CN115780811A - Method for reducing hydrogen release temperature of aluminum hydride by using hydrogen storage alloy - Google Patents
Method for reducing hydrogen release temperature of aluminum hydride by using hydrogen storage alloy Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 213
- 239000001257 hydrogen Substances 0.000 title claims abstract description 211
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 211
- 238000003860 storage Methods 0.000 title claims abstract description 87
- 239000000956 alloy Substances 0.000 title claims abstract description 65
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 33
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 34
- 239000011232 storage material Substances 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 18
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical group [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000006104 solid solution Substances 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 14
- SPRIOUNJHPCKPV-UHFFFAOYSA-N hydridoaluminium Chemical compound [AlH] SPRIOUNJHPCKPV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910010084 LiAlH4 Inorganic materials 0.000 claims abstract description 10
- 239000012280 lithium aluminium hydride Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims description 32
- 229910010082 LiAlH Inorganic materials 0.000 claims description 24
- 238000003795 desorption Methods 0.000 claims description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000000713 high-energy ball milling Methods 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000002829 reductive effect Effects 0.000 abstract description 4
- 239000000446 fuel Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 2
- 239000011651 chromium Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000000523 sample Substances 0.000 description 10
- 238000003723 Smelting Methods 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 229910052845 zircon Inorganic materials 0.000 description 8
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 8
- 238000005303 weighing Methods 0.000 description 7
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- 229910052723 transition metal Inorganic materials 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
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- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
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- 238000005265 energy consumption Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
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- 229910052761 rare earth metal Inorganic materials 0.000 description 2
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- 150000002910 rare earth metals Chemical class 0.000 description 1
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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
- Y02E60/32—Hydrogen storage
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Abstract
The invention relates to the technical field of hydrogen storage materials, in particular to a method for reducing the hydrogen release temperature of an alanate by utilizing a hydrogen storage alloy, which comprises the steps of putting the alanate and a promoter into a container, and uniformly mixing in a reaction atmosphere to obtain a composite hydrogen storage material; the aluminum hydride comprises at least one of LiAlH4, li3AlH6, mg (AlH 4) 2, ca (AlH 4) 2, caAlH5, na3AlH6, KAlH4, naAlH4 or AlH 3; the active assistant is titanium-vanadium solid solution type hydrogen storage alloy powder. The hydrogen releasing temperature of the alanate material prepared by the method is reduced, the production efficiency is improved, the production cost is reduced, and the original 90% hydrogen storage capacity is kept; the method is simple, quick and efficient, is particularly suitable for utilizing the high specific energy alanate material in the fields of fuel cell vehicles, aerospace, portable power supplies and the like, and has important practical value for the application of the alanate in the field of hydrogen energy.
Description
Technical Field
The invention relates to the technical field of hydrogen storage materials, in particular to a method for reducing the hydrogen release temperature of an alanate by utilizing a hydrogen storage alloy.
Background
The prior hydrogen storage and transportation modes mainly comprise three modes of high-pressure gaseous hydrogen storage, liquid hydrogen storage and metal solid hydrogen storage, the high-pressure gaseous hydrogen storage is a mode with higher technical maturity, the hydrogen in China is mainly transported by a high-pressure steel cylinder with the pressure of 15-35MPa in a long distance, the steel cylinder needs a certain thickness to ensure the strength for ensuring the high safety, the quality of the high-pressure steel cylinder is about 100kg, and 0.5kg of hydrogen can be stored, so that the quality hydrogen storage density and the volume hydrogen storage density of the high-pressure steel cylinder are respectively about 0.5wt.% and 10kg/m 3 . Obviously, the hydrogen storage density is low and cannot meet the requirement of high-density energy storage, the hydrogen can be liquefied below-252.7 ℃, the mass energy density and the volume energy density of the liquid hydrogen are respectively about 120MJ/kg and 10MJ/L, the liquid hydrogen has significant advantages in terms of hydrogen storage density, but the energy consumed by liquefying the hydrogen is about 40% of the combustion value of the hydrogen, and the maintenance of the liquid hydrogen also needs extremely low temperature and special containers, which undoubtedly increases the energy consumption and the cost, so a novel efficient, safe and reliable hydrogen storage mode needs to be found in order to meet the requirement of hydrogen energy as portable energy.
The solid hydrogen storage alloy is realized by storing hydrogen into a solid materialCompared with high-pressure gaseous and low-temperature liquid hydrogen storage methods, the material for storing hydrogen has the advantages of high volume hydrogen storage density, good safety, energy consumption reduction, capability of obtaining ultrahigh-purity hydrogen and the like, and the existing hydrogen storage alloy with mature technology mainly contains rare earth AB 5 Type hydrogen storage alloy (1.5 wt.%), AB 2 Type Hydrogen storage alloy (1.8-2.4 wt.%), A 2 B 7 Type hydrogen storage alloy (1.8 wt.%), type AB hydrogen storage alloy (1.8 wt.%), and V-based solid solution alloy (3 wt.%), but even the V-based solid solution with the largest theoretical hydrogen storage capacity is still far below the applicable standard and costs are generally higher, compared to alanate, which has significant advantages in that it has high theoretical hydrogen storage capacity, naAlH 4 The mass hydrogen storage density reaches 7.5wt.%, liAlH 4 Mass hydrogen storage density up to 10.6wt.%; alH 3 Theoretical maximum hydrogen storage up to 10.1wt.%; the hydrogen releasing process of the alanate can be carried out under normal pressure without high-pressure environment; hydrogen is released through chemical reaction, and the purity of the product is high; at about 200 deg.C, naAlH 4 And LiAlH 4 Hydrogen can be released at 5.5wt.% and 7.0wt.%, respectively, while alpha-AlH 3 Most hydrogen gas (-9 wt.%) can be evolved by heating to about 160 ℃ at atmospheric pressure, which is an ideal solid-state hydrogen storage material.
The high hydrogen storage capacity is really attractive, but the large-scale application of the alanate is limited by the higher hydrogen release temperature and the limited cycle performance, and the current researches show that materials such as transition metal elements, rare earth oxides and the like can be used as catalysts to reduce the hydrogen release temperature of the alanate. The hydrogen storage alloy contains a large amount of transition metal elements and rare earth elements, such as LaNi 5 For example, the following steps are carried out: alH 3 Doped LaNi 5 The apparent activation energy of the composite material is pure AlH 3 30-40% lower, and the enthalpy change value is about 5.1kJ/mol H 2 It can be seen that LaNi 5 Is an effective dehydrogenation catalyst, and the modified material provides a promising solution for the commercial application of the fuel cell, so that the interaction between the hydrogen storage alloy and the aluminum hydride can be utilized to improve the hydrogen discharge condition and the cycle performance of the aluminum hydride, thereby realizing the high-efficiency reversible storage of hydrogen.
Disclosure of Invention
The invention aims to provide a method for reducing the hydrogen desorption temperature of an alanate by utilizing a hydrogen storage alloy, and the composite hydrogen storage material has high hydrogen storage capacity and low hydrogen desorption temperature, thereby successfully solving the application problems of high hydrogen desorption temperature and difficult reversible hydrogen storage of the alanate.
The above object of the present invention is achieved by the following technical solutions:
a method for reducing the hydrogen release temperature of an alanate by using a hydrogen storage alloy comprises the steps of putting the alanate and a promoter into a container, and uniformly mixing in a reaction atmosphere to obtain a composite hydrogen storage material;
the aluminum hydride comprises at least one of LiAlH4, li3AlH6, mg (AlH 4) 2, ca (AlH 4) 2, caAlH5, na3AlH6, KAlH4, naAlH4 or AlH 3;
the active assistant is titanium-vanadium solid solution type hydrogen storage alloy powder.
The invention is further configured to: the titanium vanadium solid solution type hydrogen storage alloy powder includes:
TiV2-xMnx，1.4≥x≥0.6；
TiV2-x-yCrxMny，1.4≥x+y≥0.6；
or Tix-uVyCrzMnvReu, re is one or more elements of La, ce, pr, nd, sm and Gd; x + y + z + v + u =100, 50 is more than or equal to x and more than or equal to 15, 40 is more than or equal to y and more than or equal to 20, 40 is more than or equal to z is more than or equal to 20,1.0 is more than or equal to y/z is more than or equal to 0.7, 15 is more than or equal to v is more than or equal to 1,10 is more than or equal to u and more than or equal to 3.
The invention is further configured to: the active auxiliary agent accounts for (0.1-15)% of the mass of the main material.
The invention is further configured to: the average particle size of the titanium-vanadium solid solution type hydrogen storage alloy powder is 100-300 mu m.
The invention is further configured to: the composite hydrogen storage material consists of LiAlH4 and TiV1.1-Cr0.3Mn0.6, and the expression of the composite hydrogen storage material is xwt.% LiAlH4+ (100-x) wt.% TiV1.1Cr0.3Mn0.6, wherein x represents the mass percent of LiAlH4 in the composite hydrogen storage material and is 1 x 100.
The invention is further configured to: the value range of x is 75-90.
The invention is further configured to: the rotating speed of the ball mill is 300-500rpm, and the ball milling time is 30-300min.
The invention is further configured to: the uniform mixing mode is selected from one of high-energy ball milling, planetary ball milling, mechanical stirring, crushing and grinding, and the ball-to-material ratio in the ball milling process is (10-50): 1.
The invention is further configured to: the atmosphere of the reaction atmosphere is one or more than two of nitrogen, argon and hydrogen.
In conclusion, the beneficial technical effects of the invention are as follows:
1. the invention utilizes the hydrogen storage alloy as the additive has the advantages that the hydrogen storage alloy can be used as an independent hydrogen storage system, the reduction of the hydrogen storage capacity caused by the introduction of the catalyst can not be brought, and compared with the catalysts of transition metal elements, rare earth oxides and the like, the hydrogen storage alloy can be provided with a hydrogen source after the hydrogen release of the alanate, and the hydrogen storage alloy can perform an autonomous hydrogen absorption and release process, thereby improving the effective reversible hydrogen storage capacity of the alanate.
2. The metal in the hydrogen storage alloy also has a thermally conductive effect, and the interaction between the two reduces the initial temperature of the aluminum-based material for an efficient hydrogen discharge process to about 100 ℃ and provides some improvement in the reversibility of the aluminum-based material.
3. Meanwhile, the invention provides a research idea of the interactive catalysis and provides guidance for the synthesis and preparation of the similar materials. The invention adopts a mechanical ball milling method to synthesize the composite material, has easy control of the process and simple and convenient conditions, and is suitable for large-scale production and application.
Drawings
FIG. 1 is a hydrogen absorption and desorption cycle curve measured in a hydrogen atmosphere at 150 ℃ and 4MPa after the composite hydrogen storage material of the present invention is completely dehydrogenated;
Detailed Description
The present invention will be described in further detail with reference to examples.
The invention discloses a method for reducing the hydrogen release temperature of an alanate by using a hydrogen storage alloy, which comprises the steps of putting the alanate and a promoter into a container, and uniformly mixing in a reaction atmosphere to obtain a composite hydrogen storage material;
the aluminum hydride comprises at least one of LiAlH4, li3AlH6, mg (AlH 4) 2, ca (AlH 4) 2, caAlH5, na3AlH6, KAlH4, naAlH4 or AlH 3;
the active assistant is titanium-vanadium solid solution type hydrogen storage alloy powder.
The titanium vanadium solid solution type hydrogen storage alloy powder includes:
TiV2-xMnx，1.4≥x≥0.6；
TiV2-x-yCrxMny，1.4≥x+y≥0.6；
or Tix-uVyCrzMnvReu, re is one or more elements of La, ce, pr, nd, sm and Gd; x + y + z + v + u =100, 50. Gtoreq.x.gtoreq.15, 40. Gtoreq.y.gtoreq.20, 40. Gtoreq.z.gtoreq. 20,1.0. Gtoreq.y/z.gtoreq.0.7, 15. Gtoreq.v.gtoreq. 1,10. Gtoreq.u.3, in the present embodiment, more preferably TiV 1.1 Cr 0.3 Mn 0.6 A material.
The active assistant accounts for 0.1-15% of the mass of the main material. In this embodiment, (1 to 8)%.
The average particle size of the titanium-vanadium solid solution type hydrogen storage alloy powder is 100-300 mu m.
The composite hydrogen storage material is composed of LiAlH4 and TiV1.1-Cr0.3Mn0.6, and the expression of the composite hydrogen storage material is xwt.% LiAlH4+ (100-x) wt.% TiV1.1Cr0.3Mn0.6, wherein x represents the mass percent of LiAlH4 in the composite hydrogen storage material and is formed by 1 x-100, in the embodiment, the value range of x is more preferably 75-90, and the most preferably value of x is 85.
The rotating speed of the ball mill is 300-500rpm, the ball milling time is 30-300min, and in the embodiment, the rotating speed is more preferably 300-400rpm; the ball milling time is preferably 30-300min, more preferably 60-90min.
The uniform mixing mode is selected from one of high-energy ball milling, planetary ball milling, mechanical stirring, crushing and grinding, the ball-to-material ratio in the ball milling process is (10-50): 1, and in the embodiment, the uniform mixing mode is more preferably 300-400rpm; the ball milling time is preferably 30-300min, more preferably 60-90min.
The atmosphere of the reaction atmosphere is one or more than two of nitrogen, argon and hydrogen.
Example 1
A method for reducing the hydrogen desorption temperature of alanate by using hydrogen storage alloy to prepare a composite hydrogen storage material, wherein the expression of the composite hydrogen storage material is 85wt.% LiAlH 4 +15wt.％TiV 1.1 Cr 0.3 Mn 0.6 The preparation method comprises the following steps:
firstly, preparing a titanium-vanadium solid solution alloy, wherein the preparation method comprises the following steps: (1) Vacuumizing the vacuum arc melting furnace to 2 x 10 - 3 After 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 of 99.7 percent), V metal (the purity of 99.9 percent), mn metal (the purity of 99.5 percent) and chromium metal (the purity of 99.9 percent) are mixed according to TiV 1.1 -Cr 0.3 Mn 0.6 Weighing the chemical formula, putting the alloy into a vacuum arc furnace for smelting for 4 times with arc current of 300A, smelting for 2min each time, naturally cooling and discharging to obtain an alloy ingot, and crushing the alloy ingot to 50-150 mu m to obtain the titanium-vanadium hydrogen storage alloy powder.
(2) Accurately weighing the TiV obtained in the step (1) according to the weight percentage 1.1 Cr 0.3 Mn 0.6 0.09g of the material powder and LiAlH commercially available 4 0.51g of material, and 0.6g of total mass. And (2) putting the mixture into a ball milling tank in a glove box filled with high-purity argon atmosphere, wherein the ball-material ratio is 20:1, adding zircon balls (the total mass is 18 g), selecting zircon balls with large, medium and small sizes, the diameters of which are 6mm, 4mm and 2mm respectively, the rotating speed of the ball mill is 400rpm, and the ball milling time is 60min, taking the ball milling tank down from the ball mill, opening the ball milling tank in an argon atmosphere to obtain the composite hydrogen storage material, sealing and storing in a dryer.
In order to evaluate the hydrogen storage performance of the prepared composite hydrogen storage material, a temperature programmed desorption test is carried out on a product after ball milling, the corresponding hydrogen release amount is calibrated, the initial temperature is 25 ℃, the temperature rise rate is 1 ℃/min, and the 85wt.% LiAlH after ball milling is known 4 +15wt.％TiV 1.1 Cr 0.3 Mn 0.6 The initial hydrogen release temperature of the composite hydrogen storage material is 109 ℃, and the hydrogen release amount can reach 8.7wt.%. With untreated commercial LiAlH 4 Sample (initial hydrogen release temperature 190 deg.C)(ii) a Hydrogen gas with 0.04 percent of total hydrogen content is discharged in 30min at 100 ℃, and hydrogen gas with 0.09 percent of total hydrogen content is discharged in 60 min) is reduced by 61 ℃ and the reduction range is 43 percent. Releasing hydrogen with the total hydrogen content of 91.3 percent at 100 ℃ for 30min and 99.3 percent at 60min, compared with untreated LiAlH 4 The sample had a two to three order of magnitude improvement.
Example 2
A method for reducing the hydrogen desorption temperature of alanate by using hydrogen storage alloy to prepare a composite hydrogen storage material, wherein the expression of the composite hydrogen storage material is 75wt.% LiAlH 4 +25wt.％TiV 1.1 Cr 0.3 Mn 0.6 The preparation method comprises the following steps:
firstly, preparing a titanium-vanadium solid solution alloy, wherein the preparation method comprises the following steps: (1) Vacuumizing the vacuum arc melting furnace to 2 x 10 - 3 After 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 of 99.7 percent), V metal (the purity of 99.9 percent), mn metal (the purity of 99.5 percent) and chromium metal (the purity of 99.9 percent) are mixed according to TiV 1.1 -Cr 0.3 Mn 0.6 Weighing the chemical formula, putting the alloy into a vacuum arc furnace for smelting, wherein the arc current is 300A, smelting for 4 times, smelting for 2min each time, naturally cooling and discharging to obtain an alloy ingot, and crushing the alloy ingot to 50-150 mu m to obtain the titanium-vanadium hydrogen storage alloy powder.
(2) Accurately weighing the TiV obtained in the step (1) according to weight percentage 1.1 Cr 0.3 Mn 0.6 0.15g of the material powder and LiAlH commercially available 4 0.45g of material, and 0.6g of total mass. And (2) putting the mixture into a ball milling tank in a glove box filled with high-purity argon atmosphere, wherein the ball-material ratio is 20:1 (total mass is 18 g), selecting zircon balls with three sizes of large, medium and small, the diameters of which are 6mm, 4mm and 2mm respectively, the rotating speed of the ball mill is 400rpm, and the ball milling time is 60min, taking down the ball milling tank from the ball mill, opening the ball milling tank in an argon atmosphere to obtain the composite hydrogen storage material, sealing and placing in a dryer for storage.
In order to evaluate the hydrogen storage performance of the prepared composite hydrogen storage material, a temperature programming desorption test is carried out on the product after ball milling, and the corresponding hydrogen release amount is calibratedThe initial temperature is 25 ℃, the heating rate is 1 ℃/min, and analysis shows that 75wt.% LiAlH is obtained after ball milling 4 +25wt.％TiV 1.1 Cr 0.3 Mn 0.6 The initial hydrogen release temperature of the composite hydrogen storage material is 109 ℃, and the hydrogen release amount can reach 8.7wt.%. With untreated commercial LiAlH 4 Compared with the sample (initial hydrogen release temperature 140 ℃, hydrogen gas with 0.04 percent of total hydrogen content is released at 100 ℃ for 30min, and hydrogen gas with 0.09 percent of total hydrogen content is released at 60 min), the hydrogen release temperature is reduced by 61 ℃ and the reduction range is 43 percent. Releasing hydrogen with the total hydrogen content of 91.3 percent at 100 ℃ for 30min and 99.3 percent at 60min, compared with untreated LiAlH 4 The sample had a two to three order of magnitude improvement.
Example 3
A composite hydrogen storage material was prepared having the expression 90wt.% LiAlH 4 +10wt.％TiV 1.1 Cr 0.3 Mn 0.6 The preparation method comprises the following steps:
firstly, preparing a titanium-vanadium solid solution alloy, wherein the preparation method comprises the following steps: (1) Vacuumizing the vacuum arc melting furnace to 2 x 10 - 3 After 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 of 99.7 percent), V metal (the purity of 99.9 percent), mn metal (the purity of 99.5 percent) and chromium metal (the purity of 99.9 percent) are mixed according to TiV 1.1 -Cr 0.3 Mn 0.6 Weighing the chemical formula, putting the alloy into a vacuum arc furnace for smelting, wherein the arc current is 300A, smelting for 4 times, smelting for 2min each time, naturally cooling and discharging to obtain an alloy ingot, and crushing the alloy ingot to 50-150 mu m to obtain the titanium-vanadium hydrogen storage alloy powder.
(2) Accurately weighing the TiV obtained in the step (1) according to the weight percentage 1.1 Cr 0.3 Mn 0.6 0.1g of the material powder and LiAlH commercially available 4 0.5g of material, and 0.6g of total mass. And (2) putting the mixture into a ball milling tank in a glove box filled with high-purity argon atmosphere, wherein the ball-material ratio is 20:1, adding zircon balls (the total mass is 18 g), selecting zircon balls with large, medium and small sizes, the diameters of which are 6mm, 4mm and 2mm respectively, the rotating speed of the ball mill is 400rpm, the ball milling time is 60min, taking down the ball milling tank from the ball mill, and opening the ball milling tank in an argon atmosphere to obtain the zircon ballAnd adding the composite hydrogen storage material, sealing and storing in a dryer.
In order to evaluate the reversible hydrogen storage performance of the prepared composite hydrogen storage material, a hydrogen absorption and desorption cycle test was performed on the ball-milled product of the following example 1: reacting 0.1g of composite hydrogen storage material at 150 ℃ for 2h until no gas is generated, and pumping the generated gas by using a vacuum pump until the pressure in a sample tube is lower than 10 -4 Mpa. And (3) continuously placing the sample tube filled with the sample after complete hydrogen desorption in a constant temperature environment of 150 ℃, pumping high-purity hydrogen into the sample tube until the pressure in the sample tube is 4.0Mpa, repeating the experimental steps for 5 times, wherein the experimental result is shown in figure 1, the composite material reaches the maximum capacity in the second circle, and the effective hydrogen storage capacity is 3.64wt.%. Reversibility of the product compared to commercial AlH 3 The reversible hydrogen absorption amount is lower than the detection limit, and the phenomenon that the hydrogen releasing process of the alanate is irreversible is improved.
Comparative example 1
As a comparative sample, a commercially available elemental aluminum hydride hydrogen storage material was tested and had the chemical formula LiAlH 4 。
To evaluate LiAlH 4 Hydrogen storage performance of (2) for commercial LiAlH 4 And carrying out a temperature programmed desorption test and calibrating the corresponding hydrogen release amount. Analysis revealed commercially available LiAlH 4 The initial hydrogen evolution temperature of (1) was 190 ℃, the initial hydrogen evolution temperature of the second step was 250 ℃, and the total hydrogen evolution was 7.1wt.%. Hydrogen with the total hydrogen content of 0.04 percent is discharged at 100 ℃ for 30min, and hydrogen with the total hydrogen content of 0.09 percent is discharged at 60 min.
Comparative example 2
In order to further verify the hydrogen storage performance of the composite material, a blank sample without adding a titanium-vanadium alloy material is prepared at the same time for comparison.
Weighing LiAlH of the same batch 4 And (3) 0.6g of material powder, putting the material powder into a ball milling tank in a glove box filled with high-purity argon atmosphere, and mixing the materials according to a ball-to-material ratio of 20:1, adding zircon balls (the total mass is 18 g), selecting zircon balls with large, medium and small sizes, the diameters of which are 6mm, 4mm and 2mm respectively, the rotating speed of the ball mill is 400rpm, the ball milling time is 60min, taking the ball milling tank down from the ball mill, opening the ball milling tank in argon atmosphere to obtain the composite storage tankHydrogen material, sealing and storing in a drier.
To evaluate LiAlH 4 Hydrogen storage performance of (2) for commercial LiAlH 4 Carrying out temperature programmed desorption test, calibrating corresponding hydrogen release amount, and analyzing to obtain commercially available LiAlH 4 The initial hydrogen evolution temperature of (1) was 190 ℃, the initial hydrogen evolution temperature of the second step was 250 ℃, and the total hydrogen evolution was 7.1wt.%. Hydrogen with the total hydrogen content of 0.04 percent is discharged at 100 ℃ for 30min, and hydrogen with the total hydrogen content of 0.09 percent is discharged at 60 min.
The analysis of the above embodiments and comparative examples shows that the present invention provides a short-flow preparation method for reducing the hydrogen desorption temperature of alanate by using a hydrogen storage alloy, and the advantage of using a hydrogen storage alloy as an additive is that the hydrogen storage alloy can be used as an independent hydrogen storage system without reducing the hydrogen storage capacity caused by the introduction of a catalyst, and compared with catalysts such as transition metal elements, rare earth oxides, and the like, after the hydrogen desorption of alanate, the hydrogen source can be provided for the hydrogen storage alloy, so that the hydrogen storage alloy can undergo an autonomous hydrogen absorption and desorption process, thereby improving the effective reversible hydrogen storage capacity of alanate, and on the other hand, the metal in the hydrogen storage alloy also has a heat conduction function, and the interaction between the hydrogen storage alloy and the transition metal reduces the initial temperature of the effective hydrogen desorption process of aluminum-based materials to about 100 ℃ and improves the reversibility of the aluminum-based materials to some extent.
The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.
Claims (9)
1. A method for reducing the hydrogen release temperature of alanate by using hydrogen storage alloy is characterized in that: the method comprises the steps of putting aluminum hydride and a co-agent into a container, and uniformly mixing in a reaction atmosphere to obtain a composite hydrogen storage material;
the aluminum hydride comprises at least one of LiAlH4, li3AlH6, mg (AlH 4) 2, ca (AlH 4) 2, caAlH5, na3AlH6, KAlH4, naAlH4 or AlH 3;
the active assistant is titanium-vanadium solid solution type hydrogen storage alloy powder.
2. The method for lowering a hydrogen desorption temperature of an alanate using a hydrogen storage alloy as claimed in claim 1, wherein: the titanium vanadium solid solution type hydrogen storage alloy powder includes:
TiV2-xMnx，1.4≥x≥0.6；
TiV2-x-yCrxMny，1.4≥x+y≥0.6；
or Tix-uVyCrzMnvReu, re is one or more elements of La, ce, pr, nd, sm and Gd; x + y + z + v + u =100, 50 ≥ x ≥ 15, 40 ≥ y ≥ 20,
40≥z≥20，1.0≥y/z≥0.7，15≥v≥1,10≥u≥3。
3. a method for reducing the hydrogen desorption temperature of an alanate using a hydrogen storage alloy as claimed in claim 1, wherein: the active assistant accounts for 0.1-15% of the mass of the main material.
4. A method for reducing the hydrogen desorption temperature of an alanate using a hydrogen storage alloy as claimed in claim 1, wherein: the average particle size of the titanium-vanadium solid solution type hydrogen storage alloy powder is 100-300 mu m.
5. A method for reducing the hydrogen desorption temperature of an alanate using a hydrogen storage alloy as claimed in claim 1, wherein: the composite hydrogen storage material is made of LiAlH 4 And TiV 1.1- Cr 0.3 Mn 0.6 The composite hydrogen storage material has the expression of xwt.% LiAlH 4 +(100-x)wt.％TiV 1.1 Cr 0.3 Mn 0.6 Wherein x represents LiAlH in the composite hydrogen storage material 4 1 mass% of<x<100。
6. The method for lowering the hydrogen desorption temperature of an alanate using a hydrogen occluding alloy as recited in claim 5, wherein: the value range of x is 75-90.
7. A method for reducing the hydrogen desorption temperature of an alanate using a hydrogen storage alloy as claimed in claim 1, wherein: the rotating speed of the ball mill is 300-500rpm, and the ball milling time is 30-300min.
8. A method for reducing the hydrogen desorption temperature of an alanate using a hydrogen storage alloy as claimed in claim 1, wherein: the uniform mixing mode is selected from one of high-energy ball milling, planetary ball milling, mechanical stirring, crushing and grinding, and the ball-to-material ratio in the ball milling process is (10-50): 1.
9. A method for reducing the hydrogen desorption temperature of an alanate using a hydrogen storage alloy as claimed in claim 1, wherein: the atmosphere of the reaction atmosphere is one or more than two of nitrogen, argon and hydrogen.
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