Method for growing carbon films through permeation

Abstract

A method for permeatively growing a carbon film is disclosed, comprising steps S1 of providing a foil having a first surface and a second surface, the foil being selected from a nickel foil and a copper-nickel alloy foil, and S2 of permeatively growing a carbon film on the second surface of the foil by placing the foil as a substrate against a solid carbon source such that the first surface of the foil is adjacent to the solid carbon source and the second surface of the foil is remote from the solid carbon source, and then heating the foil and the solid carbon source.

Description

Technical Field

[0001] This application claims the priority of Chinese Patent Application No. 202111318030.3 filed on November 9, 2021, and the content disclosed in the above Chinese patent application is incorporated herein by reference.

[0002] The present invention belongs to the field of materials and relates to a non-vapor deposition type carbon film infiltration growth method induced by a solid carbon source.

Background Art

[0003] Many carbon films are obtained by physical vapor deposition or chemical vapor deposition, but some are also obtained by carbonization of polymer materials, such as polyetherimide. The carbon atoms in the carbon film are usually in the sp 2 hybrid form.

[0004] Graphene is a two-dimensional atomic monolayer in which sp 2 hybrid carbon atoms are arranged in a honeycomb structure. Graphite is one of the most common forms of carbon materials. Since it is formed by stacking a very large number of graphene layers, it has high anisotropy in mechanical, thermal, acoustical, electrical and other properties. On the horizontal plane of graphite, these properties are comparable to those of graphene. Therefore, graphite is very widely applied in heat conduction, electricity conduction, fire resistance, batteries, lubrication, steelmaking, catalysts and so on.

[0005] In general, common graphite often has grain boundaries in the layer, which greatly reduces its excellent in-plane properties. Therefore, many excellent properties of graphene are not exhibited in graphite. For example, highly oriented pyrolytic graphite (HOPG) commonly used in scientific research work has poor single-crystallinity, and the size of a single domain is at the level of several hundred micrometers. Therefore, it is an urgent task in the field of materials to manufacture large single-crystal graphite.

Prior Art Documents

Non-Patent Documents

[0006] [Non-Patent Document 1] "Seeded growth of large single-crystal copper foils with high-index facets," Nature, 2020, Vol. 581, pp. 406-410. [Overview of the project] [Means for solving the problem]

[0007] The method for permeating and growing a carbon film according to the present invention is: Step S1 provides a foil having a first surface and a second surface, selected from nickel foil and copper-nickel alloy foil. The method includes step S2, which involves placing the foil as a substrate relative to the solid carbon source such that the first surface of the foil is close to the solid carbon source and the second surface is away from the solid carbon source, and then heating the foil and the solid carbon source to cause a carbon film to penetrate and grow on the second surface of the foil.

[0008] In one embodiment, the foil is a single-crystal nickel foil.

[0009] In one embodiment, the foil and the solid carbon source are heated in a tubular furnace.

[0010] In one embodiment, the foil and solid carbon source are heated under one or more gases selected from argon, nitrogen, and hydrogen. For example, the protective gas is a mixture of argon and hydrogen, preferably with flow rates of 100-1000 sccm for argon and 5-200 sccm for hydrogen.

[0011] In one embodiment, heating the foil and the solid carbon source includes raising the temperature to 900-1350°C within 60-120 minutes, and then holding it at this temperature for 10 minutes to 50 hours.

[0012] In one embodiment, after growth is complete, the environment is maintained while the system is allowed to cool naturally to room temperature.

[0013] In some embodiments, step S1 is, Step S11 involves placing polycrystalline nickel foil on a high-temperature resistant substrate and pre-oxidizing it at 150°C to 650°C for 1 to 5 hours. Step S12 involves introducing an inert protective gas and further raising the temperature to 1000-1350°C within 60-120 minutes. Step S13 involves annealing the nickel foil by holding it at 1000-1350°C for 1-20 hours, The process includes step S14, which involves cooling to room temperature while maintaining the same atmospheric conditions after the annealing time has finished, in order to obtain a single-crystal nickel foil.

[0014] In one embodiment, steps S11 to S14 are performed in a tubular furnace.

[0015] In a preferred embodiment, the inert protective gas in step S12 is a mixed gas of Ar and H2. In a more preferred embodiment, the volume ratio of Ar to H2 in step S12 is Ar:H2 = 0.5:1 to 200:1. In an even more preferred embodiment, the flow rates of the Ar gas and H2 gas in step S12 are 100 to 1000 sccm and 5 to 200 sccm, respectively.

[0016] In one embodiment, the high-temperature resistant substrate in step S11 is a quartz or corundum substrate, and the tubular furnace is a quartz tubular furnace or a corundum tubular furnace. For example, the selection of the high-temperature resistant substrate and tubular furnace in step S11 is related to the annealing temperature; if the annealing temperature is 1000 to 1150°C, a quartz material is selected, and if the annealing temperature is 1150 to 1350°C, a corundum material is selected.

[0017] In one embodiment, the solid carbon source is one or more selected from graphite paper, graphite powder, activated carbon, and carbon black.

[0018] In one embodiment, the produced carbon film is single-crystal graphite or graphene. In a preferred embodiment, the produced carbon film is single-crystal graphite, with its radial size being 1 to 10 cm and its longitudinal thickness being 0.1 to 50 μm.

[0019] In one embodiment, the orientations of the produced single-crystal graphite are consistent.

[0020] To more clearly explain the technical means of the embodiments of the present disclosure, the drawings related to the embodiments will be briefly described below. Obviously, the drawings described below only relate to some embodiments of the present disclosure and do not limit the present invention.

Brief Description of the Drawings

[0021] [Figure 1] It is a diagram showing the process of growing single-crystal graphite using single-crystal nickel foil according to the present disclosure. [Figure 2] It is an optical photograph (a) of the single-crystal nickel foil produced in Example 1 of the present disclosure and the measurement results of characteristics by electron backscatter diffraction (EBSD) (b). [Figure 3] It is a photograph of the single-crystal graphite produced in Example 4 of the present disclosure. [Figure 4] It is the electron backscatter diffraction (EBSD) patterns of highly oriented pyrolytic graphite (HOPG) and the single-crystal graphite produced in Example 4 of the present disclosure. (a), (b), and (c) are the EBSD patterns of highly oriented pyrolytic graphite in the x-direction, y-direction, and z-direction respectively, and (d), (e), and (f) are the EBSD patterns of the single-crystal graphite produced in Example 4 of the present disclosure in the x-direction, y-direction, and z-direction respectively.

Modes for Carrying Out the Invention

[0022] To further clarify the purpose, technical solutions, and advantages of the embodiments of this disclosure, the technical solutions of the embodiments of this disclosure will be described clearly and completely below with reference to the drawings of the embodiments of this disclosure. Clearly, the embodiments described are a part of the embodiments of this disclosure, but not all embodiments. Any other embodiments that a person skilled in the art could conceive without creative effort based on the embodiments of this disclosure described are all within the scope of the protection of the present invention.

[0023] The present invention can be implemented in other specific forms without departing from the fundamental attributes of the invention. It should be understood that, to the extent that they do not contradict each other, any and all embodiments of the present invention can be combined with the technical features of any or more other embodiments to obtain other embodiments. The present invention includes other embodiments obtained from such combinations.

[0024] All publications and patents referenced in this disclosure are incorporated into this disclosure by reference. Any uses or terms used in any publication or patent incorporated by reference shall be governed by the uses and terms of this disclosure if they conflict with the uses or terms used in this disclosure.

[0025] The section titles used herein are for the purpose of constructing the text and are not intended to be construed as limiting the subject matter.

[0026] Unless otherwise specified, all technical and scientific terms used herein have their common meanings in the art to which the subject matter of the patent is sought pertains. If a term has multiple definitions, the definition used herein shall prevail.

[0027] Similar words used in this disclosure, such as “include,” “contain,” or “incorporate,” are intended to mean that the element preceding the word covers the elements and their equivalents listed after the word, and do not exclude any elements not described. The terms “contain” or “include” as used herein may be open, semi-closed, or closed. In other words, the terms include “substantially consisting of” or “consisting of.”

[0028] Please understand that the singular form used in this disclosure (e.g., "kind 1") may include multiple forms unless otherwise specified.

[0029] The reagents and raw materials used in this disclosure are commercially available or can be manufactured by common manufacturing methods.

[0030] Unless otherwise specified, when disclosing or seeking protection for any type of range (e.g., thickness), it is intended that each reasonably covered numerical value, including any subranges covered by that range, be individually disclosed or sought protection for. For example, in this specification, the numerical range of thickness, for example, 1 to 200 micrometers, represents the thickness within that range, and it should be understood that 1 to 200 micrometers includes not only 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, ... 200 micrometers, but also the ranges of 1 to 5 micrometers and 1 to 10 micrometers. All numerical values ​​such as the amount of expressive material, reaction conditions, duration, and quantitative properties of the material described herein and in the claims should be understood to be modified in all cases by the term “about” unless otherwise specified in the embodiments or otherwise indicated. Any numerical range mentioned in this application is intended to include all subranges within that range and any combination of the range or each endpoint of the subrange.

[0031] In this application, a solid carbon source is a solid that provides elemental carbon with a carbon purity of 90% or more, such as carbon fiber, graphite paper, graphite powder, activated carbon, or carbon black. In one embodiment, the solid carbon source is one or more selected from graphite paper, graphite powder, activated carbon, and carbon black.

[0032] In this application, penetration growth means that carbon atoms from a solid carbon source enter from one surface of the foil, penetrate the foil, and grow in an arrangement on the other surface of the foil to form a carbon film.

[0033] In this application, the purity of the nickel foil or copper-nickel alloy foil raw material is usually 99.5% or higher. In one embodiment, the purity of the nickel foil or copper-nickel alloy foil raw material is 99.8% or higher. In a preferred embodiment, the purity of the nickel foil or copper-nickel alloy foil raw material is 99.9% or higher. In a more preferred embodiment, the purity of the nickel foil or copper-nickel alloy foil raw material is 99.99% or higher.

[0034] In this application, a single-crystal nickel foil means that the lattice orientation and arrangement within it are perfectly consistent, and that there are no grain boundary defects throughout the entire nickel foil.

[0035] In this application, single-crystal graphite means that the lattice orientation and arrangement within it are perfectly aligned, and that there are no grain boundary defects throughout the entire graphite.

[0036] This disclosure relates to a method for permeating and growing a carbon film, Step S1 provides a foil having a first surface and a second surface, selected from nickel foil and copper-nickel alloy foil. The present invention provides a method comprising step S2, which involves arranging the foil as a substrate relative to the solid carbon source such that the first surface of the foil is close to the solid carbon source and the second surface is away from the solid carbon source, and then heating the foil and the solid carbon source to permeate and grow a carbon film on the second surface of the foil.

[0037] In the growth method described herein, the foil absorbs carbon from a solid carbon source, utilizing solid-state diffusion transport to ultimately achieve penetration growth of the carbon film. Unlike conventional gas-phase deposition methods, this method achieves carbon film growth under conditions without carbon-containing gases (methane, ethylene, acetylene).

[0038] In one embodiment, the solid carbon source is one or more selected from graphite paper, graphite powder, activated carbon, and carbon black.

[0039] In step S1, the foil is selected from nickel foil and copper-nickel alloy foil, the nickel foil may be polycrystalline nickel foil or single-crystal nickel foil, and the copper-nickel alloy foil may be, for example, a foil in which the alloy composition of copper and nickel is 90 / 10 or 70 / 30. In a preferred embodiment, the foil is selected from single-crystal nickel foil.

[0040] In step S2, the foil and solid carbon source are heated to a temperature lower than the melting point of the foil, for example, 100-400°C lower. While we do not wish to be bound by any theory, it is thought that heating the foil and solid carbon source causes carbon atoms to be adsorbed onto the foil, resulting in the "dissolution" of carbon in the foil, and then, due to the diffusion of carbon by heat, carbon atoms precipitate and arrange on the other surface of the foil.

[0041] In one embodiment, the heating of the foil and solid carbon source in step S2 is performed in a tubular furnace.

[0042] In a preferred embodiment, the heating of the foil and solid carbon source in step S2 is carried out under a protective gas, which is one or more protective gases selected from argon, nitrogen, and hydrogen, for example, argon, nitrogen, hydrogen, argon and hydrogen, nitrogen and hydrogen, argon and nitrogen, or argon, nitrogen, and hydrogen. In a more preferred embodiment, the protective gas is a mixture of argon gas and hydrogen gas. In an even more preferred embodiment, the flow rates of argon gas and hydrogen gas in the mixture are, Ar: 100-1000 sccm and H2: 5-200 sccm, respectively.

[0043] In one embodiment, heating the foil and solid carbon source in step S2 includes raising the temperature to 900-1350°C within 60-120 minutes, and then holding at this temperature for 10 minutes to 50 hours. In a preferred embodiment, heating the foil and solid carbon source in step S2 is heating the nickel foil and solid carbon source, and includes raising the temperature to 1000-1350°C within 60-120 minutes, and then holding at this temperature for 10 minutes to 50 hours. The longer the holding time, the thicker the carbon film obtained. The thickness of the foil is typically 1-200 micrometers. In some embodiments, the foil thickness is 10 to 120 micrometers, for example 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, These are 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 123, 114, 115, 116, 117, 118, 119, and 120 micrometers.

[0044] In one embodiment, after the penetration growth in step S2 is completed, the atmosphere is maintained and the system is allowed to cool naturally to room temperature.

[0045] In a preferred embodiment, the foil in step S1 is a single-crystal nickel foil. As shown in Figure 1, a single-crystal nickel foil having a first surface and a second surface is provided, and the single-crystal nickel foil is placed as a substrate relative to the solid carbon source such that the first surface of the single-crystal nickel foil is close to the solid carbon source and the second surface is away from the solid carbon source, and finally, high-quality single-crystal graphite is grown on the second surface of the single-crystal nickel foil.

[0046] For the manufacturing and characterization of single-crystal nickel foil, refer to Non-Patent Document 1. For example, nickel foil (100 μm thick, 99.994%, manufactured by Alfa Aesar) is first oxidized in air at 150-650°C for 1-4 hours, then annealed in a reducing atmosphere at 1200°C and held for 3-6 hours. After heat annealing, the size is approximately 5 x 5 cm. 2 Single-crystal nickel foil is obtained. By repeating a typical annealing procedure, several high-index single-crystal nickel foils can be produced. The single-crystal nickel foil can be characterized by X-ray diffraction (XRD) and electron backscatter diffraction (EBSD).

[0047] In a preferred embodiment, a single-crystal nickel foil is provided in step S1. Step S11 involves placing polycrystalline nickel foil on a high-temperature resistant substrate and pre-oxidizing it at 150-650°C for 1-5 hours. Step S12 involves introducing an inert protective gas and further raising the temperature to 1000-1350°C within 60-120 minutes. Step S13 involves annealing the nickel foil by holding it at 1000-1350°C for 1-20 hours, The process includes step S14, which involves cooling to room temperature while maintaining the same atmospheric conditions after the annealing time has finished, in order to obtain a single-crystal nickel foil.

[0048] In one embodiment, steps S11 to S14 are performed in a tubular furnace.

[0049] The pre-oxidation in step S11 can be carried out in air or an oxygen-containing atmosphere.

[0050] In a preferred embodiment, the inert protective gas in step S12 is a mixture of nitrogen and H2, a mixture of Ar and H2, or a mixture of nitrogen, Ar, and H2. In a more preferred embodiment, the inert protective gas in step S12 is a mixture of Ar and H2. In an even more preferred embodiment, the inert protective gas in step S12 is a mixture of Ar and H2, with a volume ratio of Ar to H2 of Ar:H2 = 0.5:1 to 200:1. In an even more preferred embodiment, the flow rates of Ar gas and H2 gas in step S12 are 100 to 1000 sccm and 5 to 200 sccm, respectively.

[0051] The high-temperature resistant substrate in step S11 is either a quartz substrate or a corundum substrate, and the tubular furnace in steps S11 to S14 is either a quartz tubular furnace or a corundum tubular furnace. For example, the selection of the high-temperature resistant substrate and tubular furnace in step S11 is related to the annealing temperature; if the annealing temperature is 1000 to 1150°C, a quartz material is selected, and if the annealing temperature is 1150 to 1350°C, a corundum material is selected.

[0052] In some embodiments, the radial size of the single-crystal graphite produced is 1 to 10 cm, and the longitudinal thickness is 0.01 to 50 μm.

[0053] In one embodiment, the disclosure, Step (1) involves placing polycrystalline nickel foil on a high-temperature resistant substrate and placing it in a tubular furnace, where it is pre-oxidized at 150-600°C for 1-5 hours. Step (2) involves introducing an inert protective gas into the tubular furnace and further raising the temperature to 1000-1350°C within 60-120 minutes, Step (3) involves annealing the nickel foil by holding it at 1000-1350°C for 1-20 hours, The present invention provides a method for producing single-crystal nickel foil, which includes the step (4) of cooling to room temperature while maintaining the same atmospheric conditions after the annealing time is completed to obtain single-crystal nickel foil.

[0054] The inert protective gas is a mixture of Ar and H2, with a volume ratio of Ar:H2 = 10:1 to 100:1, and flow rates of Ar gas and H2 gas are 100 to 1000 sccm and 5 to 200 sccm, respectively.

[0055] In the method described herein, pre-oxidation treatment induces abnormal grain growth in polycrystalline nickel foil through interfacial and surface energies, ultimately yielding a large single-crystal nickel foil. The size of the single-crystal nickel foil produced by the above method is related to the size after high-temperature annealing, and this method can be widely applied not only to nickel but also to other metals.

[0056] In one embodiment, the present disclosure provides a method for growing single-crystal graphite using solid transport, Step S1 provides a single-crystal nickel foil having a first surface and a second surface, Step S2 includes arranging the single-crystal nickel foil as a substrate relative to the solid carbon source such that a first surface of the single-crystal nickel foil is close to the solid carbon source and a second surface is away from the solid carbon source, and finally growing high-quality single-crystal graphite on the second surface of the single-crystal nickel foil, Step S2 specifically means, Step S21 involves placing a single-crystal nickel foil on a solid carbon source and then placing it together in a tubular furnace. Step S22 involves introducing a mixed gas of argon and hydrogen into a tubular furnace and further raising the temperature to 1000-1350°C within 60-120 minutes, wherein the flow rates of the argon and hydrogen gases in the mixed gas are Ar: 100-1000 sccm and H2: 5-200 sccm, respectively. Step S23 involves raising the temperature to 1000-1350°C, then holding it for 10 minutes to 50 hours to allow graphite to penetrate and grow. The present invention provides a method comprising step S24, after growth is complete, allowing the atmosphere to be maintained while the graphite is allowed to cool naturally to room temperature to obtain single-crystal graphite.

[0057] This disclosure describes a method for obtaining single-crystal graphite by placing a single-crystal nickel foil, manufactured by high-temperature annealing, onto a solid carbon source, allowing carbon to be absorbed at high temperatures, and driving a chemical potential gradient. The method described in this disclosure solves the problem of difficulty in manufacturing single-crystal graphite, employing a non-vapor deposition method and obtaining large single-crystal graphite with a length and width of 1 to 10 cm and a thickness of 0.1 to 50 μm through solid-state diffusion transport of carbon.

[0058] In one embodiment, the radial size of the graphite paper is larger than the radial size of the nickel foil, and the radial size of the manufactured single-crystal graphite is approximately the same as the radial size of the single-crystal nickel foil. The radial direction is a planar direction perpendicular to the thickness direction of the graphite paper, nickel foil, or graphite. The ratio of the radial size of the graphite paper to the radial size of the nickel foil may be from 2:1 to 50:1.

[0059] The foil substrate beneath the carbon film of the present invention can be removed by conventional methods. For example, a fresh iron(III) chloride solution is prepared, the prepared carbon film sample is placed in the solution, and left to stand for 1 hour to 5 days. The foil is etched by the reaction of iron(III) chloride with nickel or copper-nickel alloy, and the resulting sample is washed multiple times in deionized water to finally obtain a carbon film sample after the transition.

[0060] A graphene thin film can be obtained from the carbon film relating to this disclosure by a mechanical exfoliation method. Specifically, an adhesive tape is attached to the manufactured single-crystal graphite, then peeled off, and this is attached to a substrate of any choice. After appropriate heating, the adhesive tape is peeled off, leaving a graphene sample on the substrate. Because the quality of the manufactured single-crystal graphite is very high, the sample obtained by exfoliation is of very pure quality and matches intrinsic graphene.

[0061] This disclosure has one or more of the following advantages:

[0062] 1. The method relating to this disclosure is a method for continuous growth of a carbon film, and the carbon film includes, but is not limited to, single-crystal graphite.

[0063] 2. This disclosure enables the production of large carbon films using commercially available nickel foil, copper-nickel alloy foil, and several types of solid carbon sources as raw materials, without complex surface treatment of the foil or carbon source, and without introducing a carbon-containing atmosphere (methane, ethylene, acetylene, etc.), thereby significantly reducing manufacturing costs.

[0064] 3. This disclosure provides a method for manufacturing single-crystal graphite, the manufactured single-crystal graphite being large in size, having few defects, excellent performance, and possessing potential for widespread applications.

[0065] 4. The method described herein is simple, effective, and low-cost, and is useful for the practical application and industrial production of large single-crystal graphite.

[0066] The present invention will be described in more detail below with reference to specific examples, but the present invention is not limited to the following examples.

[0067] The starting materials for the examples are commercially available and / or can be manufactured by various methods well known to those skilled in the art of materials.

[0068] Examples 1-3: Manufacturing of single-crystal nickel foil

[0069] Example 1 Example 1 involves manufacturing a single-crystal nickel foil. Step (1) involves placing a polycrystalline nickel foil (manufactured by Alfa Aesar, 100 μm thick, 99.99% purity) on a corundum high-temperature resistant substrate and placing it in a tubular furnace (manufactured by Tianjin Qiai Heng Electric Heating Technology Co., Ltd.) and pre-oxidizing it at 150°C for 2 hours, Step (2) involves introducing an inert protective gas (Ar gas: 500 sccm, H2: 50 sccm) into a tubular furnace and further raising the temperature to 1300°C within 100 minutes, Step (3) involves holding the nickel foil at 1300°C for 8 hours to perform annealing treatment, The process includes (4) a step in which, after the annealing time is completed, the temperature is reduced while maintaining the same atmospheric conditions until it cools to room temperature.

[0070] Figure 2 shows the optical photograph and electron beam backscatter diffraction (EBSD) characteristic measurement results of the single-crystal nickel foil produced in Example 1, with a nickel size of 4 × 3 cm. 2 The EBSD results indicate that it is a single crystal with a crystal plane index of (520). The electron backscatter diffraction measurements in this disclosure were performed using a PHI 710 Scanning Auger Nanoprobe system, and the test procedure was carried out according to standard procedures.

[0071] Example 2 Example 2 involves manufacturing a single-crystal nickel foil. Step (1) involves placing a polycrystalline nickel foil on a quartz high-temperature resistant substrate and placing it in a tubular furnace, and pre-oxidizing it at 600°C for 1 hour. Step (2) involves introducing an inert protective gas (Ar gas: 1000 sccm, H2: 10 sccm) into a tubular furnace and further raising the temperature to 1000°C within 60 minutes, Step (3) involves holding the nickel foil at 1000°C for 20 hours to perform annealing treatment, The process includes (4) a step in which, after the annealing time is completed, the temperature is reduced while maintaining the same atmospheric conditions until it cools to room temperature.

[0072] Example 3 In Example 3, single-crystal nickel foil was manufactured, Step (1) involves placing polycrystalline nickel foil on a corundum high-temperature resistant substrate and placing it in a tubular furnace, where it is pre-oxidized at 150°C for 5 hours. Step (2) involves introducing an inert protective gas (Ar gas: 700 sccm, H2: 50 sccm) into a tubular furnace and further raising the temperature to 1350°C within 120 minutes, Step (3) involves holding the nickel foil at 1350°C for 1 hour to perform annealing treatment, The process includes (4) a step in which, after the annealing time is completed, the temperature is reduced while maintaining the same atmospheric conditions until it cools to room temperature.

[0073] Similar to Example 1, the single-crystal nickel foils produced in Examples 2 and 3 were also confirmed by electron backscatter diffraction.

[0074] In Examples 4-10, single-crystal graphite is manufactured using the single-crystal nickel foil obtained in Examples 1-3.

[0075] Example 4 In Example 4, single-crystal graphite was grown using single-crystal nickel foil. Step (1) involves placing the single-crystal nickel foil obtained in Example 1 onto graphite paper (Beijing Jinglong Tent Technology Co., Ltd., 100 μm thick, 99.9% purity), and then placing them together in a tubular furnace. Step (2) involves introducing a mixed gas of argon and hydrogen (Ar: 500 sccm, H2: 10 sccm) into a tubular furnace and further raising the temperature to 1300°C within 120 minutes. Step (3) involves raising the temperature to 1300°C and then maintaining it for 10 hours to allow graphite to penetrate and grow, The process includes (4) allowing the system to naturally cool to room temperature while maintaining the atmosphere after growth is complete, removing the sample, and obtaining single-crystal graphite.

[0076] Figure 3 is a photograph of single-crystal graphite produced in Example 4 of this disclosure, the size of the produced graphite being 4 × 3 cm.2 That is the case.

[0077] Figure 4 shows the electron backscatter diffraction (EBSD) patterns of highly oriented pyrolysis graphite (HOPG) and single-crystal graphite produced in Example 4 of this disclosure. (a), (b), and (c) are the EBSD patterns of the highly oriented pyrolysis graphite in the x, y, and z directions, respectively. HOPG is a single crystal in the z direction, but the crystal planes rotate in the in-plane direction (x, y directions), indicating poor single-crystal properties. (d), (e), and (f) are the EBSD patterns of the single-crystal graphite produced in Example 4 of this disclosure in the x, y, and z directions, respectively. The graphite produced in this invention is a single crystal in the z direction, and there is no rotation of the crystal planes in the in-plane direction (x, y directions), indicating good single-crystal properties. The highly oriented pyrolysis graphite is sourced from NT-MDT and has a purity of ZYA grade.

[0078] Example 5 In Example 5, single-crystal graphite was grown using single-crystal nickel foil. Step (1) involves placing the single-crystal nickel foil obtained in Example 1 onto graphite powder (Alfa Aesar, 99%), and then placing them together in a tubular furnace. Step (2) involves introducing a mixed gas of argon and hydrogen (Ar: 500 sccm, H2: 10 sccm) into a tubular furnace and further raising the temperature to 1300°C within 120 minutes. Step (3) involves raising the temperature to 1300°C and then maintaining it for 10 hours to allow graphite to penetrate and grow, The process includes (4) allowing the system to naturally cool to room temperature while maintaining the atmosphere after growth is complete, removing the sample, and obtaining single-crystal graphite.

[0079] Example 6 In Example 6, single-crystal graphite was grown using single-crystal nickel foil. Step (1) involves placing the single-crystal nickel foil obtained in Example 2 onto activated carbon (Luoen Chemicals Co.), and then placing them together in a tubular furnace. Step (2) involves introducing a mixed gas of argon and hydrogen (Ar: 500 sccm, H2: 10 sccm) into a tubular furnace and further raising the temperature to 1300°C within 120 minutes. Step (3) involves raising the temperature to 1300°C and then maintaining it for 10 hours to allow graphite to penetrate and grow, The process includes (4) allowing the system to naturally cool to room temperature while maintaining the atmosphere after growth is complete, removing the sample, and obtaining single-crystal graphite.

[0080] Example 7 In Example 7, single-crystal graphite was grown using single-crystal nickel foil. Step (1) involves placing the single-crystal nickel foil obtained in Example 2 into carbon black (Luoen Chemicals Co.), and then placing them together in a tubular furnace. Step (2) involves introducing a mixed gas of argon and hydrogen (Ar: 500 sccm, H2: 10 sccm) into a tubular furnace and further raising the temperature to 1300°C within 120 minutes. Step (3) involves raising the temperature to 1300°C and then maintaining it for 10 hours to allow graphite to penetrate and grow, The process includes (4) allowing the system to naturally cool to room temperature while maintaining the atmosphere after growth is complete, removing the sample, and obtaining single-crystal graphite.

[0081] Example 8 In Example 8, single-crystal graphite was grown using single-crystal nickel foil. Step (1) involves placing the single-crystal nickel foil obtained in Example 3 onto graphite paper (Beijing Jinglong Tent Technology Co., Ltd., 100 μm thick, 99.9% purity), and then placing them together in a tubular furnace. Step (2) involves introducing a mixed gas of argon and hydrogen (Ar: 500 sccm, H2: 5 sccm) into a tubular furnace and further raising the temperature to 1350°C within 120 minutes. Step (3) involves raising the temperature to 1350°C and then holding it for 10 minutes to allow the graphite to penetrate and grow, The process includes (4) allowing the system to naturally cool to room temperature while maintaining the atmosphere after growth is complete, removing the sample, and obtaining single-crystal graphite.

[0082] Example 9 In Example 9, single-crystal graphite was grown using single-crystal nickel foil. Step (1) involves placing the single-crystal nickel foil obtained in Example 3 onto graphite paper (Beijing Jinglong Tent Technology Co., Ltd., 100 μm thick, 99.9% purity), and then placing them together in a tubular furnace. Step (2) involves introducing a mixed gas of argon and hydrogen (Ar: 1000 sccm, H2: 10 sccm) into a tubular furnace and further raising the temperature to 1000°C within 60 minutes. Step (3) involves raising the temperature to 1000°C and then maintaining it for 50 hours to allow graphite to penetrate and grow, The process includes (4) allowing the system to naturally cool to room temperature while maintaining the atmosphere after growth is complete, removing the sample, and obtaining single-crystal graphite.

[0083] Example 10 In Example 10, single-crystal graphite was grown using single-crystal nickel foil. Step (1) involves placing the single-crystal nickel foil obtained in Example 3 onto graphite paper (Beijing Jinglong Tent Technology Co., Ltd., 100 μm thick, 99.9% purity), and then placing them together in a tubular furnace. Step (2) involves introducing a mixed gas of argon and hydrogen (Ar: 500 sccm, H2: 100 sccm) into a tubular furnace and further raising the temperature to 1300°C within 120 minutes. Step (3) involves raising the temperature to 1300°C and then holding it for one hour to allow the graphite to penetrate and grow, The process includes (4) allowing the system to naturally cool to room temperature while maintaining the atmosphere after growth is complete, removing the sample, and obtaining single-crystal graphite.

[0084] Similar to Example 4, the single-crystal graphite produced in Examples 5-10 was also confirmed by electron backscatter diffraction.

[0085] While embodiments for carrying out the present invention have been described in detail, those skilled in the art will understand that various modifications and changes can be made to the details based on all the previously disclosed teachings, and that any such changes will fall within the scope of protection of the present invention. The scope of protection of the present invention is limited by its claims.

Claims

1. A method for growing a carbon film by penetration, Step S1 provides a single-crystal nickel foil having a first surface and a second surface, Step S2 includes: arranging the foil as a substrate relative to the solid carbon source such that the first surface of the foil is close to the solid carbon source and the second surface is away from the solid carbon source; and then heating the foil and the solid carbon source to permeate and grow a carbon film on the second surface of the foil. The aforementioned penetration growth method involves carbon atoms from the solid carbon source entering from one surface of the foil, penetrating the foil, and growing in an arrangement on the other surface of the foil to form the carbon film.

2. The method according to claim 1, wherein the crystal plane index of the single-crystal nickel foil is (520).

3. The method according to claim 1 or 2, wherein the heating of the foil and the solid carbon source is carried out in a tubular furnace.

4. The method according to claim 1 or 2, wherein the foil and the solid carbon source are heated under one or more protective gases selected from argon, nitrogen, and hydrogen.

5. The method according to claim 4, wherein the protective gas is a mixed gas of argon gas and hydrogen gas.

6. The flow rates of argon gas and hydrogen gas in the aforementioned mixed gas are, Ar: 100 sccm to 1000 sccm, H ２ The method according to claim 5, wherein the length is between 5 sccm and 200 sccm.

7. The method according to claim 1 or 2, wherein heating the foil and the solid carbon source includes raising the temperature to 900°C to 1350°C within 60 to 120 minutes, and then holding it at that temperature for 10 minutes to 50 hours.

8. The method according to claim 1 or 2, wherein after the growth of the carbon film is completed, the atmosphere is maintained and the body is allowed to cool naturally to room temperature.

9. Step S1 is, Step S11 involves placing polycrystalline nickel foil on a high-temperature resistant substrate, placing it in a tubular furnace, and pre-oxidizing it at 150°C to 650°C for 1 to 5 hours. Step S12 involves introducing an inert protective gas into the tubular furnace and further raising the temperature to 1000°C to 1350°C within 60 to 120 minutes. Step S13 involves annealing the nickel foil by holding it at 1000°C to 1350°C for 1 to 20 hours, The method according to claim 1 or 2, comprising step S14, after annealing is completed, cooling to room temperature while maintaining atmospheric conditions to obtain a single-crystal nickel foil.

10. The method according to claim 9, wherein steps S11 to S14 are performed in a tubular furnace.

11. The inert protective gas in step S12 is Ar and H ２ It is a mixed gas of Ar and H ２ The volume ratio is Ar:H ２ The method according to claim 9, wherein the ratio is 0.5:1 to 200:

1.

12. In step S12, Ar gas and H ２ The gas flow rates are as follows: Ar: 100 sccm to 1000 sccm, H ２ The method according to claim 11, wherein the length is between 5 sccm and 200 sccm.

13. The method according to claim 9, wherein the high-temperature resistant substrate in step S11 is a quartz or corundum substrate, and the tubular furnace is a quartz tubular furnace or a corundum tubular furnace.

14. The method according to claim 13, wherein the selection of the high-temperature resistant substrate and tubular furnace in step S11 is related to the annealing temperature, and when the annealing temperature is 1000°C to 1150°C, a quartz material is selected, and when the annealing temperature is 1150°C to 1350°C, a corundum material is selected.

15. The method according to claim 1 or 2, wherein the solid carbon source is one or more selected from graphite paper, graphite powder, activated carbon, and carbon black.

16. The method according to claim 1, wherein the carbon film produced is single-crystal graphite or graphene.

17. The method according to claim 16, wherein the carbon film produced is single-crystal graphite, the radial size of the single-crystal graphite is 1 cm to 10 cm, and the longitudinal thickness is 0.1 μm to 50 μm.

18. The method according to claim 17, wherein the internal crystal lattice orientation of the manufactured single-crystal graphite is consistent.

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