CN105140596B - A kind of air cell aluminum alloy anode material, preparation method and aluminium-air cell - Google Patents
A kind of air cell aluminum alloy anode material, preparation method and aluminium-air cell Download PDFInfo
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- CN105140596B CN105140596B CN201510561492.6A CN201510561492A CN105140596B CN 105140596 B CN105140596 B CN 105140596B CN 201510561492 A CN201510561492 A CN 201510561492A CN 105140596 B CN105140596 B CN 105140596B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/463—Aluminium based
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of air cell aluminum alloy anode material, preparation method and aluminium-air cell, the aluminum alloy anode material consists of the following components in percentage by weight：Zn 0.05%~6%, Ga 0.05%~4%, In 0.01%~2%, surplus Al.The air cell aluminum alloy anode material of the present invention, zinc, gallium and phosphide element are added in aluminium anodes material, electro-chemical activity is good, and self-corrosion speed is small, OCP≤1.76V (vs.SHE) in alkaline electrolyte, the electromotive force of cell are more than 1.84V；The aluminum alloy anode material passes through alloying, hence it is evident that improves the chemical property of anode and reduces self-corrosion speed, self-corrosion speed is less than 5.12mg/cm2H, surface corrosion are uniform；The aluminum alloy anode material superior performance, be it is a kind of it is new, be adapted to the aluminum alloy anode material that is used in alkaline electrolyte.
Description
Technical field
The invention belongs to aluminium-air cell technical field, and in particular to a kind of air cell aluminum alloy anode material, together
When further relate to a kind of air cell aluminum alloy anode material preparation method and using the anode material aluminium-air cell.
Background technology
Metal-air battery is new generation of green battery, and its manufacturing cost is low, raw material recyclable profit higher than energy
With superior performance.Studying more metal-air battery at present has zinc-air battery, aluminium-air cell and lithium-air battery etc.,
With the immediate only zinc-air battery of industrialization.In galvanic series, aluminum ratio zinc is more active, can obtain higher battery electricity
Pressure；One aluminium atom can discharge three electronics, and a zinc atom discharges two electronics, and aluminium can improve the energy of battery
Amount；In addition, it is aluminium rich reserves, cheap, therefore the progress of aluminium-air cell is very rapid, is a kind of rising
Air cell.
Aluminium-air cell, it is that a kind of novel battery of battery material is used as using aluminium and air.Sun of the aluminium as air cell
Pole material has the advantages of its is unique：Electrochemical equivalent is high, and the electrochemical equivalent of aluminium is 2980Ah/kg, for the highest in addition to lithium
Metal；Electrode potential is relatively negative, and its standard electrode potential is -2.35V (vs.SHE) in alkaline solution, for anode material,
Current potential is more negative better, and battery can provide bigger electromotive force；The aboundresources of aluminium, it is cheap.
At present, with aluminium anodes material compared with zinc anode material, existing matter of utmost importance is air cell：Aluminium is molten in alkalescence
Self-corrosion is very serious in liquid, causes anode utilization rate to substantially reduce, and hinders the commercial applications of aluminium-air cell.Researcher
Novel aluminum anode material, and the corresponding electrolyte corrosion inhibitor of addition are developed by microalloying, the self-corrosion of aluminium can be reduced
Speed.The conventional alloy element of aluminium-air cell anode material mainly has zinc, magnesium, sowed, indium, tin, lead, mercury, bismuth etc..These yuan
Element, which is added in aluminium, forms the multicomponent alloys such as ternary, quaternary.In the prior art, Li Xiaoxiang etc. exists《A kind of new aluminium-air cell
With the research of aluminum alloy anode material》In have studied it is several addition metals to aluminum alloy anode material in 4mol/L NaOH+15g/
L Na2SnO3The influence of liberation of hydrogen speed and chemical property in solution, show that the optimal aluminum alloy anode material of combination property is
Al-0.2Sn-0.02Ga-0.4Pb.Lu Lingbin exists《The research of aluminium-air cell aluminum alloy anode and electrolysis additive》In
The series such as melting making Al-In, Al-In-Zn, Al-In-Bi, Al-In-Pb, Al-In-Zn-Bi, Al-In-Zn-Bi-Pb is closed
Gold, using them as Electrode, and its surface property is studied by testing its SEM and EDAX.But above-mentioned aluminium closes
Golden material as aluminium-air cell anode in use, the self-corrosion speed in alkaline solution is still higher, OCP
Deficiency, it is not met by the requirement of alkaline aluminium-air cell high current density discharge.
The content of the invention
It is an object of the invention to provide a kind of air cell aluminum alloy anode material suitable for alkaline solution, in alkalescence
Self-corrosion speed in solution is low, has preferable OCP, meets wanting for alkaline aluminium-air cell high current density discharge
Ask.
Second object of the present invention is to provide a kind of preparation method of air cell aluminum alloy anode material.
It is aluminium alloy with aluminum alloy anode material that third object of the present invention, which is to provide one kind using above-mentioned air cell,
The aluminium-air cell of anode.
In order to realize the above object the technical solution adopted in the present invention is：
A kind of air cell aluminum alloy anode material, is consisted of the following components in percentage by weight：Zn 0.05%~
6%th, Ga 0.05%~4%, In 0.01%~2%, surplus Al.
A kind of preparation method of above-mentioned air cell aluminum alloy anode material, comprises the following steps：
1) under inert gas shielding, after aluminium heating fusing, zinc, gallium and indium is added and heats melting, continues to be heated to
730~780 DEG C and be incubated after, pour into ingot casting；
2) ingot casting obtained by step 1) is rolled into flaky material under the conditions of 150~200 DEG C, produced.
In step 1), the inert gas is argon gas.
In step 1), aluminium is heated into 670~720 DEG C makes it all melt.After adding zinc, gallium and indium, revolved in heating
Turn container, make metal melting and be well mixed.
In step 1), the time of the insulation is 4~10min.
In step 2), the thickness of the flaky material is 0.5~4mm.
The air cell aluminum alloy anode material of the present invention, aluminium anodes material electricity is not being reduced from the aspect of alloying
Its self-corrosion is reduced on the basis of chemical property：Based on purity is >=99.85% aluminium, added in aluminium alloy appropriate
Zinc, gallium and indium.Zinc is added in aluminium alloy, zinc current potential (- 1.29Vvs.SHE) than aluminium (- 2.35Vvs.SHE) just, passes through dissolving
It is redeposited in aluminium surface, can obviously reduce the self-corrosion speed of aluminium alloy；Furthermore zinc is advantageous to uniformly dividing for other alloying elements
Cloth, alloy uniform dissolution is promoted to improve the service life of anode alloy.Solid solubility of the gallium element in aluminium is very big, caused by dissolving
Gallium ion generates gallium aluminium amalgam, gallium aluminium amalgam because active low can be reduced again deposits to aluminum alloy surface with aluminum substrate
Peelable oxide-film and corrosion product, exposed base aluminum, promote the activation discharge of aluminium alloy；Secondly, alloying element gallium is to aluminium sun
The influence of pole, it is mainly manifested in and changes aluminium grain anisotropy present in course of dissolution, so that aluminium anodes corrosion is uniform；
Furthermore gallium and other alloy element Zns, In etc., under electrode operating temperature (about 60 DEG C), eutectic mixture is formed, destroys aluminium
Surface passivated membrane；In addition, containing In3+Solution in, due to In3+Redeposition (the defects of being deposited on alumite position),
Cause Ga3+Deposition, to aluminium anodes produce activation.Influences of the alloying element In to aluminium anodes, being mainly manifested in In has
Very strong activation capacity, destroy the passivating film of aluminium surface；Alloying element In effect, be in Alloy solid solution In elements dissolving after
Caused by redeposition, In3+There is destruction to aluminium surface passivating film；Secondly, In can also effectively suppress the liberation of hydrogen corruption of alloy
Erosion, this has higher overpotential of hydrogen evolution relevant with it.Meanwhile zinc, gallium and indium are all high overpotential of hydrogen evolution elements, can be dropped significantly
The liberation of hydrogen self-corrosion of low aluminium alloy.The addition of these alloy elements, if addition is few, does not have within the scope of certain
Due effect, if addition is big, the second larger phase of a large amount of shapes is formed, increase aluminium alloy self-corrosion speed, makes corrosion equal
Even property is deteriorated.Alloying is carried out to aluminium by adding appropriate zinc, gallium and indium and can obviously reduce the self-corrosion speed of alloy, can be with
Improve the erosion uniformity of alloy surface.
The air cell aluminum alloy anode material of the present invention, adds zinc, gallium and phosphide element in aluminium anodes material, with
Existing aluminium anodes material is compared, and has advantages below：Electro-chemical activity is good, and self-corrosion speed is small, is opened in alkaline electrolyte
Road current potential≤- 1.76V (vs.SHE), the electromotive force of cell are more than 1.84V；The aluminum alloy anode material by alloying,
Significantly improve the chemical property of anode and reduce self-corrosion speed, self-corrosion speed is less than 5.12mg/cm2H, surface
Corrosion is uniform；The aluminum alloy anode material superior performance, be it is a kind of it is new, be adapted to the aluminium alloy that is used in alkaline electrolyte
Anode material.
The preparation method of the air cell aluminum alloy anode material of the present invention, it is by after aluminium heating fusing, adds zinc, gallium
Melted with indium and heating and pour into ingot casting, then ingot rolling slabbing material, gained aluminum alloy anode material are had excellent
Chemical property and alkali resistant corrosion performance, suitable for the aluminium-air cell of alkaline electrolyte；The preparation method technique is simple,
It is easy to operate, it is adapted to large-scale industrial production.
A kind of aluminium-air cell, including aluminum alloy anode, air cathode and electrolyte, the aluminum alloy anode are above-mentioned
Air cell aluminum alloy anode material.
The air cathode is suppressed and formed by Catalytic Layer, conductive nickel screen and waterproof ventilative layer, and thickness is 0.2~0.6mm.
The Catalytic Layer is by γ-MnO2, activated carbon and polytetrafluoroethylene (PTFE) be (0.3~3) in mass ratio:(1~5):(1
~5) film layer being pressed into after ratio mixing, thickness is 0.3~0.8mm.
The waterproof ventilative layer is by weight being 1 by polytetrafluoroethylene (PTFE) and acetylene black:It is pressed into after 1 ratio mixing
Film layer, thickness are 0.3~0.8mm.
The electrolyte includes the component of following concentration：2~6mol/L of sodium hydroxide, Lavender corrosion inhibiter 20~
100ppm (v/v), surplus are water.
The Lavender corrosion inhibiter is the ethanol solution of Lavender, and the volume basis of wherein Lavender contains
Measure as 10%~60% (v/v).
The preparation method of the electrolyte is：By formula ratio, Lavender corrosion inhibiter is added in sodium hydroxide solution,
Remaining water is added, is stirred, is produced.Water used in electrolyte is distilled water.
The aluminium-air cell of the present invention, uses above-mentioned air cell aluminum alloy anode material as aluminum alloy anode, should
The open-circuit voltage of aluminum alloy anode material is good, is -1.76~-2.08V (vs.SHE), the self-corrosion speed in alkaline solution
Low (≤5.12mg/cm2H), surface corrosion is uniform；The aluminium-air cell is 100mA/cm in discharge current density2Test 10h
Electromotive force be 1.84V~2.10V, there is excellent chemical property.
Lavender is to be refined to form by lavender, the complexity being made up of many different types of aromatic compounds
Mixture, main component include：Linalool, bergamio, cineole, β-ocimenum, terpene -4- alcohol and camphor.These materials
Contained group carries more negative electrical charge, first, there is electrostatic attraction between charged group and metal surface；Furthermore group Molecule
In lone pair electrons be present, electronics can be provided to the unoccupied orbital of metal, the oxygen atom in group is adsorbed in gold by lone pair electrons
Metal surface forms insoluble complex layer, metal surface is separated with the aqueous solution, plays corrosion inhibition.
The aluminium-air cell of the present invention, Lavender corrosion inhibiter is added in electrolyte, there is advantages below：Green plants
Extract solution Lavender reduces the self-corrosion speed of aluminium anodes and improves aluminium anodes activity；Fragrant camphor tree in Lavender
Alcohol hydroxyl oxygen subbase group is adsorbed in anode surface by forming complex layer with metal cation, hinders hydrone in anode surface
Absorption, and then reduce liberation of hydrogen self-corrosion speed；Because bergamio, camphor, cineole group Molecule have oxygen key and double
Key, complex ions are formed, promote reaction product desorption, make aluminium anodes continuous activation, reduce aluminium anodes when aluminium anodes discharges
Polarization, improve discharge performance, therefore after addition Lavender corrosion inhibiter, the self-corrosion speed of anode alloy, which does not add, smokes clothing
Substantially reduced during careless essential oil, and the significantly negative shifting of the OCP of the alloy；Lavender corrosion inhibiter component composition is simple, into
This is low, safety and meets environmental requirement, aluminium anodes alloy is possessed good corrosion resistance and higher electro-chemical activity, to meet
The requirement of alkaline aluminium-air cell high current density discharge.
Using the aluminium-air cell of aluminum alloy anode material and the electrolyte composition of the present invention, alkaline aluminium air can be controlled
Battery self-corrosion is too fast, and and can ensures that aluminium anodes alloy has higher electro-chemical activity, to improving cell discharge efficiency, extends
Discharge life is significant, is advantageous to the commercial applications of aluminium-air cell.
Embodiment
With reference to embodiment, the present invention is further illustrated.
Embodiment 1
The air cell aluminum alloy anode material of the present embodiment, is consisted of the following components in percentage by weight：Zn 4%,
Ga 0.08%, In 0.06%, surplus Al.
The preparation method of the air cell aluminum alloy anode material of the present embodiment, comprises the following steps：
1) under argon gas protection, aluminium ingot is placed in ZGJL0.01-40-4 induction melting furnace crucibles, being heated to 690 DEG C makes
Aluminium ingot all after fusing, adds zinc ingot metal, gallium grain and indium grain, rotates container in heating, makes metal melting and be well mixed, continues
After being heated to 750 DEG C and being incubated 5min, block ingot casting is poured into；
2) block ingot casting obtained by step 1) is rolled into the flaky material that thickness is 3mm under the conditions of 180 DEG C, produced described
Air cell aluminum alloy anode material.
The aluminium-air cell of the present embodiment, including aluminum alloy anode, air cathode and electrolyte, the aluminum alloy anode are
Above-mentioned air cell aluminum alloy anode material；
The electrolyte is the sodium hydroxide solution that concentration is 3mol/L.The preparation method of the electrolyte is：Take formula ratio
Sodium hydroxide add distilled water in, sodium hydroxide solution is made in stirring and dissolving.
The air cathode is suppressed and formed by Catalytic Layer, conductive nickel screen and waterproof ventilative layer；The Catalytic Layer be by
γ-MnO2, activated carbon and polytetrafluoroethylene (PTFE) be 2 in mass ratio:4:Thickness made of rolling is 0.7mm's after 1 ratio mixing
Film layer；The waterproof ventilative layer is by weight being 1 by polytetrafluoroethylene (PTFE) and acetylene black:After 1 ratio mixing made of rolling
Thickness is 0.5mm film layer；It is cloudy that Catalytic Layer, conductive nickel screen and waterproof ventilative layer are finally pressed into the air that thickness is 0.4mm
Pole.
The self-corrosion speed of the aluminum alloy anode of the present embodiment in the electrolytic solution is 5.12mg/cm2H, OCP for-
1.96V (vs.SHE), discharge current density is 100mA/cm to the air cell of composition in the electrolytic solution2When test 10h it is electronic
Gesture is 1.99V, and anode alloy surface corrosion is uniform.
Embodiment 2
The air cell aluminum alloy anode material of the present embodiment, is consisted of the following components in percentage by weight：Zn 6%,
Ga 1%, In 1.5%, surplus Al.
The preparation method of the air cell aluminum alloy anode material of the present embodiment, comprises the following steps：
1) under argon gas protection, aluminium ingot is placed in ZGJL0.01-40-4 induction melting furnace crucibles, being heated to 700 DEG C makes
Aluminium ingot all after fusing, adds zinc ingot metal, gallium grain and indium grain, rotates container in heating, makes metal melting and be well mixed, continues
After being heated to 730 DEG C and being incubated 5min, block ingot casting is poured into；
2) block ingot casting obtained by step 1) is rolled into the flaky material that thickness is 1mm under the conditions of 160 DEG C, produced described
Air cell aluminum alloy anode material.
The aluminium-air cell of the present embodiment, including aluminum alloy anode, air cathode and electrolyte, the aluminum alloy anode are
Above-mentioned air cell aluminum alloy anode material；
The electrolyte includes the component of following concentration：Sodium hydroxide 3mol/L, Lavender corrosion inhibiter 80ppm (v/
V), surplus is distilled water.The preparation method of the electrolyte is：The sodium hydroxide of formula ratio is taken to add distilled water, agitating solution system
Into sodium hydroxide solution；The Lavender corrosion inhibiter of formula ratio is added in sodium hydroxide solution, adds remaining distillation
Water, stir, produce.The Lavender corrosion inhibiter is the ethanol solution of Lavender, wherein Lavender
Volumn concentration is 60%.
The air cathode is suppressed and formed by Catalytic Layer, conductive nickel screen and waterproof ventilative layer；The Catalytic Layer be by
γ-MnO2, activated carbon and polytetrafluoroethylene (PTFE) be 1 in mass ratio:4:Thickness made of rolling is 0.6mm's after 5 ratio mixing
Film layer；The waterproof ventilative layer is by weight being 1 by polytetrafluoroethylene (PTFE) and acetylene black:After 1 ratio mixing made of rolling
Thickness is 0.4mm film layer；It is cloudy that Catalytic Layer, conductive nickel screen and waterproof ventilative layer are finally pressed into the air that thickness is 0.3mm
Pole.
The self-corrosion speed of the aluminum alloy anode of the present embodiment in the electrolytic solution is 3.57mg/cm2H, OCP for-
1.92V (vs.SHE), discharge current density is 100mA/cm to the air cell of composition in the electrolytic solution2When test 10h it is electronic
Gesture is 2.05V, and anode alloy surface corrosion is uniform.
Embodiment 3
The air cell aluminum alloy anode material of the present embodiment, is consisted of the following components in percentage by weight：Zn 3%,
Ga 3%, In 0.01%, surplus Al.
The preparation method of the air cell aluminum alloy anode material of the present embodiment, comprises the following steps：
1) under argon gas protection, aluminium ingot is placed in ZGJL0.01-40-4 induction melting furnace crucibles, being heated to 710 DEG C makes
Aluminium ingot all after fusing, adds zinc ingot metal, gallium grain and indium grain, rotates container in heating, makes metal melting and be well mixed, continues
After being heated to 760 DEG C and being incubated 6min, block ingot casting is poured into；
2) block ingot casting obtained by step 1) is rolled into the flaky material that thickness is 3mm under the conditions of 200 DEG C, produced described
Air cell aluminum alloy anode material.
The aluminium-air cell of the present embodiment, including aluminum alloy anode, air cathode and electrolyte, the aluminum alloy anode are
Above-mentioned air cell aluminum alloy anode material；
The electrolyte includes the component of following concentration：Sodium hydroxide 4mol/L, Lavender corrosion inhibiter 20ppm (v/
V), surplus is distilled water.The preparation method of the electrolyte is：The sodium hydroxide of formula ratio is taken to add distilled water, agitating solution system
Into sodium hydroxide solution；The Lavender corrosion inhibiter of formula ratio is added in sodium hydroxide solution, adds remaining distillation
Water, stir, produce.The Lavender corrosion inhibiter is the ethanol solution of Lavender, wherein Lavender
Volumn concentration is 20%.
The air cathode is suppressed and formed by Catalytic Layer, conductive nickel screen and waterproof ventilative layer；The Catalytic Layer be by
γ-MnO2, activated carbon and polytetrafluoroethylene (PTFE) be 3 in mass ratio:1:Thickness made of rolling is 0.5mm's after 1 ratio mixing
Film layer；The waterproof ventilative layer is by weight being 1 by polytetrafluoroethylene (PTFE) and acetylene black:After 1 ratio mixing made of rolling
Thickness is 0.6mm film layer；It is cloudy that Catalytic Layer, conductive nickel screen and waterproof ventilative layer are finally pressed into the air that thickness is 0.6mm
Pole.
The self-corrosion speed of the aluminum alloy anode of the present embodiment in the electrolytic solution is 4.28mg/cm2H, OCP for-
1.76V (vs.SHE), discharge current density is 100mA/cm to the air cell of composition in the electrolytic solution2When test 10h it is electronic
Gesture is 1.95V, and anode alloy surface corrosion is uniform.
Embodiment 4
The air cell aluminum alloy anode material of the present embodiment, is consisted of the following components in percentage by weight：Zn
0.05%th, Ga 4%, In 2%, surplus Al.
The preparation method of the air cell aluminum alloy anode material of the present embodiment, comprises the following steps：
1) under argon gas protection, aluminium ingot is placed in ZGJL0.01-40-4 induction melting furnace crucibles, being heated to 690 DEG C makes
Aluminium ingot all after fusing, adds zinc ingot metal, gallium grain and indium grain, rotates container in heating, makes metal melting and be well mixed, continues
After being heated to 760 DEG C and being incubated 7min, block ingot casting is poured into；
2) block ingot casting obtained by step 1) is rolled into the flaky material that thickness is 4mm under the conditions of 170 DEG C, produced described
Air cell aluminum alloy anode material.
The aluminium-air cell of the present embodiment, including aluminum alloy anode, air cathode and electrolyte, the aluminum alloy anode are
Above-mentioned air cell aluminum alloy anode material；
The electrolyte includes the component of following concentration：Sodium hydroxide 5mol/L, Lavender corrosion inhibiter 90ppm (v/
V), surplus is distilled water.The preparation method of the electrolyte is：The sodium hydroxide of formula ratio is taken to add distilled water, agitating solution system
Into sodium hydroxide solution；The Lavender corrosion inhibiter of formula ratio is added in sodium hydroxide solution, adds remaining distillation
Water, stir, produce.The Lavender corrosion inhibiter is the ethanol solution of Lavender, wherein Lavender
Volumn concentration is 30%.
The air cathode is suppressed and formed by Catalytic Layer, conductive nickel screen and waterproof ventilative layer；The Catalytic Layer be by
γ-MnO2, activated carbon and polytetrafluoroethylene (PTFE) be 1.5 in mass ratio:2:Thickness made of rolling is 0.3mm after 4 ratio mixing
Film layer；The waterproof ventilative layer is by weight being 1 by polytetrafluoroethylene (PTFE) and acetylene black:Roll and be made after 1 ratio mixing
Thickness be 0.8mm film layer；Catalytic Layer, conductive nickel screen and waterproof ventilative layer are finally pressed into the air that thickness is 0.5mm
Negative electrode.
The self-corrosion speed of the aluminum alloy anode of the present embodiment in the electrolytic solution is 2.93mg/cm2H, OCP for-
1.85V (vs.SHE), discharge current density is 100mA/cm to the air cell of composition in the electrolytic solution2When test 10h it is electronic
Gesture is 1.89V, and anode alloy surface corrosion is uniform.
Embodiment 5
The air cell aluminum alloy anode material of the present embodiment, is consisted of the following components in percentage by weight：Zn 5%,
Ga 2.5%, In 0.05%, surplus Al.
The preparation method of the air cell aluminum alloy anode material of the present embodiment, comprises the following steps：
1) under argon gas protection, aluminium ingot is placed in ZGJL0.01-40-4 induction melting furnace crucibles, being heated to 710 DEG C makes
Aluminium ingot all after fusing, adds zinc ingot metal, gallium grain and indium grain, rotates container in heating, makes metal melting and be well mixed, continues
After being heated to 780 DEG C and being incubated 6min, block ingot casting is poured into；
2) block ingot casting obtained by step 1) is rolled into the flaky material that thickness is 2mm under the conditions of 150 DEG C, produced described
Air cell aluminum alloy anode material.
The aluminium-air cell of the present embodiment, including aluminum alloy anode, air cathode and electrolyte, the aluminum alloy anode are
Above-mentioned air cell aluminum alloy anode material；
The electrolyte includes the component of following concentration：Sodium hydroxide 6mol/L, Lavender corrosion inhibiter 60ppm (v/
V), surplus is distilled water.The preparation method of the electrolyte is：The sodium hydroxide of formula ratio is taken to add distilled water, agitating solution system
Into sodium hydroxide solution；The Lavender corrosion inhibiter of formula ratio is added in sodium hydroxide solution, adds remaining distillation
Water, stir, produce.The Lavender corrosion inhibiter is the ethanol solution of Lavender, wherein Lavender
Volumn concentration is 40%.
The air cathode is suppressed and formed by Catalytic Layer, conductive nickel screen and waterproof ventilative layer；The Catalytic Layer be by
γ-MnO2, activated carbon and polytetrafluoroethylene (PTFE) be 0.5 in mass ratio:2:Thickness made of rolling is 0.4mm after 2 ratio mixing
Film layer；The waterproof ventilative layer is by weight being 1 by polytetrafluoroethylene (PTFE) and acetylene black:Roll and be made after 1 ratio mixing
Thickness be 0.7mm film layer；Catalytic Layer, conductive nickel screen and waterproof ventilative layer are finally pressed into the air that thickness is 0.5mm
Negative electrode.
The self-corrosion speed of the aluminum alloy anode of the present embodiment in the electrolytic solution is 3.85mg/cm2H, OCP for-
2.08V (vs.SHE), discharge current density is 100mA/cm to the air cell of composition in the electrolytic solution2When test 10h it is electronic
Gesture is 1.84V, and anode alloy surface corrosion is uniform.
Embodiment 6
The air cell aluminum alloy anode material of the present embodiment, is consisted of the following components in percentage by weight：Zn 1%,
Ga 1.5%, In 0.8%, surplus Al.
The preparation method of the air cell aluminum alloy anode material of the present embodiment, comprises the following steps：
1) under argon gas protection, aluminium ingot is placed in ZGJL0.01-40-4 induction melting furnace crucibles, being heated to 720 DEG C makes
Aluminium ingot all after fusing, adds zinc ingot metal, gallium grain and indium grain, rotates container in heating, makes metal melting and be well mixed, continues
After being heated to 740 DEG C and being incubated 10min, block ingot casting is poured into；
2) block ingot casting obtained by step 1) is rolled into the flaky material that thickness is 3mm under the conditions of 190 DEG C, produced described
Air cell aluminum alloy anode material.
The aluminium-air cell of the present embodiment, including aluminum alloy anode, air cathode and electrolyte, the aluminum alloy anode are
Above-mentioned air cell aluminum alloy anode material；
The electrolyte includes the component of following concentration：Sodium hydroxide 4mol/L, Lavender corrosion inhibiter 70ppm (v/
V), surplus is distilled water.The preparation method of the electrolyte is：The sodium hydroxide of formula ratio is taken to add distilled water, agitating solution system
Into sodium hydroxide solution；The Lavender corrosion inhibiter of formula ratio is added in sodium hydroxide solution, adds remaining distillation
Water, stir, produce.The Lavender corrosion inhibiter is the ethanol solution of Lavender, wherein Lavender
Volumn concentration is 10%.
The air cathode is suppressed and formed by Catalytic Layer, conductive nickel screen and waterproof ventilative layer；The Catalytic Layer be by
γ-MnO2, activated carbon and polytetrafluoroethylene (PTFE) be 0.3 in mass ratio:3:Thickness made of rolling is 0.7mm after 3 ratio mixing
Film layer；The waterproof ventilative layer is by weight being 1 by polytetrafluoroethylene (PTFE) and acetylene black:Roll and be made after 1 ratio mixing
Thickness be 0.3mm film layer；Catalytic Layer, conductive nickel screen and waterproof ventilative layer are finally pressed into the air that thickness is 0.4mm
Negative electrode.
The self-corrosion speed of the aluminum alloy anode of the present embodiment in the electrolytic solution is 4.62mg/cm2H, OCP for-
1.95V (vs.SHE), discharge current density is 100mA/cm to the air cell of composition in the electrolytic solution2When test 10h it is electronic
Gesture is 2.10V, and anode alloy surface corrosion is uniform.
Embodiment 7
The air cell aluminum alloy anode material of the present embodiment, is consisted of the following components in percentage by weight：Zn 4%,
Ga 0.05%, In 1%, surplus Al.
The preparation method of the air cell aluminum alloy anode material of the present embodiment, comprises the following steps：
1) under argon gas protection, aluminium ingot is placed in ZGJL0.01-40-4 induction melting furnace crucibles, being heated to 670 DEG C makes
Aluminium ingot all after fusing, adds zinc ingot metal, gallium grain and indium grain, rotates container in heating, makes metal melting and be well mixed, continues
After being heated to 750 DEG C and being incubated 4min, block ingot casting is poured into；
2) block ingot casting obtained by step 1) is rolled into the flaky material that thickness is 0.5mm under the conditions of 180 DEG C, produces institute
State air cell aluminum alloy anode material.
The aluminium-air cell of the present embodiment, including aluminum alloy anode, air cathode and electrolyte, the aluminum alloy anode are
Above-mentioned air cell aluminum alloy anode material；
The electrolyte includes the component of following concentration：Sodium hydroxide 2mol/L, Lavender corrosion inhibiter 100ppm (v/
V), surplus is distilled water.The preparation method of the electrolyte is：The sodium hydroxide of formula ratio is taken to add distilled water, agitating solution system
Into sodium hydroxide solution；The Lavender corrosion inhibiter of formula ratio is added in sodium hydroxide solution, adds remaining distillation
Water, stir, produce.The Lavender corrosion inhibiter is the ethanol solution of Lavender, wherein Lavender
Volumn concentration is 50%.
The air cathode is suppressed and formed by Catalytic Layer, conductive nickel screen and waterproof ventilative layer；The Catalytic Layer be by
γ-MnO2, activated carbon and polytetrafluoroethylene (PTFE) be 2 in mass ratio:5:Thickness made of rolling is 0.8mm after 2.5 ratio mixing
Film layer；The waterproof ventilative layer is by weight being 1 by polytetrafluoroethylene (PTFE) and acetylene black:Roll and be made after 1 ratio mixing
Thickness be 0.5mm film layer；Catalytic Layer, conductive nickel screen and waterproof ventilative layer are finally pressed into the air that thickness is 0.2mm
Negative electrode.
The self-corrosion speed of the aluminum alloy anode of the present embodiment in the electrolytic solution is 4.06mg/cm2H, OCP for-
1.81V (vs.SHE), discharge current density is 100mA/cm to the air cell of composition in the electrolytic solution2When test 10h it is electronic
Gesture is 1.96V, and anode alloy surface corrosion is uniform.
Experimental example
This experimental example detects to the performance of aluminum alloy anode material and aluminium-air cell obtained by embodiment 1-7, as a result
As shown in table 1.Wherein, it in discharge current density is in the electrolytic solution 100mA/cm that the electromotive force of aluminium-air cell, which is,2When test
10h electromotive force.
The performance test results of aluminum alloy anode material and aluminium-air cell obtained by the embodiment 1-7 of table 1
As it can be seen from table 1 the self-corrosion speed of aluminum alloy anode material in the electrolytic solution obtained by embodiment 1-7 is as little as
2.93~5.12mg/cm2H, OCP reaches -1.76~-2.08V (vs.SHE), and the air cell of composition is in electrolyte
Middle discharge current density is 100mA/cm2When test 10h electromotive force be 1.84~2.10V, anode alloy surface corrosion is uniform.
Test result indicates that the self-corrosion speed of aluminum alloy anode material of the invention in alkaline electrolyte is low, OCP is good, group
Into air cell there is excellent chemical property.
Claims (8)
- A kind of 1. aluminium-air cell, it is characterised in that：Including aluminum alloy anode, air cathode and electrolyte, the aluminium alloy sun Pole consists of the following components in percentage by weight：Zn 0.05%~6%, Ga 0.05%~4%, In 0.01%~2%, surplus Al； The electrolyte includes the component of following concentration：2~6mol/L of sodium hydroxide, Lavender corrosion inhibiter 20~100ppm, it is remaining Measure as water.
- 2. aluminium-air cell according to claim 1, it is characterised in that：The material of the aluminum alloy anode is prepared under including Row step：1）Under inert gas shielding, after aluminium heating fusing, zinc is added, gallium and indium simultaneously heat melting, continue to be heated to 730~ 780 DEG C and be incubated after, pour into ingot casting；2）By step 1）Gained ingot casting is rolled into flaky material under the conditions of 150~200 DEG C, produces.
- 3. aluminium-air cell according to claim 2, it is characterised in that：Step 1）In, time of the insulation for 4~ 10min。
- 4. aluminium-air cell according to claim 2, it is characterised in that：Step 2）In, the thickness of the flaky material is 0.5~4mm.
- 5. aluminium-air cell according to claim 1, it is characterised in that：The air cathode is by Catalytic Layer, conductive nickel screen Suppress to be formed with waterproof ventilative layer, thickness is 0.2~0.6mm.
- 6. aluminium-air cell according to claim 5, it is characterised in that：The Catalytic Layer is by γ-MnO2, activated carbon with Polytetrafluoroethylene (PTFE) is in mass ratio（0.3~3）:（1~5）:（1~5）Ratio mixing after the film layer that is pressed into, thickness 0.3 ~0.8mm.
- 7. aluminium-air cell according to claim 5, it is characterised in that：The waterproof ventilative layer be by polytetrafluoroethylene (PTFE) and Acetylene black is 1 by weight:The film layer being pressed into after 1 ratio mixing, thickness is 0.3~0.8mm.
- 8. aluminium-air cell according to claim 1, it is characterised in that：The Lavender corrosion inhibiter is lavender essence The ethanol solution of oil, the wherein volumn concentration of Lavender are 10%~60%.
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| CN109461942B (en) * | 2018-11-22 | 2021-04-02 | 河南科技大学 | Aluminum alloy anode material for air battery, preparation method of aluminum alloy anode material and air battery |
| CN112542596B (en) * | 2019-09-23 | 2023-07-11 | 易航时代(北京)科技有限公司 | Self-corrosion-resistant metal-air battery and preparation method and application thereof |
| CN110783664B (en) * | 2019-12-09 | 2021-07-16 | 王新跃 | Container type aluminum electrode |
| CN111172562A (en) * | 2020-01-20 | 2020-05-19 | 镇江慧诚新材料科技有限公司 | Preparation method of fuel aluminum for aluminum-air battery |
| CN113097471B (en) * | 2021-03-16 | 2023-04-25 | 郑州大学 | Anode material for alkaline aluminum-air battery and preparation method thereof |
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