JP2020186144A - Method for manufacturing graphene joined body in which flat faces of graphene are bonded together by assembly of metal fine particles composed of any metal of silver, copper, gold or aluminum - Google Patents

Abstract

To provide a method for producing a graphene joined body excellent in both thermal conductivity and electrical conductivity.SOLUTION: First, a raw material of a metal is made into a liquid phase. Second, a group of graphene is produced from graphite particles in a liquid. Third, each sheet of graphene is separated in a liquid. Fourth, flat faces of the graphene are superposed on a bottom surface of a container containing the liquid. Fifth, a group of metal fine particles is deposited on the flat faces of the graphene. Sixth, the flat faces of graphene are bonded together by the group of metal fine particles. More specifically, a graphene joined body is produced in the shape of the bottom surface on the bottom surface of the container by dispersing a metal compound of silver, copper, gold or aluminum in an alcohol, superimposing flat faces of graphene produced by the separation of graphite particles through an alcohol dispersion, thermally decomposing the metal compound, and bonding the flat faces of graphene 2 by a group of fine particles 1 made of a metal.SELECTED DRAWING: Figure 1

Description

The present invention relates to a production method for producing a graphene junction in which flat surfaces of graphene are bonded to each other by a collection of metal fine particles made of any metal of silver, copper, gold, or aluminum. That is, graphene has both thermal conductivity equivalent to 4.5 times the thermal conductivity of silver and electrical conductivity equivalent to only 23 times the specific resistance of copper. For this reason, graphene junctions, which are a collection of metal fine particles made of any of silver, copper, gold, or aluminum, and which bond the graphene flat surfaces together, give priority to the graphene flat surfaces where heat is more easily transferred than metal. The heat is transferred, and the current flows in preference to the collection of metal fine particles, which are easier to flow than graphene. As a result, the graphene conjugate has better thermal conductivity than silver and near metal conductivity. The metals are silver, copper, gold, and aluminum in that order, and are excellent in both thermal conductivity and electrical conductivity.

In 2004, a physicist at the University of Manchester, UK, used cellophane tape to tear off a single crystallite from graphite, a basal plane that two-dimensionally forms a network of hexagonal carbon atoms. For the first time, we succeeded in extracting a planar substance having a thickness of carbon atoms. This new substance was called graphene. The 2010 Nobel Prize in Physics has been awarded for this research result.

Graphene is an extremely thin substance whose thickness corresponds to the size of a carbon atom, and is a completely new carbon material having almost no mass. For this reason, it has physical properties far from those of conventional materials, and is attracting attention as a material that can be applied to a wide range of applications such as new quantum materials, new electronic device materials, new heat conductive materials, and new conductive materials.
For example, it is the thinnest material with a thickness of 0.332 nm. It also has the widest surface area of 3000 m ² / g per unit mass. Further, it has a Young's modulus as large as 1020 GPa, and is the most stretchable and bendable material. Moreover, it is the toughest substance having a large shear modulus of 440 GPa. Further, the thermal conductivity is 19.5 W / Cm, which corresponds to 4.5 times the thermal conductivity of silver, which has the highest thermal conductivity among metals. Moreover, the current density exceeds 1000 times that of copper. Further, the electron mobility is 15000 cm ² / volt / sec, which is an order of magnitude higher than the electron mobility of silicone of 1400 cm ² / volt / sec. Further, it is a single crystal material having a melting point of more than 3000 ° C. and has extremely high heat resistance.
In addition, graphene has excellent electrical resistance. The specific resistance of the natural graphite particles in the direction parallel to the basal plane is 3.8 × 10 ^-7 Ωm, and the specific resistance in the direction perpendicular to the basal plane is 7.6 × 10 ^-3 Ωm. Therefore, the resistivity of graphene is only 23 times that of copper.

Graphene, on the other hand, is produced in a variety of ways. For example, the professor at Manchenster University mentioned above physically peeled graphene from graphite by hand. In this method, it is difficult to peel off a large amount of graphene in a short time, and what is peeled off from graphite is not always a single crystallite, that is, graphene.
Further, Patent Document 1 describes a method for producing graphene by thermally decomposing a single crystal of silicon carbide. That is, the silicon carbide is heated in an inert atmosphere to thermally decompose the surface. At this time, silicon having a relatively low sublimation temperature is preferentially sublimated, and graphene is produced by the remaining carbon. However, a single crystal of silicon carbide is a very expensive material. Further, when silicon is sublimated at a high temperature exceeding 1600 ° C. and an atmosphere having a high degree of vacuum and even a small amount of silicon remains, graphene is not produced as a residue after thermal decomposition. Therefore, the cost of producing the silicon carbide single crystal and the thermal decomposition treatment of the single crystal becomes very expensive. In addition, producing a large amount of graphene requires an even higher cost.
Further, Patent Document 2 describes a method for producing graphene by bringing a carbon-based substance into contact with a sheet-shaped single crystal graphitized metal catalyst and heat-treating it in a reducing atmosphere. However, this manufacturing method is not an inexpensive manufacturing method, and is not a manufacturing method having excellent mass productivity. First, the production cost of producing a single crystal graphitized metal catalyst is even higher than that of the silicon carbide single crystal described above. Second, the method of contacting a single crystal graphitized metal catalyst with a carbon-based substance is inferior in mass productivity. Thirdly, the reduction treatment of the graphitized metal catalyst at a high temperature exceeding 1000 ° C. in an atmosphere rich in nitrogen gas including hydrogen gas requires an expensive cost. Fourth, producing large quantities of graphene is even more expensive.

None of the graphene production methods to date have been, first of all, a method of simultaneously producing a large amount of graphene by an inexpensive production method. Second, the graphene produced is not necessarily graphene. That is, graphene is not produced unless the reaction of only the crystal growth of carbon atoms proceeds in an atmosphere without impurities. Furthermore, since the graphene produced is extremely thin and extremely lightweight, it is extremely difficult to verify that it is graphene.
Therefore, the present inventor has found a method in which all the graphene produced is complete graphene and a large amount of graphene is instantly produced by an extremely simple method (Patent Document 3). That is, an electric field is applied to a collection of scaly graphite particles or massive graphite particles, which are composed of only a single crystal of graphite, the crystallization rate of graphite is 100% advanced, and the cheapest carbon material, that is, graphite particles are formed. This is a production method in which all of the interlayer bonds of the graphite crystals are instantly broken, thereby producing a large amount of graphene composed of the basal plane of the graphite crystals.

JP-A-2015-110485 JP-A-2009-143799 Patent No. 6166860

Graphene is an extremely thin substance consisting of a single crystallite, so it is extremely lightweight and has almost no mass. Therefore, graphene produced by simultaneously breaking the interlayer bond of graphite crystals in scaly graphite particles or lump graphite particles by applying an electric field in Patent Document 3 is extremely easily scattered during and after production. Further, since graphene is extremely thin, it has a flat surface having an extremely large aspect ratio, which is the ratio of the size of the crystal plane to the thickness. Therefore, when graphene is produced by the production method in Patent Document 3, graphenes easily overlap each other on a flat surface. Furthermore, the number of overlapping graphenes varies. On the other hand, since graphene is an extremely lightweight and extremely thin substance, it is extremely difficult to separate graphenes that overlap in the atmosphere into individual graphenes. The graphene junction in which the graphene flat planes are bonded to each other by using the graphenes overlapping the graphene planes is the graphene junction separated by the flat planes of the overlapping graphenes. The graphite particles composed of scaly graphite particles or lump graphite particles are graphite particles obtained by crushing a mass of natural graphite crystals and selecting crushed graphite crystals, and are composed of only a single crystal of graphite and crystallize graphite. It is the cheapest carbon material with a 100% advanced rate.
On the other hand, if the interlayer bonds of the graphite crystals in the scaly graphite particles or the massive graphite particles are simultaneously broken in the liquid filled in the container to produce a graphene aggregate, the graphene will not scatter during and after the production. In addition, a huge number of graphene can be produced with a small collection of graphite particles. Further, the graphene aggregate produced in the liquid is firstly separated into individual graphenes in the liquid filled in the container, and secondly, the graphene aggregates separated into individual graphenes are separated into individual graphenes. On the bottom surface of the container, the graphene flat surfaces are overlapped with each other, and third, if the graphene flat surfaces can be bonded by a collection of metal fine particles made of any metal such as silver, copper, gold, or aluminum, graphene bonding is performed. The body is formed on the bottom of the container in the shape of the bottom. As a result, a graphene conjugate having a thin thickness, an arbitrary area and an arbitrary shape can be inexpensively manufactured on the bottom surface of the container by using inexpensive graphite particles. Such graphene joints do not separate at the joint surfaces of the flat planes of graphene. Further, in the graphene junction, heat is transferred preferentially to the flat surface of graphene where heat is more easily transferred than metal, and current flows preferentially to a collection of metal fine particles in which current is more easily flowed than graphene. As a result, the graphene conjugate has better thermal conductivity than silver and has conductivity close to that of metal.
Therefore, in producing an inexpensive graphene junction in which the flat surfaces of graphene are bonded to each other by a collection of metal fine particles made of any of silver, copper, gold, or aluminum according to the present invention, the following six There are challenges. First, the raw material for any metal, silver, copper, gold, or aluminum, is a general-purpose industrial chemical that liquefies the raw material. As a result, the liquid phased liquid can be filled in the container. Second, using graphite particles composed of scaly graphite particles or lump graphite particles as a raw material for graphene, the interlayer bonds of all graphite crystals in the graphite particles are simultaneously destroyed in the liquid filled in the container, and the graphene aggregates. To manufacture. Third, the graphene collection is separated into individual graphenes in the liquid filled in the container. Fourth, a group of graphene in which the flat surfaces of graphene overlap each other is formed on the bottom surface of a container filled with liquid as a shape of the bottom surface. Fifth, the liquid is heat treated to deposit a collection of fine metal particles made of any of silver, copper, gold, or aluminum on the flat surface of graphene. Sixth, metal bonds are formed at the sites where the metal fine particles are in contact with each other, and the flat surfaces of graphene are bonded to each other by the collection of the metal-bonded metal fine particles, which is inexpensive and has excellent both thermal conductivity and electric conductivity. A graphene bond is manufactured on the bottom surface of the container as a bottom surface shape. An object to be solved by the present invention is to solve the above six problems and find a manufacturing method for producing a graphene conjugate excellent in both thermal conductivity and electric conductivity.

The alcohol is a collection of graphene in which the flat surfaces of graphene are overlapped with each other via an alcohol dispersion in which a metal compound that precipitates a metal of silver, copper, gold, or aluminum by thermal decomposition is dispersed in alcohol. The manufacturing method of manufacturing the bottom surface of the container filled with the dispersion liquid as the shape of the bottom surface is as follows.
A metal compound that precipitates any metal of silver, copper, gold, or aluminum by thermal decomposition is dispersed in alcohol to prepare an alcohol dispersion, and the alcohol dispersion is filled in a container. On the surface of one of the parallel plate electrodes of the above, a collection of scaly graphite particles or a collection of massive graphite particles is flatly packed, and the parallel plate electrode is immersed in an alcohol dispersion filled in the container. Further, the other parallel plate electrode is superposed on the one parallel plate electrode, and in the alcohol dispersion, the two parallel plate electrodes are formed by a collection of the scaly graphite particles or the massive graphite particles. After that, a DC potential difference is applied to the gap between the two parallel plate electrodes, whereby the magnitude of the potential difference is determined by the size of the gap between the two parallel plate electrodes. An electric field corresponding to the divided value is applied to the group of scaly graphite particles or the group of lump graphite particles, and the application of the electric field causes all the graphite crystals forming the scaly graphite particles or the lump graphite particles. The interlayer bond of the two parallel plate electrodes is simultaneously broken, and a collection of graphite is produced in the gap between the two parallel plate electrodes. After that, the gap between the two parallel plate electrodes is expanded to form the two parallel plate electrodes. It is tilted in the alcohol dispersion, and further vibrated in three directions of left and right, front and back, and up and down repeatedly to the container, and the graphite aggregate is put into the alcohol dispersion through the gap between the two parallel plate electrodes. After moving, the two parallel graphite electrodes are taken out from the container, and the homogenizer device is operated in the alcohol dispersion in the container. By the operation of the homogenizer, the homogenizer device is operated through the alcohol dispersion. The impact is repeatedly applied to the graphite aggregate to separate the graphite aggregate into individual graphite particles in the alcohol dispersion, and then the homogenizer device is taken out from the container, and the right and left sides of the container are further affected. , Front-back, up-and-down vibrations are repeatedly applied, and a collection of graphite separated into individual graphite in the alcohol dispersion is diffused over the entire bottom surface of the container with the graphite flat surface facing up. At the same time, the graphite flat surfaces are overlapped with each other via the alcohol dispersion liquid, whereby a collection of graphite having the graphite planes overlapped with each other via the alcohol dispersion liquid is formed on the bottom surface of the container. Formed as a shape , Silver, copper, gold, or aluminum is thermally decomposed to precipitate a metal compound, which is dispersed in alcohol via an alcohol dispersion, and the graphene aggregates in which the flat surfaces of graphene overlap each other are described above. This is a manufacturing method in which the bottom surface of a container filled with an alcohol dispersion is manufactured as the shape of the bottom surface.

In other words, the manufacturing method for manufacturing this graphene aggregate consists of the following eight simple treatments, and when the eight treatments are carried out in succession, a metal that precipitates any metal of silver, copper, gold, or aluminum. An aggregate of graphene in which the flat surfaces of graphene are overlapped with each other is formed on the bottom surface of the container as the shape of the bottom surface at low cost through the alcohol dispersion of the compound.
First, powders and granules of a metal compound that thermally decomposes any of silver, copper, gold, or aluminum are dispersed in alcohol to prepare an alcohol dispersion, and the alcohol dispersion is placed in a container. Fill. As a result, the metal compound is dispersed in the alcohol in a molecular state, and the powder or granular material of the metal compound is liquid-phased. This alcohol dispersion is a low-viscosity liquid having the viscosity of alcohol. The metal is excellent in both thermal conductivity and electrical conductivity in the order of silver, copper, gold, and aluminum. Further, a metal compound that precipitates any metal of silver, copper, gold, or aluminum by thermal decomposition is a general-purpose industrial chemical.
Secondly, on the surface of one of the two parallel plate electrodes, a collection of scaly graphite particles or a collection of massive graphite particles is flatly packed so as not to have a gap, and the parallel plate electrode is used. Is immersed in the alcohol dispersion in the container. The graphite particles composed of scaly graphite particles or lump graphite particles are graphite particles obtained by crushing a mass of natural graphite crystals to select graphite crystals, and are composed of only a single crystal of graphite and have a high graphite crystallization rate. It is the cheapest carbon material that is 100% advanced.
Third, the other parallel plate electrode of the two parallel plate electrodes is superposed on the one parallel plate electrode described above, and a collection of scaly graphite particles or massive graphite particles is formed in the alcohol dispersion. The two parallel plate electrodes are separated from each other. The size of the gap between the two parallel plate electrodes is the value obtained by dividing the size of the DC potential difference applied to the gap between the two parallel plate electrodes in the next process by the size of the electrode gap. When an electric field is applied to a collection of scaly graphite particles or lump graphite particles existing in the electrode gap, the magnitude of the electric field required to simultaneously break the interlayer bonds of all graphite crystals of the graphite particles is set. In addition, the gap between the two parallel plate electrodes and the potential difference to be applied are obtained in advance. Therefore, based on the size of the gap between the two parallel plate electrodes obtained in advance, a collection of scaly graphite particles or a collection of massive graphite particles is narrowed to the gap between the two parallel plate electrodes. In addition, in order to produce a larger collection of graphene, a collection of scaly graphite particles or lump graphite particles that are narrowed so as not to have a gap between the two parallel plate electrodes is compressed and destroyed in advance. There is no problem in pulling a collection of more scaly graphite particles or lump graphite particles into the electrode gap. This is because, after that, the interlayer bonds of all the graphite crystals in the graphite particles are simultaneously broken by the electric field, so that there is no problem even if the interlayer bonds of the graphite particles are broken in advance.
Fourth, a DC potential difference of a magnitude required to simultaneously break all the interlayer bonds of the graphite particles is applied to the gap between the two parallel plate electrodes. As a result, an electric field corresponding to the magnitude of the applied potential difference divided by the size of the gap between the two parallel plate electrodes is a scaly graphite particle or a lump graphite particle existing in the gap between the two parallel plate electrodes. By applying the electric field, the interlayer bonds of all the graphite crystals forming the scaly graphite particles or the massive graphite particles are simultaneously destroyed, and a graphene aggregate is produced in the gap between the two parallel plate electrodes. To. The phenomenon in which the interlayer bonds of graphite crystals forming graphite particles are simultaneously destroyed by the application of an electric field will be described below. When a potential difference is applied between the two parallel plate electrodes immersed in alcohol, which is an insulator, an electric field is generated in the gap between the two parallel plate electrodes. That is, methanol is an insulator having a dielectric constant of 33, and ethanol is an insulator having a dielectric constant of 24. The electric conductivity of ethanol is 1.35 × ^10-7 S / m, and the electric conductivity of the scaly graphite particles is 43.9 S / m. Thus, ethanol, compared to the scaly graphite particles is a conductor, the electric conductivity is 3.3 × 10 ⁸ times lower insulator.
Fifth, the gap between the two parallel plate electrodes is expanded, the two parallel plate electrodes are tilted in the alcohol dispersion, and vibrations in three directions of left and right, front and back, and up and down are repeatedly applied to the container. .. As a result, the graphene aggregate moves from the gap between the two parallel plate electrodes into the alcohol dispersion. Since graphene is extremely lightweight, the vibration acceleration applied to the container is about 0.2 G.
Sixth, take out two parallel plate electrodes from the container. As a result, only the suspension in which the graphene aggregate is dispersed in the alcohol dispersion of the metal compound is present in the container.
Seventh, the homogenizer device is operated in the alcohol dispersion in the container. That is, graphene is the thinnest material with a thickness of 0.332 nm and the widest surface area with a surface area of 3000 m ² / g per unit mass, so the aspect ratio is the ratio of the surface area to the thickness. Has an extremely large flat surface. Further, the graphite particles produced by crushing a mass of natural graphite crystals and selecting fine graphite crystals have a certain shape, and the shapes of the individual graphite particles are not the same. For this reason, graphene produced by breaking the interlayer bond of graphite particles does not have the same shape of each graphene. Therefore, when a collection of graphene is deposited in the narrow gap between the two parallel plate electrodes, the graphenes are easily overlapped with each other, and there are graphenes having three or more layers overlapping with each other. The way they overlap is not uniform. Furthermore, since the thickness of graphene is extremely small, it is difficult to distinguish whether or not the flat surfaces overlap each other. Further, when a graphene junction is manufactured using graphene in which flat surfaces overlap each other, the graphene junction is separated at the junction surface in which the flat surfaces overlap. Therefore, in producing the graphene conjugate, it is necessary to separate the aggregate of graphene into individual graphenes in the alcohol dispersion in advance. On the other hand, when the homogenizer device is operated in the alcohol dispersion, the impact is repeatedly applied to the entire graphene aggregate via the alcohol dispersion. At this time, when an impact is applied to a group of graphene in which the flat surfaces are overlapped in multiple layers, a large amount of impact is applied to the graphene on the surface layer, the graphene on the surface layer moves from the group of graphene on which they are overlapped, and the overlapping of the flat surfaces is sequentially performed. It will be resolved. Therefore, by applying an impact for a certain period of time, the graphene aggregates are separated into individual graphenes in the alcohol dispersion, and a suspension in which the separated graphene aggregates are dispersed in the alcohol dispersion is produced. Will be done. In addition, when an ultrasonic homogenizer device is used, the generation and disappearance of bubbles consisting of an enormous number of ultrafine particles, which are one order of magnitude smaller than the flat surface of graphene, are generated in the vibration cycle based on the vibration frequency of ultrasonic waves. , It is continuously repeated in the alcohol dispersion (this phenomenon is called cavitation), and the shock wave generated when the bubbles burst is repeatedly added to the entire collection of graphenes. As a result, the graphene aggregate is separated into individual graphenes in an alcohol dispersion in a short time.
Eighth, vibrations in three directions of left-right, front-back, and up-down are repeatedly applied to the container. At this time, since the flat surfaces of all graphene are in contact with the alcohol dispersion by the seventh treatment, when vibration is applied to the alcohol dispersion, all graphene moves in the low-viscosity alcohol dispersion. That is, since each graphene in contact with the low-viscosity alcohol dispersion has an extremely large aspect ratio, it repeatedly moves in the liquid with the flat surface facing up. As a result, graphene with the flat surface facing up diffuses throughout the bottom surface of the container, and graphene with a small flat surface enters the gap between the graphene flat surfaces, and all graphene passes through the alcohol dispersion. The array of overlapping flat planes advances in the liquid. Finally, when vibration in the vertical direction is applied to stop the vibration to the container, a collection of graphene in which the flat surfaces are overlapped with each other via the alcohol dispersion is formed as the shape of the bottom surface of the entire bottom surface of the container. Therefore, the thickness of the graphene cluster in which the flat surfaces overlap is determined by the bottom area of the container and the amount of graphene produced. Therefore, the smaller the amount of graphene used, the thinner the thickness of the overlapping graphene clusters. In addition, the larger the bottom area of the container, the larger the area of the overlapping graphene clusters. Further, the shape of the overlapping graphene clusters is the shape of the bottom surface of the container. Therefore, a collection of graphene in which flat planes having an arbitrary thickness, an arbitrary area, and an arbitrary shape are overlapped with each other is formed on the bottom surface of the container as the shape of the bottom surface. Graphene is extremely lightweight, and the vibration acceleration applied to the container is about 0.2 G.
As a result, the problems 1-4 described in paragraph 7 were solved.
The scaly graphite particles or the massive graphite particles are the cheapest carbon materials. Further, the metal compound and alcohol that precipitate any metal of silver, copper, gold, or aluminum by thermal decomposition are general-purpose industrial chemicals. Further, all of the above eight processes are extremely simple processes. Therefore, the flat surfaces of graphene overlap each other via an alcohol dispersion of a metal compound that precipitates a metal of silver, copper, gold, or aluminum by thermal decomposition using an inexpensive material and at an inexpensive processing cost. The aggregate of graphene can be produced as a bottom surface shape on the bottom surface of the container.
Here, the phenomenon that the interlayer bond of the graphite crystals forming the graphite particles narrowed in the gap between the two parallel plate electrodes is simultaneously destroyed by the electric field applied to the gap between the two parallel plate electrodes will be described. To do.
The carbon atom forming the graphite crystal in the graphite particles has four valence electrons. Three of these valence electrons are the basal plane of the graphite crystal, that is, the σ electrons that form graphene. These σ electrons covalently bond with the σ electrons of three adjacent carbon atoms on the basal plane at an angle of 120 degrees to form a strong hexagonal network structure two-dimensionally. The remaining one valence electron is a π electron, which exists in a π orbit extending in a direction perpendicular to the basal plane. These π electrons are bonded to the π electrons of carbon atoms adjacent to each other in the vertical direction perpendicular to the basal plane with a weak bonding force, and the basal planes are laminated in layers based on this weak bonding force. That is, the basal plane, that is, graphene, is layered to each other by the interaction of π orbitals, which is a weak bonding force. Therefore, the graphite particles have a property of being easily peeled off at the basal plane made of graphite crystals, that is, having mechanical anisotropy. This mechanical anisotropy is well known as the lubricity of graphite particles.
When an electric field is applied to these 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 larger than the interaction of the π orbit acting on the π electron, the π electron is released from the constraint on the π orbit. As a result, all π electrons move away from the π orbital and become free electrons. As a result, all the π electrons that are responsible for the interlayer bonding of the graphite crystal are not in the π orbital, so that all the interlayer bonds of the graphite crystal are destroyed at the same time. That is, when the π electron moves a distance of the interlayer distance b of the graphite crystal by the Coulomb force F, the π electron performs work W (W = b · F). This work W is 35 millielectronvolts, which is the magnitude of the interaction of π orbitals per atom acting on π electrons (electron volt is a unit that expresses the magnitude of energy possessed by an electron, and 1 electron volt is 1. ^Beyond (corresponding to 62 × ^10-19 J), the π electron is released from the constraint of the interaction of the π orbit and becomes a free electron. For example, if the gap between the two parallel plate electrodes is separated by 100 μm and a DC potential difference of 10.6 kilovolts or more is applied to the electrodes, the interlayer bond of the graphite crystal is instantly broken. As described above, a large amount of graphene can be inexpensively produced by an extremely simple means of applying an electric field to a collection of inexpensive graphite particles. Further, since the interlayer bonds of all graphite crystals are broken at the same time, the obtained fine substance is surely graphene, which is the basal plane of the graphite crystals.
The group of graphite particles referred to here means a group of relatively small amounts of graphite particles of about 1 g to 100 g. That is, the scaly graphite particles or the massive graphite particles are fine particles having a bulk density of 0.2-0.5 g / cm ³ and a particle size of 1-300 microns. Therefore, it is easy to pull the aggregate of graphite particles into the gap between the two parallel plate electrodes, and it is also easy to apply a potential difference to the two parallel plate electrodes. When a potential difference is applied to the gap between the two parallel plate electrodes, an electric field is generated in all the regions where the graphite particles are attracted. This electric field acts on the π electron as a Coulomb force larger than the interaction of the π orbit, and the π electron is released from the constraint on the π orbit and becomes a free electron. As a result, all the interlayer bonds of the graphite crystals in the graphite particles are simultaneously broken, and a large amount of graphene is produced in the gap between the two parallel plate electrodes.
Here, the number of graphene dispersed in the suspension is calculated by arithmetic. Assuming that all graphite particles are composed of spheres with a diameter of 25 microns, the true density of graphite is 2.25 × 10 ³ kg / m ³ , so the weight of one graphite particle is slight. It becomes 1.84 × ^10-8 g. Assuming that the average thickness of the graphite particles is 10 microns, the interlayer distance is 3.354 angstroms. Therefore, 297,265 graphenes are laminated on the scaly graphite particles having a thickness of 10 microns. .. Therefore, if all the interlayer bonds of the graphite crystals are broken, 297,265 graphenes can be obtained from only one spherical graphite particle. Therefore, if the interlayer bonds of all graphite crystals are broken for only 1 g of spherical graphite particles, graphene consisting of 1.62 × 10 ¹³ particles can be obtained. Therefore, the suspension produced by this production method changes from a small amount of graphite particles to a suspension in which each of a huge number of graphene particles is dispersed in an alcohol dispersion.

Using a group of graphene in which the flat surfaces of graphene produced by the production method described in paragraph 8 are overlapped with each other, the flat surfaces of the graphene are metal fine particles made of any metal of silver, copper, gold, or aluminum. The manufacturing method for manufacturing graphene conjugates bonded by a collection of
The container in which the aggregates of graphenes described in paragraph 8 are overlapped with each other on the flat surfaces of the graphenes is heated to a temperature at which the metal compounds described in paragraph 8 are thermally decomposed, whereby alcohol is first released. After vaporization, a collection of fine crystals of the metal compound is deposited all at once on the flat surface of the graphene, and then the fine crystals of the metal compound are thermally decomposed to be either silver, copper, gold, or aluminum. A collection of granular metal fine particles made of the same metal are deposited all at once on the flat surface of the graphene, and the metal fine particles are metal-bonded at a site where the metal fine particles are in contact with each other, so that the flat surfaces of the graphene are bonded to each other. The container is a graphene bond in which the flat surfaces of the graphene are bonded to each other by a collection of metal fine particles made of any of the silver, copper, gold, or aluminum. Using a group of graphenes produced by the manufacturing method described in paragraph 8 in which the flat surfaces of the graphenes produced as a graphene bond having the shape of the bottom surface are overlapped with each other, the flat surfaces of the graphenes are formed. It is a manufacturing method for producing a graphene bond bonded by a collection of metal fine particles made of any metal of silver, copper, gold, or aluminum.

In other words, when the temperature of the container is raised to the temperature at which the metal compound thermally decomposes, the alcohol first evaporates, and a collection of fine crystals of the metal compound is deposited all at once in the gaps between the flat surfaces of the overlapping graphene, resulting in fine particles. A collection of crystals forms an ultra-thin film that covers the flat surface. That is, in the alcohol dispersion of a metal compound, the metal compound is dispersed in the alcohol in a molecular state. Therefore, when the alcohol is vaporized from the alcohol dispersion, a collection of fine crystals of the metal compound overlaps with each other. It precipitates all at once in the gap and covers the flat surface. Since the thickness of graphene is as thin as 0.332 nm, fine crystals of the metal compound do not precipitate on the side surface of graphene. On the other hand, since the two planes and the side surfaces of the graphene cluster in which the flat planes overlap each other are also in contact with the alcohol dispersion, the fine crystal clusters of the metal compound are deposited on the two planes and the side surfaces. The size of the fine crystals is close to the size of the precipitated fine particles. Next, when the temperature at which the metal compound begins to thermally decompose is reached, the metal compound decomposes into an inorganic substance or an organic substance and a metal. Since the density of the inorganic or organic matter is lower than the density of the metal, the inorganic or organic matter is deposited in the upper layer and the metal is deposited in the lower layer, and the inorganic or organic matter in the upper layer takes away the heat of vaporization and vaporizes, and immediately after the vaporization is completed, 40- A collection of granular metal fine particles made of any metal of silver, copper, gold, or aluminum having a size of 60 nm is deposited all at once on the entire flat surface of each graphene so as to cover the flat surface. To do. Since these metal fine particles have no impurities and are in an active state, they form metal bonds at sites where they come into contact with each other. Therefore, a collection of metal fine particles deposited on the flat surface of graphene is metal-bonded at a site where they come into contact with each other, and the collection of metal-bonded metal fine particles bonds the flat surfaces of graphene to each other, resulting in a thin graphene sheet. The bonded body is formed on the bottom surface of the container in the shape of the bottom surface. Further, the two planes and side surfaces of the graphene junction are also covered with a collection of metal-bonded metal fine particles, and the entire surface of the graphene junction is covered with a collection of metal-bonded metal fine particles. As the amount of the metal compound dispersed in the alcohol increases, the amount of metal fine particles precipitated increases, and as a result, the amount of metal fine particles precipitated on the flat surface of graphene increases, and a collection of metal-bonded metal fine particles is laminated to form a laminated metal. A collection of fine particles binds the flat surfaces of graphene to each other. Further, since the group of metal-bonded metal fine particles is laminated on the two planes and the side surface of the graphene bonded body, the entire surface of the graphene bonded body is covered with the group of laminated metal fine particles.
As a result, the problems of the fifth and sixth paragraphs described in paragraph 7 were solved, and all the problems described in paragraph 7 were solved.
The entire surface of the graphene junction is covered with a collection of metal-bonded metal fine particles, and the flats of graphene are bonded to each other by the collection of metal-bonded metal fine particles. Therefore, the collection of metal fine particles has a certain binding force. It also has a flat surface of graphene that forms a graphene junction with a constant binding force. Therefore, when the graphene joint is taken out from the container, if vibrations in three directions of front-back, left-right, and up-down are applied to the container for a short time, the graphene joint is dissociated from the container and the graphene joint can be taken out from the container. ..
The graphene conjugate produced by the production method described above brings about the following effects.
First, a graphene joint having the shape of the bottom surface is manufactured on the bottom surface of the container. Therefore, a graphene joint having a submicron thickness can be manufactured, and the shape and area of the graphene joint can be freely changed according to the shape of the bottom surface of the container. For this reason, graphene conjugates with excellent both thermal and electrical conductivity can be of any size, shape, and thickness, including electrodes and contacts with small areas, elongated wiring patterns, and heat conductive sheets with large areas. It can be freely manufactured as a graphene joint to have.
Second, graphene conjugates are excellent in both thermal and electrical conductivity. That is, as described above, graphene has both thermal conductivity equivalent to 4.5 times the thermal conductivity of silver and electrical conductivity corresponding to only 23 times the specific resistance of copper. Therefore, a graphene junction in which the flat surfaces of graphene are bonded by a collection of metal fine particles made of any of silver, copper, gold, or aluminum has a relatively high thermal conductivity, that is, heat is generated. Heat is transferred preferentially to the flat surface of graphene, which is easily transmitted, and the electric conductivity is relatively high, that is, the current flows preferentially to the collection of metal fine particles in which the current easily flows. As a result, the graphene conjugate has better thermal conductivity than silver and has conductivity close to that of metal. The specific resistance of aluminum is 1.6 times that of copper, and aluminum has a higher conductivity than graphene.
Third, the entire surface of the graphene joint is covered with a collection of metal fine particles made of soft metal of 40-60 nm, the surface has a surface roughness that is an order of magnitude smaller than that of mirror polishing, and the surface is water repellent and stain resistant. , Has lubricity properties.
Fourth, since the two planes of the graphene joint are covered with a collection of metal fine particles, the graphene joint can be crimped to the component or the base material. In other words, the metal composed of silver, copper, gold, and aluminum, which has excellent both thermal conductivity and electrical conductivity, is a soft metal with low hardness, and when compressive stress is applied to one plane of the graphene joint, this is applied. A collection of metal fine particles formed on a flat surface undergoes plastic deformation or elastic deformation on the surface of a part or a base material and bites into or pressure-bonds, and the graphene joint presses against the part or the base material. Therefore, the graphene joint can be integrated with the component or the base material by crimping, and both the properties of thermal conductivity and electric conductivity can be imparted to the component and the base material.
Fifth, corrosion of metal fine particles formed on the surface of a graphene joint when the graphene joint comes into contact with or is immersed in a liquid that corrodes or dissolves any of silver, copper, gold, or aluminum. Or dissolution progresses gradually. However, the gap between the flat surfaces of graphene is submicron or less, which corresponds to the thickness of a collection of metal fine particles, and the liquid cannot penetrate the gap between the flat surfaces due to its own surface tension. Therefore, even if the metal fine particles formed on the surface of the graphene joint gradually corrode or dissolve, the metal fine particles that bond the flat surfaces are not eroded. Therefore, even if the graphene joint comes into contact with or is immersed in a liquid that corrodes or dissolves any of silver, copper, gold, or aluminum, the metal fine particles that bond the flat surfaces are not eroded, resulting in flatness. Graphene conjugates with face-to-face bonds are not corroded by liquid. Similarly, in a graphene joint crimped to a part or base material, the gap on the crimping surface corresponds to the size of a collection of metal fine particles, the liquid cannot penetrate the crimping surface due to surface tension, and the crimping surface also penetrates with the liquid. Not done. Graphene is a chemically extremely stable single crystal material and does not react with any strong acid or strong alkaline liquid.
Sixth, the raw material of graphene is inexpensive graphite particles, and metal compounds and alcohols that precipitate any metal of silver, copper, gold, or aluminum by thermal decomposition are general-purpose industrial chemicals. Using an inexpensive material, it is possible to produce a graphene conjugate in which the flat surfaces of graphene are bonded together by a collection of metal fine particles made of any of silver, copper, gold, or aluminum with a very simple process. At a low cost, a graphene junction is a container in which the flat surfaces of graphenes of any size, shape and thickness are bonded together by a collection of metal fine particles made of any of silver, copper, gold, or aluminum. Can be manufactured arbitrarily on the bottom of the.

The manufacturing method for producing a graphene joint obtained by imparting metal properties different from silver, copper, gold, and aluminum to the surface of the graphene joint manufactured by the manufacturing method described in paragraph 10.
A graphene bond in which the flat surfaces of graphene are bonded to each other is produced on the bottom surface of the container according to the production method described in paragraph 10, and metals other than silver, copper, gold, and aluminum are deposited on the container by thermal decomposition. The metal compound to be metal compound is filled with an alcohol dispersion liquid dispersed in alcohol, and vibrations in three directions of left and right, front and back, and up and down are repeatedly applied to the container to immerse the graphene bond in the alcohol dispersion liquid. The temperature of the container is raised to a temperature at which the metal compound is thermally decomposed, whereby the alcohol is first vaporized, and a collection of fine crystals of the metal compound is formed at a site where the graphene bond is in contact with the alcohol dispersion. It precipitates all at once, after which fine crystals of the metal compound are thermally decomposed, and a metal made of a metal other than silver, copper, gold, and aluminum is formed at a site where the graphene bond is in contact with the alcohol dispersion. A collection of fine particles is precipitated all at once, and the metal fine particles are metal-bonded to the metal fine particles made of any of silver, copper, gold, or aluminum formed on the entire surface of the graphene joint, and the metal fine particles are bonded to the metal fine particles. Metallic bonds are formed at sites where the metal fine particles are in contact with each other, and a collection of the metal-bonded metal fine particles covers the entire surface of the graphene joint, whereby the silver, copper, gold, A graphene bond having the properties of a metal other than aluminum is produced on the bottom surface of the container as a graphene bond having the shape of the bottom surface of the container, and the graphene bond produced by the production method described in paragraph 10. This is a manufacturing method for producing a graphene bond in which the surface of the body is endowed with metal properties different from those of silver, copper, gold, and aluminum.

That is, the manufacturing method described in paragraph 10 is used to manufacture a graphene junction in which the flat surfaces of graphene are bonded to the bottom surface of the container by a collection of metal fine particles made of any of silver, copper, gold, or aluminum. Further, the container is filled with an alcohol dispersion of a metal compound in which metals other than silver, copper, gold, and aluminum are precipitated by thermal decomposition. After that, when vibrations in three directions are repeatedly applied to the container, the graphene conjugate is immersed in the alcohol dispersion. Since the graphene joint exists in the container, a vibration acceleration of about 0.4 G, which is larger than the vibration acceleration applied when the flat planes of graphene described in paragraph 9 are overlapped with each other, is applied. Further, the temperature of the container is raised to a temperature at which the metal compound is thermally decomposed. Alcohol is first vaporized, and a collection of fine crystals of the metal compound is deposited all at once on the site of the graphene conjugate in contact with the alcohol dispersion, that is, on the entire surface of the graphene conjugate. That is, in the alcohol dispersion of the metal compound, the metal compound is dispersed in the alcohol in a molecular state. Therefore, when the alcohol is vaporized from the alcohol dispersion, fine crystals of the metal compound are precipitated all at once. After that, the fine crystals of the metal compound are thermally decomposed, and the portion where the graphene conjugate comes into contact with the alcohol dispersion, that is, the entire surface of the graphene conjugate is composed of a metal other than silver, copper, gold, and aluminum. A collection of metal fine particles is deposited all at once. At this time, since the metal fine particles have no impurities and are in an active state, they are metal-bonded to the metal fine particles made of any of silver, copper, gold, or aluminum formed on the entire surface of the graphene joint, and are also metal-bonded. The metal fine particles are metal-bonded at a site where the metal fine particles are in contact with each other, and a collection of the metal-bonded metal fine particles is formed on the entire surface of the graphene junction. As a result, the surface of the graphene joint has the properties of metals other than silver, copper, gold, and aluminum. As the amount of the metal compound dispersed in the alcohol increases, the amount of metal fine particles precipitated increases, and as a result, the amount of metal fine particles precipitated on the surface of the graphene junction increases, and a collection of metal-bonded metal fine particles is laminated and laminated. A collection of fine metal particles covers the entire surface of the graphene junction.
That is, the metal fine particles made of metals other than silver, copper, gold, and aluminum are deposited on the portion of the graphene joint that comes into contact with the alcohol dispersion, that is, on the entire surface of the graphene joint. For this reason, new collections of metal fine particles are formed on the entire surface of the graphene junction by using only a small amount of the metal compound as a raw material for depositing metals other than silver, copper, gold, and aluminum. As a result, the graphene junction has excellent properties in both thermal conductivity and electrical conductivity described in paragraph 10, and the surface of the graphene junction has new metallic properties. That is, new properties are imparted to the surface of the graphene conjugate.
The entire surface of the graphene joint is covered with a collection of metal fine particles made of metal other than metal-bonded silver, copper, gold, and aluminum, and is also made of metal-bonded silver, copper, gold, or aluminum. Since the flats of the graphene are bonded to each other by the collection of the metal fine particles, the collection of the metal fine particles has a constant bonding force, and the flat surface of the graphene also forms a graphene bond by the constant bonding force. Therefore, similarly to the graphene joint described in paragraph 11, when the graphene joint is taken out from the container, if vibrations in three directions of front-back, left-right, and up-down are applied to the container for a short time, the graphene joint is dissociated from the container. The graphene conjugate can be removed from the container.
By the way, if the metal other than silver, copper, gold, and aluminum described in paragraphs 9 and 11 is, for example, a metal made of magnetic iron, nickel, or cobalt, the surface of the graphene junction is ferromagnetic. Has the nature of. As a result, the flat surface of the graphene junction is magnetically attracted to parts and substrates having ferromagnetic and soft magnetic properties. As a result, it is possible to impart excellent properties of both thermal conductivity and electrical conductivity to the parts and the base material magnetically attracted by the graphene joint. Further, the gap on the magnetic adsorption surface is a small gap corresponding to the size of a collection of metal fine particles, and no liquid can enter the gap. Therefore, even if the magnetically adsorbed graphene conjugate comes into contact with or is immersed in a corrosive liquid, the magnetically adsorbed surface does not change over time.
Further, if the metal other than silver, copper, gold, and aluminum is any metal made of, for example, chromium or manganese, the surface of the graphene joint has excellent wear resistance. That is, since chromium has a high Mohs hardness of 8.5 and manganese has a high Mohs hardness of 6.0, the surface of the graphene joint has wear resistance. Therefore, when the flat surface of the graphene joint is placed on the surface of the part or base material and compressive stress is applied to the graphene joint, the metal fine particles on the flat surface of the graphene joint are hard to collect, so that the metal fine particles become the part or base material. The graphene joint is crimped to the part or base material, and the part or base material is imparted with abrasion resistance as well as thermal conductivity and electric conductivity. Further, since the gap on the crimping surface of the crimped graphene joint is a small gap corresponding to the size of the aggregate of metal fine particles, the liquid cannot enter the gap. Therefore, even if the graphene joint comes into contact with or immersed in a corrosive liquid, the pressure-bonded surface does not change over time. Chromium and manganese are metals that are superior in corrosion resistance to silver, copper, gold, and aluminum, which are excellent in both thermal conductivity and electric conductivity, and iron, nickel, and cobalt, which are magnetic, and are graphene. The surface of the bonded body is corrosion resistant.
Furthermore, if the metal other than silver, copper, gold, and aluminum is a platinum group metal consisting of platinum, palladium, rhodium, ruthenium, or iridium, the surface of the graphene conjugate is a platinum group metal. Has a catalytic action by. That is, since the metal fine particles formed on the surface of the graphene bonded body are fine particles, the specific surface area, which is the ratio of the surface area to the volume, is large. Further, since the metal fine particles having a catalytic action are formed on the entire surface of the graphene conjugate, the efficiency of the catalytic action by the metal fine particles is increased. Further, if a collection of metal fine particles having a catalytic action is formed on the surface of the graphene conjugate in a single layer, the amount of an expensive metal compound in which platinum group metals are precipitated by thermal decomposition is reduced. A huge number of metal fine particles, which are highly efficient in catalysis and can be produced at low production cost, are formed on the entire surface of the graphene conjugate. Further, the type of platinum group metal can be freely changed according to the catalytic action. Therefore, the graphene conjugate can be used as a chip component or a flat sheet having a catalytic action. In addition, a collection of metal fine particles made of platinum group metal formed on one plane of the graphene joint can be used as a means of crimping, and the parts and the base material on which the graphene joint is crimped have thermal conductivity and electrical conductivity. Catalytic action can be imparted as well as sex.
The examples of metals other than silver, copper, gold, and aluminum described above are examples, and are not limited to the above three examples.
As described above, the graphene joint is manufactured by the manufacturing method described in paragraph 10, and the silver, copper, gold, and aluminum described in paragraphs 9 and 11 are excluded from the entire surface of the graphene joint. When metal fine particles are deposited, the entire surface is covered with a collection of metal fine particles consisting of metals other than silver, copper, gold, and aluminum, and the entire surface of the graphene junction is made of metal other than silver, copper, gold, and aluminum. Has the nature of. In this way, the surface of the graphene junction has thermal conductivity and electrical conductivity as well as properties according to the type of metal constituting the newly precipitated metal fine particles by only depositing a small amount of metal fine particles. It will be.

In the production method for producing a graphene aggregate described in paragraph 8, a ligand composed of an inorganic ion or a molecule is coordinate-bonded to the metal ion as a metal compound that precipitates a metal by thermal decomposition described in paragraph 8. It is a production method for producing a graphene aggregate according to the production method for producing a graphene aggregate described in paragraph 8 using a metal complex composed of an inorganic metal compound having a metal complex ion.
Or
In the production method for producing a graphene conjugate described in paragraph 10, as a metal compound that precipitates a metal by thermal decomposition described in paragraph 10, a ligand composed of an inorganic ion or a molecule is coordinate-bonded to the metal ion. It is a production method for producing a graphene conjugate according to the production method for producing a graphene conjugate described in paragraph 10, using a metal complex composed of an inorganic metal compound having a metal complex ion.
Or
In the production method for producing a graphene conjugate described in paragraph 12, as a metal compound that precipitates a metal by thermal decomposition described in paragraph 12, a ligand composed of an inorganic ion or a molecule is coordinate-bonded to the metal ion. This is a production method for producing a graphene conjugate according to the production method for producing a graphene conjugate described in paragraph 12, using a metal complex composed of an inorganic metal compound having a metal complex ion.

That is, when a metal complex composed of an inorganic metal compound having a metal complex ion in which a ligand composed of an inorganic ion or a molecule is coordinated to a metal ion is heat-treated in a reducing atmosphere, a metal is precipitated at 180-220 ° C. .. That is, when the metal complex composed of the inorganic metal compound is heat-treated in a reducing atmosphere, it is decomposed into an inorganic substance and a metal, the inorganic substance takes away heat of vaporization and vaporizes, and the vaporization of the inorganic substance is completed at 180-220 ° C., and the metal precipitates. And finish the thermal decomposition reaction.
That is, among the ions constituting the metal complex, the metal ion located in the center of the molecule is the largest, and the distance between the metal ion and the ligand is the longest. When this metal complex is heat-treated in a reducing atmosphere, the coordination bond portion where the metal ion binds to the ligand is first separated and decomposed into a metal and an inorganic substance. When the temperature rises further, the inorganic substance takes away the heat of vaporization and vaporizes, and when the vaporization of the inorganic substance is completed, the metal precipitates. Since the metal complex composed of such an inorganic metal compound has a small molecular weight, the vaporization of the inorganic substance is completed at 180-220 ° C., and the temperature at which the metal is precipitated is the lowest among the temperatures at which the metal is precipitated by the thermal decomposition of the metal compound. ..
Further, a metal complex ion in which a molecule or an ion composed of an inorganic substance serves as a ligand and is coordinate-bonded to the metal ion is easier to synthesize than other metal complex ions. As such metal complex ions, ammonia NH ₃ serves as a ligand to coordinate bond to metal ions, and water H ₂ O serves as a ligand to coordinate bond to metal ions. Hydroxometal complex ion, chlorine ion Cl ^{−, which} is coordinated to metal ion with complex ion, hydroxyl group OH ^― as a ligand, or chlorine ion Cl ⁻ and ammonia NH ₃ serve as ligand for metal ion. There are chlorometal complex ions that are coordinated to. All of these ligands have a small molecular weight. Further, a metal complex composed of an inorganic salt such as a chloride, a sulfate or a nitrate having such a metal complex ion has a small molecular weight of the inorganic salt. Therefore, the vaporization of the inorganic substance is completed in the temperature range of 180-220 ° C., and the metal is precipitated. The temperature at which this metal precipitates is the lowest among the temperatures at which the metal is precipitated by the thermal decomposition of the metal compound.
Therefore, in the production method for producing a graphene aggregate described in paragraph 8, the ligand consisting of inorganic ions or molecules is any of silver, copper, gold, or aluminum as a metal compound that precipitates a metal by thermal decomposition. When the graphene aggregate is produced according to the production method for producing a graphene aggregate described in paragraph 8, using a metal complex composed of an inorganic metal compound coordinated to a metal ion composed of the metal, the graphene aggregate is composed of the inorganic metal compound. A collection of graphenes in which the flat surfaces of graphenes are overlapped with each other is produced via an alcohol dispersion of a metal complex.
Or, in the production method for producing a graphene bond described in paragraph 10, the ligand consisting of inorganic ions or molecules is any of silver, copper, gold, or aluminum as a metal compound that precipitates a metal by thermal decomposition. When the graphene conjugate is produced according to the production method for producing a graphene conjugate described in paragraph 10, using a metal complex composed of an inorganic metal compound coordinated to a metal ion composed of the metal, 180- of a reducing atmosphere is produced. A graphene bond is produced on the bottom surface of the container by heat treatment at 220 ° C.
Or, in the production method for producing a graphene bond described in paragraph 12, the ligand consisting of an inorganic ion or molecule is excluded from silver, copper, gold, and aluminum as a metal compound that precipitates a metal by thermal decomposition. When a graphene conjugate is produced according to the production method for producing a graphene conjugate described in paragraph 12, using a metal complex composed of an inorganic metal compound coordinated to a metal ion composed of a metal, silver, copper, gold, and aluminum are produced. A graphene bond having metal properties other than the above is produced on the bottom surface of the container by heat treatment at 180-220 ° C. in a reducing atmosphere.

In the production method for producing a graphene aggregate described in paragraph 8, the oxygen ion constituting the carboxyl group of the carboxylic acid is covalently bonded to the metal ion as the metal compound that precipitates the metal by thermal decomposition described in paragraph 8. Manufacture of producing a graphene aggregate according to the production method for producing a graphene aggregate described in paragraph 8 using a carboxylic acid metal compound having both one characteristic and the second characteristic of the carboxylic acid being a saturated fatty acid. Is the way
Alternatively, in the production method for producing a graphene conjugate described in paragraph 10, the oxygen ion constituting the carboxyl group of the carboxylic acid is covalently bonded to the metal ion as the metal compound that precipitates the metal by thermal decomposition described in paragraph 10. A graphene conjugate is produced according to the production method for producing a graphene conjugate described in paragraph 10, using a carboxylic acid metal compound having both the first characteristic of the carboxylic acid and the second characteristic of the carboxylic acid being a saturated fatty acid. It is a manufacturing method to
Or
In the production method for producing a graphene conjugate described in paragraph 12, as a metal compound that precipitates a metal by thermal decomposition described in paragraph 12, oxygen ions constituting a carboxyl group of a carboxylic acid are covalently bonded to the metal ions. Manufacture of producing a graphene conjugate according to the production method for producing a graphene conjugate described in paragraph 12 using a carboxylic acid metal compound having one characteristic and the second characteristic of the carboxylic acid being a saturated fatty acid. The method.

That is, the metal ion is the most common carboxylic acid metal compound having both the first characteristic that the oxygen ion constituting the carboxyl group of the carboxylic acid is covalently bonded to the metal ion and the second characteristic that the carboxylic acid is composed of a saturated fatty acid. It is a large ion, and the distance between the oxygen ion constituting the carboxyl group and the metal ion is longer than the distance between other ions. When a metal carboxylic acid compound having such molecular structural characteristics is heat-treated in an air atmosphere, when the boiling point of the carboxylic acid is exceeded, the bond portion between the oxygen ion and the metal ion constituting the carboxyl group is first separated, and the carboxylic acid. And metal. When a carboxylic acid is composed of a saturated fatty acid, it does not have an unsaturated structure in which carbon atoms are excessive with respect to hydrogen atoms. Therefore, the structure of the hydrocarbon constituting the carboxylic acid and the molecular weight and number of the carboxylic acid Correspondingly, the carboxylic acid takes away the heat of vaporization and vaporizes, and when the vaporization is completed, the metal precipitates.
Examples of such metal carboxylate compounds include metal octylate compounds, metal laurate compounds, and metal stearate compounds. Since the hydrocarbon has a branched structure, the octyl acid has a short chain length and a low boiling point of 228 ° C. Further, the boiling point of carboxylic acid having a linear structure of hydrocarbon is lower as the molecular weight of carboxylic acid is smaller, that is, the shorter the linear chain is, the boiling point of lauric acid is 296 ° C, and the boiling point of stearic acid is. It is 361 ° C. Therefore, these metal carboxylate compounds are thermally decomposed at a temperature of 290-430 ° C. in the atmospheric atmosphere according to the boiling point described above.
The metal carboxylate compound composed of unsaturated fatty acids has an excess of carbon atoms with respect to hydrogen atoms as compared with the metal carboxylate compound composed of saturated fatty acids. Therefore, metal oxides such as copper oleate are thermally decomposed. In the case of, the cuprous oxide Cu ₂ O and the cupric oxide Cu O are precipitated at the same time, and a treatment for reducing the cuprous oxide Cu ₂ O and the cupric oxide CuO to copper is required. In particular, cuprous oxide Cu ₂ O is once oxidized to cupric oxide Cu O in an atmosphere richer in oxygen than in the air atmosphere, and further reduced to copper in a reducing atmosphere, which increases the processing cost.
Further, the metal carboxylate compound is an inexpensive industrial chemical that can be easily synthesized. That is, when a carboxylic acid, which is the most general-purpose organic acid, is reacted with a strong alkali, a carboxylic acid alkali metal compound is produced, and when a carboxylic acid alkali metal compound is reacted with an inorganic metal compound, a carboxylic acid composed of various metals is produced. Metal compounds are synthesized. Therefore, it is the cheapest organometallic compound among the organometallic compounds. Therefore, the heat treatment temperature is higher than that of the metal complex composed of the inorganic metal compound described in paragraph 15, but the metal compound is cheaper than the metal complex.
Therefore, the production method for producing the graphene aggregate described in paragraph 8 uses a metal carboxylate compound composed of any metal of silver, copper, gold, or aluminum as the metal compound that precipitates a metal by thermal decomposition. When the graphene aggregate is produced according to the production method for producing the graphene aggregate described in paragraph 8, the graphene aggregate in which the flat surfaces of the graphene are overlapped with each other is produced via the alcohol dispersion of the metal carboxylate compound. To.
Or, in the production method for producing the graphene conjugate described in paragraph 10, a metal carboxylate compound composed of any metal of silver, copper, gold or aluminum is used as the metal compound for precipitating a metal by thermal decomposition. When the graphene junction is produced according to the production method for producing a graphene conjugate described in the paragraph, the graphene conjugate is produced on the bottom surface of the container by heat treatment at 290-430 ° C. in an air atmosphere.
Alternatively, the manufacturing method for producing the graphene conjugate described in paragraph 12 uses a metal carboxylate compound composed of a metal other than silver, copper, gold, and aluminum as the metal compound that precipitates a metal by thermal decomposition, paragraph 12. When the graphene junction is produced according to the production method for producing a graphene conjugate described in the above, the surface is imparted with the properties of metals other than silver, copper, gold, and aluminum by heat treatment at 290-430 ° C. in an air atmosphere. A graphene conjugate is manufactured on the bottom of the container.

The production method for producing a graphene joint in which the properties of an alloy are imparted to the surface of the graphene joint produced by the production method described in paragraph 10 is described.
A graphene alloy is produced on the bottom surface of the container according to the production method described in paragraph 10, and the container is filled with an alcohol dispersion in which a plurality of types of metal compounds in which a plurality of metals are simultaneously precipitated by thermal decomposition are dispersed in alcohol. Then, vibrations in three directions of left-right, front-back, and up-down are repeatedly applied to the container to immerse the graphene alloy in the alcohol dispersion, and then the temperature at which the plurality of types of metal compounds are simultaneously thermally decomposed in the container. As a result, the alcohol is first vaporized, and a collection of fine crystals of the plurality of types of metal compounds is simultaneously precipitated at the site of contact with the alcohol dispersion of the graphene alloy, and then , Fine crystals of the plurality of types of metal compounds are thermally decomposed at the same time, and a plurality of metals constituting the plurality of types of metal compounds are simultaneously precipitated at the site of contact with the alcohol dispersion liquid of the graphene conjugate. The fine particles of the alloy made of the plurality of metals are metal-bonded to the fine metal particles made of any of silver, copper, gold, or aluminum formed on the entire surface of the graphene joint, and the fine particles of the alloy are bonded to each other. Are metal-bonded at the sites where they come into contact with each other, and a collection of the metal-bonded alloy fine particles is formed on the entire surface of the graphene joint, whereby the surface of the graphene joint is endowed with alloy properties. The properties of the alloy are imparted to the surface of the graphene bond produced by the production method described in paragraph 10, wherein the bond is produced on the bottom surface of the container as a graphene bond having the shape of the bottom surface of the container. This is a manufacturing method for manufacturing a graphene alloy.

That is, the graphene joint is formed on the bottom surface of the container as the shape of the bottom surface by the manufacturing method described in paragraph 10. Further, a plurality of types of metal compounds in which a plurality of metals are simultaneously precipitated by thermal decomposition are dispersed in alcohol, and the alcohol dispersion is filled in the container. As a result, the plurality of types of metal compounds are liquid-phased by being dispersed in alcohol. After that, when vibrations in three directions are repeatedly applied to the container, the graphene junction on the bottom surface of the container is immersed in an alcohol dispersion of a plurality of types of metal compounds, and the surface of the graphene junction comes into contact with the alcohol dispersion. As described in paragraph 13, since the graphene junction is present in the container, a vibration acceleration of about 0.4 G is applied. Further, the temperature of the container is raised to a temperature at which a plurality of types of metal compounds are thermally decomposed at the same time. Alcohol is first vaporized, and a collection of fine crystals of a plurality of types of metal compounds is deposited all at once on the site of the graphene conjugate in contact with the alcohol dispersion. That is, in the alcohol dispersion of a plurality of types of metal compounds, a plurality of types of metal compounds are dispersed in the alcohol in a molecular state. Therefore, when the alcohol is vaporized from the alcohol dispersion, fine crystals of the plurality of types of metal compounds are formed. Precipitate all at once. After that, fine crystals of a plurality of types of metal compounds are simultaneously thermally decomposed, and a plurality of metals constituting the plurality of types of metal compounds are simultaneously precipitated at the same time, and the site where the graphene conjugate comes into contact with the alcohol dispersion, that is, , A collection of alloy fine particles made of a plurality of metals is deposited on the entire surface of the graphene conjugate. At this time, since the alloy fine particles have no impurities and are in an active state, they are metal-bonded to the metal fine particles made of any of silver, copper, gold, or aluminum formed on the entire surface of the graphene joint, and are also metal-bonded. The alloy fine particles are metal-bonded at a portion where they come into contact with each other, and a collection of the metal-bonded alloy fine particles is formed on the entire surface of the graphene junction. As a result, the surface of the graphene joint has alloy properties. As the amount of the plurality of types of metal compounds dispersed in the alcohol increases, the number of alloy fine particles precipitated increases, which increases the number of alloy fine particles precipitated on the surface of the graphene junction, and a collection of metal-bonded alloy fine particles is laminated. The entire surface of the graphene junction is covered with a collection of laminated alloy particles. That is, since the plurality of precipitated metals are in an active state without impurities, fine particles of the alloy composed of the ratio of the number of moles of each of the plurality of types of metal compounds are spread over the entire surface of the graphene conjugate. Formed, the surface of the graphene conjugate has alloying properties.
The entire surface of the graphene junction is covered with a collection of metal-bonded alloy fine particles, and the flats of graphene are bonded to each other by a collection of metal-bonded metal fine particles made of silver, copper, gold, or aluminum. Therefore, the aggregate of alloy fine particles has a constant bonding force, and the flat surface of graphene also forms a graphene bonding body with a constant bonding force. Therefore, similarly to the graphene joint described in paragraph 11, when the graphene joint is taken out from the container, if vibrations in three directions of front-back, left-right, and up-down are applied to the container for a short time, the graphene joint is dissociated from the container. The graphene conjugate can be removed from the container.
That is, a plurality of metals simultaneously precipitated by thermal decomposition on the site where the graphene conjugate produced by the production method described in paragraph 10 comes into contact with the alcohol dispersion of a plurality of metal compounds, that is, on the entire surface of the graphene conjugate. A collection of fine particles of an alloy composed of is deposited. Therefore, a collection of alloy fine particles is formed on the entire surface of the graphene junction by using only a small amount of a plurality of types of metal compounds as raw materials for simultaneously precipitating a plurality of metals. As a result, the graphene joint has excellent properties in both thermal conductivity and electrical conductivity described in paragraph 10, and the entire surface of the graphene joint has alloy properties.
For example, when the alloy is an iron-nickel alloy, the surface of the graphene conjugate has various properties depending on the composition ratio of the alloy. For example, an alloy having a composition ratio of iron and nickel in a ratio of 1: 1 is a soft magnetic material called permalloy, which has an extremely large magnetic permeability. An alloy having a composition ratio of nickel of 42% is an alloy having a low expansion coefficient called 42 alloy, which is used for IC lead frames and the like. Further, the alloy in which nickel has a composition ratio of 36% is an alloy with high strength and low expansion coefficient called Invar. Therefore, the ratio of the number of moles of the iron compound and the nickel compound is set according to the composition ratio of the iron-nickel alloy, and two kinds of metal compounds which are thermally decomposed at the same time are used, and the iron-nickel alloy fine particles are used. When formed on the surface layer of, the surface of the graphene conjugate has the properties of an iron-nickel alloy.
When the alloy is a tin-nickel alloy, the surface of the graphene joint has various properties depending on the composition ratio of the alloy. For example, an alloy in which tin and nickel have a composition ratio of 4: 3 is a solder material having good solderability. Therefore, the surface of the graphene joint has excellent solderability. Alternatively, the material has excellent corrosion resistance, discoloration resistance, heat resistance, and the like, depending on the composition ratio of the tin-nickel alloy. As a result, the surface of the graphene conjugate has the properties of a tin-nickel alloy according to the composition ratio of tin and nickel.
Further, if the alloy is an alloy composed of a plurality of platinum group metals, or an alloy of a platinum group metal and cobalt, the surface of the graphene conjugate has a catalytic action. Examples of such platinum group metals include metals such as platinum, palladium, rhodium, ruthenium, and iridium. The alloy fine particles having a catalytic action bring about the same action and effect as those of the metal fine particles having a catalytic action described in paragraph 13.
The examples of alloys described above are examples, and are not limited to the above three cases.

In the production method for producing a graphene bond described in paragraph 18, the same ligand composed of inorganic ions or molecules is used as a plurality of types of metal compounds in which a plurality of metals are simultaneously precipitated by the thermal decomposition described in paragraph 18. , A production method for producing a graphene conjugate according to the production method for producing a graphene conjugate described in paragraph 18, using a metal complex composed of a plurality of types of inorganic metal compounds coordinated to different metal ions.

That is, for a metal complex composed of an inorganic metal compound having a metal complex ion in which a ligand composed of an inorganic ion or a molecule described in paragraph 15 is coordinated to a metal ion, the same ligand has a different metal ion. Since the metal complex composed of multiple types of inorganic metal compounds coordinated with is the same ligand, when heat-treated in a reducing atmosphere, the multiple types of metal complex are simultaneously thermally decomposed at a temperature of 180-220 ° C. , A plurality of metals constituting a plurality of types of metal complexes are precipitated at the same time, and an alloy composed of a ratio of the number of moles of each of the plurality of types of metal complexes is precipitated.
Therefore, the production method for producing a graphene bond described in paragraph 18 is the same coordination consisting of inorganic ions or molecules as a plurality of types of metal compounds in which a plurality of metals are simultaneously precipitated by the thermal decomposition described in paragraph 18. When a graphene conjugate is produced according to the production method for producing a graphene conjugate described in paragraph 18, using a metal complex composed of a plurality of types of inorganic metal compounds coordinated to different metal ions, the child has a reducing atmosphere of 180. The heat treatment at −220 ° C. produces a graphene bond having the properties of an alloy on the bottom surface of the container.

In the production method for producing a graphene bond described in paragraph 18, the oxygen ions constituting the carboxyl group of the carboxylic acid are different as a plurality of types of metal compounds in which a plurality of metals are simultaneously precipitated by the thermal decomposition described in paragraph 18. The graphene conjugate described in paragraph 18 is produced using a plurality of types of metal carboxylic acid compounds having both the first characteristic of covalently bonding to a metal ion and the second characteristic of the carboxylic acid being the same saturated fatty acid. It is a manufacturing method for manufacturing a graphene conjugate according to the manufacturing method.

That is, the carboxylic acid metal compound having both the first characteristic that the oxygen ion constituting the carboxyl group of the carboxylic acid described in paragraph 17 is covalently bonded to the metal ion and the second characteristic that the carboxylic acid is composed of a saturated fatty acid. , A plurality of types of carboxylic acid metals having the first characteristic that the oxygen ion constituting the carboxyl group of the carboxylic acid is covalently bonded to different metal ions and the second characteristic that the carboxylic acid is composed of the same saturated fatty acid. Since the compounds have the same carboxylic acid, when heat-treated in an air atmosphere, a plurality of types of carboxylic acid metal compounds are simultaneously thermally decomposed at a temperature of 290-430 ° C., a plurality of metals are simultaneously precipitated, and a plurality of types of carboxylic acids are formed. An alloy composed of the ratio of the number of moles of each of the acid metal compounds is precipitated.
Therefore, in the production method for producing a graphene bond described in paragraph 18, the oxygen ions constituting the carboxyl group of the carboxylic acid are used as a plurality of types of metal compounds in which a plurality of metals are simultaneously precipitated by the thermal decomposition described in paragraph 18. , The graphene conjugate described in paragraph 18 using a plurality of types of carboxylic acid metal compounds having both the first characteristic of covalently bonding to different metal ions and the second characteristic of the carboxylic acid being the same saturated fatty acid. When the graphene bond is produced according to the production method for producing the above, the graphene bond having the properties of an alloy on the bottom surface of the container is produced by heat treatment at 290-430 ° C. in the air atmosphere.

The production method for producing a graphene junction in which the properties of an insulating metal oxide are imparted to the surface of the graphene conjugate produced by the production method described in paragraph 10.
A graphene conjugate is produced on the bottom surface of the container according to the production method described in paragraph 10, and the container is filled with an alcohol dispersion in which a metal compound that precipitates an insulating metal oxide by thermal decomposition is dispersed in alcohol. , The container is repeatedly vibrated in three directions of left and right, front and back, and up and down to immerse the graphene conjugate in the alcohol dispersion, and then the temperature of the container is raised to a temperature at which the metal compound is thermally decomposed. As a result, the alcohol is first vaporized, and a collection of fine crystals of the metal compound is deposited all at once on the site of the graphene conjugate in contact with the alcohol dispersion, and then the fine crystals of the metal compound are deposited. Is thermally decomposed, and a collection of fine particles of the insulating metal oxide is deposited all at once on the portion of the graphene junction in contact with the alcohol dispersion, and the fine particles of the metal oxide are deposited on the surface of the graphene conjugate. A graphene junction having the properties of the insulating metal oxide imparted to the surface of the graphene conjugate, thereby covering the entire surface of the vessel, and a graphene conjugate having the shape of the bottom surface of the container. This is a production method for producing a graphene conjugate in which the properties of an insulating metal oxide are imparted to the surface of the graphene conjugate produced by the production method described in paragraph 10.

That is, first, a graphene junction is formed on the bottom surface of the container as the shape of the bottom surface by the manufacturing method described in paragraph 10. Next, the metal compound in which the insulating metal oxide is precipitated by thermal decomposition is dispersed in alcohol, and the alcohol dispersion is filled in the above-mentioned container. As a result, the metal compound is dispersed in alcohol and liquid-phased. After that, when vibrations in three directions are repeatedly applied to the container, the graphene junction on the bottom surface of the container is immersed in the alcohol dispersion of the metal compound, and the surface of the graphene junction comes into contact with the alcohol dispersion. As described in paragraph 13, since the graphene junction is present in the container, a vibration acceleration of about 0.4 G is applied. Further, the temperature of the container is raised to a temperature at which the metal compound is thermally decomposed. Alcohol evaporates first, and a collection of fine crystals of the metal compound is deposited all at once at the site of contact with the alcohol dispersion of the graphene conjugate. That is, since the metal compound is dispersed in the alcohol in the molecular state in the alcohol dispersion of the metal compound, when the alcohol is vaporized from the alcohol dispersion, fine crystals of the metal compound are precipitated all at once. After that, the fine crystals of the metal compound were thermally decomposed, and a collection of fine particles of insulating metal oxide was simultaneously deposited on the site of contact with the alcohol dispersion of the graphene conjugate, that is, on the entire surface of the graphene conjugate. However, the entire surface of the graphene conjugate is covered with fine metal oxide particles. As a result, the surface of the graphene conjugate has the property of an insulating metal oxide. As the amount of the metal compound dispersed in the alcohol increases, the number of fine particles of the metal oxide precipitated increases, which increases the number of fine particles of the metal oxide precipitated on the surface of the graphene conjugate, and the fine particles of the metal oxide are separated from each other. The entire surface of the graphene conjugate is covered with a collection of laminated and laminated metal oxide fine particles.
In addition, impurities having low conductivity or insulating property are used as metal oxides as metal oxides, such as magnetite Fe ₃ O ₄ (a type of iron oxide and also called triiron tetroxide), chromium CrO ₂ , nickel oxide NiO, zinc oxide ZnO, and tin oxide. There are metal oxides such as SnO ₂ and copper oxide CuO. Insulating metal oxides other than these metal oxides are all higher in altitude than soft metals. Mohs hardness, for example, aluminum oxide _Al 2 _{O 3} at 9, chromium oxide _Cr 2 _{O 3} 8-8.5, is 7-7.5 titanium oxide TiO ₂ (rutile). On the other hand, the moth hardness of soft metals having excellent thermal conductivity and electrical conductivity is 2.5 for silver, 2.5-3 for copper, 2.5-3 for gold, and 2 for aluminum, as described above. Lower in altitude than insulating metal oxides. The volume resistivity of aluminum oxide Al ₂ O ₃ is 10 ^14-15 Ω · cm, titanium oxide TiO ₂ is 10 ⁷ Ω · cm, and chromium oxide Cr ₂ O ₃ is 10 ¹² Ω · cm, all of which are insulated. Highly sex. The metal oxide contains impurities or deviates from the stoichiometric composition, so that the insulating property is lowered. The above-mentioned three types of highly insulating metal oxides are the insulating properties of metal oxides that do not contain substances deviating from the stoichiometric composition and do not contain impurities.

The method for removing the graphene conjugate produced by the production method described in paragraph 24 from the container is
According to the manufacturing method described in paragraph 24, a graphene junction is produced on the bottom surface of the container, the upper plane of the graphene junction is evenly compressed, and the metal oxidation formed on the surface layer of both planes of the graphene junction. A collection of fine particles of an object is allowed to bite into metal fine particles made of silver, copper, gold, or aluminum that come into contact with the fine particles of the metal oxide, and the fine particles of the metal oxide are bonded to the metal fine particles, and the metal oxidation is performed. Friction heat is generated at a portion where fine particles of an object come into contact with each other, and the frictional heat causes the fine particles of the metal oxide to be bonded to each other. Further, vibrations in three directions of front-back, left-right, and up-down are applied to the container. After that, the graphene junction is taken out from the container, which is a method of taking out the graphene junction produced by the production method according to claim 9 from the container.

That is, when the graphene conjugate is produced by the production method described in paragraph 24, a collection of fine particles of metal oxide in an active state without impurities is a metal of silver, copper, gold, and aluminum having no impurities. Although it precipitates on the surface of a collection of fine particles, the fine particles of metal oxide do not form a metal bond with the metal fine particles, so the binding force between the two is small. Further, the fine particles of the metal oxide are precipitated by contacting the fine particles with each other, but since the fine particles of the metal oxide do not form a metal bond, the bonding force between the fine particles of the metal oxide is also small. Therefore, when the graphene conjugate produced by the production method described in paragraph 24 is taken out from the container, the fine particles of the metal oxide are easily dissociated from the graphene conjugate.
On the other hand, insulating metal oxides have a hardness higher than that of silver, copper, gold, and aluminum, as described in paragraph 25. Therefore, when the entire flat surface of the graphene junction formed on the bottom surface of the container is uniformly compressed, fine metal oxide fine particles formed on the surface layers of both planes of the graphene junction are formed on the graphene junction. It comes into contact with fine particles of a soft metal made of silver, copper, gold, or aluminum, and further bites into the fine metal particles of the soft metal, and the fine particles of the metal oxide are bonded to the fine metal particles of the contacted soft metal. Further, frictional heat is generated at a portion where the fine particles of the metal oxide come into contact with each other, and the fine particles of the metal oxide are bonded to each other by the frictional heat. As a result, both planes of the graphene conjugate are covered with a collection of metal oxide fine particles bonded by frictional heat, and the metal oxide fine particles are bonded to the metal fine particles with a constant binding force. After that, the container is vibrated in three directions of front-back, left-right, and up-down, and the graphene joint is taken out from the container.
In this graphene junction, the metal oxide fine particles on the surface layer are bonded to each other by frictional heat, and the metal oxide fine particles bite into the contacted soft metal fine particles, so that the metal oxide fine particles formed on the surface layer The gathering has a certain binding force. This allows the graphene joint to be handled.
Since a collection of fine particles of metal oxide is formed on both planes of the graphene joint, the graphene joint can be pressure-bonded to a base material or a component. That is, when the graphene junction is placed on the surface of the component or base material and an even compressive stress is applied to the surface of the graphene junction, the fine particles of the metal oxide on one plane of the graphene junction become the surface of the component or substrate. It bites into the surface. As a result, the graphene joint is crimped to the component or the base material, and the other flat surface of the crimped graphene joint has an insulating property. As a result, a graphene joint having excellent thermal conductivity and electrical conductivity and an insulating surface is pressure-bonded to the component or the base material. Further, since the gap on the crimping surface of the crimped graphene joint is a small gap corresponding to the size of the fine particles of the metal oxide, the liquid cannot enter into this gap. Therefore, even if the graphene joint comes into contact with or immersed in a corrosive liquid, the pressure-bonded surface does not change over time.

In the production method for producing a graphene bond described in paragraph 24, the oxygen ion constituting the carboxyl group of the carboxylic acid is a ligand as the metal compound that precipitates an insulating metal oxide by thermal decomposition described in paragraph 24. This is a production method for producing the graphene conjugate according to the production method for producing the graphene conjugate described in paragraph 24, using the carboxylic acid metal compound coordinated to the metal ion.

That is, the oxygen ion constituting the carboxyl group of the carboxylic acid serves as a ligand, and the metal carboxylic acid compound coordinated to the metal ion precipitates a metal oxide by thermal decomposition. For this reason, the flat surfaces of graphene described in paragraph 24 are bonded to the graphene junction formed by a collection of metal fine particles made of any of silver, copper, gold, or aluminum, and the insulating metal oxide is formed. In the production method for producing a graphene conjugate to which the properties are imparted, the above metal carboxylate compound is used as the metal compound that precipitates the metal oxide by thermal decomposition, and the graphene conjugate is produced according to the production method described in paragraph 24. , Electrical insulation is imparted to the surface of the graphene joint. The thermal decomposition temperature of the metal carboxylate compound is the highest at which the metal naphthenate compound thermally decomposes at 330 ° C. Further, since the thermal decomposition of the carboxylic acid metal compound in the atmospheric atmosphere is 30 to 50 ° C. lower than the thermal decomposition in the nitrogen atmosphere, the thermal decomposition in the atmospheric atmosphere requires a low heat treatment cost. Further, these metal carboxylate compounds are dispersed in alcohol up to nearly 10% by weight.
That is, the oxygen ion constituting the carboxyl group serves as a ligand, and the carboxylate metal compound which approaches the metal ion to coordinate bond is because the oxygen ion approaches the metal ion which is the largest ion and coordinates bond. , The distance between the two becomes shorter. Therefore, the oxygen ion coordinate-bonded to the metal ion has the longest distance from the ion covalently bonded on the opposite side of the metal ion. A carboxylic acid metal compound having such molecular structural characteristics is bonded to an ion in which an oxygen ion constituting a carboxyl group is covalently bonded on the opposite side of the metal ion when the boiling point of the carboxylic acid constituting the carboxylic acid metal compound is exceeded. The part is first divided and decomposed into a metal oxide and a carboxylic acid, which are compounds of a metal ion and an oxygen ion. When the temperature is further raised, the carboxylic acid takes away the heat of vaporization and vaporizes, and the metal oxide precipitates immediately after the vaporization of the carboxylic acid is completed. Examples of such a metal carboxylate compound include a metal acetate compound, a metal caprylate oxide, a metal benzoate oxide, and a metal naphthenate oxide.
Since some of the metal acetate oxides precipitate metal oxides that have been amorphized by thermal decomposition and unstable metal oxides, the carboxylic acid metal oxide compound that precipitates metal oxides by thermal decomposition is capryl. A carboxylic acid metal oxide composed of an acid metal oxide, a benzoate metal oxide, and a naphthenate metal oxide is desirable.
In addition, the metal carboxylate compounds are inexpensive industrial chemicals that can be easily synthesized. That is, when a general-purpose carboxylic acid is reacted with a strong alkali, an alkali metal carboxylate compound is produced. After that, when the alkali metal carboxylate compound is reacted with the inorganic metal compound, the metal carboxylate compound is synthesized. The carboxylic acid used as a raw material is an organic acid having a relatively low boiling point among the boiling points of the organic acid, and a metal oxide is precipitated at a low heat treatment temperature of about 330 ° C. in an air atmosphere.
As described above, the production method for producing a graphene bond described in paragraph 24 constitutes a carboxyl group of a carboxylic acid as a metal compound in which the insulating metal oxide described in paragraph 24 is precipitated by thermal decomposition. When a graphene conjugate is produced according to the production method described in paragraph 24 using a carboxylic acid metal compound coordinated to a metal ion using the oxygen ion as a ligand, graphene having an electrically insulating surface is imparted. The joint is manufactured.

It is explanatory drawing which enlarged and represented a part of the side surface of the graphene junction in which the flat planes of graphene were overlapped and bonded in 10 layers through the collection of silver fine particles.

Example 1
This example is an example in which a group of graphene in which the flat surfaces of graphene are overlapped with each other via a methanol dispersion of a metal compound is formed on the bottom surface of the container according to the production method described in paragraph 8. In this example, a metal compound that precipitates silver by thermal decomposition is used.
First, a metal compound that precipitates silver by thermal decomposition is dispersed in methanol to prepare a methanol dispersion. As a silver compound, two ammines, which are one of the most easily synthesized silver complex ions, are chlorides of diammine silver ion [Ag (NH ₃ ) ₂ ] ^{+ 1} coordinated to silver ion Ag ^+. Using diammine silver chloride [Ag (NH ₃ ) ₂ ] Cl (for example, a product of Tanaka Kikinzoku Sales Co., Ltd.), 1 mol of diammine silver chloride was dispersed in 2 liters of methanol and 1.2 m × 1.2 m. A container having a bottom surface and a shallow bottom was filled with a methanol dispersion.
Next, a parallel plate electrode having an effective area of 1 m × 1 m in which an electric field is generated in the gap between the two parallel plate electrodes is prepared, and the two parallel plate electrodes are superposed with a gap of 100 μm, and this gap is formed. The graphite particles are evenly squeezed into the parallel. Assuming that the graphite particles are spheres having a particle size of 25 μm and the average thickness of the graphite particles is 10 μm, the graphite particles are evenly packed in the gap of 100 μm formed by the two parallel plate electrodes. In the case, there are 6.4 × 10 ⁷ graphite particles. If a DC voltage of 10.6 kilovolts or more is applied to this group of graphite particles, the interlayer bonds of all the graphite particles are broken at the same time. At this time, a collection of 1.9 × 10 ¹³ graphenes is obtained. The aggregate of graphite particles used at this time is only 1.18 g.
For this reason, 10 g of scaly graphite particles (for example, XD100 manufactured by Ito Graphite Industry Co., Ltd.) were stacked and pulled on the surface of a parallel plate electrode having an effective area of an electrode in which an electric field is generated of 1 m × 1 m. This parallel plate electrode is immersed in a container filled with a methanol dispersion of diammine silver chloride, and the other parallel plate electrode is further superposed on the parallel plate electrode to form two parallel plate electrodes. A cluster of graphenes was produced by applying a DC voltage of 12 kilovolts between the electrodes, separated by a gap of 100 μm. Next, the gap between the two parallel plate electrodes was expanded, the two parallel plate electrodes were tilted in a methanol dispersion, and vibration acceleration in three directions consisting of 0.2 G was repeatedly applied to the container, after which. , Two parallel plate electrodes were taken out from the container. Further, ultrasonic vibration of 20 kHz was applied to the methanol dispersion in the container by an ultrasonic homogenizer device (product LUH300 of Yamato Scientific Co., Ltd.) for 2 minutes, and each graphene was dispersed in the methanol dispersion. Created a turbid body. After that, the vibration acceleration in three directions consisting of 0.2 G is repeatedly applied to the container to form a collection of graphene dispersed in the methanol dispersion, and the graphene flat surfaces are overlapped with each other via the methanol dispersion. As a result, it was formed on the bottom surface of the container as the shape of the bottom surface.
In Example 1, silver was selected as a metal having excellent thermal conductivity and electrical conductivity, and a metal compound that precipitates silver by thermal decomposition was used. However, as a metal having excellent thermal conductivity and electrical conductivity. , Copper, gold, or aluminum is selected, and a metal compound that precipitates one of these metals by thermal decomposition is used, and a collection of graphenes in which the flat surfaces of the graphenes are overlapped via a methanol dispersion of the metal compound is stored in a container. It can be formed on the bottom surface of the surface as the shape of the bottom surface.

Example 2
In this embodiment, according to the production method described in paragraph 10, graphene conjugates in which the flat surfaces of graphene are bonded by a collection of silver fine particles are formed on the bottom surface of the container as the shape of the bottom surface. .. That is, the graphene aggregates prepared in Example 1 in which the flat surfaces of graphene overlap each other via the methanol dispersion of diammine silver chloride are heat-treated, the diammine silver chloride is thermally decomposed, and silver fine particles are precipitated. , A graphene junction in which the flat surfaces of graphene are bonded to each other is formed on the bottom surface of the container by metal bonding between the silver fine particles.
In Example 1, the graphene having flat planes of graphene overlapping each other via a methanol dispersion was formed on the bottom surface of the graphene, and the temperature of the container was raised to 180 ° C. in a hydrogen gas atmosphere, and the temperature was raised to 180 ° C. for 5 minutes. When left to stand, the diammine silver chloride is thermally decomposed to precipitate a collection of silver fine particles on the surface of the flat surface of graphene, and the graphene junction in which the flat surfaces of graphene are bonded by metal bonding between the silver fine particles is formed in a container. Formed on the bottom. After that, a vibration acceleration of 0.4 G in three directions was applied to the container for a short time, and the sample was taken out from the bottom of the container.
Next, observation and analysis of the two planes and sides of the sample were performed using an electron microscope. As the electron microscope, an extremely low accelerating voltage SEM manufactured by JFE Techno Research Co., Ltd. was used. This device is capable of observing the surface with an extremely low accelerating voltage from 100 volts, and has a feature that the surface of the sample can be directly observed without forming a conductive graphene-coated conjugate on the sample. First, the secondary electron beam between 900 and 1000 volts of the backscattered electron beam was taken out and image processed. Granular particles having a size of 40-60 nm were evenly formed on the surface. Next, the energy between 900 and 1000 volts of the reflected electron beam was extracted and image processing was performed, and the difference in material was observed depending on the shade of the image. Since no shade was observed, it was formed from the same substance. Furthermore, the energy of the characteristic X-ray and its intensity were image-processed, and the elements constituting the fine particles were analyzed. It was confirmed that only silver atoms were present and the granular fine particles were silver fine particles.
Next, a collection of silver fine particles formed on the side surface of the sample was peeled off, and the side surface of the sample was observed with an electron microscope. The secondary electron beam between 900 and 1000 volts of the backscattered electron beam from the side surface of the sample was taken out and image processing was performed. A substance whose thickness was significantly thinner than the size of the silver fine particles was layered in 10 layers at intervals close to 250 nm.
From these results, the flat planes of graphene were bonded to each other in 10 layers via silver fine particles, and a graphene junction was formed on the bottom surface of the container. FIG. 1 is a schematic enlarged view of a part of the side surface after peeling off the collection of silver fine particles on the side surface of the sample. 1 is silver fine particles and 2 is graphene. Although a weight of 5 kg was placed on the prepared sample, it was found that the sample had a certain mechanical strength because the sample was not destroyed.
After that, the surface resistance of a plurality of samples was measured with a surface resistance meter (for example, surface resistance meter ST-4 of Simco Japan Co., Ltd.). Since the surface resistance values were all less than 1 × 10 ³ Ω / □, the sample had a surface resistance close to that of silver. Further, the thermal conductivity of a plurality of samples was measured by a thermal conductivity measuring device (for example, a thermal conductivity measuring device of Rigaku Co., Ltd.). The thermal conductivity was about four times the thermal conductivity of silver, which was 428 W / mK. Therefore, the graphene junction prepared in this example is a graphene conjugate excellent in both thermal conductivity and electrical conductivity.
From the above results, in Example 1, a group of graphene in which the flat surfaces overlapped in 10 layers was formed on the bottom surface of the container, and in Example 2, silver granular fine particles were formed in the gaps where the flat surfaces overlapped. A collection of silver particles is deposited to form five layers, and silver particles are piled up to form five layers, metal bonds are formed at the sites where the silver particles are in contact with each other, and the flat surfaces of graphene are bonded by the metal-bonded collection of silver particles. A graphene bond was formed on the bottom of the vessel. This graphene conjugate has a certain mechanical strength, and also has a conductivity close to that of silver and a thermal conductivity close to that of graphene.

Example 3
In this embodiment, according to the manufacturing method described in paragraph 12, a graphene joint having metal properties different from silver, copper, gold, and aluminum is formed on the surface of the graphene joint on the bottom surface of the container. It is an embodiment. That is, chromium is deposited on the surface of the graphene bonded body prepared in Example 2, chromium fine particles are precipitated on the surface of silver fine particles formed on the surface of the graphene bonded body, and the surface of the graphene bonded body is made of chromium fine particles. cover. The surface of the graphene joint prepared in this embodiment is provided with abrasion resistance.
First, chromium octoate _{Cr (C 7 H 15 COO)} 3 (CAS No. 3444-17-5, imports) 0.1 mol, and dispersed in methanol 100 cc, was prepared methanol dispersion. In Example 2, this methanol dispersion was filled in the container formed on the bottom surface of the container with a graphene conjugate in which the flat surfaces of graphene were bonded by a collection of silver fine particles. After that, vibration acceleration in three directions consisting of 0.4 G was repeatedly applied to the container. Further, the container was heated to 290 ° C. in an air atmosphere and left at 290 ° C. for 1 minute to thermally decompose chromium octylate. After that, a vibration acceleration of 0.4 G in three directions was applied to the container again for a short time, and the sample was taken out from the container.
Further, as in Example 2, the two planes and sides of the sample were observed and analyzed by an electron microscope. Granular fine particles having a size of 40-60 nm were evenly stacked and formed on the surface of the sample, and the surface of the fine particles was composed of chromium. Also on the side surface of the sample, granular fine particles of chromium having a size of 40-60 nm were formed by being evenly stacked.
After that, a collection of granular fine particles on the side surface of the sample was peeled off, and the side surface was observed again with an electron microscope. As a result, chromium was not present in the gap between the flat planes of graphene bonded by the collection of silver fine particles.
From the above results, in Example 2, the flat planes of graphene formed a graphene junction formed by a collection of silver fine particles on the bottom surface of the container, and the graphene junction was bonded to the graphene junction in Example 3. Chromium was deposited on the surface of the silver fine particles formed on the surface of the body, and the surface of the graphene conjugate was covered with the fine particles of chromium to prepare a graphene conjugate. As a result, the surface of the graphene conjugate has chrome properties.
In Example 3, chromium was selected as the metal other than silver, copper, gold, and aluminum to impart the properties of chromium to the graphene joint, but the metal is not limited to chromium, and other metals can be used. By using a metal compound precipitated by thermal decomposition, the properties of the metal can be imparted to the graphene conjugate.

Example 4
In this embodiment, according to the manufacturing method described in paragraph 18, the graphene joint in which the flat surfaces of graphene are bonded by a collection of silver fine particles is provided with the graphene joint in which the properties of an alloy are imparted to the bottom surface of the container. It is an example which forms in. That is, palladium and rhodium were precipitated on the surface of the graphene conjugate prepared in Example 2 at a composition ratio of 3: 1, and palladium and rhodium were added to the surface of the silver fine particles formed on the surface of the graphene conjugate. The alloy fine particles having a composition ratio of 3: 1 are precipitated, and the surface of the graphene conjugate is covered with the alloy fine particles composed of palladium and rhodium. Therefore, the surface of the graphene conjugate has a catalytic action.
As a raw material for palladium, diammonium hexachloropalladium (NH ₄ ) ₂ [PdCl ₆ ] (CAS No. 19168-23-1, imported product) is used, and as a raw material for rhodium, ammonium hexachlorolodiadium (NH ₄ ) is used. ) ₃ [RhCl ₆ ] (for example, a product of Mitsuwa Chemical Co., Ltd.) was used.
First, 0.03 mol of diammonium hexachloropalladium acid and 0.01 mol of ammonium hexachlororodium acid were dispersed in 100 cc of methanol to prepare a methanol dispersion. In Example 2, this methanol dispersion was filled in the container formed on the bottom surface of the container with a graphene conjugate in which the flat surfaces of graphene were bonded by a collection of metal-bonded silver fine particles. After that, vibration acceleration in three directions consisting of 0.4 G was repeatedly applied to the container. Further, the container was heated to 200 ° C. in an atmosphere of hydrogen gas and left at 200 ° C. for 5 minutes to thermally decompose diammonium hexachloropalladium acid and ammonium hexachlororodium acid. After that, a vibration acceleration of 0.4 G in three directions was applied to the container again for a short time, and the sample was taken out from the container.
Further, as in Example 2, the two planes and sides of the sample were observed and analyzed by an electron microscope. Granular fine particles having a size of 40-60 nm were evenly stacked and formed on the surface of the sample, and the granular fine particles were composed of an alloy having a composition ratio of palladium and rhodium in a ratio of 3: 1. Also on the side surface of the sample, granular fine particles having a size of 40-60 nm were formed by evenly stacking them. The granular fine particles were composed of an alloy in which palladium and rhodium had a composition ratio of 3: 1.
After that, a collection of granular fine particles on the side surface of the sample was peeled off, and the side surface was observed again with an electron microscope. As a result, there was no alloy of palladium and rhodium in the gaps between the flat surfaces of graphene bonded by a collection of silver fine particles.
From the above results, in Example 2, the flat planes of graphene formed a graphene zygote formed by a collection of silver fine particles on the bottom surface of the container, and in contrast to this graphene zygote, in Example 4, graphene was formed. A graphene junction in which fine particles of an alloy composed of palladium and rhodium are precipitated on the surface of silver fine particles formed on the surface of the conjugate, and the surface of the graphene junction is covered with fine particles of an alloy composed of palladium and rhodium. It was created. As a result, the surface of the graphene conjugate has the properties of an alloy composed of palladium and rhodium.

Example 5
In this example, according to the manufacturing method described in paragraph 18, the flat planes of graphene are alloyed with a graphene junction in which the flat surfaces of graphene are bonded by a collection of metal fine particles made of any of silver, copper, gold, or aluminum. This is an example of forming a graphene alloy having the above-mentioned properties on the bottom surface of a container. That is, tin and nickel were precipitated on the surface of the graphene alloy prepared in Example 2 at a composition ratio of 4: 3, and tin and nickel were added to the surface of the silver fine particles formed on the surface of the graphene alloy. This is an example in which alloy fine particles having a composition ratio of 4: 3 are precipitated, and the surface of the graphene conjugate is covered with alloy fine particles composed of tin and nickel. The surface of the graphene joint produced in this example has excellent solderability.
Tin octylate Sn (C ₇ H ₁₅ COO) ₂ (for example, a product of Fuji Film Wako Pure Chemical Industries, Ltd.) is used as a raw material for tin, and nickel Ni octylate (C ₇ H ₁₅ COO) is used as a raw material for nickel. ₂ (for example, a product of Fuji Film Wako Pure Chemical Industries, Ltd.) was used.
First, 0.04 mol of tin octylate and 0.03 mol of nickel octylate were dispersed in 100 cc of methanol to prepare a methanol dispersion. In Example 2, this methanol dispersion was filled in the container formed on the bottom surface of the container with a graphene conjugate in which the flat surfaces of graphene were bonded by a collection of metal-bonded silver fine particles. After that, vibration acceleration in three directions consisting of 0.4 G was repeatedly applied to the container. Further, the container was heated to 290 ° C. in an air atmosphere and left at 290 ° C. for 1 minute to thermally decompose tin octylate and nickel octylate. After that, a vibration acceleration of 0.4 G in three directions was applied to the container again for a short time, and the sample was taken out from the container.
Further, as in Example 2, the two planes and sides of the sample were observed and analyzed by an electron microscope. Granular fine particles having a size of 40-60 nm were evenly stacked and formed on the surface of the sample, and the granular fine particles were composed of an alloy having a composition ratio of tin and nickel in a composition ratio of 4: 3. Also on the side surface of the sample, granular fine particles having a size of 40-60 nm were formed by evenly stacking them. The granular fine particles were also composed of an alloy in which tin and nickel had a composition ratio of 4: 3.
After that, a collection of granular fine particles on the side surface of the sample was peeled off, and the side surface was observed again with an electron microscope. As a result, there was no alloy of tin and nickel in the gaps between the flat surfaces of graphene bonded by a collection of silver fine particles.
From the above results, in Example 2, the flat planes of graphene formed a graphene junction formed by a collection of silver fine particles on the bottom surface of the container, and the graphene junction was bonded to the graphene junction in Example 5. Fine particles of an alloy of tin and nickel were precipitated on the surface of fine silver particles formed on the surface of the body, and a graphene junction in which the surface of the graphene junction was covered with fine particles of an alloy of tin and nickel was created. .. As a result, the surface of the graphene conjugate has the properties of an alloy of tin and nickel.
Although two examples have been described as examples for imparting the properties of the alloy to the graphene joint, the alloy is not limited to these two cases.

Example 6
In this example, according to the production method described in paragraph 24, a graphene junction in which the flat surfaces of graphene are bonded by a collection of silver fine particles is endowed with the properties of an insulating metal oxide. Is an embodiment of forming on the bottom surface of the container. That is, it is an example in which fine particles of aluminum oxide Al ₂ O ₃ are precipitated on the surface of the graphene conjugate prepared in Example 2, and the surface of the graphene conjugate is covered with aluminum oxide particles. The surface of the graphene joint prepared in this example becomes insulating. Aluminum oxide is an insulator having a volume resistivity of 10 ^14-15 Ω · cm and a dielectric strength of 10-15 kilovolts / mm.
First, 0.1 mol of aluminum benzoate Al (C ₆ H ₅ COO) ₃ (for example, a product of Mitsuwa Chemical Co., Ltd.) was dispersed in 100 cc of methanol to prepare a methanol dispersion. In Example 2, this methanol dispersion was filled in the container formed on the bottom surface of the container with a graphene conjugate in which the flat surfaces of graphene were bonded by a collection of silver fine particles. After that, vibration acceleration in three directions consisting of 0.4 G was repeatedly applied to the container. Further, the container was heated to 310 ° C. in an air atmosphere and left at 310 ° C. for 1 minute to thermally decompose aluminum benzoate. After that, an aluminum plate having the shape of the bottom surface of the container was placed on the sample in the container, a weight of 5 kg was placed on the aluminum plate, and then the weight and the aluminum plate were taken out. Further, a vibration acceleration of 0.2 G in three directions was applied to the container for a short time, and the sample was taken out from the container. A weight of 5 kg was placed on the sample taken out again, but the fine particles were not peeled off from the surface of the sample.
After that, as in Example 2, the two planes and sides of the sample were observed and analyzed with an electron microscope. Granular fine particles having a size of 40-60 nm were evenly stacked and formed on the surface of the sample, and the granular fine particles were composed of aluminum oxide.
After that, all the aggregates of granular fine particles on the side surface of the sample were peeled off, and the side surface was observed again with an electron microscope. As a result, aluminum oxide was not present in the gap between the flat surfaces of graphene bonded by a collection of silver fine particles.
From the above results, in Example 2, a graphene junction in which the flat surfaces of graphene were bonded by a collection of silver fine particles was formed on the bottom surface of the container, and the graphene junction was bonded to the graphene junction in Example 6. Fine particles of aluminum oxide were precipitated on the surface of fine silver particles formed on the surface of the body, and the surface of the graphene conjugate was covered with fine particles of aluminum oxide. After that, when compressive stress is evenly applied to the entire plane of the graphene joint, the aluminum oxide fine particles on the surface of the graphene joint bite into the silver fine particles, and the aluminum oxides come into contact with each other due to frictional heat. Joined. Therefore, even if a weight of 5 kg was placed, the fine particles of aluminum oxide were not peeled off from the graphene joint. This allows the graphene joint to be handled, and the surface of the graphene joint has the properties of aluminum oxide.
In Example 6, aluminum oxide was selected as the insulating metal oxide, and the flat surfaces of graphene were bonded to each other by a collection of metal fine particles made of any of silver, copper, gold, or aluminum. Although the graphene conjugate is imparted with the properties of aluminum oxide, it is not limited to aluminum oxide, and if a metal carboxylate compound that precipitates titanium oxide TiO ₂ and chromium Cr ₂ O ₃ by thermal decomposition is used, graphene is used. The bonded body can be imparted with the properties of titanium oxide or chromium oxide.

Although five examples have been described above as examples of the graphene conjugate, the graphene conjugate is not limited to these examples. The reason for this is that the metal excellent in both thermal conductivity and electrical conductivity is not limited to silver, and copper, gold or aluminum can be used. Further, by precipitating a metal other than chromium or an alloy other than an alloy of palladium and rhodium and an alloy of tin and nickel on the graphene joint, the surface of the graphene joint can be made of various metals or alloys. Has the nature of. Further, since the graphene joint is formed on the bottom surface of the container as the shape of the bottom surface, the thickness, surface area and shape of the graphene joint can be freely changed according to the use of the graphene joint. Further, in this embodiment, a graphene conjugate can be produced by using an inexpensive metal compound with an extremely simple treatment, and further, the surface of the graphene conjugate has the properties of chromium, or an alloy of palladium and rhodium, or It was possible to impart the properties of an alloy of tin and nickel.

1 silver fine particles 2 graphene

Claims (11)

The alcohol is a collection of graphene in which the flat surfaces of graphene are overlapped with each other via an alcohol dispersion in which a metal compound that precipitates a metal of silver, copper, gold, or aluminum by thermal decomposition is dispersed in alcohol. The manufacturing method of manufacturing the bottom surface of the container filled with the dispersion liquid as the shape of the bottom surface is as follows.
A metal compound that precipitates any metal of silver, copper, gold, or aluminum by thermal decomposition is dispersed in alcohol to prepare an alcohol dispersion, and the alcohol dispersion is filled in a container. On the surface of one of the parallel plate electrodes, a collection of scaly graphite particles or a collection of massive graphite particles is flatly packed, and the parallel plate electrode is applied to the alcohol dispersion filled in the container. Immerse, further superimpose the other parallel plate electrode on the one parallel plate electrode, and in the alcohol dispersion, place the two parallel plate electrodes on the aggregate of scaly graphite particles or the massive graphite. The particles are separated through a collection of particles, and then a DC potential difference is applied to the gap between the two parallel graphite electrodes, whereby the magnitude of the potential difference is adjusted to the magnitude of the gap between the two graphite plates. An electric field corresponding to the value divided by is applied to the group of scaly graphite particles or the group of lump graphite particles, and the application of the electric field causes all the graphite forming the scaly graphite particles or the lump graphite particles. The interlayer bond of the crystal is broken at the same time, and a collection of graphite is produced in the gap between the two parallel plate electrodes. After that, the gap between the two parallel plate electrodes is expanded to expand the gap between the two parallel plate electrodes. Is tilted in the alcohol dispersion, and further vibrating in three directions of left and right, front and back, and up and down is repeatedly applied to the container, and the graphite aggregate is collected in the alcohol dispersion through the gap between the two parallel plate electrodes. After that, the two parallel graphite electrodes are taken out from the container, and the homogenizer device is operated in the alcohol dispersion liquid in the container. By the operation of the homogenizer device, the homogenizer device is operated through the alcohol dispersion liquid. The impact is repeatedly applied to the graphite aggregate to separate the graphite aggregate into individual graphite particles in the alcohol dispersion, and then the homogenizer device is taken out from the container. A collection of graphite separated into individual graphite in the alcohol dispersion by repeatedly applying vibrations in three directions of left and right, front and back, and up and down is spread over the entire bottom surface of the container with the flat surface of the graphite facing up. While diffusing, the graphite flat surfaces are overlapped with each other via the alcohol dispersion liquid, whereby a collection of graphite having the graphite planes overlapped with each other via the alcohol dispersion liquid is formed on the bottom surface of the container. Formed as the shape of A collection of graphene in which the flat surfaces of graphene are overlapped with each other via an alcohol dispersion in which a metal compound that thermally decomposes any of silver, copper, gold, or aluminum is dispersed in alcohol. This is a manufacturing method in which the bottom surface of a container filled with the alcohol dispersion is manufactured as the shape of the bottom surface. Using a group of graphene in which the flat surfaces of graphene produced by the production method according to claim 1 are overlapped with each other, the flat surfaces of the graphene are a metal made of any metal of silver, copper, gold, or aluminum. The manufacturing method for producing a graphene conjugate bonded by a collection of fine particles is
The container in which the aggregates of graphenes in which the flat surfaces of the graphenes according to claim 1 are overlapped is formed on the bottom surface is heated to a temperature at which the metal compound according to claim 1 is thermally decomposed, whereby first The alcohol evaporates, and a collection of fine crystals of the metal compound is deposited all at once on the flat surface of the graphene, after which the fine crystals of the metal compound are thermally decomposed to form silver, copper, gold, or aluminum. A collection of granular metal fine particles made of any of the metals are deposited all at once on the flat surface of the graphene, and the metal bonds are formed at a site where the metal fine particles are in contact with each other. A graphene junction in which the flat surfaces of the graphenes are bonded by a collection of metal-bonded metal fine particles and the flat surfaces of the graphene are bonded by a collection of the metal-bonded metal fine particles is a graphene junction having the shape of the bottom surface on the bottom surface of the container. Using a group of graphenes in which the flat surfaces of the graphenes produced by the production method according to claim 1 are overlapped with each other, the flat surfaces of the graphenes are made of silver, copper, gold, or aluminum. It is a manufacturing method for manufacturing a graphene bond bonded by a collection of metal fine particles made of the same metal. A production method for producing a graphene joint in which properties of a metal different from silver, copper, gold, and aluminum are imparted to the surface of the graphene joint produced by the production method according to claim 2 is
A graphene bond was produced on the bottom surface of the container according to the production method according to claim 2, and a metal compound in which metals other than silver, copper, gold, and aluminum were precipitated by thermal decomposition was dispersed in alcohol in the container. The container is filled with an alcohol dispersion, and vibrations in three directions of left and right, front and back, and up and down are repeatedly applied to immerse the graphene bond in the alcohol dispersion, after which the metal compound thermally decomposes the container. The temperature is raised to a temperature, whereby the alcohol is first vaporized, and a collection of fine crystals of the metal compound is simultaneously deposited at the site where the graphene conjugate is in contact with the alcohol dispersion, and then the above. Fine crystals of the metal compound are thermally decomposed, and a collection of metal fine particles made of a metal other than silver, copper, gold, and aluminum is deposited all at once at the site where the graphene bond is in contact with the alcohol dispersion. The metal fine particles form a metal bond with the metal fine particles made of any of silver, copper, gold, or aluminum formed on the entire surface of the graphene joint, and at the site where the metal fine particles come into contact with each other. The metal is bonded, and a collection of the metal-bonded metal fine particles covers the entire surface of the graphene joint, thereby imparting the properties of metals other than silver, copper, gold, and aluminum to the surface of the graphene joint. The finished graphene bond is produced on the bottom surface of the container as a graphene bond having the shape of the bottom surface of the container, and on the surface of the graphene bond produced by the production method according to claim 2, silver, copper. It is a manufacturing method for producing a graphene bond which is endowed with metal properties different from those of gold, gold and aluminum. In the production method for producing a graphene aggregate according to claim 1, a ligand composed of an inorganic ion or a molecule is coordinated to the metal ion as the metal compound that precipitates a metal by thermal decomposition according to claim 1. A production method for producing an aggregate of graphene according to claim 1, according to the production method according to claim 1, using a metal complex composed of an inorganic metal compound having a bonded metal complex ion.
Or
In the production method for producing a graphene conjugate according to claim 2, as the metal compound that precipitates a metal by thermal decomposition according to claim 2, a ligand composed of an inorganic ion or a molecule is coordinated to the metal ion. A production method for producing a graphene conjugate according to claim 2, according to the production method according to claim 2, using a metal complex composed of an inorganic metal compound having a bonded metal complex ion.
Or
In the production method for producing a graphene conjugate according to claim 3, as the metal compound that precipitates a metal by thermal decomposition according to claim 3, a ligand composed of an inorganic ion or a molecule is coordinated to the metal ion. This is a production method for producing a graphene conjugate according to claim 3, according to the production method according to claim 3, using a metal complex composed of an inorganic metal compound having bonded metal complex ions. In the production method for producing an aggregate of graphene according to claim 1, the oxygen ion constituting the carboxyl group of the carboxylic acid is covalently bonded to the metal ion as the metal compound for precipitating a metal by the thermal decomposition according to claim 1. Using a carboxylic acid metal compound having both the first characteristic of carboxylic acid and the second characteristic of the carboxylic acid being a saturated fatty acid, the aggregate of graphene according to claim 1 is obtained according to the production method according to claim 1. It is a manufacturing method to manufacture,
Or
In the production method for producing a graphene conjugate according to claim 2, the oxygen ion constituting the carboxyl group of the carboxylic acid is covalently bonded to the metal ion as the metal compound that precipitates the metal by the thermal decomposition according to claim 2. The graphene conjugate according to claim 2 is prepared according to the production method according to claim 2, using a carboxylic acid metal compound having both the first characteristic of carboxylic acid and the second characteristic of the carboxylic acid being a saturated fatty acid. It is a manufacturing method to manufacture,
Or
In the production method for producing a graphene conjugate according to claim 3, the oxygen ion constituting the carboxyl group of the carboxylic acid is covalently bonded to the metal ion as the metal compound that precipitates the metal by the thermal decomposition according to claim 3. The graphene conjugate according to claim 3 is prepared according to the production method according to claim 3, using a carboxylic acid metal compound having both the first characteristic of carboxylic acid and the second characteristic of the carboxylic acid being a saturated fatty acid. It is a manufacturing method for manufacturing. The production method for producing a graphene joint in which the properties of an alloy are imparted to the surface of the graphene joint produced by the production method according to claim 2 is
A graphene alloy is produced on the bottom surface of the container according to the production method according to claim 2, and an alcohol dispersion in which a plurality of types of metal compounds in which a plurality of metals are simultaneously precipitated by thermal decomposition is dispersed in alcohol is placed in the container. The container is filled and vibrated in three directions of left and right, front and back, and up and down repeatedly to immerse the graphene alloy in the alcohol dispersion, and then the container is thermally decomposed by the plurality of types of metal compounds at the same time. The temperature is raised to a temperature, whereby the alcohol is first vaporized, and a collection of fine crystals of the plurality of types of metal compounds is simultaneously precipitated at the site of contact with the alcohol dispersion of the graphene alloy. After that, the fine crystals of the plurality of types of metal compounds are thermally decomposed at the same time, and a plurality of metals constituting the plurality of types of metal compounds are simultaneously precipitated at the site of contact with the alcohol dispersion of the graphene bond. Then, the fine particles of the alloy made of the plurality of metals are metal-bonded to the metal fine particles made of any of silver, copper, gold, or aluminum formed on the entire surface of the graphene joint, and the alloy is formed. Metal bonds are formed at the sites where the fine particles are in contact with each other, and a collection of the metal-bonded alloy fine particles covers the entire surface of the graphene joint, whereby the surface of the graphene joint is endowed with alloy properties. The properties of the alloy are imparted to the surface of the graphene bond produced by the production method according to claim 2, wherein the bond is produced on the bottom surface of the container as a graphene bond having the shape of the bottom surface of the container. This is a manufacturing method for manufacturing a graphene alloy. The production method for producing a graphene conjugate according to claim 6 is the same coordination consisting of inorganic ions or molecules as a plurality of types of metal compounds in which a plurality of metals are simultaneously precipitated by the thermal decomposition according to claim 6. A production method for producing a graphene conjugate according to claim 6, wherein the child uses a metal complex composed of a plurality of types of inorganic metal compounds coordinated to different metal ions, according to the production method according to claim 6. .. In the production method for producing a graphene bond according to claim 6, oxygen ions constituting a carboxyl group of a carboxylic acid are used as a plurality of types of metal compounds in which a plurality of metals are simultaneously precipitated by the thermal decomposition according to claim 6. The production method according to claim 6, wherein a plurality of types of carboxylic acid metal compounds having both the first characteristic of covalently bonding to different metal ions and the second characteristic of the carboxylic acid being the same saturated fatty acid are used. According to the production method for producing the graphene conjugate according to claim 6. The production method for producing a graphene conjugate in which the properties of an insulating metal oxide are imparted to the surface of the graphene conjugate produced by the production method according to claim 2 is
A graphene conjugate is produced on the bottom surface of the container according to the production method according to claim 2, and the container is filled with an alcohol dispersion in which a metal compound that precipitates an insulating metal oxide by thermal decomposition is dispersed in alcohol. Then, vibrations in three directions of left and right, front and back, and up and down are repeatedly applied to the container to immerse the graphene conjugate in the alcohol dispersion, and then the temperature of the container is raised to a temperature at which the metal compound is thermally decomposed. As a result, the alcohol is first vaporized, and a collection of fine crystals of the metal compound is deposited all at once on the site of the graphene conjugate in contact with the alcohol dispersion, and then the fine crystals of the metal compound are deposited. The crystals were thermally decomposed, and a collection of fine particles of the insulating metal oxide were simultaneously deposited on the site of contact with the alcohol dispersion of the graphene conjugate, and the fine particles of the metal oxide were deposited on the graphene conjugate. A graphene junction that covers the entire surface, thereby imparting the properties of the insulating metal oxide to the surface of the graphene conjugate, is formed on the bottom surface of the container in the shape of the bottom surface of the container. This is a production method for producing a graphene conjugate in which the properties of an insulating metal oxide are imparted to the surface of the graphene conjugate produced by the production method according to claim 2. The method for taking out the graphene conjugate produced by the production method according to claim 9 from the container is
According to the manufacturing method according to claim 9, a graphene joint is produced on the bottom surface of the container, the upper plane of the graphene joint is evenly compressed, and a metal formed on the surface layer of both planes of the graphene joint. The fine particles of the oxide are allowed to bite into the fine metal particles made of silver, copper, gold, or aluminum that come into contact with the fine particles of the metal oxide, and the fine particles of the metal oxide are bonded to the fine metal particles and the metal oxide is formed. A frictional heat is generated at a portion where the fine particles of the metal oxide come into contact with each other, and the fine particles of the metal oxide are joined by the frictional heat. After that, vibrations in three directions of front-back, left-right, and up-down are applied to the container. This is a method of taking out the graphene junction produced by the production method according to claim 9, wherein the graphene conjugate is taken out from the container. In the production method for producing a graphene conjugate according to claim 9, oxygen ions constituting a carboxyl group of a carboxylic acid are arranged as a metal compound that precipitates an insulating metal oxide by thermal decomposition according to claim 9. This is a production method for producing a graphene conjugate according to claim 9, according to the production method according to claim 9, using a metal carboxylate compound coordinated to a metal ion as a ligand.