CN111187947A - Aluminum alloy anode material for seawater battery and preparation method - Google Patents
Aluminum alloy anode material for seawater battery and preparation method Download PDFInfo
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- 239000010405 anode material Substances 0.000 title claims abstract description 80
- 239000013535 sea water Substances 0.000 title claims abstract description 57
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012535 impurity Substances 0.000 claims abstract description 26
- 229910052718 tin Inorganic materials 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 16
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 15
- 229910052745 lead Inorganic materials 0.000 claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 238000003723 Smelting Methods 0.000 claims description 55
- 239000000956 alloy Substances 0.000 claims description 38
- 229910045601 alloy Inorganic materials 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000002994 raw material Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000011888 foil Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 239000002893 slag Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000008399 tap water Substances 0.000 claims description 9
- 235000020679 tap water Nutrition 0.000 claims description 9
- 229910018131 Al-Mn Inorganic materials 0.000 claims description 4
- 229910018461 Al—Mn Inorganic materials 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 11
- 238000004090 dissolution Methods 0.000 abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 230000004913 activation Effects 0.000 abstract description 3
- 230000003213 activating effect Effects 0.000 abstract description 2
- 238000005275 alloying Methods 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000011701 zinc Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 5
- 238000003754 machining Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 241000251729 Elasmobranchii Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/026—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/463—Aluminium based
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The invention provides an aluminum alloy anode material for a seawater battery and a preparation method thereof, and the electrochemical performance of aluminum alloy in a seawater medium is improved by adopting a micro-alloying method. Firstly, activating elements Ga, Bi, Cd and Pb are added to promote the dissolution and the falling of an oxide film layer on the surface of the aluminum alloy, so that the potential of the anode is obviously shifted negatively, and the activation performance of the anode is improved; then, elements Sn, Zn and Mn with higher hydrogen evolution potential are added, so that the hydrogen evolution overpotential of the aluminum alloy is increased to a certain extent, the probability of hydrogen evolution corrosion of the anode is reduced, and the current efficiency of the anode is improved; and finally, the content of impurity elements Fe and Cu in the aluminum ingot is controlled, so that the self-corrosion of the aluminum alloy anode is reduced, and the dissolution morphology is improved. In the preparation process of the anode, the material has a negative working potential, higher activity and lower self-corrosion rate in a seawater medium by controlling the feeding sequence and process parameters of the components, and can effectively improve the driving potential and current efficiency of the aluminum-seawater battery.
Description
Technical Field
The invention relates to an anode material for an aluminum-seawater battery, in particular to a high-activity aluminum alloy anode material and a preparation method thereof, belonging to the field of alloy materials. The material has a negative working potential, high activity and low self-corrosion rate in a seawater medium, and can effectively improve the driving potential and current efficiency of the aluminum-seawater battery.
Background
The seawater battery consists of an anode (positive electrode), a cathode (negative electrode) and an electrolyte (seawater). When the battery works, the negative current is generated by anode metal losing electrons in seawater electrolyte to become metal ions, and dissolved oxygen in the seawater electrolyte obtains electrons on the inert electrode to generate reduction reaction to generate positive current. The electrolyte used in the seawater battery is natural seawater, which can be inexhaustible, and particularly for marine equipment such as buoys, underwater vehicles, torpedoes and the like, the seawater battery has more obvious advantages, so that the development and application of the seawater battery have wider development prospects.
The anode material for the seawater battery comprises active metals such as magnesium, aluminum, zinc and the like, wherein the aluminum alloy has the unique advantages that ① aluminum alloy has high electrochemical equivalent (2980Ah/kg), is the highest capacitance among several common anode metals and can provide high-power discharge, ② electrode potential is relatively negative, standard electrode potential is-1.66V (vs. SCE) and can provide high driving voltage for the battery, ③ aluminum has abundant resources and low price, but because of the self-passivation characteristic of aluminum, a compact surface passivation film is easily formed in a neutral medium, so that the activity is greatly reduced, therefore, most of the electrolytes of the conventional aluminum air batteries or aluminum seawater batteries adopt strong alkaline solutions, and the aim of inhibiting the passivation phenomenon of aluminum is to be achieved, for example, the aluminum alloy anode material which is good in the alkaline medium is invented by patents CN 105140596B, CN1066763343B and the like in our country.
For a seawater battery for marine equipment, the alkaline electrolyte firstly increases the manufacturing cost of the battery, and simultaneously brings difficulties to the preparation technology, storage and the like of the battery, for example, the seawater medium can be directly used as the electrolyte, so that great convenience is brought to the use of the battery, and the seawater battery has obvious economic benefits. Therefore, the development of the aluminum alloy anode material with excellent performance in the seawater medium has important significance.
Disclosure of Invention
The invention aims at the defects of the prior art and provides an aluminum alloy anode material for a seawater battery and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows:
1. the invention provides an aluminum alloy anode material for a seawater battery, which comprises the following components in percentage by mass: 0.01 to 0.1 percent of Ga0.01 to 0.5 percent of Zn, 0.1 to 0.5 percent of Bi, 0.1 to 0.5 percent of Sn, 0.01 to 0.2 percent of Cd, 0.02 to 0.1 percent of Pb, 0.02 to 0.2 percent of Mn, less than or equal to 0.1 percent of total content of impurity elements, less than or equal to 0.07 percent of impurity Fe, less than or equal to 0.005 percent of impurity Cu and the balance of Al.
Optionally, the anode material is prepared by a high-temperature smelting method, and the aluminum alloy anode material is produced according to the following steps:
1) when the smelting furnace is in a cold state, adding Al element and Mn element according to the formula dosage, and continuously heating at the heating rate of 10-20 ℃/min to melt the Al element and the Mn element;
2) then Zn, Pb and Cd elements with the formula dosage are added, the temperature is continuously raised to 780 +/-20 ℃,
3) after the raw materials in the smelting furnace are completely melted, aluminum foil is used for wrapping Ga, Bi and Sn elements with the formula dosage, the Ga, Bi and Sn elements are put into the smelting furnace, a graphite rod is used for stirring for 4-10min to enable the alloy liquid to be uniformly mixed, then the smelting furnace is kept stand for 8-15min, the alloy liquid is continuously poured into a mold at a constant speed after oxide slag is removed, the alloy liquid is washed and cooled by tap water after being solidified, and then the mold is drawn.
Optionally, the anode material prepared by smelting is subjected to further heat treatment: the anode material is subjected to solution treatment for 8 to 12 hours at the temperature of between 500 and 520 ℃, and then is tempered for 7 to 9 hours at the temperature of between 120 and 170 ℃.
Optionally, an aluminum ingot is selected for adding the Al element, wherein the content of Fe impurity is not more than 0.07%, and the content of Cu impurity is not more than 0.005%.
Optionally, the addition of Mn adopts Al-Mn intermediate alloy.
Alternatively, the purity of each constituent component should be not less than 99.99%.
2. The invention also provides a preparation method of the aluminum alloy anode material for the seawater battery, the anode material is prepared by adopting a high-temperature smelting method, and the aluminum alloy anode material is produced according to the following steps:
1) when the smelting furnace is in a cold state, adding Al element and Mn element according to the formula dosage, and continuously heating at the heating rate of 10-20 ℃/min to melt the Al element and the Mn element;
2) then Zn, Pb and Cd elements with the formula dosage are added, the temperature is continuously raised to 780 +/-20 ℃,
3) after the raw materials in the smelting furnace are completely melted, aluminum foil is used for wrapping Ga, Bi and Sn elements with the formula dosage, the Ga, Bi and Sn elements are put into the smelting furnace, a graphite rod is used for stirring for 4-10min to enable the alloy liquid to be uniformly mixed, then the smelting furnace is kept stand for 8-15min, the alloy liquid is continuously poured into a mold at a constant speed after oxide slag is removed, the alloy liquid is washed and cooled by tap water after being solidified, and then the mold is drawn.
8. The method for preparing the aluminum alloy anode material for the seawater battery as claimed in claim 7, wherein the anode material prepared by smelting is further subjected to heat treatment: the anode material is subjected to solution treatment for 8 to 12 hours at the temperature of between 500 and 520 ℃, and then is tempered for 7 to 9 hours at the temperature of between 120 and 170 ℃.
Optionally, an aluminum ingot is selected for adding the Al element, wherein the content of Fe impurity is not more than 0.07%, and the content of Cu impurity is not more than 0.005%.
Optionally, the Mn element is added by using Al-Mn master alloy, such as AlMn10-30, and specifically can be AlMn10, 15, 20 and 30 master alloy.
Compared with the prior art, the aluminum alloy anode material for the seawater battery and the preparation method thereof have the beneficial effects that:
the invention adopts a micro-alloying method to improve the electrochemical performance of the aluminum alloy in the seawater medium. Firstly, activating elements Ga, Bi, Cd and Pb are added to promote the dissolution and the falling of an oxide film layer on the surface of the aluminum alloy, so that the potential of the anode is obviously shifted negatively, and the activation performance of the anode is improved; then, elements Sn, Zn and Mn with higher hydrogen evolution potential are added, so that the hydrogen evolution overpotential of the aluminum alloy is increased to a certain extent, the probability of hydrogen evolution corrosion of the anode is reduced, and the current efficiency of the anode is improved; and finally, the content of impurity elements Fe and Cu in the aluminum ingot is controlled, so that the self-corrosion of the aluminum alloy anode is reduced, and the dissolution morphology is improved.
In the preparation process of the anode, the burning loss of the anode components is reduced to the maximum extent by controlling the feeding sequence and the smelting temperature of the components, and the preparation quality and the electrochemical performance of the anode material are ensured; the size, the number and the distribution of segregation phases in the anode material are improved through further solution treatment, crystal grains are refined to a certain degree, metallurgical defects are eliminated, and the anode is dissolved more uniformly; the low-temperature tempering causes a large amount of second phases dissolved in the anode material to be precipitated, increases the activation sites, and improves the discharge activity.
The anode material prepared by the invention has a negative working potential, high activity and low self-corrosion rate in a seawater medium, and can effectively improve the driving potential and current efficiency of an aluminum-seawater battery.
Detailed Description
The aluminum alloy anode material for a seawater battery and the preparation method thereof according to the present invention will be described in detail with reference to the following embodiments.
Example 1:
the aluminum alloy anode material for the seawater battery comprises the following components in percentage by mass: 0.1% of Ga, 0.1% of Zn, 0.1% of Bi, 0.2% of Sn, 0.2% of Cd, 0.1% of Pb, 0.2% of Mn and the balance of Al. During anode preparation, Al element is selected from aluminum ingot with the purity of 99.9 percent, wherein the content of impurity Fe is less than or equal to 0.07 percent, and the content of impurity Cu is less than or equal to 0.005 percent. Because the melting point of the Mn element is too high, the raw material is AlMn15 intermediate alloy with relatively low melting point; the purity of the rest components is not lower than 99.99%;
the anode material is prepared by adopting a high-temperature smelting method, and the aluminum alloy anode material is produced according to the following steps:
1) when the smelting furnace is in a cold state, adding Al element and Mn element according to the formula dosage, and continuously heating at the heating rate of 10 ℃/min to melt the Al element and the Mn element;
2) then Zn, Pb and Cd elements with the formula dosage are added, the temperature is continuously raised to 760 ℃,
3) after the raw materials in the smelting furnace are completely melted, aluminum foil is used for wrapping Ga, Bi and Sn elements with the formula dosage, the Ga, Bi and Sn elements are put into the smelting furnace, a graphite rod is used for stirring for 4min to enable the alloy liquid to be uniformly mixed, then the smelting furnace is kept stand for 8min, the alloy liquid is continuously poured into a die at a constant speed after oxide slag is removed, the alloy liquid is washed and cooled by tap water after being solidified, and then the die is drawn.
4) Carrying out further heat treatment on the anode material prepared by smelting: the anode material is subjected to solution treatment at 500 ℃ for 8h and then tempered at 120 ℃ for 7 h. And finally, preparing the anode material into an anode structure required by the seawater battery by adopting a machining method.
The anode material prepared by the preparation method has the actual component composition deviation of not more than +/-5% from the designed component through component analysis. By carrying out electrochemical performance tests in a seawater medium, the results are as follows: the open circuit potential of the anode was-1.306V (relative to SCE, the same applies below), and the self-etching rate was 4.31. mu.g/cm2H, at a discharge current density of 10mA/cm2Under the working state, the working potential is-1.214V, the current efficiency is 81.3 percent, and the dissolution on the surface of the anode is uniform.
Example 2:
the aluminum alloy anode material for the seawater battery comprises the following components in percentage by mass: 0.02% of Ga0.02%, 0.05% of Zn, 0.5% of Bi, 0.3% of Sn, 0.01% of Cd, 0.06% of Pb, 0.1% of Mn and the balance of Al. When the anode is prepared, the purity of an aluminum ingot is 99.9 percent, wherein the content of Fe impurity is less than or equal to 0.07 percent, and the content of Cu impurity is less than or equal to 0.005 percent; the Mn element is added by AlMn15 intermediate alloy, and the purity of the rest components is 99.99 percent.
The anode material is prepared by adopting a high-temperature smelting method, and the aluminum alloy anode material is produced according to the following steps:
1) when the smelting furnace is in a cold state, adding Al element and Mn element according to the formula dosage, and continuously heating at the heating rate of 15 ℃/min to melt the Al element and the Mn element;
2) then Zn, Pb and Cd elements with the formula dosage are added, the temperature is continuously raised to 780 ℃,
3) after the raw materials in the smelting furnace are completely melted, aluminum foil is used for wrapping Ga, Bi and Sn elements with the formula dosage, the Ga, Bi and Sn elements are put into the smelting furnace, a graphite rod is used for stirring for 5min to enable alloy liquid to be uniformly mixed, then the smelting furnace is kept still for 10min, the alloy liquid is continuously poured into a die at a constant speed after oxide slag is removed, the alloy liquid is washed and cooled by tap water after being solidified, and then the die is drawn.
4) Carrying out further heat treatment on the anode material prepared by smelting: the anode material was solution treated at 510 ℃ for 10h and then tempered at 150 ℃ for 8 h. And finally, preparing the anode material into an anode structure required by the seawater battery by adopting a machining method.
The anode material prepared by the preparation method has the actual component composition deviation of not more than +/-5% from the designed component through component analysis. By carrying out electrochemical performance tests in a seawater medium, the results are as follows: the open circuit potential of the anode is-1.383V, and the self-corrosion rate is 3.86 mu g/cm2H, at a discharge current density of 10mA/cm2Under the working state, the working potential is-1.359V, the current efficiency is 88.2 percent, and the dissolution on the surface of the anode is uniform.
Example 3:
the aluminum alloy anode material for the seawater battery comprises the following components in percentage by mass: 0.06% of Ga0.06%, 0.2% of Zn, 0.2% of Bi, 0.5% of Sn, 0.1% of Cd, 0.02% of Pb, 0.02% of Mn and the balance of Al. When the anode is prepared, the purity of an aluminum ingot is 99.95 percent, wherein the content of Fe impurity is less than or equal to 0.02 percent, and the content of Cu impurity is less than or equal to 0.005 percent; the Mn element is added by AlMn15 intermediate alloy, and the purity of the rest components is 99.99 percent.
The anode material is prepared by adopting a high-temperature smelting method, and the aluminum alloy anode material is produced according to the following steps:
1) when the smelting furnace is in a cold state, adding Al element and Mn element according to the formula dosage, and continuously heating at the heating rate of 13 ℃/min to melt the Al element and the Mn element;
2) then Zn, Pb and Cd elements with the formula dosage are added, the temperature is continuously increased to 770 ℃,
3) after the raw materials in the smelting furnace are completely melted, aluminum foil is used for wrapping Ga, Bi and Sn elements with the formula dosage, the Ga, Bi and Sn elements are put into the smelting furnace, a graphite rod is used for stirring for 8min to enable the alloy liquid to be uniformly mixed, then the smelting furnace is kept still for 12min, the alloy liquid is poured into a die at a constant speed and continuously after oxidation slag is removed, the alloy liquid is washed and cooled by tap water after being solidified, and then the die drawing is carried out.
4) Carrying out further heat treatment on the anode material prepared by smelting: the anode material is subjected to solution treatment at 515 ℃ for 11h and then tempered at 160 ℃ for 8 h. And finally, preparing the anode material into an anode structure required by the seawater battery by adopting a machining method.
The anode material prepared by the preparation method has the actual component composition deviation of not more than +/-5% from the designed component through component analysis. By carrying out electrochemical performance tests in a seawater medium, the results are as follows: the open circuit potential of the anode is-1.412V, and the self-corrosion rate is 3.71 mu g/cm2H, at a discharge current density of 10mA/cm2Under the working state, the working potential is minus 1.387V, the current efficiency is 89.7 percent, and the dissolution on the surface of the anode is uniform.
Example 4:
the aluminum alloy anode material for the seawater battery comprises the following components in percentage by mass: 0.01 percent of Ga0.01 percent, 0.5 percent of Zn, 0.2 percent of Bi, 0.1 percent of Sn, 0.02 percent of Cd, 0.05 percent of Pb, 0.1 percent of Mn and the balance of Al. When the anode is prepared, the purity of an aluminum ingot is 99.95 percent, wherein the content of Fe impurity is less than or equal to 0.02 percent, and the content of Cu impurity is less than or equal to 0.005 percent; the Mn element is added by AlMn10 intermediate alloy, and the purity of the rest components is 99.99 percent.
The anode material is prepared by adopting a high-temperature smelting method, and the aluminum alloy anode material is produced according to the following steps:
1) when the smelting furnace is in a cold state, adding Al element and Mn element according to the formula dosage, and continuously heating at the heating rate of 16 ℃/min to melt the Al element and the Mn element;
2) then Zn, Pb and Cd elements with the formula dosage are added, the temperature is continuously raised to 790 ℃,
3) after the raw materials in the smelting furnace are completely melted, aluminum foil is used for wrapping Ga, Bi and Sn elements with the formula dosage, the Ga, Bi and Sn elements are put into the smelting furnace, a graphite rod is used for stirring for 6min to enable alloy liquid to be uniformly mixed, then the smelting furnace is kept still for 12min, the alloy liquid is continuously poured into a die at a constant speed after oxidation slag is removed, the alloy liquid is washed and cooled by tap water after being solidified, and then the die is drawn.
4) Carrying out further heat treatment on the anode material prepared by smelting: the anode material was solution treated at 505 ℃ for 9h and then tempered at 140 ℃ for 7 h. And finally, preparing the anode material into an anode structure required by the seawater battery by adopting a machining method.
The anode material prepared by the preparation method has the actual component composition deviation of not more than +/-5% from the designed component through component analysis. By carrying out electrochemical performance tests in a seawater medium, the results are as follows: the open circuit potential of the anode is-1.342V, and the self-corrosion rate is 4.02 mu g/cm2H, at a discharge current density of 10mA/cm2Under the working state, the working potential is-1.313V, the current efficiency is 84.1 percent, and the dissolution of the anode surface is uniform.
Example 5:
the aluminum alloy anode material for the seawater battery comprises the following components in percentage by mass: 0.08 percent of Ga0.08 percent, 0.01 percent of Zn, 0.3 percent of Bi, 0.4 percent of Sn, 0.15 percent of Cd, 0.08 percent of Pb, 0.08 percent of Mn and the balance of Al. When the anode is prepared, the purity of an aluminum ingot is 99.95 percent, wherein the content of Fe impurity is less than or equal to 0.02 percent, and the content of Cu impurity is less than or equal to 0.005 percent; the Mn element is added by AlMn30 intermediate alloy, and the purity of the rest components is 99.99 percent.
The anode material is prepared by adopting a high-temperature smelting method, and the aluminum alloy anode material is produced according to the following steps:
1) when the smelting furnace is in a cold state, adding Al element and Mn element according to the formula dosage, and continuously heating at the heating rate of 20 ℃/min to melt the Al element and the Mn element;
2) then Zn, Pb and Cd elements with the formula dosage are added, the temperature is continuously raised to 800 ℃,
3) after the raw materials in the smelting furnace are completely melted, aluminum foil is used for wrapping Ga, Bi and Sn elements with the formula dosage, the Ga, Bi and Sn elements are put into the smelting furnace, a graphite rod is used for stirring for 10min to enable alloy liquid to be uniformly mixed, then the smelting furnace is kept still for 15min, the alloy liquid is poured into a die at a constant speed and continuously after oxidation slag is removed, the alloy liquid is washed and cooled by tap water after being solidified, and then the die is drawn.
4) Carrying out further heat treatment on the anode material prepared by smelting: the anode material was solution treated at 520 ℃ for 12h and then tempered at 170 ℃ for 9 h. And finally, preparing the anode material into an anode structure required by the seawater battery by adopting a machining method.
The anode material prepared by the preparation method has the actual component composition deviation of not more than +/-5% from the designed component through component analysis. By carrying out electrochemical performance tests in a seawater medium, the results are as follows: the open circuit potential of the anode is-1.326V, and the self-corrosion rate is 3.92 mu g/cm2H, at a discharge current density of 10mA/cm2Under the working state, the working potential is-1.362V, the current efficiency is 86.2 percent, and the dissolution of the anode surface is uniform.
While the preferred embodiments of the present application have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all alterations and modifications as fall within the scope of the application.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present application without departing from the spirit and scope of the application. Thus, if such modifications and variations of the present application fall within the scope of the claims of the present application and their equivalents, the present application is intended to include such modifications and variations as well.
In addition to the technical features described in the specification, the technology is known to those skilled in the art.
Claims (10)
1. The aluminum alloy anode material for the seawater battery is characterized by comprising the following components in percentage by mass: 0.01 to 0.1 percent of Ga0.01 to 0.5 percent of Zn, 0.1 to 0.5 percent of Bi, 0.1 to 0.5 percent of Sn, 0.01 to 0.2 percent of Cd, 0.02 to 0.1 percent of Pb, 0.02 to 0.2 percent of Mn, less than or equal to 0.1 percent of total content of impurity elements, less than or equal to 0.07 percent of impurity Fe, less than or equal to 0.005 percent of impurity Cu and the balance of Al.
2. The aluminum alloy anode material for the seawater battery as defined in claim 1, wherein the anode material is prepared by a high temperature smelting method, and the aluminum alloy anode material is produced by the following steps:
1) when the smelting furnace is in a cold state, adding Al element and Mn element according to the formula dosage, and continuously heating at the heating rate of 10-20 ℃/min to melt the Al element and the Mn element;
2) then Zn, Pb and Cd elements with the formula dosage are added, the temperature is continuously raised to 780 +/-20 ℃,
3) after the raw materials in the smelting furnace are completely melted, aluminum foil is used for wrapping Ga, Bi and Sn elements with the formula dosage, the Ga, Bi and Sn elements are put into the smelting furnace, a graphite rod is used for stirring for 4-10min to enable the alloy liquid to be uniformly mixed, then the smelting furnace is kept stand for 8-15min, the alloy liquid is continuously poured into a mold at a constant speed after oxide slag is removed, the alloy liquid is washed and cooled by tap water after being solidified, and then the mold is drawn.
3. The aluminum alloy anode material for the seawater battery as defined in claim 2, wherein the anode material prepared by smelting is further heat-treated: the anode material is subjected to solution treatment for 8 to 12 hours at the temperature of between 500 and 520 ℃, and then is tempered for 7 to 9 hours at the temperature of between 120 and 170 ℃.
4. The aluminum alloy anode material for the seawater battery as defined in claim 1, 2 or 3, wherein Al is added to the aluminum alloy anode material by using an aluminum ingot, wherein Fe is not more than 0.07% as an impurity and Cu is not more than 0.005% as an impurity.
5. The aluminum alloy anode material for the seawater battery as defined in claim 1, 2 or 3, wherein the Mn element is added by using Al-Mn master alloy.
6. The aluminum alloy anode material for the seawater battery as recited in claim 1, 2 or 3, wherein the purity of each constituent component should be not less than 99.99%.
7. The method for preparing the aluminum alloy anode material for the seawater battery as defined in any one of claims 1 to 6, wherein the anode material is prepared by a high temperature smelting method, and the aluminum alloy anode material is produced by the following steps:
1) when the smelting furnace is in a cold state, adding Al element and Mn element according to the formula dosage, and continuously heating at the heating rate of 10-20 ℃/min to melt the Al element and the Mn element;
2) then Zn, Pb and Cd elements with the formula dosage are added, the temperature is continuously raised to 780 +/-20 ℃,
3) after the raw materials in the smelting furnace are completely melted, aluminum foil is used for wrapping Ga, Bi and Sn elements with the formula dosage, the Ga, Bi and Sn elements are put into the smelting furnace, a graphite rod is used for stirring for 4-10min to enable the alloy liquid to be uniformly mixed, then the smelting furnace is kept stand for 8-15min, the alloy liquid is continuously poured into a mold at a constant speed after oxide slag is removed, the alloy liquid is washed and cooled by tap water after being solidified, and then the mold is drawn.
8. The method for preparing the aluminum alloy anode material for the seawater battery as claimed in claim 7, wherein the anode material prepared by smelting is further subjected to heat treatment: the anode material is subjected to solution treatment for 8 to 12 hours at the temperature of between 500 and 520 ℃, and then is tempered for 7 to 9 hours at the temperature of between 120 and 170 ℃.
9. The method for preparing an aluminum alloy anode material for a seawater battery as claimed in claim 7 or 8, wherein the Al element is added by using an aluminum ingot, wherein the content of Fe impurity is not more than 0.07%, and the content of Cu impurity is not more than 0.005%.
10. The method for preparing an aluminum alloy anode material for a seawater battery as claimed in claim 7 or 8, wherein the Mn element is added by using an Al-Mn intermediate alloy.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4146678A (en) * | 1976-06-24 | 1979-03-27 | Swiss Aluminium Ltd. | Primary electric cell of the dry cell type |
| CN1491288A (en) * | 2001-02-13 | 2004-04-21 | Production of aluminum alloy foils having high strength and good rollability | |
| CN103774154A (en) * | 2014-01-15 | 2014-05-07 | 青岛双瑞海洋环境工程股份有限公司 | Efficient Al alloy sacrificial anode suitable for low-temperature seawater environment and preparation process thereof |
| CN105950920A (en) * | 2016-05-17 | 2016-09-21 | 中国科学院金属研究所 | Aluminum base alloy soluble in water and aqueous medium environments and preparation method thereof |
| CN106756665A (en) * | 2016-11-28 | 2017-05-31 | 云南冶金集团创能铝空气电池股份有限公司 | Aluminium alloy, preparation method and purposes |
-
2018
- 2018-11-14 CN CN201811351266.5A patent/CN111187947A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4146678A (en) * | 1976-06-24 | 1979-03-27 | Swiss Aluminium Ltd. | Primary electric cell of the dry cell type |
| CN1491288A (en) * | 2001-02-13 | 2004-04-21 | Production of aluminum alloy foils having high strength and good rollability | |
| CN103774154A (en) * | 2014-01-15 | 2014-05-07 | 青岛双瑞海洋环境工程股份有限公司 | Efficient Al alloy sacrificial anode suitable for low-temperature seawater environment and preparation process thereof |
| CN105950920A (en) * | 2016-05-17 | 2016-09-21 | 中国科学院金属研究所 | Aluminum base alloy soluble in water and aqueous medium environments and preparation method thereof |
| CN106756665A (en) * | 2016-11-28 | 2017-05-31 | 云南冶金集团创能铝空气电池股份有限公司 | Aluminium alloy, preparation method and purposes |
Non-Patent Citations (1)
| Title |
|---|
| 王双元等: "热处理对铝合金电极性能的影响", 《电源技术》 * |
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Application publication date: 20200522 |