CN115287490B - Magnesium-based hydrolysis hydrogen production composite material and preparation method thereof - Google Patents
Magnesium-based hydrolysis hydrogen production composite material and preparation method thereof Download PDFInfo
- Publication number
- CN115287490B CN115287490B CN202210916409.2A CN202210916409A CN115287490B CN 115287490 B CN115287490 B CN 115287490B CN 202210916409 A CN202210916409 A CN 202210916409A CN 115287490 B CN115287490 B CN 115287490B
- Authority
- CN
- China
- Prior art keywords
- hydrogen production
- alloy
- magnesium
- mwcnts
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a preparation method of a magnesium-based hydrolysis hydrogen production composite material, which comprises the following steps: preparing a Mg-Ca-Ni ternary alloy by a flux protection method; step two, mechanically crushing the obtained Mg-Ca-Ni ternary alloy to obtain Mg-Mg 2 Ca‑Mg 2 Ni alloy particles; step three, performing short-time high-energy ball milling on the MWCNTs and the alloy particles to obtain refined Mg-Mg 2 Ca‑Mg 2 Ni-MWCNTs composite powder; and step four, putting the composite powder into a tabletting mold, and pressing the composite powder into a block or sheet material by using a tabletting machine to obtain the porous magnesium-based hydrogen production hydrolysis composite material. The invention also discloses the magnesium-based hydrolysis hydrogen production composite material obtained by the preparation method. The method has the advantages of simple process, short time consumption, high efficiency, low cost, capability of quickly preparing a large amount of hydrogen, high conversion rate and suitability for industrial and large-scale production.
Description
Technical Field
The invention relates to a magnesium-based hydrolysis hydrogen production composite material and a preparation method thereof, belonging to the technical field of hydrogen production materials and preparation processes thereof.
Background
The development of clean and efficient new energy is the key to solve the energy crisis and environmental pollution of the current society, hydrogen is the key point of research due to the advantages of wide source, high energy value, no pollution and the like, and the development of a simple, green, safe, efficient and cheap hydrogen production technology is crucial to the large-scale use of hydrogen energy.
At present, industrial hydrogen is mainly from cracking of organic matters, is not a green and reproducible hydrogen production method, and hydrogen production by water electrolysis also needs to consider the source of electricity, needs complex equipment and is limited by regions.
The hydrolysis hydrogen production of metal materials is concerned recently, magnesium, aluminum and other metals can spontaneously generate hydrolysis reaction with water to generate hydrogen under normal temperature and normal pressure, the hydrolysis reaction has no pollution to the environment, the theoretical hydrogen production is high, and the further development is hopeful to realize industrial application at the mobile hydrogen production end. The metal magnesium has low price, high earth storage capacity, high hydrogen production conversion rate by hydrolysis reaction, mg (OH) 2 The precipitation is the only byproduct of the reaction, has no pollution to the environment, butRapid formation of Mg (OH) 2 The reaction rate thereof is significantly reduced. Effectively promote Mg (OH) in the hydrolysis process 2 The exfoliation of the magnesium-based material has important significance for improving the hydrogen production performance of the magnesium-based material by hydrolysis.
Disclosure of Invention
The invention aims at the Mg (OH) in the existing magnesium-based material hydrolysis process 2 The problem of hindering the further progress of the hydrolysis reaction is solved by providing a preparation method of a magnesium-based hydrolysis hydrogen production composite material based on Mg 2 The Ca phase may react with water to form Mg (OH) 2 、Ca(OH) 2 And H 2 High theoretical hydrogen production, and adding small amount of Ni/Ca to magnesium to obtain layered structure, mg and Mg 2 Ca/Mg 2 Ni is alternately distributed to form a primary battery to accelerate hydrolysis reaction, the dispersibility of the carbon nano tube is utilized to prepare the porous sheet-shaped composite material, the refined magnesium-based alloy powder is effectively isolated, the mass transfer process in the hydrolysis reaction is assisted, and Mg (OH) is effectively promoted 2 The peeling of the precipitate ensures that the hydrogen production rate of the obtained magnesium-based composite material for hydrogen production by hydrolysis is continuously increased for a long time, which shows that Mg (OH) is generated by the composite material of the invention 2 Can be effectively peeled off without influencing the hydrogen production reaction rate of the composite material.
The invention also aims to provide the magnesium-based hydrolysis hydrogen production composite material obtained by the preparation method.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a magnesium-based hydrolysis hydrogen production composite material comprises the following steps:
preparing a Mg-Ca-Ni ternary alloy by a flux protection method;
step two, mechanically crushing the obtained Mg-Ca-Ni ternary alloy to obtain Mg-Mg 2 Ca-Mg 2 Ni alloy particles;
step three, mixing the MWCNTs and Mg-Mg of the multi-walled carbon nano-tube 2 Ca-Mg 2 Carrying out short-time high-energy ball milling on the Ni alloy particles to obtain refined Mg-Mg 2 Ca-Mg 2 Ni-MWCNTs composite powder;
step four, refining Mg-Mg 2 Ca-Mg 2 Putting the Ni-MWCNTs composite powder into a tabletting mold, and pressing into a blocky or flaky material by using a tabletting machine to obtain the porous magnesium-based hydrogen production composite material by hydrolysis.
In the Mg-Ca-Ni ternary alloy, the mass fraction range of Ca element is 10-20%, preferably 13-15%; the mass fraction of the Ni element is 0 to 10%, preferably 3 to 5%.
In the refined Mg-Mg2Ca-Mg2Ni-MWCNTs composite powder, the mass fraction of the multi-wall carbon nano-tube MWCNTs is 0-5%, preferably 2-5%.
The preparation method of the Mg-Ca-Ni ternary alloy comprises the steps of weighing Mg, mg-20wt.% Ca intermediate alloy and Mg-45wt.% Ni intermediate alloy according to the weight proportion, adding 5% of Mg by mass for balancing burning loss, then placing the alloy into a graphite crucible, adding a flux to cover metal, heating the alloy in a resistance furnace to 820 ℃, preserving the temperature for 30 minutes at 820 ℃, fully stirring during the preservation, and then pouring the metal melt into a stainless steel mold for solidification.
The flux is a covercoat comprising an RJ-2 covercoat.
In the second step, the mechanical crushing method comprises the following steps: adopting a high-energy ball milling crushing method under the protection of argon, wherein the ball milling time is 1 hour, and the ball-to-material ratio is 30:1, rotation speed 875 revolutions per minute.
In the third step, firstly, the MWCNTs and Mg-Mg of the multi-walled carbon nano-tubes are mixed 2 Ca-Mg 2 Mixing Ni alloy particles in a ball mill for 10 minutes, and then carrying out high-energy ball milling under the protection of argon, wherein the ball milling time is 20 minutes, and the ball-to-material ratio is 30:1, rotation speed 875 revolutions per minute.
And in the fourth step, a tabletting mould is a single-punch tablet machine, the pressure used during tabletting is 3-4MPa, the pressure maintaining time is 8min, and the diameter of the material obtained by pressing is 12-20mm, and the thickness is 3-5mm.
According to the magnesium-based hydrolysis hydrogen production composite material obtained by the preparation method, the magnesium-based hydrolysis hydrogen production composite material is Mg and Mg 2 Ca/Mg 2 The Ni is distributed in a layered structure in an alternating way.
Magnesium-based hydrolysis hydrogen production composite material and water spontaneous reaction to generate Mg (OH) 2 、Ca(OH) 2 And H 2 (ii) a The magnesium-based hydrolysis hydrogen production composite material has high hydrogen production rate, and the hydrogen production rate can reach 400mL/g in 0 minute; the hydrogen production rate is continuously increased within 0 to 110 minutes and is 400 to 800 mL/g.
The invention has the following beneficial effects:
1. Mg-Mg prepared by the invention 2 Ca-Mg 2 In the composite material for preparing hydrogen by hydrolyzing Ni-MWCNTs, matrix Mg and Mg 2 Ca/Mg 2 The second phase of Ni is distributed in a layered and alternate way, and the structure is helpful for Mg (OH) in the hydrolysis process 2 Spalling of the passivation layer and Mg 2 Ca/Mg 2 Ni phase and Mg form a primary battery to accelerate electron transfer in the hydrolysis process, and the dispersibility of MWCNTs is utilized to ensure fine Mg-Mg after tabletting 2 Ca-Mg 2 The Ni alloy powder maintains rapid and continuous hydrolysis reaction and contributes to Mg (OH) 2 And peeling off the passivation layer.
2. The obtained Mg-Mg 2 Ca-Mg 2 The composite material for preparing hydrogen by hydrolyzing Ni-MWCNTs has high hydrogen yield and Mg 2 The Ca phase reacts spontaneously with water to form Mg (OH) 2 、Ca(OH) 2 And H 2 And the utilization rate of raw materials is high.
3. The preparation method has the advantages of simple preparation process, short time consumption, high efficiency, low price, capability of quickly preparing a large amount of hydrogen, high conversion rate and suitability for industrial and large-scale production.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 shows a refined Mg-Mg of the present invention 2 Ca-Mg 2 SEM picture of Ni-MWCNTs composite powder;
FIG. 3 is a kinetic curve of hydrolysis hydrogen production in seawater at normal temperature and pressure for the magnesium-based hydrolysis hydrogen production composite material of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and specific examples. The following examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
Example 1
As shown in figure 1, a method for preparing magnesium-based composite material for hydrogen production by hydrolysis comprises the steps of adding Mg (Mg: (B))99.99 percent of Ca and 85 percent of Mg, and 5 percent of magnesium is additionally added to balance the burning loss in the smelting process, then the massive metal raw material is placed in a graphite crucible, RJ-2 covering agent is added to cover the metal, then the metal is heated to 820 ℃ in a resistance furnace and is kept at 820 ℃ for 30 minutes, the mixture is fully stirred during the heat preservation period to form a macroscopically uniform melt, then the metal melt is poured into a stainless steel mould to be solidified, and the alloy is formed by Mg and Mg 2 Ca and Mg 2 Three phases of Ni. For prepared Mg 85 Ca 10 Ni 5 And (2) performing high-energy ball milling after the alloy is mechanically crushed, wherein the ball milling time is 1 hour, and the ball-to-material ratio is 30:1, rotating speed of 875 revolutions per minute and argon protection.
5wt.% of MWCNTs and the Mg-Mg 2 Ca-Mg 2 Mixing Ni alloy particles in a ball mill for 10 minutes, and then carrying out high-energy ball milling under the protection of argon, wherein the ball milling time is 20 minutes, and the ball-to-material ratio is 30:1 at 875 rpm, and the SEM image of the ball-milled sample is shown in FIG. 2 (a).
Tabletting with a single-punch tablet press under 4MPa for 8min, wherein the diameter and thickness of the material obtained by compression are 15mm and 4mm, and FIG. 3 is a kinetic curve of hydrogen production by hydrolysis in seawater at normal temperature and pressure. As can be seen from the figure 3, the hydrogen production rate of the magnesium-based hydrolysis hydrogen production composite material is high and can reach 400mL/g in 0 minute; the hydrogen production rate is continuously increased within 0 to 110 minutes and is 400 to 800 mL/g, which shows that Mg (OH) is generated by the magnesium-based hydrolysis hydrogen production composite material in the embodiment 2 Can be effectively peeled off without influencing the hydrogen production reaction rate of the composite material.
The magnesium-based hydrolysis hydrogen production composite material obtained by the preparation method of the embodiment is adopted.
Example 2
A magnesium-based composite material for hydrogen production by hydrolysis is prepared from Mg (99.99%), ca (20-20 wt.%), and Ni (45-45 wt.%) through proportioning Ca (13 wt.%), ni (5 wt.%), mg (82 wt.%), and adding 5% Mg (82 wt.%) to obtain Mg-based composite materialBalancing the burning loss in the smelting process, then placing the blocky metal raw material into a graphite crucible, adding RJ-2 covering agent to cover the metal, heating the blocky metal raw material to 820 ℃ in a resistance furnace, preserving the heat of the blocky metal raw material for 30 minutes, fully stirring the blocky metal raw material during the heat preservation period to form macroscopically uniform melt, then pouring the macroscopically uniform melt into a stainless steel mold for solidification, wherein the alloy is formed by Mg and Mg 2 Ca and Mg 2 Three phases of Ni. For prepared Mg 82 Ca 13 Ni 5 And (2) performing high-energy ball milling on the alloy after mechanical crushing, wherein the ball milling time is 1 hour, and the ball-to-material ratio is 30:1, rotating speed of 875 revolutions per minute and argon protection.
5wt.% of MWCNTs and the Mg-Mg 2 Ca-Mg 2 Mixing Ni alloy particles in a ball mill for 10 minutes, and then carrying out high-energy ball milling under the protection of argon, wherein the ball milling time is 20 minutes, and the ball-to-material ratio is 30:1 at 875 rpm, and the SEM image of the ball-milled sample is shown in FIG. 2 (b).
Tabletting with a single-punch tablet press under 4MPa for 8min, wherein the diameter of the material obtained by pressing is 18mm, and the thickness is 3mm.
The magnesium-based hydrolysis hydrogen production composite material obtained by the preparation method of the embodiment is adopted.
Example 3
A magnesium-based composite material for hydrogen production by hydrolysis is prepared from Mg (99.99%), mg-20wt.% Ca and Mg-45wt.% Ni as intermediate alloy through proportioning, adding Ca (15 wt.%), ni (3 wt.%), mg (82 wt.%), adding Mg (5 wt.%), loading in graphite crucible, covering with RJ-2 covering agent, heating to 820 deg.C in electric resistance furnace, holding at 820 deg.C for 30 min, stirring to obtain uniform molten metal, solidifying in stainless steel mould, and preparing Mg-Mg alloy 2 Ca and Mg 2 Three phases of Ni. For prepared Mg 82 Ca 15 Ni 3 And (2) performing high-energy ball milling on the alloy after mechanical crushing, wherein the ball milling time is 1 hour, and the ball-to-material ratio is 30:1, rotating speed is 875 revolutions per minute, and argon protection is carried out.
Mixing 5wt.% MWCNTs with the Mg-Mg 2 Ca-Mg 2 Mixing Ni alloy particles in a ball mill for 10 minutes, and then carrying out high-energy ball milling under the protection of argon, wherein the ball milling time is 20 minutes, and the ball-to-material ratio is 30:1, rotation speed 875 revolutions per minute.
Tabletting with a single-punch tablet press under 4MPa for 8min, wherein the diameter of the material obtained by tabletting is 12mm, and the thickness is 4mm.
The magnesium-based hydrolysis hydrogen production composite material obtained by the preparation method of the embodiment is adopted.
Example 4
A magnesium-based composite material for hydrogen production by hydrolysis is prepared from Mg (99.99%), mg-20wt.% Ca and Mg-45wt.% Ni as intermediate alloy through proportioning, adding Ca (20 wt.%), ni (10 wt.%), mg (70 wt.%), adding Mg (5 wt.%), loading in graphite crucible, covering with RJ-2 covering agent, heating to 820 deg.C in electric resistance furnace, holding at 820 deg.C for 30 min, stirring to obtain uniform molten metal, solidifying in stainless steel mould, and preparing alloy from Mg and Mg 2 Ca and Mg 2 Three phases of Ni. For prepared Mg 70 Ca 20 Ni 10 And (2) performing high-energy ball milling on the alloy after mechanical crushing, wherein the ball milling time is 1 hour, and the ball-to-material ratio is 30:1, rotating speed of 875 revolutions per minute and argon protection.
1wt.% of MWCNTs and the Mg-Mg 2 Ca-Mg 2 Mixing Ni alloy particles in a ball mill for 10 minutes, and then carrying out high-energy ball milling under the protection of argon, wherein the ball milling time is 20 minutes, and the ball-to-material ratio is 30:1, rotating speed of 875 revolutions per minute.
Tabletting with a single-punch tablet press, wherein the pressure is 3MPa, the pressure maintaining time is 8min, and the diameter and the thickness of the material obtained by pressing are 20mm and 5mm respectively.
The magnesium-based hydrolysis hydrogen production composite material obtained by the preparation method of the embodiment is adopted.
Example 5
Magnesium-based materialA preparation method of a hydrolytic hydrogen production composite material comprises the steps of proportioning 99.99% of metal Mg, 1% of Mg, 20% of Ca and 45% of Mg, wherein the mass fraction of Ca is 10%, the mass fraction of Ni is 1%, the mass fraction of Mg is 89%, adding 5% of magnesium additionally to balance the burning loss in the smelting process, then placing the massive metal raw material into a graphite crucible, adding an RJ-2 covering agent to cover the metal, heating the metal to 820 ℃ in a resistance furnace, preserving the heat for 30 minutes at 820 ℃, fully stirring the metal during the heat preservation period to form a macroscopic uniform melt, then pouring the metal melt into a stainless steel mold for solidification, and enabling the alloy to be formed by Mg and Mg 2 Ca and Mg 2 Three phases of Ni. For prepared Mg 89 Ca 10 Ni 1 And (2) performing high-energy ball milling after the alloy is mechanically crushed, wherein the ball milling time is 1 hour, and the ball-to-material ratio is 30:1, rotating speed is 875 revolutions per minute, and argon protection is carried out.
2wt.% of MWCNTs and the Mg-Mg 2 Ca-Mg 2 Mixing Ni alloy particles in a ball mill for 10 minutes, and then carrying out high-energy ball milling under the protection of argon, wherein the ball milling time is 20 minutes, and the ball-to-material ratio is 30:1, rotation speed 875 revolutions per minute.
Tabletting with a single-punch tablet press under 3.5MPa for 8min to obtain a material with diameter of 18mm and thickness of 5mm.
The magnesium-based hydrolysis hydrogen production composite material obtained by the preparation method of the embodiment is adopted.
It should be appreciated that in the foregoing description of exemplary embodiments of the invention, various features of the invention are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure and aiding in the understanding of one or more of the various inventive aspects. However, the disclosed method should not be interpreted as reflecting an intention that: that the invention as claimed requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment. Thus, the claims following the detailed description are hereby expressly incorporated into this detailed description, with each claim standing on its own as a separate embodiment of this invention.
While the invention has been described with respect to a limited number of embodiments, those skilled in the art, having benefit of this description, will appreciate that other embodiments can be devised which do not depart from the scope of the invention as described herein. Furthermore, it should be noted that the language used in the specification has been principally selected for readability and instructional purposes, and may not have been selected to delineate or circumscribe the inventive subject matter. Accordingly, many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the appended claims. The present invention has been disclosed in an illustrative rather than a restrictive sense, and the scope of the present invention is defined by the appended claims.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (4)
1. The preparation method of the magnesium-based hydrolysis hydrogen production composite material is characterized by comprising the following steps:
preparing a Mg-Ca-Ni ternary alloy by a flux protection method;
step two, mechanically crushing the obtained Mg-Ca-Ni ternary alloy to obtain Mg-Mg 2 Ca-Mg 2 Ni alloy particles;
step three, mixing the MWCNTs and Mg-Mg of the multi-walled carbon nano-tube 2 Ca-Mg 2 Carrying out short-time high-energy ball milling on the Ni alloy particles to obtain refined Mg-Mg 2 Ca-Mg 2 Ni-MWCNTs composite powder;
step four, refining Mg-Mg 2 Ca-Mg 2 Putting the Ni-MWCNTs composite powder into a tabletting mold, and pressing into a blocky or flaky material by using a tabletting machine to obtain a porous magnesium-based hydrogen production composite material by hydrolysis;
in the Mg-Ca-Ni ternary alloy, the mass fraction of Ca element is 10% -20%, and the mass fraction of Ni element is 1-10%;
the preparation method of the Mg-Ca-Ni ternary alloy comprises the following steps of weighing Mg, mg-20wt.% Ca intermediate alloy and Mg-45wt.% Ni intermediate alloy according to the weight proportion, adding 5% of Mg by mass for balancing burning loss, then placing the alloy into a graphite crucible, adding a flux to cover metal, heating the alloy in a resistance furnace to 820 ℃, preserving the heat for 30 minutes at 820 ℃, fully stirring during the heat preservation, and then pouring the metal melt into a stainless steel mold for solidification;
refined Mg-Mg 2 Ca-Mg 2 In the Ni-MWCNTs composite powder, the mass fraction of the MWCNTs is 1-5%;
in the second step, the mechanical crushing method comprises the following steps: adopting a high-energy ball milling crushing method under the protection of argon, wherein the ball milling time is 1 hour, and the ball-to-material ratio is 30:1, the rotating speed is 875 revolutions per minute;
in the third step, firstly, the multi-wall carbon nano-tube MWCNTs and Mg-Mg are mixed 2 Ca-Mg 2 Mixing Ni alloy particles in a ball mill for 10 minutes, and then carrying out high-energy ball milling under the protection of argon, wherein the ball milling time is 20 minutes, and the ball-to-material ratio is 30:1, rotation speed 875 revolutions per minute.
2. The method of claim 1, wherein the fusing agent is a coverer comprising an RJ-2 coverer.
3. The process according to claim 1, wherein the tablet press is a single-punch press, the pressure used in the process of tablet pressing is 3 to 4MPa, the dwell time is 8min, and the material obtained by pressing has a diameter of 12 to 20mm and a thickness of 3 to 5mm.
4. The magnesium-based hydrolysis hydrogen production composite material obtained by the preparation method according to any one of claims 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210916409.2A CN115287490B (en) | 2022-08-01 | 2022-08-01 | Magnesium-based hydrolysis hydrogen production composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210916409.2A CN115287490B (en) | 2022-08-01 | 2022-08-01 | Magnesium-based hydrolysis hydrogen production composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115287490A CN115287490A (en) | 2022-11-04 |
| CN115287490B true CN115287490B (en) | 2023-04-07 |
Family
ID=83825363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210916409.2A Active CN115287490B (en) | 2022-08-01 | 2022-08-01 | Magnesium-based hydrolysis hydrogen production composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115287490B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1100154C (en) * | 2000-01-20 | 2003-01-29 | 南开大学 | Hydrogen storage alloy/carbon nanometer tube composite hydrogen storage material |
| WO2006060851A1 (en) * | 2004-12-07 | 2006-06-15 | The University Of Queensland | Magnesium alloys for hydrogen storage |
| KR101400228B1 (en) * | 2008-06-17 | 2014-05-29 | 단국대학교 산학협력단 | Nano porous material, method for preparing the nano porous material and hydrogen strorage device employing the same |
-
2022
- 2022-08-01 CN CN202210916409.2A patent/CN115287490B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN115287490A (en) | 2022-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102337438B (en) | Magnesium-based hydrogen storage alloy with long period structure and preparation method thereof | |
| Jiang et al. | Controllable hydrolysis performance of MgLi alloys and their hydrides | |
| Zhang et al. | Constructing cycle-stable Si/TiSi2 composites as anode materials for lithium ion batteries through direct utilization of low-purity Si and Ti-bearing blast furnace slag | |
| CN108754264A (en) | A kind of graphene and self-formed from reaction nano magnesia Particles dispersed enhancing magnesium-based composite material and preparation method thereof | |
| CN112725679B (en) | Light high-entropy alloy material with high specific strength and preparation method thereof | |
| CN101804978A (en) | Preparation method of micro nano graphite nodule | |
| Tan et al. | Isothermal hydrogen production behavior and kinetics of bulk eutectic Mg–Ni-based alloys in NaCl solution | |
| CN101570313B (en) | Method for preparing amorphous nano-sheets | |
| CN114058892A (en) | Wear-resistant corrosion-resistant high-entropy alloy-based composite material and preparation method thereof | |
| Wu et al. | Hydrolysis enhancing mechanisms of Mg-based alloys/hydrides from perspectives: electrochemical corrosion, active sites, mass transfer, and kinetics | |
| CN102660700A (en) | AB3-type hydrogen storage alloy and preparation method | |
| CN107227416A (en) | A kind of M6C-type alloy carbide Fe3W3C preparation method | |
| CN115287490B (en) | Magnesium-based hydrolysis hydrogen production composite material and preparation method thereof | |
| CN114799155A (en) | Preparation method of ceramic particle reinforced refractory high-entropy alloy | |
| CN107974569A (en) | A kind of preparation method of aluminium based composite material enhanced by miscellaneous granules | |
| CN110629091A (en) | High-capacity multi-phase hydrogen storage alloy for fuel cell and preparation method thereof | |
| CN101279717A (en) | Magnesium-based complex phase hydrogen storage material and preparation thereof | |
| CN101323918B (en) | Preparation of light hydrogen storage alloy | |
| CN110327936B (en) | EG-SnO 2 @ Mg-Ni nano composite catalytic hydrolysis hydrogen production material and preparation method thereof | |
| CN109554570B (en) | Method for strengthening aluminum alloy by in-situ multiphase mixed scale ceramic in melt | |
| Chen et al. | Construction and performance of an aluminum-water system for real-time hydrogen production in a severe cold environment | |
| CN111777072A (en) | Production process of hafnium disilicide | |
| CN105274374B (en) | A kind of Mg2Ni0.9Co0.1H4The preparation method of based hydrogen storage material | |
| CN116262955A (en) | Lithium tin intermetallic compound and preparation method and application thereof | |
| CN109608197B (en) | SnS2Single-phase block and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |