Patent Application
20250075294
The present disclosure relates to a magnesium-based composite material and a method of forming the same.
Hydrogen energy can be a carbon-free energy for avoiding carbon emission to endanger the climate. More applications depending on the fossil fuels have been replaced with hydrogen energy, for example, the rising population of the hydrogen-powered vehicles. A proper hydrogen carrier, therefore, to store and release the hydrogen has become the main topic of the area. However, a hydrogen carrier and a method of forming the same to include better hydrogenation and dehydrogenation properties, such as high reversible capacity, rate, and so on, are still lacking. Therefore, a material of a better hydrogen carrier and the method of forming the same are highly required.
The present disclosure provides a magnesium-based composite material. The magnesium-based composite material includes a magnesium-based solid solution and an amorphous additive mixed with the magnesium-based solid solution. The magnesium-based solid solution includes magnesium, at least one first catalytic metal selected from the group consisting of aluminum, zinc, zirconium, nickel, titanium, vanadium, chromium, cobalt, iron, copper, molybdenum, niobium, palladium, and yttrium, and at least one first carbon allotrope. The amorphous additive includes at least one second catalytic metal selected from the group consisting of zirconium, nickel, titanium, vanadium, chromium, cobalt, iron, copper, molybdenum, niobium, palladium, and yttrium, and at least one second carbon allotrope.
In some embodiments, a weight percentage of the amorphous additive in the magnesium-based composite material is from 1 wt % to 15 wt %.
In some embodiments, a weight percentage of each one of the at least one first catalytic metal in the magnesium-based solid solution is smaller than or equal to 9 wt %.
In some embodiments, when the at least one first catalytic metal includes aluminum, a weight percentage of aluminum among the at least one first catalytic metal is the largest.
In some embodiments, the at least one first carbon allotrope and the at least one second carbon allotrope are independently selected from the group consisting of graphite, graphene, fullerene, single-walled carbon nanotubes, multi-walled carbon nanotubes, activated carbon, and carbon black.
In some embodiments, a weight percentage of the at least one first carbon allotrope in the magnesium-based solid solution is smaller than or equal to 3 wt %.
In some embodiments, in the amorphous additive, a weight percentage of the at least one second carbon allotrope is larger than a weight percentage of the at least one second catalytic metal.
In some embodiments, an average particle size of the magnesium-based composite material is from 20 μm to 80 μm.
In some embodiments, an average grain size within the magnesium-based solid solution is from 4 μm to 34 μm.
In some embodiments, a maximum reversible hydrogen storage capacity of the magnesium-based composite material is from 6 wt % to 7 wt %.
In some embodiments, a hydrogen absorption rate of the magnesium-based composite material is from 2 wt % per minute to 4 wt % per minute, and a hydrogen desorption rate of the magnesium-based composite material is from 0.25 wt % per minute to 1.25 wt % per minute.
The present disclosure also provides a method of forming magnesium-based composite material. The method includes the following operations. A casting process is performed on magnesium, at least one first catalytic metal, and at least one first carbon allotrope to form a first magnesium-based solid solution, in which the at least one first catalytic metal is selected from the group consisting of aluminum, zinc, zirconium, nickel, titanium, vanadium, chromium, cobalt, iron, copper, molybdenum, niobium, palladium, and yttrium. A severe plastic deformation process is performed on the first magnesium-based solid solution to form a second magnesium-based solid solution. A high energy ball milling process is performed on the second magnesium-based solid solution and an amorphous additive to form the magnesium-based composite material, in which the amorphous additive includes at least one second catalytic metal and at least one second carbon allotrope, and the at least one second catalytic metal is selected from the group consisting of zirconium, nickel, titanium, vanadium, chromium, cobalt, iron, copper, molybdenum, niobium, palladium, and yttrium.
In some embodiments, the casting process includes heating magnesium, the at least one first catalytic metal, and the at least one first carbon allotrope at a temperature from 700° C. to 800° C.
In some embodiments, the method further includes performing a homogenization process after the casting process and before the severe plastic deformation process, in which the homogenization process includes heating the first magnesium-based solid solution at a temperature from 350° C. to 450° C.
In some embodiments, an average first grain size within the first magnesium-based solid solution is larger than an average second grain size within the second magnesium-based solid solution, and the average second grain size is from 4 μm to 34 μm.
In some embodiments, the severe plastic deformation process includes pressing the first magnesium-based solid solution to pass through an angled channel, and the angled channel has a bent angle from 90° to 120°.
In some embodiments, the severe plastic deformation process includes repeatedly pressing the first magnesium-based solid solution to pass through an angled channel, and the first magnesium-based solid solution is substantially not rotated, rotated with 90°, or rotated with 180° along a long axis of the first magnesium-based solid solution between two contiguous passes.
In some embodiments, the severe plastic deformation process includes repeatedly pressing the first magnesium-based solid solution to pass through an angled channel, and a repeat number is from 4 times to 8 times.
In some embodiments, the high energy ball milling process is performed by a high energy ball milling machine, and a rotating speed of the high energy ball milling machine is from 200 rpm to 500 rpm.
In some embodiments, an average particle size of the magnesium-based composite material is from 20 μm to 80 μm.
The present disclosure can be more fully understood by reading the following detailed description of the embodiments and the reference of the following figures.
To make the description of the present disclosure more detailed and complete, the following provides an illustrative description of the aspects of the implementation and the specific embodiments of the present disclosure. The disclosure is not to limit the implementation to only one form. The embodiments of the present disclosure may be combined or substituted with each other for a beneficial circumstance, and other embodiments may be appended without further explanation.
Spatially relative terms, such as above and below, etc., may be used in the present disclosure to describe the relation of one element or feature to another element or feature in the figures. The spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, the device may be oriented otherwise, e.g., 90 degrees or other orientations. Therefore, the spatially relative terms in the present disclosure can be interpreted correspondingly. In addition, in the present disclosure, unless otherwise stated, the same or similar reference numbers in different figures refer to the same or similar elements formed from the same or similar materials by the same or similar methods.
The terms “about”, “around”, “approximately”, “basically”, “substantially”, and so on used in the present disclosure include the stated values, characteristics, and the range of deviations from that values and characteristics that can be understood by one skilled in the art. For example, taking into account the errors of values and characteristics, the foregoing terms may include the values within one or more standard deviations (e.g., ±5%, +10%, 15%, ±20%, or +30%) of the stated value, or include the deviations from the practical operations of the stated characteristics (e.g., the “substantially parallel” may be close to parallel in practice rather than an ideally perfect parallel). In addition, the acceptable range of deviations may be selected according to the measurements or other properties, and not only one kind of deviation may be applicable to all values and characteristics.
The present disclosure provides a magnesium-based composite material. The magnesium-based composite material includes a magnesium-based solid solution and an amorphous additive mixed with the magnesium-based solid solution. The magnesium-based solid solution includes magnesium, at least one first catalytic metal selected from the group consisting of aluminum, zinc, zirconium, nickel, titanium, vanadium, chromium, cobalt, iron, copper, molybdenum, niobium, palladium, and yttrium, and at least one first carbon allotrope. The amorphous additive includes at least one second catalytic metal selected from the group consisting of zirconium, nickel, titanium, vanadium, chromium, cobalt, iron, copper, molybdenum, niobium, palladium, and yttrium, and at least one second carbon allotrope. The magnesium-based composite material of the present disclosure can be a hydrogen carrier and has better hydrogenation and dehydrogenation properties including a higher reversible hydrogen storage capacity (e.g., 6 wt % to 7 wt %), a higher hydrogen absorption rate (e.g., 2 wt % per minute to 4 wt % per minute), a higher hydrogen desorption rate (e.g., 0.25 wt % per minute to 1.25 wt % per minute), a lower working temperature (e.g., 300° C. to 400° C.), and so on. The magnesium-based composite material of the present disclosure is described in detail in the following embodiments.
The magnesium-based composite material of the present disclosure is a composite material that includes the magnesium-based solid solution and the amorphous additive. The magnesium-based solid solution and the amorphous additive have distinct characteristics. For example, the magnesium-based solid solution is a solid solution that includes a homogeneous mixture of magnesium, the at least one first catalytic metal, and the at least one first carbon allotrope in the solid state, and the magnesium-based solid solution has a crystal structure. On the other hand, the amorphous additive is amorphous, non-crystalline, and disordered in the atomic-scale structure. The magnesium-based composite material including the magnesium-based solid solution and the amorphous additive mixed together improves the hydrogenation and dehydrogenation properties of the magnesium-based composite material. For example, the hydrogen diffusion paths in the magnesium-based composite material are shorted, a desired extent of structural defects is included to reduce the activation barrier of hydrogen dissociation, and so on. In some embodiments, the magnesium-based solid solution has a single crystal structure. In some embodiments, the crystal structure of the magnesium-based solid solution is hexagonal close-packed (HCP). In some embodiments, an average grain size of the crystal structure of the magnesium-based solid solution is from 4 μm to 34 μm, for example, 4 μm, 9 μm, 14 μm, 19 μm, 24 μm, 29 μm, or 34 μm. The grain size is a volume of the crystal structure where the crystal orientation is substantially the same (see
The magnesium-based composite material of the present disclosure is further described in detail according to some embodiments. In some embodiments, the magnesium-based composite material is in particles to increase the surface area of the magnesium-based composite material. The larger surface area improves the hydrogenation and dehydrogenation properties by, for example, having more magnesium nucleation sites and shorter hydrogen diffusion paths when the composition and decomposition of magnesium hydride are happening, thereby increasing the hydrogen absorption and desorption rate. In addition, for the magnesium-based composite material having the larger surface area, lesser deformation may occur during the composition and decomposition of magnesium hydride to reduce the decrepitation to happen when heating the magnesium-based composite material. In some embodiments, a preferable average particle size of the magnesium-based composite material having improved hydrogenation and dehydrogenation properties is from 20 μm to 80 μm, for example, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 50 μm, 60 μm, 70 μm, or 80 μm.
The magnesium-based composite material of the present disclosure is further described in detail according to some embodiments. In some embodiments, the maximum reversible (i.e., hydrogen may be absorbed and desorbed reversibly) hydrogen storage capacity of the magnesium-based composite material is from 6 wt % to 7 wt %, for example, 6.0 wt %, 6.2 wt %, 6.4 wt %, 6.6 wt %, 6.8 wt %, or 7.0 wt %. In some embodiments, the hydrogen absorption rate of the magnesium-based composite material is from 2 wt % per minute to 4 wt % per minute, for example, 2.0 wt % per minute, 2.5 wt % per minute, 3.0 wt % per minute, 3.5 wt % per minute, or 4.0 wt % per minute. In some embodiments, the hydrogen desorption rate of the magnesium-based composite material is from 0.25 wt % per minute to 1.25 wt % per minute, for example, 0.25 wt % per minute, 0.50 wt % per minute, 0.75 wt % per minute, 1.00 wt % per minute, or 1.25 wt % per minute. In some embodiments, the maximum reversible hydrogen storage capacity, the hydrogen absorption rate, and the hydrogen desorption rate are measured at the working temperature from 300° C. to 400° C., for example, 300° C., 320° C., 340° C., 360° C., 380° C., or 400° C., and at the hydrogen pressure from 2.5 MPa to 3.5 MPa, for example, 2.5 MPa, 2.7 MPa, 2.9 MPa, 3.1 MPa, 3.3 MPa, or 3.5 MPa.
Next, the magnesium-based solid solution is described in detail according to some embodiments. The magnesium-based solid solution includes magnesium, the at least one first catalytic metal, and the at least one first carbon allotrope, in which magnesium has high hydrogen storage capacity, the at least one first catalytic metal is a catalyst to improve the dissociation of hydrogen from magnesium, and the at least one first carbon allotrope provides a larger surface area to improve the kinetic rate of hydrogen absorption and desorption. In some embodiments, a weight percentage of magnesium in the magnesium-based solid solution is preferably larger than or equal to 85 wt % to maintain high hydrogen storage capacity and increase the homogeneity of the solid solution. In some embodiments, the at least one first catalytic metal is preferably selected from the group consisting of aluminum, zinc, zirconium, nickel, titanium, vanadium, chromium, cobalt, iron, copper, molybdenum, niobium, palladium, and yttrium. In some embodiments, a weight percentage of each one of the at least one first catalytic metal in the magnesium-based solid solution is preferably smaller than or equal to 9 wt % to improve the catalytic effect and increase the homogeneity of the solid solution. In some embodiments, the at least one first carbon allotrope is preferably selected from the group consisting of graphite, graphene, fullerene, single-walled carbon nanotubes, multi-walled carbon nanotubes, activated carbon, and carbon black. In some embodiments, a weight percentage of the at least one first carbon allotrope in the magnesium-based solid solution is preferably smaller than or equal to 3 wt % to improve the kinetic rate and increase the homogeneity of the solid solution.
The magnesium-based solid solution of the present disclosure is further described in detail according to some embodiments. In some embodiments, a weight percentage of aluminum among the at least one first catalytic metal is the largest to have a better catalytic effect. In some embodiments, the weight percentage of aluminum in the magnesium-based solid solution is preferably from 3 wt % to 9 wt %, for example, 3 wt %, 4 wt %, 5 wt %, 6 wt %, 7 wt %, 8 wt %, or 9 wt %. In some embodiments, the weight percentage of zinc in the magnesium-based solid solution is preferably from 0.5 wt % to 6 wt %, for example, 0.5 wt %, 1 wt %, 2 wt %, 3 wt %, 4 wt %, 5 wt %, or 6 wt %. In some embodiments, the weight percentage of zirconium in the magnesium-based solid solution is preferably from 0.1 wt % to 1.6 wt %, for example, 0.1 wt %, 0.6 wt %, 1.0 wt %, 1.3 wt %, or 1.6 wt %. In some embodiments, the weight percentage of nickel, titanium, vanadium, chromium, cobalt, iron, copper, molybdenum, niobium, palladium, or yttrium in the magnesium-based solid solution are each independently preferably from 0.1 wt % to 1 wt %, for example, 0.1 wt %, 0.25 wt %, 0.5 wt %, 0.75 wt %, or 1 wt %. More specifically, in some embodiments, the at least one first catalytic metal includes aluminum, zinc, and at least one selected from the group consisting of zirconium, nickel, titanium, vanadium, chromium, cobalt, iron, copper, molybdenum, niobium, palladium, and yttrium, in which a preferable weight ratio between aluminum and zinc is from 3:1 to 9:1, for example, 3:1, 6:1, or 9:1. More specifically, in some embodiments, the at least one first catalytic metal includes zinc, zirconium, and at least one selected from the group consisting of nickel, titanium, vanadium, chromium, cobalt, iron, copper, molybdenum, niobium, palladium, and yttrium, in which a preferable weight ratio between zinc and zirconium is from 3:1 to 60:1, for example, 3:1, 5:1, 10:1, 20:1, 30:1, 40:1, 50:1, or 60:1. The at least one first catalytic metal including aluminum and zinc, or including zinc and zirconium, further improves the mechanical properties (e.g., a higher tensile strength, a higher yield strength, etc.), increases the corrosion resistance, and favors the application (e.g., better welding characteristics, etc.) of the magnesium-based solid solution. In some embodiments, the weight percentage of the at least one first carbon allotrope in the magnesium-based solid solution is preferably from 1 wt % to 3 wt %, for example, 1.0 wt %, 1.5 wt %, 2.0 wt %, 2.5 wt %, or 3.0 wt %. In some embodiments, the at least one first carbon allotrope includes multi-walled carbon nanotubes, and each of the multi-walled carbon nanotubes has the density preferably from 0.01 g/cm3 to 0.1 g/cm3, for example, 0.01 g/cm3, 0.04 g/cm3, 0.06 g/cm3, 0.08 g/cm3, or 0.10 g/cm3.
Next, the amorphous additive is described in detail according to some embodiments. The amorphous additive includes the at least one second catalytic metal and the at least one second carbon allotrope, in which the at least one second catalytic metal is a catalyst to improve the dissociation of hydrogen from magnesium, and the at least one second carbon allotrope provides a larger surface area to improve the kinetic rate of hydrogen absorption and desorption. In some embodiments, the at least one second catalytic metal is preferably selected from the group consisting of zirconium, nickel, titanium, vanadium, chromium, cobalt, iron, copper, molybdenum, niobium, palladium, and yttrium. In some embodiments, a weight percentage of the at least one second catalytic metal in the amorphous additive is preferably from 35 wt % to 45 wt %, for example, 35 wt %, 37 wt %, 40 wt %, 43 wt %, or 45 wt % to improve the catalytic effect. In some embodiments, the at least one second carbon allotrope is preferably selected from the group consisting of graphite, graphene, fullerene, single-walled carbon nanotubes, multi-walled carbon nanotubes, activated carbon, and carbon black. In some embodiments, a weight percentage of the at least one second carbon allotrope in the amorphous additive is preferably from 55 wt % to 65 wt %, for example, 55 wt %, 57 wt %, 60 wt %, 63 wt %, or 65 wt % to improve the kinetic rate. In some embodiments, the at least one first carbon allotrope and the at least one second carbon allotrope are the same. In some embodiments, the at least one first carbon allotrope and the at least one second carbon allotrope are different. In some embodiments, the weight percentage of the at least one second carbon allotrope is larger than the weight percentage of the at least one second catalytic metal to favor the production of the magnesium-based composite material in particles and the production of the desired structural defects in the magnesium-based composite material (for detail, see the method of forming the magnesium-based composite material below). In some embodiments, a preferable weight ratio between the at least one second carbon allotrope and the at least one second catalytic metal is from 1.1:1 to 2.5:1, for example, 1.1:1, 1.3:1, 1.5:1, 1.7:1, 1.9:1, 2.1:1, 2.3:1, or 2.5:1.
The present disclosure also provides a method of forming the foregoing magnesium-based composite material. The method includes the following operations. A casting process is performed on magnesium, the at least one first catalytic metal, and the at least one first carbon allotrope to form a first magnesium-based solid solution, in which the at least one first catalytic metal is selected from the group consisting of aluminum, zinc, zirconium, nickel, titanium, vanadium, chromium, cobalt, iron, copper, molybdenum, niobium, palladium, and yttrium. A severe plastic deformation process is performed on the first magnesium-based solid solution to form a second magnesium-based solid solution. A high energy ball milling process is performed on the second magnesium-based solid solution and the amorphous additive to form the magnesium-based composite material, in which the amorphous additive includes at least one second catalytic metal and at least one second carbon allotrope, and the at least one second catalytic metal is selected from the group consisting of zirconium, nickel, titanium, vanadium, chromium, cobalt, iron, copper, molybdenum, niobium, palladium, and yttrium. The magnesium-based composite material formed by the method of the present disclosure can be a hydrogen carrier and has better hydrogenation and dehydrogenation properties as described in the foregoing disclosure. Therefore, the details of the magnesium-based composite material may not be repeated in the following. Besides forming the magnesium-based composite material of the present disclosure, the method of the present disclosure is easy to implement and can perform mass production of the magnesium-based composite material. The method of the present disclosure is described in detail in the following embodiments.
In the flowchart as shown in
In some embodiments, the method 100 further includes performing a homogenization process after the operation 101 and before the operation 102. The homogenization process makes the brittle first magnesium-based solid solution formed after the operation 101 become more ductile. Therefore, the first magnesium-based solid solution that is more ductile is easier to be operated in the operation 102 to reduce the grain size of the first magnesium-based solid solution (for detail, see the operation 102 below). Furthermore, the homogenization process increases the homogeneity of the solid solution by reducing the fracture in the crystal structure of the first magnesium-based solid solution, so the second magnesium-based solid solution formed in the operation 102 not only has reduced grain size but the limited fracture to enhance the diffusion of the hydrogen in the solid solution. The crystal structure change after the operation 101, the homogenization process, and the operation 102 will be described in detail in an example as shown in
In some embodiments, the method 100 further includes performing a water jet process after the operation 101 and before the operation 102. The water jet process includes slicing the first magnesium-based solid solution into bars to prepare the operation 102. For example, in the operation 102, each bar is pressed into an angled channel to adjust the mechanical properties and the grain size of the solid solution (for detail, see the operation 102 below). In some embodiments, the length of each bar is from 5 mm to 15 mm, e.g., 11.5 mm, the width of each bar is from 5 mm to 15 mm, e.g., 11.5 mm, and the height of each bar is from 70 mm to 80 mm, e.g., 75 mm.
In the flowchart as shown in
In some embodiments, the method 100 further includes performing a rasping process after the operation 102 and before the operation 103. The rasping process includes rasping the second magnesium-based solid solution into particles manually to prepare the operation 103. In some embodiments, a particle size of the second magnesium-based solid solution after the rasping process is preferably from 80 μm to 120 μm, for example, 80 μm, 90 μm, 100 μm, 110 μm, or 120 μm.
In the flowchart as shown in
The magnesium-based composite material and the method of forming the same are described in detail in the following embodiments. The following embodiments are aimed at a better understanding of the present disclosure rather than limiting the scope of the present disclosure.
In the Embodiment 1, the magnesium-based composite material includes 96 wt % of the magnesium-based solid solution and 4 wt % of the amorphous additive, in which the magnesium-based solid solution includes 92.5 wt % of magnesium, 3 wt % of aluminum, 1 wt % of zinc, 0.5 wt % of titanium, and 3 wt % multi-walled carbon nanotubes (the density of each multi-walled carbon nanotube is around 0.057 g/cm3), and the amorphous additive includes 40 wt % of nickel and 60 wt % of graphene. Magnesium, aluminum, zinc, titanium, and the multi-walled carbon nanotubes were heated at 760° C. and stirred for 15 minutes in the casting process of the operation 101 to obtain the first magnesium-based solid solution. The first magnesium-based solid solution was heated at 410° C. for 24 hours in the homogenization process. The first magnesium-based solid solution was sliced into bars of 11.5 mm length, 11.5 mm width, and 75 mm height in the water jet process. The first magnesium-based solid solution was press to pass through an angled channel of a bent angle of 120° with a load of 210 kg and a velocity of 1.0 mm/s in the severe plastic deformation process of the operation 102. The second magnesium-based solid solution obtained from the operation 102 was mixed with nickel and graphene in the high energy ball milling process of the operation 103. The weight ratio between the weight of the steel balls and the total weight of the second magnesium-based solid solution, nickel, and graphene in the grinding jars of the high energy ball milling machine was 40:1, in which the rotating speed of the high energy ball milling machine was 400 rpm, and the rotating direction changed every 30 minutes and with a 10 minutes break before the next rotation.
The Embodiment 1 was compared with a Comparative Embodiment 1. The Comparative Embodiment 1 is substantially the same as the Embodiment 1, except that the Comparative Embodiment 1 did not include the operation 102 and the operation 103, while the Embodiment 1 includes the operation 101, the operation 102, and the operation 103. In other words, the Comparative Embodiment 1 forms the first magnesium-based solid solution only, and the Embodiment 1 forms the magnesium-based composite material.
The average grain sizes of the magnesium-based solid solution in the Embodiments 2A to 2H, the Comparative Embodiment 21, the Embodiments 3A to 3H, and the Comparative Embodiment 31 are compared in Table 1 below. The Embodiments 2A to 2H are substantially the same as the Embodiment 1 described above, except that the operation 102 in each embodiment is different. For example, the Embodiments 2A to 2B are performed as the operation shown in
The magnesium-based composite material of the present disclosure and the magnesium-based composite material formed by the method of the present disclosure have better hydrogenation and dehydrogenation properties including higher reversible hydrogen storage capacities, higher hydrogen absorption rates, higher hydrogen desorption rates, lower working temperatures, and so on. The method of the present disclosure is also easy to implement, can perform mass production, and the materials are easy to acquire.
The present disclosure is described in detail with some embodiments, but other embodiments may be possible. Therefore, the description of the embodiments in the present disclosure should not be used to limit the scope and spirit of the appended claims.
For one skilled in the art, modifications and changes to the present disclosure may be made without departing from the scope and spirit of the present disclosure. The present disclosure is intended to cover the foregoing modifications and changes as long as such modifications and changes are within the scope and spirit of the appended claims.
