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

Abstract

The application discloses a high-potential aluminum alloy plate and a preparation method and application thereof. According to mass percentage, the high-potential aluminum alloy plate comprises 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 balance is aluminum and impurity elements. The application adds a certain amount of osmium (Os) and Ga, Pb, Sn and Mg metal elements in the aluminum matrix, so that the metal elements are solid-solved in the aluminum matrix and micro-alloying occurs, an Al-Ga-Os-Mg-Pb-Sn alloy is prepared, 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 improves the electrochemical performance of the aluminum electrode, and reduces the hydrogen evolution corrosion rate.

Description

TECHNICAL FIELD

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

[0002] The positive potential of the positive electrode material of the aluminum-air battery and the aluminum silver oxide battery has little room for improvement, while the negative potential of the negative electrode material of the aluminum-air battery and the aluminum silver oxide battery has a large room for improvement. As the negative electrode material of the battery, aluminum is prone to form a dense passivation film on the surface, which leads to poor electrochemical activity. In addition, the corrosion and hydrogen evolution of aluminum in alkaline solution are too fast, which can easily cause the failure of the aluminum silver oxide battery.

[0003] To solve the above problems, the related technology adopts the method of adding alloying elements to improve the electrochemical performance and corrosion resistance of the aluminum electrode. The presence of alloying elements not only destroys the passivity of the aluminum oxide film and activates the aluminum electrode, but also has a great influence on the electrochemical performance and metallographic structure of the aluminum electrode. However, when the steady-state average potential of the obtained aluminum alloy decreases, the hydrogen evolution rate also increases significantly, and the electrochemical performance and corrosion resistance still need to be improved.

[0004] Therefore, it is necessary to provide an aluminum alloy plate with good electrochemical performance and corrosion resistance. SUMMARY

[0005] Therefore, 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 the negative electrode material.

[0006] To achieve the above technical purpose, the present application adopts the following technical scheme:

[0007] In a first aspect, the present application provides a high-potential aluminum alloy plate, which comprises the following elements in terms of 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 balance being aluminum and impurity elements, with the total amount of impurity elements being ≤0.1%.

[0008] Preferably, the thickness is 0.29-0.33 mm.

[0009] In a second aspect, the present application provides a preparation method of a high-potential aluminum alloy plate, comprising the following steps:

[0010] S1. After melting the aluminum ingot, Ga, Pb, Sn, Mg and Os are added according to the mass fraction, and then degassing and slagging are performed, followed by pouring into a mold and cooling and demolding to obtain an alloy aluminum ingot;

[0011] S2. Milling surface, annealing and hot rolling the alloy aluminum ingot in sequence to obtain semi-finished aluminum coil;

[0012] S3. Stretching and straightening the semi-finished aluminum coil after cold rolling to obtain the high-potential aluminum alloy plate.

[0013] 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%.

[0014] Preferably, in step S1, the melting temperature is 760-780℃.

[0015] Preferably, in step S2, the annealing temperature is 450-500℃, and the annealing time is 6-10h.

[0016] Preferably, in step S2, the hot rolling reduction is ≤50%.

[0017] Preferably, in step S3, the cold rolling reduction is ≤40%, and the number of cold rolling is 3-5 times.

[0018] In a third aspect, the application provides a use of the high-potential aluminum alloy plate in the field of electrode materials.

[0019] In a fourth aspect, the application provides an aluminum-air battery or an aluminum-silver oxide battery comprising the high-potential aluminum alloy plate.

[0020] The application has the following beneficial effects: by adding a certain amount of osmium (Os) and Ga, Pb, Sn and Mg metal elements in the aluminum matrix, the metal elements are dissolved in the aluminum matrix and micro-alloying occurs, and an Al-Ga-Os-Mg-Pb-Sn alloy is prepared. 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 performance of the aluminum electrode, and reduce the hydrogen evolution corrosion rate. The high-potential aluminum alloy plate obtained by the application has excellent electrochemical performance and good corrosion resistance in a metaborate alkaline solution at 80℃ and a current density of 700mA / cm 2 . BRIEF DESCRIPTION OF DRAWINGS

[0021] Fig. 1 Test results of the average potential of the high-potential aluminum alloy plate obtained in Examples 1-3;

[0022] Fig. 2 Test results of the self-corrosion hydrogen evolution rate of the high-potential aluminum alloy plate obtained in Examples 1-3;

[0023] Fig. 3 Test results of the dynamic hydrogen evolution of the high-potential aluminum alloy plate obtained in Example 1 at different temperatures. DETAILED DESCRIPTION

[0024] In order to make the objectives, technical solutions and advantages of the present application clearer, the present application will be further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and should not be used to limit the present application.

[0025] The present application provides a high-potential aluminum alloy sheet, the composition of the high-potential aluminum alloy sheet includes, in terms of 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%, the balance being aluminum and impurity elements, the total amount of impurity elements ≤0.1%, the impurities are unavoidable impurities generated during the manufacturing process, and the content of each impurity ≤0.02%. The mass percentage of Os is any value in 0.01%, 0.02%, 0.05% or 0.01-0.05%.

[0026] The thickness of the high-potential aluminum alloy sheet of the present application is 0.29-0.33 mm, which is more suitable for use as a negative electrode material.

[0027] The present application provides a preparation method of a high-potential aluminum alloy sheet, including the following steps:

[0028] S1. After melting the aluminum ingot, Ga, Pb, Sn, Mg and Os are added according to the mass fraction, and then degassing, stirring and slagging are performed, and then the alloy aluminum ingot is obtained by pouring into a mold and cooling and demolding;

[0029] S2. The alloy aluminum ingot is sequentially subjected to face milling, annealing and hot rolling to obtain a semi-finished aluminum coil;

[0030] S3. The semi-finished aluminum coil is cold-rolled, bent and straightened to obtain a high-potential aluminum alloy sheet.

[0031] The present application uses high-purity aluminum ingot as raw material, adds intermediate alloy, adopts semi-continuous casting mode, and through melting, casting, face milling, hot rolling, cold rolling and straightening, a high-potential aluminum alloy is prepared.

[0032] The raw material of the present application is a commercially available raw material, 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%.

[0033] In step S1, the melting temperature is 760-780℃.

[0034] In step S2, the annealing temperature is 450-500℃, and the annealing time is 6-10h. In step S2, the hot rolling reduction (reduction) is ≤50%.

[0035] In step S3, the cold rolling reduction is less than or equal to 40%, and the number of cold rolling is 3-5 times.

[0036] The application provides application of a high-potential aluminum alloy plate in the field of electrode materials.

[0037] The high-potential aluminum alloy plate obtained by the application has a stable average potential of-1.715 V (VS. Hg / HgO) when used as a negative electrode material under the conditions of 80±2 ℃ and a current density of 700 mA / cm 2 , and has a self-corrosion rate (static) of 0.381 mL / (min·cm 2 ) in an electrolyte solution of 5M NaOH+2.8M NaAlO2+inhibitor at 80 ℃.

[0038] The application provides an aluminum-air battery or an aluminum-silver oxide battery comprising the high-potential aluminum alloy plate.

[0039] The application is further described below through specific examples.

[0040] Example 1

[0041] A preparation method of a high-potential aluminum alloy plate comprises the following steps:

[0042] S1. 168.5825 g of aluminum ingot is added to a graphite crucible and melted in a crucible resistance furnace, the melting temperature is 773 ℃, after the aluminum ingot is completely melted, 0.0202 g of Ga, 0.0506 g of Pb, 0.0674 g of Sn, 0.8429 g of Mg and 0.0169 g of Os are sequentially added to the melt, after uniform stirring, 1 g of hexachloroethane (C2Cl6) is added for degassing, slag is removed, and finally the alloy aluminum ingot is poured into a cylindrical cast iron mold, cooled and demolded.

[0043] S2. After the alloy aluminum ingot is milled, it is annealed at 480 ℃ for 8 h, and then hot-rolled out of the furnace, the hot rolling reduction is less than or equal to 50%, and a semi-finished aluminum coil is obtained.

[0044] S3. The semi-finished aluminum coil is cold-rolled for 5 times (the cold rolling reduction is less than or equal to 40%), and then is bent and straightened to obtain a high-potential aluminum alloy plate with a thickness of 0.3±0.03 mm.

[0045] In the high-potential aluminum alloy plate obtained in this example, the content of Ga is 0.01%, the content of Pb is 0.03%, the content of Sn is 0.04%, the content of Mg is 0.5%, and the content of Os is 0.01%.

[0046] Example 2

[0047] A preparation method of a high-potential aluminum alloy plate comprises the following steps:

[0048] S1. 155.8652 g of aluminum ingot was added to a graphite crucible, melted in a crucible resistance furnace, the melting temperature was 780℃, after the aluminum ingot was completely melted, Ga 0.0187 g, Pb 0.0467 g, Sn 0.0623 g, Mg 0.7793 g, Os 0.0468 g were sequentially added to the melt, after stirring uniformly, 1 g of hexachloroethane (C2Cl6) was added for degassing, slagging, and finally poured into a cylindrical cast iron mold, cooled and demolded to obtain an alloy aluminum ingot;

[0049] S2. After the alloy aluminum ingot was milled, it was annealed at 480℃ for 8h, and then hot-rolled out of the furnace, with a hot-rolling reduction of ≤50%, to obtain a semi-finished aluminum roll;

[0050] S3. The semi-finished aluminum roll was cold-rolled in 5 passes (with a cold-rolling reduction of ≤40%), and then was drawn, bent and straightened to obtain a high-potential aluminum alloy plate with a thickness of 0.3±0.03 mm.

[0051] In the high-potential aluminum alloy plate obtained in this embodiment, the content of Ga is 0.01%, the content of Pb is 0.03%, the content of Sn is 0.04%, the content of Mg is 0.5%, and the content of Os is 0.03%.

[0052] Example 3

[0053] A method for preparing a high-potential aluminum alloy plate, comprising the following steps:

[0054] S1. 185.6382 g of aluminum ingot was added to a graphite crucible, melted in a crucible resistance furnace, the melting temperature was 778℃, after the aluminum ingot was completely melted, Ga 0.0223 g, Pb 0.0557 g, Sn 0.0742 g, Mg 0.9282 g, Os 0.0928 g were sequentially added to the melt, after stirring uniformly, 1 g of hexachloroethane (C2Cl6) was added for degassing, slagging, and finally poured into a cylindrical cast iron mold, cooled and demolded to obtain an alloy aluminum ingot;

[0055] S2. After the alloy aluminum ingot was milled, it was annealed at 480℃ for 8h, and then hot-rolled out of the furnace, with a hot-rolling reduction of ≤50%, to obtain a semi-finished aluminum roll;

[0056] S3. The semi-finished aluminum roll was cold-rolled in 5 passes (with a cold-rolling reduction of ≤40%), and then was drawn, bent and straightened to obtain a high-potential aluminum alloy plate with a thickness of 0.3±0.03 mm.

[0057] In the high-potential aluminum alloy plate obtained in this embodiment, the content of Ga is 0.01%, the content of Pb is 0.03%, the content of Sn is 0.04%, the content of Mg is 0.5%, and the content of Os is 0.05%.

[0058] Comparative Example 1

[0059] A preparation method of a high-potential aluminum alloy plate, other contents being the same as those of Example 1, except that Os is replaced by Mg.

[0060] Test and evaluation

[0061] The high-potential aluminum alloy plates prepared in Examples 1-3 are tested for average potential and self-corrosion hydrogen evolution rate to evaluate the influence 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 are: temperature 80℃, current density 700mA / cm 2 , electrolyte 5MNaOH+2.8MNaAlO2+corrosion inhibitor, electrolyte is static, the average potential test results are shown in Fig. 1 , and the self-corrosion hydrogen evolution rate test results are shown in Fig. 2 .

[0062] The high-potential aluminum alloy plate obtained in Example 1 is tested for dynamic hydrogen evolution rate at different temperatures, and the test conditions are: 700mA / cm 2 , 5MNaOH+2.8MNaAlO2+corrosion inhibitor, electrolyte flow rate 40L / h, and the results are shown in Fig. 3 .

[0063] As can be seen from Figs. 1-3 , by adding a certain amount of osmium (Os) and Ga, Pb, Sn, Mg metal elements in the aluminum matrix, the metal elements are solid-solved in the aluminum matrix and micro-alloying occurs, an Al-Ga-Os-Mg-Pb-Sn alloy is prepared, 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 improving the electrochemical performance of the aluminum electrode, and reducing the hydrogen evolution corrosion rate; the high-potential aluminum alloy plate obtained in the present application has excellent electrochemical performance and good corrosion resistance in a metaborate alkaline solution at 80℃ and a current density of 700mA / cm 2 .

[0064] The above is only a preferred specific embodiment of the present application, but the protection scope of the present application is not limited thereto, any changes or replacements within the technical range disclosed in the present application can be easily thought of by those skilled in the art, which should be covered within the protection scope of the present application.

Claims

1. A high-potential aluminum alloy sheet, characterized by, The high-potential aluminum alloy plate comprises, in percentage by mass, 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%, the balance being aluminum and impurities, the total amount of the impurities being ≤0.1%; and the thickness is 0.29-0.33 mm. A preparation method of the high-potential aluminum alloy plate comprises the following steps: S1. After melting an aluminum ingot, Ga, Pb, Sn, Mg and Os are added according to mass fraction, and then degassing and slagging are performed, and the alloy aluminum ingot is obtained by pouring into a mold and cooling and demolding; S2. The alloy aluminum ingot is sequentially subjected to face milling, annealing and hot rolling to obtain a semi-finished aluminum coil; S3. The semi-finished aluminum coil is cold-rolled, bent and straightened to obtain the high-potential aluminum alloy plate; in step S2, the annealing temperature is 450-500°C, and the annealing time is 6-10h; and the high-potential aluminum alloy plate is used for preparing an aluminum-air battery or an aluminum-silver oxide battery.

2. The high-potential aluminum alloy sheet according to claim 1, characterized by, In step S1, the melting temperature is 760-780°C.

3. The high-potential aluminum alloy sheet according to claim 1, characterized by, In step S2, the hot rolling reduction is ≤50%.

4. The high-potential aluminum alloy sheet according to claim 1, characterized by, In step S3, the cold rolling reduction is ≤40%, and the number of cold rolling is 3-5 times.

5. The high-potential aluminum alloy sheet according to claim 1, characterized by, The purity of the aluminum ingot is ≥99.99%.

6. Use of the high-potential aluminum alloy plate according to any one of claims 1-5 in the field of electrode materials.

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