TWI482660B - Electrode, and manufacturing method thereof - Google Patents

Description

Electrode and preparation method thereof

This proposal relates to a catalyst, in particular an electrode made of a catalyst and a preparation method thereof.

In recent years, with the development of electric vehicles and in order to meet the needs of future power networks and electrical energy storage, secondary batteries have become a hot research topic. In general, in order to improve the performance of the secondary battery, a common method is to improve the catalyst for the secondary battery. For example, increasing the specific surface area of a catalyst is a problem that researchers need to solve. In addition, in the process of preparing the catalyst, other heterophases which do not have catalyst performance are often generated, and these heterophases reduce the surface area that the catalyst can react, thereby reducing the performance of the catalyst, thereby causing secondary batteries. The supply voltage and the supply current drop. At present, the generation of heterogeneous phases is mainly reduced by controlling the proportion of the components of the catalyst. However, such an operation method is cumbersome and the effect is not satisfactory.

Therefore, how to design a catalyst and an electrode to reduce the occurrence of miscellaneous phases in the process of preparing the catalyst and reduce the performance of the fabricated battery has become a problem that researchers need to solve.

In view of the above problems, the present proposal relates to a catalyst, an electrode, and a preparation method thereof, thereby reducing the problem that a heterogeneous phase is generated in the process of preparing a catalyst to lower the performance of the fabricated battery.

The catalyst disclosed in one embodiment of the present invention comprises a metal oxide, the metal oxide comprises 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 comprising a three-block copolymer surfactant. Provide a metal mesh. Place the metal mesh in the solution. The heating solution and the metal mesh react the first metal and the second metal into a catalyst in the metal mesh to form an electrode between the catalyst and the metal mesh.

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

According to the catalyst, the electrode and the preparation method thereof 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, Therefore, the problem that a hetero phase is generated in the process of preparing the catalyst is solved. Therefore, the heterophase can be prevented from reducing the surface area at which the catalyst can react, thereby reducing the performance of the battery made of the catalyst.

The above description of the contents of this proposal and the following description of the implementation of the proposal are used to demonstrate and explain the principles of this proposal, and provide a further explanation of the scope of the patent application of this proposal.

100‧‧‧Battery

110‧‧‧hydrophobic layer

120‧‧‧catalyst layer

130‧‧‧ electrolyte layer

140‧‧‧metal layer

"FIG. 1" is a flow of a method for preparing a catalyst disclosed in an embodiment of the present proposal Cheng Tu.

"2A" is the X-ray diffraction analysis result of the catalyst powder of Comparative Example 1.

"Block 2B" is the X-ray diffraction analysis result of the catalyst powder of Example 2, Example 5, Comparative Example 1, and Comparative Example 2.

"2C" is the X-ray diffraction analysis result of the catalyst powders of Examples 1 to 4.

"2D" is the X-ray diffraction analysis result of the catalyst powder of Example 2, the catalyst powder of Example 6, and the catalyst powder of Example 7.

"3A" is the analysis result of the scanning electron microscope of the catalyst powder of Comparative Example 1.

"3B" is the analysis result of the scanning electron microscope of the catalyst powder of the first embodiment.

"3C" is the analysis result of the scanning electron microscope of the catalyst powder of the second embodiment.

The "3D image" is the analysis result of the scanning electron microscope of the catalyst powder of the third embodiment.

"3E" is the analysis result of the scanning electron microscope of the catalyst powder of the fourth embodiment.

"3F" is the analysis result of the scanning electron microscope of the catalyst powder of Example 5.

The "3Gth image" is the analysis result of the scanning electron microscope of the catalyst powder of Example 6.

"3H" is the analysis result of the scanning electron microscope of the catalyst powder of the seventh embodiment.

"3I" is the analysis result of the scanning electron microscope of the catalyst powder of Comparative Example 2.

Fig. 4 is a result of X-ray diffraction analysis of the catalyst powder of Comparative Example 3, the catalyst powder of Example 8, and the catalyst powder of Example 9.

"5A" is the analysis result of the scanning electron microscope of the catalyst powder of Comparative Example 3.

"5B" is the analysis result of the scanning electron microscope of the catalyst powder of the eighth embodiment.

"5C" is the analysis result of the scanning electron microscope of the catalyst powder of Example 9.

Figure 6 shows the voltage vs. time for the discharge of a zinc-air battery.

Fig. 7 is a flow chart showing a method of preparing an electrode disclosed in an embodiment of the present invention.

"8A" is the result of X-ray diffraction analysis of nickel foam.

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

"Fig. 9A" is the analysis result of a scanning electron microscope of a nickel foam material.

"Fig. 9B" is the analysis result of the scanning electron microscope of the electrode of the tenth embodiment.

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

Figure 10 is a schematic view of an improved air battery disclosed in an embodiment of the present invention.

The detailed features and advantages of the present invention are described in detail below in the embodiments, which are sufficient to enable any skilled artisan to understand the technical contents of the present invention and to implement the present invention, and to disclose the contents, the scope of the patent, and the drawings according to the present specification. Anyone familiar with the relevant art can easily understand the purpose and advantages of this proposal. The following examples further illustrate the views of this proposal in detail, but do not limit the scope of this proposal by any point of view.

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

First, a three-block copolymer surfactant is provided (step S101). In the examples of the present proposal, a three-block copolymer surfactant of ethyleneoxy-propyleneoxy-ethyleneoxy group, such as P123, having the formula HO(CH2CH2O)20(CH2CH(CH3)O)70(CH2CH2O) is used. 20H's three-block copolymer surfactant, or F127, a three-block copolymer surfactant of the formula HO(CH2CH2O)106(CH2CH(CH3)O)70(CH2CH2O)106H. Alternatively, the three-block copolymer surfactant can be uniformly dissolved in the solution by stirring using, for example, a stir bar.

Next, a first metal and a second metal are provided (step S102) as a metal for catalysis in the catalyst. In the embodiments of the present proposal, the first metal is ruthenium and the second metal is manganese, iron, co-cobalt or nickel. Among them, in order to make The first metal and the second metal form a catalyst having a perovskite structure, and the content ratio of the first metal to the second metal is approximately 1 to 1, in order to satisfy the simple ABO3 structure of the perovskite structure (A is the first The ratio of the first metal to the second metal in a metal, B is 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 second metal and triblock copolymer surfactant The molar ratio is between 100:1 and 25:1.

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

Finally, the solution is heated to react the first metal, the second metal and the triblock copolymer surfactant into a catalyst (step S104). Specifically, the solution is first heated to 100 ° C and maintained for 30 minutes, and then the solution is heated to 450 ° C and maintained for 1 hour, the triblock copolymer surfactant is removed, and finally the solution is heated to 600 ° C and maintained 2 In an hour, the solution is reacted to the catalyst powder disclosed in the proposed embodiment, and the catalyst powder has a single phase perovskite structure. Among them, the single phase means that the catalyst powder has a single crystal phase. In the examples of the present proposal, the type of the catalyst is in the form of a powder, and in the following description, the catalyst powder is used as a catalyst. However, powdered catalysts are not intended to limit this proposal.

The main component of the catalyst comprises metal oxygen of the first metal and the second metal Compound. Since the triblock copolymer surfactant is added during the preparation of the catalyst, the metal oxide has a single phase perovskite structure and has a high specific surface area.

The following is a description and experimental verification of the catalyst prepared by the present proposal in several comparative examples and examples, wherein the % listed represents the ratio of the surfactant to the first metal (for example, ruthenium).

Comparative Example 1 (LaCoO3/not using a three-block copolymer surfactant)

The scale has a molar ratio of 1:1:1 for lanthanum nitrate [La(NO3)3 ̇6H2O], cobalt sulphate [Co(NO3)2 ̇6H2O] and citric acid [C6H8H7 ̇6H2O], and deionized Water, the concentration of cerium ions and cobaltous ions in the aqueous solution was 0.35 M.

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

Example 1 (LaCoO3/1% P123)

First, P123 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 stir bar for 1 hour to uniformly dissolve P123 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, the scale has a molar ratio of 1:1:1 to lanthanum nitrate [La(NO3)3 ̇6H2O], cobaltous cobalt nitrate [Co(NO3)2 ̇6H2O] and citric acid [C6H8H7 ̇6H2O] (step S102), and deionized water is added to make the concentration of cerium ions and cobaltous ions in the aqueous solution 0.35M. .

Then, an aqueous solution containing cerium ions and cobaltous ions was slowly dropped into an aqueous solution containing P123 (step S103), and stirring was continued for 2 hours. Wherein, the molar ratio of cerium 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, the solution is poured into a crucible and placed in a high temperature furnace for heating (step S104), heated from room temperature to 100 ° C at a rate of 3 ° C per minute for 30 minutes, and then the solution is heated to 450 ° C for 1 hour. The solution was then heated to 600 ° C for 2 hours and finally the solution was cooled to room temperature. The solution, that is, the reaction, becomes the catalyst powder disclosed in the first embodiment of the present proposal.

Example 2 (LaCoO3/2% P123)

First, P123 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 stir bar for 1 hour to uniformly dissolve P123 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 was 0.02:320:1.

Next, the scale has a molar ratio of 1:1:1 of lanthanum nitrate [La(NO3)3 ̇6H2O], cobaltous cobalt [Co(NO3)2 ̇6H2O], and citric acid [C6H8H7 ̇6H2O] (step S102). And adding deionized water so that the concentration of cerium ions and cobaltous ions in the aqueous solution is 0.35M.

Then, an aqueous solution containing cerium ions and cobaltous ions was slowly dropped into an aqueous solution containing P123 (step S103), and stirring was continued for 2 hours. Wherein, the molar ratio of cerium 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, the solution is poured into a crucible and placed in a high temperature furnace for heating (step S104), heated from room temperature to 100 ° C at a rate of 3 ° C per minute for 30 minutes, and then the solution is heated to 450 ° C for 1 hour. The solution was then heated to 600 ° C for 2 hours and finally the solution was cooled to room temperature. The solution is the catalyst powder disclosed in the second embodiment of the present proposal.

Example 3 (LaCoO3/4% P123)

First, P123 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 stir bar for 1 hour to uniformly dissolve P123 in water to form a 0.014 M P123 solution (step S101). Among them, the molar number of P123, deionized water and glacial acetic acid was 0.04:320:1.

Next, the scale has a molar ratio of 1:1:1 of lanthanum nitrate [La(NO3)3 ̇6H2O], cobaltous cobalt [Co(NO3)2 ̇6H2O], and citric acid [C6H8H7 ̇6H2O] (step S102). And adding deionized water so that the concentration of cerium ions and cobaltous ions in the aqueous solution is 0.35M.

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

Finally, the solution is poured into a crucible and placed in a high temperature furnace for heating (step S104), heated from room temperature to 100 ° C at a rate of 3 ° C per minute for 30 minutes, and then the solution is heated to 450 ° C for 1 hour. The solution was then heated to 600 ° C for 2 hours and finally the solution was cooled to room temperature. The solution, that is, the reaction, becomes the catalyst powder disclosed in the third embodiment of the present proposal.

Example 4 (LaCoO3/10%P123)

First, P123 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 stir bar for 1 hour to uniformly dissolve P123 in water to form a 0.035 M P123 solution (step S101). Among them, the molar number of P123, deionized water and glacial acetic acid is 0.1:320:1.

Next, the scale has a molar ratio of 1:1:1 of lanthanum nitrate [La(NO3)3 ̇6H2O], cobaltous cobalt [Co(NO3)2 ̇6H2O], and citric acid [C6H8H7 ̇6H2O] (step S102). And adding deionized water so that the concentration of cerium ions and cobaltous ions in the aqueous solution is 0.35M.

Then, an aqueous solution containing cerium ions and cobaltous ions was slowly dropped into an aqueous solution containing P123 (step S103), and stirring was continued for 2 hours. Wherein, the molar ratio of cerium 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 the crucible and place it in a high temperature furnace for heating (step Step S104), heating from room temperature to 100 ° C at a rate of 3 ° C per minute for 30 minutes, heating the solution to 450 ° C for 1 hour, heating the solution to 600 ° C for 2 hours, and finally the solution Cool to room temperature. The solution, that is, the reaction, becomes the catalyst powder disclosed in the fourth embodiment of the present proposal.

Example 5 (LaCoO3/2% F127)

First, F127 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 stir bar for 1 hour to uniformly dissolve F127 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 was 0.02:320:1.

Next, the scale has a molar ratio of 1:1:1 of lanthanum nitrate [La(NO3)3 ̇6H2O], cobaltous cobalt [Co(NO3)2 ̇6H2O], and citric acid [C6H8H7 ̇6H2O] (step S102). And adding deionized water so that the concentration of cerium ions and cobaltous ions in the aqueous solution is 0.35M.

Then, an aqueous solution containing cerium ions and cobaltous ions was slowly dropped into an aqueous solution containing F127 (step S103), and stirring was continued for 2 hours. Among them, the molar ratio of cerium 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, the solution is poured into a crucible and placed in a high temperature furnace for heating (step S104), heated from room temperature to 100 ° C at a rate of 3 ° C per minute for 30 minutes, and then the solution is heated to 450 ° C for 1 hour. The solution was then heated to 600 ° C for 2 hours and finally the solution was cooled to room temperature. The solution is the reaction The catalyst powder disclosed in Example 5 is the same.

Example 6 (LaCoO3/2% P123/1 hour)

First, P123 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 stir bar for 1 hour to uniformly dissolve P123 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, the scale has a molar ratio of 1:1:1 of lanthanum nitrate [La(NO3)3 ̇6H2O], cobaltous cobalt [Co(NO3)2 ̇6H2O], and citric acid [C6H8H7 ̇6H2O] (step S102). And adding deionized water so that the concentration of cerium ions and cobaltous ions in the aqueous solution is 0.35M.

Then, an aqueous solution containing cerium ions and cobaltous ions was slowly dropped into an aqueous solution containing P123 (step S103), and stirring was continued for 2 hours. Wherein, the molar ratio of cerium 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, the solution is poured into a crucible and placed in a high temperature furnace for heating (step S104), heated from room temperature to 100 ° C at a rate of 3 ° C per minute for 30 minutes, and then the solution is heated to 450 ° C for 1 hour. The solution was then heated to 600 ° C for 1 hour and finally the solution was cooled to room temperature. The solution is the catalyst powder disclosed in the sixth embodiment of the present proposal.

Example 7 (LaCoO3/2% P123/4 hours)

First, dissolve P123 in 20 mL of deionized water and add 0.417 g. The glacial acetic acid was used as a catalyst and stirred with a stir bar for 1 hour to uniformly dissolve P123 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, the scale has a molar ratio of 1:1:1 of lanthanum nitrate [La(NO3)3 ̇6H2O], cobaltous cobalt [Co(NO3)2 ̇6H2O], and citric acid [C6H8H7 ̇6H2O] (step S102). And adding deionized water so that the concentration of cerium ions and cobaltous ions in the aqueous solution is 0.35M.

Then, an aqueous solution containing cerium ions and cobaltous ions was slowly dropped into an aqueous solution containing P123 (step S103), and stirring was continued for 2 hours. Wherein, the molar ratio of cerium 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, the solution is poured into a crucible and placed in a high temperature furnace for heating (step S104), heated from room temperature to 100 ° C at a rate of 3 ° C per minute for 30 minutes, and then the solution is heated to 450 ° C for 1 hour. The solution was again heated to 600 ° C for 4 hours and finally the solution was cooled to room temperature. The solution is the catalyst powder disclosed in the seventh embodiment of the present proposal.

Comparative Example 2 (LaCoO3/2% PEG)

First, PEG (Polyehylene Glycol, HO(C2H4O)nH) 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 stir bar for 1 hour to uniformly dissolve PEG in water to form 0.007 M. The PEG solution (step S101). Among them, PEG, deionized water and glacial acetic acid The ear ratio is 0.02:320:1.

Next, the scale has a molar ratio of 1:1:1 of lanthanum nitrate [La(NO3)3 ̇6H2O], cobaltous cobalt [Co(NO3)2 ̇6H2O], and citric acid [C6H8H7 ̇6H2O] (step S102). And adding deionized water so that the concentration of cerium ions and cobaltous ions in the aqueous solution is 0.35M.

Then, an aqueous solution containing cerium ions and cobaltous ions was slowly dropped into an aqueous solution containing PEG (step S103), and stirring was continued for 2 hours. Wherein, the molar ratio of cerium 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, the solution is poured into a crucible and placed in a high temperature furnace for heating (step S104), heated from room temperature to 100 ° C at a rate of 3 ° C per minute for 30 minutes, and then the solution is heated to 450 ° C for 1 hour. The solution was then heated to 600 ° C for 2 hours and finally the solution was cooled to room temperature. The solution is the catalyst powder disclosed in Comparative Example 2 of the present proposal.

X-ray Diffraction (XRD) was performed on the catalyst powder of Comparative Example 1 and Comparative Example 2 and the catalyst powders of Examples 1 to 7. The results are as shown in "A 2A" to "D 2D". As shown in the figure, "2A" is the X-ray diffraction analysis result of the catalyst powder of Comparative Example 1, and "2B" is the catalyst powder of the second embodiment, the fifth embodiment, the comparative example 1 and the comparative example 2. X-ray diffraction analysis results, "2C" is the X-ray diffraction analysis result of the catalyst powder of the first to fourth embodiments, and "2D" is the catalyst powder of the second embodiment, and the sixth embodiment Catalyst powder And the X-ray diffraction analysis result of the catalyst powder of Example 7.

First, please refer to "Phase 2A". The X-ray diffraction analysis result of the catalyst powder of Comparative Example 1 is compared with Co3O4 and La2O3. The 2θ of the catalyst powder of Comparative Example 1 has the same degree as Co3O4 at 31 degrees and 37 degrees. The signal indicates that the catalyst powder of Comparative Example 1 also has a Co3O4 crystal phase, and the 2θ of the catalyst powder of Comparative Example 1 has the same signal as La2O3 at 32 degrees and 54 degrees, which represents the catalyst powder of Comparative Example 1. There is a La2O3 crystal phase.

Please refer to "2B", where (a) is the catalyst powder of Example 2 (2% P123), (b) is the catalyst powder of Example 5 (2% F127), and (c) is a comparative example. The catalyst powder (2% PEG) and (d) were the catalyst powder of Comparative Example 1 (no triblock copolymer surfactant was added). Among them, P123 and F127 are three-block copolymer surfactants, and PEG is not a three-block copolymer surfactant.

The X-ray diffraction analysis results of these catalyst powders were compared with Co3O4. The catalyst powders of Comparative Example 1 and Comparative Example 2 had the same signal as Co3O4 at 2 θ at 31 degrees and 37 degrees, representing Comparative Example 1 and Comparative Example. The catalyst powder of the second contains Co3O4. Then, the X-ray diffraction analysis results of the catalyst powders of the second embodiment and the fifth embodiment are compared with the LaCoO3, and the signal results are in agreement. The catalyst powders of the second embodiment and the fifth embodiment should be LaCoO3. Therefore, the catalyst powder prepared by adding a three-block copolymer surfactant does have a single phase perovskite structure.

Next, please refer to "2C", wherein (e) is the catalyst powder of Example 1 (1% P123), (f) is the catalyst powder of Example 2 (2% P123), (g) is an example Three catalyst powders (4% P123) and (h) are the catalyst powder of Example 4 (10) %P123).

Comparing the X-ray diffraction analysis results of the catalyst powders of Examples 1 to 4 with Co3O4, the catalyst powders of Examples 1 to 4 have no obvious signals at 31 degrees and 37 degrees, and the examples 1 to the examples are shown. The four catalyst powder does not have Co3O4. Then, the X-ray diffraction analysis results of the catalyst powders of the first embodiment to the fourth embodiment are compared with the LaCoO3, and the signals of the catalyst powders of the first embodiment to the fourth embodiment are matched with the signals of the LaCoO3, and the first embodiment to the embodiment are shown. The catalyst powder of the four should be LaCoO3. Therefore, even if the concentration of P123 is changed, the catalyst powder produced has a single phase perovskite structure.

Please refer to "2D", where (i) is the catalyst powder of Example 6 (2% P123/1 hour), (j) is the catalyst powder of Example 2 (2% P123/2 hours), (k) is the catalyst powder of Example 7 (2% P123 / 4 hours).

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 were not at 31 degrees and 37 degrees. Obvious signals show that the catalyst powder of Example 2, Example 6 and Example 7 does not have Co3O4. Next, the X-ray diffraction analysis results of the catalyst powders of the second embodiment, the sixth embodiment and the seventh embodiment are compared with the LaCoO3, and the signals of the catalyst powders of the second embodiment, the sixth embodiment and the seventh embodiment are combined with the LaCoO3. The signal is consistent, and the catalyst powder of the second embodiment, the sixth embodiment and the seventh embodiment should be LaCoO3. Therefore, even if the calcination time of the catalyst powder is changed, the catalyst powder produced has a single phase perovskite structure.

Please refer to "3A" to "3G", "3A" For the analysis results of the Scanning Electron Microscope (SEM) of the catalyst powder of Comparative Example 1, "3B" to "3H" are scanning patterns of the catalyst powders of Examples 1 to 7, respectively. As a result of analysis by an electron microscope, "3I" is the result of analysis by a scanning electron microscope of the catalyst powder of Comparative Example 2. The catalyst powder of Comparative Example 1 was mainly composed of a broken sheet and was agglomerated into a large aggregate. The catalyst powder prepared by adding the surfactant (Examples 1 to 7 and Comparative Example 2), since P123, F127, and PEG form micelles in the preparation of the catalyst powder, the catalyst powder is mainly formed into small particles. The composition of the particles, and the catalyst powder having pores and voids, enhances the specific surface area of the catalyst powder.

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

The catalyst powder of the first embodiment and the catalyst powder of the second embodiment have a specific surface area of the catalyst powder of the first embodiment and the catalyst powder of the second embodiment, respectively, compared with the catalyst powder of the comparative example 1 in which P123 is not added. The specific surface area of the catalyst powder to which P123 was not added was 3 times and 4 times. Catalyst powder of Example 1 and Example 2 The pore volume of the catalyst powder was 3 times and 4 times the pore volume of the catalyst powder to which P123 was not added, respectively. The average pore diameter of the catalyst powder of Example 1 and the catalyst powder of Example 2 was 1.2 times and 1.1 times the average pore diameter of the catalyst powder to which P123 was not added, respectively. Therefore, P123 does increase the specific surface area of the catalyst powder produced.

Next, the catalyst particles of Example 1, Example 2 and Example 3 were subjected to specific surface area analysis, and the results are shown in the following table.

The specific surface areas of the catalyst powders of Examples 1 to 3 were larger than the specific surface area of the catalyst powder of Comparative Example 1.

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

The particle diameters of the catalyst powders of Comparative Example 1, Comparative Example 2, and Examples 1 to 5 were all nanometer grades.

Then, the particle diameters of the catalyst powders of 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. The reaction time of the second embodiment, the sixth embodiment and the seventh embodiment at 600 ° C is 1 hour, 2 hours and 4 hours, respectively.

The particle sizes of the catalyst powders of Example 2, Example 6 and Example 7 are all nanometer grades.

Comparative Example 3 (LaNiO3/not using a three-block copolymer surfactant)

The scale has a molar ratio of 1:1:1 for lanthanum nitrate [La(NO3)3 ̇6H2O], nickel nitrate [Ni(NO3)2 ̇6H2O] and citric acid [C6H8H7 ̇6H2O], and deionized Water, the concentration of cerium ions and nickelous ions in the aqueous solution was 0.35 M.

Pour the solution into a crucible and place it in a high temperature furnace for heating The rate of the clock was heated from room temperature to 100 ° C for 30 minutes, and the solution was heated to 450 ° C for 1 hour, and the solution was heated to 600 ° C for 2 hours, and finally the solution was cooled to room temperature. The solution was reacted to become a catalyst powder of Comparative Example 3.

Example 8 (LaNiO3/1% P123)

First, P123 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 stir bar for 1 hour to uniformly dissolve P123 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, the scale has a molar ratio of 1:1:1 of lanthanum nitrate [La(NO3)3 ̇6H2O], nickel nitrate [Ni(NO3)2 ̇6H2O], and citric acid [C6H8H7 ̇6H2O] (step S102). And adding deionized water so that the concentration of cerium ions and nickelous ions in the aqueous solution is 0.35M.

Then, an aqueous solution containing cerium ions and nickelous ions was slowly dropped into an aqueous solution containing P123 (step S103), and stirring was continued for 2 hours. Wherein, the molar ratio of cerium nitrate, nickel nitrite, 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, the solution is poured into a crucible and placed in a high temperature furnace for heating (step S104), heated from room temperature to 100 ° C at a rate of 3 ° C per minute for 30 minutes, and then the solution is heated to 450 ° C for 1 hour. The solution was then heated to 600 ° C for 2 hours and finally the solution was cooled to room temperature. The solution, that is, the reaction, becomes the catalyst powder disclosed in the eighth embodiment of the present proposal.

Example 9 (LaNiO3/2% P123)

First, P123 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 stir bar for 1 hour to uniformly dissolve P123 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 was 0.02:320:1.

Next, the scale has a molar ratio of 1:1:1 of lanthanum nitrate [La(NO3)3 ̇6H2O], nickel nitrate [Ni(NO3)2 ̇6H2O], and citric acid [C6H8H7 ̇6H2O] (step S102). And adding deionized water so that the concentration of cerium ions and nickelous ions in the aqueous solution is 0.35M.

Then, an aqueous solution containing cerium ions and nickelous ions was slowly dropped into an aqueous solution containing P123 (step S103), and stirring was continued for 2 hours. Wherein, the molar ratio of cerium nitrate, nickel nitrite, 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, the solution is poured into a crucible and placed in a high temperature furnace for heating (step S104), heated from room temperature to 100 ° C at a rate of 3 ° C per minute for 30 minutes, and then the solution is heated to 450 ° C for 1 hour. The solution was then heated to 600 ° C for 2 hours and finally the solution was cooled to room temperature. The solution is the catalyst powder disclosed in the ninth embodiment of the present proposal.

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 (XRD), and the results are shown in Fig. 4, wherein (1) is the catalyst powder of Comparative Example 3, (m) is the catalyst powder of the eighth embodiment, and (n) is the catalyst powder of the ninth embodiment. The X-ray diffraction analysis results of the three catalyst powders were compared with La2NiO4. The catalyst powder of Comparative Example 3 had the same signal as La2NiO4 between 31 and 32 degrees, representing the preparation of the surfactant without the addition of the triblock copolymer. The formed catalyst powder contains La2NiO4, and the catalyst powder of the eighth embodiment and the catalyst powder of the embodiment 9 have no obvious signal between 31 degrees and 32 degrees, and the catalyst powder of the embodiment 8 is shown and implemented. The catalyst powder of Example 9 did not have La2NiO4. Then, the X-ray diffraction analysis results of the catalyst powder of the eighth embodiment and the catalyst powder of the ninth embodiment are compared with the LaNiO3, and the signal results are in agreement, and the catalyst powder of the eighth embodiment and the touch of the ninth embodiment are shown. The media powder should be LaNiO3. Therefore, the catalyst powder prepared by adding a three-block copolymer surfactant does have a single phase perovskite structure.

Please refer to "5A" to "5C", "5A" is the result of scanning electron microscopy of the catalyst powder of Comparative Example 3, and "5B" is the catalyst powder of the eighth embodiment. As a result of analysis by a scanning electron microscope, "5C" is the analysis result of the scanning electron microscope of the catalyst powder of Example 9. The catalyst powder prepared by adding the triblock copolymer surfactant is mainly composed of a broken sheet and is agglomerated into a large aggregate. Adding a catalyst powder of a three-block copolymer surfactant (P123) (Examples 8 and 9), since P123 forms a microcell during the preparation of the catalyst, the catalyst powder mainly forms a small particle composition, and The catalyst powder has pores to increase the specific surface area of the catalyst powder.

Next, specific surface area analysis was performed, and the results are shown in the following table.

The catalyst powder of Example 8 and the catalyst powder of Example 9 were compared with the catalyst powder of Comparative Example 3, and the specific surface areas of the catalyst powder of Example 8 and the catalyst powder of Example 9 were respectively Comparative Example 3. The specific surface area of the catalyst powder was 1.4 times and 1.3 times. The pore volume of the catalyst powder of Example 8 and the catalyst powder of Example 9 was 1.9 times and 2 times the pore volume of the catalyst powder of Comparative Example 3, respectively. The average pore diameter of the catalyst powder of Example 8 and the catalyst powder of Example 9 was 1.2 times and 1.4 times the average pore diameter of the catalyst powder of Comparative Example 3, respectively. The microporous surface area of the catalyst powder of Example 8 and the catalyst powder of Example 9 was 3 times and 4.2 times the micropore surface area of the catalyst powder of Comparative Example 3, respectively. The micropore volume of the catalyst powder of Example 8 and the catalyst powder of Example 9 was 6 times and 9 times 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 catalyst powder produced.

In summary, whether the catalyst is prepared by using cerium nitrate and cobalt sulphate or by using cerium nitrate and nickel nitrite, as long as a three-block copolymer surfactant is added during the preparation process, Can increase the catalyst produced The specific surface area of the powder and the suppression of the heterophase produce a catalyst powder having 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 of Example 2, the carbon powder, and the proton exchange membrane (Nafion) were mixed and coated on carbon paper to complete the preparation of a simple air electrode.

The air electrode and the zinc sheet are combined into a zinc-air battery, and the relationship between the voltage and time of the discharge of the zinc-air battery is as shown in "Fig. 6", and "Fig. 6" is the relationship between the voltage of the discharge of the zinc-air battery and time. . Among them, (o) is the electrode of the double-layered carbon paper of SIGRACET® GDL Product, (p) is the electrode made of the catalyst powder of Comparative Example 1, and (q) is made of the catalyst powder of the second embodiment. The electrode. Comparing the voltage versus time of the three electrodes, the zinc-air battery using the catalyst powder of the presently claimed embodiment has a higher discharge voltage and capacitance density.

First, please refer to "FIG. 7", and "FIG. 7" is a flow chart 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 examples of the present proposal, a three-block copolymer surfactant of ethyleneoxy-propyleneoxy-vinyloxy group, such as P123, having the formula HO(CH2CH2O)20(CH2CH(CH3)O)70(CH2CH2O) is used. 20H (P123) three-block copolymer surfactant, or F127, a three-block copolymer surfactant of the formula HO(CH2CH2O)106(CH2CH(CH3)O)70(CH2CH2O)106H. In addition, stirring using, for example, a stirrer can make the three blocks altogether The polymer surfactant is uniformly dissolved in the solution. P123 will be exemplified below as a three-block copolymer surfactant.

Next, a first metal and a second metal are provided (step S702) to serve as a metal for catalysis in the catalyst. In the embodiments of the present proposal, the first metal is ruthenium and the second metal is manganese, iron, co-cobalt or nickel. Wherein, in order to form the first metal and the second metal to form a catalyst having a perovskite structure, the content ratio of the first metal to the second metal is approximately 1 to 1, in order to satisfy the simple ABO3 structure of the perovskite structure. (A is the first metal, B is the second metal) 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 second metal and triblock copolymer surfactant The molar ratio is between 100:1 and 25:1.

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

Next, a metal mesh is provided (step S704). The metal mesh is, for example but not limited to, a nickel foam material, which is supported by a metal mesh, and the metal mesh can also provide a grid as an electrode. In other embodiments, the metal mesh may be a gold mesh, a palladium mesh, or a platinum mesh, and is not limited to a nickel foam.

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

Finally, the metal mesh and the solution are calcined under an inert gas (step S706) to support the catalyst on the metal mesh, that is, the preparation of the electrode is completed. Among them, the inert gas is, for example, nitrogen, argon or helium.

Through the preparation method of the electrode disclosed in the embodiment, since the three-block copolymer surfactant is added in the process of preparing the electrode, the catalyst can be bonded to the metal mesh without using an adhesive during the manufacturing process. The catalyst is brought into direct contact with the metal mesh. In addition, the three-block copolymer surfactant can also provide the catalyst with a single phase perovskite structure and a high specific surface area.

The following is an example and experimental verification of the electrodes made by this proposal in several examples.

Example 10 (nickel foam material + LaCoO3 / 1% P123)

First, P123 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 stir bar for 1 hour to uniformly dissolve P123 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, the scale has a molar ratio of 1:1:1 of lanthanum nitrate [La(NO3)3 ̇6H2O], cobaltous cobalt [Co(NO3)2 ̇6H2O], and citric acid [C6H8H7 ̇6H2O] (step S702) And adding deionized water so that the concentration of cerium ions and cobaltous ions in the aqueous solution is 0.35M.

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

Next, a nickel foaming material is provided (step S704), and the nickel foaming material is immersed in the solution (step S705). Among them, the nickel foaming material is a porous metal mesh, and thus can have a high surface area to carry the catalyst.

Finally, the nickel foaming material and the solution were calcined under nitrogen gas at 1 atm, and were classified into two-stage calcination. First, calcination was carried out at 450 ° C for 1 hour, followed by calcination at 600 ° C for 2 hours (step S706) to carry the catalyst on the metal mesh, that is, the preparation of the electrode of Example 10 was completed.

Example 11 (nickel foam material + LaCoO3/2% P123)

First, P123 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 stir bar for 1 hour to uniformly dissolve P123 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 was 0.02:320:1.

Next, the scale has a molar ratio of 1:1:1 of lanthanum nitrate [La(NO3)3 ̇6H2O], cobaltous cobalt [Co(NO3)2 ̇6H2O], and citric acid [C6H8H7 ̇6H2O] (step S702) And adding deionized water so that the concentration of cerium ions and cobaltous ions in the aqueous solution is 0.35M.

Then, an aqueous solution containing cerium ions and cobaltous ions was slowly dropped into an aqueous solution containing P123 (step S703), and stirring was continued for 2 hours. Wherein, the molar ratio of cerium nitrate, cobaltous nitrate, citric acid, glacial acetic acid, deionized water, and P123 is 1:1:1:1:320:0.02, and the solution is clarified pink Solution.

Next, a nickel foaming material is provided (step S704), and the nickel foaming material is immersed in the solution (step S705). Among them, the nickel foaming material is a porous metal mesh, and thus can have a high surface area to carry the catalyst.

Finally, the nickel foaming material and the solution were calcined under nitrogen gas at 1 atm, and were classified into two-stage calcination. First, calcination was carried out at 450 ° C for 1 hour, followed by calcination at 600 ° C for 2 hours (step S706) to carry the catalyst on the metal mesh, that is, the preparation of the electrode of Example 11 was completed.

The nickel foaming material and the electrode of the eleventh (2% P123) were subjected to X-ray diffraction analysis. The results are shown in "8A" and "8B", wherein "8A" is nickel foaming. The X-ray diffraction analysis result of the material, "8B" is the X-ray diffraction analysis result of the electrode of the eleventh embodiment. Among them, "8A" shows signals at 44.50 degrees, 51.84 degrees, and 76.37 degrees at 2θ. These signals are compared with the database. It can be known that these signals are nickel metal phases (ICDD code: 00-004). -0850) characteristic peak. On the other hand, "8B" shows signals at 32.88 degrees, 33.29 degrees, 47.50 degrees, and 58.9 degrees at 2θ. These signals are compared with the database. It can be known that these signals are LaCoO3 perovskites. Characteristic peak of phase (ICDD code: 01-084-0848). Therefore, it can be seen from the "Fig. 8A" and "Fig. 8B" that the surface of the nickel foam material of the embodiment of the present invention does support the catalyst of LaCoO3.

Please refer to "Fig. 9A" to "9C", and "9A" to "9C" are respectively nickel foam materials, electrodes of the tenth embodiment, and scanning electron microscopes of the electrodes of the eleventh embodiment. (Scanning Electron Microscope, SEM) analysis results. As shown in "Picture 9B" and "Picture 9C", the nickel foam material does carry the catalyst of LaCoO3 and is evenly distributed on the surface of the nickel foam material without significantly changing the surface shape of the nickel foam material. appearance. Therefore, the electrode preparation method of the present invention can bond the catalyst to the carrier without using an adhesive, and has the advantages of being simple, rapid, and inexpensive 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 comprises a nickel foaming material and the Teflon, the catalyst layer 120 comprises an electrode as in the tenth embodiment, the electrolyte layer 130 comprises an alkaline solution, a colloidal electrolyte and a solid electrolyte, and the 140 metal layer may comprise, for example, lithium. Sodium or zinc.

According to the catalyst, the electrode and the preparation method thereof disclosed in the embodiments of the present invention, since the three-block copolymer surfactant is added in the process of preparing the catalyst and the electrode, the prepared catalyst has a single phase of calcium and titanium. The mineral structure thus solves the problem that during the preparation of the catalyst, a hetero phase is generated and the impurity phase reduces the surface area of the catalyst and thereby lowers the performance of the fabricated battery.

In addition, the addition of a 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 the battery, thereby increasing the discharge voltage and capacitance density of the fabricated battery. . In addition, the three-block copolymer surfactant can also make the catalyst bond with the metal mesh without the need for an adhesive, so that the catalyst directly contacts the metal mesh, and thus has the advantages of simplicity, rapidity, and low cost in preparation.

Although the present disclosure is as described above in the preferred embodiment of the foregoing, It is not intended to limit this proposal. Anyone who is familiar with the similarity of the proposal can make some changes and refinements without departing from the spirit and scope of this proposal. Therefore, the scope of patent protection of this proposal is subject to the scope of patent application attached to this specification. The definition is final.

Claims (8)

A method for preparing an electrode, comprising: providing a first metal and a second metal; mixing the first metal and the second metal in a solution, the solution comprising a three-block copolymer surfactant; providing a metal mesh And placing the metal mesh in the solution; and heating the solution and the metal mesh to react the first metal and the second metal into the catalyst to form a catalyst, so that the catalyst and the metal mesh form an electrode. The method for producing an electrode according to claim 1, wherein the first metal is ruthenium and the second metal is manganese, iron, co-cobalt or nickel. The method for preparing an electrode according to claim 1, wherein a molar ratio of the first metal to the triblock copolymer surfactant is between 100:1 and 10:1. The method for preparing an electrode according to claim 3, wherein the ratio of the molar ratio of the first metal to the triblock copolymer surfactant is between 100:1 and 25:1. The method for preparing an electrode according to claim 1, wherein a molar ratio of the second metal to the triblock copolymer surfactant is between 100:1 and 10:1. The method for preparing an electrode according to claim 5, wherein a molar ratio of the second metal to the triblock copolymer surfactant is between 100:1 and 25:1. An electrode comprising: a metal mesh; a catalyst supported on the metal mesh, the catalyst comprising a single phase of a perovskite metal oxide, the metal oxide comprising a first metal and a second metal, wherein the catalyst directly contacts the metal network. The electrode of claim 7, wherein the first metal is cerium and the second metal is manganese, iron, co-cobalt or nickel.