CN115650600A - Graphene glass and preparation method thereof - Google Patents
Graphene glass and preparation method thereof Download PDFInfo
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- CN115650600A CN115650600A CN202211262601.0A CN202211262601A CN115650600A CN 115650600 A CN115650600 A CN 115650600A CN 202211262601 A CN202211262601 A CN 202211262601A CN 115650600 A CN115650600 A CN 115650600A
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Abstract
The invention belongs to the field of material surface functionalization, and particularly relates to graphene glass and a preparation method thereof. The method comprises the following steps: 1) Providing a carbon precursor film on a glass substrate; 2) Laminating the glass substrate in a manner that the carbon precursor film is tightly attached to the graphite plate to form a hypoxic interface; and raising the temperature of at least one part of the carbon precursor film to 550-1500 ℃ in 1 us-10 s under the atmospheric environment by utilizing electromagnetic induction, so that at least one part of the carbon precursor film is converted into graphene attached to the surface of the glass substrate. By utilizing the preparation method, the ultra-fast preparation of the large-size and high-quality graphene film on the surface of the glass material can be realized.
Description
Technical Field
The invention belongs to the field of material surface functionalization, and particularly relates to graphene glass and a preparation method thereof.
Background
Graphene (Graphene) is sp 2 The hybridized and connected carbon atoms are tightly packed into a new material with a single-layer two-dimensional honeycomb lattice structure. The material has wide attention due to excellent mechanical, optical, electrical and thermal properties, has important application prospect and is considered as a revolutionary material in the future. In recent years, efforts have been made to expand the size of graphene thin filmsThe production efficiency is improved, the production cost is reduced, and the industrial application of the graphene is promoted. Glass is one of the indispensable materials in daily life due to its good light transmission and low cost. Graphene and glass are perfectly combined, a novel composite material, namely graphene glass, is developed, the advantage of good light transmittance of the glass is kept, the glass is endowed with excellent characteristics of ultrahigh electrical conductivity, thermal conductivity, surface hydrophobicity and the like of the graphene, the application space of the glass is greatly expanded, and the revolutionary transition of the glass industry from large-batch low-added-value application to conservation-oriented high-added-value application is initiated.
In the conventional graphene preparation method, the graphene is transferred by a physical method in the early days, high-quality graphene is grown on a transition metal by a CVD method and then is transferred to a target substrate, the graphene cannot form a film large enough, and the discontinuous film enables the conductivity of the graphene at room temperature to be two to three orders of magnitude lower than that of the graphene in an ideal state. Compared with a physical transfer method, the chemical vapor deposition method is gradually developed into an effective method for preparing continuous and high-quality graphene films. The direct growth of graphene on a target substrate by using a CVD method can also avoid the performance reduction of graphene caused by a transfer process, but the method for preparing graphene directly on the target substrate by chemical vapor deposition has certain limitation in the aspect of industrialization. The Liuzhong subject group adopts a low-pressure chemical vapor deposition method to prepare a high-quality graphene film on the surface of quartz glass with the size of 6cm x 60cm, and the sheet resistance is about 5.3k omega & sq -1 The growth temperature of the graphene is 1100 ℃, and the growth time is 4min. Although the high-quality graphene glass is prepared by the method, the limitation of the size of a hearth of a high-temperature growth furnace is not broken through, the size can be longitudinally enlarged, and the requirement of the transverse large size cannot be met. The requirement on vacuum degree and the requirement on temperature gradient in the graphene growth process still cause the industrial production cost for preparing the graphene film by the facility to be high. In addition, there have been some searches for methods for ultra-fast growth of graphene. For example, lu et al, using a laser source heating method, 2s intrinsic continuous magnetron sputtering produced a sheet resistance of about 105 on a substrate coated with carbon and nickel filmsΩ·sq -1 The graphene pattern of (a); forest et al immerse a glass substrate pre-coated with a nickel film of 5-28 nm thickness in olive oil, heat the substrate with laser, generate 6 layers on the glass surface in 4-6 s, and have an area larger than 3cm 2 The size of the synthesized graphene is actually limited by the size of a laser spot and the size of a magnetron sputtering vacuum cavity, the quality of the graphene is greatly influenced by the catalytic metal nickel remained on the surface of the substrate, and the requirement for preparing a large-size graphene film is difficult to realize.
The applicant's earlier patent CN113840801A proposes to use an ultra-fast quenching method to grow large-area graphene on the glass surface. However, the carbon powder slurry coating method proposed in the patent cannot ensure that the surface of the glass is covered with uniform carbon powder precursor, so that the subsequently prepared graphene film is discontinuous and has poor surface conductivity; vacuum carbon deposition can obtain a continuous precursor carbon film, but the size of the vacuum chamber limits the size of the glass. Based on the limitations of the above preparation methods, there is still a need to provide a method for preparing high-quality graphene thin films with large size and without transfer process and catalyst on different substrates.
Reference documents:
1.Chen,Z.；Qi,Y.；Liu,Z.,et al.Direct CVD Growth of Graphene on Traditional Glass:Methods and Mechanisms.Advanced Materials 2019,31(9).
2.Liu,B.；Wang,H.；Gu,W.,et al.Oxygen-assisted direct growth of large-domain and high-quality graphene on glass targeting advanced optical filter applications.Nano Res.2021,14(1).
3.Shan,J.；Cui,L.；Zhou,F.,et al.Ethanol-Precursor-Mediated Growth and Thermochromic Applications of Highly Conductive Vertically Oriented Graphene on Soda-Lime Glass.Acs Applied Materials&Interfaces 2020,12(10).
4.Xiong,W.；Zhou,Y S.；Hou,W J.,et al.Direct writing of graphene patterns on insulating substrates under ambient conditions.Scientific Reports,2014,4.
5.Huang,Y.；Sepioni,M.；Whitehead,D.,et al.Rapid growth of large area graphene on glass from olive oil by laser irradiation.Nanotechnology,2020,31(24).
disclosure of Invention
The preparation of large-size graphene glass mainly has two problems: 1. the growth time of the graphene is too long, and is generally from several hours to more than ten hours, the production efficiency is low, and the energy consumption is high; 2. the size of the graphene glass of uniform quality is limited because the CVD growth method limits the macroscopic uniformity of graphene in principle, thereby limiting the size of the graphene glass of uniform quality. The future industrial application of the graphene glass is seriously influenced by the defects of the two aspects.
Aiming at the defects of long preparation time, high energy consumption and incapability of large-area growth of the conventional graphene glass, the invention aims to provide the graphene glass and a preparation method thereof, and the preparation method can be used for realizing the ultra-fast preparation of a large-size graphene film on the surface of a glass material.
In order to achieve the above object, the present invention firstly provides a method for preparing graphene glass, comprising the following steps:
1) Providing a carbon precursor film on a glass substrate;
2) Laminating the glass substrate in a manner that a carbon precursor film is tightly attached to a graphite plate to form a hypoxic interface; and raising the temperature of at least one part of the carbon precursor film to 550-1500 ℃ in 1 us-10 s under the atmospheric environment by utilizing electromagnetic induction, so that at least one part of the carbon precursor film is converted into graphene attached to the surface of the glass substrate.
Compared with the traditional methods of vacuum evaporation carbon plating and the like, the preparation method provided by the invention has the advantages that the carbon precursor film on the glass substrate is tightly attached to the graphite plate, so that the good oxygen-deficient environment of the carbon precursor film is ensured, the glass substrate can be directly heated by using eddy current excited by electromagnetic induction in the atmospheric environment, the temperature is raised to 550-1500 ℃ in a very short time, and the large-area continuous graphene film is directly grown on the surface of the glass substrate. Furthermore, the limitation on the transverse and longitudinal sizes of the glass substrate is broken through by combining the electromagnetic induction coil with electromagnetic induction and the three-dimensional moving translation table, and the requirement of the market on large-size graphene glass is met. Meanwhile, the graphite plate has the advantages of high temperature resistance, flatness and no participation in carbonization reaction.
The size of the glass in the present invention is not particularly limited, and may be 50mm × 50mm, 100mm × 100mm, 400mm × 400mm, 1000mm × 1000mm, and larger sizes required in the market.
In a preferred embodiment, the step 1) is specifically:
A. soaking the glass substrate in the piranha solution, and then washing the glass substrate to be neutral by deionized water;
B. providing a layer comprising a polymerizable carbon-containing compound on the glass substrate treated in step a, polymerizing the carbon-containing compound and drying to thereby form a carbon precursor film.
Firstly, soaking a glass substrate by using a piranha solution, and removing impurities and simultaneously carrying out hydrophilic treatment on the surface of the glass, thereby being beneficial to the uniform film formation of subsequent carbon-containing compounds. And then, a compact and uniform carbon-containing precursor film is formed by utilizing polymerization and self-assembly deposition of carbon-containing micromolecules in the solution on the surface of the pretreated glass, an oxygen-deficient environment is provided for an interface of the compact and uniform film, a large-area continuous graphene film is formed on the surface of the glass after subsequent quenching, the conductivity and the light transmittance of the graphene glass are greatly improved, and the application in the fields of display technology, functional film materials and the like is realized.
Preferably, in step a, the glass substrate material is cleaned to remove surface impurities before being soaked in the piranha solution. For example, the cleaning agent can be used for cleaning, and deionized water, ethanol ultrasound and the like can be used.
Preferably, in the step A, the glass substrate is placed into the piranha solution and soaked for 4 to 6 hours at 70 to 90 ℃.
Preferably, in step B, the material of the carbon precursor film is at least one selected from polydopamine, polystyrene (PS), polypropylene (PP), polyethylene (PP), polyvinyl chloride (PVC), polyamide, cellulose acetate, and polyether sulfone.
Preferably, the polymerizable carbon-containing compound is dopamine hydrochloride, which is layered on the glass substrate as a blend of dopamine hydrochloride and a Tris-HCl buffer solution. The invention discovers that a graphene film formed by soaking a glass substrate in a piranha solution, coating a film by adopting a blend solution of dopamine hydrochloride and Tris-HCl buffer solution and further carbonizing the film has excellent conductivity (the surface resistance is as low as 4.3k omega. Sq.s. -1 ) And light transmittance (light transmittance up to 87%), and excellent surface hydrophobicity (contact angle of 87 °).
More preferably, the concentration of the dopamine hydrochloride in the blending liquid is 0.5-5 mg/mL -1 (ii) a The pH of the Tris-HCl buffer solution was 8.5.
Preferably, the glass substrate is a flexible glass substrate; more preferably, the flexible glass substrate has a thickness of 30-80um. The inventor of the invention unexpectedly finds that by adopting the preparation method, the flexible graphene glass with excellent performance can be prepared. If the carbon source precursor polymer is directly coated on the surface of the flexible glass substrate, the defects of uneven thickness of the graphene film, poor quality of the graphene film on the surface of the glass and the like exist, and if a conventional heating carbonization method is adopted, the defect that the flexible glass is easily damaged due to overlong heat treatment time exists.
In another preferred embodiment, the step 1) is specifically: a layer including liquid oil is provided on a glass substrate to thereby form a carbon precursor film.
According to the invention, liquid oil is adopted as a carbon precursor raw material, a continuous oil film can be formed, and a good oxygen-deficient environment is formed between the oil film and a graphite plate, so that graphene cannot be oxidized in the high-temperature growth process of graphene in the atmosphere.
In a preferred embodiment, the step 2) is specifically: fixing the glass substrate on a graphite plate in a manner that a carbon precursor film is tightly attached to the graphene plate, fixing the glass substrate by using a clamp, placing the glass substrate on a three-dimensional electric translation table, arranging an electromagnetic induction coil at a position 0.5-2 mm above the substrate, starting the electric translation table and a high-frequency electromagnetic induction power supply to enable the electric translation table to drive the substrate to move, enabling the substrate below the electromagnetic induction copper coil to be heated to a red hot state within 1-10 s, and waiting for natural cooling after the experiment is finished.
Parameters such as the diameter and the number of turns of the high-frequency induction coil, power supply power, distance between the coil and the graphite plate, induction time and the like can be accurately controlled, so that the quenching temperature can reach 550-1500 ℃ instantly, and the growth condition of graphene is met.
Further preferably, the temperature of the glass substrate is raised to 1150-1400 ℃ for 1 us-10 s by means of electromagnetic induction.
In a more preferable embodiment, in the step 2), the output power of the induction power supply is 0.1 to 6kW; the stroke range of the movable translation stage is an X axis: 0 to 300mm, Y-axis: 0-300 mm, the moving speed range is: 0.5mm · s -1 ～100mm·s -1 (ii) a The high-frequency induction current induction coil includes: diameter 8mm, 10mm, 20mm, 30mm, the number of turns includes: the induction coil is single-turn, double-turn and three-turn, and the design shape of the induction coil comprises a turn number shape and a straight shape.
In a most preferred embodiment, the graphene glass preparation process comprises the following steps:
1) Placing the glass in acetone, ethanol and deionized water in sequence, ultrasonically cleaning for 10 minutes, and drying by using nitrogen;
2) Soaking the cleaned glass in a piranha solution, heating for 4-6 h at 80 ℃, and ultrasonically cleaning for several times by using deionized water until the pH value is neutral;
3) Putting the glass substrate material after the piranha treatment into 1 mg/mL -1 Dip-coating in a buffer solution of Dop and Tris-HCl (pH = 8.5) for 12h, washing the surface with deionized water, and blow-drying with nitrogen to obtain a carbon precursor film;
4) Fixing a pre-carbonized glass substrate on a graphite plate in a manner that a carbon precursor film is tightly attached to the graphene plate, fixing the glass substrate by using a clamp, placing the glass substrate on a three-dimensional electric translation table, arranging an electromagnetic induction copper ring (phi =20 mm) at a position 0.5mm above the substrate, starting the electric translation table and a high-frequency electromagnetic induction power supply (P =6 kW), enabling the electric translation table to drive the substrate to move, enabling the substrate below the electromagnetic induction copper ring to be heated to a red hot state, enabling the temperature to reach 1400 ℃ instantly, and immediately cooling after quenching is completed;
5) And finally, after the sample is cooled to the room temperature, taking down the graphene glass sample to finish the preparation.
The invention also provides graphene glass prepared by the preparation method.
The invention has the beneficial effects that:
the preparation method of the graphene glass provided by the invention can be completed in an atmospheric environment, the size of the substrate is not limited, the requirement of the market on large-size graphene glass is met, and the preparation method has the advantages of low energy consumption and high speed.
Drawings
Fig. 1 is a schematic diagram of a large-size ultrafast graphene growth method on the surface of glass in example 1, and an inset in a dotted circle is a close-up of a glass-graphite plate-glass sandwich structure after coating.
Fig. 2 is a raman curve of the graphene glass sample obtained in example 1.
Fig. 3 is a light transmittance curve of the graphene glass sample obtained in example 1.
Fig. 4 is the sheet resistance test data of the graphene glass sample obtained in example 1.
Fig. 5 is a raman curve of the graphene glass sample obtained in example 2.
Fig. 6 is a light transmittance curve of the graphene glass sample obtained in example 2.
Fig. 7 is the sheet resistance test data of the graphene glass sample obtained in example 2.
Fig. 8 is a raman curve of the graphene glass sample obtained in example 3.
Fig. 9 is a light transmittance curve of the graphene glass sample obtained in example 3.
Fig. 10 is the sheet resistance test data of the graphene glass sample obtained in example 3.
Fig. 11 is a raman curve of the graphene glass sample obtained in example 4.
Fig. 12 is a light transmittance curve of the graphene glass sample obtained in example 4.
Fig. 13 is the sheet resistance test data of the graphene glass sample obtained in example 4.
FIG. 14 shows the corresponding contact angles of examples 1 to 3, and the contact angles of example 1 (12 to 1400), example 2 (6 to 1400) and example 3 (24 to 1400) were 84.08 °, 82.96 ° and 88.21 ° in this order.
FIG. 15 shows Raman spectrum data of different regions of the sample in example 1.
Fig. 16 is a temperature-time curve of the glass surface after applying 70V voltage to the sample of example 1 and an infrared thermal image photograph at a certain time, which shows the rapid red heating effect of the graphene glass after being electrified in the example, and the temperature bar range is 17.1-63.8 ℃.
FIG. 17 is an optical photograph of the sample of example 1 after trimming the edges.
Fig. 18 is an optical picture of a sample of example 5.
Fig. 19 is an optical picture of the flexible glass of example 6, with the glass backing substrate letter C.
Fig. 20 is an optical picture of the flexible graphene glass of example 6, the glass being backed by the letter C.
Fig. 21 is an optical image of a graphene glass sample finally obtained in comparative example 1 without pretreatment with a piranha solution.
Detailed Description
Exemplary embodiments of the invention are provided in the following examples. The following examples are given by way of illustration only and are presented to assist one of ordinary skill in the art in utilizing the present invention. The examples are not intended to limit the scope of the invention in any way.
Example 1
Referring to fig. 1, ultrasonic cleaning 100mm × 100mm glass with acetone, ethanol, and deionized water for 10min, blow-drying with nitrogen gas, and adding piranha solution (prepared from concentrated sulfuric acid and hydrogen peroxide solution (30%) at volume ratio of V) H2SO4 ：V H2O2 =3: 1) Heating at 80 deg.c for 4-6 hr, ultrasonic cleaning with deionized water several timesThe pH was neutral. The glass treated by the piranha solution is placed in a volume of 1 mg/mL -1 And (3) dip-coating the surface of the carbon precursor film for 12 hours in a dopamine hydrochloride Dop/This-HCl buffer solution (polymerization occurs in the dip-coating process), washing the surface with deionized water, and blow-drying with nitrogen to form the carbon precursor film. Fixing the pre-carbonized glass substrate on a graphite plate, fixing the glass substrate by using a dovetail clamp (the other side of the graphite plate is also provided with a piece of glass to prevent the graphite plate from directly touching the dovetail clamp to form a coated glass-graphite plate-glass sandwich structure, the same applies below), placing the glass substrate on a three-dimensional electric translation table, arranging an electromagnetic induction copper coil (phi =20mm,2 turns) at a position 0.5mm above the glass substrate, setting a coil moving path in advance, and starting the electric translation table (the moving speed: 6.5mm · s) -1 ) And a high-frequency electromagnetic induction power supply (P =6 kW) for driving the substrate to move by the electric translation table, heating the substrate below the electromagnetic induction copper ring to a red hot state, wherein the temperature can reach 1400 ℃ instantly, and immediately cooling after quenching is completed.
The obtained graphene glass samples were subjected to characterization and performance tests such as Raman, light transmittance, sheet resistance, contact angle, etc., and the results are shown in fig. 2-4 and 14-16. An optical picture of the sample is shown in fig. 17. It can be concluded that: the light transmittance of the graphene is 82%, the contact angle is 84.08 degrees, and the average value of the surface resistance is 4.3k omega sq -1 。
Example 2
Ultrasonically cleaning 100mm by 100mm glass in acetone, ethanol and deionized water for 10min respectively, then drying by nitrogen, putting into the piranha solution, heating for 4-6 h at 80 ℃, and ultrasonically cleaning by deionized water for several times until the pH value is neutral. The glass treated by the piranha solution is placed in a volume of 1 mg/mL -1 Dip-coating in Dop/This-HCl buffer solution for 6h, washing the surface with deionized water, and blowing with nitrogen. Fixing the pre-carbonized glass substrate on a graphite plate, fixing the glass substrate by using a dovetail clamp, placing the glass substrate on a three-dimensional electric translation table, arranging an electromagnetic induction copper coil (phi =20mm,2 turns) at a position 0.5mm above the glass substrate, setting a coil moving path in advance, and starting the electric translation table (moving speed: 6.5mm s) -1 ) And a high-frequency electromagnetic induction power supply (P =6 kW) for driving the electric translation stageAnd moving the substrate, heating the substrate below the electromagnetic induction copper ring to a red hot state, wherein the temperature can reach 1400 ℃ instantly, and immediately cooling after quenching is finished.
The obtained graphene glass samples were subjected to Raman, transmittance, sheet resistance, contact angle characterization and performance tests, and the results are shown in fig. 5 to 7 and 14. It can be concluded that: the light transmittance of the graphene is 87 percent, the contact angle is 82.96 degrees, and the average value of the surface resistance is 5.7k omega sq -1 。
Example 3
Ultrasonically cleaning 100mm x 100mm glass in acetone, ethanol and deionized water for 10min respectively, then drying the glass by using nitrogen, placing the glass into the piranha solution, heating the glass for 4 to 6 hours at the temperature of 80 ℃, and ultrasonically cleaning the glass by using the deionized water for several times until the pH value is neutral. The glass treated by the piranha solution is placed in a volume of 1 mg/mL -1 Dip-coating in Dop/This-HCl buffer solution for 24h, washing the surface with deionized water, and drying with nitrogen. Fixing the pre-carbonized glass substrate on a graphite plate, fixing the glass substrate by using a dovetail clamp, placing the glass substrate on a three-dimensional electric translation table, arranging an electromagnetic induction copper coil (phi =20mm,2 turns) at a position 0.5mm above the glass substrate, setting a coil moving path in advance, and starting the electric translation table (moving speed: 6.5mm · s) -1 ) And a high-frequency electromagnetic induction power supply (P =6 kW), so that the electric translation table drives the substrate to move, the substrate below the electromagnetic induction copper ring is heated to a red hot state, the temperature can reach 1400 ℃ instantly, and the substrate is cooled immediately after quenching is finished.
And performing Raman, light transmittance, surface resistance, contact angle characterization and performance test on the obtained graphene glass sample. The results are shown in FIGS. 8-10 and 14. It can be concluded that: the graphene has the light transmittance of 69%, the contact angle of 88.21 degrees and the average surface resistance of 5.8k omega sq -1 。
Example 4
Ultrasonically cleaning 100mm x 100mm glass in acetone, ethanol and deionized water for 10min respectively, then drying the glass by using nitrogen, placing the glass into the piranha solution, heating the glass for 4 to 6 hours at the temperature of 80 ℃, and ultrasonically cleaning the glass by using the deionized water for several times until the pH value is neutral. Placing the glass treated by the piranha solution at 1mg·mL -1 Dip-coating in Dop/This-HCl buffer solution for 24h, washing the surface with deionized water, and blowing with nitrogen. Fixing the pre-carbonized glass substrate on a graphite plate, fixing the glass substrate by using a dovetail clamp, placing the glass substrate on a three-dimensional electric translation table, arranging an electromagnetic induction copper coil (phi =20mm,2 turns) at a position 0.5mm above the glass substrate, setting a coil moving path in advance, and starting the electric translation table (moving speed: 9.931mm · s) -1 ) And a high-frequency electromagnetic induction power supply (P =6 kW), so that the electric translation table drives the substrate to move, the substrate below the electromagnetic induction copper ring is heated to a red hot state, the temperature can reach 1150 ℃ instantly, and the substrate is cooled immediately after quenching is finished.
And performing Raman, light transmittance, surface resistance characterization and performance test on the obtained graphene glass sample. The results are shown in FIGS. 11-13. It can be concluded that: the light transmittance of the graphene is 61%, and the average value of the surface resistance is 20k omega-sq -1 。
Example 5
Ultrasonic cleaning 50mm glass with acetone, ethanol and deionized water for 10min, blowing to dry with nitrogen, placing in piranha solution, heating at 80 deg.C for 4-6 h, and ultrasonic cleaning with deionized water several times until pH is neutral. 0.1g of polystyrene-poly (4-vinylpyridine) (PS-P4 VP) and 0.0512g of resorcinol were each dissolved in 2g of dimethylformamide, the solution was heated at 100 ℃ for 4h, after cooling to room temperature, the solution was spin-coated on a glass substrate at 1000rpm for 2min to form a film. The film was stored in an oven at 80 ℃ for 24 hours under sealed conditions, and then cured by exposure to 100 ℃ formaldehyde gas for 4 hours. Fixing the pre-carbonized glass substrate on a graphite plate, fixing the glass substrate by using a dovetail clamp, placing the glass substrate on a three-dimensional electric translation table, arranging an electromagnetic induction copper coil (phi =20mm,2 turns) at a position 0.5mm above the glass substrate, setting a coil moving path in advance, and starting the electric translation table (moving speed: 6.5mm s) -1 ) And a high-frequency electromagnetic induction power supply (P =6 kW) for driving the substrate to move by the electric translation table, heating the substrate below the electromagnetic induction copper ring to a red hot state, wherein the temperature can reach 1400 ℃ instantly, and immediately cooling after quenching is completed.
The obtained graphene glass sample is subjected to Raman, light transmittance, surface resistance characterization and performance test, and a conclusion can be drawn: the graphene film prepared by taking polystyrene as a carbon source cannot fully cover the glass substrate, and has poor conductivity and light transmittance. An optical picture of this sample is shown in fig. 18.
Example 6
Ultrasonic cleaning 50mm 30um flexible glass with acetone, ethanol and deionized water for 10min, blowing to dry with nitrogen, placing in piranha solution, heating at 80 deg.C for 4-6 h, and ultrasonic cleaning with deionized water several times until pH is neutral. Placing the flexible glass treated by the piranha solution in a place of 1 mg/mL -1 Dip-coating in Dop/This-HCl buffer solution for 24h, washing the surface with deionized water, and drying with nitrogen. Fixing the pre-carbonized glass substrate on a graphite plate, fixing the glass substrate by using a dovetail clamp, placing the glass substrate on a three-dimensional electric translation table, arranging an electromagnetic induction copper coil (phi =20mm,2 turns) at a position 0.5mm above the glass substrate, setting a coil moving path in advance, and starting the electric translation table (moving speed: 9.931mm s) -1 ) And a high-frequency electromagnetic induction power supply (P =5 kW), so that the electric translation table drives the substrate to move, the substrate below the electromagnetic induction copper ring is heated to a red hot state, the temperature can reach 980 ℃ instantly, and the substrate is naturally cooled after quenching is completed.
The obtained surface film of the flexible graphene glass sample is uniform and compact, the light transmittance is good, and optical pictures before and after the graphene film grows on the surface of the flexible glass are shown in fig. 19 and fig. 20.
Comparative example 1
And carrying out ultrasonic cleaning on the 400mm/400mm glass in ethanol and deionized water for 10min respectively, and then drying by using nitrogen. The treated glass was placed in a volume of 1 mg. ML -1 Dip-coating in Dop/This-HCl buffer solution for 12h, washing the surface with deionized water, and drying with nitrogen. Fixing the pre-carbonized glass substrate on a graphite plate, fixing with a dovetail clamp, placing on a three-dimensional electric translation table, arranging an electromagnetic induction copper coil (phi =20mm,2 turns) at a position 0.5mm above the glass substrate, setting a coil moving path in advance, and starting electricityMoving translation table (moving speed: 6.5 mm. S) -1 ) And a high-frequency electromagnetic induction power supply (P =6 kW), so that the electric translation table drives the substrate to move, the substrate below the electromagnetic induction copper ring is heated to a red hot state, the temperature can reach 1400 ℃ instantly, and the substrate is cooled immediately after quenching is finished.
After the glass which is not treated by the piranha solution is subjected to pre-carbonization coating treatment, the coated film layer is not uniform, and further, the film on the surface of the graphene glass obtained after heating is not uniform and has poor light transmittance, as shown in fig. 21.
The above examples are only for describing the preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
Claims (10)
1. The preparation method of the graphene glass is characterized by comprising the following steps:
1) Providing a carbon precursor film on a glass substrate;
2) Laminating the glass substrate in a manner that the carbon precursor film is tightly attached to the graphite plate to form a hypoxic interface; and raising the temperature of at least one part of the carbon precursor film to 550-1500 ℃ in 1 us-10 s under the atmospheric environment by utilizing electromagnetic induction, so as to convert at least one part of the carbon precursor film into graphene attached to the surface of the glass substrate.
2. The preparation method according to claim 1, wherein the step 1) is specifically:
A. soaking the glass substrate in the piranha solution, and then washing the glass substrate to be neutral by deionized water;
B. providing a layer comprising a polymerizable carbon-containing compound on the glass substrate treated in step a, polymerizing the carbon-containing compound and drying to thereby form a carbon precursor film.
3. The method according to claim 2, wherein in step a, the glass substrate is immersed in the piranha solution at 70 to 90 ℃ for 4 to 6 hours.
4. The method according to claim 2 or 3, wherein in step B, the material of the carbon precursor film is at least one selected from polydopamine, polystyrene, polypropylene, polyethylene, polyvinyl chloride, polyamide, cellulose acetate, and polyether sulfone.
5. A method of manufacturing according to claim 2 or 3 wherein the polymerisable carbon-containing compound is dopamine hydrochloride in a blend with a buffered Tris-HCl solution to form a layer on the glass substrate.
6. The preparation method according to claim 5, wherein the concentration of the dopamine hydrochloride in the blend is 0.5-5 mg-mL -1 (ii) a The pH of the Tris-HCl buffer solution was 8.5.
7. The production method according to any one of claims 2 to 6, characterized in that the glass substrate is a flexible glass substrate; preferably, the flexible glass substrate has a thickness of 30-80um.
8. The preparation method according to claim 1, wherein the step 1) is specifically: a layer including liquid oil is provided on a glass substrate to thereby form a carbon precursor film.
9. The method according to any one of claims 1 to 8, wherein the step 2) is specifically: fixing the glass substrate on a graphite plate in a manner that a carbon precursor film is tightly attached to the graphene plate, placing the glass substrate on an electric translation table, arranging an electromagnetic induction coil at a position 0.5-2 mm above the glass substrate, starting the electric translation table and an electromagnetic induction coil power supply to enable the electric translation table to drive the glass substrate to move, and enabling the glass substrate below the electromagnetic induction coil to be raised to 550-1500 ℃ within 1 us-10 s, so that at least a part of the carbon precursor film is converted into graphene attached to the surface of the glass substrate.
10. The graphene glass produced by the production method according to any one of claims 1 to 9.
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| CN110745812A (en) * | 2019-10-11 | 2020-02-04 | 中国科学院金属研究所 | Method for preparing graphene or graphite film ultra-quickly |
| CN113840801A (en) * | 2020-04-24 | 2021-12-24 | 国家纳米科学中心 | Method for ultra-fast growth of graphene |
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| CN107140625A (en) * | 2017-06-14 | 2017-09-08 | 中国海洋大学 | A kind of method that utilization vegetable oil prepares graphene film |
| CN110745812A (en) * | 2019-10-11 | 2020-02-04 | 中国科学院金属研究所 | Method for preparing graphene or graphite film ultra-quickly |
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