CN116024470B - Magnesium-silver alloy and preparation method and application thereof - Google Patents
Magnesium-silver alloy and preparation method and application thereof Download PDFInfo
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- CN116024470B CN116024470B CN202211545907.7A CN202211545907A CN116024470B CN 116024470 B CN116024470 B CN 116024470B CN 202211545907 A CN202211545907 A CN 202211545907A CN 116024470 B CN116024470 B CN 116024470B
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- 229910001316 Ag alloy Inorganic materials 0.000 title claims abstract description 39
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 66
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 62
- 239000010405 anode material Substances 0.000 claims abstract description 10
- 230000002902 bimodal effect Effects 0.000 claims abstract description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 47
- 239000000956 alloy Substances 0.000 claims description 47
- 238000007670 refining Methods 0.000 claims description 36
- 238000003723 Smelting Methods 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 29
- 229910052709 silver Inorganic materials 0.000 claims description 29
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 27
- 239000004332 silver Substances 0.000 claims description 27
- 239000012298 atmosphere Substances 0.000 claims description 25
- 230000001681 protective effect Effects 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 24
- 239000006104 solid solution Substances 0.000 claims description 22
- 238000002844 melting Methods 0.000 claims description 18
- 230000008018 melting Effects 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 238000004321 preservation Methods 0.000 claims description 9
- 238000000265 homogenisation Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- 238000007086 side reaction Methods 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 4
- 230000000903 blocking effect Effects 0.000 abstract description 2
- 230000001808 coupling effect Effects 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 238000001125 extrusion Methods 0.000 description 17
- 239000002245 particle Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- 238000010791 quenching Methods 0.000 description 11
- 230000000171 quenching effect Effects 0.000 description 11
- 239000002893 slag Substances 0.000 description 11
- 229910000861 Mg alloy Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000005498 polishing Methods 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000005266 casting Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910004261 CaF 2 Inorganic materials 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 3
- 229910001626 barium chloride Inorganic materials 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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Abstract
The invention relates to the technical field of electrode materials, in particular to a magnesium-silver alloy and a preparation method and application thereof. The invention provides a magnesium-silver alloy, which comprises the following components in percentage by mass: mg:99.70 to 99.80 percent, ag:0.30 to 0.20 percent; the magnesium-silver alloy includes a bimodal structure consisting of equiaxed grains and elongated deformed grains. According to the invention, the generation of hydrogen evolution side reaction is inhibited by utilizing the high hydrogen evolution overpotential of Ag in the magnesium-silver alloy, meanwhile, ag has high solid solubility in a magnesium matrix, so that the precipitation of a dynamic precipitated phase (second phase) can be effectively inhibited, and the micro-electric coupling effect between the second phase and the magnesium matrix is reduced, thereby reducing the hydrogen evolution side reaction. The magnesium-silver alloy provided by the invention has a bimodal structure consisting of equiaxed grains and elongated deformed grains, so that the blocking effect is effectively inhibited, and the discharge efficiency of the anode material is further improved.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a magnesium-silver alloy and a preparation method and application thereof.
Background
The magnesium air battery takes an air electrode as an anode, metal magnesium or magnesium alloy as a cathode, neutral aqueous solution is taken as electrolyte, O 2 in the air reaches a gas-solid-liquid three-phase interface through a gas diffusion electrode to react with metal Mg to release electric energy, and the product is nontoxic and recyclable and is an ideal battery system. The battery system has the advantages of rich material sources, high energy density, high reliability, safety, no pollution, low price and the like, and has wide application prospect.
However, in the practical use process, after the magnesium negative electrode material is contacted with the electrolyte, serious hydrogen evolution side reaction usually occurs in the discharge process, and the anode material is corroded, so that the anode efficiency discharge is reduced.
Disclosure of Invention
In view of the above, the invention provides a magnesium-silver alloy, a preparation method and application thereof, and the magnesium-silver alloy provided by the invention can reduce hydrogen evolution side reaction of anode materials and improve anode discharge efficiency when being used as the anode materials of magnesium air batteries.
In order to solve the problems, the invention provides a magnesium-silver alloy which comprises the following components in percentage by mass: mg:99.70 to 99.80 percent, ag:0.30 to 0.20 percent;
The magnesium-silver alloy includes a bimodal structure consisting of equiaxed grains and elongated deformed grains.
Preferably, the size of the equiaxed grains is 8.08-8.64 μm; the aspect ratio of the elongated deformed crystal grains is 6.54-6.75: 1.
The invention also provides a preparation method of the magnesium-silver alloy, which comprises the following steps:
Mixing a magnesium raw material and a silver raw material, smelting in a protective atmosphere, and forming an obtained alloy smelting liquid to obtain a prealloyed ingot;
And sequentially carrying out homogenization treatment and deformation treatment on the prealloy cast ingot to obtain the magnesium-silver alloy.
Preferably, the step of smelting comprises the steps of:
Melting a magnesium raw material in a protective atmosphere to obtain a magnesium solution;
and mixing the magnesium solution and the silver raw material, and sequentially melting and refining under a protective atmosphere to obtain alloy smelting solution.
Preferably, the melting temperature is 700-730 ℃ and the heat preservation time is 20-30 min.
Preferably, the melting temperature is 720-730 ℃, and the heat preservation time is 20-30 min.
Preferably, the refining temperature is 745-755 ℃, and the heat preservation time is 20-30 min.
Preferably, the homogenization treatment is solution treatment; the solid solution treatment comprises a first solid solution treatment and a second solid solution treatment which are sequentially carried out; the temperature of the primary solid solution treatment is 310-330 ℃, and the heat preservation time is 1-1.5 h; the temperature of the secondary solid solution treatment is 480-520 ℃ and the heat preservation time is 3-4 h.
Preferably, the deformation treatment is a mechanical working and a pressing in sequence.
The invention also provides application of the magnesium-silver alloy and the magnesium-silver alloy obtained by the preparation method in serving as an anode material in a magnesium air battery.
The invention provides a magnesium-silver alloy, which comprises the following components in percentage by mass: mg:99.70 to 99.80 percent, ag:0.30 to 0.20 percent; the magnesium-silver alloy includes a bimodal structure consisting of equiaxed grains and elongated deformed grains. According to the invention, the generation of hydrogen evolution side reaction is inhibited by utilizing the high hydrogen evolution overpotential of Ag in the magnesium-silver alloy, meanwhile, ag has high solid solubility in a magnesium matrix, so that the precipitation of a dynamic precipitated phase (second phase) can be effectively inhibited, and the micro-electric coupling effect between the second phase and the magnesium matrix is reduced, thereby reducing the hydrogen evolution side reaction. The magnesium-silver alloy provided by the invention has a bimodal structure consisting of equiaxed grains and elongated deformed grains, so that the blocking effect is effectively inhibited, and the discharge efficiency of the anode material is further improved.
The example data shows that at a current density of 5mAcm -2, the discharge voltage reaches 1.4485V, the anode utilization reaches 51.14%, and the specific discharge capacity and specific energy reach 1126.126mAhg -1 and 1631.1937mWhg -1, respectively.
Drawings
FIG. 1 is a metallographic microstructure of a magnesium-silver alloy anode material prepared in example 1;
FIG. 2 is an SEM micrograph of a magnesium-silver alloy negative electrode material prepared in example 1;
FIG. 3 is an XRD pattern of the magnesium-silver alloy anode material prepared in example 1;
FIG. 4 is a potentiodynamic curve of the magnesium-silver alloy negative electrode material prepared in example 1 in a 3.5wt% NaCl solution.
Detailed Description
The invention provides a magnesium-silver alloy, which comprises the following components in percentage by mass:
Mg：99.70～99.80％，Ag：0.30～0.20％；
The magnesium-silver alloy includes a bimodal structure consisting of equiaxed grains and elongated deformed grains.
In the invention, the magnesium-silver alloy comprises 99.70-99.80% of Mg by mass percent, preferably 99.75%.
In the invention, the magnesium-silver alloy comprises 0.30-0.20% of Ag by mass percent, and preferably 0.25% of Ag by mass percent.
In the present invention, the magnesium-silver alloy includes a bimodal structure consisting of equiaxed grains and elongated deformed grains. In the present invention, the size of the equiaxed grains is preferably 8.08 to 8.64 μm, more preferably 8.36 μm; the aspect ratio of the elongated deformed crystal grains is 6.54-6.75: 1, more preferably 6.36:1.
The invention also provides a preparation method of the magnesium-silver alloy, which comprises the following steps:
Mixing a magnesium raw material and a silver raw material, smelting in a protective atmosphere, and forming an obtained alloy smelting liquid to obtain a prealloyed ingot;
And sequentially carrying out homogenization treatment and deformation treatment on the prealloy cast ingot to obtain the magnesium-silver alloy.
The magnesium raw material and the silver raw material are mixed and smelted in a protective atmosphere, and the obtained alloy smelting liquid is molded to obtain a prealloy cast ingot.
In the invention, the mass ratio of the magnesium raw material to the silver raw material is preferably 99.70-99.80: 0.30 to 0.20, more preferably 99.75:0.25.
In the present invention, the smelting step preferably includes the steps of:
Melting a magnesium raw material in a protective atmosphere to obtain a magnesium solution;
and mixing the magnesium raw material and the silver raw material, and sequentially melting and refining under a protective atmosphere to obtain alloy smelting liquid.
The invention melts the magnesium raw material under the protective atmosphere to obtain the magnesium liquid.
In the present invention, before smelting, the method preferably further comprises polishing the magnesium block, and the polishing is preferably grinding wheel polishing. In the invention, before smelting, the method preferably further comprises preheating the polished magnesium blocks, wherein the preheating temperature is preferably 200 ℃, and the preheating time is preferably 30min. In the present invention, the preheating is preferably performed in a forced air drying oven.
In the present invention, the magnesium material is preferably magnesium block. In the present invention, the purity of the magnesium block is preferably > 99.99%. In the invention, the protective atmosphere is preferably a mixed gas of CO 2 and SF 6, and the volume ratio of CO 2 to SF 6 in the mixed gas is preferably 40:1.
In the present invention, the melting temperature is preferably 700 to 730 ℃, more preferably 710 to 720 ℃, and the holding time is preferably 20 to 30min, more preferably 25min.
In the present invention, it is preferable that the melting further includes a slag removing treatment. In the invention, the surface of the slag removing tool for removing slag is preferably coated with a paint. The paint comprises the following components in parts by mass: 22 to 23 parts of zinc oxide, more preferably 22.5 parts; 110 to 130 parts of water, more preferably 120 parts; 22 to 23 parts of water glass, more preferably 22.5 parts. In the present invention, the number of the brushing is preferably 2 to 3. In the invention, the slag removing treatment can remove impurities on the surface of magnesium. In the present invention, the pre-slagging process preferably further includes preheating the slagging-off tool, and the preheating is preferably performed with the preheating of the magnesium block, which is not described herein.
After the magnesium solution is obtained, the magnesium raw material and the silver raw material are mixed, and are sequentially melted and refined in a protective atmosphere to obtain the alloy smelting solution.
In the present invention, the refining is preferably preceded by preheating the silver raw material, and the preheating is preferably the same as the preheating of the magnesium raw material, and will not be described herein. In the present invention, the particle diameter of the silver raw material is preferably 0.5 to 1mm, more preferably 0.6 to 0.8m. In the present invention, the purity of the silver raw material is preferably not less than 99.99%.
In the present invention, the melting temperature is preferably 720 to 730 ℃, more preferably 725 to 730 ℃, and the holding time is preferably 20 to 30min, more preferably 25min.
In the present invention, the refining is preferably performed under the condition of a refining agent, which preferably includes MgCl 2、KCl、BaCl2 and CaF 2. In the present invention, the mass of the refining agent is preferably 1 to 2% of the total mass of the magnesium block and the silver particles, more preferably 1.5%. In the present invention, 46wt% MgCl 2、41wt％KCl、8wt％BaCl2 and 5wt% CaF 2 are preferably included in the refining agent. In the present invention, the refining agent preferably further comprises preheating before refining, and the preheating is preferably the same as preheating of silver particles, and is not described in detail herein.
In the present invention, the refining temperature is preferably 745 to 755 ℃, more preferably 750 ℃, and the holding time is preferably 20 to 30min, more preferably 25min. In the present invention, the refining is preferably performed in a protective atmosphere.
In the present invention, it is preferable that the refining further includes skimming.
After the alloy smelting liquid is obtained, the obtained alloy smelting liquid is molded to obtain a prealloyed cast ingot.
In the present invention, the molding is preferably casting molding. In the present invention, the casting molding is preferably performed in a casting mold. In the present invention, a protective atmosphere is preferably introduced into the casting mold before the casting molding.
After the prealloy cast ingot is obtained, the prealloy cast ingot is sequentially subjected to homogenization treatment and deformation treatment, and the magnesium-silver alloy is obtained.
In the present invention, the mode of the homogenization treatment is a solution treatment, and the solution treatment preferably includes a primary solution treatment and a secondary solution treatment which are sequentially performed. In the invention, the temperature of the primary solid solution treatment is preferably 310-330 ℃, more preferably 320 ℃, and the heat preservation time is preferably 1-1.5 h, more preferably 1.2-1.4 h; the temperature of the secondary solid solution treatment is preferably 500-550 ℃, more preferably 510-540 ℃, and the heat preservation time is preferably 3-4 h, more preferably 3.2-3.5 h. In the present invention, the solution treatment is preferably performed under an inert atmosphere, preferably argon.
The invention can solid-solution the precipitated coarse second phase into the alloy through the double-stage solid-solution treatment.
In the present invention, it is preferable that the second-stage solution treatment is further followed by water quenching. The water quenching is not particularly limited, and may be performed by operations well known to those skilled in the art.
In the present invention, the water quenching preferably further comprises polishing the pre-alloyed ingot after water quenching, the polishing is not particularly limited, and the polishing is performed by polishing to remove the oxide skin and surface defects by using operations well known in the art.
In the present invention, the deformation treatment is preferably a mechanical working and a pressing performed sequentially. In the present invention, the machining is preferably machining the pre-alloyed ingot after water quenching into a pre-alloyed ingot having a diameter of 40mm and a height of 40mm or a pre-alloyed ingot having a diameter of 60mm and a height of 50 mm. In the present invention, the conditions of the extrusion include: the extrusion speed is preferably 0.1 mm.s -1, and the extrusion temperature is preferably 240-260 ℃, more preferably 250 ℃; the extrusion ratio is preferably 16 to 25:1, more preferably 20:1.
In the invention, the extrusion can realize grain refinement, and the comprehensive performance of the alloy is improved.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The magnesium and silver materials involved in the examples and comparative examples were dried in a forced air drying oven at 200 c for 30min, the crucible was preheated at 400 c for 30min, and the surfaces of the crucible, stirring rod, and slag-off tool were all painted 3 times with the paint. Wherein the coating comprises 22.5g zinc oxide, 120mL water and 22.5g water glass. The protective atmosphere is mixed gas of CO 2 and SF 6 in a volume ratio of 40:1. The refining agent consists of 46wt% of MgCl 2、41wt％KCl、8wt％BaCl2 and 5wt% of CaF 2. The model of the heat treatment furnace is OTF-1200X.
Example 1
Firstly, placing 99.75 parts by mass of magnesium blocks in a crucible, introducing protective atmosphere, melting at 710 ℃ for 25min, and slagging off to obtain magnesium liquid;
adding silver particles (with the particle size of 0.5 mm) into the magnesium solution, melting for 30min at the temperature of 720 ℃ to enable the silver particles to fully diffuse in the magnesium solution, homogenizing alloy components, and removing slag to obtain alloy smelting solution.
Adding a refining agent into the alloy smelting liquid, refining for 30min at 750 ℃, wherein the adding amount of the refining agent is 1.5% of the total mass of magnesium blocks and silver particles, and stirring the alloy liquid vigorously in the refining process until the alloy smelting liquid surface presents a mirror surface.
After refining, the scum on the surface of the melt is salvaged, and alloy smelting liquid is poured into a metal mold preheated to 200 ℃ in advance under protective atmosphere to obtain a cylindrical sample blank. And opening the die after the ingot is solidified and cooled to obtain the prealloyed ingot.
And (3) placing the prealloyed ingot in a heat treatment furnace under the argon atmosphere, preserving heat at 320 ℃ for 1h (primary solid solution treatment), then heating to 500 ℃, preserving heat for 3h (secondary solid solution treatment), and carrying out water quenching after the secondary solid solution treatment.
After the pre-alloy cast ingot after water quenching is machined into a pre-alloy cast ingot with the diameter of 40mm and the height of 40mm, the pre-alloy cast ingot is extruded at the temperature of 250 ℃ at the extrusion speed of 0.1 mm.s -1 and the extrusion ratio of 16:1, and the extrusion bar with the diameter of 8mm is obtained.
Fig. 1 is a metallographic microstructure of the magnesium alloy prepared in example 1, and as can be seen from fig. 1: the magnesium alloy prepared in example 1 consists of equiaxed grains and elongated deformed grains, and the grain size of the equiaxed grains is 8.36+/-0.28 mu m according to Nonomeasure test software, and the length-width ratio of the elongated deformed grains is 6.54-6.75: 1.
Fig. 2 to 3 are SEM microstructure and XRD pattern of the magnesium alloy prepared in example 1, respectively, as can be seen from fig. 2 to 3: no dynamic precipitate phase was observed in the magnesium alloy prepared in example 1.
The electrochemical behavior of the magnesium alloy prepared in example 1 was also tested using a standard three-electrode system, the test method being: the three-electrode system consists of a working electrode, a reference electrode and an auxiliary electrode, which are respectively and correspondingly a magnesium alloy anode, a saturated calomel electrode and a platinum sheet, and the electrolyte is 3.5wt% NaCl solution. Potentiodynamic polarization curves from-2.0V to-1.0V (vs SCE) were recorded at a scan rate of 1mVs -1, and as a result, see FIG. 4, combined with CorShow software, a polarization curve anodic branch slope of 6.19, a polarization curve cathodic branch slope of 315.61, and a corrosion current density of 40.561 μA/cm 2 were obtained.
The invention also adopts NEWARE battery test system (CT-4008-5V 6A) and self-made battery mould to test the discharge performance of the magnesium-silver alloy prepared in example 1 as anode material. The air cathode adopts a B20 air breathing cathode produced by Changzhou Utility new energy science, inc. and adopts a MnO 2/C catalyst. The electrolyte was a 3.5wt.% NaCl solution, the distance of the magnesium anode from the air cathode being kept at 5mm. The test area of all samples was 1cm 2 and the sample thickness was 5mm. The sample is soaked in electrolyte for 15min before the test, then the current density of 5mAcm -2 is applied to the alloy, and the discharge is carried out for 10h, so that the average discharge voltage is obtained. After discharge, the samples were weighed separately and mass loss methods were used to calculate the anode efficiency, specific capacity density and specific energy density of the alloy. The calculation formula is as follows:
Wherein Mt and Ma are theoretical mass loss and actual mass loss in the discharge process respectively, and the calculation method of Mt is as follows:
wherein I, t, U and F are applied current (a), discharge time(s), cell voltage (V) and faraday constant (96485 Cmol -1),xi、ni and m i are mass fraction, ionic valence and atomic weight of the alloying elements in the material, respectively.
The test results are: at a current density of 5mAcm -2, the discharge voltage reaches 1.4485V, the anode utilization rate reaches 51.14%, and the specific discharge capacity and specific energy reach 1126.126mAhg -1 and 1631.1937mWhg -1 respectively.
Example 2
Firstly, 99.7 parts by mass of magnesium blocks are placed in a crucible, protective atmosphere is introduced, and after the magnesium blocks are melted at 700 ℃ for 25min, slag is removed, so that magnesium liquid is obtained.
And adding silver particles into the magnesium solution, melting for 25min at the temperature of 730 ℃ to enable the silver particles to fully diffuse in the magnesium solution, homogenizing alloy components, and removing slag to obtain alloy smelting solution.
Adding a refining agent into the alloy smelting liquid, refining for 30min at 750 ℃, wherein the adding amount of the refining agent is 1.5% of the total mass of magnesium blocks and silver particles, and stirring the alloy liquid vigorously in the refining process until the alloy smelting liquid surface presents a mirror surface.
After refining, the scum on the surface of the melt is salvaged, and alloy smelting liquid is poured into a metal mold preheated to 200 ℃ in advance under protective atmosphere to obtain a cylindrical sample blank. And opening the die after the ingot is solidified and cooled to obtain the prealloyed ingot.
And (3) placing the obtained pre-alloy ingot into a heat treatment furnace under the argon atmosphere, preserving heat at 310 ℃ for 1.5h (primary solid solution treatment), then heating to 550 ℃, preserving heat for 3h (secondary solid solution treatment), and then carrying out water quenching.
After the pre-alloy cast ingot after water quenching is machined into a pre-alloy cast ingot with the diameter of 40mm and the height of 40mm, the pre-alloy cast ingot is extruded at the temperature of 250 ℃ at the extrusion speed of 0.1 mm.s -1 and the extrusion ratio of 16:1, and the extrusion bar with the diameter of 8mm is obtained.
Example 3
Firstly, 99.75 parts by mass of magnesium blocks are placed in a crucible, protective atmosphere is introduced, and after the magnesium blocks are melted at 720 ℃ for 25min, slag is removed, so that magnesium liquid is obtained.
And adding silver particles into the magnesium solution, melting for 30min at the temperature of 720 ℃ to enable the silver particles to fully diffuse in the magnesium solution, homogenizing alloy components, and removing slag to obtain alloy smelting solution.
Adding a refining agent into the alloy smelting liquid, refining for 30min at 750 ℃, wherein the adding amount of the refining agent is 1.5% of the total mass of magnesium blocks and silver particles, and stirring the alloy liquid vigorously in the refining process until the alloy smelting liquid surface presents a mirror surface.
After refining, the scum on the surface of the melt is salvaged, and alloy smelting liquid is poured into a metal mold preheated to 200 ℃ in advance under protective atmosphere to obtain a cylindrical sample blank. And opening the die after the cast ingot is solidified and cooled to obtain a prealloy cast ingot with the diameter of 60mm and the height of 50 mm.
And (3) placing the prealloyed ingot in a heat treatment furnace under the argon atmosphere, preserving heat at 330 ℃ for 1h (primary solid solution treatment), then heating to 530 ℃, preserving heat for 3h (secondary solid solution treatment), and carrying out water quenching after the secondary solid solution treatment.
After the water quenched prealloyed ingot is machined into a prealloyed ingot with the diameter of 60mm and the height of 50mm, the prealloyed ingot is extruded at the temperature of 250 ℃ at the extrusion speed of 0.1 mm.s -1 and the extrusion ratio of 25:1, and the extrusion bar with the diameter of 8mm is obtained.
Comparative example 1
Smelting into ingots:
Firstly, 99.7 parts by mass of magnesium blocks are placed in a crucible, protective atmosphere is introduced, and after the magnesium blocks are melted for 25min at 700 ℃, slag is removed, so that magnesium liquid is obtained.
And adding silver particles into the magnesium solution, melting for 30min at the temperature of 720 ℃ to enable the silver particles to fully diffuse in the magnesium solution, homogenizing alloy components, and removing slag to obtain alloy smelting solution.
Adding a refining agent into the alloy smelting liquid, refining for 30min at 750 ℃, wherein the adding amount of the refining agent is 1.5% of the total mass of magnesium blocks and silver particles, and stirring the alloy liquid vigorously in the refining process until the alloy smelting liquid surface presents a mirror surface.
After refining, the scum on the surface of the melt is salvaged, and alloy smelting liquid is poured into a metal mold preheated to 200 ℃ in advance under protective atmosphere to obtain a cylindrical sample blank. And opening the die after the ingot is solidified and cooled to obtain the prealloyed ingot.
Machining the pre-alloy cast ingot after water quenching into a pre-alloy cast ingot with the diameter of 40mm and the height of 40mm, and extruding the cast ingot at the extrusion speed of 0.1 mm.s -1 and the extrusion ratio of 16:1 at the temperature of 250 ℃ to obtain an extrusion bar with the diameter of 8 mm.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The magnesium-silver alloy is characterized by comprising the following components in percentage by mass:
Mg：99.70～99.80％，Ag：0.30～0.20％；
the magnesium-silver alloy comprises a bimodal structure consisting of equiaxed grains and elongated deformed grains; the size of the equiaxed grains is 8.08-8.64 mu m; the aspect ratio of the elongated deformed crystal grains is 6.54-6.75: 1.
2. The method for preparing the magnesium-silver alloy according to claim 1, comprising the steps of:
Mixing a magnesium raw material and a silver raw material, smelting in a protective atmosphere, and forming an obtained alloy smelting liquid to obtain a prealloyed ingot;
And sequentially carrying out homogenization treatment and deformation treatment on the prealloy cast ingot to obtain the magnesium-silver alloy.
3. The method of producing according to claim 2, characterized in that the step of smelting comprises the steps of:
Melting a magnesium raw material in a protective atmosphere to obtain a magnesium solution;
and mixing the magnesium solution and the silver raw material, and sequentially melting and refining under a protective atmosphere to obtain alloy smelting solution.
4. The method according to claim 3, wherein the melting temperature is 700 to 730 ℃ and the holding time is 20 to 30min.
5. The method according to claim 3, wherein the melting temperature is 720-730 ℃ and the holding time is 20-30 min.
6. The method according to claim 3, wherein the refining temperature is 745-755 ℃ and the holding time is 20-30 min.
7. The method according to claim 2, wherein the homogenization treatment is a solution treatment; the solid solution treatment comprises a first solid solution treatment and a second solid solution treatment which are sequentially carried out; the temperature of the primary solid solution treatment is 310-330 ℃, and the heat preservation time is 1-1.5 h; the temperature of the secondary solid solution treatment is 480-520 ℃ and the heat preservation time is 3-4 h.
8. The method according to claim 2, wherein the deforming treatment is a mechanical working and a pressing in this order.
9. The magnesium-silver alloy of claim 1 and the use of the magnesium-silver alloy prepared by the preparation method of claims 2-8 as anode materials in magnesium air batteries.
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| SE307393B (en) * | 1966-01-12 | 1969-01-07 | Asea Ab | |
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| KR20100033563A (en) * | 2008-09-22 | 2010-03-31 | 지성중공업 주식회사 | Air - magnesium battery |
| US8709127B2 (en) * | 2010-02-12 | 2014-04-29 | GM Global Technology Operations LLC | Porous dendritic platinum tubes as fuel cell electrocatalysts |
| CN103190031B (en) * | 2011-08-02 | 2015-05-13 | 一般社团法人铃魏 | Magnesium metal-air battery |
| JP6032018B2 (en) * | 2012-01-19 | 2016-11-24 | 日産自動車株式会社 | Injection metal-air battery |
| JP6099257B2 (en) * | 2013-02-07 | 2017-03-22 | 国立研究開発法人物質・材料研究機構 | Magnesium-based alloy thin plate and foil material and method for producing them |
| WO2014205553A1 (en) * | 2013-06-28 | 2014-12-31 | Boom Energy Inc. | Anode element for electrochemical reactions |
| JP2015046368A (en) * | 2013-08-29 | 2015-03-12 | 古河電池株式会社 | Magnesium battery |
| JP6161589B2 (en) * | 2013-12-16 | 2017-07-12 | 木ノ本伸線株式会社 | Joining material, joining structure of magnesium (Mg) alloy material and filler material, joining method by fusion welding of magnesium (Mg) alloy material, magnesium (Mg) alloy material joining structure, and magnesium (Mg) alloy material joining Manufacturing method of structure |
| JP5847283B1 (en) * | 2014-12-03 | 2016-01-20 | 充 吉川 | Magnesium-air battery with multiple cells |
| US10752515B2 (en) * | 2015-03-23 | 2020-08-25 | Council Of Scientific & Industrial Research | Lithium-substituted magnesium ferrite material based hydroelectric cell and process for preparation thereof |
| JP2017168226A (en) * | 2016-03-14 | 2017-09-21 | 株式会社倉元製作所 | Magnesium battery and method for manufacturing the same |
| CN111793760B (en) * | 2020-07-17 | 2021-10-26 | 广东省科学院新材料研究所 | Anode alloy material for magnesium air battery, preparation method thereof and battery |
| CN113718147B (en) * | 2021-07-19 | 2022-06-03 | 南通大学 | Multi-element alloy anode material for magnesium air battery and preparation method thereof |
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