CN106784772B - A kind of battery aluminium alloy negative electrode material and preparation method thereof - Google Patents
A kind of battery aluminium alloy negative electrode material and preparation method thereof Download PDFInfo
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
A kind of battery aluminium alloy negative electrode material, is made of the component of following mass percent meter: 0.001%~1% lanthanum, 0.001%~1% gallium, 0.001%~1% magnesium, 0.001%~1% indium, surplus are aluminium.The present invention also provides a kind of preparation methods of battery aluminium alloy negative electrode material, high temperature is respectively adopted for a long time in this method, the medium temperature short time, with the cooperation of low temperature different heat treatment process and the deformation technique of three classes such as a long time, the optimization regulation to aluminium alloy negative electrode material ingredient, institutional framework and alloy phase is realized.By adjusting the appropriate additive amount of alloying element and the plastic forming process and heat treatment process of cooperation aluminum honeycomb material appropriate, realize the best collocation between multifactor, it meets under 500mA/cm2~1000mA/cm2 high current density, the requirement as electrical source of power electric discharge.The aluminium alloy negative electrode material that the present invention obtains, the technological process of production is short, and various technological parameters are easy to control, it is ensured that aluminium alloy cathode product quality, while production cost is low, is advantageously implemented large-scale production.
Description
Technical field
The present invention relates to a kind of battery aluminium alloy negative electrode materials and preparation method thereof, belong to new energy material application skill
Art field.
Background technique
Metallic aluminium is a kind of very active anode material, its normal potential is very negative, be in alkaline electrolyte solution-
2.4V(vs standard hydrogen electrode), be -1.6V(vs standard hydrogen electrode in neutral electrolyte solution).The electrochemical equivalent of aluminium is very
Greatly, it has 2980Ah/Kg, and the rich reserves of aluminium, at low cost, reaction product not will cause environmental pollution, is managed as battery
The negative electrode material thought.
In electrolyte solution, the chemical activity of aluminium is high, and the film layer that surface is easily oxidized aluminium protects, and makes electricity
Chemical reaction is difficult to continue progress, causes more serious polarization phenomena.So the electrode potential of aluminium can much deviate it at this time
Theoretical potential value, causes the reduction of discharge voltage absolute value, and discharge power is reduced, it is difficult to realize that the negative electrode material as battery carries out
It uses.In addition, aluminum honeycomb can react with the water in electrolyte under alkaline electrolyte environment, a large amount of hydrogen are generated, are caused
The control of its electrochemical reaction is become difficult.These problems can regulate and control its electricity by adding alloying element appropriate in aluminium
Chemical reaction characteristic, reduces the degree of polarization of aluminium alloy negative electrode material in the electrolytic solution, to increase substantially the electric discharge electricity of aluminium
Press absolute value.Meanwhile by the control of process conditions, to alloy phase type, composition, size, the distribution mode etc. in aluminium alloy
Feature is regulated and controled, and may be implemented to influence the parameters such as liberation of hydrogen, corrosion rate during aluminium alloy negative discharge, thus
Reach the requirement for meeting discharge performance.
For the discharge performance for improving battery cathode aluminium, the R&D work of some early periods has been carried out in aluminium alloy and has been added not
With the research method of alloying element.Patent (application number: 201410731938.0) proposes and 7 kinds of different element structures is added in aluminium
The method of Cheng Bayuan aluminium alloy negative electrode material.This 7 kinds of addition element are lithium, manganese, gallium, indium, tin, magnesium, bismuth, are then obtained a kind of high
Eight yuan of aluminium alloy cathode of the novel aluminium-air cell of performance, improve the energy density of aluminum honeycomb, reduce the liberation of hydrogen of cathode
Rate improves the utilization rate of cathode.But the alloying element type that this method is added is excessive, and so more elements to be allowed to exist
It is uniformly distributed, is difficult to realize in aluminum substrate.Moreover, so many alloying element is added, complex process is needed to configure a large amount of big-and-middle
Between alloy, the stability of manufactured aluminium alloy negative electrode material ingredient and performance is poor, in actual application it is difficult to ensure that electric discharge
The stability of performance.
Patent (application number: 201510561492.6) simplifies the value volume and range of product of addition element in aluminum substrate, alloy
Ingredient is Al-Zn-Ga-In, and after zinc, gallium, phosphide element is added, the electro-chemical activity of aluminum substrate can be improved, and reduces self-corrosion speed
Rate improves aluminium alloy negative discharge current potential, is suitble to use in alkaline electrolyte.According to the patented invention content it is found that the aluminium
Alloy material of cathode is in 100mA/cm2The discharge voltage value that the 10h that discharges under current density condition is obtained, in general, with
The increase of discharge current density and the extension of discharge time, the discharge voltage of negative electrode material can sharply decline, and lose battery military service
Function.Therefore, if discharging for a long time under high current density, it is also necessary to be changed further directed to aluminium alloy negative electrode material
Into satisfaction is as electrical source of power in use, the requirement discharged under high current density.
(application number: 201610390916.1) also having carried out ingredient improvement to aluminium alloy cathode aluminium alloy to patent, exploitation
Aluminium alloy negative electrode material in, addition is three kinds of magnesium, bismuth, manganese elements, and the aluminium alloy negative electrode material is assembled into aluminium alloy
Air cell discharges.
And Japan Patent (application number: 201180010891.3) being the magnesium that 0.0001% ~ 8% content is added in aluminum substrate,
And controlling the content of iron and silicon in aluminum substrate is respectively 0.0001%~0.03% and 0.0001%~0.02%.It can effectively adjust in this way
The corrosion behavior of aluminium alloy is controlled, discharge effect is more preferable after being assembled into aluminium-air cell.
Generally, in aluminium alloy negative electrode material, available data report: having had exploitation Al-Zn, Al-Te, Al-Ga,
The bianry alloys such as Al-In, the ternarys such as Al-Zn-In, Al-Zn-Sn, Al-Zn-Hg, Al-Mg-Mn, Al-Ga-Mn, Al-In-Mg are closed
Gold and above-mentioned quaternary or even eight yuan of alloys.From aluminum honeycomb material military service effect, the addition of alloying element is to electrification
The influence for learning performance, other than the element species of addition and content can have an important influence on the discharge performance of material, addition
The plastic processing of the aluminium alloy negative electrode material obtained after alloying element and heat treatment method, are also important influence factor, these
Technological factor will have a direct impact on and be added to alloying element using which kind of state or phase in the presence of with aluminum substrate, directly affects
Activity, duration and the stability that the chemical energy of aluminum substrate changes to electric energy.
Therefore, the aluminum substrate addition element of suitable species is selected, adjusts the appropriate additive amount of alloying element and with suitable
When aluminum honeycomb material plastic forming process and heat treatment process, realize it is multifactor between best collocation, be to prepare power
The key of battery aluminium alloy negative electrode material.Especially, for different discharging conditions, need to design different aluminium alloy cathode
The ingredient and preparation process of material, such as need in 500mA/cm2~1000mA/cm2Under high current density, as electrical source of power
When electric discharge, it is necessary to which selection, content and its processing of the element species in aluminium alloy negative electrode material and heat treatment process are realized most
Good collocation is just able to satisfy the requirement of high power discharge.
Summary of the invention
It is an object of the present invention to provide a kind of battery to discharge under high current density aluminium alloy negative electrode materials, by aluminium
Selected alloying element is added in matrix, and adjusts the appropriate additive amount of alloying element and cooperation preparation process appropriate, it is real
Best collocation between now multifactor guarantees cathode in 500mA/cm2~1000mA/cm2There is enough put under high current density
Electric potential, to meet requirement of the power battery to high-power service condition.
To achieve the above object, the present invention adopts the following technical scheme: a kind of battery aluminium alloy negative electrode material, feature
It is, is grouped as by the group of following mass percent meter: 0.001%~1% lanthanum, 0.001%~1% gallium, 0.001%~1% magnesium,
0.001%~1% indium, surplus are aluminium.
Preferably, a kind of battery is grouped as with aluminium alloy negative electrode material by the group of following mass percent meter: 0.01%~
0.1% lanthanum, 0.01%~0.1% gallium, 0.01%~0.1% magnesium, 0.01%~0.1% indium, surplus are aluminium；
It is furthermore preferred that a kind of battery is grouped as with aluminium alloy negative electrode material by the group of following mass percent meter: lanthanum
0.02%, gallium 0.05%, magnesium 0.05%, indium 0.05%, surplus is aluminium.
Above-mentioned aluminium, lanthanum, gallium, magnesium and indium purity >=99.9%；Preferably, the purity of the aluminium, lanthanum, gallium, magnesium and indium >=
99.99%。
The present invention also provides a kind of methods for preparing above-mentioned battery aluminium alloy negative electrode material comprising following steps:
S1: taking aluminium and alloying element lanthanum, gallium, magnesium, indium respectively, by the composition proportion ingredient of setting；
S2: under protective condition, aluminium being melted in elevated temperature vessel, after aluminium dissolves, be added alloying element lanthanum, gallium, magnesium,
Indium stirs, cools down, stands, pours, obtain ingot casting after all dissolving；
S3: the ingot casting that S2 is obtained carries out first time heat treatment, and annealing temperature is 400 DEG C~500 DEG C, soaking time 12
~for 24 hours, and it is cooling, take out ingot casting；
S4: the ingot casting that S3 is obtained carries out rolling process at room temperature, then by the ingot casting of deformation in heat-treatment furnace into
Second of heat treatment of row, annealing temperature are 300 DEG C~350 DEG C, and soaking time is 0.5~1h, and cooling, which can be by same
Deflection and heat treatment process repeat, and the aluminium alloy cathode plate of dimensions is met until obtaining；
S5: the aluminium alloy cathode plate for meeting dimensions that S4 is obtained is carried out in heat-treatment furnace at third time heat
Reason, annealing temperature are 100 DEG C~250 DEG C, and soaking time is 1~8h, cooling, obtain finished product.
As a preferred solution: the addition sequence melting temperature of alloying element lanthanum in S2 step, gallium, magnesium, indium is from high to low, according to
Secondary addition, specifically: lanthanum is first added, after lanthanum fusing, is sequentially added into magnesium, indium, gallium.
As a preferred solution: S2 specific steps are as follows: under the protection of argon gas, temperature exists aluminium when being 720 DEG C~750 DEG C
Melted in high purity graphite crucible, after aluminium fusing after, lanthanum is added in aluminum melt, after lanthanum fusing after, be sequentially added into magnesium, indium,
Gallium is stirred, is cooled at 700 DEG C~720 DEG C, 700 DEG C~720 DEG C after 10~15min of standing after alloying element all dissolves
It is cast in metal cast iron die, obtains ingot casting, the mold uses circulating water.Entire fusion process, is protected using argon gas
Melt is protected, the oxidation of aluminum melt under hot conditions is mitigated.
As a preferred solution: being cooled to carry out quenching cooling in the water of room temperature described in S3 step.
As a preferred solution: being cooled to cool down in air after taking out in heat treatment described in S4 step.
As a preferred solution: being cooled to described in S5 step cooling with heat-treatment furnace.
As a preferred solution: deflection is within 5%, when accumulative total deformation reaches 50% per pass when rolling in S4 step
When~70%, the ingot casting of deformation is carried out second and is heat-treated.
The present invention provides a kind of preferred battery preparation methods of aluminium alloy negative electrode material, comprise the concrete steps that:
S1: by the composition proportion of the aluminium alloy negative electrode material of setting, aluminium and the conjunction of corrresponding quality are weighed on an electronic balance
Gold element；
S2: under the protection of argon gas, temperature melts aluminium when being 720 DEG C~750 DEG C in high purity graphite crucible, to
After aluminium fusing, lanthanum is added in aluminum melt, after lanthanum fusing, is sequentially added into magnesium, indium, gallium, alloying element addition sequence is by molten
Point temperature from high to low, sequentially adds；After alloying element all dissolves, stirs, is cooled to 700 DEG C~720 DEG C, 700 DEG C~
It is cast in metal cast iron die after standing 10~15min at 720 DEG C, obtains ingot casting, the mold uses circulating water；It is whole
A fusion process protects melt using argon gas, mitigates the oxidation of aluminum melt under hot conditions；
S3: the aluminium alloy cast ingot obtained after demoulding carries out first time heat treatment, and annealing temperature is 400 DEG C~500 DEG C, temperature
Degree 12~for 24 hours, then it is directly carried out in the water of room temperature to quenching cooling, take out ingot casting；
S4: the ingot casting that S3 is obtained carries out rolling processing at room temperature, and deformation amount controlling, but can within 5% per pass
Repeatedly to deform, when the deflection of accumulation reaches 50%~70%, the aluminium alloy of deformation is put into 300 DEG C~350 DEG C temperature of preheating
It carries out being heat-treated for second in the heat-treatment furnace of degree, heat treatment time is 0.5 ~ 1h, is then taken out from furnace directly in air
It is cooling；The step can be repeated by equivalent variations amount and heat treatment process, and the aluminium alloy of dimensions is met until obtaining
Negative electrode material；
S5: after last time deforms, will obtain and meet the aluminium alloy negative electrode material of dimensions, be put into 100 DEG C~
Third time heat treatment is carried out in the heat-treatment furnace of 250 DEG C of temperature ranges, keeps the temperature 1~8h, and then furnace cooling obtains final produce
Product.
The invention has the following beneficial effects:
1, four kinds of addition element (lanthanum, gallium, magnesium, indium) have apparent effect to the promotion of aluminium alloy negative electrode material discharge capability
Fruit.Wherein, addition lanthanum (La) can refine crystal grain with the microstructure of refining aluminum alloy, when melting and casting, add Rare Earth Lanthanum
(La) slagging-off can be deoxygenated, alloy melt is purified, removes impurity effect, it is ensured that the high-purity of alloy controls impurity content, reduces
Impurity content is to the battery adverse effect of aluminium alloy negative electrode material discharge performance；Ga Element (Ga) is solid-solubilized in aluminum substrate, meeting
" amalgam " is formed with aluminium, makes aluminium atom that priming reaction occur by this compound containing gallium and electrolyte, reaches activation aluminium base
The effect of body is the inside that electrochemical reaction can be deep into aluminum substrate to destroy the oxidation film of aluminium surface densification, maintains aluminium
Activity, therefore gallium is one of aluminum honeycomb material active element；Element magnesium (Mg) improves the mechanical property of aluminum substrate, improves
The formability of battery aluminum honeycomb plate, magnesium can reduce the self-corrosion of aluminum substrate, while reduce the shape in aluminum honeycomb discharge process
At the formation of the cathode alloy phase of evolving hydrogen reaction；Element indium (In) has biggish overpotential of hydrogen evolution value, and it is negative can be substantially reduced aluminium
Liberation of hydrogen of the pole in electrochemical reaction, while also having certain activation to aluminum substrate.
2, impurity element often resulted in aluminum substrate aluminium self-corrosion it is serious, while reducing putting for aluminium in electrochemical reaction
Electric potential, it is therefore preferable that being controlled in the present invention the impurity overall content of alloy constituent element, the aluminium of high-purity in scheme
Alloy material of cathode, it can be ensured that the stabilization of discharge performance.Meanwhile the content of each constituent element (La, Ga, Mg, In) is below 1%, belongs to
The Reasonable Regulation And Control of addition alloying element may be implemented in the micro alloying element in aluminium alloy.
3, for the different phase of aluminium alloy negative electrode material processing, respectively for a long time using high temperature, medium temperature short time and low
The cooperation of warm long-time three classes different heat treatment process and deformation technique is realized to aluminium alloy negative electrode material ingredient, tissue
The regulation of the optimization of structure and alloy phase.Firstly, being directed to ingot casting high temperature long term annealing, it can be ensured that aluminium alloy negative electrode material exists
Each alloying element is distributed more uniform by flooding mechanism under high temperature；Secondly, the medium temperature short time anneals, aluminium alloy may be implemented
Crystallite dimension control, obtains the aluminum substrate recrystal grain of small and dispersed；Last low temperature long term annealing, it can be ensured that close member
Element forms the alloy phase of Dispersed precipitate, realizes being uniformly distributed for electrochemical properties.
4, the aluminium alloy negative electrode material that the present invention obtains, the technological process of production is short, and various technological parameters are easy to control, it is ensured that
Aluminium alloy cathode product quality, while production cost is low, is advantageously implemented large-scale production.
Detailed description of the invention
Fig. 1 is in embodiment 1, and three kinds of heat treatment process are to aluminium alloy negative electrode material microscopic structure impact effect.(a) high temperature
It anneals after (12h at 400 DEG C), some the second coarse phases are dissolved into aluminum substrate in alloy casting structure, reduce alloy phase
Segregation；(b) after medium annealing (0.5h at 300 DEG C), the second phase compound disperses are distributed in alloy, and due to being rolled
Processing, second hand down rolling direction arrangement；(c) after low-temperature annealing (1h at 100 DEG C), the second phase is uniformly precipitated, and reduces at this time
The directionality of second phase arrangement, alloy are mutually distributed more fine uniform, are conducive to the uniformity of aluminum honeycomb material electrochemical performance.
Fig. 2 is 2 aluminium alloy negative electrode material of embodiment respectively after three kinds of heat treatment process in 1000 mA/cm2High current is close
Sample surface morphology after the lower electric discharge of degree.(a) it discharges after high temperature long term annealing (at 500 DEG C for 24 hours), the corruption of sample surfaces
Erosion is non-uniformity, there is gully, hole etc., this is because crystallite dimension compares after cast alloy high temperature long term annealing
Coarse reason；(b) medium temperature short time annealing (1h at 350 DEG C) is discharged afterwards, due to rolling processing, erosion profile of discharging
Also there is apparent directionality, the gully of corrosion is deeper, and corrosion is uneven, this illustrates that discharge process will not be steady；(c) low temperature moves back
After fiery (8h at 250 DEG C), the obvious uniform and delicate of erosion profile, heat treatment can refine the crystallite dimension of aluminium alloy cathode after rolling
It is precipitated with the small and dispersed for being conducive to the second phase, to make corrosion process more evenly, is also beneficial to the stabilization of discharge process.
Fig. 3 is 1,2,3 three kinds of aluminium alloy negative electrode materials of embodiment respectively in (a) 650 mA/cm2, (b) 800 mA/cm2 and
(c) curve that the voltage to discharge under tri- kinds of 1000 mA/cm2 different current densities changes over time.It can be seen that alloy is close in high current
Higher voltage value is all maintained under degree.Alloy 3(Alloy 3 especially in embodiment 3), because of its purity highest, element
Addition proportion is by optimization, therefore discharge voltage value is most negative, absolute value of voltage highest, and discharge performance is best.
Fig. 4 is that embodiment 3 and general commercial fine aluminium (purity < 99.9%) discharge under 1000 mA/cm2 high current densities
When, the comparison of discharge voltage value.It can be seen that in embodiment 3 aluminium alloy negative electrode material discharge voltage absolute value, significantly larger than commonly
Commercial pure aluminum material illustrates the addition by micro alloying element and the implementation of heat treatment process, the electricity of aluminium alloy negative electrode material
Chemical property is greatly improved.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..Without departing substantially from spirit of that invention
In the case where essence, to modifications or substitutions made by the method for the present invention, step or condition, all belong to the scope of the present invention.
Unless otherwise specified, the conventional means that technological means used in embodiment is well known to those skilled in the art；
Unless otherwise specified, agents useful for same is commercially available in embodiment.
Embodiment 1
A kind of battery aluminium alloy negative electrode material, is grouped as by the group of following mass percent meter: 0.001% lanthanum (La),
0.001% gallium (Ga), 0.001% magnesium (Mg), 0.001% indium (In), surplus is aluminium.Purity requirement >=99.9% of all components.
The above-mentioned battery preparation method of aluminium alloy negative electrode material, includes the following steps:
S1: by the composition proportion of the aluminium alloy negative electrode material of setting, weigh on an electronic balance corrresponding quality aluminium and its
His several alloying elements (lanthanum, gallium, magnesium, indium)；
S2: by high purity graphite crucible, 720 DEG C is warming up in resistance furnace, is put into metallic aluminium, after aluminium fusing, in aluminium
Lanthanum is added in melt, after to be melted, is sequentially added into magnesium, indium, gallium；Alloying element addition sequence presses melting temperature from high to low,
It sequentially adds；After alloying element all dissolves, stir, be cooled at 700 DEG C, 700 DEG C stand 10min after be cast in metal casting
In swage tool, ingot casting is obtained, the mold uses circulating water；Entire fusion process protects melt using argon gas, mitigates high
The oxidation of aluminum melt under the conditions of temperature；
S3: the aluminium alloy cast ingot obtained after demoulding carries out first time heat treatment, and ingot casting is kept the temperature 12h at a temperature of 400 DEG C,
Then it is directly carried out in the water of room temperature to quenching cooling, take out ingot casting；
S4: the ingot casting that S3 is obtained carries out rolling processing at room temperature, and deformation amount controlling works as accumulation within 5% per pass
Deflection when reaching 50%, the aluminium alloy of deformation is put into the heat-treatment furnace of 300 DEG C of temperature of preheating and is carried out at second of heat
Then reason, heat treatment time 0.5h take out from furnace and directly cool down in air；The step can be by equivalent variations amount and heat
Treatment process repeats, and the aluminium alloy negative electrode material of dimensions is met until obtaining；
S5: after last time deforms, the aluminium alloy negative electrode material for meeting dimensions will be obtained, is put into 100 DEG C of temperature
Final heat treatment is carried out in the heat-treatment furnace of degree, keeps the temperature 1h, and then furnace cooling obtains final products.
Embodiment 2
A kind of battery aluminium alloy negative electrode material, is grouped as by the group of following mass percent meter: 1% lanthanum (La), 1% gallium
(Ga), 1% magnesium (Mg), 1% indium (In), surplus is aluminium.All components purity requirement >=99.9%.
The above-mentioned battery preparation method of aluminium alloy negative electrode material, includes the following steps:
S1: by the composition proportion of the aluminium alloy negative electrode material of setting, aluminium and the conjunction of corrresponding quality are weighed on an electronic balance
Gold element (lanthanum, gallium, magnesium, indium)；
S2: by high purity graphite crucible, 750 DEG C is warming up in resistance furnace, is put into metallic aluminium, after aluminium fusing, in aluminium
Lanthanum is added in melt, after to be melted, is sequentially added into magnesium, indium, gallium；Alloying element addition sequence presses melting temperature from high to low,
It sequentially adds；After alloying element all dissolves, stir, be cooled at 720 DEG C, 720 DEG C stand 15min after be cast in metal casting
In swage tool, ingot casting is obtained, the mold uses circulating water；Entire fusion process protects melt using argon gas, mitigates high
The oxidation of aluminum melt under the conditions of temperature；
S3: the aluminium alloy cast ingot obtained after demoulding carries out first time heat treatment, and ingot casting is kept the temperature for 24 hours at a temperature of 500 DEG C,
Then it is directly carried out in the water of room temperature to quenching cooling, take out ingot casting；
S4: the ingot casting that S3 is obtained carries out rolling processing at room temperature, and deformation amount controlling works as accumulation within 5% per pass
Deflection when reaching 70%, the aluminium alloy of deformation is put into the heat-treatment furnace of 350 DEG C of temperature of preheating and is carried out at second of heat
Then reason, heat treatment time 1h take out from furnace and directly cool down in air；The step can by equivalent variations amount and heat at
Science and engineering skill repeats, and the aluminium alloy negative electrode material of dimensions is met until obtaining；
S5: after last time deforms, the aluminium alloy negative electrode material for meeting dimensions will be obtained, is put into 250 DEG C of temperature
Final heat treatment is carried out in the heat-treatment furnace of degree, keeps the temperature 8h, and then furnace cooling obtains final products.
Embodiment 3
A kind of battery aluminium alloy negative electrode material, is grouped as by the group of following mass percent meter: 0.02% lanthanum (La),
0.05% gallium (Ga), 0.05% magnesium (Mg), 0.05% indium (In), surplus is aluminium；Purity >=99.99% of all components.
The above-mentioned battery preparation method of aluminium alloy negative electrode material, includes the following steps:
S1: by the composition proportion of the aluminium alloy negative electrode material of setting, aluminium and the conjunction of corrresponding quality are weighed on an electronic balance
Gold element (lanthanum, gallium, magnesium, indium)；
S2: by high purity graphite crucible, 730 DEG C is warming up in resistance furnace, is put into metallic aluminium, after aluminium fusing, in aluminium
Lanthanum is added in melt, after to be melted, is sequentially added into magnesium, indium, gallium；Alloying element addition sequence presses melting temperature from high to low,
It sequentially adds；After alloying element all dissolves, stir, be cooled at 710 DEG C, 710 DEG C stand 12min after be cast in metal casting
In swage tool, ingot casting is obtained, the mold uses circulating water；Entire fusion process protects melt using argon gas, mitigates high
The oxidation of aluminum melt under the conditions of temperature；
S3: the aluminium alloy cast ingot obtained after demoulding carries out first time heat treatment, and ingot casting is kept the temperature 18h at a temperature of 450 DEG C,
Then it is directly carried out in the water of room temperature to quenching cooling, take out ingot casting；
S4: the ingot casting that S3 is obtained carries out rolling processing at room temperature, and deformation amount controlling works as accumulation within 5% per pass
Deflection when reaching 60%, the aluminium alloy of deformation is put into the heat-treatment furnace of 320 DEG C of temperature of preheating and is carried out at second of heat
Then reason, heat treatment time 45min take out from furnace and directly cool down in air；The step can by equivalent variations amount and
Heat treatment process repeats, and the aluminium alloy negative electrode material of dimensions is met until obtaining；
S5: after last time deforms, the aluminium alloy negative electrode material for meeting dimensions will be obtained, is put into 150 DEG C of temperature
Final heat treatment is carried out in the heat-treatment furnace of degree, keeps the temperature 4h, and then furnace cooling obtains final products.
Embodiment 4
A kind of battery aluminium alloy negative electrode material, is grouped as by the group of following mass percent meter: 0.01% lanthanum (La),
0.01% gallium (Ga), 0.01% magnesium (Mg), 0.01% indium (In), surplus is aluminium；Purity >=99.99% of all components.
The above-mentioned battery preparation method of aluminium alloy negative electrode material, includes the following steps:
S1: by the composition proportion of the aluminium alloy negative electrode material of setting, aluminium and the conjunction of corrresponding quality are weighed on an electronic balance
Gold element (lanthanum, gallium, magnesium, indium)；
S2: by high purity graphite crucible, 740 DEG C is warming up in resistance furnace, is put into metallic aluminium, after aluminium fusing, in aluminium
Lanthanum is added in melt, after to be melted, is sequentially added into magnesium, indium, gallium；Alloying element addition sequence presses melting temperature from high to low,
It sequentially adds；After alloying element all dissolves, stir, be cooled at 710 DEG C, 710 DEG C stand 13min after be cast in metal casting
In swage tool, ingot casting is obtained, the mold uses circulating water；Entire fusion process protects melt using argon gas, mitigates high
The oxidation of aluminum melt under the conditions of temperature；
S3: the aluminium alloy cast ingot obtained after demoulding carries out first time heat treatment, and ingot casting is kept the temperature 20h at a temperature of 430 DEG C,
Then it is directly carried out in the water of room temperature to quenching cooling, take out ingot casting；
S4: the ingot casting that S3 is obtained carries out rolling processing at room temperature, and deformation amount controlling works as accumulation within 5% per pass
Deflection when reaching 60%, the aluminium alloy of deformation is put into the heat-treatment furnace of 330 DEG C of temperature of preheating and is carried out at second of heat
Then reason, heat treatment time 50min take out from furnace and directly cool down in air；The step can by equivalent variations amount and
Heat treatment process repeats, and the aluminium alloy negative electrode material of dimensions is met until obtaining；
S5: after last time deforms, the aluminium alloy negative electrode material for meeting dimensions will be obtained, is put into 180 DEG C of temperature
Final heat treatment is carried out in the heat-treatment furnace of degree, keeps the temperature 5h, and then furnace cooling obtains final products.
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (11)
1. a kind of battery aluminium alloy negative electrode material, which is characterized in that be grouped as by the group of following mass percent meter:
0.001%~1% lanthanum, 0.001%~1% gallium, 0.001%~1% magnesium, 0.001%~1% indium, surplus are aluminium；
The battery is prepared with the following method with aluminium alloy negative electrode material:
S1: taking aluminium and alloying element lanthanum, gallium, magnesium, indium respectively, by the composition proportion ingredient of setting；
S2: under protective condition, aluminium being melted in elevated temperature vessel, and after aluminium dissolves, alloying element lanthanum, gallium, magnesium, indium is added,
After all dissolving, stirs, cools down, stands, pours, obtain ingot casting；
S3: the ingot casting that S2 is obtained carries out first time heat treatment, and annealing temperature is 400 DEG C~500 DEG C, and soaking time is 12~
For 24 hours, cooling, take out ingot casting；
S4: the ingot casting that S3 is obtained carries out rolling process at room temperature, then the ingot casting of deformation is carried out in heat-treatment furnace
Secondary heat treatment, annealing temperature are 300 DEG C~350 DEG C, and soaking time is 0.5~1h, cooling, when rolling in the step per pass
Deflection is, when accumulative total deformation reaches 50%~70%, the ingot casting of deformation to be carried out second within 5% and is heat-treated；
S5: the aluminium alloy cathode plate obtained after S4 is handled carries out third time heat treatment, annealing temperature in heat-treatment furnace
It is 100 DEG C~250 DEG C, soaking time is 1~8h, it is cooling, obtain finished product.
2. a kind of battery aluminium alloy negative electrode material according to claim 1, which is characterized in that by following mass percent
The group of meter is grouped as: 0.01%~0.1% lanthanum, 0.01%~0.1% gallium, 0.01%~0.1% magnesium, 0.01%~0.1% indium,
Surplus is aluminium.
3. a kind of battery aluminium alloy negative electrode material according to claim 1, which is characterized in that by following mass percent
The group of meter is grouped as: lanthanum 0.02%, gallium 0.05%, magnesium 0.05%, indium 0.05%, and surplus is aluminium.
4. a kind of battery aluminium alloy negative electrode material according to any one of claim 1 to 3, it is characterised in that: described
Aluminium, lanthanum, gallium, magnesium and indium purity >=99.9%.
5. a kind of battery aluminium alloy negative electrode material according to any one of claim 1 to 3, it is characterised in that: described
Aluminium, lanthanum, gallium, magnesium and indium purity >=99.99%.
6. a kind of method for preparing aluminium alloy negative electrode material according to any one of claims 1 to 4, which is characterized in that packet
Include following steps:
S1: taking aluminium and alloying element lanthanum, gallium, magnesium, indium respectively, by the composition proportion ingredient of setting；
S2: under protective condition, aluminium being melted in elevated temperature vessel, and after aluminium dissolves, alloying element lanthanum, gallium, magnesium, indium is added,
After all dissolving, stirs, cools down, stands, pours, obtain ingot casting；
S3: the ingot casting that S2 is obtained carries out first time heat treatment, and annealing temperature is 400 DEG C~500 DEG C, and soaking time is 12~
For 24 hours, cooling, take out ingot casting；
S4: the ingot casting that S3 is obtained carries out rolling process at room temperature, then the ingot casting of deformation is carried out in heat-treatment furnace
Secondary heat treatment, annealing temperature are 300 DEG C~350 DEG C, and soaking time is 0.5~1h, cooling, when rolling in the step per pass
Deflection is, when accumulative total deformation reaches 50%~70%, the ingot casting of deformation to be carried out second within 5% and is heat-treated；
S5: the aluminium alloy cathode plate obtained after S4 is handled carries out third time heat treatment, annealing temperature in heat-treatment furnace
It is 100 DEG C~250 DEG C, soaking time is 1~8h, it is cooling, obtain finished product.
7. the preparation method of aluminium alloy negative electrode material according to claim 6, which is characterized in that alloying element in S2 step
Lanthanum, gallium, magnesium, indium addition sequence are as follows: lanthanum is first added, after lanthanum fusing after, be sequentially added into magnesium, indium, gallium.
8. the preparation method of aluminium alloy negative electrode material according to claim 6, which is characterized in that S2 specific steps are as follows:
Under argon gas protective condition, temperature melts aluminium when being 720 DEG C~750 DEG C in high purity graphite crucible, after aluminium fusing, in aluminium
Lanthanum is added in melt, after lanthanum fusing, is sequentially added into magnesium, indium, gallium, after alloying element all dissolves, stirs, is cooled to
It is cast in metal cast iron die after standing 10~15min at 700 DEG C~720 DEG C, 700 DEG C~720 DEG C, obtains ingot casting, it is described
Mold uses circulating water.
9. the preparation method of aluminium alloy negative electrode material according to claim 6, it is characterised in that: cooling described in S3 step
To carry out quenching cooling in the water of room temperature.
10. the preparation method of aluminium alloy negative electrode material according to claim 6, it is characterised in that: cold described in S4 step
It but is to be cooled down in air after being taken out in heat-treatment furnace.
11. the preparation method of aluminium alloy negative electrode material according to claim 6, it is characterised in that: cold described in S5 step
It but is cooling with heat-treatment furnace.
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