CN115874100B - Mg-Zn-Er alloy for negative electrode material of magnesium air battery, and preparation method and application thereof - Google Patents
Mg-Zn-Er alloy for negative electrode material of magnesium air battery, and preparation method and application thereof Download PDFInfo
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- 239000011777 magnesium Substances 0.000 title claims abstract description 85
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 82
- 229910001371 Er alloy Inorganic materials 0.000 title claims abstract description 14
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000011701 zinc Substances 0.000 claims abstract description 53
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 27
- 239000000956 alloy Substances 0.000 claims abstract description 27
- 239000000155 melt Substances 0.000 claims abstract description 22
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005266 casting Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000013079 quasicrystal Substances 0.000 claims abstract description 5
- 229910001018 Cast iron Inorganic materials 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 10
- 238000003723 Smelting Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract 2
- 239000008151 electrolyte solution Substances 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 14
- 238000005260 corrosion Methods 0.000 description 11
- 239000010405 anode material Substances 0.000 description 10
- 238000007599 discharging Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
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- 238000011161 development Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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Classifications
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- 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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Abstract
A Mg-Zn-Er alloy as a negative electrode material of a magnesium air battery, a preparation method and application thereof relate to the field of magnesium air batteries. The alloy comprises the following components: 0.6 to 20.0 weight percent of Zn, 0.1 to 3.5 weight percent of Er, more than or equal to 10 and more than or equal to 6 of Zn/Er, and the balance of magnesium. The preparation method comprises the following steps: (1) Taking commercial pure magnesium, pure zinc and Mg-Er intermediate alloy, and removing oxide skin on the surface; (2) Preheating the treated materials, and sequentially putting the materials into a crucible for melting; and (3) casting the melt in a mould, and cooling to obtain the casting. According to the invention, the microstructure containing the quasicrystal I phase Mg 3Zn6Er1 is obtained by controlling the mass ratio of Zn to Er, so that the hydrogen evolution reaction of the magnesium cathode in the aqueous electrolyte solution is effectively inhibited, the falling of a product is accelerated, the stacking thickness of a discharge product on the surface of the cathode is reduced, and the performance of the magnesium air battery is improved.
Description
Technical Field
The invention relates to the technical field of magnesium air batteries, in particular to a magnesium air battery negative electrode material Mg-Zn-Er alloy, a preparation method and application thereof.
Background
The world is faced with serious problems of resource shortage, environmental pollution and the like, and the global energy structure is being converted into clean energy. Development of advanced energy storage systems is one of the solutions to mitigate energy crisis. The metal-air battery is a special type of energy storage system, takes metal as a negative electrode active material, takes oxygen as a positive electrode active material, and has the advantages of low cost, light weight, safety, environmental protection, high specific energy and the like. Magnesium has the advantages of negative standard electrode potential (-2.37V vs SHE), larger theoretical specific capacity (2200 mAh g -1) and power density (6800 mWh g -1), smaller density (1.74 g cm -3) and the like, and the magnesium air battery taking magnesium or magnesium alloy as a negative electrode is widely focused, and is currently applied to the fields of emergency power supplies, special military equipment, standby power supplies and the like.
However, the magnesium negative electrode has serious self-corrosion phenomenon in the aqueous electrolyte, and a discharge product formed in the discharge process hinders the contact between the magnesium negative electrode and the electrolyte, so that the problems of low discharge voltage, low negative electrode efficiency, serious energy and capacity loss and the like are caused, the discharge performance of the magnesium negative electrode is far lower than a theoretical value, the development of a magnesium air battery is hindered, and the commercialized development of the magnesium air battery is limited. The selection of a suitable magnesium alloy anode material is critical to solving this problem.
In view of this, we have proposed the present invention.
Disclosure of Invention
Aiming at the defects and the shortcomings of the prior art of the magnesium air battery, the primary purpose of the invention is to provide a magnesium air battery cathode material Mg-Zn-Er alloy. When the magnesium alloy is used as the negative electrode of the magnesium air battery, the hydrogen evolution reaction of the negative electrode in the discharging process is effectively weakened, the discharging process is optimized, the accumulation of discharging products is reduced, and the falling of magnesium alloy particles is weakened, so that stable discharging voltage is obtained, the utilization efficiency and the discharging capacity of the negative electrode are improved, and the magnesium alloy has good discharging performance.
The invention further aims at providing a preparation method of the Mg-Zn-Er alloy serving as the negative electrode material of the magnesium air battery.
The invention also aims to provide an application of the Mg-Zn-Er alloy serving as the negative electrode material of the magnesium air battery.
The aim of the invention is realized by the following technical scheme:
A magnesium air battery negative electrode material with excellent discharge performance comprises the following components in percentage by mass: 0.6 to 20.0wt.% of Zn, 0.1 to 3.5wt.% of Er, and the balance of magnesium and unavoidable impurities; the mass ratio of Zn/Er of the alloy element is more than or equal to 6, and more preferably more than or equal to 10 and more than or equal to 6.
The invention provides a preparation method of a high-utilization magnesium air battery anode material, which comprises the following steps:
(1) According to the content of Zn 2.0-8.0 wt.%, er 0.1-3.5 wt.%, and the balance of magnesium, the mass ratio of Zn/Er is more than or equal to 6, weighing commercial pure magnesium, pure zinc and Mg-Er intermediate alloy, and removing oxide skin on the surface;
(2) Placing the pure magnesium in the step (1) into a clean cast iron crucible and placing the clean cast iron crucible and the clean cast iron crucible into a hearth of a resistance furnace together, preheating the crucible at 150-300 ℃ for 10-20 min to remove water in the crucible, placing the pure zinc and the Mg-Er intermediate alloy into another clean cast iron crucible and placing the clean cast iron crucible into the hearth of the resistance furnace for later use at the constant temperature of 250-350 ℃;
(3) Heating the resistance furnace with pure magnesium in the step (2) to 700-730 ℃, introducing protective gas with the volume ratio of 19:1 (N 2:SF6) in the smelting process, adjusting the temperature to 730-750 ℃ when the temperature of the melt after the pure magnesium is completely melted, adding all preheated Zn, keeping the temperature and standing for 10-15 min, adding all preheated Mg-Er, keeping the temperature and standing for 10-15 min, and stirring for 1-3 min;
(4) And (3) regulating the temperature in the step (3) to 710-730 ℃, fishing out the scum on the surface of the molten liquid, taking out the crucible, casting the melt into a metal mold prepared in advance, and naturally cooling after the melt is solidified to obtain an ingot. And further cutting to obtain the magnesium alloy negative plate.
The purity of the commercial pure magnesium is above 99.9%.
The Mg-Er intermediate alloy comprises Mg-20wt.% Er.
The casting is performed under a protective atmosphere which is the same as the smelting process.
The Mg-Zn-Er alloy obtained by the invention is applied to a magnesium air battery anode material and directly acts on an aqueous electrolyte.
The principle and the advantages of the invention are as follows:
(1) The addition of the alloy element Zn can improve the corrosion resistance of the magnesium alloy and reduce the hydrogen evolution side reaction of the magnesium alloy; the magnesium alloy is promoted to be uniformly dissolved while shortening the activation time of the battery.
(2) The addition of the alloy element Er can refine grains, purify melt, change the property of a discharge product film layer, slow down the self-corrosion rate of the alloy and improve the utilization efficiency of the magnesium cathode.
When both are added simultaneously, the addition of Zn and Er content affects the formation and distribution of the microstructure second phase. When the mass ratio Zn/Er is more than or equal to 6, especially when the mass ratio Zn/Er is more than or equal to 10 and more than or equal to 6, the quasicrystal I phase (Mg 3Zn6Er1) is separated out from the alloy. The quasicrystal I phase is beneficial to improving the corrosion resistance of the magnesium alloy, and the appearance, the size, the distribution and the content of the quasicrystal I phase influence the hydrogen evolution corrosion strength and the hydrogen evolution corrosion rate of the magnesium alloy in the aqueous solution. Meanwhile, the existence of the phase I is beneficial to weakening hydrogen evolution reaction, reducing the amount of the negative electrode consumed by the hydrogen evolution reaction and improving the utilization efficiency. Through optimizing the content of Zn and Er elements added, I phases with different shapes, sizes, distributions and contents can be obtained, thereby achieving the purposes of regulating and controlling microstructure and improving the discharge performance of the magnesium alloy.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides an application of a magnesium air battery cathode material with excellent discharge performance in a magnesium air battery through a traditional casting process.
Drawings
Fig. 1 is an Optical Microscope (OM) photograph of the negative electrode material of the magnesium air battery in examples 1 to 4 of the present invention.
Fig. 2 is a Scanning Electron Microscope (SEM) photograph of the negative electrode material of the magnesium air battery in examples 1 to 4 of the present invention.
FIG. 3 is a graph showing discharge curves of the magnesium air battery anode materials of examples 1 to 4 of the present invention for 2 hours at discharge currents of 1mA cm -2 and 50mA cm -2, respectively.
The specific embodiment is as follows:
The invention is further illustrated with reference to the following specific examples, which are given by way of illustration: the following examples are only illustrative of the practice of the invention and are not intended to limit the scope of the invention.
Example 1:
the magnesium air battery anode material comprises 2.0wt.% of Zn, 0.25wt.% of Er and the balance of magnesium.
(1) Weighing commercial pure magnesium (99.99 wt.%) and pure zinc and Mg-20.0wt.% Er intermediate alloy according to the weight percentage of 2.0wt.% Zn, 0.25wt.% Er and the balance of magnesium, and removing oxide scale on the surface;
(2) Placing the pure magnesium in the step (1) into a clean cast iron crucible and placing the clean cast iron crucible and the clean cast iron crucible together into a hearth of a resistance furnace, preheating the crucible at 200 ℃ for 15min to remove water in the crucible, placing the pure zinc and 20.0wt.% of Er into another clean cast iron crucible, and placing the intermediate alloy into the hearth of the resistance furnace for standby at the constant temperature of 300 ℃;
(3) Heating the resistance furnace with pure magnesium in the step (2) to 720 ℃, introducing protective gas with the volume ratio of 19:1 (N 2:SF6) in the smelting process, adjusting the temperature to 730 ℃ when the temperature of the melt after the pure magnesium is completely melted reaches 725 ℃, adding all preheated Zn, keeping the temperature and standing for 10min, adding all preheated Mg-20.0wt.% Er, keeping the temperature and standing for 10min, and stirring for 2min;
(4) And (3) adjusting the temperature in the step (3) to 715 ℃, fishing out the scum on the surface of the molten liquid, taking out the crucible, pouring the melt into a metal mold prepared in advance, and naturally cooling after the melt is solidified to obtain an ingot.
Example 2:
The magnesium air battery anode material comprises 4.0wt.% of Zn, 0.5wt.% of Er and the balance of magnesium.
(1) Weighing commercial pure magnesium (99.99 wt.%) and pure zinc and Mg-20.0wt.% Er intermediate alloy according to the weight percentage of 4.0wt.% Zn, 0.5wt.% Er and the balance of magnesium, and removing oxide scale on the surface;
(2) Placing the pure magnesium in the step (1) into a clean cast iron crucible and placing the clean cast iron crucible and the clean cast iron crucible together into a hearth of a resistance furnace, preheating the crucible at 250 ℃ for 15min to remove water in the crucible, placing the pure zinc and the intermediate alloy of Mg-20.0wt.% Er into another clean cast iron crucible and placing the clean cast iron crucible into the hearth of the resistance furnace for standby at the constant temperature of 300 ℃;
(3) Heating the resistance furnace in the step (2) to 725 ℃, introducing a protective gas with the volume ratio of 19:1 (N 2:SF6) in the smelting process, adjusting the temperature to 735 ℃ when the temperature of the melt after the pure magnesium is completely melted reaches 728 ℃, adding all preheated Zn, preserving heat and standing for 15min, adding all preheated Mg-20.0wt.% Er, preserving heat and standing for 15min, and stirring for 3min
(4) And (3) adjusting the temperature in the step (3) to 727 ℃, fishing out the scum on the surface of the molten liquid, taking out the crucible, pouring the melt into a metal mold prepared in advance, and naturally cooling after the melt is solidified to obtain an ingot.
Example 3:
The magnesium air battery anode material comprises, by mass, 6.0% of Zn, 0.75% of Er and the balance of magnesium.
(1) Weighing commercial pure magnesium (99.99 wt.%) and pure zinc and Mg-20.0wt.% Er intermediate alloy according to the weight percentage of 6.0wt.% Zn, 0.75wt.% Er and the balance of magnesium, and removing oxide scale on the surface;
(2) Placing the pure magnesium in the step (1) into a clean cast iron crucible and placing the clean cast iron crucible and the clean cast iron crucible together into a hearth of a resistance furnace, preheating the crucible at 250 ℃ for 15min to remove water in the crucible, placing the pure zinc and the intermediate alloy of Mg-20.0wt.% Er into another clean cast iron crucible and placing the clean cast iron crucible into the hearth of the resistance furnace for standby at the constant temperature of 300 ℃;
(3) Heating the resistance furnace in the step (2) to 715 ℃, introducing a protective gas with the volume ratio of 19:1 (N 2:SF6) in the smelting process, adjusting the temperature to 730 ℃ when the temperature of the melt after the pure magnesium is completely melted reaches 722 ℃, adding all preheated Zn, keeping the temperature and standing for 15min, adding all preheated Mg-20.0wt.% Er, keeping the temperature and standing for 15min, and stirring for 3min
(4) And (3) adjusting the temperature in the step (3) to 720 ℃, fishing out the scum on the surface of the molten liquid, taking out the crucible, pouring the melt into a metal mold prepared in advance, and naturally cooling after the melt is solidified to obtain an ingot.
Example 4:
the magnesium air battery anode material comprises 8.0wt.% of Zn, 1.0wt.% of Er and the balance of magnesium.
(1) Weighing commercial pure magnesium (99.99 wt.%) and pure zinc and Mg-20.0wt.% Er intermediate alloy according to the weight percentage of 8.0wt.% Zn, 1.0wt.% Er and the balance of magnesium, and removing oxide skin on the surface;
(2) Placing the pure magnesium in the step (1) into a clean cast iron crucible and placing the clean cast iron crucible and the clean cast iron crucible together into a hearth of a resistance furnace, preheating the crucible at 250 ℃ for 15min to remove water in the crucible, placing the pure zinc and the intermediate alloy of Mg-20.0wt.% Er into another clean cast iron crucible and placing the clean cast iron crucible into the hearth of the resistance furnace for standby at the constant temperature of 300 ℃;
(3) Heating the resistance furnace in the step (2) to 720 ℃, introducing a protective gas with the volume ratio of 19:1 (N 2:SF6) in the smelting process, adjusting the temperature to 735 ℃ when the temperature of the melt after the pure magnesium is completely melted reaches 728 ℃, adding all preheated Zn, preserving heat and standing for 15min, adding all preheated Mg-20.0wt.% Er, preserving heat and standing for 15min, and stirring for 2min
(4) And (3) adjusting the temperature in the step (3) to 730 ℃, fishing out the scum on the surface of the molten liquid, taking out the crucible, pouring the melt into a metal mold prepared in advance, and naturally cooling after the melt is solidified to obtain an ingot.
The discharge performance of the magnesium air battery anode materials described in examples 1-4 was measured using a LAND electrical performance monitoring device (CT 2001A), the battery experiments were conducted in a metal air battery reactor using a commercial MnO 2/C catalyst as the anode catalyst and a 3.5wt.% NaCl aqueous solution as the electrolyte at room temperature. Discharging for 2h under different current densities (1 mA cm -2,10mA cm-2,20mA cm-2 and 50mA cm -2), and taking the average value of the measured voltages as the discharge voltage, the utilization efficiency and the discharge capacity.
Table 1 discharge performance parameters provided by all examples
As can be seen from fig. 1, the second phase in example 1 exists mainly in the form of grains between grain boundaries and dendrites, and the second phase becomes continuous at the grain boundaries as the content of the additive element increases, and coarse irregular bar-shaped second phases are generated in example 4. As can be seen from FIG. 2, the granular second phase in example 1 was a quasi-crystalline I phase at the grain boundary and between dendrites, the main short-strip I phase produced in example 2, and the irregular long-strip I phase produced at the grain boundary at the surface of examples 3, 4. As the content of the additive element increases, the content of I phase generated in the Mg-Zn-Er alloy increases.
As can be seen from fig. 3, in combination with table 1, the discharge performance of comparative examples 1 to 4 shows that different magnesium alloy cathodes have higher discharge voltage, the dendrite of example 1 is distributed with granular I phase dispersed as cathode to accelerate the discharge of magnesium matrix, the granular I phase of example 2 is reduced, the formation position of the phase begins to gather at grain boundary, and intermittent strip-shaped I phase appears at the grain boundary; as the element content increases, the phase volume fraction further increases. The irregular long-shaped I phases are distributed at the cross grain boundaries of the example 3 and the example 4, and the I phase content of the example 4 is more, and part of the I phases are connected with each other. In combination with the discharge curves and the discharge parameters of the examples 1-4 under different current densities, the example 1 only contains the granular I phase and has less content, and the number of corrosion microcomputers formed on a solid-liquid interface is less, so that the hydrogen evolution self-corrosion of the magnesium alloy cathode in the water-based electrolyte is effectively inhibited, the magnesium loss caused by self-corrosion is reduced, and the utilization efficiency and the discharge capacity are improved; example 4 has a large I-phase size at the grain boundaries and is tightly connected, which is advantageous in preventing further expansion of corrosion, and suppressing hydrogen evolution self-corrosion, thus having an optimized discharge effect. Therefore, the alloy component provided by the invention is a magnesium air battery anode material with excellent performance.
Although preferred embodiments have been depicted and described in detail herein, it will be apparent to those skilled in the relevant art that various modifications, additions, substitutions and the like can be made without departing from the spirit of the invention and these are therefore considered to be within the scope of the invention as defined in the claims.
Claims (7)
1. The Mg-Zn-Er alloy which can directly act on the negative electrode material of the magnesium air battery in the aqueous electrolyte is characterized by comprising the following components in percentage by mass: 2.0-8.0 wt percent of Er 0.1-3.5 wt percent of Er and the balance of magnesium and unavoidable impurities; the mass ratio of the alloy element Zn to the alloy element Er is more than or equal to 6;
The preparation method comprises the following steps:
(1) Weighing commercial pure magnesium, pure zinc and Mg-Er intermediate alloy according to the content Zn of 2.0-8.0 wt percent, er of 0.1-3.5 wt percent and the balance of magnesium, wherein the mass ratio Zn/Er of Zn/Er is more than or equal to 6, and removing oxide skin on the surface;
(2) Placing the pure magnesium in the step (1) into a clean cast iron crucible and placing the clean cast iron crucible into a hearth of a resistance furnace together, preheating the crucible at 150-300 ℃ for 10-20 min to remove water in the crucible, placing the pure zinc and the Mg-Er intermediate alloy into another clean cast iron crucible and placing the clean cast iron crucible into the hearth of the resistance furnace for later use at the constant temperature of 250-350 ℃;
(3) Heating the resistance furnace with pure magnesium to 700-730 ℃, introducing protective gas with the volume ratio of N 2:SF6 being 19:1 in the smelting process, adjusting the temperature to 730-750 ℃ when the temperature of the melt after the pure magnesium is completely melted, adding all preheated Zn, keeping the temperature and standing for 10-15 min, adding all preheated Mg-Er, keeping the temperature and standing for 10-15 min, and stirring for 1-3 min;
(4) And (3) adjusting the temperature in the step (3) to 710-730 ℃, fishing out scum on the surface of the molten liquid, taking out the crucible, casting the melt into a metal mold prepared in advance, and naturally cooling after the melt is solidified to obtain an ingot.
2. The Mg-Zn-Er alloy as claimed in claim 1, wherein Zn/Er is more than or equal to 10 and more than or equal to 6.
3. The Mg-Zn-Er alloy as defined in claim 1 wherein quasicrystal I phase Mg 3Zn6Er1 is precipitated in the alloy.
4. A method of preparing a Mg-Zn-Er alloy as defined in any one of claims 1 to 3 comprising the steps of:
(1) Weighing commercial pure magnesium, pure zinc and Mg-Er intermediate alloy according to the content Zn of 2.0-8.0 wt percent, er of 0.1-3.5 wt percent and the balance of magnesium, wherein the mass ratio Zn/Er of Zn/Er is more than or equal to 6, and removing oxide skin on the surface;
(2) Placing the pure magnesium in the step (1) into a clean cast iron crucible and placing the clean cast iron crucible into a hearth of a resistance furnace together, preheating the crucible at 150-300 ℃ for 10-20 min to remove water in the crucible, placing the pure zinc and the Mg-Er intermediate alloy into another clean cast iron crucible and placing the clean cast iron crucible into the hearth of the resistance furnace for later use at the constant temperature of 250-350 ℃;
(3) Heating the resistance furnace with pure magnesium to 700-730 ℃, introducing protective gas with the volume ratio of N 2:SF6 being 19:1 in the smelting process, adjusting the temperature to 730-750 ℃ when the temperature of the melt after the pure magnesium is completely melted, adding all preheated Zn, keeping the temperature and standing for 10-15 min, adding all preheated Mg-Er, keeping the temperature and standing for 10-15 min, and stirring for 1-3 min;
(4) And (3) adjusting the temperature in the step (3) to 710-730 ℃, fishing out scum on the surface of the molten liquid, taking out the crucible, casting the melt into a metal mold prepared in advance, and naturally cooling after the melt is solidified to obtain an ingot.
5. The method of claim 4, wherein the commercially pure magnesium has a purity of 99.9% or more; the Mg-Er intermediate alloy comprises Mg-20 wt% Er.
6. The method of claim 4, wherein the casting of step (4) is performed in a protective atmosphere, the protective atmosphere being the same as the smelting process.
7. Use of the Mg-Zn-Er alloy of any one of claims 1-3 as a negative electrode material for a magnesium air battery directly in an aqueous electrolyte.
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| CN109161767A (en) * | 2018-10-23 | 2019-01-08 | 北京工业大学 | A kind of creep-resistant property magnesium alloy of the phase containing W and preparation 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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