CN108103337A - The preparation method of magnesium-base hydrogen storage material - Google Patents
The preparation method of magnesium-base hydrogen storage material Download PDFInfo
- Publication number
- CN108103337A CN108103337A CN201711167195.9A CN201711167195A CN108103337A CN 108103337 A CN108103337 A CN 108103337A CN 201711167195 A CN201711167195 A CN 201711167195A CN 108103337 A CN108103337 A CN 108103337A
- Authority
- CN
- China
- Prior art keywords
- magnesium
- hydrogen storage
- storage material
- base hydrogen
- preparation
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/383—Hydrogen absorbing alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/466—Magnesium based
-
- 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
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of preparation methods of magnesium-base hydrogen storage material, include the following steps：After magnesium hydride and one or more of metal simple-substance mixings, normal pressure ball milling, obtains mixed-powder in an inert atmosphere；The mixed-powder is carried out after being compressed into tablet form sample, carries out putting hydrogen at 250~450 DEG C, obtains the magnesium-base hydrogen storage material, wherein, the metal simple-substance is selected from least one of nickel, cobalt, copper and titanium.Compared with prior art, the present invention has following advantageous effect：Binary provided by the invention or polynary magnesium-base hydrogen storage material purity are high, and hydrogen storage property is excellent, such as MgH2With Co according to molar ratio be 2:The binary magnesium-base hydrogen storage material prepared after 1 ratio mixing is under the conditions of 365 DEG C, and hydrogen-sucking amount is up to 4.5wt%.
Description
Technical field
The present invention relates to a kind of preparation methods of magnesium-base hydrogen storage material, belong to hydrogen storage material technical field.
Background technology
The energy is one of important motivity for promoting development of human history.From earliest fossil energy coal, oil, natural
Gas, steam energy, electric energy or even the solar energy in modern age finally, wind energy, water energy and nuclear energy etc. are that development of human civilization is made
Immeasurable contribution.But the reserves of one side fossil fuel are limited, the mankind will be faced with unprecedented " energy danger
Machine ".On the other hand, greenhouse effects caused by combustion of fossil fuel and climate warming have seriously affected the sustainable development of the mankind.
Therefore exploitation is imperative as the new energy of representative using Hydrogen Energy.
The research early start of magnesium-base hydrogen storage material is in Brookhaven National Laboratory of the U.S., in nineteen sixty-eight first with magnesium
Mg is formed with nickel mixed smelting2There is the preparation method of mechanical alloying later in Ni alloys, had started broad scale research magnesium-based
The climax of hydrogen storage material.However two big difficult points during magnesium-base hydrogen storage material utilizes are that magnesium base alloy hydride actually puts hydrogen
Temperature requirement is higher, and activates difficulty.In addition, the suction hydrogen desorption kinetics poor performance of Mg base hydrogen bearing alloy, it is desirable to provide high temperature
Heat source.
However traditional mechanical alloying method has the defects of certain, shows that its requirement to operating process is very strict,
It must prevent the introducing of the impurity such as Fe and O, otherwise can form MgO layer on the surface of material in mechanical milling process so that material is difficult to
Activation.And the activity of Mg is high, and the introducing of impurity can generate other and be difficult to expected result.And since the plasticity of Mg is good, make
It is easily hardened in ball grinder lower curtate in mechanical milling process to obtain material, necessary timely processing caking, is further continued for carrying out during causing
Ball milling adds the difficulty of operating process.
The content of the invention
For in the prior art the defects of, the object of the present invention is to provide a kind of preparation methods of magnesium-base hydrogen storage material.
The present invention is achieved by the following technical solutions：
The present invention provides a kind of preparation methods of magnesium-base hydrogen storage material, include the following steps：
After magnesium hydride and metal simple-substance mixing, normal pressure ball milling, obtains mixed-powder in an inert atmosphere；
The mixed-powder is carried out after being compressed into tablet form sample, is heated under vacuum, hydrogen discharge reaction occurs, obtains
The magnesium-base hydrogen storage material, wherein, the metal simple-substance is selected from least one of nickel, cobalt, copper and titanium.
Preferably, the temperature of the heating is 250~450 DEG C.
Preferably, the molar ratio of the magnesium hydride and metal simple-substance is 2:1.
Preferably, the metal simple-substance is cobalt.
Preferably, the rotating speed of the ball milling is 200~500rpm, and Ball-milling Time is 2~10h.
Preferably, the pressure of the compacting is 10~300MPa.
Preferably, the ratio between the diameter of the sheet sample and thickness are not less than 5:1.
Compared with prior art, the present invention has following advantageous effect：
Binary provided by the invention or polynary magnesium-base hydrogen storage material purity are high, and hydrogen storage property is excellent, such as MgH2And Co
It is 2 according to molar ratio:For the binary magnesium-base hydrogen storage material prepared after 1 ratio mixing under the conditions of 365 DEG C, hydrogen-sucking amount is reachable
4.5wt%.
Description of the drawings
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon：
Fig. 1 is the Mg that in the present invention prepared by embodiment 12Hydrogen pressure and material is hydrogeneous under the conditions of the constant temperature and balance of Ni
Relation curve (PCT) between amount；
Fig. 2 is the Mg that in the present invention prepared by embodiment 12The XRD spectrum of Ni；
Fig. 3 is the Mg that in the present invention prepared by embodiment 22Hydrogen pressure and material is hydrogeneous under the conditions of the constant temperature and balance of Co
Relation curve (PCT) between amount；
Fig. 4 is the Mg that in the present invention prepared by embodiment 22The XRD spectrum of Co；
Fig. 5 is hydrogen pressure and material under the conditions of the constant temperature of Mg-Ni-Fe prepared by embodiment 3 and balance in the present invention
Relation curve (PCT) between hydrogen content；
Fig. 6 is the XRD spectrum of Mg-Ni-Fe prepared by embodiment 3 in the present invention.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Embodiment 1
(1) by MgH2With Ni powder according to molar ratio be 2:1 ratio is weighed and mixed；
(2) MgH that will have been configured in step (1)2With Ni mixed-powders sample high-purity argon gas normal pressure atmosphere glove box
In, it is fitted into ball grinder and seals, ball milling is carried out after taking-up, obtain mixed-powder sample；
(3) the mixed-powder sample compression moulding in tablet press machine that will be obtained in step (2), obtains sheet sample；
(4) MgH that will be obtained in step (3)2Hydrogen is put at a temperature of 380 DEG C with Ni mixing sheet sample, it is cold after finishing
But room temperature is arrived, the sample of acquisition is Mg2Ni。
PCT tests are carried out to above-mentioned obtained powder, as shown in Figure 1, platform pressure difference it is small and 375 DEG C at hydrogen-sucking amount it is reachable
3.5wt% is (for Mg2The theoretical hydrogen storage content 97% of Ni).
XRD tests are carried out to above-mentioned obtained powder, as shown in Fig. 2, XRD spectrum shows that obtained powder is pure
Mg2Ni。
Embodiment 2
(1) by MgH2With Co powder according to molar ratio be 2:1 ratio is weighed and mixed；
(2) MgH that will have been configured in step (1)2With Co mixed-powders sample high-purity argon gas normal pressure atmosphere glove box
In, it is fitted into ball grinder and seals, ball milling is carried out after taking-up, obtain mixed-powder sample；
(3) the mixed-powder sample compression moulding in tablet press machine that will be obtained in step (2), obtains sheet sample；
(4) MgH that will be obtained in step (3)2Hydrogen is put at a temperature of 370 DEG C with Co mixing sheet sample, it is cold after finishing
But room temperature is arrived, the sample of acquisition is Mg-Co binary system mixed-powders.
PCT tests are carried out to above-mentioned obtained powder, as shown in figure 3, hydrogen-sucking amount at hydrogen storage property stabilization and 365 DEG C
Up to 4.5wt%.
XRD tests are carried out to above-mentioned obtained powder, as shown in figure 4, XRD spectrum shows that obtained powder is Mg-
Co binary systems.
Embodiment 3
(1) by MgH2With Ni-Fe powder according to molar ratio be 2:1 ratio is weighed and mixed, wherein Ni:Fe
Mass ratio be 3:2；
(2) MgH that will have been configured in step (1)2With Ni-Fe mixed-powders sample high-purity argon gas normal pressure atmosphere gloves
It in case, is fitted into ball grinder and seals, ball milling is carried out after taking-up, obtain mixed-powder sample；
(3) the mixed-powder sample compression moulding in tablet press machine that will be obtained in step (2), obtains sheet sample；
(4) MgH that will be obtained in step (3)2Hydrogen is put at a temperature of 410 DEG C with Ni-Fe mixing sheet sample, after finishing
Room temperature is cooled to, the sample of acquisition is MgH2- Ni-Fe multicomponent system mixed-powders.
PCT tests are carried out to above-mentioned obtained powder, as shown in figure 5, reversible suction at hydrogen storage property stabilization and 400 DEG C
Hydrogen amount reaches 3.8wt%.
XRD tests are carried out to above-mentioned obtained powder, as shown in fig. 6, XRD spectrum shows that obtained powder is Mg-
Ni-Fe multicomponent systems.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (7)
1. a kind of preparation method of magnesium-base hydrogen storage material, which is characterized in that include the following steps：
After magnesium hydride and metal simple-substance mixing, normal pressure ball milling, obtains mixed-powder in an inert atmosphere；
The mixed-powder is carried out after being compressed into tablet form sample, is heated under vacuum, hydrogen discharge reaction occurs, is obtained described
Magnesium-base hydrogen storage material, wherein, the metal simple-substance is selected from least one of nickel, cobalt, copper and titanium.
2. the preparation method of magnesium-base hydrogen storage material as described in claim 1, which is characterized in that the temperature of the heating is 250
~450 DEG C.
3. the preparation method of magnesium-base hydrogen storage material as described in claim 1, which is characterized in that the magnesium hydride and metal simple-substance
Molar ratio be 2:1.
4. the preparation method of magnesium-base hydrogen storage material as claimed in claim 3, which is characterized in that the metal simple-substance for cobalt or
Nickel.
5. the preparation method of magnesium-base hydrogen storage material as described in claim 1, which is characterized in that the rotating speed of the ball milling is 200
~500rpm, Ball-milling Time are 2~10h.
6. the preparation method of magnesium-base hydrogen storage material as described in claim 1, which is characterized in that the pressure of the compacting for 10~
300MPa。
7. the preparation method of magnesium-base hydrogen storage material as described in claim 1, which is characterized in that the diameter of the sheet sample with
The ratio between thickness is not less than 5:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711167195.9A CN108103337B (en) | 2017-11-21 | 2017-11-21 | Preparation method of magnesium-based hydrogen storage material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711167195.9A CN108103337B (en) | 2017-11-21 | 2017-11-21 | Preparation method of magnesium-based hydrogen storage material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108103337A true CN108103337A (en) | 2018-06-01 |
| CN108103337B CN108103337B (en) | 2020-01-07 |
Family
ID=62207645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711167195.9A Active CN108103337B (en) | 2017-11-21 | 2017-11-21 | Preparation method of magnesium-based hydrogen storage material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108103337B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111041263A (en) * | 2020-01-03 | 2020-04-21 | 长沙理工大学 | MgH is improved based on NiCu solid solution catalysis2Method for storing hydrogen performance |
| CN111634884A (en) * | 2020-07-04 | 2020-09-08 | 上海镁源动力科技有限公司 | Controllable hydrogen release material, preparation method thereof and hydrolysis hydrogen production method |
| CN114105723A (en) * | 2021-11-26 | 2022-03-01 | 西安交通大学 | Method for converting carbon dioxide into methane through metal hydride |
| CN114438386A (en) * | 2022-03-15 | 2022-05-06 | 北京氢冉新能源科技有限公司 | Magnesium-based hydrogen storage material doped with single metal element and preparation method thereof |
| CN114505475A (en) * | 2022-02-18 | 2022-05-17 | 广东省科学院新材料研究所 | Low-temperature high-capacity magnesium-based hydrogen storage powder and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06299272A (en) * | 1993-02-22 | 1994-10-25 | Mazda Motor Corp | Composite hydrogen occluding metallic member and its production |
| CN1580306A (en) * | 2003-08-04 | 2005-02-16 | 北京有色金属研究总院 | Method for preparing magnesium base hydrogen-storage material using hydrogenation combustion method and its magnesium base hydrogen-storage material |
| CN101003360A (en) * | 2007-01-23 | 2007-07-25 | 太原理工大学 | Method for preparing magnesium based hydrogen storage material |
| CN101457321A (en) * | 2008-12-25 | 2009-06-17 | 浙江大学 | Magnesium base composite hydrogen storage material and preparation method |
| US7871537B2 (en) * | 2006-11-14 | 2011-01-18 | Korea Institute Of Science And Technology | Method for fabricating magnesium-based hydrogen storage material |
| CN103855371A (en) * | 2014-03-10 | 2014-06-11 | 南京工业大学 | Magnesium-based hydrogen-storage electrode alloy hydride as well as preparation method and application thereof |
-
2017
- 2017-11-21 CN CN201711167195.9A patent/CN108103337B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06299272A (en) * | 1993-02-22 | 1994-10-25 | Mazda Motor Corp | Composite hydrogen occluding metallic member and its production |
| CN1580306A (en) * | 2003-08-04 | 2005-02-16 | 北京有色金属研究总院 | Method for preparing magnesium base hydrogen-storage material using hydrogenation combustion method and its magnesium base hydrogen-storage material |
| US7871537B2 (en) * | 2006-11-14 | 2011-01-18 | Korea Institute Of Science And Technology | Method for fabricating magnesium-based hydrogen storage material |
| CN101003360A (en) * | 2007-01-23 | 2007-07-25 | 太原理工大学 | Method for preparing magnesium based hydrogen storage material |
| CN101457321A (en) * | 2008-12-25 | 2009-06-17 | 浙江大学 | Magnesium base composite hydrogen storage material and preparation method |
| CN103855371A (en) * | 2014-03-10 | 2014-06-11 | 南京工业大学 | Magnesium-based hydrogen-storage electrode alloy hydride as well as preparation method and application thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111041263A (en) * | 2020-01-03 | 2020-04-21 | 长沙理工大学 | MgH is improved based on NiCu solid solution catalysis2Method for storing hydrogen performance |
| CN111041263B (en) * | 2020-01-03 | 2021-06-01 | 长沙理工大学 | MgH is improved based on NiCu solid solution catalysis2Method for storing hydrogen performance |
| CN111634884A (en) * | 2020-07-04 | 2020-09-08 | 上海镁源动力科技有限公司 | Controllable hydrogen release material, preparation method thereof and hydrolysis hydrogen production method |
| CN111634884B (en) * | 2020-07-04 | 2022-08-16 | 上海镁源动力科技有限公司 | Controllable hydrogen release material, preparation method thereof and hydrolysis hydrogen production method |
| CN114105723A (en) * | 2021-11-26 | 2022-03-01 | 西安交通大学 | Method for converting carbon dioxide into methane through metal hydride |
| CN114505475A (en) * | 2022-02-18 | 2022-05-17 | 广东省科学院新材料研究所 | Low-temperature high-capacity magnesium-based hydrogen storage powder and preparation method thereof |
| CN114505475B (en) * | 2022-02-18 | 2023-12-05 | 广东省科学院新材料研究所 | Low-temperature high-capacity magnesium-based hydrogen storage powder and preparation method thereof |
| CN114438386A (en) * | 2022-03-15 | 2022-05-06 | 北京氢冉新能源科技有限公司 | Magnesium-based hydrogen storage material doped with single metal element and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108103337B (en) | 2020-01-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108103337A (en) | The preparation method of magnesium-base hydrogen storage material | |
| Song et al. | Hydrogen storage properties of a Mg–Ni–Fe mixture prepared via planetary ball milling in a H2 atmosphere | |
| CN102030313B (en) | Organic matter and ammonia borane compounded hydrogen storage material and preparation method thereof | |
| CN102277508A (en) | Preparation method of magnesium-based hydrogen storage alloy | |
| Chen et al. | Facile fabrication of ultrathin carbon layer encapsulated air-stable Mg nanoparticles with enhanced hydrogen storage properties | |
| CN103101880B (en) | Lithium borohydride/rare earth magnesium base alloy composite hydrogen storage material and preparation method thereof | |
| Xie et al. | Catalytic effects of decorating AlV3 nanocatalyst on hydrogen storage performance of Mg@ Mg17Al12 nanocomposite: experimental and theoretical study | |
| Sofianos et al. | Hydrogen storage properties of eutectic metal borohydrides melt-infiltrated into porous Al scaffolds | |
| Yang et al. | Improvement of dehydrogenation performance by adding CeO2 to α-AlH3 | |
| CN102807191B (en) | Method for synthesizing Li-Mg-B-H hydrogen storage material | |
| Wang et al. | The hydrogenation properties of Mg1. 8Ag0. 2Ni alloy | |
| Hu et al. | Improvement in hydrogen storage performance of Mg by mechanical grinding with molten salt etching Ti3C2Clx | |
| Huang et al. | Double regulation of Mg95Ni5 hydride in suppressing ammonia and promoting hydrogen evolution for Mg (BH4) 2· 2NH3 | |
| CN103014384B (en) | Method for preparing magnesium-silver hydrogen storage material | |
| CN109175349A (en) | Double rare earth solid solution base hydrogen storage materials of a kind of high-performance and preparation method thereof | |
| Huang et al. | Effect of different transition metal fluorides TMFx (TM= Nb, Co, Ti) on hydrogen storage properties of the 3NaBH4-GdF3 system | |
| CN105177383A (en) | Iron-containing magnesium-based composite material as well as preparation method and application thereof | |
| CN112850640A (en) | Preparation method of metal organic framework doped magnesium-based hydride | |
| Meng et al. | Hydrogen production performance of an Al-Ga-In-Sn quaternary alloy | |
| Song et al. | Improvement of hydriding and dehydriding rates of Mg via addition of transition elements Ni, Fe, and Ti | |
| CN105132838B (en) | A kind of Mg17Al12The regulation and control method of hydrogenation | |
| CN111705253A (en) | Hydrogen storage alloy suitable for high pressure-metal hydride hydrogen storage and preparation method thereof | |
| Lv et al. | 2D transition metal carbides trigger enhanced dehydrogenation and reversibility properties in Mg (BH4) 2 | |
| Abbas et al. | Influence of severe plastic deformation and some additives on hydrogenation of ZK60 alloy | |
| He et al. | Influences of sintering parameters on attainable hydrogen density and microstructure of YH2-x monoliths fabricated by spark plasma sintering |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220718 Address after: 201805 room 1405, No. 888, Moyu South Road, Anting Town, Jiading District, Shanghai Patentee after: Hydrogen storage (Shanghai) Energy Technology Co.,Ltd. Address before: 200240 No. 800, Dongchuan Road, Shanghai, Minhang District Patentee before: SHANGHAI JIAO TONG University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220817 Address after: 201805 room 1405, No. 888, Moyu South Road, Anting Town, Jiading District, Shanghai Patentee after: Hydrogen storage (Shanghai) Energy Technology Co.,Ltd. Patentee after: SHANGHAI HYFUN ENERGY TECHNOLOGY CO.,LTD. Address before: 201805 room 1405, No. 888, Moyu South Road, Anting Town, Jiading District, Shanghai Patentee before: Hydrogen storage (Shanghai) Energy Technology Co.,Ltd. |
|
| TR01 | Transfer of patent right |