CN109560296B - Perovskite type catalyst, preparation method and application thereof, and zinc-air secondary battery - Google Patents
Perovskite type catalyst, preparation method and application thereof, and zinc-air secondary battery Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 13
- 239000010439 graphite Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 8
- 239000012670 alkaline solution Substances 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- 150000003624 transition metals Chemical group 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 5
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 5
- 238000005303 weighing Methods 0.000 claims abstract description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000010979 pH adjustment Methods 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000012047 saturated solution Substances 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 19
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Inorganic materials [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
- Hybrid Cells (AREA)
Abstract
The invention relates to a perovskite type catalyst, a preparation method and application thereof, and a zinc-air secondary battery containing the perovskite type catalyst. The general formula of the perovskite catalyst is as follows: laxA1‑xBO3C; in the formula, x is more than or equal to 0.1 and less than or equal to 0.9; a is an alkaline earth metal; b is a transition metal; c is a carrier, and is selected from one or more of activated carbon, graphite and carbon nano tubes. The preparation method of the perovskite type catalyst comprises the following steps: adding a carbon material into a saturated alkaline solution, stirring and drying to obtain an alkali-treated carbon material; respectively weighing salts of all metal elements according to a stoichiometric molar ratio to obtain a mixture; adding the mixture and acid into deionized water to obtain a mixed solution, and adjusting the pH value of the mixed solution to 8-10; and ultrasonically mixing the mixed solution after the pH is adjusted with the carbon material after the alkali treatment to obtain a prefabricated solution, drying the prefabricated solution to obtain dry gel, and sintering the dry gel to obtain the perovskite type catalyst. The perovskite catalyst has lower cost.
Description
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a perovskite type catalyst, a preparation method and application thereof, and a zinc-air secondary battery containing the perovskite type catalyst.
Background
The zinc-air battery has the characteristics of high energy, zero pollution, no combustion and explosion, cyclic utilization and the like, so that the zinc-air battery can be used as a power supply of an electric vehicle. Especially, the zinc-air secondary battery has higher energy density and greater development potential, so that the research on the zinc-air secondary battery is more and more.
Generally, in the preparation process of the zinc-air secondary battery, a noble metal bifunctional catalyst such as platinum is adopted, and the zinc-air secondary battery prepared by adopting the catalyst has good stability, but the catalyst is expensive, so that the large-scale popularization of the zinc-air secondary battery is limited to a great extent.
Disclosure of Invention
In view of the above, it is necessary to provide a perovskite catalyst with low cost, a preparation method and applications thereof, and a zinc-air secondary battery containing the perovskite catalyst, in order to solve the problem of how to reduce the cost of the catalyst.
A perovskite catalyst having the general formula: laxA1-xBO3C; in the formula, x is more than or equal to 0.1 and less than or equal to 0.9; a is an alkaline earth metal; b is a transition metal; c is a carrier, and is selected from one or more of activated carbon, graphite and carbon nano tubes.
In one embodiment, the alkaline earth metal is selected from one or more of Ca, Sr, and Ba.
In one embodiment, the transition metal is selected from one or more of Fe, Co, Mn, and Ni.
In one embodiment, C is selected from activated carbon or graphite.
A method for preparing a perovskite catalyst, comprising the steps of:
adding a carbon material into a saturated alkaline solution for activity modification, stirring at room temperature, filtering, and drying to obtain the carbon material subjected to alkali treatment;
according to the stoichiometric molar ratio La: a: 1, respectively weighing one or more of inorganic salt, oxalate and acetate of each metal element, and uniformly mixing to obtain a mixture;
adding the mixture and acid into deionized water for reaction, performing ultrasonic treatment to obtain a viscous mixed solution, adjusting the pH of the mixed solution to 8-10, wherein the acid is one or more of citric acid, organic acid tartaric acid and ethylenediamine tetraacetic acid;
ultrasonically mixing the mixed solution after the pH is adjusted with the carbon material after the alkali treatment to obtain a prefabricated solution, and drying the prefabricated solution to obtain a dry gel;
and sintering the xerogel to obtain the perovskite type catalyst.
In one embodiment, the mass ratio of the mixture to the carbon material is (0.6:1) - (1.4: 1).
In one embodiment, the step of sintering the xerogel to obtain the perovskite-type catalyst comprises: and sintering the xerogel for 0.5-1 hour under 400-600 watts by adopting microwave to obtain the perovskite catalyst.
In one embodiment, in the step of adding the mixture and acid into deionized water, performing ultrasonic treatment to obtain a viscous mixed solution, and adjusting the pH of the mixed solution to 8-10, the ultrasonic treatment conditions are as follows: the power is 100 and 120 watts; the ultrasonic time is 1-2 hours.
In one embodiment, in the step of ultrasonically mixing the mixed solution after pH adjustment with the carbon material after alkali treatment, the ultrasonic conditions are as follows: the power is 100-150 watts; the ultrasonic time is 1-3 hours.
An application of perovskite catalyst in the preparation of zinc-air secondary battery.
A zinc-air secondary battery comprising the above perovskite catalyst.
The perovskite catalyst adopts alkaline earth metal and transition metal oxide, thereby reducing the cost of the catalyst and further promoting the application of the zinc-air secondary battery.
The preparation method of the perovskite catalyst is simple to operate and low in cost.
The zinc-air secondary battery comprises the perovskite catalyst, and has good stability and low cost.
Drawings
FIG. 1 is a schematic flow diagram of a process for preparing a perovskite catalyst according to one embodiment;
fig. 2 is a test chart of charge and discharge performance of the zinc-air secondary battery prepared by using the perovskite catalyst.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
An example perovskite catalyst has the general formula LaxA1-xBO3In the formula, x is more than or equal to 0.1 and less than or equal to 0.9; a is an alkaline earth metal; b is a transition metal; c is a carrier, and is selected from one or more of activated carbon, graphite and carbon nano tubes. "/" indicates that C is the carrier and LaxA1-xBO3Attached to the carrier C.
In one embodiment, the alkaline earth metal is selected from one or more of Ca, Sr, and Ba.
In one embodiment, the transition metal is selected from one or more of Fe, Co, Mn, Ni.
In one embodiment, C is selected from activated carbon or graphite.
The perovskite catalyst adopts alkaline earth metal and transition metal, thereby reducing the cost of the catalyst and further popularizing the application of the zinc-air secondary battery. In addition, the problem that hydrogen is easy to generate due to the fact that soluble precious metal is deposited on negative electrode zinc and hydrogen absorption overpotential is reduced can be avoided, and the influence on the performance of the zinc-air secondary battery is further reduced.
The perovskite catalyst can be applied to the preparation of the zinc-air secondary battery, so that the application of the zinc-air secondary battery is expanded, and the prepared zinc-air secondary battery has stable electrical property.
The zinc-air secondary battery of one embodiment comprises the perovskite type catalyst, has good stability and is low in cost.
As shown in fig. 1, the method for preparing a perovskite-type catalyst of an embodiment includes the steps of:
s110: adding a carbon material into a saturated alkaline solution for activity modification, stirring at room temperature, filtering, and drying to obtain the carbon material subjected to alkali treatment.
Specifically, the carbon material is one or more of activated carbon, graphite, and carbon nanotubes. The saturated alkaline solution is a saturated solution of sodium carbonate. The saturated alkaline solution may be a saturated solution of potassium carbonate or the like. Adding the carbon material into the saturated alkaline solution, and stirring at room temperature for 12-36 hours, thereby treating the carbon material to increase the reactive sites of the carbon material. In addition, the carbon material used not only has conductivity but also has a large specific surface, thereby further increasing the reactive sites. After stirring at room temperature for 12-36 hours, filtration and drying were carried out to obtain a treated carbon material. Wherein, the filtration can adopt membrane filtration and the like. The drying condition may be drying at 40-50 deg.C for 2-3 hr.
S120: according to the stoichiometric molar ratio La: a: and (B ═ x) (1-x) 1, weighing salts of the metal elements respectively, and mixing uniformly to obtain a mixture.
Specifically, the mass ratio of the mixture to the carbon material in step S110 is (0.6:1) - (1.4: 1). The salt of each metal element is one or more of inorganic salt, oxalate and acetate. Further, the inorganic salt of each metal element may be one or more of nitrate, carbonate, and sulfate. Further, the salt of each metal element may be a nitrate.
S130: and adding the mixture and acid into deionized water for reaction, performing ultrasonic treatment to obtain a viscous mixed solution, and adjusting the pH value of the mixed solution to 8-10.
Specifically, the acid is one or more of citric acid, organic acid tartaric acid and ethylenediamine tetraacetic acid. Adding the mixture and acid into deionized water, and carrying out ultrasonic treatment for 1-2 hours at the power of 100-120 watts to obtain a mixed solution. So that the salt of each metal element in the mixture reacts with the acid to make the mixed solution viscous. And then adjusting the pH of the mixed solution to 8-10 by adding ammonia water. Other bases may be used to adjust the pH of the mixed solution. Further, the salt of each metal element is a nitrate.
S140: and ultrasonically mixing the mixed solution after the pH is adjusted with the carbon material after the alkali treatment to obtain a prefabricated solution, and drying the prefabricated solution to obtain the xerogel.
Specifically, the mixed solution after pH adjustment obtained in step S130 and the alkali-treated carbon material obtained in step S110 are subjected to ultrasonic mixing under the conditions: the power is 100 and 120 watts; the ultrasonic treatment time is 1-2 hours, and a prefabricated solution is obtained. The pre-formed solution is then dried at 80-160 ℃ for 12-24 hours to give a xerogel.
S150: and sintering the xerogel to obtain the perovskite type catalyst.
Specifically, the xerogel in step S140 is sintered for 0.5-1 hour under 400-600 watts by microwave to obtain the perovskite catalyst. The perovskite catalyst may be obtained by drying a xerogel in an oven.
The invention is further illustrated by the following specific examples.
Example 1
(1) Adding 5g of graphite into a saturated sodium carbonate solution, stirring for 24 hours at room temperature, filtering, and drying at 50 ℃ for 2 hours to obtain alkali-treated activated carbon;
(2) respectively weighing La (NO) according to the stoichiometric molar ratio of 0.4:0.6:13)26H2O、Ca(NO3)22H2O and Co (NO)3)26H2O three nitrates, the total mass of the three nitrates being 5g, andthe seed nitrates are mixed uniformly to obtain a mixture.
(3) Adding the mixture obtained in the step (2) and 4g of citric acid into deionized water, performing ultrasonic treatment at the power of 100 watts for 1 hour to obtain a viscous mixed solution, and adding ammonia water to adjust the pH value of the mixed solution to 8;
(4) mixing the mixed solution after pH adjustment in the step (3) with the graphite after alkali treatment obtained in the step (1), and carrying out ultrasonic treatment for 1-2 hours at the power of 100-120 watts to obtain a prefabricated solution; the pre-formed solution was dried at 100 ℃ for 1.5 hours to give a xerogel.
(5) Sintering the xerogel obtained in the step (4) at 400 watts for 0.5 hour by using microwaves to obtain La0.4Ca0.6CoO3A graphitic perovskite catalyst.
Example 2
La was prepared by the procedure of example 10.4Ca0.6CoO3Activated carbon perovskite catalyst, the difference being that the carbon used is activated carbon.
Example 3
A perovskite catalyst was prepared by the procedure of example 1 except that Co (NO) was used in the step (2)3)26H2Changing O to Mn (NO)3)24H2O, thereby obtaining La as the perovskite type catalyst0.4Ca0.6MnO3Graphite.
Example 4
The perovskite-type catalyst was prepared by the procedure of example 1 except that the pH was adjusted to 9 in step (3).
Example 5
A perovskite-type catalyst was prepared by following the procedure of example 1 except that the alkali metal nitrate used in the procedure of step (2) was barium nitrate and the perovskite-type catalyst obtained was La0.4Ba0.6MnO3Graphite.
When the perovskite catalyst is applied to a zinc-air secondary battery, La is used0.4Ca0.6CoO3The zinc-air secondary battery prepared by taking graphite as a catalyst is shown in figure 2 and is at 60mA/cm2The charge and discharge performance test is carried out under the current density, the cycle is carried out for 25 times, and the performance is not obviously attenuated, which shows that the zinc-air secondary battery prepared by the catalyst is relatively stable.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A process for the preparation of a perovskite catalyst of the general formula: laxA1-xBO3C; in the formula, x is more than or equal to 0.1 and less than or equal to 0.9; a is an alkaline earth metal; b is a transition metal; c is a carrier, the alkaline earth metal is selected from one or more of Ca, Sr and Ba, the transition metal is selected from one or more of Fe, Co, Mn and Ni, and C is selected from one or more of activated carbon, graphite and carbon nano tubes; the method is characterized by comprising the following steps:
adding a carrier C into a saturated alkaline solution for activity modification, stirring for reaction, filtering and drying to obtain the carrier subjected to alkali treatment, wherein the saturated alkaline solution is selected from a sodium carbonate saturated solution or a potassium carbonate saturated solution;
according to the stoichiometric molar ratio La: a: b = x (1-x) 1, respectively weighing salts of each metal element, and uniformly mixing to obtain a mixture, wherein the salts are selected from one or more of nitrate, carbonate, sulfate, oxalate and acetate;
adding the mixture and acid into deionized water for reaction, performing ultrasonic treatment to obtain a viscous mixed solution, and adjusting the pH of the mixed solution to 8-10, wherein the acid is one or more of citric acid, tartaric acid as an organic acid and ethylenediamine tetraacetic acid;
ultrasonically mixing the mixed solution after pH adjustment with the carrier after alkali treatment to obtain a prefabricated solution, and drying the prefabricated solution to obtain dry gel;
and sintering the xerogel for 0.5-1 hour under 400-600 watts by adopting microwave to obtain the perovskite catalyst.
2. The process for producing a perovskite catalyst as claimed in claim 1, wherein the support is selected from the group consisting of activated carbon and graphite.
3. The method for producing a perovskite catalyst according to claim 1, wherein a mass ratio of the mixture to the support is (0.6:1) to (1.4: 1).
4. The process for preparing a perovskite catalyst according to claim 1, wherein the mixture and an acid are added to deionized water, and the mixture is subjected to ultrasonic treatment under conditions of: the power is 100 and 120 watts; the ultrasonic time is 1-2 hours.
5. The production method of a perovskite catalyst according to claim 1, characterized in that in the step of ultrasonically mixing the mixed solution after the pH adjustment with the support after the alkali treatment, the ultrasonic conditions are: the power is 100-150 watts; the ultrasonic time is 1-3 hours.
6. The process for producing a perovskite catalyst according to claim 1, wherein the conditions for drying the pre-formed solution are: the pre-formed solution is dried at 80-160 ℃ for 12-24 hours.
7. A perovskite catalyst produced by the method for producing a perovskite catalyst according to any one of claims 1 to 6.
8. A zinc-air secondary battery characterized in that it comprises the perovskite-type catalyst according to claim 7.
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| CN109560296B true CN109560296B (en) | 2022-01-07 |
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