CAMG2-BASED ALLOY HYDRIDE MATERIAL FOR HYDROLYSIS PRODUCTION OF HYDROGEN, PREPARATION METHOD THEREFOR AND USE THEREOF

Abstract

Provided are a CaMg.sub.2-based alloy hydride material for hydrolysis production of hydrogen, a preparation method therefor and a use thereof. The material has a general formula of CaMg.sub.xM.sub.yH.sub.z, wherein M is Ni, Co or Fe, 1.5≦x<2.0, 0<y≦0.5, and 3≦z<6. The preparation method for the material comprises the following steps: (1) stacking three pure metal block materials in a crucible, wherein a metal block material M is placed at the top; (2) installing the crucible in a high-frequency induction melting furnace, evacuating and introducing an argon gas; (3) starting the high-frequency induction melting furnace to heat at a low power first, then increasing the power to uniformly fuse same; and thereafter cooling with the furnace to obtain an alloy ingot, and hammer-milling to obtain a hydrogen storage alloy based on CaMg.sub.2; and (4) hydrogenating the hammer-milled hydrogen storage alloy to obtain the material for hydrolysis production of hydrogen. The preparation method is simple and low in cost. The material can absorb hydrogen at normal temperature with a good hydrogen absorption performance The prepared hydrogen is pure, and can be directly introduced into and used in a hydrogen fuel battery.

Claims

1. A CaMg.sub.2-based alloy hydride material for hydrolysis production of hydrogen, characterized in that: it has a general formula of CaMg.sub.xM.sub.yH.sub.z, wherein M is Ni, Co or Fe, 1.5≦x<2.0, 0<y≦0.5, and 3≦z<6.

2. The method for the material according to claim 1, characterized in that: it comprises the following steps: (1) stacking three pure metal block materials of Ca, Mg and M in a crucible, wherein the metal block material M is placed at the top; (2) installing the crucible in step (1) in a high-frequency induction melting furnace, evacuating and introducing an argon gas as a protective gas, with the crucible having a vent at the upper part; (3) starting the high-frequency induction melting furnace to heat at a low power first for 2 to 3 min, then increasing the power to melt the metal block materials into a liquid, and keeping for a certain period of time to uniformly fuse the same; and thereafter cooling with the furnace to obtain an alloy ingot, and hammer-milling the alloy ingot to obtain the CaMg.sub.2-based hydrogen storage alloy; and (4) hydrogenating the hammer-milled hydrogen storage alloy at a hydrogenation temperature of 25° C.-100 ° C. and a hydrogen pressure of 40-60 atm for 1-15 h, thus obtaining the CaMg.sub.2-based alloy hydride material for hydrolysis production of hydrogen.

3. The method according to claim 2, characterized in that: weighing according to the atomic ratio of the pure metals in step (1) as the formula, with the atomic ratio of Ca:Mg:M being 1:(1.8-1.9):(0.1-0.2).

4. The method according to claim 3, characterized in that: Ca and Mg in step (1) are excess by 6% to 8% as a burning loss.

5. The method according to claim 2 characterized in that: in step (1) the purity of Ca≧95%, and the purity of Mg and M≧99%.

6. The method according to claim 2, characterized in that: in step (2), the vessel is evacuated to 5×10.sup.−3 Pa, and the pressure of the introduced argon is 0.5 atm.

7. The method according to claim 2, characterized in that: the alloy ingot in step (3) is repeatedly molten 2 to 3 times according to the previous method.

8. The method according to claim 2, characterized in that: the process of stacking the pure metal block materials into the alumina crucible and the process of hammer-milling the alloy ingot in step (1) are carried out in a glove box filled with an inert gas.

9. Application of the materials said in claim 1, characterized in that: the materials are used for a hydrolysis device for production of hydrogen, a fuel cell, a hydride hydrogen-storage device, heat storage and heat transfer, and hydrogen separation and recovery.

10. The method according to claim 3, characterized in that: in step (1) the purity of Ca≧95%, and the purity of Mg and M≧99%.

11. The method according to claim 4, characterized in that: in step (1) the purity of Ca≧95%, and the purity of Mg and M≧99%.

12. The method according to claim 3, characterized in that: in step (2), the vessel is evacuated to 5×10.sup.−3 Pa, and the pressure of the introduced argon is 0.5 atm.

13. The method according to claim 3, characterized in that: the alloy ingot in step (3) is repeatedly molten 2 to 3 times according to the previous method.

14. The method according to claim 3, characterized in that: the process of stacking the pure metal block materials into the alumina crucible and the process of hammer-milling the alloy ingot in step (1) are carried out in a glove box filled with an inert gas.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0031] FIG. 1 shows XRD patterns of the alloys prepared according to the present invention. a, b, c and d represent CaMg.sub.1.8Co.sub.0.2, CaMg.sub.1.8Fe.sub.0.2, CaMg.sub.1.8Ni.sub.0.2 and CaMg.sub.1.9Ni.sub.0.1, respectively, the main phase is CaMg.sub.2, the Ca—Mg—Ni alloy has the MgNi.sub.2 peaks of the C36 phase between 20°-25° and 40°-50°, and the Ca—Mg—Co and Ca—Mg—Fe alloys are found to have no obvious miscellaneous peak except the main phase of CaMg.sub.2.

[0032] FIG. 2 shows the hydriding-kinetic curves of the CaMg.sub.1.9Ni.sub.0.1 alloy prepared by the present invention, with the varied hydrogen absorption temperature from room temperature to 80° C.

[0033] FIG. 3 shows the XRD pattern of the CaMg.sub.1.9Ni.sub.0.1 alloy after hydrogenation at room temperature.

[0034] FIG. 4 shows the XRD pattern of the hydrogenated CaMg.sub.1.9Ni.sub.0.1 alloy after dehydrogenation at 320° C.

[0035] FIG. 5 shows the back scattering electron image of the hydrogenated CaMg.sub.1.9Ni.sub.0.1 alloy.

[0036] FIG. 6 shows the hydrolysis kinetic curves of the alloys, with all the alloys being 300-mesh particles and subjected to the hydrolysis reaction in pure water. The alloys are the CaMg.sub.2 alloy, the hydrogenated CaMg.sub.2 alloy, the CaMg.sub.1.9Ni.sub.0.1 alloy, the hydrogenated CaMg.sub.1.9Ni.sub.0.1 alloy, and the dehydrogenated CaMg.sub.1.9Ni.sub.0.1—H alloy, respectively.

[0037] FIG. 7 shows the hydrolysis kinetic curve of the hydrogenated CaMg.sub.1.9Ni.sub.0.1.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0038] The present invention will be further described in detail below with reference to some examples; however, the embodiments of the present invention are not limited thereto.

Example 1

[0039] The method for the CaMg.sub.1.9Ni.sub.0.1—H hydride comprises the following steps:

[0040] Weighing pure metals Ca, Mg and Ni (having the purity greater than 99%) at an atomic ratio of 1:1.9:0.1, with the burning loss of Ca and Mg being 7% and 6%, respectively. And then putting the weighed metals Ca, Mg and Ni in turn into a prepared crucible (provided with a vent), wherein the metal block Ni is placed at the top. Installing the crucible in a high-frequency induction melting furnace, evacuating to 5×10.sup.−3 Pa, and then introducing 0.5 atm argon gas as a protective gas. Starting the high-frequency induction melting furnace to heat at a low power for 2 to 3 min, then increasing the power to melt the alloy into a liquid and keeping for 1 min to uniformly fuse the same, and thereafter cooling with the furnace to obtain an alloy ingot, and then cooling with the furnace after remelting 2 times to obtain a hydrogen storage alloy based on CaMg.sub.2 (the X-ray diffraction pattern is shown as the curve d in FIG. 1). Removing the alloy, putting it into a glove box filled with an inert gas and hammer-milling the alloy, and then hydrogenating the hammer-milled hydrogen storage alloy powder at a hydrogenation temperature of 25° C. and a hydrogen pressure of 50 atm for 15 h, thus obtaining a CaMg.sub.2-based alloy hydride material for hydrolysis production of hydrogen (the X-ray diffraction pattern is shown in FIG. 3). The alloy is brittle and easy to produce alloy powder. Its hydrogen storage performance has been significantly improved compared to that before alloying, and its hydrogen absorption kinetic curve is shown in FIG. 2, with the hydrogen absorption activation energy reduced by 30%. Hydrolyzing the hydrogenated material to produce hydrogen at room temperature in pure water, the hydrolysis kinetic curve is shown in FIG. 7, with 90% of the theoretical hydrogen production reached within 8 min, having a very good performance of hydrolysis production of hydrogen (FIG. 6).

Example 2

[0041] The method for the CaMg.sub.1.8Ni.sub.0.2—H hydride comprises the following steps:

[0042] Weighing pure metals Ca, Mg and Ni (having the purity greater than 99%) at an atomic ratio of 1:1.8:0.2, with the burning loss of Ca and Mg being 7%. And then putting the weighed metals Ca, Mg and Ni in turn into a prepared crucible (provided with a vent), wherein the metal block Ni is placed at the top. Installing the crucible in a high-frequency induction melting furnace, evacuating to 5×10.sup.−3 Pa, and then introducing 0.5 atm argon gas as a protective gas. Starting the high-frequency induction melting furnace to heat at a low power for 2 to 3 min, then increasing the power to melt the alloy into a liquid and keeping for 1 min to uniformly fuse the same, and thereafter cooling with the furnace to obtain an alloy ingot, and then cooling with the furnace after remelting 2 times to obtain a hydrogen storage alloy based on CaMg.sub.2 (the X-ray diffraction pattern is shown as the curve c in FIG. 1). Removing the alloy, putting it into a glove box filled with an inert gas and hammer-milling the alloy, and then hydrogenating the hammer-milled hydrogen storage alloy powder at a hydrogenation temperature of 40° C. and a hydrogen pressure of 50 atm for 12 h, thus obtaining a CaMg.sub.2-based alloy hydride material for hydrolysis production of hydrogen. The alloy is brittle and easy to produce alloy powder. Its hydrogen storage performance has been significantly improved compared to that before alloying, and its hydrogen absorption kinetic curve is shown in FIG. 2, with the hydrogen absorption activation energy reduced by 30%. Hydrolyzing the hydrogenated material to produce hydrogen at room temperature in pure water, the kinetic curve is shown in FIG. 7, with 90% of the theoretical hydrogen production reached within 8 min, having a very good performance of hydrolysis production of hydrogen.

Example 3

[0043] The method for the CaMg.sub.1.8Co.sub.0.2—H hydride comprises the following steps:

[0044] Weighing pure metals Ca, Mg and Co (having the purity greater than 99%) at an atomic ratio of 1:1.8:0.2, with the burning loss of Ca and Mg being 7%. And then putting the weighed metals Ca, Mg and Co in turn into a prepared crucible (provided with a vent), wherein the metal block Co is placed at the top. Installing the crucible in a high-frequency induction melting furnace, evacuating to 5×10.sup.−3 Pa, and then introducing 0.5 atm argon gas as a protective gas. Starting the high-frequency induction melting furnace to heat at a low power for 2 to 3 min, then increasing the power to melt the alloy into a liquid and keeping for 1 min to uniformly fuse the same, and thereafter cooling with the furnace to obtain an alloy ingot, and then cooling with the furnace after remelting 2 times to obtain a hydrogen storage alloy based on CaMg.sub.2 (the X-ray diffraction pattern is shown as the curve a in FIG. 1). Removing the alloy, putting it into a glove box filled with an inert gas and hammer-milling the alloy, and then hydrogenating the hammer-milled hydrogen storage alloy powder at a hydrogenation temperature of 100° C. and a hydrogen pressure of 50 atm for 10 h, thus obtaining a CaMg.sub.2-based alloy hydride material for hydrolysis production of hydrogen. The alloy is brittle and easy to produce alloy powder. Its hydrogen storage performance has been significantly improved compared to that before alloying, with the hydrogen absorption activation energy reduced by 30%. Hydrolyzing the hydrogenated material for hydrolysis production of hydrogen at room temperature in pure water, with 90% of the theoretical hydrogen production reached within 10 min, having a very good performance of hydrolysis production of hydrogen.

Example 4

[0045] The method for the CaMg.sub.1.9Co.sub.0.1—H hydride comprises the following steps:

[0046] Weighing pure metals Ca, Mg and Co (having the purity greater than 99%) at an atomic ratio of 1:1.9:0.1, with the burning loss of Ca and Mg being 7% and 6%, respectively. And then putting the weighed metals Ca, Mg and Co in turn into a prepared crucible (provided with a vent), wherein the metal block Co is placed at the top. Installing the crucible in a high-frequency induction melting furnace, evacuating to 5×10.sup.−3 Pa, and then introducing 0.5 atm argon gas as a protective gas. Starting the high-frequency induction melting furnace to heat at a low power for 2 to 3 min, then increasing the power to melt the alloy into a liquid and keeping for 1 min to uniformly fuse the same, and thereafter cooling with the furnace to obtain an alloy ingot, and then cooling with the furnace after remelting 2 times to obtain a hydrogen storage alloy based on CaMg.sub.2. Removing the alloy, putting it into a glove box filled with an inert gas and hammer-milling the alloy, and then hydrogenating the hammer-milled hydrogen storage alloy powder at a hydrogenation temperature of 100° C. and a hydrogen pressure of 50 atm for 14 h, thus obtaining a CaMg.sub.2-based alloy hydride material for hydrolysis production of hydrogen. The alloy is brittle and easy to produce alloy powder. Its hydrogen storage performance has been significantly improved compared to that before alloying, with the hydrogen absorption activation energy reduced by 30%. Hydrolyzing the hydrogenated material for hydrolysis production of hydrogen at room temperature in pure water, with 90% of the theoretical hydrogen production reached within 10 min, having a very good performance of hydrolysis production of hydrogen.

Example 5

[0047] The method for the CaMg.sub.1.8Fe.sub.0.2—H hydride comprises the following steps:

[0048] Weighing pure metals Ca, Mg and Fe (having the purity greater than 99%) at an atomic ratio of 1:1.8:0.2, with the burning loss of Ca and Mg being 7%. And then putting the weighed metals Ca, Mg and Fe in turn into a prepared crucible (provided with a vent), wherein the metal block Fe is placed at the top. Installing the crucible in a high-frequency induction melting furnace, evacuating to 5×10.sup.−3 Pa, and then introducing 0.5 atm argon gas as a protective gas. Starting the high-frequency induction melting furnace to heat at a low power for 2 to 3 min, then increasing the power to melt the alloy into a liquid and keeping for 1 min to uniformly fuse the same, and thereafter cooling with the furnace to obtain an alloy ingot, and then cooling with the furnace after remelting 2 times to obtain a hydrogen storage alloy based on CaMg.sub.2 (the X-ray diffraction pattern is shown as the curve b in FIG. 1). Removing the alloy, putting it into a glove box filled with an inert gas and hammer-milling the alloy, and then hydrogenating the hammer-milled hydrogen storage alloy powder at a hydrogenation temperature of 100° C. and a hydrogen pressure of 50 atm for 10 h, thus obtaining a CaMg.sub.2-based alloy hydride material for hydrolysis production of hydrogen. The alloy is brittle and easy to produce alloy powder. Its hydrogen storage performance has been significantly improved compared to that before alloying, with the hydrogen absorption activation energy reduced by 30%. Hydrolyzing the hydrogenated material for hydrolysis production of hydrogen at room temperature in pure water, with 90% of the theoretical hydrogen production reached within 10 min, having a very good performance of hydrolysis production of hydrogen.

Example 6

[0049] The method for the CaMg.sub.1.9Fe.sub.0.1—H hydride comprises the following steps:

[0050] Weighing pure metals Ca, Mg and Fe (having the purity greater than 99%) at an atomic ratio of 1:1.9:0.1, with the burning loss of Ca and Mg being 7% and 6%, respectively. And then putting the weighed metals Ca, Mg and Fe in turn into a prepared crucible (provided with a vent), wherein the metal block Fe is placed at the top. Installing the crucible in a high-frequency induction melting furnace, evacuating to 5×10.sup.−3 Pa, and then introducing 0.5 atm argon gas as a protective gas. Starting the high-frequency induction melting furnace to heat at a low power for 2 to 3 min, then increasing the power to melt the alloy into a liquid and keeping for 1 min to uniformly fuse the same, and thereafter cooling with the furnace to obtain an alloy ingot, and then cooling with the furnace after remelting 2 times to obtain a hydrogen storage alloy based on CaMg.sub.2. Removing the alloy, putting it into a glove box filled with an inert gas and hammer-milling the alloy, and then hydrogenating the hammer-milled hydrogen storage alloy powder at a hydrogenation temperature of 100° C. and a hydrogen pressure of 50 atm for 14 h, thus obtaining a CaMg.sub.2-based alloy hydride material for hydrolysis production of hydrogen. The alloy is brittle and easy to produce alloy powder. Its hydrogen storage performance has been significantly improved compared to that before alloying, with the hydrogen absorption activation energy reduced by 30%. Hydrolyzing the hydrogenated material for hydrolysis production of hydrogen at room temperature in pure water, with 90% of the theoretical hydrogen production reached within 10 min, having a very good performance of hydrolysis production of hydrogen.

Example 7

[0051] The method for the CaMg.sub.1.6Ni.sub.0.4—H hydride comprises the following steps:

[0052] Weighing pure metals Ca, Mg and Ni (having the purity greater than 99%) at an atomic ratio of 1:1.6:0.4, with the burning loss of Ca and Mg being 8%. And then putting the weighed metals Ca, Mg and Ni in turn into a prepared crucible (provided with a vent), wherein the metal block Ni is placed at the top. Installing the crucible in a high-frequency induction melting furnace, evacuating to 5×10.sup.−3 Pa, and then introducing 0.5 atm argon gas as a protective gas. Starting the high-frequency induction melting furnace to heat at a low power for 2 to 3 min, then increasing the power to melt the alloy into a liquid and keeping for 1 min to uniformly fuse the same, and thereafter cooling with the furnace to obtain an alloy ingot, and then cooling with the furnace after remelting 2 times to obtain a hydrogen storage alloy based on CaMg.sub.2. Removing the alloy, putting it into a glove box filled with an inert gas and hammer-milling the alloy, and then hydrogenating the hammer-milled hydrogen storage alloy powder at a hydrogenation temperature of 40° C. and a hydrogen pressure of 50 atm for 10 h, thus obtaining a CaMg.sub.2-based alloy hydride material for hydrolysis production of hydrogen. The alloy is brittle and easy to produce alloy powder. Its hydrogen storage performance has been significantly improved compared to that before alloying, with the hydrogen absorption activation energy reduced by 30%. Hydrolyzing the hydrogenated material for hydrolysis production of hydrogen at room temperature in pure water, with 90% of the theoretical hydrogen production reached within 8 min, having a very good performance of hydrolysis production of hydrogen.

Example 8

[0053] The method for the CaMg.sub.1.6Co.sub.0.4—H hydride comprises the following steps:

[0054] Weighing pure metals Ca, Mg and Co (having the purity greater than 99%) at an atomic ratio of 1:1.6:0.4, with the burning loss of Ca and Mg being 8%. And then putting the weighed metals Ca, Mg and Co in turn into a prepared crucible (provided with a vent), wherein the metal block Co is placed at the top. Installing the crucible in a high-frequency induction melting furnace, evacuating to 5×10.sup.−3 Pa, and then introducing 0.5 atm argon gas as a protective gas. Starting the high-frequency induction melting furnace to heat at a low power for 2 to 3 min, then increasing the power to melt the alloy into a liquid and keeping for 1 min to uniformly fuse the same, and thereafter cooling with the furnace to obtain an alloy ingot, and then cooling with the furnace after remelting 2 times to obtain a hydrogen storage alloy based on CaMg.sub.2. Removing the alloy, putting it into a glove box filled with an inert gas and hammer-milling the alloy, and then hydrogenating the hammer-milled hydrogen storage alloy powder at a hydrogenation temperature of 80° C. and a hydrogen pressure of 45 atm for 7 h, thus obtaining a CaMg.sub.2-based alloy hydride material for hydrolysis production of hydrogen. The alloy is brittle and easy to produce alloy powder. Its hydrogen storage performance has been significantly improved compared to that before alloying, with the hydrogen absorption activation energy reduced by 30%. Hydrolyzing the hydrogenated material for hydrolysis production of hydrogen at room temperature in pure water, with 90% of the theoretical hydrogen production reached within 8 min, having a very good performance of hydrolysis production of hydrogen.

Example 9

[0055] The method for the CaMg.sub.1.6Fe.sub.0.4—H hydride comprises the following steps:

[0056] Weighing pure metals Ca, Mg and Fe (having the purity greater than 99%) at an atomic ratio of 1:1.6:0.4, with the burning loss of Ca and Mg being 8%. And then putting the weighed metals Ca, Mg and Fe in turn into a prepared crucible (provided with a vent), wherein the metal block Fe is placed at the top. Installing the crucible in a high-frequency induction melting furnace, evacuating to 5×10.sup.−3 Pa, and then introducing 0.5 atm argon gas as a protective gas. Starting the high-frequency induction melting furnace to heat at a low power for 2 to 3 min, then increasing the power to melt the alloy into a liquid and keeping for 1 min to uniformly fuse the same, and thereafter cooling with the furnace to obtain an alloy ingot, and then cooling with the furnace after remelting 2 times to obtain a hydrogen storage alloy based on CaMg.sub.2. Removing the alloy, putting it into a glove box filled with an inert gas and hammer-milling the alloy, and then hydrogenating the hammer-milled hydrogen storage alloy powder at a hydrogenation temperature of 100° C. and a hydrogen pressure of 50 atm for 8 h, thus obtaining a CaMg.sub.2-based alloy hydride material for hydrolysis production of hydrogen. The alloy is brittle and easy to produce alloy powder. Its hydrogen storage performance has been significantly improved compared to that before alloying, with the hydrogen absorption activation energy reduced by 30%. Hydrolyzing the hydrogenated material for hydrolysis production of hydrogen at room temperature in pure water, with 90% of the theoretical hydrogen production reached within 8 min, having a very good performance of hydrolysis production of hydrogen.

Example 10

[0057] The method for the CaMg.sub.1.9Ni.sub.0.1—H hydride comprises the following steps:

[0058] Weighing pure metals Ca, Mg and Ni (having the purity greater than 99%) at an atomic ratio of 1:1.9:0.1, with the burning loss of Ca and Mg being 7% and 6%, respectively. And then putting the weighed metals Ca, Mg and Ni in turn into a prepared crucible (provided with a vent), wherein the metal block Ni is placed at the top. Installing the crucible in a high-frequency induction melting furnace, evacuating to 5×10.sup.−3 Pa, and then introducing 0.5 atm argon gas as a protective gas. Starting the high-frequency induction melting furnace to heat at a low power for 2 to 3 min, then increasing the power to melt the alloy into a liquid and keeping for 1 min to uniformly fuse the same, and thereafter cooling with the furnace to obtain an alloy ingot, and then cooling with the furnace after remelting 2 times to obtain a hydrogen storage alloy based on CaMg.sub.2 (the X-ray diffraction pattern is shown as the curve d in FIG. 1). Removing the alloy, putting it into a glove box filled with an inert gas and hammer-milling the alloy, and then hydrogenating the hammer-milled hydrogen storage alloy powder at a hydrogenation temperature of 40° C. and a hydrogen pressure of 50 atm for 8 h, thus obtaining a CaMg.sub.2-based alloy hydride material for hydrolysis production of hydrogen. The alloy is brittle and easy to produce alloy powder. Its hydrogen storage performance has been significantly improved compared to that before alloying, and its hydrogen absorption kinetic curve is shown in FIG. 2, with the hydrogen absorption activation energy reduced by 30%. Hydrolyzing the hydrogenated material to produce hydrogen at room temperature in pure water, and the kinetic curve is shown in FIG. 7, with 90% of the theoretical hydrogen production reached within 8 min, having a very good performance of hydrolysis production of hydrogen.

Example 11

[0059] The method for the CaMg.sub.1.9Ni.sub.0.1—H hydride comprises the following steps:

[0060] Weighing pure metals Ca, Mg and Ni (having the purity greater than 99%) at an atomic ratio of 1:1.9:0.1, with the burning loss of Ca and Mg being 7% and 6%, respectively. And then putting the weighed metals Ca, Mg and Ni in turn into a prepared crucible (provided with a vent), wherein the metal block Ni is placed at the top. Installing the crucible in a high-frequency induction melting furnace, evacuating to 5×10.sup.−3 Pa, and then introducing 0.5 atm argon gas as a protective gas. Starting the high-frequency induction melting furnace to heat at a low power for 2 to 3 min, then increasing the power to melt the alloy into a liquid and keeping for 1 min to uniformly fuse the same, and thereafter cooling with the furnace to obtain an alloy ingot, and then cooling with the furnace after remelting 2 times to obtain a hydrogen storage alloy based on CaMg.sub.2 (the X-ray diffraction pattern is shown as the curve d in FIG. 1). Removing the alloy, putting it into a glove box filled with an inert gas and hammer-milling the alloy, and then hydrogenating the hammer-milled hydrogen storage alloy powder at a hydrogenation temperature of 60° C. and a hydrogen pressure of 40 atm for 5 h, thus obtaining a CaMg.sub.2-based alloy hydride material for hydrolysis production of hydrogen. The alloy is brittle and easy to produce alloy powder. Its hydrogen storage performance has been significantly improved compared to that before alloying, and its hydrogen absorption kinetic curve is shown in FIG. 2, with the hydrogen absorption activation energy reduced by 30%. Hydrolyzing the hydrogenated material to produce hydrogen at room temperature in pure water, and the kinetic curve is shown in FIG. 7, with 90% of the theoretical hydrogen production reached within 8 min, having a very good performance of hydrolysis production of hydrogen.

Example 12

[0061] The method for the CaMg.sub.1.9Ni.sub.0.1—H hydride comprises the following steps:

[0062] Weighing pure metals Ca, Mg and Ni (having the purity greater than 99%) at an atomic ratio of 1:1.9:0.1, with the burning loss of Ca and Mg being 7% and 6%, respectively. And then putting the weighed metals Ca, Mg and Ni in turn into a prepared crucible (provided with a vent), wherein the metal block Ni is placed at the top. Installing the crucible in a high-frequency induction melting furnace, evacuating to 5×10.sup.−3 Pa, and then introducing 0.5 atm argon gas as a protective gas. Starting the high-frequency induction melting furnace to heat at a low power for 2 to 3 min, then increasing the power to melt the alloy into a liquid and keeping for 1 min to uniformly fuse the same, and thereafter cooling with the furnace to obtain an alloy ingot, and then cooling with the furnace after remelting 2 times to obtain a hydrogen storage alloy based on CaMg.sub.2 (the X-ray diffraction pattern is shown as the curve d in FIG. 1). Removing the alloy, putting it into a glove box filled with an inert gas and hammer-milling the alloy, and then hydrogenating the hammer-milled hydrogen storage alloy powder at a hydrogenation temperature of 80° C. and a hydrogen pressure of 40 atm for 3 h, thus obtaining a CaMg.sub.2-based alloy hydride material for hydrolysis production of hydrogen. The alloy is brittle and easy to produce alloy powder. Its hydrogen storage performance has been significantly improved compared to that before alloying, and its hydrogen absorption kinetic curve is shown in FIG. 2, with the hydrogen absorption activation energy reduced by 30%. Hydrolyzing the hydrogenated material to produce hydrogen at room temperature in pure water, and the kinetic curve is shown in FIG. 7, with 90% of the theoretical hydrogen production reached within 8 min, having a very good performance of hydrolysis production of hydrogen.

Example 13

[0063] The method for the CaMg.sub.1.8Co.sub.0.2—H hydride comprises the following steps:

[0064] Weighing pure metals Ca, Mg and Co (having the purity greater than 99%) at an atomic ratio of 1:1.8:0.2, with the burning loss of Ca and Mg being 7%. And then putting the weighed metals Ca, Mg and Co in turn into a prepared crucible (provided with a vent), wherein the metal block Co is placed at the top. Installing the crucible in a high-frequency induction melting furnace, evacuating to 5×10.sup.−3 Pa, and then introducing 0.5 atm argon gas as a protective gas. Starting the high-frequency induction melting furnace to heat at a low power for 2 to 3 min, then increasing the power to melt the alloy into a liquid and keeping for 1 min to uniformly fuse the same, and thereafter cooling with the furnace to obtain an alloy ingot, and then cooling with the furnace after remelting 2 times to obtain a hydrogen storage alloy based on CaMg.sub.2 (the X-ray diffraction pattern is shown as the curve a in FIG. 1). Removing the alloy, putting it into a glove box filled with an inert gas and hammer-milling the alloy, and then hydrogenating the hammer-milled hydrogen storage alloy powder at a hydrogenation temperature of 80° C. and a hydrogen pressure of 55 atm for 8 h, thus obtaining a CaMg.sub.2-based alloy hydride material for hydrolysis production of hydrogen. The alloy is brittle and easy to produce alloy powder. Its hydrogen storage performance has been significantly improved compared to that before alloying, with the hydrogen absorption activation energy reduced by 30%. Hydrolyzing the hydrogenated material for hydrolysis production of hydrogen at room temperature in pure water, with 90% of the theoretical hydrogen production reached within 10 min, having a very good performance of hydrolysis production of hydrogen.

Example 14

[0065] The method for the CaMg.sub.1.8Fe.sub.0.2—H hydride comprises the following steps:

[0066] Weighing pure metals Ca, Mg and Fe (having the purity greater than 99%) at an atomic ratio of 1:1.8:0.2, with the burning loss of Ca and Mg being 7%. And then putting the weighed metals Ca, Mg and Fe in turn into a prepared crucible (provided with a vent), wherein the metal block Fe is placed at the top. Installing the crucible in a high-frequency induction melting furnace, evacuating to 5×10.sup.−3 Pa, and then introducing 0.5 atm argon gas as a protective gas. Starting the high-frequency induction melting furnace to heat at a low power for 2 to 3 min, then increasing the power to melt the alloy into a liquid and keeping for 1 min to uniformly fuse the same, and thereafter cooling with the furnace to obtain an alloy ingot, and then cooling with the furnace after remelting 2 times to obtain a hydrogen storage alloy based on CaMg.sub.2 (the X-ray diffraction pattern is shown as the curve b in FIG. 1). Removing the alloy, putting it into a glove box filled with an inert gas and hammer-milling the alloy, and then hydrogenating the hammer-milled hydrogen storage alloy powder at a hydrogenation temperature of 80° C. and a hydrogen pressure of 50 atm for 8 h, thus obtaining a CaMg.sub.2-based alloy hydride material for hydrolysis production of hydrogen. The alloy is brittle and easy to produce alloy powder. Its hydrogen storage performance has been significantly improved compared to that before alloying, with the hydrogen absorption activation energy reduced by 30%. Hydrolyzing the hydrogenated material for hydrolysis production of hydrogen at room temperature in pure water, with 90% of the theoretical hydrogen production reached within 10 min, having a very good performance of hydrolysis production of hydrogen.

Example 15

[0067] The method for the CaMg.sub.1.6Ni.sub.0.4—H hydride comprises the following steps:

[0068] Weighing pure metals Ca, Mg and Ni (having the purity greater than 99%) at an atomic ratio of 1:1.6:0.4, with the burning loss of Ca and Mg being 8%. And then putting the weighed metals Ca, Mg and Ni in turn into a prepared crucible (provided with a vent), wherein the metal block Ni is placed at the top. Installing the crucible in a high-frequency induction melting furnace, evacuating to 5×10.sup.−3 Pa, and then introducing 0.5 atm argon gas as a protective gas. Starting the high-frequency induction melting furnace to heat at a low power for 2 to 3 min, then increasing the power to melt the alloy into a liquid and keeping for 1 min to uniformly fuse the same, and thereafter cooling with the furnace to obtain an alloy ingot, and then cooling with the furnace after remelting 2 times to obtain a hydrogen storage alloy based on CaMg.sub.2. Removing the alloy, putting it into a glove box filled with an inert gas and hammer-milling the alloy, and then hydrogenating the hammer-milled hydrogen storage alloy powder at a hydrogenation temperature of 80° C. and a hydrogen pressure of 50 atm for 6 h, thus obtaining a CaMg.sub.2-based alloy hydride material for hydrolysis production of hydrogen. The alloy is brittle and easy to produce alloy powder. Its hydrogen storage performance has been significantly improved compared to that before alloying, with the hydrogen absorption activation energy reduced by 30%. Hydrolyzing the hydrogenated material for hydrolysis production of hydrogen at room temperature in pure water, with 90% of the theoretical hydrogen production reached within 8 min, having a very good performance of hydrolysis production of hydrogen.

Example 16

[0069] The method for the CaMg.sub.1.6Co.sub.0.4—H hydride comprises the following steps:

[0070] Weighing pure metals Ca, Mg and Co (having the purity greater than 99%) at an atomic ratio of 1:1.6:0.4, with the burning loss of Ca and Mg being 8%. And then putting the weighed metals Ca, Mg and Co in turn into a prepared crucible (provided with a vent), wherein the metal block Co is placed at the top. Installing the crucible in a high-frequency induction melting furnace, evacuating to 5×10.sup.−3 Pa, and then introducing 0.5 atm argon gas as a protective gas. Starting the high-frequency induction melting furnace to heat at a low power for 2 to 3 min, then increasing the power to melt the alloy into a liquid and keeping for 1 min to uniformly fuse the same, and thereafter cooling with the furnace to obtain an alloy ingot, and then cooling with the furnace after remelting 2 times to obtain a hydrogen storage alloy based on CaMg.sub.2. Removing the alloy, putting it into a glove box filled with an inert gas and hammer-milling the alloy, and then hydrogenating the hammer-milled hydrogen storage alloy powder at a hydrogenation temperature of 40° C. and a hydrogen pressure of 45 atm for 10 h, thus obtaining a CaMg.sub.2-based alloy hydride material for hydrolysis production of hydrogen. The alloy is brittle and easy to produce alloy powder. Its hydrogen storage performance has been significantly improved compared to that before alloying, with the hydrogen absorption activation energy reduced by 30%. Hydrolyzing the hydrogenated material for hydrolysis production of hydrogen at room temperature in pure water, with 90% of the theoretical hydrogen production reached within 8 min, having a very good performance of hydrolysis production of hydrogen.

Example 17

[0071] The method for the CaMg.sub.1.6Fe.sub.0.4—H hydride comprises the following steps:

[0072] Weighing pure metals Ca, Mg and Fe (having the purity greater than 99%) at an atomic ratio of 1:1.6:0.4, with the burning loss of Ca and Mg being 8%. And then putting the weighed metals Ca, Mg and Fe in turn into a prepared crucible (provided with a vent), wherein the metal block Fe is placed at the top. Installing the crucible in a high-frequency induction melting furnace, evacuating to 5×10.sup.−3 Pa, and then introducing 0.5 atm argon gas as a protective gas. Starting the high-frequency induction melting furnace to heat at a low power for 2 to 3 min, then increasing the power to melt the alloy into a liquid and keeping for 1 min to uniformly fuse the same, and thereafter cooling with the furnace to obtain an alloy ingot, and then cooling with the furnace after remelting 2 times to obtain a hydrogen storage alloy based on CaMg.sub.2. Removing the alloy, putting it into a glove box filled with an inert gas and hammer-milling the alloy, and then hydrogenating the hammer-milled hydrogen storage alloy powder at a hydrogenation temperature of 40° C. and a hydrogen pressure of 50 atm for 12 h, thus obtaining a CaMg.sub.2-based alloy hydride material for hydrolysis production of hydrogen. The alloy is brittle and easy to produce alloy powder. Its hydrogen storage performance has been significantly improved compared to that before alloying, with the hydrogen absorption activation energy reduced by 30%. Hydrolyzing the hydrogenated material for hydrolysis production of hydrogen at room temperature in pure water, with 90% of the theoretical hydrogen production reached within 10 min, having a very good performance of hydrolysis production of hydrogen.