CN102586660A - Magnesium-based hydrogen storage alloy composite material with metal sulfide added - Google Patents
Magnesium-based hydrogen storage alloy composite material with metal sulfide added Download PDFInfo
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- CN102586660A CN102586660A CN2012100456481A CN201210045648A CN102586660A CN 102586660 A CN102586660 A CN 102586660A CN 2012100456481 A CN2012100456481 A CN 2012100456481A CN 201210045648 A CN201210045648 A CN 201210045648A CN 102586660 A CN102586660 A CN 102586660A
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Abstract
The invention relates to a magnesium-based hydrogen storage alloy composite material with metal sulfide added, which consists of a magnesium-based hydrogen storage alloy and the metal sulfide of which the mass is 10-30 percent of that of the magnesium-based hydrogen storage alloy, wherein the magnesium-based hydrogen storage alloy is Mg and REMg3 or RE2Mg17 (RE=La, Ce, Pr and Nd), the metal sulfide can be one of MoS2, CoS2 and CoS. A preparation method of the magnesium-based hydrogen storage alloy composite material with the metal sulfide added mainly comprises the following steps of: (1) enabling the magnesium-based hydrogen storage alloy to fully adsorb hydrogen in a hydrogenation reactor, and (2) performing ball milling under protection of hydrogen atmosphere. The hydrogen adsorption/releasing rate of the composite material prepared by the method is improved by over 1.5 times than that of the magnesium-based hydrogen storage alloy without adding the metal sulfide, and the initial dehydrogenation temperature of the composite material is reduced by 15-100K. The composite material is simple in preparation process and stable in performance, and can be applied to hydrogen storage and supplying in fields such as electromobiles and fuel cells.
Description
Technical field
The present invention relates to magnesium based hydrogen storing alloy composite material.
Background technology
Along with the scarcity of the environmental degradation and the energy, the friendly type energy of development environment becomes the focus of various countries' research.At present, owing to hydrogen aboundresources, high energy density and environmental friendliness become the most attractive a kind of novel energy.Thereby, adopt the defeated hydrogen of hydrogen storage material storage, can accomplish safe and efficiently, be considered to one of more satisfactory carrier.Requirements such as it is big that the hydrogen storage material of practicability must satisfy hydrogen-storage density, and suction/hydrogen discharging rate is fast, and service temperature is moderate and safe.Existing Magnuminium as storing hydrogen and transporting material is low owing to its density, the storage hydrogen capacity reaches low cost and other advantages greatly and obtains fast development, and obtains broad research.Yet because the Mg base hydrogen bearing alloy dynamic performance is relatively poor, inhale shortcomings such as putting the hydrogen condition harshness, had a strong impact on its practicability.
In recent years, many investigators carry out suction/hydrogen discharging performance that high-energy ball milling improves Magnuminium through in Magnuminium, adding additive.The patent No. be 200610118471.8 disclose a kind of by Li base hydride and Magnuminium through the synthetic a kind of hydrogen storage alloy of ball milling; Though improved the suction hydrogen kinetics of pure magnesium; But the dynamic performance under its low temperature is still not ideal enough, and hydrogen desorption kinetics improves not obvious.Document Seon-Ah Jin, Jae-Hyeok Shim, Young Whan Cho, Kyung-Woo Yi. Journal of Power Sources, 862 of 172 (2007) 859 – have proposed at MgH
2Add in the alloy that the hydrogen-absorption speed of resulting alloy has had raising behind a series of transition metal fluorides ball millings, but hydrogen discharging rate not be improved significantly, meanwhile, some transition metal fluorides such as NbF
5Owing to cost an arm and a leg, make practical application receive certain restriction.
Summary of the invention
The object of the present invention is to provide a kind of magnesium based hydrogen storing alloy composite material that adds metallic sulfide that can improve Mg base hydrogen bearing alloy suction/hydrogen discharging performance.This matrix material is made up of Mg base hydrogen bearing alloy and the metallic sulfide that is its quality 10 ~ 30 %, and wherein, described Mg base hydrogen bearing alloy is Mg, REMg
3Or RE
2Mg
17(RE=La, Ce, Pr, Nd), metallic sulfide is MoS
2, CoS
2, a kind of among the CoS.
The preparation method of the magnesium based hydrogen storing alloy composite material of above-mentioned interpolation metallic sulfide is following:
(1) with Mg base hydrogen bearing alloy under argon gas atmosphere protection mechanical disintegration to the 40-100 order.Claim that an amount of above-mentioned powdered alloy is loaded in the hydrogenation reactor, insulation 1 h naturally cools to room temperature under 300 ~ 400 ℃ and 3 ~ 4 MPa hydrogen pressures, in argon gas atmosphere protection taking-up down.
(2) in the Magnuminium after hydrogenation under the argon gas atmosphere protection, adding particle diameter is that 100 ~ 200 orders, mass percent are the metallic sulfide powder of 10 ~ 30 %, is placed in the ball grinder, and ball material mass ratio is 29 ~ 33:1; Under the hydrogen atmosphere protection, carry out ball milling, rotating speed is 450 ~ 550 r/min, and the quiescent interval is 5 ~ 30m; The ball milling time is 1 ~ 3 h; Naturally cool to room temperature behind the ball milling, under argon gas atmosphere, encapsulate, obtain magnesium based hydrogen storing alloy composite material.
The present invention compared with prior art has following advantage:
1, the suction/hydrogen discharging rate of the magnesium based hydrogen storing alloy composite material of the present invention's preparation improves more than 1.5 times than the Mg base hydrogen bearing alloy that does not add metallic sulfide, and its initial dehydrogenated temperature reduces by 15 ~ 100 K than Magnuminium simultaneously.
2, the metallic sulfide that provides among the present invention is with low cost, is prone to obtain.
3, preparation technology of the present invention is simple, easy to operate, and energy consumption is few, and preparation cost is low, is easy to industrialization and popularization.
Description of drawings:
Fig. 1 is the magnesium based hydrogen storing alloy composite material of the embodiment of the invention 1 and the hydrogen-absorption speed correlation curve figure of Mg base hydrogen bearing alloy.
Fig. 2 is the magnesium based hydrogen storing alloy composite material of the embodiment of the invention 2 and the hydrogen discharging rate correlation curve figure of Mg base hydrogen bearing alloy.
Fig. 3 is the magnesium based hydrogen storing alloy composite material and the Mg base hydrogen bearing alloy hydrogen-absorption speed correlation curve figure of the embodiment of the invention 3.
Fig. 4 is the magnesium based hydrogen storing alloy composite material and Mg base hydrogen bearing alloy DTA (DSC) the correlation curve figure of the embodiment of the invention 4.
Fig. 5 is the magnesium based hydrogen storing alloy composite material and Mg base hydrogen bearing alloy DTA (DSC) the correlation curve figure of the embodiment of the invention 5.
Fig. 6 is the magnesium based hydrogen storing alloy composite material and the Mg base hydrogen bearing alloy hydrogen discharging rate correlation curve figure of the embodiment of the invention 6.
Fig. 7 is the magnesium based hydrogen storing alloy composite material and Mg base hydrogen bearing alloy DTA (DSC) the correlation curve figure of the embodiment of the invention 7.
Fig. 8 is the magnesium based hydrogen storing alloy composite material and the Mg base hydrogen bearing alloy hydrogen-absorption speed correlation curve figure of the embodiment of the invention 8.
Fig. 9 is the magnesium based hydrogen storing alloy composite material and the Mg base hydrogen bearing alloy hydrogen discharging rate correlation curve figure of the embodiment of the invention 9.
Embodiment:
Below through specific examples technical scheme of the present invention is done and to be further described.
Embodiment 1
Under argon gas atmosphere, taking by weighing an amount of particle diameter is that 100 purpose magnesium powder are loaded in the hydrogenation reactor, and at 400 ℃, 4 MPa hydrogen pressures are insulation 1 h down, it is transformed generate MgH
2, naturally cool to room temperature, under the argon gas atmosphere protection, take out the MgH after hydrogenation
2Adding particle diameter in the powder is 100 purpose MoS
2Powder, 10:1 mixes by mass ratio, and mixed powder is placed ball grinder; Ball milling under the hydrogen atmosphere protection, ball matter is stainless steel, ball mill is the Pulverisette6 planetary ball mill; The rotating speed of ball grinder is 450 r/min, and ball material mass ratio is 29:1, and the quiescent interval is 15 min; The ball milling time is 1 h, treats to naturally cool to room temperature after ball milling finishes, and under argon gas atmosphere, encapsulates.The magnesium based hydrogen storing alloy composite material of ball milling preparation is carried out the hydrogen-absorption speed test; Its result is as shown in Figure 1; Hydrogen-absorption speed curve from figure can be found out; Matrix material of the present invention hydrogen-storage amount in 150 ℃ of following 21 min can reach 3 wt.%, when 400 s, can reach 80 % of maximum storage hydrogen quantity, and not add the MgH of metallic sulfide
2Hydrogen-storage amount only reaches 1 wt.% in 21min; And need 800 s when reaching 80 % of maximum storage hydrogen quantity, this shows that the matrix material for preparing behind metallic sulfide provided by the invention and the Mg base hydrogen bearing alloy high-energy ball milling stores up the Mg base hydrogen bearing alloy that hydrogen speed will obviously be superior to not adding metallic sulfide.
Embodiment 2
With CeMg
3Alloy is mechanical disintegration to 40 order under the argon gas atmosphere protection, takes by weighing an amount of powder and is loaded in the hydrogenation reactor, and 300 ℃, 3 MPa hydrogen pressures are insulation 1 h down, it is transformed generate CeH
3And MgH
2, naturally cool to room temperature, under the argon gas atmosphere protection, take out.Under the argon gas atmosphere protection, adding particle diameter in the Magnuminium powder after hydrogenation is 200 purpose CoS
2Powder, 10:3 mixes by mass ratio, and mixed powder is placed ball grinder; Ball milling under the hydrogen atmosphere protection, ball matter is stainless steel, ball mill is the Pulverisette6 planetary ball mill; The rotating speed of ball grinder is 550 r/min, and ball material mass ratio is 33:1, and the quiescent interval is 5 min; The ball milling time is 3 h, treats to naturally cool to room temperature after ball milling finishes, and under argon gas atmosphere, encapsulates.The magnesium based hydrogen storing alloy composite material of ball milling preparation is carried out the hydrogen discharging rate test, and its result is as shown in Figure 2, and the hydrogen discharging rate curve from figure can find out that matrix material of the present invention only needs about 300 s at 300 ℃ of 80 % that are issued to maximum hydrogen desorption capacity, and CeMg
380 % that alloy reaches maximum hydrogen desorption capacity then need 500 s, this shows that the matrix material hydrogen discharging rate for preparing behind metallic sulfide provided by the invention and the Mg base hydrogen bearing alloy high-energy ball milling will obviously be superior to not adding the Mg base hydrogen bearing alloy of metallic sulfide.
Embodiment 3
With PrMg
3Alloy is mechanical disintegration to 70 order under the hydrogen atmosphere protection, takes by weighing an amount of powder and is loaded in the hydrogenation reactor, and 350 ℃, 4 MPa hydrogen pressures are insulation 1 h down, it is transformed generate PrH
3And MgH
2, naturally cool to room temperature, under the argon gas atmosphere protection, take out.Under the argon gas atmosphere protection, adding particle diameter in the Magnuminium powder after hydrogenation is 100 purpose MoS
2Powder, 5:1 mixes by mass ratio, and mixed powder is placed ball grinder; Ball milling under the hydrogen atmosphere protection, ball matter is stainless steel, ball mill is the Pulverisette6 planetary ball mill; The rotating speed of ball grinder is 500 r/min, and ball material mass ratio is 31:1, and the quiescent interval is 30 min; The ball milling time is 2 h, treats to naturally cool to room temperature after ball milling finishes, and under argon gas atmosphere, encapsulates.The magnesium based hydrogen storing alloy composite material of ball milling preparation is carried out the hydrogen-absorption speed test, and its result is as shown in Figure 3, and the hydrogen-absorption speed curve from figure can find out that matrix material of the present invention 30 s under 150 ℃ can reach 90 % of maximum hydrogen, and does not add MoS
2PrMg
390 % that alloy reaches maximum hydrogen need 70 s.This shows that the matrix material hydrogen-absorption speed for preparing behind metallic sulfide provided by the invention and the Mg base hydrogen bearing alloy high-energy ball milling will obviously be superior to not adding the Mg base hydrogen bearing alloy of metallic sulfide.
Embodiment 4
With LaMg
3Alloy is mechanical disintegration to 100 order under the hydrogen atmosphere protection, takes by weighing an amount of powder and is loaded in the hydrogenation reactor, and 350 ℃, 3 MPa hydrogen pressures are insulation 1 h down, it is transformed generate LaH
3And MgH
2, naturally cool to room temperature, under the argon gas atmosphere protection, take out.Under the argon gas atmosphere protection, adding particle diameter in the Magnuminium powder after hydrogenation is 100 purpose CoS powder, and 10:3 mixes by mass ratio, and mixed powder is placed ball grinder; Ball milling under the hydrogen atmosphere protection, ball matter is stainless steel, ball mill is the Pulverisette6 planetary ball mill; The rotating speed of ball grinder is 500 r/min, and ball material mass ratio is 31:1, and the quiescent interval is 15 min; The ball milling time is 2 h, treats to naturally cool to room temperature after ball milling finishes, and under argon gas atmosphere, encapsulates.The magnesium based hydrogen storing alloy composite material of ball milling preparation is carried out the DSC test, and its result is as shown in Figure 4, and the DSC curve from figure can find out that matrix material of the present invention gets final product dehydrogenation when 524.95 K, and does not add the LaMg of CoS
3Alloy need just begin dehydrogenation when 627.05 K.This shows that the matrix material initial dehydrogenated temperature for preparing behind metallic sulfide provided by the invention and the Mg base hydrogen bearing alloy high-energy ball milling will be starkly lower than the Mg base hydrogen bearing alloy that does not add metallic sulfide.
Embodiment 5
With NdMg
3Alloy is mechanical disintegration to 40 order under the hydrogen atmosphere protection, takes by weighing an amount of powder and is loaded in the hydrogenation reactor, and 350 ℃, 4 MPa hydrogen pressures are insulation 1 h down, it is transformed generate NdH
3And MgH
2, naturally cool to room temperature, under the argon gas atmosphere protection, take out.Under the argon gas atmosphere protection, adding particle diameter in the Magnuminium powder after hydrogenation is 100 purpose MoS
2Powder, 5:1 mixes by mass ratio, and mixed powder is placed ball grinder; Ball milling under the hydrogen atmosphere protection, ball matter is stainless steel, ball mill is the Pulverisette6 planetary ball mill; The rotating speed of ball grinder is 500 r/min, and ball material mass ratio is 33:1, and the quiescent interval is 15 min; The ball milling time is 2 h, treats to naturally cool to room temperature after ball milling finishes, and under argon gas atmosphere, encapsulates.The magnesium based hydrogen storing alloy composite material of ball milling preparation is carried out the DSC test, and its result is as shown in Figure 5, and the DSC curve from figure can be found out, to NdMg
3Add MoS in the alloy
2The composite for hydrogen storage for preparing behind the ball milling gets final product dehydrogenation when 640.55 K, and NdMg
3Alloy need just begin dehydrogenation when 658.85 K.This shows that the matrix material initial dehydrogenated temperature for preparing behind metallic sulfide provided by the invention and the Mg base hydrogen bearing alloy high-energy ball milling will be starkly lower than the Mg base hydrogen bearing alloy that does not add metallic sulfide.
Embodiment 6
With La
2Mg
17Alloy is mechanical disintegration to 100 order under the hydrogen atmosphere protection, takes by weighing an amount of powder and is loaded in the hydrogenation reactor, and 300 ℃, 4 MPa hydrogen pressures are insulation 1 h down, it is transformed generate LaH
3And MgH
2, naturally cool to room temperature, under the argon gas atmosphere protection, take out.Under the argon gas atmosphere protection, adding particle diameter in the Magnuminium powder after hydrogenation is 200 purpose CoS
2Powder, 10:3 mixes by mass ratio, and mixed powder is placed ball grinder; Ball milling under the hydrogen atmosphere protection, ball matter is stainless steel, ball mill is the Pulverisette6 planetary ball mill; The rotating speed of ball grinder is 500 r/min, and ball material mass ratio is 33:1, and the quiescent interval is 15 min; The ball milling time is 2 h, treats to naturally cool to room temperature after ball milling finishes, and under argon gas atmosphere, encapsulates.The magnesium based hydrogen storing alloy composite material of ball milling preparation is carried out the test of hydrogen discharging rate, and its result is as shown in Figure 6, and the hydrogen discharging rate curve from figure under 350 ℃ can be learnt, to La
2Mg
17Add CoS in the alloy
2The matrix material for preparing behind the ball milling can reach 80 % of maximum hydrogen desorption capacity when 160 s, and does not add CoS
2La
2Mg
17When reaching 80 % of maximum hydrogen desorption capacity, alloy needs 200 s.This shows that the matrix material hydrogen discharging rate for preparing behind metallic sulfide provided by the invention and the Mg base hydrogen bearing alloy high-energy ball milling will obviously be superior to not adding the Mg base hydrogen bearing alloy of metallic sulfide.
Embodiment 7
With Ce
2Mg
17Alloy is mechanical disintegration to 40 order under the hydrogen atmosphere protection, takes by weighing an amount of powder and is loaded in the hydrogenation reactor, and 300 ℃, 3 MPa hydrogen pressures are insulation 1 h down, it is transformed generate CeH
3And MgH
2, naturally cool to room temperature, under the argon gas atmosphere protection, take out.Under the argon gas atmosphere protection, adding particle diameter in the Magnuminium powder after hydrogenation is 200 purpose CoS
2Powder, 10:3 mixes by mass ratio, and the powder after mixing places ball grinder; Ball milling under the hydrogen atmosphere protection, ball matter is stainless steel, ball mill is the Pulverisette6 planetary ball mill; The rotating speed of ball grinder is 500 r/min, and ball material mass ratio is 31:1, and the quiescent interval is 15 min; The ball milling time is 2 h, treats to naturally cool to room temperature after ball milling finishes, and under argon gas atmosphere, encapsulates.The magnesium based hydrogen storing alloy composite material of ball milling preparation is carried out the DSC test, and its result is as shown in Figure 7, and the DSC thermal analysis curve from figure can be known, to Ce
2Mg
17Add CoS in the alloy
2The matrix material for preparing behind the ball milling gets final product dehydrogenation when 594.99 K, and Ce
2Mg
17Alloy need just begin dehydrogenation when 610.44 K.This shows that the matrix material initial dehydrogenated temperature for preparing behind metallic sulfide provided by the invention and the Mg base hydrogen bearing alloy high-energy ball milling will be starkly lower than the Mg base hydrogen bearing alloy that does not add metallic sulfide.
With Pr
2Mg
17Alloy is mechanical disintegration to 100 order under the hydrogen atmosphere protection, takes by weighing an amount of powder and is loaded in the hydrogenation reactor, and 350 ℃, 3 MPa hydrogen pressures are insulation 1 h down, it is transformed generate PrH
3And MgH
2, naturally cool to room temperature, under the argon gas atmosphere protection, take out.Under the argon gas atmosphere protection, adding particle diameter in the Magnuminium powder after hydrogenation is 100 purpose MoS
2Powder, 5:1 mixes by mass ratio, and mixed powder is placed ball grinder; Ball milling under the hydrogen atmosphere protection, ball matter is stainless steel, ball mill is the Pulverisette6 planetary ball mill; The rotating speed of ball grinder is 500 r/min, and ball material mass ratio is 29:1, and the quiescent interval is 15 min; The ball milling time is 2 h, treats to naturally cool to room temperature after ball milling finishes, and under argon gas atmosphere, encapsulates.The magnesium based hydrogen storing alloy composite material of ball milling preparation is carried out the hydrogen-absorption speed test, and its result is as shown in Figure 8, and 350 ℃ of following hydrogen-absorption speed curves can be known from figure, to Pr
2Mg
17Add MoS in the alloy
2The composite for hydrogen storage for preparing behind the ball milling can reach 80 % of maximum storage hydrogen quantity at 40 s, and Pr
2Mg
17Alloy then needs just can reach at 65 s 80 % of maximum storage hydrogen quantity.This shows that the matrix material storage hydrogen speed for preparing behind metallic sulfide provided by the invention and the Mg base hydrogen bearing alloy high-energy ball milling is apparently higher than the Mg base hydrogen bearing alloy that does not add metallic sulfide.
Embodiment 9
With Nd
2Mg
17Alloy is mechanical disintegration to 40 order under the hydrogen atmosphere protection, takes by weighing an amount of powder and is loaded in the hydrogenation reactor, and 350 ℃, 4 MPa hydrogen pressures are insulation 1 h down, it is transformed generate NdH
3And MgH
2, naturally cool to room temperature, under the argon gas atmosphere protection, take out.。Under the argon gas atmosphere protection, adding particle diameter in the Magnuminium powder after hydrogenation is 200 purpose CoS
2Powder, 5:1 mixes by mass ratio, and mixed powder is placed ball grinder; Ball milling under the hydrogen atmosphere protection, ball matter is stainless steel, ball mill is the Pulverisette6 planetary ball mill; The rotating speed of ball grinder is 500 r/min, and ball material mass ratio is 31:1, and the quiescent interval is 15 min; The ball milling time is 2 h, treats to naturally cool to room temperature after ball milling finishes, and under argon gas atmosphere, encapsulates.The magnesium based hydrogen storing alloy composite material of ball milling preparation is carried out the hydrogen discharging rate test, and its result is as shown in Figure 9, from figure, transfers the hydrogen rate curve and can know for 300 ℃, to Nd
2Mg
17Add CoS in the alloy
2The composite for hydrogen storage for preparing behind the ball milling can reach 80 % of maximum hydrogen desorption capacity when 206 s, and Nd
2Mg
17Alloy need just can reach 80 % of maximum hydrogen desorption capacity when 245 s.This shows that the matrix material hydrogen discharging speed for preparing behind metallic sulfide provided by the invention and the Mg base hydrogen bearing alloy high-energy ball milling is apparently higher than the Mg base hydrogen bearing alloy that does not add metallic sulfide.
Claims (2)
1. magnesium based hydrogen storing alloy composite material that adds metallic sulfide is characterized in that: this matrix material is made up of Mg base hydrogen bearing alloy and the metallic sulfide that is its quality 10 ~ 30 %, and described Mg base hydrogen bearing alloy is Mg, REMg
3Or RE
2Mg
17RE=La wherein, Ce, Pr, Nd, metallic sulfide are MoS
2, CoS
2, a kind of among the CoS.
2. the preparation method of the magnesium based hydrogen storing alloy composite material of the described interpolation metallic sulfide of claim 1 is characterized in that:
(1) with Mg base hydrogen bearing alloy under argon gas atmosphere protection mechanical disintegration to the 40-100 order; Taking by weighing an amount of above-mentioned powdered alloy is loaded in the hydrogenation reactor; Insulation 1 h naturally cools to room temperature under 300 ~ 400 ℃ and 3 ~ 4 MPa hydrogen pressures, in argon gas atmosphere protection taking-up down;
(2) in the Magnuminium after hydrogenation under the argon gas atmosphere protection, adding particle diameter is that 100 ~ 200 orders, mass percent are the metallic sulfide powder of 10 ~ 30 %, is placed in the ball grinder, and ball material mass ratio is 29 ~ 33:1; Under the hydrogen atmosphere protection, carry out ball milling, rotating speed is 450 ~ 550 r/min, and the quiescent interval is 5 ~ 30m; The ball milling time is 1 ~ 3 h; Naturally cool to room temperature behind the ball milling, under argon gas atmosphere, encapsulate, obtain magnesium based hydrogen storing alloy composite material.
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| CN103159171A (en) * | 2013-03-08 | 2013-06-19 | 燕山大学 | LiBH4-doped metal sulfide hydrogen-storage composite material and preparation method thereof |
| CN103359687A (en) * | 2013-06-25 | 2013-10-23 | 燕山大学 | Magnesium hydride (MgH2) and ferrum-containing sulfide composite hydrogen storage material and preparation method thereof |
| CN103741004A (en) * | 2014-01-28 | 2014-04-23 | 内蒙古科技大学 | CoS2-catalyzed high-capacity hydrogen storage alloy and preparation method thereof |
| CN105895884A (en) * | 2016-06-13 | 2016-08-24 | 吉林大学 | Method for surface modification on hydrogen storage alloy by molybdenum disulfide, and application thereof |
| CN107338380A (en) * | 2017-07-04 | 2017-11-10 | 内蒙古科技大学 | Fuel cell high capacity hydrogen storage alloy and preparation method thereof |
| CN113802040A (en) * | 2021-09-15 | 2021-12-17 | 广东省国研科技研究中心有限公司 | Magnesium-lanthanum hydrogen storage alloy 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 |
| CN115159452A (en) * | 2022-08-19 | 2022-10-11 | 上海大学 | Bimetal sulfide composite magnesium-based hydrogen storage material and preparation method thereof |
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| CN113802040A (en) * | 2021-09-15 | 2021-12-17 | 广东省国研科技研究中心有限公司 | Magnesium-lanthanum hydrogen storage alloy and preparation method thereof |
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| CN115159452A (en) * | 2022-08-19 | 2022-10-11 | 上海大学 | Bimetal sulfide composite magnesium-based hydrogen storage material and preparation method thereof |
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