阅读说明：本技术 一种铝合金阳极材料及制备方法 (Aluminum alloy anode material and preparation method thereof ) 是由 童汇 李林 于 2021-11-01 设计创作，主要内容包括：一种铝合金阳极材料及制备方法,所述铝合金阳极材料包括以下质量百分数的组分：Mg 0.5～1.0%,Hg 0.01～0.20%,Ga 0.01～0.20%,Sn 0.02～0.20%,Pb 0.01～0.10%,Sb 0.02～0.20%,Ce 0.02～0.40%,余为Al。本发明方法还公开了所述铝合金阳极材料的制备方法。本发明铝合金阳极材料高活性、抗极化、电压平台高、析氢量低；本发明方法所得铝合金阳极材料抗腐蚀性强,工艺简单,成本低,适宜于工业化生产。(An aluminum alloy anode material and a preparation method thereof are disclosed, wherein the aluminum alloy anode material comprises the following components in percentage by mass: 0.5-1.0% of Mg, 0.01-0.20% of Hg, 0.01-0.20% of Ga, 0.02-0.20% of Sn, 0.01-0.10% of Pb, 0.02-0.20% of Sb, 0.02-0.40% of Ce and the balance of Al. The invention also discloses a preparation method of the aluminum alloy anode material. The aluminum alloy anode material has high activity, polarization resistance, high voltage platform and low hydrogen evolution amount; the aluminum alloy anode material obtained by the method has strong corrosion resistance, simple process and low cost, and is suitable for industrial production.)

1. The aluminum alloy anode material is characterized by comprising the following components in percentage by mass: 0.5-1.0% of Mg, 0.01-0.20% of Hg, 0.01-0.20% of Ga, 0.02-0.20% of Sn, 0.01-0.10% of Pb, 0.02-0.20% of Sb, 0.02-0.40% of Ce and the balance of Al.

2. A method for producing an aluminum alloy anode material according to claim 1, comprising the steps of:

(1) preparing Mg-Hg-Ga intermediate alloy;

(2) heating and insulating a pure aluminum block, heating and smelting, sequentially adding Sn, Pb, Sb, Ce and the Mg-Hg-Ga intermediate alloy obtained in the step (1) into aluminum liquid, carrying out heat-insulating smelting in the process of introducing protective gas, carrying out modification treatment along with furnace cooling, filtering, and pouring to obtain an alloy ingot;

(3) homogenizing the alloy ingot obtained in the step (2), milling the surface, hot rolling, deep cooling rolling, and annealing the finished product to obtain the aluminum alloy anode material.

3. The method for producing an aluminum alloy anode material according to claim 2, characterized in that: in the step (1), the method for preparing the Mg-Hg-Ga intermediate alloy comprises the following steps: placing Mg, Hg and Ga in a sealed tank, heating, sealing and smelting, pouring more than or equal to 3 times on the ground, and cooling by water to obtain Mg-Hg-Ga intermediate alloy; the mass ratio of Mg, Hg and Ga is 0.5-1.0: 0.01-0.2; the heating, sealing and smelting temperature is 720-740 ℃, and the time is 1-2 h.

4. The method for producing an aluminum alloy anode material according to claim 2 or 3, characterized in that: in the step (2), the purity of the pure aluminum block is more than or equal to 99.996%; the heating and heat preservation temperature is 350-450 ℃; the temperature of the heating smelting is 800-850 ℃, and the time is 50-70 min; the protective gas is argon and/or helium; the temperature of the heat-preservation smelting is 800-850 ℃, and the time is 8-15 min; the temperature of the modification treatment is 600-720 ℃, and the time is 1-2 h; the casting temperature is 600-720 ℃.

5. The method for producing an aluminum alloy anode material according to claim 2 or 3, characterized in that: in the step (3), the temperature of the homogenization treatment is 460-600 ℃, and the time is 18-30 h; the hot rolling is to perform 4-8 times of reciprocating heating rolling, and each time of the reciprocating heating rolling is to perform primary intermediate annealing; the hot rolling temperature is 360-440 ℃, and the reduction per time is 30-50%; the temperature of the intermediate annealing is 280-330 ℃, and the time is 100-120 min; the thickness of the hot-rolled plate is 1-2 mm; the deep cooling rolling is to perform 4-8 times of reciprocating cold rolling, and before each time of rolling, the steel is soaked in liquid nitrogen for 20-25 min; the total reduction of the deep cooling rolling is 70-85%; the thickness of the plate after deep cooling rolling is 0.3-0.6 mm; the annealing temperature of the finished product is 200-230 ℃, and the annealing time is 1-3 h.

6. The method for producing an aluminum alloy anode material according to claim 4, characterized in that: in the step (3), the temperature of the homogenization treatment is 460-600 ℃, and the time is 18-30 h; the hot rolling is to perform 4-8 times of reciprocating heating rolling, and each time of the reciprocating heating rolling is to perform primary intermediate annealing; the hot rolling temperature is 360-440 ℃, and the reduction per time is 30-50%; the temperature of the intermediate annealing is 280-330 ℃, and the time is 100-120 min; the thickness of the hot-rolled plate is 1-2 mm; the deep cooling rolling is to perform 4-8 times of reciprocating cold rolling, and before each time of rolling, the steel is soaked in liquid nitrogen for 20-25 min; the total reduction of the deep cooling rolling is 70-85%; the thickness of the plate after deep cooling rolling is 0.3-0.6 mm; the annealing temperature of the finished product is 200-230 ℃, and the annealing time is 1-3 h.

Technical Field

The invention relates to an anode material and a preparation method thereof, in particular to an aluminum alloy anode material and a preparation method thereof.

Background

The Al/AgO battery is a novel chemical power reserve battery with small volumeHigh specific power, high specific energy, quick activation, no noise, no environmental pollution during working and the like. Aluminum has a high electrochemical equivalent (2980A. h.kg) as an anode material for a battery^-1) Is the metal with the highest mass specific energy except lithium; the electrode potential is relatively negative (the standard electrode potential in the strong alkaline solution is-2.35V); the aluminum resource is rich, and the price is low; can be widely applied to alkaline batteries, neutral batteries, organic batteries and the like. However, pure aluminum is an active amphoteric metal material, has a high self-corrosion rate in alkaline electrolyte, generates a large amount of hydrogen, has serious self-polarization and low current efficiency, and weakens the advantage of becoming a battery material requiring high voltage and low corrosion hydrogen evolution rate.

At present, more approaches for improving the performance of aluminum anode materials are mainly applied as follows: the micro-amount alloy elements are added into the aluminum to prepare the aluminum alloy, so that the electrochemical activity of the aluminum alloy electrode is improved, the self-corrosion rate is reduced, and the current efficiency is improved.

CN 106676343A discloses an aluminum alloy anode material for a seawater battery and a preparation method thereof, wherein the aluminum alloy comprises the following components in percentage by mass: 0.4-1.2% of Mg0.01-0.2% of Ga0.01-0.2%, 0.01-0.3% of Sn0.01-0.1%, 0.01-0.1% of In0.01-0.1%, 0.01-0.1% of Pb0.01-0.5%. The preparation method comprises the following steps: the method comprises the following steps of firstly preserving heat of a pure aluminum block, then smelting at the temperature of 750-900 ℃, adding pure aluminum foil coated with alloy elements which account for 0.4-1.2% of Mg, 0.01-0.2% of Ga, 0.01-0.3% of Sn, 0.01-0.1% of Bi, 0.01-0.1% of In, 0.01-0.1% of Pb and 0.01-0.5% of Ce, preserving heat, pouring the mixture into a steel die, homogenizing, milling the mixture, then rolling the mixture into a plate at the temperature of 350-450 ℃, preserving heat, annealing, cold rolling, annealing a finished product, and obtaining the aluminum alloy anode material. However, the aluminum alloy material has the characteristics of open-circuit voltage (maximum 1.920V), working time (maximum 1285 s) and hydrogen evolution amount (static minimum 0.67mL/(min cm)²) Poor performance.

CN 106917010A discloses an aluminum alloy anode material and a casting method and application thereof, wherein the aluminum alloy anode material is cast by the following components: pb: 0.01-0.1 wt%; sn: 0.01-0.1 wt%; ga: 0.01-0.2 wt%; ti: 0.01-0.07 wt%; the balance being Al. The casting method comprises the following steps: firstly, refining alloy: (1) putting pure aluminum blocks with the purity of 99.99% into a well type furnace in a grading manner, and heating the aluminum blocks to 700-750 ℃ for melting; (2) after all the aluminum blocks are completely melted, adding the trace metal elements weighed according to a certain proportion into a high-temperature well type furnace; (3) after all the components are completely melted, stirring by using a graphite rod; (4) adding hexachloroethane to remove waste residues in the molten aluminum; secondly, casting and forming: (1) coating a layer of release agent on the inner surface of the mold, heating to 150-250 ℃, and preserving heat; (2) and pouring the molten aluminum alloy into a mold, and casting the molten aluminum alloy into an aluminum ingot. However, the aluminum alloy anode material only discloses that the open circuit potential can reach-1.82V (vs. Hg/HgO), and does not disclose key material performance parameters such as hydrogen evolution quantity.

CN 109778029A discloses a rare earth-containing aluminum alloy anode material, a preparation method and an application thereof, wherein the rare earth-containing aluminum alloy anode material comprises, by mass, 0.5-2% of magnesium, 0.02-0.12% of tin, 0.01-1.0% of rare earth elements, and the balance of aluminum; the rare earth element is zirconium or yttrium. The preparation method comprises the steps of carrying out smelting and pouring at 750-780 ℃, and then sequentially carrying out homogenization treatment, hot rolling and solid solution treatment and aging treatment to obtain the product. However, the aluminum alloy material has the self-corrosion rate (the lowest 6.54 mg/(cm)) under the conditions of open-circuit voltage (the highest 1.97V) and self-corrosion rate²H)) and the performance of the material is not good enough, and the performance parameters of key materials such as working time and the like are not disclosed.

Disclosure of Invention

The invention aims to solve the technical problem of overcoming the defects in the prior art and providing the aluminum alloy anode material with high activity, polarization resistance, high voltage plateau and low hydrogen evolution quantity.

The invention further aims to solve the technical problem of overcoming the defects in the prior art and provide a preparation method of the aluminum alloy anode material, which has the advantages of strong corrosion resistance, simple process and low cost and is suitable for industrial production.

The technical scheme adopted by the invention for solving the technical problems is as follows: an aluminum alloy anode material comprises the following components in percentage by mass: 0.5-1.0% of Mg, 0.01-0.20% of Hg, 0.01-0.20% of Ga, 0.02-0.20% of Sn, 0.01-0.10% of Pb, 0.02-0.20% of Sb, 0.02-0.40% of Ce and the balance of Al. The selection and amount of the elements are mainly determined by the factors such as the solubility of the elements in aluminum, the melting point, and the liquid phase precipitation of solute elements at solidified grain boundaries. When the total solute element content is low, the influence on high-temperature plasticity is large, and when the total solute element content is high, a strong anode polarization effect can be generated, so that the comprehensive performance of the material is influenced.

The technical scheme adopted for further solving the technical problems is as follows: a preparation method of an aluminum alloy anode material comprises the following steps:

(1) preparing Mg-Hg-Ga intermediate alloy;

(2) heating and insulating a pure aluminum block, heating and smelting, sequentially adding Sn, Pb, Sb, Ce and the Mg-Hg-Ga intermediate alloy obtained in the step (1) into aluminum liquid, carrying out heat-insulating smelting in the process of introducing protective gas, carrying out modification treatment along with furnace cooling, filtering, and pouring to obtain an alloy ingot;

(3) homogenizing the alloy ingot obtained in the step (2), milling the surface, hot rolling, deep cooling rolling, and annealing the finished product to obtain the aluminum alloy anode material.

Preferably, in the steps (1) and (2), the amount of each metal is prepared according to the proportion of each component in the target product.

Preferably, in the step (1), the method for preparing the Mg-Hg-Ga master alloy comprises the following steps: placing Mg, Hg and Ga in a sealed tank, heating, sealing, smelting, pouring more than or equal to 3 times on the ground, and cooling by water to obtain the Mg-Hg-Ga intermediate alloy.

Preferably, the mass ratio of Mg, Hg and Ga is 0.5-1.0: 0.01-0.2.

Preferably, the heating, sealing and smelting are carried out at the temperature of 720-740 ℃ for 1-2 h.

Preferably, in the step (2), the purity of the pure aluminum block is more than or equal to 99.996%.

Preferably, in the step (2), the temperature for heating and heat preservation is 350-450 ℃.

Preferably, in the step (2), the temperature of the heating smelting is 800-850 ℃, and the time is 50-70 min.

Preferably, in step (2), the protective gas is argon and/or helium, etc.

Preferably, in the step (2), the temperature of the heat-preservation smelting is 800-850 ℃, and the time is 8-15 min.

Preferably, in the step (2), the temperature of the modification treatment is 600-720 ℃, and the time is 1-2 h.

Preferably, in the step (2), the casting temperature is 600-720 ℃.

Preferably, in the step (3), the temperature of the homogenization treatment is 460-600 ℃, and the time is 18-30 h.

Preferably, in the step (3), the hot rolling is 4-8 times of reciprocating heating rolling, and each time of the reciprocating heating rolling is performed with one time of intermediate annealing.

Preferably, in the step (3), the hot rolling temperature is 360-440 ℃, and the reduction per time is 30-50%.

Preferably, in the step (3), the temperature of the intermediate annealing is 280-330 ℃ and the time is 100-120 min.

Preferably, in the step (3), the thickness of the hot-rolled plate is 1-2 mm.

Preferably, in the step (3), the cryogenic rolling refers to 4-8 passes of reciprocating cold rolling, and the rolling is soaked in liquid nitrogen for 20-25 min before each pass of rolling.

Preferably, in the step (3), the total reduction amount of the deep cooling rolling is 70-85%.

Preferably, in the step (3), the thickness of the plate after deep cooling rolling is 0.3-0.6 mm.

Preferably, in the step (3), the annealing temperature of the finished product is 200-230 ℃ and the time is 1-3 h.

The purity of other metal raw materials used in the invention is more than or equal to 99.96 percent; the protective gas used in the invention is high-purity gas with the purity of more than or equal to 99.99 percent.

The invention has the following beneficial effects:

(1) the aluminum alloy anode material has high activity, polarization resistance, high voltage platform and low hydrogen evolution amount;

(2) the aluminum alloy anode material obtained by the method has strong corrosion resistance, simple process and low cost, and is suitable for industrial production.

Drawings

FIG. 1 shows the discharge curves of Al-AgO batteries assembled with aluminum alloy anode materials of examples 1 to 3 of the present invention and commercial aluminum alloy anodes 1 and 2.

Detailed Description

The invention is further illustrated by the following examples and figures.

The purity of the pure aluminum block used in the embodiment of the invention is more than or equal to 99.996 percent, and the purity of other metal raw materials used in the embodiment of the invention is more than or equal to 99.98 percent; the protective gas used in the invention is high-purity gas with the purity of more than or equal to 99.99 percent; the starting materials or chemicals used in the examples of the present invention are, unless otherwise specified, commercially available in a conventional manner.

Examples 1 to 3 of an aluminum alloy anode material

The components and parts by weight of the aluminum alloy anode materials of examples 1 to 3 are shown in Table 1.

TABLE 1 compositions and parts by weight of aluminum alloy anode materials of examples 1 to 3

Preparation method of aluminum alloy anode material in example 1

(1) Preparing Mg-Hg-Ga intermediate alloy according to the raw materials and the parts by weight of the raw materials in the example 1 in the table 1;

the method for preparing the Mg-Hg-Ga intermediate alloy comprises the following steps: placing Mg, Hg and Ga in a sealed tank, heating, sealing and smelting for 2h at 720 ℃, pouring for 4 times on a flat ground, and cooling by water to obtain Mg-Hg-Ga intermediate alloy;

(2) according to the raw materials and the weight parts of the raw materials in the example 1 in the table 1, firstly, a pure aluminum block is heated and insulated at 350 ℃, heated and smelted for 60min at 800 ℃, then, Sn, Pb, Sb, Ce and the Mg-Hg-Ga intermediate alloy obtained in the step (1) are sequentially added into aluminum liquid, in the process of introducing high-purity argon, the pure aluminum block is subjected to heat-insulation smelting for 15min at 800 ℃, is cooled to 720 ℃ along with a furnace to be subjected to modification treatment for 2h, is filtered, and is poured into a steel die with the thickness of 300mm multiplied by 200mm multiplied by 30mm at 720 ℃ to obtain an alloy ingot;

(3) homogenizing the alloy ingot obtained in the step (2) for 30 hours at 500 ℃, milling the surface, performing 8-pass reciprocating heating rolling at 360 ℃, performing 30% reduction each time, performing 120min of intermediate annealing at 280 ℃ each time until the thickness of the plate is 1mm, performing 8-pass reciprocating cold rolling, soaking the plate in liquid nitrogen for 20min before each pass rolling, performing 70% total reduction of cryogenic rolling until the thickness of the plate is 0.4mm, and annealing the finished product for 3 hours at 200 ℃ to obtain the aluminum alloy anode material 1.

As shown in fig. 1, the aluminum alloy anode material 1 obtained in the embodiment of the present invention has a more negative constant current polarization curve and a higher operating voltage than the commercial 1, 2 aluminum alloy anode materials.

Preparation method of aluminum alloy anode material in example 2

(1) Preparing Mg-Hg-Ga intermediate alloy according to the raw materials and the parts by weight in the example 2 in the table 1;

the method for preparing the Mg-Hg-Ga intermediate alloy comprises the following steps: placing Mg, Hg and Ga in a sealed tank, heating, sealing and smelting for 1.5h at 730 ℃, pouring for 3 times on a flat ground, and cooling by water to obtain Mg-Hg-Ga intermediate alloy;

(2) according to the raw materials and the weight parts of the raw materials in the example 2 in the table 1, firstly, a pure aluminum block is heated and insulated at 400 ℃, heated and smelted for 70min at 820 ℃, then, intermediate alloys of Sn, Pb, Sb, Ce and Mg-Hg-Ga are sequentially added into aluminum liquid, and in the process of introducing high-purity argon, the pure aluminum block is subjected to heat-insulating smelting for 10min at 820 ℃, is cooled to 650 ℃ along with a furnace to perform modification treatment for 1.5h, is filtered, and is poured into a steel die of 300mm multiplied by 200mm multiplied by 30mm at 650 ℃ to obtain an alloy ingot;

(3) homogenizing the alloy ingot obtained in the step (2) for 24 hours at 550 ℃, milling the surface, performing 6-pass reciprocating heating rolling at 400 ℃, wherein the reduction per time is 40%, performing one-time intermediate annealing at 300 ℃ for 110min per pass until the thickness of the plate is 1.5mm, performing 6-pass reciprocating cold rolling, soaking the plate in liquid nitrogen for 22min before each pass rolling, performing total reduction of cryogenic rolling for 75% until the thickness of the plate is 0.45mm, and annealing the finished product for 2 hours at 220 ℃ to obtain the aluminum alloy anode material 2.

As shown in fig. 1, the aluminum alloy anode material 2 obtained in the embodiment of the present invention has a more negative constant current polarization curve and a higher operating voltage than the commercial 1, 2 aluminum alloy anode materials.

Preparation method of aluminum alloy anode material in example 3

(1) Preparing Mg-Hg-Ga intermediate alloy according to the raw materials and the parts by weight in the example 3 in the table 1;

the method for preparing the Mg-Hg-Ga intermediate alloy comprises the following steps: placing Mg, Hg and Ga in a sealed tank, heating, sealing and smelting for 1.0h at 740 ℃, pouring for 3 times on a flat ground, and cooling by water to obtain Mg-Hg-Ga intermediate alloy;

(2) according to the raw materials and the weight parts of the raw materials in the embodiment 3 shown in the table 1, firstly, a pure aluminum block is heated and insulated at 450 ℃, heated and smelted for 70min at 850 ℃, then, Sn, Pb, Sb, Ce and the Mg-Hg-Ga intermediate alloy obtained in the step (1) are sequentially added into aluminum liquid, in the process of introducing high-purity helium, the pure aluminum block is subjected to heat-insulation smelting for 8min at 850 ℃, is cooled to 700 ℃ along with a furnace to perform modification treatment for 1h, is filtered, and is poured into a steel die with the thickness of 300mm multiplied by 200mm multiplied by 30mm at 700 ℃ to obtain an alloy ingot;

(3) homogenizing the alloy ingot obtained in the step (2) for 20 hours at 600 ℃, milling the surface, performing 4-pass reciprocating heating rolling at 440 ℃, wherein the reduction is 50% at each time, performing one-time intermediate annealing at 320 ℃ for 100min at each pass till the thickness of the plate is 2mm, performing 4-pass reciprocating cold rolling, soaking the plate in liquid nitrogen for 25min before each pass rolling, performing total reduction of 80% by deep cooling rolling till the thickness of the plate is 0.5mm, and annealing the finished product for 1 hour at 230 ℃ to obtain the aluminum alloy anode material 3.

As shown in fig. 1, the aluminum alloy anode material 3 obtained in the embodiment of the invention has a more negative constant current polarization curve and a higher operating voltage than the commercial 1 and 2 aluminum alloy anode materials.

In order to evaluate the electrochemical properties of the aluminum alloy anode materials 1 to 3 obtained in examples 1 to 3, the following methods were used to test the anode materials, and the results are shown in tables 2 and 3:

battery assembly environment: and assembling the aluminum-silver oxide single battery in an atmospheric environment.

Current density: 600mA/cm²；

Electro-hydraulic temperature: 80 ℃;

the electrolyte comprises the following components: 4.5mol/L NaOH +20g/LNa₂SnO₃；

Flow rate: 151 mL/min.

TABLE 2 tables of constant-current polarization potential and static hydrogen evolution rate of examples 1 to 3 and commercial 1 and 2 aluminum alloy anode materials

As can be seen from Table 2, the aluminum alloy anode materials 1-3 of the invention have higher constant current polarization potential and lower static hydrogen evolution amount compared with the commercial 1 and 2 aluminum alloy anode materials.

TABLE 3 data table of electrical properties of examples 1-3 and commercial 1, 2 aluminum alloy anode materials

As can be seen from Table 3, the aluminum alloy anode materials 1-3 of the invention have higher voltage, 15min working time average voltage, rated 1.475V working time average voltage and shorter time to reach rated voltage compared with commercial 1, 2 aluminum alloy anode materials.