CN108374100A - A kind of hydrogen storage material high efficiency preparation method - Google Patents
A kind of hydrogen storage material high efficiency preparation method Download PDFInfo
- Publication number
- CN108374100A CN108374100A CN201810346406.3A CN201810346406A CN108374100A CN 108374100 A CN108374100 A CN 108374100A CN 201810346406 A CN201810346406 A CN 201810346406A CN 108374100 A CN108374100 A CN 108374100A
- Authority
- CN
- China
- Prior art keywords
- powder
- hydrogen storage
- preparation
- storage material
- ball mill
- 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.)
- Granted
Links
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
- C22C1/0408—Light metal alloys
-
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
-
- 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
- C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
-
- 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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
-
- 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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2202/00—Physical properties
- C22C2202/04—Hydrogen absorbing
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a kind of hydrogen storage material high efficiency preparation methods, belong to functional metal materials field, the main method being combined using high-temperature heat treatment under mechanical alloying and inert gas shielding.Including：La, Mg or La Mg alloyed powders are fitted into ball mill in proportion first, then are proportionally added into Ni powder, the one kind being proportionally added into again when necessary in B or Al powder carries out 5~10h of mechanical impact alloying using high-energy ball milling.Then powder after alloying is carried out under 0.3~0.5MPa argon atmospheres in sintering furnace to high-temperature stable heat treatment; then 400~600 DEG C for the treatment of temperature, 2~3h of processing time are down to room temperature with stove; hydrogen storage material can be obtained, hydrogen-sucking amount can reach 5.5wt% or more.Alloy material storing hydrogen prepared by the present invention is stablized with preparation efficiency by high, performance, and electrochemistry capacitance is high, and storage and transportation is convenient, and easy the advantages that realizing mass production.
Description
Technical field
The invention belongs to functional metal materials technical fields, are related to a kind of hydrogen storage material high efficiency preparation method.
Background technology
Hydrogen is considered as 21 century most potential green energy as a kind of cleaning, efficient, sustainable new energy
Source.Can the exploitation of hydrogen storage technology be one of the key link of entire hydrogen energy system, it has also become realize the decision of hydrogen economy early
The development and utilization of hydrogen storage technology is all extremely paid attention in sexual factor, countries in the world.Solid metal hydrogen storage material is because having safety and stability
Property it is high, hydrogen-storage density is big, is expected to become high energy material of new generation.According to U.S. Department of Energy revised vehicle-mounted hydrogen storage system in 2009
System, metal hydrogen storage material hydrogen storage content reaches 5.5wt% within 2015, and final goal reaches 7.5wt%.Currently, metal hydrogen storage material
It mostly uses smelting process and is prepared by mechanical attrition method.K.Kadir uses La prepared by smelting process0.65Ca0.35Mg1.32Ca0.68Ni9Hydrogen storage
Alloy material, in the case where 3.3MPa hydrogen presses 283K temperature conditions, alloy hydrogen storage content is 1.87wt%, and domestic using smelting process preparation
La-Mg base hydrogen storage alloy material hydrogen storage contents generally in 1.5wt% or so.Li Xia etc. is prepared for using mechanical attrition method
La2Mg17-50%Ni composite for hydrogen storage, Ball-milling Time are up to 80h, and maximum hydrogen-sucking amount can reach 5.13wt%, but this method
Preparation efficiency is low.And the hydrogen storage material activity Jing Guo long-time mechanical ball mill is high, and stability is poor, contacts with air and even occurs
Spontaneous combustion problems, storage and transportation is difficult, and is unfavorable for mass production.
Invention content
For above-mentioned shortcoming in the prior art, the present invention provides a kind of hydrogen storage material high efficiency preparation methods, main
The method that high-temperature heat treatment is combined under mechanical alloying and inert gas shielding is used, i.e., first uses ball-milling method when shorter
The interior microalloying for realizing powder, high-temperature stable processing is then carried out under inert gas shielding environment, promotes powder
It is secondary alloyed, and realize that powder stabilizes, there is preparation efficiency height, performance using the hydrogen storage material prepared by the combined method
Stablize, hydrogen-sucking amount is high, and storage and transportation is convenient, and easy the advantages that realizing mass production.
The purpose of the present invention is what is be achieved through the following technical solutions：
A kind of high efficiency preparation method of hydrogen storage material, using high-temperature heat treatment phase under mechanical alloying and inert gas shielding
In conjunction with method.
The high efficiency preparation method of the hydrogen storage material, comprises the steps of：
Step A：La, Mg powder or La-Mg alloyed powders are fitted into ball mill in proportion according to the composition of hydrogen storage material, then pressed
Ni powder is added in ratio, and the one kind being proportionally added into again when necessary in B or Al powder opens ball mill and carries out high speed machine alloying,
Then powder is taken out under inert gas protection；
Step B：Powder after mechanical alloying is placed in progress high-temperature stable in the sintering furnace under inert gas shielding
Processing is down to room temperature with stove, obtains hydrogen storage material.
Further, powder diameter≤100 μm of ball mill are added in step A.
Further, the powder described in step A is matched according to each simple substance element molar percentage, ingredient La2- xMg17NixOr La2-xMg17NixMy, a kind of in M Al, B, 0 ＜ x ＜ 2 of x value ranges, 0 y≤1 ＜ of y ranges.
Further, the ball mill described in step A is one in high-energy planetary ball mill machine, agitating ball mill and vibrator
Kind, mechanical mill alloying time is 5~10h.
Further, 400~600 DEG C of the high-temperature stable temperature described in step B, 2~3h of processing time.
Further, the inert gas in step A and step B is argon gas, and ar pressure is 0.3~0.5MPa in step B.
As seen from the above technical solution provided by the invention, hydrogen storage material high efficiency preparation method provided by the invention is
A kind of mechanical alloying and the method that high-temperature heat treatment is combined under inert gas protection, use mechanical ball mill to realize powder first
Then last microalloying carries out high-temperature heat treatment under inert gas protection, promote Mg in alloy system2Ni、La2Mg17And
LaNi5Deng the generation for inhaling hydrogen phase；Meanwhile surface-active is reduced, improve stability.Specifically by La, Mg or La-Mg alloyed powder with
And Ni powder is fitted into ball mill in proportion, the one kind being proportionally added into again when necessary in B or Al powder can inhale hydrogen to hydrogen storage material and rise
Catalytic action carries out 5~10h of mechanical impact alloying using high-energy ball milling.Then by the powder after alloying 0.3~
High-temperature stable heat treatment, 400~500 DEG C for the treatment of temperature, when processing are carried out in sintering furnace under 0.5MPa argon atmospheres
Between 2~3h, be then down to room temperature with stove, you can obtain hydrogen storage material, hydrogen-sucking amount can reach 5.5wt% or more.The present invention provides
Hydrogen storage material preparation method short preparation period, efficient, powder not only keeps high hydrogen-sucking amount, and stability is good, is easy to real
Existing mass production.
Description of the drawings
Fig. 1 is hydrogen storage material XRD diagram provided by the invention.
Fig. 2 is hydrogen storage material hydrogen-sucking amount figure provided by the invention.
Specific implementation mode
The technical solution in the present invention is clearly and completely described below, it is clear that described embodiment is only
A part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiment of the present invention, those of ordinary skill in the art exist
The every other embodiment obtained under the premise of creative work is not made, protection scope of the present invention is belonged to.In order to more
Add and clearly show technical solution provided by the present invention and generated technique effect, below with specific embodiment to this hair
The hydrogen storage material and its high efficiency preparation method of bright offer are described in detail.
Embodiment 1
A kind of hydrogen storage material high efficiency preparation method, comprises the steps of：
Step a1, La powder 25.16g, Mg powder 74.84g, Ni powder 10.63g is fitted into high-energy planetary ball mill machine, sets ball
Mill speed is 200rpm, time 5h, opens ball mill, carries out high speed machine alloying, is protected in argon gas after ball milling
Glove box in powder is taken out.
Step b1, high-temperature stable is carried out in the sintering furnace by the powder after alloying under argon atmosphere under 0.3MPa
Change is handled, 500 DEG C, processing time 3h for the treatment of temperature, is down to room temperature with stove, is obtained LaMg17Ni hydrogen storage materials.Prepared
LaMg17Ni hydrogen storage material XRD diagram is shown in that attached drawing 1, maximum hydrogen-sucking amount are 5.52wt%, sees attached drawing 2.
Embodiment 2
A kind of hydrogen storage material high efficiency preparation method, comprises the steps of：
Step a2, La-Mg alloyed powders 100g is fitted into high-energy planetary ball mill machine, Ni powder 4.72g, Al is added in mass ratio
Powder 2.17g sets drum's speed of rotation as 300rpm, and time 5h opens ball mill, carries out high speed machine alloying, ball milling knot
Powder is taken out in the glove box of argon gas protection after beam.
Step b2, high-temperature stable is carried out in the sintering furnace by the powder after alloying under argon atmosphere under 0.5MPa
Change is handled, 400 DEG C, processing time 2h for the treatment of temperature, is down to room temperature with stove, is obtained La1.5Mg17Ni0.5Al0.5Hydrogen storage material, it is maximum
Hydrogen-sucking amount is 5.58wt%.
Embodiment 3
A kind of hydrogen storage material high efficiency preparation method, comprises the steps of：
Step a3, La powder 14.39g, Mg powder 85.61g, Ni powder 18.24g and B powder 1.12g is fitted into vibrator,
Drum's speed of rotation is set as 60rpm, time 10h opens ball mill, carries out high speed machine alloying, in argon after ball milling
Powder is taken out in the glove box of gas shielded.
Step b3, high-temperature stable is carried out in the sintering furnace by the powder after alloying under argon atmosphere under 0.4MPa
Change is handled, 500 DEG C, processing time 3h for the treatment of temperature, is down to room temperature with stove, is obtained La0.5Mg17Ni1.5B0.5Hydrogen storage material, it is maximum
Hydrogen-sucking amount is 5.65wt%.
To sum up, the period of the embodiment of the present invention is short, efficient, and powder not only keeps high hydrogen-sucking amount, and stability is good,
Easily storage is, it can be achieved that mass production.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art is in the technical scope of present disclosure, the change or replacement that can be readily occurred in,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Subject to enclosing.
Claims (7)
1. a kind of hydrogen storage material high efficiency preparation method, which is characterized in that use the high temperature of mechanical alloying and inert gas shielding
It is heat-treated the method being combined.
2. preparation method according to claim 1, which is characterized in that include the following steps：
Step A：According to the composition of hydrogen storage material, La, Mg powder or La-Mg alloyed powders are fitted into ball mill in proportion, then by than
Ni powder is added in example, and the one kind being proportionally added into again when necessary in B or Al powder opens ball mill and carries out high speed machine alloying, so
Powder is taken out under inert gas protection afterwards；
Step B：Powder after mechanical alloying is placed in progress high-temperature stable processing in the sintering furnace under inert gas shielding,
It is down to room temperature with stove, obtains hydrogen storage material.
3. preparation method according to claim 2, which is characterized in that the μ of the powder diameter of ball mill≤100 is added in step A
m。
4. preparation method according to claim 2, which is characterized in that the powder is according to each simple substance element mole hundred
Divide than proportioning, ingredient La2-xMg17NixOr La2-xMg17NixMy, it is a kind of in M Al, B, between 0 ＜ x ＜ 2 of x value ranges, y
0 y≤1 ＜ of range.
5. preparation method according to claim 2, which is characterized in that the ball mill described in step A is high-energy planetary ball mill
A kind of in machine, agitating ball mill and vibrator, mechanical mill alloying time is 5~10h.
6. preparation method according to claim 2, which is characterized in that the high-temperature stable treatment temperature 400 described in step B
~600 DEG C, 2~3h of processing time.
7. preparation method according to claim 2, which is characterized in that the inert gas in step A and step B is argon gas,
Ar pressure is 0.3~0.5MPa in step B.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810346406.3A CN108374100B (en) | 2018-04-18 | 2018-04-18 | Efficient preparation method of hydrogen storage material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810346406.3A CN108374100B (en) | 2018-04-18 | 2018-04-18 | Efficient preparation method of hydrogen storage material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108374100A true CN108374100A (en) | 2018-08-07 |
| CN108374100B CN108374100B (en) | 2020-01-03 |
Family
ID=63032556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810346406.3A Active CN108374100B (en) | 2018-04-18 | 2018-04-18 | Efficient preparation method of hydrogen storage material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108374100B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113512674A (en) * | 2021-04-20 | 2021-10-19 | 安泰科技股份有限公司 | Modified Mg-Ni-La nanocrystalline hydrogen storage alloy and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1563453A (en) * | 2004-04-01 | 2005-01-12 | 桂林电子工业学院 | rEXmGYnI4-zAz alloy of storing hydrogen and uncrystallized preparation method |
| CN1580305A (en) * | 2003-08-04 | 2005-02-16 | 北京有色金属研究总院 | Magnesium base hydrogen storage material and its mechanical-alloying preparation method |
-
2018
- 2018-04-18 CN CN201810346406.3A patent/CN108374100B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1580305A (en) * | 2003-08-04 | 2005-02-16 | 北京有色金属研究总院 | Magnesium base hydrogen storage material and its mechanical-alloying preparation method |
| CN1563453A (en) * | 2004-04-01 | 2005-01-12 | 桂林电子工业学院 | rEXmGYnI4-zAz alloy of storing hydrogen and uncrystallized preparation method |
Non-Patent Citations (2)
| Title |
|---|
| M.BALCERZAK ET.AL: "Hydrogenation and electrochemical studies of La-Mg-Ni alloys", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
| 蒋利军等: "制备方法对La1.5Mg17Ni0.5储氢材料性能的影响", 《稀有金属材料与工程》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113512674A (en) * | 2021-04-20 | 2021-10-19 | 安泰科技股份有限公司 | Modified Mg-Ni-La nanocrystalline hydrogen storage alloy and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108374100B (en) | 2020-01-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110137488A (en) | A kind of nickelic positive electrode of secondary lithium batteries and preparation method thereof | |
| CN102337438B (en) | Magnesium-based hydrogen storage alloy with long period structure and preparation method thereof | |
| CN103526141A (en) | Magnesium-based hydrogen storage material and preparation method thereof | |
| CN102862958A (en) | Mg-based hydrogen storage material with metal oxide added and preparation method of Mg-based hydrogen storage material | |
| CN108461748B (en) | Lithium ion battery single crystal anode material and preparation method thereof | |
| CN104846224A (en) | Method for performing surface modification on AB3-type hydrogen storage alloy by utilization of graphene | |
| CN102634714A (en) | Copper-added magnesium-aluminum hydrogen storage alloy and preparation method thereof | |
| CN109817926A (en) | A kind of prelithiation material and preparation method thereof and lithium battery | |
| CN105132770A (en) | Mg2Ni-based ternary Mg-Ni-Cu reversible hydrogen storage material and preparation method thereof | |
| CN106011554B (en) | A kind of hydrolytic hydrogen production aluminium alloy and preparation method thereof | |
| CN106702191B (en) | A kind of ferrotianium yttrium base hydrogen storage material and intermediate alloy and preparation method | |
| CN103014384B (en) | Method for preparing magnesium-silver hydrogen storage material | |
| CN108374100A (en) | A kind of hydrogen storage material high efficiency preparation method | |
| CN103183314A (en) | Composite hydrogen storage material with foamed structure and preparation method thereof | |
| Kamali et al. | Green molten salt modification of cobalt oxide for lithium ion battery anode application | |
| CN109175349A (en) | Double rare earth solid solution base hydrogen storage materials of a kind of high-performance and preparation method thereof | |
| CN103879957A (en) | Catalyst-doped magnesium-based hydrogen storage material and preparation | |
| CN103894602B (en) | Surface treatment method for improving cycle life of rare earth magnesium based hydrogen storage alloy | |
| CN102618761B (en) | Magnesium-based hydrogen storage alloy material and preparation method thereof | |
| CN102888545A (en) | Method for preparing magnesium-based hydrogen storage alloy | |
| CN101898757A (en) | Method for preparing multi-component doped lithium ferrous phosphate by utilizing high phosphorus slag | |
| CN106744680A (en) | A kind of Al LiH metal oxide hydrogen manufacturing materials and preparation method thereof | |
| CN101406843B (en) | Nano-catalyst of sodium aluminum hydride complex hydride as well as preparation method and application thereof | |
| CN108574091A (en) | A kind of new type lithium ion battery vanadium base hydride negative material and preparation method thereof | |
| Yu et al. | Electrochemical hydrogen storage in Ti–V-based alloys surface-modified with carbon nanoparticles |
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 |