CN105140596B - A kind of air cell aluminum alloy anode material, preparation method and aluminium-air cell - Google Patents

Abstract

The invention discloses an aluminum alloy anode material for an air battery, a preparation method and an aluminum air battery. The aluminum alloy anode material is composed of the following components in weight percent: Zn 0.05%-6%, Ga 0.05%-4%, In 0.01% to 2%, and the balance is Al. The aluminum alloy anode material for an air battery of the present invention adds zinc, gallium and indium elements to the aluminum anode material, has good electrochemical activity, low self-corrosion rate, and an open circuit potential in an alkaline electrolyte ≤-1.76V (vs. SHE), the electromotive force of the single battery is greater ^than 1.84V; the aluminum alloy anode material obviously improves the electrochemical performance of the anode and reduces the self-corrosion rate through alloying. Uniform; the aluminum alloy anode material has superior performance and is a new type of aluminum alloy anode material suitable for use in alkaline electrolytes.

Description

A kind of aluminum alloy anode material for air battery, preparation method and aluminum air battery

technical field

The invention belongs to the technical field of aluminum-air batteries, and specifically relates to an aluminum alloy anode material for an air battery, and also relates to a preparation method of an aluminum alloy anode material for an air battery and an aluminum-air battery using the anode material.

Background technique

Metal-air battery is a new generation of green battery, which has low manufacturing cost, high specific energy, recyclable raw materials, and superior performance. At present, metal-air batteries that have been studied more include zinc-air batteries, aluminum-air batteries, and lithium-air batteries, etc., and only zinc-air batteries are closest to industrialization. In the potential series, aluminum is more active than zinc and can obtain a higher battery voltage; an aluminum atom can release three electrons, while a zinc atom can release two electrons, and aluminum can increase the energy of the battery; in addition, aluminum reserves Abundant, low price, so the research progress of aluminum-air battery is very rapid, is a very promising air battery.

Aluminum-air battery is a new type of battery that uses aluminum and air as battery materials. As the anode material of air battery, aluminum has its unique advantages: high electrochemical equivalent, the electrochemical equivalent of aluminum is 2980A h/kg, which is the highest metal except lithium; the electrode potential is relatively negative, and its standard in alkaline solution The electrode potential is -2.35V (vs. SHE). For the anode material, the more negative the potential, the better, and the battery can provide a greater electromotive force; aluminum is abundant in resources and low in price.

At present, the primary problem of aluminum anode materials for air batteries compared with zinc anode materials is that aluminum is severely self-corroded in alkaline solutions, resulting in a greatly reduced anode utilization rate, which hinders the commercial application of aluminum-air batteries. Researchers have developed new aluminum anode materials through microalloying, and adding corresponding electrolyte corrosion inhibitors can reduce the self-corrosion rate of aluminum. Alloying elements commonly used in aluminum-air battery anode materials mainly include zinc, magnesium, gallium, indium, tin, lead, mercury, bismuth, etc. These elements are added to aluminum to form multi-component alloys such as ternary and quaternary. In the prior art, Li Xiaoxiang et al. studied the addition of several metals to aluminum alloy anode materials in 4mol/L NaOH+15g/L Na ₂ SnO ₃ solution According to the influence of hydrogen evolution rate and electrochemical performance, the aluminum alloy anode material with the best comprehensive performance is Al-0.2Sn-0.02Ga-0.4Pb. Lu Lingbin made Al-In, Al-In-Zn, Al-In-Bi, Al-In-Pb, Al-In-Zn- Bi, Al-In-Zn-Bi-Pb and other series alloys are used as research electrodes, and their surface properties are studied by testing their SEM and EDAX. However, when the above-mentioned aluminum alloy materials are used as anodes of aluminum-air batteries, the self-corrosion rate in alkaline solutions is still relatively high, and the open circuit potential is insufficient, which cannot meet the high current density discharge requirements of alkaline aluminum-air batteries.

Contents of the invention

The purpose of the present invention is to provide an aluminum alloy anode material for air batteries suitable for alkaline solutions, which has a low self-corrosion rate in alkaline solutions, has a good open circuit potential, and satisfies the high current density discharge of alkaline aluminum-air batteries. requirements.

The second object of the present invention is to provide a method for preparing an aluminum alloy anode material for an air battery.

The third object of the present invention is to provide an aluminum-air battery using the above-mentioned aluminum alloy anode material for an air battery as an aluminum alloy anode.

In order to achieve the above object, the technical solution adopted in the present invention is:

An aluminum alloy anode material for an air battery is composed of the following components in weight percent: Zn 0.05%-6%, Ga 0.05%-4%, In 0.01%-2%, and the balance is Al.

A preparation method of the above-mentioned aluminum alloy anode material for an air battery, comprising the following steps:

1) Under the protection of an inert gas, after heating and melting aluminum, add zinc, gallium and indium and heat and melt, continue heating to 730-780°C and keep it warm, and then cast it into an ingot;

2) Rolling the cast ingot obtained in step 1) into a sheet-like material under the condition of 150-200° C. to obtain.

In step 1), the inert gas is argon.

In step 1), aluminum is heated to 670-720° C. to melt it completely. After adding zinc, gallium, and indium, the container is rotated while heating to melt and mix the metals.

In step 1), the time for the heat preservation is 4-10 minutes.

In step 2), the thickness of the sheet material is 0.5-4 mm.

The aluminum alloy anode material for an air battery of the present invention reduces its self-corrosion property on the basis of not reducing the electrochemical performance of the aluminum anode material from the aspect of alloying: based on aluminum with a purity of ≥99.85%, adding Moderate amounts of zinc, gallium and indium. Adding zinc to aluminum alloy, the potential of zinc (-1.29Vvs.SHE) is positive than that of aluminum (-2.35Vvs.SHE). By dissolving and re-depositing on the surface of aluminum, the self-corrosion rate of aluminum alloy can be significantly reduced; moreover, zinc has It is beneficial to the uniform distribution of other alloy elements, promotes the uniform dissolution of the alloy and improves the service life of the anode alloy. The solid solubility of gallium in aluminum is very high, and the gallium ions produced by the dissolution can be reduced and deposited on the surface of aluminum alloy due to its low activity, and form aluminum gallium amalgam with the aluminum substrate, which can peel off the oxide film and corrosion products , to expose the base aluminum to promote the activation discharge of the aluminum alloy; secondly, the influence of the alloying element gallium on the aluminum anode is mainly manifested in changing the anisotropy of the aluminum grains during the dissolution process, thereby making the aluminum anode corrode uniformly; furthermore, Gallium and other alloying elements Zn, In, etc., form a eutectic mixture at the electrode working temperature (about 60°C), destroying the passivation film on the aluminum surface; in addition, in the solution containing In ³⁺ , due to the In ³⁺ Redeposition (deposited on the defective parts of the aluminum oxide film) causes the deposition of Ga ³⁺ and activates the aluminum anode. The influence of the alloying element In on the aluminum anode is mainly manifested in the fact that In has a strong activation ability and destroys the passivation film on the aluminum surface; the effect of the alloying element In is produced by the dissolution of the In element in the alloy solid solution and then deposited, In ³⁺ It has a destructive effect on the passivation film on the aluminum surface; secondly, In can also effectively inhibit the hydrogen evolution corrosion of the alloy, which is related to its high hydrogen evolution overpotential. At the same time, zinc, gallium, and indium are elements with high hydrogen evolution overpotential, which can greatly reduce the hydrogen evolution self-corrosion of aluminum alloys. The addition amount of these alloying elements is within a certain range. If the addition amount is small, the due effect will not be achieved. If the addition amount is large, a large number of second phases with larger shapes will be formed, which will increase the self-corrosion rate of the aluminum alloy. Make the corrosion uniformity worse. Alloying aluminum by adding an appropriate amount of zinc, gallium and indium can significantly reduce the self-corrosion rate of the alloy, and can also improve the corrosion uniformity of the alloy surface.

The aluminum alloy anode material for air battery of the present invention adds zinc, gallium and indium elements to the aluminum anode material. Compared with the existing aluminum anode material, it has the following advantages: good electrochemical activity, low self-corrosion rate, The open circuit potential in the alkaline electrolyte is ≤-1.76V (vs. SHE), and the electromotive force of the single battery is greater than 1.84V; the aluminum alloy anode material is alloyed, which significantly improves the electrochemical performance of the anode and reduces the self-corrosion rate. The self-corrosion rate is less than 5.12 mg/cm ² ·h, and the surface is corroded uniformly; the aluminum alloy anode material has superior performance, and is a new type of aluminum alloy anode material suitable for use in alkaline electrolyte.

The preparation method of the aluminum alloy anode material for an air battery of the present invention is to heat and melt the aluminum, add zinc, gallium and indium, heat and melt it and pour it into an ingot, and then roll the ingot into a sheet material, and the obtained aluminum alloy The anode material has excellent electrochemical properties and alkali corrosion resistance, and is suitable for aluminum-air batteries with alkaline electrolytes; the preparation method has simple process, convenient operation, and is suitable for large-scale industrial production.

An aluminum-air battery includes an aluminum alloy anode, an air cathode and an electrolyte, and the aluminum alloy anode is the above-mentioned aluminum alloy anode material for an air battery.

The air cathode is formed by pressing a catalytic layer, a conductive nickel mesh and a waterproof and breathable layer, with a thickness of 0.2-0.6 mm.

The catalytic layer is a film layer formed by mixing γ-MnO ₂ , activated carbon and polytetrafluoroethylene in a mass ratio of (0.3-3):(1-5):(1-5), and the thickness is 0.3～0.8mm.

The waterproof and air-permeable layer is a film layer formed by mixing polytetrafluoroethylene and acetylene black at a weight ratio of 1:1 and then pressing, with a thickness of 0.3-0.8 mm.

The electrolytic solution contains components with the following concentrations: 2-6 mol/L of sodium hydroxide, 20-100 ppm (v/v) of lavender essential oil corrosion inhibitor, and the balance is water.

The lavender essential oil corrosion inhibitor is an ethanol solution of lavender essential oil, wherein the volume percentage of lavender essential oil is 10%-60% (v/v).

The preparation method of the electrolyte is as follows: according to the formula quantity, add the lavender essential oil corrosion inhibitor into the sodium hydroxide solution, add the remaining water, and stir evenly to obtain the product. The water used in the electrolyte is distilled water.

The aluminum-air battery of the present invention adopts the above-mentioned aluminum alloy anode material for an air battery as an aluminum alloy anode, and the open circuit voltage of the aluminum alloy anode material is good, being -1.76～-2.08V (vs. The self-corrosion rate is low (≤5.12mg/cm ² h), and the surface corrosion is uniform; the electromotive force of the aluminum-air battery is 1.84V-2.10V when the discharge current density is 100mA/cm ² for 10 hours, and it has excellent electrochemical performance .

Lavender essential oil is extracted from lavender and is a complex mixture of many different types of aromatic compounds, the main components include: linalool, linalyl acetate, eucalyptol, beta-ocimene, terpene-4-ol and camphor . The groups contained in these substances have more negative charges. First, there is an electrostatic attraction between the charged groups and the metal surface; secondly, there are lone pairs of electrons in the group molecules, which can provide electrons to the empty orbitals of the metal. The oxygen atoms in the group are adsorbed on the metal surface by the lone pair of electrons to form an insoluble complex layer, which separates the metal surface from the aqueous solution and acts as a corrosion inhibitor.

In the aluminum-air battery of the present invention, the lavender essential oil corrosion inhibitor is added in the electrolyte, which has the following advantages: the green plant extract lavender essential oil reduces the self-corrosion rate of the aluminum anode and improves the activity of the aluminum anode; the linalool hydroxyl group in the lavender essential oil Oxygen molecular groups are adsorbed on the surface of the anode by forming a complex layer with metal cations, which hinders the adsorption of water molecules on the surface of the anode, thereby reducing the rate of hydrogen evolution self-corrosion; because linalyl acetate, camphor, and cineole group molecules have oxygen bonds And double bonds, form complex ions, promote the desorption of reaction products, make the aluminum anode continue to activate, reduce the polarization of the aluminum anode when the aluminum anode is discharged, and improve the discharge performance. Therefore, after adding lavender essential oil corrosion inhibitor, the anode alloy The self-corrosion rate is greatly reduced compared with that without adding lavender essential oil, and the open circuit potential of the alloy is significantly negatively shifted; the composition of the lavender essential oil corrosion inhibitor is simple, low in cost, safe and meets environmental protection requirements, so that the aluminum anode alloy has good corrosion resistance And high electrochemical activity to meet the high current density discharge requirements of alkaline aluminum-air batteries.

The aluminum-air battery composed of the aluminum alloy anode material and electrolyte solution of the present invention can not only control the self-corrosion of the alkaline aluminum-air battery too fast, but also ensure that the aluminum anode alloy has high electrochemical activity, which is beneficial to improving the discharge efficiency of the battery. Prolonging the discharge life is of great significance and is conducive to the commercial application of aluminum-air batteries.

detailed description

The present invention will be further described below in combination with specific embodiments.

Example 1

The aluminum alloy anode material for an air battery in this embodiment is composed of the following components in weight percent: Zn 4%, Ga 0.08%, In 0.06%, and the balance is Al.

The preparation method of the aluminum alloy anode material for the air battery of the present embodiment comprises the following steps:

1) Under the protection of argon, place the aluminum ingot in the crucible of a ZGJL0.01-40-4 induction melting furnace, heat it to 690°C to melt the aluminum ingot, add zinc ingots, gallium grains and indium grains, and heat it while heating Rotate the container to melt and mix the metal evenly, continue heating to 750°C and keep it warm for 5 minutes, then pour into block ingots;

2) The block ingot obtained in step 1) is rolled at 180° C. into a sheet material with a thickness of 3 mm to obtain the aluminum alloy anode material for the air battery.

The aluminum-air battery of this embodiment includes an aluminum alloy anode, an air cathode, and an electrolyte, and the aluminum alloy anode is the above-mentioned aluminum alloy anode material for an air battery;

The electrolyte is a sodium hydroxide solution with a concentration of 3 mol/L. The preparation method of the electrolytic solution is as follows: adding the sodium hydroxide in the formula quantity into distilled water, stirring and dissolving to prepare the sodium hydroxide solution.

The air cathode is formed by pressing a catalytic layer, a conductive nickel mesh and a waterproof and breathable layer; the catalytic layer is formed by mixing γ-MnO ₂ , activated carbon and polytetrafluoroethylene in a mass ratio of 2:4:1 A film layer with a thickness of 0.7mm made by rolling; the waterproof and breathable layer is a film layer with a thickness of 0.5mm mixed by polytetrafluoroethylene and acetylene black in a ratio of 1:1 by weight; finally The catalytic layer, the conductive nickel mesh and the waterproof and breathable layer were pressed into an air cathode with a thickness of 0.4 mm.

The self-corrosion rate of the aluminum alloy anode in the electrolyte is 5.12mg/cm ² h, the open circuit potential is -1.96V (vs.SHE), and the discharge current density of the formed air battery in the electrolyte is 100mA/ The electromotive force of the 10h test at cm ² is 1.99V, and the surface of the anode alloy is corroded uniformly.

Example 2

The aluminum alloy anode material for an air battery in this embodiment is composed of the following components in weight percent: Zn 6%, Ga 1%, In 1.5%, and the balance is Al.

The preparation method of the aluminum alloy anode material for the air battery of the present embodiment comprises the following steps:

1) Under the protection of argon, place the aluminum ingot in the crucible of a ZGJL0.01-40-4 induction melting furnace, heat it to 700°C to melt the aluminum ingot, add zinc ingots, gallium grains and indium grains, and heat it while heating Rotate the container to melt and mix the metal evenly, continue heating to 730°C and keep it warm for 5 minutes, then pour into block ingots;

2) The block ingot obtained in step 1) is rolled at 160° C. into a sheet material with a thickness of 1 mm to obtain the aluminum alloy anode material for an air battery.

The aluminum-air battery of this embodiment includes an aluminum alloy anode, an air cathode, and an electrolyte, and the aluminum alloy anode is the above-mentioned aluminum alloy anode material for an air battery;

The electrolyte solution contains components with the following concentrations: 3 mol/L sodium hydroxide, 80 ppm (v/v) corrosion inhibitor of lavender essential oil, and the balance is distilled water. The preparation method of the electrolytic solution is as follows: take the sodium hydroxide of the formula quantity and add distilled water, stir the solution to make a sodium hydroxide solution; add the lavender essential oil corrosion inhibitor of the formula quantity into the sodium hydroxide solution, then add the remaining distilled water, stir Evenly, that is. The lavender essential oil corrosion inhibitor is an ethanol solution of lavender essential oil, wherein the volume percentage of lavender essential oil is 60%.

The air cathode is formed by pressing a catalytic layer, a conductive nickel mesh and a waterproof and breathable layer; the catalytic layer is composed of γ-MnO ₂ , activated carbon and polytetrafluoroethylene mixed in a mass ratio of 1:4:5 A film layer with a thickness of 0.6mm made by rolling; the waterproof and breathable layer is a film layer with a thickness of 0.4mm mixed by polytetrafluoroethylene and acetylene black in a ratio of 1:1 by weight; finally The catalytic layer, the conductive nickel mesh and the waterproof and breathable layer were pressed into an air cathode with a thickness of 0.3 mm.

The self-corrosion rate of the aluminum alloy anode in the electrolyte is 3.57mg/cm ² h, the open circuit potential is -1.92V (vs. SHE), and the discharge current density of the formed air battery in the electrolyte is 100mA/ The electromotive force of the test for 10 hours at cm ² is 2.05V, and the surface of the anode alloy is corroded uniformly.

Example 3

The aluminum alloy anode material for an air battery in this embodiment is composed of the following components in weight percent: Zn 3%, Ga 3%, In 0.01%, and the balance is Al.

The preparation method of the aluminum alloy anode material for the air battery of the present embodiment comprises the following steps:

1) Under the protection of argon, place the aluminum ingot in the crucible of a ZGJL0.01-40-4 induction melting furnace, heat it to 710°C to melt the aluminum ingot, add zinc ingots, gallium grains and indium grains, and heat it while heating Rotate the container to melt and mix the metal evenly, continue heating to 760°C and keep it warm for 6 minutes, then pour into block ingots;

2) Rolling the block ingot obtained in step 1) into a sheet material with a thickness of 3 mm at 200° C. to obtain the aluminum alloy anode material for the air battery.

The aluminum-air battery of this embodiment includes an aluminum alloy anode, an air cathode, and an electrolyte, and the aluminum alloy anode is the above-mentioned aluminum alloy anode material for an air battery;

The electrolyte solution contains components with the following concentrations: sodium hydroxide 4mol/L, lavender essential oil corrosion inhibitor 20ppm (v/v), and the balance is distilled water. The preparation method of the electrolytic solution is as follows: take the sodium hydroxide of the formula quantity and add distilled water, stir the solution to make a sodium hydroxide solution; add the lavender essential oil corrosion inhibitor of the formula quantity into the sodium hydroxide solution, then add the remaining distilled water, stir Evenly, that is. The lavender essential oil corrosion inhibitor is an ethanol solution of lavender essential oil, wherein the volume percentage of lavender essential oil is 20%.

The air cathode is formed by pressing a catalytic layer, a conductive nickel mesh and a waterproof and breathable layer; the catalytic layer is composed of γ-MnO ₂ , activated carbon and polytetrafluoroethylene mixed in a mass ratio of 3:1:1 A film layer with a thickness of 0.5mm by rolling; the waterproof and breathable layer is a film layer with a thickness of 0.6mm after mixing polytetrafluoroethylene and acetylene black in a ratio of 1:1 by weight; finally The catalytic layer, the conductive nickel mesh and the waterproof and breathable layer were pressed into an air cathode with a thickness of 0.6 mm.

The self-corrosion rate of the aluminum alloy anode in the electrolyte is 4.28mg/cm ² h, the open circuit potential is -1.76V (vs.SHE), and the discharge current density of the formed air battery in the electrolyte is 100mA/ The electromotive force of the test for 10 hours at cm ² is 1.95V, and the surface of the anode alloy is corroded uniformly.

Example 4

The aluminum alloy anode material for an air battery in this embodiment is composed of the following components in weight percent: Zn 0.05%, Ga 4%, In 2%, and the balance is Al.

The preparation method of the aluminum alloy anode material for the air battery of the present embodiment comprises the following steps:

1) Under the protection of argon, place the aluminum ingot in the crucible of a ZGJL0.01-40-4 induction melting furnace, heat it to 690°C to melt the aluminum ingot, add zinc ingots, gallium grains and indium grains, and heat it while heating Rotate the container to melt and mix the metal evenly, continue heating to 760°C and keep it warm for 7 minutes, then pour into block ingots;

2) The block ingot obtained in step 1) was rolled at 170° C. into a sheet material with a thickness of 4 mm to obtain the aluminum alloy anode material for the air battery.

The aluminum-air battery of this embodiment includes an aluminum alloy anode, an air cathode, and an electrolyte, and the aluminum alloy anode is the above-mentioned aluminum alloy anode material for an air battery;

The electrolyte solution contains components with the following concentrations: sodium hydroxide 5mol/L, lavender essential oil corrosion inhibitor 90ppm (v/v), and distilled water as the balance. The preparation method of the electrolytic solution is as follows: take the sodium hydroxide of the formula quantity and add distilled water, stir the solution to make a sodium hydroxide solution; add the lavender essential oil corrosion inhibitor of the formula quantity into the sodium hydroxide solution, then add the remaining distilled water, stir Evenly, that is. The lavender essential oil corrosion inhibitor is an ethanol solution of lavender essential oil, wherein the volume percentage of lavender essential oil is 30%.

The air cathode is formed by pressing a catalytic layer, a conductive nickel mesh and a waterproof and breathable layer; the catalytic layer is formed by mixing γ-MnO ₂ , activated carbon and polytetrafluoroethylene in a mass ratio of 1.5:2:4 A film layer with a thickness of 0.3mm by rolling; the waterproof and breathable layer is a film layer with a thickness of 0.8mm after mixing polytetrafluoroethylene and acetylene black in a ratio of 1:1 by weight; finally The catalytic layer, the conductive nickel mesh and the waterproof and breathable layer were pressed into an air cathode with a thickness of 0.5 mm.

The self-corrosion rate of the aluminum alloy anode in the electrolyte is 2.93mg/cm ² h, the open circuit potential is -1.85V (vs.SHE), and the discharge current density of the formed air battery in the electrolyte is 100mA/ The electromotive force of the 10h test at cm ² is 1.89V, and the surface of the anode alloy is corroded uniformly.

Example 5

The aluminum alloy anode material for an air battery in this embodiment is composed of the following components in weight percent: Zn 5%, Ga 2.5%, In 0.05%, and the balance is Al.

The preparation method of the aluminum alloy anode material for the air battery of the present embodiment comprises the following steps:

1) Under the protection of argon, place the aluminum ingot in the crucible of a ZGJL0.01-40-4 induction melting furnace, heat it to 710°C to melt the aluminum ingot, add zinc ingots, gallium grains and indium grains, and heat it while heating Rotate the container to melt and mix the metal evenly, continue heating to 780°C and keep it warm for 6 minutes, then pour into block ingots;

2) Rolling the block ingot obtained in step 1) into a sheet material with a thickness of 2 mm at 150° C. to obtain the aluminum alloy anode material for the air battery.

The aluminum-air battery of this embodiment includes an aluminum alloy anode, an air cathode, and an electrolyte, and the aluminum alloy anode is the above-mentioned aluminum alloy anode material for an air battery;

The electrolyte solution contains components with the following concentrations: sodium hydroxide 6mol/L, lavender essential oil corrosion inhibitor 60ppm (v/v), and the balance is distilled water. The preparation method of the electrolytic solution is as follows: take the sodium hydroxide of the formula quantity and add distilled water, stir the solution to make a sodium hydroxide solution; add the lavender essential oil corrosion inhibitor of the formula quantity into the sodium hydroxide solution, then add the remaining distilled water, stir Evenly, that is. The lavender essential oil corrosion inhibitor is an ethanol solution of lavender essential oil, wherein the volume percentage of lavender essential oil is 40%.

The air cathode is formed by pressing a catalytic layer, a conductive nickel mesh and a waterproof and breathable layer; the catalytic layer is formed by mixing γ-MnO ₂ , activated carbon and polytetrafluoroethylene in a mass ratio of 0.5:2:2 A film layer with a thickness of 0.4mm made by rolling; the waterproof and breathable layer is a film layer with a thickness of 0.7mm mixed by polytetrafluoroethylene and acetylene black in a ratio of 1:1 by weight; finally The catalytic layer, the conductive nickel mesh and the waterproof and breathable layer were pressed into an air cathode with a thickness of 0.5 mm.

The self-corrosion rate of the aluminum alloy anode in the electrolyte is 3.85mg/cm ² h, the open circuit potential is -2.08V (vs. SHE), and the discharge current density of the formed air battery in the electrolyte is 100mA/ The electromotive force of the 10h test at cm ² is 1.84V, and the surface of the anode alloy is corroded uniformly.

Example 6

The aluminum alloy anode material for an air battery in this embodiment is composed of the following components in weight percent: Zn 1%, Ga 1.5%, In 0.8%, and the balance is Al.

The preparation method of the aluminum alloy anode material for the air battery of the present embodiment comprises the following steps:

1) Under the protection of argon, place the aluminum ingot in the crucible of a ZGJL0.01-40-4 induction melting furnace, heat it to 720°C to melt the aluminum ingot, add zinc ingots, gallium grains and indium grains, and heat it while heating Rotate the container to melt and mix the metal evenly, continue heating to 740°C and keep it warm for 10 minutes, then pour into block ingots;

2) The block ingot obtained in step 1) was rolled at 190° C. into a sheet material with a thickness of 3 mm to obtain the aluminum alloy anode material for the air battery.

The aluminum-air battery of this embodiment includes an aluminum alloy anode, an air cathode, and an electrolyte, and the aluminum alloy anode is the above-mentioned aluminum alloy anode material for an air battery;

The electrolyte solution contains components with the following concentrations: sodium hydroxide 4mol/L, lavender essential oil corrosion inhibitor 70ppm (v/v), and the balance is distilled water. The preparation method of the electrolytic solution is as follows: take the sodium hydroxide of the formula quantity and add distilled water, stir the solution to make a sodium hydroxide solution; add the lavender essential oil corrosion inhibitor of the formula quantity into the sodium hydroxide solution, then add the remaining distilled water, stir Evenly, that is. The lavender essential oil corrosion inhibitor is an ethanol solution of lavender essential oil, wherein the volume percentage of lavender essential oil is 10%.

The air cathode is formed by pressing a catalytic layer, a conductive nickel mesh and a waterproof and breathable layer; the catalytic layer is composed of γ-MnO ₂ , activated carbon and polytetrafluoroethylene mixed in a mass ratio of 0.3:3:3 A film layer with a thickness of 0.7mm made by rolling; the waterproof and breathable layer is a film layer with a thickness of 0.3mm mixed by polytetrafluoroethylene and acetylene black in a ratio of 1:1 by weight; finally The catalytic layer, the conductive nickel mesh and the waterproof and breathable layer were pressed into an air cathode with a thickness of 0.4 mm.

The self-corrosion rate of the aluminum alloy anode of this embodiment in the electrolyte is 4.62mg/cm ² h, the open circuit potential is -1.95V (vs.SHE), and the discharge current density of the formed air battery in the electrolyte is 100mA/ The electromotive force of the test for 10 hours at cm ² is 2.10V, and the surface of the anode alloy is corroded uniformly.

Example 7

The aluminum alloy anode material for an air battery in this embodiment is composed of the following components in weight percent: Zn 4%, Ga 0.05%, In 1%, and the balance is Al.

The preparation method of the aluminum alloy anode material for the air battery of the present embodiment comprises the following steps:

1) Under the protection of argon, place the aluminum ingot in the crucible of a ZGJL0.01-40-4 induction melting furnace, heat it to 670°C to melt the aluminum ingot, add zinc ingots, gallium grains and indium grains, and heat it while heating Rotate the container to melt and mix the metal evenly, continue heating to 750°C and keep it warm for 4 minutes, then pour into block ingots;

2) The block-shaped ingot obtained in step 1) was rolled at 180° C. into a sheet-shaped material with a thickness of 0.5 mm to obtain the aluminum alloy anode material for the air battery.

The aluminum-air battery of this embodiment includes an aluminum alloy anode, an air cathode, and an electrolyte, and the aluminum alloy anode is the above-mentioned aluminum alloy anode material for an air battery;

The electrolytic solution contains components with the following concentrations: sodium hydroxide 2mol/L, lavender essential oil corrosion inhibitor 100ppm (v/v), and distilled water as the balance. The preparation method of the electrolytic solution is as follows: take the sodium hydroxide of the formula quantity and add distilled water, stir the solution to make a sodium hydroxide solution; add the lavender essential oil corrosion inhibitor of the formula quantity into the sodium hydroxide solution, then add the remaining distilled water, stir Evenly, that is. The lavender essential oil corrosion inhibitor is an ethanol solution of lavender essential oil, wherein the volume percentage of lavender essential oil is 50%.

The air cathode is formed by pressing a catalytic layer, a conductive nickel mesh and a waterproof and breathable layer; the catalytic layer is formed by mixing γ-MnO ₂ , activated carbon and polytetrafluoroethylene in a mass ratio of 2:5:2.5 A film layer with a thickness of 0.8mm made by rolling; the waterproof and breathable layer is a film layer with a thickness of 0.5mm mixed by polytetrafluoroethylene and acetylene black in a ratio of 1:1 by weight; finally The catalytic layer, conductive nickel mesh and waterproof breathable layer were pressed into an air cathode with a thickness of 0.2 mm.

The self-corrosion rate of the aluminum alloy anode of this embodiment in the electrolyte is 4.06 mg/cm ² h, the open circuit potential is -1.81V (vs.SHE), and the discharge current density of the formed air battery in the electrolyte is 100mA/ The electromotive force of the 10h test at cm ² is 1.96V, and the surface of the anode alloy is corroded uniformly.

Experimental example

In this experimental example, the performance of the aluminum alloy anode material obtained in Examples 1-7 and the performance of the aluminum-air battery is tested, and the results are shown in Table 1. Wherein, the electromotive force of the aluminum-air battery is the electromotive force tested for 10 h when the discharge current density in the electrolyte is 100 mA/cm ² .

Table 1 The performance test results of the aluminum alloy anode material and aluminum-air battery obtained in Examples 1-7

It can be seen from Table 1 that the self-corrosion rate of the aluminum alloy anode materials obtained in Examples 1-7 in the electrolyte is as low as 2.93-5.12mg/cm ² h, and the open circuit potential reaches -1.76--2.08V (vs. SHE ), the electromotive force of the air battery formed in the electrolyte is 1.84-2.10V when the discharge current density is 100mA/cm ² in the electrolyte, and the surface corrosion of the anode alloy is uniform. Experimental results show that the aluminum alloy anode material of the present invention has low self-corrosion rate and good open circuit potential in alkaline electrolyte, and the formed air battery has excellent electrochemical performance.

Claims (8)

1. A kind of 1. aluminium-air cell, it is characterised in that：Including aluminum alloy anode, air cathode and electrolyte, the aluminium alloy sun Pole consists of the following components in percentage by weight：Zn 0.05%~6%, Ga 0.05%~4%, In 0.01%~2%, surplus Al； The electrolyte includes the component of following concentration：2~6mol/L of sodium hydroxide, Lavender corrosion inhibiter 20~100ppm, it is remaining Measure as water.
2. 2. aluminium-air cell according to claim 1, it is characterised in that：The material of the aluminum alloy anode is prepared under including Row step：

   1）Under inert gas shielding, after aluminium heating fusing, zinc is added, gallium and indium simultaneously heat melting, continue to be heated to 730~ 780 DEG C and be incubated after, pour into ingot casting；

   2）By step 1）Gained ingot casting is rolled into flaky material under the conditions of 150~200 DEG C, produces.
3. 3. aluminium-air cell according to claim 2, it is characterised in that：Step 1）In, time of the insulation for 4~ 10min。
4. 4. aluminium-air cell according to claim 2, it is characterised in that：Step 2）In, the thickness of the flaky material is 0.5~4mm.
5. 5. aluminium-air cell according to claim 1, it is characterised in that：The air cathode is by Catalytic Layer, conductive nickel screen Suppress to be formed with waterproof ventilative layer, thickness is 0.2~0.6mm.
6. 6. aluminium-air cell according to claim 5, it is characterised in that：The Catalytic Layer is by γ-MnO₂, activated carbon with Polytetrafluoroethylene (PTFE) is in mass ratio（0.3~3）:（1~5）:（1~5）Ratio mixing after the film layer that is pressed into, thickness 0.3 ~0.8mm.
7. 7. aluminium-air cell according to claim 5, it is characterised in that：The waterproof ventilative layer be by polytetrafluoroethylene (PTFE) and Acetylene black is 1 by weight:The film layer being pressed into after 1 ratio mixing, thickness is 0.3~0.8mm.
8. 8. aluminium-air cell according to claim 1, it is characterised in that：The Lavender corrosion inhibiter is lavender essence The ethanol solution of oil, the wherein volumn concentration of Lavender are 10%~60%.