CN102212721A - Magnesium-nickel based hydrogen storage material and preparation method thereof - Google Patents
Magnesium-nickel based hydrogen storage material and preparation method thereof Download PDFInfo
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- CN102212721A CN102212721A CN2011101480267A CN201110148026A CN102212721A CN 102212721 A CN102212721 A CN 102212721A CN 2011101480267 A CN2011101480267 A CN 2011101480267A CN 201110148026 A CN201110148026 A CN 201110148026A CN 102212721 A CN102212721 A CN 102212721A
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Abstract
The invention relates to a novel magnesium-nickel based hydrogen storage material and a preparation method thereof. The material comprises the component of 2MgNi-xB (x=1-15%). Magnesium and nickel are mixed according to an atomic ratio of 2:1. Boron elements of different contents are added according to the percentage by weight. Hydrogen storage alloy is synthesized in a manner of mechanical ball milling. Compared with Mg2Ni, the material has higher hydrogen storage quantity and higher hydrogen absorbing rate. The material can be used for filtering, purifying and storing hydrogen.
Description
Technical field
The present invention relates to a kind of hydrogen storage material, Ni-based hydrogen storage material of particularly a kind of magnesium and preparation method.
Background technology
Along with the rapid consumption of fossil energy and fossil energy to the having a strong impact on of ecotope, make that traditional energy such as oil is exhausted day by day.Hydrogen is owing to there being advantages such as reserves are abundant, thermal conductivity is good, calorific value is high, nontoxic to be considered to the ideal secondary energy, and one of them bottleneck that utilizes that is restricting Hydrogen Energy is exactly the storage of hydrogen.Traditional storage hydrogen mode mainly is stored in the steel cylinder in the mode of high-pressure gaseous, and this storage hydrogen mode both consumed energy, danger, and hydrogen-storage amount is also not high simultaneously.Utilize some metal can generate the character of metal hydride with hydrogen generation reversible reaction, can be in metal with hydrogen storage.This mode hydrogen-storage amount is big, and safety is convenient, is effectively to store up the hydrogen mode.In hydrogen storage alloy, owing to having advantages such as hydrogen-storage amount is big, cheap, Mg is subjected to broad research, but MgH
2Suction hydrogen desorption kinetics poor-performing, therefore restricting its practical application.Mg
2Though Ni has improved the suction hydrogen desorption kinetics performance of Mg to a certain extent, hydrogen-storage amount then significantly reduces, and is reduced to 3.6wt% by the 7.6wt% of pure Mg.In recent years, for improving the performance of the Ni-based hydrogen storage alloy of magnesium, to Mg
2Ni carries out that element replaces or the complex phase modification, generally is to add various simple substance or oxide compound, and simple substance is as Cu, Co, Ti, Zr, Al, Pd etc., oxide compound such as TiO
2, V
2O
5, Fe
3O
4, Cr
2O
3Deng.Adding different simple substance carries out element and replaces and can improve Mg at different aspect
2The hydrogen storage property of Ni, but can bring other shortcoming simultaneously.Though can lower the hydrogen discharging temperature of alloy as the interpolation of Cu, improve cycle life, sacrifice the hydrogen of alloy and inhaled hydrogen speed, Mg
2Ni
0.8Cu
0.2Hydrogen have only 2.21%, but need just can finish suction hydrogen near 3 hours.Though the interpolation energy of Co is than the hydrogen height of Cu, Mg
2Ni
0.8Co
0.2Still need to surpass 100 minutes ability and inhale hydrogen 2.58%.The interpolation of Zr can improve hydrogen, and to inhale the hydrogen time longer but finish, and take 4 hours, and the Zr element is more expensive, and economy is bad.The interpolation of Al can reduce the stability of metal hydride, but obviously lowers hydrogen, and puts hydrogen platform steepen.Ti can improve the hydrogen of alloy and accelerate hydrogen-absorption speed, but still needs 1000 seconds just can finish suction hydrogen, with the present invention bigger gap is arranged.Pd can improve the antioxidant property of alloy widely as the interpolation of surface modification element, but Pd is heavier, can reduce the absorption hydrogen amount, and Pd is very rare, is not suitable for commercialization.Because the oxide compound of some transition metal has the effect of disassociation hydrogen molecule and hydrogen ion adsorption, with oxide compound and Mg
2Ni forms the hydrogen storage property that compound system can improve alloy, but because oxide compound is not to inhale the hydrogen phase, so the interpolation of oxide compound will certainly reduce the hydrogen of alloy.In addition, though have bibliographical information to add oxide compound after obtain nano level metal hydride behind the long-time ball milling, the ball milling time needs 120 hours.
Summary of the invention
The purpose of this invention is to provide a kind of assurance Mg
2Can improve it in the time of the hydrogen of Ni and inhale Ni-based hydrogen storage material of the dynamic (dynamical) magnesium of hydrogen and preparation method, described material can effectively promote the hydrogen and the hydrogen-absorption speed of alloy, with Mg
2Ni has compared and has reached hydrogen-absorption speed faster than high hydrogen storage.Can be used for filtration, purification and the accumulating of hydrogen.Production method of the present invention is easy, implements easily, and it is little to consume energy.
Technical scheme of the present invention is: the composition of the Ni-based hydrogen storage material of magnesium is 2MgNi-xB, wherein x=1%-15%.
Described 2MgNi-xB obtains by mechanical ball milling under vacuum or inert atmosphere.
Prepare the method for the Ni-based hydrogen storage material of magnesium, it is characterized in that: the metering ratio according to 2MgNi-xB is got each component powders, and under vacuum or inert atmosphere, mechanical ball milling 12 hours obtains the Ni-based hydrogen storage material of magnesium.
The mechanical ball milling parameter is ratio of grinding media to material 20: 1, and rotating speed 600rpm in the mechanical milling process, carries out break process in the vacuum glove box that alloy was placed under vacuum or the inert atmosphere in two hours.
In the mechanical milling process of the Ni-based hydrogen storage material of preparation magnesium, the solid solution of a part of B atom is in Mg
2In the Ni matrix, a part of B atom and Mg, Ni atom react and generate a kind of ternary compound Mg
3Ni
20B
6Improvement to the alloy hydrogen storage property mainly is that the solid solution of B atom is in Mg
2In the Ni matrix, cause the change of lattice parameter, increased spacing, help the diffusion of hydrogen atom, thereby accelerate the hydrogen-absorption speed of alloy, increase the hydrogen of alloy, improve the hydrogen sucking function of alloy.The applicant passes through the XRD diffraction experiment as can be known, because the solid solution of B has caused Mg
2The Ni diffraction peak is offset to Small angle, is example with the diffraction peak crystal face of (200), and side-play amount does not wait to 0.230 ° by 0.070 °, wherein adds 5% side-play amount maximum, is 0.230 °, and spacing is 2.2685A.Experimental result shows that the interpolation of B can improve the diffusibility of H atom in alloy, effectively promotes the hydrogen sucking function of alloy.Ternary compound Mg wherein
3Ni
20B
6Then little to the performance impact of alloy.
Therefore, the suction hydrogen of the Ni-based hydrogen storage material of magnesium of the present invention still is Mg mutually
2Ni, but because the interpolation of B, the solid solution of B atom is in Mg
2In the Ni matrix, increased Mg
2The lattice parameter of Ni matrix, thus improve the hydrogen of alloy and inhaled the hydrogen dynamic performance.Because the interpolation of B can be lowered the stability of metal hydride, when putting hydrogen, show as and put the rising that the hydrogen platform is pressed.
Preparation method of the present invention has following advantage:
1. produce easyly, implement easily, it is little consume energy, only needs ball milling just can synthesize hydrogen storage alloy in 12 hours;
2. effectively promote the hydrogen and the hydrogen-absorption speed of alloy, in contrast Zu Mg
2Ni takes 300 seconds and inhales hydrogen 2.6%, and 2MgNi-5%B only need just can inhale hydrogen 3% in 180 seconds; And put the hydrogen platform and press higherly, compare Mg
2High approximately 0.2 normal atmosphere of Ni.
The Ni-based hydrogen storage material of magnesium of the present invention can be used for filtration, purification and the accumulating of hydrogen.
The content of magnesium is 99.99% in the magnesium powder of the present invention, the content of nickel is 99.99% in the nickel powder, the content of boron is 99.99% in the boron powder.
Ratio of grinding media to material of the present invention is meant the mass ratio of abrading-ball and powder.
Description of drawings
Fig. 1 is the XRD figure spectrum before the Ni-based hydrogen storage material of magnesium is inhaled hydrogen, wherein, (a) is Mg
2Ni; (b) be 2MgNi-1%B; (c) be 2MgNi-5%B; (d) be 2MgNi-10%B; (e) be 2MgNi-15%B;
Fig. 2 is suction hydrogen kinetic curve and the p-C-T curve of the serial hydrogen storage alloy of 2MgNi-xB (x=0%, 1%, 5%, 10%, 15%) under 400 ℃, wherein, and (a) for inhaling the hydrogen kinetic curve; (b) for putting hydrogen p-C-T curve.
Embodiment
Mg, Ni are pressed atomic ratio to prepare burden and mixing at 2: 1, add 1% B of Mg, Ni total mass again, three kinds of powder mixes evenly are placed in the stainless cylinder of steel that is full of argon gas, with rotating speed 600rpm, 20: 1 condition ball milling of ratio of grinding media to material 12 hours, for preventing the bonding synthetic effect that influences, placed the vacuum glove box that is full of argon gas to carry out break process alloy every two hours.In kind prepare Mg
2Ni is to contrast.The alloy of finishing ball milling is carried out material phase analysis, under 400 ℃, carry out the test of gaseous state hydrogen storage property.
Embodiment 2
Mg, Ni are pressed atomic ratio to prepare burden and mixing at 2: 1, add 5% B of Mg, Ni total mass again, three kinds of powder mixes evenly are placed in the stainless cylinder of steel that is full of argon gas, with rotating speed 600rpm, 20: 1 condition ball milling of ratio of grinding media to material 12 hours, for preventing the bonding synthetic effect that influences, placed the vacuum glove box that is full of argon gas to carry out break process alloy every two hours.In kind prepare Mg
2Ni is to contrast.The alloy of finishing ball milling is carried out material phase analysis, under 400 ℃, carry out the test of gaseous state hydrogen storage property.
Embodiment 3
Mg, Ni are pressed atomic ratio to prepare burden and mixing at 2: 1, add 10% B of Mg, Ni total mass again, three kinds of powder mixes evenly are placed in the stainless cylinder of steel that is full of argon gas, with rotating speed 600rpm, 20: 1 condition ball milling of ratio of grinding media to material 12 hours, for preventing the bonding synthetic effect that influences, placed the vacuum glove box that is full of argon gas to carry out break process alloy every two hours.In kind prepare Mg
2Ni is to contrast.The alloy of finishing ball milling is carried out material phase analysis, under 400 ℃, carry out the test of gaseous state hydrogen storage property.
Embodiment 4
Mg, Ni are pressed atomic ratio to prepare burden and mixing at 2: 1, add 15% B of Mg, Ni total mass again, three kinds of powder mixes evenly are placed in the stainless cylinder of steel that is full of argon gas, with rotating speed 600rpm, 20: 1 condition ball milling of ratio of grinding media to material 12 hours, for preventing the bonding synthetic effect that influences, placed the vacuum glove box that is full of argon gas to carry out break process alloy every two hours.In kind prepare Mg
2Ni is to contrast.The alloy of finishing ball milling is carried out material phase analysis, under 400 ℃, carry out the test of gaseous state hydrogen storage property.
As shown in Figure 1, because the interpolation of B has caused Mg
2The Ni diffraction peak is offset to Small angle, is example with (200) crystal face, and side-play amount does not wait to 0.230 ° by 0.070 °, wherein adds 5% side-play amount maximum, is 0.230 °, and spacing is 2.2685A.This has illustrated that the solid solution of B atom is in Mg
2The interstitial void of Ni has changed Mg
2The lattice parameter of Ni.
Fig. 2 is the gaseous state hydrogen storage property test results of five combination gold under 400 ℃.By Fig. 2 (a) as can be known, the hydrogen sucking function that contains the B sample obviously is better than Mg2Ni, and all contain the hydrogen of B sample all than Mg2Ni height, and hydrogen-absorption speed is unlike Mg
2Ni is slow, and the hydrogen-absorption speed of 2MgNi-5%B is the highest in all samples especially, only needs 180 seconds just can finish suction hydrogen, and hydrogen is 3w%.Finally to inhale the hydrogen time longer relatively though other contains the B sample, substantially all reached 90% of maximum hydrogen at 600 to 900 seconds.Wherein 2MgNi-1%B inhales hydrogen 2.69% when 600s, and 2MgNi-10%B inhales hydrogen 2.63% when 600s, and 2MgNi-15%B inhales hydrogen 2.54% when 600s, and Mg
2The hydrogen of Ni has only 2.6%.This shows that the interpolation of B can also promote the hydrogen-absorption speed of alloy except the hydrogen that can increase alloy.Shown in Fig. 2 (b), it is then comparatively smooth to contain the B sample, and the platform pressure is higher, high approximately 0.2 normal atmosphere.Platform is pressed higher the stable relatively low of hydride that illustrated.
The above results shows that the present invention can effectively increase Mg
2The hydrogen of Ni also improves Mg
2The suction hydrogen kinetics of Ni is accelerated hydrogen-absorption speed, and reduces the stability of metal hydride, improves to put hydrogen platform pressure.
Claims (5)
1. Ni-based hydrogen storage material of magnesium, it is characterized in that: the composition of described material is 2MgNi-xB, wherein x=1%-15%.
2. the Ni-based hydrogen storage material of magnesium according to claim 1, it is characterized in that: described 2MgNi-xB obtains by mechanical ball milling under vacuum or inert atmosphere.
3. prepare the method for the Ni-based hydrogen storage material of the described magnesium of claim 1, it is characterized in that: the metering ratio according to 2MgNi-xB is got each component powders, and under vacuum or inert atmosphere, mechanical ball milling 12 hours obtains the Ni-based hydrogen storage material of the described magnesium of claim 1.
4. method according to claim 3 is characterized in that: the mechanical ball milling parameter is ratio of grinding media to material 20: 1, rotating speed 600rpm.
5. method according to claim 3 is characterized in that: in the mechanical milling process, carry out break process in the vacuum glove box that alloy was placed under vacuum or the inert atmosphere in two hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103855370A (en) * | 2014-03-11 | 2014-06-11 | 微山钢研稀土材料有限公司 | Low-magnesium RE-Mg-Ti-Ni-Al-B series hydrogen-storage alloy for Ni-MH secondary battery and preparation method |
| CN104445241A (en) * | 2014-11-03 | 2015-03-25 | 安徽工业大学 | Method for synthesizing magnesium-nickel ternary metal boride at low temperature |
| CN111647773A (en) * | 2020-05-20 | 2020-09-11 | 有研工程技术研究院有限公司 | Rare earth hydrogen storage material and preparation method thereof |
| CN114229797A (en) * | 2022-01-17 | 2022-03-25 | 重庆大学 | Method for preparing hydrogen based on hydrolysis of Mg-Ni-Y alloy containing LPSO second phase |
-
2011
- 2011-06-02 CN CN2011101480267A patent/CN102212721A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 20110315 杨丽玲 镁镍系储氢合金的机械球磨制备及改性研究 中国学术期刊(光盘版)电子杂志社 19-20 1-5 , * |
| 杨丽玲: "镁镍系储氢合金的机械球磨制备及改性研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 陈玉安等: "硼的添加对Mg2Ni储氢合金吸放氢性能的影响", 《2011中国材料研讨会论文摘要集》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103855370A (en) * | 2014-03-11 | 2014-06-11 | 微山钢研稀土材料有限公司 | Low-magnesium RE-Mg-Ti-Ni-Al-B series hydrogen-storage alloy for Ni-MH secondary battery and preparation method |
| CN104445241A (en) * | 2014-11-03 | 2015-03-25 | 安徽工业大学 | Method for synthesizing magnesium-nickel ternary metal boride at low temperature |
| CN104445241B (en) * | 2014-11-03 | 2016-06-08 | 安徽工业大学 | A kind of method of low temperature synthesis magnesium-nickel ternary metal boride |
| CN111647773A (en) * | 2020-05-20 | 2020-09-11 | 有研工程技术研究院有限公司 | Rare earth hydrogen storage material and preparation method thereof |
| CN114229797A (en) * | 2022-01-17 | 2022-03-25 | 重庆大学 | Method for preparing hydrogen based on hydrolysis of Mg-Ni-Y alloy containing LPSO second phase |
| CN114229797B (en) * | 2022-01-17 | 2024-01-12 | 重庆大学 | Method for producing hydrogen based on hydrolysis of Mg-Ni-Y alloy containing LPSO second phase |
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Application publication date: 20111012 |