CN113363543B - Solid oxide cell fuel electrode material, preparation method thereof and solid oxide cell - Google Patents
Solid oxide cell fuel electrode material, preparation method thereof and solid oxide cell Download PDFInfo
- Publication number
- CN113363543B CN113363543B CN202110609845.0A CN202110609845A CN113363543B CN 113363543 B CN113363543 B CN 113363543B CN 202110609845 A CN202110609845 A CN 202110609845A CN 113363543 B CN113363543 B CN 113363543B
- Authority
- CN
- China
- Prior art keywords
- solid oxide
- fuel electrode
- powder
- electrode material
- oxide cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inert Electrodes (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention provides a solid oxide cell fuel electrode material, which has a chemical formula shown in a formula I: m 2 Fe 1+x Mo 1‑x O 6‑δ Cl y Formula I; wherein M is an alkaline earth metal, x is more than or equal to 0 and less than or equal to 1,0, and y is less than 0.1; the preferred exposed crystal face of the solid oxide cell fuel electrode material is a (100) face. The Cl element is a doping agent and a powder morphology regulator, the fuel electrode material SFM is subjected to Cl doping, under the high-temperature condition, the chlorate is in a liquid phase and is coated on the surface of the precursor, the precursor nucleates and grows in the molten chlorate until the chlorate is consumed, the growth stops, the specific (100) crystal face is exposed, and the appearance and the morphology of the powder are regular cubic blocks. The Cl-doped powder has larger specific surface area, and can prepare a large amount of cubic morphology powder with a crystal face preferred to be exposed as (100). The invention also provides a preparation method of the solid oxide cell fuel electrode material and a solid oxide cell.
Description
Technical Field
The invention belongs to the technical field of solid oxide cells, and particularly relates to a solid oxide cell fuel electrode material, a preparation method thereof and a solid oxide cell.
Background
A Solid Oxide Cell (SOC) is a clean and efficient energy conversion device, and can be divided into a Solid Oxide Fuel Cell (SOFC) and a Solid Oxide Electrolysis Cell (SOEC) according to different operation modes, the SOFC can directly convert chemical energy in fuel into electric energy, and the SOEC can convert abundant electric energy into chemical energy for storage, and the two are operated reversibly. The SOC is mainly composed of a fuel electrode, an air electrode, and an electrolyte. Among other things, the properties of the fuel electrode material directly affect the electrochemical performance of the overall cell.
The most commonly used fuel electrode material is a cermet electrode material, such as Ni-YSZ. Wherein, the metal Ni has higher catalytic activity and electronic conductivity, and the ceramic phase YSZ has better oxygen ion conductivity, so the material has excellent electrochemistry property in fuel. However, it has been further investigated that when hydrocarbon fuels are used, cermet fuels are highly susceptible to carbon deposition and sulfur poisoning, and their redox cycle performance is poor. To overcome the disadvantages of cermet fuel electrodes, ABO has been proposed in recent years 3 Mixed ionic-electronic conductor perovskite fuel electrode materials of the general formula have attracted considerable attention. Wherein the chemical composition is M 2 Fe 1+x Mo 1- x O 6-δ The fuel electrode material (M is alkaline earth metal element) has proper conductivity, better oxidation-reduction stability, stronger carbon deposition resistance and excellent electrochemical performance, and is the most promising perovskite fuel electrode material at present.
M 2 Fe 1+x Mo 1-x O 6-δ There are various methods for preparing the fuel electrode material, for example, a solid phase reaction method, an ethylenediaminetetraacetic acid (EDTA) -citric acid combustion method. In the preparation methods, the powder phase forming temperature is high, usually above 1000 ℃, and the nano powder is easy to agglomerate and coarsen under the high temperature condition, so that the prepared SFM powder has random crystal face orientation and appearance, and the specific surface area is relatively small, so that the electrode catalytic reaction active area is reduced.
Disclosure of Invention
The invention aims to provide a solid oxide cell fuel electrode material, a preparation method thereof and a solid oxide cell, wherein the fuel electrode powder prepared by the invention has a regular cubic morphology, the preferred crystal face exposure surface is (100), the grain size is 50-200nm, the specific surface area is large, the catalytic activity is high, and the solid oxide cell fuel electrode material can be prepared in a large scale and is beneficial to the application in the field of solid oxide cells.
The invention provides a solid oxide cell fuel electrode material, which has a chemical formula shown in a formula I:
M 2 Fe 1+x Mo 1-x O 6-δ Cl y formula I;
wherein M is an alkaline earth metal, x is more than or equal to 0 and less than or equal to 1,0 is less than or equal to y is less than 0.1; the preferred exposed crystal face of the solid oxide cell fuel electrode material is a (100) face.
Preferably, M is one or more of Ca, sr and Ba.
The invention provides a method for preparing a solid oxide cell fuel electrode material as described above, comprising the steps of:
a) Dissolving soluble alkaline earth metal salt, soluble ferric salt, soluble molybdenum salt and chlorine source in secondary distilled water according to the stoichiometric ratio of the formula I to obtain metal salt solution;
b) Adding citric acid and glycine into the metal salt solution to perform a complex reaction to obtain a complex solution;
c) Heating the complexing solution until spontaneous combustion reaction occurs to obtain powder;
d) And (3) calcining the powder at high temperature to obtain the solid oxide cell fuel electrode material shown in the formula I.
Preferably, the soluble alkaline earth metal salt is an alkaline earth metal nitrate; the soluble ferric salt is ferric nitrate, and the soluble molybdenum salt is (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O。
Preferably, the chlorine source is SrCl 2 And/or FeCl 3 。
Preferably, the molar ratio of the total amount of metal ions, citric acid and glycine in the metal salt solution is 1: (0.1-0.5): (2-3).
Preferably, the heating temperature in the step C) is 200-400 ℃.
Preferably, the temperature of the high-temperature calcination in the step D) is 800-1200 ℃; the high-temperature calcination time is 1-10 hours.
Preferably, the high-temperature calcination in step D) is performed in an air atmosphere.
The invention provides a solid oxide cell, which is characterized by comprising the solid oxide cell fuel electrode material.
The invention provides a solid oxide cell fuel electrode material, which has a chemical formula shown in a formula I: m 2 Fe 1+x Mo 1- x O 6-δ Cl y Formula I; wherein M is an alkaline earth metal, x is more than or equal to 0 and less than or equal to 1,0, and y is less than 0.1; the preferred exposed crystal face of the solid oxide cell fuel electrode material is a (100) face. The Cl element is a doping agent and a powder morphology regulator, and is beneficial to the low melting point of the chloride, the fuel electrode material SFM is subjected to Cl doping (the doping amount is less than 0 < y < 0.1), the chloride is in a liquid phase and is coated on the surface of a precursor under the high-temperature condition, the precursor nucleates and grows in the molten chloride until the chloride is completely consumed, the growth stops, a specific (100) crystal face is exposed, and the appearance and morphology of the powder are in a regular cubic block. Compared with a hydrothermal synthesis method, the method is more beneficial to preparing a large amount of regular cubic powder. With undoped Sr 2 Fe 1.5 Mo 0.5 O 6-δ (SFM) compared with Cl-doped powder in the invention, the Cl-doped powder has larger specific surface area than the typical La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3-δ (LSGM) and Sm 0.2 Ce 0.8 O 2-δ (SDC) electrolytes have good chemical compatibility. The Cl doping can obviously improve the electrochemical performance of the fuel electrode, the Cl element is cheap and easy to obtain, the method is simple to operate, and the cubic morphology powder with the crystal face of (100) preferred exposure face can be prepared in large quantity, thereby being beneficial to mechanism research and practical application in the solid oxide cell fuel electrode.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 shows Sr in example 1 of the present invention 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 (SFM-Cl 0.05 )、Sr 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.1 (SFM-Cl 0.1 ) And Sr 2 Fe 1.5 Mo 0.5 O 6-δ (SFM) X-ray diffraction pattern of the powder at room temperature;
FIG. 2 shows Sr in example 1 of the present invention 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 Scanning electron micrographs of the powder;
FIG. 3 shows Sr in example 1 of the present invention 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 A high-resolution transmission electron micrograph and a corresponding Fourier transform map of the powder;
FIG. 4 shows Sr in example 1 of the present invention 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 A high-resolution transmission electron morphology graph of the powder and a corresponding selected area electron diffraction graph;
FIG. 5 shows Sr in example 1 of the present invention 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.1 Scanning electron micrographs of the powder;
FIG. 6 shows Sr in example 1 of the present invention 2 Fe 1.5 Mo 0.5 O 6-δ Scanning electron micrographs of the powder;
FIG. 7 shows Sr in example 1 of the present invention 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 Adsorption and desorption curves of the powder;
FIG. 8 shows Sr in example 1 of the present invention 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 (SFM-Cl 0.05 ) LSGM, SDC, and Sr 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 (SFM-Cl 0.05 ) Respectively mixing the obtained product with LSGM and SDC according to the mass ratio of 1:1, and calcining the obtained product for 2 hours at 1050 ℃ in an air atmosphere;
FIG. 9 shows Sr in example 1 of the present invention 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 The powder is a fuel electrode, the hydrogen is a fuel, and the electrochemical performance of a single cell is at 750 ℃.
Detailed Description
The invention provides a solid oxide cell fuel electrode material, which has a chemical formula shown in a formula I:
M 2 Fe 1+x Mo 1-x O 6-δ Cl y formula I;
wherein, M is alkaline earth metal, x is more than or equal to 0 and less than or equal to 1,0 and more than y is less than 0.1; the preferred exposed crystal face of the solid oxide cell fuel electrode material is a (100) face.
In the present invention, M is preferably one or more of Ca, sr and Ba, x is 0. Ltoreq. X.ltoreq.1, such as 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and preferably ranges in which the above values are upper or lower limits. 0 < y < 0.1, such as 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, preferably in the upper or lower range. Specifically, the solid oxide cell fuel electrode material is Sr 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 . In addition, the delta is the non-stoichiometry of oxygen, the specific numerical value is uncertain, the delta value is related to the properties, the temperature, the atmosphere and the like of the material, the delta value is not limited generally, and the content of oxygen in the chemical formula can be directly expressed as O 6-δ 。
In the invention, the solid oxide cell fuel electrode material has a regular cubic morphology, the preferred crystal face exposure surface is (100), and the grain size is 50-200 nm.
The invention also provides a preparation method of the solid oxide cell fuel electrode material, which comprises the following steps:
a) Dissolving soluble alkaline earth metal salt, soluble ferric salt, soluble molybdenum salt and chlorine source in secondary distilled water according to the stoichiometric ratio of the formula I to obtain metal salt solution;
b) Adding citric acid and glycine into the metal salt solution to perform a complex reaction to obtain a complex solution;
c) Heating the complexing solution until spontaneous combustion reaction occurs to obtain powder;
d) And (3) calcining the powder at high temperature to obtain the solid oxide cell fuel electrode material shown in the formula I.
In the present invention, the soluble alkaline earth metal salt is an alkaline earth metal nitrate, such as Sr (NO) 3 ) 2 、Ca(NO 3 ) 2 And Ba (NO) 3 ) 2 One or more of the above; the soluble ferric salt is ferric nitrate, and the soluble molybdenum salt is (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O。
In the present invention, the chlorine source is preferably SrCl 2 And/or FeCl 3 The chlorine source in the invention has double functions, and is a dopant to change chemical composition, and is a powder morphology regulator to change crystal face preferred orientation and powder morphology.
However, the chlorine source can play the above dual role on the premise that the substitution of the element Cl can only be slight, because the element Cl in the chlorine source can substitute the position of the element O, it is worth noting that the ionic radius (vi, 0.181 nm) of Cl is far larger than that (vi, 0.140 nm) of O, and if the element Cl is excessive, all the element Cl cannot be doped into the crystal lattice of the perovskite, i.e., a pure phase cannot be obtained. Therefore, the preparation method of the solid oxide cell fuel electrode material can also be regarded as a method for preferentially exposing the crystal face of the SFM material and regulating and controlling the morphology.
In the present invention, the soluble alkaline earth metal salt, the soluble iron salt, the soluble molybdenum salt and the chlorine source are used in the stoichiometric ratio in formula I, and the present invention will not be described in detail herein.
In the present invention, the solution contains all the metal ions required in formula I, and the total amount of metal ions, glycine and citric acid are preferably in a molar ratio of 1: (2-3): (0.1 to 0.5), more preferably 1: (0.2-0.4): (2.5 to 3), most preferably 1:0.3:2.5.
the invention preferably stirs the obtained solution for 1-5 hours to fully complex the solution, and then heats the obtained complex solution to dry the water until spontaneous combustion reaction occurs to obtain brownish black sponge powder.
In the present invention, the heating temperature is preferably 200 to 400 ℃, more preferably 300 ℃.
Collecting the brown black powder, grinding, and calcining at high temperature in air atmosphere to obtain M 2 Fe 1+x Mo 1-x O 6-δ Cl y Solid oxide cell fuel electrode materials.
In the present invention, the temperature of the high-temperature calcination phase is preferably 800 to 1200 ℃, more preferably 900 to 1100 ℃, such as 800 ℃,900 ℃,1000 ℃,1100 ℃,1200 ℃, and preferably any of the above values is an upper limit or a lower limit. The high-temperature calcination is preferably carried out for 1 to 10 hours, more preferably for 3 to 8 hours, most preferably for 5 to 6 hours,
the invention also provides a solid oxide cell comprising a fuel electrode, an air electrode, an electrolyte and a current collector, wherein the fuel electrode comprises the solid oxide cell fuel electrode material, and the air electrode, the electrolyte and the current collector are all the air electrode, the electrolyte and the current collector commonly used in the field.
In the present invention, when the solid oxide cell is operated as a solid oxide fuel cell, the fuel electrode is used as an anode, and when the solid oxide cell is operated as a solid oxide electrolysis cell, the fuel electrode is used as a cathode.
The invention provides a solid oxide cell fuel electrode material, which has a chemical formula shown in a formula I: m is a group of 2 Fe 1+x Mo 1- x O 6-δ Cl y Formula I; wherein M is an alkaline earth metal, x is more than or equal to 0 and less than or equal to 1,0, and y is less than 0.1; the preferred exposed crystal face of the solid oxide cell fuel electrode material is a (100) face. The Cl element is a doping agent and a powder morphology regulator, and is beneficial to the low melting point of the chlorate, the fuel electrode material SFM is subjected to Cl doping (the doping amount is less than 0 < y < 0.1), the chlorate is in a liquid phase and is coated on the surface of a precursor under the condition of high temperature phase formation, the precursor nucleates and grows in the chlorate until the chlorate is completely consumed, the growth stops, a specific (100) crystal face is exposed, and the appearance and morphology of the powder are in a regular cubic block. Compared with a hydrothermal synthesis method, the method is more beneficial to preparing a large amount of regular cubic powder. Compared with undoped SFMThe Cl-doped powder has larger specific surface area and is similar to the typical La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3-δ (LSGM) and Sm 0.2 Ce 0.8 O 2-δ (SDC) electrolytes have good chemical compatibility. The Cl doping can obviously improve the electrochemical performance of the fuel electrode, the Cl element is cheap and easy to obtain, the method is simple to operate, and the cubic morphology powder with the crystal face of (100) preferred exposure face can be prepared in large quantity, thereby being beneficial to mechanism research and practical application in the solid oxide cell fuel electrode.
In order to further illustrate the present invention, the following will describe a solid oxide cell fuel electrode material, a method for preparing the same, and a solid oxide cell in detail with reference to the examples, but the scope of the invention should not be construed as being limited thereto.
Example 1 preparation of Sr with cubic morphology having (100) crystal face preferred to be exposed by anionic Cl-doped assisted citric acid-glycinate combustion method 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 Powder body
Synthesis of Sr 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 The raw material of the powder is Sr (NO) 3 ) 2 ，Fe(NO 3 ) 3 ·9H 2 O，(NH 4 ) 6 Mo 7 O 24 ·4H 2 O，SrCl 2 Citric acid and glycine, the above reagent purities are analytically pure. According to Sr 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 Respectively weighing raw material Sr (NO) 3 ) 2 ，Fe(NO 3 ) 3 ·9H 2 O and (NH) 4 ) 6 Mo 7 O 24 ·4H 2 Dissolving O in redistilled water, adding SrCl 2 As a doping agent and a powder morphology regulator, forming a metal salt solution, then respectively adding citric acid and glycine as a complexing agent and a combustion agent, in the weighing process, ensuring that the mass ratio of total metal ions, citric acid and glycine in the solution is 1.3Combining; transferring the fully complexed solution to a heating table until a combustion reaction occurs to obtain brownish black sponge powder; collecting and grinding the powder, and finally calcining the powder in a muffle furnace at 1100 ℃ for 5 hours to obtain Sr with a cubic morphology with a crystal face of (100) being preferentially exposed 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 And (3) powder.
For comparison, 1) undoped Sr was synthesized according to the similar procedure as above 2 Fe 1.5 Mo 0.5 O 6-δ Powder and 2) Sr with Cl element doping amount of 0.1 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.1 Powder, synthesis method and Sr 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 The synthesis methods are basically the same, and the only difference is that 1) SrCl is not added 2 As a doping agent and a powder morphology regulator 2) the doping amount of Cl element is 0.1. The specific method comprises the following steps:
2 1.5 0.5 6-δ 0.05 phase structure analysis of SrFeMoOCl powder
Sr synthesized in example 1 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 、Sr 2 Fe 1.5 Mo 0.5 O 6-δ Powder and Sr 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.1 X-ray diffraction (XRD) analysis of the powder showed that the powder was mixed with Sr as shown in FIG. 1 2 Fe 1.5 Mo 0.5 O 6-δ In contrast, cl doping with x =0.05 did not produce a hetero-phase, demonstrating successful doping of Cl into Sr 2 Fe 1.5 Mo 0.5 O 6-δ Does not change the phase structure even when doped, sr 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 And Sr 2 Fe 1.5 Mo 0.5 O 6-δ All have cubic perovskite structures; when the doping amount x =0.1, a small amount of SrMoO is generated 4 Impure phase, pure phase cannot be obtained.
2 1.5 0.5 6-δ 0.05 SrFeMoOCl powderPreferred orientation of crystal face and shape analysis of body
Sr synthesized in example 1 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 The powder is subjected to shape characterization after ultrasonic dispersion in ethanol, the Cl doping obviously changes the appearance and the shape of the powder and the preferred orientation of crystal faces, sr 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 The scanning electron micrograph of the powder is shown in figure 2, the powder is in the shape of a nano-scale cube, the size is uniform, the size of crystal grains is between 50 and 200nm, and the smaller size means a larger specific surface area, so that the active area of electrochemical reaction is increased, the improvement of the cell performance is facilitated, and the application of the powder in a solid oxide cell fuel electrode is facilitated. FIG. 3 is Sr 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 The Fourier transform image of the high-resolution transmission electron micrograph of the powder also proves Sr 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 The crystal face is a (100) face; to further determine Sr 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 The crystal face exposed by the powder performs selective electron diffraction on the whole crystal grain, the experimental result is shown in fig. 4, and the experiment result proves that the crystal face of the powder is preferentially exposed as (100), and the specific crystal face is beneficial to the mechanism research and application of a fuel electrode in the field of solid oxide batteries.
FIG. 5 shows Sr 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.1 The scanning electron microscope image of the powder can be seen from fig. 5, the morphology is cubic, but the grain size is increased to 1000nm, which is not beneficial to be used as an electrode material, and the surface of the grain is covered with small particles, which may be impurities, and this is consistent with the result of the non-phase XRD in fig. 1.
FIG. 6 is Sr 2 Fe 1.5 Mo 0.5 O 6-δ Scanning Electron micrograph of the powder, as can be seen from FIG. 6, when SrCl was not added 2 When the doped form is used as a doping agent and a powder form regulator, the form is not cubic, and further illustrates that in the application, a small amount of Cl doping (doping amount: 0 < y < 0.1) is used for regulating the form and chemical composition of the powderIs critical.
2 1.5 0.5 6-δ 0.05 Specific surface area test of SrFeMoOCl powder
Sr is measured by adopting a full-automatic specific surface area and porosity analyzer 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 N of powder 2 The adsorption and desorption isotherms are shown in FIG. 7, and the results of the experiment are shown in FIG. 7, and Sr is calculated by combining the multi-layer adsorption model (BET theory) proposed in Brunauer, emmertt and Teller 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 The specific surface area of the powder was 5.73m 2 g -1 The high specific surface area increases the reactive sites of the fuel electrode, and is beneficial to improving the electrochemical performance of the fuel electrode.
2 1.5 0.5 6-δ 0.05 Compatibility research of SrFeMoOCl powder and electrolyte material
To verify Sr 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 The possibility of applying the powder in the field of solid oxide fuel cells is further researched to obtain Sr 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 Chemical compatibility of the powder and a typical electrolyte material, wherein the electrolyte material is La with a perovskite structure 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3-δ (LSGM) and Sm having fluorite structure 0.2 Ce 0.8 O 2-δ (SDC), the specific experimental step is that Sr is weighed according to the mass ratio of 1:1 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 And electrolyte powder, which is placed in an agate mortar to be fully ground until the electrolyte powder is uniformly mixed, the uniformly mixed powder is placed in a muffle furnace to be treated for 2 hours at 1050 ℃, the powder is respectively subjected to XRD (X-ray diffraction) characterization after being cooled to room temperature along with the furnace, and the result is shown in figure 8, even though the high-temperature treatment is carried out, the diffraction powder of the mixed powder is completely attributed to Sr 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 Or electrolyte material, without unwanted hetero-peaksIs detected, proving Sr 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 The powder does not chemically react with a typical electrolyte material LSGM or SDC in battery preparation and test, and has better chemical compatibility with the typical electrolyte material.
2 1.5 0.5 6-δ 0.05 Research on electrochemical performance of SrFeMoOCl powder
To study Sr 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 The electrochemical performance of the powder as the fuel electrode material of the solid oxide cell is Sr 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 Is fuel electrode, LSGM is electrolyte, la 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ Is an air electrode and is assembled with a structure of Sr 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 /LSGM/La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ The electrochemical performance of the single cell is characterized, and the result is shown in figure 9, the maximum power density measured at 750 ℃ is 640mW cm by taking humid hydrogen as fuel -2 The performance is much higher than that of Sr 2 Fe 1.5 Mo 0.5 O 6-δ The performance of the fuel electrode is that high catalytic activity is related to large specific surface area, specific crystal face orientation and powder morphology, sr 2 Fe 1.5 Mo 0.5 O 6-δ Cl 0.05 Is favorable for being used as a fuel electrode material of a solid oxide cell.
According to the embodiments, the low-melting-point chloride is used as the dopant and the powder morphology regulator, and the anionic Cl doping assisted citric acid-glycinate combustion method is adopted to prepare the powder; the preferred crystal face exposed surface of the powder prepared by the method is (100), the powder is in the shape of a nano-scale cube, the grain size is 50-200nm, the specific surface area is large, the catalytic activity is high, and the powder has better compatibility with typical electrolytes LSGM and SDC. The Cl element is cheap and easy to obtain, and the method is simple to operate, easy to prepare in large quantities and beneficial to application in the field of solid oxide batteries.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (8)
1. A solid oxide cell fuel electrode material having the formula of formula I:
Sr 2 Fe 1.5 Mo 0.5 O δ6- Cl 0.05 formula I;
the preferred exposed crystal face of the solid oxide cell fuel electrode material is a (100) face, and the solid oxide cell fuel electrode material has a regular nanoscale cubic morphology.
2. The method for preparing a solid oxide cell fuel electrode material according to claim 1, comprising the steps of:
a) Dissolving soluble strontium salt, soluble ferric salt, soluble molybdenum salt and chlorine source in secondary distilled water according to the stoichiometric ratio of the formula I to obtain a metal salt solution;
the chlorine source is SrCl 2 And/or FeCl 3 ；
B) Adding citric acid and glycine into the metal salt solution to perform a complex reaction to obtain a complex solution;
c) Heating the complexing solution until spontaneous combustion reaction occurs to obtain powder;
d) And (3) calcining the powder at a high temperature of 800-1200 ℃ to obtain the solid oxide battery fuel electrode material shown in the formula I.
3. The method of claim 2 wherein the soluble strontium salt is a nitrate salt of strontium; the soluble ferric salt is ferric nitrate, and the soluble molybdenum salt is (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O。
4. The method according to claim 2, wherein the molar ratio of the total amount of metal ions in the metal salt solution to citric acid and glycine is 1: (0.1 to 0.5): (2~3).
5. The method according to claim 2, wherein the heating temperature in the step C) is 200 to 400 ℃.
6. The method according to claim 2, wherein the high-temperature calcination is carried out for 1 to 10 hours.
7. The method of claim 2, wherein the high-temperature calcination in step E) is performed in an air atmosphere.
8. A solid oxide cell comprising the solid oxide cell fuel electrode material of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110609845.0A CN113363543B (en) | 2021-06-01 | 2021-06-01 | Solid oxide cell fuel electrode material, preparation method thereof and solid oxide cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110609845.0A CN113363543B (en) | 2021-06-01 | 2021-06-01 | Solid oxide cell fuel electrode material, preparation method thereof and solid oxide cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113363543A CN113363543A (en) | 2021-09-07 |
| CN113363543B true CN113363543B (en) | 2022-12-30 |
Family
ID=77530998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110609845.0A Active CN113363543B (en) | 2021-06-01 | 2021-06-01 | Solid oxide cell fuel electrode material, preparation method thereof and solid oxide cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113363543B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110107187A (en) * | 2010-03-24 | 2011-09-30 | 삼성전자주식회사 | Metal doping oxide particle, preparation method thereof, and solid oxide electrolyte using the same |
| CN108281677A (en) * | 2018-01-26 | 2018-07-13 | 成都新柯力化工科技有限公司 | A kind of fuel cell anode materials and preparation method of double perovskite |
| CN109742414A (en) * | 2019-01-09 | 2019-05-10 | 渤海大学 | A kind of intermediate temperature solid oxide fuel cell cathode material and the preparation method and application thereof |
| CN110581283A (en) * | 2019-09-19 | 2019-12-17 | 中国科学技术大学 | Bismuth-doped solid oxide cell fuel electrode material and preparation method and application thereof |
| CN111908512A (en) * | 2020-07-17 | 2020-11-10 | 内蒙古科技大学 | O-site halogen element doped perovskite oxide and application thereof in symmetric battery |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5196502B2 (en) * | 2007-01-31 | 2013-05-15 | テクニカル ユニヴァーシティー オブ デンマーク | Composite material suitable for use as an electrode material in SOC |
| DE112009003518T5 (en) * | 2008-12-11 | 2012-08-23 | Ezelleron Gmbh | Anode material for high temperature fuel cells |
-
2021
- 2021-06-01 CN CN202110609845.0A patent/CN113363543B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110107187A (en) * | 2010-03-24 | 2011-09-30 | 삼성전자주식회사 | Metal doping oxide particle, preparation method thereof, and solid oxide electrolyte using the same |
| CN108281677A (en) * | 2018-01-26 | 2018-07-13 | 成都新柯力化工科技有限公司 | A kind of fuel cell anode materials and preparation method of double perovskite |
| CN109742414A (en) * | 2019-01-09 | 2019-05-10 | 渤海大学 | A kind of intermediate temperature solid oxide fuel cell cathode material and the preparation method and application thereof |
| CN110581283A (en) * | 2019-09-19 | 2019-12-17 | 中国科学技术大学 | Bismuth-doped solid oxide cell fuel electrode material and preparation method and application thereof |
| CN111908512A (en) * | 2020-07-17 | 2020-11-10 | 内蒙古科技大学 | O-site halogen element doped perovskite oxide and application thereof in symmetric battery |
Non-Patent Citations (2)
| Title |
|---|
| Yanli Zhang等.Effect of Cl doping on the electrochemical performance of Sr2Fe1.5Mo0.5O6−δ cathode material for solid oxide fuel cells.《Ceramics International》.2020,第46卷(第14期), * |
| 侯明月.中温固体氧化物燃料电池Sr2Fe1.5Mo0.5O6‑δ电极材料改性研究.《中国优秀硕士学位论文全文数据库（工程科技II辑）》.2015,第2015卷(第07期), * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113363543A (en) | 2021-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xue et al. | Transition metal oxide-based oxygen reduction reaction electrocatalysts for energy conversion systems with aqueous electrolytes | |
| Teng et al. | Efficient water splitting through solid oxide electrolysis cells with a new hydrogen electrode derived from A-site cation-deficient La0. 4Sr0. 55Co0. 2Fe0. 6Nb0. 2O3-δ perovskite | |
| CN110581283B (en) | Bismuth-doped solid oxide cell fuel electrode material and preparation method and application thereof | |
| Jin et al. | Effect of nonequivalent substitution of Pr 3+/4+ with Ca 2+ in PrBaCoFeO 5+ δ as cathodes for IT-SOFC | |
| Chen et al. | Development of intertwined nanostructured multi-phase air electrodes for efficient and durable reversible solid oxide cells | |
| Jeerh et al. | Perovskite oxide LaCr0. 25Fe0. 25Co0. 5O3-δ as an efficient non-noble cathode for direct ammonia fuel cells | |
| Yu et al. | High negative voltage activating perovskite oxide with bi-vacancy synergistic regulation for water oxidation | |
| Ansari et al. | Unraveling the evolution of exsolved Fe–Ni alloy nanoparticles in Ni-doped La 0.3 Ca 0.7 Fe 0.7 Cr 0.3 O 3− δ and their role in enhancing CO 2–CO electrocatalysis | |
| Bello et al. | Effect of engineered lattice contraction and expansion on the performance and CO2 tolerance of Ba0. 5Sr0. 5Co0. 7Fe0. 3O3-δ functional material for intermediate temperature solid oxide fuel cells | |
| Bai et al. | Bi0. 5Sr0. 5FeO3-δ perovskite B-site doped Ln (Nd, Sm) as cathode for high performance Co-free intermediate temperature solid oxide fuel cell | |
| Wu et al. | In situ growth of copper-iron bimetallic nanoparticles in A-site deficient Sr2Fe1. 5Mo0. 5O6-δ as an active anode material for solid oxide fuel cells | |
| Chu et al. | Solution combustion synthesis of mixed-phase Mn-based oxides nanoparticles and their electrocatalytic performances for Al-air batteries | |
| Yin et al. | Activating ORR and OER in Ruddlesden-Popper based catalysts by enhancing interstitial oxygen and lattice oxygen redox reactions | |
| CN109473679A (en) | A kind of New Hydrogen air exhaustion material and its application | |
| Sun et al. | In situ coexsolution of metal nanoparticle-decorated double perovskites as anode materials for solid oxide fuel cells | |
| CN113299934B (en) | Anti-carbon deposition and carbon dioxide resistant fuel electrode material, preparation method thereof and solid oxide cell | |
| Shen et al. | Mo-doped Ba0. 5Sr0. 5Co0. 8Fe0. 2O3-δ as a high-performance symmetric electrode for solid oxide fuel cells | |
| CN113363543B (en) | Solid oxide cell fuel electrode material, preparation method thereof and solid oxide cell | |
| Sun et al. | In situ self-reconstructed nanoparticle-coated cathode and anode by nitric acid etching for symmetric solid oxide fuel cells | |
| Wang et al. | Investigation of the special surface state of BaCo0. 4Fe0. 4Zr0. 1Y0. 1O3-δ vs Ba0. 5Sr0. 5Co0. 8Fe0. 2O3-δ and La0. 6Sr0. 4Co0. 2Fe0. 8O3-δ for high oxygen catalysis activity on the intermediate-temperature solid oxide fuel cell | |
| Liu et al. | In-situ construction of Ni–Fe alloy nanoparticles on perovskite surface for CO2 direct electrolysis | |
| Bai et al. | Sc-doped Co-based perovskites as IT-SOFC cathode with high oxygen reduction reaction and CO2 tolerance | |
| Zhou et al. | Ba-doped LaCoO3 perovskite as novel bifunctional electrocatalyst for zinc–air batteries | |
| WO2024000742A1 (en) | Perovskite oxide-transition metal phosphide heterostructure composite electrode material, preparation method therefor, and use thereof | |
| CN114635150A (en) | Novel solid oxide electrolytic cell oxygen electrode and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |