CN109385254A - A kind of graphene elastomeric polymer phase change composite material and preparation method thereof - Google Patents
A kind of graphene elastomeric polymer phase change composite material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of graphene elastomeric polymer phase change composite materials and preparation method thereof, graphene aerogel is obtained by hydrothermal reduction first, then graphene oxide solution is mixed with phase-change material, phase-change microcapsule is prepared by Pickering emulsion method, finally a certain proportion of phase-change microcapsule is carried out by vacuum impregnation with graphene aerogel with elastomeric polymer lotion mixed liquor compound, by vacuum freeze-drying, graphene elastomeric polymer phase change composite material is obtained.Compared with prior art, the present invention provides thermally conductive modification using graphene aerogel as skeleton for composite material, provides packaging environment by complicated pore structure for phase-change material, can effectively solve easy leakage, the big technical bottleneck of poor heat conductivity two of phase change composite material；The composite consolidation of elastomeric polymer graphene skeleton can provide excellent mechanical property, therefore can realize the stored energy application under specific condition while further encapsulation to phase-change material for composite material.
Description
Technical field
The present invention relates to graphene nanocomposite material technical fields, and in particular to a kind of graphene elastomeric polymer phase transformation
Composite material and preparation method.
Background technique
Nowadays, with the high development of industrial civilization, the problems such as traditional fossil energy is in short supply and environmental pollution, is therewith
Coming, the development and utilization of renewable energy become the key of social sustainable development, and since renewable energy is inherent
Energy distribution is uneven and uncertain feature, an energy storage link is generally required in energy conversion system, to solve energy
The utilization rate of the energy is improved using mismatch problem over time and space in source.Phase-change material can be with using phase transition process
The storage and release for realizing energy, are a kind of ideal energy-accumulating mediums, so obtaining the concern of researcher.
It is stored in the form of latent heat in phase transition process or the organic phase change material of release thermal energy is due to its high storage capacity, it can
The phase transition temperature of adjusting is for one of solar energy conversion and the effective advanced energy storage material stored.Wherein organic phase
The advantages that becoming material has excellent heat stability and chemical stability, non-corrosive, low degree of supercooling, in solar energy, building gives up
Recuperation of heat, electronic/electrical pond heat management, intelligent textile etc. have huge application potential.But it due to low heat conductivity, easily lets out
The performance deficiency of dew limits the extensive use of organic phase change material.On the other hand, in military affairs, the special dimensions such as electronic device,
Often the mechanical property of phase change composite material there are certain requirements, such as thermal interfacial material, generally requiring it has
Certain flexibility is preferably to play the role of filling interface gap.
Graphene shows the performances such as excellent mechanics, electricity due to its special bi-dimensional cellular shape lattice structure, and
With high thermal conductivity, laboratory gross data is up to 5300W/ (mK).The preparation method of graphene has very much, including machine
Tool stripping method, chemical vapour deposition technique, epitaxial growth method and oxidation-reduction method etc., wherein oxidation-reduction method has preparation process letter
Single, low in cost advantage, is the now widely used method for preparing graphene.The oxidation of graphite is specifically included, stone is aoxidized
The removing of ink and three processes of reduction of graphene oxide.Graphene oxide is as the critical function product of graphene and preceding
Drive body, have it is amphipathic, be convenient to subsequent processing and application.At present in phase-change accumulation energy field, led for organic phase change material is low
Heating rate, the performance deficiency easily revealed, graphene and graphene oxide are mainly used as heat filling or phase-change microcapsule wall material.With
When making heat filling, graphene dispersion is utilized into its high thermal conductivity in phase-change material mainly by way of mechanical blending
Feature plays the role of improving heating conduction.It is to utilize the amphipathic of graphene oxide, preparation one as phase-change microcapsule wall material
The phase change composite material that kind is wrapped up by graphene oxide, is packaged phase-change material, improves the resistance to leakage energy of phase-change material.
Although the intrinsic thermal conductivity of graphene is high, makees heat filling its thermally conductive modified effect and is got well than common heat filling,
But this composite material obtained by mechanical blending is extremely unstable during reuse, and sedimentation layering can gradually occur
Phenomenon, modified effect can slowly decline, and affect the reuse characteristic of material.In addition graphene oxide is as phase-change microcapsule
Wall material, volume largely influence the energy-storage property of phase-change material compared with Gao Shihui, and in the lower situation of volume, still avoid
The not leakage of phase-change material.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of heating conduction is excellent,
The good graphene elastomeric polymer phase change composite material and preparation method thereof of temperature stability.
The purpose of the present invention can be achieved through the following technical solutions: a kind of graphene elastomeric polymer phase transformation composite wood
Material, which includes graphene aerogel skeleton, the elasticity that is filled in the network formed by graphene aerogel skeleton
Polymer and the phase-change microcapsule being wrapped in outside black alkene aeroge skeleton, the elastomeric polymer be selected from poly- CD 2 chlorobutadiene,
One of styrene-acrylic emulsion, styrene-butadiene emulsion or epoxy resin, the quality of the graphene aerogel skeleton account for the total matter of composite material
The mass ratio of the 1%~10% of amount, the elastomeric polymer and phase-change microcapsule is 1:(1~5).
Composite material of the invention is multiple using the high intrinsic thermal conductivity of graphene using graphene aerogel as skeleton
Condensation material provides thermally conductive modification, provides packaging environment by complicated pore structure for phase-change material, is phase change composite material
Easily leakage, the big technical bottleneck of poor heat conductivity two propose effective solution scheme.The compound one side of elastomeric polymer strengthens stone
Black alkene skeleton, can further be packaged phase-change material, and another aspect elastomeric polymer has high resiliency and ductility, can
Excellent mechanical property is provided for composite material.And graphene skeleton interlocks the microstructure of lapping, can effectively hinder elasticity poly-
The adduct molecule interchain changing of the relative positions can be improved composite material non-deformability, while will not be substantially reduced whole viscoplasticity.
Preferably, the structure of the phase-change microcapsule is as follows: using graphene oxide as shell, using phase-change material as nucleome,
Wherein, the phase-change material is selected from one of paraffin or hexadecanol, and the mass ratio of the graphene oxide and phase-change material is
(1~3): 100.
A kind of preparation method of graphene elastomeric polymer phase change composite material as described above, comprising the following steps:
(1) graphene oxide is placed in water, obtains uniform graphene oxide solution after stirring, ultrasound, then hydro-thermal
Reaction obtains graphene hydrogel, and then vacuum freeze drying obtains graphene aerogel skeleton；By hydrothermal reduction, stone is aoxidized
For black alkene piece while being reduced to graphene, staggeredly lapping forms graphene porous network, and freeze-drying removes wherein hydrone,
Obtain graphene aerogel.
(2) by graphene oxide and phase-change material be higher than phase-change material fusing point at a temperature of mix, stir, obtain micro- glue
Capsule lotion obtains phase-change microcapsule after cooling, washing, drying；Due to graphene oxide have it is amphipathic, in high-speed stirred,
It can be used as Pickering emulsifier and obtain stable oil-in-water Pickering lotion, graphene oxide is wrapped in as shell
Phase-change material forms microballoon.
(3) lotion of phase-change microcapsule obtained by step (2) and elastomeric polymer is mixed, then passes through vacuum impregnation and step
Suddenly the graphene aerogel skeleton that (1) is prepared is compound, and then vacuum freeze drying, obtains composite material crude product；
(4) phase-change microcapsule obtained by step (2) and elastomeric polymer are mixed, then passes through vacuum impregnation and composite material
Crude product is compound, is then freeze-dried, and this step (4) is repeated several times to get the phase-change material.Step (3) and step (4) are logical
Vacuum impregnation is crossed, microcapsules and elastomeric polymer mixed liquor fill aeroge gap, and vacuum freeze-drying removes moisture removal, it is repeated several times,
It realizes compound.
Preferably, the rate stirred in step (1) is 1000~2000r/min, and the time of stirring is 15~60min, institute
The frequency for stating ultrasound is 20~60kHz, and the ultrasonic time is 1~3h, and the temperature of the hydro-thermal reaction is 150~190 DEG C, hydro-thermal
The time of reaction is 8~30h, and the vacuum degree of vacuum freeze drying described in step (1) is less than 2Pa, and temperature is -60~-20
DEG C, the time is 20~30h.
Preferably, the phase-change material is selected from one of paraffin or hexadecanol, and the stirring rate in step (2) is 5000
~12000r/min, mixing time are 10~50min, and the washing uses its ionized water, and the temperature of the drying is 35~45
DEG C, the dry time is 24~48h.
Preferably, in the lotion of the elastomeric polymer, solid content is 50%~70%.
Preferably, in step (3) and step (4), the vacuum-impregnated vacuum degree is less than 2Pa, when vacuum-impregnated
Between be 1~5h.By vacuum impregnation, microcapsules and elastomeric polymer mixed liquor fill aeroge gap, and vacuum freeze-drying goes to remove water
Point, it is repeated several times, realizes compound.
Preferably, in step (3) and step (4), the vacuum degree of the vacuum freeze drying is less than 2Pa, and temperature is -60
~-20 DEG C, the time is 20~30h.
Preferably, the number of repetition of step (4) is 1~4 time.
Compared with prior art, the beneficial effects of the present invention are embodied in following several respects:
(1) present invention using graphene aerogel as thermally conductive skeleton, it is evenly dispersed in the composite, solve composite material
The dispersion and its endurance issues, thermal conductivity improves obvious；
(2) present invention assigns phase change composite material high resiliency and ductility with elastomeric polymer, in military affairs, electronic device etc.
Special dimension has application advantage；
(3) present invention is by microcapsules, and stephanoporate framework, elastomeric polymer is to the multiple encapsulation of phase-change material, in higher phase transformation
Under the premise of material accounting, it can effectively solve the problems, such as that phase-change material is easily revealed.
(3) process is simple, and preparation cost is cheap, is easy to industrialize expanding production.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the graphene aerogel prepared in embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of the graphene elastomeric polymer phase change composite material prepared in embodiment 1；
Fig. 3 is the graphene aerogel and graphene oxide infrared spectrum prepared in embodiment 2；
Fig. 4 is the scanning electron microscope (SEM) photograph of the phase-change microcapsule prepared in embodiment 2；
Fig. 5 is the particle diameter distribution of the phase-change microcapsule prepared in embodiment 2；
Fig. 6 is the graphene oxide afm image prepared in embodiment 3；
Fig. 7 is the DSC curve of the graphene elastomeric polymer phase change composite material prepared in embodiment 4；
Fig. 8 is the thermal coefficient of the graphene elastomeric polymer phase change composite material prepared in embodiment 3,4,5.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
(1) graphite oxide is soluble in water, 15min is stirred, ultrasonic 1h configures the graphene oxide solution of various concentration:
Concentration is 5mg/ml, 3mg/ml；
(2) 5mg/ml graphene oxide solution 60ml is taken, hydro-thermal reaction 15h in 100ml reaction kettle, hydro-thermal temperature are placed it in
Degree is 180 DEG C, obtains graphene hydrogel, and for 24 hours, vacuum degree is less than 2Pa for freeze-drying in vacuum drier, and cryogenic temperature is -60 DEG C,
Obtain graphene aerogel.
(3) 3mg/ml graphene oxide solution 100ml is taken, is mixed with the paraffin of 20g melting, is stirred 45min at 80 DEG C, stir
Rate 10000r/min is mixed, is washed with deionized after cooling, obtains phase-change microcapsule after drying at room temperature on filter paper.
(3) styrene-acrylic emulsion for the use of solid content being 50%.Phase-change microcapsule is mixed with elastomeric polymer 1:1 in mass ratio
It stirs evenly, it is by vacuum impregnation that mixed solution is compound with graphene aerogel.It is lyophilized in vacuum drier for 24 hours, vacuum degree
Less than 2Pa, cryogenic temperature is -60 DEG C, repeated impregnations with freeze-drying process 3 times.Obtain graphene elastomeric polymer phase transformation composite wood
Material.
The scanning electron microscope (SEM) photograph of graphene aerogel manufactured in the present embodiment is as shown in Figure 1, it can be seen that the stone of method preparation
Black alkene aeroge skeleton is layered porous network structure, and interlayer spacing is larger.Graphene elastomeric polymer phase change composite material
Scanning electron microscope (SEM) photograph it is as shown in Figure 2, it can be seen that the method preparation composite material using graphene aerogel as skeleton, phase transformation is micro-
Capsule is evenly distributed on graphene film, and elastomeric polymer is sufficient filling in hole.
Embodiment 2
(1) graphite oxide is soluble in water, 15min is stirred, ultrasonic 1h configures the graphene oxide solution of various concentration:
Concentration is 7mg/ml, 2mg/ml；
(2) 7mg/ml graphene oxide solution 60ml is taken, hydro-thermal reaction 15h in 100ml reaction kettle, hydro-thermal temperature are placed it in
Degree is 180 DEG C, obtains graphene hydrogel, and for 24 hours, vacuum degree is less than 2Pa for freeze-drying in vacuum drier, and cryogenic temperature is -60 DEG C,
Obtain graphene aerogel.
(3) 2mg/ml graphene oxide solution 100ml is taken, is mixed with the paraffin of 20g melting, is stirred 45min at 80 DEG C, stir
Rate 10000r/min is mixed, is washed with deionized after cooling, obtains phase-change microcapsule after drying at room temperature on filter paper.
(4) styrene-acrylic emulsion for the use of solid content being 50%.Phase-change microcapsule is mixed with elastomeric polymer 1:1 in mass ratio
It stirs evenly, it is by vacuum impregnation that mixed solution is compound with graphene aerogel.It is lyophilized in vacuum drier for 24 hours, vacuum degree
Less than 2Pa, cryogenic temperature is -60 DEG C, repeated impregnations with freeze-drying process 3 times.Obtain graphene elastomeric polymer phase transformation composite wood
Material.
The graphene aerogel and graphene oxide infrared spectrum prepared in embodiment 2 is as shown in figure 3, for graphite oxide
Alkene, it can be seen that the different vibration modes of various types of oxygen-containing functional groups, such as epoxy group (C-O-C, 1220-1320cm-1),
Edge carboxyl (COOH, the 1650-1750cm-1 of~3000-3700cm-1 and C-OH), carbonyl (C=O and O-C=O, 1500-
1750cm-1) basal plane and edge hydroxyl (C-OH, 3000-3700cm-1).By hydro-thermal, each oxygen-containing group of graphene is subtracted
It is few, illustrate that graphene oxide is restored.Scanning electron microscope (SEM) photograph and particle diameter distribution such as Fig. 4 of phase-change microcapsule shown in 5, aoxidize stone
Black alkene is wrapped in phase-change material and makees microcapsules shell, and microcapsules are spherical in rule, and size is at 7~17 μm.
Embodiment 3
(1) graphite oxide is soluble in water, 15min is stirred, ultrasonic 1h configures the graphene oxide solution of various concentration:
Concentration is 4mg/ml, 2mg/ml；
(2) 4mg/ml graphene oxide solution 60ml is taken, hydro-thermal reaction 15h in 100ml reaction kettle, hydro-thermal temperature are placed it in
Degree is 180 DEG C, obtains graphene hydrogel, and for 24 hours, vacuum degree is less than 2Pa for freeze-drying in vacuum drier, and cryogenic temperature is -60 DEG C,
Obtain graphene aerogel.
(3) 2mg/ml graphene oxide solution 100ml is taken, is mixed with the paraffin of 20g melting, is stirred 45min at 80 DEG C, stir
Rate 10000r/min is mixed, is washed with deionized after cooling, obtains phase-change microcapsule after drying at room temperature on filter paper.
(4) styrene-acrylic emulsion for the use of solid content being 50%.Phase-change microcapsule is mixed with elastomeric polymer 1:1 in mass ratio
It stirs evenly, it is by vacuum impregnation that mixed solution is compound with graphene aerogel.It is lyophilized in vacuum drier for 24 hours, vacuum degree
Less than 2Pa, cryogenic temperature is -60 DEG C, repeated impregnations with freeze-drying process 3 times.Obtain graphene elastomeric polymer phase transformation composite wood
Material.
The graphene oxide afm image prepared in embodiment 3 is as shown in fig. 6, after ultrasound, and graphene oxide thickness is in 1nm
Left and right illustrates that graphene oxide sheet is single layer, and peeling effect is preferable.
Embodiment 4
(1) graphite oxide is soluble in water, 15min is stirred, ultrasonic 1h configures the graphene oxide solution of various concentration:
Concentration is 6mg/ml, 2mg/ml；
(2) 6mg/ml graphene oxide solution 60ml is taken, hydro-thermal reaction 15h in 100ml reaction kettle, hydro-thermal temperature are placed it in
Degree is 180 DEG C, obtains graphene hydrogel, and for 24 hours, vacuum degree is less than 2Pa for freeze-drying in vacuum drier, and cryogenic temperature is -60 DEG C,
Obtain graphene aerogel.
(3) 2mg/ml graphene oxide solution 100ml is taken, is mixed with the paraffin of 20g melting, is stirred 45min at 80 DEG C, stir
Rate 10000r/min is mixed, is washed with deionized after cooling, obtains phase-change microcapsule after drying at room temperature on filter paper.
(4) styrene-acrylic emulsion for the use of solid content being 50%.Phase-change microcapsule is mixed with elastomeric polymer 1:1 in mass ratio
It stirs evenly, it is by vacuum impregnation that mixed solution is compound with graphene aerogel.It is lyophilized in vacuum drier for 24 hours, vacuum degree
Less than 2Pa, cryogenic temperature is -60 DEG C, repeated impregnations with freeze-drying process 3 times.Obtain graphene elastomeric polymer phase transformation composite wood
Material.
The DSC curve of the graphene elastomeric polymer phase change composite material prepared in embodiment 4 as shown in fig. 7, therefrom I
It can be found that fusion process there are two endothermic peaks, the peak of lower temperature is attributed to the solid-solid phase-change of paraffin, higher temperature
Solid-liquid phase change is then represented, phase transformation break size depends on contained phase-change material content.
Embodiment 5
(1) graphite oxide is soluble in water, 15min is stirred, ultrasonic 1h configures the graphene oxide solution of various concentration:
Concentration is 8mg/ml, 2mg/ml；
(2) 8mg/ml graphene oxide solution 60ml is taken, hydro-thermal reaction 15h in 100ml reaction kettle, hydro-thermal temperature are placed it in
Degree is 180 DEG C, obtains graphene hydrogel, and for 24 hours, vacuum degree is less than 2Pa for freeze-drying in vacuum drier, and cryogenic temperature is -60 DEG C,
Obtain graphene aerogel.
(3) 2mg/ml graphene oxide solution 100ml is taken, is mixed with the paraffin of 20g melting, is stirred 45min at 80 DEG C, stir
Rate 10000r/min is mixed, is washed with deionized after cooling, obtains phase-change microcapsule after drying at room temperature on filter paper.
(4) styrene-acrylic emulsion for the use of solid content being 50%.Phase-change microcapsule is mixed with elastomeric polymer 1:1 in mass ratio
It stirs evenly, it is by vacuum impregnation that mixed solution is compound with graphene aerogel.It is lyophilized in vacuum drier for 24 hours, vacuum degree
Less than 2Pa, cryogenic temperature is -60 DEG C, repeated impregnations with freeze-drying process 3 times.Obtain graphene elastomeric polymer phase transformation composite wood
Material.
The thermal coefficient of the graphene elastomeric polymer phase change composite material prepared in embodiment 3,4,5 is as shown in figure 8, phase
Than pure phase-change material, the heating conduction of composite material is promoted obviously, and thermal coefficient is with the graphene oxide of hydro-thermal reaction
Concentration increases and increases, because graphene oxide concentration increases, the graphene aerogel quality that hydrothermal reduction obtains is bigger, compound
The thermally conductive skeleton connectivity of graphene is more preferable in material, so heating conduction is more preferable.
Embodiment 6
Using preparation method similar to Example 1, difference is as follows:
(1) graphite oxide is soluble in water, 60min is stirred, ultrasonic 3h configures the graphene oxide solution of various concentration:
Concentration is 8mg/ml, 4mg/ml；
(2) 8mg/ml graphene oxide solution 60ml is taken, hydro-thermal reaction 30h in 100ml reaction kettle, hydro-thermal temperature are placed it in
Degree is 150 DEG C, obtains graphene hydrogel, and 20h is lyophilized in vacuum drier, and vacuum degree is less than 2Pa, and cryogenic temperature is -20 DEG C,
Obtain graphene aerogel skeleton.
(3) 6mg/ml graphene oxide solution 100ml is taken, is mixed with the paraffin of 20g melting, is stirred 50min at 80 DEG C, stir
Rate 5000r/min is mixed, is washed with deionized after cooling, obtains phase-change microcapsule after drying at room temperature on filter paper.
(4) the poly- CD 2 chlorobutadiene lotion for the use of solid content being 50%.Phase-change microcapsule and elastomeric polymer are pressed into quality
It is mixed evenly than 1:1, it is by vacuum impregnation that mixed solution is compound with graphene aerogel.Freeze-drying in vacuum drier
20h, vacuum degree be less than 2Pa, cryogenic temperature be -20 DEG C, repeated impregnations with freeze-drying process 4 times.Obtain graphene elastomeric polymer
Phase change composite material.
Through detecting, the composite material heating conduction that the present embodiment is prepared is excellent, and temperature stability is good.
Embodiment 7
Using preparation method similar to Example 1, difference is as follows:
(1) graphite oxide is soluble in water, 30min is stirred, ultrasonic 2h configures the graphene oxide solution of various concentration:
Concentration is 8mg/ml, 4mg/ml；
(2) 8mg/ml graphene oxide solution 60ml is taken, hydro-thermal reaction 8h in 100ml reaction kettle, hydro-thermal temperature are placed it in
Degree is 190 DEG C, obtains graphene hydrogel, and 30h is lyophilized in vacuum drier, and vacuum degree is less than 2Pa, and cryogenic temperature is -60 DEG C,
Obtain graphene aerogel skeleton.
(3) 6mg/ml graphene oxide solution 100ml is taken, is mixed with the paraffin of 20g melting, is stirred 10min at 80 DEG C, stir
Rate 12000r/min is mixed, is washed with deionized after cooling, obtains phase-change microcapsule after dry under the conditions of 45 DEG C on filter paper.
(4) the poly- CD 2 chlorobutadiene lotion for the use of solid content being 50%.Phase-change microcapsule and elastomeric polymer are pressed into quality
It is mixed evenly than 1:1, it is by vacuum impregnation that mixed solution is compound with graphene aerogel.Freeze-drying in vacuum drier
30h, vacuum degree be less than 2Pa, cryogenic temperature be -60 DEG C, repeated impregnations with freeze-drying process 2 times.Obtain graphene elastomeric polymer
Phase change composite material.
Through detecting, the composite material heating conduction that the present embodiment is prepared is excellent, and temperature stability is good.
Claims (9)
1. a kind of graphene elastomeric polymer phase change composite material, which is characterized in that the composite material includes graphene aerogel
Skeleton, the elastomeric polymer being filled in the network formed by graphene aerogel skeleton and it is wrapped in black alkene aeroge skeleton
Outer phase-change microcapsule, the elastomeric polymer is in poly- CD 2 chlorobutadiene, styrene-acrylic emulsion, styrene-butadiene emulsion or epoxy resin
One kind, the quality of the graphene aerogel skeleton account for the 1%~10% of composite material gross mass, the elastomeric polymer and phase
Become the mass ratio of microcapsules as 1:(1~5).
2. a kind of graphene elastomeric polymer phase change composite material according to claim 1, which is characterized in that the phase transformation
The structure of microcapsules is as follows: using graphene oxide as shell, using phase-change material as nucleome, wherein the phase-change material is selected from stone
The mass ratio of one of wax or hexadecanol, the graphene oxide and phase-change material is (1~3): 100.
3. a kind of preparation method of graphene elastomeric polymer phase change composite material as claimed in claim 1 or 2, feature exist
In, comprising the following steps:
(1) graphene oxide is placed in water, obtains uniform graphene oxide solution after stirring, ultrasound, then hydro-thermal reaction
Graphene hydrogel is obtained, then vacuum freeze drying obtains graphene aerogel skeleton；
(2) by graphene oxide and phase-change material be higher than phase-change material fusing point at a temperature of mix, stir, obtain microcapsules cream
Liquid obtains phase-change microcapsule after cooling, washing, drying；
(3) lotion of phase-change microcapsule obtained by step (2) and elastomeric polymer is mixed, then passes through vacuum impregnation and step
(1) the graphene aerogel skeleton being prepared is compound, then vacuum freeze drying, obtains composite material crude product；
(4) phase-change microcapsule obtained by step (2) and elastomeric polymer are mixed, then passes through vacuum impregnation and composite material crude product
It is compound, it is then freeze-dried, and this step (4) is repeated several times to get the phase-change material.
4. a kind of preparation method of graphene elastomeric polymer phase change composite material according to claim 3, feature exist
In the rate stirred in step (1) is 1000~2000r/min, and the time of stirring is 15~60min, the frequency of the ultrasound
For 20~60kHz, the ultrasonic time is 1~3h, and the temperature of the hydro-thermal reaction is 150~190 DEG C, and the time of hydro-thermal reaction is
8~30h, the vacuum degree of vacuum freeze drying described in step (1) are less than 2Pa, and temperature is -60~-20 DEG C, the time is 20~
30h。
5. a kind of preparation method of graphene elastomeric polymer phase change composite material according to claim 3, feature exist
In the phase-change material is selected from one of paraffin or hexadecanol, and the stirring rate in step (2) is 5000~12000r/
Min, mixing time are 10~50min, and the washing uses its ionized water, and the temperature of the drying is 35~45 DEG C, dry
Time is 24~48h.
6. a kind of preparation method of graphene elastomeric polymer phase change composite material according to claim 3, feature exist
In in the lotion of the elastomeric polymer, solid content is 50%~70%.
7. a kind of preparation method of graphene elastomeric polymer phase change composite material according to claim 3, feature exist
In in step (3) and step (4), the vacuum-impregnated vacuum degree is less than 2Pa, and the vacuum-impregnated time is 1~5h.
8. a kind of preparation method of graphene elastomeric polymer phase change composite material according to claim 3, feature exist
In in step (3) and step (4), the vacuum degree of the vacuum freeze drying is less than 2Pa, and temperature is -60~-20 DEG C, the time
For 20~30h.
9. a kind of preparation method of graphene elastomeric polymer phase change composite material according to claim 3, feature exist
In the number of repetition of step (4) is 1~4 time.
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| CN114230723A (en) * | 2021-12-28 | 2022-03-25 | 青岛理工大学 | Graphene oxide modified styrene-acrylic pickering emulsion, composite emulsion, and preparation method and application thereof |
| CN114963592A (en) * | 2022-04-13 | 2022-08-30 | 西安交通大学 | Solar photo-thermal conversion and heat storage system based on composite phase-change material |
| CN115678088A (en) * | 2021-07-23 | 2023-02-03 | 中国科学院大连化学物理研究所 | Porous polymer-graphene-based composite shaping phase-change material and preparation and application thereof |
| WO2024051826A1 (en) * | 2022-09-09 | 2024-03-14 | 中国石油化工股份有限公司 | Composite aerogel, recyclable heat-storage phase-change composite material with photothermal conversion function, and preparation methods therefor and use |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140110049A1 (en) * | 2012-10-19 | 2014-04-24 | The Hong Kong University Of Science And Technology | Three Dimensional Interconnected Porous Graphene-Based Thermal Interface Materials |
| CN103752234A (en) * | 2014-01-07 | 2014-04-30 | 同济大学 | Preparation method of oxidized graphene phase change microcapsule |
| CN106634855A (en) * | 2016-10-28 | 2017-05-10 | 同济大学 | Preparation method of hybrid graphene gel/phase-change heat-conducting composite material |
| CN106701033A (en) * | 2016-12-28 | 2017-05-24 | 沈阳航空航天大学 | Preparation method and preparation device of porous medium composite phase-change material |
| CN107266774A (en) * | 2016-04-08 | 2017-10-20 | 南京唯才新能源科技有限公司 | A kind of aerogel composite and preparation method thereof |
-
2018
- 2018-11-26 CN CN201811419642.XA patent/CN109385254B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140110049A1 (en) * | 2012-10-19 | 2014-04-24 | The Hong Kong University Of Science And Technology | Three Dimensional Interconnected Porous Graphene-Based Thermal Interface Materials |
| CN103752234A (en) * | 2014-01-07 | 2014-04-30 | 同济大学 | Preparation method of oxidized graphene phase change microcapsule |
| CN107266774A (en) * | 2016-04-08 | 2017-10-20 | 南京唯才新能源科技有限公司 | A kind of aerogel composite and preparation method thereof |
| CN106634855A (en) * | 2016-10-28 | 2017-05-10 | 同济大学 | Preparation method of hybrid graphene gel/phase-change heat-conducting composite material |
| CN106701033A (en) * | 2016-12-28 | 2017-05-24 | 沈阳航空航天大学 | Preparation method and preparation device of porous medium composite phase-change material |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111471251A (en) * | 2020-05-14 | 2020-07-31 | 素湃科技(上海)有限公司 | Aerogel-containing heat insulation material and preparation method thereof |
| CN111574968A (en) * | 2020-05-22 | 2020-08-25 | 南京邮电大学 | Interface material with convertible heat conduction and heat insulation performance |
| CN112852386A (en) * | 2021-01-25 | 2021-05-28 | 武汉科技大学 | High-orientation layered graphene aerogel phase-change composite material and preparation method thereof |
| CN113105871A (en) * | 2021-04-09 | 2021-07-13 | 中国科学院山西煤炭化学研究所 | Phase-change heat storage material with bionic structure and preparation method and application thereof |
| CN113265228A (en) * | 2021-04-26 | 2021-08-17 | 西南交通大学 | Multi-energy-driven shape-stabilized phase change material and preparation method thereof |
| CN115678088A (en) * | 2021-07-23 | 2023-02-03 | 中国科学院大连化学物理研究所 | Porous polymer-graphene-based composite shaping phase-change material and preparation and application thereof |
| CN113583652A (en) * | 2021-08-30 | 2021-11-02 | 上海新泊地化工技术服务有限公司 | Clean environment-friendly high-temperature-resistant nano fracturing fluid and preparation method thereof |
| CN114103125A (en) * | 2021-09-30 | 2022-03-01 | 哈尔滨工业大学（威海） | Preparation method of high-thermal-conductivity micro device |
| CN114103125B (en) * | 2021-09-30 | 2022-06-28 | 哈尔滨工业大学（威海） | Preparation method of high-thermal-conductivity micro device |
| CN114230723A (en) * | 2021-12-28 | 2022-03-25 | 青岛理工大学 | Graphene oxide modified styrene-acrylic pickering emulsion, composite emulsion, and preparation method and application thereof |
| CN114963592A (en) * | 2022-04-13 | 2022-08-30 | 西安交通大学 | Solar photo-thermal conversion and heat storage system based on composite phase-change material |
| WO2024051826A1 (en) * | 2022-09-09 | 2024-03-14 | 中国石油化工股份有限公司 | Composite aerogel, recyclable heat-storage phase-change composite material with photothermal conversion function, and preparation methods therefor and use |
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