JP2021118290A - Conductive electronic component using carbon material, and manufacturing method thereof - Google Patents

Abstract

To provide a structure and a manufacturing method which can be used for an electronic component by using a carbon material having low solid volume resistance and a large specific surface area and utilizing the characteristics of a carbon material as it is.SOLUTION: An electronic component that uses a carbon material containing a silicon component with a specific surface area of 300 m2/g or more (for example, mainly carbide 19 or graphene 113, 114, P) as a conductor is configured by contacting wiring configured by embedding the conductor (for example, mainly pattern wiring 603, 605), wiring that supplies power, and a terminal (for example, mainly light source+terminal 601 and light source-terminal 602) of an electronic drive unit (for example, mainly light source L (LED)) that supplies and drives electric power, and a resistance component having a resistance value required for the electronic drive unit is configured by the wiring.SELECTED DRAWING: Figure 58

Description

The present invention relates to a conductor that is a carbon material, an electronic component using the conductor, and a method for manufacturing the same.

Conventionally, a carbon material has been used as an electronic material, and recently, a conductive ink made into a paint has been used for a printed circuit board, and an invention using a conductive material such as carbon has been proposed in Patent Document 3.
For example, in Patent Document 1, the conductive film-coated heat-expandable sheet includes a heat-expanding layer that expands when heated to a predetermined temperature or higher, a base material on which the heat-expanding layer is laminated on one surface, and a heat-expanding layer side. It is provided with a conductive film that covers the surface of the material. A mirror image of the wiring pattern is printed on the back surface of such a conductive film-coated heat-expandable sheet with black ink as a photothermal conversion member, irradiated with near-infrared light, and the surface is raised on the generated photothermal conversion member to cause unevenness. When the conductive film is formed in the above direction, the conductive film breaks at a step of unevenness and is separated into a wiring and a wiring, and a wiring plate is obtained.

Japanese Unexamined Patent Publication No. 2020-4875

However, since each carbon material has its own constitutional characteristics and is not uniform, the performance such as solid volume resistance value and adsorption capacity varies depending on the manufacturing method.

The present invention has been made to solve the above problems, and is a structure in which a carbon material having a low solid volume resistance and a large specific surface area is used, and the characteristics of the carbon material are utilized as they are in an electronic component. And to provide manufacturing methods.

An electronic component that uses a carbon material containing a silicon component with a specific surface area of 300 m ^{2 / g or more as a conductor.}
Wiring constructed by embedding the conductor and
The wiring that supplies electric power and the terminal of the electronic drive unit that supplies and drives the electric power are in contact with each other, and a resistance component having a resistance value required for the electronic drive unit is configured by the wiring. It is a feature.

Due to the above features, the electronic component of the present invention can form a component that is lighter than metal without the need for soldering. Further, the electronic component does not require a resistor component because the wiring becomes a resistor, and can be formed lightweight.

It is a figure which shows the process flow which shows the manufacturing process of an embodiment. It is a schematic diagram which shows the structure of the plasma apparatus of embodiment. It is a schematic diagram which shows the structure of the plasma apparatus of another embodiment. It is a schematic diagram which shows the structure of the activation device of embodiment. It is a schematic diagram which shows the structure of the carbonization furnace apparatus of embodiment. It is a figure which shows the relationship between the temperature of a carbon source and the theoretical yield of a carbide in the manufacturing process of an embodiment. It is a block diagram which shows the structure of the high frequency induction heating apparatus of embodiment. It is a schematic diagram which shows the structure of the high frequency induction heating apparatus of embodiment. It is sectional drawing which shows a part of the high frequency induction heating apparatus of embodiment. It is a schematic diagram which shows a part of the high frequency induction heating apparatus of embodiment. It is a schematic diagram which shows a part of the high frequency induction heating apparatus of embodiment. It is a schematic diagram which shows the structure of the plasma apparatus of another embodiment. It is a schematic diagram which shows a part of the other high frequency induction heating apparatus of an embodiment. It is a schematic diagram which shows a part of the other microwave induction heating apparatus of an embodiment. It is explanatory drawing explaining the state that the carbon source was carbonized by the induction heating apparatus of embodiment. It is a conceptual diagram which shows the structure of the carbide obtained by the manufacturing apparatus of this invention. It is a conceptual diagram which shows the structure of graphene obtained by the manufacturing apparatus of this invention. It is an XPS spectrum figure by narrow spectrum measurement of carbide and graphene obtained by the manufacturing apparatus of this invention. It is an XPS spectrum figure by narrow spectrum measurement of carbide and graphene obtained by the manufacturing apparatus of this invention. It is a distribution map of the pore diameter of carbide and graphene obtained by the manufacturing apparatus of this invention. It is a Raman spectrum of graphene obtained by the manufacturing apparatus of this invention. It is a Raman spectrum of a carbide obtained by the manufacturing apparatus of this invention. It is a Raman spectrum of graphene obtained from a conventional mineral. It is an electron micrograph of graphene obtained by the manufacturing apparatus of this invention. It is an elemental distribution map of graphene shown in FIG. It is an electron micrograph of the carbide obtained by the manufacturing apparatus of this invention. FIG. 6 is an elemental distribution diagram of carbides shown in FIG. It is a photograph which imaged the carbide obtained by the manufacturing apparatus of this invention by a scanning transmission electron microscope. It is a photograph which imaged the carbide obtained by the manufacturing apparatus of this invention by a scanning transmission electron microscope. It is a photograph which the carbide shown in FIG. 29 was transmitted through a scanning transmission electron microscope. It is a photograph which imaged the carbide obtained by the manufacturing apparatus of this invention by a scanning transmission electron microscope. It is a photograph which the carbide shown in FIG. 31 was transmitted through a scanning transmission electron microscope. It is a photograph which imaged the graphene obtained by the manufacturing apparatus of this invention by a scanning transmission electron microscope. It is a photograph showing the graphene shown in FIG. 33 transmitted through a scanning transmission electron microscope. It is an electron micrograph of the carbide obtained by the manufacturing apparatus of this invention. It is an electron micrograph of graphene produced from a mineral. It is an electron micrograph of graphene produced from a mineral. It is a figure which showed the relationship between the temperature distribution for producing graphene and the degree of graphitization. It is a Raman spectrum of graphene obtained by the manufacturing apparatus of this invention. It is a Raman spectrum of graphene obtained by the manufacturing apparatus of this invention. It is a photograph which imaged the graphene obtained by the manufacturing apparatus of this invention by a scanning transmission electron microscope. It is a photograph showing the graphene shown in FIG. 41 transmitted through a scanning transmission electron microscope. It is a photograph which imaged the graphene obtained by the manufacturing apparatus of this invention by a scanning transmission electron microscope. It is a photograph showing the graphene shown in FIG. 41 transmitted through a scanning transmission electron microscope. It is an electron micrograph of graphene obtained by the manufacturing apparatus of this invention. It is an electron micrograph of graphene obtained by the manufacturing apparatus of this invention. It is an electron micrograph of graphene obtained by the manufacturing apparatus of this invention. It is an electron micrograph of graphene obtained by the manufacturing apparatus of this invention. It is a photograph which imaged the graphene obtained by the manufacturing apparatus of this invention by a scanning transmission electron microscope. It is a photograph showing the graphene shown in FIG. 49 transmitted through a scanning transmission electron microscope. It is a graph of the relationship between time and temperature at the time of forming carbide. It is a schematic diagram which shows the rotating apparatus of this invention. It is a schematic diagram which shows the internal mechanism of the rotating apparatus of this invention. It is a schematic diagram at the time of manufacturing the component part of the rotating apparatus of this invention. It is a schematic diagram which shows the component part of the rotating apparatus of this invention. It is a schematic diagram which shows the electric apparatus of this invention. It is a figure which shows the cross-sectional view of the electric apparatus of this invention. It is a schematic diagram which shows the electronic component of this invention. It is a schematic diagram which shows the cross-sectional view of the electronic component of this invention. It is a schematic diagram which shows the piezoelectric measuring instrument which built-in the electronic component of this invention. It is a schematic diagram which shows the structure of the piezoelectric measuring instrument which built-in the electronic component of this invention.

The present invention will describe in detail a rotating device using a carbon material manufactured by the following manufacturing method, its parts and its manufacturing method, and manufacturing methods and products of electronic parts, heating elements and the like with reference to drawings. The embodiments and drawings described below exemplify a part of the embodiments of the present invention, are not used for the purpose of limiting to these configurations, and do not deviate from the gist of the present invention. Can be changed as appropriate in.

(Carbon material)
First, the carbon material used in the present invention will be described below.
<Biomass material>
The vegetable raw materials for producing graphene will be described with reference to Examples 1 to 6. The present invention uses food residues and discarded vegetable ingredients to produce the final product, graphene. As the vegetable raw material, plants, wood, etc. are used, but if the discarded plant raw material such as the residue when the plant is harvested is used as the raw material for producing graphene, the raw material can be obtained at low cost. It is possible.

Table 1 is a composition table of vegetable raw materials. In Table 1, the ratios of the components constituting the raw materials shown on the far left are shown as percentages on the right below. For example, rice straw has 37.4% carbon (C), 0.53% nitrogen (N), 0.06% phosphorus (P), 0.14% phosphoric acid (P2O5), and potassium (K). ) Is 1.75%, potassium (K2O) is 2.11%, calcium (Ca) is 0.05%, magnesium (Mg) is 0.19%, and sodium (Na) is 0.11%. ..

Here, the plant-derived silicon-containing porous vegetable raw material does not substantially change even when carbonized at a low temperature (300 ° C. or higher and 1000 ° C. or lower), and the pores are arranged by removing silicon. Can be maintained. Many plant-derived materials have a structure in which cells are regularly arranged along the axis and silicic acid is deposited on the cell wall to thicken the cells. Then, there is a compressed narrow cell row between the silicified cell rows, and it is possible to obtain a carbon material having a high specific surface area by removing silicon and the like after carbonization. As described above, those containing as much silicic acid as 13% or more and 35% or less are suitable. Even if the amount of silicic acid is too large, the amount of graphene obtained will be small, so a vegetable raw material in the range of about 20% is preferable.

Table 1 shows examples of vegetable raw materials that contain a large amount of carbon. In addition to rice straw, wheat straw, barley straw, rice bran, rice husks, buckwheat straw, soybean straw, sugar cane vines, corn leaves, etc. There are carrot leaves, corn culms, sugar cane heads, coconut meal, peanut shells, rice husks, red cedar shavings, pine bark and ginkgo fallen leaves. In addition, the plant itself may be used instead of the residue.

For example, bamboo has fibers composed of cellulose, hemicellulose, and lignin, and minerals composed of iron, magnesium, calcium, manganese, copper, nickel, and the like. Further, when the bamboo leaves are fired, silanol groups (Si—OH) are extracted, and in the process of firing, they are extracted as SiO4.

Tables 2 and 3 are component composition tables of the vegetable raw materials most suitable for the method for producing the carbon material among the carbon sources 9 which are the plant raw materials in Table 1 described above in the present invention. Table 2 shows the ratio of the components constituting the raw material as a percentage. For example, water content is 8% to 10%, ash content is 10% to 18%, lipid content is 0.1% to 0.5%, lignin is 18% to 25%, hemicellulose is 16% to 20%, and cellulose is 30%. ~ 35% and others are 5% -10%. As described above, the main components of silica ash 19 are lignin, hemicellulose, and cellulose.

Table 3 shows the inorganic chemical components of the carbon source 9 which is the vegetable raw material shown in Table 2. The carbon source 9, which is a vegetable raw material shown in Table 2, contains 80 wt% of organic matter such as cellulose and 20 wt% of inorganic matter. The inorganic chemical components in Table 3 are 92.14 wt% for SiO2, 0.04 wt% for Al2O3, 0.48 wt% for CaO, 0.03 wt% for Fe2O3, 3.2 wt% for K2O, and 0.16 wt% for MgO. , MnO is 0.18 wt% and Na2O is 0.09 wt%. The carbon source 9, which is a vegetable raw material shown in Table 2, contains a large amount of silicon oxide (SiO2) as an inorganic substance.

(Graphene and carbides)
The carbide 19 obtained in the carbonization step S2 produced in Examples 1 to 10 and the graphene 113 obtained in the activation step S3, which is a carbon material, are shown in FIGS. 16 to 34. FIG. 24 is an electron micrograph of graphene 113, which is a carbon material obtained in the activation step S3, at a magnification of 50,000. FIG. 26 is an electron micrograph of 100,000 times as much as the carbide 19 containing 24 wt% of silicon (Si) obtained in the carbonization step S2.

FIG. 28 is an electron micrograph of a carbon material containing 24 wt% of silicon (Si) obtained in the carbonization step S2 at a magnification of 30,000. FIG. 29 is an electron micrograph of 100,000 times as much as the carbide 19 obtained in the carbonization step S2. FIG. 35 is an electron micrograph of 2,200 times the carbide 19 obtained in the carbonization step S2.

FIG. 30 is a 100,000-fold image of the carbide 19 obtained by the manufacturing apparatus of the present invention, taken with a scanning transmission electron microscope shown in FIG. 29 and transmitted. FIG. 31 is an 80,000-fold image of the carbide 19 obtained by the manufacturing apparatus of the present invention taken with a scanning transmission electron microscope. FIG. 32 is an image of the carbide 19 obtained by the manufacturing apparatus of the present invention taken with a scanning transmission electron microscope shown in FIG. 31 and transmitted at a magnification of 80,000.

FIG. 33 is a 100,000 times image taken with a scanning transmission electron microscope of graphene 113 obtained by the manufacturing apparatus of the present invention. FIG. 34 is an image of graphene 113 obtained by the manufacturing apparatus of the present invention taken with a scanning transmission electron microscope shown in FIG. 33 and transmitted at a magnification of 100,000.

FIG. 36 is an electron micrograph of graphene C produced from minerals by a conventional method at a magnification of 10,000 times. FIG. 37 is an electron micrograph of graphene C produced from minerals by a conventional method at a magnification of 100,000.

In the carbide 19 obtained in the carbonization step S2 described later, the ash content excluding carbon is as large as 37.1 wt% according to thermogravimetric analysis, and silicon (Si) is 24 wt% of the total carbide 19 in the ash content. It is 30 wt% from. In addition, K is 0.51 wt% to 7 wt%, Al is 0.1 wt% to 1.6 wt%, Ca is 0.17 wt% to 0.5 wt%, Fe is 0.4 wt%, and Cr, Ni, Mn, Mg, P, S and Na are 0.1 wt% or less.

The carbide 19 obtained in the carbonization step S2 without performing the activation step S3, which is a so-called activation treatment, contains a large amount of silicon, and when carbonized in an inert gas, it is not strongly reduced and becomes SiO2-x. It is considered that it binds to an aromatic -OH group or the like in the form of -O-Si-O-R to form a lignin polysaccharide complex, which tends to form a C / SiOx.

Further, the graphene 113 obtained in the activation step S3, which will be described later, has a large ash content excluding carbon of 26.7 wt% according to thermogravimetric analysis, of which silicon (Si) is 14 wt to 19 wt of the entire graphene 113. It is%. In addition, K is 4.3 wt%, Al is 1.5 wt%, Ca is 1.3 wt%, Fe is 0.4 wt%, and P, Mn, Cl, S, Mg is 0.1 wt% or less. It has become.

As described above, the amount of silicon in graphene 113 and carbide 19 is as large as 14 wt% to 30 wt%.
Therefore, the carbide 19 obtained in the carbonization step S2 has an effect of improving the cycle capacity when used as the negative electrode material of the battery material.

表４及び図２０に示すようにＣＯ２吸脱着測定の結果においてグラフェン１１３及び炭化物１９は、細孔径が主に０．８ｎｍから２ｎｍの微細な細孔が形成されていることが確認できた。

As shown in Table 4 and FIG. 20, as a result of CO2 adsorption / desorption measurement, it was confirmed that the graphene 113 and the carbide 19 had fine pores having a pore diameter of mainly 0.8 nm to 2 nm.

Therefore, it is considered that metal ions and the like are easily adsorbed. Further, as shown in Table 4, the volume of the mesopores measured by the gas adsorption measurement and the water vapor adsorption measurement was 0.487 ml / g for graphene 113 and 0.259 ml / g for carbide 19. The micropore volume was 0.46 ml / g for graphene 113 and 0.27 ml / g for carbide 19.

Further, as shown in Table 4, the particles of graphene 113 or carbide 19 have a distribution diameter of 15 μm to 229 μm, and the median diameter indicated by the median of the integrated values of the distribution is about 110 μm.

In this way, a mesopore volume of 0.2 ml / g to 0.6 ml / g is formed. In particular, graphene 113 after the activation treatment for removing impurities described later shows a higher value, and it is considered that mesopores and micropores are grown by removing silicon.

Moreover, as measured by water vapor adsorption measurement method, as shown in Table 4, the specific surface area by BET equation, graphene 113 showed 1792m ² / g, the width is the width of 890m ² / g~2000m ² / g .. Carbides 19 shows a 726.4m ² / g, the width is the width of 890m ² / g~1500m ² / g. In each case, the specific surface area of graphene 113 after removing the silicon component (Si) is larger than that of graphene 113. Therefore, graphene 113 has a high adsorption effect. In addition, it is possible to store a large amount of electric charge in the battery material.

Further, as shown in FIG. 35, the carbide 19 is also provided with a hole 96 having a diameter of 2 μm to 10 μm, which is 1000 to 10000 times larger than the pore 97. As described above, not only the large pores but also the pores 97 having a pore diameter of 0.8 to 2 nm are provided and have a porous property. Further, as shown in FIGS. 28 to 32, not only the pores 97 but also irregularities of about 50 nm to 100 nm are formed on the surface. As shown in FIGS. 28 to 32, the carbide 19 is formed of a spherically aggregated agglomerate 98 composed of silicon dioxide (SiO2), potassium peroxide (K2O2), potassium (K) and the like.

FIG. 27 shows the element distribution of the carbide 19 imaged in FIG. 26, and the elements of C, O, Al, Si, and K can be confirmed. As shown in FIGS. 26 and 27, the carbide 19 contains carbon and has irregularities formed on the surface by agglomerates 98 having a size of 500 nm to 1 μm and having a quadrangular or substantially spherical silicon dioxide (SiO2), potassium oxide (K2O) or the like. Is provided. As shown in FIG. 27, fine silicon dioxide and potassium oxide are formed in the carbide 19 as a whole. Since potassium oxide (K2O) contained in the carbon source 9 is decomposed into potassium peroxide and silicon at 390 ° C., the carbide 19 is a spherically aggregated aggregate composed of potassium peroxide (K2O2) and potassium (K). 98 is formed. also,

FIG. 25 shows the element distribution of the carbide 19 imaged in FIG. 24, and the elements of C, O, Al, Si, and K can be confirmed. As shown in FIGS. 25, 27, 33, and 34, the porosity of graphene 113 and carbide 19 extending in the vertical and horizontal directions, which are large and small, is the porosity and unevenness formed during the growth process of the vegetable raw material. As shown in FIGS. 24, 33 and 34, it is formed at the time of removal of impurities other than carbon including silicon (or silicon dioxide) and carbonization of organic substances by the activation step S3 for removing impurities. There is also porosity.

As shown in FIGS. 25 and 27, in the carbide 19 and the graphene 113, silicon dioxide (SiO2), potassium oxide (K2O) and the like are adhered to the carbide in a minute state. Therefore, the specific surface area is increased by removing these impurities.

Further, irregularities and pores 97 are formed on the surface of graphene 113. In particular, the charcoal 19 contains a state in which the elemental component K (potassium) is contained in the surface or inside of the charcoal 19 in the state of K (potassium) or potassium oxide (K2O) in a minute amount, and K (potassium). Alternatively, there is a state in which potassium oxide (K2O) is aggregated and formed on the surface or inside of the carbide 19.

Similarly, the carbide 19 contains Si (silicon), which is an element component, in the state of Si (silicon) or silicon dioxide (SiO2) in a minute amount on the surface or inside of the carbide 19 and Si ( In the state of silicon) or silicon dioxide (SiO2), there is a state in which the carbide 19 is aggregated and formed on the surface or inside. Then, by subjecting the carbide 19 to the activation treatment, the purity of carbon is increased and at the same time, the specific surface area is improved.

As shown in Table 4, the true density measured by gas replacement density measuring device, graphene 113 2.56 g / cm ³ and carbide 19 was 2.27 g / cm ^3. The bulk density of graphene 113 was 0.21 to 0.29 g / cm ³ .
The powder resistance values measured by the double ring method and the four-terminal method were 1.27 × 10 ^{3 to 5 Ω · cm for carbide 19, and 3.8 × 10 − for} graphene 113 by removing silicon. ^It becomes 2 Ω · cm and the conductivity is improved. Further, the carbide 19 is easily dissolved in a substance that is easily adsorbed on silicon by leaving a large amount of silicon, and at the same time, the insulating performance is improved.
The water content of graphene 113 measured by the coulometric titration method was 0.565%.

FIG. 21 is a Raman spectrum of graphene 113 obtained by the manufacturing apparatus of the present invention. FIG. 22 is a Raman spectrum of carbide 19 obtained by the production apparatus of the present invention. FIG. 23 is a Raman spectrum of graphene obtained from conventional minerals. These figures are analyzed by a Raman spectroscope, and the obtained data are ^{Raman spectra having a wavelength (wave number (Raman shift (cm -1} ))) on the horizontal axis and an intensity on the vertical axis.

Further, as shown in Table 4, the peak value ID of the peak value IG and D bands G band of the peak wavelength due to Raman spectroscopy ^{(1590cm -1) (1350cm -1)} .
Graphene C is a sheet-like monatomic film in which carbon atoms are π-bonded by sp2 hybrid orbitals and arranged in a hexagonal shape on one plane. In FIGS. 23, 36 and 37, graphene C produced from minerals is a multi-layered and highly crystalline graphene. On the other hand, it can be confirmed that the carbides 19 and graphene 113 produced in the present invention shown in FIGS. 21 to 35 are amorphous.

Then, as shown in Table 4, the value obtained by dividing the IG by ID is 1.68 for graphene 113 and 1.37 for carbide 19, indicating that the crystallinity is high among the vegetable raw materials. In particular, the carbide 19 contains a large amount of silicon and has higher crystallinity than graphene 113, and even if this silicon is removed, graphene 113 remains highly crystalline. As described above, since the carbide 19 before removing silicon has high crystallinity, graphene 113 remains high even after removing silicon.

The value obtained by dividing the IG of the carbide 19 or graphene 113 by ID is preferably 0.9 or more, and shows a value of about 0.9 to 2.0.
Graphene 113 can also leave an amount of silicon component of 10 wt% to 30 wt% by adjusting the activation step (S3) described later.

As shown in FIG. 18, the results of wide-spectrum measurement of the types and peak intensities of the elements contained in carbide 19 and graphene 113 using MgKa rays as an X-ray source by X-ray electron spectroscopy (XPS) are shown. ing. There is a Ca, P or S peak near 750 eV, an O peak near 530 eV, a C peak near 280 eV, and a Si peak near 160 eV.

Further, FIG. 19 is a diagram of an XPS spectrum showing the peak of C. It has been confirmed that the peak of graphene 113 tends to be broad as a whole, and the structure is disturbed by the activation step S3 described later, and oxygen-containing functional groups such as -OH, -CHO, and -COOH are generated. Was confirmed. In electric double layer capacitors and the like, the capacitance tends to increase with respect to the amount of functional groups applied. Therefore, graphene 113 has an increased oxygen-containing functional group in the activation step S3, so that the capacitance is also a carbide. It tends to increase compared to 19.

In particular, as a result of Fourier transform infrared spectroscopic analysis by the transmission method, it has been confirmed that ^{carbide 19 and graphene 113 have a peak near 3402 to 3424 cm -1} and a peak near 1018 to 1094 cm ^-1. ..

(Example 1)
The plasma apparatus 10 of this embodiment will be described with reference to FIG. FIG. 2 is a schematic view showing the configuration of the plasma device 10 of this embodiment. The plasma device 10 is mainly composed of an inert gas 6, a control device 20, a chamber 1, and a vacuum pump 30.

The inert gas 6 contained in the gas cylinder mainly uses argon, but other examples include helium, neon, and nitrogen. The inert gas 6 can be filled into the chamber 1 from the introduction pipe 7 via the gas amount control device 21. The gas amount control device 21 can adjust the flow rate of the inert gas 6.

The chamber 1 is connected to the control valve 22, and the inside of the chamber 1 can be depressurized to a vacuum state by the vacuum pump 30. It is connected to the chamber 1 and the inert gas 6 is introduced into the chamber 1. A leak valve 23 that opens the vacuum state in the chamber 1 to atmospheric pressure is provided between the control valve 22 and the chamber 1. Further, a control valve 14 and a leak valve 15 for opening the vacuum state in the chamber 1 to atmospheric pressure are also provided between the outlet pipe 8 for introducing the air in the chamber 1 and the vacuum pump 30.

Further, the temperature control device 24 controls the high frequency power supply 4, and manages the temperature holding, the holding time, and the like in the chamber 1. In the plasma device 10 of this embodiment, an argon gas, which is an inert gas 6, is passed as a working gas under a low pressure close to a vacuum state, a high current is passed between the cathode 2 and the anode 3 between the electrodes, and an arc discharge is performed. It is a method of obtaining thermal plasma by means of.

A carbon crucible 5 is installed between the cathode 2 and the anode 3, and the crucible 5 contains a carbon source 9 described later. The carbon source 9 is carbonized in about 10 to 30 minutes by heating in a temperature range of 300 ° C. to 1000 ° C. by thermal plasma generated by an arc discharge. In addition to the above-mentioned plasma device, there is a method of obtaining thermal plasma by a barrier discharge, a corona discharge, a pulse discharge, or a DC discharge type.

(Example 2)
The plasma apparatus 100 of the second embodiment will be described with reference to FIG. In FIG. 3, the parts showing the same configuration as the plasma device 10 are designated by the same reference numerals, and the parts having the same configuration will not be described. The plasma device 100 mainly includes an inert gas 6, a control device 20, a chamber 1, and a vacuum pump 30. Mainly different from the plasma device 100, as a method of obtaining a carbon material by high frequency induction heating, an inert gas 6 is passed so as not to oxidize, and a high frequency magnetic field of 3 to 4 MHz is applied from the high frequency power supply 32 to the high frequency coil 31. As a result, carbonization is performed by induction heating of high-frequency alternating current. The carbon source 9 is carbonized in about 10 to 30 minutes by heating in the temperature range of 300 ° C. to 1000 ° C. by induction heating.

(Example 3)
The plasma apparatus 100A of the third embodiment will be described with reference to FIG. In FIG. 12, the parts showing the same configuration as the plasma device 10 and the plasma device 100 are designated by the same reference numerals, and the parts having the same configuration will not be described.

The plasma device 100A is a thermal plasma using an inductively coupled plasma torch similar to that of the second embodiment. As a method of obtaining a carbon material by high-frequency induction heating, the plasma device 100A flows an inert gas 6 so as not to oxidize it, and applies a high-frequency magnetic field of 3 MHz from the high-frequency power source 32 to the high-frequency coil 31 to generate high-frequency alternating current. The point is that carbonization is performed by induction heating. The carbon source 9 is carbonized in about 10 to 30 minutes by heating in the temperature range of 500 ° C. to 800 ° C. by induction heating.

The moving rod 125 can move up and down. As shown in FIG. 12, the inert gas 6 in which argon gas and hydrogen gas are mixed or the inert gas 6 using nitrogen gas is heated to about 10,000 ° C. by induced heating and is several tens of m / s or less. The gas is ejected from the outlet pipe 8 by injecting at a flow velocity. Further, in addition to the outlet pipe 8, a quenching gas for quenching may be ejected from the vicinity of the outlet pipe 8 and then led out from the outlet pipe 8.

Further, since the internal temperature of the plasma device 100A is high, a water-cooled double tube 121 is adopted as the water-cooling device. The plasma device 100A supplies cold non-conductor water from the water supply pipe 123a, collects the high-temperature non-conductor water by the drain pipe 123b, and suppresses the internal temperature rise.

The method of obtaining the carbon material mainly by the plasma device 100 and the high frequency induction heating is the same, but the difference is that the ascending rod 125 is provided. As shown in FIG. 12, the torch shows a flame-type temperature distribution (Ta, Tb, Tc). For example, the region required for the carbonization step S2 described later from 500 ° C. to 800 ° C. indicates Tc, and when the moving rod 125 reaches the position of Pc, the carbonization step S2 can be performed at a temperature of 500 ° C. to 800 ° C.

Further, the region required from 800 ° C. to 1000 ° C. in the activation step S3, which will be described later, indicates Tb, and when the moving rod 125 reaches the position of Pb, the carbonization step S2 can be performed at a temperature of 800 ° C. to 1000 ° C. Further, the region requiring the carbonization step S2 or the activation step S3, such as when improving the graphitization degree of 1000 ° C. or higher or when decomposition of silicon dioxide is required, shows Tc, and the moving rod 125 reaches the position of Pc. Then, the carbonization step S2 or the activation step S3 can be performed at a temperature of 1000 ° C. or higher. As described above, since the temperature of the plasma device 100A can be adjusted by the position where the moving rod 125 is installed, one device can be used for various manufacturing processes.

Further, the inert gases 6 and 217 heated by the thermal plasma in the plasma devices 10, 100 and 100A are flowing, and the plant raw material and the object to be carbonized are instantly evaporated and gasified. Nucleation and condensation of carbonized objects such as carbon source 9 and carbide 19 are carried out, and a chemical reaction in nanoparticles is carried out by a rapid quenching step. Therefore, it is excellent in mass production because it can be made into nanoparticles and a chemical reaction can be carried out in a short time.
By using the plasma devices 10, 100, and 100A as described above, even lignin or other impurities that are difficult to be thermally decomposed can be decomposed.

The above-mentioned plasma devices 10, 100, and 100A are high-frequency inductively coupled plasma torch, and the oxidizing atmosphere and the reducing atmosphere can be freely selected.
In the plasma devices 10, 100, and 100A described above, when an AC high-frequency high voltage is applied, filamentous plasma is randomly generated between the electrodes in time and space by passing through an insulator such as silicon. In addition, the electrons emitted from the electrodes by the corona discharge collide with the electrons and molecules in the chamber 1 and the vegetable raw material, so that excitation, dissociation, and ionization occur.

In such a high-energy space, a vapor phase reaction occurs, and in particular, by mixing a small amount of reactive gas with the inert gas 6,217, -OH (hydroxyl group), -CHO, -C = O Functional groups such as (carbonyl group) and -COOH (carboxyl group) are generated to impart hydrophilicity.

(Example 4)
In this embodiment, the high frequency induction heating device 200 for producing the above-mentioned carbide 19 and the like will be described with reference to FIGS. 7 to 11. The high-frequency induction heating device 200 is a device that generates a magnetic field and heats an object to be heated, which is a conductor, by induction heating of an alternating high frequency. The object to be heated is a storage box 205 made of carbon, which will be described later.

The high-frequency induction heating device 200 is a plurality of storage boxes 205 formed of carbon or a carbon composite material containing a carbon source 9 which is a vegetable raw material inside a transparent quartz tube 203 so that mass production is possible. Is provided. In this high-frequency induction heating device 200, when an alternating high-frequency current is passed through the coil 243, an alternating magnetic field penetrates the conductor, a high-density eddy current flows, and the Joule heat rapidly heats the conductor.

Therefore, even if there is an insulator such as silicon dioxide (SiO ² ) in the carbon source 9, the magnetic flux is transmitted and the carbon source 9 is conducted, the carbon source 9 itself is heated, and the heating is accelerated and carbonized in a short time. can do. Further, since the insulator itself such as silicon dioxide (SiO ² ) penetrates the alternating magnetic flux, the silicon dioxide (SiO ² ) itself remains as it is because it is only heated from the storage box 205 and is not at the melting temperature. , Silicon dioxide (SiO ² ) and many other insulators remain.

First, the high frequency induction heating device 200 will be described with reference to FIGS. 7 and 8. A transparent cylindrical quartz tube 203 is provided between the left flange 231 and the right flange 232. The left and right flanges 231 and 232 can be sealed and opened so that the inside of the quartz tube 203 can be kept in a vacuum state or a low pressure state.

Further, the quartz tube 203 is removable from one of the left and right flanges 231 and 232 that is open. The left and right flanges 231 and 232 have a water-cooled cooling function.
The quartz tube 203 may be attached / detached and fixed so as to be sandwiched from both sides of the left and right flanges 231 and 232.

As shown in FIG. 8, the right flange 232 is connected to a pipe connected to a control valve 224 that controls the flow rate of the inert gas 217 and the combustion gas 218, and the inert gas 217 or the combustion gas 218 is connected to the quartz pipe 203. It is possible to fill the inside of. Further, the right flange 232 is connected to the low vacuum pressure gauge 219, and the left flange 231 is connected to the pressure control valve 222 and the control valve 224 via the filter 221.

Further, the control valve 224 can switch the inert gas 217 or the combustion gas 218 according to the temperature condition and the combustion time according to the process and flow into the quartz tube 203.
The control device 210 controls the pressure inside the quartz tube 203 by a dry pump 223 connected to the pressure control valve 222 and the control valve 224.

As shown in FIGS. 8 to 10, the high-frequency induction heating device 200 can create various temperatures through the quartz tube 203, and from the carbon source 9 which is a vegetable raw material, silica containing not only carbon but also silicon can be used. It is equipped with a high frequency coil 240 and an electric furnace 250 so that it can be used in the extraction and the activation process described above.

The high-frequency coil 240 is formed so as to surround the quartz tube 203, and a coil support 242 on which the coil 243 is supported is fixed to the drive device 1 (214). The drive device 1 (214) moves along the rail 236 in the X and −X directions. A motor is used in the drive device 1 (214). In addition, instead of the motor, a linear drive or the like may be used.

The high-frequency coil 240 is different in that it can move in the X and −X directions, and once installed, it is possible to sequentially carbonize a plurality of storage boxes 205 accommodating the carbon source 9, so that many at once. It is possible to carbonize the carbon source 9 of. Mainly, in the manufacturing process, it can be utilized in the carbonization process of S2 in FIG. 1, which will be described later.
Further, the high frequency coil 240 is provided with a shielding plate 241 in the vicinity of the coil 243 in order to reduce the influence of electromagnetic waves emitted from the coil 243.

The high frequency induction heating device 200 is 300 ° C. or higher and 1000 ° C. or lower by high frequency induction heating as shown in FIG. 6 by flowing an inert gas 217 and applying a high frequency magnetic field of 20 KHz from the high frequency power supply 212 to the high frequency coil 240. A relatively large yield was obtained. The inert gas 217 has a role of flowing the inert gas 217 so that the gas generated from the direct material during carbonization does not stay in the quartz tube 203, and a role of collecting the generated gas and a role of preventing oxidation. is doing.

The high-frequency induction heating device 200 as described above generates heat when lignin, which is difficult to thermally decompose by using the high-frequency coil 240 and the inert gas 217, is imparted with conductivity during carbonization. Therefore, it can be disassembled quickly. Further, unlike the combustion of gas or the like, the high-frequency induction heating device 200 is easy to control the temperature, does not generate toxic substances or the like, and is rapidly heated (from a heating rate of 10 ° C./min). It can be adjusted up to about 100 ° C./min), and it can be uniformly carbonized by raising the temperature in a short time, so it is ideal for mass production in a short time.

The high-frequency power supply 212 is provided with a coil 243 and a water-cooled cooling device 213 for cooling the power supply. Further, a filter 221 made of non-woven fabric, cotton, paper or the like is provided so that the tar component or the like generated at the time of combustion in the quartz tube 203 does not affect the dry pump 223.

Further, in the temperature control device 211 shown in FIG. 7, a thermocouple 235 is provided close to each storage box 205 as shown in FIG. Therefore, the control device 210 can be carbonized at a desired temperature based on the information obtained from these temperature control devices 211. In particular, temperature control is important because the yield varies depending on the temperature. The high-frequency induction heating device 200 can not only extract carbide 19 but also silica containing silicon and the like from a vegetable raw material by controlling the temperature.

The electric furnace 250 is formed so as to surround the quartz tube 203, and is fixed to the drive device 2 (216). The drive device 2 (216) moves along the rail 236 in the X and −X directions. A motor is used in the drive device 2 (216). In addition, instead of the motor, a linear drive or the like may be used.

The temperature of the electric furnace 250 can be raised to nearly 1000 ° C. by the heat from a heating element provided, such as using Joule heat, and the inside of the quartz tube 203 is cleaned while supplying combustion gas 218. Is possible. Further, the electric furnace 250 can be burned when activating the carbide 19.
Further, the combustion gas 218 is used for supporting combustion, and the combustion gas 218 may be oxygen or the like. It is mainly used in the step of activation step S3 shown in FIG. 22, and is used when burning at around 1000 ° C.

The electric furnace 250 may be a low-frequency induction furnace using an electromagnetic induction current, a high-frequency induction furnace using an eddy current, an arc furnace using a solitary high heat, or the like. Further, the electric furnace 250 can supply oxygen, which is a combustion gas 218, and remove it as CO2 by burning it, and remove and clean the carbides attached to the originally transparent quartz tube 203. By doing so, it is possible to remove the carbonized combustion debris attached to the inner surface of the quartz tube 203 by the high-frequency coil 240 and make it easier for the magnetic field to pass through.

Next, the quartz tube 203 and the storage box 205 will be described with reference to FIGS. 9 to 11. As shown in FIGS. 10 and 11, the storage box 205 is formed of a carbon material in a box shape having an open upper end so as to store the carbon source 9 and the carbide 19. In particular, the high-frequency induction heating device 200 is provided with a plurality of storage boxes 205 so that a larger amount can be carbonized than the above-mentioned plasma devices 10 and 100.

Further, as shown in FIGS. 11B and 11C, the storage box 205 is provided with the same carbon lid 255 as the housing 257. The lid 255 is for preventing scattering of the carbon source 9 due to bumping due to gas or steam generated from the organic matter of the carbon source 9 at the time of carbonization. The lid 255 is provided with degassing holes 256 at four corners in order to allow gas, water vapor, and the like to escape.

The storage box 205 may be further provided with a stainless steel net 258 below the lid 255. The net 258 may be provided so as to cover the periphery of the carbon source 9, or may be provided so as to cover only above the carbon source 9. The net 258 also has the effect of suppressing scattering, allowing gas to pass through, and facilitating heat transfer due to induction heating from above.

As shown in FIG. 11A, when a plurality of storage boxes 205 are provided in the vicinity and heated in order from the direction in which the inert gas 217 flows, the heated inert gas 217 is stored in the adjacent storage box 205. The carbon source 9 is warmed, and the carbon source 9 is pre-dried. Therefore, the carbonization time of the second and subsequent storage boxes 205 can be shorter than that of the first storage box 205. Further, the gas generated from the carbon source 9 does not cause bumping.

The storage box 205 is fixed to a mounting table 206 provided with an upper end piece 208 having rod-shaped pieces protruding from four corners on the front surface and a plurality of piece-shaped lower end pieces 207 protruding upward from both ends on the back surface. The storage box 205 is provided with a hole into which a piece of the upper end piece 208 can be inserted at the same position as the lower upper end piece 208, and the upper end piece 208 is fitted into the hole. It is fixed to the mounting table 206.

The mounting base 206 to which the storage box 205 is fixed is mounted on the base 202 by fitting the lower end piece 207 along the base groove 204 which is a groove provided in the base 202. A plurality of base grooves 204 are provided so as to be displaced by Y1 in the width direction so that the storage boxes 205 can be installed in a staggered manner. Further, the storage boxes 205 are provided not only in the width direction but also in the X direction with a predetermined interval X1 as shown in FIG.

By separating the storage boxes 205 in the Y1 direction or the X direction as shown in FIGS. 9 and 10, the storage boxes 205 other than the target to be carbonized are prevented from being affected as much as possible during carbonization by heating. There is. Further, in order to enable temperature control, the base 202 secures a thermocouple storage space 209 which is a space in which the thermocouple can be fixed in the vicinity of the base groove 204.

As shown in FIG. 10, the quartz tube 203 is provided in a circular tubular shape having an outer diameter of about 125 mm, which is made of transparent quartz. Further, the mounting table 206 is formed to have a width in which the storage box 205 can be installed below the center of the inside of the quartz tube 203.

Although the high-frequency induction heating device 200 is configured to obtain carbon, it is also possible to extract silica containing silicon from a biomass material depending on temperature conditions, and in particular, it is also possible to produce amorphous silica. .. Further, not only the carbonization step S2 described above but also the activation step S3 can be performed by the electric furnace 250. Therefore, it is possible to perform various processes while controlling the temperature with the same device. Since the high frequency induction heating device 200 can freely change the temperature velocity gradient and the temperature by changing the output of the high frequency, it can correspond to various raw materials.

In the above-mentioned high-frequency induction heating device 200, the high-frequency coil 240 or the electric furnace 250, which is a part for applying heat, moves to give heat to the carbon source 9 housed in the storage box 205. , It is possible to easily create a space where pressure control is possible. Further, in the conveyor type, there is a concern about a chemical reaction with the oil required for the conveyor or the like, which may cause impurities to be mixed. Further, as compared with the conveyor type, the high frequency induction heating device 200 does not have to be costly because the device such as the mixing of the inert gas becomes complicated. Since the high-frequency induction heating device 200 is provided outside the quartz tube 203, inspection and maintenance work from the outside is easy.

It is also possible to use one device for the carbonization step S2 or the activation step S3, which will be described later. Further, the high frequency induction heating device 200 can also produce other substances by changing the temperature conditions. As described above, since the high frequency induction heating device 200 is a multifunctional device, it can be applied not only to production efficiency but also to various purposes.

The high-frequency induction heating device 200 may be a compact high-frequency induction heating device 200 in which the mounting table 206 is one and the length of the quartz tube 203 is also one. As a result, the carbonization step S2 is completed in 10 minutes per unit, so mass production is possible by increasing the number of units.

(Example 5)
The high frequency induction heating device 200A of Example 5 will be described with reference to FIG. In FIG. 13, the parts showing the same configuration as the high-frequency induction heating device 200 of the fourth embodiment are designated by the same reference numerals, and the parts having the same configuration will not be described.

The high-frequency induction heating device 200A employs a water-cooled double pipe 263 as a water-cooling device so that it can heat at 3000 ° C. or higher. The high-frequency induction heating device 200A supplies cold non-conductive water from the water supply pipe 262a, collects the high-temperature non-conductive water by the drain pipe 262b, and suppresses the internal temperature rise. Further, the inert gas 17a is an exhaust gas 217b or the like containing a gas generated during carbonization of an organic substance discharged from a lid 267 having a hole above the carbon source 9 placed in a carbon storage pot 265. An exhaust pipe is provided to collect the gas.

(Example 6)
The microwave induction heating device 200B of Example 6 will be described with reference to FIG. The microwave induction heating device 200B is provided with a microwave generator 272 that irradiates an electromagnetic wave 273 having a frequency of 300 MHz to 300 GHz, and stores the carbon source 9 in a ceramic storage box 274 in a housing that shields microwaves. The microwave induction heating device 200B heats the water and the derivative contained in the carbon source 9 by induction heating in which the water and the derivative are vibrated by the microwave.

In particular, as shown in FIGS. 15A to 15D, the microwave induction heating device 200B generates heat when the carbon source 9 containing water 26 such as H2O becomes carbonized matter 19. It has good thermal efficiency, and organic substances containing water gradually become smaller and carbonize. Further, since the raw material having physical characteristics is a backbone that carries air holes and moisture, the carbon source 9 containing a large amount of water is particularly suitable for heating / decomposition by the microwave induction heating device 200B.

The effect of the high-frequency induction heating devices 200, 200A, and 200B is that the heat efficiency is good and the heating rate is high because the self or the derivative or the conductor generates heat. Further, the temperature control of the high frequency induction heating device 200 and 200A200B is easy. Further, by removing impurities such as silicon or silicon dioxide of the insulator, it is possible to form irregularities on the surface of the carbide 19 and graphene 113, and to form pores 97 as shown in FIG. 15 (D). Is.

(Example 7)
<Activator>
FIG. 4 is an example of an activator 40 that removes impurities such as silicon oxide from the carbide 19 in which the carbon source 9 is carbonized by the above-mentioned plasma devices 10 and 100.
The heating furnace 41 can heat the furnace 42 to nearly 2000 ° C. The large crucible 50 has a lid 51, and a small crucible 60 and activated carbon 53 are contained inside the jar 52. The small crucible 60 is provided with a lid 61 in which potassium hydroxide (KOH) 18 is mixed above the carbide 19 in the jar 62. For the small crucible 60 and the large crucible 50, a stable fine ceramic material or the like can be considered, and aluminum oxide Al2O3 or the like is used.

(Example 8)
The same configuration and the same configuration as in the first embodiment are designated by the same reference numerals and the description thereof will be omitted. As described in Example 1 in FIG. 5, the carbon source 9 and the oxidation inhibitor 70 produced from the vegetable raw material in the pretreatment step S1 are placed in the kettle 83. Here, it is preferable that the carbon source 9 has a capacity of about 1/10 to 2/3 of the capacity of the kettle 83. In the pretreatment step S1, the granulator may not be used and only pulverization may be performed with a mill or the like.

Here, the oxidation inhibitor 70 may be a substance that is burned while suppressing the oxygen concentration in order to prevent oxidation during combustion, and may be a gas of a halide (carbon dioxide, nitrogen, halon 2402, halon 1121, halon 1301) or the like. A liquid may be mixed and burned.
After that, the atmosphere in the furnace 81 of the combustion furnace 80 is set to 800 ° C. or higher, and the carbon source 9 is burned at 20 atm, 400 ° C. or higher, and 900 ° C. or lower for 3 hours.

(Example 9)
<Process flow 1>
With reference to FIG. 1, a manufacturing process will be described for a method of manufacturing graphene, focusing on the above-mentioned Example 2. FIG. 1 is a diagram showing a process flow showing a manufacturing process of the embodiment.
First, in the pretreatment step S1, after drying the vegetable raw material as described above, the vegetable raw material is crushed, and the crushed vegetable raw material and a granulating agent such as PVA are mixed with water at a ratio of 10: 1. The vegetable raw materials are mixed and kneaded to an appropriate size, and heated to about 100 ° C. on a drying device such as a hot plate to evaporate the water content to generate a carbon source 9. Here, examples of the crushing method include a mill, a mixer, and a grinder. In particular, the granulating agent can prevent bumping due to the steam of the carbon source 9 during induction heating.

Next, the carbonization step S2 will be described. In the pretreatment step S1, about 0.8 g of the carbon source 9 is put into the crucible 5 and covered with a metal net or the like. The crucible 5 is arranged at a predetermined heating position of the above-mentioned plasma devices 10, 100, 100A. The pressure in the chamber 1 is reduced to 80 Pa by the vacuum pump 30, the inert gas 6 is injected into the chamber 1 at a flow rate of 8 to 10 ml / min, and the pressure in the chamber 1 is maintained at 1300 to 1500 Pa. There is. In the carbonization step S2, the same graphene can be produced by using Examples 1 and 3.

As shown in FIG. 6, the applicant performed the carbonization step S2 in 100 ° C. increments between the temperatures of 200 ° C. and 1100 ° C. by thermal plasma, and determined the temperature and yield when carbonizing the carbon source 9. The value obtained by dividing the weight of graphene 113, which is the final product obtained from 0.8 g of carbon source 9, is shown in FIG.

The highest yield of 36% was measured at 500 ° C. to 800 ° C., and a relatively large yield was obtained at 300 ° C. or higher and 1000 ° C. or lower. In this measurement, rice straw, bran, coconut husks, rice husks, peanut husks, etc. were used, and similar results were obtained. In the carbonization step S2, the carbon source 9 is carbonized in about 10 to 30 minutes by heating in the temperature range of 300 ° C. to 1000 ° C. by thermal plasma by arc discharge while flowing in the inert gas 6.

Next, the activation step S3 will be described. The carbide 19 obtained above is mixed with potassium hydroxide (KOH) 18 at a weight of 5 to 1 and placed in the jar 62 of the small crucible 60 shown in FIG. 4 to cover the lid 61. The small crucible 60 is housed in the large crucible 50, and activated carbon 53 is embedded around the crucible 60. Activated carbon 53 is buried in the small crucible 60 to prevent oxygen from entering the crucible 60. In the heating furnace 41, the furnace 42 was heated to a temperature close to 950 ° C. and fired for about 2 to 3 hours.

Here, potassium hydroxide 18 is used from the viewpoint of improving the yield of graphene 113, which is the final product, in order to promote the removal of silicon. Examples of the base include alkali metal hydroxides such as sodium hydroxide and lithium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, alkali metal oxides such as sodium oxide and potassium oxide, and magnesium oxide. , Alkaline earth metal oxides such as calcium oxide, alkali metal sulfides such as sodium sulfide and potassium sulfide, and alkaline earth metal sulfides such as magnesium sulfide and calcium sulfide. In addition, the lignin that has not been completely carbonized may be removed by one or more acids selected from the group consisting of hydrochloric acid, sulfuric acid, PTSA, and aluminum chloride with an acid.

Of the charcoal 19 reacted with potassium hydroxide, silicate reacts with potassium hydroxide 18 to become potassium silicate, and the remaining water-soluble potassium hydroxide (KOH) 18 (Fig. 4) and potassium silicate are used. The silicon oxide (silicon) is removed by dissolving it in water, setting the mixed solution on a filter paper, and passing it through a vacuum or depressurized filter. Then, in the dried activation step S3, it was possible to produce graphene 113, which is a final product having a weight of about 1/8 to 1/10 as compared with the case where the first vegetable raw material was granulated.

(Example 10)
<Process flow 2>
With reference to FIG. 1, a manufacturing process will be described for a method of manufacturing graphene using the high-frequency induction heating devices 200, 200A, and 200B of Example 5. Since the pretreatment step S1 in the process flow 1 of the above-mentioned Example 4 is the same, it is omitted.

The carbonization step S2 when the high frequency induction heating device 200 shown in FIGS. 7 to 11 of this embodiment is used will be described. In the pretreatment step S1, the carbon source 9 is spread in the storage box 205 and covered with a metal net such as stainless steel. A plurality of storage boxes 205 are staggered and arranged at predetermined heating positions of the high-frequency induction heating device 200 described above. The pressure in the quartz tube 203 is reduced to 80 Pa by the dry pump 223, the inert gas 217 is injected into the quartz tube 203 at a flow rate of 8 to 10 ml / min, and the pressure in the quartz tube 203 is 1300 to 1500 Pa. It is kept.

As shown in FIG. 6, the applicant performed the carbonization step S2 in 100 ° C. increments between the temperatures of 200 ° C. and 1100 ° C. by heating, and determined the temperature and yield when carbonizing the carbon source 9. The value obtained by dividing the weight of the carbide 19 obtained from 0.8 g of the carbon source 9 is shown in FIG. The highest yield of 36% was measured at 500 ° C. to 800 ° C., and a relatively large yield was obtained at 300 ° C. or higher and 1000 ° C. or lower.

In this measurement, rice straw, bran, coconut husks, rice husks, peanut husks, etc. were used, and similar results were obtained. In the carbonization step S2, the carbon source 9 is carbonized in a temperature range of 300 ° C. to 1000 ° C. in about 10 to 30 minutes by high-frequency induction heating while flowing in the inert gas 217.

Next, the activation step S3 will be described. The carbide 19 obtained above is mixed with potassium hydroxide (KOH) 18 at a weight of 5 to 1 and placed in the jar 62 of the small crucible 60 shown in FIG. 4 to cover the lid 61. Further, the small crucible 60 is housed in the storage box 205 shown in FIG. 11, and activated carbon 53 is embedded around the crucible 60. Activated carbon 53 is buried in the small crucible 60 to prevent oxygen from entering the crucible 60. In the electric furnace 250, the inside of the quartz tube 203 was heated to a high temperature of about 950 ° C. and fired for about 2 to 3 hours.

Here, potassium hydroxide 18 is used from the viewpoint of improving the yield of graphene 113 in order to promote the removal of silicon. Examples of the base include alkali metal hydroxides such as sodium hydroxide and lithium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, alkali metal oxides such as sodium oxide and potassium oxide, and magnesium oxide. , Alkaline earth metal oxides such as calcium oxide, alkali metal sulfides such as sodium sulfide and potassium sulfide, and alkaline earth metal sulfides such as magnesium sulfide and calcium sulfide. In addition, the lignin that has not been completely carbonized may be removed by one or more acids selected from the group consisting of hydrochloric acid, sulfuric acid, PTSA, and aluminum chloride with an acid.

Of the charcoal 19 reacted with potassium hydroxide, silicate reacts with potassium hydroxide 18 to become potassium silicate, and the remaining water-soluble potassium hydroxide (KOH) 18 (Fig. 4) and potassium silicate are used. The silicon oxide (silicon) is removed by dissolving it in water, setting the mixed solution on a filter paper, and passing it through a vacuum or depressurized filter. Then, in the dried activation step S3, it was possible to produce graphene 113, which is a final product having a weight of about 1/8 to 1/10 as compared with the case where the first vegetable raw material was granulated.

(Example 11)
By further performing the following treatments in the pretreatment step (S1) of the above-described embodiment, it becomes easy to reduce the work steps of removing silicon, and graphene 113, which is a final product having high carbon purity, is produced. be able to. By removing silicon in advance, it is less likely that the inside of the furnace or chamber will be polluted by the combustion of silicon.

As a pretreatment step (S1), it is possible to pulverize the carbon source 9 which is a vegetable raw material, or use an inorganic acid before pulverizing to reduce or remove the silicon of the carbon source 9. By performing such a pretreatment step (S1), it is possible to omit the activation step (S3), and in particular, a carbonization step (S2) at around 3000 ° C. for increasing the degree of graphitization as in Example 7 is performed. By doing so, it is possible to produce graphene 113 having high purity and high crystallinity having 98% or more carbon and no metal as an impurity.

Inorganic acids include hydrochloric acid, nitrate, phosphoric acid, sulfuric acid, boric acid and hydrofluoric acid, of which water (H2O) and tetrafluoride are reacted by reaction with silicon dioxide (SiO2) and hydrofluoric acid (6HF). It is possible to produce silicon fluoride (SiF4) and remove silicon.

(Example 12)
By using the above-mentioned carbonization apparatus (10, 100, 100A, 200, 200A, 200B) and changing the temperature condition to 1000 ° C. or higher, it is possible to produce high-quality graphene 114. Further, from 300 ° C. to around 900 ° C. of A, the pretreatment step (S1) is not performed in the low temperature region 71, and after the carbide 19 containing a large amount of silicon (Si) is produced (carbide step S2), argon gas or the like is used. Silicon carbide (SiC) is formed when B is heated at a temperature of about 1700 ° C. to 2500 ° C. in the atmosphere of the inert gases 6 and 217.

(Example 13)
A method for producing graphene P of another embodiment will be described with reference to FIGS. 1 and 38. In this production method, graphene P having an improved degree of graphitization can also be produced by using the production apparatus (10, 100, 200) described above and changing the temperature conditions. In particular, since the high-frequency induction heating device 200A of Example 5 is a device capable of carbonizing at a high temperature of 3000 ° C. or higher, Example 5 will be described as an example.

Graphene P has two routes for manufacturing, and the route 1 will be described first with reference to FIG. Route 1 performs the pretreatment step S1 described above, and carbonizes the carbonization step S2 in the temperature range A of 300 ° C. to 900 ° C. of the temperature 71 described above. Next, the activation step S3 described above is performed to prepare graphene 113. Next, the graphene 113 is subjected to the second carbonization step S4 in the temperature range D of 900 ° C. to 1300 ° C. of the temperature 74 to prepare graphene 114.

Next, the graphene 114 is subjected to the above-mentioned HF treatment (S5), and the third carbonization step S6 is carried out in the temperature range C of 2500 ° C. to 3200 ° C. of the temperature 73, whereby the degree of graphitization is increased and compared with the mineral. As a result, highly pure graphene P with few metallic impurities is produced.

Further, not only this step but also the step of Route 2 enables the production of graphene P having high purity. In Route 2, after producing graphene 1113, HF treatment (S5) is performed, and the third carbonization step S6 is performed in the temperature range C of 2500 ° C. to 3200 ° C. of the temperature 73, whereby the degree of graphitization is increased. High-purity graphene P with less metallic impurities than minerals is produced.

Further, the high temperature 73 of C from 2500 ° C. to around 3500 ° C. is temperature control in the case of graphitization, and graphene P having excellent graphitization degree and further excellent electrical conductivity is formed. In particular, the temperature around 2800 ° C to 3000 ° C is the best.

As shown in FIG. 38, in an atmosphere filled with an inert gas such as nitrogen or argon, silicon dioxide does not melt in the temperature range D of 900 ° C. to 1450 ° C. or lower shown in the temperature 74, but the acid. It is a good temperature range for increasing the purity of carbon by treatment or alkali treatment. Further, the temperature zone B or the temperature zone C is a temperature zone in which the numerical value of the specific surface area can be increased by removing the silicon dioxide because the silicon dioxide melts at 1650 ° C. or higher.

(Graphene 2)
As shown in FIGS. 39 to 50, graphene P having an improved degree of graphitization produced by the present embodiment will be described. FIG. 39 is a Raman spectrum of graphene 114 obtained by the manufacturing apparatus of the present invention. FIG. 40 is a Raman spectrum of graphene P obtained by the manufacturing apparatus of the present invention.

FIG. 41 is an electron micrograph of graphene 114 obtained by the manufacturing apparatus of the present invention at a magnification of 15,000. FIG. 42 is an image of graphene 114 obtained by the manufacturing apparatus of the present invention taken with a scanning transmission electron microscope shown in FIG. 41 and transmitted at a magnification of 15,000.
FIG. 43 is an electron micrograph of graphene 114 obtained by the manufacturing apparatus of the present invention at a magnification of 200,000. FIG. 44 is an image of graphene 114 obtained by the manufacturing apparatus of the present invention taken by a scanning transmission electron microscope shown in FIG. 43 and transmitted at a magnification of 200,000.

FIG. 45 is an electron micrograph of graphene P obtained by the manufacturing apparatus of the present invention at a magnification of 1,000 times. FIG. 46 is an electron micrograph of graphene P obtained by the manufacturing apparatus of the present invention at a magnification of 5,000. FIG. 47 is an electron micrograph of graphene P obtained by the manufacturing apparatus of the present invention at a magnification of 10,000 times. FIG. 48 is an electron micrograph of graphene P obtained by the manufacturing apparatus of the present invention at a magnification of 100,000. FIG. 49 is an electron micrograph of graphene P obtained by the manufacturing apparatus of the present invention at a magnification of 40,000. FIG. 50 is a 40,000-fold image of graphene P obtained by the manufacturing apparatus of the present invention taken by a scanning transmission electron microscope shown in FIG. 49 and transmitted.

As shown in FIGS. 45 to 50, graphene P is also provided with holes 96 having a diameter of 2 μm to 10 μm, which are 1000 to 10000 times larger than the pores 97. As described above, not only the large pores but also the pores 97 having a pore diameter of 0.8 to 2 nm are provided and have a porous property. As shown in FIGS. 16 and 17, these large and small porosities extending in the vertical and horizontal directions include porosities formed during the growth process of the vegetable raw material, and removal of silicon 91 in the vicinity of the cell wall. There are also porosities formed during carbonization of organic matter. In FIGS. 42 and 44, spherical silicon dioxide 91 having a silicon component of about 15 nm to 50 nm is formed as minute irregularities.

The element number concentration of graphene P is 0.12 wt% with a small amount of metal components in impurities and a small amount of Al, and other oxygen (O) is 0.9 wt% to 1.24 wt%, and carbon is 98.6 wt%. %, And carbon has a purity of about 98%. Since the metal component is less than 1 wt% as described above, the purity of carbon is high.

FIG. 40 shows the peak of the wavelength of graphene P measured by the Raman spectroscopy method measured using a laser Raman spectrophotometer, and shows that the crystallinity is high. The peak value ID of the peak value IG and D bands G band of the peak wavelength due to Raman spectroscopy ^{(1590cm -1) (1350cm -1)} .

そして、表５及び図４０に示すようにＩＧをＩＤ割った値は、約８．６７となり、グラフェンＰにおいては非常に高い値を示し、結晶性が高いことを示している

Then, as shown in Table 5 and FIG. 40, the value obtained by dividing the IG by ID is about 8.67, which is a very high value in graphene P, indicating that the crystallinity is high.

FIG. 39 shows the wavelength peak of graphene 114 measured by the Raman spectroscopy method measured using a laser Raman spectrophotometer. As shown in FIG. 39 and Table 5, graphene 114 has an IG divided by ID of 0.91, carbon (C) of 79.82 wt%, silicon (Si) of 15.5 wt%, and potassium (K). ) Is composed of 2.13 wt%. This forms an excellent carbon material.

Further, the specific surface area measured by the water vapor adsorption measurement method and the BET method is 1780 m ² / g for graphene 114. The water content of graphene P measured by the coulometric titration method is 0.01%, preferably less than 1%.

The powder resistance value measured by the above-mentioned measuring method is 3.8 × 10 ^{-3 Ω · cm for graphene 114, and 1.6 × 10 -3} Ω · cm for graphene P by removing silicon. And the conductivity is improved.

(Relationship between carbonization temperature and time)
Table 5 and FIG. 38 show the relationship with the time during the carbonization step (S2) shown in FIG. 1 using the graphene production apparatus (10, 100, 100A, 200, 200A, 200B) described above. FIG. 38 is a diagram showing the relationship between the heating temperature and time during carbonization.

The case where the carbon source 9 is carbonized at a temperature of 500 ° C. by the high frequency induction heating device 200 will be described as an example. The heated surface area S shown in Table 5 indicates the inner surface area (cm2) including the lid 255 of the storage box 205. The heating volume V (cm3) indicates the volume of the carbon source 9 stored in the storage box 205. It represents the area to be heated per 1 cm3 of the carbon source 9, and it is considered that if the value of the heating area H is large, the area to be heated becomes large and the amount of heat increases.

In FIG. 38, the calorific value area ht is the time h (h) and the heating temperature when the temperature is raised from room temperature at a heating rate of 100 ° C./min and held at 500 ° C. for 25 minutes to carbonize the carbon source 9. It is a value expressed by the area indicated by the diagonal line. The heating coefficient K is a numerical value expressed by the product of the heating area H and the calorific value area ht. The heating coefficient K is preferably in the range of 130 to 280, and in particular, the holding temperature is 500 ° C. or higher in consideration of the yield, and the heating coefficient K is most preferably 150 to 260.

Although the high frequency induction heating device 200 is shown as an example, a graphene manufacturing device (10, 100, 100A, 200A, 200B) may be used. Further, the time from when heating is stopped (point D) to cooling (time between DE and E) may be calculated in addition to the calorific value area ht. Further, the heating coefficient K is preferably in the range of 130 to 300, and in particular, the holding temperature is 500 ° C. or higher in consideration of the yield, and the heating coefficient K is most preferably 150 to 280.

(Rotating device, its parts and its manufacturing method)
Hereinafter, the parts of the rotating device using the carbon material manufactured by the above-mentioned manufacturing method and the like and the manufacturing method thereof will be described with reference to FIGS. 52 to 55.
FIG. 52 is a schematic view showing the entire rotating device 300. FIG. 52 is a rotating device 300 provided with a shaft core 302 arranged at the center of a rotating hole 306 provided with a hole in the center of the cylindrical case 301. The rotating device 300 is a so-called motor that rotates the shaft core 302 by supplying electric power such as direct current to the + terminal 303 and the − terminal 304.

In the rotating device 300, the carbon fiber 19 or graphene 113, 114, P described above is mixed in the resin at a ratio of 10% w, and the carbon fiber cloth woven by a weave such as plain weave or twill weave is housed. It is formed by wrapping it as a skeleton of. The optimum ratio of the carbide 19 or graphene 113, 114, P mixed in the resin is about 1% wt to 30% wt.
The resin is preferably a thermosetting resin such as epoxy resin, unsaturated polyester resin, urea resin, melamine resin, diallyl phthalate resin and phenol resin, and can be used as long as it is a base material used for carbon fiber reinforced resin. be.

In the carbon fiber, carbide 19 or graphene 113, 114, P is mixed in the pitch material at a weight ratio of about 5% wt to 30% wt, and the mixed pitch material is spun and then insolubilized and graphitized. The carbon fiber may be obtained by performing heat treatment.
The rotating device 300 is provided with a heat radiating unit 305 that selectively dissipates heat by a manufacturing method described later at a desired position. The heat radiating unit 305 is configured by using a magnetic material described later.

The rotating device 300 shown in FIG. 53 will be described by taking a three-pole DC motor using a brush as an example, but can be applied to a stepping motor, a brushless DC motor, an AC motor, an ultrasonic motor, and the like. Further, the rotating device 300 of the present invention can be applied regardless of the number of poles such as 5 poles as well as 3 poles.

The rotating device 300 shown in FIG. 53 is covered with a case 301, and a shaft core 302 is arranged at the center of the case 301. The rotating device 300 is provided with a core 323 in which a plurality of iron core pieces 324 are laminated on a shaft core 302 arranged at the center of the rotating hole 306. A winding 325 made of copper wire is wound around a plurality of iron core pieces 324. The winding 325 may be made of the carbon fiber described above instead of the copper wire. It is possible to manufacture the winding 325 in a lightweight manner.

The rotating device 300 is close to the outer circumference of the core 323 around which the winding 325 is wound so that the permanent magnets 321 and 322 having the north and south poles do not come into contact with each other. Further, the winding 325 of each of the three poles is connected to each of the three rectifying pieces 328 by soldering or the like. The rectifying piece 328 is provided with a carbon brush 327 in which the above-mentioned carbide 19 or graphene 113, 114, P and ceramic or the like are kneaded and fired. The carbon brush 327 is provided at the tip of each of the + terminal 303 and the − terminal 304.

FIG. 54 is a conceptual diagram showing a configuration when the iron core piece 324 is manufactured. In this embodiment, the resin will be described by taking as an example a two-component epoxy resin that is divided or cured in a time of 5 to 24 hours. Further, as the magnetic material which is a magnetic material, iron oxide, chromium oxide, cobalt, ferrite, a non-metal oxide magnetic material and the like can be considered, but in this embodiment, iron tetroxide, which is a solid powder, will be described as an example. .. The magnetic material was mixed in at a rate of 50% wt. If there is too much magnetic material, it will not lead to weight reduction, so 30% wt to 60% wt is optimal. The core 323 manufactured by this method was achieved to be about 50% lighter than the core made of metal.

The iron core piece 324 manufactured by using a resin for weight reduction is manufactured by first molding a mold 331 into the shape of the iron core piece 324 and then pouring a resin mixed with a magnetic material into the mold 331. Since the magnetic material and the resin have different specific densities, the magnetic material is biased downward due to gravity.

Therefore, the N-pole permanent magnet 332 and the S-pole permanent magnet 333 are arranged above and below the mold 331 with the separator 334 interposed therebetween. This makes it possible to prevent the magnetic material from being biased when the resin is cured, and to control the orientation of the magnetic material toward the north and south poles in the desired direction. By aligning the magnetic materials of the iron core piece 324, the magnetic force in the electromagnetic induction flowing through the winding 325 can be improved.

Further, in the orientation of the magnetic material described later, it is also applied to the production of the heat radiating portion described later. The separator 334 prevents the magnetic material from directly sticking to the permanent magnets 332 and 333. The separator 334 may be in the form of a sheet coated with paper or silicon.
Further, instead of the permanent magnets 333 and 332, a method of controlling the orientation of the magnetic material by electromagnetic induction to cure it is also conceivable.

Further, a two-component epoxy resin, a magnetic substance and a carbide 19 or graphene 113, 114, P are mixed. In particular, the carbide 19 or graphene 113, 114, P has a specific surface area of 700 m ^{2 represented by a bed type.} Carbides 19 or graphene 113, 114, P of ^{300 m 2} / g or more, indicated by / g to 1800 m ² / g, may be used. Carbide 19 or graphene 113, 114, P is porous and has a large specific surface area, which facilitates the uptake of magnetic materials.

In particular, carbide 19 or graphene 113, 114, P has many nano-level pores, so that even a nano-level magnetic material is easily adsorbed and has an effect of dispersing in the resin. Therefore, the magnetic material is made of a resin. It is possible to further orient uniformly.

Next, FIG. 55 is a schematic view showing a cross section of the case 301 of the rotating device 300. The case 301 is formed symmetrically with respect to the center of the rotation hole 306, the surface is covered with the carbon fiber cloth 310 described above, and the intermediate member 312 is filled with resin. The tensile hardness is improved. Further, in the case 301, the heat dissipation effect is also improved by the carbon fiber cloth 310. The case 301 is carbon fiber reinforced with a carbon fiber cloth 310 using the above-mentioned two-component epoxy resin, magnetic material and carbide 19, or a thermosetting resin mixed with graphene 113, 114, and P in the middle. It is a resin. The carbon fiber is not limited to cloth, and may be a chopped material.

In particular, in the case 301, a strong permanent magnet is used to concentrate the magnetic material on the heat radiating portion 305 and cure it. The mold making and the resin compounding are the same as the method for manufacturing the iron core piece 324, but by concentrating the magnetic material on the heat radiating portion 305, the path for letting the heat radiated from the rotating device 300 escape to the outside can be fixed. Further, since the case 301 can be made of a resin and carbon fiber cloth 310 other than the heat radiating portion 305, the weight of the case 301 can be reduced. Further, since carbide 19 or graphene 113, 114, P and the like are mixed in the intermediate member 312, a heat dissipation effect can be obtained as compared with the resin alone.

A cloth 310 may be spread instead of the intermediate member 312, and at that time, a two-component epoxy resin and a carbide 19 or a thermosetting resin mixed with graphene 113, 114, P are used to bond the cloth 310. May be. Further, the heat radiating portion 305 may be formed as described above by mixing a magnetic material.

(Electronic parts, electronic parts and electrical equipment)
Hereinafter, electronic parts, electronic parts, electric devices, and methods for manufacturing the same using carbon materials manufactured by the above-mentioned manufacturing methods and the like will be described with reference to FIGS. 56 to 61.
First, the heat generating device 500 will be described with reference to FIGS. 56 and 57. 56 (A) and 56 (B) are views showing the front surface of the heat generating device 500 which is an electric device. The heating device 500 is a rectangular planar heating element.

The heat generating device 500 is provided with DC + wiring 503 and DC-wiring 504, which are wirings for supplying electric power to both lower ends. The heat generating device 500 is provided with a direct current + electrode 507 and a direct current-electrode 508 made of a material such as a copper plate or aluminum foil connected to the direct current + wiring 503 and the direct current-wiring 504 by soldering or the like inside the heating element storage case 501. ing.
The electric power is 12V DC supplied to the heat generating device 500, but it is not necessary to limit the electric power to be supplied, and AC 100, 200V, 24V DC, or the like may be used.

The heating device 500 is provided with a heating element storage case 501, and the inside of the heating element storage case 501 is hollow. The heating element storage case 501 stores carbides 19 or graphene 113, 114, P, etc. manufactured by the above-mentioned manufacturing method in the cavity as a heat generating material 506 and is sealed by a heating element storage lid 502. Although the heating element storage case 501 is formed of PLA resin mixed with carbon fiber in this embodiment, it may be formed of glass, ceramic, heat-resistant plastic, or the like.

FIG. 57 is a cross-sectional view taken along the line AA shown in the front view of FIG. 56 (B). The heat generating device 500 generates heat of the heat generating material 505 by the electric power flowing between the DC + electrode 507 and the DC-electrode 508. In this embodiment, a DC 12V voltage was passed between the DC + electrode 507 and the DC-electrode 508, and a current of 2.8A to 3.9A flowed. The power consumption is about 35W to 48W.

The heat generating device 500 can control the control temperature in the range of 30 ° C. to 70 ° C. In this embodiment, graphene 113 is used, and graphene 113 is laminated in the range of length 180 mm × width 100 mm × thickness 3 to 5 mm. The overall resistance of the heat generating device 500 at this time is 15 to 50 Ω.

The heating device 500 forms a heater separator 505 between the heating element storage lid 502 and the heating material 506. The heater separator 505 prevents the adhesive from entering the heating material 506 when the heating element storage lid 502 and the heating element storage case 501 are adhered to each other. This is because when the adhesive is mixed into the heat generating material 506, the resistance value rises and the desired resistance value cannot be realized.

Further, the heat generating device 500 contains about 5% to 15% of water and is sealed to prevent the temperature from rising, and the temperature can be adjusted to a constant temperature within a range of 100 ° C. or lower. Therefore, the heater separator 505 is preferably made of a material having an effect of absorbing moisture and moisturizing. For example, the heater separator 505 may be paper such as Japanese paper or Japanese calligraphy, heat-resistant sponge, or the like.

In the heat generating device 500, since the solid volume resistance of each carbon material tower is different in the carbide 19 or graphene 113, 114, P, it is possible to change the resistance value by mixing them to create a desired resistance value. ..
Further, since the carbide 19 or the graphenes 113 and 114 are mixed with a relatively large amount of silicon component (Si) or silicon dioxide (SiO2) as well as the carbon material, the heating device 500 is maintained at a temperature within a certain range. It is easy to do, and the temperature rises and falls slowly.
Further, the carbide 19 or graphene 113, 114 has a large specific surface area as described above, so that it is easy to moisturize water. Therefore, the heating device 500 becomes a heating element that is stable at a constant temperature.

Next, a method of manufacturing the heat generating device 500 will be described. The heating device 500 puts the powdered heating material 506 in water in a heating element storage case 501, aggregates the carbides 19 or graphene 113, 114, and P while applying pressure from above, and evaporates the water content. Carbide 19 or graphene 113, 114, P is solidified. Then, the heater separator 505 and the heating element storage lid 502 are placed on the heating material 506 in a state of containing about 5% to 15% of water, and sealed with an adhesive or the like.

The heater separator 505 is not always necessary, but it is not particularly limited as long as it is possible to maintain a state in which a certain amount of water is contained and to solidify the heating material 506 in the heating element storage case 501. The heat-generating material 506 may be a solid heat-generating material 506 obtained by kneading ceramic and carbide 19 or graphene 113, 114, P at a ratio of 50:50 and firing in an oxygen-free state.
With the above configuration, the heating device 500 can provide a heating element that is lightweight, consumes less power, and has a stable temperature.

Next, the LED substrate 600, which is an electronic component, will be described with reference to FIGS. 58 and 59.
FIG. 58 is a front view of the LED substrate 600. The LED substrate 600 is equipped with an LED that drives one light source L with a DC voltage of 3.2 V and consumes about 1 W. Then, in the LED substrate 600, three light sources L are connected in series between the light source + terminal 601 and the light source-terminal 602, and 12 V of direct current is applied. A pattern wiring 603, 605 is formed between the light source + terminal 601 and the light source-terminal 602 by using carbide 19 or graphene 113, 114, P manufactured by the above-mentioned manufacturing method.

In this embodiment, instead of the printed circuit board, a square substrate case 606 is formed of resin, pattern wirings 603 and 605 are formed in a groove shape, and carbides 19 or graphene 113, 114 and P are formed in the grooves. Pattern wirings 603 and 605 are formed as an alternative to printed patterns such as copper. Therefore, it is possible to form the LED substrate 600 lighter than using a metal typified by copper or the like.

FIG. 59 is a cross-sectional view when the LED substrate 600 is cut along the line AA shown in FIG. 58. The LED substrate 600 uses a resin having strong dielectric breakdown, and is formed of the above-mentioned carbon fiber, carbide 19, or a resin mixed with graphene 113, 114, P, or the like. As a result, the LED substrate 600 has improved heat dissipation performance as compared with ordinary resin.

The pattern wirings 603 and 605 are provided with a groove-shaped groove portion 612 in a part of the substrate case 606. The groove portion 612 constitutes a carbon laminated portion 611 in which the above-mentioned carbide 19 or graphene 113, 114, P is laminated. Further, the light source-terminal 602 of the light source L is embedded in the carbon laminated portion 611. The pattern wirings 603 and 605 are provided with a pattern sealing portion 610 above. The pattern sealing portion 610 seals the carbon laminated portion 611 by adhering resin, paper, or the like. Further, the pattern sealing portion 610 may be formed of an adhesive such as an epoxy resin as it is.

The LED substrate 600 does not use solder, and the current limiting resistor generally required for the LED is the carbide 19 or graphene 113, 114 described above because the pattern wirings 603 and 605 play a role. , P and the like are mixed with a resin or an adhesive for fixing the above-mentioned wiring, and the resistance value is adjusted to form a current limiting resistor. Therefore, the LED substrate 600 does not need to be provided with a resistor separately.

Next, a method of manufacturing the LED substrate 600 will be described. The LED substrate 600 is processed into a shape for accommodating the light source L in a substrate case 606 formed of a material such as resin in a square shape, and a groove portion 612 is processed into a shape for accommodating the carbon laminated portion 611.

After arranging the light source L, the LED substrate 600 is housed in the groove portion 612 of the substrate case 606 in a state where the powdered carbides 19 or graphene 113, 114, P are dispersed in water, and is aggregated while applying pressure from above. , Moisture is evaporated to harden the carbide 19 or graphene 113, 114, P to form the carbon laminate 611. Then, the pattern sealing portion 610 is placed on top in a state of containing about 5% to 15% of water, and sealed with an adhesive or the like. The LED substrate 600 is manufactured by the above manufacturing method.

Next, the piezoelectric measuring instrument 700 will be described with reference to FIGS. 60 and 61.
FIG. 60 is a perspective view showing an outline of the piezoelectric measuring instrument 700 incorporating the electronic component 710. In the piezoelectric measuring instrument 700, a cylindrical piezoelectric case 701 is formed above a rectangular base 703, and a piezoelectric device 710 is embedded inside the piezoelectric case 701.

The piezoelectric measuring instrument 700 is provided with a push button 702 above the piezoelectric case 701. The piezoelectric measuring instrument 700 is provided with a piezoelectric + electrode 705, a piezoelectric-electrode 704, and an analog input terminal 706 on the side of the piezoelectric case 701. The tip of the piezoelectric + electrode 705 and the piezoelectric-electrode 704 is formed of a copper plate or the like, and is in contact with the piezoelectric device 710. The tip of the analog input terminal 706 is also formed of an input terminal made of a copper plate or the like, and is in contact with the piezoelectric device 710.

FIG. 61 is a block diagram showing a configuration of a piezoelectric measuring instrument 700 incorporating an electronic component 710. A DC voltage of 5 V is applied to both ends of the piezoelectric + electrode 705 and the piezoelectric-electrode 704, for example. Further, the analog input terminal 706 inputs a voltage of 5 V by the analog input, and displays the measured value on the monitor 720.

Pressure is applied by pressing the electronic component 710 housed in the piezoelectric case 701 described above and pressing the button 702, and the conductive and elastic electronic component 710 comes into contact with these terminals (704, 705, 706). The resistance value changes depending on whether the degree of is dense or coarse. The electronic component 710 reads the change in pressure by reading the change in resistance value.

Next, a method of manufacturing the electronic component 710 will be described. Since the electronic component 710 is preferably configured in a gel-like elastic state, in this embodiment, an aqueous solution of borax or 10% wt boric acid is prepared in polyvinyl alcohol.
An elastic gel was formed by mixing an aqueous solution with polyvinyl alcohol. After forming this gel, carbide 19 or graphene 113, 114, P produced by the above-mentioned production method or the like is mixed at a ratio of 10% wt to 20% wt and kneaded.

The resistance value of the electronic component 710 manufactured by this method was a surface resistance of 50 KΩ to 200 kΩ when graphene 113 was mixed. Since the solid volume resistance values of carbide 19 or graphene 113, 114, and P are different, this resistance value can be adjusted by blending so as to obtain a desired resistance value. Further, the resistance value of the electronic component 710 can also be adjusted by adjusting the amount of polyvinyl alcohol added. It is preferable to use a material having a powder volume resistance value of 1.0 × 10-3 Ω · cm to 5 × 10 Ω · cm for each of the carbide 19 or graphene 113, 114, P when adjusting the resistance described above. The lower the powder volume resistance value, the better, and 1.0 × 10-6Ω · cm is the best.

Since this electronic component 710 is in a state close to a gel, it can be applied to a pressure sensor that senses bending pressure or the like by bending the tube by enclosing it in a tube and providing an electrode. It can be applied as a pressure sensor when bending a robot arm or the like.

(Technical features and effects of this example)
Other technical features conceivable from the above embodiments are described below along with their effects.
<Characteristic point 1>
An electronic component that uses a carbon material (for example, mainly carbide 19 or graphene 113, 114, P) containing a silicon component having a specific surface area of 300 m ^{2 / g or more as a conductor.}
Wiring configured by embedding the conductor (for example, mainly pattern wiring 603, 605) and
The wiring that supplies electric power is brought into contact with the terminals (for example, mainly light source + terminal 601 and light source-terminal 602) of an electronic drive unit (for example, mainly a light source L (LED)) that supplies and drives electric power. It is characterized in that a resistance component having a resistance value required for the electronic driving unit is configured by the wiring.

Due to the above features, the electronic component of the present invention can form a component that is lighter than metal without the need for soldering. Further, the electronic component does not require a resistor component because the wiring becomes a resistor, and can be formed lightweight.

<Characteristic point 2>
The resistance component is characterized in that it is adjusted by mixing the resin or water with the carbon material.
Due to the above features, the electronic component of the present invention can be formed lightweight without the need for a resistor component because the wiring becomes a resistor.

<Characteristic point 3>
It is an electronic component whose resistance value changes when pressure is applied.
A gel-like elastic body whose contact area increases with pressure is formed by adding a conductive carbon material containing 14% or more of a silicon component, and the contact area is changed with pressure to change the resistance value. It is characterized by having an elastic body.

Due to the above characteristics, in the present invention, by using a carbon material having a large specific surface area, it becomes easy to enter a gel-like elastic body, and the carbon material having conductivity becomes easy to maintain conductivity and elasticity, and stable piezoelectricity is obtained. The element can be formed.

<Characteristic point 4>
It is a manufacturing method of electronic parts whose resistance value changes when pressure is applied.
It is characterized in that borax or boron is mixed with polyvinyl alcohol at a ratio of 10% wt, and a carbon material containing a silicon component having ^{a specific surface area of 300 m 2 / g or more is kneaded.}
Due to the above characteristics, a carbon material having a large specific surface area is easily adsorbed on a gel-like elastic body, and a carbon material having conductivity is easy to maintain conductivity and elasticity, so that a stable piezoelectric element can be formed.

Another technical feature considered from the above embodiment is a manufacturing method for producing a carbon material (carbonized material 19), in which a heated surface surface (S) indicating an area when heated by a storage portion is used as a carbon source (9). The value divided by the heating volume (V) indicating the volume when heating is defined as the heating area (H), and the relationship between the time (h) for heating the carbonization source and the temperature for heating the carbonization source is the area. The value represented by is represented by the calorific value area (ht), the product of the heating area (H) and the calorific value area (ht) is represented by the heating coefficient (K), and the value of the heating coefficient (K) is a value of 130 to 280. A method for producing a carbon material, which comprises heating the carbon source to produce the carbon material within the range indicated by.

According to the above method, it is possible to produce a carbon material with a good yield in a short time, and it is possible to produce graphene having a large specific surface area and a small amount of metal residue as a precursor for producing graphene. It is possible. In particular, in devices such as plasma devices and carbonization devices that use high-frequency induction heating, it is possible to produce a large amount of carbon material in a short time as long as the heating coefficient (K) is in the range of 130 to 280. Is.

The electronic component of the present invention can be applied to all electronic components in the industrial field including cars, ships, aircraft and the like.

1 ... Chamber, 2 ... Cathode, 3 ... Anode, 4, 32 ... High frequency power supply, 5 ... Crucible,
6,217 ... Inert gas, 7 ... Introduction pipe, 8 ... Derivation pipe, 9 ... Carbon source,
10, 100, 100A ... Plasma device, 14, 22, 224 ... Control valve,
15, 23 ... Leak valve, 19 ... Carbide, 20 ... Control device,
21 ... Gas amount control device, 30 ... Vacuum pump, 31, 240 ... High frequency coil,
40 ... Activator, 41 ... Heating furnace, 42, 81 ... Furnace,
50 ... Large crucible,
51, 61 ... lid, 52, 62 ... jar, 53 ... activated carbon,
60 ... Small crucible,
70 ... Oxidation inhibitor, 71 ... Low temperature region, 72 ... Medium temperature region, 73 ... High temperature region,
80 ... Combustion furnace, 83 ... Pot, 96 ... Pore, 97 ... Pore, 98 ... Silicon,
113, 114, P ... Graphene,
200, 200A ... High frequency induction heating device,
200B ... Microwave induction heating device, 202 ... Base, 203 ... Quartz tube, 204 ... Base groove,
205 ... Storage box, 206 ... Mounting stand, 207 ... Lower end piece, 208 ... Upper end piece,
209 ... Storage space, 210 ... Control device, 211 ... Temperature control device,
212 ... High frequency power supply, 213 ... Cooling device, 214 ... Drive device 1, 215 ... Power supply control device,
216 ... Drive device 2, 218 ... Combustion gas, 219 ... Vacuum pressure gauge, 221 ... Filter,
223 ... Dry pump, 231 ... Left flange, 232 ... Right flange, 235 ... Thermocouple,
236 ... rail, 241 ... shielding plate, 242 ... coil support, 243 ... coil,
250 ... Electric furnace,
300 ... Rotating device, 301 ... Case, 302 ... Shaft core, 303 ... + Terminal,
304 ...- terminal, 305 ... heat dissipation part, 306 ... rotating hole, 310 ... cross, 312 ... intermediate member,
321, 322, 332, 333 ... Permanent magnets, 323 ... Cores, 324 ... Iron core pieces,
325 ... winding, 327 ... carbon brush, 328 ... rectifying piece, 331 ... type,
334 ... Separator,
500 ... heating device, 501 ... storage case, 502 ... heating element storage lid,
503 ... DC + wiring 503, 504 ... DC-wiring, 505 ... Separator, heat generating material ... 506,
507 ... DC + electrode, 508 ... DC-electrode,
600 ... LED board, 601 ... Light source + terminal, 602 ... Light source-terminal,
603, 605 ... Pattern wiring, 606 ... Board case, 610 ... Pattern sealing part,
611 ... Carbon laminated part, 612 ... Groove part,
700 ... Piezoelectric measuring instrument,
701 ... Piezoelectric case, 702 ... Push button, 703 ... Base, 705 ... Piezoelectric + electrode,
704 ... Piezoelectric electrode, 706 ... Analog input terminal, 710 ... Electronic component, L ... Light source,
S1 ... Pretreatment step S2, S4, S6 ... Carbonization step, S5 ... HF treatment, S3 ... Activation step.

Claims (4)

An electronic component that uses a carbon material containing a silicon component with a specific surface area of 300 m ^{2 / g or more as a conductor.}
Wiring constructed by embedding the conductor and
The wiring that supplies electric power and the terminal of the electronic drive unit that supplies and drives the electric power are in contact with each other, and a resistance component having a resistance value required for the electronic drive unit is configured by the wiring. Characteristic electronic components. The electronic component according to claim 1, wherein the resistance component is adjusted by mixing a resin or water with the carbon material. It is an electronic component whose resistance value changes when pressure is applied.
A gel-like elastic body whose contact area increases with pressure is formed by adding a conductive carbon material containing 14% or more of a silicon component, and the contact area is changed with pressure to change the resistance value. An electronic component characterized by having an elastic body. It is a manufacturing method of electronic parts whose resistance value changes when pressure is applied.
A method for producing an electronic component, which comprises mixing borax or boron in polyvinyl alcohol at a ratio of 10% wt and kneading a carbon material containing a silicon component having ^{a specific surface area of 300 m 2 / g or more.}

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