CN112310419A - Strontium-free and cobalt-free perovskite type composite oxide, preparation method thereof and battery - Google Patents

Strontium-free and cobalt-free perovskite type composite oxide, preparation method thereof and battery Download PDF

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CN112310419A
CN112310419A CN202011212132.2A CN202011212132A CN112310419A CN 112310419 A CN112310419 A CN 112310419A CN 202011212132 A CN202011212132 A CN 202011212132A CN 112310419 A CN112310419 A CN 112310419A
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free
strontium
cobalt
type composite
composite oxide
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李文路
王豪杰
朱尧杰
王世敏
董兵海
赵丽
吴聪聪
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Hubei University
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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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to the technical field of fuel cells, in particular to a strontium-free and cobalt-free perovskite type composite oxide, a preparation method thereof and a cell. The general formula of the composition of the strontium-free and cobalt-free perovskite type composite oxide is as follows: la1‑xNi0.6Fe0.4O3Wherein x is not less than 0<0.1. The cathode prepared from the strontium-free and cobalt-free perovskite type composite oxide is easy to form a phase, has a thermal expansion coefficient close to that of an electrolyte and good stability, and reduces the dosage of expensive lanthanide metal while improving the activity of the medium-temperature oxygen reduction reaction, namely improving the medium-temperature performance and stability, thereby reducing the manufacturing cost of the electrode material.

Description

Strontium-free and cobalt-free perovskite type composite oxide, preparation method thereof and battery
Technical Field
The invention relates to the technical field of fuel cells, in particular to a strontium-free and cobalt-free perovskite type composite oxide, a preparation method thereof and a cell.
Background
Solid Oxide Fuel Cells (SOFC) are being developed at medium and low temperatures, and the catalytic activity of the oxygen reduction reaction of the cathode material at medium and low temperatures limits the commercialization of SOFC. Therefore, development of a cathode material having superior performance at a medium and low temperature is required. The perovskite-structured cathode material has good ionic conductivity or electronic conductivity, but the conventional perovskite cathode material (such as La) is adopted0.6Sr0.4Co0.2Fe0.8O3，Ba0.5Sr0.5Co0.8Fe0.2O3Etc.) can generate high-resistance phase SrO under high-temperature conditions due to the Sr and Co elements, and then the over-potential of the battery is higher; also, such cathodes can be subject to Cr poisoning in the presence of a metal interconnect (Fe — Cr alloy). LaNi of perovskite type0.6Fe0.4O3As the cathode material of the intermediate-temperature solid oxide fuel cell (IT-SOFC), the cathode material has excellent Cr poisoning resistance and is accepted because of no existence of Sr and Co elements, but the application of the cathode material in the intermediate-temperature solid oxide fuel cell is limited due to insufficient performance at the intermediate temperature, so that the development of the electrode material with stable high oxygen reduction catalytic activity at the intermediate temperature is far-reaching.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a strontium-free and cobalt-free perovskite type composite oxide, a preparation method thereof and a battery. The embodiment of the invention provides a strontium-free and cobalt-free perovskite type composite oxide, a cathode prepared from the strontium-free and cobalt-free perovskite type composite oxide is easy to form a phase, has a thermal expansion coefficient close to that of an electrolyte and good stability, and reduces the dosage of expensive lanthanide metal while improving the activity of a medium-temperature oxygen reduction reaction, namely the medium-temperature performance and stability, thereby reducing the manufacturing cost of an electrode material.
The invention is realized by the following steps:
in a first aspect, an embodiment of the present invention provides a strontium-free and cobalt-free perovskite-type composite oxide, which has a chemical composition general formula: la1-xNi0.6Fe0.4O3Wherein x is not less than 0<0.1。
In an alternative embodiment, the strontium-free and cobalt-free perovskite-type composite oxide is an a-site deficient perovskite material.
In an alternative embodiment, the chemical composition is of the general formula: la1-xNi0.6Fe0.4O3Wherein x is more than or equal to 0 and less than or equal to 0.08.
In an alternative embodiment, the strontium-and cobalt-free perovskite-type composite oxide is selected from LaNi0.6Fe0.4O3、La0.98Ni0.6Fe0.4O3、La0.96Ni0.6Fe0.4O3、La0.94Ni0.6Fe0.4O3And La0.92Ni0.6Fe0.4O3Any one of the above; specifically, when x is 0, the strontium-free and cobalt-free perovskite-type composite oxide is LaNi0.6Fe0.4O3；
Or when x is 0.02, the strontium-free and cobalt-free perovskite type composite oxide is La0.98Ni0.6Fe0.4O3；
Or when x is 0.04, the strontium-free and cobalt-free perovskite type composite oxide is La0.96Ni0.6Fe0.4O3；
Or when x is 0.06, the perovskite type composite oxide without strontium and cobalt is La0.94Ni0.6Fe0.4O3；
Or when x is 0.08, the strontium-free and cobalt-free perovskite type composite oxide is La0.92Ni0.6Fe0.4O3。
In a second aspect, an embodiment of the present invention provides a method for preparing a strontium-free and cobalt-free perovskite-type composite oxide according to any one of the foregoing embodiments, wherein the strontium-free and cobalt-free perovskite-type composite oxide is prepared by a sol-gel method.
In an alternative embodiment, the method comprises the following steps: mixing a metal salt mixed solution containing La, Ni and Fe with a complexing agent, and then carrying out heat treatment to form the strontium-free and cobalt-free perovskite type composite oxide; wherein the molar ratio of La, Ni and Fe in the metal salt mixed solution is 1-x: 0.6: 0.4, x is more than or equal to 0 and less than 0.1;
preferably, the method comprises the following steps: after the metal salt mixed solution is mixed with EDTA and glycine, the mixture is treated at the constant temperature of 220 ℃ for 10 to 18 hours at 180 ℃ and then calcined for 2.0 to 5.0 hours at the temperature of 850 ℃ at 800 ℃;
preferably, the method comprises the following steps: mixing and dissolving EDTA and ammonia water to form a first mixed solution;
mixing the first mixed solution, the metal salt mixed solution and the glycine, then adjusting the pH value to 8-9 and stirring to be colloidal, then carrying out constant temperature treatment at 180 ℃ to 220 ℃ for 10-18 hours, and then calcining at 800 ℃ to 850 ℃ for 2.0-5.0 hours.
In an alternative embodiment, the preparation of the metal salt mixed solution includes: mixing salts respectively containing La, Ni and Fe to form the metal salt mixed solution;
preferably, the metal salt mixed solution is any one of nitrate, carbonate and acetate.
In an alternative embodiment, the molar amount of the sum of the metal cations in the metal salt mixture solution: the molar weight of EDTA to that of glycine is 1:1: 1.5-2.0.
In a third aspect, an embodiment of the present invention provides a battery, which includes the strontium-free and cobalt-free perovskite-type composite oxide according to any one of the foregoing embodiments or the strontium-free and cobalt-free perovskite-type composite oxide prepared by the preparation method of the strontium-free and cobalt-free perovskite-type composite oxide according to any one of the foregoing embodiments, where the battery is a half battery or a full battery.
In an alternative embodiment, the cell is an intermediate temperature solid oxide fuel cell;
preferably, the medium-temperature solid oxide fuel cell further comprises a selected electrolyte material;
preferably, the electrolyte material comprises GDC and YSZ.
The invention has the following beneficial effects: the invention provides a strontium-free and cobalt-free perovskite type composite oxide which can be used for preparing an intermediate-temperature solid oxide fuel cell, solves the problems of insufficient performance at intermediate temperature, insufficient long-term stability and the like of a traditional perovskite cathode, improves the long-term stability of the cathode, optimizes the catalytic activity of the oxygen reduction reaction of the cathode, and then improves the performance of the intermediate-temperature solid oxide fuel cell.
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In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 shows La provided in accordance with an embodiment of the present invention1-xNi0.6Fe0.4O3(x ═ 0,0.02,0.04,0.06,0.08) XRD spectrum of perovskite-type composite oxide;
FIG. 2 shows La according to an embodiment of the present invention1-xNi0.6Fe0.4O3(x ═ 0,0.02,0.04,0.06,0.08) the CTE spectrum of the perovskite-type composite oxide;
FIG. 3 shows La according to an embodiment of the present invention1-xNi0.6Fe0.4O3(x ═ 0,0.02,0.04,0.06,0.08) a graph of the results of electrochemical impedance test of the perovskite-type composite oxide;
FIG. 4 is a graph of the long term stability test results for LNFs and LNF94 provided in accordance with an embodiment of the present invention;
FIG. 5 is an XRD pattern of LNF and LNF94 provided by an embodiment of the present invention after 50h of incubation at 800 ℃.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The embodiment of the invention provides a strontium-free and cobalt-free perovskite type composite oxide, which has a chemical composition general formula as follows: la1-xNi0.6Fe0.4O3Wherein x is not less than 0<0.1. According to the structural general formula, the perovskite type composite oxide does not contain strontium and cobalt elements, so that the problems that the stability of an electrode is poor and Cr in a connector is poisoned due to the segregation of the strontium element and the volatilization of the cobalt can be avoided, and the performance of a battery formed by the perovskite type composite oxide is improved. Further, when X is not equal to 0, the A site of the perovskite type composite oxide is absent, so that the long-term stability of a cathode and a battery formed by the perovskite type composite oxide can be improved, and the catalytic activity of the cathode and the battery in the oxygen reduction reaction is optimized, namely the medium-temperature performance of the cathode and the battery is improved. Meanwhile, the cathode formed by the perovskite type composite oxide is easy to form a phase, has a thermal expansion coefficient close to that of the electrolyte, and further ensures that the cathode has better stability and medium-temperature performance.
Further, the general formula of the composition of the strontium-free and cobalt-free perovskite type composite oxide is as follows: la1-xNi0.6Fe0.4O3Wherein x is not less than 0 and not more than 0.08, and when x is 0, the strontium-free and cobalt-free perovskite type composite oxide is LaNi0.6Fe0.4O3(ii) a Or when x is 0.02, the strontium-free and cobalt-free perovskite type composite oxide is La0.98Ni0.6Fe0.4O3(ii) a Or when x is 0.04, the strontium-free and cobalt-free perovskite type composite oxide is La0.96Ni0.6Fe0.4O3(ii) a Or when x is 0.06, the perovskite type composite oxide without strontium and cobalt is La0.94Ni0.6Fe0.4O3(ii) a Or when x is 0.08, the strontium-free and cobalt-free calciumThe titanium ore type composite oxide is La0.92Ni0.6Fe0.4O3. The chemical formula of the strontium-free and cobalt-free perovskite-type composite oxide is given above in the case where x is different, and the A site of the strontium-free and cobalt-free perovskite-type composite oxide is deficient.
The embodiment of the invention also provides a preparation method of the strontium-free and cobalt-free perovskite-type composite oxide, and the strontium-free and cobalt-free perovskite-type composite oxide is prepared by using a sol-gel method. Specifically, the method comprises the following steps:
according to different components of La1-xNi0.6Fe0.4O3(0≤x<0.1, for example, x is 0,0.02,0.04,0.06, and 0.08) each metal salt is accurately weighed in a stoichiometric ratio of each metal element, and then the above metal salts are mixed and dissolved in water to form a metal salt mixed solution so that the molar ratio of La, Ni, and Fe in the metal salt mixed solution is 1-x: 0.6: 0.4, 0 is less than or equal to x<0.1。
Wherein, the metal salt can be any one of nitrate, carbonate and acetate, and the formed metal salt mixed solution is also any one of the nitrate, carbonate and acetate.
Then mixing and dissolving EDTA and ammonia water to form a first mixed solution;
next, the first mixed solution, the metal salt mixed solution, and the glycine are mixed and stirred to completely dissolve the glycine, and then the pH of the mixed solution is adjusted to 8 to 9, for example, any value between 8, 8.5, or 9, or 8 to 9 using ammonia water, and stirred to a gel state. The reaction can be promoted by adjusting the pH value, and the formation of the perovskite type composite oxide without strontium and cobalt is facilitated.
Meanwhile, glycine is used as a complexing agent, so that compared with citric acid, the grain size of the powder of the strontium-free and cobalt-free perovskite type composite oxide is smaller, and the performance of the formed cathode and the battery is improved.
Wherein, the molar weight of the metal cation sum in the metal salt mixed solution is as follows: the molar amount of EDTA to the molar amount of glycine is 1:1:1.5-2.0, and may be, for example, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, or any value between any two of the above ranges. The above molar ratio is favorable for the formation of the perovskite-type composite oxide without strontium and cobalt.
And then, carrying out constant temperature treatment on the colloidal substance at the temperature of 180-220 ℃ for 10-18 hours to form a dry colloidal precursor, and specifically, putting the colloidal substance into an electric heating air drying box for drying at the constant temperature of 180-220 ℃ for 10-18 hours to obtain a black bread-shaped xerogel precursor. For example, the temperature can be 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, and any value between any two of the above ranges. The time period is 10 hours, 10.5 hours, 11 hours, 12 hours, 13 hours, 13.5 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, and any number between any two of the above values forming a range. The dry colloidal precursor is then milled and then calcined at 800-850 ℃ for 2-5 hours, for example, at 800 ℃, 810 ℃, 815 ℃, 820 ℃, 825 ℃, 830 ℃, 835 ℃, 840 ℃, 845 ℃, 850 ℃ and any value between any two values, and the calcination time may be 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 5 hours and any value between any two values. And calcining to remove residual organic matters and form the perovskite type composite oxide.
The embodiment of the invention also provides a battery, which comprises the strontium-free and cobalt-free perovskite type composite oxide or the strontium-free and cobalt-free perovskite type composite oxide prepared by the preparation method, and the battery is a half battery or a full battery.
Further, the battery is an intermediate-temperature solid oxide fuel cell;
preferably, the intermediate-temperature solid oxide fuel cell further comprises an electrolyte material;
preferably, the electrolyte material comprises GDC and YSZ.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment of the invention provides a perovskite type composite oxide without strontium and cobalt, and the chemical formula of the perovskite type composite oxide is LaNi0.6Fe0.4O3(No.: LNF).
The embodiment of the invention also provides a preparation method of the strontium-free and cobalt-free perovskite type composite oxide, which comprises the following steps:
accurately weighing nitrates respectively containing La, Ni and Fe, wherein the molar ratio of La to Ni to Fe is 1: 0.6: 0.4. the EDTA and glycine were accurately weighed and the sum of metal cations: EDTA: glycine: 1:1.5 (molar ratio).
And dissolving the three nitrates in a 1000ml big beaker by using clear deionized water, completely dissolving the metal nitrates after about 15min, placing the beaker in a constant-temperature oil bath kettle, stirring at the constant temperature of 80 ℃, and stirring at the speed of 400r/min to form a metal salt mixed solution.
The EDTA was dissolved in a small 100ml beaker with ammonia, and the dissolution was allowed to proceed.
Adding EDTA which is completely dissolved into the metal nitrate mixed solution, and then adding glycine and stirring to completely dissolve the EDTA.
And adjusting the pH value of the mixed solution to 8 by ammonia water to obtain a dark red solution, stirring the mixed solution to be transparent dark red jelly, and drying the transparent dark red jelly in an electrothermal blowing drying oven at the constant temperature of 180 ℃ for 10 hours to obtain a black bread-shaped xerogel precursor.
Grinding the black bread-shaped xerogel precursor, transferring the ground black bread-shaped xerogel precursor into a crucible, and calcining the black bread-shaped xerogel precursor in a medium-temperature muffle furnace at 800 ℃ for 2 hours to remove residual organic matters, thereby obtaining cathode powder, namely the perovskite type composite oxide.
The embodiment also provides a half-cell, which is characterized in that the prepared cathode powder is prepared into cathode slurry with good fluidity, the cathode slurry is coated on one side of a GDC electrolyte sheet which is sintered and compact at 1550 ℃ in a screen printing mode and is sintered for 2 hours at 1000 ℃ to be used as a Working Electrode (WE); after high-temperature sintering, coating a layer of thin platinum slurry on the working electrode to play a current collecting role, and drying the working electrode in an oven at 180 ℃ for 10-20 minutes; and coating a platinum paste Counter Electrode (CE) with the same area as the working Electrode on the other side of the working Electrode, coating a circle of annular platinum paste serving as a Reference Electrode (RE) on the edge of the Counter Electrode side, and finally carrying out heat preservation treatment on the half cell coated with P t paste at 850 ℃ for 10 minutes to obtain the half cell to be measured.
Example 2 to example 5
Example 2 provides a strontium-and cobalt-free perovskite-type composite oxide having a chemical formula of La0.98Ni0.6Fe0.4O3(accession number: LNF 98).
Example 3 provides a strontium-and cobalt-free perovskite-type composite oxide having a chemical formula of La0.96Ni0.6Fe0.4O3(accession number: LNF 96).
Example 4 provides a strontium-and cobalt-free perovskite-type composite oxide having a chemical formula of La0.94Ni0.6Fe0.4O3(accession number: LNF 94).
Example 5 provides a strontium-and cobalt-free perovskite-type composite oxide of the formula La0.92Ni0.6Fe0.4O3(accession number: LNF 92).
Examples 2 to 5 respectively provide a method for preparing a perovskite-type composite oxide without strontium or cobalt, which is the same as example 1 except that the ratio of the corresponding metal nitrate is different, the ratio of the metal nitrate is the molar ratio of the corresponding metal, and the other conditions are the same as example 1, specifically as follows:
example 2: the molar ratio of La, Ni and Fe is 0.98: 0.6: 0.4.
example 3: molar ratio of La, Ni and Fe is 0.96: 0.6: 0.4.
example 4: the molar ratio of La, Ni and Fe is 0.94: 0.6: 0.4.
example 5: the molar ratio of La, Ni and Fe is 0.92: 0.6: 0.4.
examples 2 to 5 also provide half-cells, respectively, which were prepared in the same manner as in example 1, except that the cathode powder used was the cathode powder prepared in the corresponding example.
Characterization of
The perovskite-type composite oxides prepared in examples 1 to 5 were subjected to X-ray diffraction analysis, and the results of the detection are shown in fig. 1. No other second phase was formed in FIG. 1, and perovskite-type composite oxides were obtained in examples 1 to 5.
Experimental example 1
Measurement of thermal expansion coefficient:
the perovskite-type composite oxides prepared in examples 1 to 5 were used as samples, and the powder samples were pressed into 3 × 3 × 14mm dimensions by a square mold under a pressure of 10Mpa and sintered to be dense. The thermal expansion instrument TMA Q400EM model of TA Instruments was used at 5 ℃ for min in an air atmosphere-1The temperature rise rate of the sample is increased from 30 ℃ to 1000 ℃, the slope of the sample shape change rate in the temperature change is calculated according to the relation between the deformation amount of the test sample and the temperature change, and the average thermal expansion coefficient value of the sample strip is calculated.
As shown in FIG. 2, the LaNi content in the sample can be determined from the results of the measurement shown in FIG. 20.6Fe0.4O3The coefficient of thermal expansion of the material is: 13.75*10- 6K-1。La0.98Ni0.6Fe0.4O3The coefficient of thermal expansion of the material is: 13.55*10-6K-1。La0.96Ni0.6Fe0.4O3The coefficient of thermal expansion of the material is: 13.50*10-6K-1。La0.94Ni0.6Fe0.4O3The coefficient of thermal expansion of the material is: 13.48*10-6K-1。La0.98Ni0.6Fe0.4O3The coefficient of thermal expansion of the material is: 13.22*10-6K-1. The thermal expansion coefficient of the material after the defect is further reduced, and is closer to the thermal expansion coefficient of the common electrolyte material, so that the thermal matching with the electrolyte material is improved.
Experimental example 2
With the perovskite-type composite oxides prepared in examples 1 to 5 as samples, cathodes were formed by the same method, and polarization resistances of the cathodes at 650 ℃, 700 ℃, 750 ℃ and 800 ℃ were measured by the three-electrode method.
The test results are shown in FIG. 3. As can be seen from FIG. 3, LaNi0.6Fe0.4O3The polarization resistance of the material at 650 deg.C, 700 deg.C, 750 deg.C and 800 deg.C is 26.12 Ω cm2、9.85Ω·cm2、2.78Ω·cm2And 0.57. omega. cm2。
La0.98Ni0.6Fe0.4O3The polarization resistance of the material at 650 deg.C, 700 deg.C, 750 deg.C and 800 deg.C is 19.50 Ω cm2、6.83Ω·cm2、1.98Ω·cm2And 0.50. omega. cm2。
La0.96Ni0.6Fe0.4O3The polarization resistance of the material at 650 deg.C, 700 deg.C, 750 deg.C and 800 deg.C is 10.21 omega cm2、2.97Ω·cm2、0.78Ω·cm2And 0.28. omega. cm2。
La0.94Ni0.6Fe0.4O3The polarization resistance of the material at 650 deg.C, 700 deg.C, 750 deg.C and 800 deg.C is 5.10 Ω cm2、1.72Ω·cm2、0.61Ω·cm2And 0.18. omega. cm2。
La0.92Ni0.6Fe0.4O3The polarization resistance of the material at 650 deg.C, 700 deg.C, 750 deg.C and 800 deg.C is 13.16 Ω cm2、4.47Ω·cm2、0.91Ω·cm2And 0.22. omega. cm2。
According to the polarization resistance result, the oxygen reduction reaction activity of the perovskite type composite oxide without strontium and cobalt provided by the embodiment of the invention is improved, the stability is better, and the perovskite type composite oxide has more excellent medium-temperature performance.
Experimental example 3
The temperature is kept at 800 ℃ for 50h, and LaNi is respectively tested0.6Fe0.4O3(LNF) and La0.94Ni0.6Fe0.4O3(LNF94) the polarization resistance value of the cathode changes.
As can be seen from FIG. 4, the cathode polarization impedance of the unpopulated LNF is changed from 0.57 Ω & cm after 50h of operation2Increase in polarization resistance value of 0.66. omega. cm2The increase is about 15 percent, however, for LNF94, the polarization resistance value is 0.18 omega cm after 50 hours of operation2Fluctuating up and down without significant change, and the LNF94 cathode after vacancy has better long-term stability than the non-vacancy cathode LNF.
Meanwhile, LaNi is subjected to heat preservation for 50h at 800 DEG C0.6Fe0.4O3(LNF) and La0.94Ni0.6Fe0.4O3(LNF94) was subjected to X-ray diffraction analysis, see fig. 5. As is clear from comparison between fig. 1 and 5, the structure of the perovskite-type composite oxide free of strontium and cobalt is not changed even after long-term storage at high temperature, and the stability is further clarified to be good.
According to the embodiment of the invention, the strontium-free and cobalt-free perovskite type composite oxide is formed, so that the prepared cathode is easy to form a phase, has a thermal expansion coefficient close to that of an electrolyte and good stability, and reduces the dosage of expensive lanthanide metal while improving the activity and stability of the oxygen reduction reaction, thereby reducing the manufacturing cost of the electrode material.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A strontium-free and cobalt-free perovskite-type composite oxide is characterized by comprising the following chemical composition general formula: la1- xNi0.6Fe0.4O3Wherein x is not less than 0<0.1。
2. The strontium-free and cobalt-free perovskite-type composite oxide according to claim 1, wherein the strontium-free and cobalt-free perovskite-type composite oxide is an a-site-deficient perovskite material.
3. The strontium-free and cobalt-free perovskite-type composite oxide according to claim 1, which has a chemical composition formula of: la1-xNi0.6Fe0.4O3Wherein x is more than or equal to 0 and less than or equal to 0.08.
4. The strontium-and cobalt-free perovskite-type composite oxide according to any one of claims 1 to 3, wherein the strontium-and cobalt-free perovskite-type composite oxide is selected from the group consisting of LaNi0.6Fe0.4O3、La0.98Ni0.6Fe0.4O3、La0.96Ni0.6Fe0.4O3、La0.94Ni0.6Fe0.4O3And La0.92Ni0.6Fe0.4O3Any one of them.
5. A method for producing the strontium-free and cobalt-free perovskite-type composite oxide according to any one of claims 1 to 4, characterized in that the strontium-free and cobalt-free perovskite-type composite oxide is produced by a sol-gel method.
6. The method of claim 5, comprising: mixing a metal salt mixed solution containing La, Ni and Fe with a complexing agent, and then carrying out heat treatment to form the strontium-free and cobalt-free perovskite type composite oxide; wherein the molar ratio of La, Ni and Fe in the metal salt mixed solution is 1-x: 0.6: 0.4, x is more than or equal to 0 and less than 0.1;
preferably, the method comprises the following steps: after the metal salt mixed solution is mixed with EDTA and glycine, the mixture is treated at the constant temperature of 220 ℃ for 10 to 18 hours at 180 ℃ and then calcined for 2.0 to 5.0 hours at the temperature of 850 ℃ at 800 ℃;
preferably, the method comprises the following steps: mixing and dissolving EDTA and ammonia water to form a first mixed solution;
mixing the first mixed solution, the metal salt mixed solution and the glycine, then adjusting the pH value to 8-9 and stirring to be colloidal, then carrying out constant temperature treatment at 180 ℃ to 220 ℃ for 10-18 hours, and then calcining at 800 ℃ to 850 ℃ for 2.0-5.0 hours.
7. The method according to claim 6, wherein the preparing of the metal salt mixed solution includes: mixing and dissolving salts respectively containing La, Ni and Fe to form the metal salt mixed solution;
preferably, the metal salt mixed solution is any one of nitrate, carbonate and acetate.
8. The production method according to claim 6, wherein the molar amount of the sum of the metal cations in the metal salt mixed solution is: molar amount of EDTA: the molar weight of the glycine is 1:1: 1.5-2.0.
9. A battery comprising the strontium-free and cobalt-free perovskite-type composite oxide according to any one of claims 1 to 4 or the strontium-free and cobalt-free perovskite-type composite oxide obtained by the method according to any one of claims 5 to 8, wherein the battery is a half-cell or a full-cell battery.
10. The cell of claim 9, wherein the cell is an intermediate-temperature solid oxide fuel cell;
preferably, the medium-temperature solid oxide fuel cell further comprises a selected electrolyte material;
preferably, the electrolyte material comprises GDC and YSZ.
CN202011212132.2A 2020-11-03 2020-11-03 Strontium-free and cobalt-free perovskite type composite oxide, preparation method thereof and battery Pending CN112310419A (en)

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