CN110581295A - medium-temperature solid oxide fuel cell electrolyte and preparation method thereof - Google Patents
medium-temperature solid oxide fuel cell electrolyte and preparation method thereof Download PDFInfo
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- CN110581295A CN110581295A CN201910906345.6A CN201910906345A CN110581295A CN 110581295 A CN110581295 A CN 110581295A CN 201910906345 A CN201910906345 A CN 201910906345A CN 110581295 A CN110581295 A CN 110581295A
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- 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
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- 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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Abstract
the invention discloses an electrolyte of a medium-temperature solid oxide fuel cell and a preparation method thereof. The electrolyte of the intermediate-temperature solid oxide fuel cell is prepared by adopting a sol-gel-combustion method, the conductivity of the electrolyte at 700 ℃ can reach 0.006S/cm in the air atmosphere, and the requirement of the intermediate-temperature solid oxide fuel cell on electrolyte materials is met.
Description
Technical Field
the invention belongs to the technical field of solid oxide fuel cell materials, and particularly relates to an electrolyte of an intermediate-temperature solid oxide fuel cell and a preparation method thereof.
Background
Energy is the basis of social development, and fossil energy (coal, oil, natural gas) is still used as a main energy resource (the proportion is up to about 80%) worldwide, and the proportion of Chinese fossil energy is higher (about 90%), wherein coal is still the most main energy source in China at present and for a long time in the future. In the process of utilizing coal at the present stage, coal-fired power generation is the most important utilization form, and the coal-electricity accounts for high proportion (about 80%) of Chinese electric power, so that the improvement of the coal-electricity efficiency and the reduction of pollution are very important. The solid oxide fuel cell is a power generation device which directly converts chemical energy of fuel into electric energy, and has the characteristics of high energy conversion efficiency and small pollution. Under such a background, fuel cells have been regarded by attention from countries all over the world and have been developed in great quantities.
SOFCs that have been commercially used today typically operate at 1000 ℃, and operating at such high temperatures presents a number of problems for SOFCs: electrode densification, high interconnect material requirements, poor cell sealing performance, etc., which significantly increases the cost of the SOFC and limits its commercial development. In order to commercialize SOFCs, the operating temperature must be reduced, and the electrolyte is the most central part of the SOFC, and if the electrolyte material can obtain good performance at relatively low temperature, a moderate temperature ideal SOFC can be obtained. Traditional electrolyte materials are not suitable for working in a medium-temperature environment, so that a novel electrolyte material must be developed to meet the current requirements on the medium-temperature SOFC electrolyte material.
The sol-gel method plays an important role in chemical synthesis as an important method for synthesizing inorganic materials under low temperature or mild conditions, and enables reactants to be uniformly mixed at a molecular level. It is generally accepted that the diffusion of components in sol-gel systems is in the nanometer range, whereas the diffusion of components in the micrometer range is in solid phase reactions. Compared with solid phase reaction, the sol-gel method chemical reaction is easier to carry out; in addition, the sample prepared by the sol-gel method has uniform particle size distribution, the particle size can be controlled by controlling reaction conditions, and different microstructures are prepared, so that the performance of the sample is influenced.
Disclosure of Invention
the invention aims to provide an electrolyte of an intermediate-temperature solid oxide fuel cell and a preparation method thereof. The electrolyte has the conductivity of 0.006S/cm at 700 ℃ in the air atmosphere, and meets the requirements of the intermediate-temperature solid oxide fuel cell on electrolyte materials.
in order to achieve the purpose, the invention adopts the following technical scheme:
Preparation of Sr by sol-gel method0.55Na0.45SiO2.775。
(I) Sr0.55Na0.45SiO2.775Preparation of powder:
1) According to Sr0.55Na0.45SiO2.775weighing Sr (NO)2 、NaNO3tetraethyl orthosilicate (SiC)8H12O8) And weighing EDTA and citric acid according to the molar ratio of the metal cations to the EDTA and the citric acid of 1:1: 1.5;
2) dissolving EDTA with 10-20% ammonia water solution;
3) Adding NaNO3、Sr(NO3)2And citric acid are respectively added into distilled water for dissolution;
4) In volume ratio V (SiC)8H12O8) V (C2H5OH) =1:3 tetraethyl orthosilicate is dissolved in absolute ethyl alcohol;
5) Sequentially pouring the nitrate solution obtained in the step 3) into the solution obtained in the step 4), then dropwise adding the solution obtained in the step 2) into the solution, dropwise adding a citric acid solution, and gradually adding ammonia water with the concentration of 15% -20% into the solution by mass so as to adjust the pH value of the solution to 7;
6) Putting the mixed solution obtained in the step 5) into a constant-temperature magnetic stirrer, heating to 70 ℃, and then keeping stirring at 70 ℃ until gel is formed;
7) Transferring the gel into an evaporating dish, and heating the evaporating dish on an electric furnace until self-propagating combustion occurs to form fluffy oxide powder;
8) Heating the obtained oxide powder to 600 + -10 deg.C, maintaining the temperature for 1 + -0.1 hr to eliminate residual organic matter, maintaining the temperature at 900 + -10 deg.C for 10 + -0.1 hr, and naturally cooling to obtain Sr0.55Na0.45SiO2.775the powder is prepared by mixing the raw materials,
(II) Sr0.55Na0.45SiO2.775Preparing an electrolyte sheet:
Prepared Sr0.55Na0.45SiO2.775Grinding the powder, placing into a mold, making into wafer with diameter of 12 + -0.1 mm and thickness of 2 + -0.1 mm under 150MPa, heating the wafer to 950 + -10 deg.C at a speed of 3 deg.C per minute, and maintaining the temperature for 10 + -0.1 hr to obtain the final product with high performanceThe electrolyte wafer of the intermediate-temperature solid oxide fuel cell.
The invention has the beneficial effects that:
(1) the Sr prepared by the sol-gel-combustion method and having high ionic conductivity0.55Na0.45SiO2.775The electrolyte has the characteristics of simple process, short period and smaller granularity, and overcomes the defects of long preparation period and complex process of a solid phase method.
(2) sr of the invention0.55Na0.45SiO2.775the electrolyte sheet is a two-dimensional layered oxide ion conductor, has high conductivity, chemical stability and electrochemical performance, and has relative density of 98.9% after being insulated for 10 hours at 950 ℃; the conductivity reaches 0.006S/cm at 700 ℃ in the air, and the preparation method is suitable for being applied to medium and low temperature solid oxide fuel cells.
drawings
FIG. 1 is Sr0.55Na0.45SiO2.775XRD pattern of the powder.
Detailed Description
in order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
example 1
Sr0.55Na0.45SiO2.775the preparation method comprises the following steps:
1) According to Sr0.55Na0.45SiO2.775Weighing Sr (NO)2 、NaNO3Tetraethyl orthosilicate (SiC)8H12O8) And weighing EDTA and citric acid according to the molar ratio of the metal cations to the EDTA and the citric acid of 1:1: 1.5;
2) Dissolving EDTA with 10-20% ammonia water solution;
3) Adding NaNO3、Sr(NO3)2And citric acid are respectively added into distilled water for dissolution;
4) In volume ratio V (SiC)8H12O8):V(C2H5OH)=13, dissolving tetraethyl orthosilicate in absolute ethyl alcohol;
5) Sequentially pouring the nitrate solution obtained in the step 3) into the solution obtained in the step 4), then dropwise adding the solution obtained in the step 2) into the solution, dropwise adding a citric acid solution, and gradually adding ammonia water with the concentration of 15% -20% into the solution by mass so as to adjust the pH value of the solution to 7;
6) Putting the mixed solution obtained in the step 5) into a constant-temperature magnetic stirrer, heating to 70 ℃, and then keeping stirring at 70 ℃ until gel is formed;
7) transferring the gel into an evaporating dish, and heating the evaporating dish on an electric furnace until self-propagating combustion occurs to form fluffy oxide powder;
8) heating the obtained oxide powder to 600 + -10 deg.C, maintaining the temperature for 1 + -0.1 hr to eliminate residual organic matter, maintaining the temperature at 900 + -10 deg.C for 10 + -0.1 hr, and naturally cooling to obtain Sr0.55Na0.45SiO2.775powder;
9) Subjecting the obtained Sr0.55Na0.45SiO2.775Putting the powder into a die, preparing a wafer with the diameter of 12 +/-0.1 mm and the thickness of 2 +/-0.1 mm under the pressure of 150MPa, heating the wafer to 950 +/-10 ℃ at the speed of 3 ℃ per minute, and preserving the temperature for 10 +/-0.1 hours to obtain the high-performance medium-temperature solid oxide fuel cell electrolyte wafer.
specifically, the method comprises the following steps:
1 mol of Sr0.55Na0.45SiO2.775The preparation of (1):
Weighing 0.45 mol of NaNO3: 0.45 × 84.99 =38.2455 g
Weighing 0.55 mol of Sr (NO)3)2 : 0.55 × 211.63=116.3965 g
Weighing 1 mol of SiC8H12O8:1 × 208.33=208.33 g
weigh 1 mole of EDTA: 1 × 292.24=292.24 g
Weigh 1.5 moles of citric acid: 1.5 × 210.14=315.21 g
Dissolving EDTA with 10-20% ammonia water solution;
adding NaNO3、Sr(NO3)2And citric acid are respectively added into distilled water for dissolution;
in volume ratio V (SiC)8H12O8) V (C2H5OH) =1:3 tetraethyl orthosilicate is dissolved in absolute ethyl alcohol;
Slowly dropping a metal nitrate solution into a tetraethyl orthosilicate solution, then slowly adding an EDTA solution and a citric acid solution, then dropping the citric acid solution, finally dropping ammonia water with the concentration of 15-20%, and adjusting the pH value of the solution to 7;
Putting the obtained mixed solution into a constant-temperature magnetic stirrer, heating to 70 ℃, and then keeping stirring continuously at 70 ℃ until gel is formed;
Transferring the gel into an evaporating dish, and heating the evaporating dish on an electric furnace until self-propagating combustion occurs to form fluffy oxide powder;
Heating the obtained oxide powder to 600 + -10 deg.C, maintaining the temperature for 1 + -0.1 hr to eliminate residual organic matter, maintaining the temperature at 900 + -10 deg.C for 10 + -0.1 hr, and naturally cooling to obtain Sr0.55Na0.45SiO2.775powder;
Preparation of the wafer: prepared Sr0.55Na0.45SiO2.775Putting the powder into a die, preparing a wafer with the diameter of 12mm +/-0.1 mm and the thickness of 2mm +/-0.1 mm under the pressure of 150MPa, heating the wafer to 950 +/-10 ℃ at the heating speed of 3 ℃ per minute, and preserving the temperature for 10 +/-0.1 hours to obtain the required electrolyte wafer.
Conductivity test method:
The ac conductance of the electrolyte was measured by the two-terminal method. Sintering at 950 + -10 deg.C for 10 + -0.1 hr to obtain Sr0.55Na0.45SiO2.775coating silver paste on two sides of the electrolyte wafer, and then roasting for 2h at 450 ℃ to obtain the silver electrode. Silver electrodes at two ends are connected with an alternating current impedance instrument by silver wires. The AC impedance meter is an interfacial 1000 electrochemical workstation manufactured by Gamry of America, the application potential is 10mV, the frequency range is measured to be 1Hz-1MHz, the temperature for measuring the AC conductance is 400-700 ℃, and the measurement is carried out once every 50 ℃ in the air atmosphere. The electrical conductivity is represented by the following formulaand (3) calculating:
Wherein, sigma is electrolyte conductivity, S/cm;
h is the thickness of the electrolyte sheet, cm;
R is electrolyte resistance, omega;
S is the cross section area of the electrolyte sheet in cm2。
the ionic conductivity at 700 ℃ was 0.006S/cm.
the above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (4)
1. an electrolyte for an intermediate-temperature solid oxide fuel cell, characterized in that: has a chemical formula of Sr0.55Na0.45SiO2.775。
2. A method of preparing the electrolyte of claim 1, wherein: a sol-gel-combustion method is adopted.
3. The method of claim 2, wherein: the method comprises the following specific steps:
(1) dissolving tetraethyl orthosilicate in absolute ethyl alcohol, and sequentially adding NaNO3Solution and Sr (NO)3)2Uniformly stirring the solution;
(2) dissolving EDTA in an ammonia water solution 1, dropwise adding the EDTA into the mixed solution obtained in the step 1), and then dropwise adding a citric acid solution;
(3) dropwise adding an ammonia water solution 2, and adjusting the pH value of the solution to 7;
(4) Stirring at constant temperature of 70 ℃ until gel is formed, and heating until self-propagating combustion occurs to form fluffy oxide powder;
(5) Heating the oxide powder to 600 + -10 deg.C, maintaining for 1 + -0.1 hr, maintaining at 900 + -10 deg.C for 10 + -0.1 hr, and naturally cooling to obtain Sr0.55Na0.45SiO2.775Powder;
(6) fully grinding, preparing into a wafer with the diameter of 12 plus or minus 0.1mm and the thickness of 2 plus or minus 0.1mm under the pressure of 150MPa, heating to 950 plus or minus 10 ℃ at the speed of 3 ℃ per minute, and preserving the heat for 10 plus or minus 0.1 hours to obtain the electrolyte wafer of the intermediate-temperature solid oxide fuel cell.
4. the method of claim 3, wherein: the molar ratio of the metal cations to the EDTA and the citric acid is 1:1: 1.5;
The mass concentration of the ammonia water solution 1 is 10-20%; the volume ratio of tetraethyl orthosilicate to absolute ethyl alcohol is 1: 3; the mass concentration of the ammonia water solution 2 is 15-20%.
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Citations (4)
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|---|---|---|---|---|
| JP2006196279A (en) * | 2005-01-12 | 2006-07-27 | Tokyo Gas Co Ltd | Solid oxide fuel cell stack and its manufacturing method |
| CN107793140A (en) * | 2017-10-22 | 2018-03-13 | 桂林理工大学 | A kind of temperature-stabilized microwave medium ceramic material and preparation method thereof |
| CN108110289A (en) * | 2017-12-29 | 2018-06-01 | 福州大学 | The intermediate temperature solid oxide fuel cell electrolyte of one proton conduction |
| CN108232303A (en) * | 2018-01-17 | 2018-06-29 | 福州大学 | Oxygen ion conduction intermediate temperature solid oxide fuel cell electrolyte preparation method |
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- 2019-09-24 CN CN201910906345.6A patent/CN110581295A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006196279A (en) * | 2005-01-12 | 2006-07-27 | Tokyo Gas Co Ltd | Solid oxide fuel cell stack and its manufacturing method |
| CN107793140A (en) * | 2017-10-22 | 2018-03-13 | 桂林理工大学 | A kind of temperature-stabilized microwave medium ceramic material and preparation method thereof |
| CN108110289A (en) * | 2017-12-29 | 2018-06-01 | 福州大学 | The intermediate temperature solid oxide fuel cell electrolyte of one proton conduction |
| CN108232303A (en) * | 2018-01-17 | 2018-06-29 | 福州大学 | Oxygen ion conduction intermediate temperature solid oxide fuel cell electrolyte preparation method |
Non-Patent Citations (1)
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| PO-HSIU CHIEN ET AL: "On the origin of high ionic conductivity in Na-doped SrSiO3", 《CHEMICAL SCIENCE》 * |
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