CN107275652B - Catalyst, preparation method and zinc-air battery - Google Patents
Catalyst, preparation method and zinc-air battery Download PDFInfo
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- CN107275652B CN107275652B CN201710531820.7A CN201710531820A CN107275652B CN 107275652 B CN107275652 B CN 107275652B CN 201710531820 A CN201710531820 A CN 201710531820A CN 107275652 B CN107275652 B CN 107275652B
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- metal
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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
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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
- 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
Abstract
The present invention relates to a catalyst comprising active particles, a method for producing the catalyst, and a zinc-air battery using the catalyst. The catalyst includes active particles having: a core of metal; and a shell of a metal oxide of the metal.
Description
[ technical field ] A method for producing a semiconductor device
The present invention relates to a catalyst comprising active particles, a method for producing the catalyst, and a zinc-air battery using the catalyst.
[ background of the invention ]
Zinc air battery (zinc air battery), a kind of primary battery using active carbon to adsorb oxygen or pure oxygen in the air as positive active material, zinc as negative electrode, and ammonium chloride or caustic alkali solution as electrolyte. The oxygen electrode of the zinc-air battery has large chemical polarization, and the working voltage of the battery is very low without adding a catalyst, so that the use requirement cannot be met. The catalysts currently used for air electrodes are mainly: noble metals such as platinum and silver, metal chelates and metal oxidesAnd the like. The most noble metal catalyst is a good choice, but the cost is high and the process is complex, so manganese dioxide is generally selected as the catalyst. During discharge, MnO2Mn is generated in the catalytic process2+Ion, electrolyte will form Zn (OH)4 2-Ions thereby to react with Mn2+The ion combination consumes the content of manganese dioxide, the catalyst is reduced, and the catalytic efficiency is lowered, so that the stability of the content of the catalyst is ensured, and the key points of the stability of the discharge voltage of the zinc-air battery and the prolonging of the service life of the battery are realized.
[ summary of the invention ]
The present invention is made to solve the above problems, and provides a catalyst, a method for producing the catalyst, and a zinc-air battery using the catalyst.
One of the objects of the present invention is to provide a catalyst capable of self-replenishing catalyst content, the catalyst comprising active particles having: a core of metal; and a shell of a metal oxide of the metal.
The metal comprises one selected from transition metals of the periodic table.
The metal is one of manganese (Mn), nickel (Ni) and cobalt (Co).
The metal oxide is manganese oxide (MnO)2) Manganomanganic oxide (Mn)3O4) Nickel oxide (NiO), cobalt monoxide (CoO), cobaltic oxide (Co)2O3) Cobaltosic oxide (Co)3O4) Or (2) to (d).
The metal oxide is used as a catalyst, the catalyst is reduced after the metal oxide is consumed, the metal core can be combined with oxygen entering from the anode to form the metal oxide of the core, and the catalyst is automatically supplemented, so that the content of the catalyst is ensured, and the discharge voltage of the battery is stable.
The second object of the present invention is to provide a method for preparing the catalyst, comprising the steps of:
s1, preparing a sealed space and vacuumizing the sealed space until the vacuum degree reaches 10-3pa, placing the metal wire in a closed space;
s2, introducing protective gas into the closed space, heating the metal wire until the metal wire is boiled, and evaporating to form nano-scale metal particles;
s3, introducing oxygen into the closed space, reacting the oxygen with the metal on the surface of the nano metal particles to form a shell of metal oxide at a high temperature, and protecting the metal on the inner layer from contacting with the oxygen by the metal oxide to form a metal core;
s4, continuously introducing protective gas and oxygen into the closed space, continuously discharging gas with the same volume, keeping the air pressure in the closed space consistent, taking oxidized metal particles on the surface layer away by using the airflow formed by introducing the discharged gas, and filtering the oxidized metal particles on the surface layer with overlarge particle size by using a screen mesh;
and S5, collecting the metal particles oxidized on the surface layer passing through the screen mesh, and cooling the metal particles to obtain the catalyst.
The protective gas in step S2 is He and N2Or a mixture of both.
In step S2, a protective gas is introduced to maintain the pressure in the sealed space at 50Kpa to 110 Kpa.
The partial pressure ratio of the oxygen introduced in the step S3 to the protective gas introduced in the step S2 is 0.5-20: 100; and step S4, continuously introducing protective gas and oxygen into the closed space, wherein the partial pressure ratio of the oxygen to the protective gas is 0.5-20: 100.
In step S5, the mesh size of the screen mesh is 5000 meshes-1000 meshes, and the cooling time is 10-60 minutes.
The amount of oxygen introduced in the preparation method cannot be too high, which can result in too thick surface oxide of metal particles and too low metal content, and possibly cause insufficient supplement of metal oxide in the later period. The amount of the introduced oxygen cannot be too low, the oxygen content is too low, the surface layer of the metal particles is possibly incompletely oxidized, and a stable metal oxide protective layer cannot be formed.
The invention also aims to provide a zinc-air battery which adopts the catalyst for catalysis.
The present invention is to provide a catalyst comprising a shell of metal oxide and a core of metal, wherein the core of metal oxide can react with oxygen introduced from the positive electrode to form new metal oxide to supplement the content of catalyst by itself after the metal oxide is consumed in the discharge process, thereby stabilizing the discharge voltage. In addition, the invention provides a preparation method of the catalyst, evaporated metal particles react with oxygen at a high temperature to form a surface metal oxide shell with a stable structure, and the metal oxide shell protects the inner metal from contacting with the oxygen to form a metal core. The protective gas has the function of diffusing metal particles in the whole closed space and does not react with metal in a high-temperature state. Finally, the invention provides a zinc-air battery, which adopts the catalyst.
[ description of the drawings ]
FIG. 1 is a 20 nm TEM image of a Mn/Mn oxide catalyst with a core-shell structure.
FIG. 2 is a transmission electron microscope image of 50 nm manganese/manganese oxide catalyst with core-shell structure.
Fig. 3 is a comparison diagram of the 500mA discharge curve of the zinc-air battery of the invention and the conventional zinc-air battery.
[ detailed description ] embodiments
The following examples are further illustrative and supplementary to the present invention and do not limit the present invention in any way.
Example 1
As shown in fig. 3, the zinc-air battery of the present invention has a 500mA discharge curve, compared with the conventional zinc-air battery, and it can be seen that the discharge voltage of the conventional zinc-air battery is reduced earlier and the discharge time is shorter. The key reason is that the new catalyst is adopted in the embodiment, the transmission electron microscope image of the catalyst is shown as figures 1 and 2, the catalyst comprises active particles, and the active particles have the following characteristics: a core of metal; and a shell of a metal oxide of the metal. Wherein the metal comprises one selected from transition metals of the periodic Table, e.g. the metal core of the catalyst is manganese (Mn), and the manganese oxide (MnO) is coated outside the manganese (Mn) core2) Or trimanganese tetroxide (Mn)3O4) (ii) a The metal core of the catalyst is nickel (Ni), and then the nickel (Ni) is wrapped in the metal coreNickel oxide (NiO) is arranged outside the nickel (Ni) core; the metal core of the catalyst is cobalt (Co), and then the cobalt (Co) core is wrapped by cobalt monoxide (CoO) and cobaltous oxide (Co)2O3) Or cobaltosic oxide (Co)3O4) One or more of (a). The metal oxide has a catalytic effect, and in the reaction process of the battery, the metal oxide can react with the electrolyte, so that the content of the oxide is reduced, the catalytic effect is weakened, and the discharge voltage of the battery is reduced. In this embodiment, after the core-shell structure metal oxide reacts with the electrolyte, the metal core reacts with oxygen entering from the anode to form a new metal oxide, so that the catalyst is automatically supplemented, and the discharge voltage and the service life of the battery are ensured.
Example 2
In this embodiment, a preparation method of a catalyst is provided, which includes the following steps:
s1, preparing a sealed space and vacuumizing the sealed space until the vacuum degree reaches 10-3pa, placing the metal wire in a closed space;
s2, introducing protective gas into the closed space, heating the metal wire until the metal wire is boiled, and evaporating to form nano-scale metal particles;
s3, introducing oxygen into the closed space, reacting the oxygen with the metal on the surface of the nano metal particles to form a shell of metal oxide at a high temperature, and protecting the metal on the inner layer from contacting with the oxygen by the metal oxide to form a metal core;
s4, continuously introducing protective gas and oxygen into the closed space, continuously discharging gas with the same volume, keeping the air pressure in the closed space consistent, taking oxidized metal particles on the surface layer away by using the airflow formed by introducing the discharged gas, and filtering the oxidized metal particles on the surface layer with overlarge particle size by using a screen mesh;
and S5, collecting the metal particles oxidized on the surface layer passing through the screen mesh, and cooling the metal particles to obtain the catalyst.
The protective gas does not react with the metal particles formed by evaporation at high temperature, and after oxygen is introduced, metal oxide is formed. However, the amount of the introduced oxygen cannot be too high, which causes the surface oxide of the metal particles to be too thick, and the metal content to be too low, which may cause the metal oxide supplement amount to be insufficient in the later period. The amount of the introduced oxygen cannot be too low, the oxygen content is too low, the surface layer of the metal particles is possibly incompletely oxidized, and a stable metal oxide protective layer cannot be formed. The amount of oxygen introduced is therefore determined by the partial pressure ratio of oxygen to protective gas. The partial pressure ratio of oxygen to protective gas is 0.5: 100, 1: 100, 2: 100, 3: 100, 4: 100, 5: 100, 10: 100, 12: 100, 15: 100, 18: 100, 20: 100. The partial pressure ratio of oxygen to shielding gas can be adjusted to control the thickness of the metal oxide.
Example 3
This example was completed based on example 2, in which hydrogen or nitrogen was used as the protective gas, and in step S2, the protective gas was introduced so that the pressure in the sealed space was maintained at 50Kpa, 60Kpa, 70Kpa, 80Kpa, 90Kpa, 100Kpa, and 110 Kpa. In step S5, the mesh size of the screen mesh is 5000 meshes-1000 meshes, and the cooling time is 10-60 minutes.
Although the present invention has been described with reference to the above embodiments, the scope of the present invention is not limited thereto, and modifications, substitutions and the like of the above members are intended to fall within the scope of the claims of the present invention without departing from the spirit of the present invention.
Claims (4)
1. Zinc-air battery comprising a positive electrode, a negative electrode of gelled calamine cream, and a catalyst comprising active particles, characterized in that: the active particles have: the preparation method of the catalyst comprises the following steps:
s1, preparing a sealed space and vacuumizing the sealed space until the vacuum degree reaches 10-3pa, placing the metal wire in a closed space;
s2, introducing protective gas into the closed space, heating the metal wire until the metal wire is boiled, and evaporating to form nano-scale metal particles;
s3, introducing oxygen into the closed space, reacting the oxygen with the metal on the surface of the nano-scale metal particles to form a shell of metal oxide at a high temperature, protecting the metal on the inner layer from contacting with the oxygen by the metal oxide to form a metal core, and introducing the oxygen and the protective gas in the step S2 at a partial pressure ratio of 0.5-20: 100;
s4, continuously introducing protective gas and oxygen into the closed space, continuously discharging gas with the same volume, keeping the air pressure in the closed space consistent, taking oxidized metal particles on the surface layer away by using the air flow formed by introducing the discharged gas, and filtering the oxidized metal particles on the surface layer with overlarge particle size by using a screen, wherein the partial pressure ratio of the oxygen to the protective gas is 0.5-20: 100;
s5, collecting the oxidized metal particles passing through the surface layer of the screen, and cooling the metal particles to obtain the catalyst, wherein the mesh size of the screen is 5000-10000 meshes, and the cooling time is 10-60 minutes.
2. The zinc-air battery of claim 1, wherein: the metal oxide is manganese dioxide (MnO)2) Or trimanganese tetroxide (Mn)3O4)。
3. The zinc-air battery of claim 1, wherein: the protective gas in step S2 is He and N2Or a mixture of both.
4. The zinc-air battery of claim 1, wherein: in step S2, a protective gas is introduced to maintain the pressure in the sealed space at 50Kpa to 110 Kpa.
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