High-potential aluminum alloy plate as well as preparation method and application thereof

Abstract

The invention discloses a high-potential aluminum alloy plate and a preparation method and application thereof.The high-potential aluminum alloy plate is prepared from, by mass, 0.01%-0.15% of Ga, 0.1%-0.8% of Mg, 0.001%-0.08% of Pb, 0.01%-0.1% of Sn, 0.01%-0.05% of Os and the balance aluminum and impurity elements.Quantitative osmium (Os) and Ga, Pb, Sn and Mg metal elements are added into an aluminum matrix, the metal elements are dissolved in the aluminum matrix in a solid mode and have a microalloying effect, and therefore the high-potential aluminum alloy plate can be obtained; the Al-Ga-Os-Mg-Pb-Sn alloy is prepared, osmium is added, so that the steady-state average potential of an aluminum alloy anode is more negative on the premise that the hydrogen evolution rate is not increased, the electrochemical performance of an aluminum electrode is greatly improved, and the hydrogen evolution corrosion rate of the aluminum electrode is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of metal alloys, and in particular to a high-potential aluminum alloy plate and a preparation method and application thereof. Background Art

[0002] There is little room for improvement in the positive potential of the positive electrode materials of aluminum-air batteries and aluminum-silver oxide batteries, while there is a large room for improvement in the negative potential of the negative electrode materials of aluminum-air batteries and aluminum-silver oxide batteries. Aluminum, as the negative electrode material of the battery, easily forms a dense passivation film on the surface, resulting in poor electrochemical activity. In addition, aluminum in alkaline solution corrodes and releases hydrogen, and excessive corrosion and hydrogen release can easily cause the aluminum-silver oxide battery to fail.

[0003] To solve the above problems, relevant technologies have adopted the method of adding alloying elements to improve the electrochemical properties and corrosion resistance of aluminum electrodes. The presence of alloying elements can not only destroy the passivity of the aluminum oxide film and activate the aluminum electrode, but also have a great influence on the electrochemical properties and metallographic structure of the aluminum electrode. However, when the steady-state average potential of the obtained aluminum alloy decreases, the hydrogen evolution rate will also increase significantly, and its electrochemical properties and corrosion resistance still need to be improved.

[0004] Therefore, it is necessary to provide an aluminum alloy plate with good electrochemical properties and corrosion resistance. Summary of the invention

[0005] In view of this, the present application provides a high-potential aluminum alloy plate and a preparation method and application thereof, which are used to solve the problem of how to improve the electrochemical performance and corrosion resistance of negative electrode materials.

[0006] In order to achieve the above technical objectives, this application adopts the following technical solutions: In a first aspect, the present application provides a high potential aluminum alloy plate. The constituent elements of the high potential aluminum alloy plate include, by mass percentage: Ga 0.01~0.15%, Mg 0.1~0.8%, Pb 0.001~0.08%, Sn 0.01~0.1%, Os0.01~0.05%, and the remainder is aluminum and impurity elements, and the total amount of impurity elements is ≤0.1%.

[0007] Preferably, the thickness is 0.29-0.33 mm.

[0008] In a second aspect, the present application provides a method for preparing a high potential aluminum alloy plate, comprising the following steps: S1. After the aluminum ingot is melted, Ga, Pb, Sn, Mg, and Os are added in parts by mass, and then degassed and slag is removed, and then poured into a mold and cooled and demolded to obtain an alloy aluminum ingot; S2. The alloy aluminum ingot is sequentially milled, annealed, and hot rolled to obtain a semi-finished aluminum coil; S3. The semi-finished aluminum coil is cold rolled and then bent and straightened to obtain a high-potential aluminum alloy sheet.

[0009] Preferably, the purity of the aluminum ingot is ≥99.99%, the purity of Ga, Sn, and Os is 5N grade, the purity of Mg is ≥99.96%, and the purity of Pb is ≥99.9%.

[0010] Preferably, in step S1, the melting temperature is 760-780°C.

[0011] Preferably, in step S2, the annealing temperature is 450-500° C., and the annealing time is 6-10 h.

[0012] Preferably, in step S2, the hot rolling reduction amount is ≤50%.

[0013] Preferably, in step S3, the cold rolling reduction is ≤40%, and the number of cold rolling is 3-5 times.

[0014] In a third aspect, the present application provides an application of a high-potential aluminum alloy plate in the field of electrode materials.

[0015] In a fourth aspect, the present application provides an aluminum-air battery or an aluminum-silver oxide battery comprising a high-potential aluminum alloy plate. The beneficial effects of the present application are as follows: the present application prepares an Al-Ga-Os-Mg-Pb-Sn alloy by adding a certain amount of osmium (Os) and Ga, Pb, Sn, and Mg metal elements into an aluminum matrix, so that the metal elements are dissolved in the aluminum matrix and undergo microalloying. The addition of osmium can make the steady-state average potential of the aluminum alloy anode more negative without increasing the hydrogen evolution rate, greatly improve the electrochemical properties of the aluminum electrode, and reduce its hydrogen evolution corrosion rate; the high-potential aluminum alloy plate obtained in the present application has a high corrosion rate in an alkaline solution of aluminate at 80°C and a current density of 700 mA / cm 2 Under certain conditions, it has excellent electrochemical properties and good corrosion resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 The average potential test results of the high potential aluminum alloy plates obtained in Examples 1-3; Figure 2 The test results of the self-corrosion hydrogen evolution rate of the high potential aluminum alloy plate obtained in Examples 1-3; Figure 3 The results of dynamic hydrogen evolution tests at different temperatures for the high potential aluminum alloy plate obtained in Example 1. DETAILED DESCRIPTION

[0017] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0018] The present application provides a high-potential aluminum alloy plate. The constituent elements of the high-potential aluminum alloy plate include, by mass percentage: Ga 0.01-0.15%, Mg 0.1-0.8%, Pb 0.001-0.08%, Sn 0.01-0.1%, Os 0.01-0.05%, and the remainder is aluminum and impurity elements, the total amount of impurity elements is ≤0.1%, and impurities are inevitable impurities generated during the manufacturing process, and the content of each impurity is ≤0.02%. The mass percentage of Os is 0.01%, 0.02%, 0.05%, or any value of 0.01-0.05%.

[0019] The thickness of the high potential aluminum alloy plate of the present application is 0.29-0.33 mm, which is more suitable for use as a negative electrode material.

[0020] The present application provides a method for preparing a high-potential aluminum alloy plate, comprising the following steps: S1. After the aluminum ingot is melted, Ga, Pb, Sn, Mg, and Os are added in parts by mass, and then degassed, stirred, and slag-stripped, and then poured into a mold and cooled and demolded to obtain an alloy aluminum ingot; S2. The alloy aluminum ingot is sequentially milled, annealed, and hot rolled to obtain a semi-finished aluminum coil; S3. The semi-finished aluminum coil is cold rolled and then bent and straightened to obtain a high-potential aluminum alloy sheet.

[0021] The present application uses high-purity aluminum ingots as raw materials, adds intermediate alloys, and adopts a semi-continuous casting method to produce a high-potential aluminum alloy through melting, casting, milling, hot rolling, cold rolling, and straightening.

[0022] The raw materials of this application are commercially available raw materials, the purity of aluminum ingots is ≥99.99%, the purity of Ga, Sn, and Os is 5N grade, the purity of Mg is ≥99.96%, and the purity of Pb is ≥99.9%.

[0023] In step S1, the melting temperature is 760-780°C.

[0024] In step S2, the annealing temperature is 450-500°C, and the annealing time is 6-10 hours. In step S2, the hot rolling reduction (reduction) is ≤50%.

[0025] In step S3, the cold rolling reduction (reduction) is ≤40%, and the number of cold rolling is 3-5 times.

[0026] The present application provides an application of a high-potential aluminum alloy plate in the field of electrode materials.

[0027] When the high potential aluminum alloy plate obtained in the present application is used as the negative electrode material, the current density is 700mA / cm 2 Under the condition of 5MNaOH+2.8MNaAlO2+corrosion inhibitor as electrolyte solution, the steady-state average potential can reach -1.715V (VS.Hg / HgO), and the self-corrosion rate (static) in 80℃ electrolyte solution can reach 0.381mL / (min·cm 2 ).

[0028] The present application provides an aluminum-air battery or an aluminum-silver oxide battery comprising a high-potential aluminum alloy plate. The present solution is further described below through specific embodiments.

[0029] Example 1 A method for preparing a high potential aluminum alloy plate comprises the following steps: S1. 168.5825g of aluminum ingot is added into a graphite crucible, and smelted in a crucible resistance furnace at a smelting temperature of 773°C. After the aluminum ingot is completely melted, 0.0202g of Ga, 0.0506g of Pb, 0.0674g of Sn, 0.8429g of Mg, and 0.0169g of Os are added into the melt in sequence, and after being stirred evenly, 1g of hexachloroethane (C2Cl6) is added for degassing, slag is removed, and finally, the mixture is poured into a cylindrical cast iron mold, cooled and demolded to obtain an alloy aluminum ingot; S2. After the alloy aluminum ingot is milled, it is annealed at 480°C for 8h, and then hot-rolled with a hot-rolling reduction of ≤50% to obtain a semi-finished aluminum coil; S3. The semi-finished aluminum coil is subjected to 5 cold rolling steps (cold rolling reduction amount ≤ 40%), and then stretched, bent and straightened to obtain a high-potential aluminum alloy sheet with a thickness of 0.3±0.03mm.

[0030] In the high potential aluminum alloy plate obtained in this embodiment, the Ga content is 0.01%, the Pb content is 0.03%, the Sn content is 0.04%, the Mg content is 0.5%, and the Os content is 0.01%.

[0031] Example 2 A method for preparing a high potential aluminum alloy plate comprises the following steps: S1. 155.8652g of aluminum ingot is added into a graphite crucible, and smelted in a crucible resistance furnace at a smelting temperature of 780°C. After the aluminum ingot is completely melted, 0.0187g of Ga, 0.0467g of Pb, 0.0623g of Sn, 0.7793g of Mg, and 0.0468g of Os are added into the melt in sequence, and after being stirred evenly, 1g of hexachloroethane (C2Cl6) is added for degassing, slag is removed, and finally, the mixture is poured into a cylindrical cast iron mold, cooled and demolded to obtain an alloy aluminum ingot; S2. After the alloy aluminum ingot is milled, it is annealed at 480°C for 8h, and then hot-rolled with a hot-rolling reduction of ≤50% to obtain a semi-finished aluminum coil; S3. The semi-finished aluminum coil is subjected to 5 cold rolling steps (cold rolling reduction amount ≤ 40%), and then stretched, bent and straightened to obtain a high-potential aluminum alloy sheet with a thickness of 0.3±0.03mm.

[0032] In the high potential aluminum alloy plate obtained in this embodiment, the Ga content is 0.01%, the Pb content is 0.03%, the Sn content is 0.04%, the Mg content is 0.5%, and the Os content is 0.03%.

[0033] Example 3 A method for preparing a high potential aluminum alloy plate comprises the following steps: S1. 185.6382g of aluminum ingot is added into a graphite crucible, and smelted in a crucible resistance furnace at a smelting temperature of 778°C. After the aluminum ingot is completely melted, 0.0223g of Ga, 0.0557g of Pb, 0.0742g of Sn, 0.9282g of Mg, and 0.0928g of Os are added into the melt in sequence, and after being stirred evenly, 1g of hexachloroethane (C2Cl6) is added for degassing, slag is removed, and finally, the mixture is poured into a cylindrical cast iron mold, cooled and demolded to obtain an alloy aluminum ingot; S2. After the alloy aluminum ingot is milled, it is annealed at 480°C for 8h, and then hot-rolled with a hot-rolling reduction of ≤50% to obtain a semi-finished aluminum coil; S3. The semi-finished aluminum coil is subjected to 5 cold rolling steps (cold rolling reduction amount ≤ 40%), and then stretched, bent and straightened to obtain a high-potential aluminum alloy sheet with a thickness of 0.3±0.03mm.

[0034] In the high-potential aluminum alloy plate obtained in this embodiment, the Ga content is 0.01%, the Pb content is 0.03%, the Sn content is 0.04%, the Mg content is 0.5%, and the Os content is 0.05%.

[0035] Comparative Example 1 A method for preparing a high-potential aluminum alloy plate, the other contents are the same as those of Example 1, except that Os is replaced by Mg.

[0036] Test and Evaluation The average potential and self-corrosion hydrogen evolution rate of the high potential aluminum alloy plates prepared in Examples 1-3 were tested to evaluate the effect of Os content on the average potential and self-corrosion hydrogen evolution rate. The test conditions for the average potential and self-corrosion hydrogen evolution rate were: temperature 80°C, current density 700 mA / cm 2 The electrolyte is 5MNaOH+2.8MNaAlO2+corrosion inhibitor, the electrolyte is static, and the average potential test results are as follows Figure 1 As shown, the self-corrosion hydrogen evolution rate test results are as follows Figure 2 shown.

[0037] The dynamic hydrogen evolution rate of the high potential aluminum alloy plate obtained in Example 1 at different temperatures was tested under the following conditions: 700 mA / cm 2 , 5MNaOH+2.8MNaAlO2+corrosion inhibitor, electro-hydraulic flow rate 40L / h, the results are as follows Figure 3 shown.

[0038] Depend on Figure 1-3 It can be seen that the present application prepares Al-Ga-Os-Mg-Pb-Sn alloy by adding a certain amount of osmium (Os) and Ga, Pb, Sn, and Mg metal elements into the aluminum matrix, so that the metal elements are dissolved in the aluminum matrix and micro-alloying occurs. The addition of osmium can make the steady-state average potential of the aluminum alloy anode more negative without increasing the hydrogen evolution rate, greatly improve the electrochemical properties of the aluminum electrode, and reduce its hydrogen evolution corrosion rate; the high-potential aluminum alloy plate obtained in the present application has a high corrosion rate in an alkaline solution of metaaluminate at 80°C and a current density of 700mA / cm 2 Under certain conditions, it has excellent electrochemical properties and good corrosion resistance.

[0039] The above are only preferred specific implementations of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by any technician familiar with the technical field within the technical scope disclosed by the present invention should be covered within the protection scope of the present invention.

Claims

1. A high potential aluminum alloy plate, characterized in that: Measured by mass percentage, the constituent elements of the high-potential aluminum alloy plate include: Ga 0.01~0.15%, Mg 0.1~0.8%, Pb 0.001~0.08%, Sn 0.01~0.1%, Os 0.01~0.05%, and the remainder is aluminum and impurity elements, and the total amount of the impurity elements is ≤0.1%.

2. The high potential aluminum alloy sheet according to claim 1, characterized in that: Its thickness is 0.29~0.33mm.

3. A method for preparing a high potential aluminum alloy sheet as claimed in any one of claims 1 to 2, characterized in that: The following steps are involved: S1. After the aluminum ingot is melted, Ga, Pb, Sn, Mg, and Os are added in parts by mass, and then degassed and slag is removed, and then poured into a mold and cooled and demolded to obtain an alloy aluminum ingot; S2. The alloy aluminum ingot is sequentially milled, annealed, and hot rolled to obtain a semi-finished aluminum coil; S3. The semi-finished aluminum coil is subjected to cold rolling, bending and straightening to obtain the high-potential aluminum alloy sheet.

4. The method for preparing a high potential aluminum alloy sheet according to claim 3, characterized in that: In step S1, the melting temperature is 760-780°C.

5. The method for preparing a high potential aluminum alloy sheet according to claim 3, characterized in that: In step S2, the annealing temperature is 450-500° C., and the annealing time is 6-10 hours.

6. The method for preparing a high potential aluminum alloy sheet according to claim 3, characterized in that: In step S2, the hot rolling reduction amount is ≤50%.

7. The method for preparing a high potential aluminum alloy sheet according to claim 3, characterized in that: In step S3, the cold rolling reduction amount is ≤40%, and the number of cold rolling is 3-5 times.

8. The method for preparing a high potential aluminum alloy sheet according to claim 3, characterized in that: The purity of the aluminum ingot is ≥99.99%.

9. Use of the high-potential aluminum alloy plate obtained by the preparation method according to any one of claims 3 to 8 in the field of electrode materials.

10. An aluminum-air battery or an aluminum-silver oxide battery comprising the high-potential aluminum alloy plate obtained by the preparation method according to any one of claims 3 to 8.

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