CN105602167A - Composite film with photothermal conversion and heat energy storage/release functions and preparation method thereof - Google Patents
Composite film with photothermal conversion and heat energy storage/release functions and preparation method thereof Download PDFInfo
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- CN105602167A CN105602167A CN201610065137.4A CN201610065137A CN105602167A CN 105602167 A CN105602167 A CN 105602167A CN 201610065137 A CN201610065137 A CN 201610065137A CN 105602167 A CN105602167 A CN 105602167A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
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- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
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Abstract
The invention discloses a composite film with photothermal conversion and heat energy storage/release functions and a preparation method thereof. The composite film is prepared by carrying out self-assembly on a main body material polyvinyl alcohol by using a trace amount of gold nanoparticles as a photothermal conversion material and adding an organic phase-change material. According to the composite film with photothermal conversion and heat energy storage/release functions, by utilizing the surface plasma resonance effect of the filled nano gold and the heat storage/heat release characteristics of the phase-change material, the composite phase-change film has the functions of photothermal conversion and heat energy storage/release, and effectively solves the problem of leakage in the organic phase-change material. The preparation method is simple to operate and accessible in raw materials, can be prepared in common chemical laboratories, and thus, can be easily popularized.
Description
One, technical field
The present invention relates to a kind of thin-film material and preparation method thereof, specifically one has photo-thermal conversion and thermal energy storage concurrently and releasesLaminated film of playing function and preparation method thereof.
Two, background technology
In society production process, the energy, as the important support of modern economy, is that human society is depended on for existence and developmentImportant foundation occupies consequence in the process that promotes socio-economic development. Recently the economic development of country and each department,Level has been subject to the restriction of energy supply and safe-guard system, how to realize permanently effective energy sustainable development, is alwaysThe important component part of country's future development program strategy. But, along with a large amount of uses to energy resources, cause energy-consumingThe sustainable growth of total amount, consequent environmental pollution and the energy resource consumption problem causing become increasingly conspicuous, and the suffered money of energy resource systemFrom strength to strength, the problem of resources and environment has become the Tough questions that concerns social development in the constraint of source and environment. As generationMost populous country in boundary is production of energy and country of consumption in the world simultaneously, the energy supply of Science in Future in China and needs of problemsStill very outstanding: the utilization of the energy and seriously polluted, energy resources occupation rate is low and outstanding per capita energy reserves and structureProblem, these problems are all urgently to be resolved hurrily.
In all energy types of service, heat energy is most popular. In the use procedure of the various energy, majority is allMeet people's demand by the approach of thermal power transfer. But in the process using at the energy, wherein 58% the energy was usingIn journey, all dissipated in vain with hot form, lowered energy utilization rate. In addition, the energy utilize life period matching problem,Be not all to utilize the energy all the time, but the energy need to be collected in advance, in the time of needs, utilize.So, how to realize heat accumulation, rationally also efficiently utilize heat energy, be to solve heat energy to supply with problem and the low effective way of energy rate utilization rateFootpath. Face outstanding energy shortage problem, how effectively to use inexhaustible, nexhaustible clean energy resource---solar energy,Be one of the effective means that solves energy problem, and simultaneously due to the environmental protection of solar energy, clean and renewable, avoided ringThe pollution in border. Therefore, current, to environmental protection increasingly stringent in the situation that, the utilization of solar energy has the meaning of particular importance.Solar energy functional material has good application prospect, and outstanding optical-thermal conversion material will be conducive to realize effective utilization of the energyWith the protection to environment.
Utilize phase-change material to absorb in phase transition process and the characteristic of storage power, in photo-thermal transfer process, realize energyStoring and utilize, by changing kind and the content of phase-change material, carrying out the regulation and control of energy simultaneously, is a kind of development jointEffective research means of energy technology. Phase-change accumulation energy has that energy storage density is high, energy storage easy control of temperature and the advantage such as range of choice is wide,Phase-changing energy storage material is mainly divided into organic phase change material and inorganic phase-changing material. Inorganic phase-changing material thermal conductivity factor is high, unit volumeHeat storage capacity is strong, with low cost to be easy to obtain, heat of solution is higher, but there will be cold-peace to be separated, to separate out phenomenon, bodyLong-pending variation is larger. Organic phase change material Applicable temperature scope is wide, stable chemical performance, safety non-toxic are corrosion-free, with traditional structureThe compatibility of material is better, while solidifying, without obvious surfusion, recycles performance strong, but heat conductivility is low when solid-state, singlePosition volume heat storage capacity is poor, there will be leak of liquid when solid-liquid phase change, and thermal conductivity factor is low, these drawbacks limit its manyThe application of individual research aspect. Therefore in order to address these problems, researcher has developed shaping phase-change material gradually, and this is oneDetermine to have improved in degree the performance of phase-changing energy storage material, improved its thermal stability and heat conductivility, but traditional setting phaseBecome the problem that material still exists the aspects such as encapsulation, leakage in the process using, the study on the modification that need to shape to it.
Three, summary of the invention
The object of the invention is in order to overcome the shortcoming such as low, the easy leakage of organic phase change material photo-thermal conversion efficiency, encapsulation requirement height,A kind of laminated film that has photo-thermal conversion and thermal energy storage and release function concurrently and preparation method thereof is provided, passes through filled nanometerThe surface plasmon resonance effect of gold and the heat accumulation exothermic character of phase-change material, make composite phase-change film have photo-thermal conversion and heat concurrentlyCan store and the function discharging, realize the effective encapsulation to organic phase change material simultaneously, obtain and had photo-thermal conversion and heat energy concurrentlyLaminated film and the preparation method of storage and release function.
Technical solution problem of the present invention adopts following technical scheme:
The present invention has the laminated film of photo-thermal conversion and thermal energy storage and release function concurrently, it is characterized in that: described laminated film isTaking polyvinyl alcohol as material of main part, be filled with the organic phase change material for heat accumulation heat release ability is provided and photo-thermal transfer capability is providedOptical-thermal conversion material;
In described laminated film, organic phase change material quality accounts for 5-40%, and surplus is polyvinyl alcohol and optical-thermal conversion material;
Described optical-thermal conversion material is nanogold particle.
Wherein, described polyvinyl alcohol is PVA1750 ± 50; Described organic phase change material is fatty alcohol.
Preferably, described fatty alcohol is polyethylene glycol, and described polyethylene glycol is preferably PEG1000, PEG2000 or PEG6000.
The preparation method of the above-mentioned laminated film that has photo-thermal conversion and thermal energy storage and release function concurrently, its feature is to comprise followingStep:
The preparation of a, nanogold particle
In 50mL ultra-pure water, adding 1.25mL concentration is the aqueous solution of chloraurate of 0.1M, is heated with stirring to boiling, then addsThe trisodium citrate aqueous solution that 750 μ L mass concentrations are 10%, continues return stirring 0.5 hour at 95 DEG C, treats that solution becomesClaret, stops stirring, and is cooled to room temperature, obtains nanogold particle solution, is kept in 4 DEG C of refrigerators for subsequent use;
The preparation of b, polyvinyl alcohol water solution
The polyvinyl alcohol that 5g was dried joins in 95g ultra-pure water, and lower swelling 4 hours of room temperature (approximately 25 DEG C), then existsReflux heating 4 hours at 95 DEG C, the polyvinyl alcohol water solution that the mass fraction that obtains colourless transparent and homogeneous is 5%;
C, have the preparation of the laminated film of photo-thermal conversion and thermal energy storage and release function concurrently
Get polyvinyl alcohol water solution prepared by 20g step b, under stirring, be heated to 45 DEG C and keep 0.5 hour, then according to orderIn mark product, the quality proportioning of organic phase change material and polyvinyl alcohol adds a certain amount of organic phase-change in polyvinyl alcohol water solutionMaterial water solution, stirred after 2 hours, then added nanogold particle solution prepared by step a and mix, and obtained organic phase-changeMaterial-polyvinyl alcohol-nm of gold composite solution;
Finally measure organic phase change material-polyvinyl alcohol-nm of gold composite solution and be placed in arbitrary shape mould, in 50 DEG C of baking ovensDry 12 hours, then drying at room temperature 72 hours, solvent evaporated, must have photo-thermal conversion and thermal energy storage and release function concurrentlyLaminated film.
Laminated film of the present invention is taking polyvinyl alcohol as material of main part, has the gold nano of surface plasma resonance function with traceParticle is optical-thermal conversion material, adds that the organic phase change material self assembly with heat accumulation heat release ability forms. Of the present invention compoundIn film, the nanogold particle that is 30nm left and right due to diameter has good absorption near 530nm, therefore selects and nanometerThe 532nm green laser that gold grain surface plasma resonance (LSPR) wavelength matches, can induced nano gold as light sourceParticle produces fuel factor, realizes photo-thermal transfer process, and organic phase change material can absorb heat in the process of photo-thermal conversion simultaneouslyCarry out storage and the release of energy. And polyvinyl alcohol film forming can encapsulate organic phase change material, thereby prevent wellThe leakage of machine phase-change material and aging. Therefore, the present invention has prepared one simultaneously and has had photo-thermal conversion and thermal energy storage and release concurrentlyThe laminated film of function, for the efficient utilization of heat energy provides good material system.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the present invention mixes nanogold particle with organic phase change material after, utilize polyvinyl alcohol film forming, have photo-thermal concurrently thereby obtainThe laminated film of conversion and thermal energy storage and release function. And according to D.KeithRoper scientific research group in prior art 2007Report on year " J.Phys.Chem.C ", they adopt merely gold nanosphere to carry out photo-thermal conversion, and photo-thermal conversion efficiency is low, temperatureDegree excursion is less.
2, the polyethylene glycol that the present invention can have a different carbon chain lengths by use is used as phase-change material to obtain different phase alternating temperaturesSpend interval nm of gold composite phase change energy-storing thin-film material. Along with polyethylene glycol number-average molecular weight is increased to 6000 from 1000, byThere is different enthalpy of phase change and phase transition temperature in different polyethylene glycol, the heat energy power of storing of composite film material and storage exothermic temperatureAlso change thereupon, can meet the needs that under each service condition, different temperatures required.
3, compare with traditional organic phase change material, the present invention has the laminated film of photo-thermal conversion and thermal energy storage and release function concurrentlyAlso there is good toughness and intensity, can obtain having difformity and thickness by different moulds and different amount of solutionFilm, can also be cut into arbitrarily different shapes, is applicable in different applied environments and device design.
4, the present invention is simple to operate, and raw material is easy to get, and all can make at general chemical laboratory, is easy to promote, and is convenient to multi-fieldIn application.
Four, brief description of the drawings
Fig. 1 is different gold content organic phase change material-polyvinyl alcohol-nm of gold composite solution correspondences prepared by the embodiment of the present invention 1Optical photograph, the amount of wherein adding gold solution is followed successively by 0mL, 2mL, 6mL, 10mL from left to right.
Fig. 2 is different gold content organic phase change material-polyvinyl alcohol-nm of gold composite solution correspondences prepared by the embodiment of the present invention 1Uv absorption spectra, the amount of wherein adding gold solution is followed successively by 0mL, 2mL, 6mL, 10mL from bottom to up.
Fig. 3 is the optical photograph of the different gold content laminated films prepared of the embodiment of the present invention 1, the amount of wherein adding gold solutionBe followed successively by from left to right 0mL, 2mL, 6mL, 10mL.
Fig. 4 is the optical photograph that prevents leak case of the laminated film prepared of the embodiment of the present invention 2, as can be seen from the figure works asTemperature is during higher than the phase transition temperature of organic phase change material, and composite pattern is without any variation, but original phase-change material changes intoLiquid.
Fig. 5 is differential scanning calorimetry (DSC) resolution chart of the composite film material prepared of the embodiment of the present invention 2, can from figureTo find out, the laminated film of the present embodiment has good heat absorption exothermicity, has higher value.
Fig. 6 is that laminated film prepared by the embodiment of the present invention 2 uses 532nm laser to rise under different laser power densities irradiatesThe Time-temperature figure of temperature.
Five, detailed description of the invention
Below in conjunction with specific embodiment, technical scheme of the present invention is described further.
Embodiment 1
In the present embodiment, having the laminated film of photo-thermal conversion and thermal energy storage and release function concurrently, is taking polyvinyl alcohol as main film bodyMaterial, taking nanogold particle as optical-thermal conversion material, self assembly is filled organic phase change material and is evaporated that aqueous solvent obtains, itsThe solid content of middle organic phase change material PEG2000 is 5%.
The laminated film that has photo-thermal conversion and thermal energy storage and release function in the present embodiment concurrently prepares by the following method:
The preparation of a, nanogold particle
In 50mL ultra-pure water, adding 1.25mL concentration is the aqueous solution of chloraurate of 0.1M, is heated with stirring to boiling, then addsThe trisodium citrate aqueous solution that 750 μ L mass concentrations are 10%, continues return stirring 0.5 hour at 95 DEG C, stops stirring,Be cooled to room temperature, obtain nanogold particle solution, be kept in 4 DEG C of refrigerators for subsequent use;
The preparation of b, polyvinyl alcohol water solution
The polyvinyl alcohol that 5g was dried joins in 95g ultra-pure water, under room temperature swelling 4 hours, then at 95 DEG C, refluxesHeat the polyvinyl alcohol water solution that the mass fraction that obtains colourless transparent and homogeneous is 5% 4 hours;
C, have the preparation of the laminated film of photo-thermal conversion and thermal energy storage and release function concurrently
Get polyvinyl alcohol water solution prepared by 20g step b, under stirring, be heated to 45 DEG C and keep 0.5 hour, then to poly-secondIn the enol aqueous solution, adding 2.63mL mass fraction is 2% the polyethylene glycol PEG2000 aqueous solution, stirs after 2 hours, then dividesDo not add nanogold particle solution prepared by 0mL, 2mL, 6mL, 10mL step a and mix, obtaining organic phase change material-polyvinyl alcohol-nm of gold composite solution;
Finally measure respectively 4mL organic phase change material-polyvinyl alcohol-nm of gold composite solution and be placed in arbitrary shape mould, inIn 50 DEG C of baking ovens dry 12 hours, then drying at room temperature 72 hours, solvent evaporated, must have concurrently photo-thermal conversion and thermal energy storage andThe laminated film of release function.
Fig. 1 is optics corresponding to different gold content organic phase change material-polyvinyl alcohol-nm of gold composite solution prepared by the present embodimentPhoto, by Tu Ke get, the composite solution transparent and homogeneous of gained, in the time that the addition of gold nano solution is increased to 10mL from 0mL,Composite solution is by the colourless claret that gradually becomes.
Fig. 2 is the UV absorption of different gold content organic phase change material-polyvinyl alcohol-nm of gold composite solutions of preparing of the present embodimentFigure, by Tu Ke get, in the time that golden nanometer particle content increases, composite solution strengthens gradually in the trap at wavelength 530nm place, inhalesReceipts degree is followed successively by 0,0.417,1.219,2.031.
Fig. 3 be the different gold content laminated films prepared of the present embodiment optical photograph (film is placed on blank sheet of paper, thin for finding outThe transparency of film, prints and has pcm word body on blank sheet of paper), from photo, can find out that film color is even, and have goodTransparency.
Embodiment 2
The preparation method of the present embodiment laminated film is with embodiment 1, and the amount of the nanogold particle solution adding is 10mL, differenceBe that added organic phase change material is that 3.33mL mass fraction is 20% the PEG2000 aqueous solution, the film making thusThe solid content of middle PEG2000 is 40%.
After tested, embodiment 1 and embodiment 2 be during taking PEG2000 as organic phase change material, the phase transition temperature of gained laminated filmBe about 51～55 DEG C.
Fig. 4 is the optical photograph that laminated film prepared by the present embodiment prevents leak case, and upper figure is original PEG2000 material,Figure below is composite phase-change energy storage material (PEG/PVA/Au) prepared by the present embodiment, as can be seen from the figure, when hot platform temperature byWhile being gradually elevated to 80 DEG C from 20 DEG C, original PEG2000 material occurs to melt and reveal gradually, changes liquid into, and this enforcementThe prepared composite phase-change energy storage material of example maintains the original state always, and any variation does not occur, and can keep good structural stability.
Fig. 5 is the DSC figure of polyethylene glycol PEG2000/ polyvinyl alcohol/nm of gold composite phase-change thin-film material of preparing of the present embodiment.As can be seen from the figure, the fusing point of laminated film prepared by the present embodiment is 53.92 DEG C, and freezing point is 34.18 DEG C, has goodHeat accumulation exothermicity, value is very high.
Fig. 6 is the intensification figure of the laminated film prepared of the present embodiment under 532nm Ear Mucosa Treated by He Ne Laser Irradiation, and laser power density is respectively 1.94w/cm2、4.25w/cm2、6.58w/cm2And 7.36w/cm2. As can be seen from the figure, Ear Mucosa Treated by He Ne Laser Irradiation power is higher, and film entersRow photo-thermal conversion and the temperature that raises is higher. Visible laminated film can be realized good photo-thermal and transfer to use, and can near transformation temperatureEffectively carry out storage and the release of heat energy, show intensification platform and cooling platform. Hence one can see that, prepared laminated filmHave photo-thermal conversion and thermal energy storage and release function concurrently.
Embodiment 3
The present embodiment preparation method is with embodiment 1, and the amount of the nanogold particle solution adding is 10mL, and different is organic phaseChange material is PEG1000, and it is that 2% PEG1000 aqueous solution 2.63mL, mass fraction are that addition is respectively mass fraction2% PEG1000 aqueous solution 5.55mL, PEG1000 aqueous solution 1.25mL, the mass fraction that mass fraction is 20% are 20%PEG1000 aqueous solution 3.33mL, in gained composite phase-change material, the solid content of PEG1000 is respectively 5%, 10%, 20%And 40%. After tested, the present embodiment is during taking PEG1000 as organic phase change material, and the phase transition temperature of gained laminated film is about35～40℃。
Embodiment 4
The present embodiment preparation method is with embodiment 1, and the amount of the nanogold particle solution adding is 10mL, and different is organic phaseChange material is PEG6000, and it is that 2% PEG6000 aqueous solution 2.63mL, mass fraction are that addition is respectively mass fraction2% PEG6000 aqueous solution 5.55mL, PEG6000 aqueous solution 1.25mL, the mass fraction that mass fraction is 20% are 20%PEG6000 aqueous solution 3.33mL, in gained composite phase-change material, the solid content of PEG6000 is respectively 5%, 10%, 20%And 40%. After tested, the present embodiment is during taking PEG6000 as organic phase change material, and the phase transition temperature of gained laminated film is about60～65℃。
Claims (4)
1. a laminated film that has photo-thermal conversion and thermal energy storage and release function concurrently, is characterized in that: described laminated film isTaking polyvinyl alcohol as material of main part, be filled with organic phase change material for heat accumulation heat release ability is provided and for photo-thermal conversion is providedThe optical-thermal conversion material of ability;
In described laminated film, organic phase change material quality accounts for 5-40%, and surplus is polyvinyl alcohol and optical-thermal conversion material;
Described optical-thermal conversion material is nanogold particle.
2. the laminated film that has photo-thermal conversion and thermal energy storage and release function concurrently according to claim 1, is characterized in that:Described polyvinyl alcohol is PVA1750 ± 50; Described organic phase change material is fatty alcohol.
3. the laminated film that has photo-thermal conversion and thermal energy storage and release function concurrently according to claim 2, is characterized in that:Described fatty alcohol is polyethylene glycol.
4. the laminated film that has photo-thermal conversion and thermal energy storage and release function concurrently as described in claim 1,2 or 3Preparation method, is characterized in that comprising the following steps:
The preparation of a, nanogold particle
In 50mL ultra-pure water, adding 1.25mL concentration is the aqueous solution of chloraurate of 0.1M, is heated with stirring to boiling, then addsThe trisodium citrate aqueous solution that 750 μ L mass concentrations are 10%, continues return stirring 0.5 hour at 95 DEG C, stops stirring,Be cooled to room temperature, obtain nanogold particle solution, be kept in 4 DEG C of refrigerators for subsequent use;
The preparation of b, polyvinyl alcohol water solution
The polyvinyl alcohol that 5g was dried joins in 95g ultra-pure water, under room temperature swelling 4 hours, then at 95 DEG C, refluxesHeat the polyvinyl alcohol water solution that the mass fraction that obtains colourless transparent and homogeneous is 5% 4 hours;
C, have the preparation of the laminated film of photo-thermal conversion and thermal energy storage and release function concurrently
Get polyvinyl alcohol water solution prepared by 20g step b, under stirring, be heated to 45 DEG C and keep 0.5 hour, then according to orderIn mark product, the quality proportioning of organic phase change material and polyvinyl alcohol adds a certain amount of organic phase-change in polyvinyl alcohol water solutionMaterial water solution, stirred after 2 hours, then added nanogold particle solution prepared by step a and mix, and obtained organic phase-changeMaterial-polyvinyl alcohol-nm of gold composite solution;
Finally measure organic phase change material-polyvinyl alcohol-nm of gold composite solution and be placed in arbitrary shape mould, in 50 DEG C of baking ovensDry 12 hours, then drying at room temperature 72 hours, solvent evaporated, must have photo-thermal conversion and thermal energy storage and release function concurrentlyLaminated film.
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Cited By (12)
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| CN106047305A (en) * | 2016-07-19 | 2016-10-26 | 沈阳化工研究院有限公司 | Photothermal conversion type organic/inorganic composite phase-change energy storage material and preparation method thereof |
| CN107556562A (en) * | 2017-09-04 | 2018-01-09 | 三维天工（北京）科技有限公司 | The preparation method of customizable optical-thermal conversion material and application |
| CN107857962A (en) * | 2017-11-16 | 2018-03-30 | 成都新柯力化工科技有限公司 | A kind of the light for architecture thermal transition plastic foil and preparation method with microcellular structure |
| CN108116022A (en) * | 2017-12-08 | 2018-06-05 | 成都新柯力化工科技有限公司 | A kind of energy-saving plastic film with photothermal conversion and heat preservation heat accumulation effect |
| CN108679865A (en) * | 2018-03-22 | 2018-10-19 | 中国科学技术大学 | The preparation method of two-dimentional conducting polymer sun absorber of light for solar energy water evaporation of vapours |
| 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 |
| CN110204751A (en) * | 2019-05-23 | 2019-09-06 | 北京工商大学 | A kind of preparation method of phase-change material flexible membrane |
| CN110669304A (en) * | 2019-09-25 | 2020-01-10 | 广东工业大学 | Flexible photo-thermal conversion composite film and preparation method and application thereof |
| CN111072083A (en) * | 2018-10-18 | 2020-04-28 | 中国科学院宁波材料技术与工程研究所 | Seawater evaporation desalination membrane material, preparation method and application thereof |
| CN111732346A (en) * | 2020-07-01 | 2020-10-02 | 中国建材国际工程集团有限公司 | Preparation method of photochromic glass for improving speed of renaturation |
| CN114806510A (en) * | 2022-02-24 | 2022-07-29 | 东南大学 | Composite phase change energy storage material and preparation method thereof |
| CN116574298A (en) * | 2023-05-06 | 2023-08-11 | 四川大学 | Wearable photo-thermal phase-change energy storage composite film and preparation method thereof |
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