Hydrogen storage nanocomposite and powder preparation equipment and method

Abstract

The application relates to the technical field of hydrogen storage, in particular to a hydrogen storage nanocomposite, the composition of the hydrogen storage nanocomposite being Ti x (La a Ce b Mg c ) 2‑x (Fe d Co e Mn f ) y , wherein x is in the range of 1<=x<=1.5, y is in the range of 1<=y<=1.5, the sum of a+b+c is in the range of 1<=a+b+c<=1.2, and c>=0.5, the sum of d+e+f is in the range of 1<=d+e+f<=1.05, and f>=0.5, the application also relates to a powder preparation equipment for the hydrogen storage nanocomposite, which comprises an equipment body, support loading plates are symmetrically arranged on the two sides of the equipment body, a support bottom ring is fixedly arranged at the lower end of the support loading plate, a feeding pipe is fixedly arranged at the upper end of the equipment body, a discharging bottom opening is formed in the lower side of one end of the equipment body, a fixed material receiving plate is fixedly arranged in the equipment body corresponding to the discharging bottom opening, a plurality of upper discharging openings are formed in the equipment body above the discharging bottom opening, and the application also relates to a preparation method of the hydrogen storage nanocomposite for producing the hydrogen storage nanocomposite.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of hydrogen storage, in particular to a hydrogen storage nanocomposite material and a powder preparation device and method. BACKGROUND

[0002] Hydrogen has the advantages of high calorific value, wide sources, clean and zero carbon, etc. Due to the disadvantages of low bulk density and easy leakage of gaseous hydrogen, the large-scale storage and application of hydrogen energy are limited. In recent years, solid-state hydrogen storage technology based on reversible hydrogen absorption and desorption chemical reactions has become a research hotspot in the field of hydrogen energy application due to its high bulk density, safety, efficiency, high hydrogen purity, etc.

[0003] Common solid-state hydrogen storage alloys include rare earth, titanium and magnesium-based alloys. The rare earth alloy is represented by LaNi5, with a saturated hydrogen absorption capacity of about 1.4wt.%, good activation performance, impurity resistance and suitable room temperature hydrogen absorption and desorption pressure; the titanium alloy is represented by TiFe and TiMn2 alloy, with a saturated hydrogen absorption capacity of about 1.8wt.%, but with the disadvantages of high activation pressure and weak impurity resistance, respectively; the magnesium-based hydrogen storage material is represented by pure magnesium and Mg2Ni, with a hydrogen storage capacity of 7.6wt.% and 4.3wt.%, respectively, but with the disadvantages of high hydrogen absorption and desorption temperature (~300℃) and low hydrogen desorption pressure. In summary, there is currently a lack of solid-state hydrogen storage alloy materials that can be used at room temperature and have high capacity and easy activation performance at normal pressure. Moreover, the production process of solid-state hydrogen storage alloy materials usually involves powdering operation of the alloy, and the existing powder preparation methods include mechanical crushing method and gas atomization method. Gas atomization uses high-pressure gas (such as air, nitrogen or argon) to atomize molten metal, and the characteristics of gas atomization are fast cooling speed, fine powder grain, high yield and low cost. However, the particle size distribution of the powder produced by the gas atomization method is usually wide, and the alloy powder cannot be automatically classified when discharged, which requires manual subsequent particle size classification, resulting in a large work intensity of the workers and a more troublesome operation. SUMMARY

[0004] The present application aims to provide a hydrogen storage nanocomposite material and a powder preparation device and method to solve the problems raised in the background art.

[0005] To achieve the above-mentioned purpose, the present application provides the following technical solutions:

[0006] A hydrogen storage nanocomposite material, the composition of the hydrogen storage nanocomposite material is Ti x (La a Ce b Mg c ) 2-x (Fe d Co e Mn f )y wherein x is in the range of 1≤x≤1.5, y is in the range of 1≤y≤1.5, the sum of a+b+c is in the range of 1≤a+b+c≤1.2, and c≥0.5, the sum of d+e+f is in the range of 1≤d+e+f≤1.05, and f≥0.5.

[0007] Preferably, the hydrogen storage nanocomposite has a composition of:

[0008] The hydrogen storage nanocomposite has a composition of: Ti 1.25 (La 0.4 Ce 0.05 Mg 0.55 ) 0.75 (Fe 0.40 Co 0.03 Mn 0.6 ) 1.15 ; or Ti 1.2 (La 0.5 Ce 0.1 Mg 0.5 ) 0.8 (Fe 0.45 Co 0.05 Mn 0.5 ) 1.2 ;

[0009] or Ti 1.4 (La 0.4 Ce 0.1 Mg 0.7 ) 0.6 (Fe 0.25 Co 0.1 Mn 0.7 ) 1.3 , which can be activated to absorb hydrogen after being vacuumed to below 0.5 Pa at room temperature and then filled with 3 MPa hydrogen pressure, and the first hydrogen absorption capacity is greater than or equal to 2.0 wt.%.

[0010] The application discloses a powder preparation device for hydrogen storage nanocomposite, which comprises a device body, support loading plates symmetrically arranged on both sides of the device body, a support bottom ring fixedly arranged at the lower end of the support loading plates, a feeding pipe fixedly arranged at the upper end of the device body, a discharging bottom opening formed at the lower side of one end of the device body, a fixed material receiving plate fixedly arranged in the device body corresponding to the discharging bottom opening, a plurality of upper discharging openings formed in the device body corresponding to the upper discharging openings, a separation loading plate fixedly arranged in the device body corresponding to the upper discharging openings, a separation hole formed in the separation loading plate, a connecting plate sleeve fixedly arranged at the upper side of the discharging bottom opening and the upper discharging opening, a bearing matching plate fixedly arranged on the connecting plate sleeve, a support guide hole formed in the bearing matching plate, an insertion movable hole formed in the other end of the device body opposite to the discharging bottom opening and the upper discharging opening, a hydraulic rod fixedly arranged on the device body at the lower side of the insertion movable hole, a bearing guide rod fixedly arranged on the device body at the lower side of the hydraulic rod, a connecting loading frame fixedly arranged on the bearing guide rod, a stable connecting plate fixedly arranged at the upper end of the connecting loading frame, support matching plates symmetrically arranged at both sides of the connecting loading frame, a stable insertion hole formed in the support matching plate, a matching insertion hole formed in the hole bottom of the stable insertion hole, support strips fixedly arranged at both sides of the device body, limit guide rods fixedly arranged on the support strips, and an automatic grading type discharging mechanism arranged on the device body.

[0011] Preferably, the automatic grading type discharging mechanism comprises a driving connecting frame, a bearing frame, a movable loading plate and an installed loading rod, the lower end of the driving connecting frame is fixedly provided with a downward connecting plate, the downward connecting plate is fixedly connected with the hydraulic rod, and a guide support hole is formed in the downward connecting plate.

[0012] Preferably, the two ends of the driving connecting frame are symmetrically fixedly provided with protruding bearing plates, one side of the protruding bearing plate is fixedly provided with a connecting matching column, the other side of the protruding bearing plate is fixedly provided with a support loading rod, the support loading rod is fixedly provided with a matching rack, and the connecting matching column is connected with the bearing frame.

[0013] Preferably, a plurality of support disc bodies are fixedly arranged on the bearing frame, a receiving box body is inserted into the support disc body, a link connecting plate is fixedly arranged on the support disc body, a driving connecting rod is hinged to the link connecting plate, a sealing loading plate is hinged to the upper end of the driving connecting rod, a sealing insertion plate is fixedly arranged on the sealing loading plate, the sealing insertion plate is respectively inserted into the discharging bottom opening and the upper discharging opening when the sealing insertion plate seals the discharging bottom opening and the upper discharging opening, a guide bearing rod is fixedly arranged on the sealing loading plate and inserted into the support guide hole, and a connecting loading block is fixedly arranged on the guide bearing rod and hinged with the driving connecting rod.

[0014] Preferably, the two sides of the bearing plate frame are symmetrically and fixedly provided with a matching bearing plate, a guide through hole is formed in the matching bearing plate, a limiting guide rod is inserted into the guide through hole, an L-shaped support plate is fixedly arranged at the lower end of the matching bearing plate, a protruding bearing plate is fixedly arranged on the L-shaped support plate, an upper top column body is fixedly arranged on the protruding bearing plate, a matching channel is formed in the matching bearing plate, an upper flange plate is fixedly arranged at the end of the matching bearing plate away from the equipment body, a connection channel is formed in the upper flange plate, and a connecting matching column is inserted into the connection channel.

[0015] Preferably, the equipment body is provided with a movable load plate, a support connecting rod is fixedly arranged on the movable load plate, the support connecting rod is inserted into the insertion movable hole, a pushing material plate is fixedly arranged on the support connecting rod, and the pushing material plate is located in the interior of the equipment body.

[0016] Preferably, the two sides of the movable load plate are symmetrically and fixedly provided with a mounting load plate, a mounting through hole is formed in the mounting load plate, a mounting load rod is inserted into the mounting through hole, a limiting insertion block is fixedly arranged at the lower end of the mounting load rod, the limiting insertion block is inserted into the stable insertion hole, and a half gear is fixedly arranged at the upper end of the mounting load rod.

[0017] A preparation method of a hydrogen storage nanocomposite material, comprising the following steps:

[0018] Step one: Ti, Fe, Co, Mn and La, Ce, Mg are respectively smelted into Ti-Fe-Co-Mn alloy and La-Ce-Mg alloy by using an induction smelting furnace according to a metering ratio, and alloy powders with a particle size less than 50 μm are respectively prepared;

[0019] Step two: the Ti-Fe-Co-Mn alloy powder and the La-Ce-Mg alloy powder prepared in step one are mixed according to a stoichiometric ratio, and a Ti x (La a Ce b Mg c ) 2-x (Fe d Co e Mn f ) y The hydrogen storage nanocomposite material, wherein x is in the range of 1≤x≤1.5, y is in the range of 1≤y≤1.5, the sum of a+b+c is in the range of 1≤a+b+c≤1.2, and c≥0.5, the sum of d+e+f is in the range of 1≤d+e+f≤1.05, and f≥0.5.

[0020] Preferably, in step two, the Ti-Fe-Co-Mn alloy powder and the La-Ce-Mg alloy powder are loaded into a planetary ball mill, the ball-to-material ratio during the ball milling is 5:1-20:1, the ball mill tank is vacuumed to 1x10 -2 After the Pa, high-purity argon gas is filled to 0.05-0.1 MPa for ball milling, the ball milling speed is 500-1000 rpm, and the ball milling time is 2-5 hours. x (La a Ce b Mg c ) 2-x (Fe d Co e Mn f ) y The hydrogen storage nanocomposite material is subjected to heat treatment, the heat treatment atmosphere is vacuum or inert gas, and the heat treatment method is: the Ti x (La a Ce b Mg c ) 2-x (Fe d Co e Mn f ) y The hydrogen storage nanocomposite material is placed in a vacuum furnace, vacuumed to an air pressure of less than or equal to 1x10 -2 Pa, then argon gas is introduced and the air pressure is controlled to be 30-100 kPa, the temperature is raised to 500-800℃, and the temperature is maintained for 1-2 hours, and the furnace is cooled down.

[0021] Compared with the prior art, the hydrogen storage nanocomposite material prepared by the present application has the following advantages:

[0022] 1. The alloy composition of the nanocomposite hydrogen storage material prepared by the present application is accurately controllable, and the hydrogen storage capacity is high; the ball milling process obtains a nanocrystalline structure alloy, the hydrogen atom diffusion rate is fast, the hydrogen absorption and desorption rate is high; and the ball milling process introduces more grain defects to produce a higher catalytic active surface. Furthermore, the hydrogen storage alloy produced by the present application can be activated by hydrogen at room temperature after being vacuumed by a mechanical pump, and can quickly reach a first hydrogen absorption capacity of more than 2.0wt.%, thereby the hydrogen absorption mass ratio is high. In addition, by adjusting the proportion of Fe and Mn elements, the hydrogen absorption and desorption platform of the alloy can be adjusted, and a series of alloys with a hydrogen desorption platform matching chemical energy storage, fuel cells, etc. can be prepared, and the hydrogen absorption and desorption platform can be adjusted. The high activity and self-catalytic surface performance of the activated nanocomposite material, and the alloy can be activated once after being vacuumed to 0.1 Pa.

[0023] 2. The inside of the device body is provided with a plurality of partition plates, and a hierarchical hole is opened on the partition plate, and the hierarchical hole on the upper partition plate is larger than the hierarchical hole on the lower partition plate, so that the powder can be automatically classified during the falling of the powder forming, and manual classification operation is not needed, which is very convenient.

[0024] 3. When discharging, the hydraulic rod is started, and the driving connecting plate frame is moved under the action of the hydraulic rod. With the movement of the driving connecting plate frame, the bearing plate frame can be moved upwards, and then the receiving box body is moved to the discharge bottom opening and the upper discharge opening respectively to facilitate the receiving of the powder. Under the action of the bearing plate frame, the sealing plate is moved to make the discharge bottom opening and the upper discharge opening open, facilitating the discharge. At this time, the connecting plate sleeve, the receiving box body and the sealing plate form a closed space to ensure that the powder is stably collected in the receiving box body.

[0025] 4. In addition, when the receiving box body reaches the working point, the movable plate will be unlocked with the continuous movement of the driving connecting plate frame, and the movable plate will be moved under the cooperation of the rack and the half gear, and then the pushing plate will be moved, so that the powder can be pushed into the receiving box body to realize classified collection. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 Ti 1.25 (La 0.4 Ce 0.05 Mg 0.55 ) 0.75 (Fe 0.40 Co 0.03 Mn 0.6 ) 1.15 Schematic diagram of room temperature activation and hydrogen absorption curve of hydrogen storage nanocomposite material.

[0027] Figure 2 Ti 1.25 (La 0.4 Ce 0.05 Mg 0.55 ) 0.75 (Fe 0.40 Co 0.03 Mn 0.6 ) 1.15 Schematic diagram of 25℃ isothermal hydrogen absorption and release curve of hydrogen storage nanocomposite material.

[0028] Figure 3 Ti 1.2 (La 0.5 Ce 0.1 Mg 0.5 ) 0.8 (Fe 0.45 Co 0.05 Mn0.5 ) 1.2 Schematic diagram of hydrogen absorption curve of hydrogen storage nanocomposite at room temperature.

[0029] Figure 4 Ti 1.2 La 0.5 Ce 0.1 Mg 0.5 ) 0.8 Fe 0.45 Co 0.05 Mn 0.5 ) 1.2 Schematic diagram of hydrogen absorption and desorption curve of hydrogen storage nanocomposite at 25℃.

[0030] Figure 5 Ti 1.4 La 0.4 Ce 0.1 Mg 0.7 ) 0.6 Fe 0.25 Co 0.1 Mn 0.7 ) 1.3 Schematic diagram of hydrogen absorption curve of hydrogen storage nanocomposite at room temperature.

[0031] Figure 6 Ti 1.4 La 0.4 Ce 0.1 Mg 0.7 ) 0.6 Fe 0.25 Co 0.1 Mn 0.7 ) 1.3 Schematic diagram of hydrogen absorption and desorption curve of hydrogen storage nanocomposite at 25℃.

[0032] Figure 7 Schematic diagram of hydrogen absorption curve of hydrogen storage nanocomposite at room temperature provided by Comparative Example 1.

[0033] Figure 8 Schematic diagram of first perspective view of device body assembly.

[0034] Figure 9 Schematic diagram of second perspective view of device body assembly.

[0035] Figure 10 is Figure 9 Enlarged view of A in FIG. 7.

[0036] Figure 11 Schematic diagram of first perspective view of device body.

[0037] Figure 12 is Figure 11 Enlarged view of B in FIG. 8.

[0038] Figure 13 The second perspective view of the device body.

[0039] Figure 14 The second perspective view of the device body. Figure 13 The enlarged view of the middle C.

[0040] Figure 15 The assembly view of the driving connecting plate frame, the bearing plate frame 4, the movable carrier plate 5 and the mounting carrier rod 6.

[0041] Figure 16 The second perspective view of the device body. Figure 15 The enlarged view of the middle D.

[0042] In the figure: 1, the device body; 10, the supporting carrier plate; 101, the supporting bottom ring; 11, the feeding pipe; 12, the discharging bottom opening; 121, the fixed material receiving plate; 13, the upper discharging opening; 14, the separating carrier plate; 15, the grading hole; 16, the connecting plate sleeve; 161, the bearing matching plate; 162, the supporting guide hole; 17, the plug-in movable hole; 18, the hydraulic rod; 19, the bearing guide rod; 191, the connecting carrier frame; 192, the stabilizing connecting plate; 193, the supporting matching plate; 194, the stabilizing plug-in hole; 195, the matching plug-in hole; 2, the supporting strip; 21, the limiting guide rod; 3, the driving connecting plate frame; 31, the downward extending connecting plate; 32, the guide supporting hole; 33, the protruding bearing plate; 34, the connecting matching column; 35, the supporting carrier rod; 36, the matching rack; 4, the bearing plate frame; 41, the supporting disc body; 42, the bearing box body; 43, the linking connecting plate; 44, the driving connecting rod; 45, the sealing carrier plate; 46, the sealing plug-in plate; 47, the guide bearing rod; 48, the connecting carrier block; 49, the matching bearing plate; 491, the guide through hole; 492, the L-shaped supporting plate; 493, the protruding bearing plate; 494, the upper jacking column body; 495, the matching channel; 496, the upper upturned plate; 497, the linking channel; 5, the movable carrier plate; 51, the supporting connecting rod; 52, the pushing material plate; 53, the mounting carrier plate; 54, the mounting through hole; 6, the mounting carrier rod; 61, the limiting plug-in block; 62, the half gear. DETAILED DESCRIPTION

[0043] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0044] Please refer to Figures 1 to 16 The present application provides a technical solution:

[0045] A hydrogen storage nanocomposite, the composition of the hydrogen storage nanocomposite is Ti x (La a Ce b Mg c ) 2-x (Fe d Co e Mn f ) y , wherein x is in the range of 1≤x≤1.5, y is in the range of 1≤y≤1.5, the sum of a+b+c is in the range of 1≤a+b+c≤1.2, and c≥0.5, the sum of d+e+f is in the range of 1≤d+e+f≤1.05, and f≥0.5.

[0046] The Ti element is the main hydrogen absorption component, x is preferably in the range of 1-1.5, the addition of La can form a lanthanum-rich microzone on the surface of the material, which has a rapid hydrogen absorption capacity, thereby improving the initial activation performance and subsequent kinetic performance of the alloy.

[0047] The addition of Ce can reduce the oxygen impurity content during alloy smelting and adjust the impurity resistance performance of the alloy.

[0048] The appropriate addition of Mg element can improve the overall hydrogen absorption capacity ratio of the alloy, the sum of the addition ratios of La, Ce and Mg a+b+c is in the range of 1-1.2, and the Mg content, which has a capacity improving effect, needs to be more than 0.5.

[0049] The ratio of Fe and Mn elements realizes the adjustment of the hydrogen absorption and desorption platform pressure, the increase of the Mn element content reduces the hydrogen absorption and desorption platform, and the Co element can reduce the hydrogen absorption and desorption platform slope, so that the hydrogen absorption and desorption process pressure is more stable. The sum of the Fe, Co and Mn contents d+e+f is in the range of 1-1.05, and f≥0.5.

[0050] The preferred alloy includes: Ti 1.25 (La 0.4 Ce 0.05 Mg 0.55 ) 0.75 (Fe 0.40 Co 0.03 Mn 0.6 ) 1.15 ; Ti 1.2 (La 0.5 Ce 0.1 Mg 0.5 ) 0.8 (Fe 0.45 Co 0.05 Mn 0.5 ) 1.2 ; or Ti 1.4 (La 0.4 Ce0.1 Mg 0.7 ) 0.6 (Fe 0.25 Co 0.1 Mn 0.7 ) 1.3 .

[0051] The preparation method of the alloy specifically comprises the following steps:

[0052] Step one: according to the selected alloy composition, the amount of each alloying element is calculated, and the corresponding metal raw materials are weighed and prepared.

[0053] Step two: Ti, Fe, Co, Mn and La, Ce, Mg are respectively smelted into Ti-Fe-Co-Mn alloy and La-Ce-Mg alloy, and metal powder with a particle size of less than 50 μm is prepared, and the specific preparation method can adopt the following mechanical powdering scheme or gas atomization powdering scheme:

[0054] Mechanical powdering scheme

[0055] The alloy is smelted by vacuum induction and mechanically broken, and the alloy is placed in the smelting crucible according to the principle of high melting point elements at the bottom and low melting point and volatile elements at the top, the system is vacuumed to an air pressure of ≤1×10 -2 Pa and continues to be vacuumed for more than 30 min, while the alloy is heated to about 500℃ at low power to make the alloy surface impurity gas fully desorb; then high-purity argon is introduced, the pressure is controlled at 20-40 kPa, the smelting power is adjusted to full power to heat, and the alloy is fully melted.

[0056] The smelting temperature of Ti-Fe-Co-Mn is controlled at 1650±10℃, after complete melting, the input power of the induction power is reduced, and after refining at 1550℃±10℃ for 10 minutes, it is poured into a water-cooled mold, and after cooling, a blocky alloy with a length of about 10 cm, a width and a thickness of about 5 cm is obtained.

[0057] The smelting temperature of La-Ce-Mg alloy is controlled at 870±10℃, after the raw materials are completely melted, the power is reduced to control the temperature at 780±10℃ for 10 minutes, and then poured into a water-cooled mold, and after cooling, a blocky alloy with a length of about 10 cm, a width and a thickness of about 5 cm is obtained.

[0058] The above blocky alloy is crushed by argon atmosphere protection jaw crusher and ball mill equipment and sieved into alloy powder with a particle size of less than 50 μm for use.

[0059] Gas atomization powdering scheme

[0060] The method adopts a vacuum inert gas atomization system to melt, refine and degas the alloy in a furnace by a vacuum induction melting furnace, places the molten alloy into a gas atomization nozzle system through a tundish, and atomizes by inert gas. The specific implementation scheme is as follows: the alloy is placed in a smelting crucible according to the principle of high melting point elements at the bottom and low melting point and volatile elements at the top, the system is vacuumized to an air pressure of ≤1×10 -2 Pa, and vacuumization continues for more than 30 minutes, while the alloy is heated to about 500℃ at low power to make the impurity gas on the surface of the alloy fully desorb; then high-purity argon is introduced, the pressure is controlled at 20-40 kPa, the smelting power is adjusted to full power to heat, and the alloy is fully melted.

[0061] The smelting temperature of the Ti-Fe-Co-Mn alloy is controlled at 1650±10℃, after complete melting, the input power of the induction power is reduced, and the refining is carried out at 1550℃±10℃ for 10 minutes. The cyclone collection system of the gas atomization system is opened, the alloy liquid is injected into the preheated tundish, and the atomization nozzle of the tundish is opened. The alloy liquid in the tundish is sprayed out of the nozzle by argon flow to form mist droplets, the mist droplets are cooled and collected in the cyclone collector, and finally the alloy powder with a particle size of less than 50μm is obtained.

[0062] The smelting temperature of the La-Ce-Mg alloy is controlled at 870±10℃, after the raw materials are completely melted, the power is reduced to control the temperature at 820±10℃ for 10 minutes of refining. The cyclone collection system of the gas atomization system is opened, the alloy liquid is injected into the preheated tundish, and the atomization nozzle of the tundish is opened. The alloy liquid in the tundish is sprayed out of the nozzle by argon flow to form mist droplets, the mist droplets are cooled and collected in the cyclone collector, and finally the alloy powder with a particle size of less than 50μm is obtained.

[0063] The particle size screening equipment in the above two powder making schemes is existing, in order to facilitate the screening of the alloy powder after the crushing by the jaw crusher and ball mill equipment in the above mechanical powder making, or the metal powder alloy collected by the cyclone collector in the gas atomization powder making, a new improved powder making equipment is proposed. The powder alloy particle size screening equipment can further accurately classify and screen the alloy powder screened out by the above two schemes, and the specific structure is as follows:

[0064] The application discloses a powder preparation device for hydrogen storage nanocomposite, which comprises a device body 1, support loading plates 10 symmetrically arranged on both sides of the device body 1, a support bottom ring 101 fixedly arranged at the lower end of the support loading plates 10, a feeding pipe 11 fixedly arranged at the upper end of the device body 1, a discharging bottom opening 12 formed at the lower side of one end of the device body 1, a fixed material receiving plate 121 fixedly arranged in the device body 1 corresponding to the discharging bottom opening 12, a plurality of upper discharging openings 13 formed in the device body 1 corresponding to the discharging bottom opening 12, a separation loading plate 14 fixedly arranged in the device body 1 corresponding to the upper discharging openings 13, grading holes 15 formed in the separation loading plate 14, wherein the size of the grading holes 15 in the upper separation loading plate 14 is larger than that of the grading holes 15 in the lower separation loading plate 14, a connecting plate sleeve 16 fixedly arranged at the upper side of the discharging bottom opening 12 and the upper discharging openings 13, a bearing matching plate 161 fixedly arranged on the connecting plate sleeve 16, support guide holes 162 formed in the bearing matching plate 161, a plug-in movable hole 17 formed in the other end of the device body 1 opposite to the discharging bottom opening 12 and the upper discharging openings 13, a hydraulic rod 18 fixedly arranged on the device body 1 at the lower side of the plug-in movable hole 17, a bearing guide rod 19 fixedly arranged on the device body 1 at the lower side of the hydraulic rod 18, a connecting loading frame 191 fixedly arranged on the bearing guide rod 19, a stable connecting plate 192 fixedly arranged at the upper end of the connecting loading frame 191, support matching plates 193 symmetrically fixedly arranged at both sides of the connecting loading frame 191, stable insertion holes 194 formed in the support matching plates 193, matching insertion holes 195 formed in the hole bottoms of the stable insertion holes 194, support strips 2 symmetrically fixedly arranged at both sides of the device body 1, limit guide rods 21 fixedly arranged on the support strips 2, and an automatic grading type discharging mechanism arranged on the device body 1.

[0065] The automatic grading type discharging mechanism comprises a driving connecting frame 3, a bearing frame 4, a movable loading plate 5 and a mounting loading rod 6, wherein the lower end of the driving connecting frame 3 is fixedly provided with a lower extension connecting plate 31, the lower extension connecting plate 31 is fixedly connected with the hydraulic rod 18, and guide support holes 32 are formed in the lower extension connecting plate 31, and the bearing guide rod 19 is plugged into the guide support holes 32.

[0066] The two ends of the driving connecting frame 3 are symmetrically fixedly provided with protruding bearing plates 33, one side of each of the protruding bearing plates 33 is fixedly provided with a connecting matching column 34, the other side of each of the protruding bearing plates 33 is fixedly provided with a support loading rod 35, the support loading rod 35 is fixedly provided with a matching rack 36, and the bearing frame 4 is connected with the connecting matching column 34.

[0067] Multiple support plates 41 are fixedly mounted on the support plate frame 4. A receiving box 42 is inserted into each support plate 41, and a connecting plate 43 is fixedly mounted on each support plate 41. A driving connecting rod 44 is hinged to the connecting plate 43, and a sealing carrier plate 45 is hinged to the upper end of the driving connecting rod 44. A sealing insertion plate 46 is fixedly mounted on the sealing carrier plate 45. When sealing the bottom discharge port 12 and the upper discharge port 13, the sealing insertion plate 46 is inserted into the sealing plate 46. In the bottom discharge port 12 and the upper discharge port 13, a guide support rod 47 is fixedly installed on the sealing carrier plate 45. The guide support rod 47 is inserted into the support guide hole 162, and a connecting block 48 is fixedly installed on the guide support rod 47. The connecting block 48 is hinged to the drive connecting rod 44. In addition, when the sealing plug plate 46 seals the bottom discharge port 12 and the upper discharge port 13, the sealing carrier plate 45 contacts the outer end face of the equipment body 1.

[0068] The support plate frame 4 is symmetrically fixed with mating support plates 49 on both sides. The mating support plates 49 have guide holes 491, and limit guide rods 21 are inserted into the guide holes 491. An L-shaped support plate 492 is fixedly fixed at the lower end of the mating support plate 49. A protruding support plate 493 is fixedly fixed on the L-shaped support plate 492. An upper top column 494 is fixedly fixed on the protruding support plate 493. The mating support plate 49 also has a mating channel 495. An upward-curving plate 496 is fixedly fixed at the end of the mating support plate 49 away from the equipment body 1. A connecting channel 497 is opened on the upward-curving plate 496. A connecting mating column 34 is inserted into the connecting channel 497. The inner wall of the connecting channel 497 is in contact with the connecting mating column 34. The width of the connecting channel 497 is equal to the height of the mating channel 495.

[0069] A movable carrier plate 5 is installed on the main body 1. A support rod 51 is fixedly installed on the movable carrier plate 5. The support rod 51 is inserted into the insertion movable hole 17. A pusher plate 52 is fixedly installed on the support rod 51. The pusher plate 52 is located inside the main body 1. The surface of the pusher plate 52 is smooth and burr-free, and can push the powder on the separating carrier plate 14 and the fixed receiving plate 121.

[0070] Mounting plates 53 are symmetrically fixed on both sides of the movable carrier plate 5. Mounting plates 53 have mounting through holes 54. Mounting rods 6 are inserted into the mounting through holes 54. A limiting block 61 is fixedly installed at the lower end of the mounting rod 6. The limiting block 61 is inserted into the stabilizing socket 194. A half gear 62 is fixedly installed at the upper end of the mounting rod 6. The size of the limiting block 61 is equal to the storage capacity of the stabilizing socket 194 and larger than the size of the mating socket 195.

[0071] The powder falls on the separation plate 14 during the forming process, the powder with a size larger than the size of the classification hole 15 stays on the separation plate 14, the powder with a size smaller than the size of the classification hole 15 falls through the classification hole 15 to the next separation plate 14, and the powder with the smallest size falls on the fixed receiving plate 121, thereby realizing automatic classification without manual classification, which is very convenient. When discharging, the hydraulic rod 18 drives the driving connecting plate frame 3 to move towards the equipment body 1, so that the connecting column 34 and the connecting channel 497 cooperate to drive the bearing plate frame 4 to move upwards, thereby driving the receiving box body 42 to move upwards and be inserted into the connecting plate sleeve 16. With the upward movement of the bearing plate frame 4, the sealing plate 45 is driven to move under the action of the connecting plate 43, so that the sealing plug-in plate 46 is no longer inserted into the discharge bottom opening 12 and the upper discharge opening 13, thereby making the discharge bottom opening 12 and the upper discharge opening 13 in an open state. With the upward movement of the receiving box body 42, it will be in contact with the corresponding sealing plug-in plate 46, so that the connecting plate sleeve 16, the sealing plate 45 and the receiving box body 42 form a relatively closed space, which is convenient for the powder to fall into the receiving box body 42. When the connecting column 34 is inserted into the cooperating channel 495, the bearing plate frame 4 will no longer move upwards. During the upward movement of the bearing plate frame 4, the upper top column 494 is inserted into the cooperating hole 195 and in contact with the limiting plug 61, thereby driving the half gear 62 to move upwards. When the connecting column 34 is inserted into the cooperating channel 495, the half gear 62 is in engagement with the cooperating gear 36, and at this time the limiting plug 61 is withdrawn from the stable hole 194 and in contact with the upper end surface of the supporting cooperation plate 193, so that the movable plate 5 is in an unlocked state. Under the cooperation of the half gear 62 and the cooperating gear 36, the movable plate 5 and the driving connecting plate frame 3 are in a fixed connection state, so that the movable plate 5 can be driven to move under the action of the driving connecting plate frame 3, thereby driving the pushing plate 52 to move and pushing the alloy powder into the receiving box body 42, thereby realizing convenient classification and collection.

[0072] The above-mentioned screening preparation equipment can be set as long as the diameter of the classification hole 15 is 50 um. At this time, when the alloy powder with a particle size less than 50 um obtained by the two traditional methods is discharged once by the above-mentioned equipment, the metal powder with a particle size less than 50 um can be more accurately screened from the above-mentioned rough selection powder; and then used for the preparation of the nano-composite material in the following step.

[0073] Step three: mixing the Ti-Fe-Co-Mn alloy powder and the La-Ce-Mg alloy powder prepared in the above steps according to the stoichiometric ratio and ball milling to realize mechanical alloying, and finally preparing a Ti x (La a Ce b Mg c ) 2-x (Fed Co e Mn f ) y Hydrogen storage nanocomposite material, the specific ball milling process is:

[0074] (1) according to Ti x (La a Ce b Mg c ) 2-x (Fe d Co e Mn f ) y The required Ti-Fe-Co-Mn alloy and La-Ce-Mg alloy are weighed and the alloy powder is weighed;

[0075] (2) the two kinds of alloy powder raw materials are loaded into a planetary ball mill, and appropriate mass of stainless steel grinding balls are loaded according to the ball-to-material ratio, the ball-to-material ratio ranges from 5:1 to 20:1, the ball mill tank is sealed and locked into the ball mill working position;

[0076] (3) after the ball mill tank is vacuumed to 1×10 -2 Pa, high-purity argon is filled to 0.05-0.1 MPa for ball milling, the ball milling speed is 500-1000 revolutions per minute, and the ball milling time is 2-5 hours. The mechanical alloying Ti x (La a Ce b Mg c ) 2-x (Fe d Co e Mn f ) y Hydrogen storage nanocomposite material is obtained.

[0077] Step four: heat treatment of Ti x (La a Ce b Mg c ) 2-x (Fe d Co e Mn f ) y Hydrogen storage nanocomposite material, the specific operation process is:

[0078] (1) the Ti x (La a Ce b Mg c ) 2-x (Fe d Co e Mn f ) yThe hydrogen storage nanocomposite material is put into a vacuum heat treatment quartz tube, vacuumed to an air pressure of ≤1×10 -2 Pa, then argon is introduced and the air pressure is controlled to be 30-100 kPa;

[0079] (2) The heating power of the heat treatment furnace is turned on, the heat treatment temperature is set and heated, the heat treatment temperature is 500-800℃, and the temperature is kept for 1-2 h, then the furnace is cooled down;

[0080] (3) The cooled Ti x (La a Ce b Mg c ) 2-x (Fe d Co e Mn f ) y The hydrogen storage nanocomposite material is taken out under inert gas protection and sealed for storage.

[0081] The alloy mainly contains hydrogenated elements such as Ti and Mg, and the alloy has a relatively high hydrogen storage capacity of 1.85 wt.%.

[0082] The heat treatment atmosphere is vacuum or inert gas, and the heat treatment method is:

[0083] The Ti x (La a Ce b Mg c ) 2-x (Fe d Co e Mn f ) y The hydrogen storage nanocomposite material is put into a vacuum furnace, vacuumed to an air pressure of ≤1×10 -2 Pa, then argon is introduced and the air pressure is controlled to be 30-100 kPa, heated to 500-800℃, kept for 1-2 h, and cooled down with the furnace.

[0084] Example 1

[0085] Ti 1.25 (La 0.4 Ce 0.05 Mg 0.55 ) 0.75 (Fe 0.40 Co 0.03 Mn 0.6 ) 1.15 Preparation of the nanocomposite material.

[0086] Preparation of the alloy raw material:

[0087]

[0088] Take the preparation of 100 kg alloy as an example, and weigh the metal raw materials according to the data in the above table.

[0089] Ti-Fe-Co-Mn alloy and La-Ce-Mg alloy smelting:

[0090] The Ti-Fe-Co-Mn alloy smelting is carried out by using a 100 kg level vacuum induction melting furnace with a rated power of 200 kW:

[0091] a, furnace loading: the weighed Ti, Fe, Co and Mn are sequentially loaded into the induction melting furnace crucible, keeping Ti and Fe at the bottom of the furnace, Co in the middle, and Mn at the uppermost part of the crucible. After loading, close the furnace cover;

[0092] b, vacuum pumping: turn on the vacuum system and pump the furnace body to 1 × 10 -2 Pa and keep for 30 min;

[0093] c, material drying: turn on the heating system, adjust the heating power to 60-100 kW, heat the metal raw materials and continue to pump the vacuum for about 30 min;

[0094] d, argon filling: open the argon filling valve and fill argon into the furnace to about 30 kPa;

[0095] e, smelting: adjust the heating power to about 180 kW, continuously heat the metal raw materials until the alloy is completely melted. At this time, the temperature is about 1650 ± 10℃ measured by infrared temperature measurement;

[0096] f, refining: reduce the heating power to about 100 kW, keep the alloy liquid at 1550 ± 10℃, and refine for 10 min;

[0097] g, casting: adjust the heating power to below 40 kW, tilt the crucible, and cast the alloy liquid through the sprue at a uniform speed into the water-cooled mold. As the amount of liquid steel decreases, gradually adjust the heating power to 0 to complete the casting process.

[0098] h, cooling and collecting: turn off the heating power, keep the water cooling system open, cool the alloy in the furnace body and water-cooled mold to room temperature, and open the furnace to collect the material.

[0099] The La-Ce-Mg alloy smelting is carried out by using a 50 kg level vacuum induction melting furnace with a rated power of 100 kW:

[0100] a, furnace loading: the weighed La, Ce and Mg are sequentially loaded into the induction melting furnace crucible, keeping La at the bottom of the furnace, Ce in the middle, and Mg at the uppermost part of the crucible. After loading, close the furnace cover;

[0101] b, vacuum pumping: turn on the vacuum system and pump the furnace body to 1 × 10 -2Pa, and keep for 30 min;

[0102] c. Drying: power on the heating system, adjust the heating power to 40-50 kW, heat the metal raw material and keep vacuumizing for about 30 min;

[0103] d. Argon filling: open the argon filling valve, fill argon into the furnace to about 40 kPa;

[0104] e. Melting: adjust the heating power to about 90 kW, continuously heat the metal raw material until the alloy is completely melted, at this time, the temperature is about 870±10℃ by infrared temperature measurement;

[0105] f. Refining: reduce the heating power to about 50 kW, keep the alloy liquid at 820±10℃ for 10 min;

[0106] g. Casting: adjust the heating power to below 30 kW, tilt the crucible, and cast the alloy liquid through the sprue at a uniform speed into the water-cooled mold. As the amount of liquid steel decreases, gradually adjust the heating power to 0 to complete the casting process.

[0107] h. Cooling and collecting: turn off the heating power, keep the water cooling system on, cool the alloy in the furnace and the water-cooled mold to room temperature, and open the furnace to collect the material.

[0108] Ti-Fe-Co-Mn alloy and La-Ce-Mg alloy powder preparation:

[0109] Ti-Fe-Co-Mn alloy and La-Ce-Mg alloy powder preparation:

[0110] a. Loading: load the alloy blocks into the upper hopper of the jaw crusher;

[0111] b. Gas replacement: perform overall argon purging of the equipment until the oxygen content in the system is reduced to below 5000 ppm;

[0112] c. Start crushing: start the power system of the jaw crusher-ball mill, the blocks in the hopper enter the jaw crusher section through the vibrating feeder, and are crushed into particles with a particle size of less than 0.2 mm. Then they are transported to the ball mill equipment, crushed to a fine powder below 50 microns, and then sieved and collected into a bucket.

[0113] Ti-Fe-Co-Mn alloy and La-Ce-Mg alloy mixed ball milling preparation of Ti 1.25 (La 0.4 Ce 0.05 Mg 0.55 ) 0.75 (Fe 0.40 Co 0.03 Mn 0.6 )1.15 Hydrogen storage nanocomposite:

[0114] a. Mixing: Ti-Fe-Co-Mn alloy and La-Ce-Mg alloy powders are weighed according to the proportion and mixed uniformly by a mixer. In this embodiment, the mass ratio of the two alloys is 2.202:1;

[0115] b. Loading: The mixed powders and grinding balls are weighed according to the capacity of the ball mill, loaded into the ball mill jar and sealed. In this embodiment, the ratio of grinding balls to material is 8:1. The ball mill jar is loaded into the ball mill and locked;

[0116] c. Vacuumizing and gas protection: The ball mill jar is vacuumized to 1×10 -2 Pa, and then argon protection gas is filled, with an argon pressure of 0.1 MPa;

[0117] d. Ball milling: The ball mill is started, with a rotation speed of 900 rpm, and ball milling is performed for 2 h to realize mechanical alloying of the mixed powders under the action of ball milling;

[0118] e. Cooling and material collection: The ball mill jar is cooled to room temperature after ball milling, and then opened under inert gas protection to collect the material into a sealed bag for storage.

[0119] Ti 1.25 (La 0.4 Ce 0.05 Mg 0.55 ) 0.75 (Fe 0.40 Co 0.03 Mn 0.6 ) 1.15 Heat treatment of hydrogen storage nanocomposite:

[0120] a. Loading into the furnace:

[0121] Ti 1.25 (La 0.4 Ce 0.05 Mg 0.55 ) 0.75 (Fe 0.40 Co 0.03 Mn 0.6 ) 1.15 Hydrogen storage nanocomposite is loaded into a vacuum heat treatment quartz tube, vacuumized to an air pressure of ≤1×10 -2 Pa, and then argon

[0122] gas is introduced and the gas pressure is controlled at 60 kPa;

[0123] b. The heating power of the heat treatment furnace is turned on, the heat treatment temperature is set and heating is started. The heat treatment temperature is 800℃, and the temperature is maintained for 1 h, and then the furnace is cooled down;

[0124] c. Cool the Ti 1.25 (La 0.4 Ce 0.05 Mg 0.55 ) 0.75 (Fe 0.40 Co 0.03 Mn 0.6 ) 1.15 The hydrogen storage nanocomposite material was removed and sealed for storage under inert gas protection.

[0125] Ti 1.25 (La 0.4 Ce 0.05 Mg 0.55 ) 0.75 (Fe 0.40 Co 0.03 Mn 0.6 ) 1.15 Hydrogen absorption and desorption performance test of hydrogen storage nanocomposites:

[0126] 1g of hydrogen storage material was weighed and placed into the sample chamber of the hydrogen absorption and desorption test device. The vacuum pump was turned on to evacuate the sample to below 0.5Pa and maintained for 1 hour. Subsequently, the sample was charged with 3MPa of high-purity hydrogen gas (99.995% purity) at room temperature (25℃). The measured room temperature hydrogen absorption activation curve of the material is shown below. Figure 1 As shown, the material begins to rapidly absorb hydrogen after a short incubation period, with an initial hydrogen absorption of approximately 2.0 wt.%.

[0127] After repeatedly evacuating and absorbing hydrogen three times, the isothermal hydrogen absorption and desorption curves (PCT curves) were measured at 25°C. Figure 2 As shown in the figure, the material can begin to absorb a large amount of hydrogen at a hydrogen pressure of 1 MPa, and the hydrogen absorption at a hydrogen pressure of 2 MPa is higher than 1.80 wt%, with a saturated hydrogen storage capacity of higher than 1.9 wt.%.

[0128] Example 2

[0129] Ti 1.2 (La 0.5 Ce 0.1 Mg 0.5 ) 0.8 (Fe 0.45 Co 0.05 Mn 0.5 ) 1.2 Preparation of nanocomposite materials.

[0130] In this embodiment, an air atomization scheme is used.

[0131] Ti 1.2 (La 0.5 Ce 0.1 Mg 0.5 )0.8 (Fe 0.45 Co 0.05 Mn 0.5 ) 1.2 Preparation of nanocomposite.

[0132] Formulation of alloy raw materials

[0133]

[0134] Take the preparation of 50 kg nanocomposite as an example, and weigh the metal raw materials according to the data in the above table.

[0135] Preparation of Ti-Fe-Co-Mn and La-Ce-Mg alloy powder:

[0136] The 50 kg level vacuum inert gas atomization furnace with rated power of 100 kW is used to prepare Ti-Fe-Co-Mn alloy powder:

[0137] a. Furnace loading: The weighed Ti, Fe, Co and Mn are sequentially loaded into the induction melting furnace crucible. After loading, the order of the raw materials in the crucible from bottom to top is Ti, Fe, Co and Mn. After loading, the furnace cover is closed;

[0138] b. Vacuum pumping: The vacuum system is started, and the furnace body is pumped to 1.0 x 10 -2 Pa, and kept for 30 min;

[0139] c. Material drying: Turn on the heating system, adjust the heating power to 30-40 kW, heat the metal raw materials and continue to pump for about 30 min;

[0140] d. Argon filling: Open the argon filling valve, fill argon into the furnace to about 30 kPa;

[0141] e. Melting: Adjust the heating power to about 90 kW, continuously heat the metal raw materials until the alloy is completely melted. At this time, the temperature is about 1650±10℃ measured by infrared temperature measurement;

[0142] f. Refining: Reduce the heating power to about 70 kW, keep the alloy liquid at 1550±10℃ for 10 min;

[0143] g. Gas atomization powder preparation: open the cyclone collection system of the gas atomization system, adjust the heating power to below 30 kW, tilt the crucible to pour the alloy liquid into the preheated tundish, open the tundish atomization nozzle at the same time, adjust the argon input pressure to 120 kPa, and spray the alloy liquid in the tundish out of the nozzle to form droplets through the argon flow, and the droplets are cooled and collected in the cyclone collector, that is, when discharging, the powder falls on the separation plate 14 inside the equipment body 1, the separation plate 14 is provided with grading holes, the size of the grading holes 15 on the upper separation plate 14 is larger than that of the grading holes 15 on the lower separation plate 14, so that the powder can be automatically graded during the falling process, and manual grading operation is not needed in the later stage, and finally the Ti-Fe-Co-Mn alloy powder with a particle size of 50 microns or less is obtained.

[0144] h. Cooling and collecting: turn off the heating power, keep the water cooling system open, cool the alloy powder of the alloy in the furnace body and the cyclone collection system to room temperature, and open the furnace to collect the material.

[0145] A 50 kg level vacuum inert gas atomization furnace with a rated power of 100 kW is used to prepare La-Ce-Mg alloy powder:

[0146] a. Loading: weigh La, Ce and Mg and load them into the induction melting furnace crucible in turn, and the order of the raw materials in the crucible from bottom to top is La, Ce and Mg in turn after loading, and the furnace cover is closed after loading;

[0147] b. Vacuum pumping: open the vacuum system, vacuum pump the furnace body to 1×10 -2 Pa and keep it for 30 min;

[0148] c. Drying: turn on the heating system, adjust the heating power to 30-40 kW, heat the metal raw materials and continue to vacuum pump for about 30 min;

[0149] d. Argon filling: open the argon filling valve and fill argon into the furnace to about 40 kPa;

[0150] e. Melting: adjust the heating power to about 90 kW, continuously heat the metal raw materials, until the alloy is completely melted, at this time the temperature is about 870±10℃ measured by infrared temperature measurement;

[0151] f. Refining: reduce the heating power to about 50 kW, keep the alloy liquid at 820±10℃, and refine for 10 min;

[0152] g. Gas atomization powder making: open the cyclone collection system of the gas atomization system, adjust the heating power to below 30 kW, tilt the crucible to pour the alloy liquid into the preheated tundish, open the tundish atomization nozzle, adjust the argon input pressure to 120 kPa, and spray the alloy liquid in the tundish out of the nozzle to form droplets through the argon flow, and the droplets are cooled and collected in the cyclone collector, i.e. the powder falls on the separation plate 14 inside the equipment body 1 when discharging, the separation plate 14 is provided with grading holes, the size of the grading holes 15 on the upper separation plate 14 is larger than that of the grading holes 15 on the lower separation plate 14, so that the powder can be automatically graded during the falling process, and manual grading operation is not needed in the later stage, and finally the La-Ce-Mg alloy powder with a particle size of 50 microns or less is obtained.

[0153] h. Cooling and collecting: turn off the heating power, keep the water cooling system open, cool the alloy powder in the furnace body and the cyclone collection system to room temperature, and open the furnace to collect the material.

[0154] Ti-Fe-Co-Mn alloy and La-Ce-Mg alloy powder are mixed and ball milled to prepare Ti 1.2 (La 0.5 Ce 0.1 Mg 0.5 ) 0.8 (Fe 0.45 Co 0.05 Mn 0.5 ) 1.2 Nanocomposite:

[0155] a. Mixing: weigh the Ti-Fe-Co-Mn alloy and La-Ce-Mg alloy powder according to the proportion, and mix them uniformly with a mixer, in this embodiment, the mass ratio of the two alloys is 1.622:1;

[0156] b. Charging: weigh the mixed powder and the grinding balls according to the capacity of the ball mill, load them into the ball mill jar and seal it, in this embodiment, the ratio of grinding balls to material is 10:1, load the ball mill jar into the ball mill and lock it;

[0157] c. Vacuumizing and gas protection: vacuumize the ball mill jar to 1.0×10 -2 Pa, then fill in argon protection gas with a pressure of 0.1 MPa;

[0158] d. Ball milling: start the ball mill, set the rotating speed to 800 rpm, and ball mill for 4 h to realize mechanical alloying of the mixed powder under the action of ball milling;

[0159] e. Cooling and collecting: the ball mill will heat up during work, after the work is finished, wait for the ball mill jar to cool down to room temperature, then open the ball mill jar, collect the material into a sealed bag under the protection of inert gas, and store it.

[0160] Ti 1.2 (La 0.5 Ce 0.1 Mg 0.5 ) 0.8 (Fe 0.45 Co 0.05 Mn 0.5 ) 1.2 Heat treatment of hydrogen storage nanocomposite:

[0161] a. Furnace loading: 1 g of Ti 1.2 (La 0.5 Ce 0.1 Mg 0.5 ) 0.8 (Fe 0.45 Co 0.05 Mn 0.5 ) 1.2 The hydrogen storage nanocomposite was loaded into a vacuum heat treatment quartz tube, vacuumed to an air pressure of ≤ 1 x 10 -2 Pa, followed by the introduction of argon gas and the control of air pressure at 80 kPa;

[0162] b. Turn on the heating power of the heat treatment furnace, set the heat treatment temperature and heat, the heat treatment temperature is 700℃, and the heat preservation time is 2h, then the furnace is cooled down;

[0163] c. The cooled Ti 1.2 (La 0.5 Ce 0.1 Mg 0.5 ) 0.8 (Fe 0.45 Co 0.05 Mn 0.5 ) 1.2 The hydrogen storage nanocomposite was taken out under inert gas protection and sealed for preservation.

[0164] Ti 1.2 (La 0.5 Ce 0.1 Mg 0.5 ) 0.8 (Fe 0.45 Co 0.05 Mn 0.5 ) 1.2 Hydrogen absorption and desorption performance test of hydrogen storage nanocomposite:

[0165] 1 g of hydrogen storage material was weighed and loaded into the sample chamber of the hydrogen absorption and desorption test device, the vacuum pump was started to vacuum the sample to below 0.5 Pa and lasted for 1 h, then 3 MPa of high-purity hydrogen gas (purity 99.995%) was filled into the sample at room temperature, the measured hydrogen absorption activation curve of the material at room temperature is shown in Figure 3 After a short incubation period, the material starts to absorb hydrogen rapidly, and the first hydrogen absorption amount is about 2.0 wt.%.

[0166] After the material is repeatedly vacuumed and absorbs hydrogen three times, its isothermal hydrogen absorption and desorption curve (PCT curve) is tested at 25°C as shown in Figure 4 The hydrogen absorption platform of the material is about 2 MPa, the hydrogen absorption amount within 3 MPa is higher than 1.60 wt.%, and the saturated hydrogen storage capacity is higher than 1.75 wt.%.

[0167] Example 3

[0168] Ti 1.4 (La 0.4 Ce 0.1 Mg 0.7 ) 0.6 (Fe 0.25 Co 0.1 Mn 0.7 ) 1.3 Preparation of nanocomposite.

[0169] In this example, the gas atomization scheme is used

[0170] Ti 1.4 (La 0.4 Ce 0.1 Mg 0.7 ) 0.6 (Fe 0.25 Co 0.1 Mn 0.7 ) 1.3 Preparation of nanocomposite.

[0171] Preparation of alloy raw materials

[0172]

[0173] For example, 50 kg of nanocomposite is prepared, and the metal raw materials are weighed according to the data in the above table.

[0174] Preparation of Ti-Fe-Co-Mn and La-Ce-Mg alloy powder:

[0175] The 50 kg level vacuum inert gas atomization furnace with rated power of 100 kW is used to prepare Ti-Fe-Co-Mn alloy powder:

[0176] a. Loading: The weighed Ti, Fe, Co and Mn are sequentially loaded into the induction melting furnace crucible. After loading, the order of the raw materials in the crucible from bottom to top is Ti, Fe, Co and Mn. After loading, the furnace cover is closed;

[0177] b. Vacuumizing: The vacuum system is started, and the furnace body is vacuumized to 1.0×10 -2 Pa and maintained for 30 min;

[0178] c. Drying: Turn on the heating system, adjust the heating power to 30-40 kW, heat the metal raw material and continue to vacuum for about 30 min;

[0179] d. Argon filling: Open the argon filling valve, fill argon into the furnace to about 30 kPa;

[0180] e. Melting: Adjust the heating power to about 90 kW, continue to heat the metal raw material until the alloy is completely melted, at which time the temperature is about 1650±10℃ by infrared temperature measurement;

[0181] f. Refining: Reduce the heating power to about 70 kW, keep the alloy liquid at 1550±10℃, and refine for 10 min;

[0182] g. Gas atomization powder making: Open the cyclone collection system of the gas atomization system, adjust the heating power to below 30 kW, tilt the crucible to pour the alloy liquid into the preheated tundish, open the tundish atomization nozzle at the same time, adjust the argon input pressure to 120 kPa, and the alloy liquid in the tundish is sprayed out of the nozzle by the argon flow to form mist droplets, which are cooled and collected in the cyclone collector. When discharging, the powder falls on the separation plate 14 inside the equipment body 1, and the classification holes are opened on the separation plate 14. The size of the classification holes 15 on the upper separation plate 14 is larger than that of the classification holes 15 on the lower separation plate 14, so that the powder can be automatically classified during the falling process, and manual classification operation is not needed in the later stage. Finally, Ti-Fe-Co-Mn alloy powder with a particle size of less than 50 microns is obtained.

[0183] h. Cooling and collecting: Turn off the heating power, keep the water cooling system open, cool the alloy powder in the furnace body and cyclone collection system to room temperature, and open the furnace to collect the material.

[0184] A 50 kg level vacuum inert gas atomization furnace with a rated power of 100 kW is used to prepare La-Ce-Mg alloy powder:

[0185] a. Furnace loading: Weighed La, Ce, and Mg are sequentially loaded into the induction melting furnace crucible. After loading, the order of the raw materials in the crucible from bottom to top is La, Ce, and Mg. After loading, the furnace cover is closed;

[0186] b. Vacuum pumping: Turn on the vacuum system, vacuum pump the furnace body to 1.0×10 -2 Pa, and keep for 30 min;

[0187] c. Drying: Turn on the heating system, adjust the heating power to 30-40 kW, heat the metal raw material and continue to vacuum for about 30 min;

[0188] d. Argon filling: open the argon filling valve to fill argon into the furnace to about 40 kPa;

[0189] e. Smelting: adjust the heating power to about 90 kW to continuously heat the metal raw material until the alloy is completely melted, at which time the temperature is about 870 ± 10 °C by infrared temperature measurement;

[0190] f. Refining: reduce the heating power to about 50 kW to keep the alloy liquid at 820 ± 10 °C for 10 min;

[0191] g. Gas atomization powder production: open the cyclone collection system of the gas atomization system, adjust the heating power to below 30 kW, tilt the crucible to pour the alloy liquid into the preheated tundish, open the tundish atomization nozzle, and adjust the argon input pressure to 120 kPa. The alloy liquid in the tundish is sprayed out of the nozzle by the argon flow to form droplets, which are cooled and collected in the cyclone collector. The powder falls on the separation plate 14 inside the equipment body 1 during discharging. The separation plate 14 is provided with grading holes. The size of the grading holes 15 on the upper separation plate 14 is larger than that of the grading holes 15 on the lower separation plate 14. In this way, the powder can be automatically graded during the falling process, and manual grading operation is not needed. Finally, La-Ce-Mg alloy powder with a particle size of less than 50 microns is obtained.

[0192] h. Cooling and collecting: turn off the heating power, keep the water cooling system open, cool the alloy powder in the furnace body and cyclone collection system to room temperature, and open the furnace to collect the material.

[0193] Ti-Fe-Co-Mn alloy and La-Ce-Mg alloy powder are mixed and ball milled to prepare Ti 1.4 (La 0.4 Ce 0.1 Mg 0.7 ) 0.6 (Fe 0.25 Co 0.1 Mn 0.7 ) 1.3 nanocomposite:

[0194] a. Mixing: weigh the Ti-Fe-Co-Mn alloy and La-Ce-Mg alloy powder according to the proportion, and mix them uniformly with a mixer. In this embodiment, the mass ratio of the two alloys is 2.749:1.

[0195] b. Charging: weigh the mixed powder and grinding balls according to the capacity of the ball mill, load them into the ball mill jar and seal it. In this embodiment, the ratio of grinding balls to material is 15:1. Load the ball mill jar into the ball mill and lock it;

[0196] c. Vacuumizing and gas protection: vacuumize the ball mill jar to 1.0 × 10-2 Pa, and then argon gas was filled as a protective gas, and the argon pressure was 0.06 MPa;

[0197] d. Ball milling: the ball mill was started, the rotating speed was set to 500 rpm, and the mixed powder was subjected to mechanical alloying under the action of the ball mill for 5 h;

[0198] e. Cooling and collecting: the ball mill was heated during the work, and after the work was completed, the ball mill tank was opened after being cooled to room temperature, and the material was collected into a sealed bag under the protection of inert gas for preservation.

[0199] Ti 1.4 (La 0.4 Ce 0.1 Mg 0.7 ) 0.6 (Fe 0.25 Co 0.1 Mn 0.7 ) 1.3 Heat treatment of the hydrogen storage nanocomposite:

[0200] a. Furnace loading: the Ti 1.4 (La 0.4 Ce 0.1 Mg 0.7 ) 0.6 (Fe 0.25 Co 0.1 Mn 0.7 ) 1.3 The hydrogen storage nanocomposite was loaded into a vacuum heat treatment quartz tube, and the vacuum was pumped to an air pressure of ≤1×10 -2 Pa, and then argon gas was filled and the pressure was controlled to 50 kPa;

[0201] b. Start the heating power of the heat treatment furnace, set the heat treatment temperature and heat, the heat treatment temperature is 500℃, and the heat preservation time is 1.5h, and then the furnace is cooled down;

[0202] c. The cooled Ti 1.4 (La 0.4 Ce 0.1 Mg 0.7 ) 0.6 (Fe 0.25 Co 0.1 Mn 0.7 ) 1.3 The hydrogen storage nanocomposite was taken out under the protection of inert gas and sealed for preservation.

[0203] Ti 1.4 (La 0.4 Ce 0.1 Mg 0.7 ) 0.6 (Fe 0.25 Co 0.1 Mn0.7 ) 1.3 Hydrogen storage nanocomposite material hydrogen absorption and desorption performance test:

[0204] 1 g of hydrogen storage material was weighed into the sample chamber of the hydrogen absorption and desorption test device, the vacuum pump was started to vacuum the sample to below 0.5 Pa and lasted for 1 h, then the sample was filled with 3 MPa high-purity hydrogen gas (purity 99.995%) at room temperature. The measured hydrogen absorption activation curve of the material at room temperature (25°C) is shown in Figure 5 After a short incubation period, the material starts to absorb hydrogen rapidly, and the first hydrogen absorption amount is about 2.06 wt.%.

[0205] After three times of vacuumizing-hydrogen absorption of the material, its isothermal hydrogen absorption and desorption curve (PCT curve) was tested at 25°C as shown in Figure 6 The hydrogen absorption platform median of the material is about 0.8 MPa, the hydrogen absorption amount within 3 MPa is higher than 1.80 w%, and the saturated hydrogen storage capacity is higher than 1.95 wt.%.

[0206] Comparative Example 1

[0207] Ti 1.4 (La 0.4 Ce 0.1 Mg 0.7 ) 0.6 (Fe 0.25 Co 0.1 Mn 0.7 ) 1.3 Direct smelting preparation of hydrogen storage material.

[0208] In this comparative example, the traditional direct smelting scheme was used

[0209] Ti 1.4 (La 0.4 Ce 0.1 Mg 0.7 ) 0.6 (Fe 0.25 Co 0.1 Mn 0.7 ) 1.3 Preparation of hydrogen storage alloy. To verify the beneficial effects of the step-by-step high-temperature smelting and ball-milling nanocrystallization combined preparation scheme of the present application.

[0210] Preparation of alloy raw materials

[0211]

[0212]

[0213] Taking the direct smelting preparation of 50 kg of alloy as an example, the metal raw materials were weighed according to the data in the above table.

[0214] Ti1.4 (La 0.4 Ce 0.1 Mg 0.7 ) 0.6 (Fe 0.25 Co 0.1 Mn 0.7 ) 1.3 Direct smelting of the alloy:

[0215] The Ti 1.4 (La 0.4 Ce 0.1 Mg 0.7 ) 0.6 (Fe 0.25 Co 0.1 Mn 0.7 ) 1.3 Direct smelting of the alloy:

[0216] a, charging: the weighed Ti, Fe, Co, Mn, La, Ce, Mg are sequentially charged into the induction melting furnace crucible, after charging, the order of the raw materials in the crucible from bottom to top is Mg, Ce, La, Ti, Fe, Co, Mn, after charging, the furnace cover is closed;

[0217] b, vacuumizing: the vacuum system is started, the furnace body is vacuumized to 1.0x10 -2 Pa, and maintained for 30 min;

[0218] c, material drying: the heating system is powered on, the heating power is adjusted to 30-40 kW, the metal raw materials are heated and continuously vacuumized for about 30 min;

[0219] d, argon filling: the argon filling valve is opened, argon is filled into the furnace to about 30 kPa;

[0220] e, smelting: the heating power is adjusted to about 90 kW, the metal raw materials are continuously heated until the alloy is completely melted, at this time, the temperature is about 1450±10℃ by infrared temperature measurement;

[0221] f, refining: the heating power is reduced to about 70 kW, the alloy liquid is maintained at 1400±10℃, and refined for 10 min;

[0222] g, casting: the alloy material is directly cast into a columnar mold to obtain an alloy bar.

[0223] Ti 1.4 (La 0.4 Ce 0.1 Mg 0.7 ) 0.6 (Fe 0.25 Co 0.1Mn 0.7 ) 1.3 Hydrogen storage alloy hydrogen absorption and desorption performance test:

[0224] 1 g of hydrogen storage material was weighed into the sample chamber of the hydrogen absorption and desorption test device, the vacuum pump was started to vacuum the sample to below 0.5 Pa and lasted for 1 h, then the sample was charged with 3 MPa high-purity hydrogen gas (purity 99.995%) at room temperature. The measured hydrogen absorption activation curve of the material at room temperature (25°C) is shown in Figure 7 The material has a long incubation period and slow hydrogen absorption rate, and the first hydrogen absorption amount is only 1.1 wt.%.

[0225] In the present comparative example, the

[0226] Ti 1.4 (La 0.4 Ce 0.1 Mg 0.7 ) 0.6 (Fe 0.25 Co 0.1 Mn 0.7 ) 1.3 The composition segregation of the hydrogen storage alloy is serious, which affects the hydrogen storage performance of the alloy.

[0227] Comparative Example 2

[0228] The content of Ti element is less than 1.0;

[0229] For example, Ti 0.8 (La 0.4 Ce 0.05 Mg 0.55 ) 1.2 (Fe 0.40 Co 0.03 Mn 0.6 ) 1.15 The hydrogen absorption amount of the alloy is only 0.95 wt% under the same preparation method as Example 1. The hydrogen absorption amount of the material is low, which is not suitable for use as a high-capacity solid-state hydrogen storage material.

[0230] The content of Ti element is higher than 1.5;

[0231] For example, Ti 1.6 (La 0.4 Ce 0.05 Mg 0.55 ) 0.4 (Fe 0.40 Co 0.03 Mn 0.6 ) 1.15 The hydrogen absorption amount of the alloy is only 0.82 wt% under the same preparation method as Example 1. The hydrogen absorption amount of the material is low, which is not suitable for use as a high-capacity solid-state hydrogen storage material.

[0232] In addition, keeping the ratio of Fe-Co-Mn elements unchanged, the overall content of Fe-Co-Mn is reduced to less than 1.0, and Ti 1.2 (La 0.5 Ce 0.1 Mg 0.5 ) 0.8 (Fe 0.45 Co 0.05 Mn 0.5 ) 0.9 The alloy has a hydrogen absorption capacity of only 1.05wt% under the same preparation method and conditions as in Example 2. The low hydrogen absorption capacity of the material makes it unsuitable for use as a high-capacity solid-state hydrogen storage material.

[0233] Keeping the ratio of Fe-Co-Mn elements unchanged, the overall content of Fe-Co-Mn is increased to more than 1.5, for example, Ti 1.2 (La 0.5 Ce 0.1 Mg 0.5 ) 0.8 (Fe 0.45 Co 0.05 Mn 0.5 ) 1.6 The alloy has a hydrogen absorption capacity of only 0.97wt% under the same preparation method and conditions as in Example 2. The low hydrogen absorption capacity of the material makes it unsuitable for use as a high-capacity solid-state hydrogen storage material.

[0234] Hydrogen storage alloy A m B n Generally composed of A-side metals with higher hydrogen binding capacity and B-side metals with good hydrogen diffusion capacity. The present application proposes a nano-composite hydrogen storage material with good activation performance and higher hydrogen storage capacity by adjusting the composition of various elements on the A and B sides of the hydrogen storage alloy and optimizing the alloy preparation method. In the disclosed alloy Ti x (La a Ce b Mg c ) 2-x (Fe d Co e Mn f ) y Among them, Ti is the main element for improving hydrogen capacity in the A-side elements, La and Ce elements have the functions of adjusting activation capacity and improving resistance to impurity poisoning, and the addition of a small amount of Mg can further improve the hydrogen storage mass ratio; the adjustment of the hydrogen absorption and desorption plateau pressure is realized by the ratio of Fe and Mn elements in the B-side elements, and the Co element can reduce the hydrogen absorption and desorption plateau slope of the alloy.

[0235] In the alloy Ti x (La a Ce b Mgc ) 2-x (Fe d Co e Mn f ) y Among the constituent elements, the melting points of Ti, Fe, Co, and Mn are between 1660-1246℃, while the melting points of La, Ce, and Mg elements are in the range of 921-649℃, with a difference of up to 1011℃. Due to the differences in the melting points and activities of alloying elements, the low-melting-point elements La, Ce, and Mg are prone to oxidation, vaporization, and reaction with the crucible at high temperatures during the traditional one-pot smelting process, resulting in burning loss and affecting the stability of the alloy composition. At the same time, serious segregation occurs during solidification, resulting in a decrease in the hydrogen absorption capacity of the material. In terms of hydrogen absorption activity, the segregation and oxidation on the surface of the alloy affect the initial hydrogen absorption activation performance, and the coarse grains formed during solidification also hinder the diffusion of hydrogen atoms, reducing the hydrogen absorption and desorption rate of the material. In view of the above problems, the present application proposes a combined preparation scheme of stepwise high-temperature smelting and ball milling nanocrystallization, i.e. the material is divided into two groups of Ti-Fe-Co-Mn and La-Ce-Mg alloys according to the melting points of alloying elements, different smelting processes are developed for each group of alloys, and coarse powders less than 50μm are prepared; then, the two groups of alloys are mechanically alloyed by ball milling method, and micro-nanocrystalline structure Ti x (La a Ce b Mg c ) 2-x (Fe d Co e Mn f ) y nanocomposite.

[0236] Although embodiments of the present application have been shown and described, it is to be understood that various modifications, substitutions, replacements and changes can be made to these embodiments without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A hydrogen storage nanocomposite material, characterized in that: The hydrogen storage nanocomposite material is composed of Ti x (La a Ce b Mg c ) 2-x (Fe d Co e Mn f ) y The values ​​of x and y are in the range of 1 ≤ x ≤ 1.5, y is in the range of 1 ≤ y ≤ 1.5, the sum of a + b + c is in the range of 1 ≤ a + b + c ≤ 1.2 and c ≥ 0.5, and the sum of d + e + f is in the range of 1 ≤ d + e + f ≤ 1.05 and f ≥ 0.

5. Ti is the main hydrogen absorption component, and La, Ce, Mg, Fe, Co, and Mn are additives. The hydrogen storage nanocomposite material can be activated to absorb hydrogen under vacuum conditions at 25°C. The hydrogen storage nanocomposite material is obtained by smelting Ti, Fe, Co, Mn and La, Ce, and Mg in a stoichiometric ratio using an induction melting furnace to form Ti-Fe-Co-Mn alloy and La-Ce-Mg alloy, respectively, and then preparing alloy powders with a particle size of less than 50 μm. The Ti-Fe-Co-Mn alloy powder and La-Ce-Mg alloy powder are mixed in a stoichiometric ratio and then mechanically alloyed by ball milling.

2. The hydrogen storage nanocomposite material according to claim 1, characterized in that: The composition of the hydrogen storage nanocomposite material is as follows: Tea 1.25 (Day 0.4 Ce 0.05 Mg 0.55 ) 0.75 (Fe 0.40 Co 0.03 Mr 0.6 ) 1.15 ; Or Ti 1.2 (La 0.5 Ce 0.1 Mg 0.5 ) 0.8 (Fe 0.45 Co 0.05 Mn 0.5 ) 1.2 ; Or Ti 1.4 (La 0.4 Ce 0.1 Mg 0.7 ) 0.6 (Fe 0.25 Co 0.1 Mn 0.7 ) 1.3 The hydrogen storage nanocomposite material can be activated to absorb hydrogen after being evacuated to below 0.5 Pa at room temperature and then filled with hydrogen gas at a pressure of 3 MPa. The initial hydrogen absorption is greater than or equal to 2.0 wt.%.

3. A method for preparing a hydrogen storage nanocomposite material, characterized in that: This preparation method is used to produce the hydrogen storage nanocomposite material according to any one of claims 1-2, and includes the following steps: Step 1: The measured proportions of Ti, Fe, Co, Mn and La, Ce, Mg are smelted in an induction melting furnace to form Ti-Fe-Co-Mn alloy and La-Ce-Mg alloy, respectively, and then alloy powders with a particle size of less than 50μm are prepared. Step 2: The Ti-Fe-Co-Mn alloy powder and La-Ce-Mg alloy powder obtained in Step 1 are mixed in stoichiometric ratio and then mechanically alloyed by ball milling to obtain Ti. x (La a Ce b Mg c ) 2-x (Fe d Co e Mn f ) y The hydrogen storage nanocomposite material has the following values: x ≤ 1.5, y ≤ 1.5, a+b+c ≤ 1.2 and c ≥ 0.5, and d+e+f ≤ 1.05 and f ≥ 0.

5.

4. The method for preparing a hydrogen storage nanocomposite material according to claim 3, characterized in that: In step two, Ti-Fe-Co-Mn alloy powder and La-Ce-Mg alloy powder are loaded into a planetary ball mill. The ball-to-powder ratio during the ball milling process is 5:1-20:

1. The ball mill jar is evacuated to a vacuum of 1×10⁻⁶. -2 After Pa, high-purity argon gas at 0.05-0.1 MPa is introduced for ball milling at a speed of 500-1000 rpm for 2-5 hours. The Ti obtained in step two is then... x (La a Ce b Mg c ) 2-x (Fe d Co e Mn f ) y The hydrogen storage nanocomposite material was subjected to heat treatment in a vacuum or inert gas atmosphere, and the heat treatment method was as follows: Ti... x (La a Ce b Mg c ) 2-x (Fe d Co e Mn f ) y The hydrogen storage nanocomposite material was placed in a vacuum furnace and evacuated to a pressure ≤1×10⁻⁶. -2 Pa, then argon gas is introduced and the gas pressure is controlled at 30-100 kPa, the temperature is raised to 500-800℃, held for 1-2 hours, and then cooled down with the furnace.

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