Catalyst enhanced MgAl-based hydrogen storage material

Abstract

The invention provides a catalyst enhanced MgAl-based hydrogen storage material, which 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; 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; perform ball milling treatment to obtain composite metal powder; press the composite metal powder into the loose alloy ingots; 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.

Claims

1. A catalyst enhanced MgAl-based hydrogen storage material, characterized in that: the catalyst enhanced MgAl-based hydrogen storage material in this invention 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 a first vacuum melting on the Mg and Al metal raw materials after weighing to obtain a primary Mg alloy ingots; Crush the primary Mg alloy ingots mentioned above 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 ingots; Wire cut the dense alloy ingots after heat treatment.

2. The catalyst enhanced MgAl-based hydrogen storage material mentioned in claim 1, characterized in that: specifically, 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.

3. The catalyst enhanced MgAl-based hydrogen storage material mentioned in claim 1, characterized in that: in this process, 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.

4. The catalyst enhanced MgAl-based hydrogen storage material mentioned in claim 1, characterized in that: 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.

5. The catalyst enhanced MgAl-based hydrogen storage material mentioned in claim 1, characterized in that: 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.

6. The catalyst enhanced MgAl-based hydrogen storage material mentioned in claim 1, characterized in that: perform hot pressing treatment on the loose alloy ingots to obtain the dense alloy ingots, specifically, the hot pressing air pressure is lower than 0.03 Pa, the hot pressing temperature is 600-700C., the hot pressing pressure is 50-70 MPa, and the hot pressing time is 30-50 min.

7. The catalyst enhanced MgAl-based hydrogen storage material mentioned in claim 1, characterized in that: perform heat treatment on the dense alloy ingots, 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.

Description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] 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.

Implementation Example 1

[0014] 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.

Implementation Example 2

[0015] 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.

Implementation Example 3

[0016] 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.

Implementation Example 4

[0017] 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.

Implementation Example 5

[0018] 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.

Implementation Example 6

[0019] 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.

Implementation Example 7

[0020] 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.

Implementation Example 8

[0021] 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.

[0022] 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.

TABLE-US-00001 TABLE 1 hydrogen absorption mass hydrogen absorption mass percentage at 150 C. percentage after cycles Implementation 100% 100% example 1 Implementation 102% 106% example 2 Implementation 101% 104% example 3 Implementation 70% 62% example 4 Implementation 83% 74% example 5 Implementation 79% 72% example 6 Implementation 78% 71% example 7 Implementation 56% 17% example 8

[0023] 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.