CN114122570A - Aluminum-air battery, aluminum-air battery electrolyte and preparation method thereof - Google Patents
Aluminum-air battery, aluminum-air battery electrolyte and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000005260 corrosion Methods 0.000 claims abstract description 54
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 85
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 48
- 239000008103 glucose Substances 0.000 claims description 47
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- 239000000843 powder Substances 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 28
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- 230000007797 corrosion Effects 0.000 claims description 23
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 21
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- 238000003756 stirring Methods 0.000 claims description 5
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- 229910052739 hydrogen Inorganic materials 0.000 abstract description 30
- 239000001257 hydrogen Substances 0.000 abstract description 30
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- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 20
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- 229910001679 gibbsite Inorganic materials 0.000 description 3
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- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- RFSUNEUAIZKAJO-VRPWFDPXSA-N D-Fructose Natural products OC[C@H]1OC(O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-VRPWFDPXSA-N 0.000 description 1
- NBSCHQHZLSJFNQ-GASJEMHNSA-N D-Glucose 6-phosphate Chemical compound OC1O[C@H](COP(O)(O)=O)[C@@H](O)[C@H](O)[C@H]1O NBSCHQHZLSJFNQ-GASJEMHNSA-N 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- VFRROHXSMXFLSN-UHFFFAOYSA-N Glc6P Natural products OP(=O)(O)OCC(O)C(O)C(O)C(O)C=O VFRROHXSMXFLSN-UHFFFAOYSA-N 0.000 description 1
- LKDRXBCSQODPBY-AMVSKUEXSA-N L-(-)-Sorbose Chemical compound OCC1(O)OC[C@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-AMVSKUEXSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
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- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/005—Devices for making primary cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0014—Alkaline electrolytes
Abstract
The invention discloses an aluminum-air battery, an aluminum-air battery electrolyte and a preparation method thereof. The aluminum-air battery comprises an anode, a cathode and the electrolyte, wherein the anode is metal aluminum or aluminum alloy, and the cathode is mesoporous MnO coated by graphene2. The aluminum-air battery made of the electrolyte can greatly relieve the hydrogen evolution self-corrosion phenomenon of the aluminum-air battery, improve the use safety and stability of the battery and reduce the heating phenomenon of the battery.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to an aluminum-air battery, an aluminum-air battery electrolyte and a preparation method thereof.
Background
In the 21 st century, energy has attracted much attention as a fundamental driving force for economic development; batteries are one of the commonly used means for backup energy storage, and chemical power batteries have made considerable progress, such as lithium ion batteries, supercapacitors and fuel cells; among these new energy solutions, the metal-air fuel cell is considered as a promising battery, which is applied to power sources of new-generation electronic products, electric vehicles, and energy storage devices due to its high energy density, low cost, and good safety.
In the metal-air battery, the cathode in the system is oxygen (oxygen reduction is carried out by using a catalyst), magnesium, zinc, lithium, aluminum and the like are commonly used for a metal anode, and the aluminum-air battery is deeply concerned by the industry due to high theoretical capacity (the theoretical specific energy is 8100 Wh/kg) and low cost of anode materials (the anode (the cathode) is made of metal aluminum, and the anode (the cathode) is cheap and easy to process and the like); the advantages of the aluminum-air battery are obvious, the disadvantages are also obvious, and the main disadvantage is that the aluminum can generate serious self-corrosion phenomenon in alkaline solution (the reaction equation is: 2Al +2 OH)-+2H2O=2AlO2 -+3H2×) because there is the production of hydrogen in above-mentioned reaction, not only can produce a large amount of bubbles, and also seriously influence security and stability that battery itself used, in addition, above-mentioned reaction can emit a large amount of heats and cause generating heat of battery, and the battery generates heat and then can cause the acceleration of electrolyte solvent loss, can say that the hydrogen evolution self-corrosion phenomenon of aluminium among the aluminium-air battery has seriously influenced aluminium-air battery's popularization and application.
Disclosure of Invention
Aiming at the defects in the prior art, the technical problems to be solved by the invention are as follows: how to provide an electrolyte of an aluminum-air battery, which can greatly relieve the hydrogen evolution self-corrosion phenomenon of the aluminum-air battery, improve the use safety and stability of the battery and simultaneously reduce the heating phenomenon of the battery.
In addition, the invention also provides a preparation method of the aluminum-air battery electrolyte and an aluminum-air battery with the electrolyte.
In order to solve the technical problems, the invention adopts the following technical scheme:
an aluminium-air battery electrolyte comprises an alkaline electrolyte and a corrosion inhibitor, wherein the corrosion inhibitor comprises glucose and zinc oxide.
The working principle of the invention is as follows: according to the scheme, the corrosion inhibitor is added into the alkaline electrolyte, and the combined action of glucose and zinc oxide is utilized to jointly inhibit the hydrogen evolution self-corrosion phenomenon.
Wherein, zinc oxide can be attached to the surface of the metal anode in the alkaline aqueous solution, and a zinc protective layer with higher potential is formed on the surface, thereby inhibiting the occurrence of hydrogen evolution self-corrosion phenomenon; meanwhile, glucose is used as a natural organic carbohydrate, the structure of the natural organic carbohydrate contains five hydroxyl groups, the positive electricity of zinc ions and the negative electricity of the hydroxyl groups of the glucose are combined to further generate a protective layer, and a synergistic effect is exerted together to further inhibit the occurrence of the hydrogen evolution self-corrosion phenomenon, so that the hydrogen generation is reduced by inhibiting the occurrence of the hydrogen evolution self-corrosion phenomenon, the use safety and stability of the battery are improved, and the problem of the heat generation of the hydrogen evolution self-corrosion is reduced, so that the conditions of larger current and higher voltage can be considered.
In addition, the scheme adds glucose into the alkaline electrolyte, and the glucose structure contains five hydroxyl groups (OH)-) Compared with the similar organic matters, the electrolyte has higher electronegativity, so that the addition of glucose is beneficial to the falling off of corrosion products of the battery, and the contact area of the anode of the battery and the electrolyte is increased, thereby improving the discharge current of the battery; in addition, glucose can inhibit hydrogen evolution self-corrosion phenomenon, and is used in alkaline powerIn the preparation process of the electrolyte, when glucose and alkaline solid powder are mixed and added into deionized water to prepare the electrolyte, the alkaline solid powder can generate a dissolution heat release phenomenon, so that a hydrothermal reaction condition is formed, the glucose can generate carbon quantum dots under a local high-concentration alkaline condition under the condition, and the generated carbon quantum dots have an effect of promoting the catalytic effect of the battery.
Therefore, the scheme can greatly relieve the hydrogen evolution self-corrosion phenomenon of the aluminum-air battery, improve the use safety and stability of the battery, reduce the heating phenomenon of the battery, improve the discharge current and improve the catalytic effect.
Preferably, the aluminum-air battery electrolyte further comprises an additive, wherein the additive comprises sodium carboxymethyl cellulose.
Therefore, by further adding sodium carboxymethyl cellulose (CMC), the adhesive force of zinc oxide on the surface of the anode of the battery can be enhanced by the sodium carboxymethyl cellulose, and the sodium carboxymethyl cellulose and the zinc oxide show obvious synergistic effect, so that the adhesive force and the stability of a protective layer formed on the surface layer of the anode are improved, the corrosion inhibition effect is further enhanced, and the protection effect on the anode is better exerted.
Preferably, the additive further comprises potassium acetate and potassium formate.
Therefore, after the battery system reacts for a period of time (the alkali concentration is reduced due to the consumption of alkali in the battery electrolyte), the electrolyte generates gel to precipitate aluminum hydroxide, the precipitation of the aluminum hydroxide in the electrolyte can be accelerated by adding potassium acetate and potassium formate, so that the aluminum hydroxide can be separated from the electrolyte more easily, the pH value of the electrolyte can be maintained and stabilized in a certain range (at the moment, the electrolyte can be replaced by measures), and the use is not influenced due to the rapid attenuation of the pH value of the electrolyte.
Meanwhile, after the battery reacts for a period of time, when the potassium acetate and the potassium formate promote the formation of gel precipitated aluminum hydroxide, the pH of the electrolyte system is maintained at 12-13, so that the phenomenon of voltage water jump of the aluminum-air battery can be prevented from affecting the actual use; meanwhile, the PH of the electrolyte system is maintained at 12-13, so that whether the electrolyte needs to be replaced or not can be identified through the PH detection condition; in addition, when the potassium acetate and the potassium formate promote the formation of gel precipitated aluminum hydroxide, the internal resistance of an electrolyte system is greatly changed after the gel is generated, so that whether the electrolyte needs to be replaced can be identified by detecting the internal resistance change of the electrolyte (when the internal resistance of a single battery is greater than 80M omega).
Preferably, the alkaline electrolyte is potassium hydroxide or sodium hydroxide with the concentration of 1-7 mol/L, the concentration of glucose in the corrosion inhibitor is 50-300 g/L, and the concentration of zinc oxide is 0.1-5 g/L.
Thus, the concentration is a concentration range which is proved by experiments to have better inhibition on the hydrogen evolution self-corrosion reaction.
Preferably, the concentration of the sodium carboxymethylcellulose in the additive is 5-10 g/L, the concentration of the potassium acetate is 1-5 g/L, and the concentration of the potassium formate is 1-5 g/L.
Thus, the concentration is a concentration range which is proved by experiments to have better inhibition on the hydrogen evolution self-corrosion reaction.
The preparation method of the aluminum-air battery electrolyte comprises the following steps:
step 1) preparing alkaline solid powder and deionized water for preparing alkaline electrolyte;
step 2) dividing the alkaline solid powder into two parts, wherein one part of the alkaline solid powder is directly dissolved in deionized water, and the other part of the alkaline solid powder is mechanically mixed with glucose and then dissolved in the deionized water;
step 3) when the alkaline solid powder and glucose in the step 2) are completely dissolved in deionized water to form alkaline electrolyte, and when the alkaline electrolyte is cooled to room temperature, zinc oxide is added into the alkaline electrolyte for multiple times;
and 4) finishing the preparation of the electrolyte.
Thus, the electrolyte prepared by the method can jointly inhibit the hydrogen evolution self-corrosion phenomenon by utilizing the combined action of the glucose and the zinc oxide in the using process.
Preferably, in step 3), after zinc oxide is added to the alkaline electrolyte for a plurality of times, sodium carboxymethyl cellulose, potassium acetate and potassium formate are added to the alkaline electrolyte respectively.
Therefore, the sodium carboxymethylcellulose is used for enhancing the adhesive force of zinc oxide on the surface of the anode of the battery, and the potassium acetate and the potassium formate are used for accelerating the precipitation of aluminum hydroxide in the electrolyte, so that the influence on the actual use caused by the voltage water-jumping phenomenon of the battery is prevented, and meanwhile, the condition of whether the electrolyte needs to be replaced or not is conveniently detected.
In the step 2), the alkaline solid powder and the glucose are uniformly mixed in a grinding mode, the grinding time is 2-3min, and the alkaline solid powder and the glucose are continuously stirred when being dissolved in deionized water after being uniformly mixed.
Like this, mix alkaline solid powder and glucose through the mode of grinding, guarantee the mixed effect of both, constantly stir when dissolving in aqueous simultaneously and can guarantee to form even alkaline electrolyte.
In step 3), adding zinc oxide into the alkaline electrolyte for 3-5 times.
Thus, the zinc oxide is added into the alkaline electrolyte for 3-5 times, and the full dissolution of the zinc oxide can be ensured.
An aluminum-air battery comprises an anode, a cathode and the electrolyte, wherein the anode is metal aluminum or aluminum alloy, and the cathode is graphene-coated mesoporous MnO2。
Compared with the prior art, the invention has the following advantages:
1. the invention uses simpler and cheaper materials as the electrolyte raw materials, has simple preparation method, can be stored for a long time, can effectively control the hydrogen evolution self-corrosion of the anode under the alkaline condition, improves the aluminum used for the anode, and keeps higher open-circuit voltage in the operation of the aluminum-air battery.
2. The zinc oxide added in the invention is easy to form a protective layer attached to the surface of the aluminum plate in the alkaline electrolyte, and the protective layer is easy to fall off due to insufficient adhesive force, but after the sodium carboxymethyl cellulose is added, the zinc oxide and the sodium carboxymethyl cellulose have obvious synergistic effect, so that the adhesive force and the stability of the protective layer formed on the surface layer of the anode aluminum are improved, and the corrosion inhibition effect is further enhanced; glucose as a natural organic carbohydrate and having a structure comprising fiveThe hydroxyl has higher electronegativity compared with similar organic matters, the addition of glucose is beneficial to the shedding of the surface of a corrosion product aluminum hydroxide, and the contact area of an anode and a solution is increased, so that the discharge current of the anode is improved; in addition, after the battery reaction is carried out for a period of time (the alkali in the electrolyte is consumed, so that the alkali concentration is reduced), gel is generated in the electrolyte to precipitate aluminum hydroxide Al3++3OH-=Al(OH)3And ↓, potassium acetate and potassium formate can accelerate the precipitation of aluminum hydroxide in the electrolyte, so that the aluminum hydroxide can be easily separated from the electrolyte.
Drawings
FIG. 1 is a schematic view of the aluminum-air battery electrolyte according to the present invention after adding a corrosion inhibitor and sodium carboxymethylcellulose;
FIG. 2 is a schematic diagram showing the effect of the corrosion inhibitor additive in the electrolyte of the aluminum-air battery according to the present invention;
FIG. 3 is a graph showing the weight change of the anode aluminum after soaking in different electrolytes according to the first embodiment;
FIG. 4 is a voltage-current curve (current density of 0.045A/cm) of the electrolyte of the present invention during discharge test in a module2）。
Detailed Description
The invention will be further explained with reference to the drawings and the embodiments.
An electrolyte for an aluminum-air battery comprises an alkaline electrolyte and a corrosion inhibitor, wherein the corrosion inhibitor comprises glucose and zinc oxide (ZnO).
The working principle of the invention is as follows: according to the scheme, the corrosion inhibitor is added into the alkaline electrolyte, and the combined action of glucose and zinc oxide is utilized to jointly inhibit the hydrogen evolution self-corrosion phenomenon (as shown in figure 1).
Wherein, zinc oxide can be attached to the surface of the metal anode in alkaline aqueous solution (zinc oxide is attached to the surface of the aluminum plate in alkaline electrolyte to form a protective layer, taking KOH electrolyte as an example, the reaction formula is ZnO +2KOH + H2O=K2[Zn(OH)4]As shown in figure 2), a zinc protective layer with higher potential is formed on the surface, so that the hydrogen evolution self-corrosion phenomenon is inhibited; at the same time, glucose is used as a kind of dayHowever, the organic carbohydrate contains five hydroxyl groups in the structure, the positive electricity of the zinc ions is combined with the negative electricity of the glucose hydroxyl groups to further generate a protective layer, and the protective layer jointly exerts a synergistic effect to further inhibit the hydrogen evolution self-corrosion phenomenon, so that the generation of hydrogen is reduced by inhibiting the hydrogen evolution self-corrosion phenomenon, the use safety and the stability of the battery are improved, and the problem of heating of hydrogen evolution self-corrosion is reduced, so that the conditions of higher current and higher voltage can be considered.
In addition, the scheme adds glucose into the alkaline electrolyte, and the glucose structure contains five hydroxyl groups (OH)-) Compared with the similar organic matters, the electrolyte has higher electronegativity, so that the addition of glucose is beneficial to the falling off of corrosion products of the battery, and the contact area of the anode of the battery and the electrolyte is increased, thereby improving the discharge current of the battery; in addition, besides the hydrogen evolution self-corrosion phenomenon, in the preparation process of the alkaline electrolyte, when the glucose and the alkaline solid powder are mixed and added into deionized water to prepare the electrolyte, the alkaline solid powder can generate the dissolution and heat release phenomena, so that the hydrothermal reaction condition is formed, the glucose can generate carbon quantum dots under the alkaline condition with locally higher concentration under the condition, and the generated carbon quantum dots have the promotion effect on the catalytic effect of the battery.
Therefore, the scheme can greatly relieve the hydrogen evolution self-corrosion phenomenon of the aluminum-air battery, improve the use safety and stability of the battery, reduce the heating phenomenon of the battery, improve the discharge current and improve the catalytic effect.
As shown in fig. 1, in this embodiment, the aluminum-air battery electrolyte further includes an additive, and the additive includes sodium carboxymethyl cellulose.
Therefore, by further adding sodium carboxymethyl cellulose (CMC), the adhesive force of zinc oxide on the surface of the anode of the battery can be enhanced by the sodium carboxymethyl cellulose, and the sodium carboxymethyl cellulose and the zinc oxide show obvious synergistic effect, so that the adhesive force and the stability of a protective layer formed on the surface layer of the anode are improved, the corrosion inhibition effect is further enhanced, and the protection effect on the anode is better exerted.
In this example, the additives also included potassium acetate and potassium formate.
Thus, after the battery system has reacted for a period of time (the consumption of alkali in the battery electrolyte, resulting in a decrease in alkali concentration), the electrolyte forms a gel that precipitates aluminum hydroxide, and the reaction formula is: al (Al)3++3OH-=Al(OH)3And ↓, as shown in fig. 2, the addition of potassium acetate and potassium formate can accelerate the precipitation of aluminum hydroxide in the electrolyte, so that the aluminum hydroxide can be separated from the electrolyte more easily, and the PH value of the electrolyte can be maintained and stabilized in a certain range (at this time, the electrolyte can be replaced by measures) during this period, and the use is not affected by the rapid decay of the PH value of the electrolyte.
Meanwhile, after the battery reacts for a period of time, when the potassium acetate and the potassium formate promote the formation of gel precipitated aluminum hydroxide, the pH of the electrolyte system is maintained at 12-13, so that the phenomenon of voltage water jump of the aluminum-air battery can be prevented from affecting the actual use; meanwhile, the PH of the electrolyte system is maintained at 12-13, so that whether the electrolyte needs to be replaced or not can be identified through the PH detection condition; in addition, when the potassium acetate and the potassium formate promote the formation of gel precipitated aluminum hydroxide, the internal resistance of an electrolyte system is greatly changed after the gel is generated, so that whether the electrolyte needs to be replaced can be identified by detecting the internal resistance change of the electrolyte (when the internal resistance of a single battery is greater than 80M omega).
In the embodiment, the alkaline electrolyte is potassium hydroxide or sodium hydroxide with a concentration of 1-7 mol/L, the concentration of glucose in the corrosion inhibitor is 50-300 g/L, and the concentration of zinc oxide is 0.1-5 g/L.
Thus, the concentration is a concentration range which is proved by experiments to have better inhibition on the hydrogen evolution self-corrosion reaction.
In the embodiment, the additive contains 5-10 g/L of sodium carboxymethylcellulose, 1-5 g/L of potassium acetate, and 1-5 g/L of potassium formate.
Thus, the concentration is a concentration range which is proved by experiments to have better inhibition on the hydrogen evolution self-corrosion reaction.
In this embodiment, the glucose may be galactose, D-glucose, sorbose, D-fructose, D-mannitol, glucose-6-phosphate, 5-hydroxymethylfurfural, or the like;
the zinc oxide can be nano zinc oxide, mesoporous zinc oxide, micrometer zinc oxide, etc.
The preparation method of the aluminum-air battery electrolyte comprises the following steps:
step 1) preparing alkaline solid powder and deionized water for preparing alkaline electrolyte, wherein the alkaline solid powder is generally potassium hydroxide and sodium hydroxide, and the potassium hydroxide is taken as an example in the scheme, and the purity of the potassium hydroxide is required to be more than 95%, so that 1-7 mol/L potassium hydroxide solution can be prepared from the potassium hydroxide and the deionized water;
step 2) dividing alkaline solid powder into two parts, wherein one part of alkaline solid powder is directly dissolved in deionized water, the other part of alkaline solid powder is mechanically mixed with glucose (the purity is more than 98 percent and the preparation standard is 50-300 g/L) and then dissolved in the deionized water, and a glass rod is adopted for continuous stirring in the dissolving process;
step 3) when the alkaline solid powder and glucose in the step 2) are completely dissolved in deionized water to form alkaline electrolyte, a large amount of heat can be generated in the dissolving process, and meanwhile, the color of the solution is changed from transparent color to light yellow, in the process, the glucose can generate carbon quantum dots under the alkaline condition with local high concentration, the generated carbon quantum dots have an effect of promoting the catalytic effect of the battery, the introduction amount of the carbon quantum dots can be controlled by controlling the speed of adding the mixed powder, and the faster the speed of adding the mixed powder is, the more the carbon quantum dots are produced, the deeper the solution color is;
after the alkaline electrolyte is cooled to room temperature, adding zinc oxide (according to a configuration standard of 0.1-5 g/L) into the alkaline electrolyte for multiple times, and continuously stirring in the adding process until the solution is in a milky yellow suspension and has partial zinc oxide particles, wherein in the process, partial zinc oxide particles are settled at the bottom of the electrolyte and cannot influence the use of the battery;
and 4) finishing the preparation of the electrolyte.
Thus, the electrolyte prepared by the method can jointly inhibit the hydrogen evolution self-corrosion phenomenon by utilizing the combined action of the glucose and the zinc oxide in the using process.
In the embodiment, in the step 3), after zinc oxide is added to the alkaline electrolyte for multiple times, 5-10 g/L of sodium carboxymethyl cellulose, 1-5 g/L of potassium acetate and 1-5 g/L of potassium formate are added to the alkaline electrolyte respectively and stirred uniformly.
Therefore, the sodium carboxymethylcellulose is used for enhancing the adhesive force of zinc oxide on the surface of the anode of the battery, and the potassium acetate and the potassium formate are used for accelerating the precipitation of aluminum hydroxide in the electrolyte, so that the influence on the actual use caused by the voltage water-jumping phenomenon of the battery is prevented, and meanwhile, the condition of whether the electrolyte needs to be replaced or not is conveniently detected.
In the step 2), the alkaline solid powder and the glucose are uniformly mixed in a grinding mode, the grinding time is 2-3min, and the alkaline solid powder and the glucose are continuously stirred when being dissolved in deionized water after being uniformly mixed.
Like this, mix alkaline solid powder and glucose through the mode of grinding, guarantee the mixed effect of both, constantly stir when dissolving in aqueous simultaneously and can guarantee to form even alkaline electrolyte.
In step 3), adding zinc oxide into the alkaline electrolyte for 3-5 times.
Thus, the zinc oxide is added into the alkaline electrolyte for 3-5 times, and the full dissolution of the zinc oxide can be ensured.
An aluminum-air battery comprises an anode, a cathode and the electrolyte, wherein the anode is metal aluminum or aluminum alloy, and the cathode is mesoporous MnO coated by graphene2。
Compared with the prior art, the invention has the following advantages: the invention uses simpler and cheaper materials as the electrolyte raw materials, has simple preparation method, can be stored for a long time, can effectively control the hydrogen evolution self-corrosion of the anode under the alkaline condition, improves the aluminum used for the anode, and keeps higher open-circuit voltage in the operation of the aluminum-air battery. The zinc oxide added in the invention is easy to form a protective layer adhered to the surface of the aluminum plate in the alkaline electrolyte, and is easy to fall off due to insufficient adhesion, but the zinc oxide and the aluminum plate are easy to fall off after the sodium carboxymethyl cellulose is addedThe obvious synergistic effect is shown between the anode and the cathode, so that the adhesive force and the stability of the protective layer formed on the surface layer of the anode aluminum are improved, and the corrosion inhibition effect is further enhanced; glucose is used as a natural organic carbohydrate, the structure of the glucose contains five hydroxyl groups, and the glucose has higher electronegativity compared with similar organic matters, the addition of the glucose is beneficial to the shedding of the surface of a corrosion product, namely aluminum hydroxide, and the contact area of an anode and a solution is increased, so that the discharge current of the anode is improved; in addition, after the battery reaction is carried out for a period of time (the alkali in the electrolyte is consumed, so that the alkali concentration is reduced), gel is generated in the electrolyte to precipitate aluminum hydroxide Al3++3OH-=Al(OH)3And ↓, potassium acetate and potassium formate can accelerate the precipitation of aluminum hydroxide in the electrolyte, so that the aluminum hydroxide can be easily separated from the electrolyte.
The effect of the present invention in inhibiting anodic self-corrosion reactions is illustrated by the following specific example:
table 1: weight change of anode aluminum after soaking in different electrolytes for different time periods
Table 1 shows the weight change data of the anode aluminum after being soaked in different electrolytes for different periods of time, wherein the soaking area of each aluminum plate is 30cm2And when the aluminum plate is soaked, the weight of the aluminum plate is tested every 2 hours, and the hydrogen evolution self-corrosion condition of 3 parts of anode aluminum (C/D/E-aluminum components are completely the same) in the electrolyte is compared, and the specific description is as follows: M0-M4 are the weights of aluminum plates corresponding to the aluminum plates added with the same 7mol/l KOH electrolyte, three groups of different (including the electrode liquid of the invention) electrolytes are added after M4, and M5 and M6 are the weights of aluminum plates corresponding to the aluminum plates added with the test electrolyte.
FIG. 3 is a graph showing the weight change of the anode aluminum after soaking, which reflects the self-corrosion condition under the alkaline condition. M1-M3 are three groups of aluminum plates which are respectively soaked in alkaline electrolyte with the same concentration, and the weight change of the aluminum plates can clearly show that the self-corrosion of the aluminum is serious; electrolyte C group- (KOH solution + glucose), electrolyte D group- (KOH solution), and electrolyte E group- (electrolyte of the invention) were added to M4, respectively.
As can be seen from the data in Table 1 and FIG. 3, the aluminum plates in the C/D/E group have smaller difference in the stages M0-M3; after the M4 test stage, the weight change of the group D aluminum plates is more than that of the group C aluminum plates, which shows that the addition of glucose plays a part of corrosion inhibition effect on the anode; after the electrolyte is added into the group E, the weight of the aluminum plate of the curve of the group E is obviously found to have an inflection point at the stage of M4, the weight change of the aluminum plate is obviously weakened, and the corrosion rate is obviously reduced, which shows that the electrolyte can effectively improve the hydrogen evolution self-corrosion of the aluminum plate in an alkaline solution, and the electrolyte does not have obvious temperature change in the reaction and does not generate heat.
FIG. 4 is a voltage-current curve of discharge test using the electrolyte of the present invention (current density = 0.045A/cm)2Catalytic layer area =44cm2）。
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and those skilled in the art should understand that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all that should be covered by the claims of the present invention.
Claims (10)
1. The aluminum-air battery electrolyte is characterized by comprising an alkaline electrolyte and a corrosion inhibitor, wherein the corrosion inhibitor comprises glucose and zinc oxide.
2. The aluminum-air cell electrolyte of claim 1, further comprising an additive comprising sodium carboxymethyl cellulose.
3. The aluminum-air cell electrolyte of claim 2 wherein the additives further comprise potassium acetate and potassium formate.
4. The aluminum-air battery electrolyte as claimed in claim 1, wherein the alkaline electrolyte is potassium hydroxide or sodium hydroxide with a concentration of 1-7 mol/L, the concentration of glucose in the corrosion inhibitor is 50-300 g/L, and the concentration of zinc oxide is 0.1-5 g/L.
5. The aluminum-air battery electrolyte according to claim 3, wherein the additive comprises 5-10 g/L of sodium carboxymethyl cellulose, 1-5 g/L of potassium acetate and 1-5 g/L of potassium formate.
6. A method of preparing the aluminium-air battery electrolyte of claim 1, comprising the steps of:
step 1) preparing alkaline solid powder and deionized water for preparing alkaline electrolyte;
step 2) dividing the alkaline solid powder into two parts, wherein one part of the alkaline solid powder is directly dissolved in deionized water, and the other part of the alkaline solid powder is mechanically mixed with glucose and then dissolved in the deionized water;
step 3) when the alkaline solid powder and glucose in the step 2) are completely dissolved in deionized water to form alkaline electrolyte, and when the alkaline electrolyte is cooled to room temperature, zinc oxide is added into the alkaline electrolyte for multiple times;
and 4) finishing the preparation of the electrolyte.
7. The method for preparing an aluminum-air battery electrolyte according to claim 6, wherein in the step 3), after the zinc oxide is added to the alkaline electrolyte for a plurality of times, sodium carboxymethyl cellulose, potassium acetate and potassium formate are added to the alkaline electrolyte respectively.
8. The method for preparing the aluminum-air battery electrolyte according to claim 6, wherein in the step 2), the alkaline solid powder and the glucose are uniformly mixed by grinding for 2-3min, and stirring is continuously performed when the alkaline solid powder and the glucose are dissolved in the deionized water after being uniformly mixed.
9. The method for preparing an aluminum-air battery electrolyte according to claim 6, wherein in the step 3), the zinc oxide is added to the alkaline electrolyte 3 to 5 times.
10. An aluminum-air battery comprising an anode, a cathode and the electrolyte of claim 1, wherein the anode is aluminum metal or aluminum alloy, and the cathode is graphene-coated mesoporous MnO2。
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