CN107141430A - The preparation method of graphene-based Synergistic phase-change material - Google Patents
The preparation method of graphene-based Synergistic phase-change material Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of graphene-based Synergistic phase-change material, comprise the following steps：1) graphene oxide is uniformly dispersed in dispersant, obtains graphene oxide dispersion；2) by graphene oxide dispersion and removed polymerization inhibitor reaction monomers add reaction vessel, stir, be passed through inert gas discharge reaction vessel in oxygen, be added dropwise initiator, to initiator completion of dropping, temperature reaction obtains reaction mixture；3) by reaction mixture vacuum distillation, solid sample is obtained, constant weight is dried under vacuum to, graphene-based Synergistic phase-change material is produced.This method is using radical polymerization technique in situ, make phase change monomer covalence graft on graphene oxide layer surface, phase change monomer radical polymerization simultaneously, obtains graphene-based Synergistic phase-change material, and its heat enthalpy value and heat content efficiency stablize phase-change material apparently higher than conventional shape.
Description
Technical field
The present invention relates to phase-change material preparation field, more particularly to a kind of system of graphene-based Synergistic phase-change material
Preparation Method.
Background technology
Phase-change material is that a class utilizes the heat absorption in phase (solid-, solid-liquid, liquid-gas, consolidate-gas) transition process
And exothermic phenomenon, the material of energy storage and release is carried out, wherein organic solid-liquid phase-change material is the most commonly used.Phase-change material energy
The problems such as enough solving the mismatch of environmental pollution, shortage of resources and energy supply in the time, spatially to a certain extent, but
In actual use, there is poor thermal conductivity, the coefficient of cubical expansion is big, Gu the problems such as-liquid phase is easily revealed during becoming.
Graphene is one kind by sp2The carbon materials of the monatomic lamella with two-dimentional (2D) structure of the carbon atom composition of hydridization
Material, is the elementary cell for constituting other carbon nanomaterials.The light weight of graphene, mechanical strength and hardness are big, good heat conductivity,
It is preferable composite modified and backing material.The thermal conductivity factor of particularly graphene is up to 5000W/mK, is to lead so far
Heating rate highest material.Yet with the natural hydrophobicity of graphene so that it is hardly dissolved by most of organic solvents, this
One property limits its application in field of compound material.Graphene oxide (GO) can be regarded as graphene inside and edge contains
There are the product that a large amount of hydrophily oxygen-containing functional groups (such as carboxyl, hydroxyl, epoxy radicals) are modified, its performance and the basic phase of graphene
Seemingly.Meanwhile, GO also has excellent calorifics and mechanical property, is increasingly becoming one of current study hotspot.
Technology using the GO shape stabilities and thermal conductivity for improving phase-change material as backing material has been paid attention to.
GO is added in aliphatic acid/fatty alcohol as disclosed one kind in the A of CN 105112021, three-dimensional graphite is prepared by solution blending
The technology of alkene skeleton composite phase-change material.For another example, one kind is disclosed in the A of CN 105199675 GO is added in polyethylene glycol, led to
Cross the technology that microwave radiation technology blending prepares graphene-based shaped composite phase-change material.Sizing phase-change material is equal in two patent applications
Prepared by simple physical blending, there was only Van der Waals force between phase transformation working substrate and graphene, without chemical bond,
We term it the stable phase-change material (TPCMs) of conventional shape.In this kind of phase-change material, graphene oxide as backing material,
Although improving the shape stability of phase transformation working substrate, the heat enthalpy value and heat of phase transformation working substrate are inevitably reduced
Enthalpy efficiency value.The size of heat content efficiency value, represents in sizing phase-change material, backing material causes phase transformation working substrate heat content to lose
Degree.Heat content efficiency value is bigger, and to represent the heat content loss that backing material causes smaller.
The content of the invention
In order to solve the above-mentioned technical problem, the invention provides a kind of novel graphite alkenyl Synergistic phase-change material
(SPCMs) preparation method.Using radical polymerization technique in situ, it is grafted to monomer covalent of the part with phase-change characteristic
GO sheet surfaces, form graphene-based solid-solid phase transition material；The monomer that another part has phase-change characteristic passes through free radical autohemagglutination
Conjunction forms phase transformation working substrate, so that sizing SPCMs is made.The heat enthalpy value and heat content efficiency of this kind of phase-change material apparently higher than
TPCMs, solves the problem of TPCMs heat enthalpy values are low to be reduced with heat content efficiency well.
Therefore, technical scheme is as follows：
A kind of preparation method of graphene-based Synergistic phase-change material, comprises the following steps：
1) graphene oxide is uniformly dispersed in dispersant, obtains graphene oxide dispersion；
2) by graphene oxide dispersion and removed polymerization inhibitor reaction monomers add reaction vessel, stir, be passed through it is lazy
Property gas discharge reaction vessel in oxygen, initiator is added dropwise, to the initiator completion of dropping, 65~90 DEG C are warming up to, instead
12~48h is answered, reaction mixture is obtained；
3) by the reaction mixture vacuum distillation, solid sample is obtained, constant weight is dried under vacuum to, the graphene is produced
Base Synergistic phase-change material；
Wherein：Step 1) described in dispersant graphene oxide can not only be made to be uniformly dispersed wherein, or reaction monomers
Solvent；
The reaction monomers are：Methacrylic acid nalka base ester, acrylic acid nalka base ester, metering system acid polyethylene glycol are just
In alkyl ether acetate and acrylic acid (poly-) ethylene glycol alkyl ether-ether any one or it is any two kinds, meanwhile, reaction monomers are two
When planting, the amount of the material of one-component at least accounts for the 10% of the amount of the reaction monomers material；
The formula of the methacrylic acid nalka base ester is CH2=C (CH3)-COOCnH2n+1, 8≤n≤50；
The formula of acrylic acid nalka base ester is CH2=CH-COOCjH2j+1, 8≤j≤50；
The formula of metering system acid polyethylene glycol alkyl ether-ether is CH2=C (CH3)-COO(CH2CH2O)mCnH2n+1, m=
1~10, n=10~50；
Acrylic acid (poly-) ethylene glycol alkyl ether-ether formula is CH2=CH-COO (CH2CH2O)aCbH2b+1A=1~10, b=
10~50；
The molar fraction of the initiator is the 0.1~2% of reaction monomers molar fraction.
Further, step 1) in graphene oxide dispersion concentration be 0.5~8mg/mL.
Further, the quality of the GO is the 0.5~6% of the reactive monomer quality.
Further, the reaction monomers first eliminate polymerization inhibitor before reaction vessel is added, specifically, remove polymerization inhibitor
Method be：Handled before reaction with alkali alumina and remove polymerization inhibitor, polymerization inhibitor can also be removed with the method for vacuum distillation, also
Removing polymerization inhibitor can be washed with sig water.
Further, the dispersant is that DMF, DMA, toluene or dimethyl are sub-
Sulfone.
Further, the initiator is benzoyl peroxide, azodiisobutyronitrile or the azo two purified with absolute ethyl alcohol
Different heptonitrile.
Further, inert gas used is nitrogen or argon gas.
The reaction monomers used in the technical scheme are prepared using prior art, and graphene oxide can be the oxygen of individual layer
Graphite alkene or few layer graphene oxide.
Methacrylic acid (poly-) ethylene glycol alkyl ether-ether or acrylic acid (poly-) ethylene glycol alkyl ether-ether introduce soft
The purpose of (poly-) ethylene glycol, which can be by the adjustment degree of polymerization, suitably reduces the phase transition temperature of nalka base side chain, it is to avoid phase-change material
Temperature is too high, strengthens the applicability of product.M, a=1~10, m, a>10, it will the crystallization of polyethylene glycol block occur, with nalka
Competition is formed between the crystallization of base side chain, causes crystallizable side chain performance to decline.By adjusting the degree of polymerization m, a of polyethylene glycol, or
The carbon number n, b and the copolymer using two kinds of monomers of n-alkyl moieties are adjusted, phase can be reduced or improve as needed
Become the phase transition temperature of material, it is to avoid because of an a kind of only phase-change material of use, cause the phase transition temperature to be difficult to meet asking for use requirement
Topic, so as to obtain series of phase transitions material, meets the use requirement of varying environment or purposes；Incrystallizable flexible poly- second itself
Glycol chains (m, a=1~10) crystallizable alkyl is connected on poly- (methyl) propenoic acid main chain, it can reduce due to connection
Part carbon atom is uncrystallizable in the alkyl that key polarity height is caused, so that its melting temperature and crystallization temperature difference are larger,
Heat content is reduced, the problem of influenceing using effect.
Backing material, the TPCMs prepared using blend method, although improve and mutually exchange work are used as using (oxidation) graphene
Make the shape stability of matrix, but inevitably reduce the heat enthalpy value and heat content efficiency value of phase transformation working substrate, and it is unfavorable
The performance acted in energy storage.A kind of heat enthalpy value and the high dimensionally stable phase transformation of heat content efficiency value can be made using the present processes
Material, particular by strand of the grafting with phase-change characteristic on graphene oxide, prepares novel phase-change material, passes through
Chemical bond realizes coupling between polymer molecular chain and graphene film, preferably plays the crystalline substance of the heterogeneous nucleation crystallization of graphene
Core is acted on.
Using traditional free radical polymerization process in situ, by a part of covalence graft of monomer in reaction system to oxidation stone
In black alkene lamella C=C double bonds, form graphene oxide (GO) and be grafted poly- (methyl) acrylic acid nalka base ester/poly- (first of GO grafting
Base) acrylic acid (poly-) ethylene glycol alkyl ether-ether solid-solid phase transition material；Another part monomer autohemagglutination forms simple poly- (methyl)
Acrylic acid nalka base ester/poly- (methyl) acrylic acid (poly-) ethylene glycol alkyl ether-ether homopolymer, then belong to solid-liquid phase change material
Category.In graphene-based collaboration phase-change material made from this method, poly- (methyl) acrylic acid nalka base ester/poly- (methyl) acrylic acid
(poly-) ethylene glycol alkyl ether-ether homopolymer is as phase transformation working substrate, and GO is grafted poly- (methyl) acrylic acid nalka base ester/GO
Poly- (methyl) acrylic acid (poly-) the ethylene glycol alkyl ether-ether of grafting also functions as graphene while as phase transformation working substrate
The backing material of base Synergistic phase-change material, makes it have good shape stability.Meanwhile, in a certain temperature range,
The solid-liquid phase in version and GO of poly- (methyl) acrylic acid nalka base ester/poly- (methyl) acrylic acid (poly-) ethylene glycol alkyl ether-ether connect
The solid-solid phase that poly- (methyl) the acrylic acid nalka base ester of branch/GO is grafted poly- (methyl) acrylic acid (poly-) ethylene glycol alkyl ether-ether turns
Become and almost occur simultaneously, our this phenomenons are called collaboration phase transformation.In graphene-based collaboration phase-change material, part is poly- (methyl)
Acrylic acid nalka base ester/poly- (methyl) acrylic acid (poly-) ethylene glycol alkyl ether-ether is grafted/has been adsorbed onto on GO lamellas, therefore GO
Lamella and poly- (methyl) the acrylic acid nalka base ester of phase transformation working substrate/poly- (methyl) acrylic acid (poly-) ethylene glycol alkyl ether-ether it
Between have good compatibility.
Existing achievement in research shows, in poly- (methyl) acrylic acid nalka base ester or poly- (methyl) acrylic acid (poly-) ethylene glycol
In the crystallization process of alkyl ether-ether, main polymer chain is to the restricted crystallization of crystallizable alkyl in side chain, so as to lead
The carbon atom in nalka base side chain is caused all to crystallize, generally only when the carbon number in nalka base side chain is more than 9,
Crystallization can be formed, and this is unfavorable for improving crystallization heat content and heat content efficiency.
In graphene-based Synergistic phase-change material crystallization process, poly- (methyl) propylene of the GO induced graftings on its surface
Alkyl crystallizable side chain in sour nalka base ester or poly- (methyl) acrylic acid (poly-) ethylene glycol alkyl ether-ether, and it is used as nucleation
Agent, further induces poly- (methyl) acrylic acid nalka base ester/poly- (methyl) acrylic acid (poly-) ethylene glycol alkyl ether-ether crystallization, makes
Nucleation patterns are transformed into heterogeneous nucleation by original homogeneous nucleation, greatly reduce nucleation free energy, and cause crystallizable carbon
Atomicity increases, and then improves phase transformation heat content and heat content efficiency.Therefore, graphene-based Synergistic phase transformation material made from this method
The TPCMs of the crystallinity increase of material, heat enthalpy value and heat content efficiency apparently higher than same component.This just solves phase transformation work well
The problem of matrix heat content in TPCMs is lost and heat content efficiency is reduced, with good application prospect.
The Synergistic phase-change material dimensionally stable that this method is obtained, in addition to available for energy storage, it may also be used for but not
It is limited to drug controlled release, thermal protection, temperature sensitive reagent, the field such as temperature sensitive fiber and textile.
Brief description of the drawings
Fig. 1 is the transmission electron microscope photo of graphene oxide；
Fig. 2 is the transmission electron microscope photo for the SPCM2 that embodiment 3 is obtained；
Fig. 3 is the infrared spectrogram for the SPCM2 that graphene oxide and embodiment 3 are obtained；
Fig. 4 is the Raman spectrogram for the SPCM2 that graphene oxide and embodiment 3 are obtained；
The DSC spectrums that Fig. 5 is the TPCM2 that PHDA, the comparative example 2 that SPCM2, the comparative example 1 that embodiment 3 is obtained are obtained are obtained
Figure.
Embodiment
Technical scheme is described in detail below in conjunction with drawings and examples.
Embodiment 1
The preparation side of graphene oxide/polyacrylic acid cetyl ester Synergistic phase-change material (GO/PHDA SPCMs)
Method, comprises the following steps：
1) 74mg graphene oxides (GO, its transmission electron microscope photo is as shown in Figure 1) are weighed, by its ultrasonic disperse in 50mL bis-
In methyl sulfoxide, GO dispersion liquids are obtained；
2) above-mentioned GO dispersion liquids are added in 250mL there-necked flasks, while adding 50mmol monomeric acrylic cetyls
Ester (HDA) (having removed polymerization inhibitor), leads to nitrogen 20min, removes the oxygen in there-necked flask, backward there-necked flask in be added dropwise
The quality of 10mL AIBN dimethyl sulphoxide solution, wherein GO is 0.5%, AIBN of reactive monomer quality molar fraction
For the 2% of HDA；Reaction system is warming up under 70 DEG C, stirring condition afterwards and reacts 36h, reaction mixture is obtained；
3) by reaction mixture vacuum distillation, solid sample is obtained；Constant weight is dried under vacuum to afterwards, produces graphene-based association
With phase-change material SPCM0.5.
Wherein step 2) in HDA remove the method for polymerization inhibitor and be：After monomer HDA is melted, cross and alkali alumina is housed
Chromatographic column, to remove the polymerization inhibitor in monomer.
The heat enthalpy value of SPCM0.5 made from the present embodiment be 88J/g, heat content efficiency be 106.6%, peak melting temperature and
Crystallization peak temperature is respectively 40.1 and 25.1 DEG C.
Embodiment 2
The preparation side of graphene oxide/polyacrylic acid cetyl ester Synergistic phase-change material (GO/PHDA SPCMs)
Method, comprises the following steps：
1) 148mg GO are weighed, ultrasonic disperse obtains GO dispersion liquids in 50mL DMAc；
2) GO dispersion liquids are added in 250mL there-necked flasks, while adding 50mmol monomeric acrylic cetyl esters
(HDA) (remove polymerization inhibitor using with removing polymerization inhibitor identical method in embodiment 1), lead to nitrogen 30min, remove there-necked flask
In oxygen, backward there-necked flask in 10mL initiator Bs PO DMAc solution is added dropwise, wherein GO quality is monomer mass
1%, BPO molar fraction be monomer HDA 2%；Reaction system is warming up under 65 DEG C, stirring condition afterwards and reacts 48h,
Obtain reaction mixture；
3) by reaction mixture vacuum distillation, solid sample is obtained；Constant weight is dried under vacuum to afterwards, produces graphene-based association
With phase-change material SPCM1.
The heat enthalpy value of SPCM1 made from the present embodiment be 116J/g, heat content efficiency be 141.2%, peak melting temperature and
Crystallization peak temperature is respectively 37.2 and 25.0 DEG C.
Embodiment 3
The preparation method of graphene oxide/polyacrylic acid hexadecane ester Synergistic phase-change material (GO/PHDA SPCMs),
Comprise the following steps：
1) 296mg GO are weighed, ultrasonic disperse obtains GO dispersion liquids in 50mL toluene；
2) above-mentioned GO dispersion liquids are added in 250mL there-necked flasks, while adding 50mmol monomeric acrylic cetyls
Ester (HDA) (removes polymerization inhibitor) using with removing polymerization inhibitor identical method in embodiment 1, leads to nitrogen 40min, removes three mouthfuls
Oxygen in bottle, backward there-necked flask in 10mL initiator As IBN toluene solution is added dropwise, wherein GO quality is monomer
2%, BPO of quality molar fraction is the 2% of monomer HDA；Reaction system is warming up to 80 DEG C afterwards, reacted under stirring condition
24h, obtains reaction mixture；
3) by reaction mixture vacuum distillation, solid sample is obtained；Constant weight is dried under vacuum to afterwards, produces graphene-based association
With phase-change material SPCM2.
As shown in Fig. 2 in comparison diagram 1 GO transmission electron microscope photo, it will be seen that in Fig. 2 GO lamellas transparency
It is decreased obviously, in the graphene-based collaboration phase-change material of preparation, GO surfaces covalence graft/suction appends substantial amounts of phase transformation work
Matrix PHDA.
The heat enthalpy value of SPCM2 made from the present embodiment be 109J/g, heat content efficiency be 134.0%, peak melting temperature and
Crystallization peak temperature is respectively 39.0 and 25.0 DEG C (such as Fig. 5).
Embodiment 4
The preparation method of graphene oxide/polyacrylic acid cetyl ester collaboration phase-change material (GO/PHDA SPCMs), bag
Include following steps：
1) 593mg GO are weighed, ultrasonic disperse obtains GO dispersion liquids in 50mL DMAc；
2) above-mentioned GO dispersion liquids are added in 250mL there-necked flasks, while adding 50m mol monomeric acrylic cetyls
Ester (HDA) (removes polymerization inhibitor) using with removing polymerization inhibitor identical method in embodiment 1, leads to nitrogen 30min, removes three mouthfuls
Oxygen in bottle, backward there-necked flask in the DMAc solution of 10mL initiator ABVNs, wherein GO matter is added dropwise
Measure as the 4% of monomer mass, the BPO of ABVN molar fraction is the 2% of monomer HDA；Afterwards by reaction system liter
Temperature reacts 12h under stirring condition, obtains reaction mixture to 90 DEG C；
3) by reaction mixture vacuum distillation, solid sample is obtained；Constant weight is dried under vacuum to afterwards, produces graphene-based association
With phase-change material SPCM4.
The heat enthalpy value of SPCM4 made from the present embodiment be 110J/g, heat content efficiency be 138.1%, peak melting temperature and
Crystallization peak temperature is respectively 39.1 and 25.6 DEG C.
Embodiment 5~10
On the basis of the experimental procedure of embodiment 1, changing section parameter completes embodiment 5~10, design parameter such as table 1.
Table 1
Comparative example 1
1) 50mmol monomeric acrylics cetyl ester (HDA) (has been utilized and polymerization inhibitor identical is removed in embodiment 1
Method removes polymerization inhibitor) the 250mL there-necked flasks equipped with 50mL DMSO are added to, lead to nitrogen 30min, remove in reaction system
Oxygen, backward there-necked flask in 10mL initiator As IBN DMSO solution is added dropwise, wherein AIBN molar fraction is monomer
The 2% of HDA；Reaction system is warming up under 70 DEG C, stirring condition afterwards and reacts 36h, reaction mixture is obtained；
2) by reaction mixture vacuum distillation, solid sample is obtained；Constant weight is dried under vacuum to afterwards, produces contrast phase transformation material
Expect PHDA.
The heat enthalpy value of PHDA made from this comparative example is 83J/g, and peak melting temperature and Crystallization peak temperature are respectively
35.7 and 24.0 DEG C (such as Fig. 5).
Comparative example 2
1) 148mg GO are weighed, ultrasonic disperse obtains GO dispersion liquids in 30mL DMSO.
2) GO dispersion liquids are added in 250mL there-necked flasks, while adding what is polymerize in advance in 7.41g embodiments 1
PHDA, wherein GO quality are the 2% of PHDA mass；Reaction system, which is warming up under 65 DEG C, stirring condition, afterwards reacts 48h, obtains
To reaction mixture；
3) by reaction mixture vacuum distillation, solid sample is obtained；Constant weight is dried under vacuum to afterwards, produces control sample
TPCM2。
The heat enthalpy value of TPCM2 made from this comparative example is 78J/g, and heat content efficiency is 95.9%, peak melting temperature and knot
Brilliant peak temperature is respectively 39.8 and 26.1 DEG C (such as Fig. 5).
It is visible by characterizing (such as Fig. 2,3,4)：Graphene-based Synergistic phase-change material prepared by the present invention includes both
Solid-liquid phase is formed as backing material as the graphene-based solid-solid phase transition material of phase transformation working substrate and by monomer autohemagglutination again
Become material (1163 and 1248cm on such as Fig. 3, SPCM2 infrared spectrum-1Place occurs in that n-alkyl chain-C-C- characteristic peak；Such as Fig. 4,
SPCM2 ID/IG0.989 is increased by the 0.926 of GO, this shows sp on GO lamellas2The carbon number of hydridization is reduced, sp3It is miscellaneous
Change carbon number increase, a part of monomer has successfully been grafted on the C=C on GO lamellas by radical polymerization in situ, shape
Into graphene-based solid-solid phase transition material)；Simultaneously because graphene-based solid-solid phase transition material and polymer solid-liquid phase change material
Between collaboration cholesteric-nematic transition cause the heat enthalpy value and heat content efficiency of the graphene-based collaboration phase-change material prepared apparently higher than phase
Become working substrate and TPCMs heat enthalpy value and heat content efficiency, this just solves phase transformation working substrate heat content in TPCMs well
The problem of loss and heat content efficiency are reduced, with good application prospect.
Fig. 5 gives the DSC for the TPCM2 that PHDA, the comparative example 2 that SPCM2, the comparative example 1 that embodiment 3 obtains obtain are obtained
Spectrogram.It will be seen that three samples are respectively provided with obvious endothermic/exothermic peak from figure.Meanwhile, contrast endothermic/exothermic peak
Area it will be seen that SPCM2 ＞ PHDA ＞ TPCM2.Further relate to, graphene-based Synergistic phase prepared by this patent
Becoming material has higher heat enthalpy value and heat content efficiency value, can be good at solving phase transformation working substrate heat content in TPCMs
The problem of loss and heat content efficiency are reduced, with good application prospect.
Claims (7)
1. a kind of preparation method of graphene-based Synergistic phase-change material, it is characterised in that comprise the following steps：
1) graphene oxide is uniformly dispersed in dispersant, obtains graphene oxide dispersion；
2) by graphene oxide dispersion and removed polymerization inhibitor reaction monomers add reaction vessel, stir, be passed through indifferent gas
Oxygen in body discharge reaction vessel, is added dropwise initiator, to the initiator completion of dropping, is warming up to 65~90 DEG C, reaction 12
~48h, obtains reaction mixture；
3) by the reaction mixture vacuum distillation, solid sample is obtained, constant weight is dried under vacuum to, the graphene-based association is produced
With synergy phase-change material；
Wherein：Step 1) described in dispersant graphene oxide can not only be made to be uniformly dispersed wherein, or reaction monomers is molten
Agent；
The reaction monomers are：Methacrylic acid nalka base ester, acrylic acid nalka base ester, methacrylic acid (poly-) ethylene glycol nalka
In base ether-ether and acrylic acid (poly-) ethylene glycol alkyl ether-ether any one or it is any two kinds, meanwhile, reaction monomers be two kinds
When, the amount of the material of one-component at least accounts for the 10% of the amount of the reaction monomers material；
The formula of the methacrylic acid nalka base ester is CH2=C (CH3)-COOCnH2n+1, 8≤n≤50；
The formula of acrylic acid nalka base ester is CH2=CH-COOCjH2j+1, 8≤j≤50；
The formula of metering system acid polyethylene glycol alkyl ether-ether is CH2=C (CH3)-COO(CH2CH2O)mCnH2n+1, m=1~
10, n=10~50；
Acrylic acid (poly-) ethylene glycol alkyl ether-ether formula is CH2=CH-COO (CH2CH2O)aCbH2b+1A=1~10, b=10~
50；
The molar fraction of the initiator is the 0.1~2% of reaction monomers molar fraction.
2. the preparation method of graphene-based Synergistic phase-change material as claimed in claim 1, it is characterised in that：The initiator
For the benzoyl peroxide, azodiisobutyronitrile or ABVN purified with absolute ethyl alcohol.
3. the preparation method of graphene-based Synergistic phase-change material as claimed in claim 1, it is characterised in that：Step 1) in oxygen
The concentration of graphite alkene dispersion liquid is 0.5~8mg/mL.
4. the preparation method of graphene-based Synergistic phase-change material as claimed in claim 1, it is characterised in that：The matter of the GO
Measure as the 0.5~6% of the reactive monomer quality.
5. the preparation method of graphene-based Synergistic phase-change material as claimed in claim 1, it is characterised in that：Step 1) in it is anti-
The method for answering monomer to eliminate polymerization inhibitor is：Handled before reaction with alkali alumina and remove polymerization inhibitor, or with vacuum distillation
Method removes polymerization inhibitor, or wash with sig water and to remove polymerization inhibitor.
6. the preparation method of graphene-based Synergistic phase-change material as claimed in claim 1, it is characterised in that：The dispersant
For N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, toluene or dimethyl sulfoxide (DMSO).
7. the preparation method of graphene-based Synergistic phase-change material as claimed in claim 1, it is characterised in that：Indifferent gas used
Body is nitrogen or argon gas.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108615609A (en) * | 2018-03-26 | 2018-10-02 | 新乡学院 | A kind of preparation method of graphene/carbon nano-tube two-dimensional layer combination electrode material for ultracapacitor |
| CN110629551A (en) * | 2019-10-14 | 2019-12-31 | 天津工业大学 | Method for preparing GN @ cellulose based solid-solid phase change fiber through heterogeneous phase and application |
| CN110698597A (en) * | 2019-10-14 | 2020-01-17 | 天津工业大学 | GN @ cellulose-based solid-solid phase change material and preparation method and application thereof |
| CN111040736A (en) * | 2019-12-16 | 2020-04-21 | 天津工业大学 | Low-melting-point metal shaping phase-change material and preparation method thereof |
| CN112194809A (en) * | 2020-10-09 | 2021-01-08 | 天津工业大学 | Phase change energy storage composite membrane with sandwich structure and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718905A (en) * | 2012-07-03 | 2012-10-10 | 天津工业大学 | Preparation method of polymer type phase change materials |
| CN106832156A (en) * | 2017-02-27 | 2017-06-13 | 天津工业大学 | Temperature sensitive graphene oxide and preparation method thereof |
-
2017
- 2017-06-27 CN CN201710498814.6A patent/CN107141430A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718905A (en) * | 2012-07-03 | 2012-10-10 | 天津工业大学 | Preparation method of polymer type phase change materials |
| CN106832156A (en) * | 2017-02-27 | 2017-06-13 | 天津工业大学 | Temperature sensitive graphene oxide and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| CHANGZHONG CHEN, ET AL.: "Novel form stable phase change materials based on the composites of polyethylene glycol/polymeric solid-solid phase change material", 《SOLAR ENERGY MATERIALS & SOLAR CELLS》 * |
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| CN108615609A (en) * | 2018-03-26 | 2018-10-02 | 新乡学院 | A kind of preparation method of graphene/carbon nano-tube two-dimensional layer combination electrode material for ultracapacitor |
| CN108615609B (en) * | 2018-03-26 | 2019-11-01 | 新乡学院 | A kind of preparation method of the graphene/carbon nano-tube two-dimensional layer combination electrode material for supercapacitor |
| CN110629551A (en) * | 2019-10-14 | 2019-12-31 | 天津工业大学 | Method for preparing GN @ cellulose based solid-solid phase change fiber through heterogeneous phase and application |
| CN110698597A (en) * | 2019-10-14 | 2020-01-17 | 天津工业大学 | GN @ cellulose-based solid-solid phase change material and preparation method and application thereof |
| CN110698597B (en) * | 2019-10-14 | 2022-07-12 | 天津工业大学 | GN @ cellulose-based solid-solid phase change material and preparation method and application thereof |
| CN110629551B (en) * | 2019-10-14 | 2022-07-26 | 天津工业大学 | Method for preparing GN @ cellulose based solid-solid phase change fiber through heterogeneous phase and application |
| CN111040736A (en) * | 2019-12-16 | 2020-04-21 | 天津工业大学 | Low-melting-point metal shaping phase-change material and preparation method thereof |
| CN112194809A (en) * | 2020-10-09 | 2021-01-08 | 天津工业大学 | Phase change energy storage composite membrane with sandwich structure and preparation method thereof |
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