CN105018043A - Use of heat-storage and heat-release graphene composite phase-change material - Google Patents

Use of heat-storage and heat-release graphene composite phase-change material Download PDF

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CN105018043A
CN105018043A CN201510418866.9A CN201510418866A CN105018043A CN 105018043 A CN105018043 A CN 105018043A CN 201510418866 A CN201510418866 A CN 201510418866A CN 105018043 A CN105018043 A CN 105018043A
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heat
change material
composite phase
graphene composite
graphene
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CN105018043B (en
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张忠平
张淑东
王振洋
蒋颖畅
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Hefei Institutes of Physical Science of CAS
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Hefei Institutes of Physical Science of CAS
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Abstract

The invention discloses a use of a heat-storage and heat-release graphene composite phase-change material, and is characterized in that the heat-storage and heat-release graphene composite phase-change material is used for providing a heat source for a thermoelectric device to generate electricity; specifically, firstly the heat-storage and heat-release graphene composite phase-change material is posted on a heat dissipation body, heat conduction channels provided by graphene in the graphene composite phase-change material are used for collecting heat and transferring the heat to an organic phase-change material in the graphene composite phase-change material, and then the heat storage capacity of the organic phase-change material stores the heat in the graphene composite phase-change material; and finally, the graphene composite phase-change material having heat storage completed is used as the heat source of the thermoelectric device and realizes the difference of temperatures on both ends of the thermoelectric device, so as to generate the electricity. The used graphene composite phase-change material has huge heat-storage and heat-release performance and good heat conduction capacity, can be used as heat interface materials of various electronic devices, and provides good heat control management for heat supply and stable operation.

Description

A kind of purposes of heat accumulation heat release Graphene composite phase-change material
Technical field
The present invention relates to a kind of purposes of heat accumulation heat release Graphene composite phase-change material.
Background technology
When the closed circuit that two kinds of different conductor connection formations one are complete, as long as it is poor the two ends of contact to be placed in differing temps district formation temperature, just there will be volts lost at contact two ends, thus generation current in the loop, this phenomenon is called Seebeck effect (Seebeck).Seebeck effect is the theoretical basis realizing heat energy to be directly converted to electric energy.Along with world environments is polluted and day by day the increasing the weight of of energy dilemma, the power generation system utilizing thermoelectric material to make, because of advantages such as volume is little, lightweight, noiselessness, no pollution, long lifetives, becomes study hotspot nearly ten years.
Utilize the key issue of thermoelectric generation technology generation current be how obtain at thermounit two ends continue, stable heat thus form higher temperature head.At present, in heat power plant, adopt heat-supply type unit, except supply electric energy, also utilize the extracted steam from turbine making merit (namely having generated electricity) or steam discharge to meet production and institute in life heat requirement simultaneously.Heat to power output process (condensing-type unit generation) certainly leads to the low-grade heat loss of energy (heat release in low-temperature receiver of steam turbine steam discharge), allows higher-grade heat energy (steam heat that boiler provides) devalue ground for low grade heat supply on the other hand.And heat energy is type of service the most widely in energy utilization, in the utilization of the various energy, 85-90% is the demand meeting people by converting heat energy to.And the use of the waste of heat energy and poor efficiency thereof the difficult problem that to be countries in the world urgently to be resolved hurrily always.
Therefore, in conjunction with the characteristics and advantages of phase-change thermal storage, the present invention aims to provide a kind of purposes of heat accumulation heat release Graphene composite phase-change material.
Summary of the invention
The present invention relates to a kind of purposes of heat accumulation heat release Graphene composite phase-change material, Graphene composite phase-change material in the present invention has huge heat accumulation exothermicity and the good capacity of heat transmission, can provide thermal source for thermounit and then produce rapidly stable state and lasting electric current.
Technical solution problem of the present invention adopts following technical scheme:
The feature of the purposes of heat accumulation heat release Graphene composite phase-change material of the present invention is: for providing thermal source for thermounit, to produce electric energy.Particularly, first heat accumulation heat release Graphene composite phase-change material is placed with at radiator place, utilize passage of heat that in Graphene composite phase-change material, Graphene provides to collect heat and the organic phase change material be transferred in Graphene composite phase-change material, then utilize the heat storage capacity of organic phase change material by heat storage in Graphene composite phase-change material; Finally will complete the thermal source of Graphene composite phase-change material as thermounit of heat accumulation, realize the temperature head at thermounit two ends, produce electric energy.
Described heat accumulation heat release Graphene composite phase-change material can be rectangle, square, circle or trilateral etc.Described thermounit is p – n junction type thermounit, and N-shaped material is Bi 2te 3– Bi 2se 3, p-type material is Bi 2te 3– Sb 2te 3.
Described heat accumulation heat release Graphene composite phase-change material is obtained with the interconnective form self-assembly of three dimensional skeletal structure by Graphene in organic phase change material, in described three-dimensional graphene framework composite phase-change material, organic phase change material quality accounts for 5-95%, and surplus is Graphene; In described three-dimensional graphene framework composite phase-change material, organic phase change material provides heat storage capacity, and Graphene collects for heat and Heat transmission provides passage of heat; Described organic phase change material is fatty alcohol or lipid acid.Described fatty alcohol is preferably polyoxyethylene glycol or tetradecanol, and described lipid acid is preferably stearic acid, lauric acid or palmitinic acid.Described polyoxyethylene glycol is preferably PEG2000, PEG6000 or PEG20000.
The preparation method of described heat accumulation heat release Graphene composite phase-change material is:
The preparation of a, graphite oxide
1.2g graphite is placed in the vitriol oil of 60mL mass concentration 98%, 2g K 2s 2o 8with 2g P 2o 5mixing solutions in, 85 DEG C of reactions 4.5 hours, with 400mL deionized water dilute reaction solution after reaction, successively after filtration, obtain graphite oxide after washing and 60 DEG C of vacuum-dryings;
The preparation of b, graphene oxide
The vitriol oil and the 2g KMnO of 50mL mass concentration 98% is added in the graphite oxide that 100mg step a obtains 4in 35 DEG C of reactions 2 hours, then in reaction solution, 80mL deionized water is added, reaction 0.5 hour is continued again in 95 DEG C, add the hydrogen peroxide solution termination reaction of 120mL deionized water and 6mL mass concentration 30% subsequently, successively through centrifugal, washing and 30-40 DEG C of vacuum-drying after obtain graphene oxide;
Described washing is washed with the HCl solution of mass concentration 10% and deionization successively;
The preparation of c, Graphene
By the graphene oxide ultrasonic disperse that obtains in 100mg step b in 100mL deionized water, then add the xitix of 0.1g, room temperature condition lower magnetic force stirs 24 hours, namely obtains the Graphene of favorable dispersity;
D, there is the preparation of the energy-saving three-dimensional graphene framework composite phase-change material of heat accumulation exothermicity
Liquid state is melted in organic phase change material heating, then according to the quality proportioning of organic phase change material in target product and Graphene, adds in organic phase change material with water or the hexanaphthene graphene solution that is solvent and mix; Under the transformation temperature being not less than organic phase change material, stirring heating 5h is with evaporate to dryness major part solvent, and then keep temperature-resistant continuation to leave standstill evaporation 5h, last drying at room temperature, obtains energy-conservation three-dimensional graphene framework composite phase-change material.
As shown in Figure 1, the present invention utilizes Graphene composite phase-change material to provide thermal source to produce the effect of electric energy for thermounit, can test according to the following steps:
A, by certain length of side, different thickness and to keep flat juxtaposition on the glass sheet containing the Graphene composite phase-change material of organic phase change material of different mass mark be in 80 DEG C of baking ovens 1 hour in temperature, Graphene composite phase-change material is allowed fully to absorb heat and to reach heat saturated;
B, between Graphene composite phase-change material heating period, thermounit-thermo-electric generation sheet to be fixed in the thermos cup that mixture of ice and water (providing low-temperature receiver) is housed and the cold junction of thermo-electric generation sheet has just been immersed in mixture of ice and water.Received respectively on volt ohm-milliammeter by two of thermo-electric generation sheet wires after fixedly completing, modulating voltage/current gear is to be measured.Or connect LED lamp bead, the brightness flop of recording lamp pearl luminescence when thermo-electric generation sheet generates electricity and fluorescent lifetime.
C, the saturated Graphene composite phase-change material of heat will be reached in step a, be transferred to the surface of thermounit and airtight laminating, be convenient to heat and pass to thermounit fast, realize the temperature head at thermounit two ends, and then produce rapidly stable state and persistent current, and the brightness flop of electric current (magnitude of voltage) change starting to record on volt ohm-milliammeter or the luminescence of lamp pearl and fluorescent lifetime.
Graphene composite phase-change material of the present invention carries out thermal-arrest-heat accumulation-heat supply for thermounit provides thermal source to produce in the method for electric energy with Graphene composite phase-change material, according to the thermoelectric material of different temperature range, realize supplying and generation current the heat energy of thermounit by the content of phase change material, the thickness design of matrix material.
Compared with prior art, the present invention has following outstanding advantage and technique effect:
1, the Graphene composite phase-change material that the present invention uses integrates " thermal-arrest-heat accumulation-heat release " function, can be used for providing thermal source to multiple thermounit.
2, the Graphene composite phase-change material of the present invention's use, utilizes the heat storage capacity of its phase change material, realizes constant temperature effect in phase transition process, simultaneously for thermounit continues to provide stable hot-fluid, eliminates unmatched impact in heat provision and utilization process.
3, phase-change material energy storage technology range of application is the invention enables to widen, phase change material that is a large amount of, different transition temperature range can be selected as " thermal-arrest-heat accumulation-heat release " functional materials, lay the foundation during the utilisation technology really providing thermal source to produce electric energy for thermounit is widely used in heat energy utilization and optimizes.
Accompanying drawing explanation
Fig. 1 provides thermal source to produce the method schematic diagram of electric energy for utilizing Graphene composite phase-change material for thermounit;
Fig. 2 is that in the embodiment of the present invention 1, Graphene composite phase-change material is the optical photograph of the load bulb powered on thermo-electric generation sheet, as can be seen from photo: the Graphene composite phase-change material in the present invention can provide thermal source for the bulb continuous illumination on its generating and offered load circuit in the hot junction for thermo-electric generation sheet easily and effectively.
Fig. 3 is the change curve of time with organic phase change material massfraction utilizing Graphene composite phase-change material to supply the generating of thermo-electric generation sheet in the embodiment of the present invention 2, as can be seen from curve: thermo-electric generation sheet continues generating dutation and changes according to Graphene composite phase-change material thermal regenerator amount, the time that is can continue to generate electricity by regulating the content of organic phase change material (PEG6000) in Graphene composite phase-change material to control thermo-electric generation sheet.
Fig. 4 is the change curve of time with Graphene composite phase-change material thickness utilizing Graphene composite phase-change material to supply the generating of thermo-electric generation sheet in the embodiment of the present invention 3, as can be seen from curve: thermo-electric generation sheet continues generating dutation and changes according to Graphene composite phase-change material thermal regenerator amount, the time that is can continue to generate electricity by regulating the thickness of Graphene composite phase-change material to control thermo-electric generation sheet.
Fig. 5 is the change curve of time with organic phase change material type utilizing Graphene composite phase-change material to supply the generating of thermo-electric generation sheet in the inventive method, as can be seen from curve: the size of current that thermo-electric generation sheet continues when generating electricity changes according to the hot transformation temperature of Graphene composite phase-change material, the higher temperature difference provided of transformation temperature is larger, thermo-electric generation sheet generating efficiency is also higher, shows on curve to be exactly that the current value that continues during generating is just larger.
Embodiment
Embodiment 1
The present embodiment, for Graphene-polyoxyethylene glycol composite phase-change material, is set forth and is utilized Graphene composite phase-change material to provide thermal source to produce the method for electric energy and effect for thermounit.
A, (be 95% containing polyethylene glycol 6000 massfraction by the square graphite alkene composite phase-change material that is of a size of 2cm × 2cm × 1cm, be designated as G-PEG95%) to keep flat juxtaposition be on the glass sheet in 80 DEG C of baking ovens 1 hour in temperature, allows graphene composite material fully absorb heat and to reach heat saturated;
B, between Graphene composite phase-change material heating period, thermo-electric generation sheet to be fixed in the thermos cup that mixture of ice and water (providing low-temperature receiver) is housed and the cold junction of thermo-electric generation sheet has just been immersed in mixture of ice and water.After fixedly completing, two of thermo-electric generation sheet wires are received on volt ohm-milliammeter respectively or connected LED lamp bead, the brightness flop of record current size or the luminescence of lamp pearl when thermo-electric generation sheet generates electricity and fluorescent lifetime.
C, the Graphene composite phase-change material heat absorption in step a reached capacity are transferred to rapidly on the interface, hot junction of thermo-electric generation sheet, and the brightness flop of electric current (magnitude of voltage) change starting to record on volt ohm-milliammeter or the luminescence of lamp pearl and fluorescent lifetime.
The optical photograph of Fig. 2 to be the present embodiment Graphene composite phase-change material be load bulb powered on thermo-electric generation sheet.Can find out, Graphene composite phase-change material can provide thermal source for the bulb continuous illumination on its generating and offered load circuit in the hot junction for thermo-electric generation sheet easily and effectively.Along with the increase (Fig. 2 a-Fig. 2 d) of time, the brightness deterioration of bulb.
Embodiment 2
For the change of organic phase change material massfraction in contrast Graphene composite phase-change material is on the impact of generating dutation, the present embodiment is undertaken testing by the mode that embodiment 1 is identical and records over time current generated, be 86%, 75% unlike polyethylene glycol 6000 massfraction in Graphene composite phase-change material used, be designated as G-PEG86%, G-PEG75% respectively.Make blank assay (Blank) simultaneously, namely do not fix graphene composite material in the hot junction of thermo-electric generation sheet, but it is directly dried 1 hour in 80 DEG C of baking ovens.
Result as shown in Figure 3, as can be seen from curve, Graphene composite phase-change material has heat storage capacity, thermo-electric generation sheet continues generating dutation and changes according to Graphene composite phase-change material thermal regenerator amount, the time that is can continue to generate electricity by regulating the content of organic phase change material (PEG6000) in Graphene composite phase-change material to control thermo-electric generation sheet.
Embodiment 3
For the change of contrast Graphene composite phase-change material thickness is on the impact of generating dutation, the present embodiment is undertaken testing by the mode that embodiment 1 is identical and records over time current generated, is of a size of 2cm × 2cm × 0.5cm unlike Graphene composite phase-change material used.Make blank assay (blank) simultaneously, namely do not fix graphene composite material in the hot junction of thermo-electric generation sheet, but it is directly dried 1 hour in 80 DEG C of baking ovens.Result as shown in Figure 4.
The difference of Graphene composite phase-change material thickness, after all be also the difference of Graphene composite phase-change material heat storage capacity, can find out in curve, thermo-electric generation sheet continues generating dutation and changes according to composite phase-change material thermal regenerator amount, the time that is can continue to generate electricity by regulating the thickness of composite phase-change material to control thermo-electric generation sheet.
Embodiment 4
For the difference of organic phase change material used in contrast Graphene composite phase-change material is on the impact of generating dutation, the present embodiment is undertaken testing by the mode that embodiment 1 is identical and records over time current generated, and containing massfraction unlike Graphene composite phase-change material used is the Macrogol 2000 of 95%.Result as shown in Figure 5.As can be seen from curve, the size of current that thermo-electric generation sheet continues when generating electricity changes according to the hot transformation temperature of composite phase-change material, the higher temperature difference provided of transformation temperature is larger, thermo-electric generation sheet generating efficiency is also higher, shows on curve to be exactly that the current value that continues during generating is just larger.

Claims (6)

1. a purposes for heat accumulation heat release Graphene composite phase-change material, is characterized in that: for providing thermal source for thermounit, to produce electric energy.
2. the purposes of heat accumulation heat release Graphene composite phase-change material according to claim 1, it is characterized in that: first heat accumulation heat release Graphene composite phase-change material is placed with at radiator place, utilize passage of heat that in Graphene composite phase-change material, Graphene provides to collect heat and the organic phase change material be transferred in Graphene composite phase-change material, then utilize the heat storage capacity of organic phase change material by heat storage in Graphene composite phase-change material; Finally will complete the thermal source of Graphene composite phase-change material as thermounit of heat accumulation, realize the temperature head at thermounit two ends, produce electric energy.
3. the purposes of heat accumulation heat release Graphene composite phase-change material according to claim 1 and 2, is characterized in that: described thermounit is p – n junction type thermounit, and N-shaped material is Bi 2te 3– Bi 2se 3, p-type material is Bi 2te 3– Sb 2te 3.
4. the purposes of heat accumulation heat release Graphene composite phase-change material according to claim 1 and 2, is characterized in that:
Described heat accumulation heat release Graphene composite phase-change material is obtained with the interconnective form self-assembly of three dimensional skeletal structure by Graphene in organic phase change material, in described three-dimensional graphene framework composite phase-change material, organic phase change material quality accounts for 5-95%, and surplus is Graphene; In described three-dimensional graphene framework composite phase-change material, organic phase change material provides heat storage capacity, and Graphene collects for heat and Heat transmission provides passage of heat; Described organic phase change material is fatty alcohol or lipid acid.
5. the purposes of heat accumulation heat release Graphene composite phase-change material according to claim 4, is characterized in that: described fatty alcohol is polyoxyethylene glycol or tetradecanol, and described lipid acid is selected from stearic acid, lauric acid or palmitinic acid.
6. the purposes of heat accumulation heat release Graphene composite phase-change material according to claim 5, is characterized in that: described polyoxyethylene glycol is PEG2000, PEG6000 or PEG20000.
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