CN110042304A - A kind of high-pressure metal hydride composite hydrogen occluding tank high platform pressure hydrogen bearing alloy - Google Patents

Abstract

The invention discloses a high-platform pressure hydrogen storage alloy for a high-pressure metal hydride composite hydrogen storage tank. The chemical composition of the hydrogen storage alloy is ZrxFeyMz, wherein M is Al, Si, Cr, Mo, V, W or their combination; x, y, z represent the atomic ratio of Zr, Fe, M respectively, and x is 1-1.1 , y ranges from 1.5 to 2, and z ranges from 0 to 0.5. This series of hydrogen storage alloys has large hydrogen storage capacity, high platform pressure, easy activation, and excellent kinetic properties. It can absorb hydrogen in 2 minutes at room temperature. When the high-platform pressure hydrogen storage alloy of the present invention is applied in a 350atm vehicle-mounted high-pressure composite hydrogen storage tank, the weight density is 1.82wt%, and its bulk density reaches 40kg/m3 at this time, which is 2.4 times that of an ordinary high-pressure gaseous hydrogen storage tank. It is an excellent choice for high-platform pressure hydrogen storage alloys for vehicle-mounted high-pressure composite hydrogen storage tanks.

Description

A high-platform pressure hydrogen storage alloy for high-pressure metal hydride composite hydrogen storage tank

technical field

The invention relates to the field of solid-state hydrogen storage, in particular to a high-platform pressure hydrogen storage alloy for a high-pressure metal hydride composite hydrogen storage tank.

Background technique

Hydrogen has high combustion calorific value and non-polluting products, making it an ideal energy source for the future society. To realize the large-scale application of hydrogen energy, the three key links of hydrogen production, storage, transportation and application must be solved first, and compact, safe and efficient hydrogen storage technology is the core. Traditional hydrogen storage and transportation generally use two methods: high-pressure gaseous state and low-temperature liquid state, but from the perspective of safety and economy, these two hydrogen storage methods cannot meet practical applications. Another hydrogen storage technology—solid-state hydrogen storage—refers to storing hydrogen in solid-state hydrogen storage materials by means of physical or chemical adsorption. This new type of hydrogen storage technology has the advantages of high volumetric hydrogen storage density, convenient storage and transportation, and good safety performance, so it is considered to be the most promising hydrogen storage method. However, the mass hydrogen storage density of traditional metal hydrides is low, which still cannot meet the requirements of on-board applications. In order to develop a hydrogen storage system with excellent performance, the researchers proposed to combine a traditional high-platform pressure hydrogen storage alloy and a high-pressure gaseous hydrogen storage tank to form a composite high-pressure metal hydride hydrogen storage tank. This composite hydrogen storage tank has the advantages of high hydrogen storage capacity, less heat release, high safety, and wide applicable temperature.

At present, the 350atm composite hydrogen storage tank is an ideal vehicle-mounted hydrogen storage medium. The high platform pressure hydrogen storage alloy is the core part of the composite hydrogen storage tank, and its performance directly affects the use of the hydrogen storage tank. On the one hand, the higher the plateau pressure, the lower the stability, so hydrogen desorption can also be achieved at lower temperatures, while eliminating the need for additional heating devices. On the other hand, the reduction of the enthalpy of hydrogen absorption and desorption can reduce the thermal effect during the use of the hydrogen storage tank, which is beneficial to improve the working efficiency of the hydrogen storage tank. To ensure the large-scale vehicle application of the hydrogen storage tank, the high-platform pressure hydrogen storage alloy must have the Large mass hydrogen storage density, good platform performance, kinetic performance and cycle performance.

The hydrogen absorption plateau pressure of ZrFe2 alloy at 20°C reaches 690 atm, and the hydrogen desorption plateau pressure is 325 atm, which is the highest equilibrium pressure among the hydrogen storage alloys discovered so far, and is very suitable for high plateau pressure hydrogen storage alloys. However, the plateau pressure of the ZrFe2 alloy is much higher than the application requirements of the 350atm composite hydrogen storage tank, and the hydrogen storage capacity of the alloy at 1800atm is only 1.7wt%, which is far lower than the requirements of the composite hydrogen storage tank. Therefore, reducing the plateau pressure of alloy hydrides and increasing the hydrogen storage capacity of alloys by alloying is the key to developing ZrFe2-based high plateau pressure hydrogen storage alloys.

SUMMARY OF THE INVENTION

The invention solves the problem in the prior art that the mass hydrogen storage density of traditional metal hydrides is low and cannot meet the requirements of on-board applications, and provides a high-platform pressure hydrogen storage alloy for a high-pressure metal hydride composite hydrogen storage tank, which is In application, a composite high-pressure metal hydride hydrogen storage tank is formed by combining a traditional high-platform pressure hydrogen storage alloy and a high-pressure gaseous hydrogen storage tank. This composite hydrogen storage tank has the advantages of high hydrogen storage capacity, low heat release and safety It has the advantages of high temperature and wide applicable temperature, and effectively solves the shortcomings of insufficient hydrogen storage capacity and poor safety in a single light-weight high-pressure hydrogen storage tank.

The present invention is achieved through the following technical solutions:

A high-platform pressure hydrogen storage alloy for a high-pressure metal hydride composite hydrogen storage tank, characterized in that the chemical composition of the alloy is ZrxFeyMz, wherein M is Al, Si, Cr, Mo, V, W and combinations thereof, so The x, y and z in the hydrogen storage alloy respectively represent the corresponding atomic ratios of Zr, Fe and M, wherein the range of x is 1-1.1, the range of y is 1.5-2, and the range of z is 0-0.5.

Further, a high-platform pressure hydrogen storage alloy for a high-pressure metal hydride composite hydrogen storage tank, the range of the sum of y and z is: 2-2.5.

Further, in a high-platform pressure hydrogen storage alloy for a high-pressure metal hydride composite hydrogen storage tank, the value range of (y+z)/x is 1.9-2.

Further, a high-platform pressure hydrogen storage alloy for a high-pressure metal hydride composite hydrogen storage tank, the alloy is composed of a C15 face-centered cubic Laves type structure.

Further, a high-platform pressure hydrogen storage alloy for a high-pressure metal hydride composite hydrogen storage tank is provided, the alloy is composed of a C14 type hexagonal Laves type structure.

Further, a high-platform pressure hydrogen storage alloy for a high-pressure metal hydride composite hydrogen storage tank, the preparation method of the alloy is as follows: the alloy is prepared by the method of arc melting, and the raw metal ingot with a purity higher than 99wt% is proportionally After weighing, put it into arc smelting, clean the smelting furnace cavity with high-purity argon gas (99.99%) three times, then vacuumize for 2 hours, and then fill it with a certain amount of high-purity argon gas (99.99%) for protection, and the alloy is turned over. Melt 4 to 5 times to ensure the uniformity of ingredients.

Further, a high-platform pressure hydrogen storage alloy for a high-pressure metal hydride composite hydrogen storage tank, the prepared high-platform pressure hydrogen storage alloy can be applied to vehicle-mounted composite hydrogen storage tanks, fuel cells, heat storage and heat transfer, hydrides Hydrogen storage device, hydrogen separation and recovery, high-purity hydrogen production, hydride compression, refrigeration, heating and other technical fields.

In actual use, the high-platform pressure hydrogen storage alloy used for high-pressure metal hydride composite hydrogen storage tanks can store more than 1.5 wt% of hydrogen at 350 atm, and the hydrogen release platform pressure at room temperature exceeds 10 atm; One cycle of hydrogen absorption and desorption can be fully activated, and the hydrogen absorption and desorption process can be completed in 2 minutes at room temperature, and the kinetic performance is very excellent. According to the description of the advantages, it can be found that many advantages of the alloy can make the prepared high-platform pressure hydrogen storage alloy can be used in vehicle-mounted composite hydrogen storage tanks, fuel cells, heat storage and heat transfer, hydride hydrogen storage devices, hydrogen separation and recovery, high Purity hydrogen production, hydride compression, refrigeration, heating and other technical fields, and promote the development of the above fields.

To sum up, the following beneficial effects of the present invention:

1. A high-platform pressure hydrogen storage alloy for a high-pressure metal hydride composite hydrogen storage tank of the present invention, according to the practical application requirements of a 350 atm composite hydrogen storage tank, the alloy is replaced by multiple elements through alloying, and different hydrogen storage capacities and different hydrogen storage capacity can be obtained. Platform pressure hydrogen storage alloy.

2. The present invention is a high-platform pressure hydrogen storage alloy for a high-pressure metal hydride composite hydrogen storage tank. This series of hydrogen storage alloys has high hydrogen storage capacity, good platform performance, easy activation, and excellent kinetic performance. It can be stored in 2 minutes at room temperature. Saturated with hydrogen.

3. A high-platform pressure hydrogen storage alloy for a high-pressure metal hydride composite hydrogen storage tank of the present invention, when the high-platform pressure hydrogen storage alloy is applied in a 350atm vehicle-mounted composite hydrogen storage tank, the weight density is 1.82wt%, and its volume The density reaches 40kg/m3, which is 2.4 times that of ordinary 350atm high-pressure gaseous hydrogen storage tanks. It is an excellent choice for high-platform pressure hydrogen storage alloys for vehicle-mounted high-pressure composite hydrogen storage tanks.

Description of drawings

The accompanying drawings described herein are used to provide further understanding of the embodiments of the present invention, and constitute a part of the present application, and do not constitute limitations to the embodiments of the present invention. In the attached image:

1 is the XRD patterns of the alloys in Examples 2, 5, 8, 11, and 12.

FIG. 2 is the SEM backscattering photos and energy spectrum diagrams of alloys in Examples 2, 5 and 12. FIG.

Figure 3 is the PCT hydrogen desorption curves of the alloys in Examples 2, 5, 8, and 11 at different temperatures.

FIG. 4 is the hydrogen desorption kinetic curve of the alloy in Example 8 at different temperatures.

FIG. 5 is a graph showing the relationship between the hydrogen storage density of the alloy in Example 8 and the filling amount of the alloy in a 350 atm high pressure composite hydrogen storage system.

Detailed ways

In order to make the purpose, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the embodiments and the accompanying drawings. as a limitation of the present invention.

Example 1

Preparation of ZrFe2 alloy: The raw material Zr and Fe ingots with a purity higher than 99wt% are weighed and put into arc smelting, and the smelting furnace cavity is cleaned three times with high-purity argon gas (99.99%), followed by vacuuming for 2 hours, A certain amount of high-purity argon gas (99.99%) is filled again for protection, and the alloy is turned over and smelted for 4 to 5 times to ensure the uniformity of the composition. The obtained as-cast alloy was polished with sandpaper to remove the oxide layer on the surface, washed with anhydrous alcohol, put into a glove box (H2O<3ppm, O2<5ppm) protected by an argon atmosphere, crushed into powder and passed through a 200-mesh sieve.

The PCT curve and hydrogen absorption and desorption kinetic curve of the alloy were tested on the Advanced Materials Corporation (AMC) hydrogen storage performance tester. The amount of each test sample is about 1g, the temperature is controlled to ±1°C during measurement, and the purity of the tested hydrogen is greater than 99.99%. The alloy needs to be activated before the test. The process is as follows: first, vacuumize at room temperature for half an hour, then heat to 400 °C and vacuumize for 1 hour to remove the impurity gas on the surface of the alloy, and then rapidly cool to room temperature. Hydrogen reacts rapidly until saturation. This process was repeated 3 times to ensure complete activation of the alloy.

Example 2

Preparation of Zr1.04Fe2 alloy: The raw material Zr and Fe ingots with a purity higher than 99wt% are weighed and put into arc melting according to the proportion, and the melting furnace cavity is cleaned with high-purity argon gas (99.99%) three times, and then vacuumized for 2 After 1 hour, a certain amount of high-purity argon gas (99.99%) was filled again for protection, and the alloy was turned over and smelted for 4 to 5 times to ensure the uniformity of the composition. The obtained as-cast alloy was polished with sandpaper to remove the oxide layer on the surface, washed with anhydrous alcohol, put into a glove box (H2O<3ppm, O2<5ppm) protected by an argon atmosphere, crushed into powder and passed through a 200-mesh sieve.

The PCT curve and hydrogen absorption and desorption kinetic curve of the alloy were tested on the Advanced Materials Corporation (AMC) hydrogen storage performance tester. The amount of each test sample is about 1g, the temperature is controlled to ±1°C during measurement, and the purity of the tested hydrogen is greater than 99.99%. The alloy needs to be activated before the test. The process is as follows: first, vacuumize at room temperature for half an hour, then heat to 400 °C and vacuumize for 1 hour to remove the impurity gas on the surface of the alloy, and then rapidly cool to room temperature. Hydrogen reacts rapidly until saturation. This process was repeated 3 times to ensure complete activation of the alloy.

Example 3

Preparation of Zr1.1Fe1.7Al0.3 alloy: The raw material Zr ingot, Fe ingot and Al ingot with a purity higher than 99wt% are weighed and put into arc melting, and the melting furnace cavity is filled with high-purity argon gas (99.99%) After cleaning three times, vacuuming for 2 hours, filling with a certain amount of high-purity argon gas (99.99%) again for protection, the alloy was turned over and smelted 4 to 5 times to ensure the uniformity of the composition. The obtained as-cast alloy was polished with sandpaper to remove the oxide layer on the surface, washed with anhydrous alcohol, put into a glove box (H2O<3ppm, O2<5ppm) protected by an argon atmosphere, crushed into powder and passed through a 200-mesh sieve.

The PCT curve and hydrogen absorption and desorption kinetic curve of the alloy were tested on the Advanced Materials Corporation (AMC) hydrogen storage performance tester. The amount of each test sample is about 1g, the temperature is controlled to ±1°C during measurement, and the purity of the tested hydrogen is greater than 99.99%. The alloy needs to be activated before the test. The process is as follows: first, vacuumize at room temperature for half an hour, then heat to 400 °C and vacuumize for 1 hour to remove the impurity gas on the surface of the alloy, and then rapidly cool to room temperature. Hydrogen reacts rapidly until saturation. This process was repeated 3 times to ensure complete activation of the alloy.

Example 4

Preparation of ZrFe1.7Al0.3 alloy: The raw material Zr ingot, Fe ingot and Al ingot with a purity higher than 99wt% are weighed and put into arc melting, and the melting furnace cavity is cleaned with high-purity argon gas (99.99%) for three times. After 2 hours of vacuuming, a certain amount of high-purity argon gas (99.99%) was filled again for protection, and the alloy was turned over and smelted 4 to 5 times to ensure the uniformity of the composition. The obtained as-cast alloy was polished with sandpaper to remove the oxide layer on the surface, washed with anhydrous alcohol, put into a glove box (H2O<3ppm, O2<5ppm) protected by an argon atmosphere, crushed into powder and passed through a 200-mesh sieve.

The PCT curve and hydrogen absorption and desorption kinetic curve of the alloy were tested on the Advanced Materials Corporation (AMC) hydrogen storage performance tester. The amount of each test sample is about 1g, the temperature is controlled to ±1°C during measurement, and the purity of the tested hydrogen is greater than 99.99%. The alloy needs to be activated before the test. The process is as follows: first, vacuumize at room temperature for half an hour, then heat to 400 °C and vacuumize for 1 hour to remove the impurity gas on the surface of the alloy, and then rapidly cool to room temperature. Hydrogen reacts rapidly until saturation. This process was repeated 3 times to ensure complete activation of the alloy.

Example 5

Preparation of Zr1.04Fe1.7Al0.3 alloy: The raw material Zr ingot, Fe ingot and Al ingot with a purity higher than 99wt% are weighed and put into arc melting, and the melting furnace cavity is filled with high-purity argon gas (99.99%) After cleaning three times, vacuuming for 2 hours, filling with a certain amount of high-purity argon gas (99.99%) again for protection, the alloy was turned over and smelted 4 to 5 times to ensure the uniformity of the composition. The obtained as-cast alloy was polished with sandpaper to remove the oxide layer on the surface, washed with anhydrous alcohol, put into a glove box (H2O<3ppm, O2<5ppm) protected by an argon atmosphere, crushed into powder and passed through a 200-mesh sieve.

The PCT curve and hydrogen absorption and desorption kinetic curve of the alloy were tested on the Advanced Materials Corporation (AMC) hydrogen storage performance tester. The amount of each test sample is about 1g, the temperature is controlled to ±1°C during measurement, and the purity of the tested hydrogen is greater than 99.99%. The alloy needs to be activated before the test. The process is as follows: first, vacuumize at room temperature for half an hour, then heat to 400 °C and vacuumize for 1 hour to remove the impurity gas on the surface of the alloy, and then rapidly cool to room temperature. Hydrogen reacts rapidly until saturation. This process was repeated 3 times to ensure complete activation of the alloy.

Example 6

Preparation of ZrFe1.5Al0.5 alloy: The raw material Zr ingot, Fe ingot and Al ingot with a purity higher than 99wt% are weighed and put into arc melting, and the melting furnace cavity is cleaned with high-purity argon gas (99.99%) for three times. After 2 hours of vacuuming, a certain amount of high-purity argon gas (99.99%) was filled again for protection, and the alloy was turned over and smelted 4 to 5 times to ensure the uniformity of the composition. The obtained as-cast alloy was polished with sandpaper to remove the oxide layer on the surface, washed with anhydrous alcohol, put into a glove box (H2O<3ppm, O2<5ppm) protected by an argon atmosphere, crushed into powder and passed through a 200-mesh sieve.

The PCT curve and hydrogen absorption and desorption kinetic curve of the alloy were tested on the Advanced Materials Corporation (AMC) hydrogen storage performance tester. The amount of each test sample is about 1g, the temperature is controlled to ±1°C during measurement, and the purity of the tested hydrogen is greater than 99.99%. The alloy needs to be activated before the test. The process is as follows: first, vacuumize at room temperature for half an hour, then heat to 400 °C and vacuumize for 1 hour to remove the impurity gas on the surface of the alloy, and then rapidly cool to room temperature. Hydrogen reacts rapidly until saturation. This process was repeated 3 times to ensure complete activation of the alloy.

Example 7

Preparation of Zr1.04Fe1.5Si0.5 alloy: The raw material Zr ingot, Fe ingot and Si ingot with a purity higher than 99wt% are weighed and put into arc melting, and the melting furnace cavity is filled with high-purity argon gas (99.99%) After cleaning three times, vacuuming for 2 hours, filling with a certain amount of high-purity argon gas (99.99%) again for protection, the alloy was turned over and smelted 4 to 5 times to ensure the uniformity of the composition. The obtained as-cast alloy was polished with sandpaper to remove the oxide layer on the surface, washed with anhydrous alcohol, put into a glove box (H2O<3ppm, O2<5ppm) protected by an argon atmosphere, crushed into powder and passed through a 200-mesh sieve.

The PCT curve and hydrogen absorption and desorption kinetic curve of the alloy were tested on the Advanced Materials Corporation (AMC) hydrogen storage performance tester. The amount of each test sample is about 1g, the temperature is controlled to ±1°C during measurement, and the purity of the tested hydrogen is greater than 99.99%. The alloy needs to be activated before the test. The process is as follows: first, vacuumize at room temperature for half an hour, then heat to 400 °C and vacuumize for 1 hour to remove the impurity gas on the surface of the alloy, and then rapidly cool to room temperature. Hydrogen reacts rapidly until saturation. This process was repeated 3 times to ensure complete activation of the alloy.

Example 8

Preparation of Zr1.04Fe1.7Cr0.3 alloy: The raw material Zr ingot, Fe ingot and Cr ingot with a purity higher than 99wt% are weighed and put into arc melting, and the melting furnace cavity is filled with high-purity argon gas (99.99%) After cleaning three times, vacuuming for 2 hours, filling with a certain amount of high-purity argon gas (99.99%) again for protection, the alloy was turned over and smelted 4 to 5 times to ensure the uniformity of the composition. The obtained as-cast alloy was polished with sandpaper to remove the oxide layer on the surface, washed with anhydrous alcohol, put into a glove box (H2O<3ppm, O2<5ppm) protected by an argon atmosphere, crushed into powder and passed through a 200-mesh sieve.

The PCT curve and hydrogen absorption and desorption kinetic curve of the alloy were tested on the Advanced Materials Corporation (AMC) hydrogen storage performance tester. The amount of each test sample is about 1g, the temperature is controlled to ±1°C during measurement, and the purity of the tested hydrogen is greater than 99.99%. The alloy needs to be activated before the test. The process is as follows: first, vacuumize at room temperature for half an hour, then heat to 400 °C and vacuumize for 1 hour to remove the impurity gas on the surface of the alloy, and then rapidly cool to room temperature. Hydrogen reacts rapidly until saturation. This process was repeated 3 times to ensure complete activation of the alloy.

Example 9

Preparation of Zr1.1Fe1.7Cr0.3 alloy: The raw material Zr ingot, Fe ingot and Cr ingot with a purity higher than 99wt% are weighed and put into arc melting, and the melting furnace cavity is filled with high-purity argon gas (99.99%) After cleaning three times, vacuuming for 2 hours, filling with a certain amount of high-purity argon gas (99.99%) again for protection, the alloy was turned over and smelted 4 to 5 times to ensure the uniformity of the composition. The obtained as-cast alloy was polished with sandpaper to remove the oxide layer on the surface, washed with anhydrous alcohol, put into a glove box (H2O<3ppm, O2<5ppm) protected by an argon atmosphere, crushed into powder and passed through a 200-mesh sieve.

The PCT curve and hydrogen absorption and desorption kinetic curve of the alloy were tested on the Advanced Materials Corporation (AMC) hydrogen storage performance tester. The amount of each test sample is about 1g, the temperature is controlled to ±1°C during measurement, and the purity of the tested hydrogen is greater than 99.99%. The alloy needs to be activated before the test. The process is as follows: first, vacuumize at room temperature for half an hour, then heat to 400 °C and vacuumize for 1 hour to remove the impurity gas on the surface of the alloy, and then rapidly cool to room temperature. Hydrogen reacts rapidly until saturation. This process was repeated 3 times to ensure complete activation of the alloy.

Example 10

Preparation of Zr1.04Fe1.8Mo0.2 alloy: The raw material Zr ingot, Fe ingot and Mo ingot with a purity higher than 99wt% are weighed and put into arc smelting, and the smelting furnace cavity is filled with high-purity argon gas (99.99%) After cleaning three times, vacuuming for 2 hours, filling with a certain amount of high-purity argon gas (99.99%) again for protection, the alloy was turned over and smelted 4 to 5 times to ensure the uniformity of the composition. The obtained as-cast alloy was polished with sandpaper to remove the oxide layer on the surface, washed with anhydrous alcohol, put into a glove box (H2O<3ppm, O2<5ppm) protected by an argon atmosphere, crushed into powder and passed through a 200-mesh sieve.

The PCT curve and hydrogen absorption and desorption kinetic curve of the alloy were tested on the Advanced Materials Corporation (AMC) hydrogen storage performance tester. The amount of each test sample is about 1g, the temperature is controlled to ±1°C during measurement, and the purity of the tested hydrogen is greater than 99.99%. The alloy needs to be activated before the test. The process is as follows: first, vacuumize at room temperature for half an hour, then heat to 400 °C and vacuumize for 1 hour to remove the impurity gas on the surface of the alloy, and then rapidly cool to room temperature. Hydrogen reacts rapidly until saturation. This process was repeated 3 times to ensure complete activation of the alloy.

Example 11

Preparation of Zr1.04Fe1.7Mo0.3 alloy: The raw material Zr ingot, Fe ingot and Mo ingot with a purity higher than 99wt% are weighed and put into arc melting, and the melting furnace cavity is filled with high-purity argon gas (99.99%) After cleaning three times, vacuuming for 2 hours, filling with a certain amount of high-purity argon gas (99.99%) again for protection, the alloy was turned over and smelted 4 to 5 times to ensure the uniformity of the composition. The obtained as-cast alloy was polished with sandpaper to remove the oxide layer on the surface, washed with anhydrous alcohol, put into a glove box (H2O<3ppm, O2<5ppm) protected by an argon atmosphere, crushed into powder and passed through a 200-mesh sieve.

The PCT curve and hydrogen absorption and desorption kinetic curve of the alloy were tested on the Advanced Materials Corporation (AMC) hydrogen storage performance tester. The amount of each test sample is about 1g, the temperature is controlled to ±1°C during measurement, and the purity of the tested hydrogen is greater than 99.99%. The alloy needs to be activated before the test. The process is as follows: first, vacuumize at room temperature for half an hour, then heat to 400 °C and vacuumize for 1 hour to remove the impurity gas on the surface of the alloy, and then rapidly cool to room temperature. Hydrogen reacts rapidly until saturation. This process was repeated 3 times to ensure complete activation of the alloy.

Example 12

Preparation of Zr1.04Fe1.7V0.3 alloy: The raw material Zr ingot, Fe ingot and V ingot with a purity higher than 99wt% are weighed and put into arc melting, and the melting furnace cavity is filled with high-purity argon gas (99.99%) After cleaning three times, vacuuming for 2 hours, filling with a certain amount of high-purity argon gas (99.99%) again for protection, the alloy was turned over and smelted 4 to 5 times to ensure the uniformity of the composition. The obtained as-cast alloy was polished with sandpaper to remove the oxide layer on the surface, washed with anhydrous alcohol, put into a glove box (H2O<3ppm, O2<5ppm) protected by an argon atmosphere, crushed into powder and passed through a 200-mesh sieve.

The PCT curve and hydrogen absorption and desorption kinetic curve of the alloy were tested on the Advanced Materials Corporation (AMC) hydrogen storage performance tester. The amount of each test sample is about 1g, the temperature is controlled to ±1°C during measurement, and the purity of the tested hydrogen is greater than 99.99%. The alloy needs to be activated before the test. The process is as follows: first, vacuumize at room temperature for half an hour, then heat to 400 °C and vacuumize for 1 hour to remove the impurity gas on the surface of the alloy, and then rapidly cool to room temperature. Hydrogen reacts rapidly until saturation. This process was repeated 3 times to ensure complete activation of the alloy.

Example 13

Preparation of Zr1.04Fe1.5V0.5 alloy: The raw material Zr ingot, Fe ingot and V ingot with a purity higher than 99wt% are weighed and put into arc melting, and the melting furnace cavity is filled with high-purity argon gas (99.99%) After cleaning three times, vacuuming for 2 hours, filling with a certain amount of high-purity argon gas (99.99%) again for protection, the alloy was turned over and smelted 4 to 5 times to ensure the uniformity of the composition. The obtained as-cast alloy was polished with sandpaper to remove the oxide layer on the surface, washed with anhydrous alcohol, put into a glove box (H2O<3ppm, O2<5ppm) protected by an argon atmosphere, crushed into powder and passed through a 200-mesh sieve.

The PCT curve and hydrogen absorption and desorption kinetic curve of the alloy were tested on the Advanced Materials Corporation (AMC) hydrogen storage performance tester. The amount of each test sample is about 1g, the temperature is controlled to ±1°C during measurement, and the purity of the tested hydrogen is greater than 99.99%. The alloy needs to be activated before the test. The process is as follows: first, vacuumize at room temperature for half an hour, then heat to 400 °C and vacuumize for 1 hour to remove the impurity gas on the surface of the alloy, and then rapidly cool to room temperature. Hydrogen reacts rapidly until saturation. This process was repeated 3 times to ensure complete activation of the alloy.

Example 14

Preparation of Zr1.04Fe1.8W0.2 alloy: The raw material Zr ingot, Fe ingot and W ingot with a purity higher than 99wt% are weighed and put into arc melting, and the melting furnace cavity is filled with high-purity argon gas (99.99%) After cleaning three times, vacuuming for 2 hours, filling with a certain amount of high-purity argon gas (99.99%) again for protection, the alloy was turned over and smelted 4 to 5 times to ensure the uniformity of the composition. The obtained as-cast alloy was polished with sandpaper to remove the oxide layer on the surface, washed with anhydrous alcohol, put into a glove box (H2O<3ppm, O2<5ppm) protected by an argon atmosphere, crushed into powder and passed through a 200-mesh sieve.

The PCT curve and hydrogen absorption and desorption kinetic curve of the alloy were tested on the Advanced Materials Corporation (AMC) hydrogen storage performance tester. The amount of each test sample is about 1g, the temperature is controlled to ±1°C during measurement, and the purity of the tested hydrogen is greater than 99.99%. The alloy needs to be activated before the test. The process is as follows: first, vacuumize at room temperature for half an hour, then heat to 400 °C and vacuumize for 1 hour to remove the impurity gas on the surface of the alloy, and then rapidly cool to room temperature. Hydrogen reacts rapidly until saturation. This process was repeated 3 times to ensure complete activation of the alloy.

Example 15

Preparation of Zr1.04Fe1.7W0.3 alloy: The raw material Zr ingot, Fe ingot and W ingot with a purity higher than 99wt% are weighed and put into arc smelting, and the smelting furnace cavity is filled with high-purity argon gas (99.99%) After cleaning three times, vacuuming for 2 hours, filling with a certain amount of high-purity argon gas (99.99%) again for protection, the alloy was turned over and smelted 4 to 5 times to ensure the uniformity of the composition. The obtained as-cast alloy was polished with sandpaper to remove the oxide layer on the surface, washed with anhydrous alcohol, put into a glove box (H2O<3ppm, O2<5ppm) protected by an argon atmosphere, crushed into powder and passed through a 200-mesh sieve.

The PCT curve and hydrogen absorption and desorption kinetic curve of the alloy were tested on the Advanced Materials Corporation (AMC) hydrogen storage performance tester. The amount of each test sample is about 1g, the temperature is controlled to ±1°C during measurement, and the purity of the tested hydrogen is greater than 99.99%. The alloy needs to be activated before the test. The process is as follows: first, vacuumize at room temperature for half an hour, then heat to 400 °C and vacuumize for 1 hour to remove the impurity gas on the surface of the alloy, and then rapidly cool to room temperature. Hydrogen reacts rapidly until saturation. This process was repeated 3 times to ensure complete activation of the alloy.

The specific embodiments described above further describe the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above descriptions are only specific embodiments of the present invention, and are not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (7)

1. a kind of high-pressure metal hydride composite hydrogen occluding tank presses hydrogen bearing alloy with high platform, which is characterized in that the change of the alloy Group becomes ZrxFeyMz, and wherein M is Al, Si, Cr, Mo, V, W and combinations thereof, and the x, y, z in the hydrogen bearing alloy respectively indicates The atomic ratio of corresponding Zr, Fe, M, wherein the range of x is 1-1.1, and the range of y is 1.5-2, and the range of z is 0-0.5.

2. a kind of high-pressure metal hydride composite hydrogen occluding tank according to claim 1 presses hydrogen bearing alloy with high platform, special Sign is, the y and z's and range are as follows: 2-2.5.

3. a kind of high-pressure metal hydride composite hydrogen occluding tank according to claim 1 presses hydrogen bearing alloy with high platform, special Sign is that the value range of (y+z)/x is 1.9-2.

4. a kind of high-pressure metal hydride composite hydrogen occluding tank according to claim 1 presses hydrogen bearing alloy with high platform, special Sign is that the alloy is by C15 type face-centered cubic Laves type structure composition.

5. a kind of high-pressure metal hydride composite hydrogen occluding tank according to claim 1 presses hydrogen bearing alloy with high platform, special Sign is that the alloy is by six side's Laves type structure composition of C14 type.

6. a kind of high-pressure metal hydride composite hydrogen occluding tank according to claim 1 presses hydrogen bearing alloy with high platform, special Sign is, the alloy the preparation method comprises the following steps: alloy is prepared by the method for electric arc melting, by purity higher than 99wt%'s Raw metal ingot, which proportionally weighs, to be put into electric arc melting, and melting furnace chamber is cleaned three times with high-purity argon gas (99.99%), It is subsequently vacuumed out 2 hours, is filled with a certain amount of high-purity argon gas (99.99%) protection again, alloy is by turning over melting 4-5 all over true Protect the uniformity of ingredient.

7. a kind of high-pressure metal hydride composite hydrogen occluding tank according to claim 1 presses hydrogen bearing alloy with high platform, special Sign is, the high platform pressure hydrogen bearing alloy of the preparation can be applied to the defeated heat of vehicle-mounted composite hydrogen occluding tank, fuel cell, heat accumulation, The technical fields such as hydride hydrogen storage device, hydrogen separation and recovery, high-purity hydrogen is produced, hydride compresses, freeze, heating.