CN111834639B - Composite catalyst for cathode of metal-air battery and preparation method thereof - Google Patents

Composite catalyst for cathode of metal-air battery and preparation method thereof Download PDF

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CN111834639B
CN111834639B CN202010743455.8A CN202010743455A CN111834639B CN 111834639 B CN111834639 B CN 111834639B CN 202010743455 A CN202010743455 A CN 202010743455A CN 111834639 B CN111834639 B CN 111834639B
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CN111834639A (en
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胡俊华
武智昊
曹国钦
徐恩霞
师昊森
班锦锦
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Zhengzhou 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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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Abstract

The invention provides a composite catalyst for a cathode of a metal-air battery and a preparation method thereof. The method provided by the invention can realize nitrogen atom doping and MnO loading on the carbon material through two-step heat treatment, the experimental raw materials are easy to obtain, the preparation process is simple, and the experimental result shows that the oxygen reduction catalytic activity of the prepared composite material is greatly enhanced, and the catalyst has high stability, thereby having great significance for the development of commercial metal-air battery cathode catalysts.

Description

Composite catalyst for cathode of metal-air battery and preparation method thereof
Technical Field
The invention relates to the field of metal-air battery cathode catalysts, in particular to a composite catalyst for a metal-air battery cathode and a preparation method thereof.
Background
The rapid development of electronic devices places higher performance demands on batteries. The fuel cell can directly convert chemical energy in fuel into electric energy under the action of an oxidant, and has high energy utilization efficiency. The fuel required in the electrochemical reaction can be continuously supplied or rapidly supplemented, and the fixed capacity limit of the traditional battery is removed. Metallic materials can release a large amount of energy during oxidation compared to other cell fuels. On the basis of inheriting the advantages, the metal air fuel cell combines the high energy density of the material with the infinite storage of oxygen in the air, can effectively improve the theoretical energy density of the cell, and is one of ideal solutions of high-performance cells.
The catalyst for the cathode of the metal-air battery is usually a manganese oxide, a perovskite, a noble metal, a conductive carbon material, a composite of the above materials, or the like. Wherein, the commercial Vulcan-72XC conductive carbon black has the advantages of low price, easily obtained raw materials and 254m specific surface area compared with graphene, fullerene and carbon nano tube2The carbon material has larger/g, is more suitable to be used as a catalyst substrate, and is an ideal carbon material for large-scale production of catalysts in factories.
The nitrogen-doped carbon material loaded oxide is one of the fields of metal air battery cathode catalyst research, and has received great attention in recent years, the metal oxide is introduced into the nitrogen-doped carbon material, so that the catalytic performance of the carbon material can be improved, and at present, the reports about the introduction of the metal oxide into the nitrogen-doped carbon material are more numerous, but the method for preparing the composite catalyst disclosed at present is complex in process and high in preparation cost, cannot meet large-scale production, and cannot meet the use requirements of commercial metal air batteries. Therefore, the composite catalyst which is simple in preparation process and excellent in performance is provided, and the composite catalyst has important significance for the development of commercial metal-air batteries.
Disclosure of Invention
The invention provides a composite catalyst for a cathode of a metal-air battery and a preparation method thereof.
The technical scheme for realizing the invention is as follows:
a composite catalyst for a cathode of a metal-air battery is prepared by taking conductive carbon black and a carbon nano tube as raw materials and utilizing a two-step heat treatment method to prepare a nitrogen-doped C/carbon nano tube/MnO composite catalyst, wherein nitrogen doping enables surface defects of the carbon material to be increased, MnO-loaded active sites to be increased, and the catalytic activity of the catalyst is improved by the nitrogen-doped C/carbon nano tube/MnO composite catalyst.
The preparation method of the composite catalyst for the cathode of the metal-air battery comprises the following steps:
(1) mixing a carbon source and the carbon nano tube, adding absolute ethyl alcohol, stirring, performing ultrasonic treatment, and drying to obtain a V-CNT mixture;
(2) mixing the V-CNT mixture obtained in the step (1) with a nitrogen source, adding absolute ethyl alcohol, stirring, performing ultrasonic treatment, and drying to obtain a V-CNT-N mixture;
(3) sintering the V-CNT-N mixture obtained in the step (2) in a tube furnace under the condition of nitrogen to obtain a nitrogen-doped C/carbon nanotube material;
(4) mixing the nitrogen-doped C/carbon nanotube material obtained in the step (3) with a manganese source compound, adding absolute ethyl alcohol, stirring, performing ultrasonic treatment, and drying to obtain a mixture named as V-CNT-N-Mn;
(5) and (4) placing the V-CNT-N-Mn obtained in the step (4) in a tube furnace, and heating and sintering under the condition of nitrogen to obtain the nitrogen-doped C/carbon nano tube/MnO composite catalyst.
In the step (1), the carbon source is conductive carbon black Vulcan-72XC, and the mass ratio of the carbon source to the carbon nano tubes is (4-9): 1.
In the step (2), the nitrogen source is urea or melamine, and the mass ratio of the V-CNT mixture to the nitrogen source is 1: (2-4).
In the step (3), the heating rate is 5 ℃/min, and the temperature is increased to 550-600 ℃ and is kept for 3-5 h.
In the step (4), the mass ratio of the nitrogen-doped C/carbon nanotube material to the manganese source compound is (1-2) to 1, and the manganese source compound is manganese acetate tetrahydrate.
In the step (5), the heating rate is 5 ℃/min, and the temperature is increased to 250-300 ℃ and is kept for 3-5 h.
The invention has the beneficial effects that: the method provided by the invention can realize nitrogen atom doping and MnO loading on the carbon material through two-step heat treatment, the experimental raw materials are easy to obtain, the preparation process is simple, and the experimental result shows that the oxygen reduction catalytic activity of the prepared composite material is greatly enhanced, and the catalyst has high stability, thereby having great significance for the development of commercial metal-air battery cathode catalysts.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an XRD pattern of a nitrogen-doped Vulcan-72 XC/carbon nanotube/MnO composite catalyst prepared by an example of the present invention;
FIG. 2 is an ORR chart of nitrogen-doped Vulcan-72 XC/carbon nanotube/MnO composite catalyst prepared by the example of the invention at different rotating speeds;
FIG. 3 is an XRD pattern of the nitrogen-doped Vulcan-72 XC/carbon nanotube catalyst prepared in comparative example 1;
FIG. 4 is an ORR plot of the nitrogen-doped Vulcan-72 XC/carbon nanotube catalyst prepared in comparative example 1 at different rotation speeds;
FIG. 5 is a graph of nitrogen-doped Vulcan-72 XC/carbon nanotubes/Mn prepared in comparative example 23O4XRD pattern of (a);
FIG. 6 is a graph of nitrogen-doped Vulcan-72 XC/carbon nanotubes/Mn prepared in comparative example 23O4ORR plots at different rotational speeds;
FIG. 7 is a graph of nitrogen-doped Vulcan-72XC/Mn prepared in comparative example 33O4ORR plots at different rotational speeds;
FIG. 8 is a graph comparing ORR at 1600rpm for catalysts prepared in examples and comparative examples 1, 2, and 3;
FIG. 9 is an XRD pattern of nitrogen doped Super P/MnO prepared in comparative example 4;
FIG. 10 is an ORR plot of nitrogen doped Super P/MnO prepared in comparative example 4 at different rotation speeds;
FIG. 11 is a graph comparing ORR at 1600rpm for the catalysts prepared in example 1 and comparative example 4.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
0.2g of Vulcan-72XC and 0.05g of carbon nanotubes (mass ratio 4: 1) were weighed, added to absolute ethanol, stirred, sonicated, dried, and the mixture named V-CNT. 0.25g V-CNT and 1g urea (mass ratio 1: 4) were weighed, added to absolute ethanol, stirred, sonicated, dried, and the mixture was named V-CNT-N. And then putting the dried V-CNT-N into a tube furnace, heating to 600 ℃ at the heating rate of 5 ℃/min under the condition of nitrogen, and preserving the heat for 3 h. And finally, grinding and drying the reaction product to obtain a final product, namely the nitrogen-doped Vulcan-72 XC/carbon nanotube material which is named as V-CNT-N-600 ℃.
0.5g V-CNT-N-600 ℃ and 0.5g manganese acetate tetrahydrate (mass ratio 1: 1) were weighed, and both were added to absolute ethanol, stirred, sonicated, and dried. The dried mixture was then placed in a tube furnace and heated to 280 ℃ at a rate of 5 ℃/min under nitrogen for 3 h. And finally, grinding and drying the reaction product to obtain a final product, namely the nitrogen-doped Vulcan-72 XC/carbon nano tube/MnO composite catalyst.
XRD detection was performed on the composite catalyst obtained in example 1, and the result is shown in FIG. 1. As can be seen from the figure, the manganese oxide supported by the catalyst prepared by the invention is MnO. FIG. 2 is the electrochemical data of example 1 of the present invention, and ORR test data shows that the composite catalyst obtained in example 1 has better stability, the initial potential is 0.85V at 1600rpm, the half-wave potential is 0.65V, and the limiting current density is 7.8 mA-cm-2. FIG. 8 is the electrochemical data of the catalysts prepared in example 1 of the present invention and comparative examples 1, 2 and 3 at 1600rpm, and ORR test data shows that the composite obtained in example 1 has better performance of oxygen reduction catalyst: higher initial potential and half-wave potential, larger limiting current density, can meet the requirement of commercial goldBelongs to the use of air batteries.
Example 2
0.45g of Vulcan-72XC and 0.05g of carbon nanotubes (mass ratio 9: 1) were weighed, added to absolute ethanol, stirred, sonicated, dried, and the mixture named V-CNT. 0.25g V-CNT and 1g urea (mass ratio 1: 4) were weighed, added to absolute ethanol, stirred, sonicated, dried, and the mixture was named V-CNT-N. And then putting the dried V-CNT-N into a tube furnace, heating to 550 ℃ at the heating rate of 5 ℃/min under the condition of nitrogen, and preserving the heat for 5 h. And finally, grinding and drying the reaction product to obtain a final product, namely the nitrogen-doped Vulcan-72 XC/carbon nanotube material which is named as V-CNT-N-550 ℃.
0.5g V-CNT-N-550 ℃ and 0.25g manganese acetate tetrahydrate (mass ratio: 2: 1) were weighed, and both were added to absolute ethanol, stirred, sonicated, and dried. The dried mixture was then placed in a tube furnace and heated to 300 ℃ at a rate of 5 ℃/min under nitrogen for 5 h. And finally, grinding and drying the reaction product to obtain a final product, namely the nitrogen-doped Vulcan-72 XC/carbon nano tube/MnO composite catalyst.
XRD detection is carried out on the composite catalyst obtained in the example 2, and the supported manganese oxide is MnO. The electrochemical experiment result shows that the composite catalyst has better stability, the initial potential is 0.81V at 1600rpm, the half-wave potential is 0.6V, and the limiting current density is 7.5 mA-cm-2。
Example 3
0.45g of Vulcan-72XC and 0.05g of carbon nanotubes (mass ratio 9: 1) were weighed, added to absolute ethanol, stirred, sonicated, dried, and the mixture named V-CNT. 0.25g V-CNT and 0.75g melamine (mass ratio 1: 3) were weighed, added to absolute ethanol, stirred, sonicated, dried, and the mixture was named V-CNT-N. And then putting the dried V-CNT-N into a tube furnace, and heating to 580 ℃ at the heating rate of 5 ℃/min under the condition of nitrogen and preserving the heat for 4 h. And finally, grinding and drying the reaction product to obtain a final product, namely the nitrogen-doped Vulcan-72 XC/carbon nanotube material which is named as V-CNT-N-580 ℃.
0.5g V-CNT-N-550 ℃ and 0.5g manganese acetate tetrahydrate (mass ratio: 1) were weighed, and both were added to absolute ethanol, stirred, sonicated, and dried. The dried mixture was then placed in a tube furnace and heated to 250 ℃ at a ramp rate of 5 ℃/min under nitrogen for 4 h. And finally, grinding and drying the reaction product to obtain a final product, namely the nitrogen-doped Vulcan-72 XC/carbon nano tube/MnO composite catalyst.
XRD detection is carried out on the composite catalyst obtained in the example 3, and the supported manganese oxide is MnO. The electrochemical experiment result shows that the composite catalyst has better stability, the initial potential is 0.79V at 1600rpm, the half-wave potential is 0.6V, and the limiting current density is 7.1 mA-cm-2。
Example 4
0.25g of Vulcan-72XC and 0.05g of carbon nanotubes (mass ratio 5: 1) were weighed, added to absolute ethanol, stirred, sonicated, dried, and the mixture was named V-CNT. 0.2g V-CNT and 0.4g urea (mass ratio 1: 2) were weighed, added to absolute ethanol, stirred, sonicated, dried, and the mixture was named V-CNT-N. And then putting the dried V-CNT-N into a tube furnace, heating to 550 ℃ at the heating rate of 5 ℃/min under the condition of nitrogen, and preserving the heat for 5 h. And finally, grinding and drying the reaction product to obtain a final product, namely the nitrogen-doped Vulcan-72 XC/carbon nanotube material which is named as V-CNT-N-550 ℃.
0.24g V-CNT-N-600 ℃ and 0.16g manganese acetate tetrahydrate (mass ratio: 1.5: 1) were weighed, and both were added to absolute ethanol, stirred, sonicated, and dried. The dried mixture was then placed in a tube furnace and heated to 300 ℃ at a rate of 5 ℃/min under nitrogen for 5 h. And finally, grinding and drying the reaction product to obtain a final product, namely the nitrogen-doped Vulcan-72 XC/carbon nano tube/MnO composite catalyst.
XRD detection is carried out on the composite catalyst obtained in the example 4, and the supported manganese oxide is MnO. The electrochemical experiment result shows that the composite catalyst has better stability, the initial potential is 0.81V at 1600rpm, the half-wave potential is 0.63V, and the limiting current density is 7.5 mA-cm-2。
Example 5
0.2g of Vulcan-72XC and 0.05g of carbon nanotubes (mass ratio 4: 1) were weighed, added to absolute ethanol, stirred, sonicated, dried, and the mixture named V-CNT. 0.25g V-CNT and 1g melamine (mass ratio 1: 4) were weighed, added to absolute ethanol, stirred, sonicated, dried, and the mixture was named V-CNT-N. And then putting the dried V-CNT-N into a tube furnace, heating to 600 ℃ at the heating rate of 5 ℃/min under the condition of nitrogen, and preserving the heat for 4 h. And finally, grinding and drying the reaction product to obtain a final product, namely the nitrogen-doped Vulcan-72 XC/carbon nanotube material which is named as V-CNT-N-600 ℃.
0.25g V-CNT-N-550 ℃ and 0.25g manganese acetate tetrahydrate (mass ratio: 1) were weighed, and both were added to absolute ethanol, stirred, sonicated, and dried. The dried mixture was then placed in a tube furnace and heated to 250 ℃ at a ramp rate of 5 ℃/min under nitrogen for 4 h. And finally, grinding and drying the reaction product to obtain a final product, namely the nitrogen-doped Vulcan-72 XC/carbon nano tube/MnO composite catalyst.
XRD detection is carried out on the composite catalyst obtained in example 5, and the supported manganese oxide is MnO. The electrochemical experiment result shows that the composite catalyst has better stability, the initial potential is 0.8V at 1600rpm, the half-wave potential is 0.61V, and the limiting current density is 7.3 mA-cm-2。
Comparative example 1
0.2g of Vulcan-72XC and 0.05g of carbon nanotubes (mass ratio 4: 1) were weighed, added to absolute ethanol, stirred, sonicated, dried, and the mixture named V-CNT. 0.25g of mixed V-CNT and 1g of urea (mass ratio: 1: 4) were weighed, and the mixture was added to absolute ethanol, stirred, sonicated, dried, and named as V-CNT-N. The dried mixture V-CNT-N is then placed in a tube furnace and heated to 600 ℃ at a heating rate of 5 ℃/min for 3h under nitrogen. And finally, grinding and drying the reaction product to obtain a final product, namely the nitrogen-doped Vulcan-72 XC/carbon nanotube material. (the mass ratio of the materials, the heat preservation temperature and the heat preservation time in the comparative example 1 are the same as those in the example 1).
XRD examination of the resulting material was carried out, and the result is shown in fig. 3, showing amorphous carbon black. FIG. 4 shows electrochemical data of comparative example 1, with an initial potential of 0.78V at 1600rpm, a half-wave potential of 0.65V, and a limiting current density of 6.5mA cm-2. FIG. 8 is a drawing of the present inventionElectrochemical data of the catalysts prepared in example 1 and comparative examples 1, 2 and 3 at the rotating speed of 1600rpm can show that the catalyst prepared in example 1 has higher initial potential and half-wave potential and larger limiting current density compared with the catalyst prepared in comparative example 1 through a disc electrode test, which shows that the manganese oxide MnO loaded in example 1 has improved catalytic performance.
Comparative example 2
0.2g of Vulcan-72XC and 0.05g of carbon nanotubes (mass ratio 4: 1) were weighed, added to absolute ethanol, stirred, sonicated, dried, and the mixture named V-CNT. 0.25g of mixed V-CNT and 1g of urea (mass ratio: 1: 4) are weighed, added to absolute ethyl alcohol and stirred, subjected to ultrasonic treatment and dried, and the obtained mixture is named as V-CNT-N. The dried mixture V-CNT-N is then placed in a tube furnace and heated to 600 ℃ at a heating rate of 5 ℃/min for 3h under nitrogen. And finally, grinding and drying the reaction product to obtain a final product, namely the nitrogen-doped Vulcan-72 XC/carbon nanotube material which is named as V-CNT-N-600 ℃.
Weighing 0.5g of nitrogen-doped Vulcan-72XC material and 0.5g of manganese acetate tetrahydrate (mass ratio is 1: 1), adding the two into absolute ethyl alcohol, stirring, carrying out ultrasonic treatment, drying, and naming the obtained mixture as V-CNT-N-600-Mn. And then putting the dried mixture V-CNT-N-600-Mn into a muffle furnace, heating to 280 ℃ at the heating rate of 5 ℃/min under the air condition, and preserving the heat for 3 h. Finally grinding and drying the reaction product to obtain the final product, namely the nitrogen-doped Vulcan-72 XC/carbon nano tube/Mn3O4And (3) compounding a catalyst. (comparative example 2 wherein the material mass ratio, the holding temperature and the holding time were the same as those in example 1.)
XRD was carried out on the obtained material, and the result was shown in FIG. 5. As can be seen from the figure, the manganese oxide supported by the prepared catalyst is Mn3O4. FIG. 6 shows electrochemical data of comparative example 2, in which the initial potential at 1600rpm was 0.8V, the half-wave potential was 0.62V, and the limiting current density was 7.2mA cm-2. FIG. 8 is the electrochemical data of the catalysts prepared in example 1 of the present invention and comparative examples 1, 2 and 3 at 1600rpm, and it can be seen from the disk electrode test that example 1 has higher initial potential and half-value than comparative example 2Wave potential, greater limiting current density, illustrates the catalytic activity of MnO loaded in example 1 versus Mn loaded in comparative example 23O4And higher.
Comparative example 3
0.25g of Vulcan-72XC and 1g of urea (mass ratio is 1: 4) are weighed, added into absolute ethyl alcohol and stirred, ultrasonically treated and dried, and the mixture is named as V-N. And then putting the dried mixture V-N into a tube furnace, heating to 600 ℃ at the heating rate of 5 ℃/min under the condition of nitrogen, and preserving heat for 3 h. And finally grinding and drying the reaction product to obtain a final product, namely the nitrogen-doped Vulcan-72XC material which is named as V-N-600 ℃.
Weighing 0.5g of nitrogen-doped Vulcan-72XC material and 0.5g of manganese acetate tetrahydrate (mass ratio is 1: 1), adding the two into absolute ethyl alcohol, stirring, performing ultrasonic treatment, drying, and naming the obtained mixture as V-N-600-Mn. And then putting the dried mixture V-N-600-Mn into a muffle furnace, heating to 280 ℃ at the heating rate of 5 ℃/min under the air condition, and preserving the heat for 3 h. Finally grinding and drying the reaction product to obtain the final product, namely the nitrogen-doped Vulcan-72XC/Mn3O4And (3) compounding a catalyst. (in comparative example 3, the mass ratio of the materials, the holding temperature and the holding time were the same as in example 1.)
FIG. 7 shows electrochemical data of comparative example 3, with an initial potential of 0.75V at 1600rpm, a half-wave potential of 0.6V, and a limiting current density of 6.5mA cm-2. Fig. 8 is electrochemical data of the catalysts prepared in example 1 and comparative examples 1, 2 and 3 of the present invention at 1600rpm, and it can be seen from the disk electrode test that example 1 has higher initial potential and half-wave potential and larger limiting current density than comparative example 3, which illustrates that the doped carbon nanotubes in example 1 and supported MnO can improve catalytic performance.
Comparative example 4
Super P conductive carbon black, although having a specific surface area (62 m) compared with that of Vulcan-72XC2/g) is relatively low, but its discharge capacity is high, and thus it is widely used in a cathode catalyst for a lithium air battery. Possibly because of the large active specific surface area or the ability of the interstitial spaces to store large quantities of discharge products. In this comparative example, Super P was used as the baseThe base carbon material is preferably Super P produced with ultra-dense Swiss.
0.2g of Super P and 0.05g of carbon nanotubes (mass ratio 4: 1) were weighed, and the both were added to absolute ethanol and stirred, sonicated, dried, and the mixture was named S-CNT. 0.25g of mixed S-CNT and 1g of urea (mass ratio 1: 4) are weighed, added into absolute ethyl alcohol and stirred, subjected to ultrasonic treatment and dried, and the obtained mixture is named S-CNT-N. The dried mixture S-CNT-N is then placed in a tube furnace and heated to 600 ℃ at a heating rate of 5 ℃/min for 3h under nitrogen. And finally grinding and drying the reaction product to obtain a final product, namely the nitrogen-doped Super P material, which is named as S-CNT-N-600 ℃.
Weighing 0.5g of nitrogen-doped Super P material and 0.5g of manganese acetate tetrahydrate (mass ratio is 1: 1), adding the two into absolute ethyl alcohol, stirring, carrying out ultrasonic treatment, drying, and naming the obtained mixture as S-CNT-N-600-Mn. And then putting the dried S-CNT-N-600-Mn into a tube furnace, heating to 280 ℃ at the heating rate of 5 ℃/min under the condition of nitrogen, and preserving heat for 3 h. And finally, grinding and drying the reaction product to obtain a final product, namely the nitrogen-doped Super P/carbon nano tube/MnO composite catalyst. (comparative example 4 wherein the material mass ratio, the holding temperature and the holding time were the same as those in example 1.)
XRD detection was performed on the obtained composite material, and the result is shown in FIG. 9. As can be seen from the figure, the manganese oxide supported by the catalyst prepared by the invention is MnO. FIG. 10 is the electrochemical data of comparative example 4 of the present invention, having an initial potential of 0.8V at 1600rpm, a half-wave potential of 0.62V, and a limiting current density of 7.6mA cm-2. Fig. 11 is electrochemical data of the catalysts prepared in example 1 and comparative example 4 of the present invention at 1600rpm, and it can be seen from the disk electrode test that example 1 has higher initial potential and half-wave potential and larger current density than comparative example 4. Both have the same process flow, indicating that the Vulcan-72XC used in example 1 is more suitable as catalyst base carbon material than the Super P used in comparative example 4.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (3)

1. A composite catalyst for a cathode of a metal-air battery, characterized in that: the preparation method of the composite catalyst for the cathode of the metal-air battery comprises the following steps:
(1) mixing a carbon source and carbon nano tubes, adding absolute ethyl alcohol, stirring, performing ultrasonic treatment and drying to obtain a V-CNT mixture, wherein the carbon source is conductive carbon black Vulcan-72XC, and the mass ratio of the carbon source to the carbon nano tubes is (4-9): 1;
(2) mixing the V-CNT mixture obtained in the step (1) with a nitrogen source, adding absolute ethyl alcohol, stirring, performing ultrasonic treatment, and drying to obtain a V-CNT-N mixture, wherein the nitrogen source is urea or melamine, and the mass ratio of the V-CNT mixture to the nitrogen source is 1: (2-4);
(3) sintering the V-CNT-N mixture obtained in the step (2) in a tubular furnace under the condition of nitrogen at the sintering temperature of 550-600 ℃ to obtain a nitrogen-doped C/carbon nanotube material;
(4) mixing the nitrogen-doped C/carbon nanotube material obtained in the step (3) with a manganese source compound, adding absolute ethyl alcohol, stirring, performing ultrasonic treatment and drying to obtain a mixture named as V-CNT-N-Mn, wherein the mass ratio of the nitrogen-doped C/carbon nanotube material to the manganese source compound is (1-2): 1, and the manganese source compound is manganese acetate tetrahydrate;
(5) and (3) placing the V-CNT-N-Mn obtained in the step (4) in a tube furnace, heating and sintering under the condition of nitrogen, wherein the sintering temperature is 250-300 ℃, and thus obtaining the nitrogen-doped C/carbon nano tube/MnO composite catalyst.
2. The composite catalyst for a metal-air battery cathode according to claim 1, characterized in that: in the step (3), the heating rate is 5 ℃/min, and the temperature is increased to 550-600 ℃ and is kept for 3-5 h.
3. The composite catalyst for a metal-air battery cathode according to claim 1, characterized in that: in the step (5), the heating rate is 5 ℃/min, and the temperature is increased to 250-300 ℃ and is kept for 3-5 h.
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