A rare earth hydrogen storage material of W structure and a method for producing the same

Abstract

The present application relates to hydrogen storage material technical field, especially to IPC B29C48 field, more particularly, to a kind of W structure's rare earth hydrogen storage material and its manufacturing method.The rare earth hydrogen storage material includes A component and B component, by weight parts, the A component includes: rare earth metal 5-20 parts, deionized water 3-10 parts, high molecular polymer 3-9 parts;The B component includes: lanthanum metal 1-5 parts, magnesium oxide 2-5 parts, polyethylene 2-6 parts, coupling agent 0.01-0.1 parts.The lanthanum metal, magnesium oxide, polyethylene weight ratio is (1-3) :(3-5) :(3-5), can improve the adsorption performance of hydrogen storage material to hydrogen and the mechanical properties of material at lower specific surface area.

Description

Technical Field

[0001] This invention relates to the field of hydrogen storage materials technology, particularly to the field of IPC B29C48, and more specifically, to a W-structured rare earth hydrogen storage material and its manufacturing method. Background Technology

[0002] Hydrogen energy is hailed as the ultimate energy source for the 21st century, and the hydrogen energy industry encompasses three segments: hydrogen production, storage, and application. Hydrogen storage and transportation are currently a bottleneck in the hydrogen energy industry chain. Many hydrogen storage products are available on the market, including methanol-based hydrogen storage, high-pressure hydrogen storage, liquefied hydrogen storage, solid-state adsorption hydrogen storage, and metal hydride hydrogen storage. Except for high-pressure hydrogen storage, which is already commercialized, other hydrogen storage products are still in the experimental stage. To improve the safety of hydrogen storage and transportation, hydrogen storage metal materials have become a popular research direction because they can remain stable after absorbing hydrogen, avoiding the safety hazards associated with hydrogen as a flammable and explosive chemical during storage and transportation. However, hydrogen storage metal materials, typically utilizing hydrogen storage alloys, often suffer from poor hydrogen storage and release kinetics.

[0003] CN 113862536 A discloses a method for preparing high-performance, high-capacity Mg-Al-Y-based hydrogen storage materials. The method involves heating and melting the raw materials in an inert atmosphere using a medium-frequency induction melting furnace, casting them into shape, pulverizing and crushing the ingots into 200-300 mesh powder, mixing them with a porous carbon-based catalyst Tm@C loaded with transition metals and metal fluorides, and then ball-milling them at high energy to obtain the hydrogen storage material. However, the preparation process of this method is relatively complex. Summary of the Invention

[0004] The first aspect of this invention provides a W-structured rare earth hydrogen storage material, comprising component A and component B. By weight, component A comprises: 5-20 parts of rare earth metal, 3-10 parts of deionized water, and 3-9 parts of polymer; component B comprises: 1-5 parts of lanthanum metal, 2-5 parts of magnesium oxide, 2-6 parts of polyethylene, and 0.001-0.1 parts of coupling agent.

[0005] Preferably, the structure of the rare earth metal comprises a hexagonal unit cell.

[0006] Preferably, the particle size of the rare earth metal is 80-100 nm.

[0007] The rare earth metals include holmium oxide and yttrium oxide, wherein the weight ratio of holmium oxide to yttrium oxide is 1:(0.4-0.6).

[0008] The applicant's research has found that the rare earth metals include holmium oxide and yttrium oxide, and the weight ratio of holmium oxide to yttrium oxide is 1:(0.4-0.6), which can improve the hydrogen adsorption capacity of the material, increase the volume of the unit cell, reduce the decomposition hydrogen pressure, and expand the gaseous hydrogen adsorption capacity. The crystal structure of holmium and yttrium, holmium in rare earth metals is used as a special catalyst, which can absorb gas at low temperature and release gas at high temperature. Holmium has both hydrogen bond donors and hydrogen bond acceptors. Holmium is stable in dry air and is the strongest known paramagnetic substance. Hydrogen molecules can be converted by paramagnetic catalysis. Hydrogen at room temperature contains 75% positive hydrogen and 25% secondary hydrogen. The rare earth element yttrium can be used as a catalyst and can also be used in superconductors and superalloys. Furthermore, controlling the particle size of rare earth holmium and yttrium powder to 80-100 nm can further improve the hydrogen storage performance. If the particle size is too large, it will affect the specific surface area.

[0009] Preferably, the rare earth metals include holmium oxide and yttrium oxide, wherein the weight ratio of holmium oxide to yttrium oxide is 13:7.

[0010] The holmium oxide has a particle size of 100 nm; the yttrium oxide has a particle size of 80 nm, both purchased from Beijing Zhongke Keyou Technology Co., Ltd.

[0011] The polymer includes one of polyvinylpyrrolidone, polyethylene glycol, and polyvinyl alcohol.

[0012] Preferably, the polymer comprises polyethylene glycol, specifically PEG800, purchased from Haian Petrochemical.

[0013] The applicant discovered that a weight ratio of lanthanum metal, magnesium oxide, and polyethylene of (1-3):(3-5):(3-5) can improve the hydrogen adsorption performance and mechanical properties of hydrogen storage materials. While rare earth metal lanthanum and nano-magnesium oxide can enhance catalytic performance, lanthanum and magnesium are metallic materials with high molding temperatures, which is detrimental to controlling the surface quality of the molding process. Adding ultra-high molecular weight polyethylene (UHMWPE) with a molecular weight of 5-8 million can lower the molding temperature, facilitating sintering. Furthermore, sintering UHMWPE into porous membranes with optimal pore size further improves catalytic performance and enhances the mechanical properties of the material.

[0014] The weight ratio of lanthanum metal, magnesium oxide, and polyethylene is (1-3):(3-5):(3-5).

[0015] Preferably, the weight ratio of lanthanum metal, magnesium oxide, and polyethylene is (2-2.5):(3-4):(3-5).

[0016] Preferably, the weight ratio of lanthanum metal, magnesium oxide, and polyethylene is 2.5:3:4.5.

[0017] The lanthanum metal had a mesh size of 200 and was purchased from Changsha Deli Rare Earth Chemical Co., Ltd.

[0018] The magnesium oxide particles have a diameter of 50-100 nm, are of type HN-Mg50, and were purchased from Hangzhou Hengna New Materials Co., Ltd.

[0019] The polyethylene includes ultra-high molecular weight polyethylene.

[0020] The ultra-high molecular weight polyethylene has a molecular weight of 5-8 million.

[0021] Preferably, the ultra-high molecular weight polyethylene has a molecular weight of 6-8 million.

[0022] Preferably, the ultra-high molecular weight polyethylene has a molecular weight of 6 million, model number: UHMWPE GUR4130, and is purchased from Shenzhen Dongbang Import & Export Trading Co., Ltd.

[0023] The coupling agent includes a silane coupling agent.

[0024] A second aspect of this invention provides a method for manufacturing a W-structured rare-earth hydrogen storage material, comprising the following steps:

[0025] S1, add the polymer to deionized water to obtain a polymer solution, then add rare earth metals to the polymer solution and mix evenly to obtain component A;

[0026] S2, Lanthanum metal and magnesium oxide are added to a coupling agent and mixed at high temperature and high speed. After mixing, the mixture is poured out and cooled to obtain a mixture. The mixture is then mixed with polyethylene. After mixing, it is added into a W-shaped mold for sintering, cooling, and mold opening to obtain the W-shaped B component.

[0027] S3, spray component A onto component B of type W, and bake to obtain the final product.

[0028] The weight ratio of component A to component B is 1:(0.3-0.7).

[0029] Preferably, the weight ratio of component A to component B is 1:0.5.

[0030] The mixing time in S1 is 15-35 minutes, and the mixing temperature is 100-120℃.

[0031] Preferably, the mixing time in S1 is 25 minutes and the mixing temperature is 110°C.

[0032] The baking time is 2-4 hours, and the baking temperature is 90-110℃.

[0033] Preferably, the baking time is 3 hours and the baking temperature is 100°C.

[0034] Beneficial effects:

[0035] 1. The rare earth metal comprises holmium oxide and yttrium oxide, wherein the weight ratio of holmium oxide to yttrium oxide is 1:

[0036] (0.4-0.6), and the weight ratio of lanthanum metal, magnesium oxide, and polyethylene is (1-3):(3-5):(3-5).

[0037] The specific surface area of ​​the hydrogen storage material can be reduced to 24.137 m². 2 A high hydrogen adsorption capacity (1.481 cc / g) was achieved under the condition of / g), while improving the mechanical properties of the material.

[0038] 2. This material can reversibly absorb, store, and release large amounts of hydrogen at room temperature, promoting the safe use of hydrogen energy in power generation and combustion processes and improving the efficiency of green energy use.

[0039] 3. By using specific rare earth metals and the simplest production equipment and processes, excellent hydrogen absorption and desorption kinetics and chemical properties can be produced. Attached Figure Description

[0040] Figure 1 This is a physical image of the hydrogen storage material prepared in Example 1.

[0041] Figure 2 is Specific surface area test report of the hydrogen storage material prepared in Example 1.

[0042] Figure 3 The adsorption curves are based on the specific surface area of ​​the hydrogen storage material prepared in Example 1. Detailed Implementation

[0043] Example 1

[0044] A W-structured rare earth hydrogen storage material comprises component A and component B. By weight, component A consists of 10 parts rare earth metal, 4.5 parts deionized water, and 5.5 parts polymer; component B consists of 2.5 parts lanthanum metal, 3 parts magnesium oxide, 4.5 parts polyethylene, and 0.002 parts coupling agent.

[0045] The rare earth metals are holmium oxide and yttrium oxide, and the weight ratio of holmium oxide to yttrium oxide is 13:7.

[0046] The holmium oxide has a particle size of 100 nm; the yttrium oxide has a particle size of 80 nm, both purchased from Beijing Zhongke Keyou Technology Co., Ltd.

[0047] The polymer includes polyethylene glycol, specifically PEG800, which was purchased from Haian Petrochemical.

[0048] The lanthanum metal had a mesh size of 200 and was purchased from Changsha Deli Rare Earth Chemical Co., Ltd.

[0049] The magnesium oxide particles have a diameter of 50-100 nm, are of type HN-Mg50, and were purchased from Hangzhou Hengna New Materials Co., Ltd.

[0050] The polyethylene is ultra-high molecular weight polyethylene with a molecular weight of 6 million, model number: UHMWPE GUR4130, purchased from Shenzhen Dongbang Import & Export Trading Co., Ltd.

[0051] The coupling agent is silane coupling agent Si-550, CAS: 919-30-2, brand name: Chinese Academy of Sciences KH-550.

[0052] A method for manufacturing a W-structured rare-earth hydrogen storage material comprises the following steps:

[0053] S1, add the polymer to deionized water to obtain a polymer solution, then add rare earth metals to the polymer solution and mix evenly to obtain component A;

[0054] S2, Lanthanum metal and magnesium oxide are added to a coupling agent and mixed at high temperature and high speed. After mixing, the mixture is poured out and cooled to obtain a mixture. The mixture is then mixed with polyethylene. After mixing, it is added into a W-shaped mold for sintering, cooling, and mold opening (for specific methods of sintering, cooling, and mold opening, refer to paragraphs 37-39 of patent CN201810204766.X) to obtain the B component of the W type.

[0055] S3, spray component A onto component B of type W, and bake to obtain ( Figure 1 ).

[0056] The weight ratio of component A to component B is 1:0.5.

[0057] The mixing time in S1 is 25 minutes, and the mixing temperature is 110°C.

[0058] The baking time is 3 hours, and the baking temperature is 100℃.

[0059] The specific steps of S3 are as follows: the B component of the W-shaped material is cut into the required size and loaded into the fixture of the automatically rotating coating equipment for surface processing. A slurry hopper is installed above the frame, and several nozzles are installed below the hopper. When the frame rotates, the nozzles are automatically activated to spray the A component onto the double-sided structure of the W-shaped material. This process is repeated until both sides of the W-shaped material are filled (when filled, the mass of the A material is twice that of the B material).

[0060] Comparative Example 1

[0061] The specific implementation method is the same as in Example 1; the difference is that in Comparative Example 1, the particle size of holmium oxide is 200 nm and the particle size of yttrium oxide is 200 nm, both of which were purchased from Beijing Zhongke Keyou Technology Co., Ltd.

[0062] Comparative Example 2

[0063] The specific implementation method is the same as in Example 1; the difference is that in Comparative Example 2, the molecular weight of the ultra-high molecular weight polyethylene is 2 million, the model is XM220, and it was purchased from Mitsui Chemicals.

[0064] Comparative Example 3

[0065] The specific implementation method is the same as in Example 1; the difference is that in Comparative Example 3: 3 parts lanthanum metal, 2.5 parts magnesium oxide, and 4.5 parts polyethylene.

[0066] Performance testing methods

[0067] Performance tests were conducted on the examples and comparative examples, and the test data are listed in Table 1.

[0068] Specific surface area test ( Figure 2 Figure 3 ):

[0069] Instrument Brand: CANTA (USA); Instrument Model: Autosorb-iQ-TPX; BET Test Method: The sample is placed in a nitrogen-filled atmosphere, and physical adsorption occurs on the surface of the material at liquid nitrogen temperature. When this physical adsorption reaches equilibrium, the monolayer adsorption capacity of the material is determined by measuring the adsorption pressure and the flow rate of the adsorbed gas at equilibrium, and the specific surface area of ​​the sample is calculated.

[0070] Hydrogen adsorption: Instrument model: Quadrasorb SI, Quantachrome, USA; Specific detection method: After the sample is degassed under vacuum at 200℃, hydrogen adsorption test is performed at low pressure (equivalent to 1 atmosphere). (Hydrogen adsorption data at various temperatures below atmospheric pressure can provide quantitative and qualitative information for the characterization of porous materials, thus reflecting the suitability of hydrogen storage materials).

[0071] Performance test data

[0072] Table 1

[0073] <![CDATA[Specific surface area m 2 / g]]> Hydrogen adsorption cc / g Example 1 24.137 1.481 Comparative Example 1 209.22 1.453 Comparative Example 2 97.766 0.752 Comparative Example 3 84.565 0.651

Claims

1. A W-structured rare-earth hydrogen storage material, characterized in that, The material comprises two components, A and B. By weight, component A includes 5-20 parts rare earth metal, 3-10 parts deionized water, and 3-9 parts polymer. Component B includes 1-5 parts lanthanum metal, 2-5 parts magnesium oxide, 2-6 parts polyethylene, and 0.001-0.1 parts coupling agent. The weight ratio of lanthanum metal, magnesium oxide, and polyethylene is (1-3):(3-5):(3-5). The W-structure rare earth hydrogen storage material is prepared by separately preparing components A and B, and then spraying component A onto the surface of component B. The particle size of the rare earth metal is 80-100 nm. The rare earth metal includes holmium oxide and yttrium oxide, with a weight ratio of holmium oxide to yttrium oxide of 1:(0.4-0.6). The polyethylene includes ultra-high molecular weight polyethylene with a molecular weight of 5-8 million.

2. The W-structured rare-earth hydrogen storage material according to claim 1, characterized in that, The ultra-high molecular weight polyethylene has a molecular weight of 6-8 million.

3. The W-structured rare-earth hydrogen storage material according to claim 1, characterized in that, The polymer includes one of polyvinylpyrrolidone, polyethylene glycol, and polyvinyl alcohol.

4. A method for manufacturing a W-structured rare-earth hydrogen storage material according to claim 1, characterized in that, Includes the following steps: S1, add the polymer to deionized water to obtain a polymer solution, then add rare earth metals to the polymer solution and mix evenly to obtain component A; S2, Lanthanum metal and magnesium oxide are added to a coupling agent and mixed at high temperature and high speed. After mixing, the mixture is poured out and cooled to obtain a mixture. The mixture is then mixed with polyethylene. After mixing, it is added into a W-shaped mold for sintering, cooling, and mold opening to obtain the W-shaped B component. S3, spray component A onto the surface of component B of type W, and bake to obtain the final product.

5. The method for manufacturing a W-structured rare earth hydrogen storage material according to claim 4, characterized in that, The weight ratio of component A to component B is 1:(0.3-0.7).

6. The method for manufacturing a W-structured rare earth hydrogen storage material according to claim 5, characterized in that, The mixing time in S1 is 15-35 minutes, and the mixing temperature is 100-120℃.

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