CN104561673B - A kind of rare earth modified aluminum alloy anode sheet and preparation method thereof - Google Patents
A kind of rare earth modified aluminum alloy anode sheet and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of rare earth modified aluminum alloy anode sheet and preparation method thereof, it is that raw material is made by aluminium block, MAG block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain, wherein, the mass ratio of aluminium block, MAG block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain is 96.6 99.31: 0.5 2: 0.1 1: 0.05 0.2: 0.01 0.1: 0.01 0.05: 0.01 0.03: 0.01 0.02.Alloy casting weighs appropriate each alloying element according to formula, melts in the resistance furnace crucible of 750～800 DEG C, then alloy melt is cast in water-cooled punching block standby.In alloy solid solution heat treatment, solid solubility temperature is 500～560 DEG C, and solution time is 5～8h.In alloy rolling processing technique, one-pass roller temperature is 400～450 DEG C, and single pass heavy deformation is 35%～45%.Rare earth modified aluminum alloy anode sheet of the present invention is when high current density discharge, little from corrosion rate, electro-chemical activity height, meets the performance requirement that in alkalescence aluminum cell motor process, current efficiency is high, electric discharge is steady and hydrogen-separating quantity is little.
Description
Technical field
The invention belongs to technical field of metal material preparation, be specifically related to a kind of rare earth modified aluminum alloy anode sheet and system thereof
Preparation Method.
Background technology
Metallic aluminium is the energy carrier of a kind of high intensity, and its electrochemical equivalent is 2.98Ah/g, and volume is 8.04Ah/
cm3.And other electrode material lithium, magnesium, the electrochemical equivalent of zinc are respectively 3.86,2.20,0.82Ah/g, volume is respectively
2.06、3.83、5.85Ah/cm3.Additionally, metal aluminium electrode current potential is rich compared with negative (-1.66V vs.SHE), wide material sources, reserves
Rich, cheap, easily processed into type, there is no environmental pollution, be exploitation battery ideal electrode material.Alkaline seawater is utilized to make
Electrolyte, in air, oxygen or silver oxide make active material of cathode, and metal aluminum alloy makees anode, and the alkaline aluminum cell of composition not only has
There is energy density high, the electrochemistry advantage that discharge performance is good, also there is the low-cost advantage that bauxite resource is abundant, raw material is sufficient, and
And nontoxic pollution-free, noiselessness, environmental friendliness in cell operation.Therefore, the research of high performance alkaline aluminum cell is the most standby
Paid much attention to by departments such as many developed countries energy, traffic, telecommunications, national defence.
As the critical material of alkalescence aluminum cell, the research and development of aluminum alloy anode material enjoys material science the most always
The concern of worker.But owing to metallic aluminium is a kind of more active amphoteric metal material, especially from corrosion in alkaline electrolyte
Speed is relatively big, and can produce a large amount of hydrogen, increases cell internal pressure, brings to battery hermetization and have a strong impact on, even
Battery leakage can be caused, make battery can not give full play to the advantage of high-energy power supply.Additionally, in high current density working condition
Under, aluminum alloy anode serious polarization, steady operation current potential calibration, it is impossible to meet the electrical property engineering requirement of electrical source of power,
Seriously hinder alkalescence aluminum cell application in actual industrial production.In recent years, for making aluminium anodes material at alkalescence aluminum cell
Work process have relatively low from corrosion rate, it will usually add Pb, Hg, Cd contour overpotential of hydrogen evolution element.Added
Alloying element is negative electrode phase relative to aluminum substrate, owing to cathode hydrogen evolution reaction overpotential of hydrogen evolution on alloying element is the highest, from
And hinder the dissolving of parent metal aluminium anodes, reduce aluminum alloy anode gas-evolving electrodes speed in the solution, but Pb, Hg make
For toxic element, limit its application in aluminium alloy in recent years；On the other hand, for making aluminium anodes have in the course of the work
Higher electro-chemical activity, also can add the eutectic alloying elements such as Ga, Bi, In in aluminium alloy.After adding this dvielement,
The eutectic mixture formed can form eutectic crystal when alloy solidifies, and its fusing point is relatively low, at electrode operating temperature
Under (60-100 DEG C) be in molten condition, aluminium anodes can be promoted to enter in the electrolytic solution with the attachment between disruptive oxidation film and matrix
One step is dissolved, thus improves the electro-chemical activity of aluminum alloy anode, but this dvielement is owing to fusing point is low and ratio is great, the most easily
In aluminum substrate, form segregation, thus cause anodic attack uneven, too high from corrosion rate.
The most how to develop environmental protection, high performance novel aluminum alloy anode material, be that alkalescence aluminum cell exploitation application is badly in need of
The key issue solved.
Summary of the invention
It is an object of the invention to the shortcoming overcoming above-mentioned prior art, it is provided that a kind of rare earth modified aluminum alloy anode sheet
And preparation method thereof, this anode strip is when high current density discharge, little from corrosion rate, and electro-chemical activity is high, meets alkalescence aluminum
The performance requirement that in battery motor process, current efficiency is high, electric discharge is steady and hydrogen-separating quantity is little, and it is easy to preparation.
For reaching above-mentioned purpose, rare earth modified aluminum alloy anode sheet of the present invention by aluminium block, MAG block, bismuth granule, stannum grain,
Gallium grain, indium grain, lanthanum grain and cerium grain are that raw material is made, wherein, and aluminium block, MAG block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain
And the mass ratio of cerium grain is (96.6-99.31): (0.5-2): (0.1-1): (0.05-0.2): (0.01-0.1): (0.01-
0.05)∶(0.01-0.03)∶(0.01-0.02)。
The preparation method of rare earth modified aluminum alloy anode sheet of the present invention comprises the following steps:
1) a certain amount of aluminium block, MAG block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain, wherein, aluminium block, magnesium are weighed
The mass ratio of block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain is (96.6-99.31): (0.5-2): (0.1-1):
(0.05-0.2): (0.01-0.1): (0.01-0.05): (0.01-0.03): (0.01-0.02), aluminium block is preheated post-heating and arrives
750-800 DEG C melts, then bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain is joined in the aluminum liquid after fusing, is formed
Alloy melt, cools to 650-700 DEG C with the furnace after being stood by the alloy melt of formation, then removes the scum silica frost of alloy melt liquid level,
Then alloy melt is cast to cast molding in water-cooled punching block, obtains base substrate；
2) by step 1) base substrate that obtains carries out solution heat treatment successively and rolling processes, and obtains rare earth modified aluminum alloy anode
Sheet.
Step 1) in aluminium block preheating process be: aluminium block is placed in the Muffle furnace of 100-150 DEG C insulation 30-40min.
Step 1) in stand time be 5-10min.
Step 2) in the concrete operations of solution heat treatment be, first by step 1) base substrate that obtains is placed into 500-560 DEG C
Solution treatment 5-8h in Muffle furnace, is then cooled to room temperature.
Step 2) in rolling be processed as multistage hot deformation system, wherein, during single pass hot rolling, rolling temperature is
400-450 DEG C, single pass is deformed into 35-45%, and total deformation is more than 90%.
The purity of aluminium block, the purity of MAG block, the purity of bismuth granule, the purity of stannum grain, the purity of gallium grain, the purity of indium grain, lanthanum
The purity of grain and the purity of cerium grain are all higher than equal to 99.99%.
The method have the advantages that
Tin element and phosphide element in rare earth modified aluminum alloy anode sheet raw material of the present invention are that high liberation of hydrogen is the most electric
Bit element, can effectively reduce rare earth modified aluminum alloy anode sheet gas-evolving electrodes speed in the electrolytic solution.Additionally, work as rare earth
When modified aluminium alloy anode sheet and alkaline electrolyte generation electrochemical reaction, it is solid-solubilized in the stannum in rare earth modified aluminum alloy anode sheet
Atom can be free in the electrolytic solution with the form of tin ion, closes when these tin ions are deposited on rare earth modified aluminum by reduction further
During the pole piece of Jinyang, the carrying out that aluminium anodes gas-evolving electrodes reacts can be suppressed further.In rare earth modified aluminum alloy anode sheet
Gallium element, bismuth element and magnesium elements can form eutectic mixture in the base as eutectic alloying element, at electricity
Under the operating temperature of pond, these eutectic mixture are in melted state, dissolve along with the reaction of parent metal aluminum and dissolve,
And then destroy the integrity of aluminium anodes surface film oxide, make aluminum substrate expose the electrochemical reaction active site made new advances, improve
The electro-chemical activity of aluminum alloy anode.And elements La and the existence of cerium in rare earth modified aluminum alloy anode sheet, can significantly subtract
Little stannum and the gathering of indium isoreactivity segregation phase, when activity segregation is the distribution of fine uniform state, on the one hand ensure that active matter
The uniform dissolution of matter, improves the electro-chemical activity of aluminium anodes, on the other hand decreases the quantity of local spot corrosion, improves material
Decay resistance.During preparation, the solution heat treatment improvement master to the microstructure and property of rare earth modified aluminum alloy anode sheet
If by improving alloying element solubility, reduce what active element segregation reunion realized.Stannum and indium in the base good
Solid solution, on the one hand can reduce stannum and the indium solution loss at grain boundary defects, it is ensured that the electricity that aluminum alloy anode material is good
Chemism, on the other hand, stannum and the increase of indium solid solubility in matrix, can effectively reduce and form activity at grain boundary defects partially
The quantity of phase separation, and then decrease the stanniferous and gathering of indium segregation phase and come off so that aluminum alloy anode sheet microstructure is more
Uniformly, locally point corrosion reduces, and decay resistance is improved.And roll process to rare earth modified aluminum alloy anode sheet tissue
Improvement with performance is then realized by dynamic recrystallization, under this rolling technological parameter, and material occurrence dynamics recrystallization
Changing, matrix Dislocations tangles and cellular structure substantially reduces, and straight tiny recrystal grain occurs, active element distribution is all
Even, segregation gradually reduces mutually, and aluminium anodes decay resistance and electro-chemical activity are significantly improved.It addition, the present invention keeps away
Exempting to use toxic element, environmental protection, do not produce environment and pollute, preparation method is simple, and practicality is extremely strong.
Accompanying drawing explanation
Fig. 1 (a) is the surface corrosion shape appearance figure of the sheet of aluminum alloy anode before modified prepared by comparative example；
Fig. 1 (b) is the segregation phase energy spectrum analysis figure of the sheet of aluminum alloy anode before modified prepared by comparative example；
Fig. 2 (a) is the surface corrosion shape appearance figure of the rare earth modified aluminum alloy anode sheet of embodiment one preparation；
Fig. 2 (b) is the segregation phase energy spectrum analysis figure of the rare earth modified aluminum alloy anode sheet of embodiment one preparation；
Fig. 3 is the rare earth modified aluminum alloy anode sheet work that aluminum alloy anode sheet prepared by comparative example is prepared with embodiment one
During gas-evolving electrodes RATES's analysis chart；
Fig. 4 is the rare earth modified aluminum alloy anode sheet work that aluminum alloy anode sheet prepared by comparative example is prepared with embodiment one
During Tafel polarization curve relative analysis figure；
Fig. 5 is the rare earth modified aluminum alloy anode sheet work that aluminum alloy anode sheet prepared by comparative example is prepared with embodiment one
During electrode potential relative analysis figure.
Detailed description of the invention
Below in conjunction with the accompanying drawings the present invention is described in further detail:
Comparative example
The preparation method of aluminum alloy anode sheet comprises the following steps before modified:
1) a certain amount of aluminium block, MAG block, bismuth granule, stannum grain, gallium grain and indium grain, wherein, aluminium block, MAG block, bismuth granule, stannum are weighed
The mass ratio of grain, gallium grain and indium grain is 98.12: 1: 0.8: 0.05: 0.01: 0.02, aluminium block preheats post-heating and carries out to 750 DEG C
Fusing, then MAG block, bismuth granule, stannum grain, gallium grain and indium grain are joined in the aluminum liquid after fusing, form alloy melt, by formed
Alloy melt cools to 700 DEG C with the furnace after standing, then removes the scum silica frost of alloy melt liquid level, then alloy melt is cast to water
Cast molding in cold punching block, obtains base substrate；
2) by step 1) base substrate that obtains carries out solution heat treatment successively and rolling processes, and obtains rare earth modified aluminum alloy anode
Sheet.
Step 1) in aluminium block preheating process be: aluminium block is placed in the Muffle furnace of 150 DEG C insulation 40min.
Step 1) in stand time be 5min.
Step 2) in the concrete operations of solution heat treatment be, first by step 1) base substrate that obtains is placed into the Muffle of 500 DEG C
Solution treatment 5h in stove, is then cooled to room temperature.
Step 2) in rolling be processed as multistage hot deformation system, wherein, during single pass hot rolling, rolling temperature is
400 DEG C, single pass is deformed into 38%.
Embodiment one
The preparation method of rare earth modified aluminum alloy anode sheet of the present invention comprises the following steps:
1) a certain amount of aluminium block, MAG block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain, wherein, aluminium block, magnesium are weighed
The mass ratio of block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain is 98.09: 1: 0.8: 0.05: 0.01: 0.02: 0.02:
0.01, aluminium block is preheated post-heating and melts to 750 DEG C, then by MAG block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain
Join in the aluminum liquid after fusing, form alloy melt, cool to 700 DEG C with the furnace after being stood by the alloy melt of formation, then go
Except the scum silica frost of alloy melt liquid level, then alloy melt is cast to cast molding in water-cooled punching block, obtains base substrate；
2) by step 1) base substrate that obtains carries out solution heat treatment successively and rolling processes, and obtains rare earth modified aluminum alloy anode
Sheet.
Step 1) in aluminium block preheating process be: aluminium block is placed in the Muffle furnace of 150 DEG C insulation 40min.
Step 1) in stand time be 5min.
Step 2) in the concrete operations of solution heat treatment be, first by step 1) base substrate that obtains is placed into the Muffle of 500 DEG C
Solution treatment 5h in stove, is then cooled to room temperature.
Step 2) in rolling be processed as multistage hot deformation system, wherein, during single pass hot rolling, rolling temperature is
400 DEG C, single pass is deformed into 38%.
Embodiment two
The preparation method of rare earth modified aluminum alloy anode sheet of the present invention comprises the following steps:
1) a certain amount of aluminium block, MAG block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain, wherein, aluminium block, magnesium are weighed
The mass ratio of block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain is 98.06: 1: 0.8: 0.08: 0.01: 0.02: 0.02:
0.01, aluminium block is preheated post-heating and melts to 800 DEG C, then by MAG block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain
Join in the aluminum liquid after fusing, form alloy melt, cool to 700 DEG C with the furnace after being stood by the alloy melt of formation, then go
Except the scum silica frost of alloy melt liquid level, then alloy melt is cast to cast molding in water-cooled punching block, obtains base substrate；
2) by step 1) base substrate that obtains carries out solution heat treatment successively and rolling processes, and obtains rare earth modified aluminum alloy anode
Sheet.
Step 1) in aluminium block preheating process be: aluminium block is placed in the Muffle furnace of 150 DEG C insulation 30min.
Step 1) in stand time be 5min.
Step 2) in the concrete operations of solution heat treatment be, first by step 1) base substrate that obtains is placed into the Muffle of 540 DEG C
Solution treatment 5h in stove, is then cooled to room temperature.
Step 2) in rolling be processed as multistage hot deformation system, wherein, during single pass hot rolling, rolling temperature is
400 DEG C, single pass is deformed into 38%.
Embodiment three
The preparation method of rare earth modified aluminum alloy anode sheet of the present invention comprises the following steps:
1) a certain amount of aluminium block, MAG block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain, wherein, aluminium block, magnesium are weighed
The mass ratio of block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain is 97.87: 1.5: 0.5: 0.05: 0.01: 0.02: 0.03:
0.02, aluminium block is preheated post-heating and melts to 760 DEG C, then by MAG block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain
Join in the aluminum liquid after fusing, form alloy melt, cool to 700 DEG C with the furnace after being stood by the alloy melt of formation, then go
Except the scum silica frost of alloy melt liquid level, then alloy melt is cast to cast molding in water-cooled punching block, obtains base substrate；
2) by step 1) base substrate that obtains carries out solution heat treatment successively and rolling processes, and obtains rare earth modified aluminum alloy anode
Sheet.
Step 1) in aluminium block preheating process be: aluminium block is placed in the Muffle furnace of 150 DEG C insulation 35min.
Step 1) in stand time be 5min.
Step 2) in the concrete operations of solution heat treatment be, first by step 1) base substrate that obtains is placed into the Muffle of 500 DEG C
Solution treatment 8h in stove, is then cooled to room temperature.
Step 2) in rolling be processed as multistage hot deformation system, wherein, during single pass hot rolling, rolling temperature is
420 DEG C, single pass is deformed into 42%.
Embodiment four
The preparation method of rare earth modified aluminum alloy anode sheet of the present invention comprises the following steps:
1) a certain amount of aluminium block, MAG block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain, wherein, aluminium block, magnesium are weighed
The mass ratio of block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain is 97.81: 1.5: 0.5: 0.08: 0.01: 0.05: 0.03:
0.02, aluminium block is preheated post-heating and melts to 760 DEG C, then by MAG block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain
Join in the aluminum liquid after fusing, form alloy melt, cool to 650 DEG C with the furnace after being stood by the alloy melt of formation, then go
Except the scum silica frost of alloy melt liquid level, then alloy melt is cast to cast molding in water-cooled punching block, obtains base substrate；
2) by step 1) base substrate that obtains carries out solution heat treatment successively and rolling processes, and obtains rare earth modified aluminum alloy anode
Sheet.
Step 1) in aluminium block preheating process be: aluminium block is placed in the Muffle furnace of 100 DEG C insulation 32min.
Step 1) in stand time be 10min.
Step 2) in the concrete operations of solution heat treatment be, first by step 1) base substrate that obtains is placed into the Muffle of 540 DEG C
Solution treatment 8h in stove, is then cooled to room temperature.
Step 2) in rolling be processed as multistage hot deformation system, wherein, during single pass hot rolling, rolling temperature is
420 DEG C, single pass is deformed into 42%.
The aluminum alloy anode of preparation in above-mentioned all comparative examples and embodiment one to four is carried out decay resistance and electrification
Learning performance test, used test condition is specific as follows:
Prepared by sample: with the aluminum alloy anode sheet of preparation in embodiment one to four, comparative example is carried out rolling and shears, obtain thick
Degree is 2cm for 0.5mm, work area2Pole piece, surface through sanding and polishing, stay tail and on tail punch, with distilled water by pole piece
Surface washing dedusting, and rinse with distilled water again after acetone oil removing, remove acetone, dry up, connect copper at pole piece afterbody and lead
With AB glue by afterbody, back and electrode edge envelope painting twice after line, only retain 1cm in the middle of one side2Working region, treat AB glue
Store for future use after solidification.
Method of testing: aluminum alloy anode uses liberation of hydrogen eudiometry to measure from corrosion rate, the electrochemistry of aluminum alloy anode
Performance uses current potential-chronometry (E-T curve) and potentiodynamic polarization method (Tafel curve) to test, and all tests are all at three electricity
Carrying out under polar body system, three-electrode system is with aluminum alloy anode sample as Electrode, and graphite flake is auxiliary electrode, Hg/HgO electrode
For reference electrode, electrolyte system is 85 DEG C, 5mol L-1NaOH Yu 10g L-1Na2SnO3Mixed solution, discharge current is close
Degree is 800mA cm-2。
The decay resistance of the aluminum alloy anode sheet that comparative example of the present invention and embodiment one to four obtain and chemical property
Parameter is shown in Table 1.
Table 1
See Fig. 1, Fig. 2 it can be seen that aluminum alloy anode electric discharge terminates in the erosion profile of rear surface before modified in comparative example
There is the phenomenon that white segregation is assembled mutually and come off, segregation the most around has etch pit not of uniform size to occur, material corrosion resisting property
Poor；Middle rare earth modified aluminium alloy anode sheet surface activity segregation of the present invention is the distribution of small and dispersed shape, and bulk etch pit is bright
Aobvious disappear, alloy Microstructure Uniformity be improved significantly.
See Fig. 3,4 combine table 1 it can be seen that compared with comparative example, embodiment one middle rare earth modified aluminium alloy anode sheet
Gas-evolving electrodes speed be greatly lowered, and the gas-evolving electrodes speed of embodiment one to four middle rare earth modified aluminium alloy anode sheet is equal
Less than 0.096mL min-1·cm-2, illustrate that rare earth modified aluminum alloy anode sheet prepared by the present invention has the most corrosion-resistant
Performance.
See Fig. 5 and combine table 1 it can be seen that compared with comparative example, embodiment one middle rare earth modified aluminium alloy anode sheet
There is significantly negative shifting in electrode operating potential, and the electrode operating potential of embodiment one to four middle rare earth modified aluminium alloy anode sheet is equal
It is defeated by-1.609V, illustrates that the rare earth modified aluminum alloy anode sheet in the present invention has higher electro-chemical activity.
In sum, rare earth modified aluminum alloy anode sheet of the present invention is the alkalescence preferable anode material of aluminum cell.
Embodiment five
The preparation method of rare earth modified aluminum alloy anode sheet of the present invention comprises the following steps:
1) a certain amount of aluminium block, MAG block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain, wherein, aluminium block, magnesium are weighed
The mass ratio of block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain is 96.6: 2: 1: 0.2: 0.1: 0.05: 0.03: 0.02, will
Aluminium block preheating post-heating melts to 800 DEG C, then joins molten by MAG block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain
In aluminum liquid after change, form alloy melt, after being stood by the alloy melt of formation, cool to 700 DEG C with the furnace, then it is molten to remove alloy
The scum silica frost in body fluid face, is then cast to alloy melt cast molding in water-cooled punching block, obtains base substrate；
2) by step 1) base substrate that obtains carries out solution heat treatment successively and rolling processes, and obtains rare earth modified aluminum alloy anode
Sheet.
Step 1) in aluminium block preheating process be: aluminium block is placed in the Muffle furnace of 150 DEG C insulation 40min.
Step 1) in stand time be 10min.
Step 2) in the concrete operations of solution heat treatment be, first by step 1) base substrate that obtains is placed into the Muffle of 560 DEG C
Solution treatment 8h in stove, is then cooled to room temperature.
Step 2) in rolling be processed as multistage hot deformation system, wherein, during single pass hot rolling, rolling temperature is
450 DEG C, single pass is deformed into 45%.
Embodiment six
The preparation method of rare earth modified aluminum alloy anode sheet of the present invention comprises the following steps:
1) a certain amount of aluminium block, MAG block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain, wherein, aluminium block, magnesium are weighed
The mass ratio of block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain is 99.31: 0.5: 0.1: 0.05: 0.01: 0.01: 0.01:
0.01, aluminium block is preheated post-heating and melts to 750 DEG C, then by MAG block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain
Join in the aluminum liquid after fusing, form alloy melt, cool to 650 DEG C with the furnace after being stood by the alloy melt of formation, then go
Except the scum silica frost of alloy melt liquid level, then alloy melt is cast to cast molding in water-cooled punching block, obtains base substrate；
2) by step 1) base substrate that obtains carries out solution heat treatment successively and rolling processes, and obtains rare earth modified aluminum alloy anode
Sheet.
Step 1) in aluminium block preheating process be: aluminium block is placed in the Muffle furnace of 100 DEG C insulation 30min.
Step 1) in stand time be 5min.
Step 2) in the concrete operations of solution heat treatment be, first by step 1) base substrate that obtains is placed into the Muffle of 500 DEG C
Solution treatment 5h in stove, is then cooled to room temperature.
Step 2) in rolling be processed as multistage hot deformation system, wherein, during single pass hot rolling, rolling temperature is
400 DEG C, single pass is deformed into 35%.
Embodiment seven
The preparation method of rare earth modified aluminum alloy anode sheet of the present invention comprises the following steps:
1) a certain amount of aluminium block, MAG block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain, wherein, aluminium block, magnesium are weighed
The mass ratio of block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain is 98.38: 1.2: 0.2: 0.1: 0.05: 0.03: 0.03:
0.01, aluminium block is preheated post-heating and melts to 770 DEG C, then by MAG block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain
Join in the aluminum liquid after fusing, form alloy melt, cool to 670 DEG C with the furnace after being stood by the alloy melt of formation, then go
Except the scum silica frost of alloy melt liquid level, then alloy melt is cast to cast molding in water-cooled punching block, obtains base substrate；
2) by step 1) base substrate that obtains carries out solution heat treatment successively and rolling processes, and obtains rare earth modified aluminum alloy anode
Sheet.
Step 1) in aluminium block preheating process be: aluminium block is placed in the Muffle furnace of 130 DEG C insulation 36min.
Step 1) in stand time be 7min.
Step 2) in the concrete operations of solution heat treatment be, first by step 1) base substrate that obtains is placed into the Muffle of 530 DEG C
Solution treatment 6.5h in stove, is then cooled to room temperature.
Step 2) in rolling be processed as multistage hot deformation system, wherein, during single pass hot rolling, rolling temperature is
440 DEG C, single pass is deformed into 42%.
Embodiment eight
The preparation method of rare earth modified aluminum alloy anode sheet of the present invention comprises the following steps:
1) a certain amount of aluminium block, MAG block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain, wherein, aluminium block, magnesium are weighed
The mass ratio of block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain is 97.4: 1.7: 0.6: 0.15: 0.08: 0.04: 0.02:
0.01, aluminium block is preheated post-heating and melts to 790 DEG C, then by MAG block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain
Join in the aluminum liquid after fusing, form alloy melt, cool to 680 DEG C with the furnace after being stood by the alloy melt of formation, then go
Except the scum silica frost of alloy melt liquid level, then alloy melt is cast to cast molding in water-cooled punching block, obtains base substrate；
2) by step 1) base substrate that obtains carries out solution heat treatment successively and rolling processes, and obtains rare earth modified aluminum alloy anode
Sheet.
Step 1) in aluminium block preheating process be: aluminium block is placed in the Muffle furnace of 140 DEG C insulation 32min.
Step 1) in stand time be 9min.
Step 2) in the concrete operations of solution heat treatment be, first by step 1) base substrate that obtains is placed into the Muffle of 550 DEG C
Solution treatment 6h in stove, is then cooled to room temperature.
Step 2) in rolling be processed as multistage hot deformation system, wherein, during single pass hot rolling, rolling temperature is
430 DEG C, single pass is deformed into 43%.
It should be noted that in above example and comparative example, the purity of aluminium block, the purity of MAG block, the purity of bismuth granule, stannum
The purity of purity, the purity of gallium grain, the purity of indium grain, the purity of lanthanum grain and the cerium grain of grain is all higher than equal to 99.99%.
Claims (5)
1. the preparation method of a rare earth modified aluminum alloy anode sheet, it is characterised in that comprise the following steps:
1) a certain amount of aluminium block, MAG block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain, wherein, aluminium block, MAG block, bismuth are weighed
The mass ratio of grain, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain is (96.6-99.31): (0.5-2): (0.1-1): (0.05-
0.2): (0.01-0.1): (0.01-0.05): (0.01-0.03): (0.01-0.02), aluminium block is preheated post-heating to 750-800
DEG C melt, then MAG block, bismuth granule, stannum grain, gallium grain, indium grain, lanthanum grain and cerium grain are joined in the aluminum liquid after fusing, formed and close
Gold melt, cools to 650-700 DEG C with the furnace after being stood by the alloy melt of formation, then removes the scum silica frost of alloy melt liquid level, so
After alloy melt is cast to cast molding in water-cooled punching block, obtain base substrate；
2) by step 1) base substrate that obtains carries out solution heat treatment successively and rolling processes, and obtains rare earth modified aluminum alloy anode sheet；
Step 2) in rolling be processed as multistage hot deformation system, wherein, during single pass hot rolling, rolling temperature is 400-
450 DEG C, single pass is deformed into 35-45%, and total deformation is more than 90%.
The preparation method of rare earth modified aluminum alloy anode sheet the most according to claim 1, it is characterised in that step 1) in aluminum
The process of block preheating is: aluminium block is placed in the Muffle furnace of 100-150 DEG C insulation 30-40min.
The preparation method of rare earth modified aluminum alloy anode sheet the most according to claim 1, it is characterised in that step 1) in quiet
The time put is 5-10min.
The preparation method of rare earth modified aluminum alloy anode sheet the most according to claim 1, it is characterised in that step 2) in solid
The concrete operations of molten heat treatment are, first by step 1) base substrate that obtains is placed into solution treatment 5-in the Muffle furnace of 500-560 DEG C
8h, is then cooled to room temperature.
The preparation method of rare earth modified aluminum alloy anode sheet the most according to claim 1, it is characterised in that aluminium block pure
Degree, the purity of MAG block, the purity of bismuth granule, the purity of stannum grain, the purity of gallium grain, the purity of indium grain, the purity of lanthanum grain and cerium grain
Purity is all higher than equal to 99.99%.
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| CN105921516B (en) * | 2016-05-05 | 2018-01-05 | 广东金兰新材料有限公司 | Aluminium foil suitable for lithium ion battery and preparation method thereof |
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| CN106784772B (en) * | 2017-03-22 | 2019-10-08 | 长沙迅洋新材料科技有限公司 | A kind of battery aluminium alloy negative electrode material and preparation method thereof |
| CN109694964B (en) * | 2019-02-26 | 2021-12-03 | 中铝东南材料院（福建）科技有限公司 | Preparation method of aluminum-air battery anode material |
| CN112111673A (en) * | 2019-06-19 | 2020-12-22 | 吉林大学 | Method for preparing aluminum alloy with fine grain characteristics and aluminum alloy prepared by same |
| CN111057914B (en) * | 2019-12-30 | 2021-02-09 | 广东省材料与加工研究所 | Anode alloy material, preparation method thereof, anode for aluminum-air battery and aluminum-air battery |
| CN111560544B (en) * | 2020-05-25 | 2021-07-27 | 湖南西瑞尔新材料科技有限公司 | Preparation method of anode aluminum alloy for air battery and air battery |
| CN112708809B (en) * | 2020-11-27 | 2022-03-04 | 中国电子科技集团公司第十八研究所 | Meta-aluminate-resistant rare earth aluminum alloy anode material and manufacturing method thereof |
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