High-performance solid oxide electrolytic cell oxygen electrode material with rare earth element doped zirconium-based perovskite structure and preparation method of high-performance solid oxide electrolytic cell oxygen electrode material
By doping rare earth element Yb, the oxygen electrode material with zirconium-based perovskite structure is solved, and the problems of insufficient electronic conductivity and stability in high water vapor environment are achieved, achieving high electrolytic performance and long-term stable operation.
Patent Information
- Application Number
- CN202510197603.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-21
- Publication Date
- 2025-06-13
AI Technical Summary
The lack of electronic conductivity of traditional zirconium-based perovskite oxygen electrode materials limits its dehydrogenation reaction rate and overall performance in solid oxide electrolytic cells, and its long-term stability in high water vapor environments has not been fully verified.
The preparation method of solid oxide electrolytic cell oxygen electrode material with a zirconium-based perovskite structure is improved by doping the rare earth element Yb, including calcining the prepared precursor solution, refining it, spraying it on the surface of the electrolyte layer, and obtaining a high-performance oxygen electrode material through high temperature sintering.
It achieves high electrolytic performance and high stability, can run for a long time in a high water vapor environment, the current density reaches 2000mA/cm2, the stability reaches 100 hours, and the production cost is low and the process is simple.
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Figure CN120138680A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of electrocatalytic materials, and relates to a high-performance solid oxide electrolytic cell oxygen electrode material and a preparation method thereof, and specifically relates to a high-performance solid oxide electrolytic cell oxygen electrode material with a rare earth element-doped zirconium-based perovskite structure. Background Art
[0002] Hydrogen energy has become a key clean energy carrier to replace fossil fuels due to its high energy density (142MJ / kg) and zero carbon emission characteristics. In the technology of hydrogen production by water electrolysis, the solid oxide electrolyzer (SOEC) is regarded as the core technical route for large-scale green hydrogen production due to its all-solid-state structure, energy conversion efficiency of more than 80%, and high purity of hydrogen production. As the core component of SOEC, the oxygen electrode undertakes the key functions of water molecule oxidation and proton generation. In the proton conductor SOEC, water vapor loses electrons on the surface of the oxygen electrode to undergo a dissociation reaction, and the generated protons migrate to the fuel electrode through the electrolyte to obtain electrons to produce hydrogen. The reaction kinetic efficiency of this process is directly limited by the catalytic activity and proton / electron conduction capacity of the oxygen electrode. Therefore, the development of high-performance oxygen electrode materials is the technical key to improving the overall performance of SOEC. However, traditional oxygen electrode materials such as Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ (Advanced Functional Materials, 2022, 32(47), 2209054) The proton conductivity of zirconium-based perovskite is insufficient, resulting in sluggish dehydrogenation reaction kinetics, which limits the practical application of solid oxide electrolyzers in the electrolysis of water to produce hydrogen. Zirconium-based perovskite materials are considered to be one of the ideal candidate materials for oxygen electrodes due to their excellent proton conductivity properties. However, traditional zirconium-based perovskite materials often lack sufficient electronic conductivity, which is a key defect for the function of oxygen electrodes. Effective electrocatalytic processes require the synergistic effect of electrons and ions, and insufficient electronic conductivity limits the rate of dehydrogenation reactions, thereby affecting the overall performance of the electrolyzer. In addition, in actual operating environments, especially in the presence of high concentrations of water vapor (>30%), the long-term stability of zirconium-based perovskite oxygen electrode materials has not been fully verified. The research and invention of rare earth element doping helps to improve the ion transport capacity of the material, as well as improve the structure and thus improve stability. (Chemical Reviews, 2022, 122(6), 5519-5603; Chemical Engineering Science, 2024, 299, 120522). Therefore, it is an effective modification strategy to improve the dehydrogenation reaction performance of zirconium-based perovskite structures by doping with rare earth elements. Summary of the invention
[0003] In order to overcome the deficiencies of the existing technologies, the object of the present invention is to provide a high-performance solid oxide electrolyzer oxygen electrode material with a rare earth element-doped zirconium-based perovskite structure.
[0004] The primary object of the present invention is to provide a preparation method of a high-performance solid oxide electrolyzer oxygen electrode material with a rare earth element-doped zirconium-based perovskite structure.
[0005] Another object of the present invention is to provide the application of the above-mentioned solid oxide cell oxygen electrode in the electrolysis of water reaction.
[0006] The object of the present invention is achieved by at least one of the following technical solutions.
[0007] The present invention provides a preparation method of a high-performance solid oxide electrolyzer oxygen electrode material by doping Yb element. The preparation method includes: drying the prepared precursor solution and then putting it into a muffle furnace for calcination, refining the obtained powder and spraying it on the surface of the BZCYYb electrolyte layer according to the ratio, and obtaining the high-performance solid oxide electrolyzer oxygen electrode material after drying and high-temperature sintering.
[0008] The present invention provides a preparation method of a high-performance solid oxide electrolyzer oxygen electrode material with a rare earth element-doped zirconium-based perovskite structure, including the following steps:
[0009] (1) Dissolve barium carbonate, zirconia, cobalt tetroxide, ferric oxide and ytterbium oxide in absolute ethanol according to the stoichiometric ratio of BaZr x Co y Fe z Yb 1-x-y-z O 3-δ ; after fully ball-milling and dissolving, obtain a precursor solution; in the BaZr x Co y Fe z Yb 1-x-y-z O 3-δ , x = 0.1 - 0.2, y = 0.4 - 0.6, z = 0.2 - 0.3;
[0010] (2) Dry and grind the precursor solution obtained in step (1) to obtain a precursor powder;
[0011] (3) Calcinate the precursor powder obtained in step (2) to obtain a coarse powder of the BZCFYb phase;
[0012] (4) Add the coarse powder of the BZCFYb phase obtained in step (3) to absolute ethanol, ball-mill and refine it, and then dry it to obtain a fine powder of BZCFYb;
[0013] (5) After the fine powder of BZCFYb obtained in step (4) is sufficiently ball-milled with the addition of ethylene glycol, glycerol, and isopropyl alcohol, the mixed solution is sprayed on the surface of BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ electrolyte surface, and after calcination, a solid oxide cell oxygen electrode is obtained.
[0014] Furthermore, in step (1), the volume ratio of the total molar amount of barium carbonate, zirconium oxide, cobalt tetroxide, iron(III) oxide, and ytterbium oxide to anhydrous ethanol is (0.1 - 1) mol : (40 - 100) mL. Preferably, the dosage ratio of the total molar amount of barium carbonate, zirconium oxide, cobalt tetroxide, iron(III) oxide, and ytterbium oxide to anhydrous ethanol is (0.05 - 0.15) mol : (40 - 60) mL.
[0015] Furthermore, in step (3), the calcination temperature is 1000 - 1150 °C; the calcination time is 9 - 15 hours.
[0016] Furthermore, in step (4), the ball-milling time is 30 - 180 minutes.
[0017] Furthermore, in step (5), the dosages of ethylene glycol, glycerol, and isopropyl alcohol are 0.5 - 2 mL, 0.1 - 1 mL, and 1 - 10 mL respectively.
[0018] Preferably, in step (5), the volumes of the ethylene glycol, isopropyl alcohol, and glycerol solutions are 1 mL, 4 mL, and 0.3 mL respectively.
[0019] Furthermore, in step (5), the number of spraying times is 10 - 30 times, preferably 20 - 30 times, and each time, the next operation is carried out after drying on a heating workbench at 180 - 250 °C.
[0020] Furthermore, in step (5), the calcination temperature is 800 - 1000 °C; the calcination time is 1 - 4 hours.
[0021] The present invention provides a high-performance solid oxide electrolysis cell oxygen electrode material with a rare earth element-doped zirconium-based perovskite structure prepared by the above preparation method.
[0022] The present invention provides the application of the above high-performance solid oxide electrolysis cell oxygen electrode material with a rare earth element-doped zirconium-based perovskite structure in the electrolysis of water to produce hydrogen reaction.
[0023] The present invention relates to a highly efficient solid oxide cell oxygen electrode that is easy to prepare, environmentally friendly and harmless, highly versatile, flexibly controllable, and can be mass-produced. Under the preferred preparation conditions of the present invention, the obtained oxygen electrode exhibits excellent water electrolysis activity and high water vapor tolerance.
[0024] Using the obtained BZCFYb of the present invention as the oxygen electrode, Ni / BZCYYb as the fuel electrode, and BZCYYb as the electrolyte to assemble a solid oxide cell, 30% H 2 is introduced into the oxygen electrode, and the current density is 2000 mA / cm 2 under the conditions of 650 °C and a voltage of 1.4 V, and the operating stability reaches 100 h.
[0025] Compared with the prior art, the present invention has the following advantages and beneficial effects:
[0026] 1. The present invention provides a method for preparing a high-performance solid oxide electrolysis cell oxygen electrode material with a rare earth element-doped zirconium-based perovskite structure by spraying. The raw material cost is low, the sintering temperature is low, the energy consumption during the production process is low, and the production cost is low.
[0027] 2. The high-performance solid oxide electrolysis cell oxygen electrode material with a rare earth element-doped zirconium-based perovskite structure provided by the present invention exhibits high water electrolysis performance and high stability.
[0028] 3. The present invention provides a method for preparing a high-performance solid oxide electrolysis cell oxygen electrode material with a rare earth element-doped zirconium-based perovskite structure with high water vapor tolerance by spraying. The preparation process is simple and easy to implement, the preparation cycle is short, it can be mass-produced, and has commercial prospects.
[0029] 4. Using the obtained BZCFYb of the present invention as the oxygen electrode, Ni / BZCYYb as the fuel electrode, and BZCYYb as the electrolyte to assemble a solid oxide cell, 30% H 2 is introduced into the BZCFYb oxygen electrode, and the current density is 2000 mA / cm 2 under the conditions of 650 °C and a voltage of 1.4 V, and the operating stability reaches 100 h. Description of the Drawings
[0030] Figure 1 It is a scanning electron microscope image of a high-performance solid oxide electrolysis cell with a rare earth element-doped zirconium-based perovskite structure obtained in Example 1.
[0031] Figure 2 It is a volt-ampere characteristic curve of the oxygen electrode material of a high-performance solid oxide electrolysis cell with a rare earth element-doped zirconium-based perovskite structure obtained in Example 1.
[0032] Figure 3It is a stability test diagram of the high-performance solid oxide electrolytic cell with a rare earth element-doped zirconium-based perovskite structure obtained in Example 1. Detailed implementation mode
[0033] The following further illustrates the specific implementation of the present invention in conjunction with examples, but the implementation and protection of the present invention are not limited thereto. It should be noted that for the processes not specifically described in detail below, those skilled in the art can implement or understand them with reference to the prior art. For reagents or instruments without indicating the manufacturer, they are regarded as conventional products that can be purchased commercially.
[0034] All the oxides used were purchased from Shanghai Macklin Biochemical Co., Ltd.; anhydrous ethanol, glycerol, ethylene glycol, and isopropanol were purchased from Damao Chemical Reagent Factory.
[0035] Example 1
[0036] (1) According to the stoichiometric ratio of BaZr x Co y Fe z Yb 1-x-y-z O 3-δ (BZCFYb, x = 0.1 - 0.2, y = 0.4 - 0.6, z = 0.2 - 0.3), dissolve 0.1 mol of barium carbonate, zirconium oxide, cobalt tetroxide, iron oxide, ytterbium oxide (where 0.02 mol of barium carbonate, 0.02 mol of zirconium oxide, 0.02 mol of cobalt tetroxide, 0.02 mol of ferric oxide, 0.02 mol of ytterbium oxide) in 60 mL of anhydrous ethanol, and obtain a precursor solution after sufficient ball milling;
[0037] (2) After drying the precursor solution obtained in step (1), put it into a muffle furnace for calcination to form the phase of BZCFYb. The heating rate is 5 °C / min, and calcine at 1100 °C for 10 hours;
[0038] (3) Put the coarse powder obtained by calcination in step (2) into anhydrous ethanol for ball milling, refining, and drying to obtain fine powder;
[0039] (4) Take 0.5 g of the fine powder obtained in step (3), add 0.3 mL of glycerol, 1 mL of ethylene glycol, and 5 mL of isopropanol, and ball mill for 30 min to obtain a BZCFYb spraying solution;
[0040] (5) According to the chemical formula BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δThe total molar amount of 0.1 mol of barium carbonate, zirconium oxide, cerium oxide, yttrium oxide and ytterbium oxide (including 0.02 mol of barium carbonate, 0.02 mol of zirconium oxide, 0.02 mol of cerium oxide, 0.02 mol of yttrium oxide and 0.02 mol of ytterbium oxide) is added in a stoichiometric ratio. The weighed raw materials are placed in a ball mill, and an appropriate amount of anhydrous ethanol is added as a dispersion medium. Ball milling is performed for 20 hours to ensure that the raw materials are fully mixed. The ball-milled slurry is dried at 80°C to remove the solvent. The dried powder is then pre-burned in a high-temperature furnace, calcined at 1200°C for 10 hours, taken out for tableting, and calcined at 1400°C for 10 hours to form a BCZYYb electrolyte sheet.
[0041] (6) The BCZYYb powder obtained in (5) was mixed and ball-milled in anhydrous ethanol as a dispersion medium in a ratio of nickel oxide: BZCYYb: starch of 3:2:1 for 12 hours, and then dried and pressed and sintered to form a Ni / BCZYYb anode sheet. The electrolyte slurry was evenly coated on the surface of the Ni / BZCYYb anode substrate by spin coating, and then sintered at 1400°C for 5 hours to form a Ni / BZCYYb-BZCYYb structure.
[0042] (7) Spraying the BZCFYb spraying liquid obtained in step (4) onto the surface of the BZCYYb electrolyte electrode of the Ni / BZCYYb-BZCYYb obtained in step (6) for 20 times, drying on a heated workbench at 180° C. after each spraying; and then calcining at 1000° C. for 2 hours to obtain a solid oxide battery oxygen electrode with high water vapor tolerance.
[0043] Example 2
[0044] (1) Dissolve 0.1 mol of a total molar amount of BZCFYb (including 0.01 mol of barium carbonate, 0.0125 mol of zirconium oxide, 0.05 mol of cobalt tetraoxide, 0.025 mol of ferric oxide, and 0.0125 mol of ytterbium oxide) in deionized water according to the stoichiometric ratio of BZCFYb, and stir thoroughly to obtain a uniform solution;
[0045] (2) adding 0.1 mol ethylenediaminetetraacetic acid and 0.2 mol citric acid to the solution obtained in step (1), adding 77 mL of aqueous ammonia solution after the solution is clarified, adjusting the pH value of the solution to 6, heating and stirring until a viscous gel is formed, and further placing the gel in a forced air drying oven and drying at 200° C. for 2 hours to obtain a solid precursor; finally, placing the precursor in a muffle furnace and calcining at 1100° C. for 10 hours at a heating rate of 5° C. / min to obtain BZCFYb;
[0046] (3) Add 0.4 g of the powder obtained by calcination in step (2) to 0.24 mL of glycerol, 0.8 mL of ethylene glycol, and 4 mL of isopropanol, and ball mill for 30 min to obtain the BZCFYb spraying solution;
[0047] (4) Spray the BZCFYb spraying solution obtained in step (3) on the surface of the BZCYYb electrode of Ni / BZCYYb - BZCYYb, spray 10 times, and dry it under a heating table at 180 °C after each spraying; then calcine at 950 °C for 2 hours to obtain the oxygen electrode of the solid oxide battery with high water vapor tolerance.
[0048] The cross-sectional view of the solid oxide battery is as Figure 1 shown. The performance of the oxygen electrode of the solid oxide battery in Example 1 was evaluated in the electrolysis mode. The test conditions are as follows: Fix the battery on a ceramic tube using silver paste and Ceramabond 552 ceramic sealant. Both ends of the battery electrodes are coated with silver grids as current collectors. After the battery is heated to 650 °C, the fuel electrode is subjected to hydrogen reduction treatment for 2 hours, and the hydrogen flow rate is set at 50 mL / min, while the oxygen electrode of the solid oxide battery prepared in Example 1 is in an air atmosphere. When the temperature reaches 650 °C, the battery is switched to the electrolysis mode, 50 mL / min of argon is introduced on the fuel electrode side, and 50 mL / min of argon is introduced on the oxygen electrode side through a water vapor generating device, and the temperature of the water vapor generating device is set at 68 °C. Under the open circuit voltage condition, the current-voltage characteristic curve was recorded, as Figure 2 shown. Further, a constant current stability test was carried out, as Figure 3 shown. All electrochemical tests were carried out using a zennium series electrochemical workstation produced by ZAHNER Company, Germany.
[0049] Effect analysis of Example 3
[0050] According to Figure 1 the results, for the solid oxide battery prepared in the embodiment of the present invention, the interface between the electrolyte and the oxygen electrode is in close contact without any fault phenomenon, indicating good compatibility between the rare earth element Yb-doped zirconium-based perovskite structure oxygen electrode material and the electrolyte.
[0051] Combined with Figure 2 and Figure 3 the data results shown, in this study, a new type of zirconium-based perovskite structure solid oxide electrolysis cell oxygen electrode material was synthesized by doping rare earth element Yb, which showed excellent stability under high water vapor. Specifically, under a voltage condition of 1.4 V, the battery achieved a current density of 2000 mA / cm 2 and maintained this current density in a high water vapor environment (30% H 2O) During continuous operation at [specific condition], the battery voltage did not show obvious attenuation, which fully proves the stability of the battery under high water vapor conditions and also indicates that the method of doping with rare earth element Yb can effectively improve the water electrolysis performance of the zirconium-based perovskite oxygen electrode material.
[0052] It should be understood that the detailed description of the technical solution of the present invention by means of the optimized embodiments above is illustrative rather than restrictive. It cannot be determined that the specific implementation manners of the present invention are limited to this. For those of ordinary skill in the technical field to which the present invention pertains, without departing from the concept of the present invention, modifying the technical solutions recorded in each embodiment or equivalently replacing some of the technical features should be regarded as belonging to the patent protection scope determined by the claims submitted for the present invention.
[0053] The above embodiments of the present invention are merely examples given to clearly illustrate the present invention and are not intended to limit the implementation manners of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made on the basis of the above description. It is not necessary and impossible to list all the implementation manners here. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention shall be included within the protection scope of the claims of the present invention.
Claims
1. A method for preparing a high-performance solid oxide electrolytic cell oxygen electrode material with a rare earth element-doped zirconium-based perovskite structure, characterized in that: The steps include: (1) Press BaZr x Co y Fe z Yb 1-x-y-z O 3-δ The precursor solution is obtained by dissolving barium carbonate, zirconium oxide, cobalt oxide, ferric oxide and ytterbium oxide in anhydrous ethanol in a stoichiometric ratio and fully milling and dissolving. x Co y Fe z Yb 1-x-y- z O 3-δ In x=0.1-0.2, y=0.4-0.6, z=0.2-0.3; (2) drying and grinding the precursor solution obtained in step (1) to obtain a precursor powder; (3) calcining the precursor powder obtained in step (2) to obtain a coarse powder of BZCFYb phase; (4) adding anhydrous ethanol to the coarse powder of the BZCFYb phase obtained in step (3), ball-milling and drying to obtain fine powder of BZCFYb; (5) After adding ethylene glycol, propylene glycol and isopropanol to the fine powder of BZCFYb obtained in step (4), the mixed solution is sprayed on BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ The electrolyte surface is calcined to obtain the solid oxide battery oxygen electrode.
2. The method for preparing a high-performance solid oxide electrolytic cell oxygen electrode material having a rare earth element-doped zirconium-based perovskite structure according to claim 1, characterized in that: In step (1), the volume ratio of the total molar amount of the barium carbonate, zirconium oxide, cobalt oxide, ferric oxide and ytterbium oxide to anhydrous ethanol is (0.1-1) mol: (40-100) mL.
3. The method for preparing a high-performance solid oxide electrolytic cell oxygen electrode material having a rare earth element-doped zirconium-based perovskite structure according to claim 1, characterized in that: In step (3), the calcination temperature is 1000-1150° C. and the calcination time is 9-15 hours.
4. The method for preparing a high-performance solid oxide electrolytic cell oxygen electrode material having a rare earth element-doped zirconium-based perovskite structure according to claim 1, characterized in that: In step (4), the ball milling time is 30-180 minutes.
5. The method for preparing a high-performance solid oxide electrolytic cell oxygen electrode material having a rare earth element-doped zirconium-based perovskite structure according to claim 1, characterized in that: In step (5), the amounts of ethylene glycol, glycerol and isopropanol are 0.5-2 mL, 0.1-1 mL and 1-10 mL respectively.
6. The method for preparing a high-performance solid oxide electrolytic cell oxygen electrode material having a rare earth element-doped zirconium-based perovskite structure according to claim 1, characterized in that: In step (5), the ball milling time is 30-60 minutes.
7. The method for preparing a high-performance solid oxide electrolytic cell oxygen electrode material having a rare earth element-doped zirconium-based perovskite structure according to claim 1, characterized in that: In step (5), the spraying times are 20-30 times, and each time the spraying is dried on a heating table at 180-250°C.
8. The method for preparing a high-performance solid oxide electrolytic cell oxygen electrode material having a rare earth element-doped zirconium-based perovskite structure according to claim 1, characterized in that: In step (5), the calcination temperature is 800-1000° C. and the calcination time is 1-4 hours.
9. A high-performance solid oxide electrolytic cell oxygen electrode material having a rare earth element-doped zirconium-based perovskite structure prepared by the preparation method according to any one of claims 1 to 8.
10. The use of a rare earth element doped zirconium-based perovskite structure high-performance solid oxide electrolytic cell oxygen electrode material according to claim 9 in the electrolysis of water to produce hydrogen reaction, characterized in that: BZCFYb was used as the oxygen electrode, Ni / BZCYYb as the fuel electrode, and BZCYYb as the electrolyte to assemble a solid oxide battery. A 30% H2O atmosphere was introduced into the oxygen electrode. The current density was 2000 mA / cm at 650°C and 1.4 V. 2 , the operating stability reaches 100h.