CN116314987A - Preparation method of high-entropy double perovskite cathode material solid oxide fuel cell - Google Patents

Preparation method of high-entropy double perovskite cathode material solid oxide fuel cell Download PDF

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CN116314987A
CN116314987A CN202310325427.8A CN202310325427A CN116314987A CN 116314987 A CN116314987 A CN 116314987A CN 202310325427 A CN202310325427 A CN 202310325427A CN 116314987 A CN116314987 A CN 116314987A
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nitrate
cathode
entropy
fuel cell
solid oxide
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王程程
罗欣蕾
侯冰雪
郑梓恒
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Shenzhen Polytechnic
Civil Aviation Flight University of China
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Shenzhen Polytechnic
Civil Aviation Flight University of China
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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
    • 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

Abstract

The preparation method of the high-entropy double-perovskite cathode material solid oxide fuel cell comprises two processes of preparation of the high-entropy double-perovskite cathode material and preparation of the solid oxide fuel cell, wherein raw materials adopted in the preparation of the high-entropy double-perovskite cathode material comprise various metal nitrates, ethylenediamine tetraacetic acid, citric acid and ammonia water; the solid oxide fuel cell preparation includes five steps and the cell preparation includes four steps. The invention is based on the high-entropy double perovskite structure compound, is used for preparing the cathode material of the medium-low temperature solid oxide fuel cell, and starts from adjusting the A and B site elements of the double perovskite structure, improves the oxygen reduction catalytic activity, the chemical stability and the ionic conductivity of the double perovskite structure, and ensures that the prepared cathode material has better electrochemical performance. In conclusion, the method has good application prospect.

Description

Preparation method of high-entropy double perovskite cathode material solid oxide fuel cell
Technical Field
The invention relates to the technical field of solid oxide fuel cells, in particular to a preparation method of a high-entropy double perovskite cathode material solid oxide fuel cell.
Background
A solid oxide fuel cell is an electrochemical power generation device that directly converts chemical energy into electrical energy, and is composed of a cathode, an anode, and an electrolyte. As a cathode material for a solid oxide fuel cell, the material is required to have high electron conductivity and suitable ion conductivity in an oxidizing atmosphere, good thermal stability and chemical stability, and high oxygen reduction catalytic activity, and to have a certain porosity and good mechanical strength. Currently, the cathode materials of SOFCs that are widely studied and used are metal oxides, i.e., ceramic phase cathode materials. Conventional high temperature solid oxide fuel cell cathode materials require doping with LaMnO 3 Such materials exhibit high performance at high temperatures (1000 ℃); when the temperature is lowered, the electrochemical resistance of the material is increased sharply, which leads to a rapid decrease in performance, so that it is not suitable as a cathode material for a medium-low temperature (600-800 ℃) solid oxide fuel cell. Scientists are actively looking for a cathode material suitable for low and medium temperature solid oxide fuel cells.
Prior studies have shown that HEOs (high entropy oxides) containing more than 5 different cations can be stabilized in a single rock salt structure. Because of their lower gibbs free energy, they can be thermodynamically stable at high temperatures. The good dispersibility of all cations of HEOs suggests that it can improve stability by slowing down the diffusion of cations in the lattice structure. In addition, the prior research technology also shows that the high entropy La of the OFC cathode is caused by the homogeneous dispersion of metal elements in the A position of perovskite 0·8 Sr 0·2 MnO 3-δ (LSM) oxide (La 0.2 Pr 0.2 Nd 0.2 Sm 0.2 Sr 0·2 MnO 3-δ The HE-LSM structure is very stable and limits the precipitation rate of Sr; in high entropy (La 0.2 Sr 0.2 Pr 0.2 Y 0.2 Ba 0.2 )Co 0.2 Fe 0.8 O 3-δ Excellent Cr resistance was observed; medium entropy perovskite Sr (Fe α Ti β Co γ Mn ζ )O 3-δ (SFTCM) showsLower TEC inhibits strontium surface segregation and more stable polarization resistance. In addition, the material with the high-entropy double perovskite structure has good phase structure stability at high temperature, the oxygen vacancy concentration of the material can be improved through low-element doping, so that the oxygen ion conductivity of the material is increased, and the simple perovskite material with partial B-bit being Co-based has good electron conductivity, and can meet the rapid directional conduction of electrons at the working temperature of the SOFC, so that the double perovskite material is the main stream direction of the current SOFC cathode research. In summary, although some technical progress has been made in the research of the high-entropy oxide, there has been little research on the electrochemical properties of the high-entropy double perovskite (HEDP refers to high entropy double pervoskite high-entropy double perovskite structure) oxide for solid oxide fuel cells, which has not been effectively applied to the preparation of cathode materials for solid oxide fuel cells.
Disclosure of Invention
In order to overcome the defect that the high-entropy double perovskite is not effectively applied to the preparation of the cathode material of the solid oxide fuel cell in the prior art, the invention provides the compound based on the high-entropy double perovskite structure, which is used for preparing the cathode material of the medium-low temperature solid oxide fuel cell, and improves the oxygen reduction catalytic activity, the chemical stability and the ionic conductivity of the double perovskite structure based on the adjustment of the A and B site elements, so that the prepared cathode material has better electrochemical performance.
The technical scheme adopted for solving the technical problems is as follows:
the preparation method of the solid oxide fuel cell of the high-entropy double-perovskite cathode material is characterized by comprising two processes of preparation of the high-entropy double-perovskite cathode material and preparation of the solid oxide fuel cell; the raw materials adopted in the preparation of the high-entropy double perovskite cathode material comprise various metal nitrates, ethylenediamine tetraacetic acid, citric acid and ammonia water; the preparation of the high-entropy double perovskite cathode material comprises the following steps of: weighing different types and weights of metal nitrate and dissolving the metal nitrate in distilled water to prepare three different types of sample solutions; and (B) step (B):adding a certain amount of citric acid into each of the three sample solutions to serve as complexing agents respectively; step C: respectively mixing ethylenediamine tetraacetic acid and the three samples obtained in the step B; step D: stirring the three sample mixed solutions obtained in the step C for 4 hours at the temperature of 80 ℃ respectively, enabling the samples to gel respectively, heating the gelled samples to 600 ℃ in air to decompose nitrate and organic matters contained in the gelled samples, and firing the decomposed black precursors at the temperature of 1000 ℃ for 4 hours to obtain three powders; step E: the three powders obtained in the step D are respectively ball-milled at the speed of 600rpm for 5 hours to break up agglomerates, three high-entropy double-perovskite cathode structure cathode powders are obtained, then 50wt% of three cathode powders and gadolinium oxide doped cerium oxide electrolyte powder materials are respectively mixed and fired for 3 hours at the temperature of 1000 ℃, and the mixture is used for researching chemical compatibility of the three cathode powder materials in a test flow, and whether the three cathode powders react with the electrolyte powder materials or not is obtained; in the preparation of the solid oxide fuel cell, 3wt% of ethyl cellulose and 97wt% of terpineol binder are respectively dissolved in an oven to obtain uniform solution at 80 ℃, then the three high-entropy double perovskite structure cathode powders obtained in the step D are respectively mixed in solution to form cathode slurry, and the three high-entropy double perovskite structure cathode slurry screens are respectively coated on a surface of 0.2827cm 2 And then calcining at 1000 ℃ for 3 hours, and then sintering the cathode on the SOFC half-cell to obtain three complete SOFC full-cells.
Further, the plurality of metal nitrates respectively comprise lanthanum nitrate, praseodymium nitrate, samarium nitrate, gadolinium nitrate, neodymium nitrate, yttrium nitrate, strontium nitrate, barium nitrate, cobalt nitrate and ferric nitrate.
Further, in the step a, the first sample is 0.3891g of lanthanum nitrate, 0.3909g of praseodymium nitrate, 0.3994g of samarium nitrate, 0.4056g of gadolinium nitrate, 0.2968g of neodymium nitrate, 0.5871g of barium nitrate, 0.4754g of strontium nitrate, 1.9614g of cobalt nitrate and 0.9076g of ferric nitrate, and the prepared cathode powder with the high entropy double perovskite structure is 2g; the second sample comprises 0.3900g of lanthanum nitrate, 0.3918g of praseodymium nitrate, 0.4004g of samarium nitrate, 0.4066g of gadolinium nitrate, 0.3450g of yttrium nitrate, 0.5885g of barium nitrate, 0.4766g of strontium nitrate, 1.9662g of cobalt nitrate and 0.9098g of ferric nitrate, wherein the prepared cathode powder with the high-entropy double perovskite cathode structure is 2g; the third sample comprises 0.3923g of lanthanum nitrate, 0.3942g of praseodymium nitrate, 0.4027g of samarium nitrate, 0.2992g of neodymium nitrate, 0.3470g of yttrium nitrate, 0.5920g of barium nitrate, 0.4794g of strontium nitrate, 1.9777g of cobalt nitrate and 0.9152g of ferric nitrate, and the prepared cathode powder with the high-entropy double perovskite cathode structure is 2g.
Further, in the step B, 5.6651g of citric acid is added to the first sample, 5.6787g of citric acid is added to the second sample, and 5.7122g of citric acid is added to the third sample.
Further, in the step C, 5.2523g of ethylenediamine tetraacetic acid is added to the first sample, 5.2649g of ethylenediamine tetraacetic acid is added to the second sample, 5.2959g of ethylenediamine tetraacetic acid is added to the third sample, and the three samples are respectively mixed with 10ml of ammonia water to be dissolved, and the pH value is 10, and the metal cations of the three samples are as follows: citric acid: the fixed molar ratio of the ethylenediamine tetraacetic acid is 1:1.5:1.
further, in the step D, the chemical formulas of the three high-entropy double perovskite structure cathode powders are respectively as follows:
(La 0.2 Pr 0.2 Sm 0.2 Gd 0.2 Nd 0.2 )Ba 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5 (LPSGNBSCF)
(La 0.2 Pr 0.2 Sm 0.2 Gd 0.2 Y 0.2 )Ba 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5 (LPSGYBSCF)
(La 0.2 Pr 0.2 Sm 0.2 Nd 0.2 Y 0.2 )Ba 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5 (LPSNYBSCF)。
the invention has the beneficial effects that: the three high-entropy double-perovskite compounds (three high-entropy double-perovskite structure cathode materials) prepared by the method have stable structures, no impurity phase is formed, and the shape of the nano particles is very uniform; three high-entropy double perovskite compounds and common electrolyte materials, such as doped cerium oxide materials, have good chemical matching property; three high-entropy double perovskite compounds are used as cathode materials, and the prepared solid oxide fuel cell has good electrochemical performance under the medium-temperature test condition by adopting a cell preparation process. The (La0.2Pr0.2Sm0.2Gd0.2Nd0.2) Ba0.5Sr0.5Co1.5Fe0.5O5 (LPSGNBSCF) is used as a cathode material of the solid oxide fuel cell, and the optimal cell performance is obtained under the same test condition. The (La0.2Pr0.2Sm0.2Gd0.2Nd0.2) Ba0.5Sr0.5Co1.5Fe0.5O5 (LPSGNBSCF) is used as a cathode material of the solid oxide fuel cell, and the stability test is carried out under the same test condition, so that the solid oxide fuel cell has better durability. The invention provides favorable technical support for improving the performance and effectively using the solid oxide fuel cell. Based on the above, the invention has good application prospect.
Drawings
Fig. 1 is an XRD pattern and GDC pattern of HEDP powder (a) calcined in air at 1000 ℃ for 3 hours with chemical compatibility (b).
Fig. 2 is an SEM image of HEDP powder (a) burned in air at 1000 ℃ for 3 hours and EDS spectrum of HEDP powder (b).
Fig. 3 is a high resolution TEM image and EDS map of HEDP (LPSGNBSCF) powder.
Fig. 4 is a high resolution TEM image and EDS map of HEDP (LPSGYBSCF) powder.
Fig. 5 is a high resolution TEM image and EDS map of HEDP (LPSNYBSCF) powder.
Fig. 6 is a high resolution elemental spectrum of XPS and Gd, nd and Y elements of HEDP powder.
Fig. 7 is a SEM image of the surface and cross-section of the HEDP cathode prior to testing, including (a, b) LPSGNBSCF, (c, d) LPSGYBSCF, (e, f) LPSNYBSCF.
Fig. 8 is an AFM image of the cathode surface of the anode-supported cell HEDP prior to testing, including (a) LPSGNBSCF, (b) LPSGYBSCF, and (c) LPSNYBSCF.
Fig. 9 is a typical cross-sectional SEM image of the single cell after testing.
Fig. 10 is a cross-sectional SEM image of a HEDP cathode after testing, including (a, b) LPSGNBSCF, (c, d) LPSGYBSCF, (e, f) LPSNYBSCF.
Fig. 11 is a graph of cell performance of three HEDP anode supported cells tested from 650 ℃ to 800 ℃.
Fig. 12 is a flow chart of the preparation of a high entropy dual perovskite cathode material solid oxide fuel cell.
Detailed Description
FIG. 12 shows a method for preparing a solid oxide fuel cell of a high-entropy double-perovskite cathode material, which comprises two processes of preparing the high-entropy double-perovskite cathode material and preparing the solid oxide fuel cell; the raw materials adopted in the preparation of the high-entropy double perovskite cathode material comprise various metal nitrates, ethylenediamine tetraacetic acid, citric acid and ammonia water; the preparation of the high-entropy double perovskite cathode material comprises the following steps of: weighing different types and weights of metal nitrate and dissolving the metal nitrate in distilled water to prepare three different types of sample solutions; and (B) step (B): adding a certain amount of citric acid into each of the three sample solutions to serve as complexing agents respectively; step C: respectively mixing ethylenediamine tetraacetic acid and the three samples obtained in the step B; step D: stirring the three sample mixed solutions obtained in the step C for 4 hours at the temperature of 80 ℃ respectively, enabling the samples to gel respectively, heating the gelled samples to 600 ℃ in air to decompose nitrate and organic matters contained in the gelled samples, and firing the decomposed black precursors at the temperature of 1000 ℃ for 4 hours to obtain three powders; step E: the three powders obtained in the step D are respectively ball-milled at the speed of 600rpm for 5 hours to break up agglomerates, three high-entropy double-perovskite cathode structure cathode powders are obtained, then 50wt% of three cathode powders and gadolinium oxide doped cerium oxide electrolyte powder materials are respectively mixed and fired for 3 hours at the temperature of 1000 ℃, and the mixture is used for researching chemical compatibility of the three cathode powder materials in a test flow, and whether the three cathode powders react with the electrolyte powder materials or not is obtained;
a complete SOFC full cell is shown in fig. 12, and is composed of an anode, electrolyte and cathode, while the present invention employs a commercially available anode supported half cell (NiO-ysz|ysz|gdc) structure. Wherein NiO-YSZ is 50wt% NiO (nickel oxide) and 50wt% YSZ (yttria stabilized zirconia) as anodes, YSZ (yttria stabilized zirconia) as electrolyte, and GDC (gadolinium oxide)Doped ceria) was used as a buffer layer to modify the interface between the HEDP cathode and YSZ electrolyte. In the preparation of the solid oxide fuel cell, 3wt% of ethylcellulose and 97wt% of terpineol binder are respectively dissolved in an oven to obtain uniform solutions at 80 ℃, then the three high-entropy double perovskite structure cathode powders obtained in the step D are respectively mixed to form cathode slurry, and the three high-entropy double perovskite structure cathode slurry screens are respectively coated on a surface of 0.2827cm 2 And then calcining at 1000 ℃ for 3 hours, and then sintering the cathode on the SOFC half-cell to obtain three complete SOFC full-cells. Detecting the performance of the whole SOFC, and printing silver paste on the surface of a cathode as the effect of collecting current when testing the whole SOFC; for specific testing, cell performance of the SOFC full cells from 650 to 800 ℃ was tested in air using Solartron 1260 electrochemical device with wet hydrogen (3%H 2 O/97％H 2 ) Is fuel with flow rate of 40 mL-min -1 From 650 to 800 ℃ (Solartron 1260). And simultaneously testing open circuit impedance spectroscopy (EIS) of the cells. The test condition is frequency 10 6 To 10 -1 Hz and a voltage amplitude of 10 mV.
As shown in FIG. 12, the various metal nitrates include La (NO 3 ) 3 .6H 2 Lanthanum nitrate O, pr (NO) 3 ) 3 .6H 2 Praseodymium nitrate, sm (NO) 3 ) 3 .6H 2 Samarium O nitrate, gd (NO) 3 ) 3 .6H 2 Gadolinium O nitrate, nd (NO) 3 ) 3 .6H 2 Neodymium nitrate O, Y (NO) 3 ) 3 .6H 2 Yttrium O nitrate, sr (NO) 3 ) 2 Strontium nitrate, ba (NO) 3 ) 2 Barium nitrate, co (NO) 3 ) 2 .6H 2 Cobalt nitrate O, fe (NO) 3 ) 3 .9H 2 O ferric nitrate. In the step A, the adopted raw materials are 0.3891g of lanthanum nitrate, 0.3909g of praseodymium nitrate, 0.3994g of samarium nitrate, 0.4056g of gadolinium nitrate, 0.2968g of neodymium nitrate, 0.5871g of barium nitrate, 0.4754g of strontium nitrate, 1.9614g of cobalt nitrate and 0.9076g of ferric nitrate, and the prepared cathode powder with the high-entropy double perovskite cathode structure is 2g; the second sample is 0.3900g lanthanum nitrate, 0.3918g praseodymium nitrate and nitric acid0.4004g of samarium, 0.4066g of gadolinium nitrate, 0.3450g of yttrium nitrate, 0.5885g of barium nitrate, 0.4766g of strontium nitrate, 1.9662g of cobalt nitrate and 0.9098g of ferric nitrate, wherein the prepared cathode powder with the high-entropy double perovskite cathode structure is 2g; the third sample comprises 0.3923g of lanthanum nitrate, 0.3942g of praseodymium nitrate, 0.4027g of samarium nitrate, 0.2992g of neodymium nitrate, 0.3470g of yttrium nitrate, 0.5920g of barium nitrate, 0.4794g of strontium nitrate, 1.9777g of cobalt nitrate and 0.9152g of ferric nitrate, and the prepared cathode powder with the high-entropy double perovskite cathode structure is 2g. In step B, 5.6651g of citric acid was added to the first sample, 5.6787g of citric acid was added to the second sample, and 5.7122g of citric acid was added to the third sample. In the step C, 5.2523g of ethylenediamine tetraacetic acid is added to the first sample, 5.2649g of ethylenediamine tetraacetic acid is added to the second sample, 5.2959g of ethylenediamine tetraacetic acid is added to the third sample, and the three samples are respectively mixed with 10ml of ammonia water to be dissolved, the pH value is 10, and the metal cations of the three samples are: citric acid: the fixed molar ratio of the ethylenediamine tetraacetic acid is 1:1.5:1. in the step D, the chemical formulas of the three high-entropy double-perovskite structure cathode powders are respectively as follows:
(La 0.2 Pr 0.2 Sm 0.2 Gd 0.2 Nd 0.2 )Ba 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5 (LPSGNBSCF)
(La 0.2 Pr 0.2 Sm 0.2 Gd 0.2 Y 0.2 )Ba 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5 (LPSGYBSCF)
(La 0.2 Pr 0.2 Sm 0.2 Nd 0.2 Y 0.2 )Ba 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5 (LPSNYBSCF)。
figure 1a shows the XRD pattern of HEDP powder fired in air at 1000 ℃. In the figure, it is clearly seen that HEDP exhibits a pure perovskite structure. Furthermore, goldschmidt accommodation factors were calculated, all HEDP accommodation factors being between 0.9 and 1, which is consistent with XRD results for the pure orthorhombic perovskite structural phase. Figure 1b also shows the chemical compatibility XRD results between the HEDP cathode and the common GDC electrolyte. They show good chemical compatibility with GDC at 1000℃and do not react at this temperature.
Fig. 2a shows microstructure images of three HEDP powders fired at 1000 ℃ for 4 hours. The particles of HEDP powder are uniform and porous. However, the three powders are different in shape and size. LPSGNBSCF (No. 1) powder is well combined, and the particle size is about 200-400 nm. For LPSGYBSCF (2#) powder, the particles are well connected and have a size less than 1#, about 150-200nm. However, in the case of LPSNYBSCF (3#), the particle shape is irregular and the particle size is more than 400nm. The surface of these powders is interspersed with a few tiny particles. SEM images of HEDP cathode powders are shown in fig. 2 (b, d and e), and elemental composition analysis was performed on these three HEDP powders using SEM-EDS to determine the atomic percent of HEDP. Four different points were chosen to ensure data accuracy and EDS data results are shown in tables 1, 2 and 3. According to this table, the atomic percent of the elements is similar to the calculated chemical to physical mole ratios of the three HEDP powders. It was confirmed that these cathode materials were very stable after calcination.
FIG. 3 shows (La 0.2 Pr 0.2 Sm 0.2 Gd 0.2 Nd 0.2 )Ba 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5 High resolution TEM and map images of (LPSGNBSCF) powder. It can be seen that the lattice d-spacing was roughly calculated as 0.3657nm, corresponding to (100) lattice planes, respectively. TEM may indicate HEDP to exhibit a single phase, similar to XRD results. The corresponding map image of HEDP powder clearly shows that La, pr, sm, gd, nd, ba, sr, co, fe elements are evenly distributed in these images.
FIG. 4 shows (La 0.2 Pr 0.2 Sm 0.2 Gd 0.2 Y 0.2 )Ba 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5 High resolution TEM and map images of (LPSGYBSCF) powder. The lattice d-spacing was roughly calculated as 0.4657nm, corresponding to (100) lattice planes, respectively. The corresponding EDS map image of HEDP powder clearly shows that La, pr, sm, gd, Y, ba, sr, co, fe elements are uniformly distributed in these images.
FIG. 5 shows (La 0.2 Pr 0.2 Sm 0.2 Nd 0.2 Y 0.2 )Ba 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5 High resolution TEM and map images of (LPSNYBSCF) powder. The mapped image of the energy spectrum HEDP powder shows that La, pr, sm, gd, Y, ba, sr, co, fe elements are uniformly distributed in these images. All three TEM and EDS mapping results can indicate that elements we used to study, such as La, pr, sm, nd, gd and Y, have successfully incorporated the a site of the HEDP structure.
Fig. 6 shows XPS spectra of three HEDP powders, and shows XPS spectrum fitting results of Nd3d, gd4d, and Y3d of three samples. For LPSGNBSCF (1#) and LPSGYBSCF (2#) samples, after deconvolution, the Gd4d main peak of the electrode appears around 158eV, and 143eV also corresponds to Gd in the structure 3+ . In addition, the atomic weights of Gd and Nd correspond to the calculated stoichiometry in the high entropy structure. After fitting, for the LPSGYBSCF (2#) and LPSNYBSCF (3#) samples, the main Y3d peak of the electrode appears around 178eV, 153eV also corresponding to Yd in the structure 3+ 。
Fig. 7 shows surface and cross-sectional images of three HEDP anodes of a single cell prior to testing. It can be seen that the three HEDP anodes had significantly different surface microstructures. For the LPSGNBSCF (1 #) positive electrode in fig. 7, it depicts a uniform porous structure and good connection between particles. This may indicate that a uniform structure may be advantageous for the oxygen reduction reaction during SOFC operation. Whereas for fig. 7, the surface of the gybscf (2 #) cathode also exhibits a relatively uniform microstructure. However, for fig. 7, the surfaces of lpsnybscf (3 #) appear to be clustered together, which may indicate that the sintering temperature of the cell is relatively high, resulting in fewer pores. Taking the cross-sectional area of three cells as an example, the thickness of all three samples was around 15 μm. As can be seen from fig. 7, the microstructure of the positive electrode is relatively porous, while the electrolyte is very dense. The electrolyte has good adhesion to the anode and HEDP cathode. Atomic Force Microscopy (AFM) was used to identify three HEDP cathodes prior to surface topography testing. As shown in fig. 8, the surface topography of the three HEDP anodes remained almost unchanged. All the results show that the high entropy structure of these three HEDP (high entropy double pervoskite high entropy double perovskite structure) cathodes is relatively stable compared to the typical Sr segregation phenomenon of LSCF cathodes.
Fig. 9 shows a typical complete SEM cross-sectional image of a single cell after electrochemical measurements. The anode and cathode sides are highly porous and the electrolyte is well connected to the other layers. The electrolyte layer was dense and no significant cracking was found. Fig. 10 shows SEM cross-sectional images of three HEDP cathodes after electrochemical measurements. The YSZ electrolyte and GDC had a thickness of about 12 μm and 2 μm, respectively. From fig. 10, it is evident that HEDP-LPSGNBSCF (1 #) exhibits a finer particle surrounding phenomenon, which may be the reason for the better electrocatalytic activity of the HEDP cathode. In addition, the HEDP-LPSGNBSCF (1#) cathode structure is more uniform than the other two cathode structures (2# -3#). It can also be seen from fig. 9 that there are some aggregates inside the HEDP-LPSNYBSCF (3 #) cathode.
Fig. 11 shows electrochemical performance of a unit cell (NiO-ysz|ysz|gdc|hedp) at different temperatures of 650 ℃ to 800 ℃. The Open Circuit Voltage (OCV) of the three cells was around 1.1V at 800 ℃ and was close to the theoretical value, indicating that the cells had no cracks. For LPSGNBSCF (1#), the maximum power densities of the single cells are 0.2, 0.4, 0.6 and 1.0W cm at 650, 700, 750 and 800 ℃, respectively -2 . In general, the difference between the intercepts obtained in the high-frequency and low-frequency regions is the polarization resistance (Rp) of the single cell. As can be seen from FIG. 11b, rp is 0.3 Ω & cm at 800 ℃ 2 Is the lowest compared to the other two cells. Whereas for LPSGYBSCF (2#), the maximum power densities of the cells are 0.1, 0.2, 0.5 and 0.81Wcm at 650, 700, 750 and 800 ℃, respectively -2 . In addition, for LPSNYBSCF (3#), the maximum power densities of the cells were 0.1, 0.2, 0.35 and 0.56W cm at 650, 700, 750 and 800 ℃, respectively -2 . All these results indicate that the HEDP-LPSGNBSCF positive electrode is porous, capable of gas reaction and good connection to the GDC layer, and YSZ is dense enough to isolate the oxidizing and reducing atmospheres, thus optimizing the electrochemical performance of the cell. The method is used for electrochemical performance test. The GDC was used as a buffer layer to modify the interface between the HEDP cathode and YSZ electrolyte.
The invention has the following advantages: 1. the three high-entropy double perovskite compounds have stable structures, no hetero-phase is formed, and the appearance of the nano particles is very uniform.
Three high entropy double perovskite compounds and common electrolyte materials, such as doped cerium oxide materials, have good chemical matching property.
3. Three high-entropy double perovskite compounds are used as cathode materials, and the solid oxide fuel cell manufactured by adopting the cell preparation process has good electrochemical performance under the medium-temperature test condition.
4. In (La) 0.2 Pr 0.2 Sm 0.2 Gd 0.2 Nd 0.2 )Ba 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5 (LPSGNBSCF) is used as a cathode material of the solid oxide fuel cell, and the optimal cell performance is obtained under the same test condition.
5. In (La) 0.2 Pr 0.2 Sm 0.2 Gd 0.2 Nd 0.2 )Ba 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5 (LPSGNBSCF) as a cathode material of a solid oxide fuel cell, and shows better durability by performing a stability test under the same test conditions. The invention provides favorable technical support for improving the performance and effectively using the solid oxide fuel cell.
It should be noted that while the above describes and illustrates embodiments of the present invention, it is not intended that the embodiments include only a single embodiment, but that this description is made for the sake of clarity only, and it will be appreciated by one skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, and other embodiments will be understood by those skilled in the art, and accordingly, the scope of the invention is defined by the appended claims and their equivalents.

Claims (6)

1. The preparation method of the solid oxide fuel cell of the high-entropy double-perovskite cathode material is characterized by comprising two processes of preparation of the high-entropy double-perovskite cathode material and preparation of the solid oxide fuel cell; the raw materials adopted for preparing the high-entropy double perovskite cathode material compriseVarious metal nitrates, ethylenediamine tetraacetic acid, citric acid and ammonia water; the preparation of the high-entropy double perovskite cathode material comprises the following steps of: weighing different types and weights of metal nitrate and dissolving the metal nitrate in distilled water to prepare three different types of sample solutions; and (B) step (B): adding a certain amount of citric acid into each of the three sample solutions to serve as complexing agents respectively; step C: respectively mixing ethylenediamine tetraacetic acid and the three samples obtained in the step B; step D: stirring the three sample mixed solutions obtained in the step C for 4 hours at the temperature of 80 ℃ respectively, enabling the samples to gel respectively, heating the gelled samples to 600 ℃ in air to decompose nitrate and organic matters contained in the gelled samples, and firing the decomposed black precursors at the temperature of 1000 ℃ for 4 hours to obtain three powders; step E: the three powders obtained in the step D are respectively ball-milled at the speed of 600rpm for 5 hours to break up agglomerates, three high-entropy double-perovskite cathode structure cathode powders are obtained, then 50wt% of three cathode powders and gadolinium oxide doped cerium oxide electrolyte powder materials are respectively mixed and fired for 3 hours at the temperature of 1000 ℃, and the mixture is used for researching chemical compatibility of the three cathode powder materials in a test flow, and whether the three cathode powders react with the electrolyte powder materials or not is obtained; in the preparation of the solid oxide fuel cell, 3wt% of ethyl cellulose and 97wt% of terpineol binder are respectively dissolved in an oven to obtain uniform solution at 80 ℃, then the three high-entropy double perovskite structure cathode powders obtained in the step D are respectively mixed in solution to form cathode slurry, and the three high-entropy double perovskite structure cathode slurry screens are respectively coated on a surface of 0.2827cm 2 And then calcining at 1000 ℃ for 3 hours, and then sintering the cathode on the SOFC half-cell to obtain three complete SOFC full-cells.
2. The method for preparing the solid oxide fuel cell of the high-entropy double perovskite cathode material according to claim 1, wherein the plurality of metal nitrates respectively comprise lanthanum nitrate, praseodymium nitrate, samarium nitrate, gadolinium nitrate, neodymium nitrate, yttrium nitrate, strontium nitrate, barium nitrate, cobalt nitrate and ferric nitrate.
3. The method for preparing the solid oxide fuel cell with the high-entropy double perovskite cathode material according to claim 1, wherein in the step A, raw materials are adopted, wherein a first sample comprises 0.3891g of lanthanum nitrate, 0.3909g of praseodymium nitrate, 0.3994g of samarium nitrate, 0.4056g of gadolinium nitrate, 0.2968g of neodymium nitrate, 0.5871g of barium nitrate, 0.4754g of strontium nitrate, 1.9614g of cobalt nitrate and 0.9076g of ferric nitrate, and the prepared cathode powder with the high-entropy double perovskite cathode structure is 2g; the second sample comprises 0.3900g of lanthanum nitrate, 0.3918g of praseodymium nitrate, 0.4004g of samarium nitrate, 0.4066g of gadolinium nitrate, 0.3450g of yttrium nitrate, 0.5885g of barium nitrate, 0.4766g of strontium nitrate, 1.9662g of cobalt nitrate and 0.9098g of ferric nitrate, wherein the prepared cathode powder with the high-entropy double perovskite cathode structure is 2g; the third sample comprises 0.3923g of lanthanum nitrate, 0.3942g of praseodymium nitrate, 0.4027g of samarium nitrate, 0.2992g of neodymium nitrate, 0.3470g of yttrium nitrate, 0.5920g of barium nitrate, 0.4794g of strontium nitrate, 1.9777g of cobalt nitrate and 0.9152g of ferric nitrate, and the prepared cathode powder with the high-entropy double perovskite cathode structure is 2g.
4. The method for preparing a solid oxide fuel cell of high entropy double perovskite cathode material according to claim 1, wherein in step B, 5.6651g of citric acid is added to the first sample, 5.6787g of citric acid is added to the second sample, and 5.7122g of citric acid is added to the third sample.
5. The method for preparing a solid oxide fuel cell of high entropy double perovskite cathode material according to claim 1, wherein in step C, 5.2523g of ethylenediamine tetraacetic acid is added to the first sample, 5.2649g of ethylenediamine tetraacetic acid is added to the second sample, 5.2959g of ethylenediamine tetraacetic acid is added to the third sample, and the three samples are respectively mixed with 10ml of ammonia water to be dissolved, the pH is 10, and the metal cations of the three samples: citric acid: the fixed molar ratio of the ethylenediamine tetraacetic acid is 1:1.5:1.
6. the method for preparing a solid oxide fuel cell of high-entropy double perovskite cathode material according to claim 1, wherein in the step D, three high-entropy double perovskite cathode powder chemical formulas are respectively:
(La 0.2 Pr 0.2 Sm 0.2 Gd 0.2 Nd 0.2 )Ba 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5 (LPSGNBSCF)
(La 0.2 Pr 0.2 Sm 0.2 Gd 0.2 Y 0.2 )Ba 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5 (LPSGYBSCF)
(La 0.2 Pr 0.2 Sm 0.2 Nd 0.2 Y 0.2 )Ba 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5 (LPSNYBSCF)。
CN202310325427.8A 2023-03-30 2023-03-30 Preparation method of high-entropy double perovskite cathode material solid oxide fuel cell Pending CN116314987A (en)

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