Praseodymium modified secondary aluminum alkaline air battery anode material and preparation method thereof

Abstract

The invention provides a praseodymium modified secondary aluminum alkaline air battery anode material and a preparation method thereof, and belongs to the technical field of aluminum alloy materials, the anode material is composed of the following components by weight: 0.1-2.0% of Zn, 0.01-0.2% of Ga, 0.01-0.3% of Pr, 0.2-2% of Mn, 0.9-2.0% of Fe, 0.5-2.0% of Si, and the balance of aluminum. The balance is Al; si and Fe are from secondary aluminum. Through Pr-Ga-Mn-Si-Zn five-element alloying, high-iron-content secondary aluminum is directly utilized for preparation, and the raw material cost is reduced by 80% or above; resource waste of a traditional dilution method is avoided, and high-value utilization of the secondary aluminum is achieved; the corrosion product is Al (OH) 3 and can be directly used for aluminum oxide production, a closed loop of waste aluminum-anode-corrosion product-aluminum source is formed, and the problems of aluminum circulation imbalance and secondary aluminum excess caused by alloy element accumulation are avoided.

Description

Technical Field

[0001] The present invention relates to the technical field of aluminum alloy materials, and particularly relates to a praseodymium-modified anode material for a recycled aluminum alkaline air battery and a preparation method thereof. Background Art

[0002] With the exhaustion of fossil energy and the aggravation of environmental pollution, recycled aluminum has become a green aluminum source due to its low energy consumption (only 5% of primary aluminum). However, the accumulation of alloying elements (such as Fe, Si, etc.) during the recycling process makes it difficult to be used in high-end fields. Currently, it is mainly used to produce low-value-added casting alloys by dilution method, which requires additional refining, resulting in increased costs, aluminum recycling imbalance and secondary aluminum surplus. There is an urgent need for more efficient utilization and upgrading. Aluminum-air batteries have attracted much attention due to their high energy density and low-cost potential. However, their anode materials are generally prepared from expensive high-purity aluminum (>99.99wt%), which limits their commercial application process.

[0003] The most core problem in applying recycled aluminum alloy to aluminum-air batteries is to solve the serious self-corrosion caused by its high content of Fe impurities and the resulting positive shift of the anode potential and reduction of utilization efficiency. Therefore, the core objective of the present invention is to solve the following key technical problems: (1) suppressing the harmful effects of iron-rich phases; (2) regulating the anodic electrochemical behavior to break through the limit of Fe≤0.2% in recycled aluminum and realize the high-value utilization of recycled aluminum with Fe content of 0.9-2.0%. Summary of the Invention

[0004] The present invention provides a praseodymium-modified anode material for a recycled aluminum alkaline air battery and a preparation method thereof in view of the problems caused by iron content impurities in existing aluminum-air batteries.

[0005] A praseodymium-modified anode material for a recycled aluminum alkaline air battery, which is composed of the following components in weight percentage: 0.1-2.0% of Zn, 0.01-0.2% of Ga, 0.01-0.3% of Pr, 0.2-2% of Mn, 0.9-2.0% of Fe, 0.5-2.0% of Si, and the balance is aluminum, wherein the Fe and Si come from recycled aluminum.

[0006] Preferably, the ratio of the Mn content to the Fe content ≤1.3:1.

[0007] Preferably, the ratio of the Si content to the Fe content ≤1:1.

[0008] The preparation method of the above-mentioned praseodymium-modified alkaline air battery anode material for recycled aluminum is characterized by including the following steps: Step 1, proportionally prepare materials, and weigh recycled aluminum, pure Zn, pure Ga, aluminum-manganese master alloy and aluminum-praseodymium master alloy; Step 2, put the recycled aluminum into a crucible, heat it to 730-760 °C, and skim the slag; Step 3, wrap pure zinc, pure gallium, aluminum-manganese master alloy and aluminum-praseodymium master alloy with aluminum foil respectively, and use tools to press them below the liquid level of the aluminum melt. The pressing order is aluminum-manganese master alloy, aluminum-praseodymium master alloy, pure zinc and pure gallium in sequence. The interval between each addition is 2-3 minutes. After pressing, keep the aluminum melt slightly stirred for 5-8 minutes to uniformly disperse the alloying elements and accelerate dissolution, forming a uniformly composed aluminum melt; Step 4, press the aluminum foil wrapped with the refining agent to the bottom of the aluminum melt, let it stand for 10-15 minutes and then skim the slag; Step 5, pour the aluminum melt into a preheated metal mold, cool it and take out the ingot by splitting the mold to obtain the alkaline air battery anode material.

[0009] Preferably, in the above Step 4, the refining agent is a mixture of NaCl and KCl configured according to a weight ratio of 1:1, and the dosage of the refining agent is 0.3%-0.4% of the total weight of the aluminum melt.

[0010] Preferably, the aluminum-praseodymium master alloy is Al-14Pr.

[0011] Preferably, the aluminum-manganese master alloy is Al-20Mn.

[0012] Preferably, the preparation process of the praseodymium-modified alkaline air battery anode material for recycled aluminum is carried out under argon protection.

[0013] The beneficial effects of the present invention are as follows: (1) The present invention directly uses high-iron-containing recycled aluminum as raw material. The iron content in the recycled aluminum can reach up to 2%. There is no need to refine to reduce the iron content, and the raw material cost is reduced by more than 80%; it avoids the resource waste of the traditional dilution method and realizes the high-value utilization of recycled aluminum. (2) In the aluminum-air anode battery material of the present invention, the corrosion product is Al(OH)3, which can be directly used for alumina production, forming a closed loop of "waste aluminum - anode - corrosion product - aluminum source", avoiding the problems of aluminum cycle imbalance and secondary aluminum surplus caused by the accumulation of alloying elements. (3) The present invention applies a low-cost recycled aluminum alloy as the aluminum-air battery anode material. By adding Pr, the lowest free energy is maintained, the occurrence of lattice distortion is reduced, only a small amount of Pr is dissolved into α-Al, and most of the rest is enriched at the grain boundaries and forms Al 11Pr3 rare earth compound. This property endows Pr with the potential to refine grain size and increase the dispersion degree of the second phase. The solubility of rare earth Pr in aluminum, iron, and silicon is very small, and they interact with each other to form multi-component complex intermetallic compounds, which can also make the distribution of Si, Fe, and other elements more uniform. A certain content of Pr can also reduce segregation phases and improve corrosion resistance. In addition, the standard hydrogen potential of Pr is -2.44V vs. SHE, and the dispersed distribution can promote the uniform corrosion of aluminum anodes. Introducing Pr can make the aluminum alloy anode more active, thereby improving its electrochemical performance in aluminum-air batteries. (4) Ga is introduced in this invention. Ga will first dissolve into the electrolyte and then adhere to the surface of the aluminum anode, destroying its surface oxide film, thus enhancing the anode activity. And when the gallium content reaches 0.2%, the aluminum anode has the maximum negative potential. (5) By adding Zn, the self-corrosion of recycled aluminum anodes can be effectively reduced; (6) Si is a common impurity in recycled aluminum. In the anode material of recycled aluminum-air batteries, it can reduce the corrosion of the alloy under load conditions, eliminate the harmful effects of some impurity Fe elements, and the presence of Si increases the discharge potential. (7) Adding Mn can improve the iron-rich phase and promote the formation of α-Al8(Fe,Mn)2Si and α-Al 15 (Fe,Mn)3Si2 plays a role in balancing the potential. Description of the Drawings

[0014] Figure 1 For the open-circuit voltage of the anode and the discharge curves at a current density of 80 mA / cm of the Pr-modified anode materials of recycled aluminum alkaline air batteries obtained in Example 1 and Example 2, where: (a) Open-circuit voltage of the anode material; (b) Discharge curve at a current density of 80 mA / cm 2 current density. 2 Discharge curve at a current density of 80 mA / cm

[0015] Figure 2 Morphology diagram of the iron-rich phase of recycled aluminum before Pr modification.

[0016] Figure 3 Morphology diagram of the iron-rich phase in the Pr-modified anode materials of recycled aluminum alkaline air batteries obtained in Example 1.

[0017] Figure 4 Test device diagram of the full battery pack for Examples 1 - 5.

[0018] Figure 5 Schematic diagram of the full battery test for Examples 1 - 5. Detailed Description of the Invention

[0019] The following describes in detail the specific embodiments of the present invention in conjunction with the drawings of the specification, but it should be understood that the protection scope of the present invention is not limited by the specific embodiments.

[0020] Example 1 A praseodymium-modified anode material for a regenerated aluminum alkaline air battery. The anode material is composed of the following components by weight percentage: 1.0% Zn, 0.2% Ga, 0.1% Pr, 0.2% Mn, 1.0% Fe, 1.0% Si, and the balance is aluminum; the Fe and Si are from regenerated aluminum.

[0021] The preparation method of the above-mentioned praseodymium-modified anode material for a regenerated aluminum alkaline air battery includes the following steps: Step 1, proportion the ingredients according to the ratio, and weigh regenerated aluminum, pure Zn, pure Ga, aluminum-silicon master alloy, aluminum-manganese master alloy and aluminum-praseodymium master alloy; Step 2, put the regenerated aluminum into a crucible, heat it to 740 °C, and skim the slag; Step 3, press in the aluminum-manganese master alloy, aluminum-praseodymium master alloy, pure zinc and pure gallium in sequence, with an interval of 3 minutes for each addition. After pressing, keep the aluminum melt stirring slightly for 5 minutes to evenly disperse the alloying elements and accelerate dissolution to form a homogeneous aluminum melt; Step 4, press the aluminum foil wrapped with the refining agent to the bottom of the aluminum melt, let it stand for 15 minutes and then skim the slag; Step 5, preheat a Φ40×80mm metal mold to 200 °C, then pour the aluminum melt into the metal mold, cool it and take out the ingot by splitting the mold to obtain the anode material for the alkaline air battery. The preparation process of the praseodymium-modified anode material for a regenerated aluminum alkaline air battery is carried out under argon protection.

[0022] Among them, in the above-mentioned Step 4, the refining agent is a mixture of NaCl and KCl configured according to a weight ratio of 1:1, and the dosage of the refining agent is 0.3% of the total weight of the aluminum melt. The aluminum-praseodymium master alloy is Al-14Pr; the aluminum-manganese master alloy is Al-20Mn.

[0023] Example 2 A praseodymium-modified anode material for a regenerated aluminum alkaline air battery. The anode material is composed of the following components by weight percentage: 2.0% Zn, 0.2% Ga, 0.3% Pr, 2.0% Mn, 1.3% Fe, 1.0% Si, and the balance is Al. The Fe and Si are from regenerated aluminum.

[0024] The preparation method of the above-mentioned praseodymium-modified regenerated aluminum alkaline air battery anode material comprises the following steps: Step 1, proportionally prepare the ingredients, and weigh regenerated aluminum, pure Zn, pure Ga, aluminum-manganese master alloy and aluminum-praseodymium master alloy; Step 2, put the regenerated aluminum into a crucible, heat it to 760 °C, and skim the slag; Step 3, wrap pure zinc, pure Ga, aluminum-manganese master alloy and aluminum-praseodymium master alloy with aluminum foil respectively, and use tools to press them below the liquid level of the aluminum melt. The pressing sequence is aluminum-manganese master alloy, aluminum-praseodymium master alloy, pure zinc and pure Ga in turn. The interval between each addition is 2 min. After pressing, keep the aluminum melt stirring slightly for 6 min to make the alloying elements disperse evenly and accelerate dissolution, forming an aluminum melt with uniform composition; Step 4, press the aluminum foil wrapped with the refining agent to the bottom of the aluminum melt, let it stand for 10 min and then skim the slag; Step 5, preheat a Φ40×80 mm metal mold to 200 °C, then pour the aluminum melt into the metal mold, and after cooling, remove the ingot by splitting the mold to obtain the alkaline air battery anode material.

[0025] Among them, in the above-mentioned Step 4, the refining agent is a mixture of NaCl and KCl configured according to a weight ratio of 1:1, and the dosage of the refining agent is 0.35% of the total weight of the aluminum melt. The aluminum-praseodymium master alloy is Al-14Pr; the aluminum-manganese master alloy is Al-20Mn.

[0026] Example 3 A praseodymium-modified regenerated aluminum alkaline air battery anode material, which is composed of the following components by weight percentage: 0.1% of Zn, 0.01% of Ga, 0.01% of Pr, 0.8% of Mn, 0.9% of Fe, 0.5% of Si, and the balance is Al; the Fe and Si come from the regenerated aluminum.

[0027] The preparation method of the above-mentioned praseodymium-modified regenerated aluminum alkaline air battery anode material comprises the following steps: Step 1, proportionally prepare the ingredients, and weigh regenerated aluminum, pure Zn, pure Ga, aluminum-manganese master alloy and aluminum-praseodymium master alloy; Step 2, put the regenerated aluminum into a crucible, heat it to 750 °C, and skim the slag; Step 3, wrap pure zinc, pure Ga, aluminum-manganese master alloy and aluminum-praseodymium master alloy with aluminum foil respectively, and use tools to press them below the liquid level of the aluminum melt. The pressing sequence is aluminum-manganese master alloy, aluminum-praseodymium master alloy, pure zinc and pure Ga in turn. The interval between each addition is 2.5 min. After pressing, keep the aluminum melt stirring slightly for 8 min to make the alloying elements disperse evenly and accelerate dissolution, forming an aluminum melt with uniform composition; Step 4, press the aluminum foil wrapped with the refining agent to the bottom of the aluminum melt, let it stand for 12 min and then skim the slag; Step 5, preheat a Φ40×80 mm metal mold to 200 °C, then pour the aluminum melt into the metal mold, and after cooling, remove the ingot by splitting the mold to obtain the alkaline air battery anode material.

[0028] Among them, in the fourth step, the refining agent is a mixture of NaCl and KCl configured according to a weight ratio of 1:1, and the dosage of the refining agent is 0.4% of the total weight of the aluminum melt. The aluminum praseodymium master alloy is Al-14Pr; the aluminum manganese master alloy is Al-20Mn.

[0029] Example 4 A praseodymium-modified recycled aluminum alkaline air battery anode material, which is composed of the following components by weight percentage: 0.8% of Zn, 0.1% of Ga, 0.2% of Pr, 0.5% of Mn, 2.0% of Fe, 2.0% of Si, and the balance is Al; the Fe and Si are from recycled aluminum.

[0030] The preparation method of the above-mentioned praseodymium-modified recycled aluminum alkaline air battery anode material includes the following steps: Step 1, proportionally prepare materials, weigh recycled aluminum, pure Zn, pure Ga, aluminum manganese master alloy and aluminum praseodymium master alloy; Step 2, put the recycled aluminum into a crucible, heat it to 740 °C, and skim the slag; Step 3, wrap pure zinc, pure gallium, aluminum manganese master alloy and aluminum praseodymium master alloy with aluminum foil respectively, and use tools to press them below the surface of the aluminum melt. The pressing order is aluminum manganese master alloy, aluminum praseodymium master alloy, pure zinc and pure gallium in sequence. Each addition interval is 3 minutes. After pressing, keep the aluminum melt slightly stirred for 8 minutes to make the alloy elements evenly dispersed and accelerate dissolution, forming a uniformly composed aluminum melt; Step 4, press the aluminum foil wrapped with the refining agent to the bottom of the aluminum melt, let it stand for 15 minutes and then skim the slag; Step 5, preheat a Φ40×80mm metal mold to 200 °C, then pour the aluminum melt into the metal mold, and after cooling, take out the ingot by splitting the mold to obtain the alkaline air battery anode material.

[0031] Among them, in the fourth step, the refining agent is a mixture of NaCl and KCl configured according to a weight ratio of 1:1, and the dosage of the refining agent is 0.3% of the total weight of the aluminum melt. The aluminum praseodymium master alloy is Al-14Pr; the aluminum manganese master alloy is Al-20Mn.

[0032] Example 5 A praseodymium-modified recycled aluminum alkaline air battery anode material, which is composed of the following components by weight percentage: 1.5% of Zn, 0.15% of Ga, 0.15% of Pr, 1.3% of Mn, 1.0% of Fe, 1.5% of Si, and the balance is Al; the Fe and Si are from recycled aluminum.

[0033] The preparation method of the above-mentioned praseodymium-modified anode material for regenerated aluminum alkaline air battery includes the following steps: Step 1, proportion the ingredients, weigh regenerated aluminum, pure Zn, pure Ga, aluminum-manganese master alloy and aluminum-praseodymium master alloy; Step 2, put the regenerated aluminum into a crucible, heat it to 730 °C, and skim the slag; Step 3, wrap pure zinc, pure Ga, aluminum-manganese master alloy and aluminum-praseodymium master alloy with aluminum foil respectively, and use tools to press them below the liquid surface of the aluminum melt. The pressing sequence is aluminum-manganese master alloy, aluminum-praseodymium master alloy, pure zinc and pure Ga in turn. There is an interval of 2 minutes for each addition. After pressing, keep the aluminum melt stirred slightly for 8 minutes to make the alloy elements disperse evenly and accelerate dissolution, forming a homogeneous aluminum melt; Step 4, press the aluminum foil wrapped with the refining agent to the bottom of the aluminum melt, let it stand for 15 minutes and then skim the slag; Step 5, preheat a Φ40×80mm metal mold to 200 °C, then pour the aluminum melt into the metal mold, and take out the ingot by splitting the mold after cooling, that is, obtain the anode material for the alkaline air battery.

[0034] Among them, in the step 4, the refining agent is a mixture of NaCl and KCl configured according to a weight ratio of 1:1, and the dosage of the refining agent is 0.3% of the total weight of the aluminum melt. The aluminum-praseodymium master alloy is Al-14Pr; the aluminum-manganese master alloy is Al-20Mn.

[0035] The component contents in Examples 1-5 are shown in Table 1. The praseodymium-modified anode materials for regenerated aluminum alkaline air batteries obtained in Examples 1-5 were cut into thin slices with a thickness of 1 mm for performance testing. Electrochemical testing was carried out using a three-electrode system and a Gamry Interface 1010E electrochemical workstation. Hg / HgO was used as the reference electrode, a Pt sheet was used as the auxiliary electrode, and 4 M NaOH was used as the electrolyte. The working area of the Φ14×5 mm specimen was 1 cm², which was polished with 320-2000 mesh sandpaper and soaked for 1 h until the open circuit voltage was stable. The open circuit voltage test lasted for 1200 s, the EIS test frequency range was 10 -2 -10 5 Hz (perturbation signal 10 mV), and the scanning range of the Tafel curve was ±0.4 V of the open circuit voltage (scanning rate 1 mV / s). The EIS data was analyzed by fitting with ZSimpWin software. The full cell test was carried out on the same workstation. The anode materials for the alkaline air batteries obtained in Examples 1-5 (80×10×3 mm, effective area 12 cm 2 ) were used as the anode, and a self-made nickel mesh / waterproof layer / manganese dioxide-activated carbon composite catalytic layer was used as the cathode. 4 M NaOH electrolyte was used, and the solution concentration and temperature were maintained constant by a peristaltic pump. The test device is as shown in Figure 4 shown, and the schematic diagram of the full cell test is as shown in Figure 5The test results are shown in Table 2 and Table 3. The anode open circuit voltage and the anode open circuit voltage of the praseodymium modified regenerated aluminum alkaline air battery anode material of Example 1 and Example 2 at 80mA / cm 2 The discharge curve at the current density is as follows Figure 1 shown.

[0036] The metallographic structure of the iron-rich phase of the recycled aluminum alloy is as follows: Figure 2 As shown, the second phase is mainly β-Fe (Al6Fe and Al5FeSi), which is obviously long needle-shaped and forms a coarse and uneven network structure. Its standard potential is -0.39V vs. SHE, which has a large potential difference with the matrix (-1.66V vs. SHE), causing galvanic corrosion, exacerbating the self-corrosion reaction, and seriously affecting the potential and utilization efficiency of the aluminum anode. After the introduction of Pr element, the β-Fe phase is promoted to transform into the α-Al8Fe2Si phase (-1.15V vs. SHE) with a smaller potential difference and a denser structure. The metallographic image of the praseodymium-modified recycled aluminum-air battery anode material obtained in Example 1 is shown in FIG. Figure 3 As shown in the figure, the addition of Pr reduces the potential difference and the degree of self-corrosion. The second phase is surrounded by white bright block and rod-shaped rare earth phases (Al 11 Pr3) precipitates. Al 11 Pr3 acts as a heterogeneous nucleation core for α-Al, increasing the nucleation rate and inhibiting grain growth. At the same time, Pr is adsorbed around the iron-rich phase to limit the diffusion of Fe / Al, causing the needle-like iron phase to be refined into short strips or blocks. Polarized microscopic analysis shows that the diameter of the recycled aluminum alloy grain is 1428.86μm. After adding Pr, the alloy grain size is reduced to 602.75μm, which is half the size. This is attributed to the enrichment of Pr at the solid-liquid interface, which causes the composition to be supercooled, and the undissolved Al in the master alloy 11 The Pr3 strengthening phase is dispersed, providing heterogeneous nucleation sites and effectively refining the grain size.

[0037] The electrochemical tests on the praseodymium-modified recycled aluminum-air battery anode materials obtained in Examples 1 to 5 showed that Pr reduced the corrosion current density to a minimum of 1.73 mA / cm 2 , the size of the iron-rich phase is refined, the corrosion galvanic cell formed between the cathode phase and the anode phase will be relatively small, and the micro-current it can withstand is also less. The refinement of the cathode phase is the corrosion current density ( i corr ) is mainly due to the decrease; the open circuit voltage of the alkaline air battery anode material prepared from recycled aluminum without Pr modification is 1.24V, and the open circuit voltages of the alkaline air battery anode materials obtained in Example 1 to Example 5 are all improved. The open circuit voltages of Example 1, Example 2, and Example 5 reach 1.44 V, 1.51 V, and 1.41 V, respectively, which are close to the potential of 3N aluminum and have good activity.

[0038] Table 1 Chemical composition of the anode material of Pr-modified recycled aluminum alkaline air battery (wt%) Al alloy Fe Ga Zn Si Mn Pr Al Example 1 1 0.2 1 1 0.2 0.1 balance Example 2 1.3 0.2 2 1 2 0.3 balance Example 3 0.9 0.01 0.1 0.5 0.8 0.01 balance Example 4 2 0.1 0.8 2 0.5 0.2 balance Example 5 1 0.15 1.5 1.5 1.3 0.15 balance Table 2 Discharge performance of the anode materials of alkaline air batteries prepared from recycled aluminum in Examples 1 - 5 at a current density of 80 mA·cm -2 under anode material <![CDATA[Current density (mA.cm -2 )]]> Open circuit voltage (V) Time (S) Average discharge voltage (V) Efficiency (%) <![CDATA[Volume density (mAh·g -1 )]]> <![CDATA[Energy density (mWh·g -1 )]]> Example 1 80 1.44 10800 1.27 71.3 2199.145 2792.914 Example 2 80 1.51 10800 1.14 84.3 2598.99 2832.717 Example 3 80 1.39 10800 1.24 71.23 2117.65 2625.88 Example 4 80 1.26 10800 0.83 53.82 1600.00 1328.00 Example 5 80 1.41 10800 1.23 62.91 1870.13 2300.26 Table 3 Electrochemical test parameters of the anode materials of alkaline air batteries prepared from recycled aluminum in Examples 1 - 5 anode material Corrosion voltage (V vs. Hg / HgO) <![CDATA[Corrosion current density / (10 -2 A . cm -2 )]]> Example 1 -1.44 2.43 Example 2 -1.51 1.73 Example 3 -1.39 10.25 Example 4 -1.26 18.21 Example 5 -1.41 6.72

Claims

1. A praseodymium-modified anode material for an alkaline air battery of recycled aluminum, characterized in that, The anode material is composed of the following components by weight percentage: 0.1 - 2.0% of Zn, 0.01 - 0.2% of Ga, 0.01 - 0.3% of Pr, 0.2 - 2% of Mn, 0.9 - 2.0% of Fe, 0.5 - 2.0% of Si, and the balance is aluminum. The Fe and Si are from recycled aluminum.

2. The anode material of a praseodymium-modified recycled aluminum alkaline air battery according to claim 1, characterized in that The ratio of the Mn content to the Fe content ≤ 1.3:

1.

3. The anodic material of a praseodymium-modified recycled aluminum alkaline air battery as described in claim 1, wherein The ratio of the Si content to the Fe content ≤ 1:

1.

4. The preparation method of an anode material for a praseodymium-modified recycled aluminum alkaline air battery according to any one of claims 1-3, characterized in that, It includes the following steps: Step 1, proportionally prepare the materials, weigh recycled aluminum, pure Zn, pure Ga, aluminum - manganese master alloy and aluminum - praseodymium master alloy; Step 2, put the recycled aluminum into a crucible, heat it to 730 - 760 °C, and skim the slag; Step 3, wrap the pure zinc, pure gallium, aluminum - manganese master alloy and aluminum - praseodymium master alloy with aluminum foil respectively, and use tools to press them below the liquid level of the aluminum melt. The pressing order is aluminum - manganese master alloy, aluminum - praseodymium master alloy, pure zinc and pure gallium in sequence. There is an interval of 2 - 3 minutes between each addition. After pressing, keep the aluminum melt stirring slightly for 5 - 8 minutes to make the alloying elements disperse evenly and accelerate dissolution, forming a homogeneous aluminum melt; Step 4, then press the aluminum foil wrapped with the refining agent to the bottom of the aluminum melt, let it stand for 10 - 15 minutes and then skim the slag; Step 5, pour the aluminum melt into a pre - heated metal mold, cool it and then remove the ingot by splitting the mold, thus obtaining the anode material for the alkaline air battery.

5. The preparation method of a praseodymium-modified anode material for a regenerated aluminum alkaline air battery according to claim 4, characterized in that, In the fourth step, the refining agent is a mixture of NaCl and KCl configured by a weight ratio of 1:1, and the dosage of the refining agent is 0.3% - 0.4% of the total weight of the aluminum melt.

6. The preparation method of a praseodymium-modified anode material for a regenerated aluminum alkaline air battery according to claim 4, wherein The aluminum - praseodymium master alloy is Al - 14Pr.

7. According to the preparation method of a praseodymium - modified recycled - aluminum alkaline air battery anode material as described in claim 4, the aluminum - manganese master alloy is Al - 20Mn.

8. A praseodymium-modified anode material for an alkaline air battery of recycled aluminum according to claim 4, characterized in that, The preparation process of the praseodymium - modified recycled - aluminum alkaline air battery anode material is carried out under argon protection.

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