CN115849860B - Graphene/magneli phase TinO 2n-1 Nanoparticle composite high-heat-conductivity film and preparation method thereof - Google Patents
Graphene/magneli phase TinO 2n-1 Nanoparticle composite high-heat-conductivity film and preparation method thereof Download PDFInfo
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Abstract
The application discloses a graphene/magneli phase Ti n O 2n‑1 The preparation process of nanometer particle composite high heat conducting film includes the steps of n O 2n‑1 Preparation of nanoparticles, preparation of graphene nanoplatelets, graphene/Ti 2 O 3 Or Ti (Ti) 4 O 7 Composite of nanoparticles, graphene/Ti 2 O 3 Or Ti (Ti) 4 O 7 Preparation of a composite film. The graphene/magneli phase Ti of the application n O 2n‑1 Composite high heat conduction film of nano particles, which uses graphene as main material and magneli phase TinO 2n‑1 The nano particles are used as auxiliary additives, and in the process of assembly into a film, the nano particles have high heat conducting property, high stability and nano TinO 2n‑1 The particles effectively fill the positions of folds, gaps, holes and the like of the graphene sheets, so that the film forming is in a more uniform and flat distribution state, and the film forming has high heat conduction performance.
Description
Technical Field
The application belongs to the technical field of composite materials, and in particular relates to graphene/magneli phase TinO 2n-1 Nanoparticle composite high heat conduction film and its preparation method are provided.
Background
In recent years, with the trend of light weight, miniaturization, compact structure and high operation efficiency of electronic instruments such as mobile phones, computers, and control systems of aerospace craft, the development of such light weight and integration of electronic products generally results in higher heating temperature, while overheating often results in a significant reduction in the life and operation stability of devices. The heat generation of electronic devices directly affects the performance and reliability of equipment, and the heat dissipation problem in the 5G era is more remarkable. With the high frequency, high speed and dense and miniaturized integrated circuits of electronic devices, the total power density of the electronic devices is greatly increased and the physical size is smaller and smaller, and the heat flux density is also increased.
Graphene, also known as monolayer graphite, is a planar thin film composed of carbon atoms, which is exfoliated from graphite material, and has a thickness of only one carbon atom, which is a two-dimensional material formed by arranging the carbon atoms of a monolayer in a honeycomb lattice. The graphene has a very stable structure, carbon-carbon bonds are only the connection between carbon atoms in the graphene is very flexible, and when external force is applied to the graphene, the carbon atom faces can be bent and deformed, so that the carbon atoms do not need to be rearranged to adapt to the external force, and the structure is kept stable. This stabilizationThe lattice structure enables the graphene to have excellent thermal conductivity, and the theoretical thermal conductivity coefficient is as high as 5300 W.m -1 ·K -1 Higher than carbon nanotubes and diamond. Graphene has outstanding thermal conductivity (5300 W.m) -1 · K-1 ) Excellent electrical properties (electron mobility at room temperature of up to 2X 10) 5 cm 2 Vs), extraordinary specific surface area (2630 m 2 G), young's modulus (1100 GPa) and breaking strength (125 GPa). Meanwhile, graphene has the advantages of high temperature resistance and corrosion resistance, and has good mechanical properties and lower density, so that the graphene has the potential of replacing metal in the field of heat conducting materials.
Titanium is abundant in nature and has a variety of oxides of different valence states. Among these oxides, titanium dioxide has been intensively studied in the field of photocatalysis due to its characteristics of good photoresponsive ability, low cost, high thermal stability, and the like. However, the naturally existing titanium dioxide has a wider forbidden bandwidth, and can only respond to ultraviolet light with the wavelength below 400nm, so that the absorption of the titanium dioxide to light is limited, and the titanium dioxide cannot be used for photo-thermal conversion. Researchers have reduced TiO by different methods 2 The forbidden bandwidth of (2) improves the response and absorption of solar energy, but at most can only respond to sunlight below 800nm, thus restricting TiO 2 Application in photo-thermal conversion. Magneli phase TinO 2n-1 (2 < n < 10) is a relatively common type of titanium metal oxide that has found application in energy storage. And Ti is 2 O 3 And Ti is 4 O 7 As a Magneli phase TinO 2n-1 The most widely used materials (2 < n < 10) have been shown to absorb a wide range of ultraviolet, visible and near infrared light, and have not only high thermal and electrical conductivity but also excellent optical, thermal, electrical and chemical stability. Magneli phase TinO 2n-1 The nano particles are used as auxiliary additive materials, so that the graphene has a more uniform and flat distribution state, and the heat conduction performance of the graphene is not affected.
Disclosure of Invention
The application aims at graphene and magneli phase TinO 2n-1 The above characteristics of titanium metal oxides have attempted to combine the magneli phase TinO 2n-1 The titanium metal oxide is compounded into the graphene sheet, so that a novel film material which is uniform and smooth in film formation and high in heat conduction performance and can be applied to electronic products to solve the heating problem is obtained.
In order to achieve the above purpose, the application adopts the following technical scheme: graphene/magneli phase TinO 2n-1 The preparation method of the nanoparticle composite high-heat-conductivity film comprises the following steps:
step one, magneli phase Ti n O 2n-1 Nanoparticle preparation Using commercially available Ti 2 O 3 Or Ti (Ti) 4 O 7 The micron particles are used as raw materials, and are nanocrystallized by adopting a ball milling method to prepare Ti 2 O 3 Or Ti (Ti) 4 O 7 A nanoparticle;
step two, preparing graphene nano sheets, and respectively adding a certain amount of concentrated H into a beaker 2 SO 4 、(NH 4 ) 2 S 2 O 8 Mixing with natural graphite, stirring, and slowly dripping a certain amount of H 2 0 2 Standing the beaker at normal temperature for a period of time to obtain a graphene aggregate which is fully expanded, washing the graphene aggregate to be neutral, adding the graphene aggregate into a certain amount of nitrogen-methyl pyrrolidone, performing ultrasonic treatment for a period of time by using a cell pulverizer, and centrifuging by using a centrifuge to obtain an upper layer liquid, thereby obtaining a stable graphene nano sheet dispersion liquid;
step three, graphene/Ti 2 O 3 Or Ti (Ti) 4 O 7 Compounding nanometer particles, pouring a certain amount of water into a flask, adding 2mL of synthesized graphene dispersion liquid, uniformly dispersing by an ultrasonic instrument, and adding a certain amount of Ti 2 O 3 Or Ti (Ti) 4 O 7 Dispersing the nano particles in a certain amount of water to obtain Ti 2 O 3 Or Ti (Ti) 4 O 7 The dispersion is then stirred rapidly with Ti 2 O 3 Or Ti (Ti) 4 O 7 Adding the dispersion liquid into graphene dispersion liquid, and obtaining graphene/Ti as a product 2 O 3 Or Ti (Ti) 4 O 7 Compounding the dispersion liquid;
step four, graphene/Ti 2 O 3 Or Ti (Ti) 4 O 7 Preparation of composite film, a certain amount of graphene/Ti 2 O 3 Or Ti (Ti) 4 O 7 Diluting the composite dispersion liquid into a certain amount of deionized water, uniformly dispersing the composite dispersion liquid by using an ultrasonic instrument, performing vacuum suction filtration by using a fiber-mixed microporous filter membrane, adding an equal volume of deionized water to wash once before finishing, and forming a layer of graphene/Ti on the filter membrane after the suction filtration is finished 2 O 3 Or Ti (Ti) 4 O 7 And (3) a composite membrane. Gently transfer graphene/Ti with forceps 2 O 3 Or Ti (Ti) 4 O 7 The composite membrane is torn off from the surface of the filter membrane and dried in an oven to finally prepare the graphene/magneli phase Ti n O 2n-1 Composite high thermal conductive films of nanoparticles.
As a preferable mode of the technical scheme, in the ball milling process in the step one, a certain amount of deionized water and commercially available Ti 2 O 3 Powder or Ti 4 O 7 Sequentially adding powder and agate balls into a ball milling tank, ball milling for a certain time by adopting an intermittent ball milling method, transferring a ball-milled sample from the ball milling tank into a beaker with deionized water, and drying in an oven to obtain a Magneli phase Ti n O 2n-1 And (3) nanoparticles.
As a preferable mode of the above technical solution, graphene and Ti in the third step 2 O 3 Or Ti (Ti) 4 O 7 The mass ratio of (2) is 1:0.001- - -1.
As a preferable mode of the above technical scheme, in the first step, agate balls with diameters of 5mm and 10mm are used as grinding balls, 27g of deionized water and 27g of commercial Ti are used 2 O 3 Powder or Ti 4 O 7 And agate balls with the weight ratio of 1:1:3 are sequentially added into a ball milling tank, the ball milling tank is placed into ball milling equipment, the rotating speed is set to 300rpm, an intermittent ball milling method is adopted, the operation time is 50 minutes, the pause time is 10 minutes, the intermittent times are 24 times, the total ball milling time is 24 hours, after ball milling, a sample is transferred from the ball milling tank into a beaker with deionized water, and then the sample is dried in an oven at 60 ℃ for 24 hoursTo obtain a Magneli phase Ti n O 2n-1 A nanoparticle; in the second step, 80mL of H is added into a beaker respectively 2 S0 4 15g (NH) 4 ) 2 S 2 O 8 And 3g of 50-mesh natural graphite, and slowly dropwise adding 10mL of H after stirring at a proper amount of 300-600 rpm 2 O 2 Standing the beaker at normal temperature for 6 hours to obtain a fully expanded graphene aggregate, washing the graphene aggregate to be neutral, adding the graphene aggregate into 200mL of nitrogen-methyl pyrrolidone, performing ultrasonic treatment for 3 hours with 200W power by using a cell pulverizer, and performing centrifugal treatment for 20 minutes with a centrifugal machine at a rotating speed of 3000-4000 rpm to obtain an upper layer solution, thereby obtaining a stable graphene nanosheet dispersion; in the third step, 100mL of water is poured into a flask, then 2mL of graphene dispersion liquid synthesized above is added, the graphene dispersion liquid is uniformly dispersed by an ultrasonic instrument, and 50mg of Ti is added 2 O 3 Or Ti (Ti) 4 O 7 The nanoparticles were dispersed in 50mL of water, then Ti was stirred rapidly 2 O 3 Or Ti (Ti) 4 O 7 Adding the dispersion liquid into the graphene dispersion liquid, and obtaining a product which is graphene/Ti 2 O 3 Or Ti (Ti) 4 O 7 Compounding the dispersion liquid; in the fourth step, 10mL of graphene/Ti is used 2 O 3 Or Ti (Ti) 4 O 7 The composite dispersion is diluted into 200mL of deionized water, the deionized water is uniformly dispersed by an ultrasonic instrument, a fiber-mixed microporous filter membrane with the aperture of 0.45 mu m is used for vacuum suction filtration, the deionized water with the same volume is added for washing once before the completion of the vacuum filtration, and a layer of graphene/Ti appears on the filter membrane after the suction filtration is completed 2 O 3 Or Ti (Ti) 4 O 7 Composite film, gently mix graphene/Ti with tweezers 2 O 3 Or Ti (Ti) 4 O 7 The composite membrane is torn off from the surface of the filter membrane and dried in an oven to finally prepare the graphene/magneli phase Ti n O 2n-1 Composite high thermal conductive films of nanoparticles.
Graphene/magneli phase TinO 2n-1 The nanoparticle composite high-heat-conductivity film is prepared by the preparation method.
The application is characterized in thatThe beneficial effects are that: the graphene/magneli phase Ti of the application n O 2n-1 Composite high heat conduction film of nano particles, which uses graphene as main material and magneli phase TinO 2n-1 The nano particles are used as auxiliary additives, and in the process of assembly into a film, the nano particles have high heat conducting property, high stability and nano TinO 2n-1 The particles effectively fill the positions of folds, gaps, holes and the like of the graphene sheets, so that the film forming is in a more uniform and flat distribution state, and the film forming has high heat conduction performance. The thickness of the heat conducting film is 40-50 mu m, the heat conductivity is measured, and the heat conductivity coefficient in plane is 900-1000 W.m -1 ·K -1 The heat conductivity in the vertical direction is 9-10 W.m -1 ·K -1 。
Drawings
FIG. 1 is graphene/Ti 2 O 3 XRD pattern of the composite film;
FIG. 2 is graphene/Ti 2 O 3 Scanning electron microscope image of composite film
Detailed Description
The following description of the embodiments of the present application will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the application are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In the description of the present application, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present application will be understood in specific cases by those of ordinary skill in the art.
Example 1
Magneli phase Ti 2 O 3 Nanometer scalePreparation of particles
By using commercially available Ti 2 O 3 The micron particles are used as raw materials, and are nanocrystallized by adopting a ball milling method to prepare Ti 2 O 3 And (3) nanoparticles. In a typical ball milling process, agate balls having diameters of 5mm and 10mm (total weight of 81 g) were used as the milling balls. 27g deionized water and 27g commercially available Ti 2 O 3 Powder and agate balls with the weight ratio of 1:1:3 are sequentially added into a ball milling tank. Finally, the ball mill pot was placed in a ball mill apparatus, and the rotational speed was set to 300rpm. The batch ball milling method is adopted, the running time is 50 minutes, the pause time is 10 minutes, and the batch times are 24 times. Thus, the total ball milling time was 24 hours. After ball milling, the samples were transferred from the ball milling pot to a beaker with deionized water and then dried in an oven at 60 ℃ for 24 hours to obtain nanocrystallized powder materials having a size of 5 to 20nm.
Preparation of graphene nanoplatelets
And preparing the graphene nano-sheets by adopting a chemical intercalation method. By (NH) 4 ) 2 S 2 O 8 、H 2 SO 4 、H 2 O 2 And natural graphite as raw materials, comprising the following specific steps: 80mL of H was added to each of the 1000mL beakers 2 SO 4 15g (NH) 4 ) 2 S 2 O 8 And 3g of 50-mesh natural graphite, stirring with a proper amount of 300-600 r/min, and slowly dripping l0mL of H 2 O 2 Standing the beaker at normal temperature for 6 hours to obtain a fully expanded graphene aggregate (expanded graphite), washing the graphene aggregate to be neutral, adding the graphene aggregate into 200mL of nitrogen-methyl pyrrolidone, performing ultrasonic treatment for 3 hours with 200W power by using a cell pulverizer, and centrifuging for 20 minutes with a centrifuge at a rotating speed of 3000-4000 rpm to obtain an upper layer liquid, thereby obtaining the stable graphene dispersion liquid. The graphene nano sheet contains 2-6 graphene monolayers, and the size of the graphene nano sheet is 100-10000 nm.
graphene/Ti 2 O 3 Complexing of nanoparticles
Ti is mixed with 2 O 3 And compounding the nano particles with the graphene nano sheets. At 20Pouring 100mL of water into a 0mL flask, adding 2mL of synthesized graphene dispersion liquid, and uniformly dispersing by using an ultrasonic instrument; 50mg of Ti 2 O 3 The nanoparticles were dispersed in 50mL of water, then Ti was stirred rapidly 2 O 3 Adding the dispersion liquid into the graphene dispersion liquid, and obtaining a product which is graphene/Ti 2 O 3 Is a composite dispersion of (a) and (b).
graphene/Ti 2 O 3 Preparation of composite membranes
10mL of the prepared graphene/Ti was subjected to the above procedure 2 O 3 The composite dispersion is diluted into 200mL of deionized water, the deionized water is uniformly dispersed by an ultrasonic instrument, a fiber-mixed microporous filter membrane with the aperture of 0.45 mu m is used for vacuum suction filtration, the deionized water with the same volume is added for washing once before the completion of the vacuum filtration, and a layer of graphene/Ti appears on the filter membrane after the suction filtration is completed 2 O 3 And (3) a composite membrane. Gently transfer graphene/Ti with forceps 2 O 3 The composite membrane is torn off from the surface of the filter membrane and dried in an oven to finally prepare the graphene/magneli phase Ti n O 2n-1 Composite high thermal conductive films of nanoparticles.
Example 2
Magneli phase Ti 4 O 7 Preparation of nanoparticles
By using commercially available Ti 4 O 7 The micron particles are used as raw materials, and are nanocrystallized by adopting a ball milling method to prepare Ti 4 O 7 And (3) nanoparticles. In a typical ball milling process, agate balls having diameters of 5mm and 10mm (total weight of 81 g) were used as the milling balls. 27g deionized water, 27g commercially available or Ti 4 O 7 And agate balls with the weight ratio of 1:1:3 are sequentially added into the ball milling tank. Finally, the ball mill pot was placed in a ball mill apparatus, and the rotational speed was set to 300rpm. The batch ball milling method is adopted, the running time is 50 minutes, the pause time is 10 minutes, and the batch times are 24 times. Thus, the total ball milling time was 24 hours. After ball milling, the samples were transferred from the ball milling pot to a beaker with deionized water and then dried in an oven at 60 ℃ for 24 hours to obtain a nanocrystallized powder material having a size of 50 to 300nm.
Preparation of graphene nanoplatelets
And preparing the graphene nano-sheets by adopting a chemical intercalation method. By (NH) 4 ) 2 S 2 O 8 、H 2 SO 4 、H 2 O 2 And natural graphite as raw materials, comprising the following specific steps: 80mL of H was added to each of the 1000mL beakers 2 SO 4 15g (NH) 4 ) 2 S 2 O 8 And 3g of 50-mesh natural graphite, and slowly dropwise adding 10mL of H after stirring with a proper amount of 300-600 rpm 2 O 2 Standing the beaker at normal temperature for 6 hours to obtain a fully expanded graphene aggregate (expanded graphite), washing the graphene aggregate to be neutral, adding the graphene aggregate into 200mL of nitrogen-methyl pyrrolidone, performing ultrasonic treatment for 3 hours with 200W power by using a cell pulverizer, and centrifuging for 20 minutes with a centrifuge at a rotating speed of 3000-4000 rpm to obtain an upper layer liquid, thereby obtaining the stable graphene dispersion liquid. The graphene nano sheet contains 2-6 graphene monolayers, and the size of the graphene nano sheet is 100-10000 nm.
graphene/Ti 4 O 7 Complexing of nanoparticles
Ti is mixed with 4 O 7 And compounding the nano particles with the graphene nano sheets. Pouring 100mL of water into a 200mL flask, adding 2mL of graphene dispersion liquid synthesized above, and uniformly dispersing by using an ultrasonic instrument; 50mg of Ti 4 O 7 The nanoparticles were dispersed in 50mL of water, then Ti was stirred rapidly 4 O 7 Adding the dispersion liquid into the graphene dispersion liquid, and obtaining a product which is graphene/Ti 4 O 7 Is a composite dispersion of (a) and (b).
graphene/Ti 4 O 7 Preparation of composite membranes
10mL of the prepared graphene/Ti was subjected to the above procedure 4 O 7 The composite dispersion is diluted into 200mL of deionized water, the deionized water is uniformly dispersed by an ultrasonic instrument, a fiber-mixed microporous filter membrane with the aperture of 0.45 mu m is used for vacuum suction filtration, the deionized water with the same volume is added for washing once before the completion of the vacuum filtration, and a layer of stone appears on the filter membrane after the suction filtration is completedgraphene/Ti 4 O 7 And (3) a composite membrane. Gently transfer graphene/Ti with forceps 4 O 7 The composite membrane is torn off from the surface of the filter membrane and dried in an oven to finally prepare the graphene/magneli phase Ti n O 2n-1 Composite high thermal conductive films of nanoparticles.
Comparative example 1
No magneli phase Ti n O 2n-1 And (3) preparing the pure graphene heat conducting film introduced by the nano particles. Firstly, preparing the graphene nano-sheets by adopting a chemical intercalation method. By (NH) 4 ) 2 S 2 O 8 、H 2 SO 4 、H 2 O 2 And natural graphite as raw materials, comprising the following specific steps: 80mL of H was added to each of the 1000mL beakers 2 SO 4 15g (NH) 4 ) 2 S 2 O 8 And 3g of 50-mesh natural graphite, stirring with a proper amount of 300-600 r/min, and slowly dripping l0mL of H 2 O 2 Standing the beaker at normal temperature for 6 hours to obtain a fully expanded graphene aggregate (expanded graphite), washing the graphene aggregate to be neutral, adding the graphene aggregate into 200mL of nitrogen-methyl pyrrolidone, performing ultrasonic treatment for 3 hours with 200W power by using a cell pulverizer, and centrifuging for 20 minutes with a centrifuge at a rotating speed of 3000-4000 rpm to obtain an upper layer liquid, thereby obtaining the stable graphene dispersion liquid. The graphene nano sheet contains 2-6 graphene monolayers, and the size of the graphene nano sheet is 100-10000 nm. Then, a membrane was formed by a simple filtration method. 100mL of water was poured into a 200mL flask, and then 2mL of the graphene dispersion synthesized above was added and uniformly dispersed by an ultrasonic apparatus. Diluting 10mL of the prepared graphene dispersion liquid into 200mL of deionized water, uniformly dispersing the graphene dispersion liquid by using an ultrasonic instrument, carrying out vacuum suction filtration by using a fiber-mixed microporous filter membrane with the aperture of 0.45 mu m, adding an equal volume of deionized water to wash once before the completion of the vacuum filtration, and forming a layer of graphene membrane on the filter membrane. The graphene film is gently removed from the surface of the filter membrane by tweezers, and is dried in an oven. And obtaining the graphene film.
The graphene/Magneli phases Ti prepared in examples 1 and 2 n O 2n-1 The nanoparticle composite high thermal conductive film and the graphene film prepared in comparative example 1 were tested separately.
XRD analysis is shown in FIG. 1, which shows several distinct, strong diffraction peaks of the sample of example 1, which are/Magneli phase Ti 2 O 3 The characteristic diffraction peak of (2) is strong, so that the weak broad peak of the graphene at the diffraction angle of 20-30 degrees disappears, and the magneli phase Ti can be seen 2 O 3 The degree of crystallization of (2) is high.
The SEM scanning electron microscope results are shown in FIG. 2, from which it can be seen that graphene/Ti 2 O 3 The thickness of the composite film is 40-60 nm, and graphene sheets are well stacked layer by layer.
The four-probe mode was used for conducting the conductivity test, and the test results are shown in the following table. Conclusion is Magneli phase Ti 2 O 3 And Ti is 4 O 7 The introduction of (c) can slightly increase the conductivity.
The results of the thermal conductivity test are shown in the following table. Conclusion is Magneli phase Ti 2 O 3 And Ti is 4 O 7 The introduction of (c) can increase the thermal conductivity of the membrane.
The experimental results show that the magneli phase Ti 2 O 3 And Ti is 4 O 7 The composite graphene heat conducting film has high electric conductivity and high heat conductivity. The method is suitable for the preparation and application of heat conducting devices, and the fields of electronic instruments such as mobile phones, computers, aerospace craft control systems and the like.
It is worth mentioning that the present patent application relates to graphene/magneli phase TinO 2n-1 The technical characteristics of the nanoparticle composite high-heat-conductivity film are regarded as the upgrade of the existing graphene heat-conductivity film technology, and the specific structure and engineering of the technical characteristics are as followsThe principle and control modes and spatial arrangement modes possibly related to the principle are adopted by the conventional selection in the field, and are not considered to be the application points of the patent of the application, and the patent of the application is not further specifically developed and detailed.
While the preferred embodiments of the present application have been described in detail, it should be appreciated that numerous modifications and variations may be made in accordance with the principles of the present application by those skilled in the art without undue burden, and thus, all technical solutions which may be obtained by logic analysis, reasoning or limited experimentation based on the principles of the present application as defined by the claims are within the scope of protection as defined by the present application.
Claims (5)
1. Graphene/magneli phase TinO 2n-1 The preparation method of the nanoparticle composite high-heat-conductivity film is characterized by comprising the following steps of:
step one, magneli phase Ti n O 2n-1 Nanoparticle preparation Using commercially available Ti 2 O 3 Or Ti (Ti) 4 O 7 The micron particles are used as raw materials, and are nanocrystallized by adopting a ball milling method to prepare Ti 2 O 3 Or Ti (Ti) 4 O 7 A nanoparticle;
step two, preparing graphene nano sheets, and respectively adding a certain amount of concentrated H into a beaker 2 S0 4 、(NH 4 ) 2 S 2 O 8 Mixing with natural graphite, stirring, and slowly dripping a certain amount of H 2 0 2 Standing the beaker at normal temperature for a period of time to obtain a graphene aggregate which is fully expanded, washing the graphene aggregate to be neutral, adding the graphene aggregate into a certain amount of nitrogen-methyl pyrrolidone, performing ultrasonic treatment for a period of time by using a cell pulverizer, and centrifuging by using a centrifuge to obtain an upper layer liquid, thereby obtaining a stable graphene nano sheet dispersion liquid;
step three, graphene/Ti 2 O 3 Or Ti (Ti) 4 O 7 Compounding nanometer particle, pouring water into flask, adding 2mL of synthesized graphene dispersion liquid, anddispersing uniformly with an ultrasonic instrument, dispersing a certain amount of Ti 2 O 3 Or Ti (Ti) 4 O 7 Dispersing the nano particles in a certain amount of water to obtain Ti 2 O 3 Or Ti (Ti) 4 O 7 The dispersion is then stirred rapidly with Ti 2 O 3 Or Ti (Ti) 4 O 7 Adding the dispersion liquid into graphene dispersion liquid, and obtaining graphene/Ti as a product 2 O 3 Or Ti (Ti) 4 O 7 Compounding the dispersion liquid;
step four, graphene/Ti 2 O 3 Or Ti (Ti) 4 O 7 Preparation of composite film, a certain amount of graphene/Ti 2 O 3 Or Ti (Ti) 4 O 7 Diluting the composite dispersion liquid into a certain amount of deionized water, uniformly dispersing the composite dispersion liquid by using an ultrasonic instrument, performing vacuum suction filtration by using a fiber-mixed microporous filter membrane, adding an equal volume of deionized water to wash once before finishing, and forming a layer of graphene/Ti on the filter membrane after the suction filtration is finished 2 O 3 Or Ti (Ti) 4 O 7 Composite film, gently mix graphene/Ti with tweezers 2 O 3 Or Ti (Ti) 4 O 7 The composite membrane is torn off from the surface of the filter membrane and dried in an oven to finally prepare the graphene/magneli phase Ti n O 2n-1 Composite high thermal conductive films of nanoparticles.
2. The graphene/magneli phase tinO of claim 1 2n-1 The preparation method of the nanoparticle composite high-heat-conductivity film is characterized in that a certain amount of deionized water and commercially available Ti are added in the ball milling process in the first step 2 O 3 Powder or Ti 4 O 7 Sequentially adding powder and agate balls into a ball milling tank, ball milling for a certain time by adopting an intermittent ball milling method, transferring a ball-milled sample from the ball milling tank into a beaker with deionized water, and drying in an oven to obtain a Magneli phase Ti n O 2n-1 And (3) nanoparticles.
3. The graphene/magneli phase tinO of claim 2 2n-1 Preparation of nanoparticle composite high-heat-conductivity filmThe preparation method is characterized in that graphene and Ti in the third step 2 O 3 Or Ti (Ti) 4 O 7 The mass ratio of (2) is 1:0.001-1.
4. The graphene/magneli phase tinO of claim 3 2n-1 A method for preparing a nanoparticle composite high-heat-conductivity film is characterized in that agate balls with diameters of 5mm and 10mm are used as grinding balls in the first step, and 27g of deionized water and 27g of commercial Ti are used as grinding balls 2 O 3 Powder or Ti 4 O 7 And agate balls with the weight ratio of 1:1:3 are sequentially added into a ball milling tank, the ball milling tank is placed into ball milling equipment, the rotating speed is set to 300rpm, an intermittent ball milling method is adopted, the operation time is 50 minutes, the pause time is 10 minutes, the intermittent times are 24 times, the total ball milling time is 24 hours, after ball milling, a sample is transferred from the ball milling tank into a beaker with deionized water, and then the sample is dried in an oven at 60 ℃ for 24 hours, so that Magneli phase Ti is obtained n O 2n-1 A nanoparticle; in the second step, 80H mL H is added into a beaker respectively 2 S0 4 Of 15, g (NH) 4 ) 2 S 2 O 8 And 3g, 50 mesh natural graphite, stirring at 300-600 rpm, and slowly dripping l0mL H 2 0 2 Standing the beaker at normal temperature for 6 hours to obtain a fully expanded graphene aggregate, washing the graphene aggregate to be neutral, adding the graphene aggregate into nitrogen-methyl pyrrolidone of 200mL, performing ultrasonic treatment for 3 hours with a cell pulverizer at a power of 200W, and centrifuging for 20 minutes with a centrifuge at a rotating speed of 3000-4000 rpm to obtain an upper layer solution, thereby obtaining a stable graphene nano sheet dispersion; in the third step, 100mL of water is poured into a flask, then 2mL of graphene dispersion liquid synthesized above is added, the graphene dispersion liquid is uniformly dispersed by an ultrasonic instrument, and 50mg of Ti is added 2 O 3 Or Ti (Ti) 4 O 7 The nanoparticles were dispersed in 50mL of water, then Ti was stirred rapidly 2 O 3 Or Ti (Ti) 4 O 7 Adding the dispersion liquid into the graphene dispersion liquid, and obtaining a product which is graphene/Ti 2 O 3 Or Ti (Ti) 4 O 7 Compounding the dispersion liquid; in the fourth step, 10mL of graphene/Ti is used 2 O 3 Or Ti (Ti) 4 O 7 The composite dispersion liquid is diluted into deionized water of 200mL, the deionized water is uniformly dispersed by an ultrasonic instrument, the mixed fiber microporous filter membrane with the aperture of O.45 mu m is used for vacuum suction filtration, the deionized water with the same volume is added for washing once before the completion of the vacuum filtration, and a layer of graphene/Ti appears on the filter membrane after the suction filtration is completed 2 O 3 Or Ti (Ti) 4 O 7 Composite film, gently mix graphene/Ti with tweezers 2 O 3 Or Ti (Ti) 4 O 7 The composite membrane is torn off from the surface of the filter membrane and dried in an oven to finally prepare the graphene/magneli phase Ti n O 2n-1 Composite high thermal conductive films of nanoparticles.
5. Graphene/magneli phase TinO 2n-1 The nanoparticle composite high heat conduction film is characterized in that the graphene/magneli phase TinO 2n-1 A nanoparticle composite high thermal conductive film produced by the production method of any one of claims 1 to 4.
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| WO2011021715A1 (en) * | 2009-08-20 | 2011-02-24 | 日本電気株式会社 | Substrate, substrate production method, semiconductor element, and semiconductor element production method |
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| CN113233553A (en) * | 2021-05-28 | 2021-08-10 | 东莞理工学院 | Ti loaded with graphene nanoparticles4O7Method for preparing anode |
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| WO2011021715A1 (en) * | 2009-08-20 | 2011-02-24 | 日本電気株式会社 | Substrate, substrate production method, semiconductor element, and semiconductor element production method |
| WO2018140451A1 (en) * | 2017-01-24 | 2018-08-02 | Sabic Global Technologies B.V. | Multi-layered graphene material having a plurality of yolk/shell structures |
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