CN111533086A - Short-process preparation method for rapidly activating hydrogen storage alloy by using hydrogen-containing compound - Google Patents
Short-process preparation method for rapidly activating hydrogen storage alloy by using hydrogen-containing compound Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 182
- 239000001257 hydrogen Substances 0.000 title claims abstract description 177
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 177
- 239000000956 alloy Substances 0.000 title claims abstract description 93
- 238000003860 storage Methods 0.000 title claims abstract description 87
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 title claims abstract description 16
- 230000003213 activating effect Effects 0.000 title claims abstract description 13
- 238000001994 activation Methods 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 31
- 239000006104 solid solution Substances 0.000 claims abstract description 18
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 14
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 14
- 229910052987 metal hydride Inorganic materials 0.000 claims abstract description 12
- 150000004681 metal hydrides Chemical group 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 7
- 229910004688 Ti-V Inorganic materials 0.000 claims abstract description 4
- 229910010968 Ti—V Inorganic materials 0.000 claims abstract description 4
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 239000011777 magnesium Substances 0.000 claims abstract description 4
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 44
- 238000000498 ball milling Methods 0.000 claims description 34
- 230000004913 activation Effects 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims description 7
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 7
- 229910052772 Samarium Inorganic materials 0.000 claims description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 229910012375 magnesium hydride Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 claims description 4
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000000713 high-energy ball milling Methods 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- -1 titanium hydride Chemical compound 0.000 claims description 3
- 229910000048 titanium hydride Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000047 yttrium hydride Inorganic materials 0.000 claims description 3
- 239000011232 storage material Substances 0.000 abstract description 21
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000007787 solid Substances 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 description 25
- 229910052751 metal Inorganic materials 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 14
- 238000005303 weighing Methods 0.000 description 14
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 13
- 238000003723 Smelting Methods 0.000 description 12
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000012300 argon atmosphere Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 238000000137 annealing Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
- C01B3/0047—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof
- C01B3/0057—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof also containing nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
-
- 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
- Y02E60/32—Hydrogen storage
Abstract
The invention provides a short-process preparation method for rapidly activating a hydrogen storage alloy by using a hydrogen-containing compound, and relates to the field of hydrogen storage materials. The method comprises the following steps: putting the hydrogen storage alloy material and the active assistant into a container, and uniformly mixing in a reaction atmosphere to obtain an activated hydrogen storage alloy material; the hydrogen storage alloy material is selected from rare earth ABXType, titanium-iron AB type, titanium-zirconium AB type2Type, magnesium system A2One or more of B-type and Ti-V solid solution type hydrogen storage alloy powder; the active assistant is metal hydride. The hydrogen storage material prepared by the method not only completes the activation process, but also can absorb and release hydrogen without high-temperature or high-pressure activation process, thereby improving the production efficiency, reducing the production cost and simultaneously keeping the original hydrogen storage capacity; the method of the invention is simple and rapid,High efficiency, is particularly suitable for the activation process of the solid hydrogen storage material for the low-pressure hydrogen station, and has important practical value for applying the hydrogen storage alloy material to hydrogen energy engineering.
Description
Technical Field
The invention relates to the field of hydrogen storage materials, in particular to a short-process preparation method for rapidly activating a hydrogen storage alloy by using a hydrogen-containing compound.
Background
Since the century, hydrogen energy has received wide attention due to its clean combustion products and high calorific value. However, hydrogen fuel systems have not been well established due to the many technological challenges in hydrogen production, storage and use. Especially, the construction of hydrogen energy infrastructure becomes one of the key factors restricting the development of the hydrogen energy industry. For example, the construction of the hydrogen station, it is clearly indicated in the national strategic planning of China that 1000 hydrogen stations are expected to be built by 2030. The hydrogen station which is built and put into use mostly adopts the high-pressure hydrogen storage technology, and the problems of limited hydrogenation capacity, higher construction cost, service life of a dynamic hydrogen compressor, maintenance and the like are faced in domestic market popularization.
The solid hydrogen storage alloy is a material for storing hydrogen into a solid material to realize hydrogen storage, has the advantages of high volume hydrogen storage density, good safety, reduced energy consumption, capability of obtaining ultra-high-purity hydrogen and the like compared with high-pressure gaseous and low-temperature liquid hydrogen storage methods, and is more suitable to be used as a medium material of a hydrogen storage pool in a hydrogen filling station. However, in the process of hydrogen absorption, hydrogen molecules are firstly adsorbed on the surface of the hydrogen storage material and then dissociated into hydrogen atoms, and then the hydrogen atoms enter crystal lattices of the hydrogen storage alloy to form hydrides, so that the solid hydrogen storage alloy is activated before use so as to ensure that the hydrogen absorption and desorption performance of the hydrogen storage alloy is optimal. The activation process varies with the composition of the alloy material, and is mainly divided into: activating under vacuum or repeatedly absorbing and releasing hydrogen under high pressure and high temperature at low temperature. However, these activation methods are less effective. For example, ferrotitanium hydrogen storage alloys require long-term inoculation and activation at high temperature for several hours to tens of hours before the alloy material can absorb hydrogen. The rare earth hydrogen storage material is usually pretreated and activated by heat treatment during the production process, but secondary activation of hydrogenation is generally required after heat treatment. At present, the method of doping and replacing transition metal elements (V, Cr, Mn, Nb, Zr and the like) or rare earth metal elements (Ce, Pr, Nd, Sm, Ho and the like) is generally adopted for improving the activation performance of the hydrogen storage alloy. No patent publication or article reports on a method for activating hydrogen storage alloy powder by using metal hydride as an auxiliary agent are found.
For a low-pressure hydrogen station, the required hydrogen storage alloy material can reach over ten thousand tons, and the activation process is a key technology which needs to be mainly solved for popularization. When pure hydrogen is used for activation, the activation process, whether occurring in the hydrogen storage device or during the production process of the hydrogen storage material, will substantially increase the overall cost of the hydrogen storage material and the hydrogen storage device, and the overall requirements for the hydrogen storage device during the activation process will also become complex. For example, if the apparatus is large, the heat and mass transfer diffusions can be affected during activation; if the device is designed to be too small, the device is limited by complex connection when the hydrogenation station is used in a large scale. Therefore, the invention provides a simple, quick and effective method for activating the hydrogen storage alloy, which is very important for the large-scale application of the hydrogen storage alloy material in hydrogen energy engineering.
Disclosure of Invention
The invention aims to provide a short-flow preparation method for rapidly activating hydrogen storage alloy by using a hydrogen-containing compound. The method is simple, rapid and effective to improve the activation performance of the hydrogen storage material, so that the hydrogen storage material can directly meet the requirements of practical application.
In order to achieve the purpose, the invention can adopt the following technical scheme:
a short-process preparation method for rapidly activating hydrogen storage alloy by using hydrogen-containing compound, which comprises the following steps:
putting the hydrogen storage alloy material and the active assistant into a container, and uniformly mixing in a reaction atmosphere to obtain an activated hydrogen storage alloy material;
the hydrogen storage alloy material is selected from rare earth ABXType, titanium-iron AB type, titanium-zirconium AB type2Type, magnesium system A2One or more of B-type and Ti-V solid solution type hydrogen storage alloy powder;
the active assistant is metal hydride.
Preferably, the metal hydride is selected from one or a mixture of more than two of lithium hydride, magnesium hydride, aluminum hydride, titanium hydride and yttrium hydride.
Preferably, the coagent is present in an amount of (0.1 to 15)% by mass of the host material.
Preferably, the hydrogen absorbing alloy powder has an average particle size of 100 to 300 μm.
Preferably, the rare earth system AB isXThe model comprises:
RENix-a-bMaMnbAl0.1wherein RE is one or more elements of La, Ce, Pr, Nd, Sm and Gd; m is one or more elements of Cu, Fe and Co; x is more than or equal to 5 and more than or equal to 4.5, a is more than or equal to 1.0 and more than or equal to 0.1, b is more than or equal to 1.0 and more than or equal to 0.1, and a + b is more than 0 at 1.5 and more than or equal to 0;
or RExYyNiz-a-bMnaAlbWherein RE is one or more elements of La, Ce, Pr, Nd, Sm and Gd; x is more than 0, y is more than or equal to 0.5, and x + y is 3; z is more than or equal to 12.5 and more than or equal to 8.5, and a + b is more than or equal to 3.5 and more than 0; a is more than or equal to 2.0 and more than or equal to 0.5, and b is more than or equal to 1.0 and more than or equal to 0.3.
Preferably, the titanium vanadium solid solution type includes:
TiV2-xMnx，1.4≥x≥0.6；
or VxTiyCrzMvM is one or more elements of Mn, Fe, Zr, Si and Al; x + y + z + v is 100, x is more than or equal to 50 and more than or equal to 15, y is more than or equal to 40 and more than or equal to 20, z is more than or equal to 40 and more than or equal to 20, y/z is more than or equal to 1.0 and more than or equal to 0.7, and v is more than or equal to 15 and more than or equal to 1.
Preferably, the hydrogen storage alloy material is TiV1.1Mn0.9Materials, LaY2Ni9.7Mn0.5Al0.3Materials or La0. 6Ce0.4Ni3.45Co0.75Mn0.7Al0.1A material.
Preferably, the uniform mixing mode is selected from one of high energy ball milling, planetary ball milling, mechanical stirring, crushing and grinding.
Preferably, the weight ratio of the ball material is (0.5-50): 1; the ball milling time is 10-300 min; the vibration frequency of the ball milling tank is 100-1500 rpm.
Preferably, the reaction atmosphere is one or a mixture of two or more of hydrogen, helium, neon and argon.
The invention has the advantages of
The invention provides a short-flow preparation method for rapidly activating hydrogen storage alloy by using a hydrogen-containing compound, which takes metal hydride as an activating auxiliary agent and can rapidly and effectively activate the hydrogen storage alloy material by uniform mixing; the hydrogen storage material prepared by the method not only completes the activation process, but also can absorb and release hydrogen without high-temperature or high-pressure activation process, thereby improving the production efficiency, reducing the production cost and simultaneously keeping the original hydrogen storage capacity; the metal hydride is used as an active assistant, on one hand, the hydrogen in an atomic state is used for deactivating the hydrogen storage alloy, and on the other hand, the metal remained on the surface after the hydrogen is released also has the function of heat conduction. The method is simple, quick and efficient, is particularly suitable for the activation process of the solid hydrogen storage material for the low-pressure hydrogen station, and has important practical value for applying the hydrogen storage alloy material to hydrogen energy engineering.
Drawings
FIG. 1 is a graph of the first hydrogen absorption kinetic activation performance of the titanium vanadium solid solution systems of examples 1 and 2 and comparative example 1 of the present invention;
FIG. 2 is a rare earth AB of example 3 of the present invention and comparative examples 2 and 33.5A first hydrogen absorption kinetic activation performance diagram of the system;
FIG. 3 shows rare earth AB of example 4 and comparative examples 4 and 5 of the present invention5The first hydrogen absorption kinetic activation performance of the system is shown.
Detailed Description
A short-process preparation method for rapidly activating hydrogen storage alloy by using hydrogen-containing compound, which comprises the following steps:
putting the hydrogen storage alloy material and the active assistant into a container, and uniformly mixing in a reaction atmosphere to obtain an activated hydrogen storage alloy material;
according to the invention, the hydrogen storage alloy material is selected from the rare earth series ABXType, titanium-iron AB type, titanium-zirconium AB type2Type, magnesium system A2One or more of B-type and Ti-V solid solution type hydrogen storage alloy powder;
the rare earth system ABXThe type preferably includes:
RENix-a-bMaMnbAl0.1wherein RE is one or more elements of La, Ce, Pr, Nd, Sm and Gd; m is one or more elements of Cu, Fe and Co; x is more than or equal to 5 and more than or equal to 4.5, a is more than or equal to 1.0 and more than or equal to 0.1, b is more than or equal to 1.0 and more than or equal to 0.1, and a + b is more than 0 at 1.5 and more than or equal to 0;
or RExYyNiz-a-bMnaAlbWherein RE is one or more elements of La, Ce, Pr, Nd, Sm and Gd; x is more than 0, y is more than or equal to 0.5, and x + y is 3; z is more than or equal to 12.5 and more than or equal to 8.5, and a + b is more than or equal to 3.5 and more than 0; a is more than or equal to 2.0 and more than or equal to 0.5, and b is more than or equal to 1.0 and more than or equal to 0.3.
More preferably LaY2Ni9.7Mn0.5Al0.3Materials or La0.6Ce0.4Ni3.45Co0.75Mn0.7Al0.1A material;
the titanium vanadium solid solution type preferably comprises:
TiV2-xMnx，1.4≥x≥0.6；
or VxTiyCrzMvM is one or more elements of Mn, Fe, Zr, Si and Al; x + y + z + v is 100, x is more than or equal to 50 and more than or equal to 15, y is more than or equal to 40 and more than or equal to 20, z is more than or equal to 40 and more than or equal to 20, y/z is more than or equal to 1.0 and more than or equal to 0.7, and v is more than or equal to 15 and more than or equal to 1.
More preferably TiV1.1Mn0.9A material;
the average particle size of the hydrogen storage alloy powder is preferably 100-300 μm. The hydrogen storage alloy material is prepared by adopting a conventional method in the field.
According to the invention, the coagent is a metal hydride, preferably one or a mixture of more than two of lithium hydride, magnesium hydride, aluminum hydride, titanium hydride or yttrium hydride, more preferably lithium hydride, magnesium hydride or aluminum hydride; the invention adopts metal hydride as the active assistant, on one hand, atomic hydrogen is utilized to deactivate the hydrogen storage alloy, and on the other hand, the metal left after hydrogen is released also has the function of heat conduction.
According to the invention, the active assistant accounts for (0.1-15)%, more preferably (1-8)%, of the mass of the main material.
According to the present invention, the manner of the uniform mixing is not particularly limited, and is preferably one selected from the group consisting of high energy ball milling, planetary ball milling, mechanical stirring, pulverization, and grinding. The weight ratio of the ball material is preferably (0.5-50): 1; the ball milling time is preferably 10-300 min; the vibration frequency of the ball milling tank is preferably 100-1500 rpm.
According to the invention, the reaction atmosphere is preferably one or a mixture of more than two of hydrogen, helium, neon and argon.
The present invention will be described in further detail with reference to examples for further understanding of the present invention, but the present invention is not limited to these examples.
Example 1 a titanium vanadium solid solution system was prepared as follows:
(1) vacuumizing the vacuum arc melting furnace to 2 × 10-3After Pa, 0.5 atmosphere of high-purity argon gas with the purity of 99.99 percent (volume percentage) is filled as protective gas, and Ti metal (the purity is 99.7 percent), V metal (the purity is 99.9 percent) and Mn metal (the purity is 99.5 percent) are mixed according to TiV1.1Mn0.9And (3) smelting in a vacuum arc furnace after chemical formula weighing, wherein the arc current is 300A, the smelting is carried out for 4 times, each time of smelting is 2min, naturally cooling and discharging are carried out to obtain an alloy ingot, and the alloy ingot is crushed to 50-150 mu m to obtain hydrogen storage alloy powder to be activated.
(2) Accurately weighing the TiV obtained in the step (1) according to the weight percentage1.1Mn0.95g of powder material and 0.15g of commercially available aluminum trihydride material,and (3) putting the mixture into a stainless steel ball milling tank in a glove box filled with high-purity argon atmosphere, wherein the ball-material ratio is 5: 1, the diameter of a steel ball is 4mm, the vibration frequency is 800 rpm, the ball milling time is 15min, the ball milling tank is taken down from the ball mill, the ball milling tank is opened in the air to obtain the titanium-vanadium solid solution hydrogen storage material, and the titanium-vanadium solid solution hydrogen storage material is sealed and placed in a dryer for storage.
The hydrogen storage alloy material powder prepared in example 1 was charged into a reactor, vacuum-pumped at 25 ℃ for 30 minutes, and then charged with high-purity hydrogen gas having a purity of 99.99% (volume percentage) at 4MPa at 25 ℃ to measure hydrogen absorption kinetics. The hydrogen absorption kinetics curve at 25 ℃ is obtained as shown in FIG. 1 (wherein the abscissa is time in minutes and the ordinate is the amount of hydrogen absorbed in mass percent).
Example 2 a titanium vanadium solid solution system was prepared as follows:
1) vacuumizing the vacuum arc melting furnace to 2 × 10-3After Pa, 0.5 atmosphere of high-purity argon gas with the purity of 99.99 percent (volume percentage) is filled as protective gas, and Ti metal (the purity is 99.7 percent), V metal (the purity is 99.9 percent) and Mn metal (the purity is 99.5 percent) are mixed according to TiV1.1Mn0.9And (3) smelting in a vacuum arc furnace after chemical formula weighing, wherein the arc current is 300A, the smelting is carried out for 4 times, each time of smelting is 2min, naturally cooling and discharging are carried out to obtain an alloy ingot, and the alloy ingot is crushed to 50-150 mu m to obtain hydrogen storage alloy powder to be activated.
(2) Accurately weighing the TiV obtained in the step (1) according to the weight percentage1.1Mn0.95g of material powder and 0.40g of commercially available aluminum trihydride material were charged into a stainless steel ball mill jar in a glove box filled with a high purity argon atmosphere, at a ball-to-material ratio of 8: 1, the diameter of a steel ball is 4mm, the vibration frequency is 800 rpm, the ball milling time is 15min, the ball milling tank is taken down from the ball mill, the titanium-vanadium solid solution hydrogen storage material of the ball milling tank is opened in the air, and the ball milling tank is sealed and placed in a dryer for storage.
The hydrogen storage alloy material powder prepared in example 2 was charged into a reactor, and vacuum was applied at 25 ℃ for 30 minutes, and then hydrogen absorption kinetic properties were measured by charging high-purity hydrogen gas having a purity of 99.99% (volume percentage) at 4MPa into the reactor at 25 ℃. The hydrogen absorption kinetics curve at 25 ℃ is obtained as shown in FIG. 1.
Comparative example 1
In order to further verify the activation performance of the above hydrogen storage alloy, a blank sample without adding a metal hydride material was also prepared for comparison.
Weighing TiV of the same batch1.1Mn0.95g of material powder, and placing the material powder into a stainless steel ball milling tank in a glove box filled with high-purity argon atmosphere, wherein the diameter of a steel ball is 4mm, and the ball-material ratio is 5: 1, vibration frequency is 800 r/m, ball milling time is 15min, the ball milling tank is taken down from the ball mill, the ball milling tank is opened in the air to obtain the titanium-vanadium solid solution hydrogen storage material, and the titanium-vanadium solid solution hydrogen storage material is sealed and placed in a dryer for storage.
The titanium vanadium solid solution hydrogen storage material prepared in the comparative example 1 is vacuumized for 30 minutes at 25 ℃, and then high-purity hydrogen with purity of 99.99% (volume percentage) and 4MPa is filled into a reactor at 25 ℃ to measure the hydrogen absorption kinetic performance. The hydrogen absorption kinetics curve at 25 ℃ is obtained as shown in FIG. 1.
Example 3 preparation of rare earth AB3.5The preparation method of the system comprises the following steps:
(1) vacuumizing the vacuum arc melting furnace to 2 × 10-3After Pa, 0.5 atmosphere of high-purity argon gas with the purity of 99.99% (volume percentage) was filled as a protective gas, and La metal (the purity of 99.9%), Y metal (the purity of 99.9%), Ni metal (the purity of 99.9%), Mn metal (the purity of 99.5%) and Al metal (the purity of 99.5%) were LaY% respectively2Ni9.7Mn0.5Al0.3And (3) smelting in a vacuum arc furnace after chemical formula weighing, wherein the arc current is 300A, the smelting is carried out for 4 times, each time of smelting is 2min, naturally cooling and discharging are carried out to obtain an alloy ingot, and the alloy ingot is crushed to 50-150 mu m to obtain hydrogen storage alloy powder to be activated.
(2) Respectively and precisely weighing LaY obtained in the step (1) according to weight percentage2Ni9.7Mn0.5Al0.35g of the material powder and 0.05g of a commercially available aluminum trihydride material were charged into a stainless steel ball mill jar in a glove box filled with a high-purity argon atmosphere, at a ball-to-material ratio of 5: 1, the diameter of the steel ball is 4mm, and the vibration frequency is 800 turnsAnd (3) performing ball milling for 15min, taking the ball milling tank down from the ball mill, opening the ball milling tank in the air to obtain the material to be tested, and sealing and placing the material in a dryer for storage.
The hydrogen storage alloy material powder prepared in example 3 was charged into a reactor, and vacuum was applied at 25 ℃ for 30 minutes, and then hydrogen absorption kinetic properties were measured by charging high-purity hydrogen gas having a purity of 99.99% (volume percentage) at 4MPa into the reactor at 25 ℃. The hydrogen absorption kinetics curve at 25 ℃ is shown in FIG. 2 (wherein the abscissa is time (in minutes) and the ordinate is the amount of hydrogen absorbed (in mass percent)).
Comparative example 2
In order to further verify the activation performance of the hydrogen storage alloy, LaY which is subjected to annealing treatment is prepared2Ni9.7Mn0.5Al0.3The alloy was activated at 70 ℃ for comparison.
Weighing same batch LaY2Ni9.7Mn0.5Al0.320g of alloy ingot, annealing for 6 hours at 800 ℃, crushing the alloy ingot to 50-150 mu m to obtain hydrogen storage alloy powder, sealing and storing in a dryer.
The hydrogen absorbing alloy powder prepared in comparative example 2 was evacuated at 70 ℃ for 30 minutes, and then high-purity hydrogen gas having a purity of 99.99% (volume percentage) under 4MPa was charged into the reactor at 70 ℃ to conduct hydrogen absorption kinetic property measurement. The hydrogen absorption kinetics curve at 70 ℃ is shown in FIG. 2.
Comparative example 3
In order to further verify the activation performance of the hydrogen storage alloy, LaY which is subjected to annealing treatment is prepared2Ni9.7Mn0.5Al0.3The alloy was activated at 25 ℃ for comparison.
Weighing same batch LaY2Ni9.7Mn0.5Al0.320g of alloy ingot, annealing for 6 hours at 800 ℃, crushing the alloy ingot to 50-150 mu m, weighing 5g of hydrogen storage alloy powder, putting the hydrogen storage alloy powder into a stainless steel ball-milling tank in a glove box filled with high-purity argon atmosphere, wherein the diameter of a steel ball is 4mm, and the ball-to-material ratio is 5: 1, vibration ofThe frequency is 800 r/min, the ball milling time is 15min, the ball milling tank is taken down from the ball mill, the material to be tested is opened in the air, and the material is sealed and placed in a dryer for storage.
The hydrogen absorbing alloy material prepared in comparative example 3 was evacuated at 25 ℃ for 30 minutes, and then high-purity hydrogen gas having a purity of 99.99% (volume percentage) under 4MPa was charged into the reactor at 25 ℃ to conduct hydrogen absorption kinetic property measurement. The kinetics of hydrogen absorption at 25 ℃ are shown in FIG. 2.
Example 4 preparation of rare earth AB5The preparation method of the system comprises the following steps:
(1) vacuumizing the vacuum arc melting furnace to 2 × 10-3After Pa, 0.5 atmosphere of high-purity argon with the purity of 99.999 percent (volume percent) is filled as protective gas, and La metal (the purity of 99.9 percent), Ce metal (the purity of 99.9 percent), Ni metal (the purity of 99.9 percent), Co metal (the purity of 99.9 percent), Mn metal (the purity of 99.5 percent) and Al metal (the purity of 99.5 percent) are added according to the La0.6Ce0.4Ni3.45Co0.75Mn0.7Al0.1And (3) smelting in a vacuum arc furnace after chemical formula weighing, wherein the arc current is 300A, the smelting is carried out for 4 times, each time of smelting is 2min, naturally cooling and discharging are carried out to obtain an alloy ingot, and the alloy ingot is crushed to 50-150 mu m to obtain hydrogen storage alloy powder to be activated.
(2) Accurately weighing the La obtained in the step (1) according to the weight percentage0.6Ce0.4Ni3.45Co0.75Mn0.7Al0.15g of material powder and 0.10g of commercially available magnesium hydride material were put into a stainless steel ball mill jar in a glove box filled with a high purity argon atmosphere, and the ball-to-material ratio was 5: 1, the diameter of a steel ball is 4mm, the vibration frequency is 800 rpm, the ball milling time is 15min, the ball milling tank is taken down from the ball mill, the ball milling tank is opened in the air to obtain a material to be detected, and the material to be detected is sealed and placed in a dryer for storage.
The hydrogen storage alloy material powder prepared in example 4 was charged into a reactor, vacuum-pumped at 25 ℃ for 30 minutes, and then hydrogen absorption kinetic properties were measured by charging high-purity hydrogen gas having a purity of 99.99% (volume percentage) at 4MPa into the reactor at 25 ℃. The hydrogen absorption kinetics at 25 ℃ are shown in FIG. 3 (wherein the abscissa is time in minutes and the ordinate is the amount of hydrogen absorbed in mass percent).
Comparative example 4
In order to further verify the activation performance of the hydrogen storage alloy, La subjected to annealing treatment is prepared at the same time0.6Ce0.4Ni3.45Co0.75Mn0.7Al0.1The alloy was activated at 25 ℃ for comparison.
Weighing the same batch of La0.6Ce0.4Ni3.45Co0.75Mn0.7Al0.120g of alloy ingot, annealing for 4 hours at 600 ℃, crushing the alloy ingot to 50-150 mu m to obtain hydrogen storage alloy powder, sealing and storing in a dryer.
The hydrogen absorbing alloy powder prepared in comparative example 4 was evacuated at 25 ℃ for 30 minutes, and then high-purity hydrogen gas having a purity of 99.99% (volume percentage) under 4MPa was charged into the reactor at 25 ℃ to conduct hydrogen absorption kinetic property measurement. The kinetics of hydrogen absorption at 25 ℃ are shown in FIG. 3.
Comparative example 5
In order to further verify the activation performance of the above hydrogen storage alloy, a blank sample without adding a metal hydride material was also prepared for comparison.
Weighing the same batch of La0.6Ce0.4Ni3.45Co0.75Mn0.7Al0.15g of material powder, and placing the material powder into a stainless steel ball milling tank in a glove box filled with high-purity argon atmosphere, wherein the diameter of a steel ball is 4mm, and the ball-material ratio is 5: 1, vibration frequency is 800 r/m, ball milling time is 15min, the ball milling tank is taken down from the ball mill, the ball milling tank is opened in the air to obtain the titanium-vanadium solid solution hydrogen storage material, and the titanium-vanadium solid solution hydrogen storage material is sealed and placed in a dryer for storage.
The hydrogen absorbing alloy powder prepared in comparative example 5 was evacuated at 25 ℃ for 30 minutes, and then high-purity hydrogen gas having a purity of 99.99% (volume percentage) under 4MPa was charged into the reactor at 25 ℃ to conduct hydrogen absorption kinetic property measurement. The kinetics of hydrogen absorption at 25 ℃ are shown in FIG. 3.
Table 1 shows the activation performance of inventive examples 1, 2, 3, 4 compared to comparative examples 1, 2, 3, 4, 5 with a hydrogen absorption time of 10 minutes as a cut-off point. As can be seen from Table 1, the hydrogen storage material system treated by the method of the invention can achieve larger hydrogen absorption capacity in a shorter time when absorbing hydrogen for the first time under the condition of 25 ℃, and has excellent activation performance.
TABLE 1
Claims (10)
1. A short-process preparation method for rapidly activating hydrogen storage alloy by using hydrogen-containing compound is characterized by comprising the following steps:
putting the hydrogen storage alloy material and the active assistant into a container, and uniformly mixing in a reaction atmosphere to obtain an activated hydrogen storage alloy material;
the hydrogen storage alloy material is selected from rare earth ABXType, titanium-iron AB type, titanium-zirconium AB type2Type, magnesium system A2One or more of B-type and Ti-V solid solution type hydrogen storage alloy powder;
the active assistant is metal hydride.
2. The short-process preparation method of a hydrogen storage alloy using hydrogen containing compound for rapid activation as claimed in claim 1, wherein the metal hydride is selected from one or a mixture of two or more of lithium hydride, magnesium hydride, aluminum hydride, titanium hydride and yttrium hydride.
3. The short-process preparation method of hydrogen storage alloy by rapid activation with hydrogen-containing compound as claimed in claim 1, wherein the mass of the active assistant is 0.1-15% of the mass of the main material.
4. The short-process preparation method of hydrogen storage alloy by using hydrogen-containing compound for rapid activation according to claim 1, wherein the average particle size of the hydrogen storage alloy powder is 100 to 300 μm.
5. The method according to claim 1, wherein the rare earth AB is a rare earth metalXThe model comprises:
RENix-a-bMaMnbAl0.1wherein RE is one or more elements of La, Ce, Pr, Nd, Sm and Gd; m is one or more elements of Cu, Fe and Co; x is more than or equal to 5 and more than or equal to 4.5, a is more than or equal to 1.0 and more than or equal to 0.1, b is more than or equal to 1.0 and more than or equal to 0.1, and a + b is more than 0 at 1.5 and more than or equal to 0;
or RExYyNiz-a-bMnaAlbWherein RE is one or more elements of La, Ce, Pr, Nd, Sm and Gd; x is more than 0, y is more than or equal to 0.5, and x + y is 3; z is more than or equal to 12.5 and more than or equal to 8.5, and a + b is more than or equal to 3.5 and more than 0; a is more than or equal to 2.0 and more than or equal to 0.5, and b is more than or equal to 1.0 and more than or equal to 0.3.
6. The short-run method of claim 1, wherein the ti-v solid solution type comprises:
TiV2-xMnx，1.4≥x≥0.6；
or VxTiyCrzMvM is one or more elements of Mn, Fe, Zr, Si and Al; x + y + z + v is 100, x is more than or equal to 50 and more than or equal to 15, y is more than or equal to 40 and more than or equal to 20, z is more than or equal to 40 and more than or equal to 20, y/z is more than or equal to 1.0 and more than or equal to 0.7, and v is more than or equal to 15 and more than or equal to 1.
7. The short-process preparation method of hydrogen storage alloy by using hydrogen-containing compound for rapid activation according to claim 1, wherein the hydrogen storage alloy material is TiV1.1Mn0.9Materials, LaY2Ni9.7Mn0.5Al0.3Materials or La0.6Ce0.4Ni3.45Co0.75Mn0.7Al0.1A material.
8. The short-process preparation method of hydrogen storage alloy by rapid activation with hydrogen-containing compound according to claim 1, wherein the uniform mixing is selected from one of high energy ball milling, planetary ball milling, mechanical stirring, crushing and grinding.
9. The short-process preparation method of hydrogen storage alloy by using hydrogen-containing compound for rapid activation according to claim 1, wherein the weight ratio of the ball material is (0.5-50): 1; the ball milling time is 10-300 min; the vibration frequency of the ball milling tank is 100-1500 rpm.
10. The short-process preparation method of hydrogen storage alloy by using hydrogen-containing compound for rapid activation as claimed in claim 1, wherein the reaction atmosphere is one or more of hydrogen, helium, neon and argon.
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