CN107293760B - Preparation method of perovskite type catalyst for metal-air battery - Google Patents

Preparation method of perovskite type catalyst for metal-air battery Download PDF

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CN107293760B
CN107293760B CN201710430210.8A CN201710430210A CN107293760B CN 107293760 B CN107293760 B CN 107293760B CN 201710430210 A CN201710430210 A CN 201710430210A CN 107293760 B CN107293760 B CN 107293760B
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gel
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CN107293760A (en
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田丙伦
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Hydrogen New Shanghai New Energy Technology Co ltd
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Shanghai Bo Xuan Energy Science Co Ltd
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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
    • 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)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Inert Electrodes (AREA)
  • Hybrid Cells (AREA)

Abstract

The invention relates to a metal-air batteryA process for the preparation of a perovskite catalyst having the formula: laxY(1‑x)ZO3(ii) a In the formula, x is more than 0 and less than 1, Y is Sr or Co, and Z is Mn or Fe; it comprises the following steps: (a) lanthanum nitrate, nitric acid Y and nitric acid Z are weighed according to the molar ratio of x: 1-x: l, are respectively dissolved in water, and then glycol is added to form a mixed solution; (b) adding a complexing agent into the mixed solution, adjusting the pH value of the mixed solution to 6-7 by using ammonia water, and stirring and complexing; then moving the mixture into a constant-temperature water bath kettle, stirring the mixture until gel is formed, drying the gel, and grinding the gel into powder; (c) and calcining the powder at 250-500 ℃. High-temperature roasting at over 500 ℃ is not needed, so that the preparation process and difficulty are simplified, and the cost is reduced.

Description

Preparation method of perovskite type catalyst for metal-air battery
Technical Field
The invention belongs to the field of metal-air batteries, relates to a catalyst, and particularly relates to a preparation method of a perovskite catalyst for a metal-air battery.
Background
Currently, the increasing demand for energy has stimulated the development of alternative energy conversion and storage systems that are efficient, low cost, and environmentally friendly. Oxygen reduction (ORR) and Oxygen Evolution Reaction (OER) are the core of important renewable energy technologies, including fuel cells, lithium-air/oxygen cells and water splitting. If inexhaustible oxygen in air is continuously used to provide capacity, the theoretical energy density of a lithium-air battery is about 11140 watt-hours/kg, much higher than other energy storage devices. However, for this type of lithium-air battery, since a non-aqueous electrolyte is used, the discharge product Li, which is insoluble in organic electrolytes2O2the porous air electrode is gradually clogged. Therefore, the battery performance may deteriorate with the discharge time.
For the commercial application of lithium-air batteries, there are many problems to be solved at present, including poor electrolyte stability, poor charge/discharge efficiency of cathode catalysts, rate capability and cycle life, etc. One of the key challenges in these issues is the slow Oxygen Reduction Reaction (ORR) (discharge process) and Oxygen Evolution Reaction (OER) (charge process) kinetics. The cathode catalysts currently used to catalyze air reactions are typically carbon or carbon-supported noble metal catalysts, but are expensive. Therefore, in order to design lithium-air batteries, lithium-air fuel cells and hydrogen/air fuel cells based on polymer electrolyte membranes with high performance and long-term stability, it is highly desirable to develop low-cost, high-efficiency bifunctional electrocatalysts.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a perovskite type catalyst for a metal-air battery.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of a perovskite type catalyst for a metal-air battery is disclosed, wherein the chemical formula of the perovskite type catalyst is as follows: laxY(1-x)ZO3(ii) a In the formula, x is more than 0 and less than 1, Y is Sr or Co, and Z is Mn or Fe; it comprises the following steps:
(a) Lanthanum nitrate, nitric acid Y and nitric acid Z are weighed according to the molar ratio of x: 1-x: 1, are respectively dissolved in water, and then glycol is added to form a mixed solution;
(b) adding a complexing agent into the mixed solution, adjusting the pH value of the mixed solution to 6-7 by using ammonia water, and stirring and complexing; then moving the mixture into a constant-temperature water bath kettle, stirring the mixture until gel is formed, drying the gel, and grinding the gel into powder;
(c) And calcining the powder at 250-500 ℃.
Optimally, in the step (a), the volume ratio of the water to the glycol is 1-10: 1.
Furthermore, the mol ratio of the complexing agent to the total amount of La, Y and Z ions is 1: 1-3.
In a preferred embodiment of the present invention, the perovskite catalyst has the chemical formula: laxSr(1-x)MnO3X is more than 0.5 and less than 1; the complexing agent adopted by the method is citric acid; in the step (c), the powder is calcined for 5-10 hours at 350-500 ℃.
In another preferred embodiment of the present invention, the perovskite catalyst has the chemical formula: laxCo(1-x)FeO3and x is more than 0.5 and less than 1. The complexing agent is preferably one of 1-ethyl-3-methylimidazole halogenated salts, and is preferably a chloride salt; in the step (c), the powder is calcined for 3-5 hours at 250-350 ℃.
optimally, in the step (b), the stirring and complexing time is 2-3 hours.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: according to the preparation method of the perovskite type catalyst for the metal-air battery, the perovskite type catalyst can be prepared only by calcining at a low temperature of 250-500 ℃, and high-temperature roasting at a temperature of more than 500 ℃ is not required, so that the preparation process and difficulty are simplified, and the cost is reduced.
Detailed Description
the invention relates to a perovskite catalyst for a metal-air batterythe perovskite catalyst has the chemical formula: laxY(1-x)ZO3(ii) a In the formula, x is more than 0 and less than 1, Y is Sr or Co, and Z is Mn or Fe; it comprises the following steps: (a) lanthanum nitrate, nitric acid Y and nitric acid Z are weighed according to the molar ratio of x: 1-x: 1, are respectively dissolved in water, and then glycol is added to form a mixed solution; (b) adding a complexing agent into the mixed solution, adjusting the pH value of the mixed solution to 6-7 by using ammonia water, and stirring and complexing; then moving the mixture into a constant-temperature water bath kettle, stirring the mixture until gel is formed, drying the gel, and grinding the gel into powder; (c) and calcining the powder at 250-500 ℃. High-temperature roasting at over 500 ℃ is not needed, so that the preparation process and difficulty are simplified, and the cost is reduced.
In the step (a), the volume ratio of the water to the glycol is 1-10: 1. The mol ratio of the complexing agent to the total amount of La, Y and Z ions is 1: 1-3, and the stirring and complexing time is 2-3 hours, so as to ensure that the complexing agent is fully complexed.
The perovskite catalyst preferably has the formula: laxSr(1-x)MnO3And x is more than 0.5 and less than 1, and the complexing agent matched with the powder is citric acid, so that the corresponding powder is calcined at 350-500 ℃ for 5-10 hours. The perovskite catalyst also preferably has the formula: laxCo(1-x)FeO3And x is more than 0.5 and less than 1, the complexing agent matched with the complex is one of 1-ethyl-3-methylimidazole halogenated salts, and the powder is calcined at the temperature of 250-350 ℃ for 3-5 hours, so that the calcining temperature and time of the powder are greatly reduced.
The present invention will be further illustrated with reference to the following examples.
Example 1
this example provides a method for preparing a perovskite catalyst for a metal-air battery, where the perovskite catalyst has a chemical formula: la0.6Sr0.4MnO3it comprises the following steps:
(a) Weighing 0.6mol of lanthanum nitrate, 0.4mol of strontium nitrate and 1mol of manganese nitrate, respectively dissolving in 1000ml of water, and then adding 1000ml of ethylene glycol to form a mixed solution;
(b) Adding 2mol of citric acid into the mixed solution, adjusting the pH value of the mixed solution to 6-7 by using ammonia water, and stirring and complexing; then moving the mixture into a constant-temperature water bath kettle, stirring the mixture at 90 ℃ to form gel, then placing the gel into a drying oven at 150 ℃, drying the gel, and grinding the gel into powder;
(c) Calcining the powder at 350 deg.C for 10 hr.
Example 2
This example provides a preparation method of a perovskite catalyst for a metal-air battery, which is substantially the same as that in example 1, except that: in the step (a), 0.4mol of lanthanum nitrate, 0.6mol of strontium nitrate and 1mol of manganese nitrate are weighed, and finally the catalyst La is obtained0.4Sr0.6MnO3。
Example 3
This example provides a preparation method of a perovskite catalyst for a metal-air battery, which is substantially the same as that in example 1, except that: in the step (a), 0.8mol of lanthanum nitrate, 0.2mol of strontium nitrate and 1mol of manganese nitrate are weighed, and finally the catalyst La is obtained0.8Sr0.2MnO3。
example 4
this example provides a preparation method of a perovskite catalyst for a metal-air battery, which is substantially the same as that in example 1, except that: in step (a), 100ml of ethylene glycol was added.
Example 5
This example provides a preparation method of a perovskite catalyst for a metal-air battery, which is substantially the same as that in example 1, except that: in step (a), 500ml of ethylene glycol was added.
Example 6
This example provides a preparation method of a perovskite catalyst for a metal-air battery, which is substantially the same as that in example 1, except that: in the step (c), the powder is calcined for 5 hours at 500 ℃.
Example 7
The embodiment provides a perovskite for a metal-air batteryThe preparation method of the ore-type catalyst comprises the following steps: la0.6Co0.4FeO3It comprises the following steps:
(a) Weighing 0.6mol of lanthanum nitrate, 0.4mol of cobalt nitrate and 1mol of ferric nitrate, respectively dissolving in 1000ml of water, and then adding 1000ml of ethylene glycol to form a mixed solution;
(b) Adding 2mol of 1-ethyl-3-methylimidazole chloride into the mixed solution, adjusting the pH value of the mixed solution to 6-7 by using ammonia water, and stirring and complexing; then moving the mixture into a constant-temperature water bath kettle, stirring the mixture at 90 ℃ to form gel, then placing the gel into a drying oven at 150 ℃, drying the gel, and grinding the gel into powder;
(c) Calcining the powder at 350 deg.C for 3 hr.
Example 8
This example provides a method for preparing a perovskite-type catalyst for a metal-air battery, which is substantially the same as that of example 6, except that: in step (b), citric acid is used.
Example 9
This example provides a method for preparing a perovskite-type catalyst for a metal-air battery, which is substantially the same as that of example 6, except that: in the step (c), the powder is calcined for 5 hours at the temperature of 250 ℃.
Comparative example 1
This example provides a process for preparing a perovskite-type catalyst for a metal-air battery, which process was substantially the same as in example 7, except that 1000ml of ethylene glycol was not added.
Comparative example 2
This example provides a method of preparing a perovskite-type catalyst for a metal-air battery, which was substantially the same as that of example 7, except that citric acid was not added.
Comparative example 3
This example provides a method for preparing a perovskite-type catalyst for a metal-air battery, which is substantially the same as that of example 7, except that: calcination was carried out at 950 ℃ for 10 hours.
the perovskite catalysts prepared in examples 1-8 and comparative examples 1-3 were dispersed in Nafion solution, typically 10mg of the catalyst was added to 95. mu.l of 5% Nafion solution 5%, 350. mu.l of ethanol was added, 7. mu.l was dropped on a disk electrode, and electrochemical measurements were carried out in 6M KOH solution at-0.3V polarization current density of 0.075Acm, respectively-2、0.065Acm-2、0.070Acm-2、0.075Acm-2、0.075Acm-2、0.078Acm-2、0.092Acm-2、0.058Acm-2、0.088Acm-2、0.049Acm-2、0Acm-2、0.045Acm-2(ii) a The perovskite catalysts are subjected to a cycling stability test, and the polarization current density retention rates after 10000 cycles are respectively 99%, 90%, 92%, 95%, 96%, 99%, 85%, 92%, 80%, 0 and 75%.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.

Claims (2)

1. A preparation method of a perovskite type catalyst for a metal-air battery is disclosed, wherein the chemical formula of the perovskite type catalyst is as follows: laxY(1-x)ZO3(ii) a In the formula, x is more than 0.5 and less than 1, Y is Co, and Z is Fe; it is characterized by comprising the following steps: (a) lanthanum nitrate, nitric acid Y and nitric acid Z are weighed according to the molar ratio of x: 1-x: 1, are respectively dissolved in water, and then glycol is added to form a mixed solution; the volume ratio of the water to the glycol is 1-10: 1;
(b) Adding a complexing agent into the mixed solution, adjusting the pH value of the mixed solution to 6-7 by using ammonia water, and stirring and complexing; then moving the mixture into a constant-temperature water bath kettle, stirring the mixture until gel is formed, drying the gel, and grinding the gel into powder; the mol ratio of the complexing agent to the total amount of La, Y and Z ions is 1: 1-3; the complexing agent is one of 1-ethyl-3-methylimidazole halogenated salts;
(c) And calcining the powder at 250-350 ℃.
2. The method for producing a perovskite-type catalyst for a metal-air battery according to claim 1, characterized in that: in the step (b), the stirring and complexing time is 2-3 hours.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1529374A (en) * 2003-10-08 2004-09-15 华南理工大学 Zinc-air battery electrocatalyst and preparation method thereof
CN101845306A (en) * 2010-03-31 2010-09-29 天津大学 Preparation method and application of Lal-xSrxCoO3 perovskite catalyst
CN103831097A (en) * 2014-03-26 2014-06-04 苏州绿电能源科技有限公司 Nano-catalyst-lanthanum strontium manganese oxygen material, and preparation method and application of nano-catalyst-lanthanum strontium manganese oxygen material
CN106410226A (en) * 2016-12-08 2017-02-15 深圳大学 Graphene-doped modified nano-perovskite-type La(1-x)SrxMnO3 composite material as well as preparation method and application of composite material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1529374A (en) * 2003-10-08 2004-09-15 华南理工大学 Zinc-air battery electrocatalyst and preparation method thereof
CN101845306A (en) * 2010-03-31 2010-09-29 天津大学 Preparation method and application of Lal-xSrxCoO3 perovskite catalyst
CN103831097A (en) * 2014-03-26 2014-06-04 苏州绿电能源科技有限公司 Nano-catalyst-lanthanum strontium manganese oxygen material, and preparation method and application of nano-catalyst-lanthanum strontium manganese oxygen material
CN106410226A (en) * 2016-12-08 2017-02-15 深圳大学 Graphene-doped modified nano-perovskite-type La(1-x)SrxMnO3 composite material as well as preparation method and application of composite material

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Patentee before: SHANGHAI BOXUAN ENERGY TECHNOLOGY CO.,LTD.