Patent Application
20190390307
The present invention relates to the technical field of new energy materials, especially a catalyst enhanced MgAl-based hydrogen storage material.
Metal hydride hydrogen storage materials achieve hydrogen absorption and desorption by a reversible reaction between hydrogen and a metal hydride. When the hydride is heated, it decomposes into the corresponding metal phase and releases hydrogen. Most of the metals used for hydrogen storage are alloys composed of various elements. Currently, the alloys successfully studied in the world can be roughly divided into: rare earth based series, Mg based series and so on. Compared with gaseous hydrogen storage and liquid hydrogen storage, metal hydride hydrogen storage has the advantages of large hydrogen storage mass density ratio, large hydrogen storage volume ratio, stable pressure, simple hydrogen charging, convenience, safety, etc., and at the same temperature and pressure, the density of hydrogen storage per unit volume is 1,000 times that of hydrogen in the gas phase. Although it has many advantages, the problems are urgently needed to be solved, and the problems include improving the hydrogen storage capacity of hydrogen storage materials, reducing the cost of materials, saving precious metals in large-scale applications, and improving the thermodynamic and kinetic properties of materials in hydrogen absorption and desorption at relatively low temperature. In 2015, the United States Department of Energy proposed the standards that the hydrogen storage capacity of vehicle-mounted hydrogen storage materials is 5.5 wt %, the lowest and maximum temperature is 40 and 80° C., respectively, the service life is 1500 times, the hydrogen absorption time is 3.3 min, and the purity of hydrogen storage is 99.97%. At present, most hydrogen storage alloys can not meet the performance requirements. The Mg-based hydrogen storage material is made of Mg as a matrix, and then other metals are added, and has a high hydrogen storage capacity. The MgH2 theoretical hydrogen storage density of mass and volume are 7.6 wt % and 110 kg/m3, respectively. Mg has abundant storage in nature, low price and great application and development space, but its alloy hydride (MgH2) has great obstacles in both thermodynamics and kinetics. Thermodynamically, formation enthalpy of MgH2 is relatively higher; in terms of kinetics, MgH2 has higher hydrogen desorption activation energy, and has lower hydrogen desorption rate at lower temperatures. This requires further optimization to improve the hydrogen absorption and desorption properties of Mg based alloys.
The information disclosed in this background technology section is only intended to provide an understanding of the general background of this invention, and should not be construed as acknowledging or implying in any way that the information composition is the existing technology known to the general technical personnel in the field.
The purpose of the invention is to provide a catalyst enhanced MgAl-based hydrogen storage material, overcoming the shortcomings of existing, technologies.
To achieve the purposes mentioned above, the invention provides a catalyst enhanced MgAl-based hydrogen storage material, characterized in that: the catalyst enhanced MgAl-based hydrogen storage material is prepared by the following method: provide Mg and Al metal raw materials; weigh the Mg and Al metal raw materials according to a molar ratio of Mg: Al=(16-18):(11-13); perform the first vacuum melting on the Mg and Al metal raw materials after weighing to obtain the primary Mg alloy ingots; and crush the primary Mg alloy ingots to obtain the primary Mg alloy blocks; provide Ti, Zr and V metal raw materials; weigh the primary Mg alloy blocks and the Ti, Zr and V metal raw materials according to a predetermined weight; perform ball milling treatment on the primary Mg alloy blocks and the Ti, Zr and V metal raw materials to obtain composite metal powder; press the composite metal powder into the loose alloy ingots by using the cold isostatic pressure method; perform hot pressing treatment on the loose alloy ingots to obtain the dense alloy ingots; perform heat treatment on the dense alloy ingot; and wire cut the dense alloy ingots after heat treatment.
Preferably, in the technical scheme mentioned above, the first vacuum melting process is as follows: the vacuum degree is less than 0.01 Pa, and the smelting time is 20-30 min, the alloy ingots are flipped once every 80-10 s during the smelting process.
Preferably, in the technical scheme mentioned above, the predetermined weight is as follows: 100-150 parts of primary Mg alloy blocks, 2-4 parts of Ti metal, 3-5 parts of Zr metal, and 1-3 parts of V metal.
Preferably, in the technical scheme mentioned above, the ball milling treatment performed on the primary Mg alloy blocks and the Ti, Zr and V metal raw materials is specifically that the ratio of ball to material is 10:1-15:1, the the ball milling atmosphere is argon atmosphere, the ball milling speed is 900-1300 r/min, the ball milling time is 40-60 h.
Preferably, in the technical scheme mentioned above, the ball milling treatment performed on the primary Mg alloy blocks and the Ti, Zr and V metal raw materials further includes: in the ball milling process, each ball milling lasts 50-60 min, and suspend the ball milling for 8-15 min, the temperature in the ball milling tank is controlled to be lower than 500° C. during the ball milling process.
Preferably, in the technical scheme mentioned above, hot pressing treatment performed on the loose alloy ingots to obtain the dense alloy ingots is that, specifically, the hot pressing air pressure is lower than 0.03 Pa, the hot pressing temperature is 600-700° C., the hot pressing pressure is 50-70 MPa, and the hot pressing time is 30-50 min.
Preferably, in the technical scheme mentioned above, heat treatment performed on the dense alloy ingots is that, specifically, the heat treatment air pressure is less than 0.01 Pa, the heat treatment temperature is 150-200° C., the heat treatment time is 30-40 h, and the heating rate is 2-4° C./min.
Compared with existing technology, the present invention has the following beneficial advantages. As mentioned in the background technology, at present, the hydrogen storage materials successfully studied are rare earth based materials and Mg based materials. Because rare earth element is a valuable strategic resource, it is difficult for rare earth materials to be widely used as civilian hydrogen storage materials under the current distribution conditions of mineral. Although Mg-based materials are expected to become hydrogen storage materials for large-scale application, there are still many shortcomings in Mg based materials at present: 1. Poor hydrogen storage capacity and narrow temperature range. Some hydrogen storage materials are used in extreme situations, and the use temperature may be higher than 100° C. In these cases, the general Mg-based hydrogen storage materials can not play a role in hydrogen storage, which greatly limits the use of hydrogen storage materials. 2. It is difficult to modify. At present, in view of the narrow application range of Mg based alloys, some catalyst enhanced Mg based alloys have been designed. Limited by the technological process, the currently mature alloys can only be doped with a catalyst (some patent documents and papers have proposed a process of doping various elements, but all have poor effects and low yield). One catalyst is prone to cause catalyst poisoning, which seriously affects the performance of materials. In view of the existing technical problems, the present application designs a catalyst enhanced MgAl-based hydrogen storage material. The material in this present application does not need to add rare earth materials, so the raw materials are cheap and easy to obtain, and the manufacturing cost is low. At the same time, this application has realized the stable doping of various catalyst elements for the first time, which makes the recycling hydrogen storage effects of this application significantly better than that of the existing technology, and the effect is stable and suitable for long-term service. The material in this present application can be used under high temperature conditions by adding a catalyst, which greatly expands the application prospect of the material in the present application.
The following implementations are provided in order to better illustrate this present invention, and to communicate the scope of the invention fully to the technical personnel in this field.
The catalyst enhanced MgAl-based, hydrogen storage material is prepared by the following method: provide Mg and Al metal raw materials; weigh the Mg and Al metal raw materials according to a molar ratio of Mg: Al=16:11; perform the first vacuum melting on the Mg and Al metal raw materials after weighing to obtain the primary Mg alloy ingots; and crush the primary Mg alloy ingots to obtain the primary Mg alloy blocks; provide Ti, Zr and V metal raw materials; weigh the primary Mg alloy blocks and the Ti, Zr and V metal raw materials according to a predetermined weight; perform ball milling treatment on the primary Mg alloy blocks and the Ti, Zr and V metal raw materials to obtain composite metal powder; press the composite metal powder into the loose alloy ingots by using the cold isostatic pressure method; perform hot pressing treatment on the loose alloy ingots to obtain the dense alloy ingots; perform heat treatment on the dense alloy ingot; and wire cut the dense alloy ingots after heat treatment. The first vacuum melting process is as follows: the vacuum degree is less than 0.01 Pa, and the smelting time is 20 min, the alloy ingots are flipped once every 80 s during the smelting process. The predetermined weight is as follows: 100 parts of primary Mg alloy blocks, 2 parts of Ti metal, 3 parts of Zr metal, and 1 parts of V metal. The ball milling treatment performed on the primary Mg alloy blocks and the Ti, Zr and V metal raw materials is specifically that the ratio of ball to material is 10:1, the the ball milling atmosphere is argon atmosphere, the ball milling speed is 900 r/min, the ball milling time is 40 h. The ball milling treatment performed on the primary Mg alloy blocks and the Ti, Zr and V metal raw materials further includes: in the ball milling process, each ball milling lasts 50 min, and suspend the ball milling for 8 min, the temperature in the ball milling tank is controlled to be lower than 500° C. during the ball milling process. The hot pressing treatment performed on the loose alloy ingots to obtain the dense alloy ingots is that, specifically, the hot pressing air pressure is lower than 0.03 Pa, the hot pressing temperature is 600° C., the hot pressing pressure is 50 MPa, and the hot pressing time is 30 min. The heat treatment performed on the dense alloy ingots is that, specifically, the heat treatment air pressure is less than 0.01 Pa, the heat treatment temperature is 150° C., the heat treatment time is 30 h, and the heating rate is 2° C./min.
The catalyst enhanced MgAl-based hydrogen storage material is prepared by the following method: provide Mg and Al metal raw materials; weigh the Mg and Al metal raw materials according to a molar ratio of Mg: Al=18:13; perform the first vacuum melting on the Mg and Al metal raw materials after weighing to obtain the primary Mg alloy ingots; and crush the primary Mg alloy ingots to obtain the primary Mg alloy blocks; provide Ti, Zr and V metal raw materials; weigh the primary Mg alloy blocks and the Ti, Zr and V metal raw materials according to a predetermined weight; perform ball milling treatment on the primary Mg alloy blocks and the Ti, Zr and V metal raw materials to obtain composite metal powder; press the composite metal powder into the loose alloy ingots by using the cold isostatic pressure method; perform hot pressing treatment on the loose alloy ingots to obtain the dense alloy ingots; perform heat treatment on the dense alloy ingot; and wire cut the dense alloy ingots after heat treatment. The first vacuum melting process is as follows: the vacuum degree is less than 0.01 Pa, and the smelting time is 30 min, the alloy ingots are flipped once every 100 s during the smelting process. The predetermined weight is as follows: 150 parts of primary Mg alloy blocks, 4 parts of Ti metal, 5 parts of Zr metal, and 3 parts of V metal. The ball milling treatment performed on the primary Mg alloy blocks and the Ti, Zr and V metal raw materials is specifically that the ratio of ball to material is 15:1, the the ball milling atmosphere is argon atmosphere, the ball milling speed is 1300 r/min, the ball milling time is 60 h. The ball milling treatment performed on the primary Mg, alloy blocks and the Ti, Zr and V metal raw materials further includes: in the ball milling process, each ball milling lasts 60 min, and suspend the ball milling for 15 min, the temperature in the ball milling tank is controlled to be lower than 500° C. during the ball milling process. The hot pressing treatment performed on the loose alloy ingots to obtain the dense alloy ingots is that, specifically, the hot pressing air pressure is lower than 0.03 Pa, the hot pressing temperature is 700° C., the hot pressing pressure is 70 MPa, and the hot pressing time is 50 min. The heat treatment performed on the dense alloy ingots is that, specifically, the heat treatment air pressure is less than 0.01 Pa, the heat treatment temperature is 200° C., the heat treatment time is 40 h, and the heating rate is 4° C./min.
The catalyst enhanced MgAl-based hydrogen storage material is prepared by the following method: provide Mg and Al metal raw materials; weigh the Mg and Al metal raw materials according to a molar ratio of Mg: Al=17:12; perform the first vacuum melting on the Mg and Al metal raw materials after weighing to obtain the primary Mg alloy ingots; and crush the primary Mg alloy ingots to obtain the primary Mg alloy blocks; provide Ti, Zr and V metal raw materials; weigh the primary Mg alloy blocks and the Ti, Zr and V metal raw materials according to a predetermined weight; perform ball milling treatment on the primary Mg alloy blocks and the Ti, Zr and V metal raw materials to obtain composite metal powder; press the composite metal powder into the loose alloy ingots by using the cold isostatic pressure method; perform hot pressing treatment on the loose alloy ingots to obtain the dense alloy ingots; perform heat treatment on the dense alloy ingot; and wire cut the dense alloy ingots after heat treatment. The first, vacuum melting process is as follows: the vacuum degree is less than 0.01 Pa, and the smelting time is 25 min, the alloy ingots are flipped once every 90 s during the smelting process. The predetermined weight is as follows: 120 parts of primary Mg alloy blocks, 3 parts of Ti metal, 4 parts of Zr metal, and 2 parts of V metal. The ball milling treatment performed on the primary Mg alloy blocks and the Ti, Zr and V metal raw materials is specifically that the ratio of ball to material is 12:1, the the ball milling atmosphere is argon atmosphere, the ball milling speed is 1100 r/min, the ball milling time is 50 h. The ball milling treatment performed on the primary Mg alloy blocks and the Ti, Zr and V metal raw materials further includes: in the ball milling process, each ball milling lasts 55 min, and suspend the ball milling for 10 min, the temperature in the ball milling tank is controlled to be lower than 500° C. during the ball milling process. The hot pressing treatment performed on the loose alloy ingots to obtain the dense alloy ingots is that, specifically, the hot pressing air pressure is lower than 0.03 Pa, the hot pressing temperature is 650° C., the hot pressing pressure is 60 MPa, and the hot pressing time is 40 min. The heat treatment performed on the dense alloy ingots is that, specifically, the heat treatment air pressure is less than 0.01 Pa, the heat treatment temperature is 180° C., the heat treatment time is 35 h, and the heating rate is 3° C./min.
The catalyst enhanced MgAl-based hydrogen storage material is prepared by the following method: provide Mg and Al metal raw materials; weigh the Mg and Al metal raw materials according to a molar ratio of Mg: Al=20:10; perform the first vacuum melting on the Mg and Al metal raw materials after weighing to obtain the primary Mg alloy ingots; and crush the primary Mg alloy ingots to obtain the primary Mg alloy blocks; provide Ti, Zr and V metal raw materials; weigh the primary Mg alloy blocks and the Ti, Zr and V metal raw materials according to a predetermined weight; perform ball milling treatment on the primary Mg alloy blocks and the Ti, Zr and V metal raw materials to obtain composite metal powder; press the composite metal powder into the loose alloy ingots by using the cold isostatic pressure method; perform hot pressing treatment on the loose alloy ingots to obtain the dense alloy ingots; perform heat treatment on the dense alloy ingot; and wire cut the dense alloy ingots after heat treatment. The first vacuum melting process is, as follows: the vacuum degree is less than 0.01 Pa, and the smelting time is 40 min, the alloy ingots are flipped once every 150 s during the smelting process. The predetermined weight is as follows: 120 parts of primary Mg alloy blocks, 3 parts of Ti metal, 4 parts of Zr metal, and 2 parts of V metal. The ball milling treatment performed on the primary Mg alloy blocks and the Ti, Zr and V metal raw materials is specifically that the ratio of ball to material is 12:1, the the ball milling atmosphere is argon atmosphere, the ball milling speed is 1100 r/min, the ball milling time is 50 h. The ball milling treatment performed on the primary Mg alloy blocks and the Ti Zr and V metal raw materials further includes: in the ball milling process, each ball milling lasts 55 mm, and suspend the ball milling for 10 min, the temperature in the ball milling tank is controlled to be lower than 500° C. during the ball milling process. The hot pressing treatment performed on the loose alloy ingots to obtain the dense alloy ingots is that, specifically, the hot pressing air pressure is lower than 0.03 Pa, the hot pressing temperature is 650° C., the hot pressing pressure is 60 MPa, and the hot pressing time is 40 min. The heat treatment performed on the dense alloy ingots is that, specifically, the heat treatment air pressure is less than 0.01 Pa, the heat treatment temperature is 180° C., the heat treatment time is 35 h, and the heating rate is 3° C./min.
The catalyst enhanced MgAl-based hydrogen storage material is prepared by the following method: provide Mg and Al metal raw materials; weigh the Mg and Al metal raw materials according to a molar ratio of Mg: Al=17:12; perform the first vacuum melting on the Mg and Al metal raw materials after weighing to obtain the primary Mg alloy ingots; and crush the primary Mg alloy ingots to obtain the primary Mg alloy blocks; provide Ti, Zr and V metal raw materials; weigh the primary Mg alloy blocks and the Ti, Zr and V metal raw materials according to a predetermined weight; perform ball milling treatment on the primary Mg alloy blocks and the Ti, Zr and V metal raw materials to obtain composite metal powder; press the composite metal powder into the loose alloy ingots by using the cold isostatic pressure method; perform hot pressing treatment on the loose alloy ingots to obtain the dense alloy ingots; perform heat treatment on the dense alloy ingot; and wire cut the dense alloy ingots after heat treatment. The first vacuum melting process is, as follows: the vacuum degree is less than 0.01 Pa, and the smelting time is 25 min, the alloy ingots are flipped once every 90 s during the smelting process. The predetermined weight is as follows: 100 parts of primary Mg alloy blocks, 5 parts of Ti metal, 6 parts of Zr metal, and 4 parts of V metal. The ball milling treatment performed on the primary Mg alloy blocks and the Ti, Zr and V metal raw materials is specifically that the ratio of ball to material is 12:1, the the ball milling atmosphere is argon atmosphere, the ball milling speed is 1100 r/min, the ball milling time is 50 h. The ball milling treatment performed on the primary Mg alloy blocks and the Ti, Zr and V metal raw materials further includes: in the ball milling process, each ball milling lasts 55 min, and suspend the ball milling for 10 min, the temperature in the ball milling tank is controlled to be lower than 500° C. during the ball milling process. The hot pressing treatment performed on the loose alloy ingots to obtain the dense alloy ingots is that, specifically, the hot pressing air pressure is lower than 0.03 Pa, the hot pressing temperature is 650° C., the hot pressing pressure is 60 MPa, and the hot pressing time is 40 min. The heat treatment performed on the dense alloy ingots is that, specifically, the heat treatment air pressure is less than 0.01 Pa, the heat treatment temperature is 180° C., the heat treatment time is 35 h, and the heating rate is 3° C./min.
The catalyst enhanced MgAl-based hydrogen storage material is prepared by the following method: provide Mg and Al metal raw materials; weigh the Mg and Al metal raw materials according to a molar ratio of Mg: Al=17:12; perform the first vacuum melting on the Mg and Al metal raw materials after weighing to obtain the primary Mg alloy ingots; and crush the primary Mg alloy ingots to obtain the primary Mg alloy blocks; provide Ti, Zr and V metal raw materials; weigh the primary Mg alloy blocks and the Ti, Zr and V metal raw materials according to a predetermined weight; perform ball milling treatment on the primary Mg alloy blocks and the Ti, Zr and V metal raw materials to obtain composite metal powder; press the composite metal powder into the loose alloy ingots by using the cold isostatic pressure method; perform hot pressing treatment on the loose alloy ingots to obtain the dense alloy ingots; perform heat treatment on the dense alloy ingot; and wire cut the dense alloy ingots after heat treatment. The first vacuum melting process is as follows: the vacuum degree is less than 0.01 Pa, and the smelting time is 25 min, the alloy ingots are flipped once every 90 s during the smelting process. The predetermined weight is as follows: 120 parts of primary Mg alloy blocks, 3 parts of Ti metal, 4 parts of Zr metal, and 2 parts of V metal. The ball milling treatment performed on the primary Mg alloy blocks and the Ti, Zr and V metal raw materials is specifically that the ratio of ball to material is 20:1, the the ball milling atmosphere is argon atmosphere, the ball milling speed is 1500 r/min, the ball milling time is 70 h. The ball milling treatment performed on the primary Mg alloy blocks and the Ti, Zr and V metal raw materials further includes: in the ball milling process, each ball milling lasts 100 min, and suspend the ball milling for 20 min, the temperature in the ball milling tank is not limited during the ball milling process. The hot pressing treatment performed on the loose alloy ingots to obtain the dense alloy ingots is that, specifically, the hot pressing air pressure is lower than 0.03 Pa, the hot pressing temperature is 650° C., the hot pressing pressure is 60 MPa, and the hot pressing time is 40 min. The heat treatment performed on the dense alloy ingots is that, specifically, the heat treatment air pressure is less than 0.01 Pa, the heat treatment temperature is 180° C., the heat treatment time is 35 h, and the heating rate is 3° C./min.
The catalyst enhanced MgAl-based hydrogen storage material is prepared by the following method: provide Mg and Al metal raw materials; weigh the Mg and Al metal raw materials according to a molar ratio of Mg: Al=17:12; perform the first vacuum melting on the Mg and Al metal raw materials after weighing to obtain the primary Mg alloy ingots; and crush the primary Mg alloy ingots to obtain the primary Mg alloy blocks; provide Ti, Zr and V metal raw materials; weigh the primary Mg alloy blocks and the Ti, Zr and V metal raw materials according to a predetermined weight; perform ball milling treatment on the primary Mg alloy blocks and the Ti, Zr and V metal raw materials to obtain composite metal powder; press the composite metal powder into the loose alloy ingots by using the cold isostatic pressure method; perform hot pressing treatment on the loose alloy ingots to obtain the dense alloy ingots; perform heat treatment on the dense alloy ingot; and wire cut the dense alloy ingots after heat treatment. The first vacuum inciting process is as follows: the vacuum degree is less than 0.01 Pa, and the smelting time is 25 min, the alloy ingots are flipped once every 90 s during the smelting process. The predetermined weight is as follows: 120 parts of primary Mg alloy blocks, 3 parts of Ti metal, 4 parts of Zr metal, and 2 parts of V metal. The ball milling treatment performed on the primary Mg alloy blocks and the Ti, Zr and V metal raw materials is specifically that the ratio of ball to material is 12:1, the the ball milling atmosphere is argon atmosphere, the ball milling speed is 1100 r/min, the ball milling time is 50 h. The ball milling treatment performed on the primary Mg, alloy blocks and the Ti, Zr and V metal raw materials further includes: in the ball milling process, each ball milling lasts 55 min, and suspend the ball milling for 10 min, the temperature in the ball milling tank is controlled to be lower than 500° C. during the ball milling process. The hot pressing treatment performed on the loose alloy ingots to obtain the dense alloy ingots is that, specifically, the hot pressing air pressure is lower than 0.03 Pa, the hot pressing temperature is 800° C., the hot pressing pressure is 30 MPa, and the hot pressing time is 20 min. The heat treatment performed on the dense alloy ingots is that, specifically, the heat treatment air pressure is less than 0.01 Pa, the heat treatment temperature is 300° C., the heat treatment time is 20 h, and the heating rate is 5° C./min.
provide Mg and Al metal raw materials; weigh the Mg and Al metal raw materials according to a molar ratio of Mg: Al=17:12; only Ti metal raw materials are provided. The preparation method refers to the method of a exiting technology.
The alloy is subjected to a test for hydrogen absorption mass percentage at 150° C. and a test for hydrogen absorption mass percentage after 100 cycles (100 hydrogen absorption and desorption) at room temperature. The test method is well-known manner in this field, and the test results are normalized based on implementation example 1. The test results are listed in Table 1.
The foregoing description of specific exemplary embodiments of the invention is for the purpose of illustration and exemplification, and these descriptions are not intended to limit the invention to the exact form disclosed, moreover, it is clear that many changes can be made according to the above teachings. The description of these selected exemplary embodiments is to explain the specific principles of the invention and its practical application, so that technicians in this field can utilize various exemplary embodiments of the invention with various choices and changes. The scope of the invention is intended to be limited by claims and their equivalents.
| Number | Date | Country | Kind |
|---|---|---|---|
| 201810699799.6 | Jun 2018 | CN | national |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/CN2018/101867 | Aug 2018 | US |
| Child | 16560957 | US |
