CN116477666A - Hydrogen electrode material of solid oxide electrolytic cell, and preparation method and application thereof - Google Patents

Hydrogen electrode material of solid oxide electrolytic cell, and preparation method and application thereof Download PDF

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CN116477666A
CN116477666A CN202310375585.4A CN202310375585A CN116477666A CN 116477666 A CN116477666 A CN 116477666A CN 202310375585 A CN202310375585 A CN 202310375585A CN 116477666 A CN116477666 A CN 116477666A
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hydrogen electrode
solid oxide
cell
gdc
sfm
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杨广明
庞芳
杨美婷
杨长江
冉然
周嵬
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Nanjing Tech University
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Nanjing Tech University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0018—Mixed oxides or hydroxides
    • C01G49/0054—Mixed oxides or hydroxides containing one rare earth metal, yttrium or scandium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/23—Carbon monoxide or syngas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • 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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes

Abstract

The invention relates to a high-performance Solid Oxide Electrolytic Cell (SOEC) hydrogen electrode material composition easy to prepare in a large-scale one-step method and a preparation method thereof. Use as SOEC for electrolysis of pure CO 2 Compared with other physical mixing modes and the like, the one-step method of the hydrogen electrode has great advantages, more active centers can be introduced, a rich two-phase interface is formed, the thermal compatibility of the electrode and electrolyte is improved, and the structural stability and durability are improved. Preparation of Cu by sol gel one-step method x ‑Sr 2 Fe 1.5 Mo 0.5 O 6‑δ ‑Gd 0.1 Ce 0.9 O 2‑δ A porous hydrogen electrode. In the presence of oxygen ion conductor electrolyte La 0.8 Sr 0.2 Ga 0.8 Mg 0.2 O 3‑δ (LSGM) and with Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3‑δ When (BSCF) is an oxygen electrode, the battery shows excellent electrochemical performance, has lower polarization impedance, and improves the catalytic activity, the oxidation-reduction stability and the CO of the hydrogen electrode material 2 And can remain stable over a long period of time.

Description

Hydrogen electrode material of solid oxide electrolytic cell, and preparation method and application thereof
Technical Field
The invention relates to a high-performance solid oxide electrolytic cell hydrogen electrode material composition and a preparation method thereof, belonging to the technical field of solid oxide electrolytic cells.
Background
With the acceleration of the progress of human modernization and the rapid development of economic globalization, energy utilization and environmental protection have become two important subjects in the sustainable development of the current society. The existing energy system mainly uses fossil resources, but the utilization efficiency of the fossil resources by the traditional combustion technology is extremely low, and serious environmental pollution and energy shortage problems are brought. The electrolysis technology plays a great role in an energy system by virtue of unique advantages, wherein a Solid Oxide Electrolytic Cell (SOEC) is an efficient and pollution-free energy conversion device, and is also a reverse process of a solid oxide fuel cell, and the electrolytic cell and the fuel cell can realize the mutual conversion of electric energy and chemical energy. SOEC can convert H by using electric power generated by clean energy 2 O and CO 2 Electrolytic production of H 2 CO, etc., and the energy conversion efficiency is close to 100%. The structure of SOEC consists of porous cathodes (hydrogen electrodes) and anodes (oxygen electrodes) on both sides and a dense electrolyte in the middle, where at the three-phase interface of gas-hydrogen electrode-electrolyte, H 2 O or CO 2 Electrochemical reduction reaction takes place and fuel gas (H) is produced 2 Or CO) and then oxygen ions are transported to an oxygen electrode through an electrolyte, oxygen precipitation reaction occurs on the oxygen electrode side and O is generated 2 。
The hydrogen electrode is an electrode which is introduced by SOEC electrolysis raw material gas and works when the hydrogen electrode worksWhen water and carbon dioxide are decomposed in the vicinity of the hydrogen electrode, and the product gas is output through the electrode. Therefore, the hydrogen electrode has higher oxygen ion and electron conductivity, certain catalytic activity and certain porosity. Currently, there is mainly Ni- (Y) in solid oxide electrolytic cells 2 O 3 ) 0.08 (ZrO 2 ) 0.92 (YSZ) and Ni-Gd 0.1 Ce 0.9 O 1.95 (GDC) and the like, wherein Ni-YSZ is the most widely used cathode material of the electrolytic cell at present, and has the advantages of porous structure, higher ionic conductivity and electronic conductivity, good catalytic activity, lower cost and the like. Classical nickel-based cathodes exist for oxidizing hydrocarbon fuels or CO 2 Carbon deposition caused by high catalytic activity of electrolysis, ni nano particle agglomeration caused by long-term running at high temperature and high temperature H 2 O or CO 2 The problems of Ni oxidation, poor stability and the like are caused, so that development of a proper electrode structure and combination of electrocatalytic activity and long-term stability are critical to the performance of the battery.
Disclosure of Invention
Aiming at the problems existing in the prior art, the hydrogen electrode is optimized by the method, so that higher performance and better stability are obtained in an SOEC mode. The invention provides a solid oxide electrolytic cell cathode material, a preparation method and application thereof. In particular to a novel cathode material with perovskite structure applied to a solid oxide electrolytic cell. Cu prepared by one-step sol-gel process x The SFM-GDC hydrogen electrode improves the electrochemical performance of the reversible solid oxide battery, and the hydrogen electrode prepared by the method has the advantages of simple preparation process and H resistance 2 Oxidation and CO 2 The electrolysis shows higher catalytic activity, so that the battery performance is further optimized, and the battery has the advantage of good stability. The invention prepares Cu x SFM-GDC nano catalyst modified solid oxide cell hydrogen electrode, improving fuel gas oxidation and CO of the existing traditional hydrogen electrode 2 Insufficient electrolytic performance. The porous hydrogen electrode provided by the invention has high power density output in SOFC mode and can directly electrolyze CO in SOEC mode 2 CO is prepared.
Solid oxygenHydrogen electrode material of chemical electrolytic cell with chemical formula of Cu x -Sr 2 Fe 1.5 Mo 0.5 O 6-δ -Gd 0.1 Ce 0.9 O 2-δ Wherein x represents the relative content of Cu element, x is more than or equal to 0.05 and less than or equal to 0.1, and delta represents the oxygen vacancy content. When x=0.05 and 0.1, their corresponding abbreviations are Cu05/SFM-GDC, cu10/SFM-GDC, respectively.
The preparation method of the solid oxide battery hydrogen electrode material comprises the following steps:
step 1, according to Cu x -Sr 2 Fe 1.5 Mo 0.5 O 6-δ Gd 0.1 Ce 0.9 O 2-δ Respectively weighing Cu (NO) with certain mass 3 ) 2 、Gd(NO 3 ) 3 ·6H 2 O、Ce(NO 3 ) 3 ·6H 2 O、Sr(NO 3 ) 2 、Fe(NO 3 ) 3 ·9H 2 O and (NH) 4 ) 6 Mo 7 O 24 ·4H 2 Adding a proper amount of deionized water into O, stirring and dissolving to obtain a clear solution;
step 2, adding ethylenediamine tetraacetic acid and citric acid into the mixed solution, regulating the pH of the solution by ammonia water, and stirring until the solution becomes gel;
step 3, drying the sol to obtain precursor powder;
and step 4, calcining the precursor powder at a high temperature to obtain the hydrogen electrode.
In one embodiment, the temperature of the calcined phase is 850-1100 ℃.
Total metal ions: EDTA: the molar ratio of citric acid is 1:0.5-1.5:1.5-2.5.
The pH is adjusted by ammonia water.
The hydrogen electrode material prepared by the one-step method is applied to the preparation of a solid oxide electrolytic cell.
The solid oxide electrolytic cell adopts a hydrogen electrode-electrolyte-oxygen electrode assembly structure.
In the hydrogen electrode-electrolyte-oxygen electrode assembly, the hydrogen electrode contains the solid oxide electrolytic cell hydrogen electrode material; the oxygen electrode contains BSCF powder; the electrolyte contains LSGM powder.
In one embodiment, the]Hydrogen electrode for increasing CO of solid oxide electrolytic cell 2 Adsorption capacity, increase in output of solid oxide fuel cell or increase in CO electrolysis by solid oxide cell 2 Application in performance.
Advantageous effects
The high-performance solid oxide cell hydrogen electrode Cu10/SFM-GDC is prepared by a sol-gel one-step method, and has the following effects:
(1) The preparation process is simple, the preparation method is simpler and more convenient, more active sites are provided, the electrochemical performance is excellent, and the stability is good.
(2) When LSGM is used as electrolyte and BSCF is used as oxygen electrode, the obtained full cell has higher output power and lower polarization impedance.
(3) When LSGM is used as electrolyte and BSCF is used as oxygen electrode, the obtained full cell can be directly used for CO 2 The obtained full cell has higher electrolysis current density, and the current density corresponding to 1.6V at 850 ℃ can reach 2220mA cm -2 On the left and right, the single cell using SFM-GDC and Cu05/SFM-GDC as hydrogen electrode is superior.
(4) Compared with the traditional Ni/YSZ hydrogen electrode material, the hydrogen electrode material has the advantages of good electrochemical performance, no unstable condition under high-temperature and high-humidity environment, ni agglomeration, volatilization and the like.
(5) Compared with the traditional methods such as dipping, doping, physical mixing and the like, the sol-gel one-step method has more remarkable advantages, more active centers can be introduced, a rich two-phase interface is formed, the thermal compatibility of the electrode and electrolyte is improved, the structural stability and durability are improved, and the problems of insufficient catalytic activity and the like are effectively solved.
(6) The obtained solid oxide electrolytic cell cathode-electrolyte-anode component adopts perovskite structure materials no matter electrode materials or electrolyte materials, and the full perovskite structure is more beneficial to the integral stability of a single cell structure, and has better anti-attenuation performance and long service life. And at the interface between the electrode and the electrolyte, the charge and oxygen ions are more smoothly transferred, and the reaction activity is further improved.
Drawings
FIG. 1 is an X-ray diffraction pattern of hydrogen electrode materials Cu10/SFM-GDC, cu05/SFM-GDC and SFM-GDC according to the present invention;
FIG. 2 is an X-ray diffraction pattern of hydrogen electrode materials Cu10/SFM-GDC, cu05/SFM-GDC and SFM-GDC according to the present invention treated at 850℃for 2 hours under a hydrogen atmosphere;
FIG. 3 is an output power performance curve of an SFM-GDC|LSGM|BSCF cell over a temperature range of 750-850 ℃;
FIG. 4 is a graph of the output power performance of a Cu05/SFM-GDC|LSGM|BSCF cell over a temperature range of 750-850 ℃;
FIG. 5 is a graph of the output power performance of a Cu10/SFM-GDC|LSGM|BSCF cell over a temperature range of 750-850 ℃;
FIG. 6 is an SFM-GDC|LSGM|BSCF cell for CO electrolysis at a temperature in the range of 750-850 DEG C 2 Is a performance curve of (2);
FIG. 7 is an electrolytic CO of Cu05/SFM-GDC|LSGM|BSCF cell at a temperature in the range of 750-850 DEG C 2 Is a performance curve of (2);
FIG. 8 is an electrolytic CO of Cu10/SFM-GDC|LSGM|BSCF cell at a temperature in the range of 750-850 DEG C 2 Is a performance curve of (2); FIG. 9 is an electrochemical impedance spectrum of an SFM-GDC|LSGM|BSCF cell tested at open circuit voltage over a temperature range of 750-850 ℃;
FIG. 10 is an electrochemical impedance spectrum of a Cu05/SFM-GDC|LSGM|BSCF cell tested at open circuit voltage over a temperature range of 750-850 ℃;
FIG. 11 is an electrochemical impedance spectrum of a Cu10/SFM-GDC|LSGM|BSCF cell tested at open circuit voltage over a temperature range of 750-850 ℃;
FIG. 12 is a cross-sectional electron microscopy image after Cu10/SFM-GDC|LSGM|BSCF single cell testing;
FIG. 13 is an electron microscopic view of a Cu10/SFM-GDC hydrogen electrode;
FIG. 14 is an electrochemical impedance spectrum of an SFM-GDC|LSGM|SFM-GDC symmetric cell tested at open circuit voltage over a temperature range of 700-850 ℃; the temperatures corresponding to the four curves from left to right in the graph are 850, 800, 750 and 700 ℃;
FIG. 15 is an electrochemical impedance spectrum of a Cu05/SFM-GDC|LSGM|Cu05/SFM-GDC symmetric cell tested at open circuit voltage over a temperature range of 700-850 ℃; the temperatures corresponding to the four curves from left to right in the graph are 850, 800, 750 and 700 ℃; FIG. 16 is an electrochemical impedance spectrum of a Cu10/SFM-GDC|LSGM|Cu10/SFM-GDC symmetric cell tested at open circuit voltage over a temperature range of 700-850 ℃; the temperatures corresponding to the four curves from left to right in the graph are 850, 800, 750 and 700 ℃;
FIG. 17 is a TEM-EDS diagram of a Cu10/SFM-GDC powder;
FIG. 18 is Cu x X-ray photoelectron spectroscopy of O1s before and after SFM-GDC reduction;
FIG. 19 is Cu x SFM-GDC in CO 2 Short cycle test comparison graph under atmosphere;
FIG. 20 is Cu x SFM-GDC at 50% CO 2 -conductivity map under 50% co atmosphere;
FIG. 21 is a graph of cell stability for Cu10/SFM-GDC|LSGM|BSCF cells tested at 800 ℃;
FIG. 22 is a Raman test chart after Cu10/SFM-GDC|LSGM|BSCF cell stability test;
Detailed Description
The invention relates to a hydrogen electrode material of an oxygen ion conductor electrolytic cell prepared by a one-step method and a preparation method thereof, wherein the molecular formula of the hydrogen electrode material is Cu x -Sr 2 Fe 1.5 Mo 0.5 O 6-δ -Gd 0.1 Ce 0.9 O 2-δ Wherein x represents the relative content of Cu element, x is more than or equal to 0 and less than or equal to 0.1, delta represents the oxygen vacancy content, and belongs to the technical field of high-temperature solid oxide electrolytic cell hydrogen electrode materials. Characterized in that the high-performance and excellent stability CO is synthesized by a one-step method with simple operation and is suitable for high-temperature electrolysis 2 Hydrogen electrode material of (a). Since Cu has good CO 2 The GDC has higher ionic conductivity, and Cu, SFM, GDC is respectively synthesized into the biphase material according to proportion, so that more GDC can be introducedAnd (3) a rich two-phase interface is formed, so that the thermal compatibility of the electrode and the electrolyte is improved, and the structural stability and durability are improved.
The electrolyte and cathode materials to which the present invention relates include, but are not limited to, the materials in the following examples, and the optimization methods and preparation methods to which the present invention relates include, but are not limited to, the methods in the following examples. All modifications and equivalent substitutions to the technical proposal of the invention are included in the protection scope of the invention without departing from the spirit and scope of the technical proposal of the invention.
Example 1
This example provides a one-step method for preparing Cu05 (10)/Sr electrode material suitable for solid oxide electrolytic cell to electrolyze carbon dioxide hydrogen 2 Fe 1.5 Mo 0.5 O 6-δ -Gd 0.1 Ce 0.9 O 2-δ The preparation method comprises the following specific steps:
(1) 0.4832g of Cu (NO) 3 ) 2 0.4062g Gd (NO) 3 ) 3 ·6H 2 O, 3.5172g of Ce (NO) 3 ) 3 ·6H 2 O、3.8093g Sr(NO 3 ) 2 5.454g of Fe (NO) 3 ) 3 ·9H 2 O and 0.7945g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, adding a small amount of deionized water for dissolution. According to ethylenediamine tetraacetic acid: hydrated citric acid: 14g of ethylenediamine tetraacetic acid and 20g of hydrated citric acid are weighed according to the molar ratio of 1:2:1, and are taken as complexing agents to be dissolved in deionized water.
(2) Adding the solution dissolved with the complexing agent into the solution dissolved with the metal ions, then dripping a proper amount of ammonia water until the pH value of the solution reaches 7-8, and stirring under the condition of magnetic stirring to completely evaporate water to obtain a gel substance.
(3) The gel-like mass was placed in an oven and calcined at 250 ℃ for 5 hours to give the desired foam-like precursor.
(4) And (3) placing the precursor in a high-temperature muffle furnace, and calcining for 10 hours at the temperature of 1000 ℃ to obtain the required hydrogen electrode powder Cu10/SFM-GDC. When preparing Cu05/SFM-GDC, cu (NO) 3 ) 2 The amount of (C) is 0.2416g,the remaining steps are the same. When SFM-GDC was prepared, cu (NO) 3 ) 2 The remaining steps are the same.
Example 2:
the embodiment specifically provides a test for preparing symmetrical battery polarization impedance by taking Cu10/SFM-GDC as a battery cathode, which specifically comprises the following specific steps:
(1) 1g of the cathode powder Cu10/SFM-GDC prepared in example 1, 10mL of isopropanol, 2mL of ethylene glycol and 0.8mL of glycerol are weighed, poured into a high-energy ball mill, ball-milled for 30min under the condition of 400r/min, and transferred to a strain bottle by a straw to obtain the required cathode slurry.
(2) The prepared LSGM electrolyte is placed on a heating table to be preheated at 200 ℃, and the prepared cathode slurry is uniformly sprayed on two sides of the electrolyte by using a spray gun under the pushing of inert gas. After the liquid is completely volatilized, the sprayed battery is placed in a muffle furnace and calcined at 1000 ℃ for 2 hours to prepare the required symmetrical battery which is used for cathode materials within the range of 700 to ultra
Testing of polarization impedance in the 850 ℃ temperature range. Wherein the polarization impedance of the cell at 850 ℃ is 0.36 Ω cm 2 。
Characterization of results
XRD characterization
FIG. 1 shows XRD patterns of SFM-GDC, cu05/SFM-GDC, cu10/SFM-GDC at room temperature, showing that SFM-GDC prepared by the sol-gel one-step method has a pure perovskite phase and Cu prepared by the one-step method together with Cu x Nor does the SFM-GDC form any extra phase and the main diffraction peak (approximately 32.40 deg.) shifts to low diffraction angles as the Cu content increases. Due to Fe 4+ And Cu 2+ When smaller Fe is different in ionic radius 4+ (58.5 pm) of Cu being larger 2+ (73.0 pm) substitution, the lattice spacing increases. And H is 2 After treatment under atmosphere, the formation of RP phase and precipitation of Cu and Fe elementary substances can be obviously seen.
2. Solid oxide fuel cell mode electrochemical performance
FIG. 3 shows the performance of LSGM-supported single cell (SFM-GDC|LSGM|BSCF) at 750-850 ℃And (5) testing. At hydrogen electrode H 2 The air inflow is 80mL min -1 Under the condition of (2) that the highest power density of the single cell at 850 ℃ is 632.92mW cm -2 Left and right.
FIG. 4 shows performance tests of LSGM-supported single cells (Cu 05/SFM-GDC|LSGM|BSCF) at 750-850 ℃. At hydrogen electrode H 2 The air inflow is 80mL min -1 Under the condition of (2) that the highest power density of the single cell at 850 ℃ is 816.67mW cm -2 Left and right.
FIG. 5 shows performance tests of LSGM-supported single cells (Cu 10/SFM-GDC|LSGM|BSCF) at 750-850 ℃. At hydrogen electrode H 2 The air inflow is 80mL min -1 Under the condition of (2) that the highest power density of the single cell at 850 ℃ is 928mW cm -2 Left and right.
3. Electrochemical performance in solid oxide cell mode
FIG. 6 shows electrolysis of CO at 750-850℃in a single cell (SFM-GDC|LSGM|BSCF) supported by LSGM 2 Performance testing of (c) a). The inlet atmosphere of the hydrogen electrode is pure CO 2 The total flow rate is 40mL min -1 The oxygen electrode is directly exposed to air. The maximum electrolysis current density of the single cell at 850 ℃ is-1.54A cm -2 ；
FIG. 7 shows electrolysis of CO at 750-850℃in a single cell (Cu 05/SFM-GDC|LSGM|BSCF) supported by LSGM 2 Performance testing of (c) a). The inlet atmosphere of the hydrogen electrode is pure CO 2 The total flow rate is 40mL min -1 The oxygen electrode is directly exposed to air. The maximum electrolysis current density of the single cell at 850 ℃ is 1.88A cm -2 ；
FIG. 8 shows electrolysis of CO at 750-850℃in a single cell (Cu 10/SFM-GDC|LSGM|BSCF) supported by LSGM 2 Performance testing of (c) a). The inlet atmosphere of the hydrogen electrode is pure CO 2 The total flow rate is 40mL min -1 The oxygen electrode is directly exposed to air. The maximum electrolysis current density of the single cell at 850 ℃ is 2.22A cm -2 ；
4. Electrochemical impedance spectroscopy in solid oxide fuel cell mode
FIG. 9 shows a cell (SFM-GDC|L) supported by LSGMSgm|bscf) in the range of 750-850 ℃ for open circuit voltage testing. As can be seen from the test results, the polarization impedance was 0.22. OMEGA.cm at 850 ℃ 2 About, the polarization impedance at 800 ℃ is 0.26 Ω cm 2 About, the polarization impedance at 750 ℃ is 0.34 Ω cm 2 Left and right.
FIG. 10 is an electrochemical impedance spectrum of an LSGM supported single cell (Cu 05/SFM-GDC|LSGM|BSCF) tested at open circuit voltages in the range of 750-850 ℃. As can be seen from the test results, the polarization impedance was 0.19. OMEGA.cm at 850 ℃ 2 About, the polarization impedance at 800 ℃ is 0.25 Ω cm 2 About, the polarization impedance at 750 ℃ is 0.34 Ω cm 2 Left and right.
FIG. 11 is an electrochemical impedance spectrum of an LSGM supported single cell (Cu 10/SFM-GDC|LSGM|BSCF) tested at open circuit voltages in the range of 750-850 ℃. As can be seen from the test results, the polarization impedance was 0.13. OMEGA.cm at 850 ℃ 2 About, the polarization impedance at 800 ℃ is 0.18 Ω cm 2 About, the polarization impedance at 750 ℃ is 0.24 Ω cm 2 Left and right.
Meanwhile, by comparing fig. 9, 10 and 11, it can be seen that the ohmic impedances of the two single cells are substantially the same under the same test conditions, which indicates that the electrolyte thicknesses of the prepared single cells are substantially uniform, and errors caused by experimental operation are reduced. The resistance of the Cu10/SFM-GDC single cell synthesized by the one-step method is obviously reduced under the same condition, which is closely related to the high adsorptivity and high catalytic performance of the single cell to gas.
5. Cross-section electron microscope image of Cu10/SFM-GDC|LSGM|BSCF after test
FIG. 12 is a cross-sectional electron micrograph of a Cu10/SFM-GDC|LSGM|BSCF cell after electrolytic testing. From the test results, the whole structure of the single cell is still complete after the test, the electrolyte is quite compact and has no obvious cracks, which shows that the electrolyte is hardly attenuated in the whole test process. FIG. 13 is an enlarged electron microscopic view of a Cu10/SFM-GDC hydrogen electrode, and it can be seen from the test results that the surface distribution of the hydrogen electrode is good and no sintering phenomenon occurs.
6. Symmetrical battery impedance characterization
FIG. 14,15 and 16 are symmetrical cells supported with LSGM electrolyte at 1:1 CO-CO 2 In atmosphere measure Cu x Electrochemical Impedance Spectroscopy (EIS) of SFM-GDC at different operating temperatures. In the ac impedance spectrum, the deviation of the intercept of the low-frequency and high-frequency arcs from the real axis is regarded as polarization resistance (R p ) It is used as a main parameter for evaluating the electrochemical performance of an electrode, R p The smaller the value, the more desirable the catalytic activity in the electrochemical system. The Cu10/SFM-GDC has minimal polarization resistance compared to other materials, and the polarization resistance is 0.36 Ω cm at 850 DEG C 2 Indicating that it has excellent CO 2 Adsorption properties and catalytic activity.
7. TEM-EDS characterization of Cu10/SFM-GDC powder
FIG. 17 shows the results of one-step synthesis of Cu10/SFM-GDC powder, in which the sample is SFM and GDC phases, cu is distributed in the two phases and dispersed in the SFM phase in a large amount and in the GDC phase in a small amount, and there is self-diffusion of molecules, and the self-optimizing results are probably that it improves the catalytic activity and CO 2 The reason for the adsorption capacity.
8. XPS characterization
FIG. 18 is a distribution of binding energy of O1s atomic orbitals in SFM-GDC, cu05/SFM-GDC and Cu10/SFM-GDC to analyze oxygen species and content of different material surfaces. The fitting results in Table 1 show that the addition of Cu causes O ads ./O lat The ratio increases, indicating a substantial increase in the adsorbed oxygen content and oxygen vacancy concentration at the surface. And after reduction treatment, the surface oxygen content is obviously increased, and the catalyst is used for CO 2 The electrolytic reaction is more advantageous.
TABLE 1 Cu x Os/O before and after SFM-GDC reduction S +O L Numerical values of (2)
9. Short cycle test
FIG. 19 is a graph of Cu test x The current density of the SFM-GDC electrolytic cell is changed under different continuous voltage conditions, and the SFM-GDC electrolytic cell has better stability in a short period.
10. Conductivity characterization
For the cathode material, the conductivity of the electrode material is tested by adopting a direct current four-probe method, firstly, sample powder is pressed by a die to obtain a strip-shaped green body with the size of about 2 x 5 x 12mm, and a compact conductivity test sample is obtained by high-temperature sintering. Then coating silver colloid on two ends of the compact strip sample and connecting the silver colloid with silver wires to serve as current electrodes; and connecting two other silver wires in the middle of the sample, and fixing the two silver wires by using silver colloid to serve as a voltage electrode. The conductivity of the sample is measured from 850 ℃ to 300 ℃ at a cooling rate of 5 ℃ for min -1 One data point was tested every 25 deg.c for a test stabilization time of 5min with the test atmosphere being air. When the conductivity test is carried out, the four electrodes of the sample are respectively connected to the current and voltage ends of the Keithley 2400 digital power supply ammeter, the current I is conducted to the electrodes at the two ends of the sample, the intermediate potential difference V is measured, the direct current resistance R=V/I of the sample is measured, and the resistance R is substituted into the equation:
and calculating to obtain the conductivity sigma value of the sample. Wherein A is the cross-sectional area of the strip sample, and L is the distance between the two electrodes.
Fig. 20 is a diagram of a process at 1:1 CO-CO 2 In atmosphere measure Cu x Conductivity of SFM-GDC at different operating temperatures, CO-CO at high temperatures 2 Is reduced by (a) to Cu x Reduction of Fe and Mo within the SFM-GDC material generates more electron charges with more oxygen vacanciesThe results show that the conductivity increases with increasing temperature, wherein the Cu10/SFM-GDC has higher conductivity of 9.28S cm at 850 DEG C -1 This may make it possible to provide more active sites.
11. Single cell stability characterization
FIG. 21 is a Cu10/SFM-GDC|LSGM|BSCF cell with pure CO at 800 ℃ 2 The current density was stabilized at 1.3Acm under an atmosphere 2 About, there is no obvious degradation after 217h, providing technical support for commercialization progress.
12. Raman characterization
FIG. 22 is a pure CO at 800℃for a Cu10/SFM-GDC|LSGM|BSCF cell 2 After long-term stability test under atmosphere, no obvious carbon deposition phenomenon is observed after the Cu10/SFM-GDC hydrogen electrode is subjected to Raman test.

Claims (9)

1. A hydrogen electrode material of a solid oxide electrolytic cell is characterized in that the chemical formula is Cu x -Sr 2 Fe 1.5 Mo 0.5 O 6-δ- Gd 0.1 Ce 0.9 O 2-δ Wherein x represents the relative content of Cu element, x is more than or equal to 0.05 and less than or equal to 0.1, and delta represents the oxygen vacancy content, which is called Cux/SFM-GDC for short.
2. The method for producing a hydrogen electrode material for a solid oxide electrolytic cell according to claim 1, comprising the steps of:
step 1, according to Cu x -Sr 2 Fe 1.5 Mo 0.5 O 6-δ -Gd 0.1 Ce 0.9 O 2-δ Respectively weighing Cu (NO) with certain mass 3 ) 2 、Gd(NO 3 ) 3 ·6H 2 O、Ce(NO 3 ) 3 ·6H 2 O、Sr(NO 3 ) 2 、Fe(NO 3 ) 3 ·9H 2 O and (NH) 4 ) 6 Mo 7 O 24 ·4H 2 Adding a proper amount of deionized water into O, stirring and dissolving to obtain a clear solution;
step 2, adding ethylenediamine tetraacetic acid and citric acid into the mixed solution, adjusting the pH of the solution, and stirring until the solution becomes gel;
step 3, drying the sol to obtain precursor powder;
and step 4, calcining the precursor powder at a high temperature to obtain the hydrogen electrode.
3. The solid oxide cell hydrogen electrode material of claim 1, wherein the calcined phase has a temperature of 850-1100 ℃.
4. The solid oxide cell hydrogen electrode material of claim 1, wherein the total metal ions: EDTA: the molar ratio of citric acid is 1:0.5-1.5:1.5-2.5.
5. The solid oxide cell hydrogen electrode material of claim 1, wherein the pH adjustment is performed using aqueous ammonia.
6. Use of a solid oxide cell hydrogen electrode material for the preparation of a solid oxide cell.
7. The use according to claim 7, wherein the solid oxide electrolysis cell employs a hydrogen electrode-electrolyte-oxygen electrode assembly structure.
8. The use according to claim 7, wherein the hydrogen electrode contains the solid oxide cell hydrogen electrode material; the oxygen electrode contains BSCF powder; the electrolyte contains LSGM powder.
9. The use according to claim 7, wherein said]Hydrogen electrode for increasing CO of solid oxide electrolytic cell 2 Adsorption capacity, increase in output of solid oxide fuel cell or increase in CO electrolysis by solid oxide cell 2 Application in performance.
CN202310375585.4A 2023-04-10 2023-04-10 Hydrogen electrode material of solid oxide electrolytic cell, and preparation method and application thereof Pending CN116477666A (en)

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