CN110343898A - A kind of nanoporous aluminium and preparation method thereof - Google Patents

A kind of nanoporous aluminium and preparation method thereof Download PDF

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Publication number
CN110343898A
CN110343898A CN201810288276.2A CN201810288276A CN110343898A CN 110343898 A CN110343898 A CN 110343898A CN 201810288276 A CN201810288276 A CN 201810288276A CN 110343898 A CN110343898 A CN 110343898A
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aluminium
metal
nanoporous
active
alloy
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金海军
杨威
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Institute of Metal Research of CAS
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Institute of Metal Research of CAS
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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
    • C22C1/08—Alloys with open or closed pores
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C3/00—Removing material from alloys to produce alloys of different constitution separation of the constituents of alloys
    • C22C3/005—Separation of the constituents of alloys

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention discloses a kind of nanoporous aluminium and preparation method thereof, belong to technical field of metal material.Prepare the process of nanoporous aluminium are as follows: preparation persursor material first, the persursor material are pure metal or alloy；Persursor material is immersed in ionic liquid under an inert atmosphere, erodes metallic element more active than Al in persursor material to get the nanoporous aluminium is arrived.Gained nanoporous aluminium can keep integrality, and hole rib is having a size of 20-5000nm.Present invention process is simple, and preparation facilitates controllable, and product is reliable.

Description

A kind of nanoporous aluminium and preparation method thereof
Technical field
The present invention relates to technical field of metal material, and in particular to a kind of nanoporous aluminium and preparation method thereof.
Background technique
Nano porous metal is the material with holes of nano size rib and hole, with unique bicontinuous structure, tool Have the features such as large specific surface area, catalytic activity strong, good conductivity, catalysis, sensing, in terms of be widely applied.
Foamed aluminium light weight, specific strength are high, and with exchange capability of heat is good, energy absorption is good, electromagnetic wave absorbability is good With the functions such as good penetrability, therefore it is widely used in fields such as the energy, environmental protection.And hole rib, the hole of foamed aluminium are narrowed down to When nanoscale, due to dimensional effect, performance may be protruded more, and application is more extensive.
Removal alloying method is used to prepare nano-porous materials, is to utilize the chemical property in alloy between different constituent elements different, The removing more active constituent element of selectivity, obtains the bicontinuous structure being made of residual constituent element.Removal alloying method at Function prepares the porous materials such as nanoporous Au, Pt, Ag, Cu.But the nano porous metal prepared at present is limited to more Noble metal systems seriously limit the research and application of nano porous metal material, it is therefore desirable to prepare other metal porous materials Material, and the exploration of other metal polyporous materials is never interrupted.
With the progress of science and technology and the development of production technology, porous aluminum is faced with the hairs such as enlargement, hole imperceptibility How exhibition trend, obtain high porosity, aperture size uniformly and size is in the always urgent problem such as micro-nano-scale. Therefore, seek a kind of simple preparation process, easy to operate, the sample prepared is reliable and stable, can obtain porosity height, hole Diameter subtle nanoporous aluminium uniform in size, needs continuous exploratory development.
Summary of the invention
The nano porous metal prepared at present mostly be noble metal systems and preparation porous aluminum there are aiming at the problem that, the present invention Be designed to provide a kind of nanoporous aluminium and preparation method thereof, nanoporous aluminium prepared by the present invention hole rib size is in nanometer Scale, preparation method is simple and convenient, easy to operate, significant to the preparation of nano porous metal, theoretical research and application.
To achieve the above object, the technical solution adopted in the present invention is as follows:
A kind of preparation method of nanoporous aluminium, this method comprises the following steps:
(1) prepare persursor material, the persursor material is pure metal or alloy；
(2) persursor material is immersed in ionic liquid under an inert atmosphere, reaction post-etching falls in persursor material to compare Al active metallic element to get arrive the nanoporous aluminium.
In above-mentioned steps (1), the persursor material is the metal more active than aluminium；Alternatively, the persursor material be than The alloy of the active metal of aluminium and aluminium composition；Alternatively, the persursor material is that the metal more active than aluminium is low with than aluminium activity Metal composition alloy；Alternatively, the persursor material is the metal more active than aluminium, aluminium and the metal group lower than aluminium activity At alloy.The metal more active than aluminium is one or more of Mg, Li, Na, Ca and K；When the metal more active than aluminium is When Mg, the atomic percent of Mg is 35~100% in persursor material；The low metal of the activity more active than aluminium be Ni, Ti, One or more of Cu, Ag, Zn and Si；Atomic percent of the low metal of the activity more active than aluminium in persursor material Than less than 50%.
In above-mentioned steps (1), when the persursor material selects alloy, the preparation process of alloy type persursor material are as follows: The corresponding raw material of each element in alloy are mixed, refining master alloy is stand-by, the annealed processing of master alloy can also be made alloy It is reused after homogenization of composition；Precursor material does not need melting when being pure metal, uses directly as persursor material.
In above-mentioned steps (2) reaction process, when the persursor material selects pure metal, displacement reaction only occurs, it is preceding It drives metal more active than aluminium in body material to be displaced by the aluminium in anion, the aluminium cemented out occurs deposition and obtains nanoporous Aluminium.When precursor material selects alloy, removal alloying and displacement reaction successively occurs.During removal alloying, presoma The metallic element more active than aluminium dissolves in material, and remaining metallic element forms nano-porous structure in alloy；Remove alloy Change after occurring, displacement reaction occurs for the active metallic element of the ratio aluminium being dissolved out, and is set by the aluminium in anion in ionic liquid It changes, forms nanoporous on the hole rib for the nano-porous structure that the al deposition cemented out is formed during removal alloying Aluminium.
In above-mentioned steps (2), the ionic liquid is by organic cation and anion (such as halogenation containing aluminium element Aluminium) composition.
Structural intergrity can be kept using nanoporous aluminium prepared by the above method, hole rib is having a size of 20-5000nm.
Design Mechanism of the present invention is as follows:
1, when existing use removal alloying method prepares nano porous metal, aqueous solution or metal bath, the application are mostly used Nanoporous aluminium is prepared using ionic liquid for the first time.
2, during the application prepares nanoporous aluminium, when precursor material selects pure metal, it is anti-that displacement only occurs It answers, the metal more active than aluminium is displaced by the aluminium in anion in persursor material, and the aluminium cemented out occurs deposition and received Rice porous aluminum.When precursor material selects alloy, removal alloying and displacement reaction successively occurs.During removal alloying, The metallic element more active than aluminium dissolves in persursor material, and remaining metallic element forms nano-porous structure in alloy； After removal alloying occurs, displacement reaction occurs for the active metallic element of the ratio aluminium being dissolved out, by anion in ionic liquid Aluminium displace, form nanometer on the hole rib for the nano-porous structure that the al deposition cemented out is formed during removal alloying Porous aluminum
3, the present invention, can be by controlling reaction temperature, preceding during persursor material and ionic liquid react The ionic liquid type etc. of body material composition and anion containing aluminium element is driven, to adjust reaction time (corrosion thickness, reaction speed Deng) and gained nanoporous aluminium microstructure (such as pore size size).
It advantages of the present invention and has the beneficial effect that:
1, the present invention has prepared the nanoporous aluminium good without crackle, structural homogeneity.
2, nanoporous aluminium prepared by the present invention keeps integrality, and porosity, preparation time etc. can pass through persursor material The ionic liquid type of ingredient, reaction temperature and anion containing aluminium element is adjusted.Using nanoporous aluminium prepared by the present invention The overall dimensions for maintaining persursor material are constant, and flawless, porous structure is uniformly distributed, and hole rib is having a size of nanoscale.Institute The hole rib of nanoporous aluminium is stated having a size of 50-5000nm.
3, the ionic liquid ingredient of the invention for being used to prepare nanoporous aluminium is simple, it is convenient to prepare；It is more for preparing nanometer The simple and reliable process of hole aluminium, convenient for operation.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph that pure Mg is the nanoporous aluminium that precursor preparation goes out；Wherein: (a) after for pure Mg corrosion The surface of obtained nanoporous aluminium；It (b) is the section of nanoporous aluminium；It (c) is putting for nanoporous aluminium section centre black line Big picture；It (d) is amplified nanoporous aluminium.
Fig. 2 is the scanning electron microscope of the scanning electron microscope (SEM) photograph of magnesium alloy and the nanoporous aluminium gone out using it as precursor preparation Figure；Wherein: (a) be magnesium alloy scanned picture；(b) sectional view for the nanoporous aluminium for being；It (c) is amplified receive Rice porous aluminum sectional view.
Fig. 3 is Al2Mg3For the scanning electron microscope (SEM) photograph for the nanoporous aluminium that precursor preparation goes out；Wherein: the nanometer for being (a) The exterior view of porous aluminum；(b) cross-sectional view for the nanoporous aluminium for being；(c) and (d) is amplified nanoporous aluminium Cross section.
Specific embodiment:
The present invention provides a kind of nanoporous aluminium and preparation method thereof, in the following with reference to the drawings and specific embodiments to this hair Bright further explanation.
Several embodiments follow the steps below to implement below:
1. preparing persursor material；Persursor material is pure metal or alloy；The persursor material can be more living than aluminium Bold and vigorous metal, such as Mg；Alternatively, the persursor material is the alloy of the metal and aluminium composition more active than aluminium, such as magnesium alloy；Or Person, the persursor material are the alloy that the metal more active than aluminium is formed with the metal lower than aluminium activity, such as nickel magnesium alloy；Or Person, the persursor material is the alloy of the metal more active than aluminium, aluminium and the metal composition lower than aluminium activity, as magnalium nickel closes Gold.The metal more active than aluminium is one or more of Mg, Li, Na, Ca and K；The low gold of the activity more active than aluminium Belong to is one or more of Ni, Ti, Cu, Ag, Zn and Si.
2. preparing ionic liquid: the ionic liquid being slowly added to persursor material in the glove box full of argon gas in stirring In body, stirring is until be mixed into ionic liquid；The ionic liquid be by organic cation and the anion containing aluminium element (such as Aluminum halide) composition；The organic cation includes organoammonium cations, organic phosphorus cation, organic sulfur cation, alkyl imidazole Cation, alkyl pyrroles cation, alkylpyridiniium cation, alkyl triazole cation, alkyl thiazolium cation, alkyl pyrazole sun Ion or alkyl guanidine pyridine cation.The molar ratio of anion and cation in ionic liquid is greater than or equal to 1.
3. persursor material is polished under dehydrated alcohol with sand paper, then with washes of absolute alcohol, it is then placed in ionic liquid It impregnates and reacts in body, temperature when reaction should be lower than the decomposition temperature of the ionic liquid；Dip time is 1-120h；
4. taking out the sample after reaction after the reaction was completed, in the glove box full of argon gas, cleaned with acetone dry Only, it is taken out after drying in glove box；
5. obtained nanoporous aluminium is passed through scanning electron microscopic observation structure.
Embodiment 1:
Using pure Mg as precursor preparation nanoporous aluminium, detailed process is as follows:
Pure Mg is cut into the flake of mm size.
Ionic liquid is prepared in the glove box full of argon gas, which is by anhydrous powder AlCl3With chlorination 1- Ethyl-3-methylimidazole (EMIC) is mixed according to molar ratio for 2:1.
Mg thin slice is polished under dehydrated alcohol with sand paper, after washes of absolute alcohol, at room temperature, is put into full of argon gas Glove box in ionic liquid in.
After immersing ionic liquid 100h, in the glove box full of argon gas, the sample after reaction is taken out, it is clear with acetone Wash clean takes out after dry in glove box.
Obtained nanoporous aluminium scanning electron microscopic observation.Fig. 1 (a) is the table of the nanoporous aluminium obtained after pure Mg corrodes Face, it can be seen that have a small amount of al deposition on surface；Fig. 1 (b) is the section of nanoporous aluminium；Fig. 1 (c) is that nanoporous aluminium is cut The amplification picture of black line among face；Fig. 1 (d) is amplified nanoporous aluminium, has obtained the nano junction for being oriented perpendicularly to surface Structure.
Embodiment 2:
Using magnesium alloy as precursor preparation nanoporous aluminium, detailed process is as follows:
Magnesium alloy is cut into the flake of mm size.
Ionic liquid is prepared in the glove box full of argon gas, which is by anhydrous powder AlCl3With chlorination 1- Ethyl-3-methylimidazole (EMIC) is mixed according to molar ratio for 2:1.
Magnesium alloy thin slice is polished under dehydrated alcohol with sand paper, after washes of absolute alcohol, at room temperature, is put into and fills In ionic liquid in the glove box of full argon gas.
After immersing ionic liquid 90h, in the glove box full of argon gas, the sample after reaction is taken out, it is clear with acetone Wash clean takes out after dry in glove box.
With scanning electron microscopic observation magnesium alloy and obtained nanoporous aluminium.Fig. 2 (a) is the scanned picture of magnesium alloy, It can be seen that there is pure Mg and Al2Mg3Two parts；The sectional view for the nanoporous aluminium that Fig. 2 (b) is；Fig. 2 (c) is amplified Nanoporous aluminium sectional view.
Embodiment 3:
With Al2Mg3For precursor preparation nanoporous aluminium, detailed process is as follows:
By Al2Mg3Alloy is cut into the flake of mm size.
Ionic liquid is prepared in the glove box full of argon gas, which is by anhydrous powder AlCl3With chlorination 1- Ethyl-3-methylimidazole (EMIC) is mixed according to molar ratio for 2:1.
By Al2Mg3Thin slice is polished under dehydrated alcohol with sand paper, after washes of absolute alcohol, at room temperature, is put into and is full of In ionic liquid in the glove box of argon gas.
After immersing ionic liquid 100h, in the glove box full of argon gas, the sample after reaction is taken out, it is clear with acetone Wash clean takes out after dry in glove box.
Obtained nanoporous aluminium scanning electron microscopic observation, the exterior view for the nanoporous aluminium that Fig. 3 (a) is can be with Seeing has a small amount of al deposition on surface；The cross-sectional view for the nanoporous aluminium that Fig. 3 (b) is；Fig. 3 (c) and Fig. 3 (d) are The cross section of amplified nanoporous aluminium, it can be seen that the hole rib average-size of nanoporous aluminium is in 200nm.
From Fig. 3 (a) and Fig. 3 (d) it can further be shown that the compound with regular structure of prepared nanoporous aluminium, without obvious crackle.
Above-described embodiment and comparative example is merely exemplary illustrates the principle of the present invention and performance, not full content, people are also Other embodiments can be obtained under the premise of being not necessarily to creative work according to the present embodiment, these embodiments belong to guarantor of the present invention Protect range.

Claims (8)

1. a kind of preparation method of nanoporous aluminium, it is characterised in that: this method comprises the following steps:
(1) prepare persursor material, the persursor material is pure metal or alloy；
(2) persursor material is immersed in ionic liquid under an inert atmosphere, reaction post-etching falls more living than Al in persursor material Bold and vigorous metallic element to get arrive the nanoporous aluminium.
2. the preparation method of nanoporous aluminium according to claim 1, it is characterised in that: in step (1), the presoma Material is the metal more active than aluminium；Alternatively, the persursor material is the alloy of the metal and aluminium composition more active than aluminium；Alternatively, The persursor material is the alloy that the metal more active than aluminium is formed with the metal lower than aluminium activity；Alternatively, the presoma Material is the alloy of the metal more active than aluminium, aluminium and the metal composition lower than aluminium activity.
3. the preparation method of nanoporous aluminium according to claim 2, it is characterised in that: in step (1), the presoma When material selects alloy, the preparation process of alloy type persursor material are as follows: mix the corresponding raw material of each element in alloy, refining Master alloy processed is stand-by；Precursor material does not need melting when being pure metal, uses directly as persursor material.
4. the preparation method of nanoporous aluminium according to claim 2, it is characterised in that: the metal more active than aluminium be One or more of Mg, Li, Na, Ca and K；When the metal more active than aluminium is Mg, the atomic percent of Mg in persursor material Than being 35~100%；The low metal of the activity more active than aluminium is one or more of Ni, Ti, Cu, Ag, Zn and Si；Institute Atomic percent of the low metal of activity more active than aluminium in persursor material is stated less than 50%.
5. the preparation method of nanoporous aluminium according to claim 2, it is characterised in that: in step (2) reaction process, when When the persursor material selection pure metal, displacement only occurs and reacts, the metal more active than aluminium is by anion in persursor material In aluminium displace, the aluminium that cements out occurs deposition and obtains nanoporous aluminium；When precursor material selects alloy, successively send out Raw removal alloying and displacement reaction, during removal alloying, the metallic element more active than aluminium dissolves in persursor material, Remaining metallic element forms nano-porous structure in alloy, after removal alloying occurs, the active metal of the ratio aluminium being dissolved out Displacement reaction occurs for element, is displaced by the aluminium in anion in ionic liquid, the al deposition cemented out is in removal alloying mistake Nanoporous aluminium is formed on the hole rib of the nano-porous structure formed in journey.
6. the preparation method of nanoporous aluminium according to claim 1, it is characterised in that: in step (2), the ionic liquid Body is made of organic cation and the anion containing aluminium element.
7. a kind of nanoporous aluminium using any the method preparation of claim 1-6.
8. nanoporous aluminium according to claim 7, it is characterised in that: prepared nanoporous aluminium can keep complete Property, hole rib size is about in 20-5000nm range.
CN201810288276.2A 2018-04-03 2018-04-03 A kind of nanoporous aluminium and preparation method thereof Pending CN110343898A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114369829A (en) * 2022-01-12 2022-04-19 浙江花园新能源股份有限公司 Preparation process of porous copper foil, product and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102504769A (en) * 2011-09-30 2012-06-20 东南大学 Elastic compound metal heat interface material and preparation method thereof
US20180016139A1 (en) * 2016-07-13 2018-01-18 The Regents Of The University Of California Hydrogen storage in nanoporous and nanostructured hydride forming metals

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102504769A (en) * 2011-09-30 2012-06-20 东南大学 Elastic compound metal heat interface material and preparation method thereof
US20180016139A1 (en) * 2016-07-13 2018-01-18 The Regents Of The University Of California Hydrogen storage in nanoporous and nanostructured hydride forming metals

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114369829A (en) * 2022-01-12 2022-04-19 浙江花园新能源股份有限公司 Preparation process of porous copper foil, product and application thereof
CN114369829B (en) * 2022-01-12 2022-07-08 浙江花园新能源股份有限公司 Preparation process of porous copper foil, product and application thereof

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