CN113023717A - Method for inhibiting thermal expansion of graphene self-supporting film - Google Patents
Method for inhibiting thermal expansion of graphene self-supporting film Download PDFInfo
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Abstract
The invention provides a preparation method of a graphene oxide film, which comprises the following steps: (1) dispersing the nano metal particles in deionized water to obtain a well-dispersed nano metal solution; (2) adding the well-dispersed nano metal solution prepared in the step (1) into graphene oxide slurry, and stirring to enable the nano metal solution to be fully contacted to obtain metal element compounded graphene oxide aqueous slurry; (3) and (3) coating the metal element compounded graphene oxide aqueous slurry obtained in the step (2) on a substrate, and drying to obtain the graphene oxide film. The invention also provides a method for inhibiting the thermal expansion of the graphene self-supporting film, which is to carry out heat treatment on the obtained graphene oxide film. The invention adopts a metal compounding scheme, and improves the graphitization degree of the sample in the heat treatment process. Finally, the graphene self-supporting film with high thermal conductivity is obtained, and the method can effectively inhibit thermal expansion of the graphene self-supporting film and improve performance.
Description
Technical Field
The invention belongs to the technical field of material synthesis and application, and particularly relates to a method for inhibiting thermal expansion of a graphene self-supporting film.
Background
Graphene is a two-dimensional nanomaterial structure of a hexagonal honeycomb lattice consisting of only carbon atoms. Since the discovery, it has attracted extensive attention and research due to its excellent mechanical, optical, electrical, and thermal properties. Graphene Oxide (GO) is an oxide corresponding to graphene, and is formed by bonding oxygen-containing functional groups such as hydroxyl, carboxyl, carbonyl, epoxy and the like to graphene sheets. Just because the GO sheets contain a large number of functional groups, the GO sheets can be stacked by self-assembly such as hydrogen bonds to form a membrane material with a macroscopic size. However, graphene oxide films cannot be directly used as a material for a thermally conductive film because the carbon atom on GO is partially sp3The hybrid form exists, so that the hybrid material can be applied to the realization of the functions of electric conduction and heat conduction with less redundant pi electrons and no redundant free electrons. And in order to prepare the GO membrane into a membrane material with high heat and electricity conductivity, graphene oxide needs to be reduced, oxygen-containing functional groups on GO sheet layers are removed, and the GO membrane is changed into a graphene membrane, so that the electricity and heat conducting functional material is realized.
The mainstream method for industrially preparing the graphene self-supporting film is a redox method, which mainly comprises two processes: firstly, in the oxidation process, graphite is modified by functional groups to obtain GO, so that the dispersibility of the GO in a water phase and the regularity of assembled film forming are improved; and secondly, in the thermal reduction process, the functional groups are removed through reduction, and the defects of the graphene sheets are further repaired. The functional groups removed in the thermal reduction process are released in the form of gases such as water, carbon dioxide, carbon monoxide and the like, so that an air bag structure is generated between layers, the interaction between the layers is weakened, the heat transmission and electrical interface resistance of the graphene film is increased, the performance is reduced, the film pulverization and the equipment damage are more serious, and the yield of the product is greatly reduced. This phenomenon of increased film thickness due to gas evolution during heat treatment is referred to as "thermal expansion". Thermal expansion results in a significant reduction in graphene support film yield and performance.
How to inhibit the thermal expansion of the graphene self-supporting film in the preparation process is always a difficult point in the industry. Professor mentioned the structure of the air cell caused by Thermal expansion in the article "ultra high Thermal Conductive layer Superflexible Films" (DOI:10.1002/adma.201700589), but mainly from the viewpoint that the structure of the air cell contributes to improving the flexibility of the film, no explanation is given to the suppression of Thermal expansion, and this laboratory method cannot be applied to large-scale industrial production. In the industrial stage, no relevant patent or literature reports about a scheme for inhibiting the thermal expansion of the graphene self-supporting film at present. The cause of the generation and the management scheme are still in the initial stage of research.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for inhibiting the thermal expansion of a graphene self-supporting film.
In order to improve the preparation yield of the graphene self-supporting film, the graphene film is prepared on the basis of compounding nano metal particles and GO, wherein the nano metal particles include but are not limited to metal simple substances, chlorides, oxides and the like of iron, cobalt, nickel, titanium and chromium. Specifically, in the GO slurry preparation process, nano metal particles serving as a thermal expansion inhibitor are added into the slurry, mixed and stirred uniformly, then coated and dried to obtain a metal compounded GO membrane, and then subjected to a heat treatment process to obtain the graphene self-supporting membrane. The nanoscale metal particles can be effectively dispersed in the GO sheet layer, and play a role in modifying the porosity of the membrane at high temperature, so that the gas removal efficiency in the heat treatment process is improved, and the thermal expansion behavior is reduced. Meanwhile, the molten state of the metal at high temperature can play a role in fixing the lamella between the layers, reduce the phenomenon of lamella separation caused by overlarge interlayer air pressure and reduce expansion.
The method for compounding the nano metal inhibitor has strong controllability, and does not introduce adverse factors including stirring, coating, heat treatment and the like into the whole preparation process of the graphene film. The method can effectively inhibit the expansion of the graphene self-supporting film in the heat treatment, thereby improving the heat treatment capacity and simultaneously improving the preparation yield and performance of the product.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the invention provides a preparation method of a graphene oxide film, which comprises the following steps:
(1) dispersing the nano metal particles in deionized water to obtain a well-dispersed nano metal solution;
(2) adding the well-dispersed nano metal solution prepared in the step (1) into graphene oxide slurry to enable the nano metal solution to be fully contacted, so as to obtain metal element compounded graphene oxide aqueous slurry;
(3) and (3) coating the metal element compounded graphene oxide aqueous slurry obtained in the step (2) on a substrate, and drying to obtain the graphene oxide film.
According to the invention, firstly, the graphene oxide film is prepared, and the graphene oxide film is subjected to heat treatment to obtain the graphene self-supporting film which can effectively inhibit thermal expansion.
Preferably, in the step (1), the nano metal particles are one or more of iron, cobalt, nickel, titanium, chromium and chlorides or oxides thereof; and/or
The size of the nano metal particles is less than or equal to 100nm, preferably 10-100 nm; and/or
The dispersion is stirring at the rotation speed of 300-900rpm for 10-40min and/or ultrasonic processing for 5-20 min.
Preferably, in the step (1), the nano metal particles are nano iron oxide and nano titanium oxide; preferably, the size of the nano iron oxide is 30nm, the size of the nano titanium oxide is 40nm, and the weight ratio of the nano iron oxide to the nano titanium oxide is 1: 2.
Preferably, in the step (2), the nano metal particles account for 0.01-2% of the mass of the graphene oxide;
the selection of the range is mainly considered in two aspects, and if the content of the compounded nano metal in GO is too low, the effect of inhibiting the thermal expansion of the GO membrane is reduced; if the content of the compounded nano metal is too high, too many nano metal elements can be introduced into GO, so that more structural defects are caused in the heat treatment process, and the thermal diffusion coefficient and the heat dissipation performance in the later application process are influenced.
More preferably, the nano metal particles account for 0.8% of the mass of the graphene oxide; and/or
The sufficient contact is stirring for 1-3h at 300-800 rpm; and/or
The preparation method of the graphene oxide slurry comprises the following steps: adding graphene oxide into deionized water to prepare aqueous graphene oxide dispersion liquid with the weight percentage of 2-7%, and uniformly dispersing to obtain the graphene oxide dispersion liquid.
If the solid content of the graphene oxide slurry is too low, the viscosity of the graphene oxide slurry is low, and the graphene oxide slurry can be dispersed when being coated on a PET substrate; too high a solid content can result in too high a viscosity, which is detrimental to dispersion and assembly of the GO plies.
Preferably, in the step (2), the graphene oxide is added into deionized water, stirred at 800rpm for 1-3h, and/or shaken for 20-60min to disperse uniformly.
Preferably, in the step (3), the thickness of the coating film at the time of coating is 1-4 mm; and/or
The substrate is a PET substrate; and/or
The drying temperature is 50-90 deg.C, and the drying time is 2-5 h.
The invention also provides a graphene oxide film prepared by the method.
The invention provides a method for inhibiting thermal expansion of a graphene self-supporting film, which comprises the following steps:
(1) preparing the graphene oxide film;
(2) and (2) carrying out heat treatment on the metal compounded graphene oxide film obtained in the step (1).
Preferably, the heat treatment is carried out at 2000-3200 ℃ for 20-60 h.
The invention also provides a graphene self-supporting film prepared by applying the method.
According to the invention, the GO membrane compounded by nano-scale metal particles is added, so that the thermal expansion in the graphene membrane preparation process is obviously reduced, and the membrane density is improved. Finally, the heat treatment capacity and the yield are improved, and the cost is reduced.
The invention adopts a metal compounding scheme to improve the graphitization degree of the sample in the heat treatment process. Finally, the graphene self-supporting film with high thermal conductivity is obtained, and performance improvement is achieved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
fig. 1 is a cross-sectional SEM of a conventional graphene self-supporting film prepared in example 1.
Fig. 2 is a cross-sectional SEM of the graphene self-supporting film prepared in example 2.
Fig. 3 is a cross-sectional SEM of the graphene self-supporting film prepared in example 3.
Fig. 4 is a cross-sectional SEM of the graphene self-supporting film prepared in example 4.
Fig. 5 is a cross-sectional SEM of the graphene self-supporting film prepared in example 5.
Fig. 6 is a cross-sectional SEM of the graphene self-supporting film prepared in example 6.
Fig. 7 is a cross-sectional SEM of the graphene self-supporting film prepared in example 7.
Fig. 8 is a cross-sectional SEM of the graphene self-supporting film prepared in example 8.
Fig. 9 is a cross-sectional SEM of the graphene self-supporting film prepared in example 9.
Fig. 10 is a cross-sectional SEM of the graphene self-supporting film prepared in example 10.
Fig. 11 is a cross-sectional SEM of the graphene self-supporting film prepared in example 11.
Fig. 12 is a cross-sectional SEM of the graphene self-supporting film prepared in example 12.
Fig. 13 is a cross-sectional SEM of the graphene self-supporting film prepared in example 13.
Fig. 14 is a XRD data pattern of the conventional graphene thermal conductive film prepared in example 1 and the metal inhibitor-added graphene thermal conductive films prepared in examples 2 and 7.
Detailed Description
The following examples are given to facilitate a better understanding of the invention, but do not limit the invention. The experimental procedures in the following examples are conventional unless otherwise specified. The test materials used in the following examples are commercially available unless otherwise specified. The quantitative tests in the following examples, all set up three replicates and the results averaged. In the present invention, "%" is a weight percentage.
Experimental drugs used in the present invention: the graphite raw material is purchased from Aladdin, the purity is 99.9 percent, and the particle size is 325 meshes; 99.2 percent of concentrated sulfuric acid and 36 to 38 percent of dilute hydrochloric acid by mass, and purchasing the concentrated sulfuric acid and the dilute hydrochloric acid in a Chinese medicine reagent network; potassium permanganate is purchased from a traditional Chinese medicine reagent network; iron, ferric oxide and titanium oxide are purchased from a traditional Chinese medicine reagent net, and the particle size is 30 nm; the purity of ferric chloride was 98% and was purchased from alatin.
The test method in the embodiment of the invention comprises the following steps: the thickness of the sample film was measured using a thickness gauge model Mitutoyo 547-401, measuring the thickness of at least 5 points on the sample film, and then averaging. Calculating the multiplying power of thermal expansion according to the proportion of the thickness of the sample film; the sample film density test adopts a vacuum densitometer, and the model is BJBUIDER, TD-2200; the sample membrane thermal diffusivity was determined using a device model number Netzsch, LFA-467.
The calculation method of the thermal expansion rate comprises the following steps:
the invention has no specific requirements on the sources of the GO filter cake and the GO aqueous slurry, and can be made by self or purchased. The inventive effects of the present invention can be achieved by using GO filter cakes and GO aqueous slurries prepared by various methods in the prior art.
The preparation method of the GO filter cake in the embodiment of the invention comprises the following steps: the GO filter cake used in the invention is prepared based on an improved Hummers method, and is mainly prepared by oxidizing graphite raw materials by potassium permanganate and concentrated sulfuric acid, and finally obtaining the GO filter cake with a certain solid content through the processes of hydration, washing and the like. The performance parameters are as follows: the appearance is black paste, the solid content is 38-48%, the pH is 1.8-2.3, the carbon content is 46-56%, and the sulfur content is less than or equal to 2.0%. The I, II and III type GO filter cakes used in the invention are mainly used for adjusting preparation process parameters, and the finally obtained GO filter cakes have certain differences in performance parameters. Wherein the solid content of the I type GO filter cake is mainly distributed between 38% and 42%, the pH value is 1.8-2.0, the carbon content is 46% to 48%, and the sulfur content is less than or equal to 2.0%; wherein the solid content of the II type GO filter cake is mainly distributed between 42 and 46 percent, the pH value is between 2.0 and 2.2, the carbon content is between 48 and 50 percent, and the sulfur content is less than or equal to 2.0 percent; wherein the solid content of the III type GO filter cake is mainly distributed between 46 and 48 percent, the pH value is between 2.0 and 2.3, the carbon content is between 48 and 56 percent, and the sulfur content is less than or equal to 2.0 percent.
The preparation method of the aqueous GO slurry comprises the steps of dispersing a corresponding GO filter cake in certain deionized water, stirring and dispersing for 60min by a 500rpm stirring machine, and vibrating for 30min to obtain the well-dispersed GO slurry. Wherein the parameters of the GO filter cake water-based slurry prepared by type II mainly comprise: the solid content is 5-8%, the pH is 2.0-3.0, and the viscosity is 40000 and 80000 mPa.s.
The improved Hummers method specifically comprises the following steps: adding 230ml of 98% concentrated sulfuric acid in mass fraction into a dry 2L beaker, cooling to 0-4 ℃ by using an ice water bath at low temperature, stirring by using a stirrer at 200rpm, slowly adding 10g of a solid mixture of 100um flake graphite and 5g of sodium nitrate, stirring for 30min, after the graphite and the sodium nitrate are completely dissolved, slowly adding 30g of potassium permanganate, controlling the temperature to be 3-7 ℃, and stirring at 200rpm for 2h, wherein the solution is dark green. And then placing the beaker in a constant-temperature water bath at 35 ℃, continuously stirring and reacting for 30min, slowly adding 500ml of deionized water, controlling the temperature to be 60-80 ℃, reacting for 0.5h, then adding 20ml of 5% hydrogen peroxide, and stirring for 30min at 150rpm, wherein the solution is golden yellow. After filtration, the filter cake was taken out, dissolved in 1000ml of 5% hydrochloric acid, stirred and washed at 200rpm for 1 hour, and then, filtration and washing were carried out, and the hydrochloric acid washing and filtration operations were repeated three times in total. And finally, dissolving the obtained filter cake in 1000ml of deionized water, stirring and washing at 200rpm for 30min, and filtering to obtain the finished product I type GO filter cake. Type II GO filter cake preparation is similar with type I GO filter cake preparation process, improves the potassium permanganate quantity to 35g on this basis, and concentrated sulfuric acid quantity improves to 250ml, and other process parameters keep unanimous. Type III GO filter cake is on I type GO filter cake preparation basis, improves potassium permanganate and concentrated sulfuric acid's quantity to 40g and 260ml respectively, and the addition of deionized water improves 600ml from original 500ml, and other process parameters keep unanimous.
The method for inhibiting the thermal expansion of the graphene self-supporting film comprises the following steps:
(1) GO slurry preparation
And adding deionized water into the GO filter cake to prepare 2-7% of aqueous GO dispersion liquid, and uniformly dispersing to obtain GO slurry. For uniform dispersion, one or a combination of several common methods in the prior art such as stirring and shaking can be adopted here as long as GO can be uniformly dispersed. For example, the stirring time is 300-800rpm, the time is 1-3h, and the shaking time is 20-60 min.
For example, the stirring speed is 300, 400, 500, 600, 700, 800rpm, the stirring time is 1,1.5,2,2.5,3 hours, and the shaking time is 20, 22, 24, 26, 28, 30,35,40,45,50,55,60 min.
(2) Preparation of metal-graphene oxide compound slurry
0.01-1g of nano metal particles with the particle size of 10-100nm are added into 10-100ml of deionized water and uniformly dispersed to obtain a well-dispersed nano metal solution. For uniform dispersion, one or a combination of several common methods in the prior art, such as stirring, ultrasound, etc., can be adopted here as long as the nano metal particles can be uniformly dispersed. For example, stirring at the rotation speed of 900rpm of 300-.
For example, the stirring speed is 300, 400, 500, 600, 700, 800, 900rpm, the stirring time is 10,15,20,25,30,35,40min, and the ultrasonic time is 5,7,9,11,13,15,17,18,20 min.
Slowly adding the nano metal solution into the GO slurry, wherein the metal particles account for 0.01-2% of the weight of GO and are fully contacted to obtain the metal element compounded GO aqueous slurry. In order to sufficiently contact them, a conventional method such as stirring may be used here as long as the materials are uniformly dispersed. For example, stirring at 300-800rpm for 1-3 h.
For example, the metal particles account for 0.01%, 0.05%, 0.1%, 0.2%, 0.4%, 0.5%, 0.7%, 0.9%, 1.1%, 1.3%, 1.5%, 1.8%, 2% of the GO mass. For example, the stirring speed is 300, 400, 500, 600, 700, 800rpm, and the stirring time is 1,1.5,2,2.5,3 h.
The nano metal particles include, but are not limited to, elemental metals, chlorides, oxides, and the like of iron, cobalt, nickel, titanium, and chromium.
The inventor finds out through experiments that only the nano metal particles have the effect of inhibiting the thermal expansion of the graphene self-supporting film, and comprise metal simple substances, chlorides and oxides of iron, cobalt, nickel, titanium and chromium nano metal particles.
The smaller the size of the nanoparticles, the better in principle, the smaller the size, the more uniform the dispersion in the GO matrix, i.e. as long as the particle size is less than or equal to 100 nm. However, the smaller the price, the higher the price, and the cost of the practical production process is considered, so that the nano particles with a certain size are selected to take effect and cost into consideration.
Through experiments, the best effect for inhibiting the thermal expansion of the graphene self-supporting film is to use the nano iron oxide and the nano titanium oxide in a mixed manner, wherein the optimal weight of the nano iron oxide and the nano titanium oxide is 0.8% of the total weight of GO.
(3) Preparation of graphene heat-conducting film
Coating the obtained metal element compounded GO aqueous slurry on a substrate, wherein the coating thickness is 1-4mm, for example, the coating thickness is 1,1.5,2,2.5,3,3.5,4 mm. And then placing the membrane in an oven, and drying for 2-5h at 50-90 ℃ to finally obtain the metal compounded GO membrane.
The selection criteria for the matrix were: firstly, the slurry can form a film, cannot be dispersed and cannot permeate; secondly, the film is easily peeled off from it after drying. Such as a PET substrate.
The drying time at 50-90 ℃ for 2-5h was chosen for the purpose of: in order to enable the slurry to be formed into a film and peeled from the PET matrix, so that it can be subjected to the next heat treatment.
For example, the drying temperature is 50,55,60, 65, 70, 75, 80, 85 and 90 ℃, and the drying time is 2,2.5,3,3.5,4, 4.5 and 5 hours.
And then carrying out heat treatment on the GO membrane at 2000-3200 ℃ for 20-60 h to finally obtain the graphene self-supporting membrane.
The purpose of heat treatment for 20-60 h at 2000-3200 ℃ is to: oxygen-containing functional groups in GO are removed, structural defects caused by oxidation and reduction processes are repaired, and sp3 carbon in the material is converted into an sp2 carbon structure in the heat treatment process, so that the thermal diffusion coefficient of the graphene heat-conducting film is improved.
For example, the heat treatment temperature is 2000,2100,2200,2300,2500,2700,2900,3000,3200 ℃, and the heat treatment time is 20,25,30,35,40,45,50,55 and 60 hours.
According to the graphene self-supporting membrane, after nano-scale metal particles are dispersed, the nano-scale metal particles are added into GO slurry to be compounded to prepare the metal compounded GO membrane, and then the graphene self-supporting membrane is obtained through heat treatment. In the heat treatment process, the metal elements can effectively reduce the release rate of gas in the heat conducting film, and the preparation yield and performance of the sample are improved. Specifically, the effect of the metal element thereof in suppressing thermal expansion was determined by comparison of the thickness and density of the self-supporting film. The preparation method of the conventional sample for comparison only eliminates the process of adding the nano metal particles in the GO slurry preparation process, and the other preparation processes and preparation parameters are consistent with those of the compound sample preparation process and parameters. Finally obtaining a conventional graphene self-supporting film sample. The test parameter ratios of both are shown in table 1.
TABLE 1 thermal expansion ratio of the sample compounded with the metal element and the conventional sample
| Test items | Metal element compound sample | Conventional samples |
| Average thickness of GO film (μm) | 161.8-167.3 | 147.2-156.7 |
| Average thickness of film (. mu.m) after Heat treatment | 152.2-247.6 | 310.4-330.9 |
| Thermal expansion rate of film after heat treatment | 0.90-1.52 | 2.0-2.2 |
| Film Density (g/cm) after Heat treatment3) | 0.32-0.43 | 0.22-0.25 |
| Coefficient of thermal diffusion (mm)2/s) | 707-753 | 650-700 |
As can be seen from the comparative data in table 1, compared with the conventional graphene film, after metal compounding, the film thickness is significantly reduced and the density is significantly increased after heat treatment, which indicates that the metal element effectively inhibits the thermal expansion of the film. And the thermal diffusion coefficient is correspondingly improved to a certain degree, which shows that the heat-conducting property of the film can be improved by adding metal.
Example 1
Taking the GO filter cake of the type I, preparing 3.20% aqueous GO slurry, fully stirring for 2h at 550rpm of a stirrer, and oscillating for 30min to obtain the GO slurry with uniform dispersion. GO slurry was coated as a 3.0mm film on PET substrate at 65 deg.cAnd drying for 4h to obtain the dried GO membrane. The dried GO film thickness was 152.9-158.2 μm, with an average 155.3 μm. And performing heat treatment at 2500 ℃ for 35 hours to obtain the graphene self-supporting film. The thickness was measured to be 310.4 to 330.9 μm, with an average of 326.3 μm. The thermal expansion rate is 2.10 and the density is 0.23g/cm3Thermal diffusivity of 673mm2/s。
Fig. 1 is a cross-sectional SEM of a conventional graphene free-standing film.
Example 2
The method for inhibiting the thermal expansion of the graphene self-supporting film comprises the following steps:
taking the GO filter cake of the type I, preparing 4.50% of water-based GO slurry, fully stirring for 2.5 hours at 300rpm of a stirrer, and oscillating for 30min by an oscillator to obtain uniformly dispersed GO slurry; adding 0.01g of nano-iron particles with the size of 10nm into 50ml of deionized water, stirring at 600rpm for 15min, and then carrying out ultrasonic treatment for 15min to obtain a uniformly dispersed nano-iron solution. Slowly adding the uniformly dispersed nano iron solution into the GO slurry, wherein the iron particles account for 0.13% of the weight of GO, and stirring at 700rpm for 1h to fully contact the iron particles to obtain the GO slurry compounded by the iron particles. Coating the GO slurry compounded by the iron particles on a PET matrix into a film with the thickness of 3mm, and drying the film for 4 hours at the temperature of 70 ℃ to obtain the dried GO film compounded by the iron particles. The thickness of the GO membrane is between 160.3 and 172.4 μm, with an average thickness of 165.3 μm. And then carrying out heat treatment on the GO membrane at 2500 ℃ for 20 hours to obtain the graphene self-supporting membrane. The thickness of the graphene self-supporting film obtained by testing is 195.3-201.9 mu m, the average thickness is 198.4 mu m, the thermal expansion rate is 1.20, and the density is 0.35g/cm3Thermal diffusivity of 720mm2And s. Compared with the conventional film, the thermal expansion rate is obviously reduced, the density is obviously improved, and the thermal diffusion coefficient is also improved.
Fig. 2 is a cross-sectional SEM of the graphene self-supporting film prepared in example 2.
Example 3
The method for inhibiting the thermal expansion of the graphene self-supporting film comprises the following steps:
measuring the solid content of the GO aqueous slurry with the model number II to be 7.00%, preparing the GO aqueous slurry with the solid content of 3.77%, and fully stirring the GO aqueous slurry by a 650rpm stirrerAnd (3) after 3 hours, oscillating for 25min by an oscillator to obtain the uniformly dispersed GO slurry. Then 0.05g of nano iron oxide with the size of 15nm is added into 100ml of deionized water, stirred at 550rpm for 20min, and subjected to ultrasonic treatment for 15min to obtain a uniformly dispersed nano iron oxide solution. Slowly adding the dispersed nano iron oxide solution into the GO slurry, wherein the iron oxide particles account for 0.20% of the weight of GO, stirring at 650rpm for 1.5h, and fully contacting to obtain the GO slurry compounded by the iron oxide particles. Coating GO slurry compounded by iron oxide particles on a PET substrate to form a 2.5mm film, and treating at 80 ℃ for 3.5h to obtain the dry GO film compounded by iron oxide. The thickness of the GO membrane is between 161.2-165.8 μm, with an average thickness of 164.1 μm. And then carrying out heat treatment on the GO membrane at 3000 ℃ for 40h to obtain the graphene self-supporting membrane. The film obtained by the test has a thickness of 157.3-161.9 μm, an average thickness of 159.2 μm, a thermal expansion rate of 0.97, and a density of 0.40g/cm3Thermal diffusivity of 707mm2And s. Compared with the conventional film, the thermal expansion rate is obviously reduced, the density is obviously improved, and the thermal diffusion coefficient is improved to some extent.
Fig. 3 is a cross-sectional SEM of the graphene self-supporting film prepared in example 3.
Example 4
The method for inhibiting the thermal expansion of the graphene self-supporting film comprises the following steps:
taking the GO filter cake of the type I, preparing 4.75% of water-based GO slurry, fully stirring for 3 hours at 800rpm of a stirrer, and oscillating for 25min to obtain the uniformly dispersed GO slurry. Then 0.01g FeCl with a size of 30nm3Adding into 100ml deionized water, and performing ultrasonic treatment for 15min (the salt solution is relatively easier to dissolve than the nano particles, so that no stirring operation is added in the step, and only ultrasonic treatment is performed), so as to obtain FeCl with uniform dispersion3And (3) solution. FeCl to be dispersed uniformly3The solution was slowly added to GO slurry, FeCl3The particles account for 0.01 percent of the weight of GO, and are stirred for 3 hours at 800rpm to obtain FeCl3Compounded GO slurry. FeCl is added3The compounded GO slurry is coated on a PET substrate, the film forming thickness is 3.2mm, and the processing is carried out for 3.5h at 75 ℃ to obtain the iron oxide compounded GO film. The thickness of the GO membrane is between 160.3 and 165.5 μm, with an average thickness of 162.9 μm.And then carrying out heat treatment on the GO membrane at the temperature of 2580 ℃ for 35 hours to obtain the graphene self-supporting membrane. The film obtained by the test has a thickness of 240.7-252.6 μm, an average thickness of 247.6 μm, a thermal expansion rate of 1.52 and a density of 0.32g/cm3Thermal diffusivity of 719mm2And s. Compared with the conventional film, the thermal expansion rate is reduced to a certain extent, the density is improved, and the thermal diffusion coefficient is improved to some extent.
Fig. 4 is a cross-sectional SEM of the graphene self-supporting film prepared in example 4.
Example 5
The method for inhibiting the thermal expansion of the graphene self-supporting film comprises the following steps:
taking GO slurry of type III, wherein the solid content of GO is 2.0%, fully stirring for 2.5h by a stirrer at 500rpm, and oscillating for 20 min. Adding 0.06g of nano titanium particles with the size of 30nm into 50ml of deionized water, stirring at the rotating speed of 300rpm for 20min, and then carrying out ultrasonic treatment for 15min to obtain a uniformly dispersed nano titanium solution. Slowly adding the dispersed nano titanium solution into the GO slurry, wherein the titanium particles account for 0.15% of the GO by mass, and stirring at 650rpm for 2h to obtain the GO slurry compounded by the titanium particles. Coating the GO slurry compounded with the titanium particles on a PET substrate to form a film with the thickness of 3.6mm, and treating at 90 ℃ for 4.2h to obtain the GO film compounded with the titanium particles. The thickness of the GO membrane is between 163.9-167.8 μm, with an average thickness of 165.4 μm. And then carrying out heat treatment on the GO membrane at 2680 ℃ for 42h to obtain the graphene self-supporting membrane. The film obtained by the test has the thickness of 171.2-178.0 μm, the average thickness of 175.4 μm, the thermal expansion rate of 1.06 and the density of 0.37g/cm3Thermal diffusivity of 728mm2And s. Compared with the conventional film, the thermal expansion rate is reduced to a certain extent, the density is improved, and the thermal diffusion coefficient is improved to some extent.
Fig. 5 is a cross-sectional SEM of the graphene self-supporting film prepared in example 5.
Example 6
The method for inhibiting the thermal expansion of the graphene self-supporting film comprises the following steps:
taking the GO filter cake of the type I, preparing 4.90% of water-based GO slurry, fully stirring for 3 hours at 650rpm of a stirrer, and oscillating for 60min to obtain the uniformly dispersed GO slurry(ii) a Then 0.01g of nano iron oxide with the size of 30nm and 0.49g of nano titanium oxide with the size of 25nm are added into 100ml of deionized water, stirred for 3 hours at 800rpm and then subjected to ultrasonic treatment for 20 minutes to obtain a well-dispersed mixed solution of the nano iron oxide and the titanium oxide. Slowly adding the uniformly dispersed mixed solution of nano iron oxide and titanium oxide into the GO slurry, wherein the total amount of iron oxide and titanium oxide particles accounts for 0.10% of the weight of GO, and stirring at 750rpm for 1.5h to obtain the GO slurry compounded by iron oxide and titanium oxide. Coating GO slurry compounded by iron oxide and titanium oxide on a PET substrate to form a film with the thickness of 3mm, and treating for 4 hours at 80 ℃ to obtain the GO film compounded by dry iron oxide and titanium oxide. The thickness of the GO membrane is between 160.1 and 165.3 μm, with an average thickness of 161.8 μm. And then carrying out heat treatment on the GO membrane at 2530 ℃ for 45 hours to obtain the graphene self-supporting membrane. The film obtained by the test has the thickness of 170.6-179.3 μm, the average thickness of 175.9 μm, the thermal expansion rate of 1.08 and the density of 0.35g/cm3Thermal diffusion coefficient of 709mm2And/s, compared with the conventional film, the thermal expansion rate is obviously reduced, the density is obviously improved, and the thermal diffusion coefficient is improved to some extent.
Fig. 6 is a cross-sectional SEM of the graphene self-supporting film prepared in example 6.
Example 7
The method for inhibiting the thermal expansion of the graphene self-supporting film comprises the following steps:
preparing a 3.80% aqueous GO slurry from a GO filter cake of the type I, fully stirring for 1h at 300rpm of a stirrer, and oscillating for 30min to obtain a uniformly dispersed GO slurry; then 0.1g of nano iron oxide with the size of 30nm and 0.2g of nano titanium oxide with the size of 40nm are added into 100ml of deionized water, stirred at 900rpm for 40min and then subjected to ultrasonic treatment for 20min to obtain a well-dispersed mixed solution of nano iron oxide and titanium oxide. Slowly adding the uniformly dispersed mixed solution of nano iron oxide and titanium oxide into the GO slurry, wherein the total amount of iron oxide and titanium oxide particles accounts for 0.8% of the weight of GO, and stirring at 300rpm for 1h to obtain the GO slurry compounded by iron oxide and titanium oxide. Coating GO slurry compounded by iron oxide and titanium oxide on a PET substrate to form a 4mm film, and treating at 90 ℃ for 4h to obtain the dry GO film compounded by iron oxide and titanium oxide. The thickness of the GO film is between 164.2-169.9 μm,the average thickness was 167.3. mu.m. And then carrying out heat treatment on the GO membrane at 2500 ℃ for 60 hours to obtain the graphene self-supporting membrane. The film obtained by the test has the thickness of 150.0-155.3 μm, the average thickness of 152.2 μm, the thermal expansion rate of 0.91 and the density of 0.43g/cm3Thermal diffusivity of 753mm2And/s, compared with the conventional film, the thermal expansion rate is obviously reduced, the density is obviously improved, and the thermal diffusion coefficient is obviously improved.
Fig. 7 is a cross-sectional SEM of the graphene self-supporting film prepared in example 7.
Example 8
The method for inhibiting the thermal expansion of the graphene self-supporting film comprises the following steps:
taking the GO filter cake of the type I, preparing 4.10% aqueous GO slurry, fully stirring for 1.5h at 320rpm of a stirrer, and oscillating for 25min to obtain uniformly dispersed GO slurry; then 0.2g of nano cobalt oxide with the size of 30nm is added into 100ml of deionized water, stirred at 700rpm for 30min, and then subjected to ultrasonic treatment for 15min to obtain a well-dispersed nano cobalt oxide solution. Slowly adding the cobalt oxide into GO slurry, wherein the total amount of cobalt oxide accounts for 1.6% of the weight of GO, and stirring at 300rpm for 1h to obtain the GO slurry compounded with cobalt oxide. Then coating the film on a PET substrate into a 4mm film, and treating at 87 ℃ for 4h to obtain a dried cobalt oxide compounded GO film. The thickness of the GO membrane is between 163.2 and 168.1 μm, with an average thickness of 166.4 μm. And then carrying out heat treatment on the GO membrane at 2700 ℃ for 58h to obtain the graphene self-supporting membrane. The film obtained by the test has the thickness of 160.8-165.4 μm, the average thickness of 163.3 μm, the thermal expansion rate of 0.99 and the density of 0.40g/cm3Thermal diffusivity of 719mm2And/s, compared with the conventional film, the thermal expansion rate is obviously reduced, the density is obviously improved, and the thermal diffusion coefficient is obviously improved.
Fig. 8 is a cross-sectional SEM of the graphene self-supporting film prepared in example 8.
Example 9
The method for inhibiting the thermal expansion of the graphene self-supporting film comprises the following steps:
taking the GO filter cake of the model II, preparing 3.15% aqueous GO slurry, fully stirring for 1.6h at 380rpm of a stirrer, and oscillating for 60min to obtain the GO filter cakeA uniformly dispersed GO slurry; then 0.15g of nano chromium oxide with the size of 25nm is added into 100ml of deionized water, stirred at 600rpm for 35min, and then subjected to ultrasonic treatment for 14min to obtain a well-dispersed nano chromium oxide solution. Slowly adding the chromium oxide into GO slurry, wherein the total amount of chromium oxide accounts for 2.0% of the weight of GO, and stirring at 400rpm for 1.5h to obtain the GO slurry compounded with chromium oxide. Then coating the film on a PET substrate into a 4mm film, and treating at 89 ℃ for 4.5h to obtain a dried chromium oxide compounded GO film. The thickness of the GO membrane is between 160.1 and 165.7 μm, with an average thickness of 162.3 μm. And then carrying out heat treatment on the GO membrane at 3100 ℃ for 55h to obtain the graphene self-supporting membrane. The film obtained by the test has the thickness of 168.2-173.9 μm, the average thickness of 170.3 μm, the thermal expansion multiplying power of 1.06 and the density of 0.37g/cm3Thermal diffusivity of 728mm2And/s, compared with the conventional film, the thermal expansion rate is obviously reduced, the density is obviously improved, and the thermal diffusion coefficient is obviously improved.
Fig. 9 is a cross-sectional SEM of the graphene self-supporting film prepared in example 9.
Example 10
The method for inhibiting the thermal expansion of the graphene self-supporting film comprises the following steps:
taking a GO filter cake of the type III, preparing 2.75% of water-based GO slurry, fully stirring for 1.5h at 350rpm of a stirrer, and oscillating for 40min to obtain uniformly dispersed GO slurry; then 0.1g of nano nickel oxide with the size of 30nm is added into 100ml of deionized water, stirred at 600rpm for 30min, and then subjected to ultrasonic treatment for 15min to obtain a well-dispersed nano nickel oxide solution. Slowly adding the nickel oxide into GO slurry, wherein the total amount of nickel oxide accounts for 1.0% of the weight of GO, and stirring at 500rpm for 1.0h to obtain the GO slurry compounded with nickel oxide. Then coating the film on a PET substrate into a film with the thickness of 3.5mm, and treating the film at 80 ℃ for 5.0h to obtain the dried GO film compounded by nickel oxide. The GO membrane had a thickness between 163.3 and 167.0 μm and an average thickness of 165.7 μm. And then carrying out heat treatment on the GO membrane at 2700 ℃ for 55h to obtain the graphene self-supporting membrane. The film obtained by the test has the thickness of 190.5-198.6 μm, the average thickness of 193.9 μm, the thermal expansion ratio of 1.17 and the density of 0.35g/cm3Thermal diffusivity of 749mm2S, obviously reduced thermal expansion rate compared with the conventional membraneThe density is obviously improved, and the thermal diffusion coefficient is obviously improved.
Fig. 10 is a cross-sectional SEM of the graphene self-supporting film prepared in example 10.
Example 11
The method for inhibiting the thermal expansion of the graphene self-supporting film comprises the following steps:
taking a GO filter cake of the type III, preparing 2.5% of water-based GO slurry, fully stirring for 2 hours at 300rpm of a stirrer, and oscillating for 50min to obtain uniformly dispersed GO slurry; then 0.05g of nano nickel chloride with the size of 20nm is added into 100ml of deionized water, stirred at 600rpm for 30min, and subjected to ultrasonic treatment for 15min to obtain a well-dispersed nano nickel chloride solution. Slowly adding the nickel chloride into GO slurry, wherein the total amount of nickel chloride accounts for 0.5% of the weight of GO, and stirring at 600rpm for 1.5h to obtain the GO slurry compounded by nickel chloride. Then coating the film on a PET substrate into a 3.0mm film, and treating at 70 ℃ for 5.0h to obtain the dry GO film compounded by nickel chloride. The thickness of the GO membrane is between 156.7 and 165.9 μm, with an average thickness of 163.1 μm. And then carrying out heat treatment on the GO membrane at 3200 ℃ for 60 hours to obtain the graphene self-supporting membrane. The film obtained by the test has the thickness of 195.3-205.9 μm, the average thickness of 203.0 μm, the thermal expansion ratio of 1.26 and the density of 0.34g/cm3Thermal diffusivity of 727mm2And/s, compared with the conventional film, the thermal expansion rate is obviously reduced, the density is obviously improved, and the thermal diffusion coefficient is obviously improved.
Fig. 11 is a cross-sectional SEM of the graphene self-supporting film prepared in example 11.
Example 12
The method for inhibiting the thermal expansion of the graphene self-supporting film comprises the following steps:
taking the GO filter cake of the type I, preparing 4.5% aqueous GO slurry, fully stirring for 1.5h at 400rpm of a stirrer, and oscillating for 40min to obtain uniformly dispersed GO slurry; then 0.05g of nano iron oxide with the size of 10nm and 0.07g of chromium oxide with the size of 40nm are added into 100ml of deionized water, stirred at 500rpm for 35min and then subjected to ultrasonic treatment for 20min to obtain a well-dispersed mixed solution of nano iron oxide and chromium oxide. Slowly adding the nano-iron oxide and the nano-chromium oxide into GO slurry, wherein the total amount of the nano-iron oxide and the nano-chromium oxide accounts for the mass of GO1.0 percent and stirring at 800rpm for 2 hours to obtain the GO slurry compounded by the nano iron oxide and the chromium oxide. And then coating the film on a PET substrate to form a 2.8mm film, and treating the film at 80 ℃ for 4.5 hours to obtain the dried GO film compounded by the nano iron oxide and the chromium oxide. The thickness of the GO membrane is between 160.2 and 164.5 μm, with an average thickness of 162.9 μm. And then carrying out heat treatment on the GO membrane at 3100 ℃ for 58h to obtain the graphene self-supporting membrane. The film obtained by the test has the thickness of 187.0-193.3 μm, the average thickness of 190.6 μm, the thermal expansion ratio of 1.17 and the density of 0.38g/cm3Thermal diffusivity of 722mm2And/s, compared with the conventional film, the thermal expansion rate is obviously reduced, the density is obviously improved, and the thermal diffusion coefficient is obviously improved.
Fig. 12 is a cross-sectional SEM of the graphene self-supporting film prepared in example 12.
Example 13
The method for inhibiting the thermal expansion of the graphene self-supporting film comprises the following steps:
taking a GO filter cake of the type III, preparing a 3.9% aqueous GO slurry, fully stirring for 2 hours at 400rpm of a stirrer, and oscillating for 40min to obtain a uniformly dispersed GO slurry; then 0.09g of nano nickel oxide with the size of 100nm and 0.01g of nano titanium oxide with the size of 30nm are added into 100ml of deionized water, stirred at 600rpm for 30min and subjected to ultrasound for 15min to obtain a well-dispersed nano nickel oxide and titanium oxide mixed solution. Slowly adding the nano nickel oxide and titanium oxide into GO slurry, wherein the total amount of the nano nickel oxide and the nano titanium oxide accounts for 0.8% of the weight of GO, and stirring at 700rpm for 2h to obtain the GO slurry compounded by the nano nickel oxide and the titanium oxide. And then coating the film on a PET substrate to form a 3.3mm film, and treating the film at 90 ℃ for 5 hours to obtain the dried GO film compounded by nano nickel oxide and titanium oxide. The thickness of the GO membrane is between 163.9-167.3 μm, with an average thickness of 165.2 μm. And then carrying out heat treatment on the GO membrane at 2950 ℃ for 60 hours to obtain the graphene self-supporting membrane. The film obtained by the test has the thickness of 198.8-203.6 μm, the average thickness of 201.5 μm, the thermal expansion ratio of 1.22 and the density of 0.36g/cm3Thermal diffusivity of 740mm2And/s, compared with the conventional film, the thermal expansion rate is obviously reduced, the density is obviously improved, and the thermal diffusion coefficient is obviously improved.
Fig. 13 is a cross-sectional SEM of the graphene self-supporting film prepared in example 13.
Fig. 14 is XRD data of the graphene thermal conductive film prepared in example 1 and the graphene thermal conductive films with the metal inhibitor added prepared in examples 2 and 7. From the data, the interlayer distance after graphitization of the thermally conductive film prepared in example 1 was 0.341 nm. In contrast, in examples 2 and 7, the interlayer spacing of the graphene thermal conductive film prepared after adding the metal inhibitor is 0.338nm, which is lower than that of the conventional film in example 1, indicating that the graphene thermal conductive film has a higher graphitization degree and a higher graphitization crystallization degree in the c-axis direction perpendicular to the plane of the graphene.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing a graphene oxide film, comprising: the method comprises the following steps:
(1) dispersing the nano metal particles in deionized water to obtain a well-dispersed nano metal solution;
(2) adding the well-dispersed nano metal solution prepared in the step (1) into graphene oxide slurry to enable the nano metal solution to be fully contacted, so as to obtain metal element compounded graphene oxide aqueous slurry;
(3) and (3) coating the metal element compounded graphene oxide aqueous slurry obtained in the step (2) on a substrate, and drying to obtain the graphene oxide film.
2. The method for preparing a graphene oxide film according to claim 1, wherein: in the step (1), the nano metal particles are one or more of iron, cobalt, nickel, titanium, chromium and chlorides or oxides thereof; and/or
The size of the nano metal particles is less than or equal to 100nm, preferably 10-100 nm; and/or
The dispersion is stirring at the rotation speed of 300-900rpm for 10-40min and/or ultrasonic processing for 5-20 min.
3. The method for preparing a graphene oxide film according to claim 2, wherein: in the step (1), the nano metal particles are nano iron oxide and nano titanium oxide; preferably, the size of the nano iron oxide is 30nm, the size of the nano titanium oxide is 40nm, and the weight ratio of the nano iron oxide to the nano titanium oxide is 1: 2.
4. The method for producing a graphene oxide film according to any one of claims 1 to 3, wherein: in the step (2), the nano metal particles account for 0.01-2% of the mass of the graphene oxide; preferably, the nano metal particles account for 0.8% of the mass of the graphene oxide; and/or
The sufficient contact is stirring for 1-3h at 300-800 rpm; and/or
The preparation method of the graphene oxide slurry comprises the following steps: adding graphene oxide into deionized water to prepare aqueous graphene oxide dispersion liquid with the weight percentage of 2-7%, and uniformly dispersing to obtain the graphene oxide dispersion liquid.
5. The method for preparing a graphene oxide film according to claim 4, wherein: in the step (2), the step of uniformly dispersing is to add the graphene oxide into deionized water, stir at 300-800rpm for 1-3h, and/or shake for 20-60 min.
6. The method for producing a graphene oxide film according to any one of claims 1 to 5, wherein: in the step (3), the thickness of the coating film during coating is 1-4 mm; and/or
The substrate is a PET substrate; and/or
The drying temperature is 50-90 deg.C, and the drying time is 2-5 h.
7. A graphene oxide film prepared by the method of any one of claims 1 to 6.
8. A method for inhibiting thermal expansion of a graphene self-supporting film is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing the graphene oxide film of claim 7;
(2) and (2) carrying out heat treatment on the metal compounded graphene oxide film obtained in the step (1).
9. The method for suppressing thermal expansion of the graphene self-supporting film according to claim 8, wherein: the heat treatment is carried out at 2000-3200 ℃ for 20-60 h.
10. A graphene self-supporting film prepared by the method of claim 8 or 9.
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