CN114988482B - Perovskite type solid electrolyte and preparation method and application thereof - Google Patents

Perovskite type solid electrolyte and preparation method and application thereof Download PDF

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CN114988482B
CN114988482B CN202210814671.6A CN202210814671A CN114988482B CN 114988482 B CN114988482 B CN 114988482B CN 202210814671 A CN202210814671 A CN 202210814671A CN 114988482 B CN114988482 B CN 114988482B
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CN114988482A (en
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李鹏
梁士轩
黄祯
赵力达
赵高科
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China Automotive Innovation Corp
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
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Abstract

The invention provides a perovskite type solid electrolyte, a preparation method and application thereof. The chemical general formula of the perovskite type solid electrolyte is Y 1‑xEuxFe1‑yCuyO3, x is more than or equal to 0 and less than or equal to 0.4, Y is more than or equal to 0 and less than or equal to 0.4, and x and Y are not simultaneously 0. The perovskite solid electrolyte provided by the invention takes Y and Fe as main elements of A site and B site, eu and/or Cu are doped at the same time, and the main elements and the doping elements generate more oxygen vacancies and lattice gaps through synergistic action, so that the ion transmission channel is increased, the ion conductivity of the solid electrolyte is improved, in addition, the cost of the used elements is lower, the sintering temperature is reduced, and the preparation conditions are simplified.

Description

Perovskite type solid electrolyte and preparation method and application thereof
Technical Field
The invention belongs to the technical field of solid oxide fuel cells, and relates to a perovskite type solid electrolyte, a preparation method and application thereof.
Background
With the rapid growth of global population and economy, the problems of energy environmental pollution, ecological damage and the like are increasingly prominent, and the development of a green, environment-friendly, efficient and convenient new energy technology becomes a great topic of current great attention. The solid oxide fuel cell is a novel, green and efficient energy conversion device, and is of great interest because of its low emission, high efficiency and high fuel selectivity. However, since the last 80 th century, it has not been effectively applied on a large scale, mainly because of the lack of a solid electrolyte material capable of having a good combination of properties (high ionic conductivity, high stability) under medium temperature conditions.
Perovskite type solid electrolyte has high safety and stability under high-temperature environment and high ionic conductivity because of good mechanical properties, and is considered to be the most promising electrolyte for medium-temperature SOFC. A typical perovskite formula is ABO 3, where the A site is generally in the center of a tetrahedron composed of 12 oxygen atoms and the B site is in the center of an octahedron composed of 6 oxygen ions. The change of the valence state of the A site directly affects the state of oxygen ions, which is a direct cause of affecting oxygen vacancies, and the change of the valence state of the B site also affects the coordination state of surrounding oxygen ions, and is beneficial to the formation of oxygen vacancies due to the evolution of the polyhedral structure. Therefore, elements with different valence states and radius sizes are selected for doping the A site and the B site, so that more oxygen vacancies and lattice gaps are generated, ion migration is facilitated, and the ion conductivity is improved.
At present, oxygen ion perovskite type solid electrolyte is mainly concentrated in research of LaGaO 3, la + at A site can be replaced by Sr 2+,Ba2+,Ca+ plasma, ga 2+ at B site can be replaced by Mg 2+,Fe2+,Co3+ plasma (Li Zhongqiu and the like, shandong ceramics, 2005 (4)). Furthermore, ishihara et al further found that Sr 2+ doping at position A increased conductivity, and La 0.8Sr0.2Ga0.8Mg0.2O3 doped with Sr and Mg, respectively, at A, B had higher ionic conductivity of 0.17S/cm. (ISHIHARA T et al J am. Chem. Soc 1994 116:3801-3803). In addition, the ionic conductivity of the perovskite solid electrolyte can be improved by appropriately reducing the radius of the A-site ion in the perovskite LaGaO 3 (Liu ZG et al J Alloys Compd,2001 314 (1-2): 281-285).
At present, the preparation condition of oxide solid electrolyte is harsh, sintering is usually required to be carried out under the high temperature condition of more than 1200 ℃, for example, CN114447384A discloses an A-site defect perovskite structure fuel cell electrolyte, a preparation method thereof and a fuel cell, the solid electrolyte Ba 0.9Co0.4Fe0.4Zr0.1Y0.1O3-δ (BCFZY 0.9) with the A-site defect is prepared by a sol-gel method, and an ABO 3-delta perovskite structure oxygen ion/proton/electron mixed conduction type semiconductor electrolyte material is prepared by a citric acid sol-gel method. But the minimum temperature for preparing and sintering is 1100 ℃, and the prepared solid electrolyte particles are larger, seriously agglomerated and have no good pore channel structure, and the ion conductivity at 550 ℃ is only 0.13S/cm.
Therefore, how to obtain perovskite type solid electrolyte with higher conductivity and good performance is a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a perovskite type solid electrolyte, and a preparation method and application thereof. The perovskite solid electrolyte provided by the invention takes Y and Fe as main elements of A site and B site, eu and/or Cu are doped at the same time, and the main elements and the doping elements generate more oxygen vacancies and lattice gaps through synergistic action, so that the ion transmission channel is increased, the ion conductivity of the solid electrolyte is improved, in addition, the cost of the used elements is lower, the sintering temperature is reduced, and the preparation conditions are simplified.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
In a first aspect, the present invention provides a perovskite-type solid electrolyte having a chemical formula of Y 1-xEuxFe1-yCuyO3, wherein x is 0.ltoreq.x.ltoreq.0.4, Y is 0.ltoreq.y.ltoreq.0.4, and x and Y are not 0 at the same time.
For example, x may be 0, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, or 0.4, etc., and y may be 0, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, or 0.4, etc.
The perovskite solid electrolyte provided by the invention takes Y and Fe as main elements of A site and B site, eu and/or Cu are doped at the same time, and the main elements and the doping elements generate more oxygen vacancies and lattice gaps through synergistic action, so that the ion transmission channel is increased, the ion conductivity of the solid electrolyte is improved, and in addition, the cost of the used elements is lower.
In the invention, Y 3+ with the ionic radius smaller than La 3+ and low price is selected as the main element of A site, eu is selected for A site doping, eu has adjustable valence variation, and oxidation-reduction oscillation (Eu 2+→Eu3+) can occur under certain conditions, which is beneficial to the movement and regeneration of active oxygen and can improve the ionic conductivity; the Fe-based element has high reserves in the nature and low cost, is used as a main element of B site, and simultaneously selects Cu element for doping in the B site, so that the sintering temperature is reduced, the aim of A, B site double doping is achieved, and the ion conductivity is further improved.
In the invention, Y and Fe are used as main elements of A site and B site, eu and/or Cu are doped at the same time, and the main elements and the doping elements cooperate to jointly realize the purpose of improving the lattice defect of the solid electrolyte and further improve the lithium ion conductivity of the solid electrolyte.
In the present invention, the goal of creating more oxygen vacancies and lattice defects in the structure of ABO 3 cannot be achieved without any doping of the host element.
In the present invention, when the value of x or y is too large, either one of them exceeds 0.4, which results in a decrease in the content of the main element in A, B, and an excessive amount of the doping element adversely affects the ion conductivity of the solid electrolyte.
Preferably, in Y 1-xEuxFe1-yCuyO3, 0 < x.ltoreq.0.4, 0 < y.ltoreq.0.4, for example, x may be 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35 or 0.4, etc., and Y may be 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35 or 0.4, etc.
Preferably, the perovskite type solid electrolyte has a pore structure.
According to the invention, on the basis of taking Y and Fe as main elements of A and B, double doping of Eu and Cu is carried out simultaneously, so that the obtained perovskite type solid electrolyte has more pore structures, the pore structures are obvious and uniformly distributed, the ion migration rate is increased, and the ion conductivity of the solid electrolyte is further obviously improved.
In a second aspect, the present invention provides a method for producing a perovskite-type solid electrolyte according to the first aspect, comprising the steps of:
Mixing a Y source, a Eu source, a Fe source, a Cu source, a complexing agent and a dispersing agent, stirring to obtain a gel state, and sintering to obtain the perovskite type solid electrolyte;
Wherein, the molar weight of the Y source, the Eu source, the Fe source and the Cu source is corresponding to the stoichiometric ratio of Y 1-xEuxFe1-yCuyO3, x is more than or equal to 0 and less than or equal to 0.4, Y is more than or equal to 0 and less than or equal to 0.4, and x and Y are not simultaneously 0.
In the invention, the perovskite type solid electrolyte is prepared by adopting a sol-gel method, the method is simple, the cost of the used raw materials is low, the sintering temperature of the solid electrolyte is reduced, the energy is saved, the environment is protected, and the preparation process is simplified.
Preferably, the molar ratio of complexing agent to the sum of all metal cations is (2-3): 1, e.g., 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, or 3:1, etc.).
In the invention, the molar ratio of the complexing agent to the sum of all metal cations is too large, namely, too much complexing agent is added to influence the complexing state and uniformity of the sol, and too small molar ratio cannot form a better gel state.
Preferably, the Y source comprises Y (NO 3)3·6H2 O).
Preferably, the Eu source comprises Eu (NO 3)3·6H2 O).
Preferably, the Fe source comprises Fe (NO 3)3·9H2 O.
Preferably, the Cu source comprises Cu (NO 3)2·3H2 O.
Preferably, the complexing agent comprises citric acid.
Preferably, the dispersant comprises ethylene glycol.
Preferably, the stirring includes sequentially performing room temperature stirring and heating stirring.
Preferably, the stirring time at room temperature is 12 to 20 hours, for example 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours or 20 hours, etc., preferably 12 hours.
Preferably, the temperature of the heating and stirring is 70 to 90 ℃, for example 70 ℃, 73 ℃, 75 ℃, 78 ℃, 80 ℃, 83 ℃, 85 ℃, 88 ℃, 90 ℃, or the like, preferably 80 ℃.
Preferably, the gel-like substance is dried.
Preferably, the drying temperature is 90 to 120 ℃, for example 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃ or the like.
Preferably, the sintering includes sequentially performing primary sintering and secondary sintering.
Preferably, the temperature rising rate of the primary sintering is 1 to 20 ℃ per minute, for example, 1 ℃ per minute, 3 ℃ per minute, 5 ℃ per minute, 8 ℃ per minute, 10 ℃ per minute, 13 ℃ per minute, 15 ℃ per minute, 18 ℃ per minute or 20 ℃ per minute, etc., preferably 5 ℃ per minute.
Preferably, the temperature of the primary sintering is 400 to 500 ℃, for example 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃, or the like.
Preferably, the time of the primary sintering is 3 to 6 hours, for example, 3 hours, 4 hours, 5 hours, 6 hours, or the like.
Preferably, the temperature rise rate of the secondary sintering is 1 to 20 ℃ per minute, for example, 1 ℃ per minute, 3 ℃ per minute, 5 ℃ per minute, 8 ℃ per minute, 10 ℃ per minute, 13 ℃ per minute, 15 ℃ per minute, 18 ℃ per minute or 20 ℃ per minute, etc., preferably 5 ℃ per minute.
Preferably, the secondary sintering is performed at a temperature of 700 to 900 ℃, for example 700 ℃, 710 ℃, 720 ℃, 730 ℃, 740 ℃, 750 ℃, 760 ℃, 770 ℃, 780 ℃, 790 ℃, 800 ℃, 810 ℃, 820 ℃, 830 ℃, 840 ℃, 850 ℃, 860 ℃, 870 ℃, 880 ℃, 890 ℃, 900 ℃, or the like.
In the invention, the temperature of secondary sintering is too low, which is unfavorable for volatilization of organic solvent added in a sol-gel method and formation of porous material structure, while the temperature of secondary sintering is too high, which affects formation of a final phase of solid electrolyte.
Preferably, the secondary sintering time is 4 to 7 hours, for example, 4 hours, 5 hours, 6 hours, 7 hours, or the like.
As a preferred technical scheme, the preparation method comprises the following steps:
mixing a Y source, a Eu source, a Fe source, a Cu source, citric acid and ethylene glycol, stirring at room temperature for 12-20 h, then stirring at a heating temperature of 70-90 ℃ to obtain a gel state, drying the gel state substance at a temperature of 90-120 ℃, heating to 400-500 ℃ at a heating rate of 1-20 ℃/min, sintering for 3-6 h once, continuously heating to 700-900 ℃ at a heating rate of 1-20 ℃/min, and sintering for 4-7 h twice to obtain the perovskite type solid electrolyte;
Wherein, the molar weight of the Y source, the Eu source, the Fe source and the Cu source is corresponding to the stoichiometric ratio of Y 1-xEuxFe1-yCuyO3, x is more than or equal to 0 and less than or equal to 0.4, Y is more than or equal to 0 and less than or equal to 0.4, and x and Y are not simultaneously 0; the molar ratio of citric acid to the sum of all metal cations is (2-3): 1.
In a third aspect, the present invention also provides a solid oxide fuel cell comprising a perovskite-type solid electrolyte as described in the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
According to the perovskite type solid electrolyte provided by the invention, Y and Fe are used as main elements of A site and B site, eu and/or Cu are doped at the same time, and the main elements and the doping elements generate more oxygen vacancies and lattice gaps through synergistic action, so that ion transmission channels are increased, the ion conductivity of the solid electrolyte is improved, and when Eu and Cu are doubly doped, the solid electrolyte with a pore channel structure can be obtained, the ion migration rate is increased, in addition, the cost of the used elements is lower, the sintering temperature is reduced, the energy is saved, the environment is protected, and the preparation conditions are simplified. The perovskite type solid electrolyte provided by the invention has the total conductivity of more than 0.130S/cm under the condition of double metal doping, and the total conductivity of more than 0.150S/cm when the secondary sintering temperature is further regulated and controlled within the range of 700-900 ℃.
Drawings
Fig. 1 is an XRD pattern of the perovskite-type solid electrolyte provided in example 6.
Fig. 2 is an SEM image of the perovskite-type solid electrolyte provided in example 6.
Fig. 3 is an Electrochemical Impedance Spectroscopy (EIS) diagram of the perovskite type solid electrolyte provided in example 6.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The present embodiment provides a perovskite type solid electrolyte having a chemical formula of Y 0.9Eu0.1FeO3.
The preparation method of the solid electrolyte comprises the following steps:
(1) According to the stoichiometric ratio of each component in the chemical formula Y 0.9Eu0.1FeO3, 8.6673g of Y (NO 3)3·6H2 O (purity is 99.9%), 1.1206g of Eu (NO 3)3·6H2 O (purity is 99.99%) and 10.1481g of Fe (NO 3)3·9H2 O (purity is 99.999%) are weighed and mixed, and the mixture is kept stirring at room temperature until dissolved;
(2) Adding citric acid into the mixed solution as a complexing agent, uniformly mixing, wherein the molar ratio of the citric acid to all metal cations is 2:1, and adding 5ml of glycol as a dispersing agent;
(3) Stirring the obtained precursor solution at room temperature for 12 hours, and then placing the fully-acted solution in a magnetic stirrer to continuously heat the solution to a gel state at 80 ℃;
(4) Drying the obtained gel in a drying oven at 100 ℃ for 5 hours, roasting the dried precursor in a muffle furnace at 500 ℃ for 4 hours and at 800 ℃ for 5 hours, and controlling the heating rate at 5 ℃/min to obtain the Y 0.9Eu0.1FeO3 solid electrolyte.
Example 2
The present embodiment provides a perovskite type solid electrolyte having a chemical formula of Y 0.8Eu0.2FeO3.
The preparation method of the solid electrolyte comprises the following steps:
(1) According to the stoichiometric ratio of each component in the chemical formula Y 0.8Eu0.2FeO3, 7.4677g of Y (NO 3)3·6H2 O (purity is 99.9%), 2.1723g of Eu (NO 3)3·6H2 O (purity is 99.99%) and 9.8365g of Fe (NO 3)3·9H2 O (purity is 99.999%) are weighed and mixed, and the mixture is kept stirring at room temperature until dissolved;
(2) Adding citric acid into the mixed solution as a complexing agent, uniformly mixing, wherein the molar ratio of the citric acid to all metal cations is 2:1, and adding 5ml of glycol as a dispersing agent;
(3) Stirring the obtained precursor solution at room temperature for 18 hours, and then placing the fully-acted solution in a magnetic stirrer to continuously heat the solution to a gel state at 90 ℃;
(4) Drying the obtained gel in a drying oven at 90 ℃ for 8 hours, and roasting the dried precursor in a muffle furnace at 450 ℃ for 5 hours and at 800 ℃ for 5 hours, wherein the heating rate is controlled at 5 ℃/min, so as to obtain the Y 0.8Eu0.2FeO3 solid electrolyte.
Example 3
The present embodiment provides a perovskite type solid electrolyte having a chemical formula of Y 0.7Eu0.3FeO3.
The preparation method of the solid electrolyte comprises the following steps:
(1) According to the stoichiometric ratio of each component in the chemical formula Y 0.7Eu0.3FeO3, 6.3396g of Y (NO 3)3·6H2 O (purity is 99.9%), 3.1614g of Eu (NO 3)3·6H2 O (purity is 99.99%) and 9.5434g of Fe (NO 3)3·9H2 O (purity is 99.999%) are weighed and mixed, and the mixture is kept stirring at room temperature until dissolved;
(2) Adding citric acid into the mixed solution as a complexing agent, uniformly mixing, wherein the molar ratio of the citric acid to all metal cations is 2:1, and adding 5ml of glycol as a dispersing agent;
(3) Stirring the obtained precursor solution at room temperature for 12 hours, and then placing the fully-acted solution in a magnetic stirrer to continuously heat the solution to a gel state at 80 ℃;
(4) Drying the obtained gel in a drying oven at 100 ℃ for 5 hours, roasting the dried precursor in a muffle furnace at 500 ℃ for 4 hours and at 800 ℃ for 5 hours, and controlling the heating rate at 5 ℃/min to obtain the Y 0.7Eu0.3FeO3 solid electrolyte.
Example 4
The present embodiment provides a perovskite type solid electrolyte having a chemical formula of Y 0.6Eu0.4FeO3.
The preparation method of the solid electrolyte comprises the following steps:
(1) According to the stoichiometric ratio of each component in the chemical formula Y 0.6Eu0.4FeO3, 5.2767g of Y (NO 3)3·6H2 O (purity is 99.9%), 4.0932g of Eu (NO 3)3·6H2 O (purity is 99.99%) and 9.2673g of Fe (NO 3)3·9H2 O (purity is 99.999%)) are weighed and mixed, and the mixture is kept stirring at room temperature until dissolved;
(2) Adding citric acid into the mixed solution as a complexing agent, uniformly mixing, wherein the molar ratio of the citric acid to all metal cations is 2:1, and adding 5ml of glycol as a dispersing agent;
(3) Stirring the obtained precursor solution at room temperature for 12 hours, and then placing the fully-acted solution in a magnetic stirrer to continuously heat the solution to a gel state at 80 ℃;
(4) Drying the obtained gel in a drying oven at 100 ℃ for 5 hours, roasting the dried precursor in a muffle furnace at 500 ℃ for 4 hours and at 900 ℃ for 4 hours, and controlling the heating rate at 5 ℃/min to obtain the Y 0.6Eu0.4FeO3 solid electrolyte.
Example 5
The present embodiment provides a perovskite type solid electrolyte having a chemical formula of Y 0.8Eu0.2Fe0.9Cu0.1O3.
The preparation method of the solid electrolyte comprises the following steps:
(1) According to the stoichiometric ratio of each component in the chemical formula Y 0.8Eu0.2Fe0.9Cu0.1O3, 7.43998 g of Y (NO 3)3·6H2 O (purity: 99.9%), 2.1642g of Eu (NO 3)3·6H2 O (purity: 99.99%), 8.8198g of Fe (NO 3)3·9H2 O (purity: 99.999%) and 0.4550g of Cu (NO 3)2·3H2 O (purity: 99.99%)) are weighed out and mixed, and the mixture is kept at room temperature with continuous stirring until dissolved;
(2) Adding citric acid into the mixed solution as a complexing agent, uniformly mixing, wherein the molar ratio of the citric acid to all metal cations is 2:1, and adding 5ml of glycol as a dispersing agent;
(3) Stirring the obtained precursor solution at room temperature for 12 hours, and then placing the fully-acted solution in a magnetic stirrer to continuously heat the solution to a gel state at 80 ℃;
(4) Drying the obtained gel in a drying oven at 100 ℃ for 5 hours, roasting the dried precursor in a muffle furnace at 500 ℃ for 4 hours and at 700 ℃ for 7 hours, and controlling the heating rate at 5 ℃/min to obtain the Y 0.8Eu0.2Fe0.9Cu0.1O3 solid electrolyte.
Example 6
The present embodiment provides a perovskite type solid electrolyte having a chemical formula of Y 0.8Eu0.2Fe0.8Cu0.2O3.
The preparation method of the solid electrolyte comprises the following steps:
(1) According to the stoichiometric ratio of each component in the chemical formula Y 0.8Eu0.2Fe0.8Cu0.2O3, 7.4121g of Y (NO 3)3·6H2 O (purity: 99.9%), 2.1561g of Eu (NO 3)3·6H2 O (purity: 99.99%), 7.8106g of Fe (NO 3)3·9H2 O (purity: 99.999%) and 0.9066g of Cu (NO 3)2·3H2 O (purity: 99.99%)) are weighed out and mixed, and the mixture is kept stirring at room temperature until dissolved;
(2) Adding citric acid into the mixed solution as a complexing agent, uniformly mixing, wherein the molar ratio of the citric acid to all metal cations is 2:1, and adding 5ml of glycol as a dispersing agent;
(3) Stirring the obtained precursor solution at room temperature for 12 hours, and then placing the fully-acted solution in a magnetic stirrer to continuously heat the solution to a gel state at 80 ℃;
(4) Drying the obtained gel in a drying oven at 100 ℃ for 5 hours, roasting the dried precursor in a muffle furnace at 500 ℃ for 4 hours and at 800 ℃ for 5 hours, and controlling the heating rate at 5 ℃/min to obtain the Y 0.8Eu0.2Fe0.8Cu0.2O3 solid electrolyte.
Fig. 1 shows the XRD pattern of the perovskite-type solid electrolyte provided in example 6, and as can be seen from fig. 1, the perovskite-type solid electrolyte prepared by the present invention is identical to the standard PDF #39-1489 card of YFeO 3, which shows that it has a single ABO 3 structure and a pure phase structure is obtained.
Fig. 2 shows an SEM image of the perovskite type solid electrolyte provided in example 6, and it can be seen from fig. 2 that the double-doped perovskite type solid electrolyte is composed of nano particles with relatively uniform size, the average particle size is about 100nm, and the nano particles have relatively uniform pore channel structures, and from the micro morphology, the synthesized solid electrolyte is very loose in structure, and the volume of the synthesized solid electrolyte is obviously reduced after being slightly ground, so that the synthesized solid electrolyte is easily compressed into relatively dense blocks.
Fig. 3 shows an Electrochemical Impedance Spectroscopy (EIS) diagram of the perovskite solid electrolyte provided in example 6.
Example 7
The present embodiment provides a perovskite type solid electrolyte having a chemical formula of Y 0.8Eu0.2Fe0.7Cu0.3O3.
The preparation method of the solid electrolyte comprises the following steps:
(1) According to the stoichiometric ratio of each component in the chemical formula Y 0.8Eu0.2Fe0.7Cu0.3O3, 7.3847g of Y (NO 3)3·6H2 O (purity: 99.9%), 2.1481g of Eu (NO 3)3·6H2 O (purity: 99.99%), 6.8089g of Fe (NO 3)3·9H2 O (purity: 99.999%) and 1.3549g of Cu (NO 3)2·3H2 O (purity: 99.99%)) are weighed out and mixed, and the mixture is kept stirring at room temperature until dissolved;
(2) Adding citric acid into the mixed solution as a complexing agent, uniformly mixing, wherein the molar ratio of the citric acid to all metal cations is 2.5:1, and adding 5ml of ethylene glycol as a dispersing agent;
(3) Stirring the obtained precursor solution at room temperature for 18 hours, and then placing the fully-acted solution in a magnetic stirrer to continuously heat the solution to a gel state at 80 ℃;
(4) Drying the obtained gel in a drying oven at 100 ℃ for 5 hours, roasting the dried precursor in a muffle furnace at 500 ℃ for 4 hours and at 800 ℃ for 5 hours, and controlling the heating rate at 5 ℃/min to obtain the Y 0.8Eu0.2Fe0.7Cu0.3O3 solid electrolyte.
Example 8
The present embodiment provides a perovskite type solid electrolyte having a chemical formula of Y 0.8Eu0.2Fe0.6Cu0.4O3.
The preparation method of the solid electrolyte comprises the following steps:
(1) According to the stoichiometric ratio of each component in the chemical formula Y 0.8Eu0.2Fe0.6Cu0.4O3, 7.3574g of Y (NO 3)3·6H2 O (purity: 99.9%), 2.1402g of Eu (NO 3)3·6H2 O (purity: 99.99%), 5.8147g of Fe (NO 3)3·9H2 O (purity: 99.999%) and 1.7998g of Cu (NO 3)2·3H2 O (purity: 99.99%)) are weighed out and mixed, and the mixture is kept stirring at room temperature until dissolved;
(2) Adding citric acid into the mixed solution as a complexing agent, uniformly mixing, wherein the molar ratio of the citric acid to all metal cations is 3:1, and adding 5ml of glycol as a dispersing agent;
(3) Stirring the obtained precursor solution at room temperature for 12 hours, and then placing the fully-acted solution in a magnetic stirrer to continuously heat the solution to a gel state at 80 ℃;
(4) Drying the obtained gel in a drying oven at 100 ℃ for 5 hours, roasting the dried precursor in a muffle furnace at 400 ℃ for 6 hours and at 800 ℃ for 4 hours, and controlling the heating rate at 5 ℃/min to obtain the Y 0.8Eu0.2Fe0.6Cu0.4O3 solid electrolyte.
Example 9
The difference between this example and example 6 is that the secondary sintering temperature in step (4) of this example was 700 ℃ (800 ℃ was replaced with 700 ℃).
The remaining preparation methods and parameters were consistent with example 6.
Example 10
The difference between this example and example 6 is that the temperature of the secondary sintering in step (4) of this example was 900 ℃ (800 ℃ was replaced with 900 ℃).
The remaining preparation methods and parameters were consistent with example 6.
Example 11
The difference between this example and example 6 is that the temperature of the secondary sintering in step (4) of this example was 1000 ℃ (800 ℃ was replaced with 1000 ℃).
The remaining preparation methods and parameters were consistent with example 6.
Comparative example 1
The comparative example is different from example 1 in that the perovskite type solid electrolyte provided in the comparative example has a chemical formula of YFeO 3.
The preparation method differs from example 1 in that in step (1): 9.9454g of Y (NO 3)3·6H2 O (purity: 99.9%) and 10.4801g of Fe (NO 3)3·9H2 O (purity: 99.999%) were weighed out according to the stoichiometric ratio of the components of the chemical formula YFeO 3, and then mixed, and the mixture was kept stirring at room temperature until dissolved.
The remaining preparation methods and parameters were consistent with example 1.
Comparative example 2
The comparative example is different from example 1 in that the perovskite type solid electrolyte provided in the comparative example has a chemical formula of LaGaO 3.
The preparation method differs from example 1 in that in step (1): according to the stoichiometric ratio of each component of the chemical formula LaGaO 3, 8.9278g of La (NO 3)3·6H2 O (purity is 99.999%) and 5.2677g of Ga (NO 3)3·9H2 O (purity is 99.999%) are weighed and mixed, the mixture is continuously stirred at room temperature until dissolved, in the step (4), the obtained gel is dried in a drying box at 100 ℃ for 5 hours, the dried precursor is baked in a muffle furnace at 500 ℃ for 4 hours, the temperature is baked at 900 ℃ for 5 hours, and finally, the powder is ground, and then baked in the muffle furnace at 1250 ℃ for 3 hours, and the heating rate is controlled at 5 ℃/min.
The remaining preparation methods and parameters were consistent with example 1.
The perovskite type solid electrolytes provided in examples 1-11 and comparative examples 1-2 were characterized by testing at a frequency ranging from 10MHz to 1Hz with a bias voltage of 10mV using a Swiss Wantong PGSTAT302 electrochemical workstation. Before testing, 0.5g of powder is weighed and ground, pressed into a tablet by using a die with phi of 10mm, the thickness d=1mm, the ceramic block is prepared In a muffle furnace for 1250-20 h, and then the ion conductivity test is carried out by using Pt/In as a blocking electrode. The results are shown in Table 1.
TABLE 1
From the data results of examples 1-8, it is known that the solid electrolyte provided by the invention generates more oxygen vacancies and ion transport channels by selecting and double doping the A and B elements with different ionic radii and valence states, and has a pore structure, and the ionic conductivity is obviously more excellent.
From the data of examples 6 and examples 9 to 11, it is understood that the secondary sintering temperature is too high to generate more lattice defects and pore structures in the solid electrolyte, to ion migration, and thus the ion conductivity is poor.
From the data of examples 1 to 11 and comparative example 1, it was found that the ion conductivity could not be improved without doping the perovskite-type solid electrolyte in which Y and Fe are the main phases, and further, the effect of pure YFeO 3 was inferior to that of comparative example 2.
As can be seen from the data results of examples 1-10 and comparative example 2, the perovskite type solid electrolyte provided by the invention can reach ion conductivity comparable to LaGaO 3 or even better even if only single element doping is carried out, and the ion conductivity can be obviously improved after double doping.
In summary, the perovskite type solid electrolyte provided by the invention takes Y and Fe as main elements of A site and B site, eu and/or Cu are doped at the same time, and the main elements and the doping elements generate more oxygen vacancies and lattice gaps through synergistic effect, so that ion transmission channels are increased, the ion conductivity of the solid electrolyte is improved, and when Eu and Cu are doubly doped, the solid electrolyte with a pore channel structure can be obtained, the ion migration rate is increased, in addition, the cost of the used elements is lower, the sintering temperature is reduced, the energy is saved, the environment is protected, and the preparation conditions are simplified. The perovskite type solid electrolyte provided by the invention has the total conductivity of more than 0.130S/cm under the condition of double metal doping, and the total conductivity of more than 0.150S/cm when the secondary sintering temperature is further regulated and controlled within the range of 700-900 ℃.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.

Claims (27)

1. The perovskite type solid electrolyte is characterized in that the chemical general formula of the perovskite type solid electrolyte is Y 1- xEuxFe1-yCuyO3, x is more than 0 and less than or equal to 0.4, Y is more than 0 and less than or equal to 0.4, and x and Y are not simultaneously 0; the perovskite type solid electrolyte has a pore structure.
2. A method for producing the perovskite-type solid electrolyte according to claim 1, comprising the steps of:
Mixing a Y source, a Eu source, a Fe source, a Cu source, a complexing agent and a dispersing agent, stirring to obtain a gel state, and sintering to obtain the perovskite type solid electrolyte;
Wherein, the molar weight of the Y source, the Eu source, the Fe source and the Cu source corresponds to the stoichiometric ratio of Y 1-xEuxFe1-yCuyO3, x is more than 0 and less than or equal to 0.4, Y is more than 0 and less than or equal to 0.4, and x and Y are not 0 at the same time.
3. The method for producing a perovskite solid electrolyte according to claim 2, wherein the molar ratio of the complexing agent to the sum of all metal cations is (2 to 3): 1.
4. The method of producing a perovskite solid electrolyte according to claim 2, wherein the Y source comprises Y (NO 3)3·6H2 O.
5. The method for producing a perovskite solid electrolyte according to claim 2, wherein the Eu source includes Eu (NO 3)3·6H2 O).
6. The method for producing a perovskite solid electrolyte according to claim 2, wherein the Fe source comprises Fe (NO 3)3·9H2 O.
7. The method of producing a perovskite solid electrolyte according to claim 2, wherein the Cu source comprises Cu (NO 3)2·3H2 O.
8. The method for producing a perovskite-type solid electrolyte according to claim 2, wherein the complexing agent comprises citric acid.
9. The method for producing a perovskite-type solid electrolyte according to claim 2, wherein the dispersant comprises ethylene glycol.
10. The method for producing a perovskite solid electrolyte according to claim 2, wherein the stirring includes sequentially performing room temperature stirring and heating stirring.
11. The method for producing a perovskite solid electrolyte according to claim 10, wherein the stirring time at room temperature is 12 to 20 hours.
12. The method for producing a perovskite solid electrolyte according to claim 10, wherein the stirring time at room temperature is 12 hours.
13. The method for producing a perovskite solid electrolyte according to claim 10, wherein the temperature of the heating and stirring is 70 to 90 ℃.
14. The method for producing a perovskite solid electrolyte according to claim 13, wherein the temperature of the heating and stirring is 80 ℃.
15. The method for producing a perovskite solid electrolyte according to claim 2, wherein the substance in a gel state is dried.
16. The method for producing a perovskite-type solid electrolyte according to claim 15, wherein the drying temperature is 90 to 120 ℃.
17. The method for producing a perovskite solid electrolyte according to claim 2, wherein the sintering comprises performing primary sintering and secondary sintering in this order.
18. The method for producing a perovskite solid electrolyte according to claim 17, wherein the temperature rise rate of the primary sintering is 1 to 20 ℃/min.
19. The method for producing a perovskite solid electrolyte according to claim 18, wherein the temperature rise rate of the primary sintering is 5 ℃/min.
20. The method for producing a perovskite solid electrolyte according to claim 17, wherein the temperature of the primary sintering is 400 to 500 ℃.
21. The method for producing a perovskite solid electrolyte according to claim 17, wherein the time of the primary sintering is 3 to 6 hours.
22. The method for producing a perovskite solid electrolyte according to claim 17, wherein the rate of temperature rise of the secondary sintering is 1 to 20 ℃/min.
23. The method for producing a perovskite solid electrolyte according to claim 22, wherein the temperature rise rate of the secondary sintering is 5 ℃/min.
24. The method for producing a perovskite solid electrolyte according to claim 17, wherein the secondary sintering temperature is 700 to 900 ℃.
25. The method for producing a perovskite solid electrolyte according to claim 17, wherein the time for the secondary sintering is 4 to 7 hours.
26. The method for producing a perovskite solid electrolyte according to claim 2, characterized in that the method for producing comprises the steps of:
mixing a Y source, a Eu source, a Fe source, a Cu source, citric acid and ethylene glycol, stirring at room temperature for 12-20 h, then stirring at a heating temperature of 70-90 ℃ to obtain a gel state, drying the gel state substance at a temperature of 90-120 ℃, heating to 400-500 ℃ at a heating rate of 1-20 ℃/min, sintering for 3-6 h once, continuously heating to 700-900 ℃ at a heating rate of 1-20 ℃/min, and sintering for 4-7 h twice to obtain the perovskite type solid electrolyte;
Wherein, the molar weight of the Y source, the Eu source, the Fe source and the Cu source corresponds to the stoichiometric ratio of Y 1-xEuxFe1-yCuyO3, x is more than 0 and less than or equal to 0.4, Y is more than 0 and less than or equal to 0.4, and x and Y are not 0 at the same time; the molar ratio of citric acid to the sum of all metal cations is (2-3): 1.
27. A solid oxide fuel cell, characterized in that the solid oxide fuel cell comprises the perovskite-type solid electrolyte according to claim 1.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101467286A (en) * 2006-06-13 2009-06-24 日立麦克赛尔株式会社 Fine particle of perovskite oxide, particle having depositedperovskite oxide, catalyst material, catalyst material for oxygen reduction, catalyst material for fuel cell, and electrode for fuel cell
CN104072123A (en) * 2014-06-13 2014-10-01 华东师范大学 Perovskite YCoxFe(1-x)O3 oxide crystal and preparation method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6521202B1 (en) * 1999-06-28 2003-02-18 University Of Chicago Oxygen ion conducting materials
CN101918337A (en) * 2005-08-09 2010-12-15 休斯敦系统大学 The novel cathode and the electrolyte that are used for Solid Oxide Fuel Cell and ion transport membranes
CN101545133B (en) * 2009-03-27 2011-06-29 上海应用技术学院 Method for growing rare-earth ferrite magneto-optical crystal
CN105018087B (en) * 2015-07-11 2017-11-28 东北大学 Eu3+Adulterate laminated perovskite structure La2CuO4The preparation method of fluorescent powder

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101467286A (en) * 2006-06-13 2009-06-24 日立麦克赛尔株式会社 Fine particle of perovskite oxide, particle having depositedperovskite oxide, catalyst material, catalyst material for oxygen reduction, catalyst material for fuel cell, and electrode for fuel cell
CN104072123A (en) * 2014-06-13 2014-10-01 华东师范大学 Perovskite YCoxFe(1-x)O3 oxide crystal and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Electrical properties of perovskite YFeO3 based ceramics modified by Cu/Nb ions as negative temperature coefficient thermistors;Yuan Zeng;《Journal of Materials Science: Materials in Electronics》;第30卷(第15期);第14528-14537页 *
Study on the influence of ion doping on the crystal structure and magnetic properties of YFeO3;Lingxian Ji;《Materials Research Express》;第7卷(第6期);全文 *

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