CN114606418B - Mg-Bi-In-Y anode material of magnesium air battery and preparation method and application thereof - Google Patents
Mg-Bi-In-Y anode material of magnesium air battery and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of chemical power supply electrode materials, and discloses a Mg-Bi-In-Y anode material of a magnesium air battery, and a preparation method and application thereof. The anode material is prepared from the following raw materials in percentage by mass: 0.1-0.4% of bismuth, 0.1-0.4% of indium, 0.5-2% of intermediate alloy Mg-20Y and the balance of high-purity metal magnesium. The preparation method comprises the following steps: weighing raw materials and carrying out pretreatment; placing the pretreated high-purity magnesium in a graphite crucible, placing the graphite crucible in a well type furnace under the protection of a covering agent, heating at 710-730 ℃, sequentially adding the pretreated bismuth, indium and an intermediate alloy Mg-20Y after the high-purity magnesium is molten, stirring for 1-3 min, and then preserving heat for 10min to obtain a melt; and standing the melt In a well type furnace for 5min, and casting the melt In a preheated iron mold under the protection of sulfur powder to obtain the Mg-Bi-In-Y anode material of the magnesium air battery.
Description
Technical Field
The invention belongs to the field of chemical power supply electrode materials, and particularly relates to a Mg-Bi-In-Y anode material of a magnesium air battery, and a preparation method and application thereof.
Background
Magnesium has a more negative standard electrode potential, a larger theoretical specific capacity and a smaller density, and based on the advantages of the above aspects, magnesium is widely applied to various chemical power sources as a more ideal anode material. Meanwhile, the magnesium is rich in the earth crust, the price is low, and in addition, most magnesium alloys are nontoxic and environment-friendly. Therefore, the magnesium alloy has great application potential as a battery anode material, and the research on the electrochemical performance of the magnesium alloy as the battery anode (cathode) material has great significance.
The magnesium-air battery has the advantages of low cost, high energy conversion rate, abundant resources, no pollution and the like, and has great development and application prospects. However, magnesium anodes face the problems of difficult peeling of corrosion products, severe hydrogen evolution self-corrosion reaction, falling of metal particles, low anode utilization rate and the like in the application process, and limit the further development of magnesium-air batteries. Furthermore, magnesium-air batteries require extended storage times when not discharged, which places high demands on the corrosion resistance of the magnesium anode at open circuit potential. Therefore, the search for high-performance magnesium alloy anode materials is one of the hot spots and difficulties in the research of magnesium-air batteries, and the key is to search for novel magnesium-based anode materials with high reactivity, slow corrosion rate and high anode utilization rate to solve the contradiction between activation and passivation.
Currently, the addition of other alloying elements to magnesium is a conventional method for effectively increasing the anode utilization of magnesium alloys. One or more elements of aluminum, zinc, tin, indium, bismuth, lead, gallium, manganese and the like are added into magnesium to form binary, ternary or even multi-element magnesium alloy anode materials, so that the discharge activity of the magnesium alloy anode materials is improved, the corrosion homogenization and the grain refinement are promoted, and the corrosion electrochemical performance of the magnesium anode is improved. Currently, the following systems mainly exist in magnesium alloy anodes: Mg-Al-Zn- (RE), Mg-Al-Pb, Mg-Ca, Mg-Li, Mg-Hg-X, etc.
However, there are few reports on microalloying of more than two elements of high-purity magnesium, and there is no report on using high-purity magnesium as a research object, adopting composite addition of bismuth and indium as activating elements, and adding microalloying of yttrium as a rare earth element to solve the contradiction between passivation and activation. In view of this, the invention is particularly proposed.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a preparation method of a Mg-Bi-In-Y anode material of a magnesium air battery. The method takes high-purity magnesium as a research object, enhances the corrosion resistance of the magnesium anode under the open-circuit potential through microalloying of elements such as bismuth, indium, yttrium and the like, promotes the stripping of corrosion products in the discharging process, inhibits the hydrogen evolution and the falling of metal particles, improves the utilization rate of the anode, and further improves the comprehensive anode performance.
The invention also aims to provide the Mg-Bi-In-Y anode material for the magnesium air battery prepared by the preparation method.
The invention further aims to provide application of the Mg-Bi-In-Y anode material of the magnesium air battery.
The purpose of the invention is realized by the following technical scheme:
the Mg-Bi-In-Y anode material of the magnesium air battery is prepared from the following raw materials In percentage by mass: 0.1-0.4% of bismuth, 0.1-0.4% of indium, 0.5-2% of intermediate alloy Mg-20Y and the balance of high-purity metal magnesium.
The preparation method of the Mg-Bi-In-Y anode material of the magnesium air battery comprises the following steps:
(1) weighing high-purity magnesium, bismuth, indium and master alloy Mg-20Y according to the mass percent of the raw materials in a dry environment, and respectively pretreating the raw materials;
(2) placing the pretreated high-purity magnesium metal into a graphite crucible, placing the graphite crucible into a well-type resistance furnace under the protection of a covering agent, heating at 710-730 ℃, sequentially adding the pretreated bismuth, indium and an intermediate alloy Mg-20Y after the high-purity magnesium metal is molten, stirring for 1-3 min by using a high-purity graphite rod, and preserving heat for 10min to obtain a melt;
(3) and standing the melt In a well-type resistance furnace for 5min, and casting the melt In a preheated iron mold under the protection of sulfur powder to obtain the Mg-Bi-In-Y anode material of the magnesium air battery.
The pretreatment in the step (1) is to clean and remove oxide skin, and bake the oxide skin in an oven at 100-200 ℃ for 1-2 hours.
And (3) the covering agent in the step (2) is a mixture of magnesium chloride, potassium chloride, calcium fluoride and sodium chloride.
The preheated iron mold in the step (2) is subjected to rust removal treatment on the inner wall of the iron mold before use, coated with zinc oxide and preheated in an oven at 100-200 ℃ for 1-2 hours.
And (3) drying the covering agent in the step (2) and the sulfur powder in the step (3) for 12 hours in a vacuum drying oven at 60 ℃ before use.
The size of the cast Mg-Bi-In-Y anode material of the magnesium air battery In the step (3) is 200mm multiplied by (15-20) mm.
The Mg-Bi-In-Y anode material of the magnesium air battery prepared by the preparation method.
The Mg-Bi-In-Y anode material of the magnesium-air battery is applied to the preparation of the magnesium-air battery.
Compared with the prior art, the invention has the following advantages and effects:
the invention utilizes a smelting and casting method to prepare the Mg-Bi-In-Y anode cast ingot, takes high-purity magnesium as a matrix, adopts the compound addition of the activating elements of bismuth and indium and the rare earth element of yttrium to realize the microalloying of the high-purity magnesium, solves the contradiction between the activation and the passivation of the magnesium anode material, and increases the dissolution uniformity and the corrosion resistance of the magnesium anode. The result shows that the coexistence of the three alloy elements can reduce the corrosion current density, improve the discharge voltage and inhibit the discharge hydrogen evolution, so that the Mg-Bi-In-Y has higher anode utilization rate; the preparation process is simple and has good practicability.
Drawings
FIG. 1 is a polarization diagram of high purity magnesium with the magnesium anode materials of example 1 and comparative examples 1-3;
FIG. 2 shows the assembly of high purity magnesium and the magnesium anode materials of example 1 and comparative examples 1-3 into a magnesium air battery in a 3.5% NaCl solution at 10mA cm -2 Voltage-time curve of (d);
FIG. 3 shows the results of the comparison of high purity magnesium with the anode materials of examples 1 and 1-3 at 10mA cm -2 The discharge of (3) evolves hydrogen;
FIG. 4 shows the results of the comparison of high purity magnesium with the anode materials of example 1 and comparative examples 1-3 at 10mA cm -2 The anode utilization ratio.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
The experimental procedures referred to in this example, without particular reference to conditions, were carried out according to conditions conventional in the art; the raw materials, reagents and the like used are, unless otherwise specified, those obtained from the conventional market. Any insubstantial changes from the invention, including those variations and alterations made by those skilled in the art, are intended to be covered by the claims.
Example 1
This example provides an Mg-0.1Bi-0.1In-0.1Y anode material, which is prepared by the following steps:
1. the Mg-0.1Bi-0.1In-0.1Y anode material of the present example is composed of the following elements In mass fraction: 0.1% of bismuth, 0.1% of indium, 0.1% of yttrium and 99.97% of magnesium. The raw materials used are high-purity magnesium, high-purity bismuth, high-purity indium and magnesium-yttrium master alloy (Mg-20Y).
2. Weighing high-purity magnesium, bismuth, indium and Mg-20Y, cleaning the raw materials to remove dirt and oxide skin on the surface, and baking all the raw materials in an oven at 100-200 ℃ for 1-2 hours before smelting to remove contained water.
3. An iron mold used for smelting and casting needs to be cleaned (mainly for removing rust) on the inner wall of the iron mold before smelting, zinc oxide is coated on the iron mold, and the iron mold and a high-purity graphite rod used for stirring are preheated in an oven for 1-2 hours at the temperature of 100-200 ℃. The crucibles used for smelting have to be cleaned of slag and checked for integrity before use.
4. The covering agent and the sulfur powder added in the smelting process are dried for 12 hours in a vacuum drying oven at 60 ℃.
5. Placing the pretreated high-purity magnesium into a graphite crucible, and adding a covering agent (the covering agent consists of the following components in percentage by mass: MgCl) 2 45%、KCl 35%、CaF 2 10 percent and 10 percent of NaCl) is put in a shaft furnace, the temperature is raised to 730 ℃ until the high-purity magnesium is completely melted, and then the pretreated bismuth, indium and Mg-20Y are sequentially added; after the graphite is melted, a preheated high-purity graphite rod is adopted for stirring for 2-3 min, so that the components are uniform, and the temperature is kept for 10 min.
6. And standing the uniformly stirred melt In a well type furnace for 5min, and casting the melt In a flat iron mold under the protection of sulfur powder to obtain a Mg-0.1Bi-0.1In-0.1Y anode cast ingot with the size of 200mm multiplied by (15-20) mm. And selecting the middle area of the ingot as a test sample and marking as Mg-Bi-In-Y.
Example 2
This example provides an Mg-0.4Bi-0.4In-0.4Y anode material, which is prepared In substantially the same manner as In example 1, except that the anode material is composed of the following elements In parts by mass: 0.4% of bismuth, 0.4% of indium, 0.4% of yttrium and 98.8% of magnesium. The raw materials used are high-purity magnesium, high-purity bismuth, high-purity indium and magnesium-yttrium master alloy.
Example 3
This example provides an Mg-0.1Bi-0.1In-0.1Y anode material prepared In substantially the same manner as In example 1, except that the melting temperature of the shaft furnace was 710 ℃.
Example 4
This example provides an Mg-0.1Bi-0.1In-0.1Y anode material, which is prepared In substantially the same manner as In example 1 except that the melting temperature of the shaft furnace is 720 ℃.
Comparative example 1
The comparative example provides a Mg-Bi anode material, the preparation method is similar to that of example 1, and the difference is that high-purity magnesium and Bi are used as raw materials, the mass fractions of the high-purity magnesium and the Bi are respectively 99.9% and 0.1%, Mg-0.1% Bi anode cast ingots are obtained, and the middle regions of the cast ingots are selected as comparative test samples and are marked as Mg-Bi.
Comparative example 2
The comparative example provides a Mg-In anode material, the preparation method of which is similar to that of example 1, and the difference is that high-purity magnesium and In are used as raw materials, the mass fractions of the high-purity magnesium and the high-purity In are respectively 99.9% and 0.1%, Mg-0.1% In anode ingots are obtained, and the middle areas of the ingots are selected as comparative test samples and are marked as Mg-In.
Comparative example 3
The comparative example provides a Mg-Bi-In anode material, the preparation method is similar to that of example 1, and the difference is that high-purity magnesium, Bi and In are used as raw materials, the mass fractions are respectively 99.8%, 0.1% and 0.1%, Mg-0.1% Bi-0.1% In anode ingots are obtained, and the middle regions of the ingots are selected as comparative test samples and are marked as Mg-Bi-In.
Performance testing and analysis
As shown In FIG. 1, In comparison with high purity magnesium and corresponding comparative examples 1 to 3, the corrosion current density of the magnesium anode material (Mg-Bi-In-Y) of example 1 is significantly reduced after the addition of Y element, which indicates that the addition of Y element can improve the compactness and corrosion resistance of the surface film of magnesium alloy.
As shown in FIG. 2, at 10mA cm -2 The discharge plateaus of the magnesium anode materials of example 1 and comparative examples 1-3 were all higher than that of pure magnesium, and the highest discharge voltage of the magnesium anode material of example 1 (Mg-Bi-In-Y) indicates that the magnesium anode material of the present invention has higher discharge activity during the re-discharge process.
As shown in FIG. 3, at 10mA cm -2 The hydrogen evolution behaviors of the comparative examples 1 to 3 are relatively similar and are lower than those of pure magnesium, and the lowest hydrogen evolution rate of the magnesium anode material (Mg-Bi-In-Y) In the example 1 is lower than that of the high-purity magnesium and the comparative examples 1 to 3, so that the alloy material disclosed by the invention has good hydrogen evolution side reaction inhibition performance.
As shown In fig. 4, the magnesium anode material (Mg-Bi-In-Y) of example 1 maintained a relatively high anode utilization (61.5%).
From the above, the Mg-Bi-In-Y anode material is prepared by combining a plurality of alloy elements In a proper proportion, and can provide higher voltage and anode utilization rate In the discharging process of a magnesium-air battery, and the comprehensive electrochemical performance is excellent.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. The Mg-Bi-In-Y anode material of the magnesium-air battery is characterized In that: the anode material is prepared from the following raw materials in percentage by mass: 0.1-0.4% of bismuth, 0.1-0.4% of indium, 0.5-2% of intermediate alloy Mg-20Y and the balance of high-purity metal magnesium;
the Mg-Bi-In-Y anode material of the magnesium-air battery is prepared by the following preparation method:
(1) weighing high-purity metal magnesium, bismuth, indium and intermediate alloy Mg-20Y according to the mass percent of the raw materials in a dry environment, and respectively pretreating the raw materials;
(2) placing the pretreated high-purity magnesium metal into a graphite crucible, placing the graphite crucible into a well-type resistance furnace under the protection of a covering agent, heating at 710-730 ℃, sequentially adding the pretreated bismuth, indium and an intermediate alloy Mg-20Y after the high-purity magnesium metal is molten, stirring for 1-3 min by using a high-purity graphite rod, and preserving heat for 10min to obtain a melt;
(3) and standing the melt In a well-type resistance furnace for 5min, and casting the melt In a preheated iron mold under the protection of sulfur powder to obtain the Mg-Bi-In-Y anode material of the magnesium air battery.
2. The Mg-Bi-In-Y anode material of the magnesium-air battery as claimed In claim 1, wherein: the pretreatment in the step (1) is to clean and remove oxide skin, and bake the oxide skin in an oven at 100-200 ℃ for 1-2 hours.
3. The Mg-Bi-In-Y anode material of the magnesium-air battery as set forth In claim 1, wherein: and (3) the covering agent in the step (2) is a mixture of magnesium chloride, potassium chloride, calcium fluoride and sodium chloride.
4. The Mg-Bi-In-Y anode material of the magnesium-air battery as claimed In claim 1, wherein: and (3) the preheated iron mold is subjected to rust removal treatment on the inner wall of the iron mold before use, is coated with zinc oxide, and is preheated in an oven at 100-200 ℃ for 1-2 hours.
5. The Mg-Bi-In-Y anode material of the magnesium-air battery as set forth In claim 1, wherein: and (3) drying the covering agent in the step (2) and the sulfur powder in the step (3) for 12 hours in a vacuum drying oven at 60 ℃ before use.
6. The Mg-Bi-In-Y anode material of the magnesium-air battery as claimed In claim 1, wherein: and (3) casting the Mg-Bi-In-Y anode material of the magnesium air battery, wherein the size of the Mg-Bi-In-Y anode material is 200mm multiplied by (15-20) mm.
7. The preparation method of the Mg-Bi-In-Y anode material of the magnesium-air battery according to claim 1, which is characterized by comprising the following operation steps:
(1) weighing high-purity metal magnesium, bismuth, indium and intermediate alloy Mg-20Y according to the mass percent of the raw materials in the claim 1in a dry environment, and respectively pretreating the raw materials;
(2) placing the pretreated high-purity magnesium metal into a graphite crucible, placing the graphite crucible into a well-type resistance furnace under the protection of a covering agent, heating at 710-730 ℃, sequentially adding the pretreated bismuth, indium and an intermediate alloy Mg-20Y after the high-purity magnesium metal is molten, stirring for 1-3 min by using a high-purity graphite rod, and preserving heat for 10min to obtain a melt;
(3) and standing the melt In a well-type resistance furnace for 5min, and casting the melt In a preheated iron mold under the protection of sulfur powder to obtain the Mg-Bi-In-Y anode material of the magnesium air battery.
8. Use of the Mg-Bi-In-Y anode material for a magnesium-air battery according to claim 1In the preparation of a magnesium-air battery.
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WO2010012184A1 (en) * | 2008-07-29 | 2010-02-04 | 维恩克(鹤壁)镁基材料有限公司 | High potential magnesium alloy sacrificial anode and manufacturing method thereof |
CN111455248A (en) * | 2020-05-22 | 2020-07-28 | 北京工业大学 | Magnesium air battery anode material and preparation method thereof |
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Inventor after: Liu Jingjing Inventor after: Wang Naiguang Inventor after: Wu Tianqi Inventor after: Shi Zhicong Inventor after: Wang Guilong Inventor before: Liu Jingjing Inventor before: Wu Tianqi Inventor before: Wang Naiguang Inventor before: Shi Zhicong Inventor before: Wang Guilong |
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