CN114243029A - A perovskite composite anode loaded with nano-catalyst and its preparation method and application - Google Patents
A perovskite composite anode loaded with nano-catalyst and its preparation method and application Download PDFInfo
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- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
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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
- H01M4/8605—Porous electrodes
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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
- H01M4/88—Processes of manufacture
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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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
- H01M4/8885—Sintering or firing
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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
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
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- 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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Abstract
The invention discloses a perovskite composite anode loaded with a nano catalyst, and a preparation method and application thereof. The composite anode material is of Ruddlesden-Popper (RP) layered structure, and the molecular formula of the matrix perovskite is PrSrFe0.8Ru0.1Nb0.1O4+δThe nano catalyst is Fe0.7Ru0.3alloy-FeOyAn oxide. The preparation method comprises the following steps: firstly, the preparation is carried out by adopting a combustion method (Pr)0.5Sr0.5)xFe0.8Ru0.1Nb0.1O3‑βPrecursor, then pretreating the precursor in reducing atmosphere to obtain Fe with uniformly covered surface0.7Ru0.3alloy-FeOyThe perovskite composite anode material of the oxide core-shell structure nanometer active particles. Preparation of the inventionThe perovskite composite anode material FRA @ FO-RP-PSFRN is coral-shaped, and the FRA @ FO core-shell structure nano particles precipitated in situ on the surface provide a large number of active sites for fuel catalysis, expand the three-phase interface of electrochemical reaction, have good fuel catalysis performance, and have good application prospect in the solid oxide fuel cell anode.
Description
Technical Field
The invention belongs to the field of solid oxide fuel cells, and particularly relates to a nano-catalyst-loaded perovskite composite anode and a preparation method and application thereof.
Background
The Solid Oxide Fuel Cell (SOFC) is a novel energy conversion device with an all-solid structure, can directly convert chemical energy in fuel into electric energy, and has the advantages of low emission, wide fuel adaptability and the like.
In SOFC, H2Is the most common fuel and has the advantages of easy conversion, no pollution and the like. At the same time, however, the disadvantages of using hydrogen as a fuel are also apparent, such as high production costs, high storage risks, etc. Currently, researchers in various countries are actively seeking to replace H with carbon-based fossil fuels2An efficient method of fueling. Conventional Ni-based cermet SOFC anode materials, such as Ni-YSZ (8 mol% Y)2O3Stabilized ZrO2) Carbon deposition is likely to occur in carbon-based fuels, and it is difficult to obtain higher performance output. The use of perovskite oxides with electron/ion mixed conductivity instead of Ni-based anodes is effective in avoiding carbon deposition, however, these perovskite materials often have difficulty achieving desirable fuel catalytic properties.
The loading of the nano catalyst on the surface of the electrode material is a common modification means, and can effectively improve the catalytic activity of the electrode material. Among them, the size, particle size distribution, elemental composition and their interaction with the oxide support of the supported metal nanoparticles are the key to determine catalytic activity, catalytic selectivity and stability. In previous researches, methods such as physical mixing, physical or chemical vapor deposition, chemical impregnation and the like are often adopted to prepare the metal nanoparticle-supported catalyst. However, these methods do not provide good control over the size of the nanoparticles, resulting in a non-uniform distribution of the nanoparticles. Therefore, a loading means is needed to be found to realize the controllability of the size and the particle size of the nano catalyst, so as to realize the improvement of the performance of the perovskite oxide anode.
In recent years, with the intensive research on perovskite oxides, researchers have found that a part of perovskite material ABO is generated under the reducing atmosphere condition3The B-site metal in the perovskite anode can be reduced and precipitated on the surface of the material to form active Nano Particles (NPs), which have obvious influence on the conductivity and catalytic performance of the material, and the modification of the perovskite anode is improvedAn efficient process is provided. In the conventional in-situ precipitation technology, the obtained surface nanoparticles are generally metal simple substances or alloys. For example, Xue et al prepared surface FeNi by in-situ precipitation method3Nanoparticle modified PrBa (Fe, Ni)1.9Mo0.1O5+δA perovskite composite material.
(Xue,ShuangShuang,Nai Shi,Yan Hong Wan,Zheqiang Xu,DaomingHuan,Shaowei Zhang,Changrong Xia,Ranran Peng,and Yalin Lu.2019.'Novel carbon and sulfur-tolerant anode material FeNi3@PrBa(Fe,Ni)1.9Mo0.1O5+δfor intermediate temperature solid oxide fuel cells',Journal of Materials Chemistry A,7:21783-93.)FeNi3The nano particles are used as active sites of reaction, and have good catalytic performance on adsorption cracking of fuel. At the anode, the reaction of the fuel is carried out in several steps: (1) the fuel catalyst surface is chemically adsorbed and decomposed into H (ad)/CHx(ad)；(2)H(ad)/CHx(ad) at the active site (B)n+-O-Bn+) Reacts with lattice oxygen to produce water and carbon dioxide, forming oxygen vacancies
And releasing the electrons into an external circuit; (3) oxygen ions generated in the cathode migrate to the anode to replenish oxygen vacancies. In the process, the step (2) is a speed control step of the reaction, so that the existence of lattice oxygen on the surface of the material is beneficial to improving the catalytic performance of the material. In the traditional in-situ precipitation technology, the obtained surface nano particles are mainly metal simple substances or alloys, and the cracked product after the reaction with the fuel is transferred to the interface of the metal particle-perovskite substrate to be combined with oxygen, so that the performance improvement effect is greatly reduced.
Disclosure of Invention
Aiming at the defects or the improvement requirements of the prior art of the perovskite surface loaded nano catalyst, the invention provides the method for separating Fe out on the surface0.7Ru0.3alloy-FeOyMetal nanoparticles of oxide core-shell structure, FeOyLattice oxygen ion of (A) and H (ad)/CHx(ad) are combined to form an intermediate,the generated electrons can also pass through Fe0.7Ru0.3The alloy core is transferred, and the reaction three-phase interface is effectively expanded.
(Pr0.5Sr0.5)xFe0.8Ru0.1Nb0.1O3-βPrecursors, i.e. PSFRNxThe precursor can precipitate core-shell structure nano catalyst (FRA @ FO) in situ in the process of reducing atmosphere pretreatment, and the nano catalyst is core-shell structure nano active particles containing outer FeOyOxide shell and internal Fe0.7Ru0.3An alloy core. While the matrix phase structure is formed by ABO3Phase conversion of perovskite to Ruddlesden-Popper layered perovskite PrSrFe0.8Ru0.1Nb0.1O4+δ(RP-PSFRN)。
The FRA @ FO nano catalyst separated out on the surface provides a large number of active sites for electrochemical reaction, improves the electrochemical catalytic performance of the perovskite anode, and on the other hand, Fe0.7Ru0.3And FeOyThe carbon deposit resistant performance in hydrocarbon fuel is good, and the output stability of the battery in the hydrocarbon fuel is ensured.
One of the purposes of the invention is to provide a perovskite composite anode loaded with a nano catalyst;
the invention also aims to provide a preparation method of the perovskite composite anode loaded with the nano-catalyst;
still another object of the present invention is to provide an application of the nano-catalyst supported perovskite composite anode as a solid oxide fuel cell anode.
The purpose of the invention is realized by at least one of the following technical solutions.
The perovskite composite anode loaded with the nano catalyst is of a Ruddlesden-Popper layered structure, and the molecular formula of the matrix perovskite is PrSrFe0.8Ru0.1Nb0.1O4+δWherein delta represents the number of oxygen vacancies in the perovskite after the metallic elements of Fe and Ru are precipitated, and the value of delta is 0<Delta is less than or equal to 0.5, and the nano catalyst is Fe0.7Ru0.3alloy-FeOyOxide, wherein y represents ferriteThe coordination number of oxygen in the compound, the value of y being 3<y<4。
The invention provides a preparation method of a perovskite composite anode loaded with a nano catalyst, which comprises the following steps:
step 1: prepared by combustion method (Pr)0.5Sr0.5)xFe0.8Ru0.1Nb0.1O3-βAnd the precursor, wherein beta represents the number of oxygen vacancies in the perovskite, and the numerical value of beta is more than or equal to 0 and less than or equal to 0.15. Using PSFRNxIs represented by (Pr)0.5Sr0.5)xFe0.8Ru0.1Nb0.1O3-βA precursor, wherein x is more than or equal to 0.9 and less than or equal to 1.0; weighing praseodymium nitrate, strontium nitrate, ferric nitrate, ruthenium (III) nitrosyl nitrate solution, niobium oxalate and glycine in a stoichiometric ratio in deionized water, uniformly stirring to form a mixed solution, placing the mixed solution on a magnetic heating stirrer, heating and stirring to form gel, heating until the raw materials are completely self-ignited, collecting black powder after self-ignition, and calcining to obtain PSFRNxA precursor;
step 2: PSFRNxThe precursor is pretreated in a reducing atmosphere to obtain Fe with uniformly covered surface0.7Ru0.3alloy-FeOyThe perovskite composite anode material of oxide (FRA @ FO) core-shell structure nano active particles is FRA @ FO-RP-PSFRN. Wherein FRA @ FO represents Fe0.7Ru0.3alloy-FeOyOxide, RP-PSFRN representing a layered perovskite PrSrFe0.8Ru0.1Nb0.1O4+δ。
Further, the stoichiometric ratio of the glycine to the sum of the praseodymium, strontium, iron, ruthenium and niobium metal ions in the step 1 is 2: 1.
Further, the heating and stirring temperature in the step 1 is 100-500 ℃; and (2) heating to the completely natural temperature of the raw materials of 350-500 ℃ in the step 1.
Further, the calcining temperature in the step 1 is 800-1000 ℃; and (3) calcining for 3-5 hours.
Further, the temperature of the pretreatment in the step 2 is 850-900 ℃; and 2, the pretreatment time is 2-8 hours.
Further, the reducing atmosphere in the step 2 is humidified hydrogen, and the volume of the water vapor in the reducing atmosphere accounts for 3-7%.
Further, the nano-particles precipitated after the reduction by the preparation method comprise an outer layer of FeOyOxide shell and internal Fe0.7Ru0.3An alloy core; the whole nano-particles have the size of 30-50 nm, wherein, FeOyThe thickness of the oxide shell layer is 2-3 nm.
The invention also provides application of the nano-catalyst loaded perovskite composite anode in preparation of a solid oxide fuel cell anode. The preparation method of the solid oxide fuel cell comprises the following steps:
step 1: PSFRNxPrecursor powder and Ce0.9Gd0.1O1.95(GDC) is mixed according to the mass ratio of 1: 1-1.5: 1, then corn starch accounting for 5% of the total mass of the powder is added, finally PVB-terpineol binder accounting for 10% of the mass fraction is added into the mixture, and repeated grinding is carried out to obtain anode slurry (PSFRN)x-GDC)。
Step 2: and uniformly brushing the slurry on an electrolyte sheet, and sintering at 1100 ℃ for 2-3 h to obtain the porous anode of the solid oxide fuel cell. La is adopted as electrolyte of single cell0.8Sr0.2Ga0.83Mg0.17O2.815(LSGM) electrolyte, cathode using La0.6Sr0.4Co0.2Fe0.8O2.8And Ce0.9Gd0.1O1.95Composite cathode (LSCF-GDC).
And step 3: before testing, carrying out reduction pretreatment on the anode of the single cell in a reducing atmosphere at 850-900 ℃, wherein the treatment time is 2-8 h. PSFRN inside pretreated anodexThe precursor is completely converted into FRA @ FO-RP-PSFRN, a large number of FRA @ FO core-shell nano particles are separated out on the surface, and the perovskite substrate is converted into Ruddlesden-Popper layered perovskite from cubic perovskite.
Further, the reducing atmosphere in the step 2 is humidified hydrogen, and the volume of the water vapor in the reducing atmosphere accounts for 3-7%.
Compared with the prior art, the invention has the beneficial effects that:
(1) PSFRN prepared by glycine combustion methodxThe precursor is in a porous coral structure. After reduction pretreatment, the obtained FRA @ FO-RP-PSFRN material has small particles, is loose and porous, and the FRA @ FO nano active particles separated out on the surface provide a large number of active sites for fuel catalysis, expand the three-phase interface of electrochemical reaction, have good fuel catalysis performance, and the composite anode is suitable for being used as an anode material of a solid oxide fuel cell.
(2) The strong metal-oxide interface effect between the nano particles on the surface of the FRA @ FO-RP-PSFRN material and the matrix can effectively avoid the problems of growth and agglomeration in the long-time operation process, so that the material has higher stability. At the same time, these nano-active particles can re-enter the host lattice after the oxidation treatment. By utilizing the special reversible oxidation-reduction behavior, the active particles can be regenerated through oxidation-reduction treatment in the actual operation process, and the service life of the catalyst is prolonged.
(3) The single cell with the anode material FRA @ FO-RP-PSFRN as an electrode, the LSGM as an electrolyte and the LSCF-GDC as a cathode realizes high power density output at 750-900 ℃ in hydrocarbon fuel.
Drawings
FIG. 1 is a PSFRN in example 1 of the present invention0.9XRD patterns of the precursor, the FRA @ FO-RP-PSFRN and the FRA @ FO-RP-PSFRN subjected to reoxidation treatment;
FIG. 2 is a PSFRN in example 1 of the present invention0.9SEM and TEM spectra of the precursor and FRA @ FO-RP-PSFRN;
fig. 3 is a graph of the output performance of the assembled cell of example 1 of the present invention when propane is used as the fuel.
Detailed Description
Example 1
PrSrFe loaded with nano-catalyst0.8Ru0.1Nb0.1O4+δThe precursor molecular formula of the perovskite composite anode is (Pr)0.5Sr0.5)0.9Fe0.8Ru0.1Nb0.1O3-βThe preparation method comprises the following steps:
step 1: synthesis (Pr)0.5Sr0.5)0.9Fe0.8Ru0.1Nb0.1O3-βPerovskite precursors, i.e. PSFRN0.9And (3) precursor.
5.87g of praseodymium nitrate hexahydrate, 2.86g of strontium nitrate, 9.70g of iron nitrate nonahydrate, 20.21mL of ruthenium (III) nitrosylnitrate (Ru 1.5% w/v),1.61g of niobium oxalate in 300mL of deionized water were added with 8.55g of glycine. Heating and stirring the obtained solution at 100 ℃ in a magnetic stirrer until a reddish brown viscous colloid is formed, and then heating to 500 ℃ to enable the colloid to be self-ignited to obtain black brown precursor powder. Grinding the precursor powder, and roasting at 800 ℃ for 3h in air atmosphere to obtain PSFRN0.9And (3) precursor powder.
PSFRN0.9XRD diffractogram of the precursor is shown as PSFRN in figure 10.9Shown by the diffraction curve, PSFRN0.9The precursor is ABO3A type single perovskite structure. In FIG. 2, a is PSFRN0.9SEM image of precursor, PSFRN0.9The surface morphology of the precursor is shown as a in fig. 2, the material has a coral-shaped structure, and the surface is smooth without the distribution of nano-particles.
Step 2: and carrying out reduction pretreatment on the material.
PSFRN0.9Putting the precursor powder into a tube furnace, and introducing 50 mL/min-1Humidifying hydrogen, the volume ratio of water vapor is 3%. Keeping the temperature at 900 ℃ for 2h, and then cooling to room temperature to obtain the perovskite composite anode material FRA @ FO-RP-PSFRN.
An XRD diffraction pattern of FRA @ FO-RP-PSFRN is shown as an FRA @ FO-RP-PSFRN diffraction curve in figure 1, and the RP-PSFRN matrix material has a Ruddlesden-Popper layered perovskite structure. An XRD diffraction pattern of FRA @ FO-RP-PSFRN shows a metal diffraction peak at about 44.5 degrees, which is caused by partial precipitation of Fe and Ru elements to form Fe0.7Ru0.3Caused by the alloy.
The XRD diffraction pattern of the FRA @ FO-RP-PSFRN obtained by the reoxidation treatment is shown as the diffraction curve of the reoxidation treated FRA @ FO-RP-PSFRN in figure 1. From the XRD diffractogram of the reoxidized FRA @ FO-RP-PSFRNIt is seen that the spectrum of the FRA @ FO-RP-PSFRN re-oxidized is changed to ABO3The FRA @ FO-RP-PSFRN material has good oxidation-reduction reversibility, and surface active particles can be regenerated through oxidation-reduction treatment in the actual operation process, so that the service life of the catalyst is prolonged.
And b in the figure 2 is an SEM image of FRA @ FO-RP-PSFRN, the surface micro-morphology of the FRA @ FO-RP-PSFRN is shown as b in the figure 2, the surface of the material is distributed with a large number of nano particles, and the size of the nano particles is 30-50 nm. The nano particles uniformly distributed on the surface provide a large number of active sites for catalytic reaction, and the three-phase region of the reaction is expanded. The TEM test was further performed on FRA @ FO-RP-PSFRN, the results of which are shown in c in FIG. 2 and d in FIG. 2. Wherein d in FIG. 2 is a partial enlarged view of c in FIG. 2, it can be seen that the nanoparticles distributed on the surface of FRA @ FO-RP-PSFRN are in a core-shell structure, FeOyThe thickness of the oxide shell layer is 2-3 nm.
The preparation method of the solid oxide fuel cell comprises the following steps:
step 1: 50mg of PSFRN0.9Precursor powder and Ce0.9Gd0.1O1.95(GDC) was mixed at a mass ratio of 1:1, then 5mg of corn starch was added, and finally 105mg of PVB-terpineol (mass ratio of PVB to terpineol is 1:9) binder was added to the mixture, and repeated grinding was performed to obtain anode slurry (PSFRN)0.9-GDC)。
Step 2: and uniformly brushing the slurry on an electrolyte sheet, and sintering at 1100 ℃ for 2h to obtain the porous anode of the solid oxide fuel cell. La is adopted as electrolyte of single cell0.8Sr0.2Ga0.83Mg0.17O2.815(LSGM) electrolyte, cathode using La0.6Sr0.4Co0.2Fe0.8O2.8And Ce0.9Gd0.1O1.95Composite cathode (LSCF-GDC).
And step 3: before testing, the anode of the single cell was subjected to a reduction pretreatment at 900 ℃ in a reducing atmosphere for 2 hours. Introducing 50 mL/min-1Humidifying hydrogen, the volume ratio of water vapor is 3%. In the anode after pretreatmentPSFRN of section0.9The precursor is completely converted into FRA @ FO-RP-PSFRN, a large number of FRA @ FO core-shell nano particles are separated out on the surface, and the perovskite substrate is converted into Ruddlesden-Popper layered perovskite from cubic perovskite. When in test, humidified propane gas is introduced, and the flow rate is 20 mL/min-1While introducing 20 mL/min-1As a carrier gas. The cathode uses static air as oxidizing gas.
As shown in FIG. 3, the maximum output powers of the battery at 900 deg.C, 850 deg.C, 800 deg.C and 750 deg.C were 0.762, 0.677, 0.537 and 0.374 W.cm respectively, which were obtained from a in FIG. 3-2The material has good catalytic performance. As the temperature decreases, the open circuit voltage of the battery increases, consistent with the theoretical voltage trend with temperature. 0.15A cm is applied to the battery at 750 DEG C-2The current density was tested for 100h stability and the results are shown in fig. 3 b: after undergoing a brief decay, the voltage remained around 0.75V in subsequent tests, indicating that FRA @ FO-RP-PSFRN exhibits good stability in hydrocarbon fuels.
Example 2
PrSrFe loaded with nano-catalyst0.8Ru0.1Nb0.1O4+δThe precursor molecular formula of the perovskite composite anode is Pr0.5Sr0.5Fe0.8Ru0.1Nb0.1O3-βThe preparation method comprises the following steps:
step 1: synthesis of Pr0.5Sr0.5Fe0.8Ru0.1Nb0.1O3-βPerovskite precursors, i.e. PSFRN1.0And (3) precursor.
6.53g of praseodymium nitrate hexahydrate, 3.17g of strontium nitrate, 9.70g of ferric nitrate nonahydrate, 20.21mL of ruthenium (III) nitrosylnitrate (Ru 1.5% w/v),1.61g of niobium oxalate in 300mL of deionized water were added with 9.01g of glycine. Heating and stirring the obtained solution at 250 ℃ in a magnetic stirrer until a reddish brown viscous colloid is formed, and then heating to 500 ℃ to enable the colloid to be self-ignited to obtain black brown precursor powder. Grinding the precursor powder, and roasting at 800 ℃ for 3h in air atmosphere to obtain ABO3Type single perovskite PSFRN1.0And (3) precursor powder.
Step 2: and carrying out reduction pretreatment on the material.
PSFRN1.0Putting the precursor powder into a tube furnace, and introducing 50 mL/min-1Humidifying hydrogen, the volume ratio of water vapor is 3%. Keeping the temperature at 900 ℃ for 2h, and then cooling to room temperature to obtain the perovskite composite anode material FRA @ FO-RP-PSFRN.
The preparation method of the solid oxide fuel cell comprises the following steps:
step 1: 50mg of PSFRN1.0Precursor powder and Ce0.9Gd0.1O1.95(GDC) was mixed at a mass ratio of 1:1, then 5mg of corn starch was added, and finally 105mg of PVB-terpineol (mass ratio of PVB to terpineol is 1:9) binder was added to the mixture, and repeated grinding was performed to obtain anode slurry (PSFRN)1.0-GDC)。
Step 2: and uniformly brushing the slurry on an electrolyte sheet, and sintering at 1100 ℃ for 2h to obtain the porous anode of the solid oxide fuel cell. La is adopted as electrolyte of single cell0.8Sr0.2Ga0.83Mg0.17O2.815(LSGM) electrolyte, cathode using La0.6Sr0.4Co0.2Fe0.8O2.8And Ce0.9Gd0.1O1.95Composite cathode (LSCF-GDC).
And step 3: before testing, the anode of the single cell was subjected to a reduction pretreatment at 900 ℃ in a reducing atmosphere for 2 hours. Introducing 50 mL/min-1Humidifying hydrogen, the volume ratio of water vapor is 3%. PSFRN inside pretreated anode1.0The precursor is completely converted into FRA @ FO-RP-PSFRN, a large number of FRA @ FO core-shell nano particles are separated out on the surface, and the perovskite substrate is converted into Ruddlesden-Popper layered perovskite from cubic perovskite. When in test, humidified propane gas is introduced, and the flow rate is 20 mL/min-1While introducing 20 mL/min-1As a carrier gas. The cathode uses static air as oxidizing gas.
The maximum output power of the battery at 900 deg.C, 850 deg.C, 800 deg.C and 750 deg.C is 0.620, 0.575, 0.506, 0.464 W.cm-2. At 750 deg.C for batteryIs applied with 0.15A cm-2The current density is subjected to a stability test for 100h, the voltage is kept about 0.7V in the test, and the operation stability is good.
Example 3
PrSrFe loaded with nano-catalyst0.8Ru0.1Nb0.1O4+δThe precursor molecular formula of the perovskite composite anode is Pr0.5Sr0.5Fe0.8Ru0.1Nb0.1O3-βThe preparation method comprises the following steps:
step 1: synthesis of Pr0.5Sr0.5Fe0.8Ru0.1Nb0.1O3-βPerovskite precursors, i.e. PSFRN1.0And (3) precursor.
6.53g of praseodymium nitrate hexahydrate, 3.17g of strontium nitrate, 9.70g of ferric nitrate nonahydrate, 20.21mL of ruthenium (III) nitrosylnitrate (Ru 1.5% w/v),1.61g of niobium oxalate in 300mL of deionized water were added with 9.01g of glycine. Heating and stirring the obtained solution at 100 ℃ in a magnetic stirrer until a reddish brown viscous colloid is formed, and then heating to 500 ℃ to enable the colloid to be self-ignited to obtain black brown precursor powder. Grinding the precursor powder, and roasting at 800 ℃ for 3h in air atmosphere to obtain ABO3Type single perovskite PSFRN1.0And (3) precursor powder.
Step 2: and carrying out reduction pretreatment on the material.
PSFRN1.0Putting the precursor powder into a tube furnace, and introducing 50 mL/min-1Humidifying hydrogen, the water vapor volume ratio is 7%. Keeping the temperature at 900 ℃ for 2h, and then cooling to room temperature to obtain the perovskite composite anode material FRA @ FO-RP-PSFRN.
The preparation method of the solid oxide fuel cell comprises the following steps:
step 1: 50mg of PSFRN1.0Precursor powder and Ce0.9Gd0.1O1.95(GDC) was mixed at a mass ratio of 1:1, then 5mg of corn starch was added, and finally 105mg of PVB-terpineol (mass ratio of PVB to terpineol is 1:9) binder was added to the mixture, and repeated grinding was performed to obtain anode slurry (PSFRN)1.0-GDC)。
Step 2: and uniformly brushing the slurry on an electrolyte sheet, and sintering at 1100 ℃ for 2h to obtain the porous anode of the solid oxide fuel cell. La is adopted as electrolyte of single cell0.8Sr0.2Ga0.83Mg0.17O2.815(LSGM) electrolyte, cathode using La0.6Sr0.4Co0.2Fe0.8O2.8And Ce0.9Gd0.1O1.95Composite cathode (LSCF-GDC).
And step 3: before testing, the anode of the single cell was subjected to a reduction pretreatment at 900 ℃ in a reducing atmosphere for 2 hours. Introducing 50 mL/min-1Humidifying hydrogen, the water vapor volume ratio is 7%. PSFRN inside pretreated anode1.0The precursor is completely converted into FRA @ FO-RP-PSFRN, a large number of FRA @ FO core-shell nano particles are separated out on the surface, and the perovskite substrate is converted into Ruddlesden-Popper layered perovskite from cubic perovskite. When in test, humidified propane gas is introduced, and the flow rate is 20 mL/min-1While introducing 20 mL/min-1As a carrier gas. The cathode uses static air as oxidizing gas.
The maximum output power of the battery at 900 deg.C, 850 deg.C, 800 deg.C and 750 deg.C is 0.720, 0.625, 0.513, 0.328 W.cm-2. 0.15A cm is applied to the battery at 750 DEG C-2The current density is subjected to a stability test for 100h, the voltage is kept at about 0.73V in the test, and the operation stability is good.
The above detailed description is only intended to explain the objects, technical embodiments and practical effects of the present invention in further detail, but the scope of the present invention is not limited thereto, and any modifications, equivalent substitutions and the like within the technical scope of the present invention disclosed herein are intended to be included within the scope of the present invention.
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| CN115133042A (en) * | 2022-07-05 | 2022-09-30 | 山东科技大学 | High-activity anti-carbon deposition solid oxide fuel cell anode catalyst |
| CN118572135A (en) * | 2024-06-03 | 2024-08-30 | 渤海大学 | An in-situ constructed nano heterostructure composite cathode material and its preparation method and application |
| CN119601685A (en) * | 2024-11-18 | 2025-03-11 | 佛山仙湖实验室 | Perovskite fuel electrode and preparation method thereof, reversible solid oxide battery |
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