CN112531190A - Electrolyte of solid oxide fuel cell and preparation method and application thereof - Google Patents
Electrolyte of solid oxide fuel cell and preparation method and application thereof Download PDFInfo
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- CN112531190A CN112531190A CN202011404518.3A CN202011404518A CN112531190A CN 112531190 A CN112531190 A CN 112531190A CN 202011404518 A CN202011404518 A CN 202011404518A CN 112531190 A CN112531190 A CN 112531190A
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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
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
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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
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/126—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing cerium oxide
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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
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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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
- 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
Abstract
The invention discloses an electrolyte of a solid oxide fuel cell and a preparation method and application thereof. The chemical formula of the electrolyte of the solid oxide fuel cell is BaZryCe1‑x‑y‑z‑ rSmxYzYbrO3Wherein the value ranges of y, z and r are 0-0.15, and the value range of x is 0-0.15. BaZrO by Sm, Y and Yb three elements3‑BaCeO3The perovskite oxide is doped, and various elements are mutually matched, so that the conductivity can be improved, the sintering temperature is reduced, and the relative density of the electrolyte sheet reaches over 99 percent after sintering at 1350 ℃ for 5 hours. The electrolyte can be applied to medium-temperature fuel cells.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to an electrolyte of a solid oxide fuel cell and a preparation method and application thereof.
Background
Solid Oxide Fuel Cells (SOFC) are highly efficient clean energy conversion devices that can directly convert chemical energy into electrical energy. The study of SOFC is of great significance facing the challenges of today's environmental and energy issues. However, commercial applications of SOFCs face the challenges of higher operating temperatures and expensive manufacturing costs, and compared to conventional oxygen ion conducting solid oxide fuel cells (O-SOFCs), proton conducting oxides are promising electrolyte candidates for moderate temperature SOFCs due to their low activation energy and high ionic conductivity.
BaCeO of perovskite structure3Has the advantages of high proton conductivity, high fuel utilization rate and the like, so the material is a proton conduction type oxide fuel cell (H-SOFC) electrolyte material mainly used at present. The doped barium cerate-based perovskite structure oxide has higher conductivity which can reach more than 0.01S/cm at 600 ℃. But in the presence of H2O or CO2The stability under the atmosphere is poor, and impurities are easily generated to cause the failure of the whole battery. In contrast, the doped barium zirconate-based oxide has strong chemical stability, but its conductivity is reduced due to its poor sintering property. Thus, BaZrO3-BaCeO3Perovskite-based oxides have been investigated as electrolytes to balance conductivity and stability. However, high-temperature sintering and long-term heat treatment cause evaporation of barium oxide, thereby lowering conductivity, and the sintering temperature is high when preparing the electrolyte sheet, resulting in a large increase in operation cost. Therefore, it is of great significance to research an electrolyte material with low sintering temperature and high conductivity.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide an electrolyte of a solid oxide fuel cell, a preparation method and application thereof, so as to improve the problems.
The invention is realized by the following steps:
in a first aspect, embodiments of the present invention provide a solid oxide fuel cellAn electrolyte having a chemical formula of BaZryCe1-x-y-z-rSmxYzYbrO3Wherein the value ranges of y, z and r are 0-0.15, and the value range of x is 0-0.15.
Optionally, the value ranges of y, z and r are all 0-0.15.
Optionally, the value ranges of x, y, z and r are all 0.05-0.15.
Optionally, the electrolyte has a chemical formula of BaZr0.1Ce0.7-xSmxY0.1Yb0.1O3Wherein the value range of x is 0-0.15.
Preferably, the electrolyte has the chemical formula BaZr0.1Ce0.6Sm0.1Y0.1Yb0.1O3。
In a second aspect, an embodiment of the present invention further provides a method for preparing an electrolyte of the solid oxide fuel cell, including: preparing electrolyte according to raw materials corresponding to stoichiometric ratio of elements in the chemical formula.
Alternatively, the electrolyte is synthesized using a gel-sol method.
Preferably, the electrolyte powder is obtained by drying and calcining a gel prepared by dissolving and mixing salts corresponding to the elements according to the chemical formula.
Optionally, dissolving and mixing salts corresponding to each element of the chemical formula in deionized water, mixing with a complexing agent, adjusting the pH value to be neutral to obtain gel, and then sequentially drying and calcining;
preferably, the complexing agent is citric acid, preferably, an aqueous ammonia solution of EDTA is added to the salt solution before the complexing agent is added; according to the metal ion: EDTA: the citric acid was added in a molar ratio of 1:2:3 to EDTA and complexing agent.
Optionally, the drying is carried out in a muffle furnace at 280-350 ℃, and the drying time is 4-6 hours.
Optionally, the calcination is carried out in a muffle furnace at 1000-1100 ℃, and the calcination time is 4-6 hours, preferably 5 hours.
Optionally, when the electrolyte sheet is prepared, the electrolyte powder is prepared into an electrolyte green body by a dry pressing method and then sintered.
Optionally, the dry pressing method comprises the steps of putting electrolyte powder into a mold, and then preparing an electrolyte green body under the pressure of 5-10 Mpa.
Optionally, the sintering temperature is 1350-1450 ℃, and the sintering time is 4-6 hours.
Alternatively, the salt corresponding to each element of the formula is a nitrate or acetate salt, preferably a nitrate salt, and the salt corresponding to each element of the formula includes: zr (NO)3)4·5H2O、Ce(NO3)3·6H2O、Yb(NO3)3·5H2O、Y(NO3)3·6H2O、Ba(NO3)2And Sm (NO)3)3·6H2O。
In a third aspect, embodiments of the present invention also provide a solid oxide fuel cell, which includes the above electrolyte.
In a fourth aspect, the embodiments of the present invention also provide an application of the electrolyte in preparing a solid oxide fuel cell.
One of the technical schemes of the invention at least has the following beneficial effects: BaZrO by Sm, Y and Yb three elements3-BaCeO3The perovskite oxide is doped, and various elements are mutually matched, so that the conductivity can be improved, the sintering temperature is reduced, and the relative density of the electrolyte sheet reaches over 99 percent after sintering at 1350 ℃ for 5 hours. The electrolyte can be applied to medium-temperature fuel cells.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is an XRD pattern after calcining at 1100 ℃ for 5 hours of the electrolyte powders of examples 1, 2, 3 and 4 of the present invention and comparative example 1;
FIG. 2 is a graph showing the shrinkage of electrolyte sheets prepared from the electrolyte powders at 1250 deg.C to 1350 deg.C in example 1 and comparative example 1 according to the present invention;
FIG. 3 is a scanning electron micrograph of the surface of the electrolyte sheets of example 1(b) and comparative example (a) of the present invention after sintering at 1350 ℃ for 5 hours; cross-sectional scanning electron micrographs of the electrolyte sheets of example 1(d) and comparative example (c) after sintering at 1350 ℃ for 5 h;
FIG. 4 is a statistical plot of the surface grain sizes at 1350 ℃ for electrolyte sheets of example 1(b) and comparative example (a) of the present invention;
figure 5 is a graph of the conductivity of the electrolyte sheets of example 1 of the present invention and comparative example 1 at different temperatures.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The electrolyte of a solid oxide fuel cell, the preparation method and the application thereof provided by the invention are specifically described below.
Some embodiments of the present invention provide an electrolyte for a solid oxide fuel cell, the electrolyte having a chemical formula of BaZryCe1-x-y-z-rSmxYzYbrO3Wherein the value ranges of y, z and r are 0-0.15, and the value range of x is 0-0.15.
The inventor finds that although BaCO is generated3-BaZrO3The base electrolyte has high conductivity and sintering property, but after a long heat treatment, it causes a decrease in conductivity. Therefore, through further research and practice, the inventor proposes the technical scheme that the sintering temperature for preparing the electrolyte sheet is reduced while the conductivity is improved by doping specific multiple elements at the B site, so that the electrolyte sheet is obtainedA single-phase electrolyte material BaZryCe1-x-y-z-rSmxYzYbrO3In particular BaZr0.1Ce0.7- xSmxY0.1Yb0.1O3。
In some embodiments, the performance of the electrolyte is further optimized, y, z and r are all in the range of 0-0.15, and x is in the range of 0-0.15. It is further preferred that the electrolyte has a chemical formula of BaZr0.1Ce0.7-xSmxY0.1Yb0.1O3Wherein, the value of x is 0.1. Further preferably, the electrolyte has a chemical formula of BaZr0.1Ce0.6Sm0.1Y0.1Yb0.1O3。
In some embodiments, x, y, z, and r are all in the range of 0.05 to 0.15.
In particular, in some embodiments, the electrolyte is a powder, which is an electrolyte sheet obtained by further processing the powder electrolyte.
Further, some embodiments of the present invention also provide a method for preparing an electrolyte of the above solid oxide fuel cell, including: preparing electrolyte according to raw materials corresponding to stoichiometric ratio of elements in the chemical formula.
Specifically, in some embodiments, the electrolyte is synthesized by employing a gel-sol method. The method comprises the following specific steps:
s1, dissolving and mixing the salt corresponding to each element according to the chemical formula to prepare the gel.
First, the salt corresponding to each element of the formula may be a nitrate salt, and specifically, in some embodiments, the salt corresponding to each element of the formula includes: zr (NO)3)4·5H2O、Ce(NO3)3·6H2O、Yb(NO3)3·5H2O、Y(NO3)3·6H2O、Ba(NO3)2And Sm (NO)3)3·6H2O。
Zr (NO) was calculated from the stoichiometric ratio of each element in the electrolyte formula3)4·5H2O、Ce(NO3)3·6H2O、Yb(NO3)3·5H2O、Y(NO3)3·6H2O、Ba(NO3)2And Sm (NO)3)3·6H2The required mass of O.
In some embodiments, the salt corresponding to each element of the chemical formula is dissolved and mixed uniformly in deionized water, then mixed with a complexing agent, and the pH value is adjusted to be neutral, and the gel is prepared by stirring.
Specifically, Zr (NO) was weighed separately3)4·5H2O、Ce(NO3)3·6H2O、Yb(NO3)3·5H2O、Y(NO3)3·6H2O、Ba(NO3)2And Sm (NO)3)3·6H2And O, adding deionized water into the first container, and stirring on a magnetic stirrer at 80 ℃ in an oil bath until all the materials are dissolved. And then taking the second container, weighing EDTA and pouring into the container, adding ammonia water for dissolving, and specifically, stirring on a magnetic stirrer until the EDTA is completely dissolved. And pouring the solution in the second container into the first container, adding citric acid, adjusting the pH value to 7-8 by using ammonia water, and stirring until the solution is viscous gel. In some embodiments, after adjusting the pH, the nonwoven fabric may be covered and then agitated. According to the metal ion: EDTA: the citric acid was added in a molar ratio of 1:2:3 to EDTA and complexing agent.
Specifically, in some embodiments, the amount of EDTA is 5.8742g and the amount of ammonia is 15 ml. In some embodiments, the amount of citric acid added is 6.3359 g.
And S2, drying the gel and then calcining to obtain electrolyte powder.
Specifically, in some embodiments, in order to obtain a fluffy precursor, the precursor is dried in a muffle furnace at 300 ℃ for 4-6 hours.
Further, the mixture is calcined in a muffle furnace at 1100 ℃, and the calcination time is 4-6 hours, preferably 5 hours.
Further, when preparing the electrolyte sheet, it is necessary to further prepare the electrolyte powder into a wafer. Namely, the method also comprises the following steps:
and S3, preparing the electrolyte powder into an electrolyte green body by adopting a dry pressing method, and sintering.
Specifically, in some embodiments, the dry pressing process includes placing the electrolyte powder into a mold and then forming the green electrolyte at a pressure of 10 Mpa.
Further, in some embodiments, the sintering temperature for sintering the electrolyte green body is 1350 ℃ to 1450 ℃, and the calcination time is 4 hours to 6 hours.
Some embodiments of the present invention further provide a method for preparing an electrolyte of the solid oxide fuel cell, which specifically includes the following steps:
(1) zr (NO) was calculated from the stoichiometric ratio of each element in the electrolyte formula3)4·5H2O、Ce(NO3)3·6H2O、Yb(NO3)3·5H2O、Y(NO3)3·6H2O、Ba(NO3)2And Sm (NO)3)3·6H2The required mass of O.
(2) Taking No. 1 beaker, then weighing Zr (NO) respectively3)4·5H2O、Ce(NO3)3·6H2O、Yb(NO3)3·5H2O、Y(NO3)3·6H2O、Ba(NO3)2And Sm (NO)3)3·6H2And O, adding deionized water into the beaker. Then the mixture is put on a magnetic stirrer for stirring at the temperature of 80 ℃ in an oil bath until the mixture is completely dissolved.
(3) A clean No. 2 beaker was taken again, EDTA was weighed and poured into the beaker, and ammonia was added thereto. Stirring on a magnetic stirrer until the solution is completely dissolved.
(4) The solution in beaker No. 2 was poured slowly into beaker No. 1 and citric acid was weighed into beaker No. 1. Adding appropriate amount of ammonia water to adjust pH value, and adjusting pH value of the mixed solution in No. 1 beaker to 7-8. Covering with non-woven fabric, and stirring to obtain viscous gel.
(5) And (5) putting the gel prepared in the step (4) into a muffle furnace for drying, and drying for 5h at 300 ℃ to obtain a precursor. Then calcined in a muffle furnace at 1100 ℃ for 5h to finally obtain electrolyte powder. And putting the obtained electrolyte powder into a die, preparing an electrolyte green body under the pressure of 10MPa, and sintering the green body in a high-temperature muffle furnace for 5 hours to obtain the electrolyte sheet.
Some embodiments of the present invention also provide a solid oxide fuel cell comprising the electrolyte of any of the preceding embodiments.
Some embodiments of the present invention also provide a use of the electrolyte of any of the above embodiments in the preparation of a solid oxide fuel cell.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
Preparing electrolyte powder: is BaZr according to the chemical formula0.1Ce0.6Sm0.1Y0.1Yb0.1O3The molar ratio of each atom of the electrolyte of (2) was calculated to calculate the mass of the raw material required, and then Zr (NO) was weighed3)4·5H2O 0.4316g、Ce(NO3)3·6H2O 2.6184g、Yb(NO3)3·5H2O 0.4495g、Y(NO3)3·6H2O 0.3869g、Ba(NO3)2 2.6265g、Sm(NO3)3·6H2O0.4445 g was poured into a No. 1 beaker, and 30ml of deionized water was added and dissolved by stirring.
According to the metal ion: EDTA: the mass of the citric acid is calculated according to the molar ratio of 1:2:3, 5.8742g of EDTA and 15ml of ammonia water are added into a No. 2 beaker, the solution in the No. 2 beaker is poured into a No. 1 beaker, 6.3359g of complexing agent citric acid is added after the solution is fully dissolved, a proper amount of ammonia water is added to adjust the pH value to be about 7, and the mixture is stirred to form viscous gel. And (3) putting the synthesized gel into a muffle furnace for drying, and drying for 5h at 300 ℃ to obtain a precursor. And putting the precursor into a muffle furnace, and calcining at 1100 ℃ for 5h to obtain electrolyte powder.
(II) preparing an electrolyte sheet: the BaZr synthesized in the step (one)0.1Ce0.6Sm0.1Y0.1Yb0.1O3And (3) weighing 0.8g of powder, putting the powder into a die, preparing an electrolyte green body under the pressure of 10MPa, and sintering the green body at 1350 ℃ for 5 hours to obtain an electrolyte sheet.
Example 2
Preparing electrolyte powder: is BaZr according to the chemical formula0.1Ce0.6Sm0.05Y0.15Yb0.1O3The molar ratio of each atom of the electrolyte of (2) was calculated to calculate the mass of the raw material required, and then Zr (NO) was weighed3)4·5H2O、Ce(NO3)3·6H2O、Yb(NO3)3·5H2O、Y(NO3)3·6H2O、Ba(NO3)2、Sm(NO3)3·6H2And pouring the O into a No. 1 beaker, adding 30ml of deionized water, and stirring to dissolve.
According to the metal ion: EDTA: the mass of the citric acid is calculated according to the molar ratio of 1:2:3, EDTA and 15ml of ammonia water are added into a No. 2 beaker, the solution in the No. 2 beaker is poured into a No. 1 beaker, after the solution is fully dissolved, the complexing agent citric acid is added, a proper amount of ammonia water is added to adjust the pH value to be about 7, and the mixture is stirred to form viscous gel. And (3) putting the synthesized gel into a muffle furnace for drying, and drying for 5h at 300 ℃ to obtain a precursor. And putting the precursor into a muffle furnace, and calcining at 1100 ℃ for 5h to obtain electrolyte powder.
(II) preparing an electrolyte sheet: the BaZr synthesized in the step (one)0.1Ce0.6Sm0.05Y0.15Yb0.1O3And (3) weighing 0.8g of powder, putting the powder into a die, preparing an electrolyte green body under the pressure of 10MPa, and sintering the green body at 1350 ℃ for 5 hours to obtain an electrolyte sheet.
Example 3
Preparing electrolyte powder: is BaZr according to the chemical formula0.1Ce0.6Sm0.1Y0.15Yb0.05O3The molar ratio of each atom of the electrolyte of (2) was calculated to calculate the mass of the raw material required, and then Zr (NO) was weighed3)4·5H2O、Ce(NO3)3·6H2O、Yb(NO3)3·5H2O、Y(NO3)3·6H2O、Ba(NO3)2、Sm(NO3)3·6H2And pouring the O into a No. 1 beaker, adding 30ml of deionized water, and stirring to dissolve.
According to the metal ion: EDTA: the mass of the citric acid is calculated according to the molar ratio of 1:2:3, EDTA and 15ml of ammonia water are added into a No. 2 beaker, the solution in the No. 2 beaker is poured into a No. 1 beaker, after the solution is fully dissolved, the complexing agent citric acid is added, a proper amount of ammonia water is added to adjust the pH value to be about 7, and the mixture is stirred to form viscous gel. And (3) putting the synthesized gel into a muffle furnace for drying, and drying for 5h at 300 ℃ to obtain a precursor. And putting the precursor into a muffle furnace, and calcining at 1100 ℃ for 6h to obtain electrolyte powder.
(II) preparing an electrolyte sheet: the BaZr synthesized in the step (one)0.1Ce0.6Sm0.1Y0.15Yb0.05O3And (3) weighing 0.8g of powder, putting the powder into a die, preparing an electrolyte green body under the pressure of 10MPa, and sintering the green body at 1350 ℃ for 5 hours to obtain an electrolyte sheet.
Example 4
Preparing electrolyte powder: is BaZr according to the chemical formula0.1Ce0.6Sm0.15Y0.1Yb0.05O3The molar ratio of each atom of the electrolyte of (2) was calculated to calculate the mass of the raw material required, and then Zr (NO) was weighed3)4·5H2O、Ce(NO3)3·6H2O、Yb(NO3)3·5H2O、Y(NO3)3·6H2O、Ba(NO3)2、Sm(NO3)3·6H2And pouring the O into a No. 1 beaker, adding 30ml of deionized water, and stirring to dissolve.
According to the metal ion: EDTA: the mass of the citric acid is calculated according to the molar ratio of 1:2:3, EDTA and 15ml of ammonia water are added into a No. 2 beaker, the solution in the No. 2 beaker is poured into a No. 1 beaker, after the solution is fully dissolved, the complexing agent citric acid is added, a proper amount of ammonia water is added to adjust the pH value to be about 7, and the mixture is stirred to form viscous gel. And (3) putting the synthesized gel into a muffle furnace for drying, and drying for 5h at 300 ℃ to obtain a precursor. And putting the precursor into a muffle furnace, and calcining at 1100 ℃ for 5h to obtain electrolyte powder.
(II) preparing an electrolyte wafer: the BaZr synthesized in the step (one)0.1Ce0.6Sm0.15Y0.1Yb0.05O3And (3) weighing 0.8g of powder, putting the powder into a die, preparing an electrolyte green body under the pressure of 10MPa, and sintering the green body at 1350 ℃ for 5 hours to obtain an electrolyte sheet.
Comparative example 1
This comparative example is BaZr according to the formula0.1Ce0.7Y0.1Yb0.1O3The stoichiometric ratio of each atom of the electrolyte of (a) is calculated to calculate the mass of the required raw material. The other procedure was the same as in example 1, and the synthesized BaZr0.1Ce0.7Y0.1Yb0.1O30.8g of electrolyte powder is weighed and put into a die, an electrolyte green body is prepared under the pressure of 10MPa, and the green body is sintered for 5 hours at 1450 ℃, so that an electrolyte sheet is obtained.
The electrolyte powders of examples 1, 2, 3 and 4 and comparative example 1 were calcined at 1100 ℃ for 5 hours and tested by XRD, to obtain XRD patterns as shown in fig. 1. As can be seen from fig. 1, examples 1, 2, 3 and 4 and comparative example 1 all exhibited a cubic perovskite structure, and no other impurity phase was detected, indicating that examples 1, 2, 3 and 4 and comparative example 1 had been calcined into a phase at 1100 ℃.
The contraction performance of the electrolyte sheets in example 1 and comparative example 1 was tested at 1250-1450 ℃, and the linear contraction rate of the electrolyte sheets was calculated by measuring the diameters of the electrolyte sheets before and after sintering. As can be seen from fig. 2, the shrinkage rates of example 1 and comparative example 1 gradually increased with increasing temperature, and the doping of Sm element significantly increased the shrinkage rate of the electrolyte. This shows that Sm doping can improve the sintering performance of comparative example 1.
The surfaces (a and b) and the sections (c and d) of the electrolyte sheets obtained by sintering the electrolyte sheets of the example 1 and the comparative example 1 at 1350 ℃ are imaged by a scanning electron microscope, and the microscopic morphology of the electrolyte sheets is observed, as shown in fig. 3, the structure of the electrolyte sheets of the example 1 is obviously more compact and ordered. From the SEM images, the particle size distribution of all samples was calculated from Nanomeasure, and as shown in a and b in fig. 4, the average particle size after Sm doping was significantly increased.
The electrical conductivities of the electrolyte sheets of example 1 and comparative example 1 were measured at different temperatures as shown in fig. 5. As can be seen from FIG. 5, the conductivity of the electrolyte gradually increased with increasing temperature, and the Sm-doped electrolyte had the maximum total conductivity at 700 deg.C (0.0567 Scm)-1). Indicating that the doping of Sm can obviously improve the conductivity of the electrolyte.
From the above analysis, the density of the proton conductor electrolyte of example 1 reached 99% at 1350 ℃, the sintering temperature was significantly reduced by 100 ℃ compared to that of comparative example 1, and the electrolyte conductivity of example 1 was 0.0567Scm measured at 700 ℃ in air-1。
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An electrolyte of a solid oxide fuel cell, characterized in that the electrolyte has the chemical formula of BaZryCe1-x-y-z-rSmxYzYbrO3Wherein the value ranges of y, z and r are 0-0.15, and the value range of x is 0-0.15.
2. The electrolyte of the solid oxide fuel cell according to claim 1, wherein y, z and r are each in a range of 0 to 0.15;
preferably, the value ranges of x, y, z and r are all 0.05-0.15;
preferably, the electrolyte has a chemical formula of BaZr0.1Ce0.7-xSmxY0.1Yb0.1O3Wherein the value range of x is 0-0.15;
more preferably, the electrolyte has a chemical formula of BaZr0.1Ce0.6Sm0.1Y0.1Yb0.1O3。
3. A method for producing an electrolyte for a solid oxide fuel cell according to claim 1 or 2, wherein the electrolyte is produced from raw materials corresponding to the stoichiometric ratio of each element of the chemical formula.
4. The method for producing the electrolyte according to claim 3, wherein the electrolyte is synthesized by a gel sol method or a citric acid method;
preferably, the electrolyte powder is obtained by dissolving and mixing the salts corresponding to the elements in the chemical formula to obtain a gel, and then drying and calcining the gel.
5. The method for preparing the electrolyte according to claim 4, wherein the salt corresponding to each element of the chemical formula is dissolved and mixed uniformly in a solvent, then mixed with a complexing agent, and dried and calcined sequentially after the pH value is adjusted to be neutral to obtain a gel;
preferably, the complexing agent is citric acid, and preferably, an aqueous ammonia solution of EDTA is added to the salt solution before the complexing agent is added.
6. The method for preparing the electrolyte according to claim 5, wherein the drying is carried out in a muffle furnace at a temperature of 280-350 ℃, preferably at a temperature of 300 ℃, and the drying time is 4-6 hours;
preferably, the calcination is carried out in a muffle furnace at 1000-1100 ℃, preferably 1100 ℃, and the calcination time is 4-6 hours, preferably 5 hours.
7. The method for preparing the electrolyte according to claim 4, wherein the step of preparing the electrolyte sheet further comprises preparing the electrolyte powder into an electrolyte green body by a dry pressing method and sintering the electrolyte green body;
preferably, the dry pressing method comprises the steps of putting the electrolyte powder into a mold, and then preparing the electrolyte green body under the pressure of 5-10 MPa, preferably 10 MPa;
preferably, the sintering temperature is 1350-1450 ℃, and the sintering time is 4-6 hours.
8. The method for preparing the electrolyte according to any one of claims 4 to 7, wherein the salt corresponding to each element of the formula is a nitrate or an acetate, preferably a nitrate, and the salt corresponding to each element of the formula comprises: zr (NO)3)4·5H2O、Ce(NO3)3·6H2O、Yb(NO3)3·5H2O、Y(NO3)3·6H2O、Ba(NO3)2And Sm (NO)3)3·6H2O。
9. A solid oxide fuel cell comprising the electrolyte of claim 1 or 2.
10. Use of the electrolyte of claim 1 or 2 in the manufacture of a solid oxide fuel cell.
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