CN103872348A - catalyst, electrode and preparation method thereof - Google Patents

Abstract

A catalyst, an electrode and a preparation method thereof. The catalyst includes a metal oxide, including a first metal and a second metal. The metal oxide has a single-phase perovskite structure. The electrode includes a metal mesh and a catalyst. The catalyst is loaded on the metal mesh, and the catalyst includes a single-phase metal oxide with a perovskite structure. The electrode preparation method includes the following steps. A first metal and a second metal are provided. The first metal and the second metal are mixed in a solution containing a three-block copolymer surfactant. A metal mesh is provided. Place the metal mesh into the solution. Heating the solution and the metal mesh causes the first metal and the second metal to react with the metal mesh to form a catalyst, so that the catalyst and the metal mesh form an electrode.

Description

Catalyst, electrode and preparation method thereof

technical field

The invention relates to a catalyst, in particular to an electrode made of the catalyst and a preparation method thereof.

Background technique

In recent years, with the development of electric vehicles and in order to meet the needs of future power grids and electric energy storage, secondary batteries have become a hot research topic. Generally speaking, in order to improve the efficiency of the secondary battery, a common method is to improve the catalyst of the secondary battery. For example, increasing the specific surface area of the catalyst is a problem that researchers need to solve. In addition, in the process of preparing the catalyst, other impurity phases that do not have catalytic performance are often formed. These impurity phases will reduce the surface area where the catalyst can react, thereby reducing the efficiency of the catalyst, resulting in secondary battery power supply voltage, drop in supply current. At present, the main method is to reduce the formation of impurity phases by controlling the composition ratio of the catalyst, but such an operation method is cumbersome and the effect is not ideal.

Therefore, how to design a catalyst and electrode to reduce the generation of impurity phases during the preparation of the catalyst and reduce the performance of the battery has become a problem that researchers need to solve.

Contents of the invention

In view of the above problems, the object of the present invention is to provide a catalyst, an electrode and a preparation method thereof, so as to reduce the problem of generating impurity phases during the preparation of the catalyst and lowering the efficiency of the resulting battery.

The catalyst disclosed in an embodiment of the present invention includes a metal oxide, the metal oxide includes a first metal and a second metal, and the metal oxide has a single-phase perovskite structure.

A method for preparing an electrode disclosed in an embodiment of the present invention includes the following steps. A first metal and a second metal are provided. The first metal and the second metal are mixed in a solution containing a triblock copolymer surfactant. A metal mesh is provided. A metal mesh is placed in the solution. Heating the solution and the metal net makes the first metal and the second metal react in the metal net to form a catalyst, so that the catalyst and the metal net form an electrode.

An electrode disclosed in an embodiment of the present invention includes a metal mesh and a catalyst. The catalyst is loaded on the metal mesh. The catalyst includes a single-phase perovskite metal oxide, and the metal oxide includes a first metal and a second metal.

According to the catalyst, electrode and preparation method disclosed in the embodiments of the present invention, since the three-block copolymer surfactant is added in the process of preparing the electrode, the prepared catalyst has a single-phase perovskite structure, thus solving the problem of In the process of preparing the catalyst, the problem of impurity will be generated. Therefore, it is avoided that the impurity phase reduces the surface area available for the catalyst to react, thereby reducing the efficiency of the battery made with the catalyst.

The present invention will be described in detail below in conjunction with the accompanying drawings and specific embodiments, but not as a limitation of the present invention.

Description of drawings

FIG. 1 is a flow chart of a method for preparing a catalyst disclosed in an embodiment of the present invention;

Fig. 2A is the X-ray diffraction analysis result of the catalyst powder of comparative example one;

Fig. 2B is the X-ray diffraction analysis result of the catalyst powder of embodiment two, embodiment five, comparative example one, comparative example two;

Fig. 2 C is the X-ray diffraction analysis result of the catalyst powder of embodiment one to embodiment four;

Fig. 2D is the X-ray diffraction analysis result of the catalyst powder of embodiment two, the catalyst powder of embodiment six and the catalyst powder of embodiment seven;

Fig. 3 A is the analysis result of the scanning electron microscope of the catalytic powder of comparative example 1;

Fig. 3B is the analysis result of the scanning electron microscope of the catalytic powder of embodiment one;

Fig. 3 C is the analysis result of the scanning electron microscope of the catalytic powder of embodiment two;

Fig. 3D is the analysis result of the scanning electron microscope of the catalytic powder of embodiment three;

Fig. 3 E is the analysis result of the scanning electron microscope of the catalytic powder of embodiment four;

Fig. 3 F is the analysis result of the scanning electron microscope of the catalytic powder of embodiment five;

Fig. 3G is the analysis result of the scanning electron microscope of the catalytic powder of embodiment six;

Fig. 3H is the analysis result of the scanning electron microscope of the catalytic powder of embodiment seven;

Fig. 3I is the analysis result of the scanning electron microscope of the catalytic powder of comparative example two;

Fig. 4 is the X-ray diffraction analysis result of the catalyst powder of comparative example three, the catalyst powder of embodiment eight and the catalyst powder of embodiment nine;

Fig. 5A is the analysis result of the scanning electron microscope of the catalytic powder of comparative example 3;

Fig. 5B is the analysis result of the scanning electron microscope of the catalytic powder of embodiment eight;

Fig. 5 C is the analysis result of the scanning electron microscope of the catalytic powder of embodiment 9;

Fig. 6 is the relationship diagram of the voltage and time of zinc-air battery discharge;

FIG. 7 is a flowchart of a method for preparing an electrode disclosed in an embodiment of the present invention;

Fig. 8 A is the X-ray diffraction analysis result of nickel foam material;

Fig. 8B is the X-ray diffraction analysis result of the electrode of the eleventh embodiment;

Fig. 9 A is the analysis result of the scanning electron microscope of nickel foam;

Fig. 9B is the analysis result of the scanning electron microscope of the electrode of embodiment ten;

Fig. 9C is the analysis result of the scanning electron microscope of the electrode of the eleventh embodiment;

FIG. 10 is a schematic diagram of an improved air battery disclosed by an embodiment of the present invention.

Among them, reference signs

100 batteries

110 hydrophobic layer

120 catalyst layer

130 electrolyte layer

140 metal layers

Detailed ways

The detailed features and advantages of the present invention are described in detail below in the embodiments, the content of which is sufficient to enable any person skilled in the art to understand the technical content of the present invention and implement it accordingly, and according to the content disclosed in this specification, the scope of claims and the accompanying drawings , any person skilled in the art can easily understand the related objects and advantages of the present invention. The following examples further illustrate the concept of the present invention in detail, but do not limit the scope of the present invention in any way.

First, please refer to FIG. 1 . FIG. 1 is a flowchart of a catalyst preparation method disclosed in an embodiment of the present invention.

First, a three-block copolymer surfactant is provided (step S101 ). In the embodiment of the present invention, a three-block copolymer surfactant of ethyleneoxy-propyleneoxy-ethyleneoxy is used, such as P123, the molecular formula is HO(CH ₂ CH ₂ O) ₂₀ (CH ₂ CH(CH ₃ )O) ₇₀ (CH ₂ CH ₂ O) ₂₀ H triblock copolymer surfactant, or F127, the molecular formula is HO(CH ₂ CH ₂ O) ₁₀₆ (CH ₂ CH(CH ₃ )O) ₇₀ ( Triblock copolymer surfactant of CH ₂ CH ₂ O) ₁₀₆ H. In addition, the three-block copolymer surfactant can be uniformly dissolved in the solution by stirring with a stirring bar, for example.

Next, a first metal and a second metal are provided (step S102 ) as metals used in the catalyst for catalysis. In the embodiment of the present invention, the first metal is lanthanum, and the second metal is manganese, iron, cobaltous or nickelous. Wherein, in order to make the first metal and the second metal form a catalyst with a perovskite structure, the content ratio of the first metal and the second metal is approximately 1 to 1, so as to satisfy the _simple formula ABO of the perovskite structure (A is the first metal, B is the second metal) in the ratio of the first metal to the second metal.

Wherein, the molar ratio of the first metal to the three-block copolymer surfactant is between 100:1 and 10:1, and the molar ratio of the second metal to the three-block copolymer surfactant It is between 100:1 and 10:1. In one embodiment, the molar ratio of the first metal to the triblock copolymer surfactant is between 100:1 and 25:1, and the molar ratio of the second metal to the triblock copolymer surfactant is The molar ratio is between 100:1 and 25:1.

Then, the first metal and the second metal are added into the three-block copolymer surfactant, and mixed uniformly to form a solution (step S103 ).

Finally, the solution is heated to make the first metal, the second metal and the three-block copolymer surfactant react to form a catalyst (step S104 ). Specifically, the solution was first heated to 100°C and maintained for 30 minutes, then heated to 450°C and maintained for 1 hour to remove the three-block copolymer surfactant, and finally the solution was heated to 600°C and maintained for 2 hours, the solution is reacted with the catalyst powder disclosed in the embodiment of the present invention, and the catalyst powder has a single-phase perovskite structure. Here, a single phase means that the catalyst powder has a single crystal phase. In the embodiment of the present invention, the form of the catalyst is powder, and in the following description, catalyst powder will be used as an example for illustration. However, the powdered catalyst is not intended to limit the present invention.

The main components of the catalyst include metal oxides of the first metal and the second metal. The metal oxide has a single-phase perovskite structure and a high specific surface area due to the addition of a three-block copolymer surfactant during the preparation of the catalyst.

In the following, several comparative examples and examples will be used to illustrate and verify the catalyst prepared by the present invention, wherein the listed % represents the ratio of the surfactant to the first metal (such as lanthanum).

Comparative example 1 (LaCoO ₃ / no three-block copolymer surfactant)

Lanthanum nitrate [La(NO ₃ ) ₃ ˙6H ₂ O], cobaltous nitrate [Co(NO ₃ ) ₂ ˙6H ₂ O] and citric acid [C ₆ H ₈ H ₇ ˙6H ₂ O], and add deionized water, so that the concentration of lanthanum ion and cobaltous ion in the aqueous solution is 0.35M.

Pour the solution into a crucible and place it in a high-temperature furnace for heating, heating from room temperature to 100°C at a rate of 3°C per minute and maintaining it for 30 minutes, then heating the solution to 450°C and maintaining it for 1 hour, and then heating the solution to 600°C and maintained for 2 hours, and finally the solution was cooled to room temperature. The solution reacts to become the catalyst powder of Comparative Example 1.

Example 1 (LaCoO ₃ /1%P123)

First, dissolve P123 in 20 mL of deionized water, add 0.417 g of glacial acetic acid as a catalyst, and stir for 1 hour with a stirring bar, so that P123 is uniformly dissolved in water to form a 0.0035 M aqueous solution of P123 (step S101). Among them, the molar ratio of P123, deionized water and glacial acetic acid is 0.01:320:1.

Next, lanthanum nitrate [La(NO ₃ ) ₃ ˙6H ₂ O], cobaltous nitrate [Co(NO ₃ ) ₂ ˙6H ₂ O] and citric acid [C ₆ H ₈ H ₇ ˙6H ₂ O] (step S102 ), and adding deionized water, so that the concentration of lanthanum ion and cobaltous ion in the aqueous solution is 0.35M.

Then, slowly drop the aqueous solution containing lanthanum ions and cobaltous ions into the aqueous solution containing P123 (step S103 ), and keep stirring for 2 hours. Among them, the molar ratio of lanthanum nitrate, cobaltous nitrate, citric acid, glacial acetic acid, deionized water, and P123 is 1:1:1:1:320:0.01, and the solution is a clear pink solution.

Finally, pour the solution into a crucible and place it in a high-temperature furnace for heating (step S104), heating from room temperature to 100°C at a rate of 3°C per minute and maintaining it for 30 minutes, then heating the solution to 450°C and maintaining it for 1 hour , and then the solution was heated to 600 ° C and maintained for 2 hours, and finally the solution was cooled to room temperature. The solution reacts to become the catalyst powder disclosed in Embodiment 1 of the present invention.

Example 2 (LaCoO ₃ /2%P123)

First, dissolve P123 in 20 mL of deionized water, add 0.417 g of glacial acetic acid as a catalyst, and stir for 1 hour with a stirring bar, so that P123 is uniformly dissolved in water to form a 0.007 M P123 solution (step S101). Among them, the molar ratio of P123, deionized water and glacial acetic acid is 0.02:320:1.

Next, lanthanum nitrate [La(NO ₃ ) ₃ ˙6H ₂ O], cobaltous nitrate [Co(NO ₃ ) ₂ ˙6H ₂ O] and citric acid [C ₆ H ₈ H ₇ ˙6H ₂ O] (step S102 ), and adding deionized water, so that the concentration of lanthanum ion and cobaltous ion in the aqueous solution is 0.35M.

Then, slowly drop the aqueous solution containing lanthanum ions and cobaltous ions into the aqueous solution containing P123 (step S103 ), and keep stirring for 2 hours. Among them, the molar ratio of lanthanum nitrate, cobaltous nitrate, citric acid, glacial acetic acid, deionized water, and P123 is 1:1:1:1:320:0.02, and the solution is a clear pink solution.

Finally, pour the solution into a crucible and place it in a high-temperature furnace for heating (step S104), heating from room temperature to 100°C at a rate of 3°C per minute and maintaining it for 30 minutes, then heating the solution to 450°C and maintaining it for 1 hour , and then the solution was heated to 600 ° C and maintained for 2 hours, and finally the solution was cooled to room temperature. The solution reacts to become the catalyst powder disclosed in the second embodiment of the present invention.

Example 3 (LaCoO ₃ /4%P123)

First, dissolve P123 in 20 mL of deionized water, add 0.417 g of glacial acetic acid as a catalyst, and stir with a stirring bar for 1 hour, so that P123 is uniformly dissolved in water to form a 0.014 M P123 solution (step S101). Among them, the molar ratio of P123, deionized water and glacial acetic acid is 0.04:320:1.

Next, lanthanum nitrate [La(NO ₃ ) ₃ ˙6H ₂ O], cobaltous nitrate [Co(NO ₃ ) ₂ ˙6H ₂ O] and citric acid [C ₆ H ₈ H ₇ ˙6H ₂ O] (step S102 ), and adding deionized water, so that the concentration of lanthanum ion and cobaltous ion in the aqueous solution is 0.35M.

Then, slowly drop the aqueous solution containing lanthanum ions and cobaltous ions into the aqueous solution containing P123 (step S103 ), and keep stirring for 2 hours. Among them, the molar ratio of lanthanum nitrate, cobaltous nitrate, citric acid, glacial acetic acid, deionized water, and P123 is 1:1:1:1:320:0.04, and the solution is a clear pink solution.

Finally, pour the solution into a crucible and place it in a high-temperature furnace for heating (step S104), heating from room temperature to 100°C at a rate of 3°C per minute and maintaining it for 30 minutes, then heating the solution to 450°C and maintaining it for 1 hour , and then the solution was heated to 600 ° C and maintained for 2 hours, and finally the solution was cooled to room temperature. The solution reacts to become the catalyst powder disclosed in the third embodiment of the present invention.

Example 4 (LaCoO ₃ /10%P123)

First, dissolve P123 in 20 mL of deionized water, add 0.417 g of glacial acetic acid as a catalyst, and stir with a stirring bar for 1 hour, so that P123 is uniformly dissolved in water to form a 0.035 M P123 solution (step S101). Among them, the molar numbers of P123, deionized water and glacial acetic acid are 0.1:320:1.

Next, lanthanum nitrate [La(NO ₃ ) ₃ ˙6H ₂ O], cobaltous nitrate [Co(NO ₃ ) ₂ ˙6H ₂ O] and citric acid [C ₆ H ₈ H ₇ ˙6H ₂ O] (step S102 ), and adding deionized water, so that the concentration of lanthanum ion and cobaltous ion in the aqueous solution is 0.35M.

Then, slowly drop the aqueous solution containing lanthanum ions and cobaltous ions into the aqueous solution containing P123 (step S103 ), and keep stirring for 2 hours. Among them, the molar ratio of lanthanum nitrate, cobaltous nitrate, citric acid, glacial acetic acid, deionized water, and P123 is 1:1:1:1:320:0.1, and the solution is a clear pink solution.

Finally, pour the solution into a crucible and place it in a high-temperature furnace for heating (step S104), heating from room temperature to 100°C at a rate of 3°C per minute and maintaining it for 30 minutes, then heating the solution to 450°C and maintaining it for 1 hour , and then the solution was heated to 600 ° C and maintained for 2 hours, and finally the solution was cooled to room temperature. The solution reacts to become the catalyst powder disclosed in Example 4 of the present invention.

Example 5 (LaCoO ₃ /2%F127)

First, dissolve F127 in 20 mL of deionized water, add 0.417 g of glacial acetic acid as a catalyst, and stir for 1 hour with a stirring bar, so that F127 is uniformly dissolved in water to form a 0.035 M F127 solution (step S101). Among them, the molar ratio of F127, deionized water and glacial acetic acid is 0.02:320:1.

Next, lanthanum nitrate [La(NO ₃ ) ₃ ˙6H ₂ O], cobaltous nitrate [Co(NO ₃ ) ₂ ˙6H ₂ O] and citric acid [C ₆ H ₈ H ₇ ˙6H ₂ O] (step S102 ), and adding deionized water, so that the concentration of lanthanum ion and cobaltous ion in the aqueous solution is 0.35M.

Then, slowly drop the aqueous solution containing lanthanum ions and cobaltous ions into the aqueous solution containing F127 (step S103 ), and keep stirring for 2 hours. Among them, the molar ratio of lanthanum nitrate, cobaltous nitrate, citric acid, glacial acetic acid, deionized water, and F127 is 1:1:1:1:320:0.02, and the solution is a clear pink solution.

Finally, pour the solution into a crucible and place it in a high-temperature furnace for heating (step S104), heating from room temperature to 100°C at a rate of 3°C per minute and maintaining it for 30 minutes, then heating the solution to 450°C and maintaining it for 1 hour , and then the solution was heated to 600 ° C and maintained for 2 hours, and finally the solution was cooled to room temperature. The solution reacts to become the catalyst powder disclosed in Example 5 of the present invention.

Example 6 (LaCoO ₃ /2%P123/1 hour)

First, dissolve P123 in 20 mL of deionized water, add 0.417 g of glacial acetic acid as a catalyst, and stir for 1 hour with a stirring bar, so that P123 is uniformly dissolved in water to form a 0.007 M P123 solution (step S101). Among them, the molar ratio of P123, deionized water and glacial acetic acid is 0.02:320:1.

Next, lanthanum nitrate [La(NO ₃ ) ₃ ˙6H ₂ O], cobaltous nitrate [Co(NO ₃ ) ₂ ˙6H ₂ O] and citric acid [C ₆ H ₈ H ₇ ˙6H ₂ O] (step S102 ), and adding deionized water, so that the concentration of lanthanum ion and cobaltous ion in the aqueous solution is 0.35M.

Then, slowly drop the aqueous solution containing lanthanum ions and cobaltous ions into the aqueous solution containing P123 (step S103 ), and keep stirring for 2 hours. Among them, the molar ratio of lanthanum nitrate, cobaltous nitrate, citric acid, glacial acetic acid, deionized water, and P123 is 1:1:1:1:320:0.02, and the solution is a clear pink solution.

Finally, pour the solution into a crucible and place it in a high-temperature furnace for heating (step S104), heating from room temperature to 100°C at a rate of 3°C per minute and maintaining it for 30 minutes, then heating the solution to 450°C and maintaining it for 1 hour , and then heated the solution to 600° C. for 1 hour, and finally cooled the solution to room temperature. The solution reacts to become the catalyst powder disclosed in Example 6 of the present invention.

Example 7 (LaCoO ₃ /2%P123/4 hours)

First, dissolve P123 in 20 mL of deionized water, add 0.417 g of glacial acetic acid as a catalyst, and stir for 1 hour with a stirring bar, so that P123 is uniformly dissolved in water to form a 0.007 M P123 solution (step S101). Among them, the molar ratio of P123, deionized water and glacial acetic acid is 0.02:320:1.

Next, lanthanum nitrate [La(NO ₃ ) ₃ ˙6H ₂ O], cobaltous nitrate [Co(NO ₃ ) ₂ ˙6H ₂ O] and citric acid [C ₆ H ₈ H ₇ ˙6H ₂ O] (step S102 ), and adding deionized water, so that the concentration of lanthanum ion and cobaltous ion in the aqueous solution is 0.35M.

Then, slowly drop the aqueous solution containing lanthanum ions and cobaltous ions into the aqueous solution containing P123 (step S103 ), and keep stirring for 2 hours. Among them, the molar ratio of lanthanum nitrate, cobaltous nitrate, citric acid, glacial acetic acid, deionized water, and P123 is 1:1:1:1:320:0.02, and the solution is a clear pink solution.

Finally, pour the solution into a crucible and place it in a high-temperature furnace for heating (step S104), heating from room temperature to 100°C at a rate of 3°C per minute and maintaining it for 30 minutes, then heating the solution to 450°C and maintaining it for 1 hour , and then the solution was heated to 600° C. and maintained for 4 hours, and finally the solution was cooled to room temperature. The solution reacts to become the catalyst powder disclosed in Example 7 of the present invention.

Comparative Example 2 (LaCoO ₃ /2%PEG)

First, PEG (PolyehyleneGlycol, HO(C ₂ H ₄ O) _n H) was dissolved in 20 mL of deionized water, and 0.417 g of glacial acetic acid was added as a catalyst, and stirred with a stirring bar for 1 hour, so that PEG was uniformly dissolved in water, A 0.007 M PEG solution is formed (step S101 ). Among them, the molar ratio of PEG, deionized water and glacial acetic acid is 0.02:320:1.

Next, lanthanum nitrate [La(NO ₃ ) ₃ ˙6H ₂ O], cobaltous nitrate [Co(NO ₃ ) ₂ ˙6H ₂ O] and citric acid [C ₆ H ₈ H ₇ ˙6H ₂ O] (step S102 ), and adding deionized water, so that the concentration of lanthanum ion and cobaltous ion in the aqueous solution is 0.35M.

Then, slowly drop the aqueous solution containing lanthanum ions and cobaltous ions into the aqueous solution containing PEG (step S103 ), and keep stirring for 2 hours. Among them, the molar ratio of lanthanum nitrate, cobaltous nitrate, citric acid, glacial acetic acid, deionized water, and PEG is 1:1:1:1:320:0.02, and the solution is a clear pink solution.

Finally, pour the solution into a crucible and place it in a high-temperature furnace for heating (step S104), heating from room temperature to 100°C at a rate of 3°C per minute and maintaining it for 30 minutes, then heating the solution to 450°C and maintaining it for 1 hour , and then the solution was heated to 600 ° C and maintained for 2 hours, and finally the solution was cooled to room temperature. The solution reacts to become the catalyst powder disclosed in Comparative Example 2 of the present invention.

The catalyst powders of Comparative Example 1 and Comparative Example 2, and the catalyst powders of Examples 1 to 7 were subjected to X-ray diffraction analysis (X-Ray Diffraction, XRD). The results are shown in Figure 2A to Figure 2D, and Figure 2A is a comparison The X-ray diffraction analysis result of the catalyst powder of Example 1, Fig. 2B is the X-ray diffraction analysis result of the catalyst powder of Embodiment 2, Embodiment 5, Comparative Example 1 and Comparative Example 2, and Fig. 2C is Embodiment 1 to Embodiment The X-ray diffraction analysis results of the catalyst powder of Example 4, FIG. 2D is the X-ray diffraction analysis results of the catalyst powder of Example 2, the catalyst powder of Example 6, and the catalyst powder of Example 7.

Please refer to Fig. 2A first, compare the X-ray diffraction analysis results of the catalyst powder of Comparative Example 1 with Co ₃ O ₄ and La ₂ O ₃ , the 2θ of the catalyst powder of Comparative Example 1 has the same properties as Co ₃ at 31 degrees and 37 degrees The same signal of O ₄ means that the catalyst powder of Comparative Example 1 still has Co ₃ O ₄ crystal phase, and the 2θ of the catalyst powder of Comparative Example 1 has the same signal as La ₂ O ₃ at 32 degrees and 54 degrees, which represents the comparative example One catalyst powder still has La ₂ O ₃ crystal phase.

Then please refer to Fig. 2B, wherein (a) is the catalyst powder (2% P123) of embodiment two, (b) is the catalyst powder (2% F127) of embodiment five, (c) is the catalyst powder of comparative example two ( 2% PEG), (d) is the catalyst powder of Comparative Example 1 (no three-block copolymer surfactant was added). Among them, P123 and F127 are three-block copolymer surfactants, but PEG is not a three-block copolymer surfactant.

Comparing the X-ray diffraction analysis results of these catalyst powders with Co ₃ O ₄ , the catalyst powders of Comparative Example 1 and Comparative Example 2 have the same signals as Co ₃ O ₄ at 2θ at 31 degrees and 37 degrees, representing Comparative Example 1 and the catalyst powder of Comparative Example 2 contained Co ₃ O ₄ . Next, the X-ray diffraction analysis results of the catalyst powders of Examples 2 and 5 were compared with LaCoO ₃ , and the signal results were consistent, indicating that the catalyst powders of Examples 2 and 5 should be LaCoO ₃ . Therefore, the catalyst powder made by adding the three-block copolymer surfactant does have a single-phase perovskite structure.

Then please refer to Fig. 2C, wherein (e) is the catalyst powder (1% P123) of embodiment one, (f) is the catalyst powder (2% P123) of embodiment two, (g) is the catalyst powder of embodiment three ( 4% P123), (h) is the catalyst powder (10% P123) of Example 4.

Comparing the X-ray diffraction analysis results of the catalyst powders in Examples 1 to 4 with Co ₃ O ₄ , the catalyst powders in Examples 1 to 4 have no obvious signals at 31 degrees and 37 degrees, which shows that the catalyst powders in Examples 1 to 4 have no obvious signal. The catalyst powder of Example 4 does not have Co ₃ O ₄ . Then, compare the X-ray diffraction analysis results of the catalyst powders of Examples 1 to 4 with LaCoO ₃ , the signals of the catalyst powders of Examples 1 to 4 are consistent with the signals of LaCoO ₃ , showing that the signals of Examples 1 to 4 are The catalyst powder of IV should be LaCoO ₃ . Therefore, even if the concentration of P123 is changed, the prepared catalyst powder still has a single-phase perovskite structure.

Then please refer to Fig. 2D, wherein (i) is the catalyst powder (2%P123/1 hour) of embodiment six, (j) is the catalyst powder (2%P123/2 hour) of embodiment two, (k) is the implementation Catalyst powder (2% P123/4 hours) of example seven.

By comparing the X-ray diffraction analysis results of the catalyst powders of Example 2, Example 6, and Example 7 with Co3O4, the catalyst powders of Example 2, Example 6, and Example 7 have no obvious changes at 31 degrees and 37 degrees. The signal shows that the catalyst powders of Example 2, Example 6 and Example 7 do not contain Co ₃ O ₄ . Then, compare the X-ray diffraction analysis results of the catalyst powders of Embodiment 2, Embodiment 6, and Embodiment 7 with LaCoO ₃ , the signal of the catalyst powders of Embodiment 2, Embodiment 6, and Embodiment 7 is comparable to that of LaCoO ₃ . The signals are consistent, showing that the catalyst powders in Example 2, Example 6 and Example 7 should be LaCoO ₃ . Therefore, even if the calcination time of the catalyst powder is changed, the prepared catalyst powder still has a single-phase perovskite structure.

Please refer to Fig. 3A to Fig. 3G. Fig. 3A is the scanning electron microscope (Scanning Electron Microscope, SEM) analysis result of the catalyst powder of Comparative Example 1, and Fig. 3B to Fig. 3H are the scans of the catalyst powder of Example 1 to Example 7 respectively. 3I is the analysis result of the scanning electron microscope of the catalytic powder of Comparative Example 2. The catalyst powder in Comparative Example 1 is mainly composed of broken flakes and will agglomerate into large aggregates. The catalyst powders made by adding surfactants (Example 1 to Example 7 and Comparative Example 2), because P123, F127, and PEG will form microcells when preparing the catalyst powder, the catalyst powder is mainly composed of small particles , and make the catalyst powder have holes and holes to increase the specific surface area of the catalyst powder.

Next, the specific surface area analysis (Brunauer-Emmett-Teller analysis, BET analysis) of the catalyst powders of Comparative Example 1, Example 1, and Example 2 was carried out, and the results are shown in the following table.

S _BET (m ² /g) Vpore(cm3/g) Dp(nm) Comparative example 1 (without adding P123) 3.11 0.02 18.1 Example 1 (1% P123) 10.0 0.08 22.4 Example 2 (2% P123) 12.8 0.06 20.1

The catalyst powder of embodiment one and the catalyst powder of embodiment two are compared with the catalyst powder of the comparative example one that does not add P123, and the specific surface area of the catalyst powder of embodiment one and the catalyst powder of embodiment two is respectively the catalyst powder that does not add P123 3 times and 4 times the specific surface area of the powder. The pore volumes of the catalyst powder of Example 1 and the catalyst powder of Example 2 are 3 times and 4 times of the pore volume of the catalyst powder without adding P123, respectively. The average pore diameters of the catalyst powder of Example 1 and the catalyst powder of Example 2 are 1.2 times and 1.1 times of the average pore diameter of the catalyst powder without adding P123, respectively. Therefore, P123 can indeed increase the specific surface area of the catalyst powder produced.

Next, the catalyst powders of Example 1, Example 2, and Example 3 were analyzed for specific surface area, and the results are shown in the following table.

SBET(m ² /g) Example 1 (1% P123) 10.0 Example 2 (2% P123) 12.8 Example 3 (4% P123) 6.88

The specific surface areas of the catalyst powders of Examples 1 to 3 are larger than those of the catalyst powders of Comparative Example 1.

Next, the particle diameters of the catalyst powders of Comparative Example 1, Comparative Example 2, and Examples 1 to 5 were calculated from the X-ray diffraction analysis results, and the results are shown in the following table.

sample Particle size (nanometer) Comparative example 1 (without adding P123) 23.83 Comparative Example 2 (2% PEG) 23.83 Example 1 (1% P123) 25.26 Example 2 (2% P123) 24.89 Example 3 (4% P123) 24.89

Example 4 (10% P123) 26.05 Example five (2% F127) 24.88

The particle diameters of the catalyst powders in Comparative Example 1, Comparative Example 2, and Examples 1 to 5 are all in the nanometer range.

Then, the particle diameters of the catalyst powders in Example 2, Example 6, and Example 7 were calculated from the X-ray diffraction analysis results, and the results are shown in the following table. Wherein, the reaction times of Example 2, Example 6, and Example 7 at 600° C. are 1 hour, 2 hours, and 4 hours, respectively.

sample Particle size (nanometer) Example 2 (2% P123) 600°C/1 hour 24.89 Example 6 (2% P123) 600°C/2 hours 24.89 Example 7 (2% P123) 600°C/4 hours 25.26

The particle diameters of the catalyst powders in Embodiment 2, Embodiment 6, and Embodiment 7 are all in the nanometer range.

Comparative example 3 (LaNiO ₃ / no three-block copolymer surfactant)

Lanthanum nitrate [La(NO ₃ ) ₃ ˙6H ₂ O], nickel nitrate [Ni(NO ₃ ) ₂ ˙6H ₂ O] and citric acid [C ₆ H ₈ H ₇ ˙6H ₂ O], and add deionized water to make the concentration of lanthanum ions and nickelous ions in the aqueous solution be 0.35M.

Pour the solution into a crucible and place it in a high-temperature furnace for heating, heating from room temperature to 100°C at a rate of 3°C per minute and maintaining it for 30 minutes, then heating the solution to 450°C and maintaining it for 1 hour, and then heating the solution to 600°C and maintained for 2 hours, and finally the solution was cooled to room temperature. The solution reacts to become the catalyst powder of Comparative Example 3.

Example 8 (LaNiO ₃ /1%P123)

First, dissolve P123 in 20 mL of deionized water, add 0.417 g of glacial acetic acid as a catalyst, and stir for 1 hour with a stirring bar, so that P123 is uniformly dissolved in water to form a 0.0035 M aqueous solution of P123 (step S101). Among them, the molar ratio of P123, deionized water and glacial acetic acid is 0.01:320:1.

Next, lanthanum nitrate [La(NO ₃ ) ₃ ˙6H ₂ O], nickel nitrate [Ni(NO ₃ ) ₂ ˙6H ₂ O] and citric acid [C ₆ H ₈ H ₇ ˙6H ₂ O] (step S102 ), and adding deionized water, so that the concentration of lanthanum ion and nickelous ion in the aqueous solution is 0.35M.

Then, slowly drop the aqueous solution containing lanthanum ions and nickelous ions into the aqueous solution containing P123 (step S103 ), and keep stirring for 2 hours. Among them, the molar ratio of lanthanum nitrate, nickel nitrate, citric acid, glacial acetic acid, deionized water, and P123 is 1:1:1:1:320:0.01, and the solution is a clear emerald green solution.

Finally, pour the solution into a crucible and place it in a high-temperature furnace for heating (step S104), heating from room temperature to 100°C at a rate of 3°C per minute and maintaining it for 30 minutes, then heating the solution to 450°C and maintaining it for 1 hour , and then the solution was heated to 600 ° C and maintained for 2 hours, and finally the solution was cooled to room temperature. The solution reacts to become the catalyst powder disclosed in the eighth embodiment of the present invention.

Example 9 (LaNiO ₃ /2%P123)

First, dissolve P123 in 20 mL of deionized water, add 0.417 g of glacial acetic acid as a catalyst, and stir for 1 hour with a stirring bar, so that P123 is uniformly dissolved in water to form a 0.007 M aqueous solution of P123 (step S101). Among them, the molar ratio of P123, deionized water and glacial acetic acid is 0.02:320:1.

Next, lanthanum nitrate [La(NO ₃ ) ₃ ˙6H ₂ O], nickel nitrate [Ni(NO ₃ ) ₂ ˙6H ₂ O] and citric acid [C ₆ H ₈ H ₇ ˙6H ₂ O] (step S102 ), and adding deionized water, so that the concentration of lanthanum ion and nickelous ion in the aqueous solution is 0.35M.

Then, slowly drop the aqueous solution containing lanthanum ions and nickelous ions into the aqueous solution containing P123 (step S103 ), and keep stirring for 2 hours. Among them, the molar ratio of lanthanum nitrate, nickel nitrate, citric acid, glacial acetic acid, deionized water, and P123 is 1:1:1:1:320:0.02, and the solution is a clear emerald green solution.

Finally, pour the solution into a crucible and place it in a high-temperature furnace for heating (step S104), heating from room temperature to 100°C at a rate of 3°C per minute and maintaining it for 30 minutes, then heating the solution to 450°C and maintaining it for 1 hour , and then the solution was heated to 600 ° C and maintained for 2 hours, and finally the solution was cooled to room temperature. The solution immediately reacts to become the catalyst powder disclosed in Example 9 of the present invention.

The catalyst powder of Comparative Example 3, the catalyst powder of Example 8 and the catalyst powder of Example 9 were subjected to X-ray diffraction analysis (X-Ray Diffraction, XRD), and the results are shown in Figure 4, wherein (l) is a comparative example The catalyst powder of three, (m) is the catalyst powder of embodiment eight, (n) is the catalyst powder of embodiment nine. Comparing the X-ray diffraction analysis results of the three catalyst powders with those of La ₂ NiO ₄ , the catalyst powder of Comparative Example 3 has the same signal as La ₂ NiO ₄ between 31°C and 32°C, indicating that no three-block copolymer was added The catalyst powder prepared by the surfactant contains La ₂ NiO ₄ , while the catalyst powder of Example 8 and the catalyst powder of Example 9 have no obvious signal between 31 degrees and 32 degrees, showing that the catalyst powder of Example 8 The powder and the catalyst powder of Example 9 do not have La ₂ NiO ₄ . Then, the X-ray diffraction analysis results of the catalyst powder of Example 8 and the catalyst powder of Example 9 are compared with LaNiO ₃ , and the signal results are consistent, showing that the catalyst powder of Example 8 and the catalyst powder of Example 9 should be is LaNiO ₃ . Therefore, the catalyst powder made by adding the three-block copolymer surfactant does have a single-phase perovskite structure.

Then please refer to Fig. 5A to Fig. 5C, Fig. 5A is the analysis result of the scanning electron microscope of the catalyst powder of comparative example three, Fig. 5B is the analysis result of the scanning electron microscope of the catalyst powder of embodiment eight, Fig. 5C is embodiment 9. SEM analysis results of catalyst powders. The catalyst powder prepared without the addition of three-block copolymer surfactant is mainly composed of broken flakes and will agglomerate into large aggregates. And add the catalyst powder (embodiment eight, nine) of three-block copolymer surfactant (P123), because P123 can form microcell when preparing catalyst, make catalyst powder mainly form the composition of small particle, and make catalyst powder Having holes increases the specific surface area of the catalyst powder.

Then, the specific surface area analysis is carried out, and the results are shown in the following table.

The catalyst powder of embodiment eight and the catalyst powder of embodiment nine are compared with the catalyst powder of comparative example three, and the specific surface area of the catalyst powder of embodiment eight and the catalyst powder of embodiment nine is respectively the specific surface area of the catalyst powder of comparative example three 1.4 times and 1.3 times. The pore volumes of the catalyst powder of Example 8 and the catalyst powder of Example 9 are 1.9 times and 2 times of the pore volume of the catalyst powder of Comparative Example 3, respectively. The average pore diameters of the catalyst powder of Example 8 and the catalyst powder of Example 9 are 1.2 times and 1.4 times of the average pore diameter of the catalyst powder of Comparative Example 3, respectively. The micropore surface areas of the catalyst powder of Example 8 and the catalyst powder of Example 9 are 3 times and 4.2 times of the micropore surface area of the catalyst powder of Comparative Example 3, respectively. The micropore volumes of the catalyst powder of Example 8 and the catalyst powder of Example 9 are 6 times and 9 times of the micropore volume of the catalyst powder of Comparative Example 3, respectively. Therefore, the three-block copolymer surfactant can indeed increase the specific surface area of the prepared catalyst powder.

In summary, no matter whether lanthanum nitrate and cobaltous nitrate are used to prepare the catalyst or lanthanum nitrate and nickel nitrate are used to prepare the catalyst powder, as long as the three-block copolymer surfactant is added during the preparation process, all can The specific surface area of the prepared catalyst powder is increased and the impurity phase can be suppressed to generate a catalyst powder with a single-phase perovskite structure. These catalyst powders can be applied to electrodes, such as electrodes of fuel cells or electrodes of air batteries.

Next, the catalyst powder, carbon powder and proton exchange membrane (Nafion) of Example 2 were mixed, and coated on carbon paper, that is, the preparation of a simple air electrode was completed.

GDL Product的双层结构碳纸的电极、(p)为比较例一的触媒粉末所制成的电极、(q)为实施例二的触媒粉末所制成的电极。比较三电极的电压与时间的关系，使用本发明实施例的触媒粉末的锌空气电池具有较高的放电电压以及电容密度。The above-mentioned air electrode and zinc sheets are used to form a zinc-air battery, and the relationship between the discharge voltage and time of the zinc-air battery is shown in Figure 6, which is a graph showing the relationship between the discharge voltage and time of the zinc-air battery. Among them, (o) is

The electrodes of the double-layer structure carbon paper of GDL Product, (p) is the electrode made of the catalyst powder of Comparative Example 1, and (q) is the electrode made of the catalyst powder of Example 2. Comparing the relationship between the voltage and time of the three electrodes, the zinc-air battery using the catalyst powder of the embodiment of the present invention has a higher discharge voltage and capacitance density.

First, please refer to FIG. 7 . FIG. 7 is a flowchart of a method for preparing an electrode disclosed in an embodiment of the present invention.

First, a three-block copolymer surfactant is provided (step S701 ). In the embodiment of the present invention, a three-block copolymer surfactant of ethyleneoxy-propyleneoxy-ethyleneoxy is used, such as P123, the molecular formula is HO(CH ₂ CH ₂ O) ₂₀ (CH ₂ CH(CH ₃ )O) ₇₀ (CH ₂ CH ₂ O) ₂₀ H (P123) triblock copolymer surfactant, or F127 with the formula HO(CH ₂ CH ₂ O) ₁₀₆ (CH ₂ CH(CH ₃ ) O) ₇₀ (CH ₂ CH ₂ O) ₁₀₆ H triblock copolymer surfactant. In addition, the three-block copolymer surfactant can be uniformly dissolved in the solution by stirring with a stirring bar, for example. The following will use P123 as an example of a three-block copolymer surfactant.

Next, a first metal and a second metal are provided (step S702 ) as metals used in the catalyst for catalysis. In the embodiment of the present invention, the first metal is lanthanum, and the second metal is manganese, iron, cobaltous or nickelous. Wherein, in order to make the first metal and the second metal form a catalyst with a perovskite structure, the content ratio of the first metal and the second metal is approximately 1 to 1, so as to satisfy the simple formula ABO3 of the perovskite structure ( A is the first metal, B is the ratio of the first metal to the second metal in the second metal).

Wherein, the molar ratio of the first metal to the three-block copolymer surfactant is between 100:1 and 10:1, and the molar ratio of the second metal to the three-block copolymer surfactant It is between 100:1 and 10:1. In one embodiment, the molar ratio of the first metal to the triblock copolymer surfactant is between 100:1 and 25:1, and the molar ratio of the second metal to the triblock copolymer surfactant is The molar ratio is between 100:1 and 25:1.

Then, the first metal and the second metal are added into the three-block copolymer surfactant, and mixed uniformly to form a solution (step S703 ).

Next, a metal mesh is provided (step S704 ), the metal mesh is such as but not limited to nickel foam material, the metal mesh is used to carry the catalyst, and the metal mesh can also provide a collector network as an electrode. In other embodiments, the metal mesh can be gold mesh, palladium mesh or platinum mesh, and is not limited to nickel foam.

Then, soak the metal mesh in the solution (step S705 ).

Finally, the metal mesh and the solution are calcined under inert gas (step S706 ), so that the catalyst is loaded on the metal mesh, and the preparation of the electrode is completed. Wherein, the inert gas is, for example, nitrogen, argon or helium.

Through the preparation method of the electrode disclosed in this embodiment, since the three-block copolymer surfactant is added during the preparation of the electrode, the catalyst and the metal mesh can still be bonded without using an adhesive during the production process, so that The catalyst directly contacts the metal mesh. In addition, the three-block copolymer surfactant can also make the catalyst have a single-phase perovskite structure and a high specific surface area.

In the following, several examples will be used to illustrate and verify the electrodes made by the present invention.

Example 10 (nickel foam + LaCoO ₃ /1%P123)

First, dissolve P123 in 20ml of deionized water, add 0.417g of glacial acetic acid as a catalyst, and stir for 1 hour with a stirring bar, so that P123 is uniformly dissolved in water to form a 0.0035M aqueous solution of P123 (step S101). Among them, the molar ratio of P123, deionized water and glacial acetic acid is 0.01:320:1.

Next, lanthanum nitrate [La(NO ₃ ) ₃ ˙6H ₂ O], cobaltous nitrate [Co(NO ₃ ) ₂ ˙6H ₂ O] and citric acid [C ₆ H ₈ H ₇ ˙6H ₂ O] (step S702 ), and adding deionized water, so that the concentration of lanthanum ion and cobaltous ion in the aqueous solution is 0.35M.

Then, slowly drop the aqueous solution containing lanthanum ions and cobaltous ions into the aqueous solution containing P123 (step S703 ), and keep stirring for 2 hours. Among them, the molar ratio of lanthanum nitrate, cobaltous nitrate, citric acid, glacial acetic acid, deionized water, and P123 is 1:1:1:1:320:0.01, and the solution is a clear pink solution.

Next, a nickel foam material is provided (step S704 ), and the nickel foam material is soaked in the solution (step S705 ). Wherein, the nickel foam material is a porous metal mesh, so it can have a relatively high surface area to support the catalyst.

Finally, the nickel foam material and the solution are calcined under 1 atmosphere of nitrogen, which is divided into two stages of calcination. Firstly, calcining at 450° C. for 1 hour, and then calcining at 600° C. for 2 hours (step S706 ), so that the catalyst is loaded on the metal mesh, and the preparation of the electrode of Example 10 is completed.

Example eleven (nickel foam + LaCoO3/2% P123)

First, dissolve P123 in 20ml of deionized water, add 0.417g of glacial acetic acid as a catalyst, and stir for 1 hour with a stirring bar, so that P123 is uniformly dissolved in water to form a 0.007M aqueous solution of P123 (step S101). Among them, the molar ratio of P123, deionized water and glacial acetic acid is 0.02:320:1.

Next, lanthanum nitrate [La(NO ₃ ) ₃ ˙6H ₂ O], cobaltous nitrate [Co(NO ₃ ) ₂ ˙6H ₂ O] and citric acid [C ₆ H ₈ H ₇ ˙6H ₂ O] (step S702 ), and adding deionized water, so that the concentration of lanthanum ion and cobaltous ion in the aqueous solution is 0.35M.

Then, slowly drop the aqueous solution containing lanthanum ions and cobaltous ions into the aqueous solution containing P123 (step S703 ), and keep stirring for 2 hours. Among them, the molar ratio of lanthanum nitrate, cobaltous nitrate, citric acid, glacial acetic acid, deionized water, and P123 is 1:1:1:1:320:0.02, and the solution is a clear pink solution.

Next, a nickel foam material is provided (step S704 ), and the nickel foam material is soaked in the solution (step S705 ). Wherein, the nickel foam material is a porous metal mesh, so it can have a relatively high surface area to support the catalyst.

Finally, the nickel foam material and the solution are calcined under 1 atmosphere of nitrogen, which is divided into two stages of calcination. Firstly, calcining at 450° C. for 1 hour, and then calcining at 600° C. for 2 hours (step S706 ), so that the catalyst is loaded on the metal mesh, and the preparation of the electrode of Example 11 is completed.

The nickel foam material and the electrode of Example 11 (2%P123) are subjected to X-ray diffraction analysis, and the results are shown in Figure 8A and Figure 8B, wherein Figure 8A is the X-ray diffraction analysis result of the nickel foam material, Fig. 8B is the X-ray diffraction analysis result of the electrode of the eleventh embodiment. Among them, in Figure 8A, signals appear at 2θ of 44.50 degrees, 51.84 degrees, and 76.37 degrees. Comparing these signals with the database, it can be known that these signals are characteristics of the nickel metal phase (ICDD code: 00-004-0850) peak. On the other hand, in Figure 8B, signals appear at 2θ of 32.88 degrees, 33.29 degrees, 47.50 degrees, and 58.9 degrees. By comparing these signals with the database, it can be known that these signals are LaCoO3 perovskite phases (ICDD code: 01-084-0848) characteristic peak. Therefore, according to FIG. 8A and FIG. 8B , it can be seen that the surface of the nickel foam material according to the embodiment of the present invention is indeed loaded with the catalyst of LaCoO ₃ .

Next, please refer to FIG. 9A to FIG. 9C . FIG. 9A to FIG. 9C are the analysis results of the nickel foam material, the electrode of Example 10, and the electrode of Example 11, respectively, by a Scanning Electron Microscope (SEM). As shown in Figure 9B and Figure 9C, the LaCoO ₃ catalyst is indeed loaded on the nickel foam material and evenly distributed on the surface of the nickel foam material, and the surface morphology of the nickel foam material does not change significantly. Thereby, the preparation method of the electrode of the present invention can still join the catalyst and the carrier without using an adhesive, and has the advantages of simplicity, speed, and cheapness in preparation.

Finally, please refer to FIG. 10 , which is a schematic diagram of an improved air battery disclosed in an embodiment of the present invention. The battery 100 includes a hydrophobic layer 110 , a catalyst layer 120 , an electrolyte layer 130 and a metal layer 140 . Wherein, the hydrophobic layer 110 includes nickel foam material and Teflon, the catalyst layer 120 includes the electrode of Example 10, the electrolyte layer 130 includes alkaline solution, colloidal electrolyte and solid electrolyte, and the metal layer 140 can include lithium, sodium, for example or zinc.

According to the catalyst, electrode and preparation method thereof disclosed in the embodiments of the present invention, since a three-block copolymer surfactant is added in the process of preparing the catalyst and electrode, the prepared catalyst has a single-phase perovskite structure, Therefore, the problem that impurity phases will be generated during the preparation of the catalyst and the surface area of the catalyst will be reduced by the impurity phases will further reduce the efficiency of the fabricated battery.

In addition, adding the three-block copolymer surfactant in the process of preparing the catalyst and the electrode can also increase the specific surface area of the prepared catalyst and battery, thereby increasing the discharge voltage and capacitance density of the prepared battery. In addition, the three-block copolymer surfactant can also enable the catalyst to be bonded to the metal mesh without an adhesive, so that the catalyst directly contacts the metal mesh, and thus has the advantages of simplicity, speed, and cheapness in preparation.

Certainly, the present invention also can have other multiple embodiments, without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and deformations according to the present invention, but these corresponding Changes and deformations should belong to the scope of protection of the appended claims of the present invention.

Claims (17)

1. a catalyst, is characterized in that, comprising:

One metal oxide, comprises one first metal and one second metal, and this metal oxide has the perovskite structure of single-phase.

2. catalyst according to claim 1, is characterized in that, this first metal is lanthanum, and this second metal is manganese, iron, sub-cobalt or sub-nickel.

3. catalyst according to claim 2, is characterized in that, this second metal is sub-cobalt, and the specific area of this metal oxide is between 6.88m ²/ g and 12.8m ²between/g.

4. catalyst according to claim 2, is characterized in that, this second metal is sub-cobalt, and the hole volume of this metal oxide is between 0.06cm ³/ g and 0.08cm ³between/g.

5. catalyst according to claim 2, is characterized in that, this second metal is sub-cobalt, and the average pore size of this metal oxide is between 20.1nm and 26.05nm.

6. catalyst according to claim 2, is characterized in that, this second metal is sub-nickel, and the specific area of this metal oxide is between 12.3m ²/ g and 13.3m ²between/g.

7. catalyst according to claim 2, is characterized in that, this second metal is sub-nickel, and the hole volume of this metal oxide is between 0.073cm ³/ g and 0.076cm ³between/g.

8. catalyst according to claim 2, is characterized in that, this second metal is sub-nickel, and the average pore size of this metal oxide is between 24.32nm and 28.68nm.

9. a preparation method for electrode, is characterized in that, comprising:

One first metal and one second metal are provided;

Mix this first metal and this second metal in a solution, this solution comprises one or three block copolymer interfacial agents;

One wire netting is provided;

This wire netting is positioned over to this solution; And

Heat this solution and this wire netting and make this first metal and this second metal be reacted into a catalyst in this wire netting, so that this catalyst and this wire netting form an electrode.

10. the preparation method of electrode according to claim 9, is characterized in that, this first metal is lanthanum, and this second metal is manganese, iron, sub-cobalt or sub-nickel.

The preparation method of 11. electrodes according to claim 9, is characterized in that, the ratio of this first metal and this three blocks copolymer interfacial agent is between 100: 1 to 10: 1.

The preparation method of 12. electrodes according to claim 11, is characterized in that, the ratio of this first metal and this three blocks copolymer interfacial agent is between 100: 1 to 25: 1.

The preparation method of 13. electrodes according to claim 9, is characterized in that, the ratio of this second metal and this three blocks copolymer interfacial agent is between 100: 1 to 10: 1.

The preparation method of 14. electrodes according to claim 13, is characterized in that, the ratio of this second metal and this three blocks copolymer interfacial agent is between 100: 1 to 25: 1.

15. 1 kinds of electrodes, is characterized in that, comprise:

One wire netting; And

One catalyst, is carried on this wire netting, the metal oxide of the perovskite structure that this catalyst comprises a single-phase, and this metal oxide comprises one first metal and one second metal.

16. electrodes according to claim 15, is characterized in that, this catalyst directly contacts this wire netting.

17. electrodes according to claim 15, is characterized in that, this first metal is lanthanum, and this second metal is manganese, iron, sub-cobalt or sub-nickel.

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