JP2024019746A - Method for producing joined graphene body having larger area and larger thickness by depositing graphene mass in gap between joined graphene bodies and joining joined graphene bodies by friction-welding the graphene mass - Google Patents

Abstract

To provide a method for producing a joined graphene body having a larger area and a larger thickness.SOLUTION: A suspension obtained by dispersing a graphene mass 3 in methanol and a mass of joined graphene bodies 4 are mixed and the resultant mixture is poured into a container. The three-direction vibrational acceleration is repeatedly given to the container to cause the graphene mass to be planarly arranged with its surface facing upward and to cause the mass of the joined graphene bodies to be planarly arranged with its surface facing upward. Then, the methanol is vaporized to condense the mass of the joined graphene bodies in the container. Thus, the graphene mass fully closing a gap between the joined graphene bodies is friction-welded onto the joined graphene bodies, pieces of the graphene are friction-welded onto each other, and the joined graphene bodies are joined to each other via the friction-welded graphene mass, thereby forming a joined graphene body having a larger area and a larger thickness.SELECTED DRAWING: Figure 3

Description

In the present invention, all the gaps between graphene bonded bodies are filled with aggregates of graphene precipitated with their faces up, and then the aggregates of graphene bonded bodies are compressed, and the graphene aggregates are friction welded to the graphene bonded bodies. At the same time, the graphenes are frictionally welded to each other, and the graphene bonded bodies are bonded together through the friction welding of the graphene groups to form a graphene bonded body that has a larger area and is thicker.
In other words, since the thickness of graphene is extremely thin at 0.332 nm, the aspect ratio, which is the ratio of the area to the thickness of graphene, is extremely large. Furthermore, in a graphene bonded body in which graphene surfaces are joined, the increase in the area of the graphene bonded body is significantly greater than the increase in the thickness of the graphene bonded body, so the aspect ratio, which is the ratio of area to thickness, is even larger. On the other hand, the size of graphene is significantly smaller than that of graphene conjugates. Therefore, when forming a graphene bonded body with a larger area and a thicker thickness, rather than directly friction welding the graphene bonded bodies together, a collection of graphene is precipitated with the surface facing up in the gap between the graphene bonded bodies. It is easier to join graphene bonded bodies together by friction welding of graphene aggregates.
As a result, the larger the number of graphene bonded bodies to be bonded, or the larger the area or thickness of the bonded graphene bonded bodies, the larger the area or the thicker the bonded graphene bonded bodies. .

Graphene bonded bodies, in which graphenes are bonded together with their faces up, have properties similar to graphene. In addition, a graphene bonded body in which two graphene bonded bodies are bonded together by a collection of graphenes with their surfaces facing up has properties similar to graphene. In other words, the thermal conductivity of graphene in the thickness direction is low, and heat is preferentially transferred in the plane direction. In addition, the conductivity of graphene in the thickness direction is low, and electrons are preferentially transmitted in the in-plane direction. In this way, graphene has anisotropic properties. Therefore, if the surfaces of a graphene conjugate are joined together by a collection of graphenes joined face to face, the joined graphene conjugate will be composed of a graphene conjugate in which all the graphenes are lined up in a plane and joined together. It has properties similar to graphene. On the other hand, the thickness of graphene is extremely thin at 0.332 nm, and the aspect ratio, which is the ratio of the area to the thickness of graphene, is extremely large. Furthermore, in a graphene bonded body in which graphene is bonded to each other, the increase in area due to the bonded graphene is significantly larger than the number of bonded graphene sheets, and the aspect ratio of the graphene bonded body is even larger than that of graphene. Therefore, when bonding graphenes together, the graphenes are bonded with their surfaces facing upward. Further, when bonding the graphene bonded bodies to each other, the graphene bonded bodies are bonded to each other with their surfaces facing upward.
Here, the properties of graphene will be explained. As mentioned above, graphene has various excellent properties based on its anisotropy. In other words, since the thickness of graphene is extremely thin at 0.332 nm, the properties of graphene are in the plane direction perpendicular to the thickness direction.
For example, it has a thermal conductivity of 1880 W/mK, which is 4.5 times the thermal conductivity of silver, which has the highest thermal conductivity among metals. The specific volume resistivity is 1.3 μΩcm, which is even smaller than the specific volume resistivity of 1.6 μΩcm of silver, which has the lowest specific volume resistivity among metals. A single crystal material with a melting point of over 3000°C and a heat resistance of over 3000°C. It is a tough material with a breaking strength of 42 N/m, which is over 100 times stronger than steel, and an extremely large Young's modulus of 1020 GPa. It is an extremely stable substance that does not react with acids and alkalis. On the other hand, in a graphene bonded body in which the graphene surfaces are joined, due to the anisotropy of graphene, for example, heat is preferentially transferred in the direction of the graphene surface where graphene overlaps, and heat is transferred in the direction of the graphene surface. , electrons move preferentially. Therefore, the thermal conductivity of the graphene composite is close to that of graphene, and the electrical conductivity is close to that of graphene. Furthermore, a graphene conjugate in which the surfaces of the graphene conjugate are joined by a collection of graphenes joined face to face is composed of a graphene conjugate in which all the graphenes are lined up in a plane and joined together, so the graphene conjugate is , heat is preferentially transferred in the direction of the graphene surface, and electrons are preferentially moved in the direction of the graphene surface. Therefore, it has better thermal and electrical conductivity than silver.
By utilizing the excellent thermal conductivity and electrical conductivity of this graphene composite, it can be used, for example, as an electrode or contact with an area of less than 1 cm x 1 cm and a thickness of less than 0.1 μm. It can be used as an elongated wiring pattern with a size of 10 cm x 10 cm and a thickness of about 0.1 μm. On the other hand, due to the conductivity of graphene, the graphene bond exhibits electromagnetic wave shielding properties that correspond to the volume resistivity of graphene, and acts as an electromagnetic wave shielding film. Additionally, due to the electrical conductivity of graphene, the graphene conjugate acts as an antistatic coating. Furthermore, due to the thermal conductivity of graphene, the graphene composite acts as a heat dissipation coating. Furthermore, since the surface of the graphene bond has a flatness of only 0.332 nm, which corresponds to the thickness of graphene, it is nearly perfectly flat, and the graphene bond acts as a lubricating film. Furthermore, since graphene has excellent corrosion resistance and heat resistance, the graphene bonded body acts as a corrosion-resistant film or a heat-resistant film. Furthermore, graphene has a shear modulus of 440 GPa and is the toughest substance, so the graphene bond acts as a wear-resistant film or a non-destructive film. The area of the coating made of these graphene conjugates may exceed, for example, 1 m x 1 m, and the thickness may exceed 1 μm. By friction welding such a film to the surface of a base material or component, various properties of the graphene bonded body described above can be imparted to the base material or component.
As described above, since the graphene bonded body has a wide range of uses, the graphene bonded body requires an area and thickness depending on the purpose. On the other hand, since graphene has a shear modulus of 440 GPa and is the strongest material, graphene bonded bodies cannot be cut.
By the way, when bonding graphene bonded bodies to form a graphene bonded body with a larger area and thickness, if the graphene bonded bodies are directly friction welded on the surface where the graphene bonded bodies are overlapped, graphene bonding is performed. The bonding strength of the bonded graphene bonded body changes depending on the ratio of the surfaces where the bodies overlap. Therefore, it is necessary to overlap the graphene bonded bodies so that the ratio of the surfaces where the graphene bonded bodies overlap increases. However, if there are variations in the size and shape of the graphene bonded bodies, it becomes difficult to increase the ratio of the overlapping surfaces of the graphene bonded bodies. In addition, the larger the area of the graphene bonded bodies to be joined and the thicker the thickness, the more difficult it becomes to uniformly compress the graphene bonded bodies. becomes difficult.
On the other hand, a collection of graphene is precipitated in the gaps between all the graphene conjugates, the gaps between all the graphene conjugates are filled with the collection of graphene, and after this, the collection of all the graphene conjugates is compressed. . At this time, since the size of the graphene is significantly smaller than the size of the graphene bonded bodies, the graphene clusters are frictionally welded to all the graphene bonded bodies, and the graphenes are also frictionally welded to each other, and the gaps between all the graphene bonded bodies are , filled with clusters of friction-welded graphene. As a result, all the graphene bonded bodies are bonded to each other via the friction-welded graphene clusters. Therefore, graphene bonded bodies can be bonded to each other regardless of the ratio of the overlapping surfaces of the graphene bonded bodies and regardless of the size and thickness of the group of graphene bonded bodies to be bonded. The present invention is based on this idea.

Here, the patents previously filed by the present inventor that are related to the present invention will be explained.
The first prior patent application discloses that the interlayer bonds of graphite crystals in a collection of graphite particles are simultaneously destroyed in methanol, a collection of graphene is produced in a container, and vibrations are repeatedly applied in three directions to the container. A collection of graphenes in which the flat surfaces of the graphenes overlap with each other via methanol is formed on the bottom of the container in the shape of the bottom surface, and then the plane above the collection of graphenes is evenly compressed to simultaneously rub the graphenes together. This patent relates to a method of manufacturing a graphene bonded body by pressure welding (Patent Document 1).
The second prior application patent involves manufacturing a paste in which clusters of graphene are dispersed in a methanol diluted solution of an organic compound, transferring the paste to a new container, and then subjecting the new container to vibrational acceleration in three directions. This patent relates to a method of repeatedly adding graphenes to overlap each other via a diluted methanol solution of an organic compound, and forming a collection of graphenes in which the graphenes overlap each other via a diluted methanol solution of the organic compound (Patent Document 2).

The present invention precipitates clusters of graphene in the gaps between all the graphene junctions, fills the gaps between all the graphene junctions with the clusters of graphene, compresses the collection of graphene junctions, and is frictionally welded to the graphene bonded body, the graphenes are frictionally welded to each other, and the graphene bonded bodies are bonded to each other via the collection of frictionally welded graphenes, forming a graphene bonded body with a larger area and thicker thickness. .
On the other hand, the first prior application forms a cluster of overlapping graphene on the bottom of a container, uniformly compresses the plane above the cluster of graphene, and simultaneously frictionally welds the graphene to produce a graphene bonded body. For this reason, the larger the area and thickness of the graphene cluster, the more difficult it becomes to uniformly compress the graphene cluster. Therefore, there are restrictions on the size and thickness of the graphene bonded body to be manufactured. In contrast, in the present invention, clusters of graphene with a significantly smaller area and thickness than the graphene composites are precipitated in the gaps between the graphene composites, and the graphene clusters are frictionally welded to bond the graphene composites together. Because the graphene is bonded, there are no restrictions on the size and thickness of the graphene bonded bodies. Therefore, the present invention can form a graphene bonded body with a wider area and thicker thickness than the first prior application.
The second prior application relates to a method for producing a paste consisting of a collection of graphenes stacked on top of each other via an organic compound. Therefore, in the second prior application, as in the first prior application, the graphene bonded body is manufactured by friction welding graphenes together at the same time, so the size of the graphene bonded body to be manufactured is There are restrictions on thickness and thickness. In contrast, in the present invention, a collection of graphene conjugates is mixed with a suspension of graphene collections dispersed in methanol, the mixture is poured into a container, and after the methanol is vaporized, the entire surface of the mixture is Compress. As a result, the clusters of graphene precipitated filling all the gaps between the graphene bonded bodies are compressed, the graphene clusters are frictionally welded to the graphene bonded bodies, and the graphenes are frictionally welded to each other. The graphene bonded bodies are bonded together via this collection of friction-welded graphene. Therefore, the size of the graphene conjugate to be joined is determined by the size of the container, and the thickness of the graphene conjugate to be joined is determined by the amount of the mixture injected into the container. Therefore, the present invention can form a graphene bonded body that has a larger area and is thicker than the second prior application.
In other words, when stacking graphene bonded bodies on top of each other and friction welding all the graphene bonded bodies simultaneously to produce a graphene bonded body with a larger area and thickness, the larger the area of the graphene bonded bodies to be manufactured, the more , or, as the thickness of the graphene bonded bodies to be manufactured increases, the number of graphene bonded bodies to be stacked increases, and the area of the graphene bonded bodies to be stacked increases, so that all the graphene bonded bodies are compressed evenly, and all graphene bonded bodies are compressed evenly. It becomes difficult to frictionally weld two graphene bonded bodies at the same time.
On the other hand, if graphene aggregates are precipitated in the gaps between all the graphene bonded bodies, the gaps between all the graphene bonded bodies are filled with graphene aggregates, and then the graphene bonded bodies are compressed, the graphene Since the area is significantly smaller and the thickness is significantly thinner than that of the graphene bonded body, a collection of graphene easily frictionally welds to the graphene bonded body. is filled with clusters of friction-welded graphene. As a result, the graphene bonded bodies are easily joined to each other via the friction-welded graphene clusters. As a result, a graphene bonded body having a larger area and a larger thickness can be formed.
Therefore, the larger the number of graphene bonded bodies to be bonded, and the larger the area or thickness of the bonded graphene bonded bodies, the larger the area or the thicker the bonded graphene bonded bodies.
In other words, when directly friction-welding graphene bonded bodies, it is necessary to apply compressive stress to all surfaces of the graphene bonded bodies to be friction-welded. On the other hand, it is easy to apply compressive stress to graphene, which has a significantly smaller area and thinner thickness than the graphene bonded body. Therefore, it is easy to precipitate graphene aggregates in the gaps between all the graphene bonded bodies and join the graphene bonded bodies together through friction welding of the graphene aggregates. This idea led to the present invention.

Patent application 2019-107537 Patent application 2020-112197 Patent No. 6166860

As explained in the second paragraph, the graphene conjugate has a wide range of uses, so the area and thickness of the graphene conjugate vary greatly depending on the application. Furthermore, since graphene is the hardest substance, it is impossible to cut the graphene bond. Therefore, if many types of graphene bonded bodies with different areas and thicknesses can be easily manufactured, graphene bonded bodies having areas and thicknesses depending on the application can be selected.
On the other hand, there are the following three problems when forming a graphene bonded body with a larger area and a thicker thickness according to the present invention. The problems to be solved by the present invention are these three problems.
First, we found a method to precipitate clusters of graphene in the gaps between all the graphene conjugates and fill the gaps between all the graphene conjugates with the clusters of graphene. Note that since graphene plays the role of a bonding material that joins the graphene bonded bodies, the number of graphene particles precipitated in the gaps between the graphene bonded bodies may be small.
Second, groups of graphene are arranged randomly in a plane with their faces up, and groups of graphene junctions are arranged randomly in a plane with their faces up. A collection of bodies finds a way to create randomly layered mixtures. In other words, when the entire surface of this mixture is compressed evenly, the graphene bonded bodies arranged in a plane are compressed, and thereby the collection of graphene arranged in a plane stacked in the gaps between the graphene bonded bodies is compressed. Graphene is frictionally welded to the graphene bonded body, and the graphenes are frictionally welded to each other, and the graphene bonded bodies are joined together by the collection of frictionally welded graphenes, and a graphene bonded body with a larger area and thickness is easily formed. can.
Third, we will find a method to manufacture graphene conjugates that have the same shape and thickness. In other words, in a group of graphene bonded bodies that have the same shape and the same thickness and are bonded together via a group of friction-welded graphene, the proportion of the area where the graphene bonded bodies overlap increases, so the bonded graphene bonded bodies are The mechanical strength of the graphene conjugate assembly increases.

The method of the present invention for producing a larger and thicker graphene bonded body by precipitating graphene aggregates in the gaps between graphene bonded bodies and joining the graphene bonded bodies together by friction welding the graphene aggregates is ,
A suspension of a collection of graphene is dispersed in methanol, a collection of graphene conjugates is weighed as a weight greater than the weight of the collection of graphene, and the collection of graphene conjugates is mixed into the suspension. a first step of creating a first mixture;
A portion of the first mixture is poured into a container, and a vibration acceleration of 0.3-0.5G in three directions (left and right, front and back, and up and down) is repeatedly applied to each direction in order, and finally A vertical vibrational acceleration of 0.3-0.5G is applied to the graphene, whereby the graphene clusters are aligned in a plane with the surface facing up through the methanol, and the graphene conjugate clusters are arranged in a plane with the surface facing up. A second mixture is prepared in which the graphene clusters and the graphene conjugate clusters are arranged in a plane with their faces facing up through the methanol, and the clusters of graphene and the clusters of graphene conjugates are randomly stacked in methanol and dispersed in methanol. The second step of creating
The temperature of the container is raised to the boiling point of the methanol, and the methanol is vaporized from the container, resulting in a collection of graphene arranged in a planar shape with the surface facing up, and a graphene junction arranged in a planar shape with the surface facing up. A third step in which a third mixture is formed on the bottom surface of the container, in which the clusters of graphene bodies overlap each other and are randomly stacked, and the gaps between all the graphene bonded bodies are filled with the clusters of graphene bodies. and,
The entire surface of the third mixture is covered with a plate material, the entire surface of the plate material is evenly compressed, and the entire surface of the third mixture is evenly compressed, thereby reducing the gaps between all the graphene bonded bodies. The collection of graphene that has filled up is frictionally welded to the graphene bonded body, the graphenes are frictionally welded to each other, and the gaps between all the graphene bonded bodies are filled with the graphene that has been frictionally welded. , a fourth step in which the graphene bonded bodies are bonded to each other via the friction-welded cluster of graphene, and a graphene bonded body having a larger area and thickness is formed on the bottom surface of the container in the shape of the bottom surface. and,
An impact acceleration of 0.3-0.5G is intermittently and repeatedly applied to 5-9 locations on the bottom of the container, and the graphene bond formed on the bottom of the container is peeled off from the bottom of the container. , a fifth step of taking out the graphene conjugate,
By sequentially and continuously carrying out all of the processes in the five steps described above, clusters of graphene are precipitated in the gaps between the graphene bonded bodies, and the graphene bonded bodies are joined by friction welding of the graphene clusters. This is a method for producing a graphene bonded body with a larger area and thicker thickness.

The present invention consists of five steps.
The first step is to create a suspension by dispersing a collection of graphene in methanol, weigh the collection of graphene conjugates as a weight greater than the weight of the collection of graphene, and suspend the collection of graphene conjugates. to create a mixture.
In other words, graphene has a thickness of 0.332 nm, which is extremely thin, so it has almost no mass. By mixing this collection of graphene with low-viscosity, low-density methanol and stirring the methanol, a suspension of graphene dispersed in methanol is created. Thereafter, a graphene bonded body in which graphenes are bonded to each other is weighed as a weight greater than the weight of the graphene aggregate, and mixed into a suspension to create a mixture. In other words, since graphene plays the role of a bonding material that joins the graphene bonded bodies together, the amount of graphene aggregates that fill the gaps between the graphene bonded bodies is smaller than the amount of graphene constituting the graphene bonded bodies. In addition, graphene conjugates made by joining graphene to each other have almost no mass, so if a collection of graphene conjugates is mixed into a suspension and methanol is stirred, the graphene conjugates can be easily dispersed in methanol along with graphene. do. For example, the thickness of a graphene bonded body made by stacking and bonding 10 graphene sheets is only 3.32 nm. Therefore, even if the area of the graphene bonded body is 1 cm×1 cm, the mass of the graphene bonded body is extremely small.
In the second step, a portion of the mixture described above is poured into a container, and depending on the size of the container, a vibration acceleration of 0.3-0.5G is applied to the container in three directions: left and right, front and back, and up and down. For example, vibration acceleration in each direction is applied five times for 5 seconds each, and then vibration acceleration in the vertical direction is applied for 5 seconds.
At this time, graphene has almost no mass and has a large aspect ratio, which is the ratio of area to thickness, so when a collection of graphene dispersed in methanol is subjected to vibrational acceleration in three directions, methanol However, because the aspect ratio of graphene is large, it is best to move the graphene in methanol with its surface facing up, which will cause the least amount of stress on the graphene. Therefore, graphene moves in methanol with its surface facing up. By repeatedly subjecting a collection of graphene to vibrational acceleration in three directions, the collection of graphene is randomly arranged in a planar shape in methanol. Furthermore, the graphene composite also has almost no mass, and its aspect ratio, which is the ratio of area to thickness, is even larger than that of graphene. Therefore, when the graphene conjugate dispersed in methanol is subjected to vibrational acceleration in three directions, it moves along with the methanol in the direction of the vibrational acceleration, but because the aspect ratio of the graphene conjugate is large, it is placed face up and placed in the methanol. Moving inside the graphene is the best way to apply the least load to the graphene composite. Therefore, the graphene conjugate also moves in methanol with its surface facing up. By repeatedly subjecting a collection of graphene conjugates to vibrational acceleration in three directions, the collection of graphene conjugates is randomly arranged in a planar shape in methanol. Note that the magnitude of the vibration acceleration to be applied is 0.3 to 0.5G depending on the size of the groove.
In other words, graphene and graphene conjugate are covered with low-viscosity, low-density methanol and are dispersed in methanol. When vibrational acceleration in three directions is repeatedly applied to a container containing graphene dispersed in methanol and a graphene bond, the low-viscosity, low-density methanol forms a graphene bond with graphene, which has almost no mass. It moves along with the body in the direction of vibrational acceleration. On the other hand, if the aspect ratio of graphene is defined as the ratio of area to thickness, since the thickness is only 0.322 nm, the aspect ratio is extremely large. Further, although the graphene conjugate is thicker than graphene, the area is significantly larger than that of graphene, so the aspect ratio of the graphene conjugate is significantly larger than that of graphene. On the other hand, since graphene and graphene conjugates have a large aspect ratio, moving them through methanol with their faces facing up places the least stress on graphene and graphene conjugates. For this reason, the graphene and the graphene conjugate are moved in methanol with their faces facing up, and are repeatedly subjected to vibrational acceleration in three directions, so that the graphene and the graphene conjugate are randomly arranged in a planar manner in the methanol. As a result, a collection of graphene arranged in a plane with the face up and a collection of graphene conjugates arranged in a plane with the face up are randomly stacked in methanol and dispersed in methanol. A mixture is formed in a container. Finally, by applying vibrational acceleration in the vertical direction, the collection of graphene arranged in a plane and the collection of graphene conjugates arranged in a plane overlap each other, and the mixture randomly stacked in methanol is securely placed in the container. is formed. Note that the magnitude of the vibrational acceleration applied to the container is 0.3-0.5G depending on the size of the container. This solves the second problem described in paragraph 6.
The third step is to raise the temperature of the container to the boiling point of methanol, vaporize the methanol from the container, and form a collection of graphene arranged in a planar shape with the surface facing up, and a graphene junction arranged in a planar shape with the surface facing up. A mixture of randomly stacked bodies overlapping each other is formed on the bottom of the container in the shape of the bottom. On the other hand, since the size of graphene is significantly smaller than the size of the graphene conjugates, when methanol is vaporized, a collection of graphene precipitates filling the gaps between the graphene conjugates. As a result, the gaps between all the graphene bonded bodies arranged in a plane are filled with a collection of graphene arranged in a plane. This solves the first problem described in paragraph 6.
In the fourth step, the entire surface of the mixture formed in the container is covered with a plate material, the entire surface of the plate material is evenly compressed, and the entire surface of the mixture is evenly compressed. As a result, the graphene particles precipitated by filling all the gaps between the graphene bonded bodies are frictionally welded to the graphene bonded bodies, the graphenes are frictionally welded to each other, and all the gaps between the graphene bonded bodies are welded by friction welding. It is filled with a collection of graphene. As a result, the graphene bonded bodies are bonded to each other via the friction-welded graphene clusters, and a graphene bonded body having a larger area and thickness is formed on the bottom surface of the container in the shape of the bottom surface. In addition, both the graphene bonded bodies existing on the surface of the mixture and the graphene bonded bodies present on the back side of the mixture, the collection of graphene precipitated filling the surface causes friction on the surface of the graphene bonded body. At the same time, the graphenes are frictionally welded together, and the frictionally welded graphene is frictionally welded to the surface of the graphene bonded body.
In the fifth step, impact acceleration of 0.3-0.5G is applied repeatedly intermittently to 5-9 locations on the bottom of the container, and the graphene bond formed on the bottom of the container is removed from the bottom of the container. Peel it off and take out the graphene bond.

In the graphene bonded body formed by the method described above, the graphenes overlap each other with their faces upward, and the overlapping graphenes are directly bonded to each other by frictional heat. were joined together. Therefore, since the graphene conjugate is composed of a collection of graphene whose surfaces overlap each other, it has properties similar to those of graphene described in the second paragraph.
First, the thickness of a graphene bonded body made of 20 graphene sheets overlapped and bonded is only 6.64 nm, and even if the graphene bonded body has a size of 1 cm x 1 cm, its weight is small. Even if 10 sheets of this graphene bonded body are bonded by overlapping graphene layers forming 10 layers, the thickness will be only 3.32 nm. Therefore, even if the graphene bonded bodies are bonded together, their weight is extremely small. Therefore, the weight of the graphene composite is extremely small and has almost no mass.
Second, since the graphene bond is composed of a group of graphenes bonded with their surfaces facing upward, heat is preferentially transferred in the direction of the overlapping graphene surfaces. Therefore, the thermal conductivity of the graphene composite is close to that of graphene. In other words, the thermal conductivity of graphene in the thickness direction is extremely low, and heat is preferentially transferred in the plane direction. Therefore, the graphene composite acts as a substrate with better thermal conductivity than silver.
Thirdly, the electromagnetic waves irradiated to the graphene composite are transmitted in the direction of the overlapping graphene surfaces, and exhibit electromagnetic wave shielding properties according to the specific volume resistivity of graphene. Therefore, it acts as a film with better electromagnetic shielding properties than silver.
Fourth, graphene, which has an extremely large aspect ratio (the ratio of area to thickness), is strongly bonded to each other at the surfaces where they overlap, so the mechanical strength of the graphene bond is close to that of graphene. Graphene has a high breaking strength of 42 N/m, which is more than 100 times stronger than steel, so it acts as a coating with extremely high breaking strength.
Fifth, the heat resistance of a graphene bonded body in which graphene is bonded together by frictional heat is close to that of graphene. Therefore, it acts as a film with heat resistance exceeding the melting point of the metal.
Sixth, the shape and area of the graphene conjugate can be freely changed depending on the shape of the container into which the mixture is injected. On the other hand, since the size of graphene is significantly smaller than the size of the graphene conjugates, when methanol is vaporized from the mixture, a collection of graphene arranged in a planar shape precipitates, filling the gaps between all the graphene conjugates. As a result, all the gaps between the graphene conjugates are filled with a collection of graphene arranged in a plane. After that, when the mixture is compressed, the graphene clusters are frictionally welded to all the graphene bonded bodies, the graphenes are frictionally welded to each other, and all the graphene bonded bodies are joined via the frictionally welded graphene clusters. Ru. Therefore, there are no restrictions on the shape and area of the graphene bonded body to be manufactured.
Seventh, the larger the number of graphene bonded bodies to be bonded, and the larger the area or thickness of the bonded graphene bonded bodies, the larger the area or the thicker the bonded graphene bonded bodies. It gets thicker. Therefore, there are no restrictions on the size and thickness of the graphene bonded body for producing a graphene bonded body with a larger area and thicker thickness in the present invention. Therefore, many types of graphene conjugates having different areas and thicknesses can be easily produced, and a graphene conjugate having an area and thickness depending on the application can be selected.

The method for creating a suspension of graphene aggregates dispersed in methanol described in paragraph 7 is as follows:
One parallel plate electrode of a pair of electrode plates consisting of two parallel plate electrodes is arranged in a container, and a collection of scale-like graphite particles or a collection of lumpy graphite particles are packed flat on the surface of the one parallel plate electrode. Further, methanol is injected into the container, and the one parallel plate electrode and the collection of scale-like graphite particles or the collection of lumpy graphite particles are immersed in the methanol, further forming the electrode plate pair. The other parallel plate electrode plate is superimposed on the one parallel plate electrode via the collection of scale-like graphite particles or the collection of massive graphite particles, thereby forming an electrode plate pair consisting of the two parallel plate electrodes. is immersed in the methanol, and then, in the gap between the pair of electrode plates, the size is such that it can destroy the interlayer bond of the basal plane made of graphite crystals forming the flaky graphite particles or the massive graphite particles. Applying a direct current potential difference of By applying the electric field, all the interlayer bonds of the basal planes made of graphite crystals forming the flaky graphite particles or the massive graphite particles are simultaneously destroyed, and the basal planes are applied to the gap between the electrode plate pair. A collection of graphene consisting of planes is precipitated. After this, the gap between the electrode plate pair is enlarged, the electrode plate pair is tilted in methanol, and the container is placed in three directions: left and right, front and back, and top and bottom. A vibrational acceleration of 0.2-0.3G is applied in each direction in turn to move the graphene mass from the gap between the electrode plates into the methanol. After this, the electrode plates are removed from the container. Take out the pair,
This is a method in which a suspension of graphene aggregates dispersed in methanol is produced by sequentially and continuously performing all of the above-described processes.

In other words, by successively performing the following extremely simple process, a suspension of graphene aggregates dispersed in methanol is produced.
First, a collection of scale-like graphite particles or a collection of massive graphite particles packed in the gap between two parallel plate electrodes is immersed in methanol, which is an insulator, and a predetermined distance between the two parallel plate electrodes is immersed. A direct current potential difference with a magnitude of As a result, an electric field corresponding to the potential difference divided by the size of the gap between the two parallel plate electrodes is generated in the electrode gap where the collection of scaly graphite particles or the collection of massive graphite particles exists. This electric field simultaneously applies a Coulomb force sufficient to destroy the interlayer bonds in the basal plane made of graphite crystal to all the π electrons, which are responsible for the interlayer bonds in the basal plane, to all of the graphite particles described above. As a result, the π electrons are released from the constraints on the π orbital, and all π electrons leave the π orbital and become free electrons. In other words, when the Coulomb force acting on the π electron is applied to the π electron as a force greater than the interaction of the π orbital, the π electron is released from the constraints of the π orbital and becomes a free electron. As a result, all the π electrons, which are responsible for the interlayer bonds in the basal plane, no longer exist on the π orbitals, and for all graphite particles, all the interlayer bonds in the basal plane, which are made of graphite crystals that form graphite particles, are simultaneously removed. Destroyed. As a result, a collection of basal planes, ie, a collection of graphene, is instantaneously produced in the gap between the two parallel plate electrodes. The produced graphene is a genuine substance that is free of impurities and consists only of graphite crystals. Note that since the two parallel plate electrodes are immersed in methanol, the graphene aggregates deposited in the gap between the two parallel plate electrodes are not scattered.
Note that when a potential difference is applied between two parallel plate electrodes immersed in methanol, which is an insulator, an electric field is generated in the gap between the two parallel plate electrodes. That is, methanol is an insulator with a specific resistance of 3 MΩcm or more and a dielectric constant of 33. Further, ethanol is also an insulator with a dielectric constant of 24. Note that the electrical conductivity of ethanol is 7.5×10 ⁻⁶ S/m, and the electrical conductivity of flaky graphite particles is 43.9 S/m. Therefore, ethanol is an insulator whose electrical conductivity is 1.7×10 ⁷ times lower than that of scaly graphite particles, which are conductors.
Next, the graphene cluster is transferred from the gap between the two parallel plate electrodes into methanol. For this purpose, the gap between the two parallel plate electrodes is enlarged in methanol, and then tilted in methanol, and then vibrational acceleration is applied in three directions to the container filled with methanol. As a result, a collection of graphene moves from the gap between the two parallel plate electrodes into methanol. After this, the two parallel plate electrodes are removed from the container. As a result, a suspension of graphene aggregates dispersed in methanol is produced in the container.

Here, in the graphite particles that are packed into the gap between the two parallel plate electrode pairs by an electric field applied to the gap between the two parallel plate electrode pairs, interlayer bonding between the basal planes made of graphite crystals forming the graphite particle This explains the phenomenon in which all of the above are destroyed at the same time.
Carbon atoms forming the basal plane of graphite crystals in graphite particles have four valence electrons. Three of these valence electrons are σ electrons that form the basal plane of graphite crystal, that is, graphene. These σ electrons are covalently bonded to the σ electrons of three adjacent carbon atoms on the basal plane at an angle of 120 degrees, forming a two-dimensional hexagonal strong network structure. The remaining valence electron is a π electron, which exists on a π orbital extending perpendicular to the basal plane. These π electrons bond with the π electrons of carbon atoms adjacent in the vertical direction perpendicular to the basal plane with a weak bonding force, and based on this weak bonding force, the basal planes are stacked together in a layered manner. In other words, the base planes, that is, graphene, are bonded to each other in a layered manner by interactions of π orbitals, which are weak binding forces. Therefore, graphite particles have a property of being easily peeled off at the base surface made of graphite crystal, that is, they have mechanical anisotropy. This mechanical anisotropy is known as the lubricity of graphite particles.
When an electric field is applied to such graphite particles, a Coulomb force due to the electric field acts on all π electrons. When the Coulomb force acting on the π electron acts on the π electron as a force greater than the interaction of the π orbital acting on the π electron, the π electron is released from the restraint on the π orbital. As a result, all the π electrons leave the π orbital and become free electrons. As a result, all the π electrons, which are carriers of interlayer bonds in the basal plane made of graphite crystal, are no longer on the π orbit, so that all the interlayer bonds in the basal plane are destroyed at the same time. That is, when the π electrons move through the interlayer distance b of the graphite crystal due to the Coulomb force F, the π electrons perform work W (W=b·F). This work W is 35 millielectron volts, which is the magnitude of the interaction of π orbital per atom acting on π electrons (electron volt is a unit that expresses the amount of energy possessed by electrons, and 1 electron volt is 1. (equivalent to 62×10 ⁻¹⁹ Joules), the π electrons are released from the constraints of the π orbital interaction and become free electrons. For example, if the gap between two pairs of parallel plate electrodes is set at 100 μm and a DC potential difference of 10.6 kilovolts or more is applied between the electrodes, the interlayer bonds of all the basal planes made of graphite crystal will be instantly destroyed. be done. In this way, a large amount of graphene can be produced at low cost by the extremely simple method of applying an electric field to a collection of inexpensive graphite particles. Moreover, since the interlayer bonds of all the basal planes are destroyed at the same time, the obtained fine substance is definitely a basal plane made of graphite crystals, that is, graphene.
Note that the term "collection of graphite particles" as used herein refers to a collection of graphite particles in a relatively small amount of about 1 g to 100 g. That is, the scaly graphite particles or massive graphite particles are fine particles with a bulk density of 0.2-0.5 g/cm ³ and a particle size distribution of 1-300 microns. Therefore, it is easy to pack a collection of graphite particles into the gap between the two pairs of parallel plate electrodes, and it is also easy to apply a potential difference between the two pairs of parallel plate electrodes. When a potential difference is applied across the gap between the two pairs of parallel plate electrodes, an electric field is generated in all regions where the graphite particles are tightly packed. This electric field acts on the π electron as a Coulomb force that is stronger than the interaction of the π orbital, and the π electron is released from the constraints on the π orbital and becomes a free electron. As a result, all the interlayer bonds of the basal plane made of graphite crystals in the graphite particles are simultaneously destroyed, and a basal plane made of graphite crystals, that is, a collection of graphene, is produced in the gap between the two parallel plate electrode pairs.
Here, the number of graphenes is calculated using arithmetic. Here, it is assumed that all graphite particles are composed of spheres with a diameter of 25 microns, and since the true density of graphite is 2.25 × 10 ³ kg/m ³ , the weight of one graphite particle is is only 1.84×10 ⁻⁸ g. Furthermore, assuming that the average thickness of graphite particles is 10 microns, the interlayer distance is 3.354 angstroms, so a scaly graphite particle with a thickness of 10 microns has 297,265 basal planes, that is, graphite particles. are layered. Therefore, by destroying all the interlayer bonds in the basal plane made of graphite crystals, a collection of 297,265 graphenes can be obtained from just one spherical graphite particle. Therefore, for a collection of only 1 g of spherical graphite particles, when all the interlayer bonds in the basal plane are destroyed, a collection of 1.62×10 ¹³ graphene particles is obtained. Therefore, from a small amount of graphite particles, a huge number of graphene particles can be obtained. Note that the method for producing a graphene cluster from a graphite particle cluster described above is described in Patent Document 3 by the present inventor.

The method of manufacturing a graphene bonded body having a larger area and a thicker thickness than described in paragraph 7 is as follows:
The collection of graphene conjugates described in paragraph 7 is a plurality of graphene conjugates having the same shape and the same thickness, and the plurality of graphene conjugates having the same shape and the same thickness are described in paragraph 7. This is a method of manufacturing a graphene conjugate having a larger area and a larger thickness by using the graphene conjugate described above as a collection and following the manufacturing method described in paragraph 7.

In other words, a plurality of graphene bonded bodies having the same shape and the same thickness are used as a group of graphene bonded bodies described in paragraph 7, and the graphene bonded bodies are frictionally welded together according to the manufacturing method described in paragraph 7. When bonded through a group of graphene bonded bodies, the proportion of the area where the graphene bonded bodies overlap increases, so the mechanical strength of the bonded graphene bonded body increases.
First, a plurality of graphene conjugates having the same shape and the same thickness are manufactured. The plurality of graphene conjugates are weighed according to the manufacturing method described in paragraph 7, and the mass of graphene conjugates is mixed into a suspension in which the graphene aggregates are dispersed in methanol. to create a mixture.
Next, according to the manufacturing method described in paragraph 7, a part of the mixture is poured into a container, and depending on the size of the container, it is poured into the container from 0.3 to 0.5 G in three directions: left and right, front and back, and up and down. For example, vibration acceleration in each direction is applied five times for 5 seconds each, and then vibration acceleration in the vertical direction is applied for 5 seconds.
At this time, since graphene has almost no mass and has a large aspect ratio, when graphene is subjected to vibrational acceleration, movement through methanol with its surface facing up places the least load on graphene. Therefore, when a collection of graphene is repeatedly subjected to vibrational acceleration in three directions, the graphene is randomly arranged in a plane with the surface facing up in methanol. In addition, the graphene bond has almost no mass and has a large aspect ratio, which is the ratio of area to thickness, so when the graphene bond is subjected to vibrational acceleration, the movement of the graphene bond in methanol with its face up is The least load is applied to the joint. Therefore, when the graphene conjugates dispersed in methanol are repeatedly subjected to vibrational acceleration in three directions, the graphene conjugates are randomly arranged in a planar manner with the surface facing up in the methanol. A collection of graphene arranged in a planar shape with its face up and a collection of graphene conjugates arranged in a planar shape with its face up are randomly stacked in methanol and dispersed in methanol.
In other words, both the graphene and the plurality of graphene conjugates having the same shape and thickness are covered with low-viscosity, low-density methanol and are dispersed in the methanol. When vibrational acceleration is applied in three directions to a container in which multiple graphene conjugates having the same shape and thickness as graphene aggregates are dispersed in methanol, the low-viscosity, low-density methanol loses almost all of its mass. The graphene and the graphene bonded body move in the direction of the vibrational acceleration. On the other hand, if the aspect ratio of graphene is defined as the ratio of area to thickness, since the thickness is only 0.322 nm, the aspect ratio is extremely large. Further, graphene conjugates having the same shape and the same thickness are thicker than graphene, but have a significantly larger area than graphene, so the aspect ratio of the graphene conjugates is significantly larger than that of graphene. Therefore, when both of the plurality of graphene bonded bodies having the same shape and thickness as graphene are moved in methanol with their faces facing up, the least load is applied to the graphene and the graphene bonded bodies. Therefore, the graphene and the graphene conjugate move in methanol with their faces facing up, and the graphene and the graphene conjugate are randomly arranged in a planar manner in the methanol via the methanol. As a result, both the collection of graphene arranged in a plane and the collection of graphene conjugates arranged in a plane are randomly stacked on each other, and a mixture dispersed in methanol is formed in the container. After that, vibrational acceleration in the vertical direction is applied to ensure that a collection of graphene arranged in a plane and a collection of graphene conjugates overlap each other to form a randomly stacked collection in methanol in the container.
After that, according to the manufacturing method described in paragraph 7, when the temperature of the container is raised to the boiling point of methanol and methanol is vaporized from the container, a collection of graphene arranged in a plane with the surface facing up and a collection of graphene with the surface facing up are formed. A mixture in which a plurality of graphene bonded bodies arranged in a plane having the same shape and the same thickness and stacked on top of each other at random is formed on the bottom surface of the container in the shape of the bottom surface. On the other hand, since the size of graphene is significantly smaller than the size of the graphene conjugates, when methanol is vaporized, a collection of graphene precipitates filling the gaps between all the graphene conjugates. As a result, all the gaps between the graphene conjugates are filled with a collection of graphene arranged in a plane.
Thereafter, according to the manufacturing method described in paragraph 7, the entire surface of the mixture formed in the container is covered with a plate material, the entire surface of the plate material is evenly compressed, and the entire surface of the mixture is evenly compressed. As a result, a collection of precipitated graphene fills the gaps between all the graphene bonded bodies that have the same shape and the same thickness, and is frictionally welded to the graphene bonded body, and the graphenes are frictionally welded to each other, and all the graphene The gaps between the bonded bodies are filled with a collection of friction-welded graphene. In addition, both the graphene bonded body existing on the surface of the mixture and the graphene bonded body present on the back side of the mixture, a collection of graphene precipitated filling the surface is frictionally welded to the surface of the graphene bonded body, and Graphene is friction-welded to each other, and the friction-welded graphene fills the graphene bonded body. As a result, all graphene bonded bodies having the same shape and thickness are bonded to each other through the friction-welded cluster of graphene, and a graphene bonded body with a larger area and thickness is attached to the bottom surface of the container. It is formed as a shape.
In addition, when a collection of graphene conjugates is a collection of graphene conjugates that have the same shape and the same thickness, the proportion of the area where the graphene conjugates overlap increases, so the machine of the aggregate of the bonded graphene conjugates increases. The strength of the objective increases.

The method for simultaneously manufacturing a plurality of graphene bonded bodies having the same shape and the same thickness described in paragraph 13 is as follows:
A plurality of grooves having the same shape and the same depth are formed in the container, and the same amount of the suspension of graphene aggregates dispersed in methanol described in paragraph 7 is poured into each of the plurality of grooves. Then, vibration acceleration of 0.3-0.5G in three directions (left and right, front and back, and up and down) is repeatedly applied to the container in each direction, and finally, vibration acceleration of 0.3-0.5G is applied to the container in each direction. A vertical vibration acceleration of 5G is applied, whereby the graphene particles dispersed in the methanol in the suspension injected into the groove are arranged in a plane with the surface facing up in the methanol, and a first step in which a collection of graphene arranged in a plane is formed in the groove, in which a collection of graphene overlaps each other via the methanol;
The temperature of the container is raised to the boiling point of the methanol, the methanol is vaporized from the plurality of grooves, and the graphene is formed on the bottom surface of the plurality of grooves, in which the graphenes arranged in a planar manner overlap each other and are stacked. a first feature formed in a position in contact with a side surface of the plurality of grooves of the container, and a second feature having the same length that is longer than the depth of the plurality of grooves. and a third feature having the same number of grooves as the plurality of grooves. , the plate material is superimposed on the container, and the entire surface of the plate material on the opposite side where the protrusions are formed is evenly compressed, so that the tips of the plurality of protrusions are formed on the bottom surface of the plurality of grooves. The clusters of graphene arranged in a planar shape overlap each other and compress the stacked cluster of graphenes. As a result, the stacked graphenes arranged in a planar shape are frictionally welded on the overlapping surfaces, and the friction a second step in which a graphene bonded body consisting of a group of graphene bonded by pressure welding is formed on the bottom surface of the plurality of grooves in the shape of the bottom surface;
Impact acceleration of 0.3-0.5G is intermittently and repeatedly applied to a plurality of parts corresponding to the bottom surface of the container where the plurality of grooves are formed, and the graphene formed on the bottom surface of the plurality of grooves is a third step of peeling off the bonded body from the bottom surfaces of the plurality of grooves and taking out the graphene bonded body from the plurality of grooves,
By sequentially performing all the processes in the three steps described above, a plurality of graphene bonded bodies having the same shape and the same thickness are simultaneously manufactured in a plurality of grooves. This is a method for simultaneously manufacturing multiple graphene conjugates of various thicknesses.

First, prepare a container having a plurality of grooves with the same bottom shape and the same depth, and fill each of the plurality of grooves with the same suspension of graphene aggregates dispersed in methanol as described in paragraph 7. Inject amount. Note that the amount of suspension required to form a graphene bond with a preset thickness on the bottom of the groove is determined in advance, and the same amount of the suspension is injected into each of the plurality of grooves. . Furthermore, a vibration acceleration of 0.3-0.5G in three directions (left and right, front and back, and up and down) is applied to the container, for example, by repeating the vibration acceleration in each direction five times for 5 seconds, and then Apply directional vibrational acceleration for 5 seconds. At this time, since the aspect ratio of graphene is large, the movement of graphene in methanol with its surface facing up places the least load on graphene. Therefore, vibrational acceleration in three directions is repeatedly applied to the graphene cluster, so that the graphene cluster is randomly arranged in a plane with the graphene face up in methanol. Note that the magnitude of the vibration acceleration to be applied is 0.3 to 0.5G depending on the size of the groove.
In other words, graphene is covered with and dispersed in methanol, which has a low viscosity and low density. When vibrational acceleration is applied in three directions to a groove in which a collection of graphene dispersed in methanol is injected, the low-viscosity, low-density methanol moves in the direction of the vibrational acceleration, accompanied by graphene, which has almost no mass. Moving. On the other hand, if the aspect ratio of graphene is defined as the ratio of the major axis to the thickness, the aspect ratio of graphene produced from graphite particles is extremely large at 3×10 ³ -9×10 ⁶ . At this time, the least load is applied to the graphene when the graphene is moved in the direction of vibrational acceleration in methanol with its surface facing up. Therefore, by repeatedly receiving vibrational acceleration in three directions, a collection of graphene is arranged in a plane with the surface facing up in methanol. As a result, a collection of graphenes, in which graphenes arranged in a plane are overlapped with each other via methanol and randomly stacked, is formed in all the grooves. Finally, vibrational acceleration in the vertical direction is applied to ensure that a collection of stacked graphenes, in which graphenes arranged in a plane overlap each other via methanol, is formed into a groove. As a result, the same amount of graphene, in which graphene arranged in a plane is stacked on top of each other via methanol, is formed in all the grooves. The magnitude of the vibrational acceleration applied to the container is 0.3-0.5G depending on the size of the groove.
Note that graphene produced by destroying graphite crystals in graphite particles has a size of 1 to 300 μm because the graphite particles are fine particles. Furthermore, the thickness of graphene is extremely thin at 0.332 nm. Therefore, if the aspect ratio of graphene is the ratio of the major axis to the thickness, the aspect ratio is extremely large, 3×10 ³ -9×10 ⁶ , as described above. Therefore, when vibrational acceleration is applied in three directions to a collection of graphene dispersed in methanol, the graphene moves along with the methanol in the direction of the vibrational acceleration, with the surface on which the least load is applied to the graphene facing upward. For this reason, by repeatedly applying vibrational acceleration in three directions, the graphene is arranged in a plane with its surface facing up in methanol, and the graphene arranged in a plane overlaps with the methanol intervening, forming a collection of stacked graphene. , formed in a groove.
Next, the temperature of the container is raised to the boiling point of methanol, and methanol is vaporized from all grooves. As a result, a collection of graphene arranged in a plane and stacked on top of each other is formed in each groove. After this, a plate material is prepared that has a plurality of protrusions that are formed at positions that contact the side surfaces of the plurality of grooves, are longer than the depth of the plurality of grooves, have the same length, and have the same number as the plurality of grooves. . Lay this plate material on top of the container. Furthermore, the entire surface of the plate material is compressed evenly, and the graphene clusters formed on the bottom surfaces of the plurality of grooves are compressed by the plurality of protrusions. As a result, all the stacked graphenes arranged in a plane are compressed, and all the stacked graphenes are frictionally welded to each other on the overlapping surfaces, resulting in a graphene bonded body consisting of a collection of graphenes joined by friction welding. The shapes of the bottom surfaces are simultaneously formed on the bottom surfaces of a plurality of grooves. Furthermore, impact acceleration is applied intermittently for, for example, 5 seconds to the parts corresponding to the bottom surfaces of the container in which the plurality of grooves are formed, and the graphene bond formed in the plurality of grooves is transferred to the bottom surface of the plurality of grooves. Peel it off. Note that the magnitude of the impact acceleration applied to the container is a vibrational acceleration of 0.3-0.5G depending on the size of the container. As a result, a plurality of graphene bonded bodies having the same shape and the same thickness are manufactured at the same time. This solves the third problem described in paragraph 6. As a result, all the problems described in paragraph 6 are solved. Note that since a plurality of graphene conjugates having the same shape and the same thickness are simultaneously formed on the bottom surfaces of a plurality of grooves in the shape of the bottom surfaces, the shape of the graphene conjugates becomes the shape of the bottom surfaces of the grooves. . Furthermore, the thickness of the graphene conjugate is determined by the amount of a suspension of graphene aggregates dispersed in methanol injected into the grooves. Therefore, by changing the size of the bottom surface of the groove and by changing the amount of suspension injected into the groove, the shape and thickness of the graphene bonded body to be manufactured can be freely changed. .

FIG. 2 is a front view of a plate material in which 100 grooves are formed, which is used when simultaneously manufacturing a plurality of graphene bonded bodies having the same shape and the same thickness. 1 is a diagram schematically showing the side surface of 100 graphene bonded bodies having the same shape and the same thickness manufactured at the same time. FIG. A side surface of a graphene bonded body made of 100 sheets of graphene bonded bodies, 25 sheets of graphene bonded bodies forming one layer of graphene bonded bodies, and four layers of the graphene bonded bodies joined via a collection of graphenes frictionally welded. FIG.

Example 1
In this example, a suspension of graphene aggregates dispersed in methanol is created according to the method described in paragraph 10.
First, 3 liters of methanol was filled into a shallow container measuring 1.2 m x 1.2 m.
Next, prepare parallel plate electrodes in which the effective area of the electrode that generates an electric field in the gap between the two parallel plate electrodes is 1 m x 1 m, and overlap the two parallel plate electrodes with a gap of 100 μm. Graphite particles are evenly packed into the container and immersed in methanol. Assuming that the graphite particles are spheres with a particle size of 25 μm, if the graphite particles are evenly packed into a 100 μm gap created by two parallel plate electrodes, there will be 6.4 × 10 ⁷ graphite particles. do. When a DC voltage of 10.6 kilovolts or more is applied to this collection of graphite particles, the interlayer bonds of the basal surfaces of all graphite particles are simultaneously destroyed. At this time, a collection of 1.9×10 ¹³ graphene particles was obtained, and the collection of graphite particles used was only 1.18 g.
For this purpose, 12 g of flaky graphite particles (for example, XD100 from Ito Graphite Industries Co., Ltd.) were stacked and packed on the surface of a parallel plate electrode whose effective area for generating an electric field was 1 m x 1 m. This parallel plate electrode is immersed in a container filled with methanol, and further, the other parallel plate electrode is superimposed on the above parallel plate electrode, and the two parallel plate electrodes are separated by a gap of 100 μm, A DC voltage of 12 kilovolts was applied between the electrodes. Next, the gap between the two parallel plate electrodes was enlarged, the two parallel plate electrodes were tilted in methanol, and vibrational acceleration of 0.2G in three directions was repeatedly applied to the container. Two parallel plate electrodes were taken out from the.
Next, a part of the prepared sample was taken out, and the sample was observed and analyzed using an electron microscope. As the electron microscope, an extremely low acceleration voltage SEM manufactured by JFE Techno Research Co., Ltd. was used. This device is capable of surface observation using an extremely low accelerating voltage of 100 volts, and has the feature of directly observing the surface of a sample without forming a conductive film on the sample.
Image processing was performed by extracting a secondary electron beam between 900 and 1000 volts from the reflected electron beam from the surface of the sample. It was confirmed that the sample was a flat material with an extremely thin thickness. Furthermore, image processing of the energy and intensity of characteristic X-rays revealed that only carbon atoms were present. Therefore, it was confirmed that the sample was graphene.
As a result, a collection of scaly graphite particles was packed into the gap between the two parallel plate electrodes, a direct current potential difference was applied between the electrodes, and this potential difference was divided by the size of the gap between the two parallel plate electrodes. An electric field corresponding to the value is generated in the electrode gap where a collection of scale-like graphite particles exists, and this electric field generates a Coulomb force of sufficient magnitude to break the interlayer bonding of the basal plane of graphite crystals for all graphite particles. A force is applied simultaneously to all the π electrons that are responsible for the interlayer bonds in the basal plane, and as a result, all the interlayer bonds in the graphite crystal are simultaneously destroyed, producing a basal plane made of graphite crystal, that is, a collection of graphene. It was confirmed that it can be done.

Example 2
This example is an example in which multiple graphene conjugates having the same shape and thickness are simultaneously manufactured according to the method described in paragraph 15, and a suspension in which the graphene manufactured in Example 1 is dispersed in methanol is used. Using this method, 100 graphene bonded bodies each consisting of a disk with a diameter of 20 mm were manufactured at the same time.
In a first plate material of 31 cm x 31 cm x 2 cm (thickness), 10 cylindrical grooves with a diameter of 20 mm and a depth of 10 mm were formed at equal intervals of 10 mm in the horizontal direction and 10 in the vertical direction. . FIG. 1 shows a front view of the first plate material. 1 is a groove made of a cylinder. Further, a cylindrical protrusion with a diameter of 20 mm and a length of 15 mm was formed on a second plate material of 31 cm x 31 cm x 2 cm (thickness). Next, 0.15 g of the suspension of graphene produced in Example 1 dispersed in methanol was injected into each of the 100 grooves, and the first plate was subjected to vibration acceleration of 0.3 G in three directions. Vibration acceleration in each direction was applied repeatedly for 5 seconds five times, and then vibration acceleration in the vertical direction was applied for 5 seconds. Furthermore, the temperature of the first plate material was raised to the boiling point of methanol, and methanol was vaporized from the 100 cylindrical grooves. After this, the second plate material provided with the cylindrical protrusions is placed one on top of the other, and 100 weights of 1 kg are placed on the opposite surface corresponding to the area where the cylindrical protrusions are formed. At the tip, the graphene clusters present at the bottom of the cylinder's grooves were compressed. After this, the stacked second plate material is removed, and an impact acceleration of 0.4G is simultaneously applied three times to 100 locations on the back surface corresponding to the areas where the cylindrical grooves were formed, forming grooves on the bottom surface. The sample was peeled off from the bottom of the groove. A plate material was placed over the surface of the sample that had been peeled off from the groove, and a 10 kg weight was placed on the plate material, but no change was observed in the sample, so it was bonded with a constant bonding force.
Next, the sample peeled off from the bottom of the groove was observed and analyzed using the electron microscope used in Example 1. First, a secondary electron beam between 900 and 1000 volts of the reflected electron beam from the side of the sample was taken out and subjected to image processing. On the side surface of the sample, it was confirmed that extremely thin materials were stacked to form a thickness of 6.64 nm. Next, image processing of the energy and intensity of characteristic X-rays revealed that only carbon atoms were present. Therefore, it was confirmed that the sample was a sample in which 20 layers of graphene flat surfaces were laminated. FIG. 2 schematically shows an enlarged part of the side surface of a graphene bonded body in which flat surfaces of graphene overlap each other. 2 is a collection of overlapping graphenes.
Note that the groove formed in the first plate material was made into a cylindrical shape. The reason for this is that the shape of the bottom of the groove is a circle, and the distance from the center to the end of the circle is the same. On the other hand, in a quadrilateral, the distance from the center to the edge is not the same, and is longest at the corner. Therefore, when a group of graphene injected into a groove with a circular bottom surface is compressed, the group of graphene is likely to be compressed uniformly. On the other hand, even if a group of graphene injected into a groove with a square bottom is compressed by a square prism protrusion of the same shape, it is difficult to apply the same compressive stress at the corners; , there is a possibility that the graphenes will not be frictionally welded together. In other words, the size of graphene produced by simultaneously destroying the interlayer bonds between the basal planes of graphite crystals in graphite particles is 1 to 300 μm wide. Therefore, the finer the graphene, the more difficult it is for the graphene present in regions near the corners to be compressed. For this reason, the groove formed in the first plate material was made into a cylindrical shape.

Example 3
In this example, a suspension of graphene manufactured in Example 1 dispersed in methanol was mixed with a collection of graphene conjugates created in Example 2, and all graphene conjugates created in Example 2 were mixed with each other. This is an example in which all the graphene bonded bodies are bonded to each other via a collection of graphene friction-welded in the gap.
A groove of 10 cm x 10 cm x 1 cm (depth) was formed in a container of 11 cm x 11 cm x 2 cm (thickness). 3 g of the suspension of graphene produced in Example 1 dispersed in methanol was poured into a container, 100 sheets of the graphene conjugate produced in Example 2 were mixed, and the container was charged with 0.3 G in three directions. Vibration acceleration was applied repeatedly for 5 seconds in each direction five times, and then vibration acceleration in the vertical direction was applied for 5 seconds. Furthermore, the temperature of the container was raised to the boiling point of methanol, and methanol was vaporized from the container. Next, prepare a plate of 10 cm x 10 cm x 2 cm (thickness), cover the entire surface of the sample in the container with the plate, and then place nine 10 kg weights on the plate at equal intervals. The sample was compressed, then the plate material was removed, and an impact acceleration of 0.4G was applied three times at the same time to nine equally spaced locations on the bottom of the container, and the sample formed on the bottom of the container was peeled off from the bottom. Ta. The surface of the peeled sample was covered with a plate again, and nine 10 kg weights were placed on the plate at equal intervals, but no change was observed in the sample, so it was joined with a constant bonding force.
Next, the sample peeled off from the bottom of the container was observed and analyzed using the electron microscope used in Example 1. First, a secondary electron beam between 900 and 1000 volts of the reflected electron beam from the side of the sample was taken out and subjected to image processing. On the side of the sample, five layers are formed by stacking extremely fine materials with a thickness of 1.66 nm, and a layer of extremely thin materials is stacked to form a thickness of 6.64 nm. It was confirmed that four layers were formed and each layer was stacked one on top of the other. Next, as a result of image processing of the energy and intensity of characteristic X-rays, all substances contained only carbon atoms. Therefore, it was confirmed that the four graphene bonded bodies produced in Example 2 were a sample in which the graphene bonded bodies were bonded to each other via a collection of graphene. Therefore, the area of the sample is 100 cm ² and the thickness is 34.86 nm. FIG. 3 schematically shows an enlarged part of the side surface of the sample. 3 is a collection of graphene, and 4 is a graphene conjugate.
Furthermore, the prepared sample was allowed to fall naturally from a height of 2 m, but no change was observed in the sample. Furthermore, the prepared sample was allowed to fall naturally from a height of 4 m, but no change was observed in the sample. Therefore, the graphene bonded bodies are bonded to each other with a constant bonding force via the graphene clusters. Furthermore, the friction-welded clusters of graphene are also joined together with a constant joining force.

Example 4
In this example, 400 of the graphene junctions created in Example 2 were mixed into a suspension in which the graphene produced in Example 1 was dispersed in methanol, and all the graphene junctions created in Example 2 were mixed. This is an example in which all the graphene bonded bodies are joined together through a collection of graphene friction-welded in the gap between the bodies.
That is, in Example 3, 100 sheets of graphene bonded bodies each consisting of a disk with a diameter of 20 mm were stacked such that 25 sheets of graphene bonded bodies formed one layer, forming a total of 4 layers. For this purpose, a groove of 10 cm x 10 cm x 1 cm (depth) was formed in a container of 11 cm x 11 cm x 2 cm (thickness). Therefore, the area of the graphene bonded body manufactured in Example 3 is 100 cm ² .
On the other hand, in this example, 400 sheets of graphene bonded bodies each consisting of a disk having a diameter of 20 mm are stacked such that 100 sheets of graphene bonded bodies form one layer, forming a total of 4 layers. For this purpose, a groove of 20 cm x 20 cm x 1 cm (depth) was formed in a container of 21 cm x 21 cm x 2 cm (thickness). The area of the graphene bonded body manufactured in this example is 400 cm ² . In this way, the size of the graphene conjugate changes depending on the shape of the container into which the mixture consisting of the suspension of graphene aggregates dispersed in methanol and the graphene conjugate aggregate is injected.
First, according to the method described in Example 2, 100 pieces of graphene conjugated bodies each consisting of a disk with a diameter of 20 mm were manufactured by repeating the process four times to produce 400 pieces of graphene conjugated bodies each consisting of a disk with a diameter of 20 mm. do.
Next, a groove of 20 cm x 20 cm x 1 cm (depth) was formed in a container of 21 cm x 21 cm x 2 cm (thickness). 12 g of the suspension of graphene produced in Example 1 dispersed in methanol was poured into a container, and 400 sheets of the graphene conjugate produced in Example 2 were mixed, and the container was charged with 0.4 G in three directions. Vibration acceleration was applied repeatedly for 5 seconds in each direction five times, and then vibration acceleration in the vertical direction was applied for 5 seconds. Furthermore, the temperature of the container was raised to the boiling point of methanol, and methanol was vaporized from the container. Next, prepare a plate of 20 cm x 20 cm x 2 cm (thickness), cover the entire surface of the sample in the container with the plate, and then place nine 15 kg weights on the plate at equal intervals. The sample was compressed, then the plate was removed, and an impact acceleration of 0.5G was applied three times at the same time to nine equally spaced locations on the bottom of the container, and the sample formed on the bottom of the container was peeled off from the bottom. Ta. The surface of the peeled sample was covered with a plate again, and nine 15 kg weights were placed on the plate at equal intervals, but no change was observed in the sample, so it was joined with a constant bonding force.
Next, the sample peeled off from the bottom of the container was observed and analyzed using the electron microscope used in Example 1. First, a secondary electron beam between 900 and 1000 volts of the reflected electron beam from the side of the sample was taken out and subjected to image processing. On the side of the sample, five layers are formed by stacking extremely fine materials with a thickness of 1.66 nm, and a layer of extremely thin materials is stacked to form a thickness of 6.64 nm. It was confirmed that four layers were formed and each layer was stacked one on top of the other. Next, as a result of image processing of the energy and intensity of characteristic X-rays, all substances contained only carbon atoms. Therefore, it was confirmed that the four graphene bonded bodies produced in Example 2 were a sample in which the graphene bonded bodies were bonded to each other via a collection of graphene. Therefore, the area of the sample is 400 cm ² and the thickness is 34.86 nm.

The graphene conjugates created in Example 3 and Example 4 are only examples. That is, the shape and area of the graphene conjugate can be freely changed depending on the shape of the container into which the graphene conjugate is mixed with a suspension of graphene conjugates dispersed in methanol and the mixture is poured into the suspension. In addition, when methanol is vaporized from the mixture, a collection of graphene arranged in a plane fills the gaps between all the graphene conjugates, and when the mixture is compressed, the collection of graphene is separated from all the graphene conjugates. While friction welding is applied to the bonded body, the graphenes are also friction welded to each other, and all the graphene bonded bodies are joined via a collection of frictionally welded graphenes. Therefore, there are no restrictions on the shape and area of the graphene bonded body to be manufactured.
In other words, since the size of graphene is significantly smaller than the graphene conjugate, when methanol is vaporized from the mixture, all the gaps between the graphene conjugates are filled with a collection of graphene arranged in a plane. Additionally, graphene is an extremely strong material, and even if excessive compressive stress is applied to a collection of stacked graphenes, the graphene will not break. Therefore, when excessive compressive stress is applied to overlapping graphenes, frictional heat is generated at the overlapped portions, and the graphenes are bonded together by the frictional heat. Further, the graphene is frictionally welded to the graphene bonded body. Therefore, the shape and area of the graphene bonded body can be freely changed depending on the shape of the container into which the mixture is injected, so the graphene bonded body created in Example 3-4 is only an example.

1 Groove made of cylinder 2 Collection of overlapping graphene 3 Collection of graphene 4 Graphene conjugate

Claims (4)

A method for producing a graphene bonded body with a larger area and thickness by precipitating graphene aggregates in the gaps between graphene bonded bodies and joining the graphene bonded bodies together by friction welding the graphene aggregates is as follows:
A suspension of a collection of graphene is dispersed in methanol, a collection of graphene conjugates is weighed as a weight greater than the weight of the collection of graphene, and the collection of graphene conjugates is mixed into the suspension. a first step of creating a first mixture;
A portion of the first mixture is poured into a container, and a vibration acceleration of 0.3-0.5G in three directions (left and right, front and back, and up and down) is repeatedly applied to each direction in order, and finally A vertical vibrational acceleration of 0.3 to 0.5 G is applied to the graphene, whereby the graphene clusters are aligned in a plane with the surface facing up through the methanol, and the graphene conjugate clusters are also aligned. The collection of graphene and the collection of graphene conjugates arranged in a plane with their faces facing up through the methanol are randomly stacked in methanol to create a second mixture dispersed in methanol. A second step of
The temperature of the container is raised to the boiling point of the methanol, and the methanol is vaporized from the container, resulting in a collection of graphene arranged in a planar shape with the surface facing up, and a graphene junction arranged in a planar shape with the surface facing up. A third step in which a third mixture is formed on the bottom surface of the container, in which the clusters of graphene bodies overlap each other and are randomly stacked, and the gaps between all the graphene bonded bodies are filled with the clusters of graphene bodies. and,
The entire surface of the third mixture is covered with a plate material, the entire surface of the plate material is evenly compressed, and the entire surface of the third mixture is evenly compressed, thereby reducing the gaps between all the graphene bonded bodies. The collection of graphene that has filled up is frictionally welded to the graphene bonded body, the graphenes are frictionally welded to each other, and the gaps between all the graphene bonded bodies are filled with the graphene group that has been frictionally welded. , a fourth step in which the graphene bonded bodies are bonded to each other via the friction-welded cluster of graphene, and a graphene bonded body having a larger area and thickness is formed on the bottom surface of the container in the shape of the bottom surface. and,
An impact acceleration of 0.3-0.5G is intermittently and repeatedly applied to 5-9 locations on the bottom of the container, and the graphene bond formed on the bottom of the container is peeled off from the bottom of the container. , a fifth step of taking out the graphene conjugate,
By sequentially and continuously carrying out all of the processes in the five steps described above, clusters of graphene are precipitated in the gaps between the graphene bonded bodies, and the graphene bonded bodies are joined by friction welding of the graphene clusters. , a method in which graphene conjugates with larger area and thickness are produced. The method for creating a suspension in which a collection of graphene is dispersed in methanol according to claim 1 includes:
One parallel plate electrode of a pair of electrode plates consisting of two parallel plate electrodes is arranged in a container, and a collection of scale-like graphite particles or a collection of lumpy graphite particles are packed flat on the surface of the one parallel plate electrode. Further, methanol is injected into the container, and the one parallel plate electrode and the collection of scale-like graphite particles or the collection of lumpy graphite particles are immersed in the methanol, further forming the electrode plate pair. The other parallel plate electrode plate is superimposed on the one parallel plate electrode via the collection of scale-like graphite particles or the collection of massive graphite particles, thereby forming an electrode plate pair consisting of the two parallel plate electrodes. is immersed in the methanol, and then, in the gap between the pair of electrode plates, the size is such that it can destroy the interlayer bond of the basal plane made of graphite crystals forming the flaky graphite particles or the massive graphite particles. Applying a direct current potential difference of By applying the electric field, all the interlayer bonds of the basal planes made of graphite crystals forming the flaky graphite particles or the massive graphite particles are simultaneously destroyed, and the basal planes are applied to the gap between the electrode plate pair. A collection of graphene consisting of planes is precipitated. After this, the gap between the electrode plate pair is enlarged, the electrode plate pair is tilted in methanol, and the container is placed in three directions: left and right, front and back, and top and bottom. A vibrational acceleration of 0.2-0.3G is applied in each direction in turn to move the graphene mass from the gap between the electrode plates into the methanol. After this, the electrode plates are removed from the container. Take out the pair,
A method in which a suspension of graphene aggregates dispersed in methanol is created by sequentially performing all of the processes described above. The method of manufacturing a graphene bonded body having a larger area and a thicker thickness as described in claim 1 includes:
The collection of graphene conjugates described in claim 1 is a plurality of graphene conjugates having the same shape and the same thickness, and the plurality of graphene conjugates having the same shape and the same thickness are defined in claim 1. A method for producing a graphene bonded body having a larger area and a thicker thickness, using the graphene bonded body as a collection of the graphene bonded bodies described in claim 1, and according to the manufacturing method described in claim 1. The method of simultaneously manufacturing a plurality of graphene bonded bodies having the same shape and the same thickness according to claim 3,
A plurality of grooves having the same shape and the same depth are formed in the container, and the same amount of the suspension of graphene aggregates dispersed in methanol according to claim 1 is poured into each of the plurality of grooves. Further, vibration acceleration consisting of 0.3-0.5G in three directions (left and right, front and back, and up and down) is repeatedly applied to the container in each direction, and finally, 0.3-0. A vertical vibrational acceleration of .5 G is applied, whereby the graphene particles dispersed in the methanol in the suspension injected into the groove are arranged in a plane in the methanol with their faces facing up. a first step in which a collection of graphene arranged in a plane is formed in the groove, in which a collection of graphene overlaps each other via the methanol;
The temperature of the container is raised to the boiling point of the methanol, the methanol is vaporized from the plurality of grooves, and the graphene is formed on the bottom surface of the plurality of grooves, in which the graphenes arranged in a planar manner overlap each other and are stacked. a first feature formed in a position in contact with a side surface of the plurality of grooves of the container, and a second feature having the same length that is longer than the depth of the plurality of grooves. and a third feature having the same number of grooves as the plurality of grooves. , the plate material is superimposed on the container, and the entire surface of the plate material on the opposite side where the protrusions are formed is evenly compressed, so that the tips of the plurality of protrusions are formed on the bottom surface of the plurality of grooves. The clusters of graphene arranged in a planar shape overlap each other and compress the stacked cluster of graphenes. As a result, the stacked graphenes arranged in a planar shape are frictionally welded on the overlapping surfaces, and the friction a second step in which a graphene bonded body consisting of a group of graphene bonded by pressure welding is formed on the bottom surface of the plurality of grooves in the shape of the bottom surface;
Impact acceleration of 0.3-0.5G is intermittently and repeatedly applied to a plurality of parts corresponding to the bottom surface of the container where the plurality of grooves are formed, and the graphene formed on the bottom surface of the plurality of grooves is a third step of peeling off the bonded body from the bottom surfaces of the plurality of grooves and taking out the graphene bonded body from the plurality of grooves,
By sequentially performing all the processes in the three steps described above, a plurality of graphene bonded bodies having the same shape and the same thickness are simultaneously manufactured in a plurality of grooves. A method for simultaneously manufacturing graphene conjugates of multiple thicknesses.