CN116855231A - Multifunctional composite phase change material and preparation method and application thereof - Google Patents
Multifunctional composite phase change material and preparation method and application thereof Download PDFInfo
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- CN116855231A CN116855231A CN202310504116.8A CN202310504116A CN116855231A CN 116855231 A CN116855231 A CN 116855231A CN 202310504116 A CN202310504116 A CN 202310504116A CN 116855231 A CN116855231 A CN 116855231A
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- 239000002131 composite material Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title abstract description 13
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- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
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- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 3
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- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 3
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- 229940009714 erythritol Drugs 0.000 claims description 3
- 230000005484 gravity Effects 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- TWHBEKGYWPPYQL-UHFFFAOYSA-N aluminium carbide Chemical compound [C-4].[C-4].[C-4].[Al+3].[Al+3].[Al+3].[Al+3] TWHBEKGYWPPYQL-UHFFFAOYSA-N 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
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- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
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- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- 231100000956 nontoxicity Toxicity 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K7/00—Constructional details common to different types of electric apparatus
- H05K7/20—Modifications to facilitate cooling, ventilating, or heating
- H05K7/2029—Modifications to facilitate cooling, ventilating, or heating using a liquid coolant with phase change in electronic enclosures
-
- 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
- C09K5/066—Cooling mixtures; De-icing compositions
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Thermal Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electromagnetism (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a multifunctional composite phase change material, a preparation method and application thereof. The multifunctional composite phase-change material is formed by compounding graphene foam, MXene aerogel and a phase-change material; the MXene aerogel is a lamellar oriented structure coupled in the aperture of the GF foam, and the phase change material is encapsulated in the multifunctional composite material to form the GF foam-MXene aerogel double-network cooperatively supported multifunctional composite phase change material. The thermal conductivity reaches 11.39W m ‑1 K ‑1 The method comprises the steps of carrying out a first treatment on the surface of the The electromagnetic shielding efficiency reaches 56.6dB, and the energy storage density reaches 160.3J g ‑1 . The composite phase-change material has higher strength and a more perfect heat conduction network, double packages the molten phase-change material and strengthens the heat transfer rate, and solves the problems of generally lower out-of-plane heat conductivity and easy leakage of the current composite phase-change material. Cooling and energy storage/conversion in electronic devicesThe device has excellent working performance and outstanding application effect when applied to the device.
Description
Technical Field
The invention relates to the technical field of phase change composite materials, in particular to a multifunctional composite phase change material and a preparation method and application thereof.
Background
In the context of green clean energy, thermal Energy Storage (TES) is believed to improve energy conservation efficiencyIs an important energy source technology. The phase change energy storage is to realize energy storage and release by utilizing the characteristic of a large amount of heat absorption or heat release of a Phase Change Material (PCM) in the phase change process, and has great application prospect in the field of intermittent or unstable heat management, such as periodic intermittent solar energy utilization, high-power electronic device/battery heat management, industrial waste heat recovery and utilization and the like. Organic PCM (such as paraffin, polyethylene glycol, fatty acid, etc.) has received great attention by virtue of its high energy storage density, small volume change, stable chemical properties, low tendency to supercooling and phase separation, non-toxicity, non-corrosiveness, low cost, etc. However, the organic PCM has low melt leakage and inherent thermal conductivity (generally between 0.15 and 0.5 and W m) -1 K -1 ) The long-term bottleneck of the PCM leads to a great reduction in heat storage efficiency of the PCM, severely restricting its application in the fields of energy storage and thermal management. In response to the above problems with PCM, researchers have employed porous materials (Min Zhao, yan Ye, rui Yang. Absorption-polymerization method for synthesizing phase change composites with high enthalpy and thermal conductivity for efficient thermal energy storage [ J)]Solar Energy Materials and Solar Cells,248 (2022) 112027) or a support material (Yi-Cun Zhou, jie Yang, lu Bai, rui-Yeng Bao, ming-Bo Yang, wei Yang. Super-flexible phase change materials with a dual-supporting effect for solar thermoelectric conversion in the ocean environment [ J)]Journal of Materials Chemistry A,11 (2023) 341-351) encapsulate the phase change material to prevent melt leakage; the heat transfer process is enhanced by adopting carbon materials (diamond, carbon nano tube, graphene and the like) or metals and oxides thereof (silver, copper, aluminum oxide and the like), so that the heat conduction performance of the phase change material is improved. However, in order to achieve satisfactory shape stability and thermal conductivity of PCM, the prior art needs to rely on high loading of the thermally conductive filler, which tends to greatly reduce the PCM's duty cycle in the composite material, resulting in a decrease in the energy storage density of the overall system. The search for a balance of high thermal conductivity and high energy storage density while imparting shape stability is a critical challenge to PCM research. In addition, the phase change composite material prepared by the prior art has single functionality, and is small and high in sizeIntegrated electronic device thermal management also requires consideration of electromagnetic shielding (EMI) performance. On the one hand, high frequency electromagnetic radiation may not only reduce the operation accuracy of the device, lead to malfunction of the device, but also threaten the physical health of the operator. On the other hand, the electromagnetic shielding performance of PCM is closely related to efficient thermal management, and electromagnetic shielding will directly convert most of electromagnetic radiation into heat and eventually initiate PCM phase change processes. Therefore, on the premise of ensuring the high energy storage density of the PCM, the electromagnetic shielding performance and the thermal management capability of the PCM are improved synchronously, and the method has important significance.
Researchers propose that constructing a three-dimensional interconnected thermally conductive skeleton inside a phase-change composite material is expected to maintain high energy storage density while improving the thermal conductivity of the phase-change composite material. Patent CN 112852386A discloses a graphene aerogel phase-change composite material prepared by a hydrothermal reduction method, however, physical crosslinking of graphene aerogel prepared by graphene oxide self-assembly at high temperature and high pressure is mainly based on van der waals force, hydrogen bond and pi-pi interaction, and interfacial thermal resistance still exists between two-dimensional graphene nano sheets. Therefore, the thermal conductivity of the prepared graphene aerogel phase-change composite material is only improved to 0.727 and 0.727W m -1 K -1 The performance is far from high standard usage requirements (> 10W m) -1 K -1 ). Compared with Graphene Aerogel (GA) prepared by a self-assembly method, graphene Foam (GF) grown by chemical vapor deposition can more effectively improve the thermal conductivity of composite PCM. This is because the crosslinking of GF is mainly based on covalent bonding, which enables the formation of high quality three-dimensional interconnected graphene backbones, providing a continuous path for phonon transport. However, GF has pore diameters as high as several hundred microns, which is determined by the nickel (Ni) foam catalyst framework, resulting in poor shape stability of the composite PCM, non-ideal electromagnetic shielding effectiveness, and limited thermal conductivity enhancement.
Therefore, developing new technology to build dense secondary heat conducting network inside large aperture of GF can be an effective strategy to improve shape stability of composite PCM and further enhance its thermal conductivity and electromagnetic shielding effectiveness is a problem that needs to be solved at present.
Disclosure of Invention
Problems according to the prior artThe invention provides a GF foam-MXene (two-dimensional material) aerogel double-network collaborative supported multifunctional composite phase-change material, and a preparation method and application thereof. The problems that the traditional organic phase change material is easy to leak, low in heat conductivity, single in functionality and high in heat conductivity and high in energy storage density can not be considered generally are solved. The multifunctional composite phase-change material has an out-of-plane thermal conductivity as high as 6.72-11.39W m under the condition of low filler content (9.06-13.78 wt%) -1 K -1 The electromagnetic shielding effectiveness of the X wave band is up to 42.9-55.6dB at the thickness of 3.0mm, and 160.3-166.9J g -1 Is excellent in leakage preventing ability.
The technical scheme of the invention is as follows:
a multifunctional composite phase change material; the multifunctional composite phase change material is formed by compounding graphene foam (GF foam), MXene aerogel and a phase change material; the MXene aerogel is a lamellar oriented structure coupled in the aperture of the GF foam, and the phase change material is encapsulated in the multifunctional composite material to form the GF foam-MXene aerogel double-network cooperatively supported multifunctional composite phase change material.
The thermal conductivity of the multifunctional composite phase-change material reaches 6.72-11.39W m -1 K -1 The method comprises the steps of carrying out a first treatment on the surface of the The electromagnetic shielding efficiency reaches 42.9-56.6dB, and the energy storage density reaches 160.3-166.9J g -1 。
The invention relates to a preparation method of a multifunctional composite phase-change material; the method comprises the following steps:
1): depositing graphene foam on a foam nickel template through chemical vapor deposition, and then immersing the graphene foam in hydrochloric acid to etch out foam nickel, so as to obtain self-supporting GF foam;
2): etching titanium aluminum carbide by using lithium fluoride and hydrochloric acid to prepare single-layer or less-layer MXene;
3): dispersing MXene and a binder in deionized water to obtain aqueous slurry, immersing GF in the slurry, and vacuumizing to realize complete impregnation;
4): transferring GF and slurry into a unidirectional freezing mold for directional freezing, and freeze-drying to obtain a GF foam-MXene aerogel double-network framework, wherein the MXene aerogel is a lamellar vertical orientation structure formed by coupling in GF foam pore diameters;
5): carrying out high-temperature heat treatment on the GF foam-MXene aerogel double-network framework under the protection of protective gas;
6): and compounding the GF foam-MXene aerogel double-network framework subjected to high-temperature heat treatment with a phase-change material through a vacuum impregnation method. 4. The method of claim 3, wherein the chemical vapor deposition gas in step 1) is methane at a temperature of 800-1200 ℃; the concentration of the hydrochloric acid is 2-4mol/l.
The mass ratio of the lithium fluoride to the titanium aluminum carbide in the step 2) is 6:5-2:1; the concentration of hydrochloric acid is 8-12 mol/l; the etching temperature is 30-40 ℃; etching time is 18-30 h; the drying mode is freeze drying; freeze drying temperature is-80 to-20 ℃; the freeze drying time is 24-72 h.
The dispersion mode in the step 3) is one of ultrasonic dispersion, high-speed shearing dispersion, ball milling dispersion or planetary gravity stirring dispersion; the binder is one of graphene oxide, polyvinyl alcohol, chitosan or carboxymethyl cellulose; the total concentration of the MXene and the binder is 15-60 mg mL -1 The weight ratio of the MXene to the binder is 4:1-1:1; the vacuumizing time is 4-8 h.
The unidirectional freezing mold in the step 4) is a polytetrafluoroethylene mold, the bottom of the unidirectional freezing mold is a copper column immersed in a cold source, the cold source comprises liquid nitrogen, dry ice or low-temperature ethanol, and the temperature of the cold source is between-196 ℃ and-20 ℃; freeze drying temperature is-80 to-20 ℃; the freeze-drying pressure is below 10 Pa.
The shielding gas in the step 5) is argon or nitrogen; the high-temperature heat treatment is to heat up to 600-1000 ℃ at 3-10 ℃/min, and the temperature is kept for 30-210 min.
The vacuum degree of the vacuum impregnation in the step 6) is less than 20Pa, and the time is 6-18 h; the phase change material is at least one of polyethylene glycol, paraffin, n-hexadecane, n-octadecane, erythritol, myristic acid, fatty acid, lauric acid, polyalcohol and stearic acid.
The multifunctional composite phase change material is applied to the fields of electronic equipment cooling, energy storage/conversion and related fields.
The invention has the advantages and excellent effects that: the multifunctional composite phase-change material prepared by the invention is solid in normal state, can still keep good shape stability when the temperature is higher than the melting temperature of the phase-change material, and has high out-of-plane heat conductivity, excellent electromagnetic shielding efficiency, high energy storage density and excellent cyclic heat stability. The problems that the traditional organic phase change material is easy to leak, low in heat conductivity, single in functionality and high in heat conductivity and high in energy storage density can not be considered generally are solved.
The multifunctional composite phase-change material comprises a GF foam-MXene aerogel dual-support network structure, and the oriented MXene aerogel formed by coupling the GF foam pore diameter has triple functions: (1) The oriented MXene aerogel serving as a secondary heat conduction network can increase the density of the heat conduction network and perfect the heat conduction path, and is beneficial to promoting phonon directional transmission and reducing the interface thermal resistance of a system. (2) The dense porous structure of the oriented MXene aerogel can provide strong capillary force and huge specific surface area for phase change material encapsulation, and effectively prevent the problem of melting leakage of the phase change material. (3) The porous honeycomb structure of the oriented MXene aerogel can promote the multiple reflection and absorption of electromagnetic waves and improve the electromagnetic shielding performance of the material. Therefore, the multifunctional composite phase-change material prepared by the invention has excellent comprehensive performance, and the out-of-plane thermal conductivity is as high as 6.72-11.39W m -1 K -1 The electromagnetic shielding effectiveness of the X wave band is up to 42.9-55.6dB at the thickness of 3.0mm, and 160.3-166.9J g -1 Is excellent in leakage preventing ability.
The GF foam-MXene aerogel double-network synergistic skeleton has higher strength and more perfect heat conduction network, can double package the molten phase change material and strengthen the heat transfer rate, and overcomes the defect that the out-of-plane heat conductivity of the current composite phase change material is generally lower (less than 10W m) -1 K -1 ) And is prone to leakage.
The application of the multifunctional composite phase change material in the electronic equipment cooling and energy storage/conversion device has excellent working performance and outstanding application effect.
Drawings
Fig. 1: schematic diagrams of preparation process of multifunctional composite phase-change materials in examples 1-3
Fig. 2: scanning Electron Microscope (SEM) of GF foam-MXene aerogel double-network framework prepared in example 2
Fig. 3: thermal conductivity of multifunctional composite phase-change Material prepared in examples 1-3
Fig. 4: electromagnetic shielding Effect of multifunctional composite phase-change Material prepared in examples 1-3
Fig. 5: energy storage Density Change of multifunctional composite phase-change Material prepared in example 3 over 120 heating/Cooling cycles
Fig. 6: infrared spectral variation of the multifunctional composite phase-change material prepared in example 3 over 120 heating/cooling cycles
Fig. 7: comparative photograph of leakage of multifunctional composite phase-change material and polyethylene glycol and GF/polyethylene glycol prepared in example 3 during heating on a hot stage
Fig. 8: thermal expansion curves of multifunctional composite phase-change Material and polyethylene glycol and GF/polyethylene glycol prepared in example 3
Fig. 9: multifunctional composite phase change material prepared in example 3 and two commercially available silica gel thermal pads (CP 200 and HD 90000) as thermal interface materials surface temperature changes of LED lamp
Fig. 10: ultraviolet-visible-near infrared absorption spectra of multifunctional composite phase-change material and polyethylene glycol and GF/polyethylene glycol prepared in example 3
Fig. 11: when the multifunctional composite phase-change material prepared in example 3 is applied to a photo-thermal-electric conversion device, the output voltage, the output current and the output power are under different illumination intensities
Detailed Description
The invention is described in further detail below with reference to the attached drawings and the steps of the specific embodiments:
the invention provides a GF foam-MXene aerogel dual-network cooperatively supported multifunctional composite phase-change material, which is formed by compounding graphene foam, MXene aerogel and a phase-change material, wherein the GF foam is three-dimensional interconnected high-quality graphene foam grown by chemical vapor deposition, the MXene aerogel is a lamellar oriented structure coupled in the aperture of the GF foam, the phase-change material is effectively packaged in the multifunctional composite material, and the thermal conductivity of the GF foam-MXene aerogel dual-network cooperatively supported multifunctional composite phase-change material is 6.72-11.39W m -1 K -1 The method comprises the steps of carrying out a first treatment on the surface of the The electromagnetic shielding effectiveness is 42.9-56.6dB, and the energy storage density is 160.3-166.9J g -1 。
A preparation method of a GF foam-MXene aerogel double-network cooperatively supported multifunctional composite phase-change material comprises the following steps:
1): depositing graphene foam on a foam nickel template through chemical vapor deposition, and then immersing the graphene foam in hydrochloric acid to etch out foam nickel, so as to obtain self-supporting GF foam;
2): and (3) etching titanium aluminum carbide by using lithium fluoride and hydrochloric acid to prepare single-layer or less-layer MXene.
3): dispersing MXene and a binder in deionized water to obtain aqueous slurry, immersing GF in the slurry, and vacuumizing to realize complete impregnation;
4): transferring GF and slurry into a unidirectional freezing mold for directional freezing, and freeze-drying to obtain a GF foam-MXene aerogel double-network framework, wherein the MXene aerogel is a lamellar vertical orientation structure formed by coupling in GF foam pore diameters;
5): carrying out high-temperature heat treatment on the GF foam-MXene aerogel double-network framework under the protection of inert gas;
6): and step five, compounding the GF foam-MXene aerogel double-network framework subjected to high-temperature heat treatment with a phase-change material through a vacuum impregnation method.
Further, the gas of the chemical vapor deposition in the step 1) is methane, and the temperature is 800-1200 ℃; hydrochloric acid concentration of 2-4mol/l
Further, in the step 2), the mass ratio of the lithium fluoride to the titanium aluminum carbide is 6:5-2:1; the concentration of hydrochloric acid is 8-12 mol/l; the etching temperature is 30-40 ℃; etching time is 18-30 h; the drying mode is freeze drying; freeze drying temperature is-80 to-20 ℃; the freeze drying time is 24-72 h.
Further, the dispersion mode in the step 3) is one of ultrasonic dispersion, high-speed shearing dispersion, ball milling dispersion or planetary gravity stirring dispersion; the binder is one of graphene oxide, polyvinyl alcohol, chitosan or carboxymethyl cellulose, and preferably graphene oxide; the total concentration of the MXene and the binder is 15-60 mg mL ～1 The method comprises the steps of carrying out a first treatment on the surface of the The weight ratio of MXene to binder is 4:1-1:1, preferably 2:1; the vacuumizing time is 4-8 h.
Further, in the step 4), the unidirectional freezing mold is a customized polytetrafluoroethylene mold, the bottom is a copper column immersed in a cold source, preferably, the cold source comprises liquid nitrogen, dry ice or low-temperature ethanol, and the temperature of the cold source is between-196 ℃ and-20 ℃. Freeze drying temperature is-80 to-20 ℃; the freeze-drying pressure is below 10 Pa.
Further, the inert gas in the step 5) is argon or nitrogen; the high-temperature heat treatment is to heat up to 600-1000 ℃ at 3-10 ℃/min, and the temperature is kept for 30-210 min.
Further, the vacuum degree of the vacuum impregnation in the step 6) is less than 20Pa, and the time is 6-18 hours; the phase change material is at least one of polyethylene glycol, paraffin, n-hexadecane, n-octadecane, erythritol, myristic acid, fatty acid, lauric acid, polyalcohol and stearic acid, and is preferably polyethylene glycol.
Example 1:
1. taking foam nickel with the size of 20 multiplied by 1.5mm in a quartz tube furnace, heating to 1000 ℃ under the atmosphere of argon and hydrogen in the volume ratio of (5:2), then introducing methane for the growth of graphene, and rapidly cooling a sample to room temperature under the atmosphere of argon and hydrogen. The prepared nickel-GF was then dip coated with a 4wt% polymethyl methacrylate/anisole solution and baked at 180 ℃ for 3 hours to form a thin layer of polymethyl methacrylate to prevent GF structure collapse during nickel etching. Next, the nickel substrate was completely dissolved in 3mol/l hydrochloric acid solution at 80℃overnight to obtain GF/polymethyl methacrylate. Finally, GF was obtained by dissolving the polymethyl methacrylate layer with acetone at 55 ℃.
2. 1.0g of titanium aluminum carbide powder was added to 20mL of etchant solution (containing 12mol/l hydrochloric acid and 1.6g of lithium fluoride), followed by continuous stirring at 35℃for 24 hours. After etching, transferring the product to a centrifuge tube, centrifuging for 5min at 3500rpm, removing the acid liquor on the upper layer, adding deionized water to wash the precipitate, and repeatedly centrifuging and washing until the pH value of the supernatant is close to 6. At this point the precipitate gradually swelled and became viscous, similar to clay, and the supernatant was greenish-black, giving a multilayer MXene. Next, the multi-layered MXene was redispersed in water and sonicated under an argon atmosphere for 1h followed by centrifugation at 3500rpm for 1h, and the supernatant was collected as a few-layered MXene suspension. And finally, freeze-drying at the temperature of minus 20 ℃ for 24 hours to obtain the single-layer or less-layer MXene nano-sheets.
3. Dispersing the MXene and the bonding agent graphene oxide in a weight ratio of 2:1 into deionized water through a planetary vacuum defoaming stirrer to obtain the total concentration of the MXene/graphene oxide of 15mg mL -1 Is characterized by uniform and stable slurry liquid. Thereafter, GF was immersed in the MXene/graphene oxide slurry solution and evacuated for 6 hours to achieve complete impregnation.
4. Transferring GF and slurry into a unidirectional freezing mold (a customized polytetrafluoroethylene mold, a copper column immersed in liquid nitrogen is arranged at the bottom) for directional freezing, then freeze-drying an ice block sample in a freeze dryer (-50 ℃,0.1Pa; LGJ-20 FG), removing the ice column through sublimation effect, and obtaining the GF foam-MXene aerogel double-network framework, wherein the MXene aerogel is a lamellar vertical orientation structure formed by coupling in the aperture of GF foam.
5. Thermally annealing the GF foam-MXene aerogel double network backbone at 800 ℃ for 2h in an argon atmosphere, wherein the binder graphene oxide is thermally reduced to graphene.
6. Melting polyethylene glycol in a vacuum oven at 90 ℃, immersing the GF foam-MXene aerogel double-network skeleton after high-temperature heat treatment in polyethylene glycol melt, vacuum-immersing for 12 hours at the temperature of 90 ℃, taking out, removing polyethylene glycol with the surface not stably adsorbed by using oil absorption paper, and naturally cooling and solidifying to obtain the composite phase change material.
Example 2:
this embodiment differs from example 1 in that the total concentration of MXene and binder graphene oxide in step 3 is 30mg mL -1 Other steps and parameters were the same as in example 1.
Example 3:
this embodiment differs from examples 1 and 2 in that the total concentration of MXene and binder graphene oxide in step 3 is 60mg mL -1 Other steps and parameters were the same as in example 1.
FIG. 1 is a schematic diagram of the preparation process of the multifunctional composite phase-change material in examples 1-3. As can be seen from fig. 1, the preparation process of the composite phase change material supported by the GF foam-MXene aerogel dual network cooperation comprises four steps: (1) preparation of MXene and binder graphene oxide slurry liquid; (2) The directional freezing process of the MXene and the binder graphene oxide slurry liquid in the GF foam; (3) Freeze drying and high temperature heat treatment to obtain GF foam-MXene aerogel double-network skeleton; and (4) preparing the composite phase-change material by vacuum impregnation.
FIG. 2 is a scanning electron microscope image of the GF foam-MXene aerogel dual network framework prepared in example 2. As can be seen from fig. 2, the MXene aerogel is a lamellar oriented structure coupled within the pore size of the GF foam, and the oriented MXene aerogel effectively increases the network density of the GF foam, and the dense porous GF foam-MXene aerogel dual-network skeleton is beneficial to phase change material encapsulation and improves the thermal conductivity and electromagnetic shielding performance of the material.
FIG. 3 shows the thermal conductivity of polyethylene glycol, GF/polyethylene glycol and the multifunctional composite phase change material prepared in examples 1-3. As can be seen from FIG. 3, the thermal conductivities of polyethylene glycol and GF/polyethylene glycol are 0.32 and 5.43W m -1 K -1 Whereas the thermal conductivities of the multifunctional composite phase-change materials prepared in example 1, example 2 and example 3 were 6.72, 8.21 and 11.39W m, respectively -1 K -1 Compared with GF/polyethylene glycol, the two-network skeleton of GF foam-MXene aerogel is improved by 23.8%, 51.2% and 109.8%, which shows that the two-network skeleton of GF foam-MXene aerogel has better heat conduction property than single GF foam; in addition, anotherIn addition, the heat conduction performance of the material is increased along with the increase of the content of the MXene aerogel, and the superiority of the GF foam-MXene aerogel double-network framework in the invention is proved.
Fig. 4 shows electromagnetic shielding effectiveness of polyethylene glycol, GF/polyethylene glycol, and the multifunctional composite phase change material prepared in examples 1-3. As can be seen from fig. 4, at 8.2-12.4 GHz (X-band), the electromagnetic shielding effectiveness of polyethylene glycol is less than 2.9dB, and the electromagnetic shielding effectiveness of gf/polyethylene glycol is less than 35.8dB; the electromagnetic shielding effectiveness of the multifunctional composite phase-change materials prepared in the embodiment 1, the embodiment 2 and the embodiment 3 are respectively more than 44.5, 42.9 and 55.6dB, compared with GF/polyethylene glycol, the electromagnetic shielding effectiveness is improved by 24.3%, 19.8% and 55.3%, the electromagnetic shielding effectiveness of the multifunctional composite phase-change materials is improved by the MXene aerogel coupled in the aperture of GF foam, and the electromagnetic shielding performance of the multifunctional composite phase-change materials is improved.
Fig. 5 and Table2 are energy storage density changes of the multifunctional composite phase-change material prepared in example 3 during 120 heating/cooling cycles. As can be seen from fig. 5, after 120 heating/cooling cycles, the multifunctional composite phase-change material in example 3 has almost no change in phase-change latent heat (melting enthalpy/crystallization enthalpy) and phase-change temperature (melting point/crystallization point), which proves that the multifunctional composite phase-change material provided by the invention has excellent cycle thermal stability.
FIG. 6 is an infrared spectrum change of the multifunctional composite phase-change material prepared in example 3 in 120 heating/cooling cycles. As can be seen from fig. 6, the multifunctional composite phase-change material in example 3 has no change in molecular structure and functional group after 120 heating/cooling cycles, which proves that the multifunctional composite phase-change material provided by the invention has excellent cycle thermal stability.
FIG. 7 is a comparative photograph showing the leakage of the multifunctional composite phase-change material prepared in example 3 and polyethylene glycol and GF/polyethylene glycol during heating on a hot plate. As can be seen from fig. 7, after polyethylene glycol, GF/polyethylene glycol and the multifunctional composite phase change material of example 3 were heated to 100 ℃ on a hot stage, the polyethylene glycol was completely melted, and the GF/polyethylene glycol showed a trace of slight leakage, whereas the sample of example 3 had no leakage, and the shape stability was excellent, confirming that the multifunctional composite phase change material provided by the present invention has excellent anti-leakage performance and shape stability.
FIG. 8 is a graph showing the thermal expansion curves of the multifunctional composite phase change material and polyethylene glycol and GF/polyethylene glycol prepared in example 3. As can be seen from fig. 8, after the temperature is higher than 70 ℃, the polyethylene glycol size is greatly changed, the GF/polyethylene glycol size is greatly changed, while the sample size of example 3 is almost constant, which proves that the multifunctional composite phase-change material provided by the present invention has excellent shape stability.
Table 1 DSC heating/Cooling data for multifunctional composite phase-change Material of example 1, example 2 and example 3
Wherein T is m /T c Is the melting/crystallization point; ΔH m /ΔH c Is the melting enthalpy/crystallization enthalpy.
Table2 DSC data of multifunctional composite phase-change Material in example 3 in 120 heating/Cooling cycles
Wherein T is m /T c Is the melting/crystallization point; ΔH m /ΔH c Is the melting enthalpy/crystallization enthalpy.
Example 4:
1. taking foam nickel with the size of 20 multiplied by 1.5mm in a quartz tube furnace, heating to 800 ℃ under the atmosphere of argon and hydrogen in the volume ratio of (5:2), then introducing methane for the growth of graphene, and rapidly cooling a sample to room temperature under the atmosphere of argon and hydrogen. The prepared nickel-GF was then dip coated with a 4wt% polymethyl methacrylate/anisole solution and baked at 180 ℃ for 3 hours to form a thin layer of polymethyl methacrylate to prevent GF structure collapse during nickel etching. Next, the nickel substrate was completely dissolved in 2mol/l hydrochloric acid solution at 80℃overnight to obtain GF/polymethyl methacrylate. Finally, GF was obtained by dissolving the polymethyl methacrylate layer with acetone at 55 ℃.
2. 1.0g of titanium aluminum carbide powder was added to 20mL of etchant solution (containing 8mol/l hydrochloric acid and 1.2g of lithium fluoride), followed by continuous stirring at 40℃for 18 hours. After etching, transferring the product to a centrifuge tube, centrifuging for 5min at 3500rpm, removing the acid liquor on the upper layer, adding deionized water to wash the precipitate, and repeatedly centrifuging and washing until the pH value of the supernatant is close to 6. At this point the precipitate gradually swelled and became viscous, similar to clay, and the supernatant was greenish-black, giving a multilayer MXene. Next, the multi-layered MXene was redispersed in water and sonicated under an argon atmosphere for 1h followed by centrifugation at 3500rpm for 1h, and the supernatant was collected as a few-layered MXene suspension. And finally, freeze-drying at the temperature of minus 50 ℃ for 48 hours to obtain the single-layer or less-layer MXene nano-sheets.
3. Ultrasonically dispersing MXene and a binder polyvinyl alcohol in deionized water in a weight ratio of 4:1 to obtain the total concentration of MXene/polyvinyl alcohol of 20mg mL -1 Is characterized by uniform and stable slurry liquid. Thereafter, GF was immersed in the MXene/polyvinyl alcohol slurry and evacuated for 4 hours to achieve complete impregnation.
4. Transferring GF and slurry into a unidirectional freezing mold (a customized polytetrafluoroethylene mold, wherein a copper column immersed in dry ice at the bottom of the mold is a copper column at the temperature of minus 78 ℃) for directional freezing, then freeze-drying an ice block sample in a freeze dryer (-80 ℃ and 10 Pa), and removing the ice column through sublimation effect to obtain the GF foam-MXene aerogel double-network framework, wherein the MXene aerogel is a lamellar vertical orientation structure formed by coupling in the aperture of the GF foam.
5. The GF foam-MXene aerogel double network backbone was thermally annealed at 600 ℃ under argon atmosphere for 210min, wherein the binder polyvinyl alcohol was sintered to carbon.
6. Melting paraffin in a vacuum oven at 70 ℃, immersing the GF foam-MXene aerogel double-network skeleton after high-temperature heat treatment into paraffin melt, vacuum-immersing for 6 hours at the temperature of 70 ℃, taking out, removing paraffin with the surface not stably adsorbed by using oil absorption paper, and naturally cooling and solidifying to obtain the composite phase change material.
Example 5:
1. taking foam nickel with the size of 20 multiplied by 1.5mm in a quartz tube furnace, heating to 1200 ℃ under the atmosphere of argon and hydrogen in the volume ratio of (5:2), then introducing methane for the growth of graphene, and rapidly cooling a sample to room temperature under the atmosphere of argon and hydrogen. The prepared nickel-GF was then dip coated with a 4wt% polymethyl methacrylate/anisole solution and baked at 180 ℃ for 3 hours to form a thin layer of polymethyl methacrylate to prevent GF structure collapse during nickel etching. Next, the nickel substrate was completely dissolved in 4mol/l hydrochloric acid solution at 80℃overnight to obtain GF/polymethyl methacrylate. Finally, GF was obtained by dissolving the polymethyl methacrylate layer with acetone at 55 ℃.
2. 1.0g of titanium aluminum carbide powder was added to 20mL of etchant solution (containing 10mol/l hydrochloric acid and 2.0g of lithium fluoride), followed by continuous stirring at 30℃for 30 hours. After etching, transferring the product to a centrifuge tube, centrifuging for 5min at 3500rpm, removing the acid liquor on the upper layer, adding deionized water to wash the precipitate, and repeatedly centrifuging and washing until the pH value of the supernatant is close to 6. At this point the precipitate gradually swelled and became viscous, similar to clay, and the supernatant was greenish-black, giving a multilayer MXene. Next, the multi-layered MXene was redispersed in water and sonicated under an argon atmosphere for 1h followed by centrifugation at 3500rpm for 1h, and the supernatant was collected as a few-layered MXene suspension. And finally, freeze-drying at the temperature of minus 80 ℃ for 72 hours to obtain the single-layer or less-layer MXene nano-sheets.
3. Dispersing MXene and binder chitosan in a weight ratio of 1:1 in a 2wt% acetic acid aqueous solution by ball milling to obtain the total concentration of MXene/chitosan of 40mg mL -1 Is characterized by uniform and stable slurry liquid. Thereafter, GF was immersed in the MXene/shell poly syrup solution and evacuated for 8 hours to achieve complete impregnation.
4. Transferring GF and slurry into a unidirectional freezing mold (a customized polytetrafluoroethylene mold, wherein copper columns immersed in ethanol at low temperature of-20 ℃ below zero are arranged at the bottom) for directional freezing, then freeze-drying ice block samples in a freeze dryer (-20 ℃ below zero, 5 Pa), removing the ice columns through sublimation effect, and obtaining the GF foam-MXene aerogel double-network framework, wherein the MXene aerogel is a lamellar vertical orientation structure formed by coupling in the aperture of GF foam.
5. The GF foam-MXene aerogel double network backbone was thermally annealed at 1000 ℃ for 30min under nitrogen atmosphere, wherein the binder chitosan was sintered to carbon.
6. Melting n-octadecane in a vacuum oven at 70 ℃, immersing the GF foam-MXene aerogel double-network skeleton after high-temperature heat treatment into the n-octadecane melt, vacuum-immersing for 18 hours at the temperature of 70 ℃, taking out, removing the n-octadecane with the surface not stably adsorbed by utilizing oil absorption paper, and naturally cooling and solidifying to obtain the composite phase change material.
Test example 1
The multifunctional composite phase change material obtained in example 3 and two commercial silica gel heat conductive pads CP200 (2.0W m) -1 K -1 DOBON, china) HD90000 (7.5W m) -1 K -1 Laird Tflex, usa) as thermal management properties of thermal interface materials by the following method:
the multifunctional composite phase-change material obtained in example 3 and two commercial silica gel heat conduction pads CP200 and HD90000 are cut into 20X 1.5mm 3 The dimensions were then assembled with a 10W LED lamp and aluminum block heat sink, respectively, and the surface temperature changes were recorded within 1000s after LED ignition using a thermal infrared imager, as shown in fig. 9. As can be seen from the comparison in FIG. 9, when the multifunctional composite phase-change material of the present invention is used as a thermal interface material, the rising degree of the temperature of the inner surface of the LED lamp when the LED lamp is lighted for 1000s is far lower than the surface temperature of the LED lamp when two commercial silica gel heat conducting pads are used as the thermal interface material, which proves that the multifunctional composite phase-change material of the present invention has excellent heat dissipation performance when being used as the thermal interface material.
Test example 2
The light absorption performance of the multifunctional composite phase-change material obtained in example 3 was tested, and the ultraviolet-visible light absorption spectrum was obtained by the test method using polyethylene glycol and GF/polyethylene glycol as a comparison, and as shown in fig. 10, it can be seen that the multifunctional composite phase-change material obtained in example 3 has excellent light absorption performance, because GF foam-MXene aerogel double network skeleton can be used as an effective photon capturing agent.
Test example 3
The multifunctional composite phase change material obtained in example 3 was tested for energy storage and conversion properties by the following method:
the multifunctional composite phase change material obtained in example 3 was cut and polishedThe size of the solar energy collector is applied to a self-made photo-thermal-electric energy conversion device, and the device comprises a xenon lamp (AM 1.5), a multifunctional composite phase-change material for efficiently collecting sunlight, and a commercial thermoelectric generation sheet (40X 40 mm) 2 TEC 2-25408) and a liquid-cooled heat sink. The illumination intensity is adjusted to 150, 250, 400, 600, 800 and 1000mW cm -2 The output voltage, output current and output power of the photo-thermal-electric energy conversion device are shown in fig. 11. As can be seen from FIG. 11, the photo-thermal-electric energy conversion device was operated at 1000mW cm after using the multifunctional composite phase-change material obtained in example 3 -2 The output voltage, output current and output power under illumination intensity are up to 1046.5mV, 190.6mA and 124.7W m -2 The multifunctional composite phase change material has excellent energy storage and conversion performance.
The technical scheme disclosed and proposed by the invention can be realized by a person skilled in the art by appropriately changing the condition route and other links in consideration of the content of the present invention, although the method and the preparation technology of the invention have been described by the preferred embodiment examples, the related person can obviously modify or recombine the method and the technical route described herein to realize the final preparation technology without departing from the content, spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be included within the spirit, scope and content of the invention.
Claims (10)
1. A multifunctional composite phase change material; the multifunctional composite phase change material is characterized by being formed by compounding graphene foam (GF foam), MXene aerogel and a phase change material; the MXene aerogel is a lamellar oriented structure coupled in the aperture of the GF foam, and the phase change material is encapsulated in the multifunctional composite material to form the GF foam-MXene aerogel double-network cooperatively supported multifunctional composite phase change material.
2. The multifunctional composite phase change material of claim 1; the multifunctional composite phase-change material is characterized in that the thermal conductivity of the multifunctional composite phase-change material reaches 6.72-11.39W m -1 K -1 The method comprises the steps of carrying out a first treatment on the surface of the The electromagnetic shielding efficiency reaches 42.9-56.6dB, and the energy storage density reaches 160.3-166.9J g -1 。
3. A method of preparing the multifunctional composite phase change material of claim 1; the method is characterized by comprising the following steps of:
1): depositing graphene foam on a foam nickel template through chemical vapor deposition, and then immersing the graphene foam in hydrochloric acid to etch out foam nickel, so as to obtain self-supporting GF foam;
2): etching titanium aluminum carbide by using lithium fluoride and hydrochloric acid to prepare single-layer or less-layer MXene;
3): dispersing MXene and a binder in deionized water to obtain aqueous slurry, immersing GF in the slurry, and vacuumizing to realize complete impregnation;
4): transferring GF and slurry into a unidirectional freezing mold for directional freezing, and freeze-drying to obtain a GF foam-MXene aerogel double-network framework, wherein the MXene aerogel is a lamellar vertical orientation structure formed by coupling in GF foam pore diameters;
5): carrying out high-temperature heat treatment on the GF foam-MXene aerogel double-network framework under the protection of protective gas;
6): and compounding the GF foam-MXene aerogel double-network framework subjected to high-temperature heat treatment with a phase-change material through a vacuum impregnation method.
4. The method of claim 3, wherein the chemical vapor deposition gas in step 1) is methane at a temperature of 800-1200 ℃; the concentration of hydrochloric acid is 2-4mol/l.
5. A method according to claim 3, wherein the mass ratio of lithium fluoride to titanium aluminium carbide in step 2) is from 6:5 to 2:1; the concentration of hydrochloric acid is 8-12 mol/l; the etching temperature is 30-40 ℃; etching time is 18-30 h; the drying mode is freeze drying; freeze drying temperature is-80 to-20 ℃; the freeze drying time is 24-72 h.
6. The method of claim 3, wherein the dispersion in step 3) is one of ultrasonic dispersion, high-speed shear dispersion, ball mill dispersion or planetary gravity stirring dispersion; the binder is one of graphene oxide, polyvinyl alcohol, chitosan or carboxymethyl cellulose; the total concentration of the MXene and the binder is 15-60 mg mL -1 The weight ratio of the MXene to the binder is 4:1-1:1; the vacuumizing time is 4-8 h.
7. The method of claim 3, wherein the unidirectional freezing mold in the step 4) is a polytetrafluoroethylene mold, the bottom is a copper column immersed in a cold source, the cold source comprises liquid nitrogen, dry ice or low-temperature ethanol, and the temperature of the cold source is between-196 ℃ and-20 ℃; freeze drying temperature is-80 to-20 ℃; the freeze-drying pressure is below 10 Pa.
8. A method according to claim 3, wherein the shielding gas in step 5) is argon or nitrogen; the high-temperature heat treatment is to heat up to 600-1000 ℃ at 3-10 ℃/min, and the temperature is kept for 30-210 min.
9. A method according to claim 3, wherein the vacuum degree of the vacuum impregnation in step 6) is less than 20Pa for a period of 6 to 18 hours; the phase change material is at least one of polyethylene glycol, paraffin, n-hexadecane, n-octadecane, erythritol, myristic acid, fatty acid, lauric acid, polyalcohol and stearic acid.
10. The multifunctional composite phase change material of claim 1, wherein the application fields comprise electronic device cooling, energy storage/conversion and related fields.
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| CN117821024A (en) * | 2023-12-28 | 2024-04-05 | 兰州大学第一医院 | Preparation method of MXene/sorghum straw biomass aerogel-based composite phase-change material |
| CN117613250A (en) * | 2024-01-24 | 2024-02-27 | 帕瓦(长沙)新能源科技有限公司 | Three-dimensional conductive lead-carbon composite material, preparation method thereof, negative electrode and lead-acid battery |
| CN117613250B (en) * | 2024-01-24 | 2024-04-19 | 帕瓦(长沙)新能源科技有限公司 | Three-dimensional conductive lead-carbon composite material, preparation method thereof, negative electrode and lead-acid battery |
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