CN111916766A - Mg-Bi-Ca-In alloy as negative electrode material of magnesium air battery and preparation method thereof - Google Patents
Mg-Bi-Ca-In alloy as negative electrode material of magnesium air battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a magnesium-air battery cathode material Mg-Bi-Ca-In alloy and a preparation method thereof, belonging to the technical field of magnesium-air battery electrode materials. The alloy comprises the following components in percentage by weight: mg: 96.4 to 98.0wt.%, Bi: 1.8-2.2 wt.%, Ca: 0.1-0.7 wt.%, In: 0.1 to 0.7 wt.% in Ar + N2Under the protective atmosphere, a crucible resistance furnace is adopted for smelting to obtain an as-cast blank, and the as-cast blank is directly extruded after being mechanically processed. The extruded alloy has a micro-nano second phase and a micron-grade fine-crystalline structure which are distributed in a dispersed manner. The Mg-Bi-Ca-In negative electrode material has good discharge performance and higher anode efficiency, and solves the problem that the self-corrosion rate of the negative electrode material is highLow electrochemical activity, and low efficiency of the battery anode.
Description
Technical Field
The invention relates to a magnesium-air battery cathode material Mg-Bi-Ca-In alloy and a preparation method thereof, belonging to the technical field of magnesium-air battery electrode materials.
Background
In recent years, the problems of energy crisis, environmental pollution and the like are becoming more serious, and people are eagerly looking for a novel green alternative energy material. Under the background, the metal-air battery is expected to replace the traditional fuel battery due to a series of advantages of high energy density, environmental friendliness, abundant material reserves and the like.
As early as the past 70 s, many researches on magnesium-air batteries have been made at home and abroad. The main concerns are on the negative electrode material, the electrolyte and the battery system. Compared with other air batteries, the magnesium air battery has attracted more and more attention due to a series of advantages of higher discharge voltage, higher theoretical specific capacity, higher energy density and the like. However, the development of magnesium air batteries is limited to a certain extent by the faster self-corrosion rate of magnesium alloys and the presence of voltage hysteresis. Researches show that through the alloying and plastic deformation composite process, the discharge performance of the magnesium alloy can be improved to a certain extent by changing the crystal grain structure, orientation, second phase morphology and distribution of the magnesium alloy and regulating and controlling the morphology of a discharge product. However, high alloying leads to an increase in alloy cost and self-corrosion rate, so the invention develops a low-alloying magnesium alloy cathode material which is prepared by a short process and is suitable for a cathode material of a magnesium-air battery.
Disclosure of Invention
The invention provides a magnesium-air battery cathode material Mg-Bi-Ca-In alloy and a preparation method thereof, aiming at the problems of over-high self-corrosion rate, low anode efficiency and the like of magnesium alloy, wherein the alloy has good discharge performance.
AlloyingIs a common method for improving the discharge performance of the magnesium alloy cathode material. The Bi element as a nontoxic element with high hydrogen evolution overpotential can inhibit the generation of hydrogen evolution reaction and improve the utilization rate of the cathode material. Further, for Mg-Bi based alloys, thermally stable Mg3Bi2Phases are easily generated during solidification and deformation. These second phases not only can enhance the dissolution of the matrix but also can promote the rupture of the discharge product film, so that the discharge performance of the anode material is significantly increased. The Ca element can not only inhibit the self-corrosion of pure magnesium, but also promote the rupture of a product film, so that the discharge performance of the magnesium alloy is obviously improved. The In element can promote the combination of a discharge product and a sodium chloride solution, accelerate the rupture of a discharge product film, promote the contact of electrolyte and a matrix, further improve the activation and dissolution of the matrix and improve the discharge performance. Therefore, the invention provides the Mg-Bi-Ca-In alloy as the cathode material of the magnesium air battery and the preparation method thereof according to the characteristics of various alloying elements.
The invention provides a magnesium-air battery cathode material Mg-Bi-Ca-In alloy which comprises the following components In percentage by weight: mg: 96.4 to 98.0wt.%, Bi: 1.8-2.2 wt.%, Ca: 0.1-0.7 wt.%, In: 0.1-0.7 wt.% of Mg dispersed on the alloy matrix3Bi2And Mg2Bi2Ca reinforcing phase and uniform equiaxed crystal structure.
The invention provides a preparation method of the Mg-Bi-Ca-In alloy as the cathode material of the magnesium-air battery, which comprises the following steps:
step one, preparing a blank: pure Mg, pure Bi, pure In and Mg-30 percent Ca intermediate alloy with the purity of more than 99.9 percent are put into a graphite crucible according to the proportion and are smelted by a crucible resistance furnace, and N is adopted In the smelting process2Protecting the liquid level with Ar mixed gas, preserving heat at 730-740 ℃ for 20-30 minutes after all alloy elements are melted, adding an RJ-2 type magnesium alloy refining agent into the melted alloy liquid for refining after heat preservation, wherein the addition amount of the magnesium alloy refining agent is 1-2% of the mass of the melted alloy; standing for 20-35 minutes after refining is finished, pouring the molten liquid into a metal die at 725-740 ℃ to obtain a cylindrical sample blank, wherein the diameter of the cylindrical sample blank is 60 mm, and preheating the metal mold to 180-200 ℃ before casting;
n in the mixed gas2The volume ratio of Ar to Ar is 6: 1-2;
secondly, extrusion deformation: directly machining the cast blank into an extruded blank, wherein the diameter of the extruded blank is 55-60 mm, the height of the extruded blank is 50-55 mm, and the blank is subjected to heat preservation at 290-310 ℃ for 29-31 min before extrusion to obtain an extruded bar with the diameter of 12 mm; the technological parameters of the extrusion are as follows: the extrusion temperature is 280-320 ℃, the extrusion rate is 0.09-0.11 mm/s, and the extrusion ratio is 25: 1.
In addition, under the combined action of three-directional forces in the extrusion process, the coarse second-phase particles can be extruded into fine and dispersedly distributed second-phase particles, dynamic recrystallization is induced, and the discharge performance of the alloy is favorably improved.
The invention also provides the application and the performance of the Mg-Bi-Ca-In alloy as the experimental alloy cathode material In the performance test of the half battery and the full battery. In a half-cell test, an experimental alloy is taken as a working electrode (the experimental alloy only needs to be polished smoothly without other treatment) on an electrochemical workstation, a platinum electrode is taken as a counter electrode, and a saturated calomel electrode is taken as a reference electrode to measure the discharge potential and the utilization rate of the experimental alloy under constant current density by a chronopotentiometry method. In the performance test of the full battery, experimental alloy is taken as a negative electrode material (the experimental alloy only needs to be polished smoothly without other treatment), MnO is added2The battery voltage and power density of the experimental alloy under constant current density were determined under the condition that a commercial electrode using/C as a catalyst was used as a positive electrode material and a magnesium-air battery was assembled with 3.5 wt.% NaCl solution as an electrolyte.
The invention has the beneficial effects that:
(1) according to the invention, nontoxic alloy elements Bi, Ca and In are added into the magnesium alloy, and the addition amount of the alloy elements is not more than 2.0%, so that the cost of the cathode material is reduced.
(2) The Mg-Bi-Ca-In alloy of the invention has refined crystal grains after extrusion and improved electrochemical activity. The stable discharge voltage can be provided when the discharge is carried out under a lower current density, and the long-time stable discharge of the cathode material is facilitated.
(3) The Mg-Bi-Ca-In alloy provided by the invention is directly extruded after being cast, so that the preparation process is shortened, and the nanoscale Mg dispersed and distributed on the substrate can be realized after being extruded3Bi2And micron-sized Mg2Bi2The Ca reinforcing phase improves the comprehensive performance of the alloy. In a half-cell performance test, the discharge potential under low current density is-1.63 to-1.66V, and the utilization rate is 40 to 47 percent; the discharging potential under the large current density is-1.45 to-1.60V, and the utilization rate is 64 to 75 percent. In a full battery performance test, the discharge potential under low current density is 1.35-1.50V, and the power density is 13.5-15.0 mW/cm2(ii) a The discharge potential under heavy current density is 0.60-0.75V, and the power density is 13.5-15.0 mW/cm2。
Drawings
FIG. 1 is a metallographic microstructure of an alloy prepared in example 1 of the present invention.
FIG. 2 is an SEM microstructure of an alloy prepared according to example 1 of the present invention.
Fig. 3 is an XRD pattern of the prepared alloy. (a) Mg-2Bi-0.5In-0.1Ca alloy, (b) Mg-2Bi-0.5Ca-0.1In alloy, and (c) Mg-2Bi-0.5Ca-0.5In alloy.
FIG. 4 is a metallographic microstructure of an alloy prepared in example 2 of the present invention.
FIG. 5 is an SEM microstructure of an alloy prepared according to example 2 of the present invention.
FIG. 6 is a metallographic microstructure of an alloy prepared in example 3 of the present invention.
FIG. 7 is an SEM microstructure of an alloy prepared according to example 3 of the present invention.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
The RJ-2 type magnesium alloy refining agent used by the invention comprises the following components in percentage by weight:
TABLE 1 RJ-2 type magnesium alloy refining agent composition ratio
Example 1
High-purity magnesium ingot (Mg purity is 99.99%), high-purity bismuth (Bi purity is 99.99%), high-purity indium (In purity is 99.99%), and Mg-30% Ca intermediate alloy are adopted, and the alloy components are mixed according to Mg-2Bi-0.5In-0.1Ca (mass fraction), namely the mass percentages are respectively: 97.4 percent of Mg, 2.0 percent of Bi, 0.5 percent of In and 0.1 percent of Ca (reasonable impurities are not considered In the mass percentage, and the raw materials with less impurities are selected as much as possible when the raw materials are selected).
Step one, preparing a blank: when smelting, firstly adding a high-purity magnesium ingot into a resistance furnace, and heating under a protective gas environment; n starts to be introduced when the temperature of the furnace rises to 280 DEG C2Mixed gas of Ar, N2And Ar in a volume ratio of 6: 1; keeping the temperature for 20 minutes when the temperature is increased to 730 ℃; adding bismuth and indium after the magnesium ingot is melted, heating to 740 ℃, keeping the temperature for 30 minutes, then refining at 740 ℃ by using an RJ-2 type magnesium alloy refining agent, wherein the addition amount of the refining agent is 1 percent of the mass of the melt, stirring for 5 minutes, standing for 20 minutes, and then casting into a metal mold at 725 ℃; the preheating temperature of the mold is 180 ℃ and the refining method is well known to those skilled in the art.
Step two, forward extrusion: and (4) directly carrying out mechanical processing on the blank obtained by casting in the step one to obtain an extruded blank with the diameter of 55 mm and the height of 50 mm. And then polishing the surface of the blank by using sand paper to be bright, preserving the heat of the blank for 30 min at 290 ℃ before extrusion, wherein the extrusion process parameters are as follows: the extrusion temperature is 290 ℃, the extrusion rate is 0.1 mm/s, the extrusion ratio is 25: 1, and finally the extrusion bar with the diameter of 12 mm is obtained.
When the alloy material prepared by the method is used for testing a half cell, the discharge potential and the utilization rate measured under different current densities are respectively as follows: at 10 mA/cm2Under the current density of (2), the discharge potential of the alloy is-1.63V, the utilization rate is 40.31 percent and the discharge potential is 120 mA/cm2The discharge potential of the alloy was-1.50V at a current density of (2), and the utilization rate was 64.56%. When the alloy material is used for the performance test of the full cell, the cell voltage and the power density of the alloy cathode measured under different current densities are respectively as follows: at 10 mA/cm2At a current density of 1.38V, the cell voltage of the alloy is 1.38V, workThe specific density is 13.8 mW/cm2At 120 mA/cm2The battery voltage of the alloy is 0.60V and the power density is 72.0 mW/cm under the current density of (2)2。
FIG. 1 is a metallographic microstructure (ED-TD plane) of a Mg-2Bi-0.5In-0.1Ca alloy material prepared In example 1. As can be seen from the figure, the dynamic recrystallization grains of the alloy structure are relatively fine, and FIG. 2 is an SEM microstructure of the alloy prepared in example 1, and a large amount of nano-scale reinforcing phase is dispersed in the matrix. When the XRD spectrum of FIG. 3 is combined, it can be confirmed that the nanophase is Mg3Bi2And (4) a reinforcing phase.
Example 2
High-purity magnesium ingot (Mg purity is 99.99%), high-purity bismuth (Bi purity is 99.99%), high-purity indium (In purity is 99.99%), and Mg-30% Ca intermediate alloy are adopted, and the alloy components are mixed according to Mg-2Bi-0.5Ca-0.1In (mass fraction), namely the mass percentages are respectively: 97.4 percent of Mg, 2.0 percent of Bi, 0.5 percent of Ca and 0.1 percent of In (reasonable impurities are not considered In the mass percentage, and the raw materials with less impurities are selected as much as possible when the raw materials are selected).
Step one, preparing a blank: when smelting, firstly adding a high-purity magnesium ingot into a resistance furnace, and heating under a protective gas environment; n is introduced when the temperature of the furnace rises to 300 DEG C2Mixed gas of Ar, N2The volume ratio of Ar to Ar is 6: 1.5; holding the temperature for 25 minutes when the temperature is raised to 735 ℃; adding bismuth and Mg-Ca intermediate alloy after the magnesium ingot is melted, heating to 740 ℃, keeping the temperature for 30 minutes, then refining at 740 ℃ by using RJ-2 type magnesium alloy refining agent, wherein the addition amount of the refining agent is 1.5 percent of the mass of the melt, stirring for 5 minutes, standing for 25 minutes, and then casting into a metal mold at 730 ℃; the mold preheating temperature is 190 ℃ and the refining method is well known to those skilled in the art.
Step two, forward extrusion: and (4) directly machining the blank cast in the step one to obtain an extruded blank with the diameter of 58 mm and the height of 52 mm. And then polishing the surface of the blank by using sand paper to be bright, preserving the heat of the blank for 30 min at 300 ℃ before extrusion, wherein the extrusion process parameters are as follows: the extrusion temperature is 300 ℃, the extrusion rate is 0.1 mm/s, the extrusion ratio is 25: 1, and finally the extrusion bar with the diameter of 12 mm is obtained.
When the alloy material prepared by the method is used for testing a half cell, the discharge potential and the utilization rate measured under different current densities are respectively as follows: at 10 mA/cm2Under the current density of (A), the discharge potential of the alloy is-1.64V, the anode efficiency is 42.12 percent and the discharge current is 120 mA/cm2The discharge potential of the alloy was-1.55V at a current density of (2), and the utilization rate was 67.36%. When the alloy material is used for the performance test of the full cell, the cell voltage and the power density of the alloy cathode measured under different current densities are respectively as follows: at 10 mA/cm2The battery voltage of the alloy is 1.42V and the power density is 14.2 mW/cm under the current density of (2)2At 120 mA/cm2The battery voltage of the alloy is 0.65V and the power density is 78.0 mW/cm2。
FIG. 4 is a metallographic microstructure (ED-TD plane) of an Mg-2.0Bi-0.5Ca-0.1In alloy material prepared In example 2. As can be seen from the figure, the dynamic recrystallization grains of the alloy structure are relatively fine, and the combination of the figure 3 and the figure 5 confirms that the matrix contains a large amount of nano-scale Mg distributed in a dispersed way3Bi2And micron-sized Mg2Bi2A Ca reinforcing phase.
Example 3
High-purity magnesium ingot (Mg purity is 99.99%), high-purity bismuth (Bi purity is 99.99%), high-purity indium (In purity is 99.99%), and Mg-30% Ca intermediate alloy are adopted, and the alloy components are mixed according to Mg-2Bi-0.5Ca-0.5In (mass fraction), namely the mass percentages are respectively: mg 97%, Bi 2.0%, Ca 0.5%, and In 0.5% (In this mass percentage, reasonable impurities are not considered, and when selecting the raw material, the raw material with less impurities should be selected as much as possible).
Step one, preparing a blank: when smelting, firstly adding a high-purity magnesium ingot into a resistance furnace, and heating under a protective gas environment; n is introduced when the temperature of the furnace rises to 300 DEG C2Mixed gas of Ar, N2And Ar in a volume ratio of 6: 2; keeping the temperature for 30 minutes when the temperature is increased to 740 ℃; adding bismuth, indium and Mg-Ca intermediate alloy after the magnesium ingot is melted, heating to 740 ℃, preserving heat for 30 minutes, and then refining with RJ-2 type magnesium alloy refining agent at 740 DEG CRefining, wherein the addition amount of a refining agent is 2% of the mass of the melt, stirring for 5 minutes, standing for 30 minutes, and then casting into a metal mold at 740 ℃; the preheating temperature of the die is 200 ℃, and the refining method is well known to those skilled in the art.
Step two, forward extrusion: and (4) directly machining the blank obtained by casting in the step one to obtain an extruded blank with the diameter of 60 mm and the height of 55 mm. And then polishing the surface of the blank by using sand paper to be bright, preserving the heat of the blank for 30 min at 310 ℃ before extrusion, wherein the extrusion process parameters are as follows: the extrusion temperature is 310 ℃, the extrusion rate is 0.1 mm/s, the extrusion ratio is 25: 1, and finally the extrusion bar with the diameter of 12 mm is obtained.
When the alloy material prepared by the method is used for testing a half cell, the discharge potential and the utilization rate measured under different current densities are respectively as follows: at 10 mA/cm2The discharge potential of the alloy is-1.66V, the anode efficiency is 46.74%, and the discharge current is 120 mA/cm2The discharge potential of the alloy was-1.58V at a current density of (2), and the utilization rate was 74.22%. When the alloy material is used for the performance test of the full cell, the cell voltage and the power density of the alloy cathode measured under different current densities are respectively as follows: at 10 mA/cm2The battery voltage of the alloy is 1.48V and the power density is 14.8 mW/cm under the current density of (2)2At 120 mA/cm2The battery voltage of the alloy is 0.72V and the power density is 86.4 mW/cm under the current density of (2)2。
FIG. 6 is a metallographic microstructure (ED-TD plane) of an Mg-2.0Bi-0.5Ca-0.5In alloy material prepared In example 3. As can be seen from the figure, the dynamic recrystallization grains of the alloy structure are relatively fine, and as can be seen from figure 7, the matrix contains a large amount of nano-Mg which is dispersed and distributed3Bi2And micron-sized Mg2Bi2A Ca reinforcing phase.
Half-cell performance tests were conducted on the experimental alloys in the three examples above and were determined to be at 10 mA/cm2And 120 mA/cm2Discharge potential and utilization rate at current density of (a); the experimental alloy cathode is subjected to full battery performance test, and the battery performance is measured to be 10 mA/cm2And 120 mA/cm2Voltage and power of the battery at a current density ofDensity. The results are summarized in Table 2.
TABLE 2 half-cell and full-cell test Performance of each experimental alloy
Claims (9)
1. A magnesium-air battery negative electrode material Mg-Bi-Ca-In alloy is characterized In that: comprises the following components in percentage by weight: mg: 96.4 to 98.0wt.%, Bi: 1.8-2.2 wt.%, Ca: 0.1-0.7 wt.%, In: 0.1-0.7 wt.% of Mg dispersed on the alloy matrix3Bi2And Mg2Bi2Ca reinforcing phase and uniform equiaxed crystal structure.
2. A preparation method of the Mg-Bi-Ca-In alloy of the magnesium air battery negative electrode material In the claim 1 is characterized by comprising the following steps:
step one, preparing a blank: pure Mg, pure Bi, pure In and Mg-30 percent Ca intermediate alloy with the purity of more than 99.9 percent are put into a graphite crucible according to the proportion and are smelted by a crucible resistance furnace, and N is adopted In the smelting process2Protecting the liquid level with Ar mixed gas, preserving heat for 20-30 minutes at 730-740 ℃ after all alloy elements are melted, adding a magnesium alloy refining agent into the melted alloy liquid for refining after heat preservation, standing for 20-35 minutes after refining is finished, and pouring the molten liquid into a metal mold at 725-740 ℃ to obtain a cylindrical sample blank;
secondly, extrusion deformation: directly machining the cast blank to prepare an extruded blank, wherein the diameter of the extruded blank is 55-60 mm, the height of the extruded blank is 50-55 mm, and the blank is subjected to heat preservation at 280-320 ℃ for 20-60 minutes before extrusion to obtain an extruded bar with the diameter of 12 mm.
3. The preparation method of the Mg-Bi-Ca-In alloy as the negative electrode material of the magnesium-air battery as claimed In claim 2, wherein: n in the mixed gas2And the volume ratio of Ar to Ar is 6: 1-2.
4. The preparation method of the Mg-Bi-Ca-In alloy as the negative electrode material of the magnesium-air battery as claimed In claim 2, wherein: the addition amount of the magnesium alloy refining agent is 1-2% of the mass of the smelted alloy.
5. The preparation method of the Mg-Bi-Ca-In alloy as the negative electrode material of the magnesium-air battery as claimed In claim 2, wherein: the diameter of the cylindrical sample blank is 60 mm, and the used metal mold is preheated to 180-200 ℃ before casting.
6. The preparation method of the Mg-Bi-Ca-In alloy as the negative electrode material of the magnesium-air battery as claimed In claim 2, wherein: the technological parameters of the extrusion are as follows: the extrusion temperature is 280-320 ℃, the extrusion rate is 0.09-0.11 mm/s, and the extrusion ratio is 25: 1.
7. Use of the Mg-Bi-Ca-In alloy as the negative electrode material of the magnesium-air battery In the magnesium-air battery negative electrode material.
8. Use according to claim 7, characterized in that: in a half-cell test, an experimental alloy is taken as a working electrode, a platinum electrode is taken as a counter electrode, a saturated calomel electrode is taken as a reference electrode on an electrochemical workstation, and the discharge potential and the utilization rate of the experimental alloy under constant current density are measured by a chronopotentiometry method;
in a half-cell performance test, the discharge potential under low current density is-1.63 to-1.66V, and the utilization rate is 40 to 47 percent; the discharging potential under the large current density is-1.45 to-1.60V, and the utilization rate is 64 to 75 percent.
9. Use according to claim 7, characterized in that: in the performance test of the full battery, the experimental alloy is taken as a negative electrode material, MnO2The commercial electrode using the/C as the catalyst is used as a positive electrode material, a 3.5 wt.% NaCl solution is used as an electrolyte to assemble the magnesium-air battery, and the battery voltage and the power density of the experimental alloy under the constant current density are measured;
at full powerIn the cell performance test, the discharge potential under low current density is 1.35-1.50V, and the power density is 13.5-15.0 mW/cm2(ii) a The discharge potential under heavy current density is 0.60-0.75V, and the power density is 13.5-15.0 mW/cm2。
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| CN114107771A (en) * | 2021-11-30 | 2022-03-01 | 东北大学 | Anode material suitable for high-power magnesium air battery at low temperature and preparation method thereof |
| CN114606418A (en) * | 2022-01-26 | 2022-06-10 | 广东工业大学 | Mg-Bi-In-Y anode material of magnesium air battery and preparation method and application thereof |
| CN114990400A (en) * | 2022-06-07 | 2022-09-02 | 山西瑞格金属新材料有限公司 | Magnesium alloy negative electrode material and preparation method and application thereof |
| CN115786790A (en) * | 2022-12-14 | 2023-03-14 | 中国电子科技集团公司第十八研究所 | Seawater corrosion resistant high-current efficiency Mg-Ca-In magnesium alloy and preparation method thereof |
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| CN114990400A (en) * | 2022-06-07 | 2022-09-02 | 山西瑞格金属新材料有限公司 | Magnesium alloy negative electrode material and preparation method and application thereof |
| CN115786790A (en) * | 2022-12-14 | 2023-03-14 | 中国电子科技集团公司第十八研究所 | Seawater corrosion resistant high-current efficiency Mg-Ca-In magnesium alloy and preparation method thereof |
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