CN111996400A - Method for preparing aluminum anode material from Zn-modified waste aluminum pop can and application - Google Patents

Method for preparing aluminum anode material from Zn-modified waste aluminum pop can and application Download PDF

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CN111996400A
CN111996400A CN202010867437.0A CN202010867437A CN111996400A CN 111996400 A CN111996400 A CN 111996400A CN 202010867437 A CN202010867437 A CN 202010867437A CN 111996400 A CN111996400 A CN 111996400A
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aluminum
anode material
preparing
waste
melt
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彭国胜
王鹏杰
陈双双
顾亦城
宋广生
敬和民
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Anhui University of Technology AHUT
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    • 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
    • C22C1/06—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
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/10—Alloys based on aluminium with zinc as the next major constituent
    • 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
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • 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
    • H01M4/46—Alloys based on magnesium or aluminium
    • H01M4/463—Aluminium based
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Processing Of Solid Wastes (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a method for preparing an aluminum anode material by using a Zn modified waste aluminum zip-top can and application thereof, and relates to the technical field of aluminum-air battery preparation. The preparation method comprises the following steps: (1) pressing the waste aluminum pop cans into cakes; (2) adding the pressed aluminum cake into the cleaned crucible, heating to 500-550 ℃, preserving heat for 10-30 min, and performing paint removal treatment; (3) continuously heating to 680-760 ℃, and preserving the temperature until the waste aluminum pop-top can is completely melted; (4) adding an aluminum melt refining agent, and performing degassing and deslagging treatment; (5) adding a Zn simple substance, wherein the adding amount is 0.1-0.5% of the mass of the aluminum melt; (6) standing for 12-20 min, and casting and solidifying the aluminum melt to obtain the aluminum air battery anode material. The aluminum-air battery anode material prepared by the invention has the characteristics of simple process, low cost and excellent discharge performance, is easy to realize industrial production, and has important value for high value-added utilization of waste aluminum ring-pull cans.

Description

Method for preparing aluminum anode material from Zn-modified waste aluminum pop can and application
Technical Field
The invention relates to the technical field of air battery preparation, in particular to a method for preparing an aluminum anode material by using a Zn modified waste aluminum zip-top can and application thereof.
Background
At present, the number of pop cans consumed worldwide is more than 2100 hundred million annually, and the consumption of aluminum is nearly 300 million tons, which accounts for about 15 percent of the total consumption of aluminum worldwide. According to research, the number of waste aluminum pop cans in China currently exceeds 2100 hundred million. Compared with the 3004/3003 aluminum alloy produced by electrolyzing aluminum ore, the aluminum material for the regenerated pop can only consumes 3 percent of energy. Therefore, the high value-added utilization waste aluminum pop cans have very important social and economic values. The method for preparing the aluminum air battery anode material from the waste aluminum pop can is a feasible way for realizing high added value application of the waste aluminum pop can.
In the published patent (publication number: CN201910574176.0), it was found that the aluminum anode material prepared by smelting the waste aluminum pop can discharge normally in NaOH and NaCl solutions, but the corrosion resistance is poor and the utilization rate of the aluminum anode is poor. Aiming at the problems, the technology can greatly improve the corrosion resistance of the anode material of the pop can in NaOH solution and the discharge performance of the aluminum-air battery by preparing the aluminum anode material from the Zn modified waste aluminum pop can.
Disclosure of Invention
The invention aims to provide an aluminum anode material prepared from a modified and recycled pop can and application thereof, which can realize high-added-value application of waste aluminum pop cans, and the prepared aluminum anode material can be applied to aluminum-air batteries.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a method for preparing an aluminum anode material by using a Zn modified waste aluminum zip-top can comprises the following steps:
(1) pressing the waste aluminum pop cans into aluminum cakes with the thickness of 2-3 cm, and carrying out no paint removal and separation treatment on the can covers and the can bodies;
(2) adding the pressed aluminum cake into the cleaned crucible, heating to 500-550 ℃, preserving heat for 10-30 min, and performing paint removal treatment;
(3) continuously heating to 680-760 ℃, and preserving the temperature until the waste aluminum pop-top can is completely melted;
(4) adding an aluminum melt refining agent, and performing degassing and deslagging treatment;
(5) adding a Zn simple substance into the aluminum melt obtained in the step (4), wherein the adding amount of the Zn simple substance is 0.1-0.5% of the mass of the aluminum melt;
(6) standing for 12-20 min, and casting and solidifying the aluminum melt to obtain the aluminum air battery anode material.
Preferably, in step (2), the temperature is increased to 500 ℃ and kept for 10 min.
Preferably, the adding amount of the aluminum melt refining agent is 0.35-0.5% of the mass of the aluminum melt.
Preferably, the aluminum melt refining agent consists of the following components in percentage by weight: 29% of sodium chloride, 55% of potassium chloride, 8.5% of calcium fluoride and 7.5% of sodium fluosilicate.
Preferably, in the step (5), the addition amount of the Zn simple substance is 0.1% of the mass of the aluminum liquid.
Preferably, in step (6), the mixture is left standing for 15 min.
The aluminum anode material prepared by the method is applied to alkaline electrolyte of an aluminum-air battery and neutral electrolyte of the aluminum-air battery.
Compared with the prior art, the invention has the following technical effects:
1. the waste aluminum pop-top can contains more iron impurity elements, and the impurity elements have adverse effects on the corrosion resistance and the discharge performance of the aluminum anode; the invention aims to improve the corrosion resistance of the anode of the waste aluminum zip-top can and the discharge performance in the aluminum-air battery by utilizing the beneficial effect of the alloy element zinc on the anode material of the waste aluminum zip-top can.
2. The preparation method of the aluminum anode is simple and easy to control, has low price and is easy to realize industrial production.
3. The aluminum anode material prepared by the invention has low cost, and realizes high value-added utilization of the waste aluminum zip-top can.
4. Compared with the unmodified waste aluminum pop can anode, the aluminum anode material prepared by the invention has excellent corrosion resistance and discharge performance.
Drawings
FIG. 1 is a hydrogen evolution comparison curve of different aluminum alloy anodes in a 4M NaOH solution.
FIG. 2 is a graph showing the weight loss comparison of different aluminum alloy anodes in a 4M NaOH solution.
FIG. 3 is a graph showing the discharge comparison curves (80mA cm) of different aluminum alloy anodes in a 4M NaOH solution-2)。
FIG. 4 is a comparison of the appearance of different aluminum alloy anodes after 4M NaOH solution discharge.
FIG. 5 is a discharge contrast curve (20mA cm) of different aluminum alloy anodes in 0.6M NaCl solution-2)。
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a method for preparing an aluminum anode material by using a Zn modified waste aluminum zip-top can comprises the following steps:
(1) pressing the waste aluminum pop cans into aluminum cakes with the thickness of 2-3 cm, and carrying out no paint removal and separation treatment on the can covers and the can bodies;
(2) adding the pressed aluminum cake into the cleaned crucible, heating to 500 ℃, preserving heat for 10min, and performing paint removal treatment;
(3) continuously heating to 680 ℃, and preserving the heat until the waste aluminum zip-top can is completely melted;
(4) adding an aluminum melt refining agent, and performing degassing and deslagging treatment;
the adding amount of the aluminum melt refining agent is 0.45 percent of the mass of the aluminum melt; the aluminum melt refining agent comprises the following components in percentage by weight: 29% of sodium chloride, 55% of potassium chloride, 8.5% of calcium fluoride and 7.5% of sodium fluosilicate;
(5) adding a Zn elementary substance into the aluminum melt obtained in the step (4), wherein the addition amount of the Zn elementary substance is 0.1% of the mass of the aluminum melt;
(6) standing for 15min, and casting and solidifying the aluminum melt to prepare the aluminum air battery anode material.
Example 2:
a method for preparing an aluminum anode material by using a Zn modified waste aluminum zip-top can comprises the following steps:
(1) pressing the waste aluminum pop cans into aluminum cakes with the thickness of 2-3 cm, and carrying out no paint removal and separation treatment on the can covers and the can bodies;
(2) adding the pressed aluminum cake into the cleaned crucible, heating to 550 ℃, preserving heat for 20min, and performing paint removal treatment;
(3) continuously heating to 760 ℃, and preserving the heat until the waste aluminum zip-top can is completely melted;
(4) adding an aluminum melt refining agent, and performing degassing and deslagging treatment;
the adding amount of the aluminum melt refining agent is 0.5 percent of the mass of the aluminum melt; the aluminum melt refining agent comprises the following components in percentage by weight: 29% of sodium chloride, 55% of potassium chloride, 8.5% of calcium fluoride and 7.5% of sodium fluosilicate;
(5) adding a Zn elementary substance into the aluminum melt obtained in the step (4), wherein the addition amount of the Zn elementary substance is 0.3% of the mass of the aluminum melt;
(6) standing for 12min, and casting and solidifying the aluminum melt to prepare the aluminum air battery anode material.
Example 3:
a method for preparing an aluminum anode material by using a Zn modified waste aluminum zip-top can comprises the following steps:
(1) pressing the waste aluminum pop cans into aluminum cakes with the thickness of 2-3 cm, and carrying out no paint removal and separation treatment on the can covers and the can bodies;
(2) adding the pressed aluminum cake into the cleaned crucible, heating to 520 ℃, preserving heat for 30min, and performing paint removal treatment;
(3) continuously heating to 700 ℃, and preserving the heat until the waste aluminum zip-top can is completely melted;
(4) adding an aluminum melt refining agent, and performing degassing and deslagging treatment;
the adding amount of the aluminum melt refining agent is 0.35 percent of the mass of the aluminum melt; the aluminum melt refining agent comprises the following components in percentage by weight: 29% of sodium chloride, 55% of potassium chloride, 8.5% of calcium fluoride and 7.5% of sodium fluosilicate;
(5) adding a Zn elementary substance into the aluminum melt obtained in the step (4), wherein the addition amount of the Zn elementary substance is 0.5% of the mass of the aluminum melt;
(6) standing for 20min, and casting and solidifying the aluminum melt to prepare the aluminum air battery anode material.
Comparative example 1:
a method for preparing an aluminum anode material from a waste aluminum pop can comprises the following steps:
(1) pressing the waste aluminum pop cans into aluminum cakes with the thickness of 2-3 cm, and carrying out no paint removal and separation treatment on the can covers and the can bodies;
(2) adding the pressed aluminum cake into the cleaned crucible, heating to 500 ℃, preserving heat for 10min, and performing paint removal treatment;
(3) continuously heating to 680 ℃, and preserving the heat until the waste aluminum zip-top can is completely melted;
(4) adding an aluminum melt refining agent, and performing degassing and deslagging treatment;
the adding amount of the aluminum melt refining agent is 0.45 percent of the mass of the aluminum melt; the aluminum melt refining agent comprises the following components in percentage by weight: 29% of sodium chloride, 55% of potassium chloride, 8.5% of calcium fluoride and 7.5% of sodium fluosilicate;
(5) and then standing for 15min, and casting and solidifying the aluminum melt to prepare the aluminum air battery anode material.
Test example 1:
the aluminum anode materials prepared in example 1 and comparative example 1 were respectively subjected to the following treatments:
the aluminum anode material is placed in 4M NaOH solution, and weight loss and drainage gas collection are adoptedThe device is used for characterizing the corrosion resistance of the material under the condition of water bath at 25 ℃. The aluminum anode material is an aluminum air battery anode, MnO2A catalyst layer formed by the catalyst, the activated carbon and the polytetrafluoroethylene is a cathode, and the electrolyte is a NaOH solution to assemble the aluminum-air battery; and carrying out constant current discharge for 1h, measuring the stable working voltage, weighing the weight of the aluminum anode before and after discharge, and calculating the utilization rate, capacity density and energy density of the aluminum anode.
The results of the comparison of the corrosion resistance and the discharge performance are shown in FIGS. 1 to 4 and Table 1. In fig. 1-3, a can, Cans corresponds to the aluminum anode material prepared in comparative example 1, and a Zn modified can, Cans-0.1Zn corresponds to the aluminum anode material prepared in example 1. In fig. 4, the left drawing corresponds to the aluminum anode material prepared in comparative example 1, and the right drawing corresponds to the aluminum anode material prepared in example 1.
TABLE 1
Figure BDA0002649199280000061
Comparative example 2:
the aluminum anode materials prepared in example 1 and comparative example 1 were respectively subjected to the following treatments:
the aluminum anode material prepared in comparative example 1 was an aluminum air cell anode, MnO2And (3) assembling an aluminum-air battery by taking a catalyst layer consisting of the catalyst, the activated carbon and the polytetrafluoroethylene as a cathode and an electrolyte as a NaCl solution, carrying out a constant current discharge experiment for 3h, measuring the stable working voltage, weighing the weight of the aluminum anode before and after discharge, and calculating the utilization rate, the capacity density and the energy density of the aluminum anode.
The results of the discharge performance comparison are shown in fig. 5 and table 2. In fig. 5, the can corresponds to the aluminum anode material prepared in comparative example 1, and the zinc-modified can corresponds to the aluminum anode material prepared in example 1.
TABLE 2
Figure BDA0002649199280000071
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (9)

1. A method for preparing an aluminum anode material by using a Zn modified waste aluminum zip-top can is characterized by comprising the following steps:
(1) pressing the waste aluminum pop cans into aluminum cakes with the thickness of 2-3 cm, and carrying out no paint removal and separation treatment on the can covers and the can bodies;
(2) adding the pressed aluminum cake into the cleaned crucible, heating to 500-550 ℃, preserving heat for 10-30 min, and performing paint removal treatment;
(3) continuously heating to 680-760 ℃, and preserving the temperature until the waste aluminum pop-top can is completely melted;
(4) adding an aluminum melt refining agent, and performing degassing and deslagging treatment;
(5) adding a Zn simple substance into the aluminum melt obtained in the step (4), wherein the adding amount of the Zn simple substance is 0.1-0.5% of the mass of the aluminum melt;
(6) standing for 12-20 min, and casting and solidifying the aluminum melt to obtain the aluminum air battery anode material.
2. The method for preparing an aluminum anode material from a Zn-modified waste aluminum zip-top can according to claim 1, wherein in the step (2), the temperature is increased to 500 ℃ and maintained for 10 min.
3. The method for preparing the aluminum anode material from the Zn-modified waste aluminum zip-top can according to claim 1, wherein the adding amount of the aluminum melt refining agent is 0.35-0.5% of the mass of the aluminum melt.
4. The method for preparing an aluminum anode material from a Zn-modified waste aluminum zip-top can according to claim 1, wherein the aluminum melt refining agent consists of the following components in percentage by weight: 29% of sodium chloride, 55% of potassium chloride, 8.5% of calcium fluoride and 7.5% of sodium fluosilicate.
5. The method for preparing the aluminum anode material by using the Zn modified waste aluminum zip-top can as claimed in claim 1, wherein in the step (5), the addition amount of the Zn simple substance is 0.1 percent of the mass of the aluminum liquid.
6. The method for preparing an aluminum anode material from a Zn-modified scrap aluminum zip-top can as set forth in claim 1, wherein in the step (6), the standing is carried out for 15 min.
7. An aluminium anode material prepared according to the method of any one of claims 1 to 6.
8. The use of the aluminum anode material according to claim 7, wherein the aluminum anode material is used in an alkaline electrolyte of an aluminum-air battery.
9. The use of an aluminum anode material according to claim 7 in a neutral electrolyte of an aluminum-air battery.
CN202010867437.0A 2020-08-25 2020-08-25 Method for preparing aluminum anode material from Zn-modified waste aluminum pop can and application Pending CN111996400A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110129602A (en) * 2019-06-28 2019-08-16 安徽工业大学 A kind of aluminium scrap pop can prepares aluminium anodes MATERIALS METHODS and application

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110129602A (en) * 2019-06-28 2019-08-16 安徽工业大学 A kind of aluminium scrap pop can prepares aluminium anodes MATERIALS METHODS and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
吴子彬等: "铝-空气电池阳极材料及其电解液的研究进展", 《材料导报》 *
夏炳仁: "《船舶及海洋工程结构物的腐蚀与防护》", 31 December 1993 *

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Application publication date: 20201127