CN103864012B - MgH 2-BiVO 4composite for hydrogen storage and preparation method thereof - Google Patents

MgH 2-BiVO 4composite for hydrogen storage and preparation method thereof Download PDF

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Publication number
CN103864012B
CN103864012B CN201410034027.2A CN201410034027A CN103864012B CN 103864012 B CN103864012 B CN 103864012B CN 201410034027 A CN201410034027 A CN 201410034027A CN 103864012 B CN103864012 B CN 103864012B
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bivo
mgh
hydrogen
ball milling
hydrogen storage
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CN103864012A (en
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张伟
沈娜
程颖
陈阳
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Yanshan University
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Yanshan University
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    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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Abstract

A kind of MgH 2-BiVO 4composite for hydrogen storage, it is by MgH 2with BiVO 4composition, wherein BiVO 4content accounts for 10 ~ 40% of matrix material total mass.The preparation method of above-mentioned composite for hydrogen storage is: in the glove box of argon shield, by MgH 2powder and BiVO 4be placed in ball grinder and carry out ball milling, ball material mass ratio is 15 ~ 35:1, and rotating speed is 450 ~ 550r/min; under the protection of 0.1 ~ 0.5MPa argon gas, ball milling 1 ~ 3h, every ball milling 20 ~ 45min; interval 15 ~ 25min, naturally cools to room temperature, obtains MgH after ball milling terminates 2-BiVO 4composite for hydrogen storage.At relatively low temperature, hydrogen-absorption speed and maximum hydrogen－sucking amount are than not adding BiVO for composite for hydrogen storage of the present invention 4mgH 2improve more than 1 times, preparation method is simple simultaneously, and preparation cost is low, is applicable to industrially scalable preparation.

Description

MgH 2-BiVO 4composite for hydrogen storage and preparation method thereof
Technical field
The present invention relates to a kind of composite for hydrogen storage and preparation method thereof.
Background technology
The energy is the basic substance of human survival and development, comprises expanding economy, the progress of society, and the development of science and technology, all be unable to do without the consumption of the energy.Along with energy-output ratio significantly increases, Sustainable Socioeconomic Development can not be met in the near future.Meanwhile, the water pollutions caused by traditional energy consumption, topsoil (Greenhouse effect) etc. create significant damage to human society and physical environment, not only make human habitat be deteriorated, and cause a large amount of animals and plants extinctions.Therefore, a kind of new energy is found quite crucial to meet human wants.Hydrogen Energy, as a kind of novel energy, has reserves are large, safety and environmental protection, energy per mass are high feature and receives and pay close attention to widely, but storing comparatively difficulty due to it, thus limiting the widespread use of its reality.In research for many years, a lot of scholar thinks that employing hydrogen storage material storage of hydrogen is safely and efficiently.At present because magnesium-base hydrogen storage material has that theoretical storage hydrogen richness is high, cheaper starting materials is easy to get, inhales/put the advantages such as hydrogen good cycle and receive and pay close attention to widely, but this hydrogen storage material also also exists weak point, as suction/hydrogen desorption kinetics performance is relatively poor and hydrogen discharging temperature is higher, if reach acceptable hydrogen discharging rate, hydrogen discharging temperature must more than 350 DEG C, thus limit magnesium-based hydride in the middle of reality widespread use.
In recent years, many investigators pass through to MgH 2in add additive and carry out high-energy ball milling to improve its kinetics and thermodynamic (al) performance.The patent No. is 200810164115.6 disclose a kind of Mg adding melting 17al 12and Ni has prepared Mg-Al-Ni matrix material by ball milling, although the kinetics of this patent improves effect comparatively obviously, preparation technology's more complicated, cost is also relatively high.Baricco, M., M.W.Rahman, etal.JournalofAlloysandCompounds.536, Supplement1 (0): S216-S221 then proposes to MgH 2middle interpolation BaRuO 3improve its performance by ball milling, but the hydrogen desorption capacity of this magnesium base composite material is relatively less, actual widespread use can not be met.
Summary of the invention
The object of the present invention is to provide that a kind of hydrogen storage property is good, preparation technology be simple, the MgH of easy handling 2-BiVO 4composite for hydrogen storage and preparation method thereof.
Composite for hydrogen storage of the present invention is by MgH 2with BiVO 4composition, wherein BiVO 4content accounts for 10 ~ 40% of matrix material total mass.Above raw materials market is on sale or (wherein synthesize BiVO according to document synthesis 4synthesized reference document JournalofAlloysandCompounds.581 (0): 40-45).
Above-mentioned MgH 2-BiVO 4the preparation method of composite for hydrogen storage is as follows:
In the glove box of argon shield, by MgH 2and BiVO 4the ball grinder being placed in planetary high-energy ball mill carries out ball milling; ball material mass ratio is 15 ~ 35:1; rotating speed is 450 ~ 550r/min; under the protection of 0.1 ~ 0.5MPa argon gas, ball milling 1 ~ 3h, every ball milling 20 ~ 45min; interval 15 ~ 25min; after ball milling terminates, naturally cool to room temperature, in the glove box of argon shield, take out this matrix material and encapsulate, obtaining MgH 2-BiVO 4matrix material.
The present invention compared with prior art tool has the following advantages:
1, composite for hydrogen storage of the present invention effectively improves MgH 2suction/hydrogen discharging performance, it is inhaled hydrogen discharging rate and is not added BiVO than under the same terms 4mgH 2improve more than 1 times.
2, the BiVO of the present invention's use 4be easy to synthesis, raw material is easy to get.
3, preparation method is simple, and easy to operate, energy consumption is few, and preparation cost is low, is easy to realize industrialization and popularization.
Accompanying drawing explanation
Fig. 1 is the MgH that the embodiment of the present invention 1 obtains 2-BiVO 4composite for hydrogen storage under 423K, 3MPa hydrogen pressure, with MgH 2hydrogen-absorption speed comparison diagram.
Fig. 2 is the MgH that the embodiment of the present invention 2 obtains 2-BiVO 4composite for hydrogen storage under 473K, 3MPa hydrogen pressure, with MgH 2hydrogen-absorption speed comparison diagram.
Fig. 3 is the MgH that the embodiment of the present invention 3 obtains 2-BiVO 4composite for hydrogen storage under 623K, 0.01MPa hydrogen pressure, with MgH 2hydrogen discharging rate comparison diagram.
Fig. 4 is the MgH that the embodiment of the present invention 4 obtains 2-BiVO 4composite for hydrogen storage under 573K, 0.01MPa hydrogen pressure, with MgH 2hydrogen discharging rate comparison diagram.
Embodiment:
Embodiment 1
In the glove box of argon shield, get 2.7gMgH 2and 0.3gBiVO 4mixing is placed in ball grinder; adopt Pulverisette6 planetary ball mill to carry out ball milling, put into Stainless Steel Ball 45g, rotating speed is 450r/min; the high-purity argon gas being filled with 0.1MPa carries out ball milling; Ball-milling Time is 1h, every ball milling 20min, interval 15min; after ball milling terminates, naturally cool to room temperature, encapsulate under the glove box of argon shield.By obtained MgH 2composite for hydrogen storage carries out hydrogen-absorption speed test, and its result as shown in Figure 1.From figure, under 423K, hydrogen-absorption speed curve is known, to MgH 2middle interpolation BiVO 4the composite for hydrogen storage prepared after ball milling is when about 400s, and hydrogen－sucking amount is simple MgH 23 times, and add BiVO 4maximum hydrogen－sucking amount and hydrogen-absorption speed have all had larger lifting afterwards.As can be seen here, BiVO provided by the invention 4with MgH 2its hydrogen-absorption speed of the composite for hydrogen storage prepared after high-energy ball milling will obviously be better than not adding BiVO 4mgH 2.
Embodiment 2
In the glove box of argon shield, get 2.4gMgH 2and 0.6gBiVO 4mixing is placed in ball grinder; adopt Pulverisette6 planetary ball mill to carry out ball milling, put into Stainless Steel Ball 60g, rotating speed is 500r/min; the high-purity argon gas being filled with 0.2MPa carries out ball milling; Ball-milling Time is 2h, every ball milling 30min, interval 20min; after ball milling terminates, naturally cool to room temperature, encapsulate under the glove box of argon shield.By obtained MgH 2composite for hydrogen storage carries out hydrogen-absorption speed test, and its result as shown in Figure 2.From figure, under 473K, hydrogen-absorption speed curve is known, to MgH 2middle interpolation BiVO 4the hydrogen-absorption speed of the composite for hydrogen storage prepared after ball milling will significantly be better than not adding BiVO 4mgH 2.In addition, when hydrogen－sucking amount reaches 2wt%, add BiVO 4the composite for hydrogen storage prepared after ball milling only needs 150s, and MgH 2need 1200s.As can be seen here, BiVO provided by the invention 4with MgH 2its hydrogen-absorption speed of the composite for hydrogen storage prepared after high-energy ball milling is obviously better than not adding BiVO 4mgH 2.
Embodiment 3
In the glove box of argon shield, get 2.1gMgH 2and 0.9gBiVO 4mixing is placed in ball grinder; adopt Pulverisette6 planetary ball mill to carry out ball milling, put into Stainless Steel Ball 75g, rotating speed is 500r/min; the high-purity argon gas being filled with 0.3MPa carries out ball milling; Ball-milling Time is 2h, every ball milling 30min, interval 20min; after ball milling terminates, naturally cool to room temperature, encapsulate under the glove box of argon shield.By obtained MgH 2composite for hydrogen storage carries out hydrogen discharging rate test, and its result as shown in Figure 3.From figure, to transfer hydrogen rate curve known for 573K, to MgH 2middle interpolation BiVO 4the composite for hydrogen storage hydrogen discharging rate prepared after ball milling and hydrogen desorption capacity have had and have significantly promoted, the MgH when 700s 2-BiVO 4matrix material hydrogen desorption capacity can reach 1.00w.t%, and does not add BiVO 4mgH 2hydrogen desorption capacity is only 0.11wt.%.As can be seen here, BiVO provided by the invention 4with MgH 2its hydrogen discharging rate of the composite for hydrogen storage prepared after high-energy ball milling will obviously be better than not adding BiVO 4mgH 2.
Embodiment 4
In the glove box of argon shield, get 1.8gMgH 2and 1.2gBiVO 4mixing is placed in ball grinder; adopt Pulverisette6 planetary ball mill to carry out ball milling, put into Stainless Steel Ball 105g, rotating speed is 550r/min; the high-purity argon gas being filled with 0.5MPa carries out ball milling; Ball-milling Time is 3h, every ball milling 45min, interval 25min; after ball milling terminates, naturally cool to room temperature, encapsulate under the glove box of argon shield.By obtained MgH 2composite for hydrogen storage carries out hydrogen discharging rate test, and its result as shown in Figure 4.From figure, to transfer hydrogen rate curve known for 623K, to MgH 2middle interpolation BiVO 4the composite for hydrogen storage prepared after ball milling hydrogen desorption capacity when 400s can reach 3.13wt.%, and simple MgH 2be only 0.94wt.%.In addition, BiVO is added 4after, the maximum hydrogen desorption capacity of matrix material there has also been very large raising.As can be seen here, BiVO provided by the invention 4with MgH 2its hydrogen-absorption speed of the composite for hydrogen storage prepared after high-energy ball milling will obviously be better than not adding BiVO 4mgH 2.

Claims (1)

1. a MgH 2-BiVO 4the preparation method of composite for hydrogen storage, this matrix material is by MgH 2with BiVO 4composition, wherein BiVO 4content accounts for 10 ~ 40% of matrix material total mass, it is characterized in that: in the glove box of argon shield, by MgH 2and BiVO 4the ball grinder being placed in planetary high-energy ball mill carries out ball milling; ball material mass ratio is 15 ~ 35:1; rotating speed is 450 ~ 550r/min; under the protection of 0.1 ~ 0.5MPa argon gas, ball milling 1 ~ 3h, every ball milling 20 ~ 45min; interval 15 ~ 25min; after ball milling terminates, naturally cool to room temperature, in the glove box of argon shield, take out this matrix material and encapsulate, obtaining MgH 2-BiVO 4composite for hydrogen storage.
CN201410034027.2A 2014-01-23 2014-01-23 MgH 2-BiVO 4composite for hydrogen storage and preparation method thereof Expired - Fee Related CN103864012B (en)

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CN104692322B (en) * 2015-03-13 2017-01-11 桂林电子科技大学 K2TiF6 doped Mg/PMMA composite material and preparation method thereof
CN108467064A (en) * 2018-06-11 2018-08-31 佛山腾鲤新能源科技有限公司 A kind of preparation method of low temperature hydrogen release type composite for hydrogen storage

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006036553A2 (en) * 2004-09-23 2006-04-06 General Motors Corporation Methods of storing hydrogen in hydrogen storage systems
CN103157498A (en) * 2013-03-29 2013-06-19 黑龙江大学 Synthesis method of phosphoric acid bridged and compounded TiO2-BiVO4 nanometer photocatalyst

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006036553A2 (en) * 2004-09-23 2006-04-06 General Motors Corporation Methods of storing hydrogen in hydrogen storage systems
CN103157498A (en) * 2013-03-29 2013-06-19 黑龙江大学 Synthesis method of phosphoric acid bridged and compounded TiO2-BiVO4 nanometer photocatalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
纳米晶MgH2和MgH2基复合物粉末的水解制氢;胡连喜等;《2005全国粉末冶金学术及应用技术会议论文集》;20060529;第443-445页 *

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