JP2018104249A - Compound with coated film and manufacturing method of compound with coated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a calcium aluminate compound having a carbon coated film.SOLUTION: A manufacturing method of a compound 1 with a coated film has a process for mixing a compound raw material which is a raw material of a calcium aluminate compound and a coated film raw material containing carbon to generate a raw material. The manufacturing method has a process for generate the compound 1 with the coated film by heating the raw material under inert gas atmosphere. The compound 1 with the coated film has a body part 12 formed by the calcium aluminate compound and a carbon coated film 13 covering the body part 12. By the manufacturing method, the compound 1 with the coated film having the body part 12 and the carbon coated film 13 can be easily manufactured.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a coated compound.

  In recent years, a technique for generating hydrogen using mayenite, which is a kind of calcium aluminate compound, has been proposed. For example, Patent Document 1 proposes to use hydrogen-substituted mayenite in which free oxygen of mayenite is substituted with hydrogen for hydrogen production. Patent Document 1 also proposes producing conductive mayenite by irradiating the hydrogen-substituted mayenite with ultraviolet rays.

JP 2014-136661 A

  By the way, Patent Document 1 does not disclose a technique for forming a film on the surface of mayenite.

  This invention is made | formed in view of the said subject, and aims at providing the calcium aluminate compound which has a carbon film.

  Invention of Claim 1 is a compound with a film, Comprising: The main-body part formed with the calcium aluminate compound, and the carbon film which coat | covers the said main-body part are provided.

  Invention of Claim 2 is a compound with a film of Claim 1, Comprising: The said main-body part contains the void structure which has several void which can take in an ion, an atom, a molecule | numerator, or an electron.

According to a third aspect of the invention, a coating with a compound according to claim 2, wherein the void _structure, a mayenite containing Ca _{12 Al} 14 _{O 33.}

  A fourth aspect of the present invention is the compound with a film according to any one of the first to third aspects, wherein the carbon film includes carbon fiber or carbon nanotube.

  A fifth aspect of the present invention is the film-coated compound according to any one of the first to fourth aspects, wherein the compound is a hydrogen storage body that stores hydrogen molecules in the main body portion and the carbon film.

  Invention of Claim 6 is a manufacturing method of a compound with a film | membrane, Comprising: The process of producing | generating a raw material by mixing the compound raw material which is a raw material of a calcium aluminate compound, and the film raw material containing carbon, b) heating the raw material in an inert gas atmosphere to produce a coated compound comprising a main body formed of a calcium aluminate compound and a carbon film covering the main body.

  The invention according to claim 7 is the method for producing the coated compound according to claim 6, wherein the heating temperature in the step b) is 700 ° C. or higher and 1400 ° C. or lower.

  Invention of Claim 8 is a manufacturing method of the compound with a film of Claim 6 or 7, Comprising: The ratio of the said film raw material in the said raw material is 0.5 mol% or more and 70 mol% or less. .

  The invention according to claim 9 is the method for producing a compound with a film according to claim 8, wherein the ratio of the raw material for the film in the raw material is 10 mol% or more and 70 mol% or less.

  A tenth aspect of the present invention is the method for producing a film-coated compound according to any one of the sixth to ninth aspects, wherein the film material contains a saccharide.

  Invention of Claim 11 is a manufacturing method of the compound with a film in any one of Claim 6 thru | or 10, Comprising: The said film raw material contains hydrocarbon, The said hydrocarbon is two or more carbon atoms It contains two or more OH groups and two or more CO bonds.

  The invention according to claim 12 is the method for producing a film-coated compound according to any one of claims 6 to 11, wherein the main body portion includes a plurality of voids capable of taking in ions, atoms, molecules or electrons. A void structure.

The invention of claim 13 is a method of manufacturing a coated compound according to claim 12, wherein the void _structure, a mayenite containing Ca _{12 Al} 14 _{O 33.}

  A fourteenth aspect of the present invention is the process for producing a coated compound according to any one of the sixth to thirteenth aspects, wherein the carbon coating includes carbon fibers or carbon nanotubes.

  The invention according to claim 15 is the method for producing a coated compound according to any one of claims 6 to 14, wherein the inert gas atmosphere in the step b) is a hydrogen-containing gas atmosphere, and the b ), The film-coated compound in which hydrogen molecules are occluded in the main body and the carbon film is generated.

  In the present invention, a calcium aluminate compound having a carbon coating can be provided.

It is sectional drawing which shows the structure of the compound with a film which concerns on one embodiment. It is a figure which shows the flow of manufacture of the compound with a film. It is a figure which shows the manufacturing conditions and hydrogen storage amount in Examples 1-6 and Comparative Example 1. 2 is a photograph showing a cross section of the coated compound produced in Example 1. FIG. It is a figure which shows the structure of the measuring apparatus utilized for the measurement of the hydrogen storage amount of the compound with a film. 4 is a photograph showing the surface of a film-coated compound of Example 3. 2 is a photograph showing the surface of a film-coated compound of Example 4. It is a figure which shows the Raman spectrum of the compound with a film of Example 1,5,6. It is a figure which shows the Raman spectrum of the compound with a film of Example 1,3,4. It is a figure which shows the relationship between the analysis result of the Raman spectrum and hydrogen storage amount in the compound with a film of Examples 1-5. It is a figure which shows the relationship between the analysis result of the Raman spectrum and hydrogen storage amount in the compound with a film of Examples 1-5. It is a figure which shows the hydrogen storage amount in Examples 1-4 and Comparative Example 1. FIG.

FIG. 1 is a cross-sectional view showing a coated compound 1 according to one embodiment of the present invention. The coated compound 1 includes a main body 12 and a carbon coating 13. The main body 12 is substantially formed of a calcium aluminate compound. The carbon coating 13 is a thin film formed substantially of carbon and covers the main body 12. Specifically, the carbon coating 13 covers the outer surface of the main body 12. The thickness of the carbon coating 13 is, for example, not less than 2 nm (nanometers) and not more than 1000 nm. The film-coated compound 1 is used as, for example, a hydrogen occlusion body that occludes hydrogen molecules (H ₂ ) in the main body 12 and the carbon coating 13.

The calcium aluminate compound of the main body 12 includes a void structure, for example. The void structure is a crystal structure having a plurality of voids (also referred to as cages) that can take in ions, atoms, molecules, or electrons. In the void structure, the plurality of voids are connected, for example, three-dimensionally. The void structure included in the main body 12 is, for example, mayenite. Mayenite is a compound having a crystal structure in which voids having a diameter of about 0.4 nm are three-dimensionally connected (that is, a mayenite type crystal structure), and is also called a mayenite type compound. The mayenite is a compound mainly containing Ca ₁₂ Al ₁₄ O ₃₃ (also expressed as 12CaO · 7Al ₂ O ₃ ). In other words, mayenite has Ca ₁₂ Al ₁₄ O ₃₃ as a representative composition. The molar ratio of calcium (Ca) to aluminum (Al) in the mayenite is preferably 13:12 to 11:16. In the mayenite, some of the calcium atoms and aluminum atoms may be substituted with other atoms. Further, some or all of the free oxygen ions in the void may be substituted with other anions.

Next, an example of a method for producing the coated compound 1 will be described with reference to FIG. In the manufacturing method, first, a compound raw material that is a raw material of the calcium aluminate compound is prepared (step S11). In this production example, the compound raw material and the calcium aluminate compound are cataite (Ca ₃ Al ₂ (OH) ₁₂ ) and mayenite. In step S11, for example, calcium aluminate and hydrogen are generated by stirring aluminum powder and calcium hydroxide (Ca (OH) ₂ ) in an aqueous medium. The stirring is performed, for example, until hydrogen generation stops. Calcium aluminate precipitates in water. The cataite is obtained by filtering the calcium aluminate, which is a precipitate, and drying (ie, removing water).

  The above-mentioned aqueous medium is preferably ion-exchanged water. Moreover, the weight ratio of the aluminum powder to be mixed and calcium hydroxide is, for example, 2: 1 to 3: 1. The weight of the aqueous medium added to the mixture of aluminum powder and calcium hydroxide is, for example, 10 times or less with respect to the weight of the mixture. There are no particular limitations on the temperature conditions, pressure conditions, atmospheric conditions, and the like during the above-described stirring treatment. The stirring process is performed, for example, at normal temperature, normal pressure, and an air atmosphere. Further, the temperature condition, pressure condition, atmospheric condition and the like in the drying treatment of the precipitate collected by filtration are not particularly limited. The drying process is performed, for example, at 70 ° C., normal pressure, and air atmosphere. The drying time may be appropriately determined.

  When step S11 ends, the aqueous medium, the film raw material containing carbon, and the above-described compound raw material are mixed, and the mixture is stirred. Then, the mixture is dried to remove moisture, thereby generating a raw material in which the film raw material and the compound raw material are mixed (step S12). The aqueous medium is preferably ion exchange water. There are no particular limitations on the temperature conditions, pressure conditions, atmospheric conditions, and the like during the drying treatment of the mixture in step S12. The drying process is performed, for example, at 70 ° C., normal pressure, and air atmosphere. The drying time may be appropriately determined.

  In this production example, the coating material preferably contains a saccharide. The coating material preferably contains a hydrocarbon, and the hydrocarbon includes two or more carbon atoms (C), two or more hydroxyl groups (OH groups), and two or more carbon-oxygen bonds (CO Preferably). Examples of the hydrocarbon satisfying the condition include sugars, PEG (polyethylene glycol), citric acid, EG (ethylene glycol), and polyol. More preferably, the coating material contains a saccharide that is a hydrocarbon that satisfies the above-described conditions. In this production example, the coating material is, for example, sucrose, fructose or glucose.

  The ratio of the coating material in the raw materials described above (that is, the ratio of the number of moles of the coating material to the total number of moles of the coating material and the compound material, hereinafter also referred to as “coating material ratio”) is preferably 0.5. It is more than mol% and less than 70 mol%, More preferably, it is more than 10 mol% and less than 70 mol%. The above-mentioned raw materials may contain substances other than the coating material and the compound raw material.

  When step S12 ends, the above-described raw materials are heated and fired under an inert gas atmosphere (that is, an inert gas atmosphere). Thereby, as shown in FIG. 1, the compound 1 with a film | membrane provided with the main-body part 12 and the carbon film 13 is produced | generated (step S13). There are no particular limitations on the pressure conditions during the heat treatment (ie, the firing treatment) of the raw material in step S13. The pressure condition during the heat treatment may be any of a normal pressure atmosphere, a reduced pressure atmosphere lower than atmospheric pressure, and a pressurized atmosphere higher than atmospheric pressure.

The heating temperature in step S13 is preferably 700 ° C. or higher and 1400 ° C. or lower, and more preferably 1100 ° C. or higher and 1250 ° C. or lower. The inert gas atmosphere in step S13 is formed by at least one kind of gas among hydrogen gas, nitrogen (N ₂ ) gas, helium (He) gas, and argon (Ar) gas, for example. In this production example, the inert gas atmosphere in step S13 is a hydrogen-containing gas atmosphere. For this reason, the compound 1 with a film | membrane in which the hydrogen molecule was occluded by the main-body part 12 and the carbon film 13 is produced | generated by step S13. The volume ratio of hydrogen in the hydrogen-containing gas atmosphere is, for example, 5% by volume or more and 100% by volume or less.

  Below, the several Examples 1-6 of the compound 1 with a film manufactured with the above-mentioned manufacturing method are demonstrated. Moreover, the comparative example 1 for comparing with Examples 1-6 is also demonstrated. FIG. 3 is a diagram showing production conditions and hydrogen storage amounts in Examples 1 to 6 and Comparative Example 1.

  In Example 1, in Step S11, in a separable flask which is a reactor having a volume of 1 L (liter), 100 mL (milliliter) of ion-exchanged water, 1.5 g of aluminum powder (# 150 manufactured by Minalco), 4.5 g of calcium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added and the whole was stirred. Then, after confirming the completion | finish of the production | generation of hydrogen gas in a reactor (namely, completion | finish of a foaming phenomenon) visually, the reaction liquid in a reactor was filtered. Then, the solid content collected by filtration was heated at 70 ° C. in an air atmosphere (that is, in an air atmosphere at normal pressure) to perform a drying treatment. The cataite was acquired by performing the said drying process over 2 hours.

  Next, in Step S12, 20 mL of ion-exchanged water, 2 g of katoite, and sucrose having a coating raw material ratio of 2 mol% were mixed, and the mixture was stirred. And the said mixture was heated at 70 degreeC by air | atmosphere atmosphere, the drying process was performed, and the raw material was produced | generated. After the production of the raw material, in step S13, the raw material is heated and calcined at 1250 ° C. for 2 hours in a hydrogen atmosphere (that is, in a hydrogen-containing gas atmosphere in which the volume ratio of hydrogen is about 100% by volume). By doing this, the compound 1 with a film | membrane which occluded the hydrogen molecule was produced | generated. 4 is a photograph showing a cross section of the coated compound 1 produced in Example 1. FIG. As shown in FIG. 4, in the coated compound 1, the surface of the main body portion 12, which is mayenite produced by firing katoite, is covered with a carbon coating 13 formed of carbon.

  Thereafter, hydrogen molecules were released from the coated compound 1, and the hydrogen storage amount of the coated compound 1 was measured. The coated compound 1 does not release the occluded hydrogen molecules at room temperature and normal pressure (specifically, at atmospheric pressure around 25 ° C.). In order to efficiently release hydrogen molecules from the coated compound 1, it is necessary to heat to 40 ° C. or higher. Although there is no restriction | limiting in particular about the upper limit of the heating temperature of the compound 1 with a film, For example, it is 90 degrees C or less. That is, the heating temperature of the coated compound 1 is preferably 40 ° C. or higher and 90 ° C. or lower. More preferably, the heating temperature of the coated compound 1 is 40 ° C. or higher and 80 ° C. or lower, and more preferably 60 ° C. or higher and 70 ° C. or lower. The coating compound 1 is heated, for example, by bringing a heating medium into direct contact or indirect contact with the coating compound 1. As the heat medium, for example, water, air, or an inert gas can be used.

  FIG. 5 is a diagram showing the configuration of the measuring device 8 used for measuring the hydrogen storage amount of the coated compound 1. The measuring device 8 includes a reactor 81, a dehumidifier 82 filled with a dehumidifying agent (for example, silica gel), and a gas chromatography 83. In the measurement of the hydrogen storage amount, 0.045 g of the coated compound 1 and 1 mL of water are put into a reactor 81 having a capacity of 20 mL and heated to 60 ° C. by a heater. The hydrogen-containing gas flowing out of the reactor 81 passes through the dehumidifier 82 to remove moisture and become hydrogen gas. The hydrogen gas is guided to the gas chromatography 83, and the amount of hydrogen gas generated from the coated compound 1 is measured by the gas chromatography 83. And from the measured value of the gas chromatography 83, the hydrogen occlusion amount of the compound 1 with a film is calculated | required. The amount of hydrogen occluded in the coated compound 1 in Example 1 was 9 mL / g. The gas chromatography 83 identified that the gas was hydrogen gas. As the gas chromatography 83, a TCD (Thermal Conductivity Detector) gas chromatography (GC-8A manufactured by Shimadzu Corporation) was used.

  In Examples 2-6, except that the coating material ratio or the type of coating material is changed in Step S12, the coated compound 1 is produced in the same procedure as in Example 1, and the hydrogen storage amount is measured by the measuring device 8. Measured. In Example 2, the coating material and the coating material ratio in Step S12 were sucrose and 5 mol%, and the hydrogen storage amount was 11 mL / g. In Example 3, the coating material and the coating material ratio in Step S12 were sucrose and 10 mol%, and the hydrogen storage amount was 12 mL / g. FIG. 6 is a photograph showing the surface of the coated compound 1 produced in Example 3 (that is, the carbon coating 13). In the example shown in FIG. 6, the carbon coating 13 includes carbon fibers.

  In Example 4, the coating material and the coating material ratio in Step S12 were sucrose and 50 mol%, and the hydrogen storage amount was 14 mL / g. FIG. 7 is a photograph showing the surface of the coated compound 1 produced in Example 4 (that is, the carbon coating 13). In the example shown in FIG. 7, the carbon coating 13 includes carbon fibers and carbon nanotubes.

  In Example 5, the coating material and the coating material ratio in Step S12 were fructose and 2 mol%, and the hydrogen storage amount was 10 mL / g. In Example 6, the coating material and the coating material ratio in Step S12 were glucose and 2 mol%, and the hydrogen storage amount was 7 mL / g.

  8, FIG. 9, FIG. 10 and FIG. 11 are diagrams showing the results of Raman spectroscopic analysis of the coated compound 1 produced in Examples 1-6. Raman spectroscopic analysis was performed using “NRS-3100” manufactured by JASCO Corporation under the conditions of an excitation wavelength of 532 nm, an exposure time of 30 seconds, an integration count of 2 times, an objective lens 100X, and a laser power of about 1 mW. The analysis results of the respective examples shown in FIGS. 8, 9, 10 and 11 are the average values of the measured values obtained by measuring at the five measurement points in the coated compound 1 of each example. .

  FIG. 8 is a graph showing the Raman spectrum of coated compound 1 of Examples 1, 5, and 6 (sucrose 2 mol%, fructose 2 mol%, glucose 2 mol%). FIG. 9 is a diagram showing the Raman spectrum of the coated compound 1 of Examples 1, 3, 4 (sucrose 2 mol%, 10 mol%, 50 mol%). 8 and 9, the horizontal axis indicates the Raman shift, and the vertical axis indicates the Raman intensity (that is, the scattering intensity). A line 71 in FIG. 8 shows the spectrum of Example 6, a line 72 shows the spectrum of Example 1, and a line 73 shows the spectrum of Example 5. A line 74 in FIG. 9 shows the spectrum of Example 1, a line 75 shows the spectrum of Example 3, and a line 76 shows the spectrum of Example 4.

  In FIG. 9, the peak on the right side of the line 75 and the line 76 (that is, the peak of the G band) is positioned on the left side (that is, the side where the Raman shift is smaller) than the peak on the right side of the line 74. Further, the shape near the peak on the right side of the line 75 and the line 76 is deformed compared to the shape near the peak on the right side of the line 74, and the smoothness is reduced. Thereby, in Examples 3 and 4 corresponding to lines 75 and 76, it turns out that carbon coat 13 contains carbon fiber and / or carbon nanotube. Although not shown in the examples, it is confirmed that the carbon coating 13 includes carbon fibers and carbon nanotubes even when sucrose is used as the coating material and the coating material ratio is 70 mol%.

  FIG. 10 shows the relationship between the results of Raman spectrum analysis of Example 1-5 (sucrose 2 mol%, 5 mol%, 10 mol%, 50 mol%, fructose 2 mol%) and the amount of hydrogen occlusion in the coated compound 1. FIG. The horizontal axis in FIG. 10 indicates the Raman shift of the peak position of the G band, and the vertical axis indicates the hydrogen storage amount. In FIG. 10, the hydrogen storage amount of the coated compound 1 tends to increase as the Raman shift of the peak position of the G band decreases.

  FIG. 11: is another figure which shows the relationship between the analysis result of the Raman spectrum and hydrogen storage amount in the compound 1 with a film of Examples 1-5. The horizontal axis in FIG. 11 indicates D / G, and the vertical axis indicates the hydrogen storage amount. The D / G is obtained by dividing the peak value of the D band of the Raman spectrum by the peak value of the G band, and is also referred to as a peak intensity ratio. This means that the ratio of carbon nanofibers and / or carbon nanotubes in the carbon coating 13 increases as D / G approaches 1, and the hydrogen storage amount of the carbon coating 13 increases as the ratio increases. I understand that.

  The coated compound 1 after releasing hydrogen in Examples 1 to 6 can occlude hydrogen molecules again, for example, by firing in a hydrogen-containing gas atmosphere. The heating temperature at the time of baking is, for example, 400 ° C. or more and 1350 ° C. or less.

  In Comparative Example 1, mayenite was generated in the same procedure as in Example 1 except that no coating material was added in Step S12, and the hydrogen storage amount was measured by the measuring device 8. There is no carbon coating on the surface of the produced mayenite. In Comparative Example 1, the hydrogen storage amount was 3 mL / g.

  FIG. 12 is a diagram showing the hydrogen storage amounts in Examples 1 to 4 and Comparative Example 1. The horizontal axis in FIG. 12 indicates the coating material ratio, and the vertical axis indicates the hydrogen storage amount. In the example shown in FIG. 12, the hydrogen storage amount increases as the coating material ratio increases.

  As described above, the coated compound 1 includes the main body portion 12 formed of the calcium aluminate compound and the carbon film 13 that covers the main body portion 12. The coated compound 1 can be used as a hydrogen storage material that stores hydrogen molecules in the main body 12 and the carbon coating 13. In this case, as shown in Examples 1 to 6 described above, the hydrogen storage amount can be increased as compared with Comparative Example 1 that does not have a carbon coating.

As described above, the main body portion 12 includes a void structure having a plurality of voids. The plurality of voids can take in ions, atoms, molecules or electrons. Thereby, the hydrogen occlusion amount of the coated compound 1 can be further increased. The void structure is mayenite containing Ca ₁₂ Al ₁₄ O ₃₃ . For example, mayenite can be produced at a relatively low cost by heating katoite formed of an inexpensive material such as aluminum powder and calcium hydroxide. Therefore, the manufacturing cost of the compound 1 with a film can be reduced.

  In Examples 3 and 4 described above, the carbon coating 13 of the coated compound 1 includes carbon fibers or carbon nanotubes. In the coated compound 1, hydrogen molecules can also be stored in carbon fibers or carbon nanotubes, so that the hydrogen storage amount of the coated compound 1 can be further increased.

  The manufacturing method of the above-mentioned compound 1 with a film is equipped with the process (step S12) which mixes the compound raw material which is a raw material of a calcium aluminate compound, and the film raw material containing carbon, and produces | generates a raw material. Moreover, the said manufacturing method is equipped with the process (step S13) which produces | generates the compound 1 with a film by heating the said raw material in inert gas atmosphere. According to the manufacturing method, the coated compound 1 including the main body portion 12 formed of the calcium aluminate compound and the carbon coating 13 covering the main body portion 12 can be easily manufactured.

  Moreover, in the manufacturing method of the compound 1 with a film, the inert gas atmosphere in step S13 is a hydrogen-containing gas atmosphere, and the compound 1 with a film | membrane in which the hydrogen molecule was occluded by the main-body part 12 and the carbon film 13 is produced | generated by step S13. Is done. Thus, the production | generation of the compound 1 with a film | membrane with which the hydrogen molecule was occluded can be simplified by performing simultaneously the production | generation of the compound 1 with a film | membrane, and occlusion of the hydrogen molecule to the compound 1 with a film | membrane. In addition, after producing | generating the compound 1 with a film | membrane, occlusion of the hydrogen molecule to the compound 1 with a film | membrane may be performed by baking etc. in hydrogen-containing gas atmosphere.

  In the manufacturing method of the compound 1 with a film, the heating temperature in the process (step S13) which heats the above-mentioned raw material is 700 degreeC or more and 1400 degreeC or less. Thereby, the specific surface area of the main-body part 12 can be enlarged. As a result, the surface of the main body portion 12 can be brought into a state more suitable for hydrogen adsorption, and the hydrogen storage amount of the coated compound 1 can be further increased.

  Moreover, in the manufacturing method of the compound 1 with a film, the ratio of the film raw material in the raw material produced | generated in step S12 (namely, film raw material ratio) is 0.5 mol% or more and 70 mol% or less. Thereby, the carbon film 13 can be suitably generated on the surface of the main body 12. Furthermore, when the ratio of the coating material in the raw material is 10 mol% or more and 70 mol% or less, carbon fibers and / or carbon nanotubes can be generated in the carbon coating 13 (see Example 3 and Example 4 above). ). When the carbon film 13 contains carbon fibers or carbon nanotubes, the hydrogen storage amount of the coated compound 1 can be further increased as described above.

  In the manufacturing method of the above-mentioned compound 1 with a film, Preferably, a film raw material contains saccharides. Thereby, the carbon film 13 can be formed suitably.

  In addition, the coating material contains a hydrocarbon, and the hydrocarbon preferably contains two or more carbon atoms, two or more hydroxyl groups, and two or more carbon-oxygen bonds. Also in this case, the carbon coating 13 can be suitably formed.

  Various changes can be made in the above-described methods for producing the coated compound 1 and the coated compound 1.

  For example, the main body portion 12 of the coated compound 1 may contain other substances as long as it is substantially formed of a calcium aluminate compound. The carbon coating 13 may contain other substances as long as it is substantially made of carbon.

The void structure contained in the calcium aluminate compound of the main body 12 does not necessarily need to be mayenite. For example, the void structure includes [HN (CH ₂ CH ₂ ) 3 NH) K _1.35 [V ₅ O ₉ (PO ₄ ) ₂ ] · xH ₂ O, or (CS ₃ [V ₅ O ₉ (PO ₄ ) ₂ ] · xH ₂ O. The calcium aluminate compound of the main body 12 may not include a void structure, for example, the calcium aluminate compound of the main body 12 is Or Katoite.

  In the said manufacturing method of the compound 1 with a film, the ratio of the film raw material in the raw material produced | generated by step S12 may be changed from the above-mentioned example. Further, the coating material is not limited to sugars and the above-mentioned hydrocarbons, and may be variously changed. Further, when the carbon coating 13 includes carbon fibers and / or carbon nanotubes, the carbon fibers and / or carbon nanotubes may be generated by a method other than the above-described control of the coating material ratio. The heating temperature in step S13 may be changed from the above example. Furthermore, the manufacturing method of the compound 1 with a film is not limited to the above example, and the compound 1 with a film may be manufactured by various other methods.

  The coated compound 1 may be used for various purposes other than the hydrogen storage material.

  The configurations in the above-described embodiments and modifications may be combined as appropriate as long as they do not contradict each other.

1 Compound with Film 12 Body Part 13 Carbon Film S11-S13 Step

Claims (15)

A coated compound comprising:
A main body formed of a calcium aluminate compound;
A carbon coating covering the main body,
A film-coated compound comprising: The coated compound according to claim 1,
The film-coated compound, wherein the main body portion includes a void structure having a plurality of voids capable of taking in ions, atoms, molecules, or electrons. A coated compound according to claim 2,
The compound with a coating film, wherein the void structure is mayenite containing Ca ₁₂ Al ₁₄ O ₃₃ . A coated compound according to any one of claims 1 to 3,
A compound with a coating, wherein the carbon coating contains carbon fiber or carbon nanotube. A coated compound according to any one of claims 1 to 4,
A film-coated compound, which is a hydrogen storage material that stores hydrogen molecules in the main body and the carbon film. A method for producing a coated compound comprising:
a) a step of mixing a compound raw material that is a raw material of the calcium aluminate compound and a film raw material containing carbon to produce a raw material;
b) generating the film-coated compound comprising a main body formed of a calcium aluminate compound and a carbon film covering the main body by heating the raw material in an inert gas atmosphere;
The manufacturing method of the compound with a film characterized by comprising. It is a manufacturing method of the compound with a film of Claim 6, Comprising:
The method for producing a coated compound, wherein the heating temperature in the step b) is 700 ° C. or higher and 1400 ° C. or lower. A method for producing a coated compound according to claim 6 or 7,
A method for producing a film-coated compound, wherein a ratio of the film material in the raw material is 0.5 mol% or more and 70 mol% or less. A method for producing a coated compound according to claim 8,
The method for producing a compound with a coating film, wherein a ratio of the coating material in the raw material is 10 mol% or more and 70 mol% or less. It is a manufacturing method of the compound with a film in any one of Claims 6 thru | or 9, Comprising:
The method for producing a film-coated compound, wherein the film material contains a saccharide. A method for producing a film-coated compound according to any one of claims 6 to 10,
The method for producing a coated compound, wherein the coating material contains a hydrocarbon, and the hydrocarbon contains two or more carbon atoms, two or more OH groups, and two or more CO bonds. It is a manufacturing method of the compound with a film in any one of Claims 6 thru | or 11, Comprising:
The method for producing a coated compound, wherein the main body portion includes a void structure having a plurality of voids capable of taking in ions, atoms, molecules or electrons. A method for producing a coated compound according to claim 12,
The method for producing a film-coated compound, wherein the void structure is mayenite containing Ca ₁₂ Al ₁₄ O ₃₃ . A method for producing a film-coated compound according to any one of claims 6 to 13,
The method for producing a coated compound, wherein the carbon coating contains carbon fiber or carbon nanotube. A method for producing a coated compound according to any one of claims 6 to 14,
The inert gas atmosphere in the step b) is a hydrogen-containing gas atmosphere;
By the step b), the film-coated compound in which hydrogen molecules are occluded in the main body and the carbon film is produced.