CN102585776A - Three-dimensional graphene/phase change energy storage composite material and preparation method thereof - Google Patents
Three-dimensional graphene/phase change energy storage composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a three-dimensional graphene/phase change energy storage composite material and a preparation method thereof. The technical scheme is as follows: graphene and a phase change energy storage material are in situ compounded, wherein porous graphene with a three-dimensional structure is used as a heat conductor and a compound die, and a solid-liquid phase change organic material is used as the energy storage material and filler. The three-dimensional porous graphene is compounded with the phase change material, the phase change energy storage material is partitioned in a plurality of pore spaces and is in tight joint with the graphene wall so as to greatly increase the effective heat contact area, and the highly linked graphene three-dimensional heat conduction network channels can realize rapid system heat exchange. In addition, due to the capillary adsorption capacity of porous graphene, the liquid-state phase change energy storage material is localized, so as to effectively prevent seepage. Therefore, the three-dimensional graphene foam has good designability, and becomes a lighter and more effective heat dissipation material for electronic devices.
Description
Technical field
The present invention relates to the preparing technical field of graphene composite material, be specifically related to a kind of three-dimensional Graphene/phase-change energy-storage composite material and preparation method thereof.
Background technology
In the storage of heat energy with utilize in the process, usually exist between the supply and demand in time with the space on unmatched contradiction, like the heat radiation of the high-power electronic device of the peak-valley difference of the intermittence of sun power, electric load, periodic duty and industrial exhaust heat utilization etc.Absorb or discharge a large amount of heats when phase-changing energy storage material undergoes phase transition through material, realize the storage and the utilization of energy, can effectively solve energy supply and demand unmatched contradiction on time and space.Therefore; Phase change energy storage technology is widely used in having discontinuity or instable heat management field, like the field such as energy-conservation of recycling, covil construction heating and the air-conditioning of " peak load shifting " of the heat radiation of the heat management of aerospace large power assembly, cyclical intermission formula work electron device, sun power utilization, electric power, industrial waste heat waste heat.In recent years, phase change energy storage technology becomes forward position research direction that ten minutes is active in energy science and the material science.
It is big that phase-changing energy storage material has an energy storage density, the advantage of energy storage exoergic process approximately constant temperature.But most phase-change heat-storage materials exist thermal conductivity low, shortcomings such as heat exchange property difference.Employing has high heat conduction, low density, raw material of wood-charcoal material corrosion-resistant and good chemical stability it is carried out intensifying heat transfer, can effectively improve system's heat exchange efficiency.Solid-liquid setting phase change energy storage material commonly used is actually one type of composite phase-change material, mainly is to be grouped into by two kinds of one-tenth: the one, and operation material; The 2nd, carrier matrix.Operation material utilizes its solid-liquid phase change to carry out energy storage, and operation material can be various solid-liquid phase change materials, like paraffin, Triple Pressed Stearic Acid, salt hydrate, inorganic salt and metal and alloy material thereof etc.Carrier matrix mainly is immobility and the workability that is used for keeping phase change material, and it is carried out intensifying heat transfer.
Graphene (graphene) is a kind of novel charcoal material, and it has by the tightly packed bi-dimensional cellular shape crystalline structure that forms of monolayer carbon atom, and it is the elementary cell that makes up other dimension blacking (like zero dimension soccerballene, one dimension carbon nanotube, three-dimensional graphite).Graphene itself has very high thermal conductivity, and thermal conductivity can reach 5000Wm
-1K
-1, and have that density is little, thermal expansivity is low concurrently and advantage such as corrosion-resistant, be expected to become a kind of desirable heat sink material.Graphene as the intensifying heat transfer carrier, might be overcome the low shortcoming of single phase change material thermal conductivity, shorten the compound system thermal response time, improve heat exchange efficiency, realize that matrix material conducts heat and heat accumulation is integrated.
Can adopt the foamed metal that has plane and curved-surface structure characteristics concurrently as growing substrate, the spumescence grapheme material that utilizes the CVD method to prepare to have the three-dimensional networks structure.The structure that grapheme material through the preparation of this method has intactly duplicated foamed metal, Graphene constitutes the integral body of a full-mesh with the mode of seamless link, has excellent charge-conduction ability, huge specific surface area, porosity and extra-low density.And this method controllability is good, is easy to amplify, and can regulate and control the average number of plies of Graphene, specific surface area, density and the electroconductibility of Graphene network through changing processing condition.
Three-dimensional grapheme foam with metal form CVD method preparation has abundant pore structure characteristic, and its specific surface area is high, and hole wall vestibule height is communicated with, for body material provide can be composite filled the space.If three-dimensional porous Graphene and phase change material is compound, phase-changing energy storage material is isolated in each vestibule, combines closely with the Graphene wall, and the net heat contact area increases substantially, and the three-dimensional heat conduction network channel of the Graphene of height UNICOM is with the heat exchange of Rapid Realization system.On the other hand, the capillary adsorptive power of porous graphite alkene can effectively prevent seepage flow with the localization of liquid phase-change energy storage material.
Along with the integrated fast development of electron device, heat management becomes the bottleneck that the restriction high power device is used.The thermal management materials that the development over-all properties is good, manufacturing cost is cheap relatively is one of gordian technique that prolongs high-power electronic device work-ing life.Methods such as adding aluminium radiating fin, heat-conducting plastic shell, surface emissivity radiating treatment, fan and heat pipe is mainly adopted in the heat radiation of high-power electronic device at present, but existing scatterer effect is unsatisfactory.
In addition; Present high thermal conductivity based on aluminum oxide, Natural manganese dioxide, graphite etc.; Usually aluminum oxide, Natural manganese dioxide, graphite etc. are dispersed in the heat sink material as the heat conduction additive,, reach the purpose of the thermal diffusivity that improves device through improving exothermic material self heat conduction rate.Though these class methods can improve the thermal diffusivity of device,, also increased the add-on of heat conduction additive along with the raising that the thermal diffusivity of device requires.
Summary of the invention
The purpose of this invention is to provide three-dimensional Graphene/phase-change energy-storage composite material that a kind of electron device heat management is used, to solve the low problem of phase-changing energy storage material thermal conductivity that exists in the prior art.This matrix material of the present invention has good thermal conductivity and erosion resistance, can the Rapid Realization heat exchange.
At this; Three-dimensional Graphene/the phase-change energy-storage composite material of the heat conduction that the present invention provides a kind of dissipation from electronic devices to use; It is characterized in that Graphene and phase-changing energy storage material original position are compound; Wherein with porous graphite alkene with three-dimensional structure as heat conductor and composite shuttering, with the organic materials of solid-liquid phase change as energy storage material and weighting agent.
Three-dimensional Graphene/phase-change energy-storage composite material provided by the invention can realize conducting heat and heat accumulation integrated.The present invention makes to have heat absorption and combines with three-dimensional Graphene with the phase-changing energy storage material of exothermic effects, utilizes the high thermal conductivity coefficient of three-dimensional Graphene and thermal conductivity one-tenth that cellular structure makes the phase-change accumulation energy system to be improved several fold.
Energy storage material of the present invention can select to have good infiltrating organic energy storage material with Graphene, for example can be Triple Pressed Stearic Acid, LAURIC ACID 99 MIN or paraffin.
As heat conductor and composite shuttering, the present invention adopts the grapheme foam with three-dimensional structure, is to be template through adopting foamed metal, CVD method growing three-dimensional Graphene and making.
Make phase-changing energy storage material compound with three-dimensional porous Graphene with foamy structure; Phase-changing energy storage material is isolated in each vestibule; Combine closely with the Graphene wall, the net heat contact area increases substantially, and the three-dimensional heat conduction network channel of the Graphene of height UNICOM is with the heat exchange of Rapid Realization system.On the other hand, the capillary adsorptive power of porous graphite alkene can effectively prevent seepage flow with the localization of liquid phase-change energy storage material.Therefore, as solid-liquid phase change energy storage material of the present invention, the material that liquid state viscosity is lower than 5Pa.s also can be suitable for.
The present invention adopts the three-dimensional Graphene of CVD method growth to may be controlled to multilayered structure.Preferably be 2 to 8 layers multilayered structure, more preferably be 4 to 7 layers multilayered structure.Like this, formability is improved, help compound preparation.In addition, the three-dimensional Graphene by the growth of CVD method is that multilayered structure can make the heat conductance of the three-dimensional Graphene/phase-change energy-storage composite material of preparation be further enhanced.
In addition, the aperture of three-dimensional grapheme foam is adjustable at submicron to hundreds of micrometer ranges.Porosity can reach 80%-95%.Aperture and porosity can be through the number of plies controls of growth Graphene.
Again, in three-dimensional Graphene/phase-change energy-storage composite material of the present invention, the volume loading level of energy storage material (hole utilization ratio) scope is 10%-98%.The vesicular structure of three-dimensional Graphene be phase-changing energy storage material provide can be composite filled enough spaces, loading level can reach 10%-98% in the present invention; And then the thermal conductivity of matrix material is increased substantially.Make the loading level of phase-changing energy storage material reach suitable scope, thereby can guarantee the high heat conductance and the latent heat of phase change of composite system.
Matrix material provided by the invention is to utilize vacuum impregnation technology to be composited by three-dimensional Graphene and said phase-changing energy storage material.Like this, can regulate the loading level of phase-changing energy storage material through adjusting vacuum tightness, thus the thermal conductivity of regulating matrix material.
Again; Can there be the foamed metal template of three-dimensional Graphene directly to utilize the complex body of the compound formation earlier of vacuum impregnation technology Graphene/foamed metal/phase-changing energy storage material growth, makes Graphene/phase-change energy-storage composite material through the metal that defoams again with phase-changing energy storage material.In addition, the Graphene/phase-change energy-storage composite material that can also be further the metal that defoams be formed utilize once more vacuum impregnation technology further with the compound acquisition Graphene/phase-change energy-storage composite material of phase-changing energy storage material.Compound and the matrix material that makes of metal pattern and then enforcement and phase-changing energy storage material that defoams earlier, Graphene " skeleton " very easily occurs damaged.After foamed metal " skeleton " is etched away by hydrochloric acid, the Graphene strength degradation that obtains, and then breakage appears in Graphene " skeleton " in follow-up recombination process, Graphene " skeleton " integrity is poor.
The present invention also provides a kind of preparation method of three-dimensional Graphene/phase-change energy-storage composite material, comprises that adopting foamed metal is template, with CVD method growing three-dimensional Graphene, obtains the operation A of Graphene/foamed metal complex body;
Utilize vacuum impregnation technology Graphene/foamed metal complex body that operation A is made and the process B that is compounded to form the complex body of Graphene/foamed metal/phase-changing energy storage material through the phase-changing energy storage material that melts;
The complex body of Graphene/foamed metal/phase-changing energy storage material that process B the is made metal that defoams makes the operation C of Graphene/phase-changing energy storage material complex body;
Graphene/phase-changing energy storage material complex body to operation C utilizes vacuum impregnation technology further to be compounded to form the step D of Graphene/phase-change energy-storage composite material with phase-changing energy storage material once more.
Also comprise the process B 1 of utilizing vacuum drying oven to make the energy storage material fusing at a certain temperature in the process B again.
All right, in process B and/or step D, complex body impregnated in phase-changing energy storage material make it with phase-changing energy storage material compound process in system is vacuumized.
Utilize vacuum impregnation technology can further improve the filling ratio of phase-changing energy storage material.Thereby further improve the thermal conductivity of matrix material.
Three-dimensional grapheme foam is as heat sink material, has the thermal conductivity height, density is little, thermal expansivity is low, resistance to acids and bases and be prone to advantage such as processing.Few the time, three-dimensional Graphene has thermal conductivity preferably, can overcome the low shortcoming of single phase change material thermal conductivity than the Graphite Powder 99 consumption, shortens the compound system thermal response time, improves heat exchange efficiency, realizes that matrix material conducts heat and heat accumulation is integrated.Three-dimensional grapheme foam with metal form CVD method preparation has abundant pore structure characteristic, and its specific surface area is high, and hole wall vestibule height is communicated with, for body material provide can be composite filled the space.Three-dimensional porous Graphene and phase change material are compound, and phase-changing energy storage material is isolated in each vestibule, combine closely with the Graphene wall, and the net heat contact area increases substantially, and the three-dimensional heat conduction network channel of the Graphene of height UNICOM is with the heat exchange of Rapid Realization system.On the other hand, the capillary adsorptive power of porous graphite alkene can effectively prevent seepage flow with the localization of liquid phase-change energy storage material.Therefore three-dimensional grapheme foam has designability preferably, becomes lighter and dissipation from electronic devices material more efficiently.
Description of drawings
Fig. 1 is the signal preparation flow figure of the three-dimensional Graphene/phase-change energy-storage composite material of one embodiment of the invention;
Fig. 2 nickel foam SEM photo;
Fig. 3 Graphene/froth nickel complex SEM photo;
Fig. 4 Graphene/nickel foam/Triple Pressed Stearic Acid complex body SEM photo;
Fig. 5 Graphene Triple Pressed Stearic Acid matrix material SEM photo.
Embodiment
With reference to Figure of description, and combine following embodiment to further specify the present invention, should be understood that Figure of description and following embodiment only are used to explain the present invention, and unrestricted the present invention.
At first; The present invention provides a kind of three-dimensional Graphene/phase-change energy-storage composite material, and this matrix material is composite filled in as three-dimensional Graphene vesicular structure carrier, that have the heat conduction network channel of UNICOM " height ", thermally conductive material and constitute by phase-changing energy storage material.
Three-dimensional Graphene/phase-change energy-storage composite material of the present invention used have the thermal conductivity height, density is little and the three-dimensional Graphene of advantage such as corrosion-resistant, has improved the erosion resistance and the thermal conductivity of matrix material.Intensifying heat transfer body as composite system; The vesicular structure of three-dimensional Graphene be phase-changing energy storage material provide can be composite filled the space; Than conventional graphite heat conduction additive amount few the time; Three-dimensional Graphene " the heat conduction network channel of height UNICOM " can be apace dissipates the heat of thermal source, improves the thermal diffusivity of radiating element.
Referring to the signal preparation flow figure of Fig. 1, wherein with nickel foam as the foamed metal template, be the preparing method's of example description three-dimensional Graphene/phase-change energy-storage composite material of the present invention block diagram with the Triple Pressed Stearic Acid.Should be understood that as foamed metal, can also be the metal that copper, aluminium etc. can form foamy structure.
Referring to Fig. 1, the preparation method of three-dimensional Graphene/phase-change energy-storage composite material provided by the invention comprises:
Adopting foamed metal 1 is template, with CVD method growing three-dimensional Graphene, obtains the operation A of Graphene/foamed metal complex body 2;
Utilize vacuum impregnation technology Graphene/foamed metal complex body that operation A is made and the process B that is compounded to form the complex body 3 of Graphene/foamed metal/phase-changing energy storage material through the phase-changing energy storage material that melts;
The complex body of Graphene/foamed metal/phase-changing energy storage material that process B the is made metal that defoams makes the operation C of Graphene/phase-changing energy storage material complex body;
Graphene/phase-changing energy storage material complex body to operation C utilizes vacuum impregnation technology further to be compounded to form the step D of Graphene/phase-change energy-storage composite material 4 with phase-changing energy storage material once more.
In operation A, be that template adopts the CVD method to prepare three-dimensional grapheme foam with foamed metal (its SEM photo is seen Fig. 2), obtain Graphene/foamed metal compound system (its SEM photo is seen Fig. 3).Can control the structure that makes grapheme foam in the compound system is multilayered structure, for example can be the structure of 2-8 layer.Aperture and porosity can be through the number of plies controls of growth Graphene.The thermal conductivity of multi-layer graphene prepared composite system is higher.
Also comprise the process B 1 of utilizing vacuum drying oven to make the energy storage material fusing at a certain temperature in the process B again.For example can phase-changing energy storage material (Triple Pressed Stearic Acid, or LAURIC ACID 99 MIN, or paraffin) be placed in 80 ℃ of (this temperature is higher than phase change material softening temperature or fusing point, can the temperature that phase change material is fused into liquid be got final product) vacuum drying ovens and make it fusing.
Preparing method of the present invention can also vacuumize system in first time steeping process (in the process B), and for example can make the system vacuum degree is 0～0.09MPa.After treating the phase-changing energy storage material fusing, Graphene/foamed metal is impregnated in the phase-changing energy storage material, system is vacuumized, vacuum tightness is 0.09MPa, obtains Graphene/nickel foam/phase-changing energy storage material compound system (its SEM photo is seen Fig. 4).
Example as operation C; Can be at room temperature; Graphene/nickel foam/phase-changing energy storage material compound system is impregnated in the certain density hydrochloric acid, alternatively, also can selects to react with foamed metal and to make it other suitable solution (for example sulfuric acid, nitric acid etc.) of dissolved.React after 12-48 hour, treat that nickel foam takes out sample fully with behind the hydrochloric acid reaction, washing obtains Graphene/phase-change energy-storage composite material system (its SEM photo is seen Fig. 5) to neutrality;
All right, in second time steeping process (in the step D), also system is vacuumized, making the system vacuum degree is 0.01～0.09MPa.And the system vacuum state was kept 1～3 hour.For example, can Graphene/phase-change energy-storage composite material system be impregnated in the Triple Pressed Stearic Acid of fusing once more, put into loft drier, system repeatedly is vacuumized 3～5 times, take out sample after waiting to reach the compactedness of phase-changing energy storage material.System is repeated to vacuumize repeatedly.Like this, can guarantee that the phase-changing energy storage material that melts is composite filled in the three-dimensional Graphene of vesicular structure with certain compactedness.
Embodiment further give an example below to specify example preparation technology of the present invention.Should be understood that following embodiment is for the present invention is described better, and unrestricted the present invention.Although in following embodiment, adopt Triple Pressed Stearic Acid, LAURIC ACID 99 MIN and paraffin, should be understood that other any suitable phase-changing energy storage materials also are suitable for.
Embodiment 1
Adopting the CVD method, is that template prepares three-dimensional grapheme foam (1-3 layer) with nickel foam (its SEM photo is seen Fig. 2), obtains Graphene/froth nickel complex system (its SEM photo is seen Fig. 3, and thermal conductivity is seen table 1);
The phase-changing energy storage material Triple Pressed Stearic Acid is placed in 80 ℃ of vacuum drying ovens; After treating the Triple Pressed Stearic Acid fusing, above-mentioned Graphene/nickel foam is impregnated in the Triple Pressed Stearic Acid, system is vacuumized; Vacuum tightness is 0.09MPa; Keep vacuum state 1 hour, and obtained Graphene/nickel foam/Triple Pressed Stearic Acid compound system (its SEM photo is seen Fig. 4, and thermal conductivity is seen table 1);
Under the room temperature, above-mentioned Graphene/nickel foam/Triple Pressed Stearic Acid compound system is impregnated in 65% the hydrochloric acid, after 48 hours, treats that nickel foam takes out sample fully with behind the hydrochloric acid reaction, washing obtains Graphene/Triple Pressed Stearic Acid compound system to neutrality;
Gained Graphene/Triple Pressed Stearic Acid compound system is impregnated in the Triple Pressed Stearic Acid of fusing once more; Put into 80 ℃ of loft drier, vacuumize repeatedly 3～5 times, wait not have bubble and produce back taking-up sample; Be designated as CVD3D Graphene/Triple Pressed Stearic Acid (its SEM photo is seen Fig. 5, and thermal conductivity is seen table 1);
Then, the density of specimen, specific heat, thermal diffusivity and thermal conductivity, test result is seen table 1.
Embodiment 2
Preparation process in the present embodiment and step and the foregoing description 1 are identical.Different is: phase-changing energy storage material is selected LAURIC ACID 99 MIN, and test result is seen table 1;
Test result shows that Graphene/LAURIC ACID 99 MIN compound system and Graphene/Triple Pressed Stearic Acid compound system has the thermal physical property parameter of close thermal conductivity.
Embodiment 3
Preparation process in the present embodiment and step and the foregoing description 1 are identical.Different is: phase-changing energy storage material is selected paraffin, and test result is seen table 1;
Test result shows that Graphene/paraffin compound system and above-mentioned Graphene/LAURIC ACID 99 MIN compound system and Graphene/Triple Pressed Stearic Acid compound system have the thermal physical property parameter of close thermal conductivity, the more preceding two kinds of matrix material height of thermal conductivity.
Embodiment 4
Preparation process in the present embodiment and step and the foregoing description 3 are identical.Different is: 4 Graphenes/froth nickel complex system is compressed into 1, as carrier;
Test result shows, the stack adjustable carrier aperture and the porosity of multi-layered foamed nickel template, and the thermal conductivity of prepared composite system is higher than single tier templates.
Embodiment 5
Preparation process in the present embodiment and step and the foregoing description 4 are identical.Different is: steeping process adopts antivacuum, the normal pressure dipping.Test result is seen table 1;
Test result shows that because phase-changing energy storage material and Graphene have wellability preferably, gained matrix material filling degree is still better, and the thermal conductivity of prepared composite system is more lower slightly than single tier templates.
Embodiment 6
Preparation process in the present embodiment and step and the foregoing description 1 are identical.Different is: adopting the CVD method, is that template prepares three-dimensional grapheme foam (4-7 layer) with the nickel foam, obtains Graphene/froth nickel complex system.Test result is seen table 1; Test result shows that aperture and porosity can be through the number of plies controls of growth Graphene, and the thermal conductivity of multi-layer graphene prepared composite system is higher.
Embodiment 7
Preparation process in the present embodiment and step and the foregoing description 1 are identical.Different is: time of immersion is 170 hours, and test result is seen table 1;
The result shows that after 170 hours, thermal physical property parameters such as the thermal conductivity of matrix material do not descend.
Comparative Examples 1
Adopt modification Hummers method to prepare graphene oxide, the hydrothermal method reduction obtains three-dimensional grapheme foam (its thermal conductivity is seen table 1).The phase-changing energy storage material Triple Pressed Stearic Acid is placed in 80 ℃ of vacuum drying ovens.After treating the Triple Pressed Stearic Acid fusing, above-mentioned Graphene is impregnated in the Triple Pressed Stearic Acid, vacuum tightness is 0.09MPa, keeps vacuum state 1 hour.Vacuumize repeatedly 3～5 times, wait not have bubble and produce back taking-up sample, be designated as hydro-thermal 3D Graphene/Triple Pressed Stearic Acid (its thermal conductivity is seen table 1).Then, the density of specimen, specific heat, thermal diffusivity and thermal conductivity, test result is seen table 1;
As shown in table 1; Compare with the thermal conductivity test data of Comparative Examples 1 sample, the thermal conductivity of phase-change energy-storage composite material of the present invention (1.954W/ (mK)) has improved 7 times than the thermal conductivity (0.244W/ (mK)) of the phase-change energy-storage composite material that Hydrothermal Preparation Graphene in the Comparative Examples obtains.Simultaneously, the thermal conductivity of matrix material has improved 5 times than the stearic thermal conductivity of phase-changing energy storage material.
Comparative Examples 2
(1) is that template adopts the CVD method to prepare three-dimensional grapheme foam with the nickel foam, obtains Graphene/froth nickel complex system;
(2) under the room temperature, Graphene/froth nickel complex system is impregnated in 65% the hydrochloric acid, after 48 hours, treats that nickel foam takes out sample fully with behind the hydrochloric acid reaction, washing obtains three-dimensional Graphene to neutrality;
(3) the three-dimensional Graphene of gained and phase-changing energy storage material Triple Pressed Stearic Acid (or LAURIC ACID 99 MIN, or paraffin) are placed in 80 ℃ of vacuum drying ovens;
(4) treat Triple Pressed Stearic Acid fusing after, system is vacuumized, vacuum tightness is 0.09MPa, keeps vacuum state 1 hour;
(5) vacuumize 3～5 times repeatedly, take out sample after waiting to reach the compactedness of phase-changing energy storage material;
The sample moulding that obtains in the Comparative Examples 2 is relatively poor, and Graphene " skeleton " has breakage.In (2) step, after nickel foam " skeleton " is etched away by hydrochloric acid, the Graphene strength degradation that obtains, Graphene in follow-up recombination process " skeleton " has breakage, and forming materials is relatively poor.
Comparative Examples 3
(1) is that template adopts the CVD method to prepare three-dimensional grapheme foam with the nickel foam, obtains Graphene/froth nickel complex system, 3 Graphenes/froth nickel complex system is compressed into 1, as carrier;
(2) under the room temperature, Graphene/froth nickel complex system is impregnated in 65% the hydrochloric acid, after 48 hours, treats that nickel foam takes out sample fully with behind the hydrochloric acid reaction, washing obtains three-dimensional Graphene to neutrality;
(3) the three-dimensional Graphene of gained and phase-changing energy storage material Triple Pressed Stearic Acid (or LAURIC ACID 99 MIN, or paraffin) are placed in 80 ℃ of vacuum drying ovens;
(4) treat Triple Pressed Stearic Acid fusing after, system is vacuumized, vacuum tightness is 0.09MPa, keeps vacuum state 1 hour;
(5) vacuumize 3～5 times repeatedly, take out sample after waiting to reach the compactedness of phase-changing energy storage material;
The sample moulding that obtains in the Comparative Examples 3 is relatively poor, and demixing phenomenon appears in three layer graphenes, and forming materials is relatively poor.
Following table be the sample that makes of above each embodiment density, specific heat, thermal diffusivity and thermal conductivity test result relatively.As shown in table 1, compare the thermal conductivity (1.954Wm of phase-change energy-storage composite material of the present invention with the thermal conductivity test data of comparative example
-1K
-1) thermal conductivity (0.244Wm of the phase-change energy-storage composite material that obtains than Hydrothermal Preparation Graphene in the Comparative Examples
-1K
-1) improved 7 times.Simultaneously, the thermal conductivity of matrix material has improved 5 times than the stearic thermal conductivity of phase-changing energy storage material.
Table 1:
Table 1
Claims (15)
1. the three-dimensional Graphene/phase-change energy-storage composite material of heat conduction used of a dissipation from electronic devices; It is characterized in that Graphene and phase-changing energy storage material original position are compound; Wherein with porous graphite alkene with three-dimensional structure as heat conductor and composite shuttering, with the organic materials of solid-liquid phase change as energy storage material and weighting agent.
2. three-dimensional Graphene/phase-change energy-storage composite material according to claim 1 is characterized in that, said energy storage material is Triple Pressed Stearic Acid, LAURIC ACID 99 MIN or paraffin.
3. three-dimensional Graphene/phase-change energy-storage composite material according to claim 1 is characterized in that, said Graphene is that the employing foamed metal is a template, with the three-dimensional Graphene of CVD method growth.
4. three-dimensional Graphene/phase-change energy-storage composite material according to claim 3 is characterized in that, the three-dimensional Graphene of said CVD method growth is 2 to 8 layers a multilayered structure.
5. three-dimensional Graphene/phase-change energy-storage composite material according to claim 3 is characterized in that, the aperture of the three-dimensional Graphene of said growth is adjustable at submicron to hundreds of micrometer ranges.
6. according to each described three-dimensional Graphene/phase-change energy-storage composite material of claim 1 to 5, it is characterized in that the volume loading level scope of said energy storage material is 10%-98%.
7. according to each described three-dimensional Graphene/phase-change energy-storage composite material of claim 1 to 5, it is characterized in that Graphene and phase-changing energy storage material utilize vacuum impregnation technology to be composited.
8. three-dimensional Graphene/phase-change energy-storage composite material according to claim 3; It is characterized in that; There is the foamed metal template of three-dimensional Graphene directly to utilize the compound complex body that forms Graphene/foamed metal/phase-changing energy storage material earlier of vacuum impregnation technology growth, again through the metal formation Graphene/phase-change energy-storage composite material that defoams with phase-changing energy storage material.
9. three-dimensional Graphene/phase-change energy-storage composite material according to claim 8; It is characterized in that Graphene/phase-change energy-storage composite material that the metal that defoams is formed utilizes vacuum impregnation technology further to be compounded to form Graphene/phase-change energy-storage composite material with phase-changing energy storage material once more.
10. the preparation method of a three-dimensional Graphene/phase-change energy-storage composite material is characterized in that may further comprise the steps:
The employing foamed metal is a template, with CVD method growing three-dimensional Graphene, obtains the operation A of Graphene/foamed metal complex body;
Graphene/foamed metal complex body that operation A is made impregnated in the phase-changing energy storage material of fusing, be compounded to form the process B of the complex body of Graphene/foamed metal/phase-changing energy storage material with phase-changing energy storage material;
The complex body of Graphene/foamed metal/phase-changing energy storage material that process B the is made metal that defoams makes the operation C of Graphene/phase-changing energy storage material complex body;
Graphene/phase-changing energy storage material complex body to operation C further impregnated in the phase-changing energy storage material, make it further to be compounded to form with phase-changing energy storage material the step D of Graphene/phase-change energy-storage composite material.
11. preparation method according to claim 10 is characterized in that also comprising in the said process B process B 1 of utilizing vacuum drying oven to make the energy storage material fusing at a certain temperature.
12., it is characterized in that said process B and/or said step D vacuumize system at steeping process according to claim 10 or 11 described preparing methods.
13., it is characterized in that also being included in after the said operation A multi-disc Graphene/foamed metal complex body be pressed into the operation A1 that uses as follow-up process B behind the full wafer according to claim 10 or 11 described preparing methods.
14., it is characterized in that said foamed metal is a nickel foam according to claim 10 or 11 described preparing methods.
15., it is characterized in that said energy storage material is Triple Pressed Stearic Acid, LAURIC ACID 99 MIN or paraffin according to claim 10 or 11 described preparing methods.
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