CN109988943A - Al-Ga-In-Sn-Mg alloy of hydrogen manufacturing and preparation method thereof - Google Patents
Al-Ga-In-Sn-Mg alloy of hydrogen manufacturing and preparation method thereof Download PDFInfo
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- CN109988943A CN109988943A CN201711488510.8A CN201711488510A CN109988943A CN 109988943 A CN109988943 A CN 109988943A CN 201711488510 A CN201711488510 A CN 201711488510A CN 109988943 A CN109988943 A CN 109988943A
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- 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
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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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
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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
- C22C21/003—Alloys based on aluminium containing at least 2.6% of one or more of the elements: tin, lead, antimony, bismuth, cadmium, and titanium
Abstract
The invention discloses Al-Ga-In-Sn-Mg alloy of a kind of hydrogen manufacturing and preparation method thereof, the present invention reduces the dosage of noble metal Ga, In using the doping of Mg, therefore reduces production cost；In addition, big calorimetric can be discharged in magnesium and water reaction process, catalytic action is played to entire hydrogen production reaction, to control hydrogen-producing speed, while magnesium can be improved the energy density of material by adding magnesium as active light metal.
Description
Technical field
The present invention relates to aluminium alloy hydrogen preparation fields, and in particular to one kind can quickly react the Al-Ga- of release hydrogen with water
In-Sn-Mg alloy and preparation method thereof and its fuel cell middle application.
Background technique
Fossil energy is closely bound up with daily life, and irreplaceable work is played in the development of human society
With.The electric energy and heat energy in coal gas or industrial production either used in people's daily life is mostly by fossil energy
It provides.However such traditional energy belongs to disposable non-renewable energy, unsustainable property and the mankind's continuously huge consumption,
Lead to the gradually atrophy of its yield.In addition, a large amount of consumption of fossil fuel cause the discharge of a large amount of greenhouse gases, cause global temperature
Degree increases, and sea level rise, exacerbates greenhouse effects.Therefore, caused by the greenhouse gases generated by combustion of fossil fuel
Greenhouse effects have seriously threatened the existence of the mankind, and the new energy that people are badly in need of finding cleanliness without any pollution replaces fossil fuel,
Mainstay as future source of energy application.
Currently, the research of new energy and application are mainly reflected in following several various aspects: solar energy, wind energy, tide energy, nuclear energy
And Hydrogen Energy etc..Wherein hydrogen is a kind of renewable, and the energy with high combustion heat value, and heat is about gasoline etc.
Three times of fossil fuel, and hydrogen reacts generation water with oxygen and is known as clean energy without any pollution.Meanwhile hydrogen is next
Source is very extensive, can produce through a variety of ways, is converted to other various forms of energy, this is just largely promoted
Its development and application.Now, Hydrogen Energy has more and more been seen in the weapon application of the universe exploration of high-end point, military field volume
The figure utilized, these again demonstrate the huge advantage of Hydrogen Energy to the field that technology overall performance has strict demand.But
The transport and storage of hydrogen there is also some problems that hydrogen belongs to explosion hazard gases at present, extremely unstable in air, easily occur quick-fried
It is fried.Therefore, an important factor for transport of hydrogen is current limitation hydrogen development.
Now, the preparation approach of common hydrogen have hydrogen production of laboratory method, industrial hydrogen production method, other hydrogenous material hydrogen manufacturing with
And the new method of some hydrogen manufacturing.Wherein, hydrogen production of laboratory method specifically includes that metal is reacted with acid, metal is reacted with alkali, metal
It is reacted with water and use for laboratory water electrolysis hydrogen production etc..The method of industrial hydrogen production specifically includes that non-renewable energy conversion hydrogen manufacturing, electrolysis
Water hydrogen manufacturing and other hydrogenous material hydrogen manufacturing etc..
Hydrogen storage method is generally divided into five major class, they be liquid hydrogen storage, high-pressure hydrogen storing, organic compound hydrogen storage,
Metallic compound hydrogen storage and adsorption hydrogen-storing.One of the most common is metallic compound hydrogen storage.Now, it laboratory and industrial produces
Be related to most alloy hydrogen storage materials substantially and can be summarized as magnesium system hydrogen storage material, lanthanon hydrogen storage material, titanium system hydrogen storage material and
Vanadium system hydrogen storage material.
Above-mentioned hydrogen production process and hydrogen storage material, it is each defective.Therefore, people are in the new side for constantly probing into a kind of hydrogen manufacturing
Method.And metallic aluminium is shown one's talent with its excellent performance.Aluminium is one of the element that content is most on the earth, rich reserves, tool
There is very high energy density, receives the concern of scientist extensively.Theoretically, metallic aluminium can directly be made high-purity with reactive aluminum
Hydrogen is spent, but since its surface has oxidation film so seriously limiting the further progress of reaction.Current main task
It is to study how to destroy oxidation film, continues reaction.Existing method mainly include the following types: make aluminium directly and soda acid into
Row reaction；Aluminium and other materials is set to carry out ball milling；It is made by the modified method etc. in surface to remove the oxidation film on surface
Hydrogen.But the above method existed to the disadvantages of reaction vessel requires height, energy consumption is high.So the new method of aluminum hydrolization hydrogen production also exists
In constantly exploring.
U.S. professor Woodall, can be at room temperature using the bianry alloy that Al and Ga is formed by a large amount of experiment discovery
It is reacted with water, generates hydrogen, but its H2-producing capacity is not too ideal；Then researches show that Al-Ga bianry alloy
In be mixed in the quaternary alloy of In and Sn preparation due to foring metallic compound In3Sn, there is extraordinary H2-producing capacity,
However since metal In demand is big, higher cost.
In life, we can usually have found to stack a large amount of recycling metal there are many waste reclamation, these recycling gold
Most common in category is exactly aluminium alloy, and scrap aluminium alloy all causes stress present resource, environment and economy.Laboratory at present
Used when carrying out the research of al-rich alloy hydrogen manufacturing material is all the fine aluminium generated by industrial electrolysis.It is common in scrap aluminium alloy
Metallic element be magnesium.It is a kind of argenteous lightweight alkaline-earth metal to magnesium metal, rich reserves, cheap, chemically
Matter is active, can react with acid and generate hydrogen, have certain ductility and the dissipation of heat, industrially often magnesium is added in aluminium and makes
At almag, as being applied to production hydrogen aluminium alloy will be very significant.
In addition, there are also powder is made in aluminium alloy for currently used mode in order to further increase the H2-producing capacity of aluminium alloy
Last shape product, but its transport is clearly present deficiency with storage aspect.In contrast, alloy block is transported and is stored and is more convenient,
It is not afraid of remote way and transports, and explosion phenomenon not enough will not occur because of purity, as long as simple packaging, completely cuts off air and water,
It can realize prolonged transport and storage, there is very good application and development prospect.
Summary of the invention
The purpose of the present invention is to provide a kind of with the Al-Ga-In-Sn-Mg alloy of excellent H2-producing capacity and its preparation
Method, application in a fuel cell, the usage amount of gallium, indium in reducing aluminium base hydrogen manufacturing alloy are guaranteeing its production hydrogen
Under the premise of energy, its cost is effectively reduced, while the H2-producing capacity of material has raising largely.
One aspect to achieve the above object, Al-Ga-In-Sn-Mg alloy provided by the invention use following technical side
Case:
A kind of Al-Ga-In-Sn-Mg alloy, wherein introduce magnesium metal into the Al-Ga-In-Sn alloy of hydrolyzable hydrogen manufacturing
To obtain Al-Ga-In-Sn-Mg alloy, the content of the magnesium is not more than 10wt%；Optionally, the Al-Ga-In-Sn-Mg is closed
For gold also containing one of iron, copper and bismuth or a variety of, content is preferably smaller than 1wt%, such as 0.1wt%, 0.2wt%,
0.4wt%, 0.6wt% or 0.8wt% etc..
In the present invention, the Al-Ga-In-Sn alloy refers to containing the alloy of aluminium, gallium, indium and tin metal, can be
The Al-Ga-In-Sn alloy known in the art that can be used for hydrolytic hydrogen production.
In the present invention, magnesium is introduced into Al-Ga-In-Sn alloy, either preparing Al-Ga-In-Sn alloy
It is mixed into magnesium raw material or the raw material containing magnesium metal in raw metal, is also possible to pass through melting into Al-Ga-In-Sn alloy product
Again it is mixed into magnesium raw material or the raw material containing magnesium metal etc., finally prepares Al-Ga-In-Sn-Mg alloy.
Alloy according to the present invention, in the Al-Ga-In-Sn-Mg alloy, the content of the gallium be preferably 2wt%~
5wt%, further preferably 2.5wt%~5wt%, such as 3wt% or 4wt%；The content of the magnesium be preferably 0.1wt%~
5wt%, such as 0.2wt%, 0.5wt%, 1wt%, 2wt%, 3wt% or 4wt%；The sum of the indium and the content of tin are
2wt%~17.5wt%, further preferred 5wt%~15wt%, such as 3wt%, 8wt%, 10wt% or 12wt%；Wherein,
The ratio between amount of substance (i.e. mole) of indium and tin is 1:4~3:1, and surplus can be aluminium.
Alloy according to the present invention, it is preferable that the content of the aluminium be 80wt%~95wt%, such as 82wt%,
85wt% or 90wt%.
In Al-Ga-In-Sn-Mg alloy of the invention, it is preferable that at least partly indium and tin form metallic compound
InSn4.In the present invention, the metallic compound InSn4Including InSn4And its further GaInSn in conjunction with Ga4.Into one
Preferably, the ratio between amount of substance of indium and tin is not more than 1:1, preferably no greater than 1:2 to step, is not more than 1:3, further preferably with into one
Step improves metallic compound InSn4Relative amount.
Other side for achieving the above object, preparation method provided by the invention adopt the following technical scheme that
A method of preparing above-mentioned Al-Ga-In-Sn-Mg alloy, comprising the following steps:
(1) each metal is weighed according to the ratio, and the metal weighed up is put into the furnace of nitrogen protection, at 700-1000 DEG C,
For example 800 DEG C heated and kept the temperature 0.5-2h, such as 1h；Preferably, at least partly magnesium and at least partly aluminium is with the shape of almag
Formula is added, such as 5 ××× series almag aluminium sheets, and can be described as alloy aluminium sheet, and representative has 5052 aluminium sheets, 5005 aluminium
Plate, 5083 aluminium sheets, 5754 aluminium sheets, 5A02l aluminium sheet, 5A05 aluminium sheet etc.；
(2) sample after heat preservation is stirred, and poured into mold, cooled down, preferably natural cooling in air.
Alloy after cooling is packed, can long term storage.
Based on the considerations of its application, the present invention can also relate to: above-mentioned Al-Ga-In-Sn-Mg alloy is in a fuel cell
Application, wherein using the Al-Ga-In-Sn-Mg alloy hydrolysis react be made hydrogen as the fuel of the fuel cell.
The fuel cell is known in the art, such as hydrogen fuel cell, phosphate fuel cell or solid oxide fuel cell
Deng usually requiring to provide fuel to electrode, another electrode provides oxidant, to convert the chemical energy of fuel to
Electric energy, and alloy of the invention is then suitable for providing it hydrogen fuel.
Compared with prior art, the invention has the following advantages that
(1) present invention reduces the dosage of noble metal Ga, In using the doping of Mg, therefore reduces production cost；
In addition, big calorimetric can be discharged in magnesium and water reaction process, catalytic action is played to entire hydrogen production reaction, to control
Hydrogen-producing speed, while magnesium can be improved the energy density of material by adding magnesium as active light metal.
(2) present invention is dissolved by reconciling composition of alloy, the Al-Ga-In-Sn-Mg object phase composition comprising Al (Ga)
Body, InSn4With In that may be present3Sn phase and InSn4With In that may be present3GaInSn of the Sn in conjunction with Ga4With
GaIn3Sn phase, due to forming metallic compound InSn in the alloy with definite composition4, such as InSn4And/or GaInSn4
Phase, the study found that since the object amount ratio for adjusting In and Sn is to due to forming InSn4In and Sn object amount ratio it is close, more have
Conducive to the oxidation film formed on destruction Al crystal grain, hence it is evident that improve hydrogen-producing speed；In addition, compared to In3The dosage of Sn, In can be bright
It is aobvious to reduce, be conducive to save cost, kill two birds with one stone；
(3) present invention due to above-mentioned (1) and/or (2) improvement, to be more suitable for the hydrogen supply of fuel cell；And it can be with
It is used for hydrogen manufacturing using bulk aluminium block alloy, without carrying out excessive processing, energy consumption is reduced, simplifies preparation process.Meanwhile
Discarded almag can be used to prepare and produce hydrogen aluminium alloy by the present invention, reduce discarded almag cost recovery.
Detailed description of the invention
Fig. 1 is the Al-Ga-In-Sn-Mg alloy hydrolysis hydrogen-producing speed figure of embodiment 1-5 preparation；
Fig. 2 is the Al-Ga-In-Sn-Mg alloy hydrolysis hydrogen output figure of embodiment 1-5 preparation.
Specific embodiment
Below with reference to embodiment, the present invention is described in detail, but the present invention is not limited to this.
Embodiment 1-5
The preparation of Al-Ga-In-Sn-Mg alloy
(1) composition of alloy is shown in Table 1:
The alloying element of 1 embodiment 1-4 of table forms mass percent (wt%)
(2) preparation process:
Raw material: each metal of purity >=99wt% that wherein raw material of embodiment 1,2 and 3 is；The raw material of embodiment 4 and 5
In, it further include 5052 type almags, wherein 80% magnesium comes from 5052 type almags, remaining component is added on demand.
Load weighted metal is put in high temperature furnace under nitrogen protection, is sintered at 800 DEG C, and is protected at 800 DEG C
Temperature one hour.It is stirred and casts after heat preservation, cooled down under field conditions (factors) after casting, packed after cooling.
(3) hydrogen output index:
The cubic block that the alloy of embodiment 1-5 preparation is divided into side length X carries out vigorous reaction in 40 DEG C of water, generates big
Hydrogen is measured, hydrogen output is shown in Table 2 and Fig. 2.
The hydrogen output of 2 embodiment 1-4 aluminium alloy of table
(4) hydrogen-producing speed index:
The alloy of embodiment 1-5 preparation carries out vigorous reaction in 40 DEG C of water, generates a large amount of hydrogen, hydrogen-producing speed is shown in Table
3 and Fig. 1.
Table 3
Claims (7)
1. a kind of Al-Ga-In-Sn-Mg alloy, which is characterized in that
Magnesium metal is introduced into the Al-Ga-In-Sn alloy of hydrolyzable hydrogen manufacturing to obtain Al-Ga-In-Sn-Mg alloy, wherein institute
The content of magnesium is stated no more than 10wt%；It is optional, the Al-Ga-In-Sn-Mg alloy also contain one of iron, copper and bismuth or
It is a variety of.
2. Al-Ga-In-Sn-Mg alloy according to claim 1, which is characterized in that the Al-Ga-In-Sn-Mg alloy
Element composition are as follows: the gallium of 2wt%~5wt%, the magnesium of 0.1wt%~5wt%, 2wt%~17.5wt% indium and tin, Yi Jiyu
The aluminium of amount；Wherein, the ratio between amount of substance of indium and tin is 1:4~3:1.
3. Al-Ga-In-Sn-Mg alloy according to claim 1 or 2, which is characterized in that the content of the aluminium is, described
The content of aluminium is 75wt%~95wt%, preferably 80wt%~95wt%.
4. Al-Ga-In-Sn-Mg alloy described in any one of claim 1 to 3, which is characterized in that the Al-Ga-
In In-Sn-Mg alloy, the ratio between amount of substance of indium and tin is not more than 1:1, preferably no greater than 1:2, is further preferably not more than 1:3.
5. Al-Ga-In-Sn-Mg alloy according to any one of claims 1 to 4, which is characterized in that the Al-Ga-
In In-Sn-Mg alloy, the content of gallium is 2.5wt%~5wt%, the content of indium and tin is 5wt%~15%wt%.
6. a kind of method for preparing Al-Ga-In-Sn-Mg alloy according to any one of claims 1-5, including it is following
Corresponding metal: (1) being put into the vacuum drying oven of nitrogen protection by step according to the ratio, heats at 700-1000 DEG C and keeps the temperature 0.5-
2h；
(2) sample after heat preservation is stirred, and poured into mold, carry out natural cooling in air.
7. according to the method described in claim 6, it is characterized in that, at least partly magnesium and at least partly aluminium is with the shape of almag
Formula is added.
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Cited By (3)
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| CN110724857A (en) * | 2019-12-04 | 2020-01-24 | 河南科技大学 | Aluminum-rich alloy for fracturing ball, preparation method of aluminum-rich alloy and control method of hydrogen production rate of aluminum-rich alloy for fracturing ball |
| CN111705241A (en) * | 2020-07-03 | 2020-09-25 | 兰州理工大学 | Al alloy for preparing hydrogen and preparation method and application thereof |
| CN116179898A (en) * | 2023-01-16 | 2023-05-30 | 中南大学 | Hydrogen-producing aluminum alloy material capable of being rapidly reacted with water and preparation method thereof |
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Cited By (3)
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| CN110724857A (en) * | 2019-12-04 | 2020-01-24 | 河南科技大学 | Aluminum-rich alloy for fracturing ball, preparation method of aluminum-rich alloy and control method of hydrogen production rate of aluminum-rich alloy for fracturing ball |
| CN111705241A (en) * | 2020-07-03 | 2020-09-25 | 兰州理工大学 | Al alloy for preparing hydrogen and preparation method and application thereof |
| CN116179898A (en) * | 2023-01-16 | 2023-05-30 | 中南大学 | Hydrogen-producing aluminum alloy material capable of being rapidly reacted with water and preparation method thereof |
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