CN116505048A - Yttrium doped cathode material and its preparation method and application - Google Patents
Yttrium doped cathode material and its preparation method and application Download PDFInfo
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Classifications
-
- 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
-
- 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
-
- 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
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Fuel Cell (AREA)
Abstract
The invention relates to the technical field of solid oxide fuel cells, in particular to an yttrium-doped cathode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: to ABO 3 Adding inorganic salt hydrate containing yttrium element into the cathode material solution to obtain mixed solution; adding a first complexing agent, a second complexing agent and a pH regulator into the mixed solution, mixing, and heating and stirring to obtain a gel mixture; and drying, calcining and grinding the gel mixture to obtain the yttrium-doped cathode material. The polarization resistance of the cathode material is reduced after yttrium element doping; the attenuation degree of the impedance is reduced under long-time thermal cycle use; CO resistance 2 The ability to poison the attack increases; the high current density and long-term stability are maintained in the test of the single cell. In the aspect of mechanical properties, after yttrium element is doped, the thermal expansion coefficient can be reduced, and the fracture strength, young modulus and hardness of the cathode material are improved.
Description
Technical Field
The invention relates to the technical field of solid oxide fuel cells, in particular to an yttrium-doped cathode material, and a preparation method and application thereof.
Background
A solid oxide fuel cell (Solid Oxide Fuel Cell, SOFC) is an all-solid chemical power generation device that converts chemical energy stored in fuels and oxidants directly into electrical energy at medium and high temperatures with high efficiency and is environmentally friendly. At present, when the electrochemical performance of the cathode material is improved, the improvement of the mechanical performance of the cathode material is neglected, and the mechanical performance is often a key factor influencing the service life and the stability of the solid oxide fuel cell.
The improvement of the mechanical property of the cathode material is neglected, so that the cathode material of the existing solid oxide fuel cell is easy to peel, break and deform under long-time cyclic use.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a yttrium doped cathode material, and a preparation method and application thereof, which aims to solve the problems of easy peeling, breakage and deformation of the existing cathode material.
The technical scheme of the invention is as follows:
a method for preparing an yttrium-doped cathode material, comprising the steps of:
to ABO 3 Adding inorganic salt hydrate containing yttrium element into the cathode material solution to obtain mixed solution; wherein A is selected from one or two of rare earth elements and alkaline earth elements, and B is a transition metal element;
adding a first complexing agent, a second complexing agent and a pH regulator into the mixed solution, and heating and stirring after mixing to obtain a gel mixture;
and drying, calcining and grinding the gel mixture to obtain the yttrium-doped cathode material.
The preparation method of the yttrium-doped cathode material, wherein the inorganic salt hydrate containing yttrium is selected from Y (NO 3 ) 3 ·6H 2 O、Y(C 2 H 3 O 2 ) 3 ·4H 2 O、YCl 3 ·6H 2 One or more of O.
The preparation method of the yttrium-doped cathode material comprises the steps that the rare earth element is one or more selected from La, pr, sm, gd, nd; the alkaline earth metal element is selected from one or more of Be, mg, ca, sr, ba, ra; the transition metal element is selected from one or more of Mn, fe, co, ce.
The preparation method of the yttrium doped cathode material comprises the following steps of selecting one or more of citric acid, malic acid and oxalic acid as a first complexing agent; the second complexing agent is selected from one or more of ethylenediamine tetraacetic acid, nitrilotriacetic acid and diethylenetriamine pentacarboxylate; the pH regulator is one or more selected from ammonia water, acetone and ethanolamine.
The preparation method of the yttrium doped cathode material comprises the steps of (1) - (2) and (9) - (11) wherein the molar ratio of metal ions in the mixed solution to the first complexing agent, the second complexing agent and the pH regulator is 1.
The preparation method of the yttrium-doped cathode material comprises the step of doping 10-20% of yttrium element in the B site in a mole percentage.
The preparation method of the yttrium-doped cathode material comprises the steps of drying at 150-200 ℃ for 5-10 hours.
The preparation method of the yttrium-doped cathode material comprises the steps of calcining at the temperature of 1000-1200 ℃ for 5-10 hours.
An yttrium-doped cathode material prepared by the preparation method of the yttrium-doped cathode material.
Use of yttrium doped cathode materials in solid oxide fuel cells.
The beneficial effects are that: the invention provides an yttrium-doped cathode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: to ABO 3 Adding inorganic salt hydrate containing yttrium element into the cathode material solution to obtain mixed solution; wherein A is selected from one or two of rare earth elements and alkaline earth elements, and B is a transition metal element; adding a first complexing agent, a second complexing agent and a pH regulator into the mixed solution, and heating and stirring after mixing to obtain a gel mixture; and drying, calcining and grinding the gel mixture to obtain the yttrium-doped cathode material. According to the invention, when the material is synthesized by a sol-gel method, the inorganic salt hydrate containing yttrium element is added, and when the material is fired at a high temperature, the yttrium element and other elements are self-assembled together to form a multiphase perovskite compound, so that the mechanical property of the compound can be improved while the electrochemical property of the original material is maintained. In terms of electrochemical performance, after yttrium element doping, the polarization resistance of the cathode material is reduced; the attenuation degree of the impedance is reduced under long-time thermal cycle use; anti-CO 2 The ability to poison the attack increases; the high current density and long-term stability are maintained in the test of the single cell. In terms of mechanical properties, the thermal expansion coefficient can be reduced after yttrium element doping; under the test of the breaking strength of the ball-ring model at normal temperature and high temperature, the breaking strength can be obviously improved; can obviously improve Young modulus and hardness under the nano indentation test at normal temperature and high temperature.
Drawings
FIG. 1 is a schematic process flow diagram of a method for preparing yttrium-doped cathode materials according to the present invention;
FIG. 2 is an XRD pattern of BCCY after BCC and doping Y in example 1;
FIG. 3 is a graph showing the polarization resistance change of the cathode material after doping yttrium in example 1;
FIG. 4 is a graph showing the improvement in thermal cycling performance of the cathode material after doping with yttrium in example 1;
FIG. 5 is a graph showing the CO resistance of the cathode material after doping with yttrium in example 1 2 An erosion capacity enhancement data map;
FIG. 6 is a graph showing the improvement in the breaking strength of the cathode material at various temperatures after doping with yttrium in example 1;
FIG. 7 is a graph of the improvement data for Young's modulus of the cathode material after doping with yttrium in example 1 under different temperature tests;
fig. 8 is a graph of the improvement data for the hardness of the cathode material at various temperature tests after doping with yttrium in example 1.
Detailed Description
The invention provides an yttrium doped cathode material, a preparation method and application thereof, and aims to make the purposes, technical schemes and effects of the invention clearer and more definite, and the invention is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
It will be understood by those skilled in the art that all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs unless defined otherwise. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
As shown in fig. 1, the present invention provides a method for preparing an yttrium-doped cathode material, comprising the steps of:
step S10: to ABO 3 Adding inorganic salt hydrate containing yttrium element into the cathode material solution to obtain mixed solution; wherein A is selected from one or two of rare earth elements and alkaline earth elements, and B is a transition metal element;
step S20: adding a first complexing agent, a second complexing agent and a pH regulator into the mixed solution, and heating and stirring after mixing to obtain a gel mixture;
step S30: and drying, calcining and grinding the gel mixture to obtain the yttrium-doped cathode material.
In the embodiment, when synthesizing a cathode material by a sol-gel method, adding inorganic salt hydrate containing yttrium element to obtain a mixed solution, adding a first complexing agent, a second complexing agent and a pH regulator into the mixed solution, regulating the pH value of the mixed solution by the pH regulator, and generating a complex by utilizing the first complexing agent and the second complexing agent and metal ions in the mixed solution, so that all components of raw materials are uniformly mixed, the purity of a product is improved, and the stoichiometric ratio can be accurately controlled; and finally, drying and firing the gel mixture in sequence through drying and calcining treatment, wherein yttrium element and other elements are self-assembled together to generate a multiphase perovskite compound during high-temperature firing, and the compound can improve the mechanical property while maintaining the electrochemical property of the original material. Specifically, the doping of yttrium is mainly used for the doping of B site by the doping of the yttrium in ABO 3 The B site in the cathode material realizes the doping of yttrium element, and can improve the mechanical properties of the cathode material in a multi-temperature range from normal temperature (25 ℃) to high temperature (700 ℃). After yttrium doping in the cathode material is realized by the preparation method, the impedance is reduced by more than 20 percent, the cyclic attenuation is reduced by more than 20 percent, and the thermal expansion coefficient is reducedThe fracture strength is improved by more than 30%, the Young modulus and the hardness are improved by more than 70%.
Further, the above preparation method can be applied to all ABO 3 The yttrium doping is carried out on the cathode material, so that the improvement of mechanical properties is realized and the original electrochemical properties are maintained. By way of example, the ABO 3 The cathode material may be, but is not limited to BSCF, LSCF, LSM, SSC, BCC.
In some embodiments, in addition to sol-gel methods for preparing yttrium doped cathode materials, solid phase methods, co-precipitation methods, hydrothermal methods, template methods, and the like can be employed; the method has the advantages that the effect of preparing the yttrium-doped cathode material by adopting the sol-gel method is optimal, the yttrium-doped cathode material is mainly prepared by adopting the sol-gel method, the impurities are minimum, the purity is highest, the particle size of the cathode material is most proper and uniform, the process is easy to control, and the stoichiometric amount is most accurate.
In some embodiments, in the step S10, ABO 3 The cathode material solution is obtained by mixing metal nitrate solutions containing different metal ions, namely, nitrate solutions of one or two of rare earth elements and alkaline earth elements are mixed with nitrate solutions of transition metal elements; by BaCo 0.7 Ce 0.3 For example, ba (NO 3 ) 2 、Co(NO 3 ) 2 ·6H 2 O、Ce(NO 3 ) 3 ·6H 2 Dissolving the mixture of O in water, heating and stirring to dissolve thoroughly to obtain ABO 3 A solution of a cathode material.
In some embodiments, the yttrium-containing inorganic salt hydrate is selected from, but not limited to, Y (NO) 3 ) 3 ·6H 2 O、Y(C 2 H 3 O 2 ) 3 ·4H 2 O、YCl 3 ·6H 2 One or more of O; yttrium element in inorganic salt hydrate and ABO during high temperature firing 3 The elements in the cathode material are self-assembled together to generate multiphase perovskite type compound, and the compound can improve the mechanical property of the cathode material while maintaining the electrochemical property of the original material. I.e. the thermal expansion coefficient of the cathode material can be reduced, and the cathode can be liftedBreaking strength, young's modulus and hardness of the pole material.
In some embodiments, the rare earth element is selected from, but is not limited to, one or more of La, pr, sm, gd, nd; the alkaline earth metal element is selected from one or more of Be, mg, ca, sr, ba, ra; the transition metal element is selected from one or more of Mn, fe, co, ce; ABO using these elemental compositions 3 When the perovskite structure cathode material is doped with yttrium element at the B site, the mechanical property of the cathode material can be effectively improved, and the original electrochemical property is maintained.
In some embodiments, the first complexing agent is selected from, but is not limited to, one or more of citric acid, malic acid, oxalic acid; the second complexing agent is selected from one or more of ethylenediamine tetraacetic acid, nitrilotriacetic acid and diethylenetriamine pentacarboxylate; the pH regulator is selected from one or more of ammonia water, acetone and ethanolamine.
In a preferred embodiment, the first complexing agent is citric acid; the second complexing agent is ethylenediamine tetraacetic acid; the pH regulator is ammonia water.
Specifically, in the process of preparing a cathode material by a sol-gel method, citric Acid (CA) may form a complex with metal ions; along with the evaporation of the solvent in the gel process, the metal cations and the citric acid are mutually crosslinked and condensed to form a three-dimensional network structure, so that all components of the raw materials can be uniformly combined, the purity of the product is improved, and the stoichiometric ratio can be accurately controlled. Ethylenediamine tetraacetic acid (EDTA) is a good complexing agent as citric acid, can form stable water-soluble complex with alkaline earth metals, rare earth elements, transition metals and the like, and can exist stably in alkaline solution, so that the complexing capability for ions is greatly improved, and the EDTA is often used together with CA. In order to promote dissolution, an appropriate amount of ammonia water is required to be added to adjust the pH value of the solution, because the pH value of the solution is too low, the solubility of EDTA acid becomes small to cause precipitation, and too high pH value can lead to competitive complexation of ammonia and metal ions and increase the temperature of the solution for gelation.
In some embodiments, the molar ratio of the metal ions in the mixed solution to the first complexing agent, the second complexing agent and the pH regulator is 1 (1-2): 1 (9-11).
In a preferred embodiment, the molar ratio of the metal ions in the mixed solution to the first complexing agent, the second complexing agent and the pH regulator is 1:2:1:10, and a gel mixture can be obtained by uniformly mixing the metal ions in the mixed solution with the first complexing agent, the second complexing agent and the pH regulator.
In some embodiments, in the yttrium-doped cathode material, the doping mole percentage of yttrium element at the B site is 10-20%, the doping of yttrium element is mainly used for the doping of the B site, compared with Mn, fe, co, etc., the yttrium element itself is not an element which can well promote the oxygen reduction capability of the cathode when doped at the B site, and the electrochemical performance of the original material is affected by the excessive yttrium content. The yttrium element doping is mainly used for improving the strength of the material, and too little yttrium element doping can not play a role in improving the mechanical property. Therefore, the doping mole percentage of yttrium element at the B site is controlled to be 10-20%, so that the mechanical property of the yttrium doped cathode material can be effectively improved while the original electrochemical property is maintained.
In a preferred embodiment, in the yttrium doped cathode material, the doping mole percentage of yttrium element at the B site is 15%, so that the mechanical property of the cathode material is greatly improved, and the original electrochemical property is maintained.
In some embodiments, the temperature of the drying treatment is 150-200 ℃, the time of the drying treatment is 5-10 hours, and the drying treatment is performed on the gel mixture under the condition, so that the water on the surface of the gel can be removed, the pores of the gel are eliminated, the gel is densified, and the phase composition and microstructure of the product can meet the requirement of product performance.
In some embodiments, the temperature of the calcination treatment is 1000-1200 ℃, the time of the calcination treatment is 5-10 hours, and the high-temperature calcination treatment is performed under the condition, so that yttrium element and other elements can be self-assembled together to generate a multiphase perovskite type composite, namely, yttrium doped cathode material; the composite can improve the mechanical property while maintaining the electrochemical property of the original material.
In a preferred embodiment, the temperature of the calcination treatment is 1000 ℃ and the time of the calcination treatment is 5 hours.
In addition, the invention also provides the yttrium doped cathode material prepared by the yttrium doped cathode material preparation method.
In the embodiment, the yttrium-doped cathode material prepared by the preparation method of the yttrium-doped cathode material not only can keep the original electrochemical performance, but also can improve the mechanical performance; further, maintaining electrochemical performance is manifested in: the polarization resistance of the cathode decreases; the attenuation degree of the impedance is reduced under long-time thermal cycle use; CO resistance 2 The ability to poison the attack increases; the high current density and the long-time stability are maintained in the test of the single cell; the improvement of the mechanical properties is shown in the following steps: the coefficient of thermal expansion can be reduced; under the test of the breaking strength of the ball-ring model at normal temperature and high temperature, the breaking strength can be obviously improved; can obviously improve Young modulus and hardness under the nano indentation test at normal temperature and high temperature.
Specifically, ABO 3 After yttrium doping is utilized in the cathode material, the impedance is reduced by more than 20%, the cyclic attenuation is reduced by more than 20%, the thermal expansion coefficient is reduced by more than 30%, the breaking strength is improved by more than 70%, and the Young modulus and the hardness are improved by more than 50%.
In addition, the invention also provides application of the yttrium doped cathode material in a solid oxide fuel cell.
In this embodiment, the yttrium doped cathode material is used in a solid oxide fuel cell, so that the problems of peeling, fracture, deformation and the like do not occur under long-time cyclic use, and the service life of the solid oxide fuel cell is prolonged.
The following examples are further given to illustrate the invention in detail. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure.
Example 1
This example shows that at 0.1mol BaCo 0.7 Ce 0.3 Preparation of BaCo by doping 15% Y element in B position in (BCC) 0.7 Ce 0.15 Y 0.15 (BCCY) prepared by sol-gel method, and adding proper Y (NO) in sol stage 3 ) 3 ·6H 2 O is doped, and the specific steps are as follows:
26.123g of Ba (NO) 3 ) 2 、20.3721g Co(NO 3 ) 2 ·6H 2 O、6.5433g Ce(NO 3 ) 3 ·6H 2 Mixing O and then dissolving in water, heating and stirring, and obtaining ABO after fully dissolving 3 A cathode material solution;
to said ABO 3 5.7452g Y (NO) is added to the cathode material solution 3 ) 3 ·6H 2 O, obtaining a mixed solution; weighing 58.448g of ethylenediamine tetraacetic acid and 84.056g of citric acid monohydrate, weighing 77.07ml of ammonia water, adding the ammonia water into the mixed solution, wherein the molar ratio of metal ions in the mixed solution to the ethylenediamine tetraacetic acid, the citric acid monohydrate and the ammonia water is 1:1:2:10, heating and stirring the mixed sol until water is fully evaporated, and enabling the solution to be gel-like to obtain a gel mixture;
placing the gel mixture in an oven at 150-200 ℃ and drying for 5-10 hours; and then transferring the mixture to a muffle furnace for firing at 1000 ℃ for 5 hours, and grinding the sintered agglomerated powder to obtain the yttrium doped cathode material (BCCY).
Performance test and characterization were performed on the yttrium-doped cathode material prepared in this example, and the specific steps are as follows:
1. XRD characterization of yttrium doped cathode materials
XRD refinement analysis of yttrium-doped cathode material (BCCY) shows that yttrium element automatically recombines original BCC into two-phase composite material during firing of the material, and the two-phase composite material comprises BaCe with 89% phase content 0.094 Co 0.74 Y 0.166 O 3 And 11% phase content BaCe 0.86 Co 0.11 Y 0.03 O 3 . The XRD patterns before and after doping are shown in fig. 2, and the cathode material after doping with Y element is a two-phase composite material.
2. Electrochemical testing after doping
Electrochemical testing was performed primarily by Keithley2460 digital source list and Princeton electrochemical workstation. Specifically includes impedance, thermal cycle and CO 2 Cathode performance test after erosion.
Sample impedance testing was accomplished by symmetric cell Electrochemical Impedance Spectroscopy (EIS). The symmetrical battery is prepared as follows: compact bzxyyb discs of diameter 15 mm and thickness 0.8 mm were prepared by dry pressing 0.4. 0.4 g powder and then sintered at 1450 ℃ for 5 hours.
The cathode powder obtained by grinding yttrium doped cathode material (BCCY) is first dispersed in a pre-mixed solution of glycerol, ethylene glycol and isopropanol. Colloidal suspensions were made from these mixtures by planetary milling at 400 rpm for half an hour. The suspension was deposited on both sides of BZCYYb by spray gun spraying and calcined at 800 ℃ for 2 hours in an air atmosphere to obtain a porous electrode. The test frequency range is 0.01Hz to 100kHz, the impedance signal amplitude of 10mV, and the impedance spectrum test at 450-700 ℃ is completed under the condition of symmetrical battery open-circuit voltage. As shown in FIG. 3, the doping of Y can reduce 28% polarization impedance (0.32. OMEGA cm 2 To 0.23 Ω cm 2 ， 600℃)。
The thermal cycle test is carried out at 300-600 ℃, the polarization impedance of the symmetrical battery at 600 ℃ is measured firstly, then the temperature is naturally reduced to 300 ℃ and kept for 10 minutes, and then the temperature is increased to 600 ℃ at the temperature rising condition of 10 ℃/minute for carrying out the second impedance test, thus carrying out the thermal cycle test for 35 times in a reciprocating way. The improvement in thermal cycle performance is shown in fig. 4, and the polarization resistance decay is reduced from 62.5% to 37.8% over 35 thermal cycles.
CO resistance 2 Erosion test at 1% CO 2 The process is carried out under air with the content. Impedance testing was performed by air ventilation followed by 300 minutes 1% CO 2 The air content was recorded for impedance change during the process, and then passed through for another 300 minutesIs recorded for the recovery of the process impedance. CO resistance 2 Erosion ability enhancement as shown in FIG. 5, CO resistance 2 The erosion capacity is also greatly improved, at 1% CO 2 The polarization impedance of BCCY is increased by 7.8 times and increased to 2.2 Ω cm in 300 minutes of erosion 2 Whereas the polarization impedance of the BCC increases by a factor of 7.8 to 3.7 Ω cm 2 。
And (3) testing the performance of the single cell, preparing two half cells of BZCYYb|NiO+BZCYb and YSZ|NiO+YSZ by a tape casting mode, depositing a cathode by a spraying mode, and firing at 800 ℃ for 2 hours to obtain the single cell. The cell performance was then tested in an air, hydrogen environment. Single cell power density of BCCY cathode doped with Y element, 619 mW cm under BZTYYb electrolyte -2 (700 ℃), stability for 280h; 1026 mW cm under YSZ electrolyte -2 (800 ℃ C.) and stability for 380h.
3. Mechanical testing after doping
The thermal expansion meter measures the thermal expansion coefficient. The cathode material was prepared into 4×3×10mm compact cathode sheets by dry pressing for testing.
The high temperature creep tester tests the breaking strength. And (3) adopting a ball-ring model to press and break cathode wafers with different thicknesses and diameters, recording a load displacement curve in the process, and calculating to obtain the breaking strength of the material. The BCC cathode powder and the Y-doped BCCY powder were press-formed by powder pressing at a pressure of 12MPa and then fired at 1100 ℃ for 5 hours to obtain a dense cathode sheet. And (3) assembling a spherical punch by adopting a high-temperature creep deformation instrument of Kejing, and placing the fired and molded circular cathode plate between the circular ring table and the punch. And applying a force to the cathode sheet in a displacement control manner until the cathode sheet breaks. In the process, a load displacement curve of the whole process is obtained through the displacement and the pressure sensor. The breaking strength of the two materials can be obtained by analyzing and processing the curve. To ensure the credibility of the test results, 25 breaking tests were performed for each material. With 65% confidence [，/>]The average value within the confidence interval was used as the final experimental data. The same method was used for high temperature testing at 150, 300, 450, 600, 700 ℃. The breaking strength was improved by 76.8% (from 27.98MPa to 49.46 MPa) as shown in FIG. 6.
The Young modulus and hardness were measured by a nanoindenter, bruker nanoindenter Hysicron PI 89 series, and a berkovich probe was used to control probe displacement indentation test of the cathode material. To avoid contingency of experimental results, samples were subjected to multi-region dotting tests with 65% confidence [，/>]The average value within the confidence interval was used as the final experimental data. In the test process, a displacement control mode is adopted to carry out indentation test at 1500nm to obtain a load displacement curve, and the Young modulus and hardness of the cathode material are calculated according to the slope of the unloading point, the maximum load point and the contact area. And carrying out vacuum heating on the material to obtain the Young's modulus and hardness of the cathode at different temperatures, especially at the working condition temperature. Young's modulus and hardness increases by 56% and 58% (27.33 GPa to 42.64GPa, 1.29GPa to 2.04 GPa) respectively under nanoindentation test as shown in FIGS. 7 and 8.
Thus, BCCY (BaCo) 0.7 Ce 0.15 Y 0.15 O) compared to BCC (BaCo 0.7 Ce 0.3 O) has great improvement in electrochemical and mechanical properties.
In summary, the yttrium doped cathode material and the preparation method and application thereof provided by the invention, wherein the preparation method comprises the following steps: to ABO 3 Adding inorganic salt hydrate containing yttrium element into the cathode material solution to obtain mixed solution; wherein A is selected from one or two of rare earth elements and alkaline earth elements, and B is a transition metal element; adding a first complexing agent, a second complexing agent and pH adjustment into the mixed solutionThe preparation method comprises the steps of (1) mixing the components, and heating and stirring to obtain a gel mixture; and drying, calcining and grinding the gel mixture to obtain the yttrium-doped cathode material. According to the invention, when the material is synthesized by a sol-gel method, the inorganic salt hydrate containing yttrium element is added, and when the material is fired at a high temperature, the yttrium element and other elements are self-assembled together to form a multiphase perovskite compound, so that the mechanical property of the compound can be improved while the electrochemical property of the original material is maintained. In terms of electrochemical performance, after yttrium element doping, the polarization resistance of the cathode material is reduced; the attenuation degree of the impedance is reduced under long-time thermal cycle use; CO resistance 2 The ability to poison the attack increases; the high current density and long-term stability are maintained in the test of the single cell. In terms of mechanical properties, the thermal expansion coefficient can be reduced after yttrium element doping; under the test of the breaking strength of the ball-ring model at normal temperature and high temperature, the breaking strength can be obviously improved; can obviously improve Young modulus and hardness under the nano indentation test at normal temperature and high temperature.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (10)
1. A method for preparing an yttrium-doped cathode material, comprising the steps of:
to ABO 3 Adding inorganic salt hydrate containing yttrium element into the cathode material solution to obtain mixed solution; wherein A is selected from one or two of rare earth elements and alkaline earth elements, and B is a transition metal element;
adding a first complexing agent, a second complexing agent and a pH regulator into the mixed solution, and heating and stirring after mixing to obtain a gel mixture;
and drying, calcining and grinding the gel mixture to obtain the yttrium-doped cathode material.
2. The method for producing an yttrium-doped cathode material according to claim 1, wherein the yttrium-containing inorganic salt hydrate is selected from Y (NO 3 ) 3 ·6H 2 O、Y(C 2 H 3 O 2 ) 3 ·4H 2 O、YCl 3 ·6H 2 One or more of O.
3. The method of preparing a yttrium-doped cathode material according to claim 1, wherein the rare earth element is selected from one or more of La, pr, sm, gd, nd; the alkaline earth metal element is selected from one or more of Be, mg, ca, sr, ba, ra; the transition metal element is selected from one or more of Mn, fe, co, ce.
4. The method of preparing a yttrium-doped cathode material according to claim 1, wherein the first complexing agent is selected from one or more of citric acid, malic acid, oxalic acid; the second complexing agent is selected from one or more of ethylenediamine tetraacetic acid, nitrilotriacetic acid and diethylenetriamine pentacarboxylate; the pH regulator is one or more selected from ammonia water, acetone and ethanolamine.
5. The method for preparing a yttrium-doped cathode material according to claim 1, wherein the molar ratio of metal ions in the mixed solution to the first complexing agent, the second complexing agent and the pH regulator is 1 (1-2): 1 (9-11).
6. The method for preparing a yttrium-doped cathode material according to claim 1, wherein the doping mole percentage of yttrium element at the B-site is 10-20%.
7. The method for preparing a yttrium-doped cathode material according to claim 1, wherein the temperature of the drying treatment is 150-200 ℃, and the time of the drying treatment is 5-10 hours.
8. The method for preparing a yttrium-doped cathode material according to claim 1, wherein the temperature of the calcination treatment is 1000-1200 ℃, and the time of the calcination treatment is 5-10 hours.
9. An yttrium-doped cathode material obtainable by the process for the preparation of an yttrium-doped cathode material according to any one of claims 1-8.
10. Use of the yttrium-doped cathode material according to claim 9 in a solid oxide fuel cell.
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