CN108822805A - Composite phase-change material and preparation method thereof based on spongy graphene oxide - Google Patents
Composite phase-change material and preparation method thereof based on spongy graphene oxide Download PDFInfo
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Abstract
The present invention relates to a kind of composite phase-change material and preparation method thereof based on spongy graphene oxide, preparation method：Spongy graphene oxide and phase change material are combined using physical impregnation method, the composite phase-change material based on spongy graphene oxide is made, wherein spongy graphene oxide is as made from freeze-drying.Product obtained is mainly made of spongy graphene oxide and the phase change material being fixed in spongy graphene oxide, and the minimum content of spongy graphene oxide is 8~10wt% when not revealing within 250~320 DEG C.Preparation method of the invention has many advantages, such as simple process, easy to operate, low in cost, has that carrier material additive amount is small, low in cost, enthalpy is high, size is small, great application prospect using composite phase-change material made from preparation method of the invention.
Description
Technical field
The invention belongs to phase transformation spinning matrix preparation field, be related to a kind of composite phase-change material based on graphene oxide and
Preparation method.
Background technique
The energy is the basis of human survival and development, but nowadays, and energy shortage has been to restrict the significant problem of social development
One of.Since phase-change material (Phase Change Material, PCM) was able to solve to energy storage and release in the time
Contradiction spatially, therefore be widely used in heat storage technology, energy-saving and emission-reduction can be realized well.Currently, phase-change material exists
There is good application in the fields such as industrial waste heat recycling, solar thermal utilization, building heat insulation, textile garment and agricultural.It will
Phase-change material is combined with fibrous woven technology can be made into the fiber with heat-accumulation temperature-adjustment performance, referred to as phase change fiber, the fiber
The stabilization of human body microenvironment temperature can be maintained, " air-conditioning fiber " is also known as by image, in freezer uniforms for worker, fire-entry suit, too
Sky clothes and home wear etc. have good application.
Phase-change material can be stored in the form of latent heat in melting or solidification or be discharged a large amount of thermal energy, but single
Phase-change material is difficult directly to apply, therefore we must be using carrier material to phase transformation due to haveing the defects that Solid-Liquid Separation
Material, which is fixed, prepares composite phase-change material, leak it will not when undergoing phase transition, and this composite phase-change material is referred to as
Shaping phase-change material.Shaping phase-change material, which need to have following characteristic, just can be suitably used for preparing air-conditioning fiber：1 shaping effect is good,
It will not be leaked when undergoing phase transition；2 thermal conductivities are higher, enthalpy is higher (150J/g or more)；3 phase transition temperatures are suitable, generally
Between 25~40 DEG C；4 good thermal stabilities；For 5 suitable packages in fiber, partial size is 1~5 μm；6 is nontoxic, corrosion-free, raw material
It is easy to get, it is inexpensive, it can be recycled.
Can have at present to the carrier material that phase-change material is fixed very much, as montmorillonite, foam metal, expanded graphite and
Graphite flake etc., montmorillonite haves the shortcomings that thermal conductivity is low in these materials, although foam metal, expanded graphite and graphite flake heat
Conductance is high, but since adsorption effect is poor, fixable phase change material is limited, causes material enthalpy lower, in addition, also having point
The prior arts of the three-dimensional structures as carrier material such as sub- sieve, aeroge, but these materials limit it again because size is larger
Application.
Therefore, the great realistic meaning of shaping phase-change material that a kind of thermal conductivity is high, material enthalpy is high and size is small is studied.
Summary of the invention
Shaping phase-change material thermal conductivity is low, enthalpy is low the technical problem to be solved by the present invention is to overcoming in the prior art and
The big defect of size provides the shaping phase-change material that a kind of thermal conductivity is high, material enthalpy is high and size is small.The present invention is from thermal conductivity
The graphene oxide with numerous oxygen-containing functional groups (carboxyl, hydroxyl etc.) is had chosen in higher Carbon materials as carrier material
Material.Graphene oxide has the characteristics that size is small, thermal conductivity is high and oxygen-containing functional group is numerous, and the presence of numerous oxygen-containing functional groups can
So that physical bond occurs with phase change material in it, good fixed effect is reached to phase change material.In order to enable carrier material
There is better adsorption capacity, the present invention has carried out freeze-drying process to graphene oxide and spongy graphene oxide has been made,
So that graphene oxide obtained has spongiform porous three-dimensional structure, increase graphene oxide interlamellar spacing, reduces crystal grain ruler
It is very little, greatly improve setting and the absorption property of graphene oxide.Finally using spongy graphene oxide as carrier material, choosing
It is by physical impregnation method that the two is compound with all suitable phase change material of phase transition temperature, enthalpy of phase change and thermal stability, load has been made
Body material additive amount is only that 8~10wt% can guarantee the composite phase-change material that do not reveal within 250~320 DEG C, together
When the composite phase-change material thermal conductivity it is high, enthalpy is high, size is small, application prospect is good.
In order to achieve the above object, the present invention adopts the following technical scheme that：
Based on the composite phase-change material of spongy graphene oxide, mainly by spongy graphene oxide and it is fixed on sea
Phase change material in continuous shape graphene oxide is constituted, and the composite phase-change material based on spongy graphene oxide is at 250~320 DEG C
Within when not revealing the minimum content of spongy graphene oxide be 8~10wt%.Spongy graphite oxide of the invention
The content of alkene is that the composite phase-change material of 8~10wt% is not revealed within 250~320 DEG C, no decomposition, in industrial production
The hot melt processing temperature of polypropylene fibre is 240 DEG C, and composite phase-change material of the invention will not leak at 240 DEG C, meets production
Demand.Carrier material additive amount in the composite phase-change material of the prior art is greater than 20wt%, just can guarantee it 250~320
It is not revealed within DEG C.The present invention compared with the prior art, significantly reduces the additive amount of carrier material, reduces production
Cost.Content is that the carrier material (spongy graphene oxide) of 8~10wt% can be inhaled in composite phase-change material of the invention
The phase change material of attached 90~92wt%, the middle block carrier material used, adsorption effect are good compared with the prior art.
Composite phase-change material as described above based on spongy graphene oxide, the spongy graphene oxide contain
The enthalpy retention rate of the composite phase-change material based on spongy graphene oxide is 98.6~101.2% when amount is 8~10wt%.
The enthalpy retention rate of composite phase-change material of the carrier material additive amount of the prior art greater than 20wt% is 70~80%.The present invention
Compared with prior art, while reducing carrier material additive amount, the enthalpy retention rate of composite material is improved.The present invention
The enthalpy retention rate of composite phase-change material is huge compared to being promoted with the prior art, is because spongy graphene oxide is evenly dispersed
In phase change material, spongy graphene oxide plays the role of nucleating agent when phase change material crystallizes, and facilitates phase change material
Crystallization, thus greatly improve enthalpy retention rate.
Composite phase-change material as described above based on spongy graphene oxide, the fixation are by spongy oxidation
Graphene and phase change material occur what physical bond was realized.
Composite phase-change material as described above based on spongy graphene oxide, the layer of the spongy graphene oxide
Spacing is 0.800~1.000nm, and crystallite dimension is 8.00~10.00nm.
Composite phase-change material as described above based on spongy graphene oxide, the spongy graphene oxide is logical
It crosses to be frozen into solid in liquid nitrogen after graphene oxide aqueous dispersions ultrasonic disperse and be placed in freeze drier again and be freeze-dried
It is obtained；Graphene oxide after freeze-drying is loose porous powder, in spongy；
The partial size of the graphene oxide is 1~2 μm, the concentration of the graphene oxide aqueous dispersions is 0.3~
0.6wt%, the power of the ultrasonic disperse are 300W, and the time is 1.5~2h, and the temperature of the freeze-drying is -50~-40
DEG C, pressure is 30Pa hereinafter, the time is 2 days.It is only 1~2 μm that the present invention, which selects the partial size of graphene oxide, and size is smaller, answers
It is good with prospect.
Composite phase-change material as described above based on spongy graphene oxide, the phase transition temperature of the phase change material are
25~40 DEG C, enthalpy of phase change is 150J/g or more.The enthalpy of phase change of phase change material and the enthalpy of composite phase-change material are proportional, enthalpy of phase change
Higher, the enthalpy of composite phase-change material is higher, and the phase change material that enthalpy of phase change is lower than 150J/g, but this meeting greatly shadow also may be selected
Ring the enthalpy of composite phase-change material.Composite phase-change material produced by the present invention can be used for human body, and the temperature of human comfort is located at 25
Between~40 DEG C, when ambient temperature is lower than this range, crystallization exotherm can occur for the phase change material inside shaping phase-change material,
When ambient temperature is higher than this range, melting heat absorption can occur for phase change material, simultaneously as heat is in the form of latent heat
Occur, heating, cooling can't occur for composite phase-change material itself, therefore human body microenvironment temperature can be maintained to keep constant.
Phase transition temperature meets human body comfort requirement within this range.
Composite phase-change material as described above based on spongy graphene oxide, the phase change material are polyethyleneglycol
Methyl ether, polyethylene glycol, octadecyl alcolol, solid n-docosane, palmitinic acid or stearic acid.Protection scope of the present invention is not limited in
This, only enumerates the substance that part meets " phase transition temperature is 25~40 DEG C, and enthalpy of phase change is 150J/g or more ", other routines herein
Phase change material be equally applicable to the present invention, select the substance of " phase transition temperature is 25~40 DEG C, enthalpy of phase change be 150J/g or more "
It can guarantee the enthalpy of product of the invention.
The present invention also provides a kind of sides for preparing the composite phase-change material as described above based on spongy graphene oxide
Spongy graphene oxide and phase change material are combined using physical impregnation method and answering based on spongy graphene oxide are made by method
Close phase-change material.Method as described above, concrete operations are：The solution of phase change material is added drop-wise to spongy graphene oxide
It is separated after 6~8h of reaction under conditions of temperature is 60~75 DEG C, stirring rate is 600~800r/min after in dispersion liquid, is dry
It is dry that the composite phase-change material based on spongy graphene oxide is made；The concentration of the dispersion liquid of the spongy graphene oxide is
0.3~0.6wt%.
Invention mechanism：
The present invention has chosen the work of the graphene oxide with numerous oxygen-containing functional groups from the higher Carbon materials of thermal conductivity
For carrier material.Graphene oxide has the characteristics that size is small, thermal conductivity is high and oxygen-containing functional group is numerous, numerous oxygen-containing functional groups
Presence can make itself and phase change material that physical bond occur, good fixed effect is reached to phase change material.In order into one
The adsorption capacity of lifting carrier material is walked, the present invention has carried out freeze-drying process to graphene oxide and spongy oxidation has been made
Graphene, graphene oxide obtained have spongiform porous three-dimensional structure, increase graphene oxide interlamellar spacing, reduce crystal grain
Size greatly improves setting and the absorption property of graphene oxide.Spongy graphene oxide is compared to other carrier materials
Material and three-dimensional net structure, possess better adsorption capacity and fixed effect, no matter from the enthalpy of material, thermal conductivity, thermal finalization
For effect or size, the application of the melt spinning of phase change fiber can be met very well.
In subsequent adsorbtion phase change material, the lamellar structure of spongy graphene oxide makes it with biggish specific surface
Product, strong adsorption force, simultaneously as graphene oxide interlamellar spacing is big, the gap in graphene oxide can generate capillary absorption power, into
One step enhances adsorption capacity, in addition, spongy graphene oxide and phase change material contain a large amount of oxygen-containing group (such as hydroxyl
Base), the two binding force, significant increase adsorption capacity can be enhanced by Hydrogenbond.The fiber similar with graphene oxide structure
Element and possesses large specific surface area, one-dimensional, two-dimensional material containing more oxygen-containing functional group at chitosan, after treatment may be used
As carrier material, it is compound that good physics is generated with phase change material.
Finally using spongy graphene oxide as carrier material, and select phase transition temperature, enthalpy of phase change and thermal stability all suitable
Suitable phase change material, by physical impregnation method that the two is compound, it is only that 8~10wt% can be protected that carrier material additive amount, which has been made,
The composite phase-change material that do not reveal within 250~320 DEG C is demonstrate,proved, while the enthalpy of the composite phase-change material is high, size is small,
Application prospect is good.
Beneficial effect：
(1) preparation method of the composite phase-change material of the invention based on spongy graphene oxide, simple process, operation
Simplicity, low in cost, great application prospect；
(2) composite phase-change material of the invention based on spongy graphene oxide, the additive amount of carrier material is small, reduces
Production cost；
(3) composite phase-change material of the invention based on spongy graphene oxide, enthalpy is high, and size is small, application prospect
It is good.
Detailed description of the invention
Fig. 1 be spongy graphene oxide, poly glycol monomethyl ether and it is produced by the present invention be based on spongy graphite oxide
The infrared spectrum of the composite phase-change material of alkene；
Fig. 2 be graphene oxide, spongy graphene oxide, poly glycol monomethyl ether and it is produced by the present invention be based on sponge
The XRD spectra of the composite phase-change material of shape graphene oxide；
In figure, GO represents graphene oxide, and SG represents spongy graphene oxide, and MPEG represents poly glycol monomethyl ether,
SG/MPEG represents the composite phase-change material produced by the present invention based on spongy graphene oxide.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
The preparation method of composite phase-change material based on spongy graphene oxide, its step are as follows：
(1) graphene oxide is prepared：
Flask is placed in 0 DEG C of ice-water bath, the concentrated sulfuric acid and 3g graphite powder of 70mL is added into flask, stirs evenly,
14gKMnO is slowly added in 1h later4It is reacted, is continued reaction system dislocation in 35 DEG C of oil bath pans after reaction 3h
Distilled water is added dropwise after reaction 2h, and with the heating of the rate of 1 DEG C/min, solution colour is observed in temperature-rise period, is warming up to
75~85 DEG C, when solution starts to become golden yellow by black, stop adding water.By solution down to diluted aqueous hydrogen peroxide solution
In, quiescent setting.Supernatant is poured out, twice, then with water and ethyl alcohol respectively washed once with the HCl solution washing precipitate of 10v%,
Place the dry graphene oxide that partial size can be obtained and be 1~2 μm in 50 DEG C of baking oven.
(2) spongy graphene oxide is prepared：
Graphene oxide made from step (1) is first dispersed in water the graphene oxide water that obtained concentration is 0.3wt%
Then dispersion liquid is the ultrasonic disperse of 300W into 2h, power to graphene oxide aqueous dispersions, then it is frozen into liquid nitrogen
Solid, which is placed in freeze drier to be freeze-dried, is made interlamellar spacing as 0.905nm, and crystallite dimension is the spongy oxygen of 8.90nm
Graphite alkene, the temperature of freeze-drying are -50 DEG C, pressure 29Pa, and the time is 2 days.
(3) composite phase-change material is prepared：
The sponge that concentration is 0.3wt% is made in spongy graphene oxide dispersion obtained in step (2) in ethanol
Then phase change material poly glycol monomethyl ether solution is added drop-wise to spongy graphene oxide and dispersed by shape graphene oxide dispersion
Separation, drying are made based on spongy after reaction 6h under conditions of temperature is 70 DEG C, stirring rate is 600r/min after in liquid
The composite phase-change material of graphene oxide, wherein the mass ratio of spongy graphene oxide and poly glycol monomethyl ether is 8:92.
The final obtained composite phase-change material based on spongy graphene oxide mainly by spongy graphene oxide with
And the poly glycol monomethyl ether being fixed in spongy graphene oxide is constituted, it should the compound phase based on spongy graphene oxide
Change material does not occur leakage within 300 DEG C and without deformation, and enthalpy retention rate is 98.6%.
The composite phase-change material (SG/MPEG) based on spongy graphene oxide and poly glycol monomethyl ether (MPEG),
The infrared spectrogram of spongy graphene oxide (SG) is as shown in Figure 1, in SG spectrogram, 3400cm-1For the characteristic peak of-OH,
1721cm-1And 1409cm-1The stretching vibration peak of C=O and C-OH respectively on carboxyl, 1631cm-1For the characteristic peak of C=C,
1120cm-1For the stretching vibration peak of C-O-C, it can be seen from the figure that SG has successfully born hydroxyl, carboxylic by oxidation process
The oxygen-containing groups such as base and epoxy group.In the infrared spectrum of MPEG, 3428cm-1Caused by stretching vibration for-OH, 2879cm-1
For-CH2Stretching vibration characteristic peak, 1108cm-1For the stretching vibration peak of-C-O-C-, 954cm-1、844cm-1For-CH2It is curved
Bent vibration performance peak.And in terms of the infrared spectrum of SG/MPEG composite phase-change material, it can be found that two kinds of raw materials are corresponding main red
Outer peak all exists and without apparent displacement, and not new characteristic peak generates, and illustrates it is that a kind of physics is compound between the two.
The composite phase-change material (SG/MPEG) based on spongy graphene oxide and poly glycol monomethyl ether (MPEG),
Spongy graphene oxide (SG), graphene oxide (GO) XRD spectrum as shown in Fig. 2, can by the XRD curve of GO in figure and SG
To find out that there are an apparent characteristic peak in 2 θ=10 ° or so, this is the characteristic peak of graphene oxide.According to Bragg equation：
2dsin θ=n λ；
D is interplanar distance in formula, and θ is the angle of incident beam and reflecting surface, and λ is the wavelength of X-ray, and n is diffraction progression, can
Obtain its interplanar distance d:d(GO)=0.899nm, d(SG)=0.905nm.
Simultaneously according to Scherrer formula：
K is Scherrer constant in formula, and L is average thickness of the crystal grain perpendicular to crystal plane direction, and β is actual measurement sample diffraction peak
Halfwidth degree, θ are the angle of diffraction, and λ is X-ray wavelength, are 0.154nm.Its crystallite dimension L can be obtained:L(GO)=12.94nm, L(SG)=
8.90nm。
From interlamellar spacing and the crystallite dimension of SG, it can be concluded that, after freeze-dried processing, interlamellar spacing expands, and grain
Sub- size reduces, and illustrates that freeze-drying process destroys the regularity inside graphene oxide to a certain extent, is more advantageous to it
Afterwards and the combination of MPEG.In the XRD curve of MPEG, 2 θ=19.91 °, 21.13 ° and 26.40 ° are respectively polyethyleneglycol first
Characteristic peak of the ether on (100), (100) and (110) crystal face, can be found that the characteristic peak of MPEG all by the XRD curve of SG/MPEG
Retained, illustrates that the addition of SG does not destroy the structure of MPEG, but the characteristic peak of 2 θ=10 ° of SG itself has been difficult to send out again
Existing, this is seldom related with the additive amount of SG.
Comparative example 1
Poly glycol monomethyl ether phase-change material, and experience base identical as the poly glycol monomethyl ether structure in embodiment 1
This identical treatment process, the difference is that not in conjunction with spongy graphene oxide.Research finds the poly- second in comparative example 1
Glycol monomethyl ether phase-change material starts to melt when being higher than 35 DEG C, and apparent solid-liquid phase change process is presented, and has melted at 50 DEG C
Entirely, original shape is lost.It compares and finds with embodiment 1, when spongy graphene oxide is not added, pure polyethyleneglycol first
Ether heat setting is very poor, and 50 DEG C or more i.e. leakage completely can not apply, but when spongy graphene oxide additive amount is 8%,
Composite phase-change material reaches 300 DEG C in temperature and does not leak yet, and keeps good shape, can be very good to be applied to phase transformation
The preparation of fiber.
Comparative example 2
The preparation method of composite phase-change material based on graphene oxide, step is substantially the same manner as Example 1, and difference exists
In, without step (2), directly by graphene oxide made from step (1) dispersion carry out subsequent reactions in ethanol.
The final composite phase-change material obtained based on graphene oxide mainly by graphene oxide and is fixed on oxidation
Poly glycol monomethyl ether in graphene is constituted, and is revealed based on the composite phase-change material of graphene oxide at 100 DEG C,
Start to melt at 260 DEG C, enthalpy retention rate is 75%.It compares and finds with embodiment 1, the freeze-dried processing of graphene oxide
Afterwards, possess better adsorption effect, under equal conditions, more poly glycol monomethyl ethers can be adsorbed, therefore in performance, it is multiple
It closes phase-change material and possesses more preferably thermal finalization effect and enthalpy retention rate.
Embodiment 2
The preparation method of composite phase-change material based on spongy graphene oxide, step is substantially the same manner as Example 1,
Difference is that the mass ratio of spongy graphene oxide and poly glycol monomethyl ether is 10:90.
The final obtained composite phase-change material based on spongy graphene oxide mainly by spongy graphene oxide with
And the poly glycol monomethyl ether being fixed in spongy graphene oxide is constituted, it should the compound phase based on spongy graphene oxide
Change material does not occur leakage within 320 DEG C and without deformation, and enthalpy retention rate is 101.2%.
Embodiment 3
The preparation method of composite phase-change material based on spongy graphene oxide, step is substantially the same manner as Example 1,
Difference is that the mass ratio of spongy graphene oxide and poly glycol monomethyl ether is 2:98.
The final obtained composite phase-change material based on spongy graphene oxide mainly by spongy graphene oxide with
And the poly glycol monomethyl ether being fixed in spongy graphene oxide is constituted, it should the compound phase based on spongy graphene oxide
Become material phase change material at 50 DEG C to be precipitated on a small quantity, phase change material is largely precipitated and without deformation, enthalpy retention rate at 100 DEG C
It is 99.2%.It compares and finds with comparative example 1, the addition of spongy graphene oxide considerably enhances the heat of composite phase-change material
Shaping performance, when spongy graphene oxide additive amount is 2wt%, material still maintains good in 100 DEG C of just a large amount of leakages
Good shape.
Embodiment 4
The preparation method of composite phase-change material based on spongy graphene oxide, step is substantially the same manner as Example 1,
Difference is that the mass ratio of spongy graphene oxide and poly glycol monomethyl ether is 4:96.
The final obtained composite phase-change material based on spongy graphene oxide mainly by spongy graphene oxide with
And the poly glycol monomethyl ether being fixed in spongy graphene oxide is constituted, it should the compound phase based on spongy graphene oxide
Become material phase change material at 50 DEG C to start to leak, phase change material is largely precipitated and without deformation, enthalpy retention rate at 150 DEG C
It is 99.4%.
Embodiment 5
The preparation method of composite phase-change material based on spongy graphene oxide, step is substantially the same manner as Example 1,
Difference is that the mass ratio of spongy graphene oxide and poly glycol monomethyl ether is 6:96.
The final obtained composite phase-change material based on spongy graphene oxide mainly by spongy graphene oxide with
And the poly glycol monomethyl ether being fixed in spongy graphene oxide is constituted, it should the compound phase based on spongy graphene oxide
Become material phase change material at 100 DEG C to start to leak, phase change material is largely precipitated and without deformation at 200 DEG C, and enthalpy retains
Rate is 99.6%.Integrated embodiment 1~5 and 1 analysis of comparative example are found, multiple when spongy graphene oxide additive amount is 2%
The heat setting for closing phase-change material can be obviously improved, and the temperature leaked has larger mention with pure poly glycol monomethyl ether
It rises, while shape keeps good, in different embodiments, with the increase of spongy graphene oxide additive amount, composite phase-change
The temperature that material leaks constantly is promoted, and remains good shape, when additive amount is 8wt% or 8wt% or more,
Any leakage does not occur yet at 300 DEG C or more for phase-change material, and shape is kept to fix, and meets the molten of the phase change fibers such as polypropylene fibre, polyester
Melt the requirement of preparation.
Embodiment 7
The preparation method of composite phase-change material based on spongy graphene oxide, step is substantially the same manner as Example 1,
Difference is that phase change material is polyethylene glycol.
The final obtained composite phase-change material based on spongy graphene oxide mainly by spongy graphene oxide with
And the polyethylene glycol being fixed in spongy graphene oxide is constituted, and leakage and composition deformation, enthalpy does not occur within 250 DEG C
Being worth retention rate is 100.2%.
Embodiment 8
The preparation method of composite phase-change material based on spongy graphene oxide, step is substantially the same manner as Example 1,
Difference is that phase change material is octadecyl alcolol.
The final obtained composite phase-change material based on spongy graphene oxide mainly by spongy graphene oxide with
And the octadecyl alcolol being fixed in spongy graphene oxide is constituted, and leakage and composition deformation, enthalpy does not occur within 260 DEG C
Retention rate is 99.5%.
Embodiment 9
The preparation method of composite phase-change material based on spongy graphene oxide, its step are as follows：
(1) the step of preparing graphene oxide is same as Example 1.
(2) spongy graphene oxide is prepared：
Graphene oxide made from step (1) is first dispersed in water the graphene oxide water that obtained concentration is 0.6wt%
Dispersion liquid, then to graphene oxide aqueous dispersions carry out 1.5h, power be 300W ultrasonic disperse, then by its in liquid nitrogen it is cold
Being frozen into solid and being placed on freeze-drying in freeze drier interlamellar spacing is made is 0.800nm, and crystallite dimension is the sponge of 8.00nm
Shape graphene oxide, the temperature of freeze-drying are -40 DEG C, pressure 25Pa, and the time is 2 days.
(3) composite phase-change material is prepared：
The sponge that concentration is 0.6wt% is made in spongy graphene oxide dispersion obtained in step (2) in ethanol
Shape graphene oxide dispersion, after then solid n-docosane solution is added drop-wise in spongy graphene oxide dispersion
Separation, dry be made are based on spongy graphite oxide after reaction 8h under conditions of temperature is 60 DEG C, stirring rate is 800r/min
The composite phase-change material of alkene, wherein the mass ratio of spongy graphene oxide and solid n-docosane is 12:88.
The final obtained composite phase-change material based on spongy graphene oxide mainly by spongy graphene oxide with
And the solid n-docosane being fixed in spongy graphene oxide is constituted, the composite phase-change based on spongy graphene oxide
Material does not occur leakage within 320 DEG C and without deformation, and enthalpy retention rate is 100.8%.
Embodiment 10
The preparation method of composite phase-change material based on spongy graphene oxide, its step are as follows：
(1) the step of preparing graphene oxide is same as Example 1.
(2) spongy graphene oxide is prepared：
Graphene oxide made from step (1) is first dispersed in water the graphene oxide water that obtained concentration is 0.4wt%
Dispersion liquid, then to graphene oxide aqueous dispersions carry out 1.6h, power be 300W ultrasonic disperse, then by its in liquid nitrogen it is cold
Being frozen into solid and being placed on freeze-drying in freeze drier interlamellar spacing is made is 1.000nm, and crystallite dimension is the sponge of 10.00nm
Shape graphene oxide, the temperature of freeze-drying are -45 DEG C, pressure 28Pa, and the time is 2 days.
(3) composite phase-change material is prepared：
The sponge that concentration is 0.5wt% is made in spongy graphene oxide dispersion obtained in step (2) in ethanol
Shape graphene oxide dispersion, after then palm acid solution is added drop-wise in spongy graphene oxide dispersion temperature be 75
DEG C, stirring rate reacts separation after 7h, dry is made based on the compound of spongy graphene oxide under conditions of being 700r/min
Phase-change material, wherein the mass ratio of spongy graphene oxide and palmitinic acid is 9:91.
The final obtained composite phase-change material based on spongy graphene oxide mainly by spongy graphene oxide with
And the palmitinic acid being fixed in spongy graphene oxide is constituted, the composite phase-change material based on spongy graphene oxide exists
Leakage does not occur within 320 DEG C and without deformation, enthalpy retention rate is 101.2%.
Embodiment 11
The preparation method of composite phase-change material based on spongy graphene oxide, its step are as follows：
(1) the step of preparing graphene oxide is same as Example 1.
(2) spongy graphene oxide is prepared：
Graphene oxide made from step (1) is first dispersed in water the graphene oxide water that obtained concentration is 0.45wt%
Dispersion liquid, then to graphene oxide aqueous dispersions carry out 1.8h, power be 300W ultrasonic disperse, then by its in liquid nitrogen it is cold
Being frozen into solid and being placed on freeze-drying in freeze drier interlamellar spacing is made is 0.905nm, and crystallite dimension is the sponge of 8.90nm
Shape graphene oxide, the temperature of freeze-drying are -44 DEG C, pressure 25Pa, and the time is 2 days.
(3) composite phase-change material is prepared：
The sponge that concentration is 0.5wt% is made in spongy graphene oxide dispersion obtained in step (2) in ethanol
Shape graphene oxide dispersion, after then stearic acid solution is added drop-wise in spongy graphene oxide dispersion temperature be 65
DEG C, stirring rate separation, dry obtained answering based on spongy graphene oxide after 6.5h are reacted under conditions of being 650r/min
Phase-change material is closed, wherein spongy graphene oxide and stearic mass ratio are 8.5:91.5.
The final obtained composite phase-change material based on spongy graphene oxide mainly by spongy graphene oxide with
And the stearic acid being fixed in spongy graphene oxide is constituted, the composite phase-change material based on spongy graphene oxide exists
Leakage does not occur within 310 DEG C and without deformation, enthalpy retention rate is 100.4%.
Claims (9)
1. based on the composite phase-change material of spongy graphene oxide, it is characterized in that：Mainly by spongy graphene oxide and
The phase change material being fixed in spongy graphene oxide is constituted, and the composite phase-change material based on spongy graphene oxide exists
The minimum content of spongy graphene oxide is 8~10wt% when not revealing within 250~320 DEG C.
2. the composite phase-change material according to claim 1 based on spongy graphene oxide, which is characterized in that the sea
The enthalpy of the composite phase-change material based on spongy graphene oxide retains when the content of continuous shape graphene oxide is 8~10wt%
Rate is 98.6~101.2%.
3. the composite phase-change material according to claim 2 based on spongy graphene oxide, which is characterized in that described solid
It surely is that physical bond occurs with phase change material by spongy graphene oxide to realize.
4. the composite phase-change material according to claim 3 based on spongy graphene oxide, which is characterized in that the sea
The interlamellar spacing of continuous shape graphene oxide is 0.800~1.000nm, and crystallite dimension is 8.00~10.00nm.
5. the composite phase-change material according to claim 4 based on spongy graphene oxide, which is characterized in that the sea
Continuous shape graphene oxide be by will be frozen into liquid nitrogen after graphene oxide aqueous dispersions ultrasonic disperse solid be placed in again it is cold
In lyophilizer made from freeze-drying；
The partial size of the graphene oxide is 1~2 μm, and the concentration of the graphene oxide aqueous dispersions is 0.3~0.6wt%,
The power of the ultrasonic disperse is 300W, and the time is 1.5~2h, and the temperature of the freeze-drying is -50~-40 DEG C, and pressure is
30Pa is hereinafter, the time is 2 days.
6. the composite phase-change material according to claim 5 based on spongy graphene oxide, which is characterized in that the phase
Become the phase transition temperature of substance as 25~40 DEG C, enthalpy of phase change is 150J/g or more.
7. the composite phase-change material according to claim 6 based on spongy graphene oxide, which is characterized in that the phase
Change substance is poly glycol monomethyl ether, polyethylene glycol, octadecyl alcolol, solid n-docosane, palmitinic acid or stearic acid.
8. the method for preparing the composite phase-change material as described in any one of claims 1 to 7 based on spongy graphene oxide,
It is characterized in that：Spongy graphene oxide and phase change material are combined to be made using physical impregnation method and are based on spongy graphite oxide
The composite phase-change material of alkene.
9. according to the method described in claim 8, it is characterized in that, concrete operations are：The solution of phase change material is added drop-wise to sea
It is anti-under conditions of temperature is 60~75 DEG C, stirring rate is 600~800r/min after in the dispersion liquid of continuous shape graphene oxide
Answer separation after 6~8h, the dry obtained composite phase-change material based on spongy graphene oxide；The spongy graphene oxide
Dispersion liquid concentration be 0.3~0.6wt%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112680195A (en) * | 2020-12-24 | 2021-04-20 | 广东工业大学 | Preparation method and device of graphene-based polyethylene glycol phase-change material |
| CN113265230A (en) * | 2021-06-07 | 2021-08-17 | 山东国烯新材料创新中心有限公司 | Graphene-based composite phase change material with graded heat conduction structure and preparation method thereof |
| CN115260994A (en) * | 2022-07-23 | 2022-11-01 | 中国电建集团华东勘测设计研究院有限公司 | Polyol nanocomposite phase change material with high heat storage energy density and power density |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058179A (en) * | 2013-01-21 | 2013-04-24 | 张家港市东大工业技术研究院 | Method for preparing spongy graphene oxide by using freeze-drying method |
| CN105199675A (en) * | 2015-09-17 | 2015-12-30 | 湖北大学 | Composite phase change material set by oxidized graphene and preparing method thereof |
-
2018
- 2018-07-11 CN CN201810757154.3A patent/CN108822805B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058179A (en) * | 2013-01-21 | 2013-04-24 | 张家港市东大工业技术研究院 | Method for preparing spongy graphene oxide by using freeze-drying method |
| CN105199675A (en) * | 2015-09-17 | 2015-12-30 | 湖北大学 | Composite phase change material set by oxidized graphene and preparing method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JIALI WANG, ET. AL.: "Novel graphene oxide sponge synthesized by freeze-drying process for the removal of 2,4,6-trichlorophenol", 《RSC ADV.》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112680195A (en) * | 2020-12-24 | 2021-04-20 | 广东工业大学 | Preparation method and device of graphene-based polyethylene glycol phase-change material |
| US11339316B1 (en) | 2020-12-24 | 2022-05-24 | Guangdong University Of Technology | Method and device for preparing graphene-based polyethylene glycol phase change material |
| CN113265230A (en) * | 2021-06-07 | 2021-08-17 | 山东国烯新材料创新中心有限公司 | Graphene-based composite phase change material with graded heat conduction structure and preparation method thereof |
| CN113265230B (en) * | 2021-06-07 | 2022-05-17 | 山东国烯新材料创新中心有限公司 | Graphene-based composite phase change material with graded heat conduction structure and preparation method thereof |
| CN115260994A (en) * | 2022-07-23 | 2022-11-01 | 中国电建集团华东勘测设计研究院有限公司 | Polyol nanocomposite phase change material with high heat storage energy density and power density |
| CN115260994B (en) * | 2022-07-23 | 2023-12-26 | 中国电建集团华东勘测设计研究院有限公司 | Polyol nanocomposite phase change material with high heat storage energy density and power density |
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