Monocell with thulium-doped proton conductor solid oxide electrolytic cell oxygen electrode and preparation method and application thereof
By introducing thulina elements into the Ba(ZrCoFeY)O3 system, an efficient proton conductor solid oxide electrolytic cell oxygen electrode was constructed, which solved the problems of sintering and aggregation of nickel-based electrode materials, and achieved efficient ethylene dehydrogenation reaction and low-energy electrolysis process.
Patent Information
- Application Number
- CN202510191657.9
- 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
In existing proton ceramic electrochemical cells (PCECs), nickel-based electrode materials are prone to sintering and agglomeration during operation, resulting in a decrease in active sites and affecting the effective activation and dehydrogenation reaction efficiency of ethylene.
By introducing thulina (Tm) elements doped into the Ba(ZrCoFeY)O3 system, an efficient proton conductor solid oxide electrolytic cell oxygen electrode was constructed, and the electrode material was prepared by solid phase method to improve its proton mobility and catalytic activity at lower temperatures.
An efficient ethylene dehydrogenation reaction at lower temperatures is achieved, which significantly increases the current density of electrolytic water and ethane dehydrogenation, reduces energy consumption, and avoids the generation of by-products.
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Figure CN120138658A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of electrocatalytic materials, and particularly relates to a single cell with a thulium-doped proton conductor solid oxide electrolyzer oxygen electrode, a preparation method thereof, and an application thereof. Background Art
[0002] Ethylene is widely used in the manufacture of plastics, synthetic rubbers, and other chemicals, and is an indispensable basic raw material in the modern chemical industry. Traditionally, the industrial sector relies on thermal catalytic methods to drive the ethane dehydrogenation reaction to produce ethylene. This process requires high-temperature conditions (usually exceeding 800 °C), consumes a large amount of energy, and has a huge carbon emission. With the increasing global attention to sustainable development and low-carbon economy, it has become particularly important to develop new conversion technologies to overcome this challenge.
[0003] A proton ceramic electrochemical cell (PCEC) is an electrochemical energy conversion device based on a solid-state proton conductor electrolyte, and its operating temperature range is between 400 and 700 °C. The core components of a PCEC include an anode, a cathode, and an electrolyte, and these three parts form a closed electrochemical circuit. When operating, ethane is introduced to the oxygen electrode side to undergo a dehydrogenation reaction. When a bias voltage is applied, protons migrate from the oxygen electrode to the fuel electrode side, accompanied by electrons flowing through the external circuit. Therefore, a PCEC can selectively dehydrogenate from the reaction system, making the reaction not restricted by the thermodynamic equilibrium. This means that even at a relatively low temperature, this device can achieve a high ethane conversion rate. In addition, due to the relatively mild operating conditions, the possibility of forming by-products can be reduced. Moreover, compared with the traditional thermal catalytic process, the CO 2 emissions are greatly reduced. Although PCECs exhibit great application prospects, there are certain problems with the commonly used nickel-based electrode materials in current PCECs. Nickel-based particles are prone to sintering and agglomeration during operation, resulting in a reduction in the number of active sites and affecting the effective activation of ethane molecules. It is necessary to develop new catalyst materials to address this challenge. In recent years, Ba(ZrCoFe)O 3 -based materials have attracted much attention as a new generation of proton conductor oxygen electrodes. Such materials have high proton conduction capabilities and maintain good structural stability and catalytic activity under medium and low temperature conditions, and have great potential in applications as electrodes for electrolyzing water, such as the typical proton conductor electrode material Ba(ZrCoFeY)O 3 . However, in more complex chemical processes such as ethane electrolysis reactions, Ba(ZrCoFeY)O 3The dehydrogenation reaction activity still cannot meet the actual needs, and it is urgent to improve its proton conductivity for the ethane dehydrogenation process. Research shows that the introduction of thulium (Tm) element can effectively improve the proton conductivity (Materials Today Energy, 2021, 20, 100661), enabling the material to exhibit excellent proton mobility even at lower temperatures. Therefore, introducing Tm as a dopant into the Ba(ZrCoFeY)O 3 system is a potential effective way to optimize the ethane dehydrogenation performance of the electrode. Summary of the Invention
[0004] In order to overcome the deficiencies of the existing technology, the purpose of the present invention is to provide a single cell with a thulium-doped proton conductor solid oxide electrolysis cell oxygen electrode, its preparation method and application.
[0005] The primary purpose of the present invention is to provide a preparation method of a proton conductor solid oxide electrolysis cell oxygen electrode and a single cell with high efficiency in electrolyzing water and high C 2 H 4 selectivity through thulium doping.
[0006] Another purpose of the present invention is to provide a proton conductor solid oxide electrolysis cell oxygen electrode and a single cell with high efficiency in electrolyzing water and dehydrogenating ethane prepared by the above preparation method.
[0007] Another purpose of the present invention is to provide the application of the above-mentioned proton conductor solid oxide electrolysis cell oxygen electrode with high efficiency in electrolyzing water and dehydrogenating ethane in the reactions of electrolyzing water and electrolyzing ethane.
[0008] The purpose of the present invention is achieved by at least one of the following technical solutions.
[0009] The present invention provides a preparation method for constructing a proton conductor solid oxide electrolysis cell oxygen electrode with high efficiency in electrolyzing water and dehydrogenating ethane by the solid-phase method. The preparation method includes: ball-milling stoichiometric carbonates or oxides, putting the obtained precursor into a muffle furnace for calcination to obtain a perovskite powder with a cubic crystal structure, and further obtaining the proton conductor solid oxide electrolysis cell oxygen electrode BaZr x Co y Fe z Tm 1-x-y-z O 3 (BZCFTm, x = 0.1 - 0.2, y = 0.2 - 0.4, z = 0.2 - 0.4) through ball-milling.
[0010] The present invention provides a preparation method for a single cell with a thulium-doped proton conductor solid oxide electrolysis cell oxygen electrode, including the following steps:
[0011] (1) Weigh barium carbonate, zirconia, cobalt(III) oxide and thulium oxide according to the stoichiometric ratio of BZCFTm, transfer them to a ball milling jar, add an anhydrous ethanol solution, and perform high-energy ball milling to obtain a precursor powder;
[0012] (2) Calcinate the precursor powder obtained in step (1) at a high temperature to obtain a powder with a cubic phase structure;
[0013] (3) Perform ball milling on the powder with a cubic phase structure obtained in step (2) to obtain a solid oxide electrolyzer oxygen electrode BZCFTm;
[0014] (4) Dissolve the BZCFTm powder in a mixed solution of ethylene glycol, glycerol and isopropyl alcohol. After sufficient ball milling, place a half cell with BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ (BZCYYb) as the electrolyte and Ni / BZCYYb as the fuel electrode on a high-temperature heating furnace. Spray the mixed solution onto the surface of the BZCYYb electrolyte using a spray gun, and after calcination, obtain a single cell with a proton-conducting solid oxide fuel cell oxygen electrode BZCFTm.
[0015] Further, in step (1), the ball milling time is 5 - 10 hours, preferably 7 - 10 hours, and more preferably 10 hours.
[0016] Further, in step (2), the calcination temperature is 1100 - 1200 °C, and the calcination time is 5 - 20 hours.
[0017] Further, in step (2), the heating rate of the calcination is 2 - 10 °C / min, preferably 5 °C / min.
[0018] Further, in step (3), the ball milling time is 3 - 5 hours.
[0019] Further, in step (4), the usage ratio of the solution of ethylene glycol, glycerol and isopropyl alcohol is 1 - 4:1 - 2:5 - 10, and the total usage is 5 - 30 mL.
[0020] Further, in step (4), the calcination temperature of the obtained single cell is 800 - 1200 °C, and the heating rate of the calcination is 1 - 8 °C / min.
[0021] The present invention provides a single cell with a thulium-doped proton-conducting solid oxide electrolyzer oxygen electrode prepared by the above preparation method.
[0022] The present invention provides the application of a single cell with a thulium-doped proton-conducting solid oxide electrolysis cell oxygen electrode in the reaction of electrolyzing water or electrolyzing ethane to produce ethylene. Using the BZCFTm as the oxygen electrode, Ni / BZCYYb as the fuel electrode, and BZCYYb as the electrolyte to assemble a proton-conducting solid oxide electrolysis cell, at 650 °C and an applied voltage of 1.3 V, when electrolyzing water, it reaches a high current density of -1618 mA cm -2 and when electrolyzing ethane, it reaches a high current density of -225 mA cm -2 .
[0023] The present invention introduces a porous oxygen electrode for a high-efficiency proton-conducting solid oxide electrolysis cell. This electrode not only exhibits high catalytic activity towards C 2 H 6 , but also has a series of remarkable advantages. Its preparation process uses a non-toxic raw material system to achieve green synthesis, and through parameter regulation strategies to meet the requirements of industrial production, it has environmental friendliness and scalability. Based on the oxygen electrode manufactured under the optimized conditions provided by the present invention, in the direct dehydrogenation reaction of ethane, it shows excellent catalytic activity and high selectivity towards C 2 H 4 , thus providing new possibilities for improving the application efficiency of such battery systems in the field of energy conversion. Using the highly efficient BCFZTm obtained in the present invention as the oxygen electrode, NI / BZCYYb as the fuel electrode, and BZCYYb as the electrolyte to assemble a proton-conducting solid oxide electrolysis cell, at 650 °C and an applied voltage of 1.3 V, when electrolyzing water, it can reach a high current density of -1618 mA cm -2 and when electrolyzing ethane, it reaches a high current density of -225 mA cm -2 .
[0024] Compared with the prior art, the present invention has the following advantages and beneficial effects:
[0025] 1. The present invention provides a method for preparing an oxygen electrode of a proton-conducting solid oxide electrolysis cell for efficient electrolysis of water and dehydrogenation of ethane by a solid-phase method. Through the optimized preparation process, the energy consumption is significantly reduced, and it has significant economic advantages.
[0026] 2. The method provided by the present invention for preparing an oxygen electrode of a proton-conducting solid oxide electrolysis cell for efficient electrolysis of water and dehydrogenation of ethane by simple impregnation avoids the generation of toxic gases, demonstrating the feasibility of a green synthesis process.
[0027] 3. When the oxygen electrode of the proton-conducting solid oxide electrolysis cell prepared in the present invention is at 650 °C and an applied voltage of 1.3 V, when electrolyzing water, it can reach a high current density of -1618 mA cm -2 and when electrolyzing ethane, it reaches -225 mA cm-2 High current density. Description of the Drawings
[0028] Figure 1 XRD pattern of BZCFTm for efficient electrolytic water and ethane dehydrogenation prepared by the solid-phase method in Example 1.
[0029] Figure 2 Voltammogram of the oxygen electrode of the proton-conducting solid oxide electrolytic cell prepared by the solid-phase method in electrolytic water mode in Example 1.
[0030] Figure 3 Voltammogram of the oxygen electrode of the proton-conducting solid oxide electrolytic cell prepared by the solid-phase method in electrolytic ethane mode in Example 2.
[0031] Figure 4 Element distribution map of the oxygen electrode material of the proton-conducting solid oxide electrolytic cell prepared by the solid-phase method in Example 2. Detailed Description of the Invention
[0032] The following further illustrates the specific implementation of the present invention in combination 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. The reagents or instruments used without indicating the manufacturer are regarded as conventional products that can be obtained through commercial purchase.
[0033] The carbonates or oxides used are all purchased from Shanghai Macklin Biochemical Technology Co., Ltd.; the proton-conducting anode support is prepared by the dry pressing method.
[0034] Example 1
[0035] (1) Weigh 0.05 mol of barium carbonate, 0.05 mol of zirconium oxide, 0.05 mol of cobalt trioxide, 0.05 mol of iron oxide, and 0.05 mol of thulium oxide according to the stoichiometric ratio of BZCFTm, place them in a ball mill jar, use anhydrous ethanol as a solvent, and ball mill for 10 h to obtain a slurry;
[0036] (2) Place the slurry obtained in step (1) in an oven and dry at 180 °C for 5 h to obtain a precursor;
[0037] (3) Put the precursor powder collected in step (2) into a muffle furnace and calcine it into cubic-phase BZCFTm, with a heating rate of 5 °C / min and calcine at 1100 °C for 10 hours;
[0038] (4) Ball mill the BZCFTm obtained in step (3) for 1 h to obtain a powder with a smaller particle size;
[0039] (5) Spray the BZCFTm powder obtained in step (4) on the surface of the Ni-BZCYYb / BZCYYb electrode (0.25 cm 2 , with a thickness of 20 μm), and then calcine it at 1000 °C for 2 hours to obtain a proton-conducting solid oxide electrolytic cell for efficient electrolysis of water and dehydrogenation of ethane (with a thickness of 400 μm).
[0040] Example 2
[0041] (1) Weigh 0.1 mol of barium carbonate, 0.1 mol of zirconium oxide, 0.1 mol of cobalt trioxide, 0.1 mol of iron oxide, and 0.1 mol of thulium oxide according to the stoichiometric ratio of BZCFTm, place them in a ball-milling jar, use absolute ethanol as a solvent, and ball-mill for 15 h to obtain a slurry;
[0042] (2) Place the slurry obtained in step (1) in an oven and dry it at 180 °C for 10 h to obtain a precursor;
[0043] (3) Put the precursor powder collected in step (2) into a muffle furnace and calcine it into cubic-phase BZCFTm at a heating rate of 5 °C / min and calcine it at 1100 °C for 10 hours;
[0044] (4) Ball-mill the BZCFTm obtained in step (3) for 5 h to obtain a powder with a smaller particle size;
[0045] (5) Brush the BZCFTm powder obtained in step (4) on the surface of the Ni / BZCYYb-BZCYYb electrode (0.25 cm 2 , with a thickness of 15 μm), and then calcine it at 1000 °C for 2 hours to obtain a proton-conducting solid oxide electrolytic cell for efficient electrolysis of water and dehydrogenation of ethane (with a thickness of 300 μm).
[0046] Perform performance tests on the oxygen electrode of the proton-conducting solid oxide electrolytic cell prepared by the solid-phase method in Example 2 under the modes of water electrolysis and ethane electrolysis. Silver paste and ceramic sealant (Ceramabond 552) are used to seal the PCEC to the ceramic tube. Silver glue is applied as a current collector on both electrodes of the cell. After heating the cell to 650 °C, hydrogen is introduced into the fuel electrode for reduction for 2 hours at a flow rate of 50 mL / min. After the voltage is stable, it is switched to argon, and the current-voltage (I-V) curve is measured at 650 °C, as Figure 2 shown. The gas on the porous oxygen electrode side of the proton-conducting solid oxide electrolytic cell in Example 2 is switched to 10% (the volume ratio of ethane to the total volume of ethane and argon) ethane (flow rate 20 mL / min), and the current-voltage curve is tested, as Figure 3 shown. All the instruments used for the electrochemical tests are the zennium series electrochemical workstations of ZAHNER Company in Germany.
[0047] Example 3
[0048] (1) Weigh 0.02 mol of barium carbonate, 0.02 mol of zirconia, 0.02 mol of cobalt sesquioxide, 0.02 mol of iron oxide, and 0.02 mol of thulium oxide according to the stoichiometric ratio of BZCFTm, place them in a ball mill jar, use absolute ethanol as the solvent, and ball mill for 5 h to obtain a slurry;
[0049] (2) Place the slurry obtained in step (1) in an oven and dry it at 180 °C for 5 h to obtain a precursor;
[0050] (3) Put the precursor powder collected in step (2) into a muffle furnace and calcine it into cubic-phase BZCFTm at a heating rate of 4 °C / min and calcine it at 1100 °C for 8 hours;
[0051] (4) Ball mill the BZCFTm obtained in step (3) for 2 h to obtain a powder with a smaller particle size;
[0052] (5) Spray the BZCFTm powder obtained in step (4) on the surface of the Ni / BZCYYb - BZCYYb electrode (0.25 cm 2 , with a thickness of 25 μm), and then calcine it at 1000 °C for 2 hours to obtain a proton-conducting solid oxide electrolysis cell for efficient electrolysis of water and dehydrogenation of ethane (with a thickness of 380 μm).
[0053] Effect analysis
[0054] Combined with Figure 1 、 Figure 2 and Figure 3 The results show that through the solid-phase method, the cubic-phase BZCFTm can be synthesized in the embodiments of the present invention, and a porous oxygen electrode of a proton-conducting solid oxide electrolysis cell can be prepared, which has excellent electrochemical activity in the water electrolysis mode. When the working temperature is set at 650 °C and the applied voltage is 1.3 V, the current density during water electrolysis reaches -1618 mA cm -2 at a high level, and the current density during ethane electrolysis reaches -225 mA cm -2 at a high level.
[0055] It should be understood that the above detailed description of the technical solution of the present invention with the help of the optimized embodiments is illustrative rather than restrictive. It cannot be determined that the specific implementation manner of the present invention is limited to this. For those of ordinary skill in the technical field to which the present invention belongs, 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 by the present invention.
[0056] The above embodiments of the present invention are merely examples for clearly illustrating the present invention, rather than limitations on 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 based on the above description. It is not necessary and impossible to enumerate all implementation manners here. Any modifications, equivalent substitutions, 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 single cell having a thulium-doped proton conductor solid oxide electrolyzer oxygen electrode, characterized in that: The steps include: (1) Press BaZr x Co y Fe z Tm 1-x-y-z The stoichiometric ratio of barium carbonate, zirconium oxide, cobalt trioxide and thulium oxide were weighed, transferred to a ball mill, anhydrous ethanol was added, and a uniform slurry was obtained after sufficient ball milling, and a precursor was obtained after drying; the BaZr x Co y Fe z Tm 1-x-y-z In O3, x=0.1-0.2, y=0.2-0.4, z=0.2-0.4; (2) calcining the precursor obtained in step (1) at high temperature to obtain a powder having a cubic crystal structure; (3) further ball-milling the powder obtained in step (2) to obtain a proton conductor solid oxide electrolytic cell porous oxygen electrode powder BZCFTm; (4) Dissolve BZCFTm powder in a mixed solution of ethylene glycol, propylene glycol, and isopropanol, and after sufficient ball milling, mix BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ A half-cell with (BZCYYb) as the electrolyte and Ni / BZCYYb as the fuel electrode was placed on a high-temperature heating furnace, and the mixed solution was sprayed on the surface of the BZCYYb electrolyte using a spray gun. After calcination, a single cell with a proton conductor solid oxide cell oxygen electrode BZCFTm was obtained.
2. The method for preparing a single cell having a thulium-doped proton conductor solid oxide electrolyzer oxygen electrode according to claim 1, characterized in that: In step (1), the ball milling time is 5-10 hours.
3. The method for preparing a single cell having a thulium-doped proton conductor solid oxide electrolyzer oxygen electrode according to claim 1, characterized in that: In step (2), the calcination temperature is 1000-1100° C. and the calcination time is 10-20 hours.
4. The method for preparing a single cell having a thulium-doped proton conductor solid oxide electrolyzer oxygen electrode according to claim 1, characterized in that: In step (2), the heating rate of calcination is 2-10°C / min.
5. The method for preparing a thulium-doped proton conductor solid oxide electrolytic cell oxygen electrode according to claim 1, characterized in that: In step (3), the ball milling time is 3-5 hours.
6. The method for preparing a single cell having a thulium-doped proton conductor solid oxide electrolyzer oxygen electrode according to claim 1, characterized in that: In step (4), the ratio of ethylene glycol, propylene glycol and isopropanol solution used is 1-4:1-2:5-10, and the total amount used is 5-30 mL.
7. The method for preparing a single cell having a thulium-doped proton conductor solid oxide electrolyzer oxygen electrode according to claim 1, characterized in that: In step (4), the calcination temperature of the single cell is 800-1200° C., and the calcination heating rate is 1-8° C. / min.
8. A single cell having a thulium-doped proton conductor solid oxide electrolyzer oxygen electrode prepared by the preparation method according to any one of claims 1 to 7.
9. Use of a single cell having a thulium-doped proton conductor solid oxide electrolyzer oxygen electrode as claimed in claim 8 in the electrolysis of water or the electrolysis of ethane to produce ethylene.
10. The use according to claim 9, characterized in that: The BZCFTm was used as an oxygen electrode, Ni / BZCYYb as a fuel electrode, and BZCYYb as an electrolyte to assemble a proton conductor solid oxide electrolytic cell. When the applied voltage was 1.3 V at 650 ° C, the electrolysis of water reached -1618 mA cm -2 High current density, reaching -225mA cm in ethane electrolysis -2 high current density.