CN111560542A - Calcium-containing aluminum alloy anode material for alkaline aluminum-air battery and preparation method thereof - Google Patents
Calcium-containing aluminum alloy anode material for alkaline aluminum-air battery and preparation method thereof Download PDFInfo
- Publication number
- CN111560542A CN111560542A CN202010392069.9A CN202010392069A CN111560542A CN 111560542 A CN111560542 A CN 111560542A CN 202010392069 A CN202010392069 A CN 202010392069A CN 111560542 A CN111560542 A CN 111560542A
- Authority
- CN
- China
- Prior art keywords
- calcium
- melt
- anode material
- aluminum alloy
- containing aluminum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/026—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a calcium-containing aluminum alloy anode material for an alkaline aluminum-air battery and a preparation method thereof, wherein the calcium-containing aluminum alloy anode material comprises the following components in percentage by mass: ca: 0.01 to 1.0%, Sn: 0 to 1.0%, Bi: 0-1.0%, impurity content less than or equal to 0.30%, and the balance of Al; the calcium-containing aluminum alloy anode material is prepared by smelting, degassing, slagging off, casting, homogenizing annealing, rolling and solid dissolving. The anode material adopts industrial pure aluminum as a raw material, does not contain valuable elements such as In and Ga, does not contain elements such as Pb and Hg which are harmful to the environment, and contains calcium which can refine crystal grains and improve the electrochemical performance of the anode, thereby reducing the production cost and simultaneously keeping the activity of the anode; the alloy element Sn has higher hydrogen overpotential, can inhibit hydrogen evolution corrosion, increases the effective utilization rate of the alloy, can reduce the passivation performance of the surface of the aluminum alloy and improve the utilization rate of the anode, and can reduce the nonuniformity of the microstructure of the anode and improve the current efficiency.
Description
Technical Field
The invention relates to the field of metal-air batteries, in particular to a calcium-containing aluminum alloy anode material for an alkaline aluminum-air battery and a preparation method thereof.
Background
In recent years, research on metal-air batteries has been gradually a hot topic due to its extremely high theoretical energy density and specific capacitance, its discharge process is not strongly dependent on load and temperature, and its manufacturing cost is low, recyclability and environmental friendliness. The metal-air battery is a semi-fuel battery which takes metal as an anode, oxygen in air as a cathode and adopts neutral or alkaline electrolyte as a medium. The discharge principle is that the metal anode loses electrons to obtain electric energy.
Currently, metal-air batteries include lithium-air batteries, aluminum-air batteries, magnesium-air batteries, zinc-air batteries, and the like. Wherein the aluminum-air battery has a theoretical energy density of 8.1 kWh.kg-1Second only to lithium-air batteries (13.0 kWh.kg)-1) Higher than that of a magnesium-air battery (6.8 kWh.kg)-1) And a zinc-air battery (1.3 kWh. kg)-1). In addition, the aluminum anode has the advantages of rich resources, low manufacturing cost, easy processing and forming, no toxicity, high recoverability and the like. The lithium anode is relatively expensive and is prone to safety hazards due to its thermal instability. Therefore, aluminum-air batteries are expected to be sustainable, inexpensive, and high energy density electrochemical storage devices. Alkaline aluminum-air cells can provide higher and more stable operating potentials. However, pure aluminum anodes undergo severe hydrogen evolution corrosion in alkaline electrolytes, which reduces the discharge efficiency of the anode and causes voltage hysteresis during discharge, so that pure aluminum cannot be directly used as an anode material. In recent years, it has been found that by adding alloying elements to pure aluminum or to the electrolyteThe corrosion inhibitor can greatly improve the discharge performance of the anode material. At present, there are many patents and literature reports that alloy elements such as Ga, Sn, Mg, Zn, In, Hg, Pb, etc. are added into pure aluminum to improve the electrochemical performance of the aluminum anode. A plurality of anodes with better performance are obtained by adding alloy elements, such as Al-Ga-Mg, Al-In-Zn, Al-Zn-Hg, Al-In-Mg, Al-In-Sn, Al-Mg-Ga-Sn-Pb, Al-Ga-Sn-Mg-Mn (grant No. CN102820472B), Al-In-Ga-Zn (grant No. CN105140596B) and other alloys, but the components of the anodes contain noble elements such as In and Ga, which causes the production cost to be overhigh; in addition, Hg and Pb are harmful to the ecological environment. Therefore, the method has great significance in seeking an anode material which is low in cost, environment-friendly, good in discharge activity and low in self-corrosion rate.
Disclosure of Invention
The technical task of the invention is to provide an anode material for an alkaline aluminum-air battery, which has good discharge characteristics, low cost and environmental friendliness, and a preparation method thereof.
The invention provides a calcium-containing aluminum alloy anode material for an alkaline aluminum-air battery, which comprises the following components in percentage by mass: ca: 0.01 to 1.00%, Sn: 0 to 1.00%, Bi: 0-1.00%, less than or equal to 0.30% of impurity content, and the balance of Al.
Further, the calcium-containing aluminum alloy anode material comprises the following components in percentage by mass: ca: 0.01 to 1.00%, Sn: 0.01-1.00%, impurity content less than or equal to 0.30%, and the balance of Al.
Further, the calcium-containing aluminum alloy anode material comprises the following components in percentage by mass: ca: 0.01 to 1.00%, Bi: 0.01-1.00%, impurity content less than or equal to 0.30%, and the balance of Al.
Further, the calcium-containing aluminum alloy anode material comprises the following components in percentage by mass: ca: 0.01 to 1.00%, Sn: 0.01 to 1.00%, Bi: 0.01-1.00%, impurity content less than or equal to 0.30%, and the balance of Al.
Further, the open-circuit voltage of the calcium-containing aluminum alloy anode material is 1.87-1.99V (Vs.SHE) and is 40mAcm-2The discharge efficiency reaches 91.2-98.9% at the current density of (2), and the energy density is 3587.4-4037.7 Wh.kg-1。
The invention also provides a preparation method of the calcium-containing aluminum alloy anode material for the alkaline aluminum-air battery based on the components, the calcium-containing aluminum alloy anode material is prepared by smelting, degassing, slagging off, casting, homogenizing annealing, rolling and solid solution, wherein the smelting process comprises the following steps: proportioning according to alloy components, adding industrial pure aluminum into a medium-frequency smelting furnace, heating to 760-790 ℃ for melting, controlling the temperature to 720-750 ℃, adding an aluminum-calcium intermediate alloy into the melt, electromagnetically stirring the melt for 5-30 min when the aluminum-calcium intermediate alloy is completely melted, controlling the temperature to 670-720 ℃ after the electromagnetic stirring if the alloy components contain low-melting-point alloy elements, adding the low-melting-point alloy elements, and electromagnetically stirring the melt for 5-15 min after the low-melting-point alloy elements are melted; the low-melting-point alloy element is Sn and/or Bi.
Further, the degassing and slagging-off process comprises the following steps: introducing the melt obtained after smelting into a standing furnace at 730-750 ℃, introducing mixed gas into the standing furnace for 5-10 min, introducing argon for 10-15 min, then standing for 5-15 min, and removing floating slag on the surface of the melt; the mixed gas is a mixture of argon and hexachloroethane powder, wherein the concentration of hexachloroethane is 40-60 g/m3。
Further, the casting and homogenizing annealing process comprises the following steps: and continuously heating the melt obtained after degassing and slagging-off to 720-740 ℃ under the protection of argon, preserving heat for 5-20 min, then casting into a block-shaped cast ingot, and carrying out homogenizing annealing on the cast ingot at 550-600 ℃ for 12-24 h.
Further, the rolling process comprises: and (3) hot rolling the cast ingot obtained by casting and homogenizing annealing to 3-5 mm at 300-400 ℃, and then cold rolling to finally obtain an anode plate with the thickness of 1-1.5 mm.
Further, the solid solution process comprises: and carrying out solution treatment on the rolled anode plate at 400-600 ℃ for 4-12 h.
The invention discloses a preferable technical scheme of a preparation method of a calcium-containing aluminum alloy anode material for an alkaline aluminum-air battery, which comprises the following steps:
(1) preparing materials: taking industrial pure aluminum, industrial pure tin, industrial pure bismuth and aluminum calcium intermediate alloy as raw materials, and batching according to alloy components;
(2) smelting: in the smelting process, firstly adding industrial pure aluminum into a medium-frequency smelting furnace, heating to 760-790 ℃ for melting, controlling the temperature to 720-750 ℃, adding an aluminum-calcium intermediate alloy into the melt, electromagnetically stirring the melt for 5-30 min when the intermediate alloy is completely melted, controlling the temperature to 670-720 ℃ after the electromagnetic stirring if the alloy components contain low-melting-point alloy elements, adding the low-melting-point alloy elements, electromagnetically stirring the melt for 5-15 min after the low-melting-point alloy elements are melted, and introducing argon as a protective gas in the whole smelting process; the low-melting-point alloy element is Sn and/or Bi, and the low-melting-point alloy element is pressed in by a bell jar in an aluminum foil coating mode for 2-4 min;
(3) degassing and slagging off: introducing the melt obtained in the step (2) into a standing furnace at 730-750 ℃, introducing mixed gas into the standing furnace for 5-10 min, introducing argon for 10-15 min, standing for 5-15 min, and removing floating slag on the surface of the melt by using a graphite tool, wherein the mixed gas is a mixture of argon and hexachloroethane powder (the hexachloroethane concentration is 40-60 g/m)3)；
(4) Pouring: continuously heating the melt obtained in the step (3) to 720-740 ℃ under the protection of argon, preserving heat for 5-20 min, then casting into a block-shaped cast ingot, and carrying out homogenizing annealing on the cast ingot at 550-600 ℃ for 12-24 h;
(5) rolling: hot rolling the cast ingot obtained in the step (4) to 3-5 mm at 300-400 ℃, and then finally rolling the cast ingot into an anode plate with the thickness of 1-1.5 mm through cold rolling;
(6) solid solution: and (4) carrying out solution treatment on the anode plate obtained in the step (5) at 400-600 ℃ for 4-12 h.
The invention adopts binary or ternary alloy as the anode material of the alkaline aluminum-air battery, wherein trace Ca in the aluminum alloy is beneficial to reducing the tendency of over-activation of the anode and is beneficial to displaying better voltage recovery after the precipitation of aluminum hydroxide; in addition, calcium is an environmentally friendly element, and its standard electrode potential is higher than that of aluminum (-2.35V (vs. she)), i.e., -3.02V (vs. she), in an alkaline solution, and can improve the discharge voltage of an aluminum anode. Sn in the aluminum alloy can activate the anode through the principle of dissolution-redeposition; meanwhile, the alloy element Sn has higher hydrogen overpotential, so that the hydrogen evolution corrosion can be inhibited, and the effective utilization rate of the alloy is increased. The alloy element Bi can expand the crystal lattice of the aluminum alloy, so that the solid solubility of other alloy elements is increased, the passivation performance of the surface of the aluminum alloy can be reduced, and the utilization rate of the anode is improved; bi can also reduce the nonuniformity of the anode microstructure and improve the current efficiency; in addition, Bi element has the advantages of low price and relative innocuity.
The invention has the beneficial effects that:
1. the anode material adopts industrial pure aluminum as a raw material, does not contain valuable elements such as In and Ga, does not contain elements such as Pb and Hg which are harmful to the environment, contains Ca which can refine crystal grains and improve the electrochemical performance of the anode, reduces the production cost, simultaneously maintains the activity of the anode, and the alloy element Sn has higher hydrogen overpotential, can inhibit hydrogen evolution corrosion and increase the effective utilization rate of the alloy;
2. according to the preparation method, the anode material is processed into the anode plate which can be directly used at any time by adopting a rolling process, the process is simple, the method is suitable for batch production, the defects of the anode material are reduced, the yield is improved, the energy consumption is reduced, the production cost is reduced, and good economic benefits are achieved;
3. according to the anode material, through a solid solution process after rolling, the solid solubility of each alloy element is increased, and the formation of segregation phase is reduced, so that the discharge characteristics (discharge efficiency, energy density and specific capacitance) of the anode are greatly improved, and the open-circuit potential of the aluminum alloy anode is 1.87-1.99V (Vs.SHE) in 4mol/L NaOH electrolyte; at 40mA cm-2The discharge efficiency and the energy density respectively reach 91.2-98.9% and 3587.4～4037.7Wh·kg-1And the problems of serious hydrogen evolution corrosion, serious polarization, voltage hysteresis and the like are solved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified, and the raw materials in the examples have a purity of, in terms of mass fraction, 99.8% of commercially pure aluminum Al, 99.9% of commercially pure tin Sn, 99.9% of commercially pure bismuth Bi, and 75% of Ca in an aluminum-calcium master alloy.
Table 1 composition (mass%) of the calcium-containing aluminum alloy anode material in each example
| Examples | Ca/wt％ | Sn/wt％ | Bi/wt％ | Al/wt％ |
| 1 | 0.01 | - | - | Balance of |
| 2 | 0.05 | - | - | Balance of |
| 3 | 0.10 | - | - | Balance of |
| 4 | 0.20 | - | - | Balance of |
| 5 | 1.0 | - | - | Balance of |
| 6 | 0.01 | 0.01 | - | Balance of |
| 7 | 0.10 | 0.10 | - | Balance of |
| 8 | 0.50 | 0.5 | - | Balance of |
| 9 | 1.0 | 1.0 | - | Balance of |
| 10 | 0.01 | - | 0.01 | Balance of |
| 11 | 0.10 | - | 0.10 | Balance of |
| 12 | 0.50 | - | 0.50 | Balance of |
| 13 | 1.0 | - | 1.0 | Balance of |
| 14 | 0.10 | 0.10 | 0.10 | Balance of |
| 15 | 0.50 | 0.50 | 0.50 | Balance of |
Example 1:
proportioning according to the components in the table 1, putting industrial pure aluminum (99.8 wt% Al) into a smelting furnace, and heating to 760 ℃ to form an aluminum melt; and then adding Al-75% Ca intermediate alloy into the melt when the temperature of the melt is 720 ℃, electromagnetically stirring the aluminum alloy melt for 10min after the intermediate alloy is completely melted, and introducing argon for protection in the whole process. The melt was introduced into a standing furnace at 730 ℃ and a mixed gas of argon and hexachloroethane powder (hexachloroethane concentration 40 g/m) was introduced into the standing furnace3) Introducing pure argon for 15min after 10min, and standing for 15 min; then removing the oxidized dross on the surface of the melt by using a graphite slagging-off tool. And continuously heating the melt to 720 ℃ under the protection of argon, preserving the heat for 5min, then casting the aluminum alloy melt into a blocky ingot, and carrying out 550 ℃ homogenization annealing on the ingot for 24 h. The obtained ingot was hot-rolled to 5mm at 350 ℃ and then finally rolled into an anode plate having a thickness of 1.5mm by cold rolling. Carrying out solution treatment on the obtained anode plate for 12h at 400 ℃, removing oxide skin on the surface of the anode plate by using a steel brush, and then cleaning by using ultrasonic waves; and finally, placing the dried anode plate into a sealing bag, vacuumizing, sealing and storing so that the anode plate can be used at any time.
Example 2:
proportioning according to the components in the table 1, putting industrial pure aluminum (99.8 wt% Al) into a smelting furnace, and heating to 770 ℃ to form an aluminum melt; and then adding Al-75% Ca intermediate alloy into the melt when the temperature of the melt is 730 ℃, electromagnetically stirring the aluminum alloy melt for 15min after the intermediate alloy is completely melted, and introducing argon for protection in the whole process. Introducing the melt into a standing furnace at 740 ℃, and introducing the mixture of argon and hexachloroethane powder into the standing furnaceGas (hexachloroethane concentration 50 g/m)3) Introducing pure argon for 10min after 8min, and standing for 10 min; then removing the oxidized dross on the surface of the melt by using a graphite slagging-off tool. And continuously heating the melt to 730 ℃ under the protection of argon, preserving the heat for 10min, then casting the aluminum alloy melt into a block-shaped ingot, and carrying out 550 ℃ homogenization annealing on the ingot for 18 h. The obtained ingot was hot-rolled to 4mm at 350 ℃ and then finally rolled into an anode plate having a thickness of 1mm by cold rolling. Carrying out solution treatment on the obtained anode plate for 8h at 500 ℃, removing oxide skin on the surface of the anode plate by using a steel brush, and then cleaning by using ultrasonic waves; and finally, placing the dried anode plate into a sealing bag, vacuumizing, sealing and storing so that the anode plate can be used at any time.
Example 3:
the method comprises the following steps of proportioning according to the components in the table 1, putting industrial pure aluminum (99.8 wt% of Al) into a smelting furnace, heating to 780 ℃ to form an aluminum melt, then adding Al-75% of Ca intermediate alloy into the melt when the temperature of the melt is 740 ℃, electromagnetically stirring the aluminum alloy melt for 5min after the intermediate alloy is completely melted, and introducing argon for protection in the whole process. The melt was introduced into a standing furnace at 740 ℃ and a mixed gas of argon and hexachloroethane powder (hexachloroethane concentration 50 g/m) was introduced into the standing furnace3) Introducing pure argon for 10min after 5min, and standing for 5 min; then removing the oxidized dross on the surface of the melt by using a graphite slagging-off tool. And continuously heating the melt to 740 ℃ under the protection of argon, preserving the heat for 10min, then casting the aluminum alloy melt into a block-shaped ingot, and carrying out homogenization annealing on the ingot at 600 ℃ for 12 h. The obtained ingot was hot-rolled to 5mm at 350 ℃ and then finally rolled into an anode plate having a thickness of 1.5mm by cold rolling. Carrying out solution treatment at 550 ℃ on the obtained anode plate for 6h, removing oxide skin on the surface of the anode plate by using a steel brush, and then cleaning by using ultrasonic waves; and finally, placing the dried anode plate into a sealing bag, vacuumizing, sealing and storing so that the anode plate can be used at any time.
Example 4:
the compounding was carried out according to the composition of Table 1, by placing commercially pure aluminum (99.8 wt.% Al) into a melting furnace, heating to 790 ℃ to form an aluminum melt, and then cooling to 740 ℃ to melt temperatureWhen in use, Al-75% Ca intermediate alloy is added into the melt, after the intermediate alloy is completely melted, the aluminum alloy melt is electromagnetically stirred for 20min, and argon is introduced into the whole process for protection. Introducing the melt into a standing furnace at 750 ℃, and introducing a mixed gas of argon and hexachloroethane powder (the hexachloroethane concentration is 40 g/m) into the standing furnace3) Introducing pure argon for 10min, and standing for 10 min; then removing the oxidized dross on the surface of the melt by using a graphite slagging-off tool. And continuously heating the melt to 740 ℃ under the protection of argon, preserving the heat for 5min, then casting the aluminum alloy melt into a block-shaped ingot, and carrying out homogenization annealing on the ingot at 600 ℃ for 12 h. The obtained ingot was hot-rolled to 5mm at 300 ℃ and then finally rolled into an anode plate having a thickness of 1.5mm by cold rolling. Carrying out solution treatment on the obtained anode plate for 4h at 600 ℃, removing oxide skin on the surface of the anode plate by using a steel brush, and then cleaning by using ultrasonic waves; and finally, placing the dried anode plate into a sealing bag, vacuumizing, sealing and storing so that the anode plate can be used at any time.
Example 5:
the method comprises the following steps of proportioning according to the components in the table 1, putting industrial pure aluminum (99.8 wt% of Al) into a smelting furnace, heating to 760 ℃ to form an aluminum melt, adding Al-75% of Ca intermediate alloy into the melt when the melt temperature is 750 ℃, electromagnetically stirring the aluminum alloy melt for 25min after the intermediate alloy is completely melted, and introducing argon for protection in the whole process. Introducing the melt into a standing furnace at 750 ℃, and introducing a mixed gas of argon and hexachloroethane powder (the hexachloroethane concentration is 50 g/m) into the standing furnace3) Introducing pure argon for 10min after 5min, and standing for 5 min; then removing the oxidized dross on the surface of the melt by using a graphite slagging-off tool. And continuously heating the melt to 730 ℃ under the protection of argon, preserving the heat for 5min, then casting the aluminum alloy melt into a block-shaped ingot, and carrying out 550 ℃ homogenization annealing on the ingot for 24 h. The obtained ingot was hot-rolled to 5mm at 400 ℃ and then finally rolled into an anode plate having a thickness of 1mm by cold rolling. Carrying out solution treatment on the obtained anode plate for 6h at 600 ℃, removing oxide skin on the surface of the anode plate by using a steel brush, and then cleaning by using ultrasonic waves; finally, the dried anode plate is put into a sealing bag, vacuumized, sealed and stored,so that the anode plate can be used at any time.
Example 6:
proportioning according to the components in the table 1, putting industrial pure aluminum (99.8 wt% of Al) into a smelting furnace, heating to 760 ℃ to form an aluminum melt, then adding Al-75% of Ca intermediate alloy into the melt when the temperature of the melt is 720 ℃, and electromagnetically stirring the aluminum alloy melt for 30min after the intermediate alloy is completely melted; and (3) when the temperature of the melt is 670 ℃, pressing an alloy element Sn (99.9 wt.%) (wrapped by aluminum foil) into the melt for 3min by using a graphite pressure cover, then electromagnetically stirring for 10min, and introducing argon for protection in the whole process. The melt was introduced into a standing furnace at 730 ℃ and a mixed gas of argon and hexachloroethane powder (hexachloroethane concentration 50 g/m) was introduced into the standing furnace3) Introducing pure argon for 10min after 5min, and standing for 5 min; then removing the oxidized dross on the surface of the melt by using a graphite slagging-off tool. And continuously heating the melt to 740 ℃ under the protection of argon, preserving the heat for 5min, then casting the aluminum alloy melt into a block-shaped ingot, and carrying out homogenization annealing on the ingot at 600 ℃ for 12 h. The obtained ingot was hot-rolled to 5mm at 350 ℃ and then finally rolled into an anode plate having a thickness of 1.5mm by cold rolling. Carrying out solution treatment on the obtained anode plate for 12h at 400 ℃, removing oxide skin on the surface of the anode plate by using a steel brush, and then cleaning by using ultrasonic waves; and finally, placing the dried anode plate into a sealing bag, vacuumizing, sealing and storing so that the anode plate can be used at any time.
Example 7:
proportioning according to the components in the table 1, firstly putting industrial pure aluminum (99.8 wt% of Al) into a smelting furnace, heating to 770 ℃ to form an aluminum melt, then adding Al-75% of Ca intermediate alloy into the melt when the temperature of the melt is 730 ℃, and after the intermediate alloy is completely melted, electromagnetically stirring the aluminum alloy melt for 10 min; and (3) pressing an alloy element Sn (99.9 wt.%) (wrapped by aluminum foil) into the melt for 3min by using a graphite pressure cover when the temperature of the melt is 690 ℃, then electromagnetically stirring for 10min, and introducing argon for protection in the whole process. The melt was introduced into a standing furnace at 740 ℃ and a mixed gas of argon and hexachloroethane powder (hexachloroethane concentration 60 g/m) was introduced into the standing furnace3) Introducing pure argon for 10min after 5min, and standing for 5 min; then removing slag by graphiteThe oxidation scum on the surface of the melt is removed. And continuously heating the melt to 740 ℃ under the protection of argon, preserving the heat for 20min, then casting the aluminum alloy melt into a block-shaped ingot, and carrying out homogenization annealing on the ingot at 550 ℃ for 24 h. The obtained ingot was hot-rolled to 5mm at 350 ℃ and then finally rolled into an anode plate having a thickness of 1.5mm by cold rolling. Carrying out solution treatment on the obtained anode plate for 4h at 600 ℃, removing oxide skin on the surface of the anode plate by using a steel brush, and then cleaning by using ultrasonic waves; and finally, placing the dried anode plate into a sealing bag, vacuumizing, sealing and storing so that the anode plate can be used at any time.
Example 8:
proportioning according to the components in the table 1, putting industrial pure aluminum (99.8 wt% of Al) into a smelting furnace, heating to 770 ℃ to form an aluminum melt, then adding Al-75% of Ca intermediate alloy into the melt when the temperature of the melt is 740 ℃, and electromagnetically stirring the aluminum alloy melt for 10min after the intermediate alloy is completely melted; when the temperature of the melt is 700 ℃, a graphite pressure cover is used for pressing an alloy element Sn (99.9 wt.%) (wrapped by aluminum foil) into the melt for 3min, then the mixture is electromagnetically stirred for 15min, and argon is introduced into the whole process for protection. The melt was introduced into a standing furnace at 740 ℃ and a mixed gas of argon and hexachloroethane powder (hexachloroethane concentration 50 g/m) was introduced into the standing furnace3) Introducing pure argon for 10min after 5min, and standing for 5 min; then removing the oxidized dross on the surface of the melt by using a graphite slagging-off tool. And continuously heating the melt to 740 ℃ under the protection of argon, preserving the heat for 10min, then casting the aluminum alloy melt into a block-shaped ingot, and carrying out homogenization annealing on the ingot at 600 ℃ for 18 h. The obtained ingot was hot-rolled to 5mm at 350 ℃ and then finally rolled into an anode plate having a thickness of 1.5mm by cold rolling. Carrying out solution treatment at 550 ℃ on the obtained anode plate for 6h, removing oxide skin on the surface of the anode plate by using a steel brush, and then cleaning by using ultrasonic waves; and finally, placing the dried anode plate into a sealing bag, vacuumizing, sealing and storing so that the anode plate can be used at any time.
Example 9:
the compounding was carried out according to the composition of Table 1, by first charging commercially pure aluminum (99.8 wt.% Al) into a melting furnace, then heating to 780 ℃ to form an aluminum melt, followed by meltingThen when the temperature of the melt is 750 ℃, adding Al-75% Ca intermediate alloy into the melt, and after the intermediate alloy is completely melted, performing electromagnetic stirring on the aluminum alloy melt for 10 min; and (3) pressing an alloy element Sn (99.9 wt.%) (wrapped by aluminum foil) into the melt for 3min by using a graphite pressure cover when the temperature of the melt is 720 ℃, then electromagnetically stirring for 10min, and introducing argon for protection in the whole process. Introducing the melt into a standing furnace at 750 ℃, and introducing a mixed gas of argon and hexachloroethane powder (the hexachloroethane concentration is 50 g/m) into the standing furnace3) Introducing pure argon for 10min after 5min, and standing for 5 min; then removing the oxidized dross on the surface of the melt by using a graphite slagging-off tool. And continuously heating the melt to 740 ℃ under the protection of argon, preserving the heat for 5min, then casting the aluminum alloy melt into a block-shaped ingot, and carrying out homogenization annealing on the ingot at 550 ℃ for 24 h. The obtained ingot was hot-rolled to 3mm at 400 ℃ and then finally rolled into an anode plate having a thickness of 1.5mm by cold rolling. Carrying out solution treatment on the obtained anode plate for 6h at 450 ℃, removing oxide skin on the surface of the anode plate by using a steel brush, and then cleaning by using ultrasonic waves; and finally, placing the dried anode plate into a sealing bag, vacuumizing, sealing and storing so that the anode plate can be used at any time.
Example 10:
proportioning according to the components in the table 1, putting industrial pure aluminum (99.8 wt% of Al) into a smelting furnace, heating to 760 ℃ to form an aluminum melt, adding Al-75% of Ca intermediate alloy into the melt when the melt temperature is 730 ℃, and electromagnetically stirring the aluminum alloy melt for 10min after the intermediate alloy is completely melted; and (3) when the temperature of the melt is 670 ℃, pressing an alloy element Bi (99.9 wt.%) (wrapped by aluminum foil) into the melt for 3min by using a graphite pressure cover, then electromagnetically stirring for 10min, and introducing argon for protection in the whole process. The melt was introduced into a standing furnace at 740 ℃ and a mixed gas of argon and hexachloroethane powder (hexachloroethane concentration 50 g/m) was introduced into the standing furnace3) Introducing pure argon for 10min after 5min, and standing for 5 min; then removing the oxidized dross on the surface of the melt by using a graphite slagging-off tool. And continuously heating the melt to 740 ℃ under the protection of argon, preserving the heat for 10min, then casting the aluminum alloy melt into a block-shaped ingot, and carrying out homogenization annealing on the ingot at 600 ℃ for 12 h. The obtained cast ingot is heated at 350 deg.CHot rolled to 5mm under the condition, and then finally rolled into an anode plate with the thickness of 1.5mm by cold rolling. Carrying out solution treatment on the obtained anode plate for 4h at 600 ℃, removing oxide skin on the surface of the anode plate by using a steel brush, and then cleaning by using ultrasonic waves; and finally, placing the dried anode plate into a sealing bag, vacuumizing, sealing and storing so that the anode plate can be used at any time.
Example 11:
proportioning according to the components in the table 1, putting industrial pure aluminum (99.8 wt% of Al) into a smelting furnace, heating to 770 ℃ to form an aluminum melt, then adding Al-75% of Ca intermediate alloy into the melt when the temperature of the melt is 740 ℃, and electromagnetically stirring the aluminum alloy melt for 10min after the intermediate alloy is completely melted; and (3) pressing an alloy element Bi (99.9 wt.%) (wrapped by aluminum foil) into the melt for 3min by using a graphite pressure cover when the temperature of the melt is 690 ℃, then electromagnetically stirring for 5min, and introducing argon for protection in the whole process. The melt was introduced into a standing furnace at 740 ℃ and a mixed gas of argon and hexachloroethane powder (hexachloroethane concentration 40 g/m) was introduced into the standing furnace3) Introducing pure argon for 10min, and standing for 5 min; then removing the oxidized dross on the surface of the melt by using a graphite slagging-off tool. And continuously heating the melt to 730 ℃ under the protection of argon, preserving the heat for 10min, then casting the aluminum alloy melt into a block-shaped ingot, and carrying out 550 ℃ homogenization annealing on the ingot for 24 h. The obtained ingot was hot-rolled to 5mm at 350 ℃ and then finally rolled into an anode plate having a thickness of 1.5mm by cold rolling. Carrying out solution treatment at 550 ℃ on the obtained anode plate for 6h, removing oxide skin on the surface of the anode plate by using a steel brush, and then cleaning by using ultrasonic waves; and finally, placing the dried anode plate into a sealing bag, vacuumizing, sealing and storing so that the anode plate can be used at any time.
Example 12:
proportioning according to the components in the table 1, firstly putting industrial pure aluminum (99.8 wt% of Al) into a smelting furnace, heating to 780 ℃ to form an aluminum melt, then adding Al-75% of Ca intermediate alloy into the melt when the temperature of the melt is 750 ℃, and after the intermediate alloy is completely melted, electromagnetically stirring the aluminum alloy melt for 10 min; when the temperature of the fused mass is 670 ℃, a graphite pressure hood is used for covering the alloy element Bi (99.9 wt%) (aluminum foil is wrappedWrapping) the mixture in the molten metal for 3min, then electromagnetically stirring for 10min, and introducing argon for protection in the whole process. The melt was introduced into a standing furnace at 740 ℃ and a mixed gas of argon and hexachloroethane powder (hexachloroethane concentration 50 g/m) was introduced into the standing furnace3) Introducing pure argon for 10min after 5min, and standing for 5 min; then removing the oxidized dross on the surface of the melt by using a graphite slagging-off tool. And continuously heating the melt to 730 ℃ under the protection of argon, preserving the heat for 5min, then casting the aluminum alloy melt into a block-shaped ingot, and carrying out 550 ℃ homogenization annealing on the ingot for 24 h. The obtained ingot was hot-rolled to 5mm at 350 ℃ and then finally rolled into an anode plate having a thickness of 1mm by cold rolling. Carrying out solution treatment on the obtained anode plate for 12h at 400 ℃, removing oxide skin on the surface of the anode plate by using a steel brush, and then cleaning by using ultrasonic waves; and finally, placing the dried anode plate into a sealing bag, vacuumizing, sealing and storing so that the anode plate can be used at any time.
Example 13:
proportioning according to the components in the table 1, firstly putting industrial pure aluminum (99.8 wt% of Al) into a smelting furnace, heating to 790 ℃ to form an aluminum melt, then adding Al-75% of Ca intermediate alloy into the melt when the melt temperature is 730 ℃, and after the intermediate alloy is completely melted, electromagnetically stirring the aluminum alloy melt for 10 min; and (3) when the temperature of the melt is 670 ℃, pressing an alloy element Bi (99.9 wt.%) (wrapped by aluminum foil) into the melt for 3min by using a graphite pressure cover, then electromagnetically stirring for 10min, and introducing argon for protection in the whole process. The melt was introduced into a standing furnace at 740 ℃ and a mixed gas of argon and hexachloroethane powder (hexachloroethane concentration 50 g/m) was introduced into the standing furnace3) Introducing pure argon for 10min after 5min, and standing for 5 min; then removing the oxidized dross on the surface of the melt by using a graphite slagging-off tool. And continuously heating the melt to 740 ℃ under the protection of argon, preserving the heat for 5min, then casting the aluminum alloy melt into a block-shaped ingot, and carrying out homogenization annealing on the ingot at 550 ℃ for 24 h. The obtained ingot was hot-rolled to 4mm at 350 ℃ and then finally rolled into an anode plate having a thickness of 1.5mm by cold rolling. Carrying out solution treatment on the obtained anode plate for 12h at 400 ℃, removing oxide skin on the surface of the anode plate by using a steel brush, and then cleaning by using ultrasonic waves; finally drying the mixtureThe anode plate is put into a sealing bag, and is vacuumized, sealed and stored so that the anode plate can be used at any time.
Example 14:
proportioning according to the components in the table 1, putting industrial pure aluminum (99.8 wt% of Al) into a smelting furnace, heating to 760 ℃ to form an aluminum melt, then adding Al-75% of Ca intermediate alloy into the melt when the temperature of the melt is 730 ℃, and electromagnetically stirring the aluminum alloy melt for 10min after the intermediate alloy is completely melted; and (3) when the temperature of the melt is 720 ℃, pressing alloy elements Sn (99.9 wt.%), Bi (99.9 wt.%) (aluminum foil wrapping) into the melt for 3min by using a graphite pressure cover, then electromagnetically stirring for 10min, and introducing argon for protection in the whole process. The melt was introduced into a standing furnace at 740 ℃ and a mixed gas of argon and hexachloroethane powder (hexachloroethane concentration 50 g/m) was introduced into the standing furnace3) Introducing pure argon for 10min after 5min, and standing for 5 min; then removing the oxidized dross on the surface of the melt by using a graphite slagging-off tool. And continuously heating the melt to 740 ℃ under the protection of argon, preserving the heat for 5min, then casting the aluminum alloy melt into a block-shaped ingot, and carrying out homogenization annealing on the ingot at 600 ℃ for 24 h. The obtained ingot was hot-rolled to 5mm at 350 ℃ and then finally rolled into an anode plate having a thickness of 1.5mm by cold rolling. Carrying out solution treatment on the obtained anode plate for 12h at 500 ℃, removing oxide skin on the surface of the anode plate by using a steel brush, and then cleaning by using ultrasonic waves; and finally, placing the dried anode plate into a sealing bag, vacuumizing, sealing and storing so that the anode plate can be used at any time.
Example 15:
proportioning according to the components in the table 1, firstly putting industrial pure aluminum (99.8 wt% of Al) into a smelting furnace, heating to 780 ℃ to form an aluminum melt, then adding Al-75% of Ca intermediate alloy into the melt when the temperature of the melt is 740 ℃, and after the intermediate alloy is completely melted, electromagnetically stirring the aluminum alloy melt for 10 min; and (3) when the temperature of the melt is 720 ℃, pressing alloy elements Sn (99.9 wt.%), Bi (99.9 wt.%) (aluminum foil wrapping) into the melt for 3min by using a graphite pressure cover, then electromagnetically stirring for 10min, and introducing argon for protection in the whole process. Introducing the melt into a standing furnace at 740 ℃, and introducing a mixed gas of argon and hexachloroethane powder (hexachloroethane)The concentration is 50g/m3) Introducing pure argon for 10min after 5min, and standing for 5 min; then removing the oxidized dross on the surface of the melt by using a graphite slagging-off tool. And continuously heating the melt to 740 ℃ under the protection of argon, preserving the heat for 5min, then casting the aluminum alloy melt into a block-shaped ingot, and carrying out 550 ℃ homogenization annealing on the ingot for 18 h. The obtained ingot was hot-rolled to 5mm at 350 ℃ and then finally rolled into an anode plate having a thickness of 1.5mm by cold rolling. Carrying out solution treatment on the obtained anode plate for 12h at 400 ℃, removing oxide skin on the surface of the anode plate by using a steel brush, and then cleaning by using ultrasonic waves; and finally, placing the dried anode plate into a sealing bag, vacuumizing, sealing and storing so that the anode plate can be used at any time.
Performing electrochemical performance detection on the calcium-containing aluminum alloy anode materials obtained in the embodiments 1 to 15, wherein the open circuit potential is determined under a standard three-electrode system, and the working potential, the energy density and the current efficiency are that the discharge density of the battery in 4mol/L NaOH electrolyte is 40mA/cm2The electrochemical performance of the anode material of each example in a 4mol/L NaOH electrolyte is shown in Table 2.
TABLE 2 electrochemical performance of the anode materials in 4mol/L NaOH electrolyte for each example
The technical idea of the present invention is described in the above technical solutions, and the protection scope of the present invention is not limited thereto, and any changes and modifications made to the above technical solutions according to the technical essence of the present invention belong to the protection scope of the technical solutions of the present invention.
Claims (10)
1. A calcium-containing aluminum alloy anode material for an alkaline aluminum-air battery is characterized in that: the calcium-containing aluminum alloy anode material comprises the following components in percentage by mass: ca: 0.01 to 1.00%, Sn: 0 to 1.00%, Bi: 0-1.00%, less than or equal to 0.30% of impurity content, and the balance of Al.
2. The calcium-containing aluminum alloy anode material for alkaline aluminum-air batteries according to claim 1, wherein: the calcium-containing aluminum alloy anode material comprises the following components in percentage by mass: ca: 0.01 to 1.00%, Sn: 0.01-1.00%, impurity content less than or equal to 0.30%, and the balance of Al.
3. The calcium-containing aluminum alloy anode material for alkaline aluminum-air batteries according to claim 1, wherein: the calcium-containing aluminum alloy anode material comprises the following components in percentage by mass: ca: 0.01 to 1.00%, Bi: 0.01-1.00%, impurity content less than or equal to 0.30%, and the balance of Al.
4. The calcium-containing aluminum alloy anode material for alkaline aluminum-air batteries according to claim 1, wherein: the calcium-containing aluminum alloy anode material comprises the following components in percentage by mass: ca: 0.01 to 1.00%, Sn: 0.01 to 1.00%, Bi: 0.01-1.00%, impurity content less than or equal to 0.30%, and the balance of Al.
5. The calcium-containing aluminum alloy anode material for alkaline aluminum-air batteries according to claim 1, wherein: the open-circuit voltage of the calcium-containing aluminum alloy anode material is 1.87-1.99V (Vs.SHE) and is 40 mA-cm-2The discharge efficiency reaches 91.2-98.9% at the current density of (2), and the energy density is 3587.4-4037.7 Wh.kg-1。
6. A method for preparing the calcium-containing aluminum alloy anode material for alkaline aluminum-air batteries according to claim 1, characterized in that: the calcium-containing aluminum alloy anode material is prepared by smelting, degassing, slagging off, casting, homogenizing annealing, rolling and solid solution, wherein the smelting process comprises the following steps: the method comprises the steps of proportioning according to alloy components, adding industrial pure aluminum into a medium-frequency smelting furnace, heating to 760-790 ℃ for melting, controlling the temperature to 720-750 ℃, adding an aluminum-calcium intermediate alloy into a melt, carrying out electromagnetic stirring on the melt for 5-30 min when the aluminum-calcium intermediate alloy is completely melted, controlling the temperature to 670-720 ℃ after the electromagnetic stirring if the alloy components contain low-melting-point alloy elements, adding the low-melting-point alloy elements, carrying out electromagnetic stirring on the melt for 5-15 min after the low-melting-point alloy elements are melted, wherein the low-melting-point alloy elements are Sn and/or Bi.
7. The method for preparing a calcium-containing aluminum alloy anode material for an alkaline aluminum-air battery according to claim 6, wherein: the degassing and slagging-off process comprises the following steps: introducing the melt obtained after smelting into a standing furnace at 730-750 ℃, introducing mixed gas into the standing furnace for 5-10 min, introducing argon for 10-15 min, then standing for 5-15 min, and removing floating slag on the surface of the melt; the mixed gas is a mixture of argon and hexachloroethane powder, wherein the concentration of hexachloroethane is 40-60 g/m3。
8. The method for preparing a calcium-containing aluminum alloy anode material for an alkaline aluminum-air battery according to claim 6, wherein: the casting and homogenizing annealing processes comprise: and continuously heating the melt obtained after degassing and slagging-off to 720-740 ℃ under the protection of argon, preserving heat for 5-20 min, then casting into a block-shaped cast ingot, and carrying out homogenizing annealing on the cast ingot at 550-600 ℃ for 12-24 h.
9. The method for preparing a calcium-containing aluminum alloy anode material for an alkaline aluminum-air battery according to claim 6, wherein: the rolling process comprises the following steps: and (3) hot rolling the cast ingot obtained by casting and homogenizing annealing to 3-5 mm at 300-400 ℃, and then cold rolling to finally obtain an anode plate with the thickness of 1-1.5 mm.
10. The method for preparing a calcium-containing aluminum alloy anode material for an alkaline aluminum-air battery according to claim 6, wherein: the solid solution process comprises the following steps: and carrying out solution treatment on the rolled anode plate at 400-600 ℃ for 4-12 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010392069.9A CN111560542A (en) | 2020-05-11 | 2020-05-11 | Calcium-containing aluminum alloy anode material for alkaline aluminum-air battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010392069.9A CN111560542A (en) | 2020-05-11 | 2020-05-11 | Calcium-containing aluminum alloy anode material for alkaline aluminum-air battery and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111560542A true CN111560542A (en) | 2020-08-21 |
Family
ID=72074684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010392069.9A Pending CN111560542A (en) | 2020-05-11 | 2020-05-11 | Calcium-containing aluminum alloy anode material for alkaline aluminum-air battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111560542A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109321766A (en) * | 2018-10-22 | 2019-02-12 | 昆明理工大学 | A kind of aluminium-air cell anode material and preparation method thereof |
| CN113953504A (en) * | 2021-09-03 | 2022-01-21 | 福建祥鑫股份有限公司 | Manufacturing method of calcium-containing wrought aluminum alloy |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61214361A (en) * | 1985-03-18 | 1986-09-24 | Matsushita Electric Ind Co Ltd | Sealed alkaline storage battery |
| CN101901893A (en) * | 2010-08-06 | 2010-12-01 | 浙江巨科铝业有限公司 | Aluminum alloy anode material for battery and method for producing same |
| CN109295350A (en) * | 2018-11-13 | 2019-02-01 | 东北大学 | A kind of seawater aluminium-air cell anode material and preparation method thereof |
| CN110707283A (en) * | 2018-12-13 | 2020-01-17 | 中国科学院大连化学物理研究所 | Aluminum-air battery |
-
2020
- 2020-05-11 CN CN202010392069.9A patent/CN111560542A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61214361A (en) * | 1985-03-18 | 1986-09-24 | Matsushita Electric Ind Co Ltd | Sealed alkaline storage battery |
| CN101901893A (en) * | 2010-08-06 | 2010-12-01 | 浙江巨科铝业有限公司 | Aluminum alloy anode material for battery and method for producing same |
| CN109295350A (en) * | 2018-11-13 | 2019-02-01 | 东北大学 | A kind of seawater aluminium-air cell anode material and preparation method thereof |
| CN110707283A (en) * | 2018-12-13 | 2020-01-17 | 中国科学院大连化学物理研究所 | Aluminum-air battery |
Non-Patent Citations (1)
| Title |
|---|
| 《铝合金热处理》编写小组: "《铝合金热处理 普及读物》", 31 July 1972, 冶金工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109321766A (en) * | 2018-10-22 | 2019-02-12 | 昆明理工大学 | A kind of aluminium-air cell anode material and preparation method thereof |
| CN113953504A (en) * | 2021-09-03 | 2022-01-21 | 福建祥鑫股份有限公司 | Manufacturing method of calcium-containing wrought aluminum alloy |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102820472B (en) | Manganese-aluminum containing anode material and preparation method thereof, as well as air cell prepared by using anode material | |
| CN109321766B (en) | Aluminum-air battery anode material and preparation method thereof | |
| CN109295350B (en) | Anode material for seawater aluminum-air battery and preparation method thereof | |
| CN104561673B (en) | A kind of rare earth modified aluminum alloy anode sheet and preparation method thereof | |
| CN111755662B (en) | Multi-element composite alloy negative electrode material and preparation method thereof | |
| CN112952079A (en) | Aluminum alloy anode material for aluminum-air battery and preparation method | |
| CN111455248B (en) | Magnesium air battery anode material and preparation method thereof | |
| CN101388457A (en) | Aluminum alloy anode material for battery | |
| CN109930042A (en) | A kind of magnesium-alloy anode material and the preparation method and application thereof | |
| CN111560542A (en) | Calcium-containing aluminum alloy anode material for alkaline aluminum-air battery and preparation method thereof | |
| CN110004340A (en) | A kind of preparation method and application of as-cast magnesium alloy anode material | |
| CN109338181B (en) | Anode material for alkaline aluminum-air battery and preparation method thereof | |
| CN112048652A (en) | Magnesium air battery anode material and preparation method thereof | |
| CN106917010B (en) | A kind of aluminum alloy anode material and its casting method and application | |
| CN110707283A (en) | Aluminum-air battery | |
| CN103280565A (en) | Aluminium alloy anode material and preparation method thereof | |
| CN111705337B (en) | Method for preparing lead-calcium master alloy by molten salt galvanic cell method | |
| CN111740094A (en) | Aluminum air battery aluminum anode plate material and preparation method thereof, aluminum air battery aluminum anode plate and preparation method and application thereof | |
| CN103894602B (en) | Surface treatment method for improving cycle life of rare earth magnesium based hydrogen storage alloy | |
| CN110042278A (en) | A kind of aluminium-air cell anode material and preparation method thereof | |
| CN104532037A (en) | Production method of octonary aluminum alloy anode for aluminum-air batteries | |
| CN109988943A (en) | Al-Ga-In-Sn-Mg alloy of hydrogen manufacturing and preparation method thereof | |
| CN109461942B (en) | Aluminum alloy anode material for air battery, preparation method of aluminum alloy anode material and air battery | |
| CN111560544B (en) | Preparation method of anode aluminum alloy for air battery and air battery | |
| CN110931812B (en) | Alloy anode material for aluminum-air battery, preparation method of alloy anode material and aluminum-air battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |