CN112694085A - Graphene composite membrane and preparation method and application thereof - Google Patents

Graphene composite membrane and preparation method and application thereof Download PDF

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CN112694085A
CN112694085A CN202011603189.5A CN202011603189A CN112694085A CN 112694085 A CN112694085 A CN 112694085A CN 202011603189 A CN202011603189 A CN 202011603189A CN 112694085 A CN112694085 A CN 112694085A
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graphene
film
graphene oxide
composite membrane
graphene composite
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刘科海
张超
陈益
王恩哥
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Songshan Lake Materials Laboratory
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Songshan Lake Materials Laboratory
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/186—Preparation by chemical vapour deposition [CVD]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R31/00—Apparatus or processes specially adapted for the manufacture of transducers or diaphragms therefor
    • H04R31/003—Apparatus or processes specially adapted for the manufacture of transducers or diaphragms therefor for diaphragms or their outer suspension
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R7/00—Diaphragms for electromechanical transducers; Cones
    • H04R7/02—Diaphragms for electromechanical transducers; Cones characterised by the construction
    • H04R7/04—Plane diaphragms
    • H04R7/06—Plane diaphragms comprising a plurality of sections or layers
    • H04R7/10—Plane diaphragms comprising a plurality of sections or layers comprising superposed layers in contact
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/26—Mechanical properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/32—Size or surface area
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R2307/00—Details of diaphragms or cones for electromechanical transducers, their suspension or their manufacture covered by H04R7/00 or H04R31/003, not provided for in any of its subgroups
    • H04R2307/023—Diaphragms comprising ceramic-like materials, e.g. pure ceramic, glass, boride, nitride, carbide, mica and carbon materials

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Abstract

The invention discloses a graphene composite membrane and a preparation method and application thereof, and belongs to the technical field of graphene. The graphene composite membrane is obtained by compounding a reduced graphene oxide membrane and a graphene membrane arranged on at least one side surface of the reduced graphene oxide membrane. The graphene composite membrane has high mechanical property and electrical property, is easy to prepare, low in cost, high in quality, smooth and free of wrinkles. The preparation method is simple, easy to operate and suitable for industrial production. The graphene composite membrane can be used in an acoustic diaphragm, a new energy battery, a water purification diaphragm or an NEM electromechanical system. The acoustic diaphragm or the battery or the water purification diaphragm or the NEM electromechanical system containing the graphene composite membrane has high application value.

Description

Graphene composite membrane and preparation method and application thereof
Technical Field
The invention relates to the technical field of graphene, and particularly relates to a graphene composite membrane and a preparation method and application thereof.
Background
High-quality graphene has excellent mechanical properties, and multilayer graphene has good advantages in terms of acoustic diaphragms, but the preparation of the high-quality multilayer graphene is difficult. In addition, in order to grow a plurality of layers of graphene with a certain thickness, the growth period of the corresponding method is long, the price is high, and the plurality of layers of graphene can generate wrinkles.
In view of this, the invention is particularly proposed.
Disclosure of Invention
An object of the present invention includes providing a graphene composite film to solve the above technical problems.
Another object of the present invention is to provide a method for preparing the graphene composite film.
A further object of the present invention is to provide a use of the graphene composite membrane described above, for example for the preparation of an acoustic diaphragm or a battery or a water purification diaphragm or a NEM electromechanical system.
The fourth object of the present invention is to provide an acoustic diaphragm containing the graphene composite film.
The fifth object of the present invention is to provide a battery comprising the graphene composite film.
The sixth object of the present invention is to provide a water purification membrane comprising the graphene composite membrane.
The seventh object of the present invention is to provide a NEM electromechanical system including the graphene composite film.
The application can be realized as follows:
in a first aspect, the present application provides a graphene composite film, which is obtained by compositing a reduced graphene oxide film and a graphene film disposed on at least one side surface of the reduced graphene oxide film.
In an alternative embodiment, the graphene membrane is composed of at least one graphene layer, each graphene layer having a thickness of 0.3-0.5 nm.
In an alternative embodiment, the reduced graphene oxide film has a thickness of 10 to 1000 nm.
In an alternative embodiment, the reduced graphene oxide membrane has a diameter of 1-100 cm.
In an alternative embodiment, the fracture strength of the graphene composite film is 500-650 MPa.
In a second aspect, the present application provides a method for preparing a graphene composite film according to any one of the previous embodiments, wherein a graphene film is disposed on at least one surface of a reduced graphene oxide film.
In an alternative embodiment, a graphene film is placed on at least one side surface of the reduced graphene oxide film, followed by heating to combine the reduced graphene oxide film and the graphene film.
In an alternative embodiment, the graphene film is prepared by: and depositing the graphene layer on the surface of the preset substrate by adopting a vapor deposition mode.
In an alternative embodiment, the gas used in the vapor deposition process comprises a mixed gas consisting of methane and an inert gas, wherein the content of methane in the mixed gas is 180-220ppm, the flow rate of the mixed gas is 1.8-2.2sccm, and the flow rate of hydrogen is 18-22 sccm.
In an alternative embodiment, the time for vapor deposition is 3.5 to 4.5 hours.
In an alternative embodiment, before depositing the graphene layer, annealing the predetermined substrate is further included.
In an alternative embodiment, the annealing process is performed by heating to 1100 ℃ under the conditions of an inert gas flow of 450-550sccm and a hydrogen flow of 80-120 sccm.
In an alternative embodiment, the reduced graphene oxide is prepared by: and spin-coating the dispersion liquid of the graphene oxide, and reducing by using a reducing agent.
In an alternative embodiment, the concentration of graphene oxide in the dispersion is 1-10 wt%.
In an alternative embodiment, the spin speed is 500-.
In an alternative embodiment, the reducing agent comprises at least one of hydroiodic acid, hydrazine hydrate, and sodium citrate.
In an alternative embodiment, after the reducing the graphene oxide film and the graphene film are combined, removing the predetermined substrate is further included.
In an optional embodiment, the predetermined substrate is removed by an etching solution, and the etching solution includes ammonium persulfate or ferric chloride.
In a third aspect, the present application provides the use of a graphene composite membrane according to any one of the preceding embodiments, for example in an acoustic diaphragm or a battery or a water purification diaphragm or a NEM electromechanical system.
In a fourth aspect, the present application provides an acoustic diaphragm comprising a graphene composite membrane according to any one of the preceding embodiments.
In a fifth aspect, the present application provides an acoustic diaphragm comprising the graphene composite membrane according to any one of the previous embodiments.
In a sixth aspect, the present application provides a water purification membrane comprising the graphene composite membrane according to any one of the preceding embodiments.
In a seventh aspect, the present application provides a NEM electromechanical system comprising a graphene composite film according to any one of the preceding embodiments.
The beneficial effect of this application includes:
according to the graphene composite film prepared by compounding the reduced graphene oxide and the graphene, under the condition of the same thickness, the reduced graphene oxide replaces the graphene with partial thickness, and the graphene product prepared from the graphene can have better mechanical property and electrical property. The preparation method is simple, easy to operate and suitable for industrial production. The graphene composite membrane can be used in an acoustic diaphragm, a new energy battery, a water purification diaphragm or an NEM electromechanical system. The acoustic diaphragm or the battery or the water purification diaphragm or the NEM electromechanical system containing the graphene composite membrane has high application value.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic structural view of a rGO/Gr composite membrane provided herein;
FIG. 2 is a schematic structural view of a Gr/rGO/Gr composite membrane provided herein.
Icon: 10-a graphene film; 20-reduction of graphene oxide films.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The graphene composite film provided by the present application, and a preparation method and an application thereof are specifically described below.
At present, although high-quality graphene has excellent mechanical properties, the preparation of high-quality multilayer graphene is difficult. Especially, when the CVD method is used, in order to grow a plurality of layers of graphene with a certain thickness, the method requires a long growth period and is expensive, and the multilayer graphene also has wrinkles.
In view of this, the inventor creatively proposes that the graphene composite film is prepared by compounding reduced graphene oxide and graphene, and under the condition of the same thickness, the reduced graphene oxide replaces part of the graphene with the same thickness, so that a graphene product prepared from the graphene completely has better mechanical property and electrical property, and the reduced graphene oxide is low in cost and easy to prepare.
Specifically, with reference to fig. 1 and 2, the present application provides a graphene composite film, which is obtained by compounding a reduced graphene oxide film 20 and a graphene film 10 disposed on at least one side surface of the reduced graphene oxide film 20.
Referring to fig. 1, one side surface of a reduced graphene oxide (rGO) film may be composited with a graphene (Gr) film to form an rGO/Gr composite film. Referring to fig. 2, both side surfaces of the reduced graphene oxide film 20 may be composited with the graphene film 10, under which condition, the graphene film 10 on one side surface of the reduced graphene oxide film 20 is referred to as a first graphene film, and the graphene film 10 on the other side surface is referred to as a second graphene film, so as to form a Gr/rGO/Gr composite film.
In alternative embodiments, the graphene membrane 10 is composed of at least one graphene layer, and each graphene layer has a thickness of 0.3-0.5nm, such as 0.3nm, 0.35nm, 0.4nm, 0.45nm, or 0.5 nm.
When the number of graphene layers is greater than or equal to 5, the graphene layers can be directly grown to a target thickness and then compounded on the rGO thin film by using metal Ni as a substrate. When the number of layers is less than 5, the metal Cu can be used as a substrate to be compounded to the rGO film, and if a thicker graphene layer is needed, the metal Cu can be repeatedly copied for preparation until the target thickness is assembled.
Preferably, the number of graphene layers is preferably no more than 10, i.e. the thickness of the graphene film 10 is no more than 5 nm. The graphene film 10 at this thickness is relatively easy to obtain. Beyond 10 layers, especially 100 layers, the preparation of graphene film 10 requires more severe conditions.
In the present application, the reduced graphene oxide film 20 has a thickness of 10 to 1000nm, such as 10nm, 50nm, 100nm, 200nm, 400nm, 500nm, 800nm, or 1000 nm. The reduced graphene oxide film 20 is also composed of a plurality of pieces of reduced graphene oxide.
In alternative embodiments, the reduced graphene oxide membrane 20 may have a diameter of 1-100cm, such as 1cm, 5cm, 10cm, 20cm, 50cm, 80cm, or 100cm, etc.
In an alternative embodiment, the breaking strength of the graphene composite film provided herein may be, but is not limited to, 500-710MPa, such as 500MPa, 550MPa, 600MPa, 640MPa, or 710MPa, etc.
In summary, the graphene composite film prepared by compounding graphene and reduced graphene oxide provided by the invention can overcome the disadvantages of long growth period, high price and poor mechanical property of the reduced graphene oxide on one hand, and can fully exert the advantages of excellent mechanical property of the CVD graphene and easy preparation and low cost of the reduced graphene oxide on the other hand, so as to obtain the ultrathin, ultra-light and easily-driven composite nano film.
Moreover, the mechanical property and the electrical property of the graphene composite membrane obtained by compounding are obviously improved compared with rGO, for example: the strength of the rGO is 100-500MPa, and the strength of the graphene composite membrane can be higher than that of the rGO; the sheet resistance of rGO is 10-100k omega/sq, and the sheet resistance of the graphene composite membrane is less than that of rGO. And the existing CVD multilayer graphene has folds, which can affect the performance of the CVD multilayer graphene, and the compounded graphene composite membrane is very flat and has no folds due to the existence of the rGO supporting layer.
In addition, the present application provides a method for preparing the graphene composite film according to any one of the above embodiments, in which the graphene film 10 is disposed on at least one surface of the reduced graphene oxide film 20.
In an alternative embodiment, the graphene film 10 is placed on at least one surface of the reduced graphene oxide film 20, followed by air-drying and heating to combine the reduced graphene oxide film 20 and the graphene film 10. This process is mainly coupled by pi-pi bonds and the action of van der waals forces.
The heating temperature may, by reference, be 75-85 deg.C, such as 75 deg.C, 80 deg.C or 85 deg.C.
In alternative embodiments, the graphene film 10 is made by: and depositing the graphene layer on the surface of the preset substrate by adopting a vapor deposition mode. The predetermined substrate may be a Cu substrate or a Ni substrate.
In an alternative embodiment, the gas used in the vapor deposition process comprises a mixture of methane and an inert gas, and hydrogen. Wherein the inert volume is preferably argon.
The content of methane in the mixed gas may be, for example, 180-220ppm, such as 180ppm, 190ppm, 200ppm, 210ppm or 220 ppm. The flow rate of the mixed gas can be 1.8-2.2sccm, such as 1.8sccm, 1.9sccm, 2sccm, 2.1sccm, or 2.2 sccm. The flow rate of the hydrogen gas can be 18-22sccm, such as 18sccm, 19sccm, 20sccm, 21sccm, or 22 sccm.
In alternative embodiments, the vapor deposition time may be 3.5 to 4.5 hours, such as 3.5 hours, 4 hours, or 4.5 hours, etc. The pressure during deposition is atmospheric, i.e. one atmosphere or about 1X 105Pa。
It should be noted that, the process conditions of vapor deposition and the like not mentioned in the present application can refer to the prior art, and are not described in detail herein.
In a preferred embodiment, before depositing the graphene layer, annealing the predetermined substrate is further included.
For reference, the annealing process is performed by heating to 900-1100 deg.C (e.g., 900 deg.C, 1000 deg.C or 1100 deg.C) under the conditions of inert gas (e.g., argon) flow rate of 450-550sccm (e.g., 450sccm, 500sccm or 550 sccm) and hydrogen flow rate of 80-120sccm (e.g., 80-120sccm, 100sccm or 120 sccm).
In alternative embodiments, reduced graphene oxide may be prepared by: and spin-coating the dispersion liquid of the graphene oxide, and reducing by using a reducing agent. Spin coating can be performed using a spin coater.
In reference, the concentration of graphene oxide in the dispersion may be 1-10 wt%, such as 1 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, or 10 wt%.
The spin coating speed can be 500-3000r/min, such as 500r/min, 1000r/min, 1400r/min, 1500r/min, 2000r/min, 2500r/min, 3000r/min, etc.
In alternative embodiments, the reducing agent comprises hydroiodic acid and may also comprise other reducing substances, such as hydrazine hydrate and/or sodium citrate, and the like.
Further, after the graphene oxide film 20 and the graphene film 10 are combined, removing the predetermined substrate is further included.
In an alternative embodiment, the predetermined substrate may be removed by an etching liquid. For reference, the etching liquid may include ammonium persulfate or ferric chloride.
Specifically, the preparation process of the graphene composite membrane can be summarized as follows:
(I), rGO/Gr composite membrane
Growing a graphene film 10(Gr film) composed of a single layer or a plurality of graphene layers on a substrate;
coating a graphene oxide dispersion liquid (GO dispersion liquid) on the surface of the graphene film 10 on the side away from the substrate to form a graphene oxide film 10 with a certain thickness, and then reducing the graphene oxide film 10 to form a reduced graphene oxide film 20(rGO film) with a certain thickness;
heating the Gr film and the rGO film to combine the contact surfaces of the Gr film and the rGO film;
and removing the substrate by using an etching method to obtain the Gr/rGO composite membrane.
(II) Gr/rGO/Gr composite membrane
Growing a graphene film 10(Gr film) composed of a single layer or a plurality of graphene layers on a substrate;
coating a graphene oxide dispersion liquid (GO dispersion liquid) on the surface of the graphene film 10 on the side away from the substrate to form a graphene oxide film 10 with a certain thickness, and then reducing the graphene oxide film 10 to form a reduced graphene oxide film 20(rGO film) with a certain thickness;
heating the Gr film and the rGO film to combine the contact surfaces of the Gr film and the rGO film, and removing the substrate to form a Gr/rGO composite film;
transferring the Gr/rGO composite membrane to the surface of the other Gr membrane obtained by the same method, which is away from the substrate side;
heating the Gr film and the rGO film to combine the contact surfaces of all the Gr film and the rGO film;
and removing the substrate by using an etching method to obtain a Gr/rGO/Gr composite membrane.
In addition, the application also provides the application of the graphene composite membrane, for example, the graphene composite membrane is used for preparing an acoustic diaphragm (including an acoustic diaphragm sensor) or a battery (such as a new energy battery) or a water purification diaphragm or a NEM (nanoelectromechanical systems) electromechanical system. Correspondingly, the application also provides an acoustic diaphragm or a battery or a water purification diaphragm or an NEM electromechanical system comprising the graphene composite membrane.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
Preparing the graphene film 10: taking Ni as a substrate, and preparing a multilayer graphene film with the thickness of 3nm by a CVD method, wherein the size is 10cm in diameter.
The preparation process conditions comprise: ni foil at Ar gas flow rate of 500sccm, H2Heating to 1000 ℃ under the condition of the flow rate of 100sccm for annealing, and after annealing lasts for 10 hours, starting to introduce CH4Mixed gas of Ar, CH4The content of the mixed gas was 200ppm, the flow rate of the mixed gas was 2sccm, and H was adjusted2The flow rate is 20sccm, the flow rate of Ar gas is kept unchanged, the working pressure is normal pressure (one atmosphere), and the growth time is 4 h.
Preparation of reduced graphene oxide film 20: spin-coating 6 wt% of GO dispersion liquid by a spin coater at 1500r/min, reducing by hydroiodic acid, and preparing a rGO nano film with the diameter of 10cm and the thickness of 30 nm.
Preparing a Gr/rGO composite membrane: the rGO nano-film was transferred to a multilayer graphene film with a metal substrate and heated at 80 ℃.
And then, etching by using 1mol/L etching solution (ammonium persulfate) to remove the metal substrate to obtain a Gr/rGO composite membrane with the thickness of 33 nm.
Through tests (test conditions: the suspended round hole membrane with the diameter of 8mm is tested by a barometer), the mechanical property of the composite membrane is that the breaking strength is 600MPa, and the breaking strength of single rGO is only 300 MPa.
Example 2
Preparing the graphene film 10: a multilayer graphene film with the thickness of 1nm is prepared by a CVD method by taking Cu as a substrate, and the size of the film is 10cm in diameter.
The preparation process conditions comprise: cu foil at Ar gas flow rate of 500sccm, H2Heating to 1000 ℃ under the condition of the flow rate of 100sccm for annealing, and after annealing lasts for 10 hours, starting to introduce CH4Mixed gas of Ar, CH4The content of the mixed gas is 200ppm, and the flow rate of the mixed gas is2sccm while adjusting H2The flow rate is 20sccm, the flow rate of Ar gas is kept unchanged, the working pressure is normal pressure (one atmosphere), and the growth time is 4 h.
Preparation of reduced graphene oxide film 20: spin-coating 6 wt% of GO dispersion liquid by a spin coater at 1500r/min, reducing by hydroiodic acid, and preparing a rGO nano film with the diameter of 10cm and the thickness of 30 nm.
Preparing a Gr/rGO composite membrane: the rGO nano-film was transferred to a multilayer graphene film with a metal substrate and heated at 80 ℃.
And then etching by using 1mol/L etching solution (ferric trichloride) to remove the metal substrate to obtain the Gr/rGO composite membrane.
And transferring the Gr/rGO composite membrane to another multi-layer graphene film with a metal substrate, and heating at 80 ℃.
And etching the metal substrate by using 1mol/L etching solution (ferric trichloride) to obtain a Gr/rGO/Gr composite membrane with the thickness of 32 nm.
Through tests (test conditions: the suspended round hole membrane with the diameter of 8mm is tested by a barometer), the mechanical property of the composite membrane is that the breaking strength is 710MPa, and the breaking strength of single rGO is only 300 MPa.
Example 3
Preparing the graphene film 10: a multilayer graphene film with the thickness of 1nm is prepared by a CVD method by taking Cu as a substrate, and the size of the film is 10cm in diameter.
The preparation process conditions comprise: cu foil at Ar gas flow rate of 450sccm and H2Heating to 1100 deg.C at a flow rate of 80sccm for annealing, and introducing CH after annealing for 12 hr4Mixed gas of Ar, CH4The content of the mixed gas was 180ppm, the flow rate of the mixed gas was 1.8sccm, and H was adjusted2The flow rate is 18sccm, the flow rate of Ar gas is kept unchanged, the working pressure is normal pressure (one atmosphere), and the growth time is 4.5 h.
Preparation of reduced graphene oxide film 20: spin-coating 1 wt% of GO dispersion liquid by a spin coater at 1000r/min, reducing by hydroiodic acid, and preparing a rGO nano film with the diameter of 10cm and the thickness of 50 nm.
Preparing a Gr/rGO composite membrane: the rGO nanofilm was transferred to a multilayer graphene film with a metal substrate and heated at 75 ℃.
And then, etching by using 0.8mol/L etching solution (ammonium persulfate) to remove the metal substrate to obtain a Gr/rGO composite membrane with the thickness of 51 nm.
Through tests (test conditions: the suspended round hole membrane with the diameter of 8mm is tested by a barometer), the mechanical property of the composite membrane is that the fracture strength is 640MPa, and the fracture strength of single rGO is only 300 MPa.
Example 4
Preparing the graphene film 10: taking Ni as a substrate, and preparing a multilayer graphene film with the thickness of 5nm by a CVD method, wherein the size is 20cm in diameter.
The preparation process conditions comprise: ni foil at Ar gas flow rate of 550sccm, H2Heating to 900 ℃ under the condition of the flow rate of 120sccm for annealing, and starting to introduce CH after 8 hours of annealing4Mixed gas of Ar, CH4The content of the mixed gas was 220ppm, the flow rate of the mixed gas was 2.2sccm, and H was adjusted2The flow rate is 22sccm, the flow rate of Ar gas is kept unchanged, the working pressure is normal pressure (one atmosphere), and the growth time is 3.5 h.
Preparation of reduced graphene oxide film 20: spin-coating 10 wt% of GO dispersion liquid by a spin coater at 1500r/min, reducing by hydroiodic acid, and preparing a rGO nano film with the diameter of 20cm and the thickness of 100 nm.
Preparing a Gr/rGO composite membrane: the rGO nanofilm was transferred to a multilayer graphene film with a metal substrate and heated at 85 ℃.
And then etching by using 1.2mol/L etching solution (ferric trichloride) to remove the metal substrate to obtain the Gr/rGO composite membrane.
And transferring the Gr/rGO composite membrane to another multi-layer graphene film with a metal substrate, and heating at 85 ℃.
And etching the metal substrate by using 1.2mol/L etching solution (ferric trichloride) to obtain a Gr/rGO/Gr composite membrane with the thickness of 110 nm.
Through tests (test conditions: the suspended round hole membrane with the diameter of 8mm is tested by a barometer), the mechanical property of the composite membrane is that the breaking strength is 550MPa, and the breaking strength of single rGO is only 300 MPa.
To sum up, this application prepares graphite alkene complex film through will reducing graphene oxide and graphite alkene complex, and it can overcome vapour deposition graphite alkene growth cycle length, and the price is expensive and the shortcoming that reducing graphene oxide mechanical properties is slightly poor, and full play vapour deposition graphite alkene mechanical properties is excellent and the easy advantage of preparing low-cost of reducing graphene oxide obtains ultra-thin ultralight composite nanometer film, is applicable to fields such as acoustics, new energy battery.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. 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. The graphene composite film is characterized by being obtained by compounding a reduced graphene oxide film and a graphene film arranged on at least one side surface of the reduced graphene oxide film.
2. The graphene composite membrane according to claim 1, wherein the graphene membrane is composed of at least one graphene layer, and each graphene layer has a thickness of 0.3 to 0.5 nm.
3. The graphene composite film according to claim 1 or 2, wherein the reduced graphene oxide film has a thickness of 10 to 1000 nm;
preferably, the reduced graphene oxide film has a diameter of 1 to 100 cm.
4. The method for producing the graphene composite film according to any one of claims 1 to 3, wherein the graphene film is provided on at least one surface of the reduced graphene oxide film;
preferably, the graphene film is placed on at least one side surface of the reduced graphene oxide film, followed by heating to combine the reduced graphene oxide film and the graphene film;
preferably, the graphene film is prepared by the following steps: depositing a graphene layer on the surface of a preset substrate by adopting a vapor deposition mode;
preferably, the gas used in the vapor deposition process comprises a mixed gas consisting of methane and an inert gas, wherein the content of the methane in the mixed gas is 180-220ppm, the flow rate of the mixed gas is 1.8-2.2sccm, and the flow rate of the hydrogen is 18-22 sccm;
preferably, the time of vapor deposition is 3.5-4.5 h;
preferably, before depositing the graphene layer, annealing the preset substrate;
preferably, the annealing treatment is to heat to 900-1100 ℃ under the conditions of inert gas flow rate of 450-550sccm and hydrogen flow rate of 80-120 sccm;
preferably, the reduced graphene oxide is prepared by the following steps: spin-coating the dispersion liquid of the graphene oxide, and reducing by using a reducing agent;
preferably, the concentration of the graphene oxide in the dispersion liquid is 1-10 wt% o;
preferably, the spin coating rotation speed is 500-;
preferably, the reducing agent comprises at least one of hydroiodic acid, hydrazine hydrate, and sodium citrate.
5. The method according to claim 4, wherein the step of removing the predetermined substrate after the step of combining the reduced graphene oxide film and the graphene film;
preferably, the preset substrate is removed by etching liquid, and the etching liquid comprises ammonium persulfate or ferric trichloride.
6. Use of the graphene composite membrane according to any one of claims 1 to 3, wherein the graphene composite membrane is used in an acoustic diaphragm or a battery or a water purification membrane or a NEM electromechanical system.
7. An acoustic diaphragm, comprising the graphene composite membrane according to any one of claims 1 to 3.
8. A battery comprising the graphene composite film according to any one of claims 1 to 3.
9. A water purification membrane comprising the graphene composite membrane according to any one of claims 1 to 3.
10. A NEM electromechanical system comprising the graphene composite film according to any one of claims 1 to 3.
CN202011603189.5A 2020-12-30 2020-12-30 Graphene composite membrane and preparation method and application thereof Pending CN112694085A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114953635A (en) * 2022-05-30 2022-08-30 安徽天富环保科技材料有限公司 Activated carbon fiber cloth for gas diffusion of new energy battery

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120021224A1 (en) * 2010-07-23 2012-01-26 Clean Energy Labs, Llc Graphene/graphene oxide platelet composite membranes and methods and devices thereof
KR101615827B1 (en) * 2014-12-30 2016-04-27 한양대학교 산학협력단 Reduced graphene oxide/graphene composite film, Energy Storage Device Having the Same, and Method for Fabricating the composite film

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120021224A1 (en) * 2010-07-23 2012-01-26 Clean Energy Labs, Llc Graphene/graphene oxide platelet composite membranes and methods and devices thereof
KR101615827B1 (en) * 2014-12-30 2016-04-27 한양대학교 산학협력단 Reduced graphene oxide/graphene composite film, Energy Storage Device Having the Same, and Method for Fabricating the composite film

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHANG WANG等: ""A Reduced GO-Graphene Hybrid Gas Sensor for Ultra-Low Concentration Ammonia Detection"", 《SENSORS》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114953635A (en) * 2022-05-30 2022-08-30 安徽天富环保科技材料有限公司 Activated carbon fiber cloth for gas diffusion of new energy battery
CN114953635B (en) * 2022-05-30 2023-09-15 安徽天富环保科技材料有限公司 Activated carbon fiber cloth for gas diffusion of new energy battery

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