of inorganic material described in the technical scheme and phase-change material volume ratio are 1: 0.1~1:
10。
It is highly preferred that the sol precursor of the inorganic material is 1: 1~1: 9 with phase-change material volume ratio.
Preferably, the volume ratio of the sol precursor of inorganic material and water described in the technical scheme is 1: 1~1: 6.
It is highly preferred that the sol precursor of the inorganic material and the volume ratio of water are 1: 1~1: 3.
Preferably, the sol precursor of inorganic material described in the technical scheme and the cosolvent of the sol-gel process
Volume ratio is 1: 1~1: 6.
It is highly preferred that the volume ratio of the sol precursor of the inorganic material and the cosolvent of the sol-gel process is 1
: 1~1: 3.
Preferably, the volume ratio of the catalyst of sol-gel process and water described in the technical scheme is 1: 1~1: 100.
It is highly preferred that the catalyst of the sol-gel process and the volume ratio of water are 1: 5~1: 50.
In the present invention, the optical-thermal conversion material is the black powder that directly can be bought or be prepared.It is described in situ poly-
Legal, interfacial polymerization, suspension polymerization, to condense legal and sol-gel process again be existing mature technology, no longer does and has herein
Body illustrates that specific preparation process will be described in detail in embodiment.
(3) beneficial effect
Compared with prior art, the invention has the advantages that：
(1) phase-changing energy storage material provided by the invention with photothermal deformation performance can according to be actually needed preparation with
The phase-changing energy storage material of different photo-thermal conversion efficiencies, such as：Its photothermal deformation performance of the optical-thermal conversion material of use it is stronger and/or
Mass percent is bigger, and the photo-thermal conversion efficiency of prepared phase-changing energy storage material is higher.
(2) phase-changing energy storage material provided by the invention with photothermal deformation performance, can not only convert light energy into heat
It and can be stored in phase-changing energy storage material, and there is good heat conductivility.
(3) phase-changing energy storage material provided by the invention with photothermal deformation performance can be made with wide applicability
A series of standby phase-changing energy storage material (phases with photothermal deformation performance being made up of inner core and shell for encapsulating different phase-change materials
Change energy-storage material I) and/or composite setting phase-changing energy storage material (phase-changing energy storage material II) with photothermal deformation performance, can be with
Realize to phase-changing energy storage material phase transition temperature and the quantitatively regulating and controlling of latent heat of phase change.
(4) the composite setting phase-changing energy storage material (phase-changing energy storage material II) provided by the invention with photothermal deformation performance
And preparation method thereof have the advantages that cost-effective, technique is simple, product homogeneity is good.
Brief description of the drawings
The ESEM that Fig. 1 is the obtained phase-changing energy storage material I with photothermal deformation performance of the embodiment of the present invention 1 shines
Piece；
Fig. 2 is the embodiment of the present invention 1, the obtained phase-changing energy storage material I with photothermal deformation performance of embodiment 4, not added
Add the SiO of optical-thermal conversion material2Coat the phase-changing energy storage material of paraffin and the absorbent properties curve of paraffin；
Fig. 3 is the embodiment of the present invention 4, the obtained phase-changing energy storage material I with photothermal deformation performance of embodiment 5, not added
Add the SiO of optical-thermal conversion material2The phase-changing energy storage material and paraffin of cladding paraffin are in intensity 100mW/cm2AM1.5 light sources irradiation
Under temperature-time curve.
Embodiment
According to the basic conception of the present invention, there is provided a kind of phase-changing energy storage material with photothermal deformation performance, phase transformation storage
Energy material contains phase-change material and can convert light energy into the optical-thermal conversion material of heat energy, can effectively convert solar energy into
Heat energy, help to solve at present there is good photothermal deformation performance (to refer to by reflecting, absorbing or other modes are solar radiant energy
Put together, be converted into the process of high enough temp, effectively to meet the requirement of different loads) phase-changing energy storage material research
The problem of insufficient.
One side according to embodiments of the present invention, there is provided a kind of phase-changing energy storage material I with photothermal deformation performance and its
Preparation method, comprise the following steps that：
(1) phase-change material is mixed with emulsifying agent, (inner core material is designated as in the emulsified emulsion that obtains of 20~100 DEG C of conditions
I), or directly using phase-change material as inner core (being designated as inner core material II)；
(2) prepare sheathing material using any one method in following (a), (b), (c) and inner core material I is sealed
Dress：
(a) prepared using any one method in situ aggregation method, interfacial polymerization, suspension polymerization, complex coacervation
Organic shell material：The solution (being designated as shell solution A) of organic polymer system is added dropwise in inner core I and continues to stir, most
The shell obtained eventually is organic material (being designated as sheathing material A), and inner core material I is encapsulated in into inside；
(b) inorganic shell material is prepared using sol-gel process：By the sol precursor of inorganic material, water, cosolvent,
The mixed solution (being designated as shell solution B) of catalyst composition is added dropwise in inner core material I and continues to stir, and what is finally given is outer
Shell is inorganic material (being designated as sheathing material B), and inner core material I is encapsulated in into inside；
(c) macroencapsulation：The sheathing material (is designated as shell using organic material (being designated as sheathing material C), inorganic material
Material D), in metal material (being designated as sheathing material E) or three at least two compositions composites (being designated as sheathing material F),
The container with hollow cavity is made, inner core material I or inner core material II are fitted into the above-mentioned container with hollow cavity；
(3) optical-thermal conversion material is added with three kinds of forms, comprises the following steps that：
(a) optical-thermal conversion material addition is in inner core material：
Optical-thermal conversion material is dispersed in inner core material I or inner core material II, obtains inner core material I ' and inner core
Material II ', then phase-changing energy storage material I is obtained by step (2).Phase-changing energy storage material I includes inner core material I '/inner core material
II ' and sheathing material A/B/C/D/E/F, wherein inner core material I ', inner core material II ' have photothermal deformation performance；
(b) optical-thermal conversion material addition is in sheathing material：
Optical-thermal conversion material is dispersed in the shell solution A or shell solution B of step (2), obtains outer shell solution
A ' or shell solution B ', afterwards according to method (a) in step (2) or method (b) by shell solution A ' or shell solution B ' dropwise
Add in the inner core material I that step (1) obtains and continue to stir, obtain phase-changing energy storage material I.Phase-changing energy storage material I is included
Inner core material I and sheathing material A '/B ', wherein sheathing material A ', sheathing material B ' have photothermal deformation performance；
It will be prepared into after optical-thermal conversion material and above-mentioned steps (2) the sheathing material C/D/F blendings with hollow cavity
Container, obtain sheathing material C '/D '/F ', the inner core material I/ for afterwards obtaining step (1) according to method (c) in step (2)
II is fitted into sheathing material C '/D '/F ', obtains phase-changing energy storage material I.Phase-changing energy storage material I include inner core material I/II and
Sheathing material C '/D '/F ', wherein sheathing material C ', sheathing material D ', sheathing material F ' have photothermal deformation performance；
Optical-thermal conversion material is coated in step (2) sheathing material E surface, sheathing material E ' is obtained, presses afterwards
The inner core material I/II that step (1) obtains is fitted into sheathing material E ' according to method (c) in step (2), obtains phase-change accumulation energy material
Expect I.The phase-changing energy storage material includes inner core material I/II and sheathing material E ', and wherein sheathing material E ' has photothermal deformation
Energy；
(c) optical-thermal conversion material adds in inner core material and sheathing material/sheathing material surface simultaneously：
By step (a) and (b), phase-changing energy storage material I is prepared.Phase-changing energy storage material I inner core material and outer shell material
Material all has photothermal deformation performance.
Another aspect according to embodiments of the present invention, there is provided a kind of phase-changing energy storage material II with photothermal deformation performance and
Its preparation method, there are following several ways：
(1) sol-gel process is used by the sol precursor of inorganic material, water, cosolvent, catalyst, photothermal deformation material
Material, and phase-change material are added in flask, and 0.5~24h is stirred at 20~100 DEG C, is put into afterwards in baking oven in 20~100 DEG C
0.5~48h of lower ageing, obtains the phase-changing energy storage material II with photothermal deformation performance.
(2) phase-change material is mixed with emulsifying agent, obtains emulsion 20~100 DEG C of conditions are emulsified；Using sol-gel
The sol precursor of inorganic backing material, water, cosolvent, catalyst, optical-thermal conversion material, and above-mentioned emulsion are added and burnt by method
In bottle, 0.5~24h is stirred at 20~100 DEG C, 0.5~48h of ageing at 20~100 DEG C is put into baking oven afterwards, is had
There is the phase-changing energy storage material II of photothermal deformation performance.
(3) phase-change material is mixed with emulsifying agent, obtains emulsion 20~100 DEG C of conditions are emulsified；Photo-thermal is turned afterwards
Conversion materials, stratiform or porous material are well mixed with above-mentioned emulsion, be then placed in 15~60 DEG C of vacuum tanks and vacuumize 5~
120min, obtain the phase-changing energy storage material II with photothermal deformation performance.
Each specific scheme is illustrated with reference to dependent claims.It should be pointed out that following examples are only this hair
Bright simple example, does not represent or limits the scope of the invention, the scope of the present invention is defined by claims.
Embodiment 1：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to a kind of sheathing material
B ' is inlaid with the phase-changing energy storage material I of optical-thermal conversion material, and its preparation method is as follows：
(1) inner core material I preparation：10g solid paraffins (58~60 DEG C of fusing point) are weighed to be put into three-necked flask at 70 DEG C
Fusing, lauryl sodium sulfate (the Sodium Dodecyl for being 0.3wt% with 150ml mass concentrations are heated under water-bath
Sulfate, SDS) emulsified, obtain emulsion.
(2) sol-gel process prepares sheathing material B ' and inner core material I is packaged：By 20ml tetraethyl orthosilicates,
20ml absolute ethyl alcohols, 40ml distilled water and 1ml mixed in hydrochloric acid, add 0.1g Ti4O7Powder stirs 0.5-1h, then will mix molten
Liquid is added dropwise in emulsion obtained by step (1), continues 0.5~2h of stirring, it is SiO to obtain sheathing material2Inlay Ti4O7Particle
Phase-changing energy storage material I with photothermal deformation performance.
Embodiment 2：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to a kind of inner core material
Phase-changing energy storage material Is of the I ' containing optical-thermal conversion material, its preparation method are as follows：
(1) inner core material I ' preparation：10g solid paraffins (58-60 DEG C of fusing point) are weighed to be put into three-necked flask at 70 DEG C
Fusing is heated under water-bath, the SDS for being 0.3wt% with 150ml mass concentrations is emulsified, and obtains emulsion, adds 0.1g Ti4O7Powder
End, which is stirred until homogeneous, to be dispersed in emulsion.
(2) sol-gel process prepares sheathing material B and inner core material I ' is packaged：By 20ml tetraethyl orthosilicates,
20ml absolute ethyl alcohols, 40ml distilled water and 1ml mixed in hydrochloric acid stirring 0.5-1h, are then added dropwise above-mentioned emulsion by mixed solution
In, continue 0.5~2h of stirring, it is SiO to obtain sheathing material2, inner core material contain Ti4O7Particle has photothermal deformation performance
Phase-changing energy storage material I.
Embodiment 3：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to a kind of inner core material
Phase-changing energy storage material Is of the I ' and sheathing material B ' all containing optical-thermal conversion material, its preparation method are as follows：
(1) inner core material I ' preparations：10g solid paraffins (58-60 DEG C of fusing point) are weighed to be put into three-necked flask in 70 DEG C of water
The lower heating fusing of bath, the SDS for being 0.3wt% with 150ml mass concentrations are emulsified, are obtained emulsion, add 0.1g Ti4O7Powder
It is stirred until homogeneous and is dispersed in emulsion.
(2) sol-gel process prepares sheathing material B ' and inner core material I ' is packaged：By 20ml tetraethyl orthosilicates,
20ml absolute ethyl alcohols, 40ml distilled water and 1ml mixed in hydrochloric acid, add 0.1g Ti4O7Powder stirs 0.5-1h, then will mix molten
Liquid is added dropwise in above-mentioned emulsion, continues 0.5~2h of stirring, obtains inner core material and sheathing material all contains Ti4O7The tool of particle
There is the phase-changing energy storage material I of photothermal deformation performance.
Embodiment 4：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to a kind of sheathing material
B ' is inlaid with the phase-changing energy storage material I of optical-thermal conversion material, and its preparation method is same as Example 1, and difference is step
(2) " 0.1g Ti will be added in4O7Powder " is changed to " add 0.3g Ti4O7Powder ", it is SiO to finally give sheathing material2Inlay
Ti4O7The phase-changing energy storage material I with photothermal deformation performance of particle, its photothermal deformation performance higher than embodiment 1 (referring specifically to
" performance characterization " part).
Embodiment 5：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to a kind of sheathing material
B ' is inlaid with the phase-changing energy storage material I of optical-thermal conversion material, and its preparation method is same as Example 4, and difference is step
(2) optical-thermal conversion material is by " Ti in4O7Powder " is changed to " black oxidation aluminium powder ", and it is SiO to finally give sheathing material2Inlay
The phase-changing energy storage material I with photothermal deformation performance of black oxidation alumina particles.
Embodiment 6：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to a kind of sheathing material
B ' is inlaid with the phase-changing energy storage material I of optical-thermal conversion material, and its preparation method is same as Example 4, and difference is step
(2) optical-thermal conversion material is by " Ti in4O7Powder " is changed to " Cu nanometers optical-thermal conversion material ", and it is SiO to finally give sheathing material2
Inlay the phase-changing energy storage material I with photothermal deformation performance of Cu nanometer optical-thermal conversion materials.
Embodiment 7：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to a kind of sheathing material
B ' is inlaid with the phase-changing energy storage material I of optical-thermal conversion material, and its preparation method is same as Example 4, and difference is step
(2) optical-thermal conversion material is by " Ti in4O7Powder " is changed to " ZnS optical-thermal conversion materials ", and it is SiO to finally give sheathing material2Inlay
The phase-changing energy storage material I with photothermal deformation performance of ZnS optical-thermal conversion materials.
Embodiment 8：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to a kind of sheathing material
B ' is inlaid with the phase-changing energy storage material I of optical-thermal conversion material, and its preparation method is same as Example 4, and difference is step
(1) phase-change material is changed to " n-eicosane " by " solid paraffin (58-60 DEG C of fusing point) " in, and it is SiO to finally give sheathing material2Edge
Embedding Ti4O7The phase-changing energy storage material I with photothermal deformation performance of particle.
Embodiment 9：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to a kind of sheathing material
A ' is inlaid with the phase-changing energy storage material I of optical-thermal conversion material, and its preparation method is as follows：
(1) inner core material I preparation：10g solid paraffins (58-60 DEG C of fusing point) are weighed to be put into three-necked flask in 70 DEG C of water
The lower heating fusing of bath, the styrene-maleic anhydride copolymer solution for being 2.5wt% with 70ml mass concentrations are emulsified, obtained
Emulsion.
(2) situ aggregation method prepares sheathing material A ' and inner core material I is packaged：Weigh 3.0g melamines with
5ml formaldehyde and the mixing of 12ml deionized waters, stir to clarify transparent at 70 DEG C, and pH to 8 is adjusted with 10wt% triethanolamine
~9, add 0.1g Ti4O7Powder, which is stirred until homogeneous, to be disperseed in the solution, then to add in emulsion it dropwise, continue stirring 2
~3h, obtain sheathing material and inlay Ti for melamine resin4O7The phase-change accumulation energy material with photothermal deformation performance of particle
Expect I.
Embodiment 10：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to a kind of sheathing material
A ' is inlaid with the phase-changing energy storage material I of optical-thermal conversion material, and its preparation method is same as Example 9, and difference is step
(1) phase-change material is changed to " lauryl alcohol " by " solid paraffin (58-60 DEG C of fusing point) " in, and it is melamine to finally give sheathing material
Formaldehyde resin inlays Ti4O7The phase-changing energy storage material I with photothermal deformation performance of particle.
Embodiment 11：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to a kind of inner core material
Phase-changing energy storage material Is of the I ' containing optical-thermal conversion material, its preparation method are as follows：
(1) inner core material I ' preparation：10g solid paraffins (58-60 DEG C of fusing point) are weighed to be put into three-necked flask at 70 DEG C
Fusing is heated under water-bath, adds 2.5g Toluene-2,4-diisocyanates, 4 diisocyanate (TDI) and 10g hexamethylenes are sufficiently stirred, with 100ml mass
Concentration is that 3wt% OP-10 solution is emulsified, and obtains emulsion, adds 0.1g Ti4O7Powder, which is stirred until homogeneous, is dispersed in emulsion
In.
(2) interfacial polymerization prepares sheathing material A and inner core material I ' is packaged：Into step (1) emulsion slowly
0.88g ethylene glycol (EG) solution initiated polymerization is added dropwise, after being added dropwise, continues 2~3h of stirring at 70 DEG C, obtains shell
Material is that carbamide resin inlays Ti4O7The phase-changing energy storage material I with photothermal deformation performance of particle.
Embodiment 12：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to a kind of sheathing material
C ' is inlaid with the phase-changing energy storage material of optical-thermal conversion material, and its preparation method is as follows：
By 5g Ti4O7Powder, which is mixed into 500g polyvinyl alcohol and is pressed into center band, the plate-shaped container of cavity, then will
500g CaCl2·6H2O (inner core material II) is poured into cavity, is obtained sheathing material and is inlayed Ti for polyvinyl alcohol4O7The plate of particle
Shape phase-changing energy storage material I.
Embodiment 13：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to a kind of sheathing material
C ' is inlaid with the phase-changing energy storage material I of optical-thermal conversion material, and its preparation method is identical with embodiment 12, and difference is, should
Polyvinyl alcohol shell is made into center band in embodiment the tubular container of cavity, finally gives sheathing material and is inlayed for polyvinyl alcohol
Embedding Ti4O7The tube phase change energy storage material I of particle.
Embodiment 14：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to a kind of sheathing material
C ' is inlaid with the phase-changing energy storage material I of optical-thermal conversion material, and its preparation method is identical with embodiment 12, and difference is, should
Polyvinyl alcohol shell is made into center band in embodiment the spheroid of cavity, finally gives sheathing material and is inlayed for polyvinyl alcohol
Embedding Ti4O7The spherical phase-changing energy storage material I of particle.
Embodiment 15：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to a kind of sheathing material
C ' is inlaid with the phase-changing energy storage material of optical-thermal conversion material, and its preparation method is identical with embodiment 12, and difference is, the reality
Apply in example and " polyvinyl alcohol " is changed to " polystyrene ", finally give sheathing material and inlay Ti for polystyrene4O7The tabular of particle
Phase-changing energy storage material I.
Embodiment 16：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to a kind of sheathing material
E ' scribbles the phase-changing energy storage material I of optical-thermal conversion material, and its preparation method is as follows：
100g coppers are had to the tubular container of cavity into center band, by 2.5g Ti4O7With 2.5g Ti3O5It is evengranular
Tubular container outer surface is coated in, then pours into 500g solid paraffins (inner core material II) in cavity, it is copper to obtain sheathing material
And surface scribbles Ti4O7The tube phase change energy storage material I of particle.
Embodiment 17：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to a kind of colloidal sol-solidifying
Glue method prepares the composite setting phase-changing energy storage material II with photothermal deformation performance of backing material, and its preparation method is as follows：
(1) 10g solid paraffins (58-60 DEG C of fusing point) are weighed and are put into three-necked flask to heat under 70 DEG C of water-baths and are melted, are used
150ml mass concentrations are that 0.2wt% SDS is emulsified, and obtain emulsion, add 0.1g Ti4O7Powder is stirred until homogeneous scattered
In emulsion.
(2) by 20ml tetraethyl orthosilicates, 20ml absolute ethyl alcohols, 40ml deionized waters, 1ml hydrochloric acid, step (1) described breast
Liquid, 0.3g ferroferric oxide powders are added in flask, are stirred 1.5h at 60 DEG C, are then placed in baking oven and are aged at 60 DEG C
20h, finally give the phase-changing energy storage material II with photothermal deformation performance.
Embodiment 18：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to a kind of colloidal sol-solidifying
Glue method prepares the composite setting phase-changing energy storage material II with photothermal deformation performance of backing material, its preparation method and embodiment
17 is identical, and difference is in step (2) that " 0.3g ferroferric oxide powders " is changed to " 0.15g Ti4O7With 0.15g Ti5O9
Mixed-powder ", finally give the phase-changing energy storage material II with photothermal deformation performance.
Embodiment 19：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to a kind of colloidal sol-solidifying
Glue method prepares the phase-changing energy storage material II with photothermal deformation performance of backing material, and its preparation method is identical with embodiment 17,
Difference is in step (2) that " tetraethyl orthosilicate " is changed to " tetraethyl titanate ", finally gives with photothermal deformation performance
Phase-changing energy storage material II.
Embodiment 20：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to a kind of colloidal sol-solidifying
Glue method prepares the composite setting phase-changing energy storage material II with photothermal deformation performance of backing material, its preparation method and embodiment
17 is identical, and difference is in step (2) that " tetraethyl orthosilicate " is changed to " zinc acetate ", finally gives with photothermal deformation performance
Phase-changing energy storage material II.
Embodiment 21：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to a kind of colloidal sol-solidifying
Glue method prepares the composite setting phase-changing energy storage material II with photothermal deformation performance of backing material, its preparation method and embodiment
17 is identical, and difference is in step (1) that " solid paraffin (58-60 DEG C of fusing point) " is changed to " CaCl2·6H2O ", finally give
Phase-changing energy storage material II with photothermal deformation performance.
Embodiment 22：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to it is a kind of by stratiform or
Composite setting phase-changing energy storage material II with photothermal deformation performance of the porous material as backing material, its preparation method is such as
Under：
(1) 5g solid paraffins (58-60 DEG C of fusing point) are weighed and are put into three-necked flask to heat under 70 DEG C of water-baths and are melted, are used
75ml mass concentrations are that 0.2wt% SDS is emulsified, and obtain emulsion, add 0.1g Ti4O7Powder, which is stirred until homogeneous, to be dispersed in
In emulsion.
(2) 10g expanded graphites and above-mentioned emulsion are sufficiently mixed uniformly, are then placed in 25 DEG C of vacuum tanks and vacuumize
30min, obtain the phase-changing energy storage material II with photothermal deformation performance.
Embodiment 23：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to it is a kind of by stratiform or
Composite setting phase-changing energy storage material II with photothermal deformation performance of the porous material as backing material, its preparation method and reality
It is identical to apply example 22, difference is in step (2) that " expanded graphite " is changed to " celluar concrete ", finally gives and turns with photo-thermal
The phase-changing energy storage material II of transsexual energy.
Embodiment 24：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to it is a kind of by stratiform or
Composite setting phase-changing energy storage material II with photothermal deformation performance of the porous material as backing material, its preparation method is such as
Under：
(1) 5g CaCl are weighed2·6H2O is put into beaker, the OP-10 emulsifier solutions for being 10wt% with 2.5ml mass concentrations
Emulsified, obtain emulsion, add 0.1g Ti4O7Powder, which is stirred until homogeneous, to be dispersed in emulsion.
(2) 10g expanded graphites and above-mentioned emulsion are sufficiently mixed uniformly, are then placed in 25 DEG C of vacuum tanks and vacuumize
30min, obtain the phase-changing energy storage material II with photothermal deformation performance.
Embodiment 25：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to it is a kind of by stratiform or
Composite setting phase-changing energy storage material II with photothermal deformation performance of the porous material as backing material, its preparation method and reality
It is identical to apply example 24, difference is " CaCl in step (1)2·6H2O " is changed to " Na2HPO4·12H2O ", finally giving has
The phase-changing energy storage material II of photothermal deformation performance.
Embodiment 26：
Present embodiments provide a kind of phase-changing energy storage material with photothermal deformation performance, and in particular to it is a kind of by stratiform or
Composite setting phase-changing energy storage material II with photothermal deformation performance of the porous material as backing material, its preparation method and reality
It is identical to apply example 24, difference is in step (2) that " expanded graphite " is changed to " Woelm Alumina ", finally gives and turns with photo-thermal
The phase-changing energy storage material II of transsexual energy.
Performance characterization
Test parameter
1.SEM interface topographies：Morphology observation is carried out to sample using SEM (SEM).
Obtained phase-changing energy storage material (the paraffin@SiO with photothermal deformation performance in embodiment 12/0.1gTi4O7) sweep
Retouch electromicroscopic photograph as shown in Figure 1, as can be seen from the figure solid paraffin success is by SiO2Cladding, and Ti4O7Particle too it is small not by
It was observed that.
2. absorption spectrum：Using the ultraviolet-visible equipped with integrating sphere-near infrared spectrometer equipment test sample to purple
(＜ 400nm), visible (400~760nm) and near-infrared (760~2500) light absorption outside.
From accompanying drawing 2 it can be seen that the obtained phase-changing energy storage material pair with photothermal deformation performance of embodiment 1, embodiment 4
The absorbent properties of light are far superior to paraffin refined wax and shell is SiO2Paraffin microcapsule, and optical-thermal conversion material addition increase,
Gained sample increases the absorbent properties of light.
3. temperature-time curve：Solid powder sample to be tested is pressed into thin rounded flakes, with intensity 100mW/cm2's
AM1.5 light sources are irradiated, and record temperature changes over time.
From accompanying drawing 3 it can be seen that the obtained phase-changing energy storage material with photothermal deformation performance of embodiment 4, embodiment 5 exists
Intensity 100mW/m2The lower temperature rate-of-rise of AM1.5 light sources irradiation much larger than paraffin refined wax and shell be SiO2Paraffin microcapsule；
And optical-thermal conversion material is Ti4O7Phase-changing energy storage material heating rate be more than optical-thermal conversion material for black oxidation aluminium powder
Phase-changing energy storage material, therefore, optical-thermal conversion material Ti4O7Phase-changing energy storage material photo-thermal conversion efficiency it is higher；The opposing party
Face, paraffin refined wax and shell are SiO2The heating curve of paraffin microcapsule to can be seen that shell be SiO2Paraffin microcapsule heating
Speed is significantly greater than paraffin refined wax, and it will be less than paraffin refined wax for the absorbability of light, have made from embodiment 4, embodiment 5
The phase-changing energy storage material heating rate highest of photothermal deformation performance, thus, it can be known that SiO2Shell and optical-thermal conversion material improve
The thermal conductivity of microcapsules；Can be seen that embodiment 4, embodiment 5 are obtained from the temperature lowering curve of several samples has photothermal deformation
The phase-changing energy storage material rate of temperature fall of performance is maximum, shell SiO2Paraffin microcapsule take second place, paraffin refined wax is minimum, therefore enters one
Step proves SiO2Shell and optical-thermal conversion material substantially increase the heat conductivility of microcapsules.
Particular embodiments described above, the purpose of the present invention, technical scheme and beneficial effect are carried out further in detail
Describe in detail bright, it should be understood that the foregoing is only the present invention specific embodiment, be not intended to limit the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements done etc., the protection of the present invention should be included in
Within the scope of.
Claims (10)
1. a kind of phase-changing energy storage material with photothermal deformation performance, it is characterised in that the phase-changing energy storage material contains phase transformation material
Material and the optical-thermal conversion material that can convert light energy into heat energy, the optical-thermal conversion material are black metal oxide particle, received
Any one in meter level inorganic non-metallic, nano level metal, micro-/ nano metal sulfide or at least two mixture or compound
Material.
2. phase-changing energy storage material according to claim 1, it is characterised in that the phase-change material is organic phase-change material
Or hydrated salt class phase transformation material.
3. phase-changing energy storage material according to claim 1, it is characterised in that the phase-changing energy storage material include inner core material with
And the sheathing material of cladding inner core material, wherein：
The inner core material includes phase-change material；
The sheathing material and/or inner core material include optical-thermal conversion material, and the mass fraction of the optical-thermal conversion material is 0.01
~90wt%, it is preferable that be 0.01-50wt%；
The sheathing material is included in organic sheathing material, inorganic shell material, metal shell material and composite skin material
It is at least one.
4. phase-changing energy storage material according to claim 1, it is characterised in that the phase-changing energy storage material is to include photothermal deformation
The composite setting phase-changing energy storage material of material, phase-change material and backing material；Using the quality of the phase-changing energy storage material as total amount
Meter, the mass content of the phase-changing energy storage material each component are：
Phase-change material：10~90wt%；
Backing material：10~90wt%；
Optical-thermal conversion material：0.01~80wt%, preferably 0.01-50wt%.
5. phase-changing energy storage material according to claim 4, it is characterised in that the backing material includes following any one
Kind：
The inorganic material prepared using sol-gel process；
Using stratiform or the finished product raw material of porous material.
6. the phase-changing energy storage material according to claim 3 or 5, it is characterised in that the inorganic material include silica,
Any one in titanium dioxide, zinc oxide, zirconium oxide or tin oxide.
7. a kind of preparation method of phase-changing energy storage material, comprises the following steps：
(1) inner core material is prepared；
(2) sheathing material of encapsulation inner core material is prepared；
Wherein, when preparing inner core material and/or sheathing material, optical-thermal conversion material is added；
The optical-thermal conversion material is black metal oxide particle, nano grade inorganic is nonmetallic, nano level metal, micro-/ nano
Any one in metal sulfide or at least two mixture or composite.
8. the preparation method of phase-changing energy storage material according to claim 7, it is characterised in that：
Prepare inner core material and use any one following mode：
(1a) is mixed using phase-change material with emulsifying agent, is emulsified obtained emulsion as inner core material；
(1b) is directly using phase-change material as inner core material；
The sheathing material is made using any one following method and inner core material is packaged：
(2a), which uses any one method in situ aggregation method, interfacial polymerization, suspension polymerization or complex coacervation to prepare, to be had
Machine sheathing material, and inner core material is encapsulated in inside；
(2b) prepares inorganic shell material using sol-gel process, and inner core material is encapsulated in into inside；
(2c) is made with hollow cavity with organic shell material/inorganic shell material/metal shell material/composite skin material
Container, and inner core material is encapsulated in inside.
Addition optical-thermal conversion material uses any one following mode：
(2d) optical-thermal conversion material is added in inner core material；
(2e) optical-thermal conversion material is added in organic shell material, inorganic shell material or composite skin material；
(2f) optical-thermal conversion material is coated in metal shell material surface；
(2g) optical-thermal conversion material is added in inner core material and organic/inorganic/composite skin material simultaneously, or is added simultaneously
Inner core material and coated in metal shell material surface.
9. a kind of preparation method of phase-changing energy storage material, including following three kinds of modes：
(1) inorganic backing material is prepared using sol-gel process, and it is directly mixing cured with optical-thermal conversion material, phase-change material；
(2) phase-change material mixed with emulsifying agent, emulsify emulsion is made, inorganic fid is prepared using sol-gel process afterwards
Material, and it is mixing cured with optical-thermal conversion material and above-mentioned emulsion；
(3) phase-change material mixed with emulsifying agent, emulsify emulsion is made, afterwards by optical-thermal conversion material, stratiform or porous material
It is well mixed with above-mentioned emulsion, is then placed in vacuum tank and vacuumizes；
Wherein, the optical-thermal conversion material be nonmetallic black metal oxide particle, nano grade inorganic, nano level metal, it is micro-/
Any one in nano metal sulphide or at least two mixture or composite.
10. the preparation method of phase-changing energy storage material according to claim 8 or claim 9, it is characterised in that the sol-gel
The sol precursor that method is used includes methyl silicate, tetraethyl orthosilicate, butyl silicate, positive isopropyl silicate, metatitanic acid tetramethyl
Ester, tetraethyl titanate, butyl titanate, tetraisopropyl titanate, zinc acetate, the methyl esters of zirconic acid four, zirconic acid tetra-ethyl ester, the fourth of zirconic acid four
At least one of ester, the isopropyl ester of zirconic acid four, the methyl esters of stannic acid four, stannic acid tetra-ethyl ester, the butyl ester of stannic acid four or positive stannic acid isopropyl ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710837917.0A CN107603570A (en) | 2017-09-15 | 2017-09-15 | Phase-changing energy storage material with photothermal deformation performance and preparation method thereof |
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| CN108517199A (en) * | 2018-05-15 | 2018-09-11 | 王成 | A kind of preparation method of compound photothermal conversion phase-change material |
| CN109135683A (en) * | 2018-08-22 | 2019-01-04 | 北京科技大学 | A method of preparing fused salt-ceramics phase-change heat-storage material |
| CN109705820A (en) * | 2019-01-23 | 2019-05-03 | 上海理工大学 | Compound thermal chemical heat storage material and preparation method |
| CN109735310A (en) * | 2019-01-16 | 2019-05-10 | 南京航空航天大学 | A kind of full spectrum light hot-cast socket heat accumulating and preparation method thereof |
| CN110157386A (en) * | 2019-06-12 | 2019-08-23 | 北京科技大学 | A kind of preparation method of the metallic silver shell composite phase-change capsule with high thermal conductivity |
| CN110270283A (en) * | 2019-07-13 | 2019-09-24 | 武汉中科先进技术研究院有限公司 | A kind of preparation method of photothermal conversion microcapsules of storing energy through phase change |
| CN110408365A (en) * | 2019-07-10 | 2019-11-05 | 浙江工业大学 | A kind of preparation method of phase-change microcapsule |
| CN110437805A (en) * | 2019-07-25 | 2019-11-12 | 北京科技大学 | A kind of preparation method of nanoparticle doped type photothermal conversion composite phase-change material |
| CN111559759A (en) * | 2020-05-19 | 2020-08-21 | 东南大学 | Multifunctional composite nano particle for enhancing laser desorption ionization and preparation method thereof |
| CN112090378A (en) * | 2020-07-29 | 2020-12-18 | 淮阴工学院 | Preparation method of photo-thermal conversion enhanced microcapsule phase change material |
| CN112251197A (en) * | 2020-10-23 | 2021-01-22 | 上海驰纺材料科技有限公司 | Phase-change microcapsule with full-band photo-thermal conversion function and preparation method thereof |
| CN112480872A (en) * | 2020-11-27 | 2021-03-12 | 南京航空航天大学 | Positive-displacement integrated composite phase-change heat storage material and preparation method thereof |
| CN112521158A (en) * | 2020-11-27 | 2021-03-19 | 南京航空航天大学 | Bone-like hierarchical pore ceramic-based photothermal storage material and preparation method thereof |
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| CN114703693A (en) * | 2022-03-08 | 2022-07-05 | 西北工业大学 | Preparation method of photo-thermal rewritable energy storage nano paper |
| CN115432762A (en) * | 2022-09-01 | 2022-12-06 | 宿州学院 | SSG system based on quaternary composite material |
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| CN108517199A (en) * | 2018-05-15 | 2018-09-11 | 王成 | A kind of preparation method of compound photothermal conversion phase-change material |
| CN109135683B (en) * | 2018-08-22 | 2021-01-12 | 北京科技大学 | Method for preparing molten salt-ceramic phase change heat storage material |
| CN109135683A (en) * | 2018-08-22 | 2019-01-04 | 北京科技大学 | A method of preparing fused salt-ceramics phase-change heat-storage material |
| CN109735310A (en) * | 2019-01-16 | 2019-05-10 | 南京航空航天大学 | A kind of full spectrum light hot-cast socket heat accumulating and preparation method thereof |
| CN109705820A (en) * | 2019-01-23 | 2019-05-03 | 上海理工大学 | Compound thermal chemical heat storage material and preparation method |
| CN110157386A (en) * | 2019-06-12 | 2019-08-23 | 北京科技大学 | A kind of preparation method of the metallic silver shell composite phase-change capsule with high thermal conductivity |
| CN110408365A (en) * | 2019-07-10 | 2019-11-05 | 浙江工业大学 | A kind of preparation method of phase-change microcapsule |
| CN110270283B (en) * | 2019-07-13 | 2021-08-10 | 武汉中科先进技术研究院有限公司 | Preparation method of photo-thermal conversion phase change energy storage microcapsule |
| CN110270283A (en) * | 2019-07-13 | 2019-09-24 | 武汉中科先进技术研究院有限公司 | A kind of preparation method of photothermal conversion microcapsules of storing energy through phase change |
| CN110437805A (en) * | 2019-07-25 | 2019-11-12 | 北京科技大学 | A kind of preparation method of nanoparticle doped type photothermal conversion composite phase-change material |
| CN111559759A (en) * | 2020-05-19 | 2020-08-21 | 东南大学 | Multifunctional composite nano particle for enhancing laser desorption ionization and preparation method thereof |
| CN112090378A (en) * | 2020-07-29 | 2020-12-18 | 淮阴工学院 | Preparation method of photo-thermal conversion enhanced microcapsule phase change material |
| CN112251197A (en) * | 2020-10-23 | 2021-01-22 | 上海驰纺材料科技有限公司 | Phase-change microcapsule with full-band photo-thermal conversion function and preparation method thereof |
| CN112480872A (en) * | 2020-11-27 | 2021-03-12 | 南京航空航天大学 | Positive-displacement integrated composite phase-change heat storage material and preparation method thereof |
| CN112521158A (en) * | 2020-11-27 | 2021-03-19 | 南京航空航天大学 | Bone-like hierarchical pore ceramic-based photothermal storage material and preparation method thereof |
| CN112521158B (en) * | 2020-11-27 | 2021-12-21 | 南京航空航天大学 | Bone-like hierarchical pore ceramic-based photothermal storage material and preparation method thereof |
| CN113667269A (en) * | 2021-09-15 | 2021-11-19 | 中国科学院兰州化学物理研究所 | Light response intelligent friction composite material with three-dimensional network sandwich structure and preparation method and application thereof |
| CN114703693A (en) * | 2022-03-08 | 2022-07-05 | 西北工业大学 | Preparation method of photo-thermal rewritable energy storage nano paper |
| CN114703693B (en) * | 2022-03-08 | 2023-03-10 | 西北工业大学 | Preparation method of photo-thermal rewritable energy storage nano paper |
| US20240018404A1 (en) * | 2022-07-13 | 2024-01-18 | King Fahd University Of Petroleum And Minerals | Doped phase change material and method of preparation thereof |
| CN115432762A (en) * | 2022-09-01 | 2022-12-06 | 宿州学院 | SSG system based on quaternary composite material |
| CN115432762B (en) * | 2022-09-01 | 2024-05-03 | 宿州学院 | SSG system based on quaternary composite material |
| CN115491074A (en) * | 2022-09-26 | 2022-12-20 | 中国海洋大学 | Cuprous sulfide quantum dot-loaded reduced graphene oxide nano particle and composite coating |
| CN115491074B (en) * | 2022-09-26 | 2023-12-05 | 中国海洋大学 | Cuprous sulfide quantum dot loaded reduced graphene oxide nanoparticle and composite coating |
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