CN111187600A - Organic-inorganic composite phase change based heat storage material and preparation method thereof - Google Patents
Organic-inorganic composite phase change based heat storage material and preparation method thereof Download PDFInfo
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- CN111187600A CN111187600A CN202010138343.XA CN202010138343A CN111187600A CN 111187600 A CN111187600 A CN 111187600A CN 202010138343 A CN202010138343 A CN 202010138343A CN 111187600 A CN111187600 A CN 111187600A
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- 239000002131 composite material Substances 0.000 title claims abstract description 109
- 238000005338 heat storage Methods 0.000 title claims abstract description 54
- 239000011232 storage material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000010949 copper Substances 0.000 claims abstract description 73
- 239000000463 material Substances 0.000 claims abstract description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 235000021357 Behenic acid Nutrition 0.000 claims abstract description 43
- 229940116226 behenic acid Drugs 0.000 claims abstract description 43
- KFEVDPWXEVUUMW-UHFFFAOYSA-N docosanoic acid Natural products CCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 KFEVDPWXEVUUMW-UHFFFAOYSA-N 0.000 claims abstract description 39
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 22
- 239000010432 diamond Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- AFCUGQOTNCVYSW-UHFFFAOYSA-H lanthanum(3+);tricarbonate;hydrate Chemical compound O.[La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O AFCUGQOTNCVYSW-UHFFFAOYSA-H 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 66
- 238000010438 heat treatment Methods 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000005245 sintering Methods 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- 238000000498 ball milling Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000012153 distilled water Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- 239000008247 solid mixture Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229940079593 drug Drugs 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 3
- 239000002113 nanodiamond Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 2
- 239000012782 phase change material Substances 0.000 abstract description 14
- 239000011159 matrix material Substances 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 125000003368 amide group Chemical group 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 7
- 229910021389 graphene Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the technical field of composite phase-change heat storage materials, and discloses an organic-inorganic composite phase-change heat storage material and a preparation method thereof, wherein the organic-inorganic composite phase-change heat storage material comprises the following formula raw materials: aminated graphene, docosanoic acid, lanthanum carbonate hydrate, diamond and nano copper powder. According to the organic-inorganic composite phase-change heat storage material and the preparation method thereof, the docosanoic acid is used as the phase-change material, and the docosanoic acid and the aminated graphene are combined together in an amide group forming mode through a hydro-thermal synthesis-melting blending method, so that the problems that organic compatibility is easy to leak and a matrix is easy to denature in the phase-change process of the material are solved, and La3+The diamond-Cu composite is embedded into crack defects in an internal interface of the diamond-Cu composite, so that a bonding interface between the diamond and Cu is improved, the density of the diamond-Cu composite is improved, the porosity is reduced, and the matrix strength and the structural stability of the composite are enhanced, so that the diamond-Cu composite has higher heat absorption performance and thermal conductivity.
Description
Technical Field
The invention relates to the technical field of composite phase-change heat storage materials, in particular to an organic-inorganic composite phase-change heat storage material and a preparation method thereof.
Background
The phase-change material is a substance which changes the form of the substance to provide latent heat under the condition of constant temperature, the phase-change process is a process of converting the physical form property of the object, the phase-change material has the capacity of changing the physical state within a certain temperature range, at the moment, a large amount of heat energy can be absorbed or released, the phase-change material has excellent heat storage performance, the heat is stored in the forms of sensible heat and latent heat, the sensible heat is stored by the temperature rise of the heat storage material, the latent heat storage is the process of absorbing and storing the heat by utilizing the characteristic that a large amount of heat of fusion is needed when the material is melted from a solid state to a liquid state, a medium returns to the solid state after the heat is released.
The classified phase-change materials of the phase-change material mainly comprise inorganic phase-change materials, such as molten inorganic salt, crystalline hydrated salt, metal alloy and the like; the organic phase-change material mainly comprises paraffin, acetic acid and other organic matters; the composite phase-change heat storage material can effectively overcome the defects of a single inorganic or organic phase-change heat storage material, improve the application effect of the phase-change material and expand the application range of the phase-change material, but the existing composite phase-change material has a plurality of obvious defects, such as leakage of a molten phase-change organic phase material, poor heat conductivity of the phase-change material, incapability of meeting the requirements of quick heat charging and discharging of a heat storage system, easy denaturation of a matrix in a long-time continuous phase-change process and the like
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides an organic-inorganic composite phase-change heat storage material and a preparation method thereof, and solves the problems that the existing composite phase-change heat storage material leaks from a molten phase-change organic phase material, a matrix is easy to denature in a phase-change process which lasts for a long time, and the phase-change heat storage material has poor heat conductivity and cannot be rapidly charged and discharged.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: an organic-inorganic composite phase-change heat storage material and a preparation method thereof comprise the following formula raw materials in parts by weight: 24-30 parts of aminated graphene, 3-5 parts of behenic acid, 1-2 parts of lanthanum carbonate hydrate, 37-50 parts of diamond and 22-26 parts of nano copper powder, and the preparation method comprises the following experimental medicines: distilled water, dilute hydrochloric acid and ethyl acetate.
Preferably, the aminated graphene is polyethylene glycol modified aminated graphene, the content of active amino and imino is 8%, and the structural formula is shown in the specification.
Preferably, the behenic acid, lanthanum carbonate hydrate, copper powder, distilled water, diluted hydrochloric acid and ethyl acetate are chemical analytical purifiers.
Preferably, the diamond is nano diamond powder with the particle size of 5-15 nm.
Preferably, the mass fraction of the nano copper powder is more than or equal to 99.5%, and the particle size is 15-20 nm.
Preferably, the amount concentration of the dilute hydrochloric acid substance is 1.9-3.5mol/L, and the mass fraction is 7-12%.
Preferably, the preparation method of the organic-inorganic composite phase-change heat storage material comprises the following steps:
(1) preparation of La-doped diamond-Cu composite: sequentially adding 1-2 parts of lanthanum carbonate hydrate, 37-50 parts of diamond and 22-26 parts of nano copper powder into a high-energy planetary ball mill, adding 400-600mL of absolute ethyl alcohol, setting the revolution speed of the ball mill to be 50-80rpm and the rotation speed to be 620-660rpm, carrying out ball milling for 3-6h, passing the materials through a high-speed centrifuge, centrifuging at the centrifugal speed of 6000-10000rpm, centrifuging to remove the absolute ethyl alcohol, placing the obtained solid mixture into an SPS discharge plasma sintering furnace, setting the pressure to be 55-70MPa and the heating rate to be 10 ℃/min, heating to 1200-1250 ℃, carrying out a sintering process, cooling the materials to room temperature after sintering molding, sequentially washing the solid sintered product with 100-200mL of dilute hydrochloric acid with the mass concentration of 1.9-3.5mol/L and a proper amount of distilled water, placing the washed solid sintered product into an oven, heating to 80-120 ℃ and fully drying the water, and obtaining the La-doped diamond-Cu composite.
(2) Loading aminated graphene on the La-doped diamond-Cu composite: adding 800mL of anhydrous ethanol into a beaker, sequentially adding 24-30 parts of aminated graphene and the La-doped diamond-Cu composite prepared in the step (1), uniformly stirring, placing the beaker into an ultrasonic dispersion instrument, heating to 60-75 ℃, carrying out ultrasonic treatment for 2-4h at the ultrasonic frequency of 20KHz, placing the beaker into an oven, heating to 75-80 ℃, and completely evaporating the anhydrous ethanol to obtain the La-doped diamond-Cu composite loaded aminated graphene.
(3) Preparing an organic-inorganic composite phase-change heat storage material: adding 3-5 parts of docosanoic acid into a high-energy planetary ball mill, setting the revolution speed of the ball mill to be 150 plus of 150rpm and the rotation speed to be 640 plus of 660rpm, carrying out ball milling for 6-12h until all the docosanoic acid passes through a 800 mesh screen to obtain particles with the particle size of 16-18um, transferring the ball-milled docosanoic acid into an automatic hydrothermal synthesis reaction kettle, sequentially adding 300 plus 500mL of anhydrous ethyl acetate solvent and the La-doped diamond-Cu compound prepared in the step (2) to load aminated graphene, setting the reaction temperature of the reaction kettle to be 160 plus of 180 ℃, carrying out uniform stirring reaction for 12-15h, cooling the material after the reaction is finished, transferring the material to a rotating cup, placing the material into an oven, heating the material to 70-75 ℃, drying the anhydrous ethyl acetate, then placing the material into a mold, and tightly compressing the material in the die by using a tablet press to obtain the organic-inorganic composite phase change based heat storage material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
1. according to the organic-inorganic composite phase-change heat storage material and the preparation method thereof, the docosanoic acid is used as the phase-change material, the aminated graphene has a large number of network pore structures and a large specific surface area, the docosanoic acid can be uniformly attached to the graphene through capillary force, and the docosanoic acid and the aminated graphene are combined together in an amide group forming mode through a hydro-thermal synthesis-melting blending method, so that the phenomenon that the docosanoic acid is easy to leak in the heat absorption deformation process is effectively prevented, the graphene with good structural stability and chemical stability can be well compatible with the docosanoic acid, and the phenomenon that a matrix of the material is easy to denature in the continuous phase-change process is avoided.
2. The organic-inorganic composite phase-change heat storage material is prepared by adding La-doped diamond-Cu composite and La3+The La-doped diamond-Cu composite is embedded into crack defects in an internal interface of a diamond-Cu composite, Cu atoms are optimized and fully relaxed, the atomic distance is reduced, the interaction force between the Cu atoms and diamond is enhanced, the bonding interface between the diamond and Cu is improved, the bonding between the diamond and a copper matrix is obviously improved, the density of the La-doped diamond-Cu composite is improved, the porosity of the composite is reduced, and the matrix strength and the structural stability of the composite are enhanced, so that the La-doped diamond-Cu composite has higher heat absorptivity and higher heat absorptivity than a common diamond-Cu compositeThe heat conductivity enhances the overall heat conductivity and heat storage performance of the material, so that the heat storage material can more rapidly charge and release heat in the phase change process.
Detailed Description
In order to achieve the purpose, the invention provides the following technical scheme: an organic-inorganic composite phase-change heat storage material and a preparation method thereof comprise the following formula raw materials in parts by weight: 24-30 parts of aminated graphene, 3-5 parts of behenic acid, 1-2 parts of lanthanum carbonate hydrate, 37-50 parts of diamond and 22-26 parts of nano copper powder, and the preparation method comprises the following experimental medicines: distilled water, diluted hydrochloric acid, ethyl acetate, wherein the aminated graphene is polyethylene glycol modified aminated graphene, the content of active amino and imino is 8%, the structural formula is shown in the specification, the docosanoic acid, lanthanum carbonate hydrate and copper powder are adopted as the structural formula, the distilled water, the diluted hydrochloric acid and the ethyl acetate are chemical analysis pure molecules, the diamond is nano diamond powder, the particle size is 5-15nm, the mass fraction of the nano copper powder is more than or equal to 99.5%, the particle size is 15-20nm, the mass concentration of the diluted hydrochloric acid is 1.9-3.5mol/L, and the mass fraction is 7-12%.
An organic-inorganic composite phase-change heat storage material is prepared by the following steps:
(1) preparation of La-doped diamond-Cu composite: sequentially adding 1-2 parts of lanthanum carbonate hydrate, 37-50 parts of diamond and 22-26 parts of nano copper powder into a high-energy planetary ball mill, adding 400-600mL of absolute ethyl alcohol, setting the revolution speed of the ball mill to be 50-80rpm and the rotation speed to be 620-660rpm, carrying out ball milling for 3-6h, passing the materials through a high-speed centrifuge, centrifuging at the centrifugal speed of 6000-10000rpm, centrifuging to remove the absolute ethyl alcohol, placing the obtained solid mixture into an SPS discharge plasma sintering furnace, setting the pressure to be 55-70MPa and the heating rate to be 10 ℃/min, heating to 1200-1250 ℃, carrying out a sintering process, cooling the materials to room temperature after sintering molding, sequentially washing the solid sintered product with 100-200mL of dilute hydrochloric acid with the mass concentration of 1.9-3.5mol/L and a proper amount of distilled water, placing the washed solid sintered product into an oven, heating to 80-120 ℃ and fully drying the water, and obtaining the La-doped diamond-Cu composite.
(2) Loading aminated graphene on the La-doped diamond-Cu composite: adding 800mL of anhydrous ethanol into a beaker, sequentially adding 24-30 parts of aminated graphene and the La-doped diamond-Cu composite prepared in the step (1), uniformly stirring, placing the beaker into an ultrasonic dispersion instrument, heating to 60-75 ℃, carrying out ultrasonic treatment for 2-4h at the ultrasonic frequency of 20KHz, placing the beaker into an oven, heating to 75-80 ℃, and completely evaporating the anhydrous ethanol to obtain the La-doped diamond-Cu composite loaded aminated graphene.
(3) Preparing an organic-inorganic composite phase-change heat storage material: adding 3-5 parts of docosanoic acid into a high-energy planetary ball mill, setting the revolution speed of the ball mill to be 150 plus of 150rpm and the rotation speed to be 640 plus of 660rpm, carrying out ball milling for 6-12h until all the docosanoic acid passes through a 800 mesh screen to obtain particles with the particle size of 16-18um, transferring the ball-milled docosanoic acid into an automatic hydrothermal synthesis reaction kettle, sequentially adding 300 plus 500mL of anhydrous ethyl acetate solvent and the La-doped diamond-Cu compound prepared in the step (2) to load aminated graphene, setting the reaction temperature of the reaction kettle to be 160 plus of 180 ℃, carrying out uniform stirring reaction for 12-15h, cooling the material after the reaction is finished, transferring the material to a rotating cup, placing the material into an oven, heating the material to 70-75 ℃, drying the anhydrous ethyl acetate, then placing the material into a mold, and tightly compressing the material in the die by using a tablet press to obtain the organic-inorganic composite phase change based heat storage material.
Example 1:
(1) preparation of La-doped diamond-Cu composite: adding 1 part of lanthanum carbonate hydrate, 50 parts of diamond and 22 parts of nano copper powder into a high-energy planetary ball mill in sequence, adding 400mL of absolute ethyl alcohol, setting the revolution speed of the ball mill to be 50rpm and the rotation speed to be 620rpm, carrying out ball milling for 3h, passing the materials through a high-speed centrifuge, setting the centrifugation speed to be 6000rpm, centrifuging to remove the absolute ethyl alcohol, placing the obtained solid mixture into an SPS discharge plasma sintering furnace, setting the pressure to be 55MPa and the heating rate to be 10 ℃/min, heating to 1200 ℃ for sintering, cooling the materials to room temperature after sintering molding, washing the solid sintered product with 100mL of dilute hydrochloric acid with the mass concentration of 1.9mol/L and a proper amount of distilled water in sequence, placing the solid sintered product into an oven, heating to 80 ℃, and fully drying the water to obtain the La-doped diamond-Cu composite component 1.
(2) Loading aminated graphene on the La-doped diamond-Cu composite: adding 500mL of absolute ethyl alcohol into a beaker, sequentially adding 24 parts of aminated graphene and the La-doped diamond-Cu composite component 1 prepared in the step (1), uniformly stirring, placing the beaker into an ultrasonic dispersion instrument, raising the temperature to 60 ℃, carrying out ultrasonic treatment for 2 hours at the ultrasonic frequency of 20KHz, placing the beaker into an oven, heating to 75 ℃, and completely evaporating the absolute ethyl alcohol to obtain the La-doped diamond-Cu composite loaded aminated graphene component 1.
(3) Preparing an organic-inorganic composite phase-change heat storage material: adding 3 parts of docosanoic acid into a high-energy planetary ball mill, setting the revolution speed of the ball mill to be 120rpm and the rotation speed to be 640rpm, carrying out ball milling for 6 hours until all the docosanoic acid passes through a 800 mesh screen to obtain particles with the particle size of 16-18um, transferring the ball-milled docosanoic acid into a hydrothermal synthesis automatic reaction kettle, sequentially adding 300mL of anhydrous ethyl acetate solvent and the La-doped diamond-Cu composite loaded aminated graphene component 1 prepared in the step (2), setting the reaction temperature of the reaction kettle to 160 ℃, uniformly stirring and reacting for 12 hours, cooling the material to room temperature after the reaction is finished, transferring the material into a beaker, placing the beaker into a drying oven, heating the material to 70 ℃, drying and removing the anhydrous ethyl acetate, and then placing the material in a die, and tightly compressing the material in the die by using a tablet press to obtain the organic-inorganic composite phase-change heat storage material 1.
Example 2:
(1) preparation of La-doped diamond-Cu composite: adding 1.5 parts of lanthanum carbonate hydrate, 47 parts of diamond and 23 parts of nano copper powder into a high-energy planetary ball mill in sequence, adding 400mL of absolute ethyl alcohol, setting the revolution speed of the ball mill to be 50rpm and the rotation speed to be 640rpm, carrying out ball milling for 4h, passing the materials through a high-speed centrifuge, centrifuging at the speed of 8000rpm to remove the absolute ethyl alcohol, placing the obtained solid mixture into an SPS discharge plasma sintering furnace, setting the pressure to be 60MPa and the heating rate to be 10 ℃/min, heating to 1200 ℃ to carry out sintering process, cooling the materials to room temperature after sintering molding, washing the solid sintered product with 150mL of dilute hydrochloric acid with the mass concentration of 2.5mol/L and a proper amount of distilled water in sequence, placing the solid sintered product into an oven, and heating to 90 ℃ to fully dry the water to obtain the La-doped diamond-Cu composite component 2.
(2) Loading aminated graphene on the La-doped diamond-Cu composite: adding 500mL of absolute ethyl alcohol into a beaker, sequentially adding 25 parts of aminated graphene and the La-doped diamond-Cu composite component 2 prepared in the step (1), uniformly stirring, placing the beaker into an ultrasonic dispersion instrument, raising the temperature to 60 ℃, carrying out ultrasonic treatment for 2 hours at the ultrasonic frequency of 20KHz, placing the beaker into an oven, heating to 75 ℃, and completely evaporating the absolute ethyl alcohol to obtain the La-doped diamond-Cu composite loaded aminated graphene component 2.
(3) Preparing an organic-inorganic composite phase-change heat storage material: adding 3.5 parts of docosanoic acid into a high-energy planetary ball mill, setting the revolution speed of the ball mill to be 120rpm and the rotation speed to be 640rpm, carrying out ball milling for 8 hours until all the docosanoic acid passes through a 800 mesh screen to obtain particles with the particle size of 16-18um, transferring the ball-milled docosanoic acid into an hydrothermal synthesis automatic reaction kettle, sequentially adding 300mL of anhydrous ethyl acetate solvent and the La-doped diamond-Cu composite loaded aminated graphene component 2 prepared in the step (2), setting the reaction temperature of the reaction kettle to 160 ℃, uniformly stirring and reacting for 12 hours, cooling the material to room temperature after the reaction is finished, transferring the material into a beaker, placing the beaker into a drying oven, heating the material to 70 ℃, drying and removing the anhydrous ethyl acetate, and then placing the material in a die, and tightly compressing the material in the die by using a tablet press to obtain the organic-inorganic composite phase-change heat storage material 2.
Example 3:
(1) preparation of La-doped diamond-Cu composite: adding 1.5 parts of lanthanum carbonate hydrate, 45 parts of diamond and 24 parts of nano copper powder into a high-energy planetary ball mill in sequence, adding 500mL of absolute ethyl alcohol, setting the revolution speed of the ball mill to be 70rpm and the rotation speed to be 640rpm, carrying out ball milling for 5h, passing the materials through a high-speed centrifuge, centrifuging at the speed of 8000rpm to remove the absolute ethyl alcohol, placing the obtained solid mixture into an SPS discharge plasma sintering furnace, setting the pressure to be 60MPa and the heating rate to be 10 ℃/min, heating to 1250 ℃ to carry out sintering process, cooling the materials to room temperature after sintering molding, washing the solid sintered product with 150mL of dilute hydrochloric acid with the mass concentration of 2.5mol/L and a proper amount of distilled water in sequence, placing the solid sintered product into an oven, and heating to 100 ℃ to fully dry the water to obtain the La-doped diamond-Cu composite component 3.
(2) Loading aminated graphene on the La-doped diamond-Cu composite: adding 600mL of absolute ethyl alcohol into a beaker, sequentially adding 26 parts of aminated graphene and the La-doped diamond-Cu composite component 3 prepared in the step (1), uniformly stirring, placing the beaker into an ultrasonic dispersion instrument, raising the temperature to 70 ℃, carrying out ultrasonic treatment for 2 hours at the ultrasonic frequency of 20KHz, placing the beaker into an oven, heating to 75 ℃, and completely evaporating the absolute ethyl alcohol to obtain the La-doped diamond-Cu composite loaded aminated graphene component 3.
(3) Preparing an organic-inorganic composite phase-change heat storage material: adding 3.5 parts of docosanoic acid into a high-energy planetary ball mill, setting the revolution speed of the ball mill to be 130rpm and the rotation speed to be 660rpm, carrying out ball milling for 10 hours until all the docosanoic acid passes through a 800 mesh screen to obtain particles with the particle size of 16-18um, transferring the ball-milled docosanoic acid into an hydrothermal synthesis automatic reaction kettle, sequentially adding 400mL of anhydrous ethyl acetate solvent and the La-doped diamond-Cu composite loaded aminated graphene component 3 prepared in the step (2), setting the reaction temperature of the reaction kettle to 170 ℃, uniformly stirring and reacting for 15h, cooling the material to room temperature after the reaction is finished, transferring the material into a beaker, placing the beaker into a drying oven, heating the material to 75 ℃, drying and removing the anhydrous ethyl acetate, and then placing the material in a die, and tightly compressing the material in the die by using a tablet press to obtain the organic-inorganic composite phase-change heat storage material 3.
Example 4:
(1) preparation of La-doped diamond-Cu composite: adding 2 parts of lanthanum carbonate hydrate, 41 parts of diamond and 25 parts of nano copper powder into a high-energy planetary ball mill in sequence, adding 500mL of absolute ethyl alcohol, setting the revolution speed of the ball mill to be 60rpm and the rotation speed to be 640rpm, carrying out ball milling for 5h, passing the materials through a high-speed centrifuge, centrifuging at the speed of 8000rpm to remove the absolute ethyl alcohol, placing the obtained solid mixture into an SPS discharge plasma sintering furnace, setting the pressure to be 65MPa and the heating rate to be 10 ℃/min, heating to 1250 ℃ to carry out sintering process, cooling the materials to room temperature after sintering molding, washing the solid sintered product with 200mL of dilute hydrochloric acid with the mass concentration of 3.5mol/L and a proper amount of distilled water in sequence, placing the solid sintered product into an oven, heating to 100 ℃, and fully drying the water to obtain the La-doped diamond-Cu composite component 4.
(2) Loading aminated graphene on the La-doped diamond-Cu composite: adding 700mL of absolute ethyl alcohol into a beaker, sequentially adding 28 parts of aminated graphene and the La-doped diamond-Cu composite component 4 prepared in the step (1), uniformly stirring, placing the beaker into an ultrasonic dispersion instrument, raising the temperature to 70 ℃, carrying out ultrasonic treatment for 4 hours at the ultrasonic frequency of 20KHz, placing the beaker into an oven, heating to 80 ℃, and completely evaporating the absolute ethyl alcohol to obtain the La-doped diamond-Cu composite loaded aminated graphene component 4.
(3) Preparing an organic-inorganic composite phase-change heat storage material: adding 4 parts of docosanoic acid into a high-energy planetary ball mill, setting the revolution speed of the ball mill to be 150rpm and the rotation speed to be 660rpm, carrying out ball milling for 102h until all the docosanoic acid passes through an 800 mesh screen to obtain particles with the particle size of 16-18um, transferring the ball-milled docosanoic acid into a hydrothermal synthesis automatic reaction kettle, sequentially adding 500mL of anhydrous ethyl acetate solvent and the La-doped diamond-Cu composite loaded aminated graphene component 4 prepared in the step (2), setting the reaction temperature of the reaction kettle to 170 ℃, uniformly stirring and reacting for 15h, cooling the material to room temperature after the reaction is finished, transferring the material into a beaker, placing the beaker into a drying oven, heating the material to 75 ℃, drying and removing the anhydrous ethyl acetate, and then placing the material in a die, and tightly compressing the material in the die by using a tablet press to obtain the organic-inorganic composite phase-change heat storage material 4.
Example 5:
(1) preparation of La-doped diamond-Cu composite: adding 2 parts of lanthanum carbonate hydrate, 37 parts of diamond and 26 parts of nano copper powder into a high-energy planetary ball mill in sequence, adding 600mL of absolute ethyl alcohol, setting the revolution speed of the ball mill to be 80rpm, the rotation speed to be 660rpm, carrying out ball milling for 6h, passing the materials through a high-speed centrifuge, setting the centrifugation speed to be 10000rpm, centrifuging to remove the absolute ethyl alcohol, placing the obtained solid mixture into an SPS discharge plasma sintering furnace, setting the pressure to be 70MPa, the heating rate to be 10 ℃/min, heating to 1250 ℃ for sintering, cooling the materials to room temperature after sintering forming, washing the solid sintered product with 200mL of dilute hydrochloric acid with the mass concentration of 3.5mol/L and a proper amount of distilled water in sequence, placing the solid sintered product into an oven, heating to 120 ℃, and fully drying the water to obtain the La-doped diamond-Cu composite component 5.
(2) Loading aminated graphene on the La-doped diamond-Cu composite: adding 800mL of absolute ethyl alcohol into a beaker, sequentially adding 30 parts of aminated graphene and the La-doped diamond-Cu composite component 5 prepared in the step (1), uniformly stirring, placing the beaker into an ultrasonic dispersion instrument, raising the temperature to 75 ℃, carrying out ultrasonic treatment for 4 hours at the ultrasonic frequency of 20KHz, placing the beaker into an oven, heating to 80 ℃, and completely evaporating the absolute ethyl alcohol to obtain the La-doped diamond-Cu composite loaded aminated graphene component 5.
(3) Preparing an organic-inorganic composite phase-change heat storage material: adding 5 parts of docosanoic acid into a high-energy planetary ball mill, setting the revolution speed of the ball mill to be 150rpm and the rotation speed to be 660rpm, carrying out ball milling for 12 hours until all the docosanoic acid passes through a 800 mesh screen to obtain particles with the particle size of 16-18um, transferring the ball-milled docosanoic acid into a hydrothermal synthesis automatic reaction kettle, sequentially adding 500mL of anhydrous ethyl acetate solvent and the La-doped diamond-Cu composite loaded aminated graphene component 5 prepared in the step (2), setting the reaction temperature of the reaction kettle to 180 ℃, uniformly stirring and reacting for 15h, cooling the material to room temperature after the reaction is finished, transferring the material into a beaker, placing the beaker into a drying oven, heating the material to 75 ℃, drying and removing the anhydrous ethyl acetate, and then placing the material in a die, and tightly compressing the material in the die by using a tablet press to obtain the organic-inorganic composite phase-change heat storage material 5.
The thermal conductivity measurement, the heat storage performance measurement and the phase change stability test were performed on examples 1 to 5 by the galvanostatic cyclic voltammetry, according to the organic-inorganic composite phase-change heat storage material and the preparation method thereof, the docosanoic acid is used as the phase-change material, the aminated graphene has a large amount of network pore structures and a large specific surface area, the docosanoic acid can be uniformly attached to the graphene through capillary force, and through a hydrothermal synthesis-melt blending method, the docosanoic acid and the aminated graphene are combined together in a mode of forming an amide group, so that the phenomenon that the docosanoic acid is easy to leak in the heat absorption deformation process is effectively prevented, the graphene with good structural stability and chemical stability can be well compatible with the docosanoic acid, and the phenomenon that a matrix is easy to denature in the continuous phase change process of the material is avoided.
The organic-inorganic composite phase-change heat storage material is prepared by adding La-doped diamond-Cu composite and La3+The La-doped diamond-Cu composite is embedded into crack defects in an internal interface of a diamond-Cu composite, Cu atoms are optimized and fully relaxed, the atomic distance is reduced, the interaction force between the Cu atoms and diamond is enhanced, the bonding interface between the diamond and Cu is improved, the bonding between the diamond and a copper matrix is obviously improved, the density of the La-doped diamond-Cu composite is improved, the porosity of the composite is reduced, and the matrix strength and the structural stability of the composite are enhanced, so that the La-doped diamond-Cu composite has higher heat absorption and heat conduction compared with a common diamond-Cu composite, the overall heat conductivity and the heat storage performance of the material are enhanced, and heat can be rapidly charged and discharged in the phase change process of the heat storage material.
Claims (7)
1. The organic-inorganic composite phase-change heat storage material comprises the following raw materials in parts by weight: 24-30 parts of aminated graphene, 3-5 parts of behenic acid, 1-2 parts of lanthanum carbonate hydrate, 37-50 parts of diamond and 22-26 parts of nano copper powder, and the preparation method comprises the following experimental medicines: distilled water, dilute hydrochloric acid and ethyl acetate.
2. The organic-inorganic composite phase-change based heat storage material and the preparation method thereof as claimed in claim 1, wherein: the aminated graphene is polyethylene glycol modified aminated graphene, the content of active amino and imino is 8%, and the structural formula is shown in the specification.
3. The organic-inorganic composite phase-change based heat storage material and the preparation method thereof as claimed in claim 1, wherein: the docosanoic acid, the lanthanum carbonate hydrate, the copper powder, the distilled water, the diluted hydrochloric acid and the ethyl acetate are chemical analysis purees.
4. The organic-inorganic composite phase-change based heat storage material and the preparation method thereof as claimed in claim 1, wherein: the diamond is nano diamond powder with the particle size of 5-15 nm.
5. The organic-inorganic composite phase-change based heat storage material and the preparation method thereof as claimed in claim 1, wherein: the mass fraction of the copper nanopowder is greater than or equal to 99.5%, and the particle size is 15-20 nm.
6. The organic-inorganic composite phase-change based heat storage material and the preparation method thereof as claimed in claim 1, wherein: the amount concentration of the dilute hydrochloric acid substance is 1.9-3.5mol/L, and the mass fraction is 7-12%.
7. The organic-inorganic composite phase-change based heat storage material and the preparation method thereof as claimed in claim 1, wherein: the preparation method of the organic-inorganic composite phase-change heat storage material comprises the following steps:
(1) preparation of La-doped diamond-Cu composite: sequentially adding 1-2 parts of lanthanum carbonate hydrate, 37-50 parts of diamond and 22-26 parts of nano copper powder into a high-energy planetary ball mill, adding 400-600mL of absolute ethyl alcohol, setting the revolution speed of the ball mill to be 50-80rpm and the rotation speed to be 620-660rpm, carrying out ball milling for 3-6h, passing the materials through a high-speed centrifuge, centrifuging at the centrifugal speed of 6000-10000rpm, centrifuging to remove the absolute ethyl alcohol, placing the obtained solid mixture into an SPS discharge plasma sintering furnace, setting the pressure to be 55-70MPa and the heating rate to be 10 ℃/min, heating to 1200-1250 ℃, carrying out a sintering process, cooling the materials to room temperature after sintering molding, sequentially washing the solid sintered product with 100-200mL of dilute hydrochloric acid with the mass concentration of 1.9-3.5mol/L and a proper amount of distilled water, placing the washed solid sintered product into an oven, heating to 80-120 ℃ and fully drying the water, and obtaining the La-doped diamond-Cu composite.
(2) Loading aminated graphene on the La-doped diamond-Cu composite: adding 800mL of anhydrous ethanol into a beaker, sequentially adding 24-30 parts of aminated graphene and the La-doped diamond-Cu composite prepared in the step (1), uniformly stirring, placing the beaker into an ultrasonic dispersion instrument, heating to 60-75 ℃, carrying out ultrasonic treatment for 2-4h at the ultrasonic frequency of 20KHz, placing the beaker into an oven, heating to 75-80 ℃, and completely evaporating the anhydrous ethanol to obtain the La-doped diamond-Cu composite loaded aminated graphene.
(3) Preparing an organic-inorganic composite phase-change heat storage material: adding 3-5 parts of docosanoic acid into a high-energy planetary ball mill, setting the revolution speed of the ball mill to be 150 plus of 150rpm and the rotation speed to be 640 plus of 660rpm, carrying out ball milling for 6-12h until all the docosanoic acid passes through a 800 mesh screen to obtain particles with the particle size of 16-18um, transferring the ball-milled docosanoic acid into an automatic hydrothermal synthesis reaction kettle, sequentially adding 300 plus 500mL of anhydrous ethyl acetate solvent and the La-doped diamond-Cu compound prepared in the step (2) to load aminated graphene, setting the reaction temperature of the reaction kettle to be 160 plus of 180 ℃, carrying out uniform stirring reaction for 12-15h, cooling the material after the reaction is finished, transferring the material to a rotating cup, placing the material into an oven, heating the material to 70-75 ℃, drying the anhydrous ethyl acetate, then placing the material into a mold, and tightly compressing the material in the die by using a tablet press to obtain the organic-inorganic composite phase change based heat storage material.
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