CN106756665A - Aluminium alloy, preparation method and purposes - Google Patents
Aluminium alloy, preparation method and purposes Download PDFInfo
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- CN106756665A CN106756665A CN201611067212.7A CN201611067212A CN106756665A CN 106756665 A CN106756665 A CN 106756665A CN 201611067212 A CN201611067212 A CN 201611067212A CN 106756665 A CN106756665 A CN 106756665A
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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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- 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
- C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
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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
- C22F1/047—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 of alloys with magnesium as the next major constituent
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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
- H01M4/06—Electrodes for primary cells
-
- 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
Abstract
The invention discloses aluminium alloy, preparation method and purposes.The method includes：(1) hot melt treatment is carried out to solid feed aluminium and alloy raw material, to form aluminium alloy；(2) casting treatment is carried out to the aluminium alloy, to form aluminium alloy ingots；(3) aluminium alloy ingots is made annealing treatment, the temperature of the annealing is 400~550 degrees Celsius, and the time is 2~6 hours；(4) hot rolling treatment is carried out to the aluminium alloy ingots processed by step (3)；And (5) are heat-treated wherein to the aluminium alloy ingots processed by step (4), in the solid feed aluminium, based on the gross weight of the solid feed aluminium, Al content >=99.85wt%；The alloy raw material includes Mg, Bi, Sn, Mn and Ga.The method can be using the relatively low solid feed aluminium of purity as aluminium base raw material, and the aluminium alloy of acquisition has good chemical property and chemical stability.
Description
Technical field
The present invention relates to new energy and field of batteries, specifically, the present invention relates to aluminium alloy, preparation method and purposes,
More particularly it relates to aluminium alloy negative material.
Background technology
Metallic aluminium is a kind of energy carrier very high, is the ideal electrode material metal for developing battery.The specific energy of aluminium is very
Height, theoretical electrochemistry specific capacity reaches 2980mAh/g, and lithium (3870mAh/g), the volume of aluminium are only second in all of metallic element
Specific capacity is 8050mAh/cm3, is highest in current all cell metallic electrode materials, and the light weight of aluminium, it is pollution-free, can
By property it is high, using safety and low cost and aboundresources, it is exploitation, processing, very low using cost, have as anode material
The unrivaled advantage of other metal materials.As the aluminum metal of the anode material of aluminium-air cell, it is necessary to have excellent resistance to
Corrosive nature and good chemical property.In order to meet above-mentioned performance, it usually needs add corrosion inhibiter in the electrolytic solution, with
Reduce the oxidation of anode aluminium；Or use the aluminium alloy containing trace alloying element to be carried to reach as the anode of aluminium-air cell
The electro-chemical activity of high anode, the purpose for reducing anode self-corrosion speed.
However, current aluminium alloy and preparing the method for aluminium alloy and still having much room for improvement.
The content of the invention
It is contemplated that at least solving one of technical problem in correlation technique to a certain extent.
The present invention be based on inventor following understanding and discovery and complete：
The aluminium alloy that current aluminium-air cell anode is used, in OCP, operating potential, actual capacitance, electricity
The aspect of performances such as stream efficiency, anode utilization rate and surface dissolving situation still suffer from undesirable factor.Also, for aluminium air electricity
The aluminium alloy in pond, needs to prepare alloy using based on rafifinal base material (for example, purity is more than 99.99%) more.And it is high-purity
Aluminium causes aluminum alloy anode production cost high, and raw material not enough enriches, therefore, weaken aluminium-air cell and other electrochmical power sources
The cost advantage of competition.
In view of this, the present invention proposes a kind of method for preparing aluminium alloy.The method is by alloying element (doping unit
Element) selection and content adjustment, and the operating procedures such as the annealing in aluminium alloy preparation process, heat treatment are regulated and controled,
The production for using technical pure aluminium ingot (purity is more than 99.85%) that aluminium alloy is carried out for aluminium base can be realized.The method is obtained
Aluminium alloy there is good chemical property and chemical stability, the demand of aluminium-air cell anode can be met.Thus,
The production cost of aluminium-air cell can be greatly reduced, be conducive to the significantly popularization of aluminium-air cell.
In the first aspect of the present invention, the present invention proposes a kind of method for preparing aluminium alloy.Implementation of the invention
Example, the method includes：(1) hot melt treatment is carried out to solid feed aluminium and alloy raw material, to form aluminium alloy；(2) to institute
Stating aluminium alloy carries out casting treatment, to form aluminium alloy ingots；(3) aluminium alloy ingots is made annealing treatment, the annealing
The temperature for the treatment of is 400~550 degrees Celsius, and the time is 2~6 hours；(4) aluminium alloy ingots to being processed by step (3)
Carry out hot rolling treatment；And (5) are heat-treated to the aluminium alloy ingots processed by step (4), the heat treatment includes：
First isothermal holding, the temperature of first isothermal holding is 200~600 degrees Celsius, and the time is 1~10 hour；Second insulation
Treatment, the temperature of second isothermal holding is 200~600 degrees Celsius, and the time is 2~8 hours, wherein, the solid feed
In aluminium, based on the gross weight of the solid feed aluminium, Al content >=99.85wt%；The alloy raw material includes Mg, Bi, Sn, Mn
And Ga, based on the gross weight of the solid feed aluminium, the alloy raw material includes：The Mg of 0.005-1.5wt%, 0.01~
The Ga of the Mn and 0.01-0.5wt% of Sn, 0.005-0.5wt% of Bi, 0.01-0.5wt% of 0.2wt%.
Inventor by further investigation and many experiments find, added in solid feed aluminium above-mentioned alloying element (Mg,
Bi, Sn, Mn and Ga), it is possible to use the mutual synergy between above-mentioned 5 kinds of alloying elements, and to moving back in preparation process
The regulation and control of the step such as fire and heat treatment, effectively reduce the alloy phase in the aluminium alloy for obtaining, and suppress aluminium alloy in aluminium air electricity
Liberation of hydrogen self-corrosion is produced in the course of work of pond, alloy corrosion rate under that loading condition is reduced, aluminum alloy surface passivation is reduced
The resistance of film so that the aluminium alloy has more excellent chemical property, oxidizing potential is negative to be moved, and electrode is activated.Therefore,
The method can be using the relatively low solid feed aluminium of purity as aluminium base raw material, it is also ensured that the performance of the aluminium alloy of acquisition
It is unaffected, can still meet requirement of the aluminium-air cell for anode aluminium alloy.Thus, it is possible to reduce aluminium-air cell
Production cost, is conducive to the popularization and application of aluminium-air cell.
Embodiments in accordance with the present invention, the method can also include following additional technical feature：
Embodiments in accordance with the present invention, step (1) is further included：It is under 700~950 degrees Celsius, the solid-state is former
Material aluminium carries out hot melt treatment, to form aluminium liquid；To the alloy raw material is added in the aluminium liquid, under 700~950 degrees Celsius
Insulation 15 minutes, to form the aluminium alloy.Thus, it is possible to so that alloy raw material mixes more with Al substrate materials (aluminium liquid)
Plus it is uniform.
Embodiments in accordance with the present invention, in step (3), the temperature of the annealing is 450~500 degrees Celsius.Thus,
The structural stress of aluminium alloy ingots can be eliminated.
Embodiments in accordance with the present invention, in step (4), the finishing temperature of the hot rolling treatment is not less than 280 degrees Celsius.By
This, can eliminate the segmental defect in aluminium alloy ingots.
Embodiments in accordance with the present invention, in step (5), the temperature of first isothermal holding is 300~550 Celsius
Degree, the time is 3~8 hours；Second isothermal holding, the temperature of second isothermal holding is 300~550 degrees Celsius, and the time is 3
~6 hours.Thus, it is possible to so that the impurity in aluminium alloy ingots is solidly soluted into Al matrixes, rather than separated out in grain boundaries.Thus, may be used
With the further quality for improving the aluminium alloy for obtaining.
Embodiments in accordance with the present invention, the heat treatment is further included：It is described after first isothermal holding
Before second isothermal holding, Quenching Treatment is carried out to the aluminium alloy ingots；And after second isothermal holding, will be described
Aluminium alloy ingots natural cooling.Inventor is it was unexpectedly observed that quenching processing technology is attached in above-mentioned heat treatment step, Ke Yijin
One step improves the quality of the aluminium alloy for obtaining.
In another aspect of this invention, the present invention proposes a kind of aluminium alloy.Embodiments in accordance with the present invention, the aluminium is closed
Gold is prepared using foregoing method.Thus, the aluminium alloy possesses the complete of aluminium alloy prepared by previously described method
Portion's feature and advantage, will not be repeated here.Generally speaking, the aluminium alloy analysis have be not susceptible to hydrogen self-corrosion, in load bar
Corrosion rate under part is relatively low compared with the resistance of slow, aluminum alloy surface passivating film, oxidizing potential is relatively born, stable chemical performance and electricity
Chemical property is excellent, it is with low cost the advantages of at least one of.
In still another aspect of the invention, the present invention proposes foregoing aluminium alloy in aluminium-air cell anode is prepared
Purposes.
In still another aspect of the invention, the present invention proposes a kind of aluminium-air cell.Embodiments in accordance with the present invention, the aluminium
Air cell includes：Body, reaction compartment is limited in the body；Air electrode, the air electrode is arranged on described
Internal portion and and air contact；And anode, the anode is arranged on the body interior and electrically connected with the air electrode,
The anode is made up of foregoing aluminium alloy.Thus, the aluminium-air cell have with low cost, anode it is corrosion-resistant,
At least one of the advantages of electro-chemical activity is high.
Brief description of the drawings
Fig. 1 shows the schematic flow sheet of the method for preparing aluminium alloy according to an embodiment of the invention；
Fig. 2 shows the part schematic flow sheet of the method for preparing aluminium alloy in accordance with another embodiment of the present invention；With
And
Fig. 3 shows the structural representation of aluminium-air cell according to an embodiment of the invention.
Specific embodiment
Embodiments of the invention are described below in detail, the example of the embodiment is shown in the drawings.Below with reference to
The embodiment of Description of Drawings is exemplary, it is intended to for explaining the present invention, and be not considered as limiting the invention.
In the first aspect of the present invention, the present invention proposes a kind of method for preparing aluminium alloy.Implementation of the invention
Example, with reference to Fig. 1, the method includes：
S100：Hot melt treatment
Embodiments in accordance with the present invention, in this step, hot melt treatment are carried out to solid feed aluminium and alloy raw material, with
Just aluminium alloy is formed.Specifically, in this step, can be (total based on solid feed aluminium by Al content >=99.85wt% first
Quality) solid feed aluminium be placed in the heaters such as the crucible of such as medium frequency induction melting furnace, be heated to 700 DEG C -950 DEG C melt
Chemical conversion aluminium liquid.As previously described, because selection of the present invention for the species, content of the alloying element of doping, and for follow-up
The regulation and control of handling process, in this step, solid feed aluminium can select the relatively low industrial aluminium ingot of purity, and need not use
Purity is the rafifinal base material of 49 or more (Al content >=99.99wt%).Solid feed aluminothermy is melted after forming aluminium liquid, will
Alloy raw material is added in aluminium liquid, is well mixed and is incubated a period of time, you can obtain aluminium alloy.For example, tool of the invention
Body embodiment, by mass percentage, can be separately added into the Mg of 0.005-1.5wt%, 0.01~0.2wt% in aluminium liquid
The Ga alloying elements of the Mn and 0.01-0.5wt% of Sn, 0.005-0.5wt% of Bi, 0.01-0.5wt%.Above-mentioned alloy unit
Element is wrapped up using aluminium foil, and is pressed into aluminium liquid with bell jar, to prevent scaling loss.After the completion of alloying element addition, stirred with graphite rod
The aluminium liquid of alloying element is added, its composition is well mixed.After insulation 15 minutes, you can obtain aluminium alloy.
Inventor by further investigation and many experiments find, added in solid feed aluminium above-mentioned alloying element (Mg,
Bi, Sn, Mn and Ga), it is possible to use the mutual synergy between above-mentioned 5 kinds of alloying elements, the aluminium for effectively improving acquisition is closed
The quality of gold.According to a particular embodiment of the invention, matched using above-mentioned five kinds of alloying elements, wherein alloying element Mg can
To cause that the area and quantity of negative electrode phase in aluminium alloy are reduced such that it is able to which the aluminium alloy that improvement is obtained is when as galvanic anode
The performance such as electrochemistry, the driving force of electrode surface microcosmic corrosion galvanic cell is reduced while current potential is born shifting.But it is excessive
Mg easily with Al generation with anode characteristic intermediate product Mg2Al3, this product can cause intercrystalline corrosion, and make current efficiency
Reduce.Therefore, inventor has found that the content of Mg, can be effective between 0.005-1.5wt% in aluminium alloy by many experiments
Improve the electrode performance of the aluminium alloy for obtaining, while serious intercrystalline corrosion will not be caused.Alloying element Sn is due to higher
Hydrogen overpotential, therefore in aluminium alloy add Sn can effectively suppress liberation of hydrogen self-corrosion.The Sn of high price4+In substitution passivating film
Al3+, an additional cavity is produced, the compactness of oxide-film is destroyed, while Sn can also reduce the resistance of aluminium surface passivating film, and
Eutectic mixture can be formed with Ga etc. by other alloying elements, destroy aluminium surface passivating film, play a part of activated electrode.Work as Sn
When the addition of element is between 0.01-0.5wt%, preferable activation effect can be obtained, while will not also destroy aluminium alloy
Chemical stability.Ga elements can change anisotropy of the fine aluminium crystal grain in course of dissolution, make anodic attack uniform, and
Ga and other alloying elements such as Sn etc., forms eutectic mixture, the passivating film of aluminium surface can be destroyed, in anode reaction process
In play a part of activating aluminum alloy electrode.Inventor has found by further investigation and many experiments, with the increasing of Ga contents
Plus, the current potential of aluminum alloy anode becomes negative, but too high Ga contents, can raise anodic attack rate, reduces anode utilization rate.Work as Ga
When content is 0.01-0.5wt%, can effectively with the activation of the element cooperative achievement electrode such as Sn, while will not also significantly improve
Anodic attack rate.Addition alloying element Mn can play a part of crystal grain thinning and hinder to recrystallize, and can improve aluminium alloy
The illeffects of the impurity F e for containing.During without Mn, impurity iron with to base aluminum in cathodic FeAl3Form is present, when having Mn,
Then it is converted into and base aluminum property identical FeMnAl6Form is present, such that it is able to reduce alloy corrosion under that loading condition
Speed.When Mn contents are 0.005-0.5wt%, can effectively suppress negative effects of the impurity F e to alloy, without to obtaining
The physical and chemical performance of the aluminium alloy itself for obtaining is impacted.Addition bismuth additions, can make due to its electrode potential than Al just
The electrode potential of aluminium anodes is negative to be moved, and couples to form corrosion micro cell with Al in the electrolytic solution, so as to destroy the passivating film of densification, is made
Aluminum substrate dissolves, but too high Bi easily assembles to form the second phase in grain boundaries, causes intercrystalline corrosion serious, so as to increase aluminium sun
The self-corrosion rate of pole.When Bi contents are 0.01~0.2wt%, aluminum anodic passivation can be effectively prevented, while will not lead again
Cause the increase of self-corrosion rate.
S200：Casting is processed
Embodiments in accordance with the present invention, in this step, casting treatment are carried out to aluminium alloy, to form aluminium alloy ingots.
In this step, the aluminium alloy that casting is formed can be designed according to the specific requirement of the shape of the aluminium alloy for ultimately forming
The concrete shape of ingot.For example, according to a particular embodiment of the invention, aluminium alloy can be cast into the aluminium of 300 × 300 × 50mm
Alloy sheets ingot.After after the cooling of plate ingot, the treatment of milling face can be carried out to aluminium alloy plate ingot, to obtain more even curface.
S300：Annealing
Embodiments in accordance with the present invention, in this step, make annealing treatment to aluminium alloy ingots.Thus, it is possible in annealing
During treatment so that each component mixing is more uniform in aluminium alloy ingots, to reduce or to eliminate inside aluminium alloy ingots
Structural stress.According to a particular embodiment of the invention, the temperature of annealing is 400~550 degrees Celsius, and the time is 2~6 small
When.Inventor is by many experiments discovery, the aluminium alloy ingots being made up of above-mentioned 4 kinds of alloying elements and solid-state aluminum feedstock, upper
Homogenizing annealing treatment is carried out at a temperature of stating, the structural stress of aluminium alloy ingots can be effectively eliminated.Thus, it is possible to improve finally obtain
The mechanical performance of the aluminium alloy for obtaining.According to a particular embodiment of the invention, the temperature of annealing can be 450~500 Celsius
Degree.
S400：Hot rolling treatment
Embodiments in accordance with the present invention, in this step, hot rolling treatment are carried out to the aluminium alloy ingots by annealing.Root
According to embodiments of the invention, above-mentioned hot rolling treatment is after annealing terminates, to be carried out when aluminium alloy ingots is uncolled.For example,
After annealing, the temperature of aluminium alloy ingots is 500 DEG C, then hot rolling is since 500 DEG C.The finishing temperature of hot rolling treatment can be for not
Less than 280 degrees Celsius.Thus, it is possible to the segmental defect in eliminating aluminium alloy ingots.According to a particular embodiment of the invention, Ke Yi
It is not less than under 280 degrees Celsius of finishing temperature, aluminium alloy ingots is rolled into the aluminium alloy plate that thickness is 6~8mm.Treat that aluminium alloy plate is cold
But to after room temperature, then cold-rolling treatment is carried out to the aluminium alloy plate, aluminium alloy plate is processed as aluminium alloy of the thickness in 1~3mm
Thin plate.Thus, it is possible to using hot rolling treatment, the defect in aluminium alloy ingots is further eliminated, such that it is able to improve final acquisition
The quality of aluminium alloy.
S500：Heat treatment
Embodiments in accordance with the present invention, in this step, to aluminium alloy ingots (or the aluminum alloy thin by hot rolling treatment
Plate) it is heat-treated.According to a particular embodiment of the invention, the heat treatment includes：At first isothermal holding and the second insulation
Reason.The temperature of the first isothermal holding can be 200~600 degrees Celsius, and the time is 1~10 hour.Then, to by the first insulation
The aluminium alloy ingots for the treatment of carries out the second isothermal holding.The temperature of the second isothermal holding can be 200~600 degrees Celsius, and the time can
Think 2~8 hours.According to a particular embodiment of the invention, the temperature of the first isothermal holding can be 300~550 degrees Celsius, when
Between be 3~8 hours；The temperature of the second isothermal holding can be 300~550 degrees Celsius, and the time is 3~6 hours.Thus, it is possible to
So that during the impurity in aluminium alloy ingots (or aluminium alloy sheet) is solidly soluted into Al matrixes, rather than separated out in grain boundaries, so that can
With the further quality for improving the aluminium alloy for obtaining.
In order to further improve the efficiency and effect of heat treatment, embodiments in accordance with the present invention, with reference to Fig. 2, above-mentioned heat
Treatment can further include：
S520：Quenching Treatment
Embodiments in accordance with the present invention, after the first isothermal holding is completed, before carrying out the second isothermal holding, can be right
Aluminium alloy ingots (or aluminium alloy sheet) carries out Quenching Treatment.Inventor is it was unexpectedly observed that quenching processing technology is attached to
State in heat treatment step, can further improve the quality of the aluminium alloy of acquisition.By the aluminium alloy ingots of Quenching Treatment continue into
The isothermal holding of row second.Thus, it is possible to further improve the effect of the second isothermal holding.
S540：Natural cooling
Embodiments in accordance with the present invention, after the second isothermal holding, can be by aluminium alloy ingots (or aluminium alloy sheet)
Natural cooling.It should be noted that in this step, natural cooling refers to not to by the aluminium alloy after the second isothermal holding
Ingot carries out any extra cooling treatment, is passed to the temperature exchange with external environment, naturally cools to and environment temperature phase
Deng or close temperature.For example, according to a particular embodiment of the invention, in this step, taking out by the second isothermal holding
Aluminium alloy ingots, disposed within or outdoor makes its temperature be reduced to interior by 200~600 degrees Celsius of the second isothermal holding
Or outdoor temperature (such as 0~30 degree).Thus, it is possible to further improve the effect of the second isothermal holding, grain boundaries impurity is reduced
The amount of precipitation, it is hereby achieved that the more excellent aluminium alloy of chemical property.
In sum, above-mentioned method according to embodiments of the present invention in solid feed aluminium by adding rational alloy unit
Plain (Mg, Bi, Sn, Mn and Ga), using the mutual synergy between alloying element, and in preparation process to annealing and
The regulation and control (such as annealing temperature, time) of the steps such as heat treatment, can effectively reduce the alloy phase in the aluminium alloy of acquisition, suppress
Liberation of hydrogen self-corrosion, reduces corrosion rate.Therefore, even if being carried out using the aluminium base of purity relatively low (Al content >=99.85wt%)
Prepare, it is also possible to obtain the good aluminium alloy of chemical property.Therefore, the method can reduce being produced into for aluminium-air cell
This, is conducive to the popularization and application of aluminium-air cell.
In the second aspect of the present invention, the present invention proposes a kind of aluminium alloy.Embodiments in accordance with the present invention, the aluminium alloy
It is to be prepared using foregoing method.Thus, the aluminium alloy possesses the whole of aluminium alloy prepared by previously described method
Feature and advantage, will not be repeated here.Generally speaking, the aluminium alloy analysis have be not susceptible to hydrogen self-corrosion, in loading condition
Under corrosion rate it is relatively low compared with the resistance of slow, aluminum alloy surface passivating film, oxidizing potential is relatively born, stable chemical performance and electrification
Learn function admirable, it is with low cost the advantages of at least one of.
In the third aspect of the present invention, the present invention proposes foregoing aluminium alloy in aluminium-air cell anode is prepared
Purposes.
In the fourth aspect of the present invention, the present invention proposes a kind of aluminium-air cell.Embodiments in accordance with the present invention, reference
Fig. 3, the aluminium-air cell includes：Body 100, air electrode 200 and anode 300.According to a particular embodiment of the invention, originally
Limit reaction compartment in body 100, air electricity, 200 be arranged on the inside of body 100 and and air contact, so as to using in air
Oxygen carry out cathode reaction.Anode 30 0 is made up of foregoing aluminium alloy, be arranged on the inside of body 100 and with sky
Pneumoelectric pole 200 electrically connects.Thus, the aluminium-air cell has the advantages that with low cost, anode is corrosion-resistant, electro-chemical activity is high
At least one.
Below by specific embodiment, the present invention will be described, it is necessary to explanation, specific embodiment below is only
It is to be for the purpose of illustration, and limits the scope of the present invention never in any form, in addition, unless otherwise specified, then it is not specific to remember
The method of carrier strip part or step is conventional method, and the reagent and material for being used commercially are obtained.
Embodiment 1
Technical pure aluminium ingot (Al content >=99.85wt%) is put into medium frequency induction melting furnace, heating is fused into 800 DEG C
Aluminium liquid, adds the Ga stones of the Mn and 0.4wt% of Sn, 0.4wt% of Bi, 0.4wt% of Mg, 0.17wt% of 1.3wt%
Inker stirs, and is cast into the aluminium alloy plate ingot of 300 × 300 × 50mm.Treat after aluminium alloy ingots cooling, aluminium alloy ingots is entered
Row milling face.Aluminium alloy ingots after milling face is loaded into Muffle furnace and is incubated 2h at 550 DEG C, be then hot-rolled down to 6mm, treat that it is cooled down completely
1mm thickness aluminium alloy plates are cold rolled to after to room temperature, are reinstalled and be heated in Muffle furnace 450 DEG C, constant temperature is taken out after 3 hours quickly quench into
In water, then the aluminium alloy plate after quenching is put into Muffle furnace and is heated to 400 DEG C, with stove Slow cooling after being incubated 3 hours.Place
The aluminum alloy sheet that 50 × 110mm is cut into after the completion of reason is aluminum alloy anode finished product.Above-mentioned aluminium anodes is made aluminium air monomer
Battery, is tested in 6mol/L KOH media, and aluminium electrode OCP is -1.914V (V.S.Hg/HgO), 200mA/cm2
Current density is discharged, and monomer battery voltage stabilization is in more than 1.42V, 300mA/cm2Current density is discharged, and monomer battery voltage is steady
It is scheduled on more than 1.27V.Constant 200mA/cm2Current density operation, aluminium anodes material specific energy is 3447Wh/kg, and anode is utilized
Rate is higher than 95%.And aluminium anodes is in discharge process and when electric discharge midway stops-being again started up without passivation phenomenon.
Embodiment 2
Technical pure aluminium ingot (Al content >=99.85wt%) is put into medium frequency induction melting furnace, heating is fused into 760 DEG C
Aluminium liquid, adds the Ga of the Mn and 0.02wt% of Sn, 0.01wt% of Bi, 0.02wt% of Mg, 0.02wt% of 0.05wt%
Stirred with graphite rod, be cast into the aluminium alloy plate ingot of 300 × 300 × 50mm.After treating that aluminium alloy ingots is cooled down, by aluminium alloy
Ingot carries out milling face.Aluminium alloy ingots after milling face is loaded into Muffle furnace and is incubated 2h at 500 DEG C, be then hot-rolled down to 6mm, treat that its is complete
1mm thickness aluminium alloy plates are cold rolled to after being cooled to room temperature, are reinstalled and be heated in Muffle furnace 550 DEG C, constant temperature takes out quickly after 3 hours
Quench in water, then the aluminium alloy plate after quenching is put into Muffle furnace and is heated to 450 DEG C, it is slowly cold with stove after being incubated 3 hours
But.The aluminum alloy sheet that 50 × 110mm is cut into after the completion for the treatment of is aluminum alloy anode finished product.Above-mentioned aluminium anodes is made aluminium air
Cell, is tested in 6mol/L KOH media, and aluminium electrode OCP is -1.861V (V.S.Hg/HgO),
200mA/cm2Current density is discharged, and monomer battery voltage stabilization is in more than 1.39V, 300mA/cm2Current density is discharged, monomer electricity
Cell voltage stabilization is in more than 1.24V.Constant 200mA/cm2Current density operation, aluminium anodes material specific energy is 3447Wh/kg,
Anode utilization rate is higher than 96%.And aluminium anodes is in discharge process and when electric discharge midway stops-being again started up without passivation
Phenomenon.
Embodiment 3
Technical pure aluminium ingot (Al content >=99.85wt%) is put into medium frequency induction melting furnace, heating is fused into 820 DEG C
Aluminium liquid, adds the Ga of the Mn and 0.15wt% of Sn, 0.1wt% of Bi, 0.15wt% of Mg, 0.15wt% of 0.8wt% to use
Graphite rod stirs, and is cast into the aluminium alloy plate ingot of 300 × 300 × 50mm.After treating that aluminium alloy ingots is cooled down, by aluminium alloy ingots
Carry out milling face.Aluminium alloy ingots after milling face is loaded into Muffle furnace and is incubated 2h at 450 DEG C, be then hot-rolled down to 6mm, treat that it is completely cold
But to 1mm thickness aluminium alloy plates are cold rolled to after room temperature, reinstall and be heated in Muffle furnace 500 DEG C, constant temperature takes out after 3 hours quickly to be quenched
Enter in water, then the aluminium alloy plate after quenching is put into Muffle furnace and is heated to 500 DEG C, with stove Slow cooling after being incubated 3 hours.
The aluminum alloy sheet that 50 × 110mm is cut into after the completion for the treatment of is aluminum alloy anode finished product.Above-mentioned aluminium anodes is made aluminium air list
Body battery, is tested in 6mol/L KOH media, and aluminium electrode OCP is -1.893V (V.S.Hg/HgO), 200mA/
cm2Current density is discharged, and monomer battery voltage stabilization is in more than 1.40V, 300mA/cm2Current density is discharged, monomer battery voltage
Stabilization is in more than 1.23V.Constant 200mA/cm2Current density operation, aluminium anodes material specific energy is 3401Wh/kg, anode profit
It is higher than 94% with rate.And aluminium anodes is in discharge process and when electric discharge midway stops-being again started up without passivation phenomenon.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means to combine specific features, structure, material or spy that the embodiment or example are described
Point is contained at least one embodiment of the invention or example.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.And, the specific features of description, structure, material or feature can be with office
Combined in an appropriate manner in one or more embodiments or example.Additionally, in the case of not conflicting, the skill of this area
Art personnel can be tied the feature of the different embodiments or example described in this specification and different embodiments or example
Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
Claims (9)
1. a kind of method for preparing aluminium alloy, it is characterised in that including：
(1) hot melt treatment is carried out to solid feed aluminium and alloy raw material, to form aluminium alloy；
(2) casting treatment is carried out to the aluminium alloy, to form aluminium alloy ingots；
(3) aluminium alloy ingots is made annealing treatment, the temperature of the annealing is 400~550 degrees Celsius, and the time is 2
~6 hours；
(4) hot rolling treatment is carried out to the aluminium alloy ingots processed by step (3)；And
(5) aluminium alloy ingots processed by step (4) is heat-treated, the heat treatment includes：
First isothermal holding, the temperature of first isothermal holding is 200~600 degrees Celsius, and the time is 1~10 hour；
Second isothermal holding, the temperature of second isothermal holding is 200~600 degrees Celsius, and the time is 2~8 hours,
Wherein, in the solid feed aluminium, based on the gross weight of the solid feed aluminium, Al content >=99.85wt%；The conjunction
Golden raw material includes Mg, Bi, Sn, Mn and Ga, and based on the gross weight of the solid feed aluminium, the alloy raw material includes：
The Mg of 0.005-1.5wt%, the Mn of Sn, 0.005-0.5wt% of Bi, 0.01-0.5wt% of 0.01~0.2wt% and
The Ga of 0.01-0.5wt%.
2. the method according to right wants 1, it is characterised in that step (1) is further included：
Under 700~950 degrees Celsius, the solid feed aluminium is carried out into hot melt treatment, to form aluminium liquid；
To the alloy raw material is added in the aluminium liquid, 15 minutes are incubated under 700~950 degrees Celsius, to form the conjunction
Golden liquid.
3. the method according to right wants 1, it is characterised in that in step (3), the temperature of the annealing is 450~500
Degree Celsius.
4. the method according to right wants 1, it is characterised in that in step (4), the finishing temperature of the hot rolling treatment is not less than
280 degrees Celsius.
5. the method according to right wants 1, it is characterised in that in step (5), the temperature of first isothermal holding is
300~550 degrees Celsius, the time is 3~8 hours；Second isothermal holding, the temperature of second isothermal holding is taken the photograph for 300~550
Family name's degree, the time is 3~6 hours.
6. the method according to right wants 1, it is characterised in that the heat treatment is further included：
After first isothermal holding, before second isothermal holding, Quenching Treatment is carried out to the aluminium alloy ingots；With
And
After second isothermal holding, by the aluminium alloy ingots natural cooling.
7. a kind of aluminium alloy, it is characterised in that the aluminium alloy is prepared using the method described in any one of claim 1~6
's.
8. purposes of the aluminium alloy described in claim 7 in aluminium-air cell anode is prepared.
9. a kind of aluminium-air cell, it is characterised in that including：
Body, reaction compartment is limited in the body；
Air electrode, the air electrode is arranged on the body interior and and air contact；And
Anode, the anode is arranged on the body interior and is electrically connected with the air electrode, and the anode is will by right
Ask what the aluminium alloy described in 7 was constituted.
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| CN109461942A (en) * | 2018-11-22 | 2019-03-12 | 河南科技大学 | A kind of air cell aluminum alloy anode material and preparation method thereof, air cell |
| WO2019201070A1 (en) * | 2018-04-20 | 2019-10-24 | 东深金属燃料动力实验室有限责任公司 | Method for producing aluminum hydroxide from aluminum waste material |
| CN111187947A (en) * | 2018-11-14 | 2020-05-22 | 中国船舶重工集团公司第七二五研究所 | Aluminum alloy anode material for seawater battery and preparation method |
| CN114351011A (en) * | 2022-01-11 | 2022-04-15 | 东北大学 | High-power aluminum air battery anode material used at low temperature and preparation method thereof |
| CN114976037A (en) * | 2022-06-23 | 2022-08-30 | 华星先进科学技术应用研究(天津)有限公司 | Aluminum-based negative electrode plate for lithium ion battery and lithium ion secondary battery |
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| CN114351011B (en) * | 2022-01-11 | 2022-09-20 | 东北大学 | High-power aluminum air battery anode material used at low temperature and preparation method thereof |
| CN114976037A (en) * | 2022-06-23 | 2022-08-30 | 华星先进科学技术应用研究(天津)有限公司 | Aluminum-based negative electrode plate for lithium ion battery and lithium ion secondary battery |
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