CN110911751B - Alkaline aluminum-air battery electrolyte additive, electrolyte and application thereof - Google Patents

Alkaline aluminum-air battery electrolyte additive, electrolyte and application thereof Download PDF

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CN110911751B
CN110911751B CN201911228140.3A CN201911228140A CN110911751B CN 110911751 B CN110911751 B CN 110911751B CN 201911228140 A CN201911228140 A CN 201911228140A CN 110911751 B CN110911751 B CN 110911751B
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aluminum
air battery
concentration
alkaline
quinoline
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CN110911751A (en
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张大全
杨寒雪
高立新
戴希洋
李晓徽
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Shanghai Electric Power University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides an alkaline aluminum-air battery electrolyte additive, an electrode solution and application thereof, wherein the alkaline aluminum-air battery electrolyte additive comprises quinoline-8-sulfonic acid and calcium oxide, wherein in an electrolyte system, the concentration of the quinoline-8-sulfonic acid is 0.1-1 mM, and the concentration of the calcium oxide is 0.02-0.04 g/L. The electrolyte comprises a sodium hydroxide solution, quinoline-8-sulfonic acid and calcium oxide, wherein the concentration of the sodium hydroxide solution is 4M, the concentration of the quinoline-8-sulfonic acid is 0.1-1 mM, and the concentration of the calcium oxide is 0.02-0.04 g/L. According to the invention, the optimal effect is achieved when the concentration of quinoline-8-sulfonic acid is 1mM and the concentration of calcium oxide is 0.04g/L, the utilization rate of the corrosion inhibitor is enhanced through a synergistic effect, the utilization rate of an anode is improved, the use amount of the corrosion inhibitor can be greatly reduced, and the environment-friendly effect is achieved. The electrochemical test in alkaline electrolyte shows that the invention has excellent corrosion inhibition capability on the aluminum anode, the optimal corrosion inhibition rate is 82.11%, and the anode utilization rate is improved to 81.9%.

Description

Alkaline aluminum-air battery electrolyte additive, electrolyte and application thereof
Technical Field
The invention belongs to the technical field of battery electrolyte, and particularly relates to an alkaline aluminum-air battery electrolyte additive, an alkaline aluminum-air battery electrolyte and application of the alkaline aluminum-air battery electrolyte additive.
Background
Energy serves as the basis for survival and development of human society, and fossil energy supports human civilization for nearly 200 years. However, excessive consumption of primary fuels such as fossil fuels also brings energy crisis and serious environmental pollution. Metal-air batteries are one of the most promising energy storage devices in the future due to their high energy density and high battery capacity. Among them, Al (aluminum) has the highest content in earth crust, low price, high theoretical specific capacity and light weight, so the aluminum-air battery is one of the most potential metal-air batteries. And because the air required by the cathode of the aluminum-air battery is mainly from the ambient air, the extra volume of the battery is not increased.
At present, the most widely used is the aqueous electrolyte, in which systemThe battery of (2) has high ionic conductivity. In neutral electrolyte, Al (aluminum) surface is easy to form oxide film to protect metal and prevent Al3+The transfer of (2). In the alkaline electrolyte, the oxide protective film is damaged, so that the potential of the Al electrode is lower. However, the Al electrode undergoes hydrogen evolution self-corrosion in the alkaline electrolyte, which reduces the discharge performance and service life of the battery, and the problem of hydrogen evolution also brings about a safety hazard.
In order to reduce the self-corrosion problem of the aluminum-air battery, researchers carry out a series of researches to achieve the purpose of slowing down the self-corrosion of the anode, and the method mainly comprises the steps of replacing pure aluminum with aluminum alloy, covering an anticorrosive coating on the surface of metal and adding an additive into electrolyte. Therefore, there is a need in the art for an alkaline aluminum-air battery electrolyte additive and a preparation method thereof, which are simple to operate, low in cost, reliable and efficient.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above and/or other problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art of the electrolyte additive of the battery and provide the electrolyte additive of the alkaline aluminum-air battery.
In order to solve the technical problems, the invention provides the following technical scheme: the alkaline aluminum-air battery electrolyte additive comprises quinoline-8-sulfonic acid and calcium oxide, wherein in an electrolyte system, the concentration of the quinoline-8-sulfonic acid is 0.1-1 mM, and the concentration of the calcium oxide is 0.02-0.04 g/L.
As a preferable embodiment of the additive for the electrolyte of the alkaline aluminum-air battery of the present invention, wherein: the concentration of the quinoline-8-sulfonic acid is 1mM, and the concentration of the calcium oxide is 0.04 g/L.
As a preferable embodiment of the additive for the electrolyte of the alkaline aluminum-air battery of the present invention, wherein: the electrolyte system further comprises a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 4M.
It is another object of the present invention to overcome the deficiencies of the prior art battery electrolytes and to provide an alkaline aluminum-air battery electrolyte containing an alkaline aluminum-air battery electrolyte additive.
In order to solve the technical problems, the invention provides the following technical scheme: the electrolyte of the alkaline aluminum-air battery comprises a sodium hydroxide solution, quinoline-8-sulfonic acid and calcium oxide, wherein the concentration of the sodium hydroxide solution is 4M, the concentration of the quinoline-8-sulfonic acid is 0.1-1 mM, and the concentration of the calcium oxide is 0.02-0.04 g/L.
As a preferable embodiment of the alkaline aluminum-air battery electrolyte containing the alkaline aluminum-air battery electrolyte additive according to the present invention, wherein: the concentration of the quinoline-8-sulfonic acid is 1mM, and the concentration of the calcium oxide is 0.04 g/L.
It is a further object of the present invention to provide an alkaline aluminum-air battery electrolyte containing an alkaline aluminum-air battery electrolyte additive for use in an aluminum-air battery.
As a preferable embodiment of the application of the alkaline aluminum-air battery electrolyte containing the alkaline aluminum-air battery electrolyte additive of the present invention, wherein: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
polishing the aluminum alloy step by step from coarse to fine by using waterproof abrasive paper;
cleaning the polished aluminum sheet with deionized water, removing surface grease with absolute ethyl alcohol, and washing away residual absolute ethyl alcohol on the surface with deionized water;
and (3) soaking the treated aluminum sheet in electrolyte containing an additive, wherein the additive in the solution can be well adsorbed on the surface of the aluminum alloy and a layer of corrosion inhibition film is constructed.
As a preferable embodiment of the application of the alkaline aluminum-air battery electrolyte containing the alkaline aluminum-air battery electrolyte additive of the present invention, wherein: the step-by-step polishing of the aluminum alloy by using the waterproof abrasive paper refers to the step-by-step polishing of 400-mesh, 800-mesh, 1200-mesh and 2000-mesh waterproof abrasive paper from coarse to fine.
As a preferable embodiment of the application of the alkaline aluminum-air battery electrolyte containing the alkaline aluminum-air battery electrolyte additive of the present invention, wherein: soaking the treated aluminum sheet in electrolyte containing additives for 5-60 min at 25 ℃ in a face-to-face ratio of 20-40 mL/cm2。
As a preferable embodiment of the application of the alkaline aluminum-air battery electrolyte containing the alkaline aluminum-air battery electrolyte additive of the present invention, wherein: the aluminum sheet is AA5052 aluminum alloy.
The invention has the beneficial effects that:
(1) the invention provides an alkaline aluminum-air battery electrolyte additive and electrolyte, the aluminum alloy sheet which is polished and cleaned is put into the electrolyte containing the additive to be soaked for a certain time, and the operation mode is simple; the quinoline-8-sulfonic acid and the calcium oxide have low price, and the dosage is less than that of the drugs in the prior assembly technology, thereby saving the cost and having good economic benefit;
(2) the invention provides an alkaline aluminum-air battery electrolyte additive and electrolyte, which are green and environment-friendly, and avoid the pollution of environment caused by the use of rare heavy metal ions and harmful compounds;
(3) compared with the prior art, the invention has the advantages that the concentration of quinoline-8-sulfonic acid is 1mM, the concentration of calcium oxide is 0.04g/L, the effect is optimal, the utilization rate of the corrosion inhibitor is enhanced through the synergistic effect, the utilization rate of the anode is improved, the use amount of the corrosion inhibitor can be greatly reduced, and the environment-friendly effect is realized. The electrochemical test in alkaline electrolyte shows that the invention has excellent corrosion inhibition capability on the aluminum anode, the optimal corrosion inhibition rate is 82.11%, and the anode utilization rate is improved to 81.9%.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is a graph of electrochemical impedance spectroscopy measurements of pretreated aluminum electrodes in 4M NaOH solutions containing varying concentrations of quinoline-8-sulfonic acid and calcium oxide additives in the practice of the present invention.
FIG. 2 is a test chart of the polarization curve of the pretreated aluminum electrode after being soaked in 4M NaOH solution containing quinoline-8-sulfonic acid and calcium oxide additives with different concentrations for 1h in the practice of the present invention.
FIG. 3 is a plot of constant current discharge for pretreated aluminum alloys in 4M NaOH solutions containing varying concentrations of quinoline-8-sulfonic acid and calcium oxide additives in accordance with the practice of the present invention.
FIG. 4 is an SEM image of pretreated aluminum alloy after being soaked in 4M NaOH solutions containing different concentrations of quinoline-8-sulfonic acid and calcium oxide additives for 1h in the practice of the present invention. Wherein (a) is a blank group; (b) SEM picture after 1h soaking in 1mM quinoline-8-sulfonic acid additive in 4M NaOH solution; (c) SEM picture after soaking in 0.04g/L CaO additive 4M NaOH solution for 1 h; (d) SEM image after 1h soaking in 1mM quinoline-8-sulfonic acid and 0.04g/L calcium oxide additive in 4M NaOH solution.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The invention comprises the following steps: quinoline-8-sulfonic acid, 98% pure, commercially available. Other raw materials in the present invention are not specifically described, and are commercially available.
The method for evaluating the corrosion inhibition rate of the corrosion inhibition film of the aluminum surface composite additive comprises the following steps: testing the soaked aluminum electrode by using an electrochemical workstation (Solartron 1287/Solartron 1260), fitting the test result by using ZSimDemo software, and calculating the corrosion inhibition rate; and (3) taking an SEM surface topography of the aluminum alloy after being soaked in a 4M NaOH solution containing quinoline-8-sulfonic acid and calcium oxide additives for 1h, comparing the SEM surface topography with a corrosion picture of a blank aluminum sheet, and visually judging the corrosion inhibition performance of the corrosion inhibition film according to the corrosion topography.
The electrochemical test employs a three-electrode system, in which a platinum electrode and a saturated calomel electrode (SCE, Cl)-Concentration of 0.357g/mL) are respectively used as an auxiliary electrode (CE) and a Reference Electrode (RE), an AA5052 aluminum alloy sheet with the area of 0.5cm2 is selected for manufacturing a Working Electrode (WE), the working electrode and a pure aluminum wire are firmly welded, and then the working electrode is sealed by epoxy resin, so that the exposed aluminum area is 0.5cm 2. The working electrode was treated in the same manner as the pretreatment of the aluminum anode. The electrochemical measurement adopts a sine wave with an excitation signal amplitude of 5mV, and the test frequency is 10 < -2 > to 105; the scan rate of the polarization curve was chosen to be 1mV/min, with a scan range of + -300 mV (relative to the open circuit potential). The corrosion inhibition rate calculation formula is as follows:
Figure GDA0002678324860000051
wherein Rp and inh are the polarization resistance of the aluminum electrode containing the compound corrosion inhibitor, and Rp and 0 are the polarization resistance of the blank aluminum electrode.
Example 1
The additive of the alkaline aluminum-air battery electrolyte in the embodiment is quinoline-8-sulfonic acid and calcium oxide with different concentrations, and the solvent is sodium hydroxide aqueous solution with the concentration of 4M, wherein the concentration of the quinoline-8-sulfonic acid is 0.001mM, 0.01mM, 0.1mM and 1mM, and the concentration of the calcium oxide is 0.04 g/L.
The preparation method of the mercaptan salt assembled film on the surface of the aluminum comprises the following steps:
(1) polishing an aluminum electrode by using 400, 800, 1200 and 2000-mesh waterproof abrasive paper step by step, then washing the surface of the aluminum electrode by using ethanol and deionized water for multiple times to ensure that no residual impurities exist on the surface of the aluminum sheet, and then drying the surface by using nitrogen for later use;
(2) the treated aluminum electrode is put into electrolyte containing quinoline-8-sulfonic acid and calcium oxide additive, and the surface-to-volume ratio is 20mL/cm2The composite additive in the solution can be adsorbed on the surface of the aluminum to form a film.
The pretreated aluminum electrode was placed in a 4M NaOH solution to test the open circuit potential for 5min first, so that the potential of the electrode tended to be stable, and then an ac impedance test and a polarization curve test were performed, with the results shown in fig. 1, fig. 2 and table 1.
Electrochemical impedance fitting parameters of aluminum electrodes in 4M NaOH solutions containing varying concentrations of quinoline-8-sulfonic acid (8-QS) and calcium oxide additives are shown in Table 1.
TABLE 1
Figure GDA0002678324860000052
Figure GDA0002678324860000061
As can be seen from FIG. 1, FIG. 2 and Table 1, the corrosion inhibition rate of the composite membrane on the aluminum electrode increases with the increase of the concentration of quinoline-8-sulfonic acid, and the corrosion inhibition rate is the greatest when the concentration of quinoline-8-sulfonic acid is 1mM, therefore, the concentration of quinoline-8-sulfonic acid is preferably 1mM, and the composite additive has the best corrosion inhibition effect on aluminum.
As can be seen from the observation of FIG. 1, the capacitive arc of the aluminum electrode in the blank solution is the smallest, while the capacitive arc of the aluminum electrode in the solution added with quinoline-8-sulfonic acid with different concentrations is larger, which proves the protection effect of the corrosion inhibition film on aluminum. Wherein, when the concentration of quinoline-8-sulfonic acid in the solution is 1mM and the concentration of calcium oxide is 0.04g/L, the capacitive arc of the aluminum electrode is the largest, and the protection effect at the concentration is the best. Therefore, the concentration of quinoline-8-sulfonic acid is 1mM and the concentration of calcium oxide is 0.04 g/L.
By observing fig. 2, it can be seen that the cathodic and anodic corrosion current densities of the aluminum electrode in the electrolyte containing the compound additive are both reduced, and the potentials are both shifted to the negative direction, which represents that the additive compounded by quinoline-8-sulfonic acid and calcium oxide is a mixed corrosion inhibitor. After the quinoline-8-sulfonic acid and the calcium oxide are added, the corrosion is mainly prevented by changing the reaction sites on the surface of the aluminum anode.
The protection effect of the corrosion inhibition film is reduced along with the increase of the concentration of the assembly liquid, because the adhesion of the film layer to the aluminum surface is reduced due to the thickening of the film layer, and the film layer can be loosened or fallen off, so that the corrosion inhibition effect of the corrosion inhibition film to the aluminum is reduced.
The comparison between the present invention and the prior art publicly reported is shown in Table 2.
TABLE 2
Figure GDA0002678324860000062
As can be seen from Table 2, the usage amount of quinoline-8-sulfonic acid and calcium oxide in the invention is far less than that in the prior invention, and the anode utilization rate is higher and the applicability is stronger. Compared with the prior art, the invention has the advantages that the concentration of quinoline-8-sulfonic acid is 1mM, the concentration of calcium oxide is 0.04g/L, the effect is optimal, the utilization rate of the corrosion inhibitor is enhanced through the synergistic effect, the utilization rate of the anode is improved, the use amount of the corrosion inhibitor can be greatly reduced, and the environment-friendly effect is realized. The electrochemical test in alkaline electrolyte shows that the invention has excellent corrosion inhibition capability on the aluminum anode, the optimal corrosion inhibition rate is 82.11%, and the anode utilization rate is improved to 81.9%.
Example 2
(1) Polishing an aluminum electrode by using 400, 800, 1200 and 2000-mesh waterproof abrasive paper step by step, then washing the surface of the aluminum electrode by using ethanol and deionized water for multiple times to ensure that no residual impurities exist on the surface of the aluminum sheet, and then drying the surface by using nitrogen for later use;
(2) directly putting a group of aluminum sheets into a 4M NaOH solution for corrosion for 1h, taking out the aluminum sheets, and repeatedly washing the aluminum sheets by using deionized water to remove surface residues.
Example 3
The aluminum corrosion inhibitor in the embodiment is a quinoline-8-sulfonic acid and calcium oxide compound additive, and deionized water is selected as a solvent, wherein the concentration of the quinoline-8-sulfonic acid is 1mM, and the solvent is a sodium hydroxide aqueous solution with the concentration of 4M.
(1) Polishing an aluminum electrode by using 400, 800, 1200 and 2000-mesh waterproof abrasive paper step by step, then washing the surface of the aluminum electrode by using ethanol and deionized water for multiple times to ensure that no residual impurities exist on the surface of the aluminum sheet, and then drying the surface by using nitrogen for later use;
(2) soaking the treated aluminum electrode in electrolyte containing composite additive at 25 deg.C for 5min to obtain a surface-to-volume ratio of 40mL/cm2。
Example 4
The aluminum corrosion inhibitor in the embodiment is a quinoline-8-sulfonic acid and calcium oxide compound additive, and deionized water is selected as a solvent, wherein the concentration of calcium oxide is 0.04g/L, and the solvent is a sodium hydroxide aqueous solution with the concentration of 4M.
(1) Polishing an aluminum electrode by using 400, 800, 1200 and 2000-mesh waterproof abrasive paper step by step, then washing the surface of the aluminum electrode by using ethanol and deionized water for multiple times to ensure that no residual impurities exist on the surface of the aluminum sheet, and then drying the surface by using nitrogen for later use;
(2) soaking the treated aluminum electrode in an electrolyte containing a composite additive for 60min at 25 ℃ with a surface-to-volume ratio of 40mL/cm2。
Example 5
(1) Polishing an aluminum sheet by using 400, 800, 1200 and 2000-mesh waterproof abrasive paper step by step, then washing the surface of the aluminum sheet by using ethanol and deionized water for multiple times to ensure that no residual impurities exist on the surface of the aluminum sheet, and then drying the surface by using nitrogen for later use;
(2) and corroding the other group of aluminum sheets in a 4M NaOH solution with the concentration of quinoline-8-sulfonic acid of 1mM and the concentration of calcium oxide of 0.04g/L for 1h, taking out the aluminum sheets, and repeatedly washing the aluminum sheets with deionized water to remove surface residues. An SEM surface topography of the aluminum sheet was taken, as shown in figure 4,
wherein (a) is a blank group (example 2); (b) SEM picture after 1h soaking in 4M NaOH solution of 1mM quinoline-8-sulfonic acid additive (example 3); (c) SEM picture after 1h soaking in 4M NaOH solution of 0.04g/L CaO additive (example 4); (d) SEM image (example 5) after 1h soaking in 1mM quinoline-8-sulfonic acid and 0.04g/L calcium oxide additive in 4M NaOH solution, and the difference between the two was analyzed and compared. The element distributions in the portions A to I in FIG. 4 are shown in Table 3.
TABLE 3
Figure GDA0002678324860000081
As can be seen from FIG. 4, the corrosion of the aluminum sheet is severe in FIG. 4(a), FIG. 4(b) and FIG. 4(c), and the corrosion pits are distributed on the surface, while the number and area of the corrosion pits on the surface of the aluminum with quinoline-8-sulfonic acid and calcium oxide added in FIG. 4(d) are greatly reduced, which indicates that the corrosion inhibition film can protect the aluminum well.
The additives of the existing aluminum-air battery mainly comprise two major types of inorganic corrosion inhibitors (oxides and salts) and organic corrosion inhibitors (proteins, aminophenols and sulfonic acid substances). In the actual production process, a single corrosion inhibitor cannot meet the actual requirement, so two or more corrosion inhibitors are usually compounded for use.
The quinoline-8-sulfonic acid is used as a quinoline derivative, has a sulfonic group in a chemical structure, and has the characteristics of quinoline and sulfonic acid substances. The quinoline-8-sulfonic acid and calcium oxide are compounded to have obvious inhibition effect on the corrosion of AA5052 aluminum alloy in alkaline solution. The two corrosion inhibitors are compounded to generate a synergistic effect to inhibit the anode hydrogen evolution self-corrosion of the alkaline aluminum-air battery, and have important significance for the development of the aluminum-air battery and the application of the green energy technology. The invention firstly proposes that the quinoline-8-sulfonic acid and calcium oxide compound corrosion inhibitor technology forms a layer of composite film on the surface of the aluminum alloy through the synergistic interaction, and can inhibit the cathodic hydrogen evolution reaction and the anodic dissolution behavior at the same time.
The invention discloses an alkaline aluminum-air battery electrolyte additive and an electrolyte action mechanism: quinoline-8-sulfonic acid is used as a mixed corrosion inhibitor mainly for a cathode, and can inhibit the corrosion process of the cathode and an anode simultaneously. The calcium oxide reacts with the alkaline solution to generate calcium hydroxide, the corrosion reaction of the active sites of the aluminum anode is inhibited mainly by the geometric coverage effect, and the mechanism of inhibiting the corrosion reaction is not changed by the addition of the calcium oxide. Meanwhile, the calcium ions can promote quinoline-8-sulfonic acid to be adsorbed on the surface of the aluminum anode, so that the corrosion inhibition effect of the compound corrosion inhibitor is greatly improved. Therefore, the quinoline-8-sulfonic acid and calcium oxide compound corrosion inhibitor has good theoretical basis when being applied to the corrosion inhibition field of the aluminum-air battery anode.
The application number is CN201310330770.8, an electrolyte corrosion inhibitor for an aluminum-air battery, an electrolyte and a preparation method are researched, the formula adopts that the corrosion inhibitor mainly comprises sodium thiosulfate and an auxiliary additive sodium stannate, a certain amount of auxiliary corrosion inhibitor needs to be added into the electrolyte before the corrosion inhibitor is added, the auxiliary corrosion inhibitor is uniformly mixed, and the problems that the used medicines are not environment-friendly enough, the corrosion inhibition efficiency is not high and the like are solved.
The patent with the application number of CN201610244635.5 researches a compound corrosion inhibitor for reducing hydrogen evolution self-corrosion while realizing aluminum anode activation, the electrolyte corrosion inhibitor mainly comprises an inorganic phase-forming corrosion inhibitor and an organic adsorption corrosion inhibitor, the inorganic phase-forming corrosion inhibitor is selected from at least one of zinc acetate, manganate and scandium nitrate, the organic adsorption corrosion inhibitor is selected from at least one of benzotriazole, natural amino acid and a cationic surfactant, and the compound corrosion inhibitor is added into the electrolyte under the condition of constant-temperature water bath to play a role in corrosion inhibition. The method has the defects of complex preparation process, high technical requirement, not very wide applicability and the like. The quinoline derivative has better adsorption and corrosion inhibition effects on aluminum, can be complexed with metal ions, and simultaneously, in view of the interaction between sulfonic groups and metal oxides, the inventor firstly proposes that quinoline-8-sulfonic acid and calcium oxide are compounded for use as an alkaline aluminum-air battery electrolyte additive, and the additive is characterized in that: the electrolyte comprises quinoline-8-sulfonic acid and calcium oxide, wherein in the electrolyte system, the concentration of the quinoline-8-sulfonic acid is 0.1-1 mM, and the concentration of the calcium oxide is 0.02-0.04 g/L. Compared with the prior art, the invention has the advantages that the concentration of quinoline-8-sulfonic acid is 1mM, the concentration of calcium oxide is 0.04g/L, the effect is optimal, the utilization rate of the corrosion inhibitor is enhanced through the synergistic effect, the utilization rate of the anode is improved, the use amount of the corrosion inhibitor can be greatly reduced, and the environment-friendly effect is realized. The electrochemical test in alkaline electrolyte shows that the invention has excellent corrosion inhibition capability on the aluminum anode, the optimal corrosion inhibition rate is 82.11%, and the anode utilization rate is improved to 81.9%.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.

Claims (10)

1. An alkaline aluminum-air battery electrolyte additive is characterized in that: the electrolyte comprises quinoline-8-sulfonic acid and calcium oxide, wherein in the electrolyte system, the concentration of the quinoline-8-sulfonic acid is 0.1-1 mM, and the concentration of the calcium oxide is 0.02-0.04 g/L.
2. The alkaline aluminum-air battery electrolyte additive of claim 1 wherein: the concentration of the quinoline-8-sulfonic acid is 1mM, and the concentration of the calcium oxide is 0.04 g/L.
3. The alkaline aluminum-air battery electrolyte additive of claim 1 wherein: the electrolyte system further comprises a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 4M.
4. An alkaline aluminum-air battery electrolyte solution containing the alkaline aluminum-air battery electrolyte additive according to any one of claims 1 to 3, characterized in that: the electrolyte comprises a sodium hydroxide solution, quinoline-8-sulfonic acid and calcium oxide, wherein the concentration of the sodium hydroxide solution is 4M, the concentration of the quinoline-8-sulfonic acid is 0.1-1 mM, and the concentration of the calcium oxide is 0.02-0.04 g/L.
5. The alkaline aluminum-air battery electrolyte containing an alkaline aluminum-air battery electrolyte additive as claimed in claim 4 wherein: the concentration of the quinoline-8-sulfonic acid is 1mM, and the concentration of the calcium oxide is 0.04 g/L.
6. Use of an alkaline aluminium-air battery electrolyte comprising an alkaline aluminium-air battery electrolyte additive according to claim 4 in an aluminium-air battery.
7. Use of an alkaline aluminium-air battery electrolyte comprising an alkaline aluminium-air battery electrolyte additive according to claim 6, wherein: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
polishing the aluminum alloy step by step from coarse to fine by using waterproof abrasive paper;
cleaning the polished aluminum sheet with deionized water, removing surface grease with absolute ethyl alcohol, and washing away residual absolute ethyl alcohol on the surface with deionized water;
and (3) soaking the treated aluminum sheet in electrolyte containing an additive, wherein the additive in the solution can be well adsorbed on the surface of the aluminum alloy and a layer of corrosion inhibition film is constructed.
8. Use of an alkaline aluminium-air battery electrolyte comprising an alkaline aluminium-air battery electrolyte additive according to claim 7, wherein: the step-by-step polishing of the aluminum alloy by using the waterproof abrasive paper refers to the step-by-step polishing of 400-mesh, 800-mesh, 1200-mesh and 2000-mesh waterproof abrasive paper from coarse to fine.
9. Use of an alkaline aluminium-air battery electrolyte comprising an alkaline aluminium-air battery electrolyte additive according to claim 7, wherein: soaking the treated aluminum sheet in electrolyte containing additives for 5-60 min at 25 ℃ in a face-to-face ratio of 20-40 mL/cm2。
10. Use of an alkaline aluminium-air battery electrolyte comprising an alkaline aluminium-air battery electrolyte additive according to claim 7, wherein: the aluminum sheet is AA5052 aluminum alloy.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1263362A (en) * 1999-02-11 2000-08-16 陆安民 High-energy low-consumption long-life environment-protecting type lead battery and its preparation method
CN104593793A (en) * 2015-02-12 2015-05-06 佛山市仁昌科技有限公司 Neutralization solution for surface pretreatment of aluminum and aluminum alloy
CN106148964A (en) * 2015-04-27 2016-11-23 中国石油化工股份有限公司 A kind of corrosion inhibiter and application thereof and a kind of oil-field flooding pit shaft anti-corrosion method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1263362A (en) * 1999-02-11 2000-08-16 陆安民 High-energy low-consumption long-life environment-protecting type lead battery and its preparation method
CN104593793A (en) * 2015-02-12 2015-05-06 佛山市仁昌科技有限公司 Neutralization solution for surface pretreatment of aluminum and aluminum alloy
CN106148964A (en) * 2015-04-27 2016-11-23 中国石油化工股份有限公司 A kind of corrosion inhibiter and application thereof and a kind of oil-field flooding pit shaft anti-corrosion method

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