CN105140595A - Electrolyte corrosion inhibitor, electrolyte for aluminum air cell and aluminum air cell - Google Patents
Electrolyte corrosion inhibitor, electrolyte for aluminum air cell and aluminum air cell Download PDFInfo
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Abstract
The invention discloses an electrolyte corrosion inhibitor, an electrolyte for aluminum air cell and an aluminum air cell. The electrolyte corrosion inhibitor is an ethanol solution of lavender essential oil, and the volume percentage content of lavender essential oil is 10%-60%. The main components of lavender essential oil comprise linalool, linalyl acetate, eucalyptol, beta-ocimene, 4-terpineol and camphor. Group molecules contain lone pair electrons, oxygen atoms in the groups are absorbed on a metal surface through the lone pair electrons, an insoluble complex layer is formed, thus the metal surface is separated from an aqueous solution, and a corrosion inhibition function is achieved. The electrolyte corrosion inhibitor prepared from lavender essential oil extracted from plants and ethanol is a novel green environmental protection corrosion inhibitor, and has advantages of low cost, low toxicity or no toxicity, no environmental pollution and the like. The electrolyte corrosion inhibitor is added in an electrolyte, a self corrosion rate of an aluminum anode can be lowered remarkably, the electrochemical performance can be raised, and the electrolyte corrosion inhibitor has good economic benefits and environmental benefits.
Description
Technical field
The invention belongs to aluminum-air cell technical field, be specifically related to a kind of electrolyte sustained release agent, also relate to a kind of aluminum-air cell electrolyte simultaneously and use the aluminum-air cell of this electrolyte.
Background technology
Metal-air cell is new generation of green storage battery, and its low cost of manufacture, specific energy are high, raw material recoverable, superior performance.The more metal-air cell of current research has zinc-air cell, aluminum-air cell and lithium-air battery etc., only has zinc-air cell with industrialization is immediate.In galvanic series, aluminum ratio zinc is more active, can obtain higher cell voltage; An aluminium atom can discharge three electronics, and a zinc atom discharges two electronics, and aluminium can improve the energy of battery; In addition, aluminium rich reserves, cheap, therefore the progress of aluminum-air cell is very rapid, is a kind of rising air cell.
Aluminum-air cell is using aluminium and air as a kind of novel battery of battery material.Aluminium has the advantage of its uniqueness as the anode material of air cell: electrochemical equivalent is high, and the electrochemical equivalent of aluminium is 2980Ah/kg, is metal the highest except lithium; Electrode potential is more negative, and in alkaline solution, its standard electrode potential is-2.35V (vs.SHE), antianode material, and current potential is more negative better, and battery can provide larger electromotive force; The aboundresources of aluminium, cheap.At present, air cell aluminium anodes material is compared with zinc anode material, and the matter of utmost importance of existence is: aluminium is very serious from corrosion in alkaline solution, causes anode utilance greatly to reduce, hinders the commercial applications of aluminum-air cell.Researcher develops novel aluminum anode material by microalloying, and adds corresponding electrolyte corrosion inhibitor, can reduce aluminium from corrosion rate.The alloy element that aluminum-air cell anode material is conventional mainly contains zinc, magnesium, sows, indium, tin, lead, mercury, bismuth etc.These elements add in aluminium and form the multicomponent alloy such as ternary, quaternary.
Aluminum-air cell is made up of aluminium anodes, air cathode and electrolyte; In discharge process, the oxygen in air enters electrolyte arrival reaction interface generation reduction reaction by air cathode and discharges electric energy.Electrolyte is generally alkaline solution, as potassium hydroxide solution or sodium hydroxide solution; Early stage research adopts potassium hydroxide solution more, being recycled from the viewpoint of discharging product, uses sodium hydroxide solution at present more.Because of very large from corrosion rate in strong alkali solution of aluminium, therefore need to add in alkali lye some inhibitor to slow down aluminium anodes from corrosion.In prior art, mostly what generally use is inorganic inhibitor, as NaSnO
3, In (OH)
3, Ga (OH)
3, K
2mnO
4deng.Although most inorganic inhibitor can reduce to a certain extent aluminium anodes aluminum alloy materials used from corrosion rate, active in sacrificial anode is often cost; And inorganic corrosion agent mostly is chemical synthesis, preparation cost is high, expensive, and some component may cause environmental pollution, has certain toxic action, do not meet environmental requirement to the mankind.Therefore, seek a kind of electrolyte corrosion inhibitor of new green environment protection, that reduces aluminium anodes improves the chemical property of aluminum-air cell from corrosion rate, is significant.
Summary of the invention
The object of this invention is to provide a kind of electrolyte corrosion inhibitor, to be added in electrolyte significantly can reduce aluminium anodes improve its chemical property, environmental protection from corrosion rate.
Second object of the present invention is to provide a kind of aluminum-air cell electrolyte.
3rd object of the present invention is to provide a kind of aluminum-air cell using above-mentioned electrolyte.
In order to realize above object, the technical solution adopted in the present invention is:
A kind of electrolyte corrosion inhibitor, described electrolyte corrosion inhibitor is the ethanolic solution of Lavender, and wherein the volumn concentration of Lavender is 10% ~ 60%.
A kind of aluminum-air cell electrolyte, comprise the component of following concentration: NaOH 2 ~ 6mol/L, electrolyte corrosion inhibitor 20 ~ 100ppm, surplus is water; Described electrolyte corrosion inhibitor is the ethanolic solution of Lavender, and wherein the volumn concentration of Lavender is 10% ~ 60%.
The preparation method of described electrolyte is: by formula ratio, adds in sodium hydroxide solution by Lavender corrosion inhibiter, adds remaining water, stirs, to obtain final product.Electrolyte water used is distilled water.
In electrolyte corrosion inhibitor of the present invention, Lavender is refined by lavender and forms, and wide material sources are cheap, environment-protecting asepsis; The complex mixture that Lavender is made up of many dissimilar aromatic compounds, main component comprises: linalool, bergamio, cineole, β-ocimenum, terpene-4-alcohol and camphor.Contained by these materials, group is with more negative electrical charge, first, has electrostatic attraction between charged group and metal surface; Moreover there are lone pair electrons in group Molecule, can provide electronics to the unoccupied orbital of metal, the oxygen atom in group is adsorbed on metal surface by lone pair electrons and forms insoluble complex layer, makes metal surface and the aqueous solution separate, plays corrosion inhibition.The electrolyte corrosion inhibitor that the present invention adopts the Lavender that extracts from plant and ethanol to prepare is a kind of new green environment protection corrosion inhibiter; have that cost is low, the advantage such as low toxicity or nontoxic, non-environmental-pollution; to be added in electrolyte significantly can reduce aluminium anodes improve its chemical property from corrosion rate, there is good economic benefit and environmental benefit.
A kind of aluminum-air cell, comprise aluminium anodes, air cathode and electrolyte, described electrolyte is above-mentioned aluminum-air cell electrolyte.
Aluminum-air cell of the present invention, adds containing the electrolyte corrosion inhibitor of Lavender in electrolyte, has the following advantages: what green plants extract Lavender reduced aluminium anodes improves aluminium anodes activity from corrosion rate; Linalool hydroxyl oxygen molecule group in Lavender is adsorbed on anode surface by forming complex layer with metal cation, hinders hydrone in the absorption of anode surface, and then reduces liberation of hydrogen from corrosion rate; Because bergamio, camphor, cineole group Molecule have oxygen key and double bond, form complex ions, promote product desorption, make aluminium anodes continuous activation, reduce aluminium anodes polarization when aluminium anodes discharges, improve discharge performance, after therefore adding Lavender corrosion inhibiter, greatly reducing when corrosion rate does not add Lavender of anode alloy, and the Open Circuit Potential of this aluminium anodes is significantly negative moves; Lavender corrosion inhibiter component forms simple, and cost is low, safety and meet environmental requirement, makes aluminium anodes alloy have good corrosion resistance and higher electro-chemical activity, with the requirement of satisfied alkaline aluminum-air cell high current density discharge.
In described aluminum-air cell, described aluminium anodes is aluminum alloy anode material, is made up of the component of following percentage by weight: Zn0.05% ~ 6%, Ga0.05% ~ 4%, In0.01% ~ 2%, and surplus is Al.
Described aluminum alloy anode material is prepared by the method comprised the following steps:
1) under inert gas shielding, after aluminium heat fused, add zinc, gallium and indium and heating and melting, continue to be heated to 730 ~ 780 DEG C and after insulation, pour into ingot casting;
2) by step 1) gained ingot casting is rolled into flaky material under 150 ~ 200 DEG C of conditions, to obtain final product.
Step 1) in, the time of described insulation is 4 ~ 10min.
Step 2) in, the thickness of described flaky material is 0.5 ~ 4mm.
Described aluminum alloy anode material, from alloying aspect consider reduce it from corrosivity on the basis not reducing aluminium anodes material electrochemical performance: by purity be >=99.85% aluminium based on, in aluminium alloy, add appropriate zinc, gallium and indium.In aluminium alloy, add zinc, zinc current potential (-1.29Vvs.SHE) than aluminium (-2.35Vvs.SHE) just, by dissolve be deposited on aluminium surface again, can obviously reduce aluminium alloy from corrosion rate; Moreover zinc is conducive to being uniformly distributed of other alloying elements, alloy uniform dissolution is impelled to improve the useful life of anode alloy.The solid solubility of gallium element in aluminium is very large, the gallium ion dissolving generation again can be reduced because activity is low and deposit to aluminum alloy surface, generates gallium aluminium amalgam, the peelable oxide-film of gallium aluminium amalgam and corrosion product with aluminum substrate, exposed base aluminum, promotes the activation discharge of aluminium alloy; Secondly, alloying element gallium, on the impact of aluminium anodes, is mainly manifested in the anisotropy changing aluminium grain and exist in course of dissolution, thus makes aluminium anodes corrode evenly; Moreover gallium and other alloy element Zn, In etc., under electrode operating temperature (about 60 DEG C), form eutectic mixture, destroy aluminium surface passivated membrane; In addition, containing In
3+solution in, due to In
3+deposit again (rejected region being deposited on alumite), cause Ga
3+deposition, to aluminium anodes produce activation.Alloying element In, on the impact of aluminium anodes, is mainly manifested in In and has very strong activation capacity, destroys the passivating film on aluminium surface; The effect of alloying element In is In element deposition generation again after dissolving in Alloy solid solution, In
3+to aluminium surface passivated membrane, there is destruction; Secondly, In can also suppress the gas-evolving electrodes of alloy effectively, and to have higher overpotential of hydrogen evolution relevant with it for this.Meanwhile, zinc, gallium and indium are all high overpotential of hydrogen evolution elements, greatly can reduce the liberation of hydrogen of aluminium alloy from corrosion.The addition of these alloy elements, within certain scope, if addition is few, does not have due effect, if addition is large, forms the second-phase that a large amount of shape is larger, increase aluminium alloy from corrosion rate, erosion uniformity is deteriorated.Alloying is carried out to aluminium can obviously fall low-alloyed from corrosion rate by adding appropriate zinc, gallium and indium, the erosion uniformity of alloy surface can also be improved.
Described aluminum alloy anode material, zinc, gallium and phosphide element is added in aluminium anodes material, compared with existing aluminium anodes material, have the following advantages: electro-chemical activity is good, little from corrosion rate, Open Circuit Potential≤-1.76V (vs.SHE) in aluminum-air cell electrolyte of the present invention, the electromotive force of cell is greater than 1.84V; This aluminum alloy anode material, by alloying, significantly improves the chemical property of anode and reduces from corrosion rate, being less than 4.62mg/cm from corrosion rate
2h, surface corrosion is even; This aluminum alloy anode material superior performance, be a kind of novel, be adapted at the aluminum alloy anode material that uses in electrolyte of the present invention.
Described aluminum alloy anode material is by after aluminium heat fused, add zinc, gallium and indium and heating and melting pour into ingot casting, again by ingot rolling slabbing material, gained aluminum alloy anode material has excellent chemical property and alkali resistant corrosion performance, is applicable to the aluminum-air cell of alkaline electrolyte; This preparation method's technique is simple, easy to operate, is applicable to large-scale industrial production.
In described aluminum-air cell, described air cathode is suppressed by Catalytic Layer, conduction nickel screen and waterproof ventilative layer and is formed, and thickness is 0.2 ~ 0.6mm.
Described Catalytic Layer is by γ-MnO
2, active carbon and polytetrafluoroethylene be (0.3 ~ 3) in mass ratio: (1 ~ 5): the rete be pressed into after the ratio of (1 ~ 5) mixes, thickness is 0.3 ~ 0.8mm.
Described waterproof ventilative layer is the rete by weight for being pressed into after the ratio mixing of 1:1 by polytetrafluoroethylene and acetylene black, and thickness is 0.3 ~ 0.8mm.
Aluminum-air cell of the present invention, adopt the above-mentioned electrolyte containing Lavender and aluminum alloy anode material, alkaline aluminum-air cell can be controlled too fast from corrosion, can ensure that again aluminium anodes alloy has higher electro-chemical activity, to raising cell discharge efficiency, extend discharge life significant, be conducive to the commercial applications of aluminum-air cell; The open circuit voltage of this aluminum alloy anode material is good, is-1.76 ~-2.08V (vs.SHE), in the electrolytic solution from the low (≤4.62mg/cm of corrosion rate
2h), surface corrosion is even; This aluminum-air cell is 100mA/cm at discharge current density
2the electromotive force of test 10h is 1.84V ~ 2.10V, has excellent chemical property.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1
The electrolyte corrosion inhibitor of the present embodiment is the ethanolic solution of Lavender, and wherein the volumn concentration of Lavender is 45%.
The aluminum-air cell electrolyte of the present embodiment, comprises the component of following concentration: NaOH 3mol/L, above-mentioned electrolyte corrosion inhibitor 60ppm (v/v), surplus is distilled water.The preparation method of this electrolyte is: the NaOH getting formula ratio adds distilled water, and agitating solution makes sodium hydroxide solution; The Lavender corrosion inhibiter of formula ratio is added in sodium hydroxide solution, then adds remaining distilled water, stir, to obtain final product.
The aluminum-air cell of the present embodiment, comprises aluminium anodes, air cathode and electrolyte, and described electrolyte is above-mentioned aluminum-air cell electrolyte.
Described aluminium anodes is aluminum alloy anode material (ALCAN(Aluminium Company of Canada researches and develops the earliest), is made up of: Mg0.6%, Sn0.1%, Ga0.05% the component of following percentage by weight, and surplus is Al.
Described air cathode is suppressed by Catalytic Layer, conduction nickel screen and waterproof ventilative layer and is formed; Described Catalytic Layer is by γ-MnO
2, active carbon and polytetrafluoroethylene be the rete of 0.6mm for the ratio of 1:4:5 mix the thickness that roll extrusion is made afterwards in mass ratio; Described waterproof ventilative layer is the thickness that after being mixed by weight the ratio for 1:1 by polytetrafluoroethylene and acetylene black, roll extrusion is made is the rete of 0.4mm; Finally Catalytic Layer, conduction nickel screen and waterproof ventilative layer are pressed into the air cathode that thickness is 0.3mm.
The aluminum alloy anode of the present embodiment in the electrolytic solution from corrosion rate be 4.24mg/cm
2h, Open Circuit Potential are-1.86V (vs.SHE), and the air cell of composition in the electrolytic solution discharge current density is 100mA/cm
2time test 10h electromotive force be 1.91V, anode alloy surface corrosion is even.
Embodiment 2
The electrolyte corrosion inhibitor of the present embodiment is the ethanolic solution of Lavender, and wherein the volumn concentration of Lavender is 60%.
The aluminum-air cell electrolyte of the present embodiment, comprises the component of following concentration: NaOH 3mol/L, above-mentioned electrolyte corrosion inhibitor 80ppm (v/v), surplus is distilled water.The preparation method of this electrolyte is: the NaOH getting formula ratio adds distilled water, and agitating solution makes sodium hydroxide solution; The Lavender corrosion inhibiter of formula ratio is added in sodium hydroxide solution, then adds remaining distilled water, stir, to obtain final product.
The aluminum-air cell of the present embodiment, comprises aluminium anodes, air cathode and electrolyte, and described electrolyte is above-mentioned aluminum-air cell electrolyte.
Described aluminium anodes is aluminum alloy anode material, is made up of: Zn6%, Ga1%, In1.5% the component of following percentage by weight, and surplus is Al.
The preparation method of described aluminum alloy anode material, comprises the following steps:
1) under argon shield, aluminium ingot is placed in ZGJL0.01-40-4 induction melting furnace crucible, be heated to 700 DEG C aluminium ingot is all melted after, add zinc ingot metal, gallium grain and indium grain, limit heating edge rotary container, make metal melting and mix, continue to be heated to 730 DEG C and after being incubated 5min, pour into block ingot casting;
2) by step 1) the block ingot casting of gained is rolled into the flaky material that thickness is 1mm under 160 DEG C of conditions, obtains described air cell aluminum alloy anode material.
Described air cathode is suppressed by Catalytic Layer, conduction nickel screen and waterproof ventilative layer and is formed; Described Catalytic Layer is by γ-MnO
2, active carbon and polytetrafluoroethylene be the rete of 0.6mm for the ratio of 1:4:5 mix the thickness that roll extrusion is made afterwards in mass ratio; Described waterproof ventilative layer is the thickness that after being mixed by weight the ratio for 1:1 by polytetrafluoroethylene and acetylene black, roll extrusion is made is the rete of 0.4mm; Finally Catalytic Layer, conduction nickel screen and waterproof ventilative layer are pressed into the air cathode that thickness is 0.3mm.
The aluminum alloy anode of the present embodiment in the electrolytic solution from corrosion rate be 3.57mg/cm
2h, Open Circuit Potential are-1.92V (vs.SHE), and the air cell of composition in the electrolytic solution discharge current density is 100mA/cm
2time test 10h electromotive force be 2.05V, anode alloy surface corrosion is even.
Embodiment 3
The electrolyte corrosion inhibitor of the present embodiment is the ethanolic solution of Lavender, and wherein the volumn concentration of Lavender is 20%.
The aluminum-air cell electrolyte of the present embodiment, comprises the component of following concentration: NaOH 4mol/L, above-mentioned electrolyte corrosion inhibitor 20ppm (v/v), surplus is distilled water.The preparation method of this electrolyte is: the NaOH getting formula ratio adds distilled water, and agitating solution makes sodium hydroxide solution; The Lavender corrosion inhibiter of formula ratio is added in sodium hydroxide solution, then adds remaining distilled water, stir, to obtain final product.
The aluminum-air cell of the present embodiment, comprises aluminium anodes, air cathode and electrolyte, and described electrolyte is above-mentioned aluminum-air cell electrolyte.
Described aluminium anodes is aluminum alloy anode material, is made up of: Zn3%, Ga3%, In0.01% the component of following percentage by weight, and surplus is Al.
The preparation method of described aluminum alloy anode material, comprises the following steps:
1) under argon shield, aluminium ingot is placed in ZGJL0.01-40-4 induction melting furnace crucible, be heated to 710 DEG C aluminium ingot is all melted after, add zinc ingot metal, gallium grain and indium grain, limit heating edge rotary container, make metal melting and mix, continue to be heated to 760 DEG C and after being incubated 6min, pour into block ingot casting;
2) by step 1) the block ingot casting of gained is rolled into the flaky material that thickness is 3mm under 200 DEG C of conditions, obtains described air cell aluminum alloy anode material.
Described air cathode is suppressed by Catalytic Layer, conduction nickel screen and waterproof ventilative layer and is formed; Described Catalytic Layer is by γ-MnO
2, active carbon and polytetrafluoroethylene be the rete of 0.5mm for the ratio of 3:1:1 mix the thickness that roll extrusion is made afterwards in mass ratio; Described waterproof ventilative layer is the thickness that after being mixed by weight the ratio for 1:1 by polytetrafluoroethylene and acetylene black, roll extrusion is made is the rete of 0.6mm; Finally Catalytic Layer, conduction nickel screen and waterproof ventilative layer are pressed into the air cathode that thickness is 0.6mm.
The aluminum alloy anode of the present embodiment in the electrolytic solution from corrosion rate be 4.28mg/cm
2h, Open Circuit Potential are-1.76V (vs.SHE), and the air cell of composition in the electrolytic solution discharge current density is 100mA/cm
2time test 10h electromotive force be 1.95V, anode alloy surface corrosion is even.
Embodiment 4
The electrolyte corrosion inhibitor of the present embodiment is the ethanolic solution of Lavender, and wherein the volumn concentration of Lavender is 30%.
The aluminum-air cell electrolyte of the present embodiment, comprises the component of following concentration: NaOH 5mol/L, above-mentioned electrolyte corrosion inhibitor 90ppm (v/v), surplus is distilled water.The preparation method of this electrolyte is: the NaOH getting formula ratio adds distilled water, and agitating solution makes sodium hydroxide solution; The Lavender corrosion inhibiter of formula ratio is added in sodium hydroxide solution, then adds remaining distilled water, stir, to obtain final product.
The aluminum-air cell of the present embodiment, comprises aluminium anodes, air cathode and electrolyte, and described electrolyte is above-mentioned aluminum-air cell electrolyte.
Described aluminium anodes is aluminum alloy anode material, is made up of: Zn0.05%, Ga4%, In2% the component of following percentage by weight, and surplus is Al.
The preparation method of described aluminum alloy anode material, comprises the following steps:
1) under argon shield, aluminium ingot is placed in ZGJL0.01-40-4 induction melting furnace crucible, be heated to 690 DEG C aluminium ingot is all melted after, add zinc ingot metal, gallium grain and indium grain, limit heating edge rotary container, make metal melting and mix, continue to be heated to 760 DEG C and after being incubated 7min, pour into block ingot casting;
2) by step 1) the block ingot casting of gained is rolled into the flaky material that thickness is 4mm under 170 DEG C of conditions, obtains described air cell aluminum alloy anode material.
Described air cathode is suppressed by Catalytic Layer, conduction nickel screen and waterproof ventilative layer and is formed; Described Catalytic Layer is by γ-MnO
2, active carbon and polytetrafluoroethylene be the rete of 0.3mm for the ratio of 1.5:2:4 mix the thickness that roll extrusion is made afterwards in mass ratio; Described waterproof ventilative layer is the thickness that after being mixed by weight the ratio for 1:1 by polytetrafluoroethylene and acetylene black, roll extrusion is made is the rete of 0.8mm; Finally Catalytic Layer, conduction nickel screen and waterproof ventilative layer are pressed into the air cathode that thickness is 0.5mm.
The aluminum alloy anode of the present embodiment in the electrolytic solution from corrosion rate be 2.93mg/cm
2h, Open Circuit Potential are-1.85V (vs.SHE), and the air cell of composition in the electrolytic solution discharge current density is 100mA/cm
2time test 10h electromotive force be 1.89V, anode alloy surface corrosion is even.
Embodiment 5
The electrolyte corrosion inhibitor of the present embodiment is the ethanolic solution of Lavender, and wherein the volumn concentration of Lavender is 40%.
The aluminum-air cell electrolyte of the present embodiment, comprises the component of following concentration: NaOH 6mol/L, above-mentioned electrolyte corrosion inhibitor 60ppm (v/v), surplus is distilled water.The preparation method of this electrolyte is: the NaOH getting formula ratio adds distilled water, and agitating solution makes sodium hydroxide solution; The Lavender corrosion inhibiter of formula ratio is added in sodium hydroxide solution, then adds remaining distilled water, stir, to obtain final product.
The aluminum-air cell of the present embodiment, comprises aluminium anodes, air cathode and electrolyte, and described electrolyte is above-mentioned aluminum-air cell electrolyte.
Described aluminium anodes is aluminum alloy anode material, is made up of: Zn5%, Ga2.5%, In0.05% the component of following percentage by weight, and surplus is Al.
The preparation method of described aluminum alloy anode material, comprises the following steps:
1) under argon shield, aluminium ingot is placed in ZGJL0.01-40-4 induction melting furnace crucible, be heated to 710 DEG C aluminium ingot is all melted after, add zinc ingot metal, gallium grain and indium grain, limit heating edge rotary container, make metal melting and mix, continue to be heated to 780 DEG C and after being incubated 6min, pour into block ingot casting;
2) by step 1) the block ingot casting of gained is rolled into the flaky material that thickness is 2mm under 150 DEG C of conditions, obtains described air cell aluminum alloy anode material.
Described air cathode is suppressed by Catalytic Layer, conduction nickel screen and waterproof ventilative layer and is formed; Described Catalytic Layer is by γ-MnO
2, active carbon and polytetrafluoroethylene be the rete of 0.4mm for the ratio of 0.5:2:2 mix the thickness that roll extrusion is made afterwards in mass ratio; Described waterproof ventilative layer is the thickness that after being mixed by weight the ratio for 1:1 by polytetrafluoroethylene and acetylene black, roll extrusion is made is the rete of 0.7mm; Finally Catalytic Layer, conduction nickel screen and waterproof ventilative layer are pressed into the air cathode that thickness is 0.5mm.
The aluminum alloy anode of the present embodiment in the electrolytic solution from corrosion rate be 3.85mg/cm
2h, Open Circuit Potential are-2.08V (vs.SHE), and the air cell of composition in the electrolytic solution discharge current density is 100mA/cm
2time test 10h electromotive force be 1.84V, anode alloy surface corrosion is even.
Embodiment 6
The electrolyte corrosion inhibitor of the present embodiment is the ethanolic solution of Lavender, and wherein the volumn concentration of Lavender is 10%.
The aluminum-air cell electrolyte of the present embodiment, comprises the component of following concentration: NaOH 4mol/L, above-mentioned electrolyte corrosion inhibitor 70ppm (v/v), surplus is distilled water.The preparation method of this electrolyte is: the NaOH getting formula ratio adds distilled water, and agitating solution makes sodium hydroxide solution; The Lavender corrosion inhibiter of formula ratio is added in sodium hydroxide solution, then adds remaining distilled water, stir, to obtain final product.
The aluminum-air cell of the present embodiment, comprises aluminium anodes, air cathode and electrolyte, and described electrolyte is above-mentioned aluminum-air cell electrolyte.
Described aluminium anodes is aluminum alloy anode material, is made up of: Zn1%, Ga1.5%, In0.8% the component of following percentage by weight, and surplus is Al.
The preparation method of described aluminum alloy anode material, comprises the following steps:
1) under argon shield, aluminium ingot is placed in ZGJL0.01-40-4 induction melting furnace crucible, be heated to 720 DEG C aluminium ingot is all melted after, add zinc ingot metal, gallium grain and indium grain, limit heating edge rotary container, make metal melting and mix, continue to be heated to 740 DEG C and after being incubated 10min, pour into block ingot casting;
2) by step 1) the block ingot casting of gained is rolled into the flaky material that thickness is 3mm under 190 DEG C of conditions, obtains described air cell aluminum alloy anode material.
Described air cathode is suppressed by Catalytic Layer, conduction nickel screen and waterproof ventilative layer and is formed; Described Catalytic Layer is by γ-MnO
2, active carbon and polytetrafluoroethylene be the rete of 0.7mm for the ratio of 0.3:3:3 mix the thickness that roll extrusion is made afterwards in mass ratio; Described waterproof ventilative layer is the thickness that after being mixed by weight the ratio for 1:1 by polytetrafluoroethylene and acetylene black, roll extrusion is made is the rete of 0.3mm; Finally Catalytic Layer, conduction nickel screen and waterproof ventilative layer are pressed into the air cathode that thickness is 0.4mm.
The aluminum alloy anode of the present embodiment in the electrolytic solution from corrosion rate be 4.62mg/cm
2h, Open Circuit Potential are-1.95V (vs.SHE), and the air cell of composition in the electrolytic solution discharge current density is 100mA/cm
2time test 10h electromotive force be 2.10V, anode alloy surface corrosion is even.
Embodiment 7
The electrolyte corrosion inhibitor of the present embodiment is the ethanolic solution of Lavender, and wherein the volumn concentration of Lavender is 50%.
The aluminum-air cell electrolyte of the present embodiment, comprises the component of following concentration: NaOH 2mol/L, above-mentioned electrolyte corrosion inhibitor 100ppm (v/v), surplus is distilled water.The preparation method of this electrolyte is: the NaOH getting formula ratio adds distilled water, and agitating solution makes sodium hydroxide solution; The Lavender corrosion inhibiter of formula ratio is added in sodium hydroxide solution, then adds remaining distilled water, stir, to obtain final product.
The aluminum-air cell of the present embodiment, comprises aluminium anodes, air cathode and electrolyte, and described electrolyte is above-mentioned aluminum-air cell electrolyte.
Described aluminium anodes is aluminum alloy anode material, is made up of: Zn4%, Ga0.05%, In1% the component of following percentage by weight, and surplus is Al.
The preparation method of described aluminum alloy anode material, comprises the following steps:
1) under argon shield, aluminium ingot is placed in ZGJL0.01-40-4 induction melting furnace crucible, be heated to 670 DEG C aluminium ingot is all melted after, add zinc ingot metal, gallium grain and indium grain, limit heating edge rotary container, make metal melting and mix, continue to be heated to 750 DEG C and after being incubated 4min, pour into block ingot casting;
2) by step 1) the block ingot casting of gained is rolled into the flaky material that thickness is 0.5mm under 180 DEG C of conditions, obtains described air cell aluminum alloy anode material.
Described air cathode is suppressed by Catalytic Layer, conduction nickel screen and waterproof ventilative layer and is formed; Described Catalytic Layer is by γ-MnO
2, active carbon and polytetrafluoroethylene be the rete of 0.8mm for the ratio of 2:5:2.5 mix the thickness that roll extrusion is made afterwards in mass ratio; Described waterproof ventilative layer is the thickness that after being mixed by weight the ratio for 1:1 by polytetrafluoroethylene and acetylene black, roll extrusion is made is the rete of 0.5mm; Finally Catalytic Layer, conduction nickel screen and waterproof ventilative layer are pressed into the air cathode that thickness is 0.2mm.
The aluminum alloy anode of the present embodiment in the electrolytic solution from corrosion rate be 4.06mg/cm
2h, Open Circuit Potential are-1.81V (vs.SHE), and the air cell of composition in the electrolytic solution discharge current density is 100mA/cm
2time test 10h electromotive force be 1.96V, anode alloy surface corrosion is even.
Experimental example
The performance of this experimental example to embodiment 1-7 gained electrolyte corrosion inhibitor and aluminum-air cell detects, and result is as shown in table 1.Wherein, the electromotive force of aluminum-air cell is 100mA/cm at discharge current density in the electrolytic solution
2time test 10h electromotive force.
The performance test results of table 1 embodiment 1-7 gained aluminum alloy anode material and aluminum-air cell
As can be seen from Table 1, aluminum alloy anode material is low to moderate 2.93 ~ 4.62mg/cm from corrosion rate in embodiment 1-7 gained electrolyte
2h, Open Circuit Potential reach-1.76 ~-2.08V (vs.SHE), and the air cell of composition in the electrolytic solution discharge current density is 100mA/cm
2time test 10h electromotive force be 1.84 ~ 2.10V, anode alloy surface corrosion is even.Experimental result shows, electrolyte corrosion inhibitor of the present invention be added in electrolyte can significantly reduce aluminium anodes from corrosion rate, make aluminium anodes alloy have good corrosion resistance and higher electro-chemical activity, meet the requirement of alkaline aluminum-air cell high current density discharge.
Claims (10)
1. an electrolyte corrosion inhibitor, is characterized in that: described electrolyte corrosion inhibitor is the ethanolic solution of Lavender, and wherein the volumn concentration of Lavender is 10% ~ 60%.
2. an aluminum-air cell electrolyte, is characterized in that: the component comprising following concentration: NaOH 2 ~ 6mol/L, electrolyte corrosion inhibitor 20 ~ 100ppm, and surplus is water; Described electrolyte corrosion inhibitor is the ethanolic solution of Lavender, and wherein the volumn concentration of Lavender is 10% ~ 60%.
3. an aluminum-air cell, is characterized in that: comprise aluminium anodes, air cathode and electrolyte, and described electrolyte is aluminum-air cell electrolyte according to claim 2.
4. aluminum-air cell according to claim 3, is characterized in that: described aluminium anodes is aluminum alloy anode material, is made up of the component of following percentage by weight: Zn0.05% ~ 6%, Ga0.05% ~ 4%, In0.01% ~ 2%, and surplus is Al.
5. aluminum-air cell according to claim 4, is characterized in that: described aluminum alloy anode material is prepared by the method comprised the following steps:
1) under inert gas shielding, after aluminium heat fused, add zinc, gallium and indium and heating and melting, continue to be heated to 730 ~ 780 DEG C and after insulation, pour into ingot casting;
2) by step 1) gained ingot casting is rolled into flaky material under 150 ~ 200 DEG C of conditions, to obtain final product.
6. aluminum-air cell according to claim 5, is characterized in that: step 1) in, the time of described insulation is 4 ~ 10min.
7. aluminum-air cell according to claim 5, is characterized in that: step 2) in, the thickness of described flaky material is 0.5 ~ 4mm.
8. the aluminum-air cell according to any one of claim 3-7, is characterized in that: described air cathode is suppressed by Catalytic Layer, conduction nickel screen and waterproof ventilative layer and formed, and thickness is 0.2 ~ 0.6mm.
9. aluminum-air cell according to claim 8, is characterized in that: described Catalytic Layer is by γ-MnO
2, active carbon and polytetrafluoroethylene be (0.3 ~ 3) in mass ratio: (1 ~ 5): the rete be pressed into after the ratio of (1 ~ 5) mixes, thickness is 0.3 ~ 0.8mm.
10. aluminum-air cell according to claim 8, is characterized in that: described waterproof ventilative layer is the rete by weight for being pressed into after the ratio mixing of 1:1 by polytetrafluoroethylene and acetylene black, and thickness is 0.3 ~ 0.8mm.
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Cited By (6)
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| CN105870545A (en) * | 2016-04-19 | 2016-08-17 | 中南大学 | Electrolyte corrosion inhibitor, aluminum-air battery electrolyte and preparation method of aluminum-air battery electrolyte |
| CN107275720A (en) * | 2017-05-23 | 2017-10-20 | 深圳市航盛新材料技术有限公司 | Aluminium-air cell electrolyte, aluminium-air cell and preparation 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 |
| 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 |
| KR20230039913A (en) * | 2021-09-15 | 2023-03-22 | 성균관대학교산학협력단 | Electrolyte for aluminum air battery and method of fabricating the same |
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| CN105870545A (en) * | 2016-04-19 | 2016-08-17 | 中南大学 | Electrolyte corrosion inhibitor, aluminum-air battery electrolyte and preparation method of aluminum-air battery electrolyte |
| CN105870545B (en) * | 2016-04-19 | 2019-04-26 | 中南大学 | Electrolyte corrosion inhibitor, aluminium-air cell electrolyte and preparation method thereof |
| CN107275720A (en) * | 2017-05-23 | 2017-10-20 | 深圳市航盛新材料技术有限公司 | Aluminium-air cell electrolyte, aluminium-air cell and preparation method thereof |
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| 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 |
| KR20230039913A (en) * | 2021-09-15 | 2023-03-22 | 성균관대학교산학협력단 | Electrolyte for aluminum air battery and method of fabricating the same |
| WO2023043229A1 (en) * | 2021-09-15 | 2023-03-23 | 성균관대학교 산학협력단 | Electrolyte for aluminum-air battery, and preparation method therefor |
| 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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