CN114988482A - 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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CN114988482A
CN114988482A CN202210814671.6A CN202210814671A CN114988482A CN 114988482 A CN114988482 A CN 114988482A CN 202210814671 A CN202210814671 A CN 202210814671A CN 114988482 A CN114988482 A CN 114988482A
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solid electrolyte
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perovskite
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type solid
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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
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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    • C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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
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    • H01M2300/0085—Immobilising or gelification of electrolyte
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Abstract

The invention provides a perovskite type solid electrolyte and a preparation method and application thereof. The chemical general formula of the perovskite type solid electrolyte is Y 1‑x Eu x Fe 1‑y Cu y O 3 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 0 at the same time. 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 the transmission channel of ions is increased, the ionic conductivity of the solid electrolyte is improved, in addition, the used elements have lower cost, the sintering temperature is also 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, and a preparation method and application thereof.
Background
With the rapid increase of global population and economy, the problems of energy environmental pollution, ecological damage and the like are increasingly prominent, and the development of a new energy technology which is green, environment-friendly, efficient and convenient becomes a major subject of great attention at present. Solid oxide fuel cells are a new, green, and efficient energy conversion device, and are receiving attention due to their low emissions, high efficiency, and high fuel selectivity. However, the development of the electrolyte in the last 80 th century has not yet achieved large-scale effective application, and the main reason is the lack of a solid electrolyte material with good comprehensive performance (high ionic conductivity and high stability) under the condition of medium temperature.
The perovskite solid electrolyte has good mechanical properties, higher safety and stability in a high-temperature environment and higher ionic conductivity, and is considered to be the most promising electrolyte for the medium-temperature SOFC. A typical perovskite formula is ABO 3 Wherein the A site is generally centered in a tetrakaidecahedron of 12 oxygen atoms and the B site is centered in an octahedron of 6 oxygen ions. The change of the valence state of the A site directly influences the state of the oxygen ions and is a direct reason for influencing oxygen vacancies, and the change of the valence state of the B site ions also influences the coordination state of the surrounding oxygen ions and is beneficial to the formation of the oxygen vacancies due to the evolution of the polyhedral structure. Therefore, the A site and the B site are doped by selecting elements with different valence states and radii, so that more oxygen vacancies and crystal lattice gaps are generated, and ion migration is facilitated, and the ion conductivity of the material is improved.
At present, the oxygen ion perovskite type solid electrolyte is mainly concentrated in LaGaO 3 Study of La at the A-position + Can be coated with Sr 2+ ，Ba 2+ ，Ca + Plasma substitution of Ga in B position 2+ Can be coated with Mg 2+ ，Fe 2+ ，Co 3+ Plasma substitution (Lizhou et al, Shandong ceramics, 2005 (4)). And further found by Ishihara et al that Sr was performed at the A-position 2+ The doping can increase the conductivity, and A, B is doped with Sr and Mg La respectively 0.8 Sr 0.2 Ga 0.8 Mg 0.2 O 3 Has higher ion conductivity of 0.17S/cm. (Ishihara T et al J am chem Soc 1994116: 3801-3803). In addition, the perovskite content is appropriately reducedMine LaGaO 3 The radius of the A site ion can improve the ion conductivity of the perovskite solid electrolyte (Liu ZG et al J Alloys Compd, 2001314 (1-2): 281-.
Currently, the preparation conditions for oxide solid electrolytes are relatively harsh, and sintering is usually required to be performed under the high temperature condition of more than 1200 ℃, for example, CN114447384A discloses an a-site defective perovskite structure fuel cell electrolyte, a preparation method thereof and a fuel cell, and the a-site defective solid electrolyte Ba is prepared by a sol-gel method 0.9 Co 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3-δ (BCFZY0.9), and preparing the 'oxygen ion/proton/electron' mixed conduction type semiconductor electrolyte material with an ABO 3-delta type perovskite structure by adopting a citric acid sol-gel method. But the lowest sintering temperature of the preparation method reaches 1100 ℃, the prepared solid electrolyte particles are large and seriously agglomerated, no good pore channel structure exists, and the ionic conductivity at 550 ℃ is only 0.13S/cm.
Therefore, how to obtain a perovskite solid electrolyte with high 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. 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 the transmission channel of ions is increased, the ionic conductivity of the solid electrolyte is improved, in addition, the used elements have lower cost, the sintering temperature is also reduced, and the preparation conditions are simplified.
In order to achieve the purpose, 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-x Eu x Fe 1-y Cu y O 3 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 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, 0.4, etc., and y may be 0, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, etc.
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 the transmission channel of ions is increased, the ion conductivity of the solid electrolyte is improved, and in addition, the used elements are low in cost.
In the invention, the selected ionic radius is less than La 3+ And low-cost Y 3+ As main element of A site, Eu is selected for A site doping, Eu has adjustable valence change, and oxidation reduction oscillation (Eu) can occur under certain conditions 2+ →Eu 3+ ) This will facilitate the movement and regeneration of active oxygen, which can improve the ionic conductivity; the Fe element has high storage capacity and low cost in nature, is used as a B-site main element, and simultaneously selects a Cu element for doping at the B site, so that the sintering temperature is reduced, the aim of A, B-site double doping is fulfilled, and the ionic conductivity is further improved.
According to 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 doped elements jointly realize the improvement of the lattice defect of the solid electrolyte through the synergistic action, so that the lithium ion conductivity of the solid electrolyte is improved.
In the invention, if the main bit element is not doped at all, ABO cannot be realized 3 To generate more oxygen vacancies and lattice defects in the structure of (a).
In the present invention, too large values of x or y, either exceeding 0.4, result in a decrease in the main element content of A, B, and an excessive amount of doping element adversely affects the ion conductivity of the solid electrolyte.
Preferably, said Y is 1-x Eu x Fe 1-y Cu y O 3 In the formula, 0 < x.ltoreq.0.4 and 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, etcThe above-mentioned 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 site and B site, Eu and Cu are simultaneously doped, so that the obtained perovskite type solid electrolyte has more pore channel structures, the pore channel structures are obvious and uniform in distribution, the ion migration rate is increased, and further the ion conductivity of the solid electrolyte is obviously improved.
In a second aspect, the present invention provides a method for producing a perovskite-type solid electrolyte as defined in the first aspect, the method 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 amounts of the Y source, the Eu source, the Fe source and the Cu source are equal to Y 1-x Eu x Fe 1-y Cu y O 3 The stoichiometric ratio of (A) corresponds to that of (B), 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 0 simultaneously.
According to 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 the 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 the complexing agent is added too much, which can affect the complexing state and the homogeneity of the sol, and the molar ratio is too small, which can not form a better gel state.
Preferably, the Y source comprises Y (NO) 3 ) 3 ·6H 2 O。
Preferably, the Eu source comprises Eu (NO) 3 ) 3 ·6H 2 O。
Preferably, the Fe source comprises Fe (NO) 3 ) 3 ·9H 2 O。
Preferably, the Cu source comprises Cu (NO) 3 ) 2 ·3H 2 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 12-20 h, such as 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h or 20h, and the like, and is preferably 12 h.
Preferably, the temperature of the heating and stirring is 70 to 90 ℃, such as 70 ℃, 73 ℃, 75 ℃, 78 ℃, 80 ℃, 83 ℃, 85 ℃, 88 ℃ or 90 ℃, preferably 80 ℃.
Preferably, the gel-state material is dried.
Preferably, the drying temperature is 90-120 ℃, such as 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃.
Preferably, the sintering includes sequentially performing a primary sintering and a secondary sintering.
Preferably, the temperature rise rate of the primary sintering is 1-20 ℃/min, such as 1 ℃/min, 3 ℃/min, 5 ℃/min, 8 ℃/min, 10 ℃/min, 13 ℃/min, 15 ℃/min, 18 ℃/min or 20 ℃/min, and the like, preferably 5 ℃/min.
Preferably, the temperature of the primary sintering is 400 to 500 ℃, for example, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃ or 500 ℃.
Preferably, the time of the primary sintering is 3-6 h, such as 3h, 4h, 5h or 6 h.
Preferably, the temperature rise rate of the secondary sintering is 1-20 ℃/min, such as 1 ℃/min, 3 ℃/min, 5 ℃/min, 8 ℃/min, 10 ℃/min, 13 ℃/min, 15 ℃/min, 18 ℃/min or 20 ℃/min, and the like, preferably 5 ℃/min.
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 the secondary sintering is too low, which is not beneficial to the volatilization of the organic solvent added in the sol-gel method and the formation of the porous material structure, and the temperature of the secondary sintering is too high, which can affect the formation of the final phase of the solid electrolyte.
Preferably, the time of the secondary sintering is 4-7 h, such as 4h, 5h, 6h or 7 h.
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 for primary sintering for 3-6 h, and continuing heating to 700-900 ℃ at a heating rate of 1-20 ℃/min for secondary sintering for 4-7 h to obtain the perovskite type solid electrolyte;
wherein the molar weight of Y source, Eu source, Fe source and Cu source is equal to Y 1-x Eu x Fe 1-y Cu y O 3 The stoichiometric ratio of (A) corresponds to that of (B), 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 0 simultaneously; the molar ratio of the 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 the transmission channel of ions is increased, the ionic conductivity of the solid electrolyte is improved, and when Eu and Cu are subjected to double doping, the solid electrolyte with a pore channel structure can be obtained, the ionic migration rate is increased, in addition, the used elements are low in cost, the sintering temperature is reduced, the energy is saved, the environment is protected, and the preparation conditions are simplified. The perovskite solid electrolyte provided by the invention has the total conductivity of over 0.130S/cm under the condition of bimetal doping, and the total conductivity of over 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) chart of the perovskite-type solid electrolyte provided in example 6.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
This example provides a perovskite-type solid electrolyte having a chemical formula of Y 0.9 Eu 0.1 FeO 3 。
The preparation method of the solid electrolyte comprises the following steps:
(1) according to the formula Y 0.9 Eu 0.1 FeO 3 Weighing Y (NO) according to the stoichiometric ratio of each component 3 ) 3 ·6H 2 8.6673g of O (purity 99.9%), Eu (NO) 3 ) 3 ·6H 2 1.1206g of O (purity 99.99%), Fe (NO) 3 ) 3 ·9H 2 10.1481g of O (99.999 percent purity) are mixed, and the mixture is placed at room temperature and stirred continuously until dissolved;
(2) adding citric acid serving as a complexing agent into the mixed solution, uniformly mixing, wherein the molar ratio of the citric acid to all metal cations is 2:1, and adding 5ml of ethylene glycol serving as a dispersing agent;
(3) stirring the obtained precursor solution at room temperature for 12 hours, and then putting the solution with sufficient effect in a magnetic stirrer, and continuously heating the solution at 80 ℃ to a gel state;
(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 800 ℃ for 5 hours, and controlling the heating rate at 5 ℃/min to obtain Y 0.9 Eu 0.1 FeO 3 A solid electrolyte.
Example 2
This example provides a perovskite-type solid electrolyte having a chemical formula of Y 0.8 Eu 0.2 FeO 3 。
The preparation method of the solid electrolyte comprises the following steps:
(1) according to the formula Y 0.8 Eu 0.2 FeO 3 Weighing Y (NO) according to the stoichiometric ratio of each component 3 ) 3 ·6H 2 7.4677g of O (purity 99.9%), Eu (NO) 3 ) 3 ·6H 2 2.1723g of O (purity 99.99%), Fe (NO) 3 ) 3 ·9H 2 9.8365g of O (99.999% purity) are mixed, and the mixture is kept stirring at room temperature until dissolved;
(2) adding citric acid serving as a complexing agent into the mixed solution, uniformly mixing, wherein the molar ratio of the citric acid to all metal cations is 2:1, and adding 5ml of ethylene glycol serving as a dispersing agent;
(3) stirring the obtained precursor solution at room temperature for 18 hours, and then putting the solution with sufficient effect in a magnetic stirrer, and continuously heating the solution at 90 ℃ to a gel state;
(4) drying the obtained gel in a drying oven at 90 ℃ for 8 hours, roasting the dried precursor in a muffle furnace at 450 ℃ for 5 hours and at 800 ℃ for 5 hours, controlling the heating rate at 5 ℃/min to obtain Y 0.8 Eu 0.2 FeO 3 A solid electrolyte.
Example 3
This example provides a perovskite-type solid electrolyte having a chemical formula of Y 0.7 Eu 0.3 FeO 3 。
The preparation method of the solid electrolyte comprises the following steps:
(1) according to the formula Y 0.7 Eu 0.3 FeO 3 Weighing Y (NO) according to the stoichiometric ratio of each component 3 ) 3 ·6H 2 6.3396g of O (purity 99.9%), Eu (NO) 3 ) 3 ·6H 2 3.1614g of O (purity 99.99%), Fe (NO) 3 ) 3 ·9H 2 9.5434g of O (99.999% purity) are mixed, and the mixture is kept stirring at room temperature until dissolved;
(2) adding citric acid serving as a complexing agent into the mixed solution, uniformly mixing, wherein the molar ratio of the citric acid to all metal cations is 2:1, and adding 5ml of ethylene glycol serving as a dispersing agent;
(3) stirring the obtained precursor solution at room temperature for 12 hours, and then putting the solution with sufficient effect in a magnetic stirrer, and continuously heating the solution at 80 ℃ to a gel state;
(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 Y 0.7 Eu 0.3 FeO 3 A solid electrolyte.
Example 4
This example provides a perovskite-type solid electrolyte having a chemical formula of Y 0.6 Eu 0.4 FeO 3 。
The preparation method of the solid electrolyte comprises the following steps:
(1) according to the formula Y 0.6 Eu 0.4 FeO 3 Weighing Y (NO) according to the stoichiometric ratio of each component 3 ) 3 ·6H 2 5.2767g of O (purity 99.9%), Eu (NO) 3 ) 3 ·6H 2 4.0932g of O (purity 99.99%), Fe (NO) 3 ) 3 ·9H 2 9.2673g of O (99.999 percent purity) are mixed, and the mixture is placed at room temperature and stirred continuously until dissolved;
(2) adding citric acid serving as a complexing agent into the mixed solution, uniformly mixing, wherein the molar ratio of the citric acid to all metal cations is 2:1, and adding 5ml of ethylene glycol serving as a dispersing agent;
(3) stirring the obtained precursor solution at room temperature for 12 hours, and then putting the solution with sufficient effect in a magnetic stirrer, and continuously heating the solution at 80 ℃ to a gel state;
(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, controlling the heating rate at 5 ℃/min to obtain Y 0.6 Eu 0.4 FeO 3 A solid electrolyte.
Example 5
This example provides a perovskite-type solid electrolyte having a chemical formula of Y 0.8 Eu 0.2 Fe 0.9 Cu 0.1 O 3 。
The preparation method of the solid electrolyte comprises the following steps:
(1) according to the formula Y 0.8 Eu 0.2 Fe 0.9 Cu 0.1 O 3 Weighing Y (NO) according to the stoichiometric ratio of each component 3 ) 3 ·6H 2 7.4398g of O (purity 99.9%), Eu (NO) 3 ) 3 ·6H 2 2.1642g of O (purity 99.99%), Fe (NO) 3 ) 3 ·9H 2 8.8198g of O (purity 99.999%), Cu (NO) 3 ) 2 ·3H 2 0.4550g of O (99.99% purity) are mixed, and the mixture is kept stirring at room temperature until dissolved;
(2) adding citric acid serving as a complexing agent into the mixed solution, uniformly mixing, wherein the molar ratio of the citric acid to all metal cations is 2:1, and adding 5ml of ethylene glycol serving as a dispersing agent;
(3) stirring the obtained precursor solution at room temperature for 12 hours, and then putting the solution with sufficient effect in a magnetic stirrer, and continuously heating the solution at 80 ℃ to a gel state;
(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 Y 0.8 Eu 0.2 Fe 0.9 Cu 0.1 O 3 A solid electrolyte.
Example 6
This example provides a perovskite-type solid electrolyte having a chemical formula of Y 0.8 Eu 0.2 Fe 0.8 Cu 0.2 O 3 。
The preparation method of the solid electrolyte comprises the following steps:
(1) according to the formula Y 0.8 Eu 0.2 Fe 0.8 Cu 0.2 O 3 Weighing Y (NO) according to the stoichiometric ratio of each component 3 ) 3 ·6H 2 7.4121g of O (purity 99.9%), Eu (NO) 3 ) 3 ·6H 2 2.1561g of O (purity 99.99%), Fe (NO) 3 ) 3 ·9H 2 7.8106g of O (purity 99.999%), Cu (NO) 3 ) 2 ·3H 2 0.9066g of O (99.99% pure) are mixed, and the mixture is kept stirring at room temperature until dissolved;
(2) adding citric acid serving as a complexing agent into the mixed solution, uniformly mixing, wherein the molar ratio of the citric acid to all metal cations is 2:1, and adding 5ml of ethylene glycol serving as a dispersing agent;
(3) stirring the obtained precursor solution at room temperature for 12 hours, and then putting the solution with sufficient effect in a magnetic stirrer, and continuously heating the solution at 80 ℃ to a gel state;
(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 800 ℃ for 5 hours, and controlling the heating rate at 5 ℃/min to obtain Y 0.8 Eu 0.2 Fe 0.8 Cu 0.2 O 3 A solid electrolyte.
Fig. 1 shows XRD patterns of perovskite-type solid electrolyte provided in example 6, and it can be seen from fig. 1 that perovskite-type solid electrolyte prepared by the present invention is combined with YFeO 3 The standard PDF #39-1489 card of (A) 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 nanoparticles with uniform size, has an average particle size of about 100nm, and has a relatively uniform pore structure, and from the micro-morphology, the synthesized solid electrolyte has a very loose structure, is significantly reduced in volume by slight grinding, and is easily compressed into a relatively dense block.
Fig. 3 shows an Electrochemical Impedance Spectroscopy (EIS) diagram of the perovskite-type solid electrolyte provided in example 6.
Example 7
This example provides a perovskite-type solid electrolyte having a chemical formula of Y 0.8 Eu 0.2 Fe 0.7 Cu 0.3 O 3 。
The preparation method of the solid electrolyte comprises the following steps:
(1) according to the chemical formula Y 0.8 Eu 0.2 Fe 0.7 Cu 0.3 O 3 Weighing Y (NO) according to the stoichiometric ratio of each component 3 ) 3 ·6H 2 7.3847g of O (purity 99.9%), Eu (NO) 3 ) 3 ·6H 2 2.1481g of O (purity 99.99%), Fe (NO) 3 ) 3 ·9H 2 6.8089g of O (purity 99.999%), Cu (NO) 3 ) 2 ·3H 2 1.3549g of O (99.99% purity) are mixed, and the mixture is kept stirring at room temperature until dissolved;
(2) adding citric acid serving as a complexing agent into the mixed solution, uniformly mixing, wherein the molar ratio of the citric acid to all metal cations is 2.5:1, and adding 5ml of ethylene glycol serving as a dispersing agent;
(3) stirring the obtained precursor solution at room temperature for 18 hours, and then putting the solution with sufficient effect in a magnetic stirrer, and continuously heating the solution at 80 ℃ to a gel state;
(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 800 ℃ for 5 hours, and controlling the heating rate at 5 ℃/min to obtain Y 0.8 Eu 0.2 Fe 0.7 Cu 0.3 O 3 A solid electrolyte.
Example 8
This example provides a perovskite-type solid electrolyte having a chemical formula of Y 0.8 Eu 0.2 Fe 0.6 Cu 0.4 O 3 。
The preparation method of the solid electrolyte comprises the following steps:
(1) according to the chemical formula Y 0.8 Eu 0.2 Fe 0.6 Cu 0.4 O 3 Weighing Y (NO) according to the stoichiometric ratio of each component 3 ) 3 ·6H 2 7.3574g of O (purity 99.9%), Eu (NO) 3 ) 3 ·6H 2 2.1402g of O (purity 99.99%), Fe (NO) 3 ) 3 ·9H 2 5.8147g of O (purity 99.999%), Cu (NO) 3 ) 2 ·3H 2 1.7998g of O (99.99% pure) are mixed, and the mixture is kept stirring at room temperature until dissolved;
(2) adding citric acid serving as a complexing agent into the mixed solution, uniformly mixing, wherein the molar ratio of the citric acid to all metal cations is 3:1, and adding 5ml of ethylene glycol serving as a dispersing agent;
(3) stirring the obtained precursor solution at room temperature for 12 hours, and then putting the solution with sufficient effect in a magnetic stirrer, and continuously heating the solution at 80 ℃ to a gel state;
(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 800 ℃ for 4 hours, and controlling the heating rate at 5 ℃/min to obtain Y 0.8 Eu 0.2 Fe 0.6 Cu 0.4 O 3 A solid electrolyte.
Example 9
The present example was different from example 6 in that the temperature of the secondary sintering in step (4) of this example was 700 ℃ (800 ℃ was replaced with 700 ℃).
The remaining preparation methods and parameters were in accordance with example 6.
Example 10
The present example was different from example 6 in 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 in accordance with example 6.
Example 11
This example is different from example 6 in that the temperature of the secondary sintering in step (4) of this example was 1000 deg.C (800 deg.C was replaced with 1000 deg.C).
The remaining preparation methods and parameters were in accordance with example 6.
Comparative example 1
The difference between the comparative example and the example 1 is that the chemical formula of the perovskite type solid electrolyte provided by the comparative example is YFeO 3 。
The preparation method differs from example 1 in that, in step (1): according to the chemical formula YFeO 3 Weighing Y (NO) according to the stoichiometric ratio of each component 3 ) 3 ·6H 2 9.9454g of O (purity 99.9%), Fe (NO) 3 ) 3 ·9H 2 10.4801g of O (99.999% purity) were mixed, and the mixture was kept stirring at room temperature until dissolved.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 2
The difference between the comparative example and the example 1 is that the perovskite type solid electrolyte provided by 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 chemical formula LaGaO 3 The La (NO) is weighed according to the stoichiometric ratio of each component 3 ) 3 ·6H 2 8.9278g of O (purity 99.999%), Ga (NO) 3 ) 3 ·9H 2 5.2677g of O (99.999% purity) are mixed, and the mixture is kept stirring at room temperature until dissolved; in the step (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 5 hours, finally grinding the powder, roasting in the muffle furnace at 1250 ℃ for 3 hours, and controlling the heating rate at 5 ℃/min.
The remaining preparation methods and parameters were in accordance with example 1.
The perovskite solid electrolytes provided in examples 1-11 and comparative examples 1-2 were tested and characterized by adopting a Switzerland PGSTAT302 electrochemical workstation, the test frequency range was 10 MHz-1 Hz, and the bias voltage was 10 mV. Before testing, 0.5g of powder is weighed and ground, a die with the diameter of 10mm is used for pressing the powder into a tablet with the thickness d being 1mm, a ceramic block is prepared In a muffle furnace for 1250-20 h, and then the Pt/In is used as a blocking electrode for ion conductivity testing. The results are shown in Table 1.
TABLE 1
Figure BDA0003740576930000141
Figure BDA0003740576930000151
From the data results of examples 1 to 8, it can be seen that the solid-state electrolyte provided by the present invention, through selecting and double doping a and B elements with different ionic radii and valence states, generates more oxygen vacancies and ion transport channels, and has a channel structure, and the ion conductivity thereof is significantly more excellent.
From the data results of example 6 and examples 9 to 11, it is understood that the temperature of the secondary sintering is too high to generate more lattice defects and channel structures in the solid electrolyte, and to be unfavorable to ion migration, and thus the ion conductivity is poor.
From the data results of examples 1 to 11 and comparative example 1, it is understood that if the perovskite type solid electrolyte having Y and Fe as main phases is not doped, the ion conductivity cannot be improved, and further, as compared with comparative example 2, it can be found that pure YFeO is also obtained 3 The effect of (c) is poor.
From the data results of examples 1 to 10 and comparative example 2, it can be seen that the perovskite solid electrolyte provided by the present invention can achieve the same effect as LaGaO even if only a single element is doped 3 Compared with the prior art, the ionic conductivity is even more excellent, and after double doping, the ionic conductivity can be obviously improved, and the material provided by the invention has lower cost of the used raw materials, andthe preparation process is more environment-friendly, and the sintering temperature is lower.
In conclusion, 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 ion transmission channels are increased, the ion conductivity of the solid electrolyte is improved, and when Eu and Cu are doped in a double mode, the solid electrolyte with a pore channel structure can be obtained, the ion migration rate is increased, in addition, the used elements have lower cost, 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 bimetal doping, and further has the total conductivity of more than 0.150S/cm when the secondary sintering temperature is regulated and controlled within the range of 700-900 ℃.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. A perovskite-type solid electrolyte characterized in that the general chemical formula of the perovskite-type solid electrolyte is Y 1- x Eu x Fe 1-y Cu y O 3 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 0 at the same time.
2. The perovskite-type solid electrolyte according to claim 1, wherein Y is 1-x Eu x Fe 1-y Cu y O 3 In the formula, x is more than 0 and less than or equal to 0.4, and y is more than 0 and less than or equal to 0.4;
preferably, the perovskite-type solid electrolyte has a pore structure.
3. A production method of the perovskite-type solid electrolyte according to claim 1 or 2, characterized by 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 Y source, Eu source, Fe source and Cu source is equal to Y 1-x Eu x Fe 1-y Cu y O 3 The stoichiometric ratio of (A) corresponds to that of (B), 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 0 simultaneously.
4. The method for producing a perovskite-type solid electrolyte according to claim 3, wherein the molar ratio of the complexing agent to the sum of all metal cations is (2-3): 1;
preferably, the Y source comprises Y (NO) 3 ) 3 ·6H 2 O；
Preferably, the Eu source comprises Eu (NO) 3 ) 3 ·6H 2 O；
Preferably, the Fe source comprises Fe (NO) 3 ) 3 ·9H 2 O；
Preferably, the Cu source comprises Cu (NO) 3 ) 2 ·3H 2 O；
Preferably, the complexing agent comprises citric acid;
preferably, the dispersant comprises ethylene glycol.
5. The production method of a perovskite-type solid electrolyte according to claim 3 or 4, characterized in that the stirring comprises sequentially performing room-temperature stirring and heating stirring;
preferably, the stirring time at room temperature is 12-20 h, preferably 12 h;
preferably, the heating and stirring temperature is 70-90 ℃, and preferably 80 ℃.
6. The production method of a perovskite-type solid electrolyte according to any one of claims 3 to 5, characterized in that the gel-state substance is dried;
preferably, the drying temperature is 90-120 ℃.
7. The production method of a perovskite-type solid electrolyte according to any one of claims 3 to 6, characterized in that the sintering comprises sequentially performing primary sintering and secondary sintering.
8. The method for producing a perovskite solid electrolyte according to claim 7, wherein the temperature rise rate of the primary sintering is 1 to 20 ℃/min, preferably 5 ℃/min;
preferably, the temperature of the primary sintering is 400-500 ℃;
preferably, the time of the primary sintering is 3-6 h;
preferably, the temperature rise rate of the secondary sintering is 1-20 ℃/min, preferably 5 ℃/min;
preferably, the temperature of the secondary sintering is 700-900 ℃;
preferably, the time of the secondary sintering is 4-7 h.
9. The production method of a perovskite-type solid electrolyte according to any one of claims 3 to 8, characterized by comprising 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 hours, 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, performing primary sintering for 3-6 hours, and continuously heating to 700-900 ℃ at a heating rate of 1-20 ℃/min, and performing secondary sintering for 4-7 hours to obtain the perovskite type solid electrolyte;
wherein the molar weight of Y source, Eu source, Fe source and Cu source is equal to Y 1-x Eu x Fe 1-y Cu y O 3 The stoichiometric ratio of the compounds is corresponding, 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 0 simultaneously; the molar ratio of the citric acid to the sum of all metal cations is (2-3): 1.
10. A solid oxide fuel cell comprising the perovskite-type solid electrolyte according to claim 1 or 2.
CN202210814671.6A 2022-07-11 2022-07-11 Perovskite type solid electrolyte and preparation method and application thereof Pending CN114988482A (en)

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