阅读说明：本技术 一种空气电池用阳极铝合金的制备方法和空气电池 (Preparation method of anode aluminum alloy for air battery and air battery ) 是由 易祖成 吴辉 于 2020-05-25 设计创作，主要内容包括：本申请公开了一种空气电池用阳极铝合金的制备方法和空气电池,该方法包括：称取工业纯铝、高纯镧、KBF<Sub>4</Sub>、K<Sub>2</Sub>TiF<Sub>6</Sub>,控制元素的重量百分比为：Ti5～10％,B0.1～0.5％,La0.5～1％,余量为Al；将工业纯铝完全熔化,控制温度在800℃以上,用石墨钟罩将预先混匀的KBF<Sub>4</Sub>、K<Sub>2</Sub>TiF<Sub>6</Sub>粉末压入铝熔体中搅匀,恒温15～30min,再加入高纯镧搅匀,恒温20～40min,搅拌过程中充覆盖剂；将熔体浇铸成铸锭,得到晶粒细化剂；按重量百分比称取Zn0.05～0.2％,Ga0.2～0.4％,Sn0.01～0.05％,In0.05～0.1％,Bi0.1～0.2％,Mg0.5～1％,Ce0.1～0.3％,该晶粒细化剂0.3～0.5％,余量为铝；将铝熔化,加入Zn、Ga、Sn、In、Bi、Mg、Ce熔炼,再加入晶粒细化剂精炼,浇铸成铸坯,退火,轧制成铝板,再退火,退火时间为30～40min/mm。所制得的材料用作铝空气电池阳极,可以提高开路电位,降低自腐蚀速率。(The application discloses a preparation method of an anode aluminum alloy for an air battery and the air battery, wherein the method comprises the following steps: weighing industrial pure aluminum, high-purity lanthanum and KBF 4 、K 2 TiF 6 The weight percentage of the control elements is as follows: 5-10% of Ti, 0.1-0.5% of B, 0.5-1% of Las and the balance of Al; completely melting industrial pure aluminum, and controlling the temperature to be withinMixing KBF with graphite bell at 800 deg.C 4 、K 2 TiF 6 Pressing the powder into an aluminum melt, stirring uniformly, keeping the temperature constant for 15-30 min, adding high-purity lanthanum, stirring uniformly, keeping the temperature constant for 20-40 min, and filling a covering agent in the stirring process; casting the melt into an ingot to obtain a grain refiner; weighing 0.05-0.2% of Zns, 0.2-0.4% of Gas, 0.01-0.05% of Sns, 0.05-0.1% of In, 0.1-0.2% of Bis, 0.5-1% of Mgs, 0.1-0.3% of Ces, 0.3-0.5% of grain refiner and the balance of aluminum according to weight percentage; melting aluminum, adding Zn, Ga, Sn, In, Bi, Mg and Ce for melting, adding a grain refiner for refining, casting into a casting blank, annealing, rolling into an aluminum plate, and annealing for 30-40 min/mm. The prepared material is used as the anode of the aluminum-air battery, can improve the open-circuit potential and reduce the self-corrosion rate.)

1. A preparation method of anode aluminum alloy for an air battery is characterized by comprising the following steps:

weighing industrial pure aluminum, high-purity lanthanum and KBF₄、K₂TiF₆The weight percentage of the control elements is as follows: 5-10% of Ti, 0.1-0.5% of B, 0.5-1% of Las and the balance of Al; melting industrial pure aluminum in a resistance furnace until the industrial pure aluminum is softened, adding a covering agent until the industrial pure aluminum is completely melted, controlling the temperature to be more than 800 ℃, and using a graphite bell jar to uniformly mix KBF₄、K₂TiF₆Pressing the powder into an aluminum melt, stirring uniformly, keeping the temperature constant for 15-30 min, adding high-purity lanthanum, stirring uniformly, keeping the temperature constant for 20-40 min, and supplementing a covering agent in the stirring process;

casting the melt into an ingot to obtain a grain refiner;

weighing 0.05-0.2% of Zns, 0.2-0.4% of Gas, 0.01-0.05% of Sns, 0.05-0.1% of In, 0.1-0.2% of Bis, 0.5-1% of Mgs, 0.1-0.3% of Ces, 0.3-0.5% of grain refiner prepared by the steps and the balance of aluminum according to the weight percentage; melting aluminum, adding Zn, Ga, Sn, In, Bi, Mg and Ce for smelting, adding the grain refiner for refining, casting into a casting blank, heating to 450-500 ℃ at the speed of 10-15 ℃/min, annealing for 10-15 h, cooling to room temperature, removing a surface oxide layer, rolling into an aluminum plate, annealing at the temperature of 400-420 ℃, taking the thickness of the aluminum plate as the reference, and cooling to room temperature after annealing.

2. The preparation method according to claim 1, wherein the temperature of the smelting is 800-850 ℃.

3. The method according to claim 1, wherein the temperature of the refining is 780 to 800 ℃.

4. The preparation method of claim 1, further comprising a step of performing secondary annealing treatment on the annealed aluminum plate, wherein the annealing temperature is 400-450 ℃ and the annealing time is 30-40 min/mm.

5. The method according to claim 4, wherein the aluminum sheet is rolled before the re-annealing treatment to reduce the thickness of the aluminum sheet by 50% or more.

6. The method according to claim 1, wherein the purity of the commercially pure aluminum is 99.7% or more.

7. The method according to claim 1, wherein the purity of the high-purity lanthanum is 99.99% or more.

8. The method of claim 1, wherein the covering agent is KCl.

9. An air battery, characterized in that the aluminum alloy obtained by the method of any one of claims 1 to 8 is used as an anode.

Technical Field

The application relates to the technical field of metal fuel cells, in particular to a preparation method of an anode aluminum alloy for an air cell and the air cell.

Background

The aluminum has high electrochemical equivalent, high specific energy and abundant resources, so that the aluminum-air battery becomes a research hotspot of the metal fuel battery. However, aluminum is easy to undergo self-corrosion and hydrogen evolution corrosion in alkaline electrolyte, and a compact oxide film is easily formed on the surface of the aluminum, so that the anode is passivated, and the electrochemical activity of the aluminum is influenced.

The above problems can be overcome to some extent by adding metal elements such as Ga, In, Sn, etc., and the main principle thereof is that: the methods of forming a low melting point compound, destroying a passivation film on the surface of aluminum, reducing self-corrosion by increasing a hydrogen evolution potential, and the like, are difficult to consider an open circuit voltage while reducing corrosion of an aluminum plate, or are easy to aggravate self-corrosion of the aluminum plate while improving activity of the aluminum plate, and limit application of aluminum-air batteries.

Disclosure of Invention

In order to solve one of the technical problems in the prior art, the preparation method of the anode aluminum alloy for the air battery and the air battery are provided, and the prepared material is used as the anode of the aluminum-air battery, so that the open-circuit potential can be improved, and the self-corrosion rate can be reduced.

In one aspect, a preparation method of an anode aluminum alloy for an air battery is provided, which comprises the following steps:

weighing industrial pure aluminum, high-purity lanthanum and KBF₄、K₂TiF₆The weight percentage of the control elements is as follows: 5-10% of Ti, 0.1-0.5% of B, 0.5-1% of Las and the balance of Al; melting industrial pure aluminum in a resistance furnace until the industrial pure aluminum is softened, adding a covering agent until the industrial pure aluminum is completely melted, controlling the temperature to be more than 800 ℃, and using a graphite bell jar to uniformly mix KBF₄、K₂TiF₆Pressing the powder into an aluminum melt, stirring uniformly, keeping the temperature constant for 15-30 min, adding high-purity lanthanum, stirring uniformly, keeping the temperature constant for 20-40 min, and supplementing a covering agent in the stirring process;

casting the melt into an ingot to obtain a grain refiner;

weighing 0.05-0.2% of Zns, 0.2-0.4% of Gas, 0.01-0.05% of Sns, 0.05-0.1% of In, 0.1-0.2% of Bis, 0.5-1% of Mgs, 0.1-0.3% of Ces, 0.3-0.5% of grain refiner prepared by the steps and the balance of aluminum according to the weight percentage; melting aluminum, adding Zn, Ga, Sn, In, Bi, Mg and Ce for smelting, adding the grain refiner for refining, casting into a casting blank, heating to 450-500 ℃ at the speed of 10-15 ℃/min, annealing for 10-15 h, cooling to room temperature, removing a surface oxide layer, rolling into an aluminum plate, annealing at the temperature of 400-420 ℃, taking the thickness of the aluminum plate as the reference, and cooling to room temperature after annealing.

Preferably, the smelting temperature is 800-850 ℃, and the refining temperature is 780-800 ℃.

Preferably, the method further comprises the step of carrying out secondary annealing treatment on the annealed aluminum plate, wherein the annealing temperature is 400-450 ℃, and the annealing time is 30-40 min/mm.

Preferably, the aluminum plate is rolled before the re-annealing treatment to reduce the thickness of the aluminum plate by 50% or more.

Preferably, the purity of the industrial pure aluminum is 99.7% or more.

Preferably, the purity of the high-purity lanthanum is 99.99% or more.

Preferably, the covering agent is KCl.

On the other hand, the air battery is provided, and the aluminum alloy prepared by the preparation method is used as an anode.

The technical scheme provided by the specific embodiment of the application has at least the following beneficial effects:

zn and Sn can improve the hydrogen evolution potential and reduce the hydrogen evolution corrosion of the anode, but excessive Zn and Sn can influence the discharge voltage, a certain amount of Zn and Sn are matched with Mg and Bi, the voltage is ensured, meanwhile, the obvious effect of reducing the self-corrosion rate is generated, Ga, In and Sn are matched to form a low-temperature eutectic body, so that the aluminum surface passivation film is subjected to microporosity, the utilization rate of the aluminum anode is improved, active sites can be formed by Ga and In, the voltage is shifted negatively, Ce and a grain refiner act on the refining of aluminum grains together, and the annealing and rolling treatment are matched to perfect the intercrystalline morphology, further reduce the self-corrosion and improve the discharge performance. The inventor finds that the preparation method of the grain refiner has a large influence on the electrochemical performance of the anode, and experimental results show that the grain refiner prepared by the method is more beneficial to improving open-circuit voltage and reducing the self-corrosion rate of an aluminum plate.

Detailed Description

In order to make the objects, technical solutions and advantages of the present application more apparent, the following detailed description is further provided in conjunction with specific embodiments.