CN111020302A - High-temperature hydrogen release metal composite material and preparation method thereof - Google Patents

High-temperature hydrogen release metal composite material and preparation method thereof Download PDF

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Publication number
CN111020302A
CN111020302A CN201911398405.4A CN201911398405A CN111020302A CN 111020302 A CN111020302 A CN 111020302A CN 201911398405 A CN201911398405 A CN 201911398405A CN 111020302 A CN111020302 A CN 111020302A
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China
Prior art keywords
hydrogen
hydrogen release
hydride
temperature
metal
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CN201911398405.4A
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Chinese (zh)
Inventor
马书旺
吕政�
王健
杨剑
杨志民
梁秋实
刘坤
甘斌
谭波
陈富财
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GRIMN Engineering Technology Research Institute Co Ltd
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GRIMN Engineering Technology Research Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
    • 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 discloses a high-temperature hydrogen release metal composite material and a preparation method thereof, belonging to the technical field of hydrogen storage materials. The material is compounded by a metal matrix and a metal hydride. The metal matrix is one or more of aluminum, aluminum alloy or magnesium alloy; the metal hydride is one or more of zirconium hydride or titanium hydride. The hydrogen release amount of the material is accurately regulated and controlled by adjusting the content of the metal hydride, and the adjustable range of the hydrogen release amount is as follows: 1000 mu g/g-10000 mu g/g. The densification and sintering of the material are realized through a hot isostatic pressing forming process of a powder metallurgy method. The material has higher density, good mechanical property and high-temperature stability, and the appearance and the hydrogen release amount of the material are not obviously changed after the material is placed in the air for a long time for storage, so that the material can be used for hydrogen content test standards and other occasions needing to accurately control the hydrogen release amount at the high temperature of more than 650 ℃.

Description

High-temperature hydrogen release metal composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of hydrogen storage materials, and particularly relates to a high-temperature hydrogen release metal composite material and a preparation method thereof.
Background
At present, the domestic standard for testing the hydrogen content in the material mainly comprises an inert gas pulse melting heat conductivity method for testing the hydrogen content of steel, and a standard number GB/T223.82-2007, wherein the standard is suitable for testing the hydrogen content of the steel with the mass fraction of 0.2 mu g/g-30.0 mu g/g. In the test, the used standard sample is a steel hydrogen standard substance with the mass of 0.5 g-2.5 g, and the hydrogen content of the standard sample is lower and is close to or slightly larger than that of an unknown sample.
For materials with high hydrogen content (such as hydrogen mass fraction > 30 mug/g), no specific applicable standard exists at present, and the test method generally adopts an inert gas pulse infrared absorption method and refers to standard ASTM E1447-2009 or GB/T4698.15. Both the two standards are suitable for measuring the hydrogen content of the titanium alloy with the mass fraction of 6-260 mu g/g. In the test, the used standard sample is a titanium hydrogen standard substance with the mass of 0.15 g-0.3 g, and the hydrogen content of the standard sample is close to or slightly larger than that of an unknown sample. At present, the hydrogen standard substance in titanium mainly comprises a specific hydrogen content standard sample with the hydrogen content of about 200 mug/g and the hydrogen content of about 20000 mug/g, the standard sample with the hydrogen content in the middle range is difficult to prepare, and if the standard sample is still adopted to calibrate and test the material with the hydrogen content in the middle range, a test value can bring about great errors. In addition, the specific hydrogen content standard sample or hydrogen storage material with higher hydrogen content is hydride powder, is easy to absorb water in the air, cannot be exposed in the air for a long time, and has poor service performance. Therefore, in order to expand the range of hydrogen content test and improve the stability and environmental resistance of the hydrogen standard substance, it is necessary to develop a stable hydrogen standard substance with precisely adjustable hydrogen release amount.
Disclosure of Invention
Aiming at the problems, the invention provides a high-temperature hydrogen release metal composite material, which is compounded by a metal matrix and a metal hydride, wherein the metal matrix is one or more of aluminum, aluminum alloy or magnesium alloy; the metal hydride is one or more of zirconium hydride or titanium hydride.
The hydrogen release amount of the material is accurately regulated and controlled by adjusting the content of the metal hydride, and the adjustable range of the hydrogen release amount is as follows: 1000 mu g/g-10000 mu g/g.
The temperature of the initial hydrogen release of the material is not less than 560 ℃, and the release of the hydrogen amount in the material can be completely finished when the temperature is not less than 650 ℃.
The material has high density, good mechanical property and stability, and the appearance and the hydrogen release amount of the material are not obviously changed after the material is placed in the air for a long time for storage.
A high-temperature hydrogen release metal composite material and a preparation method thereof are provided, wherein the material is prepared by a powder metallurgy hot isostatic pressing forming process.
The invention has the beneficial effects that:
1. the material provided by the invention has higher density, good mechanical property and stability, and the appearance and hydrogen release amount of the material do not change obviously after the material is placed in air for a long time for storage.
2. The temperature of the initial released hydrogen of the material is not less than 560 ℃, and the material can completely release the hydrogen amount in the material when the temperature is not less than 650 ℃, and can be used for hydrogen content test standards and other occasions requiring accurate control of the hydrogen release amount at a high temperature of more than 650 ℃.
3. The preparation method of the invention can not generate the loss of hydrogen content in the process of material forming and sintering.
Drawings
FIG. 1 is a DSC curve of a metal composite material capable of releasing hydrogen at high temperature
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
the metal composite material capable of releasing hydrogen at high temperature adjusts the content of metal hydride by changing the proportion of the metal matrix powder and the hydride powder, and the range of the hydrogen release amount can be realized as follows: 1000 mu g/g-10000 mu g/g. Taking the metal hydride raw material with the hydrogen content of 2.0% as an example, when the volume fraction of the metal hydride is less than 2% (at this time, the hydrogen release amount of the material is less than 1000 μ g/g), the dispersion uniformity of the hydrogen element in the material is poor, and the hydrogen release amount is difficult to accurately control; when the volume fraction of the metal hydride is more than 35 percent (at the moment, the hydrogen release amount of the material is more than 10000 mug/g), the material is difficult to prepare and form by adopting a powder metallurgy method, and the compactness and the mechanical property of the material are poor. Only by scientifically controlling the content of the metal hydride to ensure that the hydrogen release amount of the material is within the range of 1000 to 10000 mu g/g, the metal composite material with accurately controlled hydrogen release amount and good mechanical property and environmental resistance can be obtained. The material is applied to the hydrogen standard substance, so that the test range of the hydrogen content can be effectively expanded.
Example 1
95g of pure aluminum powder and 5g of zirconium hydride powder with the hydrogen content of 2.0 percent are weighed, and the weighed two raw materials are mixed under the argon protective atmosphere to ensure that the two powders are uniformly mixed. And (3) putting the mixed powder into a sheath for hot isostatic pressing to realize densification of the material, wherein the hot isostatic pressing temperature is 540 ℃. The metal composite material prepared by the method has the hydrogen content of 1000 mug/g, the density of more than 99 percent and the bending strength of more than 200MPa, and has good environmental-resistant service performance. FIG. 1 shows the DSC curve of the material. It can be seen that above 560 ℃ there are two exothermic peaks, corresponding respectively to the hydrogen evolution reaction of the material. The material can release all hydrogen elements contained in the material after being heated at a high temperature of 650 ℃ and above.
Example 2
Weighing 80g of 6061 aluminum alloy powder and 20g of zirconium hydride powder with the hydrogen content of 2.0%, and mixing the two weighed raw materials under the argon protective atmosphere to ensure that the two powders are uniformly mixed. And (3) putting the mixed powder into a sheath for hot isostatic pressing, wherein the hot isostatic pressing temperature is 540 ℃. The metal composite material prepared by the method has the hydrogen content of 4000 microgram/g, the compactness of more than 99 percent and the bending strength of more than 200MPa, and has good environmental-resistant service performance. The material can release all hydrogen elements contained in the material after being heated at a high temperature of 650 ℃ and above.
Example 3
Weighing 50g of pure aluminum powder and 50g of zirconium hydride powder with the hydrogen content of 2.0%, and mixing the two weighed raw materials under the argon protective atmosphere to ensure that the two powders are uniformly mixed. And (3) putting the mixed powder into a sheath for hot isostatic pressing to realize densification of the material, wherein the hot isostatic pressing temperature is 540 ℃. The metal composite material prepared by the method has the hydrogen content of 10000 mug/g, the density of more than 98 percent and the bending strength of more than 200MPa, and has good environmental-resistant service performance. The material can release all hydrogen elements contained in the material after being heated at a high temperature of 650 ℃ and above.
Example 4
Weighing 50g of AZ91 magnesium alloy powder and 50g of zirconium hydride powder with the hydrogen content of 2.0%, and mixing the weighed two raw materials under the argon protective atmosphere to ensure that the two powders are uniformly mixed. And (3) putting the mixed powder into a sheath for hot isostatic pressing, wherein the hot isostatic pressing temperature is 500 ℃. The metal composite material prepared by the method has the hydrogen content of 10000 mug/g, the density of more than 99 percent and the bending strength of more than 200MPa, and has good environmental-resistant service performance. The material can release all hydrogen elements contained in the material after being heated at a high temperature of 650 ℃ and above.
Comparative example 1
Weighing 96g of AZ91 magnesium alloy powder and 4g of zirconium hydride powder with the hydrogen content of 2.0%, and mixing the weighed two raw materials under the argon protective atmosphere to ensure that the two powders are uniformly mixed. And (3) putting the mixed powder into a sheath for hot isostatic pressing, wherein the hot isostatic pressing temperature is 500 ℃. The metal composite material prepared by the method has the integral hydrogen content of less than 1000 mug/g, but the dispersion uniformity of zirconium hydride in the material is poor, and the hydrogen release amount is difficult to be accurately controlled.
Comparative example 2
Weighing 45g of AZ91 magnesium alloy powder and 55g of titanium hydride powder with hydrogen content of about 4.0%, and mixing the weighed two raw materials under the argon protective atmosphere to ensure that the two powders are uniformly mixed. And (3) putting the mixed powder into a sheath for hot isostatic pressing, wherein the hot isostatic pressing temperature is 500 ℃. The density of the metal composite material prepared by the method is less than 90%, and the bending strength is less than 50 MPa. The overall hydrogen content of the metal composite material prepared by the method is more than 10000 mug/g, and the density, the mechanical property and the environmental resistance service performance of the prepared composite material are poor due to the high hydride content (the volume fraction is more than 35%), so that the composite material is easy to absorb water after being placed in humid air for a long time, and the application performance is limited.

Claims (5)

1. The high-temperature hydrogen release metal composite material is characterized by being formed by compounding a metal matrix and a metal hydride, wherein the metal matrix is one or more of aluminum, aluminum alloy or magnesium alloy; the metal hydride is one or more of zirconium hydride or titanium hydride.
2. The high-temperature hydrogen release metal composite material according to claim 1, wherein the hydrogen release amount of the material can be accurately controlled by adjusting the content of the metal hydride, and the adjustable range of the hydrogen release amount is as follows: 1000 mu g/g-10000 mu g/g.
3. The high-temperature hydrogen release metal composite material as claimed in claim 1, wherein the temperature of initial hydrogen release of the material is not less than 560 ℃, and the release of the hydrogen amount in the material can be completely completed at the temperature of not less than 650 ℃.
4. The high-temperature hydrogen release metal composite material according to claim 1, wherein the material has high compactness, good mechanical properties and stability, and does not change significantly in appearance and hydrogen release amount after being stored in air for a long time.
5. The high-temperature hydrogen release metal composite material is characterized by being prepared by a powder metallurgy hot isostatic pressing process.
CN201911398405.4A 2019-12-30 2019-12-30 High-temperature hydrogen release metal composite material and preparation method thereof Pending CN111020302A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116964684A (en) * 2020-12-16 2023-10-27 托卡马克能量有限公司 Design of composite hydride metals suitable for hydride decomposition

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1208392A (en) * 1996-01-19 1999-02-17 魁北克水电公司 Nanocrystalline composite for hydrogen storage
CN1380136A (en) * 2002-03-24 2002-11-20 浙江大学 Paste-like hydrogen storage material
CN105734346A (en) * 2014-12-12 2016-07-06 北京有色金属研究总院 Hydrogen content-adjustable metal block material and preparation method thereof
CN109722229A (en) * 2017-10-31 2019-05-07 中南大学 A kind of metal hydride heat-storage medium and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1208392A (en) * 1996-01-19 1999-02-17 魁北克水电公司 Nanocrystalline composite for hydrogen storage
CN1380136A (en) * 2002-03-24 2002-11-20 浙江大学 Paste-like hydrogen storage material
CN105734346A (en) * 2014-12-12 2016-07-06 北京有色金属研究总院 Hydrogen content-adjustable metal block material and preparation method thereof
CN109722229A (en) * 2017-10-31 2019-05-07 中南大学 A kind of metal hydride heat-storage medium and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116964684A (en) * 2020-12-16 2023-10-27 托卡马克能量有限公司 Design of composite hydride metals suitable for hydride decomposition

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