CN115874100A - Mg-Zn-Er alloy as negative electrode material of magnesium air battery and preparation method and application thereof - Google Patents
Mg-Zn-Er alloy as negative electrode material of magnesium air battery and preparation method and application thereof Download PDFInfo
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 81
- 229910001371 Er alloy Inorganic materials 0.000 title claims abstract description 15
- 239000007773 negative electrode material Substances 0.000 title claims description 19
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 51
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 30
- 239000000956 alloy Substances 0.000 claims abstract description 30
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005266 casting Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000000155 melt Substances 0.000 claims description 25
- 229910001018 Cast iron Inorganic materials 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 8
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- 238000000034 method Methods 0.000 claims description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
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- 239000001257 hydrogen Substances 0.000 abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- 239000010406 cathode material Substances 0.000 abstract description 7
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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 magnesium-air battery cathode material Mg-Zn-Er alloy and 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 weight percent of Zn/Er more than or equal to 6 weight percent, 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) Will be provided withPreheating the treated materials, and sequentially putting the materials into a crucible for melting; and (3) casting the molten liquid in a mould, and cooling to obtain a casting. The invention obtains the quasi-crystal I-phase Mg by controlling the mass ratio of Zn to Er 3 Zn 6 Er 1 The microstructure of the magnesium air battery effectively inhibits the hydrogen evolution reaction of the magnesium cathode in aqueous electrolyte solution, accelerates the falling of the product, reduces the accumulation thickness of the discharge product on the surface of the cathode, and improves the performance of the magnesium air battery.
Description
Technical Field
The invention relates to the technical field of magnesium air batteries, in particular to a magnesium air battery cathode material Mg-Zn-Er alloy and a preparation method and application thereof.
Background
The world faces serious problems of resource shortage, environmental pollution and the like, and the global energy structure is changing to clean energy. The development of advanced energy storage systems is one of the solutions to alleviate the energy crisis. The metal-air battery is a special type of energy storage system, takes metal as a negative active material and oxygen as a positive active material, and has the advantages of low cost, light weight, safety, environmental protection, high specific energy and the like. Magnesium has relatively negative standard electrode potential (-2.37V vs SHE), and relatively large theoretical specific capacity (2200 mAh g) -1 ) And power density (6800 mWh g) -1 ) Lower density (1.74 g cm) -3 ) The magnesium air battery taking magnesium or magnesium alloy as the cathode has attracted wide attention, and is applied to the fields of emergency power supplies, special military equipment, standby power supplies and the like.
However, the magnesium negative electrode has a serious self-corrosion phenomenon in an aqueous electrolyte, and a discharge product is formed during a discharge process to block the contact between the magnesium negative electrode and an electrolyte, thereby causing problems of low discharge voltage, low negative electrode efficiency, serious energy and capacity loss, and the like, so that the discharge performance thereof is far lower than a theoretical value, the development of a magnesium air battery is blocked, and the commercial development thereof is limited. The selection of a suitable magnesium alloy anode material is the key to solving this problem.
In view of this, we propose the present invention.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art of the magnesium-air battery, the invention mainly aims to provide a magnesium-air battery cathode material Mg-Zn-Er alloy. When the magnesium alloy is used as the cathode of the magnesium air battery, the hydrogen evolution reaction of the cathode 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 the stable discharging voltage is obtained, the utilization efficiency and the discharging capacity of the cathode are improved, and the magnesium alloy cathode has good discharging performance.
The invention also aims to provide a preparation method of the Mg-Zn-Er alloy as the negative electrode material of the magnesium-air battery.
The invention further aims to provide application of the Mg-Zn-Er alloy as the negative electrode material of the magnesium-air battery.
The purpose of the invention is realized by the following technical scheme:
the magnesium air battery cathode 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 inevitable impurities; the mass ratio of the alloy element Zn/Er is not less than 6, preferably not less than 10 and not less than 6.
The invention provides a preparation method of a high-utilization-rate magnesium air battery cathode material, which comprises the following steps of:
(1) Weighing commercial pure magnesium, pure zinc and Mg-Er intermediate alloy according to the contents of Zn of 2.0-8.0 wt.% and Er of 0.1-3.5 wt.% and the balance of magnesium, wherein the mass ratio of Zn to Er is more than or equal to 6, and removing oxide skins on the surface;
(2) Putting the pure magnesium in the step (1) into a clean cast iron crucible and putting the pure magnesium and the pure magnesium into a resistance furnace hearth together, preheating the crucible at the temperature of between 150 and 300 ℃ for 10 to 20 minutes to remove water in the crucible, putting the pure zinc and the Mg-Er master alloy into another clean cast iron crucible and putting the pure zinc and the Mg-Er master alloy into another resistance furnace hearth for standby at the constant temperature of between 250 and 350 ℃;
(3) And (3) putting the pure magnesium in the step (2) into a resistance furnace, heating to 700-730 ℃, and introducing a material with a volume ratio of 19 (N 2 :SF 6 ) When the temperature of the melt of the completely molten pure magnesium reaches 720-730 ℃, adjusting the temperature to 730-750 ℃, 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 then stirring for 1-3 min;
(4) And (4) adjusting the temperature in the step (3) to 710-730 ℃, taking out the scum on the surface of the melt, taking out the crucible, casting the melt into a prepared metal mold, and naturally cooling the melt after the melt is solidified to obtain the ingot. Further cutting to prepare the magnesium alloy negative plate.
The purity of the commercial pure magnesium is more than 99.9 percent.
The Mg-Er master alloy comprises Mg-20wt.% Er.
The casting is carried out in a protective atmosphere, which is the same as the smelting process.
The Mg-Zn-Er alloy obtained by the invention is applied as a negative electrode material of a magnesium air battery 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 activation time of the battery is shortened, and the magnesium alloy is promoted to be uniformly dissolved.
(2) The addition of the alloy element Er can refine crystal 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 the two are added simultaneously, the addition of Zn and Er will affect the formation and distribution of the second phase in the microstructure. When the mass ratio Zn/Er is more than or equal to 6, particularly when the mass ratio Zn/Er is more than or equal to 10 and more than or equal to 6, a quasicrystal I phase (Mg) is precipitated in the alloy 3 Zn 6 Er 1 ). The quasicrystal I phase is beneficial to improving the corrosion resistance of the magnesium alloy, and the appearance, size, distribution and content of the quasicrystal I phase influence the hydrogen evolution corrosion strength and rate of the magnesium alloy in an aqueous solution. Meanwhile, the existence of the phase I is favorable for weakening the hydrogen evolution reaction and reducing the cathode consumed by the hydrogen evolution reactionThe amount of (2) improves the utilization efficiency. By optimizing the content of the added Zn and Er elements, I phases with different shapes, sizes, distributions and contents can be obtained, thereby achieving the purposes of regulating and controlling the 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 the application of the magnesium air battery cathode material with excellent discharge performance in the magnesium air battery through the 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 shows that the negative electrode materials of the magnesium air battery in examples 1-4 of the present invention are respectively at 1mA cm -2 And 50mA cm -2 Discharge current of (2) for 2 h.
The specific implementation mode is as follows:
the invention is further illustrated by the following specific examples, in which: the following examples are intended to illustrate specific embodiments of the present invention and are not intended to limit the scope of the claims.
Example 1:
the negative electrode material for the magnesium air battery comprises, by mass, 2.0wt.% of Zn, 0.25wt.% of Er and the balance of magnesium.
(1) Weighing commercial pure magnesium (99.99 wt.%), pure zinc and Er intermediate alloy with the content of Zn being 2.0wt.% and Er being 0.25wt.% and the balance being magnesium, and removing oxide skin on the surface;
(2) Putting the pure magnesium in the step (1) into a clean cast iron crucible and putting the pure magnesium and the pure magnesium together into a resistance furnace hearth, preheating the crucible at 200 ℃ for 15min to remove water in the crucible, putting pure zinc and Mg-20.0wt.% Er, putting the intermediate alloy into another clean cast iron crucible and putting the intermediate alloy into another resistance furnace hearth for standby at a constant temperature of 300 ℃;
(3) Putting the pure magnesium into the (2) resistance furnace for heatingTo 720 ℃, a volume ratio of 19 (N 2 :SF 6 ) When the temperature of the melt of the completely molten pure magnesium reaches 725 ℃, adjusting the temperature to 730 ℃, 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 then stirring for 2min;
(4) And (4) adjusting the temperature in the step (3) to 715 ℃, fishing out the scum on the surface of the melt, taking out the crucible, pouring the melt into a prepared metal mold, and naturally cooling to obtain the ingot after the melt is solidified.
Example 2:
the negative electrode material for the magnesium air battery comprises, by mass, 4.0wt.% of Zn, 0.5wt.% of Er and the balance of magnesium.
(1) Weighing commercial pure magnesium (99.99 wt.%), pure zinc and Er intermediate alloy with the contents of Zn 4.0wt.% and Er 0.5wt.% and the balance of magnesium, and removing oxide skins on the surfaces of the intermediate alloy;
(2) Putting the pure magnesium in the step (1) into a clean cast iron crucible and putting the pure magnesium and the pure magnesium together into a resistance furnace hearth, preheating at 250 ℃ for 15min to remove water in the crucible, putting the pure zinc and the Er master alloy with the Mg content of 20.0wt.% into another clean cast iron crucible and putting the Er master alloy into another resistance furnace hearth for standby at the constant temperature of 300 ℃;
(3) Heating the electric resistance furnace with pure magnesium in the step (2) to 725 ℃, and introducing a mixed solution of N 2 :SF 6 ) The protective gas is prepared by adjusting the temperature to 735 ℃ when the temperature of the melt of pure magnesium is 728 ℃, 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 (4) adjusting the temperature in the step (3) to 727 ℃, fishing out the scum on the surface of the melt, taking out the crucible, pouring the melt into a prepared metal mold, and naturally cooling to obtain the ingot after the melt is solidified.
Example 3:
the negative electrode material for the magnesium air battery comprises, by mass, 6.0wt.% of Zn, 0.75wt.% of Er and the balance of magnesium.
(1) Weighing commercial pure magnesium (99.99 wt.%), pure zinc and Er intermediate alloy with the content of Zn being 6.0wt.% and Er being 0.75wt.% and the balance being magnesium, and removing oxide skin on the surface;
(2) Putting the pure magnesium in the step (1) into a clean cast iron crucible and putting the pure magnesium and the clean cast iron crucible together into a resistance furnace hearth, preheating the crucible at 250 ℃ for 15min to remove water in the crucible, putting the pure zinc and the Mg-20.0wt.% Er master alloy into another clean cast iron crucible and putting the pure zinc and the Mg-20.0wt.% Er master alloy into another resistance furnace hearth for standby at a constant temperature of 300 ℃;
(3) Heating the pure magnesium resistance furnace in the step (2) to 715 ℃, and introducing a material with the volume ratio of 19 (N 2 :SF 6 ) When the temperature of the melt of the completely molten pure magnesium reaches 722 ℃, adjusting the temperature to 730 ℃, adding the completely preheated Zn, keeping the temperature and standing for 15min, adding the completely preheated Mg-20.0wt.% Er, keeping the temperature and standing for 15min, and stirring for 3min
(4) And (4) adjusting the temperature in the step (3) to 720 ℃, fishing out the scum on the surface of the melt, taking out the crucible, pouring the melt into a prepared metal mold, and naturally cooling to obtain the ingot after the melt is solidified.
Example 4:
the negative electrode material for the magnesium air battery comprises, by mass, 8.0% of Zn, 1.0% of Er and the balance of magnesium.
(1) Weighing commercial pure magnesium (99.99 wt.%), pure zinc and Er intermediate alloy with the content of Zn being 8.0wt.% and Er being 1.0wt.% and the balance being magnesium, and removing oxide skin on the surface;
(2) Putting the pure magnesium in the step (1) into a clean cast iron crucible and putting the pure magnesium and the pure magnesium together into a resistance furnace hearth, preheating at 250 ℃ for 15min to remove water in the crucible, putting the pure zinc and the Er master alloy with the Mg content of 20.0wt.% into another clean cast iron crucible and putting the Er master alloy into another resistance furnace hearth for standby at the constant temperature of 300 ℃;
(3) Heating the pure magnesium resistance furnace in the step (2) to 720 ℃, and introducing a mixed solution of N 2 :SF 6 ) Protective gas of (1), until pure magnesium is finishedAdjusting the temperature of the completely melted melt to 728 ℃, adjusting the temperature to 735 ℃, adding completely preheated Zn, keeping the temperature and standing for 15min, adding completely preheated Mg-20.0wt.% Er, keeping the temperature and standing for 15min, and stirring for 2min
(4) And (4) adjusting the temperature in the step (3) to 730 ℃, fishing out the scum on the surface of the melt, taking out the crucible, pouring the melt into a prepared metal mold, and naturally cooling to obtain the ingot after the melt is solidified.
The discharge performance of the negative electrode materials of the magnesium air batteries of examples 1 to 4 was measured using a LAND electric performance monitoring device (CT 2001A), and the battery test was conducted in a metal air battery reactor using a commercial MnO as a positive electrode catalyst 2 catalyst/C, electrolyte 3.5wt.% NaCl aqueous solution, test temperature room temperature. At different current densities (1 mA cm) -2 ，10mA cm -2 ，20mA cm -2 And 50mA cm -2 ) Discharging for 2h, and taking the average value of the measured voltage as the discharge voltage, the utilization efficiency and the discharge capacity.
Table 1 discharge performance parameters provided for all examples
As can be seen from fig. 1, in example 1, the second phase exists mainly in the form of particles between the grain boundaries and dendrites, and as the content of the additive element increases, the second phase becomes continuous at the grain boundaries, and in example 4, a coarse irregular stripe-shaped second phase is generated. As can be seen from FIG. 2, the granular second phases in example 1 are quasicrystalline I phases at the grain boundaries and between dendrites, the short-striped I phases are mainly generated in example 2, and the irregular long-striped I phases are generated at the grain boundaries on the surfaces of examples 3 and 4. The content of I phase generated in the Mg-Zn-Er alloy increases with the content of the added elements.
As can be seen from fig. 3, in combination with table 1, the discharge performance of examples 1 to 4 is compared, and it can be seen that different magnesium alloy cathodes all have higher discharge voltage, the interdendritic dispersion distribution granular I phase of example 1 is used as a cathode to accelerate magnesium matrix discharge, the granular I phase of example 2 is reduced, the formation position of the phase starts to gather at the grain boundary, and the discontinuous strip-shaped I phase appears on the grain boundary; as the element content increases, the phase volume fraction further increases. Irregular long strip I phases are distributed at the crossed grain boundaries of the embodiment 3 and the embodiment 4, the I phase content of the embodiment 4 is more, and the I phases are connected with each other. By combining the discharge curves and discharge parameters of the examples 1-4 under different current densities, the example 1 only contains the granular I phase and has a small content, and the corrosion micro-electricity even number formed on a solid-liquid interface is small, so that the hydrogen evolution self-corrosion of the magnesium alloy cathode in the aqueous electrolyte is effectively inhibited, the magnesium amount lost due to the self-corrosion is reduced, and the utilization efficiency and the discharge capacity are improved; example 4 the phase I has a larger size and is tightly connected at the grain boundary, which is advantageous to prevent further propagation of corrosion and inhibit hydrogen evolution self-corrosion, thus having an optimized discharge effect. Therefore, the alloy component provided by the invention is a magnesium air battery cathode 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 following claims.
Claims (7)
1. The Mg-Zn-Er alloy as the negative electrode material of the magnesium-air battery is characterized by comprising 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 inevitable impurities; the mass ratio Zn/Er of the alloy elements Zn and Er is more than or equal to 6.
2. The Mg-Zn-Er alloy as the negative electrode material of magnesium-air battery as recited in claim 1, wherein Zn/Er is 10. Gtoreq.6.
3. The Mg-Zn-Er alloy as negative electrode material for Mg-air battery as claimed in claim 1, wherein the Mg-Zn-Er alloy is used as a negative electrode material for Mg-air batteryPrecipitation of quasicrystalline I phase Mg 3 Zn 6 Er 1 。
4. A method of making a Mg-Zn-Er alloy according to 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 contents of Zn of 2.0-8.0 wt.% and Er of 0.1-3.5 wt.% and the balance of magnesium, wherein the mass ratio of Zn to Er is more than or equal to 6, and removing oxide skins on the surface;
(2) Putting the pure magnesium in the step (1) into a clean cast iron crucible and putting the pure magnesium and the clean cast iron crucible together into a resistance furnace hearth, preheating the crucible at the temperature of between 150 and 300 ℃ for 10 to 20 minutes to remove water in the crucible, putting the pure zinc and the Mg-Er intermediate alloy into another clean cast iron crucible and putting the pure zinc and the Mg-Er intermediate alloy into another resistance furnace hearth for standby at the constant temperature of between 250 and 350 ℃;
(3) Heating the resistance furnace with pure magnesium in the step (2) to 700-730 ℃, and introducing a solution with a volume ratio of 19 (N 2 :SF 6 ) When the temperature of the melt of the completely molten pure magnesium reaches 720-730 ℃, adjusting the temperature to 730-750 ℃, 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 then stirring for 1-3 min;
(4) And (4) adjusting the temperature in the step (3) to 710-730 ℃, taking out the scum on the surface of the melt, taking out the crucible, casting the melt into a prepared metal mold, and naturally cooling the melt after the melt is solidified to obtain the ingot.
5. The method of claim 4, wherein the purity of commercially pure magnesium is above 99.9%; the Mg-Er master alloy comprises Mg-20wt.% Er.
6. The method according to claim 4, wherein the step (4) of casting is carried out under a protective atmosphere, which is the same as the melting process.
7. Use of the Mg-Zn-Er alloy of any one of claims 1 to 3 as a negative electrode material for a magnesium air battery, directly in an aqueous electrolyte.
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