CN105505330B - A kind of three-dimensional phase-change material and preparation method thereof based on graphene - Google Patents
A kind of three-dimensional phase-change material and preparation method thereof based on graphene Download PDFInfo
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- CN105505330B CN105505330B CN201610049411.9A CN201610049411A CN105505330B CN 105505330 B CN105505330 B CN 105505330B CN 201610049411 A CN201610049411 A CN 201610049411A CN 105505330 B CN105505330 B CN 105505330B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The present invention relates to a kind of three-dimensional phase-change material and preparation method thereof based on graphene.Certain density graphene oxide water solution is put into liquid nitrogen and is rapidly frozen, then graphite oxide aerogel is obtained by freeze-drying, it is sent into high temperature furnace and carries out 500 DEG C of -3000 DEG C of heat treatments of high temperature under an inert atmosphere, then it is immersed in the dichloromethane solution of the paraffin of various concentration, after fully absorbing, it is put in drying in 30 DEG C of vacuum drying ovens again, obtains the three-dimensional phase-change material based on graphene.The three-dimensional phase-change material of the graphene is excellent to paraffin packaging effect, paraffin loading is 0.1-99.9%, and film-paraffin is compound uniformly, after heating for multiple times cooling cycle, the melt phase change enthalpy and solidification enthalpy of phase change of material are held essentially constant, to realize that efficient heat energy stores.
Description
Technical field
The present invention relates to carbon composite phase-change material field more particularly to a kind of three-dimensional phase-change material based on graphene and its
Preparation method.
Background technique
Phase-change material is the physical change that is occurred by temperature change to be absorbed or be discharged thermal energy.There are commonly
Since performance is stablized, the advantages that phase transition temperature is wide and temperature is adjustable, is widely used machine phase-change material, however organic
The disadvantages of phase-change material exists simultaneously that heating conduction is poor, and the coefficient of cubical expansion is big, is easy leakage.
Graphene (Graphene) is a kind of monolayer two dimensional crystal, has the highest intensity of known materials, extraordinary
Specific surface area and excellent electric conductivity and thermal conductivity are current optimal two-dimension nano materials.The graphene of macroscopic view assembling
Film has given full play to graphene surface product greatly, and intensity is high, the characteristic of excellent thermal conductivity.If by graphene film and paraffin perfection knot
Conjunction prepares excellent composite phase-change material as a challenge.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of three-dimensional phase-change material based on graphene and its
Preparation method.Present invention graphene aerogel bore hole size obtained is adjustable, is based on graphene three to effectively adjust
Tie up the structure of phase-change material.The composite phase-change material thermal storage performance based on graphene aerogel of method preparation is excellent, it is big to be suitble to
Large-scale production application.
It is achieved through the following technical solutions in the purpose of the present invention: a kind of three-dimensional phase-change material based on graphene, by
Graphene aerogel and the paraffin being filled in graphene aerogel fenestra hole form, and the loading of the paraffin is 0.1-
99.9vol%.
A kind of preparation method of the three-dimensional phase-change material based on graphene, its step are as follows:
(1) graphene oxide water solution that concentration is 1-100mg/mL is connected from the preparation facilities with linear type die orifice
Enter solidification liquid after continuous at the uniform velocity extrusion, is frozen into graphene oxide gel film, graphene oxide gel film is put into liquid nitrogen fastly
Quickly cooling is frozen.
(2) by the graphene oxide gel film after freezing processing under atmosphere of inert gases first with the speed of 0.1-1 DEG C/min
Rate is warming up to 500-800 DEG C, keeps the temperature 0.5-2h；
(3) it is warming up to 1000-1300 DEG C with the rate of 1-3 DEG C/min under atmosphere of inert gases, keeps the temperature 0.5-3h；
(4) it is warming up to 2000-3000 DEG C with the rate of 5-8 DEG C/min under atmosphere of inert gases, keeps the temperature 0.5-4h, obtains
Graphene aerogel film
(5) dichloromethane solution of the graphene aerogel film for obtaining step 4 in the paraffin that concentration is 0.1-100g/ml
Middle immersion 0.5-10h, then it is put in drying in 30 DEG C of vacuum drying ovens, obtain the composite phase-change film based on graphene.
Further, the average-size of the graphene oxide in the step 1 be greater than 50um, breadth coefficient be 0.2~
0.5。
Further, the time that the graphene oxide gel film is rapidly frozen in liquid nitrogen is set as 5-30min.
The beneficial effects of the present invention are:
(1) by the independent temperature-rise period of three steps, so that the functional group of graphene surface gradually disengages, and in gaseous form
It discharges step by step, meanwhile, graphitizing process stepwise development forms the micro- air bag of graphene；And in the forming process of micro- air bag, graphene
Surface functional group the most stable also falls off therewith, in addition gas expansion under high temperature, thereby produces aerogel structure, is conducive to
The filling of paraffin.
(2) the melt phase change enthalpy of the composite phase-change film based on graphene obtained through the invention is 175.3J/g, solidification
Enthalpy of phase change is 186.2J/g.
Specific embodiment
The content of present invention is further illustrated below in conjunction with example:
Embodiment 1
(1) by concentration be 60mg/mL graphene oxide water solution be respectively placed in liquid nitrogen freeze 3min, 5min,
15min,30min,35min.Graphene oxide gel (a, b, c, d, e) after freezing processing is placed under scanning electron microscope and is observed,
Graphene oxide gel a lamella stacking is more, and hole is few；Graphene oxide gel b, c, d hole is uniform, and compactness extent successively increases
Add, graphene oxide gel e structure is destroyed.
(2) graphene oxide gel after freezing processing is first heated up under atmosphere of inert gases with the rate of 1 DEG C/min
To 800 DEG C, 0.5h is kept the temperature；
(3) 1300 DEG C are warming up to the rate of 3 DEG C/min under atmosphere of inert gases, keep the temperature 0.5h；
(4) 3000 DEG C are warming up to the rate of 8 DEG C/min under atmosphere of inert gases, keep the temperature 0.5h, obtains graphene gas
Gel；
(5) graphene aerogel is impregnated into 3h in the dichloromethane solution for the paraffin that concentration is 80g/ml, then be put in
It is dry in 30 DEG C of vacuum drying ovens, the composite phase-change material based on graphene is obtained, paraffin loading is 99.9%.By showing that difference is swept
Calorimetry (DSC) test is retouched, the melt phase change enthalpy for obtaining the three-dimensional phase-change material based on graphene is 156.3J/g, solidifies phase transformation
Enthalpy is 168.2J/g.
Embodiment 2
(1) graphene oxide water solution that concentration is 1mg/mL is placed in liquid nitrogen and carries out 25min.
(2) graphene oxide gel after freezing processing is first heated up under atmosphere of inert gases with the rate of 1 DEG C/min
To 800 DEG C, 0.5h is kept the temperature；
(3) 1300 DEG C are warming up to the rate of 3 DEG C/min under atmosphere of inert gases, keep the temperature 0.5h；
(4) 3000 DEG C are warming up to the rate of 8 DEG C/min under atmosphere of inert gases, keep the temperature 0.5h, obtains graphene gas
Gel；
(5) aeroge that step 4 obtains is impregnated into 5h in the dichloromethane solution for the paraffin that concentration is 10g/ml, then put
It is dry in 30 DEG C of vacuum drying ovens, the three-dimensional phase-change material based on graphene is obtained, paraffin loading is 70%.By showing that difference is swept
Calorimetry (DSC) test is retouched, the melt phase change enthalpy for obtaining the three-dimensional phase-change material based on graphene is 126.3J/g, solidifies phase transformation
Enthalpy is 164.2J/g.
Embodiment 4
(1) graphene oxide water solution that concentration is 100mg/mL is placed in liquid nitrogen and carries out 25min.
(2) by the graphene oxide gel after freezing processing under atmosphere of inert gases with shown in 1~table of table 3 be heat-treated
Mode is heat-treated,
(3) aeroge after step 3 heat treatment is impregnated into 3h in the dichloromethane solution for the paraffin that concentration is 10g/ml,
It is put in drying in 30 DEG C of vacuum drying ovens again, obtains the three-dimensional phase-change material based on graphene.
Table 1
Table 2
Table 3
From 1~table of table 3 as can be seen that being determined in terms of the performance of this material mainly has two, one material internal graphite oxide
Alkene chip architecture repair situation, i.e., functional group fall off and high temperature under carbon conjugated structure reparation.Second, material internal three-dimensional takes
To the continuity of structure, i.e., the connectivity of internal lamellar structure.The performance of the two collective effect graphene three-dimensional phase-change material.
In table 1, by comparing A1 B1 C1 D1 E1, the temperature of A1 is too low, is not enough to remove most of degradable official
It can roll into a ball, cause gas in second step pyroprocess largely quickly to generate, tear lamellar structure at high temperature；E1 temperature is excessively high, produces
Angry body is too fast, can largely tear material internal structure, both can make deterioration in material properties.It has only in B1, C1, D1 temperature
Under, functional group will be slow and thoroughly remove, to ensure material property.By comparing C1 F1 G1 H1, F1 heating rate is too low,
Gas release is excessively slow, and material internal cannot be made to form through-hole；H1 temperature-rise period is too fast, and gas release is too fast, tears material
Expect internal structure, is unfavorable for forming transmission channel.C1 I1 J1 K1 L1 M1, I1 soaking time is too short, it cannot be guaranteed that most of
The degradation of functional group；M1 insulating process is too long, can absorb the tar inside stove, is unfavorable for the promotion of performance.J1, K1, L1 are just
Avoid both of the above well.
In table 2, by comparing A2 B2 C2 D2 E2, A2 heating rate is too low, seriously affects heating conduction.E heating speed
Height is spent, graphene interlayer structure can be torn, so that the degradation of graphene aerogel.Have the heating rate of B2, C2, D2 only
Under, it just capable can not only guarantee aerogel structure but also guarantee the thermal conductivity of graphene.By comparing C2 F2 G2 H2, F2 temperature
It is too low, prevent stable functional group discharges gas from being sufficiently disengaged from, in subsequent graphited transition easy in the process, destroy gas
The internal structure of gel；By comparing C2 I2 J2 K2 L2 M2, I2 soaking time is too short, and stable functional group cannot be abundant
It falls off；M2 overlong time, graphene aerogel are easy tar adsorption, are unfavorable for the promotion of graphene aerogel performance；And C2,
Not only it can guarantee sufficiently falling off for stabilising functional group under the conditions of J2, K2, but also be avoided that the puzzlement of tar.
In table 3, by comparing A3 B3 C3 D3 E3, A3 heating rate is too low, and most stabilising functional group falls off excessively slow, no
Conducive to the formation of graphene aerogel conjugate network；E3 temperature-rise period is too fast, and gas release and high-temperature expansion are too fast, is easy broken
The structure of bad graphene aerogel.Only in the case where B3, C3, D3, shape that the graphene aerogel of conductive network could be stable
At the structure on graphene could be repaired slowly.By comparing C3 F3 G3 H3 I3, F3 outlet temperature is too low, graphene
Aerogel structure reparation is incomplete, so various performances are all very poor；It could both guarantee graphene knot at a temperature of C3, G3, H3
The reparation of structure, and will not be destroyed.By comparing C3 J3 K3 L3 M3, J3 soaking time is too low, graphene aerogel structure
It cannot sufficiently repair, M3 soaking time is too long, can also to adsorb the tar in furnace body, influence graphene three-dimensional phase-change material
Performance.
Claims (4)
1. a kind of preparation method of the three-dimensional phase-change material based on graphene, which is characterized in that its step are as follows:
(1) graphene oxide water solution that concentration is 1-100mg/mL is put into liquid nitrogen and is freezed；
(2) by the graphene oxide gel film after freezing processing under atmosphere of inert gases first with 0.1-1oThe rate of C/min heats up
To 500-800oC keeps the temperature 0.5-2h；
(3) with 1-3 under atmosphere of inert gasesoThe rate of C/min is warming up to 1000-1300 DEG C, keeps the temperature 0.5-3h；
(4) with 5-8 under atmosphere of inert gasesoThe rate of C/min is warming up to 2000-3000 DEG C, keeps the temperature 0.5-4h, obtains graphite
Alkene aeroge；
(5) graphene aerogel that step 4 obtains is impregnated in the dichloromethane solution for the paraffin that concentration is 0.1-100g/ml
0.5-10h, then it is put in drying in 30 DEG C of vacuum drying ovens, obtain the three-dimensional phase-change material based on graphene.
2. preparation method as described in claim 1, which is characterized in that the average-size of the graphene oxide in the step 1
Greater than 50um, breadth coefficient is 0.2 ~ 0.5.
3. preparation method as described in claim 1, which is characterized in that the graphene oxide gel film is quick in liquid nitrogen
The time of freezing is set as 2-30min.
4. the three-dimensional phase-change material that method as described in claim 1 is prepared, which is characterized in that by three-dimensional grapheme aeroge
With the paraffin composition being filled in graphene aerogel hole, the loading of the paraffin is 0.1-99.9vol%.
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