CN106917010A - A kind of aluminum alloy anode material and its casting method and application - Google Patents
A kind of aluminum alloy anode material and its casting method and application Download PDFInfo
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- CN106917010A CN106917010A CN201710275859.7A CN201710275859A CN106917010A CN 106917010 A CN106917010 A CN 106917010A CN 201710275859 A CN201710275859 A CN 201710275859A CN 106917010 A CN106917010 A CN 106917010A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
- B22D21/002—Castings of light metals
- B22D21/007—Castings of light metals with low melting point, e.g. Al 659 degrees C, Mg 650 degrees C
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- 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
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of aluminum alloy anode material and its casting method and application, the aluminum alloy anode material is formed by Pb, Sn, Ga, Ti and Al casting, and specific casting step is as follows：First, refined alloy：（1）Fine aluminium block is inserted by several times fusing is heated in shaft furnace；（2）After all of aluminium block melts completely, minor metallic element is added in high temperature shaft furnace；（3）After after all components all fusing, it is stirred using graphite rod；（4）Carbon trichloride is added, the waste residue in molten aluminum is removed；2nd, cast molding：（1）Last layer releasing agent is applied in mould inner surface, is heated and is incubated；（2）The aluminium alloy of melting is poured into mould, aluminium ingot is cast into.Aluminum alloy anode material of the invention has the overpotential of hydrogen evolution of relatively low overpotential and Geng Gao so that electrode can reach electro-chemical activity and anode utilization rate higher in cell operation.
Description
Technical field
The invention belongs to metallurgical and materials processing technology field, it is related to a kind of five yuan of new aluminium alloys and its casting method
With application.
Background technology
With the sternness in short supply and China's environmental problem of the non-renewable energy resources such as oil, people start to continually develop newly
, green regenerative resource.From the metal-air battery that the lead-acid battery of the first generation gets most of the attention by now again to lithium battery,
The development of battery power supply system is increasingly paid close attention to by people.Metal-air battery has as the green battery of a new generation
Many advantages such as standby low cost of manufacture, the high, environment-protecting asepsis of specific energy.
More metal-air battery is studied at present including zinc-air battery, aluminium-air cell, lithium-air battery etc.,
Only zinc-air battery wherein immediate with industrialization.But due to aluminum ratio zinc is more active, battery electricity higher can be obtained
Press and more cheap, therefore the research of aluminium-air cell still has a wide prospect.
Aluminium is a kind of anode material of preferable metal-air battery, and its electrochemical equivalent is 2980 Ahkg-1, it is to remove
Specific energy highest metal outside lithium.Meanwhile, the electrode potential of metallic aluminium is relatively born, its normal electrode in neutral solution
Current potential is -1.66 V（vs.SCE）, it is -2.35 V in strong alkali solution Plays electrode potential（vs.SCE）.For battery
For anode material, electrode potential is more negative, and battery can provide bigger power.But in fact, the work potential of aluminium-air cell
Far below its theoretical value, because：（1）Aluminium is more active, easily generates one layer of aluminum oxide of densification with the oxygen reaction in air
Film, causes the anodic overpotential of aluminium to raise, and reduces the voltage efficiency of anode, that is, reduce the power output of battery.（2）Containing
It is corrosive in solion or strong alkali solution, the dissolution velocity of fine aluminium is quite fast, now, aluminum metal self discharge is larger, produces
The a large amount of hydrogen of life, causing the faradic efficiency of anode reduces.Therefore, in order that aluminum alloy materials are closed in turning into aluminium-air cell
The anode material of lattice, it is necessary to meet following condition：（1）Enough electro-chemical activities；（2）Gas-evolving electrodes are few enough；（3）Reaction is produced
Thing is easy to come off, precipitates；（4）Each component should keep uniform state in anode finished product；（5）Anode material should be according to the difference of purposes
And there are different characteristics.
At present, the solution that can improve aluminum alloy anode material performance mainly has two：（1）It is micro- to being adulterated in rafifinal
Secondary element, the electro-chemical activity and utilization rate of aluminium electrode are improved with this；（2）To corrosion inhibiter is added in electrolyte, anode pole is reduced
Change, improve electrode potential.Wherein, scheme（1）Middle added trace element mainly has Ga, In, Mg, Bi, Sn etc..As adulterated
Ga, Sn etc. can change anisotropy of the fine aluminium crystal grain in course of dissolution, form eutectic alloy, destroy the oxidation of aluminium surface
Film；Doping Ga, In etc. can make aluminium surface produce space, reduce aluminium surface passivation film resistance；The liberations of hydrogen high such as doping Pb, Bi are excessively electric
Bit element, can improve the corrosion resistance of the overall overpotential of hydrogen evolution of aluminium electrode and alloy；Due in rafifinal always or it is many or
Adulterate the trace elements such as some Fe less so that the self-corrosion of aluminium anodes increase at double.Add Ti and Si can refine α-
Al crystal grain, content is higher can to cause that crystal grain is thinner, and crystal grains fine can allow the mobility of aluminium alloy solution more preferable, make its inside
Trace element disperses more uniform, improves the performance of aluminium alloy.
Early in 20 century 70s, the U.S. has begun to the research to aluminium-air cell.The eighties, Canadian U.S. aluminium
Company uses the aluminium anodes and effective air electrode of alloying so that the battery system of research and development is in compact power, standby electricity
The application aspect of source and underwater propulsion unit all obtains swift and violent development.Domestic Harbin Institute of Technology's Specialty Chemical power supply
Team of institute has also begun to the research of domestic aluminium-air cell in phase early 1980s, have developed Ga0.3-Bi0.3-
Pb0.45-Al quaternary aluminum alloy materials.To the nineties in 20th century, the team investigated five yuan of less expensive aluminium alloy materials again
Expect in 3W aluminium-air cells, its electrode potential to reach -1.426 V（vs.SCE）, electrode utilization rate reaches 91%, while tool
There is less reaction polarization.Although the aluminum alloy anode material can effectively improve anode electrochemical activity and utilization rate,
It is that it still suffers from certain defect at aspects such as open-circuit voltage, operating potential, current efficiency, actual capacitances.
The content of the invention
In order to solve, anode utilization rate present in existing aluminium-air cell is low, electro-chemical activity is not high asks the present invention
Topic, there is provided a kind of suitable for the aluminum alloy anode material and its casting method of aluminium-air cell and application, the aluminum alloy anode
Material has the overpotential of hydrogen evolution of relatively low overpotential and Geng Gao so that electrode can reach higher in cell operation
Electro-chemical activity and anode utilization rate.
The purpose of the present invention is achieved through the following technical solutions：
A kind of aluminum alloy anode material, is formed by following components casting：Pb：0.01~0.1wt%；Sn：0.01~0.1wt%；Ga：
0.01~0.2wt%；Ti：0.01~0.07wt%；Balance of Al.
In aluminum alloy anode material of the invention, to being doped with tetra- kinds of trace elements of Pb, Sn, Ga and Ti in rafifinal, its
In：Alloying element Ga and Sn can form eutectic mixture with Al under electrode operating temperature, and it can change fine aluminium crystal grain
Anisotropy in course of dissolution, enables anodic attack to become uniform, and destroys the fine and close oxide-film of aluminium surface.But Ga's contains
Amount can make electrode potential become negative more than 0.5wt%, will substantially reduce current efficiency.Meanwhile, doping Sn elements can produce aluminium surface
Raw space, reduces aluminium surface passivation film resistance.And the overpotential of hydrogen evolution elements Pb high that adulterates can effectively suppress gas-evolving electrodes, improve
The corrosion resistance and anode utilization rate of alloy.Adding Ti can refine Al element crystal grain so that the mobility of aluminium alloy solution is big
It is big to improve, and the trace element of its inside is uniformly dispersed, improve the performance of aluminium alloy.
A kind of casting method of above-mentioned aluminum alloy anode material, comprises the following steps：
First, refined alloy：
（1）The fine aluminium block that purity is 99.99% is inserted in shaft furnace by several times, aluminium block is heated into 700 ~ 750 DEG C is melted；
（2）After all of aluminium block melts completely, high temperature well formula will be added to by load weighted minor metallic element according to a certain ratio
In stove；
（3）After after all components all fusing, it is stirred using graphite rod；
（4）Carbon trichloride is added, the waste residue in molten aluminum is removed.
2nd, cast molding：
（1）Last layer releasing agent is applied in mould inner surface, 150 ~ 250 DEG C is heated to and is incubated；
（2）The aluminium alloy of melting is poured into mould, the aluminium alloy of melting is cast into aluminium ingot.
In above-mentioned casting method, preferably, divide 4~5 times in step one for fine aluminium block and foundry alloy to be added to high temperature well
In formula stove, this be in order to allow melting aluminium alloy inside component keep uniform.
In above-mentioned casting method, preferably, the minor metallic element added in step one is first weighed and uses thin aluminium afterwards
Paper tinsel is encased, and especially Ga fusing points at normal temperatures and pressures are relatively low, it is necessary to individually want aluminium foil to encase, afterwards, then by the whole micro unit of bag
Element is added in shaft furnace.
In above-mentioned casting method, preferably, in step one carbon trichloride addition for aluminium alloy gross mass 6~
8%, and addition is removed the gred by several times.
In above-mentioned casting method, preferably, in step 2 keep mould internal temperature is at 150~250 DEG C and maintains
More than half an hour, to ensure cast temperature between 250~450 DEG C.
Aluminum alloy anode material of the invention can be applied not only in aluminium-air cell, can also be applied to aluminium-sulphur electricity
In the battery with aluminum alloy materials as anode such as pond, aluminium-seawater battery.
The present invention has advantages below：
1st, five kinds of reasonable mixture ratios of alloying element that the present invention is used, alloying element is mainly present in matrix in the form of solid solution
In, chemical property is good, active height, reachable -1.82 V of its OCP（Vs.Hg/HgO）；
2nd, the liberation of hydrogen self-corrosion speed of aluminum alloy anode material of the invention is small, and with the increase of current density, liberation of hydrogen speed
Incrementss it is little.
Specific embodiment
Technical scheme is further described with reference to embodiment, but is not limited thereto, it is every right
Technical solution of the present invention is modified or equivalent, without deviating from the spirit and scope of technical solution of the present invention, all should be contained
Cover in protection scope of the present invention.
Embodiment 1：
In the present embodiment, aluminum alloy anode material is formed by Pb, Sn, Ga, Ti and Al casting, and specific casting step is as follows：
First, refined alloy：
（1）Each component mass percent according to embodiment 1 in table 1 carries out dispensing；
（2）The fine aluminium block that purity is 99.99% is put into shaft furnace several times first, 750 DEG C is heated to and is melted；
（3）Tetra- kinds of metallic elements of Pb, Sn, Ga, the Ti that will previously prepare afterwards are also added in shaft furnace；
（4）After after all components all fusing, at interval of 5 minutes stirred the aluminium alloy that once melts using graphite rod and repeat many
It is secondary, each metallic element is in uniform state；
（5）It is last to add carbon trichloride at twice, the waste residue in molten aluminum is removed, the addition of carbon trichloride is the total matter of aluminium alloy
The 8% of amount.
2nd, cast molding：
（1）Last layer releasing agent is applied in mould inner surface, 200 DEG C is heated to and is maintained more than half an hour；
（2）In the mould for the aluminium alloy of melting is poured into heating, putting up, keep the aluminium alloy of melting it is coherent pour into mould and
Make flow velocity first quick and back slow, the aluminium alloy for most melting at last is cast into aluminium ingot.
The aluminum alloy anode material of the present embodiment casting can be applied not only in aluminium-air cell, can also be applied to
In aluminium-sulphur battery, aluminium-seawater battery etc..
Embodiment 2：
In the present embodiment, it is adaptable to which the aluminium alloy of aluminium-air cell is formed by Pb, Sn, Ga, Ti and Al casting, specific casting step
It is as follows：
First, refined alloy：
（1）Each component mass percent according to embodiment 2 in table 1 carries out dispensing；
（2）The fine aluminium block that purity is 99.99% is put into shaft furnace several times first, 700 DEG C is heated to and is melted；
（3）Tetra- kinds of metallic elements of Pb, Sn, Ga, the Ti that will previously prepare afterwards are also added in shaft furnace；
（4）After after all components all fusing, at interval of 5 minutes stirred the aluminium alloy that once melts using graphite rod and repeat many
It is secondary, each metallic element is in uniform state；
（5）It is last to add carbon trichloride at twice, the waste residue in molten aluminum is removed, the addition of carbon trichloride is the total matter of aluminium alloy
The 6% of amount.
2nd, cast molding：
（1）Last layer releasing agent is applied in mould inner surface, 150 DEG C is heated to and is maintained more than half an hour；
（2）In the mould for the aluminium alloy of melting is poured into heating, putting up, keep the aluminium alloy of melting it is coherent pour into mould and
Make flow velocity first quick and back slow, the aluminium alloy for most melting at last is cast into aluminium ingot.
The aluminum alloy anode material of the present embodiment casting can be applied not only in aluminium-air cell, can also be applied to
In aluminium-sulphur battery, aluminium-seawater battery etc..
Embodiment 3：
In the present embodiment, it is adaptable to which the aluminium alloy of aluminium-air cell is formed by Pb, Sn, Ga, Ti and Al casting, specific casting step
It is as follows：
First, refined alloy：
（1）Each component mass percent according to embodiment 3 in table 1 carries out dispensing；
（2）The fine aluminium block that purity is 99.99% is put into shaft furnace several times first, 700 DEG C is heated to and is melted；
（3）Tetra- kinds of metallic elements of Pb, Sn, Ga, the Ti that will previously prepare afterwards are also added in shaft furnace；
（4）After after all components all fusing, at interval of 5 minutes stirred the aluminium alloy that once melts using graphite rod and repeat many
It is secondary, each metallic element is in uniform state；
（5）It is last to add carbon trichloride at twice, the waste residue in molten aluminum is removed, the addition of carbon trichloride is the total matter of aluminium alloy
The 8% of amount.
2nd, cast molding：
（1）Last layer releasing agent is applied in mould inner surface, 200 DEG C is heated to and is maintained more than half an hour；
（2）In the mould for the aluminium alloy of melting is poured into heating, putting up, keep the aluminium alloy of melting it is coherent pour into mould and
Make flow velocity first quick and back slow, the aluminium alloy for most melting at last is cast into aluminium ingot.
The aluminum alloy anode material of the present embodiment casting can be applied not only in aluminium-air cell, can also be applied to
In aluminium-sulphur battery, aluminium-seawater battery etc..
Embodiment 4：
In the present embodiment, it is adaptable to which the aluminium alloy of aluminium-air cell is formed by Pb, Sn, Ga, Ti and Al casting, specific casting step
It is as follows：
First, refined alloy：
（1）Each component mass percent according to embodiment 4 in table 1 carries out dispensing；
（2）The fine aluminium block that purity is 99.99% is put into shaft furnace several times first, 750 DEG C is heated to and is melted；
（3）Tetra- kinds of metallic elements of Pb, Sn, Ga, the Ti that will previously prepare afterwards are also added in shaft furnace；
（4）After after all components all fusing, at interval of 5 minutes stirred the aluminium alloy that once melts using graphite rod and repeat many
It is secondary, each metallic element is in uniform state；
（5）It is last to add carbon trichloride at twice, the waste residue in molten aluminum is removed, the addition of carbon trichloride is the total matter of aluminium alloy
The 6% of amount.
2nd, cast molding：
（1）Last layer releasing agent is applied in mould inner surface, 150 DEG C is heated to and is maintained more than half an hour；
（2）In the mould for the aluminium alloy of melting is poured into heating, putting up, keep the aluminium alloy of melting it is coherent pour into mould and
Make flow velocity first quick and back slow, the aluminium alloy for most melting at last is cast into aluminium ingot.
The aluminum alloy anode material of the present embodiment casting can be applied not only in aluminium-air cell, can also be applied to
In aluminium-sulphur battery, aluminium-seawater battery etc..
The content of the embodiment 1-4 aluminium alloy each components of table 1
Note：The purity of aluminium block is 99.99%.
Claims (10)
1. a kind of aluminum alloy anode material, it is characterised in that the aluminum alloy anode material is formed by following components casting：Pb：
0.01~0.1wt%；Sn：0.01~0.1wt%；Ga：0.01~0.2wt%；Ti：0.01~0.07wt%；Balance of Al.
2. aluminum alloy anode material according to claim 1, it is characterised in that the aluminum alloy anode material is by with the following group
Casting is divided to form：Pb：0.01wt%；Sn：0.01wt%；Ga：0.01wt%；Ti：0.01wt%；Balance of Al.
3. aluminum alloy anode material according to claim 1, it is characterised in that the aluminum alloy anode material is by with the following group
Casting is divided to form：Pb：0.05wt%；Sn：0.03wt%；Ga：0.1wt%；Ti：0.03wt%；Balance of Al.
4. aluminum alloy anode material according to claim 1, it is characterised in that the aluminum alloy anode material is by with the following group
Casting is divided to form：Pb：0.08wt%；Sn：0.05wt%；Ga：0.15wt%；Ti：0.03wt%；Balance of Al.
5. aluminum alloy anode material according to claim 1, it is characterised in that the aluminum alloy anode material is by with the following group
Casting is divided to form：Pb：0.1wt%；Sn：0.1wt%；Ga：0.05wt%；Ti：0.07wt%；Balance of Al.
6. a kind of casting method of the aluminum alloy anode material described in claim 1-5 any claims, it is characterised in that institute
State casting method step as follows：
First, refined alloy：
（1）The fine aluminium block that purity is 99.99% is inserted in shaft furnace by several times, aluminium block is heated into 700 ~ 750 DEG C is melted；
（2）After all of aluminium block melts completely, high temperature well formula will be added to by load weighted minor metallic element according to a certain ratio
In stove；
（3）After after all components all fusing, it is stirred using graphite rod；
（4）Carbon trichloride is added, the waste residue in molten aluminum is removed；
2nd, cast molding：
（1）Last layer releasing agent is applied in mould inner surface, 150 ~ 250 DEG C is heated to and is incubated；
（2）The aluminium alloy of melting is poured into mould, the aluminium alloy of melting is cast into aluminium ingot.
7. the casting method of aluminum alloy anode material according to claim 6, it is characterised in that in the step one, points 4
~5 times fine aluminium block and foundry alloy are added in high temperature shaft furnace.
8. the casting method of aluminum alloy anode material according to claim 6, it is characterised in that in the step one, chlordene
The addition of ethane is the 6~8% of aluminium alloy gross mass, and addition is removed the gred by several times.
9. the casting method of aluminum alloy anode material according to claim 6, it is characterised in that the step 2, during insulation
Between be it is more than half an hour.
10. described in aluminum alloy anode material described in claim 1-5 any claims or claim 6-9 any claims
Application of the aluminum alloy anode material that casting method is prepared in aluminium-air cell, aluminium-sulphur battery, aluminium-seawater battery.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108642327A (en) * | 2018-04-26 | 2018-10-12 | 广东省材料与加工研究所 | A kind of aluminium-air cell anode material and preparation method thereof |
| CN109321766A (en) * | 2018-10-22 | 2019-02-12 | 昆明理工大学 | A kind of aluminium-air cell anode material and preparation method thereof |
| CN110042278A (en) * | 2019-05-14 | 2019-07-23 | 上海汉行科技有限公司 | A kind of aluminium-air cell anode material and preparation method thereof |
| CN110484788A (en) * | 2019-09-06 | 2019-11-22 | 宁波烯铝新能源有限公司 | Aluminium-air cell anode material and preparation method thereof and aluminium-air cell |
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| CN102820472A (en) * | 2012-08-07 | 2012-12-12 | 河南科技大学 | Manganese-aluminum containing anode material and preparation method thereof, as well as air cell prepared by using anode material |
| CN104532037A (en) * | 2014-12-06 | 2015-04-22 | 昆明冶金研究院 | Production method of octonary aluminum alloy anode for aluminum-air batteries |
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| CN108642327A (en) * | 2018-04-26 | 2018-10-12 | 广东省材料与加工研究所 | A kind of aluminium-air cell anode material and preparation method thereof |
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| CN109321766A (en) * | 2018-10-22 | 2019-02-12 | 昆明理工大学 | A kind of aluminium-air cell anode material and preparation method thereof |
| CN110042278A (en) * | 2019-05-14 | 2019-07-23 | 上海汉行科技有限公司 | A kind of aluminium-air cell anode material and preparation method thereof |
| CN110484788A (en) * | 2019-09-06 | 2019-11-22 | 宁波烯铝新能源有限公司 | Aluminium-air cell anode material and preparation method thereof and aluminium-air cell |
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