CN103752234B - A kind of preparation method of graphene oxide phase-change microcapsule - Google Patents

A kind of preparation method of graphene oxide phase-change microcapsule Download PDF

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CN103752234B
CN103752234B CN201410006689.9A CN201410006689A CN103752234B CN 103752234 B CN103752234 B CN 103752234B CN 201410006689 A CN201410006689 A CN 201410006689A CN 103752234 B CN103752234 B CN 103752234B
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graphene oxide
phase
change
microcapsule
microcapsules
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CN201410006689.9A
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CN103752234A (en
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张东
尚玉
刘艳云
李秀强
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同济大学
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Abstract

The present invention relates to a kind of preparation method of graphene oxide phase-change microcapsule, comprise the following steps: graphite oxide is soluble in water, stir, ultrasonic, configuration graphene oxide solution; Phase-change material is joined in graphene oxide solution, heat at the temperature higher than phase-change material fusing point, phase-change material is melted, stir the stable Pickering emulsion obtaining graphene oxide coating phase-change materials; In Pickering emulsion, add acid, the pH value of regulation system is 2 ~ 3, and graphene oxide envelopes phase-change material emulsion droplet completely by functional group's intermolecular forces, forms graphene oxide cyst wall; Cooling encystation is separated out, and obtains graphene oxide phase-change microcapsule.Compared with prior art, graphene oxide as a kind of emulsifying agent and enhanced thermal conduction wall material, just can be obtained the microencapsulated phase change material with good heat conductive performance without the need to other emulsifying agent additional by the present invention.These microcapsules have that thermal conductivity factor is high, quantity of heat storage high.Preparation method has the advantages such as easy and simple to handle, with low cost.

Description

A kind of preparation method of graphene oxide phase-change microcapsule
Technical field
The invention belongs to graphene nano material and phase-change microcapsule technical field, especially relate to a kind of preparation method of graphene oxide phase-change microcapsule.
Background technology
Phase-change material absorbs or discharges a large amount of heats in phase transition process, can realize the control of the storage of energy, utilization and temperature.Therefore, the fields such as energy-conservation energy storage, construction material, Aero-Space and heat management can be widely used in.Phase-change material mainly can be divided into solid-solid phase change and solid-liquid phase change by phase transition forms.Solid-liquid phase change material is current most widely used phase-change material, but it becomes liquid phase after melting mutually, has mobility, need be stablized and could use.Phase-change material in use also exists some defects in addition, and as corrosivity, excessively cold, heat transfer property is poor, limits the application of phase-change material.
Phase transformation capsule utilizes encapsulation techniques, and the material that will undergo phase transition is coated in filmogen, even if the solid-liquid phase change material in capsule is in liquid state, also seepage can not occur.Overcome the limitation of phase-change material application technically, improve stability and the service efficiency of phase-change material.Phase-change material capsule comprises phase-change material micro-capsule and nanocapsules, and capsule diameter is microcapsules when 1-500 micron, is Nano capsule when capsule diameter is below 1 micron.They have good application prospect in fields such as electrical equipment cooling, the preparation of heat-storage thermoregulation fiber, thermal fluid circulation additive and energy saving building materials.Although it is relatively large that Nano capsule overcomes Microcapsules Size, easily block the problems such as duct, due to the reduction along with particle diameter, the loss etc. of surfusion and enthalpy of phase change, makes microcapsules still have wide investigation and application and is worth.
At present, problem both ways is mainly deposited in the development of phase transformation capsule material: one is that the enthalpy of phase change of unit mass is not high; Next is that the heat transfer performance of phase-change material is poor, the problem that wall material fragility is large.The wall material of microcapsules mainly contains inorganic material and macromolecular material two class at present.Different types of material has respective feature, but all there is certain application limitation.Graphene oxide is as the presoma preparing Graphene, and be also a kind of nano material of two dimension, itself also has the character of many uniquenesses.Its character and Graphene basic simlarity, have excellent mechanical property and hot property.Graphene oxide has excellent pliability, firmly can envelope phase-change material.Due to the high heat conduction conductance of itself, the thermal conductivity of phase-change material can be significantly improved.And graphene oxide has fire resistance, therefore, graphene oxide can be used as excellent wall material.
In addition, the structure of graphene oxide, primarily of oxide regions (hydrophilic area) and non-oxide regions (hydrophobic region) two parts composition, can be considered it is that the inner and edge of graphene sheet layer is by the product after oxygen-containing functional group (mainly comprising hydroxyl, carboxyl and epoxy radicals etc.) modification.This special construction makes graphene oxide can be regarded as the polymer, anisotropic colloid, amphiphilic species etc. of two dimension.Therefore, it can be used as surfactant and uses, and can regulate the amphipathic of graphene oxide by the size of the pH of system, lamella and reducing degree.
The preparation method of microcapsules mainly contains Physical, chemical method (situ aggregation method, interfacial polymerization etc.), physical-chemical process (coacervation).The part but these preparation methods come with some shortcomings, preparation technology's relative complex, all needs additional emulsifying agent ability stable dispersion in water, has an impact to the performance of capsule.And wall material itself does not make moderate progress to the thermal conductivity factor of phase-change material.
Summary of the invention
Object of the present invention is exactly provide a kind of preparation method of graphene oxide phase-change microcapsule to overcome defect that above-mentioned prior art exists.Graphene oxide as a kind of emulsifying agent and enhanced thermal conduction wall material, just can be obtained the microencapsulated phase change material with good heat conductive performance without the need to other emulsifying agent additional by the present invention.These microcapsules have that thermal conductivity factor is high, quantity of heat storage high.Preparation method has the advantages such as easy and simple to handle, with low cost.
Object of the present invention can be achieved through the following technical solutions:
A preparation method for graphene oxide phase-change microcapsule, the method comprises the following steps:
(1) graphite oxide is soluble in water, stir 30 ~ 60min, ultrasonic 2 ~ 4h, configuration graphene oxide solution;
(2) phase-change material is joined in the graphene oxide solution of step (1) gained, heat at the temperature higher than phase-change material fusing point, phase-change material is melted, stirs the stable Pickering emulsion obtaining graphene oxide coating phase-change materials;
(3) in the Pickering emulsion of step (2) gained, acid is added, the pH value of regulation system is 2 ~ 3, graphene oxide condenses, and graphene oxide envelopes phase-change material emulsion droplet completely by functional group's intermolecular forces, forms graphene oxide cyst wall;
(4) cool encystation to separate out, obtain graphene oxide phase-change microcapsule, the cyst wall of these microcapsules is graphene oxide, and core is phase-change material.
In step (1), the average grain diameter of graphite oxide is 30 ~ 70 μm.
In step (1), the concentration of graphene oxide solution is 0.05mg/mL ~ 2mg/mL.
In step (2), the weight ratio of phase-change material and graphene oxide is 1g:(10 ~ 20) mg.
Phase-change material described in step (2) is oiliness class organic phase change material.
Phase-change material described in step (2) is hexadecanol or hexadecylic acid.
When phase-change material is hexadecanol, in step (2), the temperature of heating is 70 ~ 80 DEG C.
The acid added in step (3) is sulfuric acid.
Principle of the present invention is as follows:
The structure of graphene oxide has hydrophilic radical, hydrophobic regions simultaneously.Hydrophilic radical can be ionic also can be nonionic.This characteristic makes graphene oxide can as emulsifying agent, dispersion and emulsion phase-change material.Do not need additional emulsifying agent just can obtain the microcapsules of small particle diameter.And the microballoon by regulating the concentration, size etc. of graphene oxide just can obtain different-grain diameter size.
In addition, the amphipathic of graphene oxide can be regulated by the size of the pH of system and lamella.Graphene oxide contains-COOH, is dissociated into-COO in aqueous -, therefore its amphipathic impact by pH value, as pH value >7 ,-COOH dissociates, with more negative electrical charge, more hydrophilic.Undersized graphene sheet layer has the ratio in higher margin and center region in addition, more hydrophilic.And the amphipathic of graphene oxide can be regulated by redox condition.Therefore, amphipathic according to graphene oxide, as the pH<7 of regulation system, graphene oxide can condense encystation and separate out.And graphene oxide is under acid effect, utilize the effect of functional group, produce firmly coated.
Graphene oxide has sp 2the carbon skeleton two-dimensional structure of hybrid structure, makes it have excellent mechanical property, has certain intensity and pliability as cyst wall.The cyst wall with some strength can be obtained by the crosslinked action power between oxygenated functional group between graphene oxide.
Compared with prior art, tool of the present invention has the following advantages:
(1) just can obtain microcapsules without the need to adding other emulsifying agents, eliminating emulsifying agent to the impact of capsule performance.
(2) only have graphene oxide, phase-change material and water in emulsion after dispersion, composition is simple, and preparation technology is simple, and with low cost.
(3) graphene oxide has Modulatory character, and the size of graphene oxide capsule regulates by the size, concentration etc. of graphene oxide.Be easy to operation.There is good mechanical strength and pliability simultaneously, can be used as excellent cyst wall.
(4) graphene oxide is the material of two dimension, and thickness only has about 1nm, and has excellent thermal conductivity.As cyst wall, even if multilayer coating structure, can not have an impact to enthalpy of phase change, and the heat transfer property of material can be improved.Therefore, these microcapsules have that thermal conductivity factor is high, quantity of heat storage high.
(5) by the parameter of regulation and control graphene oxide, the graphene oxide capsule size that the present invention obtains can be controlled between tens to hundreds of micron.
Accompanying drawing explanation
Fig. 1 is the microscope photograph of the graphene oxide hexadecanol microcapsules of preparation in embodiment 1;
Fig. 2 is the field emission scanning electron microscope figure of graphene oxide hexadecanol microcapsules under different amplification of preparation in embodiment 1;
Fig. 3 is the microscope photograph of the graphene oxide hexadecanol microcapsules of preparation in embodiment 2;
Fig. 4 is the microscope photograph of the graphene oxide hexadecanol microcapsules of preparation in embodiment 3;
Fig. 5 is the field emission scanning electron microscope figure of graphene oxide hexadecanol microcapsules under different amplification of preparation in embodiment 3;
Fig. 6 is the DSC curve map of the graphene oxide hexadecanol microcapsules of preparation in embodiment 3;
Fig. 7 is the microscope photograph of the graphene oxide phase transformation capsule of preparation in embodiment 4;
Fig. 8 is the DSC curve map of the graphene oxide hexadecylic acid microcapsules of preparation in embodiment 4.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
The preparation of graphene oxide hexadecanol microcapsules
(1) preparation of graphene oxide solution.
Take the graphite oxide of 50 μm of 0.25g, add 500mL deionized water, stir 30min, ultrasonic 3h, be mixed with the graphene oxide solution of 0.05mg/mL.
(2) preparation of emulsion.
Take 1g hexadecanol, add the graphene oxide solution of 10mL, 0.05mg/mL.Heat at 80 DEG C, hexadecanol melts, and stir 60min, stir speed (S.S.) is 400r/min, obtains stable Pickering emulsion.
(3) preparation of microcapsules.
H is dripped in emulsion 2sO 4, reaction 2h.The pH value of system is 2 ~ 3, and graphene oxide condenses, and graphene oxide envelopes phase-change material emulsion droplet completely by active force, separates out through cooling encystation.
As shown in Figure 1, the field emission scanning electron microscope figure of the graphene oxide phase transformation capsule prepared of the present embodiment under different amplification as shown in Figure 2 for the microscope photograph of graphene oxide phase transformation capsule prepared by the present embodiment.Find out from Fig. 1 and Fig. 2, graphene oxide capsule size mostly is about 100 μm, and cyst wall forms by multilayer graphene oxide is coated.
Embodiment 2
The preparation of graphene oxide hexadecanol microcapsules
(1) preparation of graphene oxide solution.
Take the graphite oxide of 50 μm of 0.5g, add 500mL deionized water, stir 30min, ultrasonic 3h, be mixed with the graphene oxide solution of 1mg/mL.
(2) preparation of emulsion.
Take 1g hexadecanol, add the graphene oxide solution of 10mL 1mg/mL.Heat at 80 DEG C, hexadecanol melts, and stir 60min, stir speed (S.S.) is 400r/min, obtains stable Pickering emulsion.
(3) preparation of microcapsules.
H is dripped in emulsion 2sO 4, reaction 2h.The pH value of system is 2 ~ 3, and graphene oxide condenses, and graphene oxide envelopes phase-change material emulsion droplet completely by active force, separates out, obtain graphene oxide hexadecanol microcapsules through cooling encystation.
As shown in Figure 3, as can be seen from Figure 3, graphene oxide capsule size mostly is about 100 μm to the microscope photograph of graphene oxide phase transformation capsule prepared by the present embodiment.
Embodiment 3
The preparation of graphene oxide hexadecanol microcapsules
(1) preparation of graphene oxide solution.
Take the graphite oxide of 50 μm of 1g, add 500mL deionized water, stir 30min, ultrasonic 3h, be mixed with the graphene oxide solution of 2mg/mL.
(2) preparation of emulsion.
Take 1g hexadecanol, add the graphene oxide solution of 10mL 2mg/mL.Heat at 80 DEG C, hexadecanol melts, and stir 1h, stir speed (S.S.) is 400r/min, obtains stable Pickering emulsion.
(3) preparation of microcapsules.
The H of 1mL is dripped in emulsion 2sO 4, reaction 2h.The pH value of system is 2 ~ 3, and graphene oxide condenses, and graphene oxide envelopes phase-change material emulsion droplet completely by active force, separates out, obtain graphene oxide hexadecanol microcapsules through cooling encystation.
As shown in Figure 4, the grain size of graphene oxide hexadecanol microcapsules is about 90 μm to the microscope figure of graphene oxide phase transformation capsule prepared by the present embodiment.The field emission scanning electron microscope figure of the graphene oxide hexadecanol microcapsules prepared of the present embodiment under different amplification as shown in Figure 5.The particle diameter of graphene oxide microcapsules is 90 μm.Cyst wall forms by multilayer graphene oxide is coated.The DSC curve map of graphene oxide phase transformation capsule prepared by the present embodiment as shown in Figure 6.In temperature-rise period, the enthalpy of phase change of graphene oxide phase transformation capsule is 91.4% of pure phase-change material.In temperature-fall period, its enthalpy of phase change is 95.1% of pure phase-change material, and enthalpy of phase change does not significantly lose.Its degree of supercooling does not also significantly change.
Embodiment 4
The preparation of graphene oxide hexadecylic acid microcapsules
(1) preparation of graphene oxide solution.
Take the graphite oxide of 50 μm of 1g, add 500mL deionized water, stir 30min, ultrasonic 3h, be mixed with the graphene oxide solution of 2mg/mL.
(2) preparation of emulsion.
Take 1g hexadecylic acid, add the graphene oxide solution of 10mL 2mg/mL.Heat at 80 DEG C, hexadecylic acid melts, and stir 1h, stir speed (S.S.) is 400r/min, obtains stable Pickering emulsion.
(3) preparation of microcapsules.
1mL H is dripped in emulsion 2sO 4, reaction 2h.The pH value of system is 2 ~ 3, and graphene oxide condenses, and graphene oxide envelopes phase-change material emulsion droplet completely by active force, separates out through cooling encystation.
As shown in Figure 7, the particle diameter of graphene oxide hexadecylic acid microcapsules is about 80 μm to the microscope photograph of graphene oxide hexadecylic acid microcapsules prepared by the present embodiment.The DSC curve map of graphene oxide hexadecylic acid microcapsules prepared by the present embodiment as shown in Figure 8.In temperature-rise period, the enthalpy of phase change of graphene oxide hexadecylic acid microcapsules is 98% of pure phase-change material.In temperature-fall period, its enthalpy of phase change is 92.3% of pure phase-change material, and its enthalpy of phase change does not significantly lose.Its degree of supercooling does not also significantly change.

Claims (7)

1. a preparation method for graphene oxide phase-change microcapsule, is characterized in that, the method comprises the following steps:
(1) graphite oxide is soluble in water, stir, ultrasonic, configuration graphene oxide solution;
(2) phase-change material is joined in the graphene oxide solution of step (1) gained, the weight ratio of phase-change material and graphene oxide is 1g:(10 ~ 20) mg, heat at the temperature higher than phase-change material fusing point, phase-change material is melted, stirs the stable Pickering emulsion obtaining graphene oxide coating phase-change materials;
(3) in the Pickering emulsion of step (2) gained, add acid, the pH value of regulation system is 2 ~ 3, and graphene oxide envelopes phase-change material emulsion droplet completely by functional group's intermolecular forces, forms graphene oxide cyst wall;
(4) cool encystation to separate out, obtain graphene oxide phase-change microcapsule.
2. the preparation method of a kind of graphene oxide phase-change microcapsule according to claim 1, is characterized in that, in step (1), the concentration of graphene oxide solution is 0.05mg/mL ~ 2mg/mL.
3. the preparation method of a kind of graphene oxide phase-change microcapsule according to claim 1, is characterized in that, in step (1), the average grain diameter of graphite oxide is 30 ~ 70 μm.
4. the preparation method of a kind of graphene oxide phase-change microcapsule according to claim 1, is characterized in that, the phase-change material described in step (2) is oiliness class organic phase change material.
5. the preparation method of a kind of graphene oxide phase-change microcapsule according to claim 4, is characterized in that, the phase-change material described in step (2) is hexadecanol or hexadecylic acid.
6. the preparation method of a kind of graphene oxide phase-change microcapsule according to claim 5, is characterized in that, when phase-change material is hexadecanol, in step (2), the temperature of heating is 70 ~ 80 DEG C.
7. the preparation method of a kind of graphene oxide phase-change microcapsule according to claim 1, is characterized in that, the acid added in step (3) is sulfuric acid.
CN201410006689.9A 2014-01-07 2014-01-07 A kind of preparation method of graphene oxide phase-change microcapsule CN103752234B (en)

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