CN111799474A - Method for preparing solid oxide fuel cell cathode - Google Patents

Method for preparing solid oxide fuel cell cathode Download PDF

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Publication number
CN111799474A
CN111799474A CN201911256838.6A CN201911256838A CN111799474A CN 111799474 A CN111799474 A CN 111799474A CN 201911256838 A CN201911256838 A CN 201911256838A CN 111799474 A CN111799474 A CN 111799474A
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cathode
fuel cell
oxide fuel
solid
solid oxide
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CN201911256838.6A
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杨九福
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Miluo Fuyuan New Material Co ltd
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Miluo Fuyuan New Material 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
    • 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
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • 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
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8896—Pressing, rolling, calendering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • 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
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8684—Negative electrodes
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Fuel Cell (AREA)
  • Inert Electrodes (AREA)

Abstract

The invention belongs to the technical field of battery material preparation, and particularly discloses a method for preparing a solid oxide fuel cell cathode, which takes dysprosium nitrate hexahydrate, barium nitrate and cobalt nitrate hexahydrate as raw materials and utilizes an EDTA (ethylene diamine tetraacetic acid) -citric acid method to obtain DyBaCo with a double perovskite structure2O5The cathode material can be used for preparing a solid oxide fuel cell cathode which can be suitable for medium and low temperature environments and has good conductivity.

Description

Method for preparing solid oxide fuel cell cathode
Technical Field
The invention belongs to the technical field of battery material preparation, and particularly relates to a method for preparing a solid oxide fuel cell cathode.
Background
A Solid Oxide Fuel Cell (SOFC) is a device that converts the chemical energy of a fuel into electrical energy, with the cell cathode being a major component of the solid oxide fuel cell and also a major part of the polarization loss. The cathode materials which are commonly used at present are mainly pure electron conductor oxide materials, and the materials have more limitations in the application of the cathode of the battery. LaMnO doped with strontium element3The pure electronic conductor oxide material as an example has high electronic conductivity at an operating temperature of 1000 ℃, but will cause rapid decrease in oxygen ion conductivity when the operating temperature is lowered. Therefore, the solid oxide fuel cell cathode prepared by the material is difficult to meet the requirements of medium and low temperature working environment, and the development of a cathode capable of being prepared by the material is neededThe cathode of the solid oxide fuel cell is suitable for the medium and low temperature environment requirements.
Disclosure of Invention
In view of the above technical problems, the present invention provides a method for preparing a solid oxide fuel cell cathode, which comprises the following specific steps:
step one, respectively weighing 20-25 parts by weight of dysprosium nitrate hexahydrate solid, 10-15 parts by weight of barium nitrate solid and 13-17 parts by weight of cobalt nitrate hexahydrate solid, mixing and crushing to obtain mixed powder, dissolving the mixed powder into deionized water, and fully stirring to form a uniform aqueous solution;
step two, adding an ethylene diamine tetraacetic acid solution with the mass fraction of 5-10% into the aqueous solution obtained in the step one, and adding a weak alkaline solution to adjust the pH value of the aqueous solution to 7-8; standing for 20-40 min, and adding citric acid serving as a co-complexing agent into the aqueous solution;
step three, transferring the aqueous solution obtained in the step two to an evaporation dish, and stably evaporating water to obtain a viscous reddish brown colloid; transferring the colloid into an oven to be carbonized to obtain a black solid; transferring the black solid to a muffle furnace to be roasted to obtain cathode powder;
step four, grinding the cathode powder to 60-100 meshes, and mixing the ground cathode powder with ethanol and carboxymethyl cellulose to prepare cathode slurry;
and fifthly, calcining the cathode slurry in a 600-800 ℃ muffle furnace for 7-9 h, sintering in a high-temperature furnace for 10-14 h at 1000-1200 ℃ to obtain a cathode material, gradually rolling the cathode material into a membrane, and bonding the membrane and an electrolyte sheet to obtain the solid oxide fuel cell cathode.
Further, the mixed powder in the step one is obtained by mixing the solid raw materials and then crushing the mixture in a high-speed crusher at the rotating speed of 1500-1800 rpm for 30-40 minutes.
Further, the weak alkaline solution in the second step is one of an ammonia monohydrate solution, a sodium carbonate solution or a sodium bicarbonate solution.
Furthermore, the evaporation temperature in the third step is controlled within the range of 70-90 ℃, and the temperature of the oven is controlled within the range of 220-250 ℃.
Furthermore, the cathode material comprises DyBaCo2O5And (3) powder.
Has the advantages that: the DyBaCo with double perovskite structure is obtained by EDTA (ethylene diamine tetraacetic acid) -citric acid method for the cathode of the solid oxide fuel cell prepared by the method2O5The cathode material of (a), has a higher electrical conductivity in a low temperature environment than a battery cathode of other materials; can keep good stability in the temperature rising process, thereby being more suitable for medium and low temperature environment.
Drawings
FIG. 1 is a process for preparing a cathode for a battery according to an embodiment of the present invention;
FIG. 2 shows the results of the electron conductivity test in example 1 of the present invention;
fig. 3 shows the results of the electron conductivity test in embodiment 2 of the present invention.
Detailed Description
The present invention is described in detail below with reference to specific examples and related experimental data. The following examples are intended to further illustrate, but not limit, the present invention.
Example 1, taking dysprosium nitrate hexahydrate, barium nitrate and cobalt nitrate hexahydrate in a mass fraction ratio of 20: 10: 13.
1. taking 1000g dysprosium nitrate hexahydrate (DyH)12N3O15) Solid, 500g barium nitrate (Ba (NO)3)2) Solid and 650g of cobalt nitrate hexahydrate (CoH)12N2O12) Putting the solid into a high-speed grinder in sequence, setting parameters to be 1500-1800 rpm, grinding for 15min, uniformly mixing the ground powder to obtain mixed powder, adding the mixed powder into 9500g of deionized water, pouring the mixed powder into a planetary stirrer with the capacity of 100L, setting stirring parameters to be 380-400 rpm, stirring for 6-8 min, and starting a power supply of the stirrer to mix and stir; fully and uniformly stirring to obtain a uniform aqueous solution.
2. Transferring the uniformly mixed aqueous solution into a solid container,adding 21500g of 10 wt% EDTA solution, adjusting pH with ammonium monohydrate solution, maintaining pH at 7-8, standing for 30min, and adding 350g citric acid (C)6H8O7) As a co-complexing agent, and simultaneously keeping the pH within 7-8.
3. Transferring the solution in the solid container to an evaporating dish, controlling the temperature to be about 80 ℃ to ensure that water is stably evaporated until viscous reddish brown colloid which is transparent is obtained in the evaporating dish, transferring the colloid to an oven, and controlling the baking temperature to be 240 ℃ to ensure that the colloid is carbonized to obtain black solid; and transferring the black solid into a muffle furnace for roasting, controlling the temperature of the muffle furnace to be about 950 ℃, ensuring the atmosphere to be air atmosphere, roasting for 2h, and fully removing the organic ligand to obtain the powder material for manufacturing the cathode of the solid oxide fuel cell.
4. And transferring the powder material into a planetary ball mill for grinding to enable the particle diameter of the powder to be 180-160 um, and fully mixing the ground powder with ethanol and carboxymethyl fiber to obtain cathode slurry.
5. And transferring the cathode slurry into a muffle furnace, controlling the temperature of the muffle furnace to be about 800 ℃, calcining the slurry in the muffle furnace for 8 hours, transferring the slurry into a high-temperature furnace, controlling the temperature of the high-temperature furnace to be about 1100 ℃, sintering the slurry for 12 hours to obtain a cathode material, gradually rolling the cathode material into a membrane, and attaching the membrane and an electrolyte sheet to obtain the cathode of the solid oxide fuel cell.
6. Setting the temperature gradient to be 20 ℃, measuring the temperature in the range of 200-500 ℃, and measuring the electronic conductivity of the battery cathode by adopting a four-probe method, wherein the measurement result is shown in figure 2.
Example 2, taking dysprosium nitrate hexahydrate, barium nitrate and cobalt nitrate hexahydrate in a mass fraction ratio of 20: 15: 17.
1. taking 1000g dysprosium nitrate hexahydrate (DyH)12N3O15) Solid, 750g barium nitrate (Ba (NO)3)2) Solid and 850g of cobalt nitrate hexahydrate (CoH)12N2O12) Sequentially pulverizing the solid at high speedIn the machine, setting parameters of 1500-1800 rpm, crushing for 15min, uniformly mixing all the crushed powder to obtain mixed powder, adding the mixed powder into 9500g of deionized water, pouring the mixed powder into a planetary stirrer with the capacity of 100L, setting stirring parameters to be 380-400 rpm, stirring for 6-8 min, and starting a power supply of the stirrer to mix and stir; fully and uniformly stirring to obtain a uniform aqueous solution.
2. Transferring the uniformly mixed aqueous solution into a solid container, adding 21500g of 10% ethylene diamine tetraacetic acid solution by mass, adjusting pH with ammonium monohydrate solution, keeping pH within 7-8, standing for 30min, adding 350g of citric acid (C)6H8O7) As a co-complexing agent, and simultaneously keeping the pH within 7-8.
3. Transferring the solution in the solid container to an evaporating dish, controlling the temperature to be about 80 ℃ to ensure that water is stably evaporated until viscous reddish brown colloid which is transparent is obtained in the evaporating dish, transferring the colloid to an oven, and controlling the baking temperature to be 240 ℃ to ensure that the colloid is carbonized to obtain black solid; and transferring the black solid into a muffle furnace for roasting, controlling the temperature of the muffle furnace to be about 950 ℃, ensuring the atmosphere to be air atmosphere, roasting for 2h, and fully removing the organic ligand to obtain the powder material for manufacturing the cathode of the solid oxide fuel cell.
4. And transferring the powder material into a planetary ball mill for grinding to enable the particle diameter of the powder to be 180-160 um, and fully mixing the ground powder with ethanol and carboxymethyl fiber to obtain cathode slurry.
5. And transferring the cathode slurry into a muffle furnace, controlling the temperature of the muffle furnace to be about 800 ℃, calcining the slurry in the muffle furnace for 8 hours, transferring the slurry into a high-temperature furnace, controlling the temperature of the high-temperature furnace to be about 1100 ℃, sintering the slurry for 12 hours to obtain a cathode material, gradually rolling the cathode material into a membrane, and attaching the membrane and an electrolyte sheet to obtain the cathode of the solid oxide fuel cell.
6. The temperature gradient is set to be 20 ℃, the measurement range is 200-500 ℃, the electron conductivity of the battery cathode is measured by adopting a four-probe method, and the measurement result is shown in figure 3.
According to the test results of the embodiment 1 and the embodiment 2, when the temperature is lower than 320 ℃, the charge transfer is influenced by the temperature, the conductivity gradually increases along with the temperature increase, when the temperature reaches about 320 ℃, the conductivity reaches the highest and the conductivity is the best at the moment, and then the conductivity decreases along with the temperature increase, so that the solid oxide fuel cell cathode prepared by the method can adapt to the requirements of medium and low temperature environments.
The use of these examples is intended to illustrate the invention only and not to limit the scope of the invention. In addition, after reading the technical content of the invention, the skilled person can make various changes, modifications or variations to the invention, and all the equivalents thereof also belong to the protection scope defined by the claims of the present application.

Claims (5)

1. A method of making a solid oxide fuel cell cathode comprising the steps of:
step one, respectively weighing 20-25 parts by weight of dysprosium nitrate hexahydrate solid, 10-15 parts by weight of barium nitrate solid and 13-17 parts by weight of cobalt nitrate hexahydrate solid, mixing and crushing to obtain mixed powder, dissolving the mixed powder into deionized water, and fully stirring to form a uniform aqueous solution;
step two, adding an ethylene diamine tetraacetic acid solution with the mass fraction of 5-10% into the aqueous solution obtained in the step one, and adding a weak alkaline solution to adjust the pH value of the aqueous solution to 7-8; standing for 20-40 min, and adding citric acid serving as a co-complexing agent into the aqueous solution;
step three, transferring the aqueous solution obtained in the step two to an evaporation dish, and stably evaporating water to obtain a viscous reddish brown colloid; transferring the colloid into an oven to be carbonized to obtain a black solid; transferring the black solid to a muffle furnace to be roasted to obtain cathode powder;
step four, grinding the cathode powder to 60-100 meshes, and mixing the ground cathode powder with ethanol and carboxymethyl cellulose to prepare cathode slurry;
and fifthly, calcining the cathode slurry in a 600-800 ℃ muffle furnace for 7-9 h, sintering in a high-temperature furnace for 10-14 h at 1000-1200 ℃ to obtain a cathode material, gradually rolling the cathode material into a membrane, and bonding the membrane and an electrolyte sheet to obtain the solid oxide fuel cell cathode.
2. The method of making a solid oxide fuel cell cathode of claim 1, wherein: and D, mixing the solid raw materials, and crushing the mixed powder in the step I for 30-40 minutes in a high-speed crusher at the rotating speed of 1500-1800 rpm.
3. The method of making a solid oxide fuel cell cathode of claim 1, wherein: and the weak alkaline solution in the second step is one of an ammonia monohydrate solution, a sodium carbonate solution or a sodium bicarbonate solution.
4. The method of making a solid oxide fuel cell cathode of claim 1, wherein: and in the third step, the evaporation temperature is controlled within the range of 70-90 ℃, and the temperature of the oven is controlled within the range of 220-250 ℃.
5. The method of making a solid oxide fuel cell cathode of claim 1, wherein: the cathode material comprises DyBaCo2O5And (3) powder.
CN201911256838.6A 2019-12-10 2019-12-10 Method for preparing solid oxide fuel cell cathode Withdrawn CN111799474A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102180523A (en) * 2011-02-01 2011-09-14 吉林大学 Cathode material of mesotherm solid oxide fuel battery and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102180523A (en) * 2011-02-01 2011-09-14 吉林大学 Cathode material of mesotherm solid oxide fuel battery and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
熊明文: "中温固体氧化物燃料电池钴基钙钛矿结构阴极材料性能研究", 《中国优秀博硕士学位论文全文数据库(博士)工程科技Ⅱ辑》 *

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