CN105274374A - Preparation method for Mg2Ni0.9Co0.1H4-based hydrogen storage material - Google Patents
Preparation method for Mg2Ni0.9Co0.1H4-based hydrogen storage material Download PDFInfo
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- CN105274374A CN105274374A CN201510578254.6A CN201510578254A CN105274374A CN 105274374 A CN105274374 A CN 105274374A CN 201510578254 A CN201510578254 A CN 201510578254A CN 105274374 A CN105274374 A CN 105274374A
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- hydrogen storage
- storage material
- preparation
- based hydrogen
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 80
- 239000001257 hydrogen Substances 0.000 title claims abstract description 80
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000011232 storage material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 65
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 35
- 239000000956 alloy Substances 0.000 claims abstract description 35
- 238000000498 ball milling Methods 0.000 claims abstract description 24
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 239000006104 solid solution Substances 0.000 claims abstract description 19
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 17
- 239000010935 stainless steel Substances 0.000 claims description 22
- 229910001220 stainless steel Inorganic materials 0.000 claims description 22
- 238000000227 grinding Methods 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000003795 desorption Methods 0.000 abstract description 11
- 238000003860 storage Methods 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 4
- 229910012375 magnesium hydride Inorganic materials 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 10
- 229910017961 MgNi Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 150000004678 hydrides Chemical class 0.000 description 5
- -1 hydride Chemical compound 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 238000003991 Rietveld refinement Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002483 hydrogen compounds Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
Abstract
The invention discloses a preparation method for a Mg2Ni0.9Co0.1H4-based hydrogen storage material, and belongs to the technical field of hydrogen storage materials. The preparation method comprises the following steps: obtaining Ni(Co) solid solution powder by virtue of wet ball-milling; according to components of a master alloy Mg2Ni1-xCox (x=0.1-0.2), sintering certain amount of solid solution and Mg powder in vacuum to obtain the master alloy, wherein the chemical component range of the master alloy is as follows: 65-70% (in atomic percentage) of Mg and the balance of Ni+Co, Co accounting for 10-20% (in atomic percentage) of Ni+Co; then, putting sintered alloy into a hydrogenation furnace for hydrogenation to obtain a target hydrogen storage material which consists of 85-90wt% of a Mg2Ni0.9Co0.1H4 matrix phase, 6-7wt% of MgH2 and 4-8wt% of MgNi3Co. The hydrogen storage material has high hydrogen storage capacity (greater than 3.5wt%), a low initial hydrogen desorption temperature (220 DEG C) and excellent hydrogen desorption dynamic performance. The preparation method disclosed by the invention has the remarkable characteristics that the process is simple, efficient, high in yield and free of pollution.
Description
Technical field
The present invention relates to hydrogen storage material technical field, be specifically related to a kind of Mg
2ni
0.9co
0.1h
4the preparation method of based hydrogen storage material.
Background technology
In metal hydrogen storage material, due to low price, low weight density and high hydrogen storage capability (weight ratio 7.6wt%), metal M g is considered to the most promising hydrogen storage material.But slow suction hydrogen desorption kinetics and high thermodynamic stability, limit its further application.People introduce transition metal (TM) in Mg, form Mg-TM-H system hydride by changing phase structure, can reach the object improving Magnuminium storage hydrogen thermodynamics and kinetics performance.This approach comprises two kinds of situations: one is prepare stable intermetallic compound Mg by the usual way such as melting, sintering
2ni, then direct hydrogenation forms Mg
2niH
4hydride; Although another kind of situation there is not stable Mg-TM (TM=Co, Fe, Cr, Mn etc.) intermetallic compound, Mg can be prepared by the method for reaction under high pressure ball milling
2feH
6, Mg
2coH
5, Mg
3crH
~ 6and Mg
3mnH
~ 6in hydride.Because a rear hydrogen-like compound is generally prepared (needing the hydrogen pressure up to ~ GPa and long reaction ball milling) under unconventional means, in fact their large-scale application is very difficult.
Mg
2niH
4there is the hydride of two kinds of different structures, i.e. high temperature cubic structure (LT) and low temperature monocline (HT).In order to improve Mg further
2niH
4hydrogen storage property, people attempt development Mg-Ni-Co-H quaternary material new system.The Mg of nano-crystalline and amorphous can be prepared by melt-blown method
2ni
1-xco
x(x=0-0.4) alloy; Although nano-crystalline and amorphous can improve the hydrogen storage property of alloy, but Co can not form any hydride together with other elements, the beneficial effect of Co to hydrogen storage property do not have be effectively played [Y.H.Zhang, B.W.Li, H.P.Ren, etal., JournalofAlloysandCompounds, 509 (2011), 2808.].In addition, melt-blowing equipment investment is large, productive rate is low, and it is not suitable for the demand that industrialization is produced.In the recent period, people study and have found that structure is different from LT and HT type Mg completely
2niH
4mg
2ni
0.5co
0.5h
4.4and Mg
2ni
0.9co
0.1h
4two kinds of New Hydrogen compounds.Wherein, by Mg, Ni, Co powder under the hydrogen pressure being greater than 7MPa, under the rotational speed of ball-mill of 400 ~ 800rpm, long-time reaction ball milling obtains Mg
2ni
0.5co
0.5h
4.4hydride [Yu.Verbovytskyy, J.Zhang, F.Cuevas, etal., JournalofAlloysandCompounds, http://dx.doi.org/10.1016/j.jallcom.2014.12092.].Although at Mg prepared by fast quenching+mechanical alloying two-step approach
60ni
30la
10-xco
xa small amount of Mg has been found in (x=2,4) alloy hydride sample
2ni
0.9co
0.1h
4hydride [Lv Peng, Guilin: Guilin Electronic Science and Technology Univ., 2014.], but, from Mg
2ni
0.9co
0.1h
4hydride stores up the angle of hydrogen application on a large scale, with Mg
2ni
0.9co
0.1h
4for the novel hydrogen storage material of base and new preparation method's needs obtain further breakthrough.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides that a kind of technique is simple, efficient, productive rate high, free of contamination preparation Mg
2ni
0.9co
0.1h
4the method of based hydrogen storage material.
The present invention prepares Mg
2ni
0.9co
0.1h
4the method of based hydrogen storage material, specifically comprises the following steps:
(1) be 10 ~ 20% in the atomic percent of Co in Ni+Co, take Co powder and Ni powder remaining as the ratio of Ni;
(2) pour in stainless steel jar mill by Co powder and Ni powder, add stainless steel abrading-ball by ratio of grinding media to material 20:1, pour industrial spirit into and powder and stainless steel abrading-ball are flooded, sealed tank cap, is placed in ball mill wet ball grinding by stainless steel jar mill;
(3), after ball milling terminates, dry in an oven and remove industrial spirit, obtain Ni (Co) solid-solution powder;
(4) taking atomic percent is that the Mg powder of 65 ~ 70% and Ni (Co) solid-solution powder of residue atomic percent carry out ball milling mixing, ratio of grinding media to material 20:1 during ball milling mixing;
(5) alloy powder that step (4) mixes is placed on stainless steel to burn in boat, in vacuum sintering furnace, vacuum sintering obtains Mg
2ni
1-xco
xsintered alloy, wherein, x=0.1 ~ 0.2;
(6) by the Mg of sintering
2ni
1-xco
xalloy is placed in hydrogenation furnace hydrogenation, obtains Mg
2ni
0.9co
0.1h
4based hydrogen storage material.
In described step (1), the granularity of Co powder and Ni powder is not less than 200 orders, purity is not less than 99.5%.
In described step (2), the time of wet ball grinding is 30 ~ 50h, and drum's speed of rotation is 150 ~ 250rpm.
In described step (3), industrial spirit dries 0.5 ~ 1h removal in 30 ~ 50 DEG C of baking ovens.
In described step (4), the granularity of Mg powder is not less than 200 orders, purity is not less than 99.5%;
In described step (4), drum's speed of rotation is 100 ~ 300rpm, and Ball-milling Time is 0.5 ~ 1.5h.
In described step (5), vacuum sintering is carried out in 550 DEG C of vacuum sintering furnaces, and the vacuum sintering time is 15 ~ 25h.
In described step (6), the hydrogen pressure in hydrogenation furnace is 3 ~ 5MPa, temperature is 300 DEG C, and hydrogenation time is 2h.
The Mg that preparation method of the present invention obtains
2ni
0.9co
0.1h
4based hydrogen storage material, it is by the Mg of 85 ~ 90wt%
2ni
0.9co
0.1h
4the MgH of matrix phase, 6 ~ 7wt%
2with the MgNi of 4 ~ 8wt%
3co phase composite.
Compared with prior art, the invention has the beneficial effects as follows:
1, this invention has successfully prepared a kind of Mg first
2ni
0.9co
0.1h
4based hydrogen storage material system, the Mg in material
2ni
0.9co
0.1h
4matrix phase phase content is greater than 85wt%, thus makes material have high hydrogen storage capability (being greater than 3.5wt%).
2, sintered by Ni (Co) sosoloid of Mg powder and wet ball grinding and prepare mother alloy, containing a small amount of MgNi in mother alloy
3co phase, it is the cenotype of a kind of undiscovered (report), and this cenotype has the characteristic of magnesium-yttrium-transition metal, and the hydrogen storage property of alloy has good katalysis, in conjunction with Mg
2ni
0.9co
0.1h
4the high reactivity of matrix self makes material system have low initial hydrogen discharging temperature (220 DEG C) and excellent hydrogen desorption kinetics performance.
3, this preparation method has that technique is simple, efficient, high, the free of contamination distinguishing feature of productive rate.
Accompanying drawing explanation
Fig. 1 is Ni (Co) solid-solution powder X-ray diffractogram prepared by the present invention.
Fig. 2 is Mg prepared by the present invention
2ni
1-xco
xthe X-ray diffractogram of (x=0.1 ~ 0.2) sintered alloy.
Fig. 3 is Mg prepared by the present invention
2ni
0.9co
0.1h
4the X-ray diffractogram of based hydrogen storage material.
Fig. 4 is Mg prepared by the present invention
2ni
0.9co
0.1h
4based hydrogen storage material intensification Hydrogen desorption isotherms.
Embodiment
Below in conjunction with specific embodiment in detail the present invention is described in detail, but the present invention is not limited to following embodiment.
Embodiment 1
By Ni
0.9co
0.1composition take Ni powder (granularity 200 order, purity 99.5%) and Co powder (granularity 200 order, purity 99.5%) respectively, totally 50 grams, Ni powder and Co powder.The Ni powder taken and Co powder are put into stainless steel jar mill, adds stainless steel abrading-ball by ratio of grinding media to material 20:1, then pour industrial spirit into and ball and material are flooded, ball sealer grinding jar lid.Ball grinder is placed in ball mill wet ball grinding 40h, drum's speed of rotation is 200rpm.After ball milling terminates, 40 DEG C in an oven, 0.5h oven dry removing industrial spirit, obtain the Ni of high chemical stability
0.9cu
0.1solid-solution powder, powder is made up of (see Fig. 1: Ni (Co) solid-solution powder X-ray diffractogram) single Ni (Co) solid solution phase.By Mg
2ni
0.9co
0.1composition take Mg powder (granularity 200 order, purity 99.5%) and Ni respectively
0.9co
0.1solid-solution powder totally 80 grams, puts it in stainless steel jar mill and carries out ball milling mixing.Ratio of grinding media to material 20:1 during ball milling mixing, drum's speed of rotation is 200rpm, and Ball-milling Time is 0.5h.The alloy powder of mixing is placed on stainless steel and burns in boat, and in vacuum sintering furnace, 550 DEG C of vacuum sintering 20h obtain Mg
2ni
0.9co
0.1alloy, sintered alloy is by Mg
2ni
0.9co
0.1with a small amount of Mg and MgNi
3co phase composite is (see Fig. 2: Mg
2ni
1-xco
xthe X-ray diffractogram of (x=0.1 ~ 0.2) sintered alloy).Finally sintered alloy is placed in hydrogenation furnace, at 3MPa hydrogen pressure and 300 DEG C, hydrogenation 2h obtains Mg
2ni
0.9co
0.1h
4based hydrogen storage material; Calculate through X-ray diffraction Rietveld method, it is by the Mg of 90wt%
2ni
0.9co
0.1h
4the MgH of matrix phase, 6wt%
2with the MgNi of 4wt%
3co phase composite is (see Fig. 3: Mg
2ni
0.9co
0.1h
4the X-ray diffractogram of based hydrogen storage material).Mg
2ni
0.9co
0.1h
4based hydrogen storage material puts hydrogen from 220 DEG C, puts hydrogen substantially complete to 320 DEG C, and hydrogen desorption capacity is 3.72wt% (Fig. 4: Mg
2ni
0.9co
0.1h
4based hydrogen storage material intensification Hydrogen desorption isotherms).Put hydrogen sample identical with the phase composite of mother alloy, show that the hydrogen storage material prepared has good reversibility.
Embodiment 2
By Ni
0.85co
0.15composition take Ni powder (granularity 200 order, purity 99.5%) and Co powder (granularity 200 order, purity 99.5%) respectively, totally 50 grams, Ni powder and Co powder.The Ni powder taken and Co powder are put into stainless steel jar mill, adds stainless steel abrading-ball by ratio of grinding media to material 20:1, then pour industrial spirit into and ball and material are flooded, ball sealer grinding jar lid.Ball grinder is placed in ball mill wet ball grinding 40h, drum's speed of rotation is 200rpm.After ball milling terminates, 40 DEG C in an oven, 0.5h oven dry removing industrial spirit, obtain the Ni of high chemical stability
0.9cu
0.1solid-solution powder, powder is made up of (see Fig. 1: Ni (Co) solid-solution powder X-ray diffractogram) single Ni (Co) solid solution phase.By Mg
2ni
0.85co
0.15composition take Mg powder (granularity 200 order, purity 99.5%) and Ni respectively
0.85co
0.15solid-solution powder totally 80 grams, puts it in stainless steel jar mill and carries out ball milling mixing.Ratio of grinding media to material 20:1 during ball milling mixing, drum's speed of rotation is 200rpm, and Ball-milling Time is 0.5h.The alloy powder of mixing is placed on stainless steel and burns in boat, and in vacuum sintering furnace, 550 DEG C of vacuum sintering 20h obtain Mg
2ni
0.85co
0.15alloy, sintered alloy is by Mg
2ni
0.9co
0.1with a small amount of Mg and MgNi
3co phase composite is (see Fig. 2: Mg
2ni
1-xco
xthe X-ray diffractogram of (x=0.1 ~ 0.2) sintered alloy).Finally sintered alloy is placed in hydrogenation furnace, at 3MPa hydrogen pressure and 300 DEG C, hydrogenation 2h obtains Mg
2ni
0.9co
0.1h
4based hydrogen storage material; Calculate through X-ray diffraction Rietveld method, it is by the Mg of 88wt%
2ni
0.9co
0.1h
4the MgH of matrix phase, 6wt%
2with the MgNi of 6wt%
3co phase composite is (see Fig. 3: Mg
2ni
0.9co
0.1h
4the X-ray diffractogram of based hydrogen storage material).Mg
2ni
0.9co
0.1h
4based hydrogen storage material puts hydrogen from 220 DEG C, puts hydrogen substantially complete to 320 DEG C, and hydrogen desorption capacity is 3.65wt% (Fig. 4: Mg
2ni
0.9co
0.1h
4based hydrogen storage material intensification Hydrogen desorption isotherms).Put hydrogen sample consistent with the phase composite of mother alloy, show that the hydrogen storage material prepared has good reversibility.
Embodiment 3
By Ni
0.8co
0.2composition take Ni powder (granularity 200 order, purity 99.5%) and Co powder (granularity 200 order, purity 99.5%) respectively, totally 50 grams, Ni powder and Co powder.The Ni powder taken and Co powder are put into stainless steel jar mill, adds stainless steel abrading-ball by ratio of grinding media to material 20:1, then pour industrial spirit into and ball and material are flooded, ball sealer grinding jar lid.Ball grinder is placed in ball mill wet ball grinding 40h, drum's speed of rotation is 200rpm.After ball milling terminates, 40 DEG C in an oven, 0.5h oven dry removing industrial spirit, obtain the Ni of high chemical stability
0.8cu
0.2solid-solution powder, powder is made up of (see Fig. 1: Ni (Co) solid-solution powder X-ray diffractogram) single Ni (Co) solid solution phase.By Mg
2ni
0.8co
0.2composition take Mg powder (granularity 200 order, purity 99.5%) and Ni respectively
0.8co
0.2solid-solution powder totally 80 grams, puts it in stainless steel jar mill and carries out ball milling mixing.Ratio of grinding media to material 20:1 during ball milling mixing, drum's speed of rotation is 200rpm, and Ball-milling Time is 0.5h.The alloy powder of mixing is placed on stainless steel and burns in boat, and in vacuum sintering furnace, 550 DEG C of vacuum sintering 20h obtain Mg
2ni
0.8co
0.2alloy, sintered alloy is by Mg
2ni
0.9co
0.1with a small amount of Mg and MgNi
3co phase composite is (see Fig. 2: Mg
2ni
1-xco
xthe X-ray diffractogram of (x=0.1 ~ 0.2) sintered alloy).Finally sintered alloy is placed in hydrogenation furnace, at 3MPa hydrogen pressure and 300 DEG C, hydrogenation 2h obtains Mg
2ni
0.9co
0.1h
4based hydrogen storage material; Calculate through X-ray diffraction Rietveld method, it is by the Mg of 85wt%
2ni
0.9co
0.1h
4the MgH of matrix phase, 7wt%
2with the MgNi of 8wt%
3co phase composite is (see Fig. 3: Mg
2ni
0.9co
0.1h
4the X-ray diffractogram of based hydrogen storage material).Mg
2ni
0.9co
0.1h
4based hydrogen storage material puts hydrogen from 220 DEG C, puts hydrogen substantially complete to 320 DEG C, and hydrogen desorption capacity is 3.56wt% (Fig. 4: Mg
2ni
0.9co
0.1h
4based hydrogen storage material intensification Hydrogen desorption isotherms).Put hydrogen sample consistent with the phase composite of mother alloy, show that the hydrogen storage material prepared has good reversibility.
Claims (9)
1. a Mg
2ni
0.9co
0.1h
4the preparation method of based hydrogen storage material, is characterized in that, comprises the steps:
(1) be 10 ~ 20% in the atomic percent of Co in Ni+Co, take Co powder and Ni powder remaining as the ratio of Ni;
(2) pour in stainless steel jar mill by Co powder and Ni powder, add stainless steel abrading-ball by ratio of grinding media to material 20:1, pour industrial spirit into and powder and stainless steel abrading-ball are flooded, sealed tank cap, is placed in ball mill wet ball grinding by stainless steel jar mill;
(3), after ball milling terminates, dry in an oven and remove industrial spirit, obtain Ni (Co) solid-solution powder;
(4) taking atomic percent is that the Mg powder of 65 ~ 70% and Ni (Co) solid-solution powder of residue atomic percent carry out ball milling mixing, ratio of grinding media to material 20:1 during ball milling mixing;
(5) alloy powder that step (4) mixes is placed on stainless steel to burn in boat, in vacuum sintering furnace, vacuum sintering obtains Mg
2ni
1-xco
xsintered alloy, wherein, x=0.1 ~ 0.2;
(6) by the Mg of sintering
2ni
1-xco
xalloy is placed in hydrogenation furnace hydrogenation, obtains Mg
2ni
0.9co
0.1h
4based hydrogen storage material.
2. Mg as claimed in claim 1
2ni
0.9co
0.1h
4the preparation method of based hydrogen storage material, is characterized in that, in step (1), the granularity of Co powder and Ni powder is not less than 200 orders, purity is not less than 99.5%.
3. Mg as claimed in claim 1
2ni
0.9co
0.1h
4the preparation method of based hydrogen storage material, is characterized in that, in step (2), the time of wet ball grinding is 30 ~ 50h, and drum's speed of rotation is 150 ~ 250rpm.
4. Mg as claimed in claim 1
2ni
0.9co
0.1h
4the preparation method of based hydrogen storage material, is characterized in that, in step (3), industrial spirit dries 0.5 ~ 1h removal in 30 ~ 50 DEG C of baking ovens.
5. Mg as claimed in claim 1
2ni
0.9co
0.1h
4the preparation method of based hydrogen storage material, is characterized in that, in step (4), the granularity of Mg powder is not less than 200 orders, purity is not less than 99.5%.
6. Mg as claimed in claim 1
2ni
0.9co
0.1h
4the preparation method of based hydrogen storage material, is characterized in that, in step (4), drum's speed of rotation is 100 ~ 300rpm, and Ball-milling Time is 0.5 ~ 1.5h.
7. Mg as claimed in claim 1
2ni
0.9co
0.1h
4the preparation method of based hydrogen storage material, is characterized in that, in step (5), vacuum sintering is carried out in 550 DEG C of vacuum sintering furnaces, and the vacuum sintering time is 15 ~ 25h.
8. Mg as claimed in claim 1
2ni
0.9co
0.1h
4the preparation method of based hydrogen storage material, is characterized in that, in step (6), the hydrogen pressure in hydrogenation furnace is 3 ~ 5MPa, temperature is 300 DEG C, and hydrogenation time is 2h.
9. one kind as arbitrary in claim 1 ~ 8 as described in preparation method obtain Mg
2ni
0.9co
0.1h
4based hydrogen storage material.
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Cited By (2)
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| CN108520946A (en) * | 2018-03-28 | 2018-09-11 | 华南理工大学 | A kind of magnesium iron hydride-graphite combination electrode material and its preparation method and application |
| CN108588455A (en) * | 2018-04-08 | 2018-09-28 | 安徽工业大学 | A kind of improvement Mg2The method of Ni alloy hydrogen storage properties |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108520946A (en) * | 2018-03-28 | 2018-09-11 | 华南理工大学 | A kind of magnesium iron hydride-graphite combination electrode material and its preparation method and application |
| CN108520946B (en) * | 2018-03-28 | 2020-06-19 | 华南理工大学 | Magnesium-iron hydride-graphite composite electrode material and preparation method and application thereof |
| CN108588455A (en) * | 2018-04-08 | 2018-09-28 | 安徽工业大学 | A kind of improvement Mg2The method of Ni alloy hydrogen storage properties |
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