Rare-earth-based hydrogen storage material having w structure and preparation method therefor

Abstract

The present invention relates to the technical field of hydrogen storage materials, in particular to the field of IPC B29C48, and more particularly to a rare-earth-based hydrogen storage material having a W structure and a preparation method therefor. The rare-earth-based hydrogen storage material comprises a component A and a component B; in parts by weight, the component A comprises: 5-20 parts of rare-earth metal, 3-10 parts of deionized water and 3-9 parts of a high-molecular polymer; and the component B comprises: 1-5 parts of lanthanum metal, 2-5 parts of magnesium oxide, 2-6 parts of polyethylene and 0.01-0.1 part of a coupling agent. 1. The rare-earth metal comprises holmium oxide and yttrium oxide, the weight ratio of the holmium oxide to the yttrium oxide is 1:(0.4-0.6), and thus, the specific surface area (24.137 m2 / g) and the hydrogen adsorption capacity (1.481 cc / g) of the hydrogen storage material can be improved.

Description

A W-structured rare earth hydrogen storage material and its manufacturing method

[0001] This application claims the benefit of Chinese patent application No. 2023111863437, filed on September 13, 2023. This application incorporates the entirety of the aforementioned Chinese patent application. Technical Field

[0002] The present invention relates to the technical field of hydrogen storage materials, in particular to the field of IPC B29C48, and more specifically to a W-structured rare earth hydrogen storage material and a manufacturing method thereof. Background Art

[0003] Hydrogen energy is known as the ultimate energy source for mankind in the 21st century. The hydrogen energy industry includes three links: hydrogen production, hydrogen storage, and application. The storage and transportation of hydrogen is a bottleneck problem in the current hydrogen energy industry chain. There are many hydrogen storage products on the market, generally including methanol 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 has been commercialized, other hydrogen storage products are still in the experimental stage. In order to improve the safety of hydrogen storage and transportation, hydrogen storage metal materials have become a popular research direction, because the hydrogen storage material can exist stably after absorbing hydrogen, avoiding the safety hazards of hydrogen as a flammable and explosive chemical in storage and transportation. However, hydrogen storage metal materials generally use hydrogen storage alloys, which often have the problem of poor hydrogen storage and desorption kinetics.

[0004] CN 113862536 A discloses a method for preparing a high-performance, high-capacity Mg-Al-Y-based hydrogen storage material. The method comprises heating and melting the raw materials in a medium-frequency induction melting furnace under an inert atmosphere, casting and molding the raw materials, pulverizing and crushing the ingot into a powder of 200-300 mesh, and mixing a porous carbon-based catalyst Tm@C loaded with a transition metal and a metal fluoride and performing high-energy ball milling to obtain the hydrogen storage material. However, the preparation process of this method is relatively complex.

[0005] Summary of the Invention

[0006] The first aspect of the present invention provides a W-structured rare earth hydrogen storage material, comprising a component A and a component B. Component A comprises, by weight, 5-20 parts of a rare earth metal, 3-10 parts of deionized water, and 3-9 parts of a high molecular polymer; and component B comprises 1-5 parts of a lanthanum metal, 2-5 parts of magnesium oxide, 2-6 parts of polyethylene, and 0.001-0.1 parts of a coupling agent.

[0007] Preferably, the structure of the rare earth metal comprises a hexagonal unit cell.

[0008] Preferably, the particle size of the rare earth metal is 80-100 nm.

[0009] The rare earth metal includes holmium oxide and yttrium oxide, and the weight ratio of the holmium oxide to the yttrium oxide is 1:(0.4-0.6).

[0010] The applicant 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 increase the specific surface area and hydrogen adsorption capacity of the material, increase the volume of the unit cell, reduce the decomposition hydrogen pressure, and expand the gaseous hydrogen absorption 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 temperatures and release gas at high temperatures. Holmium not only has hydrogen bond donors but also 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 contains 75% orthohydrogen and 25% parahydrogen at room temperature; 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 powders to 80-100nm can further improve hydrogen storage performance. If the particle size is too large, it will affect the specific surface area.

[0011] Preferably, the rare earth metal includes holmium oxide and yttrium oxide, and the weight ratio of holmium oxide to yttrium oxide is 13:7.

[0012] The particle size of the holmium oxide is 100 nm; the particle size of the yttrium oxide is 80 nm, both of which were purchased from Beijing Zhongke Keyou Technology Co., Ltd.

[0013] The high molecular polymer includes one of polyvinyl pyrrolidone, polyethylene glycol and polyvinyl alcohol.

[0014] Preferably, the high molecular polymer includes polyethylene glycol, the polyethylene glycol model is PEG800, purchased from Haian Petrochemical.

[0015] The applicant has discovered that a weight ratio of lanthanum metal, magnesium oxide, and polyethylene of (1-3): (2-5): (3-5) can improve the hydrogen adsorption performance and mechanical properties of the hydrogen storage material. Rare earth metal lanthanum and nano-magnesium oxide can enhance catalytic performance, but lanthanum and magnesium are metallic materials with high molding temperatures, which is not conducive to controlling the surface quality of the formed material. Adding ultra-high molecular weight polyethylene (UHMWPE) with a molecular weight of 5-8 million can lower the molding temperature and facilitate sintering. Furthermore, the UHMWPE sintered into a porous membrane with an optimal pore size at a specific molecular weight further enhances catalytic performance and improves the mechanical properties of the material.

[0016] The weight ratio of the lanthanum metal, magnesium oxide and polyethylene is (1-3): (2-5): (3-5).

[0017] Preferably, the weight ratio of the lanthanum metal, magnesium oxide, and polyethylene is 2.5:3:4.5.

[0018] The lanthanum metal mesh number is 200 mesh and was purchased from Changsha Deli Rare Earth Chemical Co., Ltd.

[0019] The magnesium oxide particle size is 50-100 nm, model: HN-Mg50, purchased from Hangzhou Hengna New Materials Co., Ltd.

[0020] The polyethylene includes ultra-high molecular weight polyethylene.

[0021] The molecular weight of the ultra-high molecular weight polyethylene is 5-8 million.

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

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

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

[0025] S1, adding a polymer to deionized water to obtain a polymer solution, then adding a rare earth metal to the polymer solution, mixing them evenly, to obtain component A;

[0026] S2, adding lanthanum metal and magnesium oxide to a coupling agent and mixing them at high temperature and high speed, pouring out and cooling after mixing to obtain a mixture, then mixing the mixture with polyethylene, adding the mixed mixture into a W-shaped mold, sintering, cooling, and opening the mold to obtain a W-shaped B component;

[0027] S3, spraying component A onto the W-shaped component B and baking.

[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°C.

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

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

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

[0034] 1. The rare earth metal includes holmium oxide and yttrium oxide, and the weight ratio of holmium oxide to yttrium oxide is 1: (0.4-0.6), which can increase the specific surface area of ​​the hydrogen storage material (24.137m 2 / g) and hydrogen adsorption (1.481cc / g).

[0035] 2. The weight ratio of lanthanum metal, magnesium oxide and polyethylene is (1-3): (2-5): (3-5), which can improve the hydrogen adsorption performance of the hydrogen storage material and the mechanical properties of the material.

[0036] 3. The material can reversibly absorb, store and release large amounts of hydrogen at room temperature, promoting the safe use of hydrogen in power generation and combustion, and improving the efficiency of green energy use.

[0037] 4. Use specific rare earth metals and the simplest production equipment and process equipment to produce excellent hydrogen absorption and desorption kinetics and chemical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] 1. Actual picture of the hydrogen storage material prepared in Example 1.

[0039] 2. Test report on the specific surface area of ​​the hydrogen storage material prepared in Example 1.

[0040] 3. Specific surface area adsorption curve of the hydrogen storage material prepared in Example 1. DETAILED DESCRIPTION

[0041] Example 1

[0042] A W-structured rare earth hydrogen storage material comprises a component A and a component B. Component A comprises, by weight, 10 parts of rare earth metal, 4.5 parts of deionized water, and 5.5 parts of a high molecular polymer; and component B comprises 2.5 parts of lanthanum metal, 3 parts of magnesium oxide, 4.5 parts of polyethylene, and 0.002 parts of a coupling agent.

[0043] The rare earth metals are holmium oxide and yttrium oxide, and the weight ratio of holmium oxide to yttrium oxide is 13:7.

[0044] The particle size of the holmium oxide is 100 nm; the particle size of the yttrium oxide is 80 nm, both of which were purchased from Beijing Zhongke Keyou Technology Co., Ltd.

[0045] The high molecular polymer includes polyethylene glycol, the polyethylene glycol model is PEG800, purchased from Haian Petrochemical.

[0046] The lanthanum metal mesh number is 200 mesh and was purchased from Changsha Deli Rare Earth Chemical Co., Ltd.

[0047] The magnesium oxide particle size is 50-100 nm, model: HN-Mg50, purchased from Hangzhou Hengna New Materials Co., Ltd.

[0048] The polyethylene is ultra-high molecular weight polyethylene with a molecular weight of 6 million, model: UHMWPE GUR4130, purchased from Shenzhen Dongbang Import and Export Trading Co., Ltd.

[0049] The coupling agent is silane coupling agent Si-550, CAS: 919-30-2, brand: Chinese Academy of Sciences KH-550.

[0050] A method for manufacturing a W-structured rare earth hydrogen storage material comprises the following steps:

[0051] S1, adding a polymer to deionized water to obtain a polymer solution, then adding a rare earth metal to the polymer solution, mixing them evenly, to obtain component A;

[0052] S2, adding lanthanum metal and magnesium oxide to a coupling agent and mixing them at high temperature and high speed, pouring out and cooling after mixing to obtain a mixture, then mixing the mixture with polyethylene, adding the mixture into a W-shaped mold after mixing, sintering, cooling, and mold opening (for the specific methods of sintering, cooling, and mold opening, refer to paragraphs 37-39 of patent CN201810204766.X), and obtaining a W-shaped B component;

[0053] S3, spraying component A onto the W-shaped component B and baking to obtain (Figure 1).

[0054] The weight ratio of component A to component B is 1:0.5.

[0055] The mixing time in S1 is 25 min and the mixing temperature is 110°C.

[0056] The baking time is 3 hours and the baking temperature is 100°C.

[0057] The specific steps of S3 are as follows: cutting the W-shaped B component into the required size, loading it into the automatically flipping coating equipment fixture for surface processing, installing a slurry silo above the frame, and installing a number of nozzles below the silo. When the frame flips, the nozzles automatically start to spray the A component onto the double-sided structure of the W profile, and repeat this cycle until both sides of the W shape are filled (the mass of the A material is twice that of the B material when filled).

[0058] Comparative Example 1

[0059] The specific implementation is the same as Example 1; the difference is that in Comparative Example 1: the particle size of the holmium oxide is 200 nm; the particle size of the yttrium oxide is 200 nm, both of which are purchased from Beijing Zhongke Keyou Technology Co., Ltd.

[0060] Comparative Example 2

[0061] The specific implementation is the same as that of Example 1; except that, in Comparative Example 2, the ultra-high molecular weight polyethylene has a molecular weight of 2 million, model: XM220, purchased from Mitsui Chemicals.

[0062] Comparative Example 3

[0063] The specific implementation is the same as Example 1; the difference is that in Comparative Example 3: 3 parts of lanthanum metal, 2.5 parts of magnesium oxide, and 4.5 parts of polyethylene.

[0064] Performance testing methods

[0065] The performance tests were carried out in the embodiments and comparative examples, and the test data are listed in Table 1.

[0066] Specific surface area test (Figure 2, Figure 3):

[0067] Instrument Brand: Quantachrome, Model: Autosorb-iQ-TPX. BET Test Method: The sample is placed in a nitrogen-filled atmosphere, where physical adsorption occurs on the material's surface at liquid nitrogen temperature. When this physical adsorption reaches equilibrium, the adsorption pressure and adsorbed gas flow rate are measured at equilibrium to determine the monolayer adsorption capacity of the material and calculate the sample's specific surface area.

[0068] Hydrogen Adsorption: Instrument Model: Quadrasorb SI, Quantachrome, USA; Specific Testing Method: After vacuum degassing at 200°C, the sample is tested for hydrogen adsorption 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, thereby reflecting the suitability of hydrogen storage materials.)

[0069] Performance test data

[0070] Table 1

Claims

1. A W-structured rare earth hydrogen storage material, characterized in that: The invention comprises component A and component B. Calculated by weight, the component A comprises: 5-20 parts of rare earth metal, 3-10 parts of deionized water, and 3-9 parts of high molecular polymer; the 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.

2. A W-structured rare earth hydrogen storage material according to claim 1, characterized in that: The structure of the rare earth metal includes a hexagonal unit cell.

3. A W-structured rare earth hydrogen storage material according to claim 2, characterized in that: The rare earth metal includes holmium oxide and yttrium oxide, and the weight ratio of holmium oxide to yttrium oxide is 1:(0.4-0.6).

4. A W-structured rare earth hydrogen storage material according to claim 1, characterized in that: The polyethylene includes ultra-high molecular weight polyethylene.

5. A W-structured rare earth hydrogen storage material according to claim 4, characterized in that: The molecular weight of the ultra-high molecular weight polyethylene is 5-8 million.

6. A W-structured rare earth hydrogen storage material according to claim 2, characterized in that: The weight ratio of the lanthanum metal, magnesium oxide and polyethylene is (1-3): (2-5): (3-5).

7. A W-structured rare earth hydrogen storage material according to claim 3, characterized in that: The high molecular polymer includes one of polyvinyl pyrrolidone, polyethylene glycol and polyvinyl alcohol.

8. A method for manufacturing the W-structured rare earth hydrogen storage material according to claim 1, characterized in that: The following steps are involved: S1, adding a high molecular polymer into deionized water to obtain a high molecular solution, then adding a rare earth metal into the high molecular solution, mixing evenly, to obtain component A; S2, adding lanthanum metal and magnesium oxide to a coupling agent for high-temperature and high-speed mixing, pouring out and cooling after mixing to obtain a mixture, then mixing the mixture with polyethylene, adding the mixture into a W-shaped mold after mixing, sintering, cooling, and opening the mold to obtain a W-shaped B component; S3, spraying component A onto the surface of component B of the W-shaped product and baking the product.

9. The method for manufacturing a W-structured rare earth hydrogen storage material according to claim 8, characterized in that: The weight ratio of component A to component B is 1:(0.3-0.7).

10. The method for manufacturing a W-structured rare earth hydrogen storage material according to claim 9, characterized in that: The mixing time in S1 is 15-35 minutes, and the mixing temperature is 100-120°C.

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