KR20210012773A - Sheet with graphene attached on and Method for making the same - Google Patents

Abstract

Provided is a graphene-attached sheet, where graphene is directly attached to a sheet so as to easily realize the original performance of graphene and the sheet and enable economical manufacture. The graphene-attached sheet includes: a base sheet; and a graphene layer attached directly on the base sheet and having a constant arrangement continuously on a plane.

Description

Graphene-attached sheet and its manufacturing method {Sheet with graphene attached on and Method for making the same}

The present invention relates to a graphene-attached sheet and a method of manufacturing the same, and in particular, graphene is directly attached to the sheet, so that it is easy to realize the original performance of graphene and the sheet, and graphene that can be manufactured continuously economically in a large area. -It relates to the attachment sheet and its manufacturing method.

Graphene plays an important role as an industrial material because it has a single layer of carbon atoms having a hexagonal structure and has excellent heat resistance, excellent thermal conductivity, low electrical conductivity and high mechanical strength.

For example, graphene is composed of one planar layer constituting graphite, which facilitates charge transfer and can be used in various ways in the electronics industry, nano industry, etc. due to its high surface area compared to mass.

As a method of manufacturing such graphene, a mechanical separation manufacturing method using a tape, a manufacturing method using a chemical vapor deposition method (CVD) and a metal catalyst, and a method of reducing after making graphene oxide are disclosed. However, the mechanical separation method of producing graphene by attaching a tape to a graphite sheet or graphite powder and separating the tape has a problem that it is difficult to have uniform quality and mass production is difficult, and the method using CVD and a metal catalyst has a high manufacturing cost and There is a problem of graphene contamination and oxide generation caused when the metal thin film is removed, and it is difficult to continuously manufacture a large area. In addition, the method of reducing after preparing graphene oxide has a disadvantage in that it is difficult to completely reduce, and thus characteristics deteriorate due to residual oxygen, and it is difficult to mass-produce high-purity graphene.

In addition, a plurality of graphenes prepared by the above methods are attached to an object that graphene actually needs, such as an optical PET sheet, in a continuous and uniform arrangement on a plane without a separate attachment means, such as an adhesive solution. It is difficult to do, and there is a disadvantage in that it has the above problems even when it is attached using a pressure-sensitive adhesive, and there is a limitation in implementing the inherent performance of graphene by the pressure-sensitive adhesive.

According to the conventional Korean Patent Registration No. 10-1289389, after immersing a cathode comprising highly-aligned pyrolytic graphite and an anode comprising aluminum metal in an electrolyte solution comprising an alcohol solution of perchloric acid having a concentration of 01 to 30 M, 001 between the cathode and the anode. A method of manufacturing graphene is disclosed, characterized in that a current of ~ 06A is applied at a time with a voltage of 20 ~ 200V.

However, even a large number of graphenes prepared in this way, as described above, are difficult to attach continuously and uniformly in a plane without a separate attaching means on the object of a large area required by graphene, as described above, and attach using an adhesive. In this case, there is a disadvantage in that it is difficult to realize the inherent performance of graphene by the adhesive.

In addition, there is a disadvantage in that the size of graphene is not uniform depending on the concentration and distribution of the electrolyte, the shape of the electrode, or the current density.

In particular, the thickness of graphene is very thin, about angstroms (Å), so it is difficult to classify, arrange, and handle graphene.

Accordingly, an object of the present invention is to provide a sheet in which graphene is continuously attached directly onto the sheet in a uniform arrangement.

Another object of the present invention is to provide a sheet having good adhesion between graphene and sheet reliably.

Another object of the present invention is to provide a graphene-attached sheet having low electrical resistance, good heat conduction in a plane direction, and good optical transmittance.

Another object of the present invention is to provide a graphene-attached sheet that causes less damage to the appearance during manufacture of the sheet.

Another object of the present invention is to provide a graphene-attached sheet that is easy to provide various types of graphene on a sheet of various materials.

Another object of the present invention is to provide a graphene-attached sheet that can be supplied in a roll and is easily provided in a large area.

Another object of the present invention is to provide a manufacturing method capable of economically continuously manufacturing the graphene-attached sheet.

According to one aspect of the invention, the base sheet; And a graphene layer that is directly attached to the base sheet and has a constant arrangement in a plane, wherein the graphene layer is transferred from an artificial graphite sheet having graphene of the graphene layer on the outermost layer. Graphene-attached sheet, characterized in that formed is provided.

Preferably, the base sheet is a polymer sheet, a glass or a ceramic substrate, and the polymer sheet is a light-transparent film, and may be any one of PET, EVA, PI, or silicone rubber.

Preferably, the graphene layer may be a single layer or a multilayer.

Preferably, the attachment is made by a high current flowing directly through the artificial graphite sheet, and the high current may be provided in an electroplating process.

Preferably, the adhesion may be provided in the process of electroplating the metal on the artificial graphite sheet in a roll-to-roll process while the artificial graphite sheet passes through an electrolyte solution containing a metal element.

Preferably, the artificial graphite sheet is a polyimide sheet containing a large amount of carbon is provided through heat treatment of carbonization and graphitization, and the thermal conductivity of the artificial graphite sheet is 800W/mK or more, and the surface electrical resistance is 5ohm/ㅁ or less. It may be an artificial graphite sheet of.

Preferably, the adhesion between the graphene layer and the base sheet may be greater than the adhesion between a plurality of graphenes constituting the artificial graphite sheet corresponding to the graphene layer.

According to another aspect of the present invention, a light-transparent base sheet; A metal coating layer directly attached to the base sheet having a constant arrangement in a plane shape; And a graphene-attached sheet is provided, characterized in that consisting of a graphene layer directly attached to the metal coating layer.

According to another aspect of the present invention, a light-transparent base sheet; A graphene layer directly attached to the base sheet and having a constant arrangement in a plane; And a base sheet portion to which the graphene layer is not attached, and a metal coating layer directly attached to the graphene layer, and a graphene-attached sheet is provided.

Preferably, the surface electrical resistance of the surface on which the metal coating layer and the graphene layer are formed may be 200 ohm/ㅁ or less, and the light transmittance of the base sheet may be 40% to 85%.

According to another aspect of the present invention, a step of forming a laminate by closely laminating an artificial graphite sheet made of a roll by pressure on a base sheet made of a roll; Washing the laminate; Electrolyzing the electrolyte by applying a negative (-) electrode and applying a positive (+) electrode to the electrolyte while applying pressure to the graphite sheet in a state in which the laminate is deposited in the electrolyte solution by roll-to-roll; Transferring graphene of at least an outermost layer of the graphite sheet to the base sheet and in close contact with the base sheet during the electrolysis process; Drying the laminate; And gradually separating the graphite sheet from the base sheet to complete a graphene adhesion-sheet consisting of a graphene layer by the graphene in close contact with the base sheet. A manufacturing method is provided.

Preferably, the electrolyte solution includes a metal element, and the metal element may be electroplated on a surface exposed to the outside of the graphite sheet during the electrolysis process.

Preferably, a metal coating layer may be formed on the surface of the base sheet in contact with the graphite sheet, or a metal coating layer may be additionally formed on the graphene layer of the graphene-attached sheet.

According to the present invention, graphene of the outermost layer of an artificial graphite sheet having a smooth surface on both sides by being rolled is directly attached to the sheet having a smooth surface so that the grain boundaries are continuously attached to the sheet in a uniform arrangement.

In addition, since a negative current is applied to the graphite sheet stacked on the base sheet and a positive current is applied to an electrolyte containing or not containing metal ions, electrolysis is performed to transfer and adhere the graphene of the graphite sheet to the sheet. This allows the pin to be reliably attached to the sheet.

In addition, high-purity artificial graphite is used for good electrical and thermal conduction, and when a transparent optical sheet is used, the thickness of graphene is thin and grain boundaries are continuously and uniformly arranged to have good optical transmittance.

In addition, by attaching graphene on a sheet coated with optically transparent ITO to reinforce the defects of the grain boundary, electrical resistance can be reduced and heat transfer in the plane direction is fast. Likewise, by attaching graphene to the base sheet and then adding a light-transparent ITO coating, electrical resistance can be reduced and heat transfer is fast in the plane direction.

In addition, graphene of the outermost layer of artificial graphite can be transferred and attached to the sheet by the electroplating method by depositing in the electrolyte by a roll to roll process, so that it can be economically manufactured in a large area and the appearance of the graphene layer and sheet Less damage to

In addition, the metal-plated artificial graphite sheet remaining after preparing the graphene-attached sheet can be used for other applications requiring thermal conductivity and electrical conductivity.

1 is a cross-sectional view schematically showing a graphene-attached sheet according to an embodiment of the present invention.
2 is a photographic image showing a graphene-attached sheet according to an embodiment of the present invention.
3(a) is a photograph of the surface of the artificial graphite sheet after the graphene of the outermost layer is transferred to the base sheet, and 3(b) is a photograph of the surface of the graphene of the outermost layer of the artificial graphite sheet transferred to a transparent PET film. .

It should be noted that the technical terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. In addition, the technical terms used in the present invention should be interpreted as generally understood by those of ordinary skill in the technical field to which the present invention belongs, unless otherwise defined in the present invention, and is excessively comprehensive. It should not be construed as a human meaning or an excessively reduced meaning.

Hereinafter, specific embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 is a cross-sectional view schematically showing a graphene-attached sheet according to an embodiment of the present invention.

The graphene-attached sheet 100 is composed of a base sheet 110 and a graphene layer 120 that is directly attached to the base sheet 110 and has a constant arrangement continuously in a plane.

The adhesion between the base sheet 110 and the graphene layer 120 is greater than the adhesion between a plurality of graphene layers constituting an artificial graphite sheet corresponding to the graphene layer.

The base sheet 110 may be a polymer sheet, glass or ceramic.

In the case of the polymer sheet, the base sheet 110 is provided as a roll, and PET, EVA, PI, PVC, PE, PP, or silicone rubber may be applied, and in the case of light transmittance, the light transmittance may be about 60% to 95%. Not limited.

When the base sheet 110 is made of glass or ceramic, the base sheet 110 is not supplied as a roll, but is provided in a sheet shape having a certain size, and the graphene-attached sheet 100 is formed by a precise manufacturing process required by the semiconductor process. Can provide.

As will be described later, the graphene layer 120 may be formed by transferring the outermost layer of the compressed artificial graphite sheet after the polyimide sheet is carbonized and graphitized.

Hereinafter, a process of manufacturing the graphene-attached sheet 100 into a roll will be described.

A polyimide sheet containing a large amount of carbon is subjected to carbonization, expansion, graphitization, and compression processes to produce an artificial graphite sheet with a smooth surface.

Since the polyimide sheet used when manufacturing artificial graphite has a high carbon content and a large molecular weight, a lot of carbon remains after carbonization and graphitization of the polyimide sheet, resulting in good thermal and electrical conduction, especially expansion and graphite When it is formed, the arrangement of carbon in the plane direction is relatively constant, and heat conduction in the plane direction is good.

A polyimide sheet containing a large amount of carbon having a thickness of about 50 μm and a constant width and stretched in the width direction is supplied to the thermal decomposition furnace in the form of a roll.

Since the polyimide sheet is composed of approximately 20% polyimide resin and approximately 80% solvent, the carbon molecules can be horizontally aligned by stretching in the width direction during the curing process after casting.

For example, whether in the width direction or the length direction, carbon molecules are aligned in the plane direction by stretching, and as a result, the thermal conductivity in the plane direction after graphitization is improved.

The polyimide sheet is carbonized in a thermal decomposition furnace to form a carbonized sheet in which only carbon and a blowing agent remain. Carbonization may be performed in a vacuum atmosphere of 1000°C to 1400°C, for example.

The carbonized sheet is mostly removed from impurities except carbon and foaming agent.

Subsequently, when the carbonized polyimide sheet is taken out and placed in a thermal decomposition furnace to increase the temperature to volatilize the remaining foaming agent, the carbonized polyimide sheet is expanded and graphitized to become a graphitized expanded sheet. Graphitization may be performed in an argon gas atmosphere of 2500°C to 3200°C.

When a polymer sheet 110, for example, a transparent PET film, is provided in a roll form on the lower or upper surface of the graphitized expansion sheet provided in a roll form according to the roll-to-roll process, and a large force is applied with a rolling roller. The expanded sheet graphitized by pressure becomes thinner, the surface becomes smooth, and is closely laminated on the polymer sheet 110 to form a laminate composed of an artificial graphite sheet and a polymer sheet 110.

In this embodiment, the thickness of the compressed high-purity artificial graphite sheet is around 25 microns, the thermal conductivity is about 1000 W/m.K, and the surface electrical resistance is 5 ohm/ㅁ or less.

In this way, the artificial graphite sheets are laminated on the polymer sheet 110 through a roll-to-roll process, and then closely adhered to each other under a high pressure by a pressing roller to form a laminate.

In order for the compressed artificial graphite sheet to have a very smooth surface and uniform thickness, the surface of the pressing roller must be very smooth and a very large force must be provided.

The artificial graphite sheet thus manufactured has a structure in which hexagonal graphenes uniformly arranged in a plane are stacked in a very large number of layers.

For example, the thickness of graphene is very thin, about several angstroms (Å), and each graphene can be separated by force.

When the surface of the artificial graphite sheet thus prepared is oxidized, the oxide layer can be removed by reducing it through chemical surface treatment in order to have good electrical conduction.

After that, the laminate is deposited in an electrolyte containing metal ions in the form of a roll and electroplated continuously on the surface of the graphite sheet exposed to the outside.A negative (-) electrode is applied to the graphite sheet, and a positive (+) electrode is applied to the electrolyte, and high current. Is applied.

Preferably, the metal ion may be a copper ion, an aluminum ion, or a nickel ion.

The sheet electrical resistance of the graphite sheet of such a laminate is as low as 5 ohm/ㅁ, but when electroplating a metal such as copper on the surface of the graphite sheet, the arrangement of the honeycomb structure of each graphene forming the graphite sheet and the grain bound of the honeycomb structure As the actual electrical resistance increases due to the grain boundary, a large current must be applied to the graphite sheet, but since a large amount of heat is generated in the electrical contact area by the large current, an electrode structure that provides a large area and large pressure is provided so that electrical contact is not possible. It needs to be done.

For example, when electroplating on a graphite sheet, the amount of current varies depending on the area of the graphite sheet to be electroplated, but a low voltage of about 15V is applied and the current may be a large current of 300A or more.

When a negative current of a high current is applied to the graphite sheet and a positive current is applied to the electrolyte of metal ions, the surface of the graphite sheet exposed to the outside by electrolysis of the electrolyte between them, that is, a graphite sheet that does not contact the polymer sheet The surface is electroplated with a metal such as copper.

At this time, in the electroplating process performed in a roll-to-roll method, the pressure applied by the rollers to supply a large current to the graphite sheet, the electric charge generated by the electrolysis of the electrolyte by the large current, and the temperature applied to the graphite sheet by electrolysis. As a result, the graphene forming the outermost layer of the graphite sheet is adhered to the polymer sheet 110 by more reliably.

Here, when the electrolytic solution contains a sulfate metal salt such as copper sulfate (Cu2SO4) to perform the electroplating process, a copper plating layer is formed on the surface of the graphite sheet as in the embodiment of the present invention by the electroplating process.

Thereafter, when the laminate is removed from the electrolyte, the electrolyte is washed with water, dried, and then the copper-plated graphite sheet is gradually separated from the polymer sheet 110, the graphene of the outermost layer of the graphite sheet in contact with the polymer sheet 110 The polymer sheet 110 is directly transferred and attached to the surface to form the graphene layer 120.

Here, the graphene layer 120 is composed of at least one layer of graphene, and may be composed of a plurality of stacked graphene. In this case, a plurality of graphene layers are formed through a wide gap in the honeycomb constituting the lowermost graphene. A portion of the stacked graphene may be transferred and attached to the surface of the polymer sheet 110.

For example, the graphene layer 120 may be composed of one layer of graphene as the outermost layer or graphene stacked on one layer as the outermost layer.

Through this manufacturing process, graphene in the outermost layer in contact with the polymer sheet 110 at least in the artificial graphite sheet made of high-purity carbon is transferred and attached to the surface of the polymer sheet 110 to produce the graphene-attached sheet 100 do.

Here, the adhesion between the graphene layer 120 and the polymer sheet 110 is greater than the adhesion between a plurality of graphenes constituting the artificial graphite sheet corresponding to the graphene layer 120.

The graphene layer 120 transferred and attached to the polymer sheet 110 thus prepared has a very thin thickness and has a grain boundary of a hexagonal honeycomb structure.

However, the graphene-attached sheet 100 must be well handled or processed because the graphene layer 120 directly attached to the polymer sheet 110 may be damaged or separated by friction or contact during the handling process. There are drawbacks, and there are many limitations in applying the graphene-attached sheet 100 alone to an actual optical product.

For example, graphenes adjacent to each other in the vertical direction of graphene are connected only by contact by stacking, so that the electrical resistance is large, and the graphene layer 120 is very thin, making it difficult to measure the electrical resistance and to form an electrical electrode there. It has the disadvantage of being difficult.

In addition, when the probe of these measuring instruments is touched on the graphene to measure the electrical resistance or thermal resistance of graphene transferred to the polymer sheet 110 with a measuring instrument, the graphene itself is damaged or its shape is changed, resulting in accurate data. It is very difficult to obtain and the inventors have not been able to obtain accurate data.

Moreover, graphene has a slippery lubricity property and has a very small dimension, so it is difficult to properly respond to graphene alone due to external forces.

For this reason, after ITO is deposited on the polymer sheet 110 by sputtering, a graphene layer 120 is formed thereon, or a graphene layer 120 is formed and then ITO is deposited thereon to finally graphene-attachment. The surface electrical resistance of the sheet can be lowered, and according to the processing method, it is less damaged or prevented from being separated by friction or contact.

In this case, there is an advantage in that electrical resistance can be easily measured and an electrical electrode can be easily formed.

ITO-coated optical film coated with ITO on a light-transmitting PET film is a well-known technology and is widely used for TVs, smartphones, or monitors, and has the disadvantage that the cost of ITO material is expensive and is precisely manufactured by expensive sputtering equipment. . In addition, there is a disadvantage in that ITO is arranged in the form of particles in an optical film by sputtering to form a continuous line, and in particular, heat conduction in the plane direction is insufficient.

Since the grain boundary of the graphene layer 120 of the graphene-attached sheet 100 of the present invention is in a line shape and is connected in a line shape, the heat transfer property in the plane direction is good, whereas the ITO layer formed by sputtering is In the form of the graphene layer 120, heat transfer characteristics are inferior.

However, by applying the ITO layer to the graphene-attached sheet 100, it is possible to replace the grain boundary damaged or cut by friction or contact, thereby improving the overall heat transfer characteristics.

In addition, it is possible to partially reduce the existing ITO coating thickness or the amount of ITO, shorten the working time, or apply an ITO coated optical film using an inexpensive ITO coating facility.

Here, when the base sheet 110 is light transmissive, the light transmittance of the graphene-attached sheet 100 on which the ITO layer and the graphene layer are formed may be 40% to 85%, and the ITO layer and the graphene layer are formed. The surface electrical resistance on the surface may be 200 ohm/ㅁ or less.

The base sheet 110 on which the ITO layer is formed may be light-transmitting colorless PET or EVA.

Here, it goes without saying that a metal such as aluminum can be replaced with a coating layer instead of ITO.

Similar to the above embodiment, in practical application, it is desirable to provide a product in which additional electrical, mechanical or optical properties are additionally imparted to the graphene-attached sheet 100 of the present invention.

For example, after forming electric electrodes on both ends of the polymer sheet 110 in advance, the graphene-attached sheet 100 of the present invention is precisely manufactured to a predetermined size or less. Optical pressure-sensitive adhesive can be coated.

2 is a photographic image showing a graphene-attached sheet according to an embodiment of the present invention.

In the photographic image, the left part is the graphene-attached sheet of the present invention, the middle part is the artificial graphite sheet from which the graphene of the outermost layer is separated, and the right part shows the copper plated part of the artificial graphite sheet.

3(a) is a photograph of the surface of an artificial graphite sheet after the graphene of the outermost layer is transferred to the base sheet, and 3(b) is a photograph of the surface of the graphene of the outermost layer of the artificial graphite sheet transferred to a transparent PET film. .

3(b), the graphene layer 120 of the graphene-attached sheet 100 has a generally hexagonal structure, but a portion where some grain boundaries are torn or missing and overlapping portions are found. It should be interpreted to be included in the present invention because it can be solved with precise or partial supplementation.

For reference, the artificial graphite sheet used in FIGS. 2 and 3 (a) and 3 (b) was a PI film for manufacturing artificial graphite manufactured by SKC-Kolon PI, and the transparent PET film is a market purchased product, and one side of the artificial graphite sheet Copper was electroplated on the plate, and the picture in FIG. 3 is a picture taken at 50 times magnification using a Japanese Nikon Microscope model name MM-400.

Although the above has been described with the focus on the embodiments of the present invention, it goes without saying that various changes can be made at the level of those skilled in the art. Therefore, the scope of the present invention is limited to the above-described embodiments and cannot be interpreted, and should be interpreted by the claims set forth below.

100: graphene-attached sheet
110: base sheet
120: graphene layer

Claims (25)

Base sheet; And
And a graphene layer attached directly on the base sheet and having a constant arrangement continuously in a plane,
The graphene layer is a graphene-attached sheet, characterized in that the graphene of the graphene layer is transferred from an artificial graphite sheet having an outermost layer of graphene. In claim 1,
The base sheet is a graphene-attached sheet, characterized in that the polymer sheet, glass or ceramic substrate. In claim 2,
The polymer sheet is a graphene-attached sheet, characterized in that the light-transparent film. In claim 1,
The polymer sheet is a graphene-attached sheet, characterized in that any one of PET, EVA, PI or silicone rubber. In claim 1,
The graphene layer is a graphene-attached sheet, characterized in that the single layer or multi-layer. In claim 1,
The adhesion is graphene-attachment sheet, characterized in that by high current flowing directly to the artificial graphite sheet. In claim 6,
Graphene-attached sheet, characterized in that the high current is provided in the electroplating process. In claim 1,
The adhesion is provided in the process of electroplating the metal on the artificial graphite sheet while the artificial graphite sheet passes through an electrolyte solution containing a metal element. In claim 8,
The metal element is a graphene-attached sheet, characterized in that any one of copper, aluminum or nickel. In claim 8,
Graphene-attached sheet, characterized in that the electroplating is made of a roll-to-roll process. In claim 1,
The artificial graphite sheet is a graphene-attached sheet, characterized in that a polyimide sheet containing a lot of carbon is provided through heat treatment of carbonization and graphitization. In claim 1,
Graphene-attached sheet, characterized in that the thermal conductivity of the artificial graphite sheet is 800W/mK or more and a surface electrical resistance of 5 ohm/ㅁ or less. In claim 1,
The graphene-attached sheet is a graphene-attached sheet, characterized in that provided by a roll-to-roll process. In claim 1,
The graphene-attached sheet, characterized in that the adhesion between the graphene layer and the base sheet is greater than the adhesion between a plurality of graphenes constituting an artificial graphite sheet corresponding to the graphene layer. Light transparent base sheet;
A metal coating layer directly attached to the base sheet having a constant arrangement in a plane shape; And
Graphene-attached sheet, characterized in that consisting of a graphene layer directly attached to the metal coating layer. Light transparent base sheet;
A graphene layer directly attached to the base sheet and having a constant arrangement in a plane; And
Graphene-attached sheet comprising a base sheet portion to which the graphene layer is not attached, and a metal coating layer directly attached to the graphene layer. In claim 15 or 16,
Graphene-attached sheet, characterized in that the surface electrical resistance of the surface on which the metal coating layer and the graphene layer are formed is 200 ohm/ㅁ or less. In claim 15 or 16,
Graphene-attached sheet, characterized in that the light transmittance of the base sheet is 40% to 85%. In claim 15 or 16,
The graphene layer is a graphene-attached sheet, characterized in that the graphene of the graphene layer is transferred from an artificial graphite sheet having an outermost layer of graphene. Forming a laminate by closely laminating the rolled artificial graphite sheet by pressure on the rolled base sheet;
Washing the laminate;
Electrolyzing the electrolyte by applying a negative (-) electrode and applying a positive (+) electrode to the electrolyte while applying pressure to the graphite sheet in a state in which the laminate is deposited in the electrolyte solution by roll-to-roll;
Transferring graphene of at least an outermost layer of the graphite sheet to the base sheet and in close contact with the base sheet during the electrolysis process;
Drying the laminate; And
Preparation of a graphene-attached sheet, comprising the step of gradually separating the graphite sheet from the base sheet to complete a graphene adhesion-sheet consisting of a graphene layer by the graphene in close contact with the base sheet Way. In claim 20,
The electrolyte solution contains a metal element,
The method of manufacturing a graphene-attached sheet, characterized in that the metal element is electroplated on the surface exposed to the outside of the graphite sheet during the electrolysis process. In claim 20,
The base sheet is a graphene-attached sheet manufacturing method, characterized in that the electrical insulation and transparent optical sheet. In claim 20,
The step proceeds in a roll-to-roll method,
Graphene-attached sheet manufacturing method, characterized in that the surface of the graphite sheet is smooth. In claim 20,
A method of manufacturing a graphene-attached sheet, characterized in that a metal coating layer is formed on the surface of the base sheet in contact with the graphite sheet. In claim 20,
A method of manufacturing a graphene-attached sheet, characterized in that a metal coating layer is additionally formed on the graphene layer of the graphene-attached sheet.

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