TWI458675B - Hydrogen storage material and its manufacturing method - Google Patents

Description

Hydrogen storage material and method of manufacturing same

The present invention relates to a gas storage material and a method of manufacturing the same, and more particularly to a hydrogen storage material for hydrogen storage and a method of manufacturing the same.

The by-product of hydrogen energy use is mainly water, so it has the advantages of environmental protection and low pollution. It is considered as one of the secondary energy sources of energy safety, reducing greenhouse gas emissions, reducing air pollution and replacing fossil energy. Therefore, the development and application of hydrogen energy has attracted great attention in recent years. However, if hydrogen energy is convenient to use, one of the obstacles to be overcome is the storage technology of hydrogen energy, that is, hydrogen storage technology.

Hydrogen storage methods can generally be divided into two types, one is the hydrogen storage method of the container, that is, the high pressure is used to press the hydrogen into the container (such as a steel bottle), or the hydrogen is liquefied and stored in the container, and the high pressure or liquefaction The hydrogen storage method is not only expensive to handle, but also the container is relatively bulky, and the safety concerns, such as the problem of gas leakage, are also large.

The other is to use hydrogen storage materials to store hydrogen by chemical bonding. The hydrogen storage method of hydrogen storage materials has the characteristics of safe, high-density storage, small volume and light weight. Therefore, the development of hydrogen storage materials is also in recent years. One of the research and development directions of various related research teams, and the application of nano carbon materials has attracted attention from all walks of life due to its low operating pressure, light weight of materials and diversified container shape.

A device for storing hydrogen gas as disclosed in U.S. Patent Application Serial No. 12/297,259, wherein the adsorbent used is selected from the group consisting of nanocarbon materials. Buckminster Fullerenes; and, as in Taiwan Patent Application No. 099102025, is a hydrogen storage material that absorbs hydrogen by Kubas adsorption, by using a scaffold material (Example 2 discloses the use of nanocarbon) The tube - also one of the fullerene structures) is chemically stable with the strong bond strength between the transition metal, so that the metal material still has high hydrogen absorption capacity at room temperature, and the hydrogen absorption/dehydrogenation effect is repeated Under the circumstance, the structure can be kept stable and not deformed, so that the complex of the invention can safely and reversibly store a large amount of hydrogen.

In general, there are two main ways to store hydrogen by using the fullerene structure in nano-carbon materials. One is to coat the surface of fullerene with an active metal to attach hydrogen atoms, such as Sun et al. at J. Am. Studies published by Chem. Soc., Vol 128, pp. 9741 (2006) indicate that uniform plating of lithium metal on the surface of carbon 60 can adsorb up to 120 hydrogen atoms, increasing the hydrogen storage capacity to 9 wt%; The spherical internal space composed of fullerenes is used to store hydrogen atoms or hydrogen molecules. Similarly, carbon 60 is used as an example. It is also pointed out that the internal space can reach 7.5 wt% of hydrogen storage, and how to hydrogen or hydrogen. Molecular insertion, Murata et al., J. Am. Chem. Soc., Vol. 125, pp. 7152-7153 (2003), mentions the chemical reaction to open pores of sufficient size on the spherical fullerene structure to allow hydrogen Molecules are stored inside the fullerene structure via pores.

In summary, one of the goals of hydrogen storage technology is to increase the hydrogen storage capacity per unit volume and the cost of hydrogen storage. Therefore, the inventors used this as a research direction, and specifically have a unique chemical and physical properties for fullerene structures. The potential of the application has developed a novel hydrogen storage material.

Accordingly, it is an object of the present invention to provide a hydrogen storage material which can increase the amount of hydrogen storage.

Further, another object of the present invention is to provide a method for producing a hydrogen storage material which has an increased hydrogen storage amount and a low production cost.

Thus, the hydrogen storage material of the present invention comprises an inner casing and an outer casing surrounding the inner casing.

The inner casing is hollow spherical and is composed of a fullerene structure having at least one first opening through which hydrogen atoms can pass.

The outer casing has a shell body mainly formed of a fullerene structure and surrounding the outer casing, and an active metal plating on the outer surface of the inner shell opposite to the inner shell to adsorb hydrogen atoms a metal film body, and at least one second opening formed in the shell body to allow hydrogen atoms to enter the outer casing from the outside, wherein the carbon number of the fullerene structure constituting the inner casing and the shell body is not An even number less than 20.

Furthermore, the method for producing a hydrogen storage material of the present invention comprises the steps of: (A) producing a spherical and multi-layered fullerene structure comprising an even number of carbon atoms and having a carbon number of Not less than 20 inner casings, and a casing body composed of an even number of carbon atoms and having a carbon number of not less than 60, and the inner casing is completely covered inside the casing body; (B) Applying stress during the fabrication of the multilayer fullerene structure to form at least one first opening through which the hydrogen atoms pass through the fullerene structure of the inner shell, and on the fullerene structure of the shell body Forming at least one second opening through which hydrogen atoms pass; and (C) An active metal film body for adsorbing hydrogen atoms is plated on an outer surface of the case body having the second opening opposite to the inner case.

The above and other technical contents, features and advantages of the present invention will be apparent from the following detailed description of the preferred embodiments.

Referring to FIG. 1, a preferred embodiment of the hydrogen storage material of the present invention comprises an inner hollow shell 2 formed of a fullerenes structure, and an inner casing 2 surrounded by the inner casing 2; The outer casing 3 is formed into a double-layer fullerene structure.

The inner casing 2 has at least one first opening 21 through which the hydrogen atoms 100 can pass, whereby the first opening 21 allows the hydrogen atoms 100 to enter the space in the inner casing 2, and the inner casing The fullerene structure of the shell 2 is composed of more than 20 even carbon atoms, including carbon 20, carbon 60, carbon 76, carbon 78, carbon 80, carbon 82, carbon 84, carbon 90, carbon 96, carbon 100, Carbon 360, carbon 540 and carbon 560, in addition to the pure carbon component, the fullerene structure of the inner shell 2 may also be a modified fullerene compound, such as a hetero-fluorene fullerene (Silicon-substituted) Fullerenes), Nitrogen-substituted fullerenes, Boron-substituted fullerenes, Phosphorous-substituted fullerenes, Heterogeneous Titanium Carbon Fullerene (Titanium) -substituted fullerenes), and Lithium-substituted fullerenes.

The outer casing 3 has a fullerene structure and is formed into a hollow spherical shape. a shell body 31, at least one second opening 32 formed in the shell body 31 and capable of passing hydrogen atoms 100, and an active metal film body 33 composed of an active metal element 331 capable of adsorbing hydrogen atoms 100; The second opening 32 provides a path for the hydrogen atoms 100 to enter the interior space of the hydrogen storage material of the present invention from the outside.

The shell body 31 has an outer surface 311 opposite to the inner casing 2, and the active metal film body 33 is evenly plated on the outer surface 311, and the active metal film body 33 can be used by the outer surface 311. The active metal element 331 reacts with hydrogen to dissociate hydrogen into a single hydrogen atom 100. The hydrogen atoms 100 can be adsorbed to form hydrogen storage in combination with the active metal element 331 constituting the active metal film body 33. Passing through the specially formed second opening 32 and the first opening 21 into the space in the inner casing 2, and then tending to be stored in a molecular form and stored therein; supplementaryly, the generally usable activity The metal element 331 includes lithium (Li), platinum (Pt), calcium (Ca), palladium (Pd), strontium (Sc), and titanium (Ti).

In addition, it can be understood that the carbon number of the fullerene structure of the shell body 31 must be higher than the carbon number of the fullerene structure of the inner shell 2 to form a larger spherical shell to surround the inner shell. The body 2 is internal, and the fullerene structure of the shell body 31 has a composition similar to that of the inner shell 2, including carbon 60, carbon 76, carbon 78, carbon 80, carbon 82, carbon 84, carbon 90, carbon 96. , carbon 100, carbon 360, carbon 540 and carbon 560, in addition to the pure carbon composition, the fullerene structure of the shell body 31 may also be a modified fullerene compound, such as a heterogeneous fluorene fullerene, Heterogenous nitrogen-carbon fullerenes, heterogeneous boron-carbon fullerenes, heterogeneous phosphorus-carbon fullerenes, heterogeneous titanium-carbon fullerenes, and heterogeneous lithium-carbon fullerenes.

In the preferred embodiment, the fullerene structure of the inner casing 2 is carbon 60, the fullerene structure of the shell body 31 is carbon 240, and the active metal is plated on the outer surface 311 of the shell body 31. The element 331 is lithium, and the hydrogen atom 100 dissociated by the active metal film body 33 can enter the inner space of the hydrogen storage material of the present invention by the channel path formed by the second opening 32 and the first opening 21 being spaced apart from each other. The active metal element 331 stored in the active metal film body 33 on the outer surface 311 of the shell body 31 further adsorbs more dissociated hydrogen atoms 100, so that the preferred embodiment is only relative to the conventional one. In the case where the metal adsorbs hydrogen or the hydrogen storage inside the buckerball cannot exceed 10% by weight, the amount of hydrogen that can be stored in the preferred embodiment can reach 15 wt% or more, that is, the hydrogen storage material of the present invention utilizes double-layered spherical fullerene. The characteristics of the structure, in addition to the hydrogen storage in the internal space, also have the capacity of surface adsorption hydrogen storage, compared to the conventional nano carbon material hydrogen storage method which can only be stored in the internal space or only surface adsorption, the present invention Hydrogen storage materials can greatly enhance the unit body The hydrogen storage capacity.

In addition, the relative positions of the first opening 21 and the second opening 32 are opposite to each other as shown in FIG. 1 , and may be as shown in FIG. 2 , and the second opening 32 is located at the same. The first opening 21 and the second opening 32 are directly opposite to each other, and the first opening 21 and the second opening 32 are directly opposed to each other through a longitudinal line of the spherical inner casing 21 (not shown); The holes 21 and the second openings 32 are staggered so that the energy barrier of the hydrogen atoms 100 entering the shell body 31 along the channel is small, so that the hydrogen atoms 100 can be easily passed again after entering the second opening 32. The first opening 21 enters the inner casing 2 for storage, so the efficiency of adsorbing the hydrogen atoms 100 is still better. The interval formed by the embodiment and the staggered relative state are higher.

Referring to Fig. 3, the present invention also provides a manufacturing method for manufacturing the above preferred embodiment. Through the description of the manufacturing method, a clearer understanding of the structure and efficacy of the hydrogen storage material of the present invention can be obtained.

First, step 41 is described to fabricate a spheroidal and multi-layered fullerene structure, which in the preferred embodiment is described by a double-layer fullerene structure including the even number of carbons. The inner casing 2 having an atomic composition and having a carbon number of not less than 20, and the shell body 31 composed of an even number of carbon atoms and having a carbon number of not less than 60, and the inner casing 2 is completely coated Inside the shell body 31.

Step 42 is to apply stress during the step 41 to fabricate the double-layer fullerene structure to form at least one first opening of the fullerene structure of the inner casing 2 to pass the hydrogen atom 100. The hole 21 and the second opening 32 through which the hydrogen atom 100 passes are formed on the fullerene structure of the shell body 31.

In more detail, there are generally four methods for manufacturing the double-layer fullerene structure:

The first is to use a laser vaporization to produce a double-layered fullerene when the carbon cluster is treated by a thermal annealing method in a high temperature environment.

The second method is to inject high temperature carbon ions into silver substrates by means of implantation. During the implantation process, the precipitated carbon is an Amorphous structure, and the temperature increases with temperature. When the amount of precipitated carbon reaches a certain level, the amorphous carbon is transformed into a double-rich Leyne.

The third type is a double-layered fullerene (Spherical or polyhedral multishell fullerenes) which is transformed into a spherical or polyhedral multi-shell fullerenes by thermal annealing at 1500 ° C to 2000 ° C.

The fourth is an arc discharge method using a graphite electrode and controlling the helium pressure at 70 mbar to form a spherical or polyhedral double-layer fullerene.

It should be noted that in the process of preparing and growing the above-mentioned double-layered fullerene, if an external force (such as high-energy radiation or mechanical stress) is applied, the energy of the fullerene system will increase, and the energy of this increase will become Shidong. - The driving force behind the formation of Stone-Wales defect.

The Stone-Wells defect means that the surface curvature of the fullerene changes due to the strain energy caused by the application of external energy or stress on the complete fullerene structure composed of the carbon five ring and the carbon six ring. It includes changes in the fullerene structure caused by changes in the bond length and bond angle. That is to say, during the growth of fullerenes, due to the uneven force of the atoms, two adjacent carbon six rings of the four carbon six rings (6-6-6-6) on the intact fullerene structure. The carbon bond is transposed at 90° and produces two carbon five rings and two carbon seven rings (7-5-5-7). The chemical structure changes as shown in the following chemical formula:

The heptagon formed by the carbon seven-ring carbon bond will change the carbon bond length and bond angle of the original carbon five-ring and carbon six-ring, which will increase the interval between carbon atoms. The size of the opening sufficient to pass the hydrogen atom 100, thereby forming the first opening 21 and the second opening 32 in the present invention, and the external energy or stress applied by the control can further control the Shidong- The number of Wells defects.

Compared with the conventional method of opening a fullerene sphere structure, it is conventional to use a molecular reaction such as a chemical reaction to open a carbon-carbon bond and bond other compounds to make the pores larger, so the reaction process is more Complex and cumbersome; another method that does not open holes to implant hydrogen atoms into the internal space by ion bombardment requires higher energy, so the cost of molecular surgery or ion bombardment is not low, and it becomes a fullerene structure. One of the bottlenecks in the practical application of hydrogen storage. However, the present invention utilizes high energy radiation or mechanical stress to form the first opening 21, which is sufficient for the hydrogen atom 100 to pass through the generation of the Stone-Wells defect during the growth of the double-layer fullerene structure. The second opening 32, the opening process of the invention is not only simple and does not require complicated chemical reactions, so the process cost is of course relatively reduced, and the market competitiveness of the fullerene structure hydrogen storage can be improved and improved.

Finally, step 43 is performed, and then the active metal element 331 is formed by plating the active metal element 331 for adsorbing the hydrogen atoms 100 on the outer surface 311 of the inner casing 31 opposite to and away from the inner casing 2, thereby obtaining the present invention. A hydrogen storage material having a double-layer fullerene structure; as described in the preferred embodiment, the active metal film body 33 can adsorb and fix the hydrogen atoms 100 on the outer surface 311 of the shell body 31 without dissipating, so The hydrogen storage material of the invention can be in the spherical interior space While the hydrogen atoms 100 are being stored, the hydrogen atoms 100 are also adsorbed by the active metal element 331 on the outer surface 311 of the shell body 31, thereby increasing the unit hydrogen storage capacity of the conventional single-layer fullerene structure.

In summary, in addition to the internal hydrogen storage space, the hydrogen storage material of the present invention can also store and store hydrogen atoms on the surface, providing a hydrogen storage based on the fullerene structure, but novel and greatly increasing the hydrogen storage capacity per unit volume. The material, and the manufacturing process is simpler and lower in cost, so the object of the present invention can be achieved.

The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent.

100‧‧‧Hydrogen atom

2‧‧‧ inner casing

21‧‧‧First opening

3‧‧‧ Shell

31‧‧‧Shell body

311‧‧‧ outer surface

32‧‧‧Second opening

33‧‧‧Active metal film body

331‧‧‧Active metal elements

41‧‧‧Steps

42‧‧‧Steps

43‧‧‧Steps

1 is a cross-sectional view showing a preferred embodiment of the hydrogen storage material of the present invention; FIG. 2 is a schematic cross-sectional view showing another aspect of the preferred embodiment; and FIG. 3 is a flow chart illustrating the fabrication The fabrication steps of the preferred embodiment.

100‧‧‧Hydrogen atom

2‧‧‧ inner casing

21‧‧‧First opening

3‧‧‧ Shell

31‧‧‧Shell body

311‧‧‧ outer surface

32‧‧‧Second opening

33‧‧‧Active metal film body

331‧‧‧Active metal elements

Claims (12)

A hydrogen storage material comprising: an inner casing formed into a hollow sphere and composed of a fullerene structure, having at least one first opening through which hydrogen atoms can pass; and an outer casing having a structure formed by a fullerene structure a shell body surrounding the inner casing, an active metal film body coated with an active metal on the outer surface of the inner casing opposite to the outer casing, and at least one formed on the shell body The second opening of the outer casing is allowed to pass from the outside, and the first opening and the second opening are staggered and spaced apart, wherein the fullerene structure constituting the inner casing The carbon number is an even number of not less than 20, and the carbon number of the fullerene structure constituting the shell body is an even number of not less than 60. The hydrogen storage material according to claim 1, wherein the fullerene structure constituting the inner casing is selected from the group consisting of carbon 20, carbon 60, carbon 70, carbon 76, carbon 78. , carbon 80, carbon 82, carbon 84, carbon 90, carbon 96, carbon 100, carbon 240, carbon 360, carbon 540, carbon 560, heterogeneous fluorene fullerene, heterogeneous nitrogen-carbon fullerene, heterogeneous boron-carbon fullerene Alkene, heterogeneous phosphorus-carbon fullerene, heterogeneous titanium carbon fullerene, and heterogeneous lithium carbon fullerene. The hydrogen storage material according to claim 1, wherein the fullerene structure constituting the shell body of the outer shell is selected from the group consisting of carbon 60, carbon 70, carbon 76, carbon 78, carbon. 80, carbon 82, carbon 84, carbon 90, carbon 96, carbon 100, carbon 240, carbon 360, carbon 540, carbon 560, heterogeneous fluorene fullerene, heterogeneous nitrogen-carbon fullerenes, heterogeneous boron-carbon fullerenes, Heterophosphorus carbon fullerene, heterogeneous titanium carbon fullerene, and heterogeneous lithium carbon fullerene. The hydrogen storage material according to claim 1, wherein the active metal film body is selected from the group consisting of lithium, platinum, calcium, palladium, rhodium, and titanium. The hydrogen storage material according to claim 1, wherein the first opening is a heptagonal opening formed by a carbon seven-ring carbon bond. The hydrogen storage material according to claim 1, wherein the second opening is a heptagonal opening formed by a carbon seven-ring carbon bond. A method for producing a hydrogen storage material, comprising: (A) fabricating a spheroidal and multi-layered fullerene structure comprising an inner carbon compound having an even number of carbon atoms and having a carbon number of not less than 20 a shell, and a shell body composed of an even number of carbon atoms and having a carbon number of not less than 60, and the inner shell is completely coated inside the shell body; (B) making the multilayer fuller Stress is applied during the structure of the olefin to form at least one first opening through which the hydrogen atoms pass through the fullerene structure of the inner shell and at least one hydrogen atom through the fullerene structure of the shell body And (C) an active metal film body for adsorbing hydrogen atoms is plated on the outer surface of the inner casing having a relatively small distance from the outer surface of the inner casing having the second opening; The first opening and the second opening are staggered and spaced apart. The method for producing a hydrogen storage material according to claim 7, wherein the stress in the step (B) is caused by the application of high-energy radiation and/or mechanical stress to grow the double-layer fullerene structure. The increase in system energy results in the creation of a Stone-Wells defect, forming the first opening and the second opening. The method for manufacturing a hydrogen storage material according to claim 8, wherein the first opening and the second opening formed by using the Stone-Wells defect in the step (B) are made of carbon seven rounds. A heptagonal opening formed by a ring carbon bond. The method for producing a hydrogen storage material according to the seventh aspect of the invention, wherein the material of the inner casing in the step (A) is a group selected from the group consisting of carbon 20, carbon 60, carbon 70, Carbon 76, carbon 78, carbon 80, carbon 82, carbon 84, carbon 90, carbon 96, carbon 100, carbon 240, carbon 360, carbon 540, carbon 560, heterogeneous fluorene fullerene, heterogeneous nitrogen-carbon fullerene, Hetero boron boro richerene, heterogeneous phosphorus carbon fullerene, heterogeneous titanium carbon fullerene, and heterogeneous lithium carbon fullerene. The method for producing a hydrogen storage material according to claim 7, wherein the material of the shell body in the step (A) is a group selected from the group consisting of carbon 60, carbon 70, carbon 76, carbon. 78, carbon 80, carbon 82, carbon 84, carbon 90, carbon 96, carbon 100, carbon 240, carbon 360, carbon 540, carbon 560, heterogeneous fluorene fullerene, heterogeneous nitrogen carbon fullerenes, heterogeneous boron carbon rich A olefin, a heterogeneous phosphorus-carbon fullerene, a heterogeneous titanium carbon fullerene, and a heterogeneous lithium carbon fullerene. According to the method for manufacturing a hydrogen storage material according to claim 7 of the patent application scope, Wherein, the active metal plated on the outer surface of the outer layer fullerene in the step (C) is selected from the group consisting of lithium, platinum, calcium, palladium, rhodium, and titanium.