CN102820472A - Manganese-aluminum containing anode material and preparation method thereof, as well as air cell prepared by using anode material - Google Patents
Manganese-aluminum containing anode material and preparation method thereof, as well as air cell prepared by using anode material Download PDFInfo
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- CN102820472A CN102820472A CN201210281070XA CN201210281070A CN102820472A CN 102820472 A CN102820472 A CN 102820472A CN 201210281070X A CN201210281070X A CN 201210281070XA CN 201210281070 A CN201210281070 A CN 201210281070A CN 102820472 A CN102820472 A CN 102820472A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a manganese-aluminum containing anode material for an air cell, and a preparation method and an application of the manganese-aluminum containing anode material. The air cell comprises a manganese-aluminum containing anode, an air cathode and neutral electrolyte. The anode material comprises the following elements in percentage by weight: 0.05 to 2.5 percent of Mg, 0.05 to 1.5 percent of Sn, 0.05 to 2.5 percent of Ga, 0.1 to 1 percent of Mn and the balance of Al, and is prepared through an inert gases protection induction smelting method. With the adoption of the manganese-aluminum containing anode material, the open-circuit voltage is negative (minus 1.6 to minus 1.8V (vs.SHE)), the anode utilization is high (larger than or equal to 94%), the self-corrosion speed is low (smaller than or equal to 0.03mg/cm<2>*h), the surface corrosion is uniform, and the manganese-aluminum containing anode material belongs to high-performance anode material for the air cell operated in a neutral solution.
Description
Technical field
The present invention relates to the air cell field, relating in particular to a kind of is the preparation method of the air cell and the anode material of anode material with the manganese-containing aluminum alloy.
Background technology
Metal-air cell is the new generation of green storage battery, its low cost of manufacture, nontoxic, specific energy is high, the recyclable utilization of raw material, superior performance.At present the more metal-air cell of research has zinc-air cell, aluminum-air cell and lithium-air battery etc., has only zinc-air cell with industrialization is immediate.Because in galvanic series, aluminum ratio zinc is more active, can obtain higher cell voltage, and an aluminium atom can emit three electronics, and a zinc atom discharges two electronics, and aluminium can improve the energy of battery.In addition, aluminium is can mass-produced cheap metal, so a wide prospect has been opened up in the research of aluminum-air cell, its progress is a kind of rising air cell very rapidly.
Aluminium has its unique advantage as the anode material of air cell: (1) electrochemical equivalent is high, and the electrochemical equivalent of aluminium is 2980Ah/kg, is metal the highest except that lithium; (2) electrode potential is more negative; Its standard electrode potential is-1.66V (vs.SHE) in neutral solution, and its standard electrode potential is-2.35V (vs.SHE) in alkaline solution, the antianode material; Current potential is negative more good more, and battery can provide bigger electromotive force; (3) aboundresources of aluminium is cheap.
At present, air cell is compared with zinc anode material with the aluminium anodes material, and the matter of utmost importance of existence is exactly that very strong affinity is arranged between aluminium and the oxygen, thus fine aluminium very easily passivation in the aqueous solution, the stable fine and close Al of surface coverage one deck
2O
3Oxide-film is merely-0.8V (vs.SHE) current potential of fine aluminium in neutral solution, does not reach its theoretic electrode potential, can not satisfy the requirement of anode material to voltage; Another serious problems that the aluminum-air cell anode material exists are, aluminium is particularly very serious from corroding liberation of hydrogen in the alkaline solution in neutral solution, causes the anode utilance to reduce greatly, and the voltage delay phenomenon is arranged during discharge.More than two problems hindered the commercial applications of aluminum-air cell.In order to eliminate the oxide-film on aluminium surface, adopt alloying process usually, add some alloying element aluminium is carried out activation, stop effectively or suppress the aluminium surface to form fine and close continuously oxide-film; For reduce aluminium from corrosion rate, generally all adopt the higher aluminium of purity (>=99.9%) and add some alloying element aluminium is carried out alloying with high overpotential of hydrogen evolution.
Study verifiedly, in aluminium, add a spot of one or more alloying elements, can significantly improve the chemical property of aluminium alloy, destroying its oxide-film increases its activity, and the fine aluminium current potential is negative to be moved thereby make.The alloy element that the aluminum-air cell anode material is commonly used mainly contains zinc, magnesium, sows, indium, tin, lead, mercury, bismuth etc.These elements add multicomponent alloys such as forming ternary, quaternary in the aluminium to.Better performances Al-In-Mg (electrochemical behavior of Al-In-Mg line aluminium alloy anode in NaOH solution, light-alloy process technology, 2004 are arranged; 10:39-42), Al-Ga-Mg (Al-Ga-Mg alloy structure and anode performance research, Chinese corrosion and protection journal, 2005; 6:336-339), the Al-Ga-Bi-Pb (electrochemical behavior of Al-Ga-Bi-Pb alloy in alkaline electrolyte; Power technology, 2009,5:368-370) waiting is alloy.The purity of the raw material aluminium that current aluminum-air cell uses is all more than 99.9%, and this mainly is in order to reduce the corrosion certainly of the aluminium anodes material that impurity element iron causes, but the costing an arm and a leg of rafifinal.
Summary of the invention
The object of the present invention is to provide a kind of manganese-containing aluminum alloy anode material.
In addition, the present invention also aims to provide a kind of preparation method of anode material.
The present invention also aims to provide a kind of from corrosion rate low be the air cell of anode material with the manganese-containing aluminum alloy.
In order to solve the problems of the technologies described above; The present invention realizes through following scheme: the aluminium (Al) with purity >=99.7% is primary raw material; Add element magnesium (Mg), tin (Sn), sow (Ga) and manganese (Mn), add element mass percent be: Mg:0.05～2.5%; Sn:0.05～1.5%; Ga:0.05～2.5%; Mn:0.1～1%.
Adopt the air cell of technique scheme to use the manganese-containing aluminum alloy anode material; Be basis with purity for>=99.7% aluminium, add Mg, Sn, Ga and the Mn element of trace, purpose is its fine and close alumina protective layer of destruction; Improve its chemical property and surface dissolution uniformity; And reduce it from corrosion rate, and particularly in aluminium alloy, adding trace manganese, manganese and iron can preferentially combine to form second Al mutually that contains manganese and iron
6(Fe, Mn), this phase current potential is close with the base aluminum current potential, can slow down the corrosion certainly of aluminium alloy, thereby improves the anode utilance.
The preparation method of anode material is: (1) is under inert gas shielding; With aluminium ingot all fusings in elevated temperature vessel, add magnesium ingot, aluminium manganese intermediate alloy, tin grain then and sow grain, limit heating edge rotary container when temperature is 680～700 ℃; Motlten metal is mixed; Continue to be heated to 750～770 ℃, behind insulation 5～7min, pour into block slab ingot; (2) with the slab ingot of cast molding in 400～550 ℃ of homogenizing annealing 4-10h, make alloying element even diffused at high temperature; (3) slab ingot after the annealing is rolling to the thick manganese-containing aluminum alloy anode material of 0.5～4mm under 150～200 ℃.Can obtain open circuit voltage negative (1.6～-1.8V (vs.SHE)), anode utilance high (>=94%) is from the low (≤0.03mg/cm of corrosion rate
2H), cell is 100～300mA/cm at discharge current density
2The electromotive force of scope build-in test 120h is that the uniform high-performance air cell of 1.5V～1.8V, surface corrosion is used the manganese-containing aluminum alloy anode material.
Adopting the material of such scheme preparation is the anode of air cell, and the negative electrode of this air cell is made up of Catalytic Layer, nickel screen conducting matrix grain and waterproof ventilative layer, and wherein Catalytic Layer is γ-MnO
2, active carbon and polytetrafluoroethylene be by weight (0.5～2): (2 ~ 4): (1 ~ 3) is mixed roll extrusion and is processed the thick film of 0.3～0.5mm; Watertight composition is that polytetrafluoroethylene and acetylene black are processed the thick film of 0.3～0.5mm by weight 1:1 mixing roll extrusion, at last Catalytic Layer, nickel screen and waterproof ventilative layer is pressed into the thick air cathode of 0.3～0.5mm.Electrolyte is 1～4MNaCl.
The present invention considers with the chemical property that improves the aluminium anodes material and reduces it from corrosivity from the alloying aspect: aluminium alloy, add an amount of magnesium, tin and sow, particularly add manganese element.Impurity element iron in the aluminium alloy is dissolved in aluminum substrate hardly, but with big block Fe
3The form of Al second phase is present in the aluminum substrate, and this phase current potential calibration forms the microcorrosion galvanic couple with base aluminum, causes that aluminium anodes causes the anode utilance extremely low from corrosion, and big block iron phase causes that also the alloy surface dissolving is inhomogeneous.In aluminium alloy, adding trace manganese, is because manganese and iron can preferentially combine to form second Al mutually that contains manganese and iron
6(Fe, Mn), this phase current potential is close with the base aluminum current potential, can slow down the corrosion certainly of aluminium alloy, thereby improves the anode utilance; Adding trace magnesium can refinement aluminium alloy crystal grain, and magnesium can form Mg in alloy
2Al
3Compound, dystectic Mg
2Al
3Compound has the effect of crystal grain thinning, makes the aluminium anodes uniform dissolution.The solid solubility of sowing element and aluminium is very big; Corrosion produces sows ion because active low can being reduced again can generate sowing of liquid state and deposit to aluminum alloy surface, sows amalgam with aluminum substrate generation aluminium, and aluminium is sowed peelable oxide-film of amalgam and corrosion product; Exposed base aluminum promotes the activation discharge of aluminium alloy.Simultaneously, tin is high overpotential of hydrogen evolution element with sowing, and the liberation of hydrogen that can reduce aluminium alloy greatly is from corrosion.The addition of these alloy elements is within certain scope; If addition is few; Do not have due effect,, form the second bigger phase of a large amount of shapes if addition is big; Do not have the effect of crystal grain thinning, increase on the contrary aluminium alloy from corrosion rate, reduce the anode utilance and make corrosion uniformity variation.Through adding an amount of magnesium, tin and sowing, manganese element particularly, to aluminium carry out alloying can obviously improve alloy the anode utilance, reduce from corrosion rate, can also improve the corrosion uniformity of alloy surface.
Manganese-containing aluminum alloy anode material of the present invention is compared with existing aluminium anodes material; Summarize to get up to have the following advantages: (1) has prepared a kind of novel manganese-containing aluminum alloy anode material; Electrochemical activation property is fine; OCP in neutral electrolyte≤-1.6V (vs.SCE), the electromotive force of cell is greater than 1.5V; (2) anode material has added micro-magnesium, tin, has sowed and manganese element, and manganese element particularly slows down the adverse effect of impurity element iron, refinement alloy grain, improved the utilance of aluminium anodes, reduced aluminium alloy from corrosion rate; (3) anode material has obviously improved the chemical property of anode and has improved tissue through microalloying, and its anode utilance reaches more than 94%, from corrosion rate less than 0.03mg/cm
2H; (4) purity of the raw materials used aluminium of aluflex anode material of the present invention is loosened to general aluminium (>=99.7%) by rafifinal (>=99.9%), and the cost of preparation aluminum alloy anode material is obviously reduced; (5) the aluflex anode material superior performance of the present invention's preparation, surface corrosion is even.
Embodiment
Embodiment 1:
The negative electrode of air cell is made up of Catalytic Layer, nickel screen conducting matrix grain and waterproof ventilative layer, and wherein Catalytic Layer is γ-MnO
2, active carbon processes the thick film of 0.5mm with polytetrafluoroethylene by weight 0.5:2:1 mixing roll extrusion; Watertight composition is that polytetrafluoroethylene and acetylene black are processed the thick film of 0.3mm by weight 1:1 mixing roll extrusion, at last Catalytic Layer, nickel screen and waterproof ventilative layer is pressed into the thick air cathode of 0.3mm.Electrolyte is 4MNaCl.
Each composition percentage by weight of aluflex anode material is: Mg:0.05%; Sn:1%; Ga:2.5%; Mn:0.1%; All the other are Al.
Under argon shield; With aluminium ingot all fusings in ZGJL0.01-40-4 induction melting furnace crucible, add magnesium ingot, aluminium manganese intermediate alloy (90%Al-10%Mn), tin grain then and sow grain, limit heating edge rotary container when temperature is 700 ℃; Motlten metal is mixed; Continue to be heated to 750 ℃, behind the insulation 7min, pour into block slab ingot; The slab ingot of cast molding in 400 ℃ of homogenizing annealing 10h, is made alloying element even diffused at high temperature; Slab ingot after the annealing is rolling to the thick aluflex anode material of 2mm under 200 ℃.Anode alloy is 0.006mg/cm from corrosion rate in 4MNaCl solution
2H, OCP are-1.783V (vs.SHE) that the air cell of composition discharge current density in 4MNaCl electrolyte is 100mA/cm
2The electromotive force of time test 120h is 1.629V, and the anode utilance is 95.7%, and surface corrosion is even.Concrete electrochemical properties is seen table 1.
Embodiment 2:
The negative electrode of air cell is made up of Catalytic Layer, nickel screen conducting matrix grain and waterproof ventilative layer, and wherein Catalytic Layer is γ-MnO
2, active carbon processes the thick film of 0.3mm with polytetrafluoroethylene by weight 2:4:3 mixing roll extrusion; Watertight composition is that polytetrafluoroethylene and acetylene black are processed the thick film of 0.35mm by weight 1:1 mixing roll extrusion, at last Catalytic Layer, nickel screen and waterproof ventilative layer is pressed into the thick air cathode of 0.5mm.Electrolyte is 2MNaCl.
Each composition percentage by weight of aluflex anode material is: Mg:2.5%; Sn:0.05%; Ga:0.05%; Mn:1%; All the other are Al.
Under argon shield; With aluminium ingot all fusings in ZGJL0.01-40-4 induction melting furnace crucible, add magnesium ingot, aluminium manganese intermediate alloy (90%Al-10%Mn), tin grain then and sow grain, limit heating edge rotary container when temperature is 680 ℃; Motlten metal is mixed; Continue to be heated to 755 ℃, behind the insulation 5min, pour into block slab ingot; The slab ingot of cast molding in 550 ℃ of homogenizing annealing 4h, is made alloying element even diffused at high temperature; Slab ingot after the annealing is rolled to the thick aluflex anode material of 1mm in 150 ℃.Anode alloy is 0.03mg/cm from corrosion rate in 2MNaCl solution
2H, OCP are-1.796V (vs.SHE) that the air cell of composition discharge current density in 2MNaCl electrolyte is 300mA/cm
2The electromotive force of time test 120h is 1.741V, and the anode utilance is 97.2%, and surface corrosion is even.Concrete electrochemical properties is seen table 1.
Embodiment 3:
The negative electrode of air cell is made up of Catalytic Layer, nickel screen conducting matrix grain and waterproof ventilative layer, and wherein Catalytic Layer is γ-MnO
2, active carbon processes the thick film of 0.4mm with polytetrafluoroethylene by weight 1:3:2 mixing roll extrusion; Watertight composition is that polytetrafluoroethylene and acetylene black are processed the thick film of 0.5mm by weight 1:1 mixing roll extrusion, at last Catalytic Layer, nickel screen and waterproof ventilative layer is pressed into the thick air cathode of 0.35mm.Electrolyte is 1MNaCl.
Each composition percentage by weight of aluflex anode material is: Mg:2%; Sn:1.5%; Ga:1%; Mn:0.5%; All the other are Al.
Under argon shield; With aluminium ingot all fusings in ZGJL0.01-40-4 induction melting furnace crucible, add magnesium ingot, aluminium manganese intermediate alloy (90%Al-10%Mn), tin grain then and sow grain, limit heating edge rotary container when temperature is 690 ℃; Motlten metal is mixed; Continue to be heated to 765 ℃, behind the insulation 6min, pour into block slab ingot; The slab ingot of cast molding in 450 ℃ of homogenizing annealing 8h, is made alloying element even diffused at high temperature; Slab ingot after the annealing is rolled to the thick aluflex anode material of 4mm in 170 ℃.Anode alloy is 0.012mg/cm from corrosion rate in 1MNaCl solution
2H, OCP are-1.615V (vs.SHE) that the air cell of composition discharge current density in 1MNaCl electrolyte is 150mA/cm
2The electromotive force of time test 120h is 1.569V, and the anode utilance is 94.5%, and surface corrosion is even.Concrete electrochemical properties is seen table 1.
Embodiment 4:
The negative electrode of air cell is made up of Catalytic Layer, nickel screen conducting matrix grain and waterproof ventilative layer, and wherein Catalytic Layer is γ MnO
2, active carbon processes the thick film of 0.5mm with polytetrafluoroethylene by weight 1.5:2:3 mixing roll extrusion; Watertight composition is that polytetrafluoroethylene and acetylene black are processed the thick film of 0.45mm by weight 1:1 mixing roll extrusion, at last Catalytic Layer, nickel screen and waterproof ventilative layer is pressed into the thick air cathode of 0.35mm.Electrolyte is 3MNaCl.
Each composition percentage by weight of aluflex anode material is: Mg:1%; Sn:0.75%; Ga:2.5%; Mn:0.8%; All the other are Al.
Under argon shield; With aluminium ingot all fusings in ZGJL0.01-40-4 induction melting furnace crucible, add magnesium ingot, aluminium manganese intermediate alloy (90%Al-10%Mn), tin grain then and sow grain, limit heating edge rotary container when temperature is 695 ℃; Motlten metal is mixed; Continue to be heated to 760 ℃, behind the insulation 6min, pour into block slab ingot; The slab ingot of cast molding in 500 ℃ of homogenizing annealing 6h, is made alloying element even diffused at high temperature; Slab ingot after the annealing is rolled to the thick aluflex anode material of 0.5mm in 160 ℃.Anode alloy is 0.024mg/cm from corrosion rate in 3MNaCl solution
2H, OCP are-1.734V (vs.SHE) that the air cell of composition discharge current density in 3MNaCl electrolyte is 200mA/cm
2The electromotive force of time test 120h is 1.628V, and the anode utilance is 96.2%, and surface corrosion is even.Concrete electrochemical properties is seen table 1.
Embodiment 5:
The negative electrode of air cell is made up of Catalytic Layer, nickel screen conducting matrix grain and waterproof ventilative layer, and wherein Catalytic Layer is γ-MnO
2, active carbon processes the thick film of 0.45mm with polytetrafluoroethylene by weight 1:4:2 mixing roll extrusion; Watertight composition is that polytetrafluoroethylene and acetylene black are processed the thick film of 0.3mm by weight 1:1 mixing roll extrusion, at last Catalytic Layer, nickel screen and waterproof ventilative layer is pressed into the thick air cathode of 0.4mm.Electrolyte is 2.5MNaCl.
Each composition percentage by weight of aluflex anode material is: Mg:1.5%; Sn:0.5%; Ga:1.5%; Mn:0.6%; All the other are Al.
Under argon shield; With aluminium ingot all fusings in ZGJL0.01-40-4 induction melting furnace crucible, add magnesium ingot, aluminium manganese intermediate alloy (90%Al-10%Mn), tin grain then and sow grain, limit heating edge rotary container when temperature is 685 ℃; Motlten metal is mixed; Continue to be heated to 770 ℃, behind the insulation 5min, pour into block slab ingot; The slab ingot of cast molding in 510 ℃ of homogenizing annealing 7h, is made alloying element even diffused at high temperature; Slab ingot after the annealing is rolled to the thick aluflex anode material of 3mm in 200 ℃.Anode alloy is 0.018mg/cm from corrosion rate in 2.5MNaCl solution
2H, OCP are-1.758V (vs.SHE) that the air cell of composition discharge current density in 2.5MNaCl electrolyte is 300mA/cm
2The electromotive force of time test 120h is 1.705V, and the anode utilance is 95.4%, and surface corrosion is even.Concrete electrochemical properties is seen table 1.
Can find out that through above embodiment aluflex anode material of the present invention has high chemical property really, and the alloy surface dissolving evenly.
The chemical property of table 1 embodiment 1～5 manganese-containing aluminum alloy anode material
It should be noted last that: above embodiment is the unrestricted technical scheme of the present invention in order to explanation only; Although the present invention is specified with reference to the foregoing description; Those of ordinary skill in the art is to be understood that: still can make amendment or be equal to replacement the present invention; And replace any modification or the part that do not break away from the spirit and scope of the present invention, and it all should be encompassed in the middle of the claim scope of the present invention.
Claims (6)
1. an air cell is used the manganese-containing aluminum alloy anode material, it is characterized in that: the element by following weight ratio is formed: Mg:0.05～2.5%; Sn:0.05～1.5%; Ga:0.05～2.5%; Mn:0.1～1%; Surplus is Al.
2. a kind of air cell as claimed in claim 1 is used the aluflex anode material, it is characterized in that: aluminium purity is >=99.7%.
3. an air cell as claimed in claim 1 is characterized in that with the preparation method of aluflex anode material: adopt the induction melting preparation, may further comprise the steps:
(1) under inert gas shielding; With aluminium ingot all fusings in elevated temperature vessel, add magnesium ingot, aluminium manganese intermediate alloy, tin grain then and sow grain, limit heating edge rotary container when temperature is 680～700 ℃; Motlten metal is mixed; Continue to be heated to 750～770 ℃, behind insulation 5～7min, pour into block slab ingot;
(2) with the slab ingot of cast molding in 400～550 ℃ of homogenizing annealing 4-10h, make element even diffused at high temperature;
(3) slab ingot after the annealing is rolling to the thick aluflex anode material of 0.5～4mm under 150～200 ℃.
4. air cell as claimed in claim 3 is characterized in that with the preparation method of aluflex anode material: elevated temperature vessel is a crucible.
5. air cell as claimed in claim 3 is characterized in that with the preparation method of aluflex anode material: aluminium manganese intermediate alloy is 90%Al-10%Mn.
6. air cell that adopts manganese-containing aluminum alloy anode material as claimed in claim 1, it is characterized in that: air cell comprises the manganese-containing aluminum alloy anode, air cathode and electrolyte; Air cathode is made up of Catalytic Layer, conduction nickel screen and waterproof ventilative layer, and wherein Catalytic Layer is γ-MnO
2, active carbon and polytetrafluoroethylene be by weight (0.5～2): (2～4): (1～3) is mixed roll extrusion and is processed the thick film of 0.3～0.5mm; Watertight composition is that polytetrafluoroethylene and acetylene black are processed the thick film of 0.3～0.5mm by weight 1:1 mixing roll extrusion, and last Catalytic Layer, nickel screen and waterproof ventilative layer are pressed into the thick air cathode of 0.3～0.5mm; Electrolyte is 1～4MNaCl solution.
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| CN104372206A (en) * | 2014-09-18 | 2015-02-25 | 河南科技大学 | Rare earth-containing amorphous/nanocrystal aluminum anode composite material, preparation method and aluminum air battery |
| CN105140596A (en) * | 2015-09-06 | 2015-12-09 | 河南科技大学 | Aluminum alloy anode material for air cell, preparation method and aluminum air cell |
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| CN106756665A (en) * | 2016-11-28 | 2017-05-31 | 云南冶金集团创能铝空气电池股份有限公司 | Aluminium alloy, preparation method and purposes |
| CN106917010A (en) * | 2017-04-25 | 2017-07-04 | 哈尔滨工业大学 | A kind of aluminum alloy anode material and its casting method and application |
| CN106917010B (en) * | 2017-04-25 | 2018-11-13 | 哈尔滨工业大学 | A kind of aluminum alloy anode material and its casting method and application |
| CN108666561A (en) * | 2018-05-16 | 2018-10-16 | 湖南源达新材料有限公司 | A kind of air cell electrode material and preparation method thereof |
| CN108808007A (en) * | 2018-06-01 | 2018-11-13 | 安徽工业大学 | A kind of preparation method of the aluminium-air cell anode material of high Fe content |
| CN109338181A (en) * | 2018-11-13 | 2019-02-15 | 东北大学 | A kind of alkalinity aluminium-air cell anode material and preparation method thereof |
| CN109338181B (en) * | 2018-11-13 | 2020-05-12 | 东北大学 | Anode material for alkaline aluminum-air battery and preparation method thereof |
| 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 |
| CN110010885A (en) * | 2019-04-08 | 2019-07-12 | 上海交通大学 | Aluminium-air cell anode material and preparation method thereof |
| CN111180720A (en) * | 2019-10-22 | 2020-05-19 | 超威电源集团有限公司 | Aluminum air battery anode and preparation method thereof |
| CN111180720B (en) * | 2019-10-22 | 2022-06-21 | 超威电源集团有限公司 | Aluminum air battery anode and preparation method thereof |
| CN111740094A (en) * | 2020-07-01 | 2020-10-02 | 昆明冶金研究院有限公司 | Aluminum air battery aluminum anode plate material and preparation method thereof, aluminum air battery aluminum anode plate and preparation method and application thereof |
| CN113584351A (en) * | 2021-06-08 | 2021-11-02 | 昆明理工大学 | Rare earth-free aluminum alloy and preparation method and application thereof |
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