CN111261916B - Thin-film proton conductor electrolyte and preparation method thereof - Google Patents
Thin-film proton conductor electrolyte and preparation method thereof Download PDFInfo
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- CN111261916B CN111261916B CN201811460281.3A CN201811460281A CN111261916B CN 111261916 B CN111261916 B CN 111261916B CN 201811460281 A CN201811460281 A CN 201811460281A CN 111261916 B CN111261916 B CN 111261916B
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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
- 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 a thin-film proton conductor electrolyte and a preparation method thereof. The preparation method comprisesThe prepared proton conductor electrolyte is perovskite structure oxide, and the structural characteristic composition of the proton conductor electrolyte is as follows: BaZr1‑xMxO3‑δ(ii) a Wherein x is more than or equal to 0 and less than or equal to 1, and delta represents non-stoichiometric oxygen; m is at least one of Ce, Y, Al, Yb, Gd, Mg and Ti. The preparation method takes a fluorite structure oxide compact or porous sheet as a matrix, and the characteristic composition of the matrix is Zr1‑xMxO2‑δWherein x, M, and δ have the same meanings as described above; reacting with gas-phase Ba source under specific conditions to form a thin-film proton conductor electrolyte with a thickness of less than 10 μm, wherein the gas-phase Ba source is BaCO3、Ba(NO3)2、Ba(CH3COO)2One of (1) and (b). The preparation method is expected to be used in solid oxide fuel cells and electrolytic cells.
Description
Technical Field
The invention belongs to the field of solid oxide batteries, and particularly relates to a thin-film proton conductor electrolyte and a preparation method thereof.
Technical Field
The use of fossil fuels has brought enormous productivity to the development of society, but at the same time, a series of problems have been derived. Non-renewable, CO, such as fossil fuel resources2Excessive emission of, NOxAnd SOxAnd the like, the emission of acid gases, and the like. Therefore, reducing the dependence on fossil fuels is particularly important on a socially sustainable way. In recent years, Solid Oxide batteries (Solid Oxide Fuel Cells (SOFCs) and Solid Oxide Electrolysis Cells (SOECs)) have attracted much attention as an efficient energy conversion device. The SOFCs can break through the limitation of the Carnot heat engine, can efficiently convert combustible gases such as hydrogen, methane, ethane and the like into electric energy, improves the energy utilization efficiency, does not discharge a large amount of pollutants in the energy conversion process, and is a very promising method for solving the problems of energy shortage, environmental pollution, sustainable development and the like faced by people at presentOne of them. SOECs drive electrolysis H with electricity2O、CO2The unstable renewable electric energy can be converted into chemical energy to be stored in H2And combustible gases such as CO. At present, the operating temperatures of SOFCs and SOECs based on proton conductor electrolytes need to be above 700 ℃ to achieve good electrochemical performance, one of the reasons being that the resistance of the electrolyte increases significantly with decreasing temperature. Therefore, reducing the thickness of the electrolyte is critical to reducing the operating temperature of the solid oxide cell. At present, the preparation methods for the proton conductor electrolyte film mainly comprise a casting method, a co-pressing method, a suspension coating method, a drop coating method and the like, but the electrolyte prepared by the method is still thicker (> 10 μm). Therefore, a method for preparing a proton conductor electrolyte thin film needs to be further explored.
Disclosure of Invention
Aiming at the problems in the electrolyte thinning preparation of the existing solid oxide battery, the invention provides a thinned proton conductor electrolyte and a preparation method thereof, and the thickness of the proton conductor electrolyte prepared by the method can be less than 10 mu m.
The technical purpose of the invention is realized by the following technical scheme:
the technical purpose of the first aspect of the invention is to provide a thin-film proton conductor electrolyte, which is a perovskite structure oxide and has the structural characteristic composition as follows: BaZr1-xMxO3-δ(ii) a Wherein x is more than or equal to 0 and less than or equal to 1, and delta represents non-stoichiometric oxygen; m is at least one of Ce, Y, Al, Yb, Gd, Mg and Ti. BaZr1-xMxO3-δWhere δ denotes non-stoichiometric oxygen (number of oxygen vacancies), oxygen vacancies, meaning that the oxygen content exhibits a composition in the range of 3- δ.
In its structural composition expression, further, 0.1. ltoreq. x.ltoreq.0.3, as a more specific example, 0.1. ltoreq. x.ltoreq.0.2; further, as a more specific example, M is selected from Y.
Further, as a more specific example, the thickness of the proton conductor electrolyte is less than 10 μm.
Second aspect of the inventionThe technical purpose of the aspect is to provide a preparation method of the thin-film proton conductor electrolyte, which comprises the following steps: by sintered Zr1-xMxO2-δUsing fluorite phase oxide porous or compact piece as matrix, placing proper amount of Ba source around it, said Ba source is selected from BaCO3、Ba(NO3)2、Ba(CH3COO)2At least one of; and preserving the heat for 1 to 100 hours under the conditions of specific temperature, atmosphere, air pressure and gas flow rate to obtain the thin-film proton conductor electrolyte.
The invention takes fluorite phase oxide as a substrate and reacts with a gas phase Ba source under specific conditions to generate the thin-film BaZr1-xMxO3-δA proton conductor electrolyte;
the fluorite phase oxide has a structural composition of Zr1-xMxO2-δWherein x, M and delta have the same meanings as above, i.e. x is more than or equal to 0 and less than or equal to 1, and delta represents non-stoichiometric oxygen (oxygen vacancy number) and is closely related to the selection and use conditions of M; m is at least one of Ce, Y, Al, Yb, Gd, Mg and Ti. Zr1-xMxO2-δWhere δ represents non-stoichiometric oxygen, it is an oxygen vacancy, indicating that the oxygen content exhibits a composition in the range of 2- δ.
In its structural composition expression, further, 0.1. ltoreq. x.ltoreq.0.3, as a more specific example, 0.1. ltoreq. x.ltoreq.0.2; further, as a more specific example, M is selected from Y.
Further, as a more specific example, the temperature of the reaction is 1000 ℃ to 1600 ℃, and the optimum temperature can be determined according to the kind of the selected M.
Further, as a more specific example, the atmosphere of the reaction is Ar, He, N2Air or vacuum, the flow rate is 0ml/min-100ml/min, and the gas pressure is 0atm-2.5 atm.
Further, as a more specific example, the mass ratio of the fluorite phase oxide to the Ba source is 1:5 to 15, preferably 1: 10.
A preparation method of a thin-film proton conductor electrolyte specifically comprises the following steps:
a. root of herbaceous plantAccording to the structure composition expression BaZr1-xMxO3-δZrO is weighed according to the stoichiometric ratio2And CeO2、Y2O3、Al2O3、Yb2O3、Gd2O3、MgO、TiO2Mixing for 4-6h by ball milling to obtain mixed oxide powder;
b. sintering the mixed oxide powder dry pressed tablet for 8-12h at 1450-1550 ℃ in an air atmosphere to obtain the fluorite structure oxide matrix, wherein the thickness of the fluorite structure oxide matrix is less than 300 mu m;
c. and placing a Ba source around the fluorite phase structure oxide matrix, and preserving the temperature for 1-100h to obtain the thin-film proton conductor electrolyte, wherein the thickness of the thin-film proton conductor electrolyte can be less than 10 mu m.
Further, as more specific examples, in step b, the conditions of the dry-compressed tablet are: the pressure is 150-250MPa, and the pressure is maintained for 60-90 s.
Further, as a more specific example, in step c, a Ba source is placed around the above fluorite phase structured oxide sheet, depending on the preparation material and preparation thickness, in Ar, He, N2Selecting a proper atmosphere condition from Air and vacuum, controlling the gas flow rate to be 0ml/min-100ml/min, controlling the temperature to be 1000-1600 ℃, and preserving the heat for 1-100 h.
The thickness of the prepared thin-film proton conductor electrolyte can be easily controlled below 10 mu m, and the prepared proton conductor electrolyte has an obvious perovskite structure. The doped fluorite phase structure oxide is used as a matrix and has a gas-solid reaction with a gas phase Ba source under specific reaction conditions, and the gas phase Ba can enter fluorite phase crystal lattices to obtain a thin-film proton conductor electrolyte; in addition, by controlling the doping element types and the doping proportion in the fluorite phase oxide, the method can be suitable for the thin-film preparation of a series of proton conductor electrolytes.
Drawings
FIG. 1 thin film BaZr obtained in example 1Ar (35ml/min), atmospheric pressure 1atm, temperature 1400 ℃ reaction for 72 hours0.84Y0.16O3-δXRD spectrum of electrolyte.
FIG. 2 thin film BaZr obtained in example 1 by reacting Ar (35ml/min) under a pressure of 1atm and a temperature of 1400 ℃ for 72 hours0.84Y0.16O3-δSEM pictures of the electrolyte surface and cross-section, where (a) is the surface and (b) is the cross-section.
FIG. 3 example 3 reaction of Air (0ml/min), atmospheric pressure of 1atm, and temperature of 1450 ℃ for 20 hours to obtain BaZr in the form of a thin film0.84Y0.16O3-δSEM pictures of the electrolyte surface and cross-section, where (a) is the surface and (b) is the cross-section.
FIG. 4 example 4 reaction of Air (0ml/min), atmospheric pressure of 1atm, and temperature of 1450 ℃ for 20 hours to obtain BaZr in the form of a thin film0.84Y0.16O3-δSEM pictures of the electrolyte surface and cross-section, where (a) is the surface and (b) is the cross-section.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The following detailed description of the invention refers to the accompanying drawings.
Example 1 thin film formation of BaZr0.84Y0.16O3-δProton conductor electrolyte preparation
According to BaZr0.84Y0.16O3-δPreparation of 10g of Zr0.84Y0.16O2-δA substrate, ZrO is accurately weighed by a stoichiometric ratio2、Y2O3According to ZrO2、Y2O3Adding ethanol in a mass ratio of the total amount of the raw materials to the ethanol of 1:1, ball-milling and mixing for 5h, drying the powder under an infrared lamp, putting 0.5g of dried oxide powder into a mold with the diameter of 18mm, pressing the oxide powder into sheets under the pressure of 200MPa for 60s, and sintering the sheets at 1450 ℃ for 10h to obtain compact Zr0.84Y0.16O2-δA substrate with a thickness of 0.45 mm; 5g of BaCO are taken3Uniformly placed with Zr0.84Y0.16O2-δReacting for 72 hours around the matrix under the conditions of Ar (35ml/min), the air pressure of 1atm and the temperature of 1400 ℃, thus obtaining the thin-film BaZr0.84Y0.16O3-δElectrolyte, thickness about 8 μm. The XRD spectrum is shown in figure 1, the surface is in a cubic perovskite structure instead of a fluorite structure, the SEM image is shown in figure 2, and a layer of BaZr with the thickness of 8 mu m is formed on the surface0.84Y0.16O3-δ。
Example 2 thin film formation of BaZr0.84Y0.16O3-δProton conductor electrolyte preparation
According to BaZr0.84Y0.16O3-δPreparation of 10g of Zr0.84Y0.16O2-δA substrate, ZrO is accurately weighed by a stoichiometric ratio2、Y2O3According to ZrO2、Y2O3Adding ethanol in a mass ratio of the total amount of the raw materials to the ethanol of 1:1, ball-milling and mixing for 5h, drying the powder under an infrared lamp, putting 0.5g of dried oxide powder into a mold with the diameter of 18mm, pressing the oxide powder into sheets under the pressure of 200MPa for 60s, and sintering the sheets at 1450 ℃ for 10h to obtain compact Zr0.84Y0.16O2-δA substrate with a thickness of 0.45 mm; 5g of BaCO are taken3Uniformly placed with Zr0.84Y0.16O2-δReacting for 12h around the matrix under the conditions of Ar (35ml/min), the air pressure of 1atm and the temperature of 1000 ℃ to obtain the thin-film BaZr0.84Y0.16O3-δAn electrolyte having a thickness of about 2 μm.
Example 3 thin film formation of BaZr0.84Y0.16O3-δProton conductor electrolyte preparation
According to BaZr0.84Y0.16O3-δPreparation of 10g of Zr0.84Y0.16O2-δThe matrix is prepared by accurately weighing ZrO2 and Y2O3 according to the stoichiometric ratio2、Y2O3Adding ethanol in a mass ratio of the total amount of the components to the ethanol of 1:1, ball-milling and mixing for 5h, drying the powder under an infrared lamp, putting 0.5g of dried oxide powder into a mold with the diameter of 18mm, and keeping the pressure of 200MPaPressing into slices within 60s, and sintering the slices at 1450 ℃ for 10h to obtain compact Zr0.84Y0.16O2-δA substrate with a thickness of 0.45 mm; 5g of BaCO are taken3Uniformly placed with Zr0.84Y0.16O2-δReacting for 48h around the matrix under the conditions of Ar (35ml/min), the air pressure of 1atm and the temperature of 1400 ℃ to obtain the thin-film BaZr0.84Y0.16O3-δThe electrolyte, which has a thickness of about 10 μm, is shown in the SEM image of FIG. 3.
Example 4 thin film formation of BaZr0.84Y0.16O3-δProton conductor electrolyte preparation
According to BaZr0.84Y0.16O3-δPreparation of 10g of Zr0.84Y0.16O2-δA substrate, ZrO is accurately weighed by a stoichiometric ratio2、Y2O3According to ZrO2、Y2O3Adding ethanol in a mass ratio of the total amount of the raw materials to the ethanol of 1:1, ball-milling and mixing for 5h, drying the powder under an infrared lamp, putting 0.5g of dried oxide powder into a mold with the diameter of 18mm, pressing the oxide powder into sheets under the pressure of 200MPa for 60s, and sintering the sheets at 1450 ℃ for 10h to obtain compact Zr0.84Y0.16O2-δA substrate with a thickness of 0.45 mm; 5g of BaCO are taken3Uniformly placed with Zr0.84Y0.16O2-δReacting for 20 hours around the substrate under the conditions of Air (0ml/min), Air pressure of 1atm and temperature of 1450 ℃, thus obtaining the thin-film BaZr0.84Y0.16O3-δThe electrolyte, which has a thickness of about 4 μm, is shown in the SEM image of FIG. 4.
Example 5 thin film formation of BaZr0.84Y0.16O3-δProton conductor electrolyte preparation
According to BaZr0.84Y0.16O3-δPreparation of 10g of Zr0.84Y0.16O2-δA substrate, ZrO is accurately weighed by a stoichiometric ratio2、Y2O3According to ZrO2、Y2O3Adding ethanol in a mass ratio of the total amount of the raw materials to the ethanol of 1:1, ball-milling and mixing for 5 hours, drying the powder under an infrared lamp,taking 0.5g of dry oxide powder in a mold with the diameter of 18mm, pressing the powder into a sheet by keeping the pressure of 200MPa for 60s, and sintering the sheet at 1450 ℃ for 10h to obtain compact Zr0.84Y0.16O2-δA substrate with a thickness of 0.45 mm; 5g of BaCO are taken3Uniformly placed with Zr0.84Y0.16O2-δAround the substrate, N2(35ml/min), the reaction is carried out for 96 hours under the conditions that the air pressure is 1atm and the temperature is 1600 ℃, and then the thinned BaZr can be obtained0.84Y0.16O3-δAn electrolyte having a thickness of about 20 μm.
Example 6 thin film formation of BaZr0.84Y0.16O3-δProton conductor electrolyte preparation
According to BaZr0.84Y0.16O3-δPreparation of 10g of Zr0.84Y0.16O2-δA substrate, ZrO is accurately weighed by a stoichiometric ratio2、Y2O3According to ZrO2、Y2O3Adding ethanol in a mass ratio of the total amount of the raw materials to the ethanol of 1:1, ball-milling and mixing for 5h, drying the powder under an infrared lamp, putting 0.5g of dried oxide powder into a mold with the diameter of 18mm, pressing the oxide powder into sheets under the pressure of 200MPa for 60s, and sintering the sheets at 1450 ℃ for 10h to obtain compact Zr0.84Y0.16O2-δA substrate with a thickness of 0.45 mm; 5g of BaCO are taken3Uniformly placed with Zr0.84Y0.16O2-δReacting for 72 hours around the matrix under the conditions of vacuum and 1400 ℃ to obtain the thin-film BaZr0.84Y0.16O3-δAn electrolyte having a thickness of about 12 μm.
Claims (3)
1. A proton conductor electrolyte, characterized in that the proton conductor electrolyte is a perovskite structure oxide having a structural composition of: BaZr1-xMxO3-δ(ii) a Wherein x is more than or equal to 0 and less than or equal to 1, and delta represents non-stoichiometric oxygen; m is at least one of Ce, Y, Al, Yb, Gd, Mg and Ti;
the thickness of the proton conductor electrolyte is less than 10 μm;
the preparation method of the proton conductor electrolyte comprises the following steps:
a. composition of expression BaZr according to Structure1-xMxO3-δZrO is weighed according to the stoichiometric ratio2And CeO2、Y2O3、Al2O3、Yb2O3、Gd2O3、MgO、TiO2Mixing for 4-6h by ball milling to obtain mixed oxide powder;
b. sintering the mixed oxide powder dry pressed tablet for 8-12h at 1450-1550 ℃ in an air atmosphere to obtain a fluorite structure oxide matrix;
c. placing a Ba source around the fluorite phase structure oxide matrix by taking fluorite phase oxide as the matrix, and reacting the fluorite phase structure oxide with a gas phase Ba source to generate the thinned BaZr1-xMxO3-δA proton conductor electrolyte;
the fluorite phase oxide has a structural composition of Zr1-xMxO2-δWherein x is more than or equal to 0 and less than or equal to 1, and delta represents non-stoichiometric oxygen; m is selected from at least one of Ce, Y, Al, Yb, Gd, Mg and Ti, and the thickness of the fluorite structure oxide matrix is less than 300 mu M;
the mass ratio of the fluorite phase oxide to the Ba source is 1: 5-15;
the reaction temperature is 1000-1600 ℃, and the heat preservation time is 1-72 h;
the reaction atmosphere is Ar, He and N2Air or vacuum, the flow rate is 0ml/min-100ml/min, and the gas pressure is 0atm-2.5 atm.
2. The proton conductor electrolyte as claimed in claim 1, wherein the Ba source is selected from BaCO3、Ba(NO3)2、Ba(CH3COO)2At least one of (1).
3. The proton conductor electrolyte as claimed in claim 1, wherein in the step b, the conditions of the dry-pressed tablet are: the pressure is 150-250MPa, and the pressure is maintained for 60-90 s.
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