CN110042278A - A kind of aluminium-air cell anode material and preparation method thereof - Google Patents
A kind of aluminium-air cell anode material and preparation method thereof Download PDFInfo
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- CN110042278A CN110042278A CN201910401388.9A CN201910401388A CN110042278A CN 110042278 A CN110042278 A CN 110042278A CN 201910401388 A CN201910401388 A CN 201910401388A CN 110042278 A CN110042278 A CN 110042278A
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- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/38—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling sheets of limited length, e.g. folded sheets, superimposed sheets, pack rolling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B37/00—Control devices or methods specially adapted for metal-rolling mills or the work produced thereby
- B21B37/58—Roll-force control; Roll-gap control
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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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
- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
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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
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/463—Aluminium based
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/38—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling sheets of limited length, e.g. folded sheets, superimposed sheets, pack rolling
- B21B2001/386—Plates
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- 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
- Y02E60/10—Energy storage using batteries
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a kind of aluminium-air cell anode materials and preparation method thereof, consist of the following mass percentage components: antimony: 0.2~0.4%, manganese: 0.3~0.6%, zirconium: 0.1~0.3%, lead: 0.01~0.05%, tin: 0.01~0.05%, surplus is aluminium.Preparation method comprises the steps of: ingredient, melting: proportioned aluminium ingot, aluminium manganese intermediate alloy and aluminium zirconium hardener being added several times and melted；After melting completely, metallic antimony, metallic lead and metallic tin is added；Carbon trichloride and titanium dioxide mixture is added, removes waste residue, pours into mold, natural cooling rolls aluminium flake, and heat treatment obtains Aluminium Anode for Aluminium air Battery material.The self-corrosion liberation of hydrogen rate of this material substantially reduces, and aluminium anodes utilization rate reaches 90% or more.Its technique simplifies, easy to operate, can be realized high-volume processing aluminium anodes, and reduce the cost of refining to a certain extent.
Description
Technical field
The invention belongs to aluminium-air cell technical field, it is specifically related to a kind of aluminium-air cell anode material and its system
Preparation Method.
Background technique
With the fast development and development and utilization of the mankind for earth resource of human society, the environment of the earth by
Huge threat, in order to protect environment and due to the exhaustion of fossil fuel, mankind's urgent need new energy meets
Our production activity.Metal-air battery has the characteristics that efficient, cleaning, is weighed as the storage device of new energy
Depending on.It is anode that metal-air battery, which is by the oxygen in cathode, air of metal, and uses certain electrolyte for medium,
Chemical reaction occurs under the effect of the catalyst and produces electricl energy.
Currently, the research direction of metal-air battery specifically includes that zinc-air battery, aluminium-air electricity in world wide
Pond, lithium-air battery etc., but can be realized the only zinc-air battery of industrialization at present, but metallic aluminium is compared to gold
It is more active to belong to zinc, there is higher electro-chemical activity.Therefore, aluminium-air cell should have broader development prospect.
Aluminium is most perfect metal material in metal-air battery, because (1) aluminium is the metal that content is most in the earth's crust,
It is resourceful, there is very big advantage compared to the price of lithium metal；(2) electrochemical equivalent of aluminium is 2980Ah/kg, only secondary
Yu Li；(3) electrode potential of aluminium is relatively negative, its standard electrode potential is -1.66V (vs.SHE) in neutral solution, molten in alkalinity
Its standard electrode potential is -2.35V (vs.SHE) in liquid.
The working environment of aluminium-air cell is generally neutral, alkaline electrolyte, wherein can obtain in alkaline electrolyte
Higher performance, operating voltage are higher, more stable.Since aluminium and oxygen are capable of forming one layer of fine and close aluminum oxide film in air
Film, so that aluminium, in neutral electrolyte, theoretical work current potential is not achieved in current potential；Simultaneously because fine aluminium is analysed in alkaline electrolyte
Hydrogen-type corrosion rate is very high, and the utilization rate of aluminium is caused to reduce, and has voltage delay phenomenon when electric discharge.
Through a large number of experiments, it has been found that novel aluminum anode material is developed by microalloying, aluminium oneself can be reduced
Corrosion rate increases substantially the chemical property of aluminium.Current existing many patents and other document reports, by pure
The height that the alloying elements such as Ga, Sn, Mg, Zn, In, Hg, Pb can destroy oxidation film or reduce the self-corrosion rate of aluminium is added in aluminium
Hydrogen-evolution overpotential, and electrochemical behavior of aluminum anode in alkaline is improved with this.But since raw material aluminium generally uses 99.99% rafifinal, with
And the noble metal of addition improves battery cost；Simultaneously because the density of the elements such as Ga, Sn, Hg, Pb is larger and in aluminium
Solid solubility is lower to be easy segregation in aluminium, prevents the element of addition from completely playing oneself effect, causes the liberation of hydrogen of aluminium rotten
Erosion is still very serious.So finding the suitable aluminum alloy anode material of a kind of alloying element adding proportion, just seem especially heavy
It wants；Meanwhile seeking a kind of suitable, simple production technology, the segregation for reducing addition alloying element is also particularly important.
Summary of the invention
The present invention is to provide for a kind of aluminium-air cell anode material and preparation method thereof, have high electrochemical activity,
Low self-corrosion rate.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of Aluminium Anode for Aluminium air Battery material, which is characterized in that consist of the following mass percentage components: antimony:
0.2~0.4%, manganese: 0.3~0.6%, zirconium: 0.1~0.3%, lead: 0.01~0.05%, tin: 0.01~0.05%, surplus
For aluminium.
The present invention also has following technical characteristic:
1, the rafifinal that aluminium as described above is 99.99%, group by mass percentage are grouped as: aluminium: 99.99%,
Copper: 0.004%, silicon: 0.003%, iron: 0.003%.
2, a kind of Aluminium Anode for Aluminium air Battery material as described above, consists of the following mass percentage components:
Antimony: 0.20%, manganese: 0.30%, zirconium: 0.10%, lead: 0.01%, tin: 0.01%, surplus is aluminium.
3, a kind of Aluminium Anode for Aluminium air Battery material as described above, consists of the following mass percentage components:
Antimony: 0.25%, manganese: 0.40%, zirconium: 0.15%, lead: 0.02%, tin: 0.02%, surplus is aluminium.
4, a kind of Aluminium Anode for Aluminium air Battery material as described above, consists of the following mass percentage components:
Antimony: 0.35%, manganese: 0.60%, zirconium: 0.25%, lead: 0.04%, tin: 0.04%, surplus is aluminium.
5, a kind of Aluminium Anode for Aluminium air Battery material as described above, consists of the following mass percentage components:
Antimony: 040.%, manganese: 0.60%, zirconium: 0.30%, lead: 0.05%, tin: 0.05%, surplus is aluminium.
6, the preparation method of Aluminium Anode for Aluminium air Battery material as described above comprising the steps of:
Step 1, ingredient: raffinal, antimony, lead, tin, aluminium manganese intermediate alloy and aluminium zirconium hardener are used, as requested
Ratio matched；
Step 2, melting: proportioned aluminium ingot, aluminium manganese intermediate alloy and aluminium zirconium hardener are added several times and melted
Melt, enables to the alloying elements distribution of addition uniform in this way；After melting completely, metallic antimony, metallic lead and metal is added
Tin；Carbon trichloride and titanium dioxide mixture is added, removes waste residue, pours into mold, natural cooling；
Step 3, it rolls aluminium flake: the aluminium sheet cast in step 2 being rolled, and is cut to obtain required specification aluminium
Piece；
Step 4, it is heat-treated: aluminium flake rolling in step 3 being heat-treated, is then cooled down, obtain aluminium air electricity
Pond aluminium anodes material.
7, the preparation method of Aluminium Anode for Aluminium air Battery material as described above comprising the steps of:
Step 1, ingredient: the present invention is with the aluminium ingot of purity >=99.99%, the metallic antimony of purity >=99.99%, and purity >=
99.99% metallic lead, the metallic tin of purity >=99.99%, aluminium manganese intermediate alloy and aluminium zirconium hardener are raw material；And according to
Desired ratio is matched；
Step 2, proportioned aluminium ingot, aluminium manganese intermediate alloy and aluminium zirconium hardener melting: are put into pretreatment several times
750 DEG C are heated in the graphite crucible crossed to be melted；After melting completely, metallic antimony, metallic lead and metallic tin is added and stirs
It mixes uniformly；Carbon trichloride and titanium dioxide mixture is added, removes the waste residue in molten liquid, keeps the temperature 20min, it then will melting
Liquid pours into the mold of 200-300 DEG C of heat preservation, natural cooling；
Step 3, roll aluminium flake: the aluminium sheet that will be cast in step 2 first carries out surface preparation, then at 300 DEG C of 200-
Under rolled, finally obtain the aluminium flake with a thickness of 1.7 ± 0.1mm；And it is cut to obtain required specification aluminium flake；
Step 4, be heat-treated: it is 500 DEG C, time 1h that aluminium flake rolling in step 3, which is placed on temperature in shaft furnace,
Then furnace cooling obtains Aluminium Anode for Aluminium air Battery material.
8, the preparation method of Aluminium Anode for Aluminium air Battery material as described above, in step 2, the carbon trichloride of addition
And titanium dioxide mixture, wherein carbon trichloride: mass ratio=2:1 of titanium dioxide, overall additive amount are total molten liquid matter
The 0.5%-0.7% of amount, and be added in two portions.
9, in step 3, aluminium sheet is heated to for the preparation method of Aluminium Anode for Aluminium air Battery material as described above
200-300 DEG C, roll-in is then carried out, the deformation quantity rolled for the first time is the 30% of residual thickness, and the deformation quantity of second of rolling is
The 30% of residual thickness, the deformation quantity of third time rolling are the 20% of residual thickness, are then answered using the method elimination of quenching
Power, the deformation quantity of the 4th rolling are the 40% of residual thickness, and the deformation quantity of the 5th rolling is the 40% of residual thickness, the
The deformation quantity of six rollings is the 40% of residual thickness.
11, in above-mentioned preparation method, in step (2), pretreated graphite crucible refers to, new processing or long-time do not make
Used graphite crucible, is pre-processed.Processing method are as follows: by graphite crucible at 900 DEG C, constant temperature 12h, then with
Furnace is cooling.
12, it in above-mentioned preparation method, in step (2), when adding metallic antimony, metallic lead and metallic tin into molten liquid, answers
Metal is wrapped up with high-purity aluminum foil, is then sent with graphite rod to molten liquid middle and lower part, and at the uniform velocity stirs 2- in one direction
3min, so that the alloying elements distribution of addition is uniform
13, in above-mentioned preparation method, in step (2), addition carbon trichloride is to take waste residue out of to refine, and dioxy is added
The effect of change titanium is reaction speed when slowing down refining, extends refining time.The mass ratio of carbon trichloride and titanium dioxide is 2:
1, overall additive amount is the 0.5%-0.7% of total molten liquid quality.When refining, generally divide 2-3 addition, method is with height
Pure aluminum foil wraps up the mixture of carbon trichloride and titanium dioxide, is sent with graphite rod to the middle and lower part of graphite crucible, and stirred
It mixes.
14, in above-mentioned preparation method, in step (3), the rolling of aluminium sheet heats aluminium sheet using the method for hot rolling
To 200-300 DEG C, roll-in is then carried out, the deformation quantity rolled for the first time is the 30% of residual thickness, the deformation quantity of second of rolling
It is the 30% of residual thickness, the deformation quantity of third time rolling is the 20% of residual thickness, is then answered using the method elimination of quenching
Power, the deformation quantity of the 4th rolling are the 40% of residual thickness, and the deformation quantity of the 5th rolling is the 40% of residual thickness, the
The deformation quantity of six rollings is the 40% of residual thickness.Finally obtain the aluminium flake with a thickness of 1.7 ± 0.1mm.
Aluminium Anode for Aluminium air Battery material provided by the invention, be added into 99.99% rafifinal calcium halophosphate activated by antimony andmanganese, zirconium,
Five kinds of microelements of lead and tin.Wherein, addition antimony is that have positive metamorphism to the silicon in rafifinal due to antimony, through thin
The crystal grain of Eutectic Silicon in Al-Si Cast Alloys after change is in lamelliform, then after solution treatment, Eutectic Silicon in Al-Si Cast Alloys disjunction granulates, and improves the mechanics of alloy
Performance；Adding manganese is since manganese forms MnAl in aluminium alloy6Dispersoid particle, prevent recrystallization coarsening, raising tie again
Brilliant temperature effectively refines recrystal grain, and can form Al with the impurity F e in rafifinal3Compounds such as (Fe, Mn),
So that the compound form of iron is become blocky from needle-shaped, toughness can be improved to a certain extent, it can dissolved impurity Fe, reduction Fe
Illeffects, last manganese can also make the electrode potential of aluminium become smaller, improve the corrosion resistance of aluminium anodes；Addition Zr be due to
Zr can form Al with Al3Zr becomes the external heterogeneous crystallization nuclei of αsolidsolution, makes crystalline grain refinement, while Zr can be with
Hydrogen reaction in molten alloy liquid, the defects of generating ZrH, be dissolved in aluminium alloy and play getter action, reduce pin hole, conveying；Addition
It is high overpotential of hydrogen evolution element that lead, which is due to lead, can effectively inhibit gas-evolving electrodes, improve aluminium anodes corrosion resistance and
Utilization rate；Addition tin be can effectively inhibit the growth of aluminium anode oxide film due to it, meanwhile, Sn is also that high liberation of hydrogen is excessively electric
Bit element, is also able to suppress gas-evolving electrodes, improves aluminium anodes utilization rate.
The present invention has the following advantages and beneficial effects: the present invention is obtained by ingredient, melting, rolling, heat treatment step
High electrochemical activity, the lower Aluminium Anode for Aluminium air Battery material of self-corrosion liberation of hydrogen rate are arrived.In the NaOH electricity of 4mol/L
Solving the open-circuit voltage in liquid is -1.85~-1.93V (vs.Hg/HgO)；Self-corrosion liberation of hydrogen rate substantially reduces, and aluminium anodes utilizes
Rate reaches 90% or more.Meanwhile casting method provided by the invention, technique simplifies, and it is easy to operate, it can be realized high-volume
Aluminium anodes is processed, and reduces the cost of refining to a certain extent.
Specific implementation method
Below with reference to embodiment, further description of the technical solution of the present invention.
Embodiment 1:
A kind of Aluminium Anode for Aluminium air Battery material forms mass percent are as follows: antimony (Sb) 0.20wt%, manganese (Mn)
0.30wt%, zirconium (Zr) 0.10wt%, lead (Pb) 0.01wt%, tin (Sn) 0.01wt%, surplus are aluminium (Al).The aluminium
For 99.99% rafifinal, group by mass percentage is grouped as: aluminium: 99.99%, copper: and 0.004%, silicon: 0.003%,
Iron: 0.003%.
The preparation method of the present embodiment Aluminium Anode for Aluminium air Battery material, steps are as follows:
(1) ingredient: weighing Sb, Pb, Sn, aluminium manganese intermediate alloy and aluminium zirconium hardener according to said components, will be at measuring
Sb, Pb and Sn wrapped up with high-purity aluminum foil.Purity >=99.99% of Al, Sb, Pb and Sn.
(2) melting: dividing 2-3 times, proportioned aluminium ingot, aluminium manganese intermediate alloy and aluminium zirconium hardener is placed on pretreated
It must be heated to be melted in 750 DEG C of graphite crucibles；Completely after melting, the antimony (Sb) that is wrapped high-purity aluminum foil with graphite rod,
Lead (Pb) and tin (Sn) are respectively fed to molten liquid middle and lower part, stir 1- 2min when adding metal every time, and keep the temperature 10min.So
Afterwards, the mixture of carbon trichloride and titanium dioxide is added in two portions, skims, wherein m (carbon trichloride): m (titanium dioxide)
=2:1, overall additive amount are the 0.5%-0.7% of total molten liquid quality.And then heat preservation 20min.Finally, by molten liquid
It pours into the mold of 200-300 DEG C of heat preservation, natural cooling.
(3) roll aluminium flake: will in (2) casting aluminium sheet, first carry out surface preparation, then carry out hot rolling, by aluminium sheet plus
Heat arrives 200-300 DEG C, then carries out roll-in, and the deformation quantity rolled for the first time is the 30% of residual thickness, the deformation of second of rolling
Amount is the 30% of residual thickness, and the deformation quantity of third time rolling is the 20% of residual thickness, is then eliminated using the method for quenching
Stress, the deformation quantity of the 4th rolling are the 40% of residual thickness, and the deformation quantity of the 5th rolling is the 40% of residual thickness,
The deformation quantity of 6th rolling is the 40% of residual thickness.The aluminium flake with a thickness of 1.7 ± 0.1mm is finally obtained, and is cut
Obtain the aluminium flake of required size.
(4) be heat-treated: will aluminium flake rolling in (3) to be placed in shaft furnace temperature be 500 DEG C, time 1h, then with
Furnace is cooling, obtains Aluminium Anode for Aluminium air Battery material.
Embodiment 2:
A kind of Aluminium Anode for Aluminium air Battery material forms mass percent are as follows: antimony (Sb) 0.25wt%, manganese (Mn)
0.40wt%, zirconium (Zr) 0.15wt%, lead (Pb) 0.02wt%, tin (Sn) 0.02wt%, surplus are aluminium (Al).The aluminium
For 99.99% rafifinal, group by mass percentage is grouped as: aluminium: 99.99%, copper: and 0.004%, silicon: 0.003%,
Iron: 0.003%.
The preparation method of the present embodiment Aluminium Anode for Aluminium air Battery material, steps are as follows:
(1) ingredient: weighing Sb, Pb, Sn, aluminium manganese intermediate alloy and aluminium zirconium hardener according to said components, will be at measuring
Sb, Pb and Sn wrapped up with high-purity aluminum foil.Purity >=99.99% of Al, Sb, Pb and Sn.
(2) melting: dividing 2-3 times, proportioned aluminium ingot, aluminium manganese intermediate alloy and aluminium zirconium hardener is placed on pretreated
It must be heated to be melted in 750 DEG C of graphite crucibles；Completely after melting, the antimony (Sb) that is wrapped high-purity aluminum foil with graphite rod,
Lead (Pb) and tin (Sn) are respectively fed to molten liquid middle and lower part, stir 1- 2min when adding metal every time, and keep the temperature 10min.So
Afterwards, the mixture of carbon trichloride and titanium dioxide is added in two portions, skims, wherein m (carbon trichloride): m (titanium dioxide)
=2:1, overall additive amount are the 0.5%-0.7% of total molten liquid quality.And then heat preservation 20min.Finally, by molten liquid
It pours into the mold of 200-300 DEG C of heat preservation, natural cooling.
(3) roll aluminium flake: will in (2) casting aluminium sheet, first carry out surface preparation, then carry out hot rolling, by aluminium sheet plus
Heat arrives 200-300 DEG C, then carries out roll-in, and the deformation quantity rolled for the first time is the 30% of residual thickness, the deformation of second of rolling
Amount is the 30% of residual thickness, and the deformation quantity of third time rolling is the 20% of residual thickness, is then eliminated using the method for quenching
Stress, the deformation quantity of the 4th rolling are the 40% of residual thickness, and the deformation quantity of the 5th rolling is the 40% of residual thickness,
The deformation quantity of 6th rolling is the 40% of residual thickness.The aluminium flake with a thickness of 1.7 ± 0.1mm is finally obtained, and is cut
Obtain the aluminium flake of required size.
(4) be heat-treated: will aluminium flake rolling in (3) to be placed in shaft furnace temperature be 500 DEG C, time 1h, then with
Furnace is cooling, obtains Aluminium Anode for Aluminium air Battery material.
Embodiment 3:
A kind of Aluminium Anode for Aluminium air Battery material forms mass percent are as follows: antimony (Sb) 0.30wt%, manganese (Mn)
0.50wt%, zirconium (Zr) 0.20wt%, lead (Pb) 0.03wt%, tin (Sn) 0.03wt%, surplus are aluminium (Al).The aluminium
For 99.99% rafifinal, group by mass percentage is grouped as: aluminium: 99.99%, copper: and 0.004%, silicon: 0.003%,
Iron: 0.003%.
The preparation method of the present embodiment Aluminium Anode for Aluminium air Battery material, steps are as follows:
(1) ingredient: weighing Sb, Pb, Sn, aluminium manganese intermediate alloy and aluminium zirconium hardener according to said components, will be at measuring
Sb, Pb and Sn wrapped up with high-purity aluminum foil.Purity >=99.99% of Al, Sb, Pb and Sn.
(2) melting: dividing 2-3 times, proportioned aluminium ingot, aluminium manganese intermediate alloy and aluminium zirconium hardener is placed on pretreated
It must be heated to be melted in 750 DEG C of graphite crucibles；Completely after melting, the antimony (Sb) that is wrapped high-purity aluminum foil with graphite rod,
Lead (Pb) and tin (Sn) are respectively fed to molten liquid middle and lower part, stir 1- 2min when adding metal every time, and keep the temperature 10min.So
Afterwards, the mixture of carbon trichloride and titanium dioxide is added in two portions, skims, wherein m (carbon trichloride): m (titanium dioxide)
=2:1, overall additive amount are the 0.5%-0.7% of total molten liquid quality.And then heat preservation 20min.Finally, by molten liquid
It pours into the mold of 200-300 DEG C of heat preservation, natural cooling.
(3) roll aluminium flake: will in (2) casting aluminium sheet, first carry out surface preparation, then carry out hot rolling, by aluminium sheet plus
Heat arrives 200-300 DEG C, then carries out roll-in, and the deformation quantity rolled for the first time is the 30% of residual thickness, the deformation of second of rolling
Amount is the 30% of residual thickness, and the deformation quantity of third time rolling is the 20% of residual thickness, is then eliminated using the method for quenching
Stress, the deformation quantity of the 4th rolling are the 40% of residual thickness, and the deformation quantity of the 5th rolling is the 40% of residual thickness,
The deformation quantity of 6th rolling is the 40% of residual thickness.The aluminium flake with a thickness of 1.7 ± 0.1mm is finally obtained, and is cut
Obtain the aluminium flake of required size.
(4) be heat-treated: will aluminium flake rolling in (3) to be placed in shaft furnace temperature be 500 DEG C, time 1h, then with
Furnace is cooling, obtains Aluminium Anode for Aluminium air Battery material.
Embodiment 4:
A kind of Aluminium Anode for Aluminium air Battery material forms mass percent are as follows: antimony (Sb) 0.35wt%, manganese (Mn)
0.60wt%, zirconium (Zr) 0.25wt%, lead (Pb) 0.04wt%, tin (Sn) 0.04wt%, surplus are aluminium (Al).The aluminium
For 99.99% rafifinal, group by mass percentage is grouped as: aluminium: 99.99%, copper: and 0.004%, silicon: 0.003%,
Iron: 0.003%.
The preparation method of the present embodiment Aluminium Anode for Aluminium air Battery material, steps are as follows:
(1) ingredient: weighing Sb, Pb, Sn, aluminium manganese intermediate alloy and aluminium zirconium hardener according to said components, will be at measuring
Sb, Pb and Sn wrapped up with high-purity aluminum foil.Purity >=99.99% of Al, Sb, Pb and Sn.
(2) melting: dividing 2-3 times, proportioned aluminium ingot, aluminium manganese intermediate alloy and aluminium zirconium hardener is placed on pretreated
It must be heated to be melted in 750 DEG C of graphite crucibles；Completely after melting, the antimony (Sb) that is wrapped high-purity aluminum foil with graphite rod,
Lead (Pb) and tin (Sn) are respectively fed to molten liquid middle and lower part, stir 1- 2min when adding metal every time, and keep the temperature 10min.So
Afterwards, the mixture of carbon trichloride and titanium dioxide is added in two portions, skims, wherein m (carbon trichloride): m (titanium dioxide)
=2:1, overall additive amount are the 0.5%-0.7% of total molten liquid quality.And then heat preservation 20min.Finally, by molten liquid
It pours into the mold of 200-300 DEG C of heat preservation, natural cooling.
(3) roll aluminium flake: will in (2) casting aluminium sheet, first carry out surface preparation, then carry out hot rolling, by aluminium sheet plus
Heat arrives 200-300 DEG C, then carries out roll-in, and the deformation quantity rolled for the first time is the 30% of residual thickness, the deformation of second of rolling
Amount is the 30% of residual thickness, and the deformation quantity of third time rolling is the 20% of residual thickness, is then eliminated using the method for quenching
Stress, the deformation quantity of the 4th rolling are the 40% of residual thickness, and the deformation quantity of the 5th rolling is the 40% of residual thickness,
The deformation quantity of 6th rolling is the 40% of residual thickness.The aluminium flake with a thickness of 1.7 ± 0.1mm is finally obtained, and is cut
Obtain the aluminium flake of required size.
(4) be heat-treated: will aluminium flake rolling in (3) to be placed in shaft furnace temperature be 500 DEG C, time 1h, then with
Furnace is cooling, obtains Aluminium Anode for Aluminium air Battery material.
Embodiment 5:
A kind of Aluminium Anode for Aluminium air Battery material forms mass percent are as follows: antimony (Sb) 0.40wt%, manganese (Mn)
0.60wt%, zirconium (Zr) 0.30wt%, lead (Pb) 0.05wt%, tin (Sn) 0.05wt%, surplus are aluminium (Al).The aluminium
For 99.99% rafifinal, group by mass percentage is grouped as: aluminium: 99.99%, copper: and 0.004%, silicon: 0.003%,
Iron: 0.003%.
The preparation method of the present embodiment Aluminium Anode for Aluminium air Battery material, steps are as follows:
(1) ingredient: weighing Sb, Pb, Sn, aluminium manganese intermediate alloy and aluminium zirconium hardener according to said components, will be at measuring
Sb, Pb and Sn wrapped up with high-purity aluminum foil.Purity >=99.99% of Al, Sb, Pb and Sn.
(2) melting: dividing 2-3 times, proportioned aluminium ingot, aluminium manganese intermediate alloy and aluminium zirconium hardener is placed on pretreated
It must be heated to be melted in 750 DEG C of graphite crucibles；Completely after melting, the antimony (Sb) that is wrapped high-purity aluminum foil with graphite rod,
Lead (Pb) and tin (Sn) are respectively fed to molten liquid middle and lower part, stir 1- 2min when adding metal every time, and keep the temperature 10min.So
Afterwards, the mixture of carbon trichloride and titanium dioxide is added in two portions, skims, wherein m (carbon trichloride): m (titanium dioxide)
=2:1, overall additive amount are the 0.5%-0.7% of total molten liquid quality.And then heat preservation 20min.Finally, by molten liquid
It pours into the mold of 200-300 DEG C of heat preservation, natural cooling.
(3) roll aluminium flake: will in (2) casting aluminium sheet, first carry out surface preparation, then carry out hot rolling, by aluminium sheet plus
Heat arrives 200-300 DEG C, then carries out roll-in, and the deformation quantity rolled for the first time is the 30% of residual thickness, the deformation of second of rolling
Amount is the 30% of residual thickness, and the deformation quantity of third time rolling is the 20% of residual thickness, is then eliminated using the method for quenching
Stress, the deformation quantity of the 4th rolling are the 40% of residual thickness, and the deformation quantity of the 5th rolling is the 40% of residual thickness,
The deformation quantity of 6th rolling is the 40% of residual thickness.The aluminium flake with a thickness of 1.7 ± 0.1mm is finally obtained, and is cut
Obtain the aluminium flake of required size.
(4) be heat-treated: will aluminium flake rolling in (3) to be placed in shaft furnace temperature be 500 DEG C, time 1h, then with
Furnace is cooling, obtains Aluminium Anode for Aluminium air Battery material.
Claims (10)
1. a kind of Aluminium Anode for Aluminium air Battery material, which is characterized in that consist of the following mass percentage components: antimony: 0.2
~0.4%, manganese: 0.3~0.6%, zirconium: 0.1~0.3%, lead: 0.01~0.05%, tin: 0.01~0.05%, surplus is aluminium.
2. a kind of Aluminium Anode for Aluminium air Battery material as described in claim 1, which is characterized in that the aluminium is
99.99% rafifinal, group by mass percentage are grouped as: aluminium: 99.99%, copper: and 0.004%, silicon: 0.003%, iron:
0.003%.
3. a kind of Aluminium Anode for Aluminium air Battery material as claimed in claim 1 or 2, which is characterized in that by following quality hundred
The group of ratio is divided to be grouped as: antimony: 0.20%, manganese: 0.30%, zirconium: 0.10%, lead: 0.01%, tin: 0.01%, surplus is aluminium.
4. a kind of Aluminium Anode for Aluminium air Battery material as claimed in claim 1 or 2, which is characterized in that by following quality hundred
The group of ratio is divided to be grouped as: antimony: 0.25%, manganese: 0.40%, zirconium: 0.15%, lead: 0.02%, tin: 0.02%, surplus is aluminium.
5. a kind of Aluminium Anode for Aluminium air Battery material as claimed in claim 1 or 2, which is characterized in that by following quality hundred
The group of ratio is divided to be grouped as: antimony: 040.%, manganese: 0.60%, zirconium: 0.30%, lead: 0.05%, tin: 0.05%, surplus is aluminium.
6. the preparation method of Aluminium Anode for Aluminium air Battery material as described in claim 1, which is characterized in that include following step
It is rapid:
Step 1, raffinal, antimony, lead, tin, aluminium manganese intermediate alloy and aluminium zirconium hardener, ratio as requested ingredient: are used
Example is matched；
Step 2, melting: proportioned aluminium ingot, aluminium manganese intermediate alloy and aluminium zirconium hardener are added several times and melted；To
Completely after melting, metallic antimony, metallic lead and metallic tin is added；Carbon trichloride and titanium dioxide mixture is added, removes waste residue, pours into
Mold, natural cooling；
Step 3, it rolls aluminium flake: the aluminium sheet cast in step 2 being rolled, and is cut to obtain required specification aluminium flake；
Step 4, it is heat-treated: aluminium flake rolling in step 3 being heat-treated, is then cooled down, obtain aluminium-air cell use
Aluminium anodes material.
7. the preparation method of Aluminium Anode for Aluminium air Battery material as claimed in claim 6, which is characterized in that include following step
It is rapid:
Step 1, ingredient: the present invention is with the aluminium ingot of purity >=99.99%, the metallic antimony of purity >=99.99%, and purity >=
99.99% metallic lead, the metallic tin of purity >=99.99%, aluminium manganese intermediate alloy and aluminium zirconium hardener are raw material；And according to wanting
The ratio asked is matched；
Step 2, melting: proportioned aluminium ingot, aluminium manganese intermediate alloy and aluminium zirconium hardener are put into several times pretreated
750 DEG C are heated in graphite crucible to be melted；After melting completely, metallic antimony, metallic lead and metallic tin is added and stirs equal
It is even；Carbon trichloride and titanium dioxide mixture is added, removes the waste residue in molten liquid, keeps the temperature 20min, then pours into molten liquid
In the mold of 200-300 DEG C of heat preservation, natural cooling；
Step 3, roll aluminium flake: the aluminium sheet that will be cast in step 2 first carries out surface preparation, then carries out at 200-300 DEG C
Rolling, finally obtains the aluminium flake with a thickness of 1.7 ± 0.1mm；And it is cut to obtain required specification aluminium flake；
Step 4, be heat-treated: it is 500 DEG C, time 1h that aluminium flake rolling in step 3, which is placed in shaft furnace temperature, then with
Furnace is cooling, obtains Aluminium Anode for Aluminium air Battery material.
8. the preparation method of Aluminium Anode for Aluminium air Battery material according to claim 6 or 7, which is characterized in that step 2
In, when adding metallic antimony, metallic lead and metallic tin into molten liquid, metal is wrapped up using high-purity aluminum foil, then uses graphite rod
It send to molten liquid middle and lower part, and at the uniform velocity stirs 2-3min in one direction, so that the alloying elements distribution of addition is uniform.
9. the preparation method of Aluminium Anode for Aluminium air Battery material according to claim 6 or 7, which is characterized in that step 2
In, the carbon trichloride and titanium dioxide mixture of addition, wherein carbon trichloride: mass ratio=2:1 of titanium dioxide, overall adds
Dosage is the 0.5%-0.7% of total molten liquid quality, and is added in two portions.
10. the preparation method of Aluminium Anode for Aluminium air Battery material according to claim 6 or 7, which is characterized in that step
In 3, aluminium sheet is heated to 200-300 DEG C, then carries out roll-in, the deformation quantity rolled for the first time is the 30% of residual thickness, second
The deformation quantity of secondary rolling is the 30% of residual thickness, and the deformation quantity of third time rolling is the 20% of residual thickness, then uses and quenches
The method of fire eliminates stress, and the deformation quantity of the 4th rolling is the 40% of residual thickness, and the deformation quantity of the 5th rolling is residue
The 40% of thickness, the deformation quantity of the 6th rolling are the 40% of residual thickness.
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Application publication date: 20190723 |