CN106654292B - Air electrode, air electrode preparation method and aluminum-air battery - Google Patents
Air electrode, air electrode preparation method and aluminum-air battery Download PDFInfo
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- CN106654292B CN106654292B CN201611185216.5A CN201611185216A CN106654292B CN 106654292 B CN106654292 B CN 106654292B CN 201611185216 A CN201611185216 A CN 201611185216A CN 106654292 B CN106654292 B CN 106654292B
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
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- H—ELECTRICITY
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- 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
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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Abstract
The invention provides an air electrode, an air electrode preparation method and an aluminum-air battery. The air electrode includes: a diffusion layer; the catalyst layer is arranged on one side of the diffusion layer and comprises carbon nanotubes and a catalyst, and the catalyst layer does not contain a binder; and the current collecting layer is arranged between the diffusion layer and the catalyst layer or arranged on one side of the catalyst layer far away from the diffusion layer. The catalyst layer of the air electrode adopts the carbon nano tube with higher electrochemical activity and specific surface area, and avoids introducing a binder into the catalyst layer, so the air electrode has at least one of the advantages of higher catalytic activity, stable electrochemical performance, simple preparation, good electrode conductivity and the like.
Description
Technical Field
The invention relates to the field of materials, in particular to an air electrode, an air electrode preparation method and an aluminum-air battery.
Background
The air battery is one of chemical batteries, and utilizes oxygen in the air as an oxidant to perform chemical reaction to form one pole of the battery, and the metal electrode is the other pole of the battery to convert chemical energy into electric energy to realize energy supply. The current air batteries mainly include lithium air batteries, zinc air batteries and aluminum air batteries. The air battery realizes an important step of energy conversion, namely, oxygen in the air is reduced by utilizing an air electrode. Therefore, the electrochemical performance and stability of the air electrode are referred to as a stress factor affecting the performance of the air battery cell.
However, the current air electrode and the method for manufacturing the same still remain to be improved.
Disclosure of Invention
The present application is based on the discovery and recognition by the inventors of the following facts and problems:
The problems of complex preparation process, and non-ideal electrochemical performance and catalytic performance generally exist in the conventional air electrode. Since the air electrode needs to reduce oxygen in the air, the air electrode generally has a catalyst layer on which a catalyst is supported to lower the reduction potential of oxygen. In addition, the air electrode is required to have not only good electrochemical properties but also good gas diffusion properties at the surface of the electrode so that air (oxygen) can easily contact the catalyst layer. Therefore, in the conventional air electrode, it is generally necessary to perform processes such as rolling and kneading on an electrode material such as a catalyst for many times, or repeatedly coat the electrode material on the surface of a structure such as a current collector and a diffusion layer, and then perform a molding process to prepare the air electrode. In addition, since most of the catalyst material is a powder material, it is necessary to mix a binder and the catalyst material and repeatedly roll them to form the catalyst layer or to bond the catalyst layer to another structure of the electrode when preparing the catalyst layer of the air electrode. The binder material is usually an insulator, so that the actual catalytic performance of the air electrode cannot reach the catalytic performance of the catalyst material itself, and the overall electrical performance of the electrode will be negatively affected.
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art.
In a first aspect of the invention, an air electrode is presented. According to an embodiment of the present invention, the air electrode includes: a diffusion layer; the catalyst layer is arranged on one side of the diffusion layer and comprises carbon nanotubes and a catalyst, and the catalyst layer does not contain a binder; and the current collecting layer is arranged between the diffusion layer and the catalyst layer or arranged on one side of the catalyst layer far away from the diffusion layer. The catalyst layer of the air electrode adopts the carbon nano tube with higher electrochemical activity and specific surface area, and avoids introducing a binder into the catalyst layer, so the air electrode has at least one of the advantages of higher catalytic activity, stable electrochemical performance, simple preparation, good electrode conductivity and the like.
According to the embodiment of the invention, in the catalyst layer, the length-diameter ratio of the carbon nano tube is 500: 1-3000: 1. The inventors have intensively studied and have found through a large number of experiments that when carbon nanotubes having an aspect ratio within the above range are used, a catalyst layer can be formed by, for example, a simple roll forming process without introducing a binder.
According to an embodiment of the present invention, the catalyst layer includes carbon nanopaper formed by subjecting carbon nanotubes to a roll forming process at one time. Therefore, the preparation process of the air electrode can be simplified, the production cost is reduced, and the popularization of the air electrode is facilitated.
according to an embodiment of the present invention, the carbon nanotubes are pre-loaded with the catalyst on the surface thereof before the one-time roll-forming process. This can increase the amount of catalyst supported by the catalyst layer and the uniformity of catalyst support, thereby further improving the electrode performance of the air electrode.
In a second aspect of the invention, the invention proposes a method of preparing an air electrode as described above. According to an embodiment of the invention, the method comprises: (1) preparing a catalyst layer, wherein the catalyst layer comprises carbon nanotubes and a catalyst, and the catalyst layer does not contain a binder; and (2) carrying out pressing treatment on the catalyst layer, the diffusion layer and the current collecting layer so as to obtain the air electrode. The method has the advantages of simple operation steps, short preparation period and low production cost, and is beneficial to popularization and application of the air electrode.
according to an embodiment of the present invention, the step (1) further comprises: carrying out one-time rolling forming treatment on the carbon nano tube so as to form carbon nano paper; and supporting the catalyst on the carbon nanopaper to obtain the catalyst layer.
According to an embodiment of the present invention, the step (1) further comprises: performing one-time roll forming treatment on the carbon nanotubes previously loaded with the catalyst to obtain the catalyst layer. This can further improve the uniformity of the catalyst loading, and is advantageous for further improving the electrode performance of the air electrode obtained.
according to an embodiment of the present invention, the one-time roll forming process is implemented by the following steps: mixing the carbon nano tube with ethanol and a dispersing agent to obtain a mixed solution, sequentially performing suction filtration and drying treatment on the mixed solution, and performing rolling treatment on a solid obtained by the drying treatment. This can further improve the effect of the one-time roll forming treatment.
In a third aspect of the invention, a method of making an air electrode is provided. According to an embodiment of the invention, the method comprises: (1) mixing a carbon nanotube and ethanol according to a liquid-solid ratio of 3:1-10:1, adding a manganese nitrate solution into a mixed solution of the carbon nanotube and the ethanol according to a mass ratio of manganese nitrate to the carbon nanotube of 1: 5-2: 1, adding distilled water according to a mass ratio of distilled water to the ethanol of 1: 10-1: 5, and performing ultrasonic dispersion for 5-30 min to obtain a dispersion liquid, wherein the length-diameter ratio of the carbon nanotube is 500: 1-3000: 1; (2) standing and aging the dispersion liquid for 1-10h at room temperature; (3) drying the aged dispersion liquid at the temperature of 50-100 ℃ so as to obtain a catalyst solid raw material, wherein the drying time is 2-5 h; (4) and (2) loading the solid catalyst raw material into a closed atmosphere furnace for roasting treatment, wherein the roasting treatment is carried out at the temperature of 200-500 ℃ in the atmosphere of inert gas, and the roasting time is 2-10 h. Grinding the roasted catalyst solid raw material to obtain a powdery catalyst material; (5) mixing and stirring the powdery catalyst material and ethanol according to a liquid-solid ratio of 3:1-10:1, and then adding a dispersing agent to stir and disperse for 10-60 min. The mass ratio of the dispersing agent to the powdery catalyst material is 0.1-1.0%; (6) sequentially carrying out suction filtration, drying and rolling treatment on the mixture obtained in the step (5) to obtain a catalyst layer; (7) and pressing the catalyst layer, the diffusion layer and the current collecting layer under a tablet press to obtain the air electrode, wherein the pressing pressure is 5-30MPa, and the pressing time is 30-300 s. The method has the advantages of simple operation steps, short preparation period and low production cost, and is beneficial to popularization and application of the air electrode.
In a fourth aspect of the present invention, an aluminum-air battery is presented. According to an embodiment of the present invention, the aluminum-air battery includes: a body defining a reaction space therein; the air electrode described above; and an anode disposed inside the body and electrically connected with the air electrode. The air battery has at least one of the advantages of low cost, simple and convenient electrode preparation, excellent battery performance and the like.
Drawings
FIG. 1 shows a schematic structural diagram of an air electrode according to an embodiment of the present invention;
FIG. 2 shows a schematic structural view of an air electrode according to another embodiment of the present invention;
Fig. 3 shows a schematic structural view of an aluminum-air battery according to an embodiment of the present invention; and
Fig. 4 shows a schematic structural view of an aluminum-air battery according to another embodiment of the present invention;
Reference numerals:
10: catalyst layer
20: diffusion layer
30: current collecting layer
100: body
200: air electrode
300: anode
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In a first aspect of the invention, an air electrode is presented. According to an embodiment of the present invention, referring to fig. 1, the air electrode includes: catalyst layer 10, diffusion layer 20, and collector layer 30. The catalyst layer 10 is disposed on one side of the diffusion layer 20, and includes carbon nanotubes and a catalyst and does not contain a binder. The current collecting layer 30 is provided on the side of the catalyst layer 10 remote from the diffusion layer 20, or, referring to fig. 2, the current collecting layer 30 is provided between the catalyst layer 10 and the diffusion layer 20. The inventor finds through intensive research and a large number of experiments that the catalyst layer of the air electrode adopts the carbon nano tube with higher electrochemical activity and specific surface area, and the binder is prevented from being introduced into the catalyst layer, so that the air electrode has at least one of the advantages of higher catalytic activity, stable electrochemical performance, simple preparation, good electrode conductivity and the like.
since this air electrode is used to generate a chemical reaction by using oxygen in the air, it is necessary to ensure that the diffusion layer 20 can contact the air in actual use. That is, the diffusion layer 20 of the air electrode needs to be disposed outside the air electrode, and cannot be disposed between the current collecting layer 30 and the catalyst layer 10. The specific types of the diffusion layer 20 and the collector layer 30 are not particularly limited, and those skilled in the art can form the collector layer and the diffusion layer by using a familiar air electrode collector material and diffusion layer material.
According to the embodiment of the invention, in the catalyst layer 10, the aspect ratio of the carbon nano tube used is 500: 1-3000: 1. The inventors have intensively studied and have found through a large number of experiments that when carbon nanotubes having an aspect ratio within the above range are used, a catalyst layer can be formed by, for example, a simple roll forming process without introducing a binder. The inventors of the present invention have conducted extensive studies and found that one of the main reasons why the conventional air electrode needs to be repeatedly subjected to roll forming several times during the production process is that the catalyst material of the catalyst layer is often a powder material having no stickiness. Therefore, the catalyst layer material and the binder are mixed, and are subjected to rolling treatment for multiple times, so that the binder and the catalyst material are sufficiently mixed, and are subjected to compression molding. The above process is complicated in operation steps and not suitable for mass production, and since most of the binder materials are electronic insulators, the introduction of the binder has a negative effect on the electrode performance of the finally formed air electrode. When the carbon nanotubes with the length-diameter ratio of 500: 1-3000: 1 are used as the main material of the catalyst layer, the carbon nanotubes with the length-diameter ratio have certain adsorption capacity and are easy to agglomerate and entangle, and the carbon nanopaper with the network structure and formed by the carbon nanotubes can be formed through simple one-time rolling treatment. The carbon nano tube has good conductivity and catalytic performance and large specific surface area, so the carbon nano paper has good conductivity and catalyst adsorption performance, and is suitable for preparing a catalyst layer in an air electrode. The inventors have found through a large number of experiments that in order to realize the formation of carbon nanopaper using carbon nanotubes by a simple processing method such as one-time roll forming, the aspect ratio of the carbon nanotubes needs to be controlled. When the length-diameter ratio of the carbon nano tube is too small, a network structure which is entangled with each other is difficult to form through one-time rolling forming, so that the prepared carbon nano paper has poor forming effect, and the conductivity and the uniformity are difficult to guarantee. When the length-diameter ratio of the carbon nanotube is too large, the cost of raw materials for preparing the air electrode is greatly increased, and because the length of the carbon nanotube is too long, a large amount of dispersing agent needs to be introduced to ensure that the carbon nanotube can be uniformly dispersed before roll forming, so that the electrical performance of the finally formed air electrode is also influenced.
According to an embodiment of the present invention, in order to further improve the electrode performance of the air electrode, the carbon nanotubes may be loaded with a catalyst on the surface of the carbon nanotubes before the primary roll forming process is performed. This can increase the amount of catalyst supported by the catalyst layer and the uniformity of catalyst support, thereby further improving the electrode performance of the air electrode. According to an embodiment of the present invention, the catalyst may be a catalyst commonly used in an air battery, and for example, may be a metal or a metal oxide. According to a specific embodiment of the present invention, the catalyst may be an oxide of a metal element having a catalytic function, such as Mn element. Thus, the carbon nanotubes and the water-soluble salt solution of the metal are mixed and aged in a simple manner, and a metal oxide formed by oxidizing the metal element is formed on the surface of the carbon nanotubes by a simple baking treatment, thereby realizing the loading of the catalyst. The carbon nanotubes loaded with the catalyst are subjected to one-time roll forming treatment, so that the catalyst layer according to the embodiment of the invention can be obtained.
In a second aspect of the invention, the invention proposes a method of preparing an air electrode as described above. According to an embodiment of the invention, the method comprises:
preparation of the catalyst layer
According to the embodiment of the present invention, in this step, the catalyst layer is formed using the carbon nanotubes and the catalyst preparation, and no binder is introduced in the process of preparing the catalyst layer. According to the specific embodiment of the present invention, in this step, carbon nano-paper is formed by a roll forming process using carbon nano-tubes having a certain aspect ratio. The catalyst can be formed by loading the catalyst on the carbon nano paper after the carbon nano paper is formed; alternatively, the catalyst layer may be formed by loading the catalyst on the carbon nanotubes in advance before the carbon nanopaper is roll-formed, and then performing a roll-forming process once. This can further improve the uniformity of the catalyst loading, and is advantageous for further improving the electrode performance of the air electrode obtained.
As described above, the inventors have found through a large number of experiments that the aspect ratio of the carbon nanotube has an important influence on the treatment effect of the one-time roll forming treatment. When the carbon nanotubes with the length-diameter ratio of 500: 1-3000: 1 are used as the main material of the catalyst layer, the carbon nanotubes with the length-diameter ratio have certain adsorption capacity and are easy to agglomerate and entangle, and the carbon nanopaper with the network structure and formed by the carbon nanotubes can be formed through simple one-time rolling treatment. The carbon nano tube has good conductivity and catalytic performance and large specific surface area, so the carbon nano paper has good conductivity and catalyst adsorption performance, and is suitable for preparing a catalyst layer in an air electrode.
According to the specific embodiment of the invention, the one-time roll forming process is realized by the following steps: first, carbon nanotubes are mixed with ethanol and a dispersant to obtain a mixed solution. And carrying out suction filtration treatment on the mixed solution, and keeping filter residues subjected to suction filtration and drying. Subsequently, the solid obtained after the drying treatment is subjected to a rolling treatment. This can further improve the effect of the one-time roll forming treatment. The carbon nano tube has better dispersibility in the ethanol solution, and the ethanol has smaller molecular weight, can be removed by subsequent drying treatment, and cannot influence the performance of the catalyst layer due to the residue of the solvent. The dispersing agent can be a carbon nanotube dispersing agent commonly used in the field, so that the carbon nanotubes can be prevented from being unevenly dispersed in the solution or being locally agglomerated, and the carbon nanotubes are prevented from being unevenly distributed in the catalyst layer formed after the rolling treatment. For example, polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, or the like can be used. As can be understood by those skilled in the art, the catalyst may be supported on the carbon nanopaper after the carbon nanotubes are subjected to the above-mentioned one-time roll forming process to form the carbon nanopaper; alternatively, the catalyst may be loaded on the surface of the carbon nanotube first, and then the above-mentioned one-time roll forming treatment may be performed, so as to realize the preparation of the catalyst layer.
According to a specific embodiment of the present invention, the catalyst layer may be prepared by: the carbon nano tube and ethanol are mixed according to the liquid-solid ratio of 3:1-10:1, and then roasting treatment is carried out, so that the loading of a catalyst (metal oxide) on the surface of the carbon nano tube can be realized. When the solid-to-liquid ratio of the carbon nanotubes to the ethanol solution is within the range, the content of the carbon nanotubes in the formed mixed solution is moderate, the effect of roll forming is not influenced due to the low content of the carbon nanotubes, and a large amount of dispersing agent is not required to be introduced to prevent the carbon nanotubes from aggregating due to the high content of the carbon nanotubes. And then, adding a metal salt solution for forming the catalyst into the mixed solution, for example, adding a manganese nitrate solution into the mixed solution, wherein the mass ratio of the manganese nitrate to the carbon nano tubes in the added solution can be 1: 5-2: 1. The inventor finds out through a large number of experiments that when the mass of the manganese nitrate is too small, the loading amount of the manganese oxide catalyst is not ideal, and the finally formed air electrode cannot obtain good catalytic performance; when the mass of the added manganese nitrate is too large, too much metal oxide is generated, so that the forming effect of the roll forming treatment is influenced, and the electrical property of the air electrode is greatly reduced. In order to further improve the efficiency and effect of catalyst loading, a certain amount of distilled water can be added for dispersion. For example, distilled water can be added according to the mass ratio of the distilled water to the ethanol of 1:10 to 1:5, and ultrasonic dispersion is carried out for 5 to 30min, so as to obtain a dispersion liquid. And standing and aging the dispersion liquid for 1-10h at room temperature, and drying at 50-100 ℃ to obtain the catalyst solid raw material. The drying time can be 2-5 h. And roasting and grinding the solid catalyst raw material to obtain the powdery catalyst material. The roasting treatment can be carried out in a closed space of inert atmosphere, the roasting temperature can be 200-500 ℃, and the roasting time is 2-10 h. And then mixing and stirring the powdery catalyst material and ethanol according to a liquid-solid ratio of 3:1-10:1, adding a dispersing agent, stirring and dispersing, wherein the mass ratio of the dispersing agent to the powdery catalyst material can be 0.1-1.0%, and dispersing (such as ultrasonic dispersion) for 10-60 min. Subsequently, the treatment is performed in accordance with the operation steps of the one-time roll forming treatment described above, and the catalyst layer can be obtained simply.
Laminating treatment
According to an embodiment of the present invention, in this step, the catalyst layer prepared previously is subjected to a press-fitting treatment with the diffusion layer and the current collecting layer so as to obtain the air electrode. The method has the advantages of simple operation steps, short preparation period and low production cost, and is beneficial to popularization and application of the air electrode. According to the embodiment of the present invention, the specific operation parameters of the press-fitting process are not particularly limited as long as the three-layer structure (catalyst layer, diffusion layer, and current collecting layer) described above can be stacked and press-fitted in accordance with the structure of the air electrode described above. According to the specific embodiment of the invention, a tablet press can be adopted to carry out pressing treatment under the condition of 5-30MPa, and the pressing time can be 30-300 seconds.
in a third aspect of the invention, a method of making an air electrode is provided. According to an embodiment of the invention, the method comprises:
(1) Mixing the carbon nano tube and ethanol according to a liquid-solid ratio of 3:1-10:1, and adding a manganese nitrate solution into a mixed solution of the carbon nano tube and the ethanol according to a mass ratio of the manganese nitrate to the carbon nano tube of 1: 5-2: 1. Adding distilled water according to the mass ratio of the distilled water to the ethanol of 1: 10-1: 5, and performing ultrasonic dispersion for 5-30 min to obtain a dispersion liquid. Wherein the length-diameter ratio of the carbon nano tube is 500: 1-3000: 1
(2) standing and aging the dispersion liquid for 1-10h at room temperature.
(3) and drying the aged dispersion liquid at the temperature of 50-100 ℃ so as to obtain the catalyst solid raw material. The drying time is 2-5 h.
(4) the solid raw material of the catalyst is put into a closed atmosphere furnace for roasting treatment, the roasting treatment is carried out in the atmosphere of inert gas (nitrogen or argon) at the temperature of 200-500 ℃, and the roasting time is 2-10 h. Grinding the calcined catalyst solid raw material to obtain the powdery catalyst material.
(5) mixing and stirring the powdery catalyst material and ethanol according to a liquid-solid ratio of 3:1-10:1, and then adding a dispersing agent to stir and disperse for 10-60 min. The mass ratio of the dispersing agent to the powdery catalyst material is 0.1-1.0%.
(6) and sequentially carrying out suction filtration, drying and rolling treatment on the mixture to obtain the catalyst layer.
(7) and pressing the catalyst layer, the diffusion layer and the current collecting layer under a tablet press, wherein the pressing pressure is 5-30MPa, and the pressing time is 30-300 s. Thereby, an air electrode can be obtained. The method has the advantages of simple operation steps, short preparation period and low production cost, and is beneficial to popularization and application of the air electrode.
in a fourth aspect of the present invention, an aluminum-air battery is presented. According to an embodiment of the present invention, referring to fig. 3, the aluminum-air battery includes: a body 100, an air electrode 200, and an anode 300, wherein the body 100 defines a reaction space therein, the air electrode 200 is the air electrode described above, the air electrode 200 is disposed inside the body 100, and a diffusion layer (not shown) in the air electrode 200 is in contact with air; the anode 300 is disposed inside the body 100 and electrically connected to the air electrode 200. The air battery has at least one of the advantages of low cost, simple and convenient electrode preparation, excellent battery performance and the like.
It should be noted that the arrangement of the electrodes (the air electrode 200 and the anode 300) shown in fig. 3 is only exemplary, and should not be construed as limiting the present invention. According to the embodiment of the present invention, the air electrode 200 and the anode 300 are disposed inside the body 100, electrically connected to each other to form a conductive loop, and the diffusion layer of the air electrode 200 may be in contact with air to react with oxygen. The specific arrangement and positions of the air electrode 200 and the anode 300 are not particularly limited. For example, referring to fig. 4, the air electrode 200 and the anode 300 may also be vertically disposed inside the body 100, and the diffusion layer of the air electrode 200 is disposed at the sidewall of the body 100 so as to contact the air.
The present invention is illustrated below by way of specific examples, which are intended to be illustrative only and not to limit the scope of the present invention in any way, and unless otherwise specified, conditions or steps not specifically recited are generally conventional and reagents and materials used therein may be commercially available.
Example 1
(1) Mixing ethanol and the carbon nano tube according to the liquid-solid ratio of 10:1, and adding a manganese nitrate solution into the mixed liquid of the carbon nano tube and the ethanol according to the mass ratio of the manganese nitrate to the carbon nano tube of 2: 5. Adding distilled water according to the mass ratio of distilled water to ethanol of 1:5, and ultrasonically dispersing for 30min to obtain dispersion. Wherein the length-diameter ratio of the carbon nano tube is 3000:1
(2) And standing and aging the dispersion liquid for 10 hours at room temperature.
(3) And drying the aged dispersion liquid at the temperature of 70 ℃ so as to obtain the catalyst solid raw material. The drying time is 5 h.
(4) And (3) putting the solid catalyst raw material into a closed atmosphere furnace for roasting treatment, wherein the roasting treatment is carried out at the temperature of 300 ℃ in the nitrogen atmosphere, and the roasting time is 10 hours. Grinding the calcined catalyst solid raw material to obtain the powdery catalyst material.
(5) Mixing and stirring the powdery catalyst material and ethanol according to a liquid-solid ratio of 10:1, and then adding polyethylene glycol as a dispersing agent to stir and disperse for 60 min. The mass ratio of the dispersant to the powdery catalyst material was 1.0%.
(6) And sequentially carrying out suction filtration, drying and rolling treatment on the mixture to obtain the catalyst layer.
(7) And pressing the catalyst layer, the diffusion layer and the current collecting layer under a tablet press, wherein the pressing pressure is 30MPa, and the pressing time is 30 s. Thereby, an air electrode can be obtained.
(8) The air electrode is assembled into an aluminum-air battery according to the structure shown in fig. 3 to perform a discharge performance test, the aluminum plate adopts high-purity aluminum with the content of 99.99%, the electrolyte adopts 6mol/L KOH solution, and the test is performed at normal temperature, and the discharge power density can reach 400mW/cm 2.
Example 2
(1) Mixing ethanol and the carbon nano tube according to the liquid-solid ratio of 5:1, and adding a manganese nitrate solution into the mixed liquid of the carbon nano tube and the ethanol according to the mass ratio of the manganese nitrate to the carbon nano tube of 1: 5. Adding distilled water according to the mass ratio of the distilled water to the ethanol of 2:5, and performing ultrasonic dispersion for 10min to obtain a dispersion liquid. Wherein the length-diameter ratio of the carbon nano tube is 500:1
(2) And standing and aging the dispersion liquid for 2 hours at room temperature.
(3) And drying the aged dispersion liquid at the temperature of 100 ℃ so as to obtain the catalyst solid raw material. The drying time is 3 h.
(4) And (3) putting the solid catalyst raw material into a closed atmosphere furnace for roasting treatment, wherein the roasting treatment is carried out at the temperature of 500 ℃ in the argon atmosphere, and the roasting time is 2 hours. Grinding the calcined catalyst solid raw material to obtain the powdery catalyst material.
(5) mixing and stirring the powdery catalyst material and ethanol according to a liquid-solid ratio of 5:1, and then adding polyvinylpyrrolidone as a dispersing agent to stir and disperse for 30 min. The mass ratio of the dispersant to the powdery catalyst material was 0.1%.
(6) And sequentially carrying out suction filtration, drying and rolling treatment on the mixture to obtain the catalyst layer.
(7) And pressing the catalyst layer, the diffusion layer and the current collecting layer under a tablet press, wherein the pressing pressure is 15MPa, and the pressing time is 300 s. Thereby, an air electrode can be obtained.
(8) The air electrode is assembled into an aluminum-air battery according to the structure shown in fig. 4 to perform a discharge performance test, the aluminum plate adopts high-purity aluminum with the content of 99.99%, the electrolyte adopts 6mol/L KOH solution, and the test is performed at normal temperature, and the discharge power density can reach 300mW/cm 2.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (2)
1. A method of making an air electrode, comprising:
(1) Mixing a carbon nanotube and ethanol according to a liquid-solid ratio of 3:1-10:1, adding a manganese nitrate solution into a mixed solution of the carbon nanotube and the ethanol according to a mass ratio of manganese nitrate to the carbon nanotube of 1: 5-2: 1, adding distilled water according to a mass ratio of distilled water to the ethanol of 1: 10-1: 5, and performing ultrasonic dispersion for 5-30 min to obtain a dispersion liquid, wherein the length-diameter ratio of the carbon nanotube is 500: 1-3000: 1;
(2) standing and aging the dispersion liquid for 1-10h at room temperature;
(3) Drying the aged dispersion liquid at the temperature of 50-100 ℃ so as to obtain a catalyst solid raw material, wherein the drying time is 2-5 h;
(4) Loading the solid catalyst raw material into a closed atmosphere furnace for roasting treatment, wherein the roasting treatment is carried out in an inert gas atmosphere at the temperature of 200-500 ℃, the roasting time is 2-10h, and the solid catalyst raw material subjected to roasting treatment is ground so as to obtain a powdery catalyst material;
(5) Mixing and stirring the powdery catalyst material and ethanol according to a liquid-solid ratio of 3:1-10:1, then adding a dispersing agent, stirring and dispersing for 10-60min, wherein the mass ratio of the dispersing agent to the powdery catalyst material is 0.1-1.0%;
(6) sequentially carrying out suction filtration, drying and rolling treatment on the mixture obtained in the step (5) to obtain a catalyst layer;
(7) And pressing the catalyst layer, the diffusion layer and the current collecting layer under a tablet press to obtain the air electrode, wherein the pressing pressure is 5-30MPa, and the pressing time is 30-300 s.
2. an aluminum-air battery, comprising:
A body defining a reaction space therein;
An air electrode made by the method of claim 1; and
An anode disposed inside the body and electrically connected with the air electrode.
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| CN102439783B (en) * | 2009-04-30 | 2017-09-08 | 佛罗里达大学研究基金会公司 | Air cathode based on single-walled carbon nanotube |
| CN104716331B (en) * | 2013-12-15 | 2017-12-15 | 中国科学院大连化学物理研究所 | A kind of zinc-air battery air cathode |
| CN104505520B (en) * | 2014-12-06 | 2017-07-04 | 云南冶金集团创能金属燃料电池股份有限公司 | Aluminium-air cell air electrode and preparation method thereof |
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