CN103633396A - Electrolyte corrosion inhibitor for aluminum-air cell, electrolyte and preparation method - Google Patents
Electrolyte corrosion inhibitor for aluminum-air cell, electrolyte and preparation method Download PDFInfo
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Abstract
The invention discloses an electrolyte corrosion inhibitor for an aluminum-air cell, an electrolyte and a preparation method, belonging to the technical field of chemical batteries. The electrolyte corrosion inhibitor mainly comprises sodium hyposulfite which has a concentration of 0.005 to 0.2 mol/L in the electrolyte and may further comprise the auxiliary additive sodium stannate which has a concentration of 0.01 to 0.03 mol/L in the electrolyte. The aluminum-air cell provided by the invention has the advantages of simple composition, low cost, safety and accordance with environmental protection requirements, can substantially reduce the hydrogen evolution self-corrosion rate of an aluminum anode, enables the open circuit potential of the aluminum anode and working potential under the condition of impressed current to undergo substantial negative transfer, allows an aluminum anode alloy to have good corrosion resistance and high electrochemical activity and meets the requirement of an alkaline aluminum-air cell for large current density discharging.
Description
Technical field
The present invention is specifically related to a kind of aluminium-air cell electrolyte corrosion inhibiter, and adopts alkaline electrolyte of this corrosion inhibiter and preparation method thereof, belongs to chemical cell technical field.
Background technology
Due to advantages such as metal-air cell have efficiently, cleans, therefore one of ideal power power supply of 21 century will be become.China has strengthened metal-air cell, and especially the research and development of aluminium-air cell and zinc-air battery etc. drop into.Aluminium-air cell be take air electrode as anodal, and metal aluminum or aluminum alloy is as negative pole, and neutrality or alkaline aqueous solution be as electrolyte, airborne O
2by gas-diffusion electrode, arrive gas-solid-liquid three phase boundary and metal A l and react and emit electric energy, the nontoxic and recoverable of its product, is desirable battery system.The advantages such as it is abundant that this battery system has material source, and energy density is large, and reliability is high, safe and pollution-free, price is low, have very wide application prospect.
From the seventies in last century, aluminium-air cell has been made to large quantity research both at home and abroad, all in all, research mainly concentrates on the aspects such as aluminium anodes material, electrolyte corrosion inhibiter and battery system.Because fine aluminium is a kind of more active amphoteric metal material, larger from corrosion rate in alkaline solution, and produce a large amount of hydrogen, make battery can not give full play to the advantage of high-energy power supply, especially under high current density condition of work, its steady operation current potential is lower, and anode polarization is serious, has limited industrial sector and the practical application of aluminum-air cell.Research is in recent years found, develops novel aluminum anode material, and add corresponding electrolyte corrosion inhibiter by microalloying, can greatly improve the chemical property of aluminium anodes and the application performance in battery thereof.
Although most of single type electrolyte corrosion inhibiter can reduce aluminium anodes alloy from corrosion rate, take often sacrificial anode activity as cost; Can meet simultaneously and reduce aluminium anodes alloy from corrosion rate, and do not affect or even can improve the corrosion inhibiter of aluminium anodes activity, it is generally composite inhibiter, but most of composite inhibiter complicated components, can cause material, the wasting of resources on the one hand, some component may cause environmental pollution on the other hand, does not meet environmental requirement.Therefore seek the novel single type corrosion inhibiter of a class or simple composite type corrosion inhibiter, can significantly improve aluminium anodes activity and can significantly reduce from corrosion rate again, be significant.
Summary of the invention
The object of this invention is to provide a kind of aluminium-air cell electrolyte corrosion inhibiter.
Secondly, the present invention also provides a kind of aluminium-air cell electrolyte.
Again, the present invention also provides the preparation method of a kind of aluminium-air cell with electrolyte.
In order to realize above object, the technical solution adopted in the present invention is:
An aluminium-air cell electrolyte corrosion inhibiter, described corrosion inhibiter mainly comprises sodium thiosulfate, the concentration in electrolyte is 0.005～0.2mol/L.
The chemical formula of sodium thiosulfate is Na
2s
2o
3, under normal temperature, be water white transparency monoclinic crystal.
Described electrolyte is alkaline electrolyte, preferred sodium hydroxide solution, and concentration is 4～6mol/L.
Preferably, described corrosion inhibiter also comprises auxiliary additive sodium stannate, and the concentration in electrolyte is 0.01～0.03mol/L.
The chemical formula of sodium stannate is Na
2snO
3, under normal temperature, be white powder or colourless hexagonal plate crystal.
An aluminium-air cell electrolyte, every liter of electrolyte is mainly comprised of the component of following content: NaOH 4～6mol, sodium thiosulfate 0.005～0.2mol, surplus is water.Wherein, alkaline hydrogen sodium oxide molybdena is electrolyte mother liquor main component, and sodium thiosulfate is electrolyte corrosion inhibiter main component.
Preferably, described electrolyte also comprises corrosion inhibiter auxiliary additive sodium stannate, and the content of sodium stannate is 0.01～0.03mol.Wherein, alkaline hydrogen sodium oxide molybdena is electrolyte mother liquor main component, and sodium thiosulfate is electrolyte corrosion inhibiter main component, and sodium stannate is corrosion inhibiter auxiliary additive.
Preferably, the content of described sodium thiosulfate is 0.005～0.1mol.
Preferred, the content of described sodium stannate is 0.01mol.
A preparation method for electrolyte for aluminium-air cell, comprises the following steps: according to constituent content preparation sodium hydroxide solution, cooling, more accurately take sodium thiosulfate, join in sodium hydroxide solution stirring and dissolving.
A preparation method for electrolyte for aluminium-air cell, comprises the following steps: according to constituent content preparation sodium hydroxide solution, cooling, more accurately take sodium thiosulfate, join in sodium hydroxide solution stirring and dissolving; According to constituent content, accurately take sodium stannate again, join in the sodium hydroxide solution that is dissolved with sodium thiosulfate stirring and dissolving.
Described chilling temperature is lower than 40 ℃.
Beneficial effect of the present invention:
Aluminium-air cell of the present invention is compared and is had the following advantages with existing corrosion inhibiter with electrolyte corrosion inhibiter:
(1) the present invention proposes to adopt zwitterionic compound Na first
2s
2o
3the liberation of hydrogen that reduces aluminium anodes is from corrosion rate and improve aluminium anodes activity.Na
2s
2o
3be a kind of zwitterionic compound, very stable in alkaline solution, in molecular formula, the Average oxidation number of two sulphur atoms is+2, and one of them oxidized sulfur atom number is+6, and another oxidized sulfur atom number is-2, therefore has certain reproducibility, to O
2, CO
2affinity is stronger; In addition S
2o
3 2-also have very strong complexing power, can form complex ions with metal ion.Typical phase boundary type anodic corrosion inhibitor and the cathodic corrosion inhibitor mechanism of action are: by anode reaction or cathode reaction, on aluminium anodes surface, form diaphragm (film of passivating film or protective value); the existence of diaphragm has reduced liberation of hydrogen activation point; aluminium anodes liberation of hydrogen is reduced from corrosion rate, but easily cause anode polarization.Na
2s
2o
3the mechanism of action different from phase boundary type corrosion inhibiter, its Main Function has 2 points: 1. S
2o
3 2-by complexing, reduce H atom and H
+activity, hinder two electron transfer reactions (evolving hydrogen reaction) and occur, and then reduce liberation of hydrogen from corrosion rate; 2. S
2o
3 2-with product reaction intermediate (Al (OH) particularly
ads, Al (OH)
2ads, Al (OH)
3adsdeng) form complex ions, promote to make aluminium anodes continuous activation by product desorption, when discharging, aluminium anodes reduces aluminium anodes polarization, improve discharge performance.Therefore add corrosion inhibiter Na
2s
2o
3afterwards, Al-0.1Sn-0.1Ga anode alloy does not add Na from corrosion rate
2s
2o
3shi great great reduces (as shown in table 1 below), and also remarkable negative moving (as shown in Figure 1 to 4) of the Open Circuit Potential of this alloy and operating potential.
(2) the corrosion inhibiter auxiliary additive in the present invention adopts Na
2snO
3, appropriate Na wherein
2snO
3to suppressing liberation of hydrogen, there is significant effect, and can reduce aluminium anodes polarization, aluminium anodes current potential is born and moved.Main cause is SnO
3 2-with aluminium, redox reaction has occurred, SnO is reduced into simple substance Sn, when micro-Sn is deposited on aluminium anodes surface, while forming micro cell with aluminum substrate, as the Sn of negative electrode, owing to having higher overpotential of hydrogen evolution, can significantly reduce anode liberation of hydrogen.In addition the main active element Ga of aluminium anodes can be on Sn underpotential deposition, thereby make aluminium anodes activation, current potential is negative to be moved.But excessive SnO
3 2-can mechanically be adsorbed on aluminium anodes surface, when hindering corrosion liberation of hydrogen, also can cause aluminium anodes current potential to shuffle.Adding separately corrosion inhibiter Na
2s
2o
3basis on, the Na that compound interpolation is appropriate
2snO
3, can reduce aluminium anodes liberation of hydrogen in corrosion, aluminium anodes Open Circuit Potential is born and moved.
Aluminium-air cell of the present invention electrolyte corrosion inhibiter, component forms simple, cost is low, safety and meet environmental requirement, not only can significantly reduce the liberation of hydrogen of aluminium anodes from corrosion rate (as shown in table 1 below), can also make Open Circuit Potential and the operating potential under impressed current condition of aluminium anodes significantly bear and move (as shown in Fig. 1～Fig. 6), make aluminium anodes alloy have good corrosion resistance and higher electro-chemical activity, to meet the requirement of alkaline aluminium-air cell high current density discharge.
Adopt electrolyte of the present invention can control alkaline aluminium-air cell liberation of hydrogen corrosion too fast, can guarantee that again aluminium anodes alloy has higher electro-chemical activity, to improving battery discharge efficiency, prolongation discharge life is significant, is beneficial to large-scale promotion application.
Accompanying drawing explanation
Fig. 1 is that Al-0.1Sn-0.1Ga aluminium anodes alloy is prepared Open Circuit Potential and the time history in electrolyte at embodiment 1～6;
Fig. 2 is that Al-0.1Sn-0.1Ga aluminium anodes alloy is prepared operating potential and the time history in electrolyte at embodiment 1～6;
Fig. 3 is that Al-0.1Sn-0.1Ga aluminium anodes alloy is prepared Open Circuit Potential and the time history in electrolyte at embodiment 7～10;
Fig. 4 is that Al-0.1Sn-0.1Ga aluminium anodes alloy is prepared operating potential and the time history in electrolyte at embodiment 7～10;
Fig. 5 is that Al-1Mg-0.1Sn-0.1Ga-1Zn aluminium anodes alloy is prepared Open Circuit Potential and the time history in electrolyte at embodiment 11～14;
Fig. 6 is that Al-1Mg-0.1Sn-0.1Ga-1Zn aluminium anodes alloy is prepared operating potential and the time history in electrolyte at embodiment 11～14.
Embodiment
Following embodiment is only described in further detail the present invention, but does not form any limitation of the invention.
Embodiment 1
The sodium hydroxide solution that aluminium-air cell in the present embodiment is 4mol/L with electrolyte mother liquor, corrosion inhibiter adopts sodium thiosulfate, and the concentration in electrolyte is 0.005mol/L.The preparation method of this electrolyte is: the sodium hydroxide solution that compound concentration is 4mol/L, be cooled to room temperature, and add the sodium thiosulfate of accurate weighing, stir, dissolve complete and get final product.
Utilize gas collection method test Al-0.1Sn-0.1Ga aluminium anodes alloy the present embodiment prepare in electrolyte under static state from corrosion rate, testing time 30min, the results detailed in following table 1.Utilize at the Open Circuit Potential of three-electrode system test Al-0.1Sn-0.1Ga aluminium anodes alloy in above-mentioned electrolyte and 25 ℃, 100mA/cm
2operating potential curve under current density, the results detailed in Fig. 1, Fig. 2.Contrasting from corrosion rate, Open Circuit Potential, operating potential curve with Al-0.1Sn-0.1Ga aluminium anodes alloy in 4mol/L NaOH electrolyte.
From table 1, Fig. 1, Fig. 2, can find out, above-mentioned alloy is 0.283ml/cm from corrosion rate in the present embodiment electrolyte
2min, be respectively-1.74V(vs of Open Circuit Potential and operating potential Hg/HgO) and-1.42V(vs Hg/HgO), is 0.303ml/cm from corrosion rate in 4mol/L NaOH electrolyte
2min, be respectively-1.62V of Open Circuit Potential and operating potential and-1.38V.As can be seen here, above-mentioned alloy reducing to some extent from corrosion rate in the present embodiment electrolyte, Open Circuit Potential and position, working point are all significantly born and are moved.
Embodiment 2
The sodium hydroxide solution that aluminium-air cell in the present embodiment is 4mol/L with electrolyte mother liquor, corrosion inhibiter adopts sodium thiosulfate, and the concentration in electrolyte is 0.01mol/L.The preparation method of this electrolyte is: the sodium hydroxide solution that compound concentration is 4mol/L, be cooled to room temperature, and add the sodium thiosulfate of accurate weighing, stir, dissolve complete and get final product.
Utilize gas collection method test Al-0.1Sn-0.1Ga aluminium anodes alloy the present embodiment prepare in electrolyte under static state from corrosion rate, testing time 30min, the results detailed in following table 1.Utilize at the Open Circuit Potential of three-electrode system test Al-0.1Sn-0.1Ga aluminium anodes alloy in above-mentioned electrolyte and 25 ℃, 100mA/cm
2operating potential curve under current density, the results detailed in Fig. 1, Fig. 2.Contrasting from corrosion rate, Open Circuit Potential, operating potential curve with Al-0.1Sn-0.1Ga aluminium anodes alloy in 4mol/L NaOH electrolyte.
From table 1, Fig. 1, Fig. 2, can find out, above-mentioned alloy is 0.256ml/cm from corrosion rate in the present embodiment electrolyte
2min, be respectively-1.78V of Open Circuit Potential and operating potential and-1.43V, compare with its data of testing in 4mol/L NaOH electrolyte, from corrosion rate, reduce to some extent, Open Circuit Potential and position, working point be remarkable negative moving all.
Embodiment 3
The sodium hydroxide solution that aluminium-air cell in the present embodiment is 4mol/L with electrolyte mother liquor, corrosion inhibiter adopts sodium thiosulfate, and the concentration in electrolyte is 0.05mol/L.The preparation method of this electrolyte is: the sodium hydroxide solution that compound concentration is 4mol/L, be cooled to room temperature, and add the sodium thiosulfate of accurate weighing, stir, dissolve complete and get final product.
Utilize gas collection method test Al-0.1Sn-0.1Ga aluminium anodes alloy the present embodiment prepare in electrolyte under static state from corrosion rate, testing time 30min, the results detailed in following table 1.Utilize at the Open Circuit Potential of three-electrode system test Al-0.1Sn-0.1Ga aluminium anodes alloy in above-mentioned electrolyte and 25 ℃, 100mA/cm
2operating potential curve under current density, the results detailed in Fig. 1, Fig. 2.Contrasting from corrosion rate, Open Circuit Potential, operating potential curve with Al-0.1Sn-0.1Ga aluminium anodes alloy in 4mol/L NaOH electrolyte.
From table 1, Fig. 1, Fig. 2, can find out, above-mentioned alloy is 0.185ml/cm from corrosion rate in the present embodiment electrolyte
2min, be respectively-1.73V of Open Circuit Potential and operating potential and-1.47V, compare with its data of testing in 4mol/L NaOH electrolyte, from corrosion rate, reduce to some extent, Open Circuit Potential and position, working point be remarkable negative moving all.
Embodiment 4
The sodium hydroxide solution that aluminium-air cell in the present embodiment is 4mol/L with electrolyte mother liquor, corrosion inhibiter adopts sodium thiosulfate, and the concentration in electrolyte is 0.2mol/L.The preparation method of this electrolyte is: the sodium hydroxide solution that compound concentration is 4mol/L, be cooled to room temperature, and add the sodium thiosulfate of accurate weighing, stir, dissolve complete and get final product.
Utilize gas collection method test Al-0.1Sn-0.1Ga aluminium anodes alloy the present embodiment prepare in electrolyte under static state from corrosion rate, testing time 30min, the results detailed in following table 1.Utilize at the Open Circuit Potential of three-electrode system test Al-0.1Sn-0.1Ga aluminium anodes alloy in above-mentioned electrolyte and 25 ℃, 100mA/cm
2operating potential curve under current density, the results detailed in Fig. 1, Fig. 2.Contrasting from corrosion rate, Open Circuit Potential, operating potential curve with Al-0.1Sn-0.1Ga aluminium anodes alloy in 4mol/L NaOH electrolyte.
From table 1, Fig. 1, Fig. 2, can find out, above-mentioned alloy is 0.196ml/cm from corrosion rate in the present embodiment electrolyte
2min, be respectively-1.66V of Open Circuit Potential and operating potential and-1.40V, compare with its data of testing in 4mol/L NaOH electrolyte, from corrosion rate, reduce to some extent, Open Circuit Potential and position, working point be remarkable negative moving all.
Embodiment 5
The sodium hydroxide solution that aluminium-air cell in the present embodiment is 4mol/L with electrolyte mother liquor, corrosion inhibiter adopts sodium thiosulfate, concentration in electrolyte is 0.01mol/L, and corrosion inhibiter auxiliary additive is sodium stannate, and the concentration in electrolyte is 0.01mol/L.The preparation method of this electrolyte is: the sodium hydroxide solution that compound concentration is 4mol/L, be cooled to room temperature, and add the sodium thiosulfate of accurate weighing, stirring and dissolving; According to constituent content, accurately take sodium stannate again, join in the sodium hydroxide solution that is dissolved with sodium thiosulfate stirring and dissolving.
Utilize gas collection method test Al-0.1Sn-0.1Ga aluminium anodes alloy the present embodiment prepare in electrolyte under static state from corrosion rate, testing time 30min, the results detailed in following table 1.Utilize at the Open Circuit Potential of three-electrode system test Al-0.1Sn-0.1Ga aluminium anodes alloy in above-mentioned electrolyte and 25 ℃, 100mA/cm
2operating potential curve under current density, the results detailed in Fig. 1, Fig. 2.Contrasting from corrosion rate, Open Circuit Potential, operating potential curve with Al-0.1Sn-0.1Ga aluminium anodes alloy in 4mol/L NaOH electrolyte.
From table 1, Fig. 1, Fig. 2, can find out, above-mentioned alloy is 0.232ml/cm from corrosion rate in the present embodiment electrolyte
2min, be respectively-1.81V of Open Circuit Potential and operating potential and-1.44V, compare with its data of testing in 4mol/L NaOH electrolyte, from corrosion rate, reduce to some extent, Open Circuit Potential and position, working point be remarkable negative moving all.
Embodiment 6
The sodium hydroxide solution that aluminium-air cell in the present embodiment is 4mol/L with electrolyte mother liquor, corrosion inhibiter adopts sodium thiosulfate, concentration in electrolyte is 0.05mol/L, and corrosion inhibiter auxiliary additive is sodium stannate, and the concentration in electrolyte is 0.02mol/L.The preparation method of this electrolyte is: the sodium hydroxide solution that compound concentration is 4mol/L, be cooled to room temperature, and add the sodium thiosulfate of accurate weighing, stirring and dissolving; According to constituent content, accurately take sodium stannate again, join in the sodium hydroxide solution that is dissolved with sodium thiosulfate stirring and dissolving.
Utilize gas collection method test Al-0.1Sn-0.1Ga aluminium anodes alloy the present embodiment prepare in electrolyte under static state from corrosion rate, testing time 30min, the results detailed in following table 1.Utilize at the Open Circuit Potential of three-electrode system test Al-0.1Sn-0.1Ga aluminium anodes alloy in above-mentioned electrolyte and 25 ℃, 100mA/cm
2operating potential curve under current density, the results detailed in Fig. 1, Fig. 2.Contrasting from corrosion rate, Open Circuit Potential, operating potential curve with Al-0.1Sn-0.1Ga aluminium anodes alloy in 4mol/L NaOH electrolyte.
From table 1, Fig. 1, Fig. 2, can find out, above-mentioned alloy is 0.154ml/cm from corrosion rate in the present embodiment electrolyte
2min, be respectively-1.75V of Open Circuit Potential and operating potential and-1.46V, compare with its data of testing in 4mol/L NaOH electrolyte, from corrosion rate, reduce to some extent, Open Circuit Potential and position, working point be remarkable negative moving all.
Embodiment 7
The sodium hydroxide solution that aluminium-air cell in the present embodiment is 5mol/L with electrolyte mother liquor, corrosion inhibiter adopts sodium thiosulfate, and the concentration in electrolyte is 0.05mol/L.The preparation method of this electrolyte is: the sodium hydroxide solution that compound concentration is 5mol/L, be cooled to room temperature, and add the sodium thiosulfate of accurate weighing, stir, dissolve complete and get final product.
Utilize gas collection method test Al-0.1Sn-0.1Ga aluminium anodes alloy the present embodiment prepare in electrolyte under static state from corrosion rate, testing time 30min, the results detailed in following table 1.Utilize at the Open Circuit Potential of three-electrode system test Al-0.1Sn-0.1Ga aluminium anodes alloy in above-mentioned electrolyte and 25 ℃, 100mA/cm
2operating potential curve under current density, the results detailed in Fig. 3, Fig. 4.Contrasting from corrosion rate, Open Circuit Potential, operating potential curve with Al-0.1Sn-0.1Ga aluminium anodes alloy in 5mol/L NaOH electrolyte.
From table 1, Fig. 3, Fig. 4, can find out, above-mentioned alloy is 0.208ml/cm from corrosion rate in the present embodiment electrolyte
2min, be respectively-1.74V of Open Circuit Potential and operating potential and-1.48V, is 0.326ml/cm from corrosion rate in 5mol/L NaOH electrolyte
2min, be respectively-1.72V of Open Circuit Potential and operating potential and-1.41V.As can be seen here, above-mentioned alloy reducing to some extent from corrosion rate in the present embodiment electrolyte, Open Circuit Potential and position, working point are all significantly born and are moved.
Embodiment 8
The sodium hydroxide solution that aluminium-air cell in the present embodiment is 5mol/L with electrolyte mother liquor, corrosion inhibiter adopts sodium thiosulfate, concentration in electrolyte is 0.05mol/L, and corrosion inhibiter auxiliary additive is sodium stannate, and the concentration in electrolyte is 0.01mol/L.The preparation method of this electrolyte is: the sodium hydroxide solution that compound concentration is 5mol/L, be cooled to room temperature, and add the sodium thiosulfate of accurate weighing, stirring and dissolving; According to constituent content, accurately take sodium stannate again, join in the sodium hydroxide solution that is dissolved with sodium thiosulfate stirring and dissolving.
Utilize gas collection method test Al-0.1Sn-0.1Ga aluminium anodes alloy the present embodiment prepare in electrolyte under static state from corrosion rate, testing time 30min, the results detailed in following table 1.Utilize at the Open Circuit Potential of three-electrode system test Al-0.1Sn-0.1Ga aluminium anodes alloy in above-mentioned electrolyte and 25 ℃, 100mA/cm
2operating potential curve under current density, the results detailed in Fig. 3, Fig. 4.Contrasting from corrosion rate, Open Circuit Potential, operating potential curve with Al-0.1Sn-0.1Ga aluminium anodes alloy in 5mol/L NaOH electrolyte.
From table 1, Fig. 3, Fig. 4, can find out, above-mentioned alloy is 0.194ml/cm from corrosion rate in the present embodiment electrolyte
2min, be respectively-1.75V of Open Circuit Potential and operating potential and-1.46V, compare with its data of testing in 5mol/L NaOH electrolyte, from corrosion rate, reduce to some extent, Open Circuit Potential and position, working point be remarkable negative moving all.
Embodiment 9
The sodium hydroxide solution that aluminium-air cell in the present embodiment is 6mol/L with electrolyte mother liquor, corrosion inhibiter adopts sodium thiosulfate, and the concentration in electrolyte is 0.1mol/L.The preparation method of this electrolyte is: the sodium hydroxide solution that compound concentration is 6mol/L, be cooled to room temperature, and add the sodium thiosulfate of accurate weighing, stir, dissolve complete and get final product.
Utilize gas collection method test Al-0.1Sn-0.1Ga aluminium anodes alloy the present embodiment prepare in electrolyte under static state from corrosion rate, testing time 30min, the results detailed in following table 1.Utilize at the Open Circuit Potential of three-electrode system test Al-0.1Sn-0.1Ga aluminium anodes alloy in above-mentioned electrolyte and 25 ℃, 100mA/cm
2operating potential curve under current density, the results detailed in Fig. 3, Fig. 4.Contrasting from corrosion rate, Open Circuit Potential, operating potential curve with Al-0.1Sn-0.1Ga aluminium anodes alloy in 6mol/L NaOH electrolyte.
From table 1, Fig. 3, Fig. 4, can find out, above-mentioned alloy is 0.251ml/cm from corrosion rate in the present embodiment electrolyte
2min, be respectively-1.76V of Open Circuit Potential and operating potential and-1.47V, is 0.347ml/cm from corrosion rate in 6mol/L NaOH electrolyte
2min, be respectively-1.73V of Open Circuit Potential and operating potential and-1.42V.As can be seen here, above-mentioned alloy reducing to some extent from corrosion rate in the present embodiment electrolyte, Open Circuit Potential and position, working point are all significantly born and are moved.
Embodiment 10
The sodium hydroxide solution that aluminium-air cell in the present embodiment is 6mol/L with electrolyte mother liquor, corrosion inhibiter adopts sodium thiosulfate, concentration in electrolyte is 0.1mol/L, and corrosion inhibiter auxiliary additive is sodium stannate, and the concentration in electrolyte is 0.03mol/L.The preparation method of this electrolyte is: the sodium hydroxide solution that compound concentration is 6mol/L, be cooled to room temperature, and add the sodium thiosulfate of accurate weighing, stirring and dissolving; According to constituent content, accurately take sodium stannate again, join in the sodium hydroxide solution that is dissolved with sodium thiosulfate stirring and dissolving.
Utilize gas collection method test Al-0.1Sn-0.1Ga aluminium anodes alloy the present embodiment prepare in electrolyte under static state from corrosion rate, testing time 30min, the results detailed in following table 1.Utilize at the Open Circuit Potential of three-electrode system test Al-0.1Sn-0.1Ga aluminium anodes alloy in above-mentioned electrolyte and 25 ℃, 100mA/cm
2operating potential curve under current density, the results detailed in Fig. 3, Fig. 4.Contrasting from corrosion rate, Open Circuit Potential, operating potential curve with Al-0.1Sn-0.1Ga aluminium anodes alloy in 6mol/L NaOH electrolyte.
From table 1, Fig. 3, Fig. 4, can find out, above-mentioned alloy is 0.239ml/cm from corrosion rate in the present embodiment electrolyte
2min, be respectively-1.78V of Open Circuit Potential and operating potential and-1.47V, compare with its data of testing in 6mol/L NaOH electrolyte, from corrosion rate, reduce to some extent, Open Circuit Potential and position, working point be remarkable negative moving all.
Embodiment 11
The sodium hydroxide solution that aluminium-air cell in the present embodiment is 4mol/L with electrolyte mother liquor, corrosion inhibiter adopts sodium thiosulfate, concentration in electrolyte is 0.01mol/L, and corrosion inhibiter auxiliary additive is sodium stannate, and the concentration in electrolyte is 0.01mol/L.The preparation method of this electrolyte is: the sodium hydroxide solution that compound concentration is 4mol/L, be cooled to room temperature, and add the sodium thiosulfate of accurate weighing, stirring and dissolving; According to constituent content, accurately take sodium stannate again, join in the sodium hydroxide solution that is dissolved with sodium thiosulfate stirring and dissolving.
Utilize gas collection method test Al-1Mg-0.1Sn-0.1Ga-1Zn aluminium anodes alloy the present embodiment prepare in electrolyte under static state from corrosion rate, testing time 30min, the results detailed in following table 1.Utilize at the Open Circuit Potential of three-electrode system test Al-1Mg-0.1Sn-0.1Ga-1Zn aluminium anodes alloy in above-mentioned electrolyte and 25 ℃, 100mA/cm
2operating potential curve under current density, the results detailed in Fig. 5, Fig. 6.Contrasting from corrosion rate, Open Circuit Potential, operating potential curve with Al-1Mg-0.1Sn-0.1Ga-1Zn aluminium anodes alloy in 4mol/L NaOH electrolyte.
From table 1, Fig. 5, Fig. 6, can find out, above-mentioned alloy is 0.162ml/cm from corrosion rate in the present embodiment electrolyte
2min, be respectively-1.77V of Open Circuit Potential and operating potential and-1.48V, is 0.202ml/cm from corrosion rate in 4mol/L NaOH electrolyte
2min, be respectively-1.72V of Open Circuit Potential and operating potential and-1.41V.As can be seen here, above-mentioned alloy reducing to some extent from corrosion rate in the present embodiment electrolyte, Open Circuit Potential and position, working point are all significantly born and are moved.
Embodiment 12
The sodium hydroxide solution that aluminium-air cell in the present embodiment is 4mol/L with electrolyte mother liquor, corrosion inhibiter adopts sodium thiosulfate, concentration in electrolyte is 0.01mol/L, and corrosion inhibiter auxiliary additive is sodium stannate, and the concentration in electrolyte is 0.03mol/L.The preparation method of this electrolyte is: the sodium hydroxide solution that compound concentration is 4mol/L, be cooled to room temperature, and add the sodium thiosulfate of accurate weighing, stirring and dissolving; According to constituent content, accurately take sodium stannate again, join in the sodium hydroxide solution that is dissolved with sodium thiosulfate stirring and dissolving.
Utilize gas collection method test Al-1Mg-0.1Sn-0.1Ga-1Zn aluminium anodes alloy the present embodiment prepare in electrolyte under static state from corrosion rate, testing time 30min, the results detailed in following table 1.Utilize at the Open Circuit Potential of three-electrode system test Al-1Mg-0.1Sn-0.1Ga-1Zn aluminium anodes alloy in above-mentioned electrolyte and 25 ℃, 100mA/cm
2operating potential curve under current density, the results detailed in Fig. 5, Fig. 6.Contrasting from corrosion rate, Open Circuit Potential, operating potential curve with Al-1Mg-0.1Sn-0.1Ga-1Zn aluminium anodes alloy in 4mol/L NaOH electrolyte.
From table 1, Fig. 5, Fig. 6, can find out, above-mentioned alloy is 0.141ml/cm from corrosion rate in the present embodiment electrolyte
2min, be respectively-1.78V of Open Circuit Potential and operating potential and-1.46V, compare with its data of testing in 4mol/L NaOH electrolyte, from corrosion rate, reduce to some extent, Open Circuit Potential and position, working point be remarkable negative moving all.
Embodiment 13
The sodium hydroxide solution that aluminium-air cell in the present embodiment is 5mol/L with electrolyte mother liquor, corrosion inhibiter adopts sodium thiosulfate, and the concentration in electrolyte is 0.05mol/L.The preparation method of this electrolyte is: the sodium hydroxide solution that compound concentration is 5mol/L, be cooled to room temperature, and add the sodium thiosulfate of accurate weighing, stir, dissolve complete and get final product.
Utilize gas collection method test Al-1Mg-0.1Sn-0.1Ga-1Zn aluminium anodes alloy the present embodiment prepare in electrolyte under static state from corrosion rate, testing time 30min, the results detailed in following table 1.Utilize at the Open Circuit Potential of three-electrode system test Al-1Mg-0.1Sn-0.1Ga-1Zn aluminium anodes alloy in above-mentioned electrolyte and 25 ℃, 100mA/cm
2operating potential curve under current density, the results detailed in Fig. 5, Fig. 6.Contrasting from corrosion rate, Open Circuit Potential, operating potential curve with Al-1Mg-0.1Sn-0.1Ga-1Zn aluminium anodes alloy in 5mol/L NaOH electrolyte.
From table 1, Fig. 5, Fig. 6, can find out, above-mentioned alloy is 0.176ml/cm from corrosion rate in the present embodiment electrolyte
2min, be respectively-1.79V of Open Circuit Potential and operating potential and-1.528V, is 0.237ml/cm from corrosion rate in 5mol/L NaOH electrolyte
2min, be respectively-1.78V of Open Circuit Potential and operating potential and-1.521V.As can be seen here, above-mentioned alloy reducing to some extent from corrosion rate in the present embodiment electrolyte, Open Circuit Potential and position, working point are all significantly born and are moved.
Embodiment 14
The sodium hydroxide solution that aluminium-air cell in the present embodiment is 6mol/L with electrolyte mother liquor, corrosion inhibiter adopts sodium thiosulfate, concentration in electrolyte is 0.2mol/L, and corrosion inhibiter auxiliary additive is sodium stannate, and the concentration in electrolyte is 0.01mol/L.The preparation method of this electrolyte is: the sodium hydroxide solution that compound concentration is 6mol/L, be cooled to room temperature, and add the sodium thiosulfate of accurate weighing, stirring and dissolving; According to constituent content, accurately take sodium stannate again, join in the sodium hydroxide solution that is dissolved with sodium thiosulfate stirring and dissolving.
Utilize gas collection method test Al-1Mg-0.1Sn-0.1Ga-1Zn aluminium anodes alloy the present embodiment prepare in electrolyte under static state from corrosion rate, testing time 30min, the results detailed in following table 1.Utilize at the Open Circuit Potential of three-electrode system test Al-1Mg-0.1Sn-0.1Ga-1Zn aluminium anodes alloy in above-mentioned electrolyte and 25 ℃, 100mA/cm
2operating potential curve under current density, the results detailed in Fig. 5, Fig. 6.Contrasting from corrosion rate, Open Circuit Potential, operating potential curve with Al-1Mg-0.1Sn-0.1Ga-1Zn aluminium anodes alloy in 6mol/L NaOH electrolyte.
From table 1, Fig. 5, Fig. 6, can find out, above-mentioned alloy is 0.179ml/cm from corrosion rate in the present embodiment electrolyte
2min, be respectively-1.81V of Open Circuit Potential and operating potential and-1.557V, is 0.255ml/cm from corrosion rate in 6mol/L NaOH electrolyte
2min, be respectively-1.80V of Open Circuit Potential and operating potential and-1.550V.As can be seen here, above-mentioned alloy reducing to some extent from corrosion rate in the present embodiment electrolyte, Open Circuit Potential and position, working point are all significantly born and are moved.
Table 1 different aluminum anode alloy embodiment 1～14 prepare in electrolyte from corrosion rate
Claims (9)
1. an aluminium-air cell electrolyte corrosion inhibiter, is characterized in that: described corrosion inhibiter mainly comprises sodium thiosulfate, and the concentration in electrolyte is 0.005～0.2mol/L.
2. aluminium-air cell according to claim 1 electrolyte corrosion inhibiter, is characterized in that: described corrosion inhibiter also comprises auxiliary additive sodium stannate, and the concentration in electrolyte is 0.01～0.03mol/L.
3. aluminium-air cell according to claim 1 and 2 electrolyte corrosion inhibiter, is characterized in that: described electrolyte is sodium hydroxide solution, and concentration is 4～6mol/L.
4. an aluminium-air cell electrolyte, is characterized in that: every liter of electrolyte is mainly comprised of the component of following content: NaOH 4～6mol, and sodium thiosulfate 0.005～0.2mol, surplus is water.
5. aluminium-air cell electrolyte according to claim 4, is characterized in that: the content of described sodium thiosulfate is 0.005～0.1mol.
6. according to the aluminium-air cell electrolyte described in claim 4 or 5, it is characterized in that: described electrolyte also comprises corrosion inhibiter auxiliary additive sodium stannate, the content of sodium stannate is 0.01～0.03mol.
7. aluminium-air cell electrolyte according to claim 6, is characterized in that: the content of described sodium stannate is 0.01mol/L.
8. the preparation method of electrolyte for an aluminium-air cell as described in claim 4 or 5, it is characterized in that: comprise the following steps: according to constituent content preparation sodium hydroxide solution, cooling, more accurately take sodium thiosulfate, join in sodium hydroxide solution stirring and dissolving.
9. the preparation method of electrolyte for an aluminium-air cell as claimed in claim 6, it is characterized in that: comprise the following steps: according to constituent content preparation sodium hydroxide solution, cooling, more accurately take sodium thiosulfate, join in sodium hydroxide solution stirring and dissolving; According to constituent content, accurately take sodium stannate again, join in the sodium hydroxide solution that is dissolved with sodium thiosulfate stirring and dissolving.
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