CN105140595B - A kind of electrolyte corrosion inhibitor, aluminium-air cell electrolyte and aluminium-air cell - Google Patents
A kind of electrolyte corrosion inhibitor, aluminium-air cell electrolyte and aluminium-air cell Download PDFInfo
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- CN105140595B CN105140595B CN201510561491.1A CN201510561491A CN105140595B CN 105140595 B CN105140595 B CN 105140595B CN 201510561491 A CN201510561491 A CN 201510561491A CN 105140595 B CN105140595 B CN 105140595B
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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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- 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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Abstract
The invention discloses a kind of electrolyte corrosion inhibitor, aluminium-air cell electrolyte and aluminium-air cell, the electrolyte corrosion inhibitor is the ethanol solution of Lavender, and wherein the volumn concentration of Lavender is 10%~60%.The main component of Lavender includes linalool, bergamio, cineole, β ocimenums, the alcohol of terpene 4 and camphor, lone pair electrons be present in contained group Molecule, oxygen atom in group forms insoluble complex layer in metal surface by lone pair electrons absorption, metal surface is separated with the aqueous solution, play corrosion inhibition.The electrolyte corrosion inhibitor that the present invention is prepared using the Lavender extracted from plant with ethanol is a kind of new green environment protection corrosion inhibiter; have the advantages that cost is low, less toxic or nontoxic, non-environmental-pollution; the self-corrosion speed of aluminium anodes can be significantly reduced added in electrolyte and improves its chemical property, there is good economic benefit and environmental benefit.
Description
Technical field
The invention belongs to aluminium-air cell technical field, and in particular to a kind of electrolyte sustained release agent, also relate to one kind
Aluminium-air cell electrolyte and the aluminium-air cell using the electrolyte.
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, air cell aluminium sun
Compared with zinc anode material, existing matter of utmost importance is pole material：Aluminium self-corrosion in alkaline solution is very serious, causes anode sharp
Substantially reduced with rate, hinder the commercial applications of aluminium-air cell.Researcher develops novel aluminum sun by microalloying
Pole material, and the corresponding electrolyte corrosion inhibitor of addition, the self-corrosion speed of aluminium can be reduced.Aluminium-air cell anode material is commonly used
Alloy element mainly have zinc, magnesium, sow, indium, tin, lead, mercury, bismuth etc..These elements, which are added in aluminium, forms ternary, quaternary etc.
Multicomponent alloy.
Aluminium-air cell is made up of aluminium anodes, air cathode and electrolyte；In discharge process, the oxygen in air passes through
Air cathode enters electrolyte and reaches reaction interface generation reduction reaction and discharge electric energy.Electrolyte is generally alkaline solution,
Such as potassium hydroxide solution or sodium hydroxide solution；The research of early stage uses potassium hydroxide solution more, from the recycling of discharging product
Use aspects consider, at present to use sodium hydroxide solution more.Because self-corrosion speed of the aluminium in strong alkali solution is very big, therefore need
Some inhibitor are added in alkali lye to slow down the self-corrosion of aluminium anodes.In the prior art, it is common to use it is mostly be inorganic slow
Lose agent, such as NaSnO3、In(OH)3、Ga(OH)3、K2MnO4Deng.Although most inorganic inhibitor can reduce to a certain extent
The self-corrosion speed of aluminum alloy materials used in aluminium anodes, but often using sacrificial anode activity as cost；And inorganic corrosion agent
Mostly chemical synthesis, cost height is prepared, expensive, some components are likely to result in environmental pollution, there is certain poison to the mankind
Evil effect, does not meet environmental requirement.Therefore, seek a kind of electrolyte corrosion inhibitor of new green environment protection, reduce aluminium anodes oneself
Corrosion rate and the chemical property for improving aluminium-air cell, are significant.
The content of the invention
It is an object of the invention to provide a kind of electrolyte corrosion inhibitor, can be significantly reduced added in electrolyte aluminium anodes from
Corrosion rate simultaneously improves its chemical property, green.
Second object of the present invention is to provide a kind of aluminium-air cell electrolyte.
Third object of the present invention is to provide a kind of aluminium-air cell using above-mentioned electrolyte.
In order to realize the above object the technical solution adopted in the present invention is：
A kind of electrolyte corrosion inhibitor, the electrolyte corrosion inhibitor are the ethanol solutions of Lavender, wherein lavender essence
The volumn concentration of oil is 10%~60%.
A kind of aluminium-air cell electrolyte, include the component of following concentration：2~6mol/L of sodium hydroxide, electrolyte delay
20~100ppm of agent is lost, surplus is water；The electrolyte corrosion inhibitor is the ethanol solution of Lavender, wherein Lavender
Volumn concentration be 10%~60%.
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.
In the electrolyte corrosion inhibitor of the present invention, Lavender is refined by lavender and formed, wide material sources, and price is low
It is honest and clean, it is environment-protecting and non-poisonous；The complex mixture that Lavender is made up of many different types of aromatic compounds, main component
Including：Linalool, bergamio, cineole, β-ocimenum, terpene -4- alcohol and camphor.Group contained by these materials is with more
Negative electrical charge, first, there is electrostatic attraction between charged group and metal surface；Furthermore lone pair electrons in group Molecule be present, can
To provide electronics to the unoccupied orbital of metal, the oxygen atom in group adsorbed by lone pair electrons formed in metal surface it is insoluble
Complex layer, metal surface is separated with the aqueous solution, play corrosion inhibition.The present invention is using the lavender essence extracted from plant
The electrolyte corrosion inhibitor that oil is prepared with ethanol is a kind of new green environment protection corrosion inhibiter, has cost low, less toxic or nontoxic, acyclic
The advantages that border is polluted, the self-corrosion speed of aluminium anodes can be significantly reduced added in electrolyte and improves its chemical property, had
There are good economic benefit and environmental benefit.
A kind of aluminium-air cell, including aluminium anodes, air cathode and electrolyte, the electrolyte are above-mentioned aluminium air electricity
Pond electrolyte.
The aluminium-air cell of the present invention, the electrolyte corrosion inhibitor containing Lavender is added in electrolyte, had following
Advantage：Green plants extract solution Lavender reduces the self-corrosion speed of aluminium anodes and improves aluminium anodes activity；Smoke clothing
Linalool hydroxyl oxygen subbase group in careless essential oil with metal cation by forming complex layer absorption in anode surface, obstruction water
Molecule anode surface absorption, and then reduce liberation of hydrogen self-corrosion speed；Due to bergamio, camphor, cineole group point
Son has oxygen key and double bond, forms complex ions, promotes reaction product desorption, makes aluminium anodes continuous activation, put in aluminium anodes
Reduce aluminium anodes polarization when electric, improve discharge performance, therefore after addition Lavender corrosion inhibiter, the self-corrosion of anode alloy
Speed does not add to be substantially reduced during Lavender, and the significantly negative shifting of the OCP of the aluminium anodes；Lavender inhibition
Agent component forms simple, and cost 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.
In the aluminium-air cell, the aluminium anodes is aluminum alloy anode material, by following components in percentage by weight group
Into：Zn 0.05%~6%, Ga 0.05%~4%, In 0.01%~2%, surplus Al.
The aluminum alloy anode material is prepared by the method comprised 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 time of the insulation is 4~10min.
In step 2), the thickness of the flaky material is 0.5~4mm.
The aluminum alloy anode material, the basis of aluminium anodes material electrochemical performance is not being reduced from the aspect of alloying
Upper its self-corrosion of reduction：Based on purity is >=99.85% aluminium, appropriate zinc, gallium and indium are added in aluminium alloy.In aluminium
Adding zinc in alloy, zinc current potential (- 1.29Vvs.SHE) is than aluminium (- 2.35Vvs.SHE) just, redeposited in aluminium surface by dissolving,
It can obviously reduce the self-corrosion speed of aluminium alloy；Furthermore zinc is advantageous to being uniformly distributed for other alloying elements, promote alloy uniform
Dissolving improves the service life of anode alloy.Solid solubility of the gallium element in aluminium is very big, and gallium ion is due to activity caused by dissolving
Low can be reduced again deposits to aluminum alloy surface, with aluminum substrate generate gallium aluminium amalgam, the peelable oxide-film of gallium aluminium amalgam and
Corrosion product, exposed base aluminum, promote the activation discharge of aluminium alloy；Secondly, influence of the alloying element gallium to aluminium anodes, main table
Change aluminium grain anisotropy present in course of dissolution now, so that aluminium anodes corrosion is uniform；Furthermore gallium and other conjunctions
Gold element Zn, In etc., under electrode operating temperature (about 60 DEG C), eutectic mixture is formed, destroys aluminium surface passivating film；Separately
Outside, In is being contained3+Solution in, due to In3+Redeposition (the defects of being deposited on alumite position), cause Ga3+It is heavy
Product, activation is produced to aluminium anodes.Influences of the alloying element In to aluminium anodes, being mainly manifested in In has very strong activation energy
Power, destroy the passivating film of aluminium surface；Alloying element In effect, it is redeposited after the dissolving of In elements in Alloy solid solution produce
, In3+There is destruction to aluminium surface passivating film；Secondly, In can also effectively suppress the gas-evolving electrodes of alloy, and this has with it
There is higher overpotential of hydrogen evolution relevant.Meanwhile zinc, gallium and indium are all high overpotential of hydrogen evolution elements, can substantially reduce aluminium alloy
Liberation of hydrogen self-corrosion.The addition of these alloy elements, if addition is few, does not have due work within the scope of certain
With if addition is big, forming the second larger phase of a large amount of shapes, increase aluminium alloy self-corrosion speed, erosion uniformity is deteriorated.
The self-corrosion speed of alloy is can obviously reduce to aluminium progress alloying by adding appropriate zinc, gallium and indium, alloy can also be improved
The erosion uniformity on surface.
The aluminum alloy anode material, zinc, gallium and phosphide element are added in aluminium anodes material, with existing aluminium anodes material
Material is compared, and has advantages below：Electro-chemical activity is good, and self-corrosion speed is small, in the aluminium-air cell electrolyte of the present invention
OCP≤- 1.76V (vs.SHE), the electromotive force of cell are more than 1.84V；The aluminum alloy anode material passes through alloy
Change, hence it is evident that improve the chemical property of anode and reduce self-corrosion speed, self-corrosion speed is less than 4.62mg/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 present invention electrolyte in use
Aluminum alloy anode material.
The aluminum alloy anode material is after aluminium heating fusing, will to add zinc, gallium and indium and heat to melt and pour into casting
Ingot, then ingot rolling slabbing material, gained aluminum alloy anode material are had into excellent chemical property and alkali resistant corrosion
Performance, suitable for the aluminium-air cell of alkaline electrolyte；The preparation method technique is simple, easy to operate, is adapted to large-scale industry
Metaplasia is produced.
In described aluminium-air cell, the air cathode is suppressed and formed by Catalytic Layer, conductive nickel screen and waterproof ventilative layer,
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 aluminium-air cell of the present invention, using above-mentioned electrolyte and aluminum alloy anode material containing Lavender,
Alkaline aluminium-air cell self-corrosion can be controlled too fast, and can ensures that aluminium anodes alloy has higher electro-chemical activity, to carrying
High cell discharge efficiency, extension discharge life is significant, is advantageous to the commercial applications of aluminium-air cell；The aluminium alloy
The open-circuit voltage of anode material is good, is -1.76~-2.08V (vs.SHE), self-corrosion speed in the electrolytic solution it is low (≤
4.62mg/cm2H), surface corrosion is uniform；The aluminium-air cell is 100mA/cm in discharge current density2Test the electronic of 10h
Gesture is 1.84V~2.10V, has excellent chemical property.
Embodiment
With reference to embodiment, the present invention is further illustrated.
Embodiment 1
The electrolyte corrosion inhibitor of the present embodiment is the volume basis of the ethanol solution of Lavender, wherein Lavender
Content is 45%.
The aluminium-air cell electrolyte of the present embodiment, include the component of following concentration：It is sodium hydroxide 3mol/L, above-mentioned
Electrolyte corrosion inhibitor 60ppm (v/v), surplus are distilled water.The preparation method of the electrolyte is：The sodium hydroxide of formula ratio is taken to add
Enter distilled water, sodium hydroxide solution is made in agitating solution；The Lavender corrosion inhibiter of formula ratio is added into sodium hydroxide solution
In, remaining distilled water is added, is stirred, is produced.
The aluminium-air cell of the present embodiment, including aluminium anodes, air cathode and electrolyte, the electrolyte are above-mentioned aluminium
Air cell electrolyte.
The aluminium anodes is aluminum alloy anode material (ALCAN(Aluminium Company of Canada researches and develops earliest), by following percentage by weight
Component forms：Mg 0.6%, Sn 0.1%, Ga 0.05%, surplus Al.
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 4.24mg/cm2H, OCP for-
1.86V (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 1.91V, and anode alloy surface corrosion is uniform.
Embodiment 2
The electrolyte corrosion inhibitor of the present embodiment is the volume basis of the ethanol solution of Lavender, wherein Lavender
Content is 60%.
The aluminium-air cell electrolyte of the present embodiment, include the component of following concentration：It is sodium hydroxide 3mol/L, above-mentioned
Electrolyte corrosion inhibitor 80ppm (v/v), surplus are distilled water.The preparation method of the electrolyte is：The sodium hydroxide of formula ratio is taken to add
Enter distilled water, sodium hydroxide solution is made in agitating solution；The Lavender corrosion inhibiter of formula ratio is added into sodium hydroxide solution
In, remaining distilled water is added, is stirred, is produced.
The aluminium-air cell of the present embodiment, including aluminium anodes, air cathode and electrolyte, the electrolyte are above-mentioned aluminium
Air cell electrolyte.
The aluminium anodes is aluminum alloy anode material, is consisted of the following components in percentage by weight：Zn 6%, Ga 1%,
In1.5%, surplus Al.
The preparation method of the aluminum alloy anode material, 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 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 electrolyte corrosion inhibitor of the present embodiment is the volume basis of the ethanol solution of Lavender, wherein Lavender
Content is 20%.
The aluminium-air cell electrolyte of the present embodiment, include the component of following concentration：It is sodium hydroxide 4mol/L, above-mentioned
Electrolyte corrosion inhibitor 20ppm (v/v), surplus are distilled water.The preparation method of the electrolyte is：The sodium hydroxide of formula ratio is taken to add
Enter distilled water, sodium hydroxide solution is made in agitating solution；The Lavender corrosion inhibiter of formula ratio is added into sodium hydroxide solution
In, remaining distilled water is added, is stirred, is produced.
The aluminium-air cell of the present embodiment, including aluminium anodes, air cathode and electrolyte, the electrolyte are above-mentioned aluminium
Air cell electrolyte.
The aluminium anodes is aluminum alloy anode material, is consisted of the following components in percentage by weight：Zn 3%, Ga 3%,
In0.01%, surplus Al.
The preparation method of the aluminum alloy anode material, 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 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 electrolyte corrosion inhibitor of the present embodiment is the volume basis of the ethanol solution of Lavender, wherein Lavender
Content is 30%.
The aluminium-air cell electrolyte of the present embodiment, include the component of following concentration：It is sodium hydroxide 5mol/L, above-mentioned
Electrolyte corrosion inhibitor 90ppm (v/v), surplus are distilled water.The preparation method of the electrolyte is：The sodium hydroxide of formula ratio is taken to add
Enter distilled water, sodium hydroxide solution is made in agitating solution；The Lavender corrosion inhibiter of formula ratio is added into sodium hydroxide solution
In, remaining distilled water is added, is stirred, is produced.
The aluminium-air cell of the present embodiment, including aluminium anodes, air cathode and electrolyte, the electrolyte are above-mentioned aluminium
Air cell electrolyte.
The aluminium anodes is aluminum alloy anode material, is consisted of the following components in percentage by weight：Zn 0.05%, Ga
4%th, In 2%, surplus Al.
The preparation method of the aluminum alloy anode material, 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 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 electrolyte corrosion inhibitor of the present embodiment is the volume basis of the ethanol solution of Lavender, wherein Lavender
Content is 40%.
The aluminium-air cell electrolyte of the present embodiment, include the component of following concentration：It is sodium hydroxide 6mol/L, above-mentioned
Electrolyte corrosion inhibitor 60ppm (v/v), surplus are distilled water.The preparation method of the electrolyte is：The sodium hydroxide of formula ratio is taken to add
Enter distilled water, sodium hydroxide solution is made in agitating solution；The Lavender corrosion inhibiter of formula ratio is added into sodium hydroxide solution
In, remaining distilled water is added, is stirred, is produced.
The aluminium-air cell of the present embodiment, including aluminium anodes, air cathode and electrolyte, the electrolyte are above-mentioned aluminium
Air cell electrolyte.
The aluminium anodes is aluminum alloy anode material, is consisted of the following components in percentage by weight：Zn 5%, Ga
2.5%th, In0.05%, surplus Al.
The preparation method of the aluminum alloy anode material, 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 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 electrolyte corrosion inhibitor of the present embodiment is the volume basis of the ethanol solution of Lavender, wherein Lavender
Content is 10%.
The aluminium-air cell electrolyte of the present embodiment, include the component of following concentration：It is sodium hydroxide 4mol/L, above-mentioned
Electrolyte corrosion inhibitor 70ppm (v/v), surplus are distilled water.The preparation method of the electrolyte is：The sodium hydroxide of formula ratio is taken to add
Enter distilled water, sodium hydroxide solution is made in agitating solution；The Lavender corrosion inhibiter of formula ratio is added into sodium hydroxide solution
In, remaining distilled water is added, is stirred, is produced.
The aluminium-air cell of the present embodiment, including aluminium anodes, air cathode and electrolyte, the electrolyte are above-mentioned aluminium
Air cell electrolyte.
The aluminium anodes is aluminum alloy anode material, is consisted of the following components in percentage by weight：Zn 1%, Ga
1.5%th, In0.8%, surplus Al.
The preparation method of the aluminum alloy anode material, 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 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 electrolyte corrosion inhibitor of the present embodiment is the volume basis of the ethanol solution of Lavender, wherein Lavender
Content is 50%.
The aluminium-air cell electrolyte of the present embodiment, include the component of following concentration：It is sodium hydroxide 2mol/L, above-mentioned
Electrolyte corrosion inhibitor 100ppm (v/v), surplus are distilled water.The preparation method of the electrolyte is：Take the sodium hydroxide of formula ratio
Distilled water is added, sodium hydroxide solution is made in agitating solution；It is molten that the Lavender corrosion inhibiter of formula ratio is added into sodium hydroxide
In liquid, remaining distilled water is added, is stirred, is produced.
The aluminium-air cell of the present embodiment, including aluminium anodes, air cathode and electrolyte, the electrolyte are above-mentioned aluminium
Air cell electrolyte.
The aluminium anodes is aluminum alloy anode material, is consisted of the following components in percentage by weight：Zn 4%, Ga
0.05%th, In 1%, surplus Al.
The preparation method of the aluminum alloy anode material, 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 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 electrolyte corrosion inhibitor obtained by embodiment 1-7 and the performance of aluminium-air cell, as a result such 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 self-corrosion speed of the aluminum alloy anode material in electrolyte obtained by embodiment 1-7 is as little as
2.93~4.62mg/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 electrolyte corrosion inhibitor of the invention is added in electrolyte the self-corrosion speed that can significantly reduce aluminium anodes,
Aluminium anodes alloy is possessed good corrosion resistance and higher electro-chemical activity, meet alkaline aluminium-air cell high current density
The requirement of electric discharge.
Claims (9)
- A kind of 1. aluminium-air cell electrolyte, it is characterised in that：Include the component of following concentration：2~6mol/L of sodium hydroxide, 20~100ppm of electrolyte corrosion inhibitor, surplus are water；The electrolyte corrosion inhibitor is the ethanol solution of Lavender, wherein smoking The volumn concentration of clothing grass essential oil is 10%~60%.
- A kind of 2. aluminium-air cell, it is characterised in that：Including aluminium anodes, air cathode and electrolyte, the electrolyte is right It is required that the aluminium-air cell electrolyte described in 1.
- 3. aluminium-air cell according to claim 2, it is characterised in that：The aluminium anodes is aluminum alloy anode material, by Following components in percentage by weight forms：Zn 0.05%~6%, Ga 0.05%~4%, In 0.01%~2%, surplus Al.
- 4. aluminium-air cell according to claim 3, it is characterised in that：The aluminum alloy anode material is by including following Prepared by the method for 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.
- 5. aluminium-air cell according to claim 4, it is characterised in that：Step 1）In, time of the insulation for 4~ 10min。
- 6. aluminium-air cell according to claim 4, it is characterised in that：Step 2）In, the thickness of the flaky material is 0.5~4mm.
- 7. the aluminium-air cell according to any one of claim 2~6, it is characterised in that：The air cathode is by being catalyzed Layer, conductive nickel screen and waterproof ventilative layer are suppressed to be formed, and thickness is 0.2~0.6mm.
- 8. aluminium-air cell according to claim 7, 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.
- 9. aluminium-air cell according to claim 7, 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.
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| CN107275720B (en) * | 2017-05-23 | 2021-01-15 | 深圳市航盛新材料技术有限公司 | Aluminum-air battery electrolyte, aluminum-air battery and manufacturing method thereof |
| CN108277493A (en) * | 2018-04-03 | 2018-07-13 | 西北工业大学 | A kind of cleaning solution and method using perilla leaf extract as corrosion inhibiter |
| CN109811207A (en) * | 2019-03-14 | 2019-05-28 | 上海交通大学 | By recycling aluminum for the method for aluminium-air cell anode |
| KR102639459B1 (en) * | 2021-09-15 | 2024-02-21 | 성균관대학교산학협력단 | Electrolyte for aluminum air battery and method of fabricating the same |
| CN113851665A (en) * | 2021-10-14 | 2021-12-28 | 湖南西瑞尔新材料科技有限公司 | Electrolyte and aluminum-air battery |
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