CN-117488143-B - Sb-doped Al-Ga-based online hydrogen supply alloy for high-flow-rate hydrogen supply system

Abstract

The invention discloses an Sb-doped Al-Ga-based on-line hydrogen supply alloy for a high-flow-rate hydrogen supply system. The invention changes the preferred growth orientation and grain size of Al grains in the alloy by controlling the doping amount of Sb in the alloy, thereby influencing the hydrogen release performance of the alloy. Compared with an alloy without doping Sb, the hydrogen production alloy has high yield at 30 ℃ and can reach 92.68 percent. And the average hydrogen production rate of the alloy at 60 ℃ is approximately 1.78 times that of the alloy without doped Sb. And the price of the Sb-doped alloy is cheaper than that of the alloy without Sb, about 2000 yuan per ton. The alloy can be well used at a lower temperature, the yield is higher, the price is low, and the rapid hydrogen production can be realized in a high-power hydrogen supply system, so that the actual requirements are met. Has great application prospect in the field of hydrogen production materials.

Inventors

• GAO QIAN
• SHI JIE
• JIN ZHIJIANG
• ZHANG ZHONGYUAN

Assignees

• 吉林大学

Dates

Publication Date

20260512

Application Date

20231107

Claims (3)

1. 1. The Sb-doped Al-Ga-based online hydrogen supply alloy for the high-flow-rate hydrogen supply system is characterized In that Sb is added into an Al-Ga-In-Sn alloy for hydrolysis hydrogen production through a two-step method, so that after all components In the alloy are uniformly mixed, the aluminum-gallium-based alloy for hydrolysis hydrogen production is obtained after casting and forming at 300 ℃, wherein the weight ratio of an Sb refiner In the alloy is 0.01-0.2wt.%, and the total weight ratio of Ga, in and Sn is 9.99-9.8 wt.%; 90wt.% of Al, 6.7-6.85 wt.% of Ga, 2.1-2.15 wt.% of In, 0.98-1 wt.% of Sn, and 100% of Al-Ga-In-Sn-Sb; The preparation method of the Sb-doped Al-Ga-based on-line hydrogen supply alloy for the high-flow-rate hydrogen supply system comprises the following steps of: (1) In order to ensure the uniformity of each component In the alloy, an indirect smelting method is adopted, namely, firstly, two simple substances of Al and Sb are placed In a crucible, placed In a box-type atmosphere stirring furnace, a vacuum pump is turned on, and after vacuumizing, the crucible is burned under the protection atmosphere of nitrogen; (2) After the temperature of the box-type atmosphere stirring furnace is raised to be higher than 650 ℃, preserving the heat for 0.5-1h, stirring for 10-20min, and casting in a mould preheated to 200-400 ℃; (3) The method comprises the steps of weighing the remaining three elements in proportion, placing the three elements and the Al-Sb alloy prepared in advance in a crucible, placing the crucible in a high-temperature atmosphere stirring furnace, vacuumizing for 10min firstly, then introducing nitrogen, vacuumizing again to enable the whole hearth to be full of nitrogen, heating the alloy to 700-900 ℃ under the protection of nitrogen, heating at a constant speed of 8-12 ℃ per min, and keeping the temperature for 1h to enable the alloy to be completely melted, stirring at a speed of 30r/min for no more than 15min; (4) Casting the alloy after melting and stirring in a preheated mould, cooling the mould at the temperature of not lower than 300 ℃ and room temperature, and sealing and preserving the alloy by a sealing film to prevent oxidation.
2. 2. The hydrogen supplying alloy according to claim 1, wherein the grain size of each of the Sb-doped samples is reduced, and the Sb-doped Al-Ga-In-Sn-Sb alloy is prepared by doping Sb, and the grain size of the hydrogen supplying alloy is not more than 50 μm.
3. 3. The hydrogen supplying alloy according to claim 2, wherein the Sb-doped samples all deteriorate the mechanical properties thereof, the powder is easily made during the reaction, and the Sb-doped Al-Ga-In-Sn-Sb alloy is prepared by Sb doping, wherein the hardness of the hydrogen supplying alloy is less than 0.3GPa.

Description

Sb-doped Al-Ga-based online hydrogen supply alloy for high-flow-rate hydrogen supply system Technical Field The invention belongs to the technical field of hydrolysis online hydrogen supply, and particularly relates to an Sb-doped Al-Ga-based online hydrogen supply material with a rapid hydrolysis hydrogen production performance at normal temperature and a preparation method thereof. Background Currently, with the increasing consumption of fossil energy, hydrogen energy is receiving attention as a new clean energy. In the process of accelerating the popularization and application of hydrogen energy, seeking a safe, convenient and low-cost storage and transportation technology of hydrogen is one of the problems to be solved urgently. The online hydrogen supply technology represented by metal hydrolysis hydrogen production has the advantages of low dependency on infrastructure, low storage and transportation cost and the like, and gradually shows great application potential. In order to meet the requirements of hydrogen fuel cells in practical processes, the conventional hydrogen production modes mainly comprise metal hydrolysis hydrogen production, biomass hydrogen production and electrolytic water hydrogen production, but the hydrogen production modes and hydrogen production materials have some problems to limit the development of the hydrogen production modes and the hydrogen production materials. In addition, the high cost of hydrogen station construction and the safety problem in the storage and transportation process limit the application of hydrogen to a great extent in the practical application process of hydrogen. Compared with other hydrogen production modes, the Al-based alloy hydrolysis hydrogen production mode has the advantages that the preparation method is relatively simple, the method is suitable for large-scale production, hydrogen production can be realized in a neutral water environment, the hydrogen production rate of the alloy can be regulated and controlled by adjusting the formula of the alloy, the purity of hydrogen produced by an aluminum water reaction is relatively high, and the reaction can be carried out spontaneously without providing additional energy. However, since Al is relatively reactive, it is easily oxidized in air, and a dense oxide film is formed on the surface, which limits its application to a large extent. The common solving method comprises the steps of breaking a surface oxide layer through the spherical ink of Al and other substances, directly reacting the Al with acid and alkali, and adding Ga, in, sn and other elements into the Al. Compared with other methods for damaging oxide films, the method for preparing the alloy by adding Ga, in, sn and other elements into Al overcomes the defects of high energy consumption, high requirement on equipment and the like. In order to further improve the performance of the material, the related researches are continuously in depth, and the prior researches show that the appearance of Al grains in the alloy can be changed by introducing Al 2O3, al-Ti-B, ti and other refiners, so that the hydrogen production performance of the alloy is influenced to a certain extent. For example, c.d.wei.; z.liu.; j.l.wei.; d.liu.; etc.chemical PHYSICS LETTERS 2020,738, indicate that Al 2O3 can be used as a refiner for Al alloys. Al 2O3 can accelerate the solidification rate of the alloy, resulting in a reduction in the grain and grain boundary grain size of the Al alloy. When the doping amount of Al 2O3 is 1.0wt.%, the alloy shows the maximum instantaneous hydrogen production rate and the shortest reaction time, however Al 2O3 is used as a refiner, and the grain refining effect can be achieved only when the doping amount is relatively large. T.t.he., w.wang., d.m.chen., k.yang., international Journal ofHydrogen Energy, 2014, (39), 684-691, indicate that nucleation of Al on TiAl 3 results in grain refinement of the Al. At 50 ℃, a hydrogen production rate of 50mL/gAl.B.D.Du.;W.Wang.;W.Chen.;D.M.Chen.;K.Yang.,International Journal ofHydrogen Energy 2017,(42),21586-21596, for an alloy with a Ti content of 0.1wt.% indicates that Al-Ti-B as a refiner, the grain size decreases from 129 μm to 57 μm as the Ti content increases from 0.03wt.% to 0.24wt.%, with a Ti content of 0.12wt.% having the greatest hydrogen production rate. However, ti and Al-Ti-B, although reducing the grain size, form Ti layers on the Al surface, occupying the sites of Al-water reaction, so that the rate and yield of the alloy are affected. in summary, the previous researches show that the crystal grain in the alloy can promote the hydrolysis hydrogen release rate of the material to a certain extent, but the promotion effect is poor, particularly, the hydrogen yield of the material is often not ideal under normal working conditions (below 40 ℃), and is usually lower than 90%, so that the actual working condition requirement is difficult to meet. According to the inventi