Preparation method of anode, anode structure and solid oxide fuel cell system
By adding a catalyst layer and a dilution layer to the anode structure of the solid oxide fuel cell, the performance degradation caused by carbon deposition is solved, the treatment efficiency of biomass waste is improved, and the cost and environmental impact are reduced.
Patent Information
- Application Number
- CN202311815656.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-12-25
- Publication Date
- 2025-06-27
AI Technical Summary
In solid oxide fuel cells, carbon deposition phenomenon leads to a decrease in fuel cell performance, a decrease in reaction rate, and a low efficiency in handling biomass waste.
In the anode structure, an independent catalyst layer and a dilution layer are added. The catalyst layer is composed of nickel-based nanoparticles and cerium-zirconium composite oxide. The dilution layer serves as a transition layer between the catalyst layer and the electrolyte layer to reduce reaction and diffusion.
Effectively inhibit the formation of solid carbon layers, reduce the impact of carbon deposition on electrode performance, improve the treatment and utilization efficiency of solid oxide fuel cell systems on biomass waste, and reduce cost and environmental impact.
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Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of solid oxide fuel cells, and particularly relates to a preparation method of an anode, an anode structure, and a solid oxide fuel cell system. Background Art
[0002] High-efficiency, clean, and low-cost energy conversion technologies using renewable energy as raw materials help alleviate the shortage of fossil energy and environmental pollution problems. Biomass, as a renewable energy source, is known as the "fourth-largest energy source" after coal, oil, and natural gas, and is an ideal alternative energy source. Its utilization and conversion process can achieve carbon dioxide (CO2) recycling, which helps reduce carbon dioxide emissions.
[0003] A solid oxide fuel cell (SOFC) can use biomass gas as fuel for power generation. A solid oxide fuel cell system based on biomass gasification is a feasible and promising energy conversion technology. However, when a carbon-containing fuel gas reacts with the porous anode (usually composed of nickel and ceramics) of a solid oxide fuel cell at high temperature, some side reactions will occur, such as the thermal decomposition of methane and the disproportionation of carbon monoxide, resulting in the deposition of carbon atoms on the anode surface to form solid carbon. This phenomenon is called carbon deposition. Carbon deposition has a great negative impact on fuel cells, such as hindering the mass transfer and diffusion of fuel gas in the porous medium, increasing the resistance and overpotential of the anode, reducing the reaction rate and reactivity, etc. Therefore, in order to improve the performance and durability of fuel cells, it is urgent to take some measures to inhibit or eliminate carbon deposition. Summary of the Invention
[0004] To solve or improve at least one of the above technical problems, an object of the present invention is to provide a preparation method of an anode of a solid oxide fuel cell.
[0005] Another object of the present invention is to provide an anode structure.
[0006] Another object of the present invention is to provide a solid oxide fuel cell system.
[0007] To achieve the above object, the first aspect of the present invention provides a preparation method of an anode of a solid oxide fuel cell, including: preparing an anode support; preparing an electrolyte layer, the electrolyte layer covering the anode support; preparing a dilution layer composed of yttria-stabilized zirconia, nickel-based nanoparticles, and cerium-zirconium composite oxide, the dilution layer covering the electrolyte layer; preparing a catalyst layer composed of nickel-based nanoparticles and cerium-zirconium composite oxide, the catalyst layer covering the dilution layer.
[0008] According to the technical solution of the preparation method of the anode of the solid oxide fuel cell provided by the present invention, on the one hand, by adding an independent catalyst layer to the anode structure, it can effectively convert the biogas into carbon monoxide (CO) and hydrogen (H2) that can be used in the solid oxide fuel cell system in a carbon-containing fuel atmosphere. This can avoid the direct contact between hydrocarbons and the anode, which is beneficial to inhibiting the formation of the solid carbon layer and reducing the influence of carbon deposition on the electrode performance. It can also improve the treatment and utilization efficiency of the solid oxide fuel cell system for biomass waste, reduce costs and environmental impacts; on the other hand, by adding a dilution layer to the anode structure, the dilution layer, as a transition layer between the catalyst layer and the electrolyte layer, can reduce reactions and diffusion and maintain the structural stability of the battery.
[0009] Specifically, the specific steps of the preparation method of the anode of the solid oxide fuel cell include:
[0010] The first step is to prepare the anode support. The anode support is the support structure of the electrode. Optionally, the anode support includes yttria-stabilized zirconia and nickel oxide. Among them, the chemical formula of yttria (Y2O3)-stabilized zirconia (ZrO2) is YSZ. The chemical formula of nickel oxide is NiO. Optionally, the mass ratio of yttria-stabilized zirconia in the anode support is 35% to 45%. By controlling the mass ratio of yttria-stabilized zirconia in the anode support, the chemical properties of the anode structure can be ensured. Optionally, the mass ratio of nickel oxide in the anode support is 55% to 65%. By controlling the mass ratio of nickel oxide in the anode support, the structural properties of the anode structure can be ensured, so that the anode structure has sufficient structural strength. In the anode support, the mass ratio between yttria-stabilized zirconia and nickel oxide is preferably 2:3.
[0011] The second step is to prepare the electrolyte layer, and the electrolyte layer covers the anode support. Optionally, the electrolyte layer includes YSZ (yttria-stabilized zirconia). By covering the electrolyte layer on the anode support, the chemical properties of the anode structure can be ensured.
[0012] The third step is to prepare a dilution layer composed of yttria-stabilized zirconia, nickel-based nanoparticles, and cerium-zirconium composite oxide, and the dilution layer covers the electrolyte layer. The dilution layer (DL layer) is mixed with YSZ, nickel-based nanoparticles, and cerium-zirconium composite oxide. The dilution layer, as a transition layer between the catalyst layer and the electrolyte layer, can reduce reactions and diffusion and maintain the structural stability of the battery.
[0013] Step 4: Prepare a catalyst layer composed of nickel-based nanoparticles and cerium-zirconium composite oxide, which covers the dilution layer. The catalyst layer (Ni-CZO) includes nickel-based nanoparticles and cerium-zirconium composite oxide, and has a high specific surface area and high catalytic activity. Among them, the specific surface area refers to the total area possessed by a unit mass of material. The catalyst layer exhibits excellent electrochemical performance and durability in a biomass atmosphere containing hydrocarbons such as methane, ethane, and propane. Compared with traditional YSZ-based anode materials, its maximum power density increases from 320.3 mW / cm 2 to 486.2 mW / cm 2 , an increase of 51.8%, and no obvious carbon deposition phenomenon is found after long-term operation. Optionally, the catalyst layer adopts a tape casting-isostatic pressing-sintering process and can be prepared in batches.
[0014] In the technical solution defined by the present invention, on the one hand, by adding an independent catalyst layer in the anode structure, it is possible to effectively convert biomass gas into carbon monoxide (CO) and hydrogen (H2) that can be used in a solid oxide fuel cell system in a carbonaceous fuel atmosphere. In this way, it is possible to avoid direct contact between hydrocarbons and the anode, which is conducive to suppressing the formation of a solid carbon layer and reducing the influence of carbon deposition on the electrode performance. It can also improve the treatment and utilization efficiency of biomass waste in the solid oxide fuel cell system, reduce costs and environmental impacts; on the other hand, by adding a dilution layer in the anode structure, the dilution layer, as a transition layer between the catalyst layer and the electrolyte layer, can reduce reactions and diffusion and maintain the structural stability of the battery.
[0015] In addition, the above technical solution provided by the present invention may also have the following additional technical features:
[0016] In some technical solutions, optionally, to prepare a catalyst layer composed of nickel-based nanoparticles and cerium-zirconium composite oxide, which covers the dilution layer, includes: mixing nickel nitrate, cerium nitrate, and zirconium nitrate to obtain a mixed metal precipitate; obtaining nickel-based nanoparticles and cerium-zirconium composite oxide in powder form from the mixed metal precipitate; covering the nickel-based nanoparticles and cerium-zirconium composite oxide on the dilution layer to obtain the catalyst layer.
[0017] In this technical solution, the specific steps for preparing the catalyst layer include:
[0018] Mixing nickel nitrate, cerium nitrate, and zirconium nitrate to obtain a mixed metal precipitate. Mix nickel nitrate, cerium nitrate, and zirconium nitrate in a certain molar ratio, add a complex, adjust the pH value of the solution, stir evenly and then let it stand, and finally obtain a mixed metal precipitate.
[0019] Nickel-based nanoparticles and cerium-zirconium composite oxide in powder form are obtained by mixing metal precipitates. After subjecting the mixed metal precipitates to a series of treatments such as filtration, washing, and drying, nickel-based nanoparticles and cerium-zirconium composite oxide in powder form are obtained.
[0020] The nickel-based nanoparticles and the cerium-zirconium composite oxide are coated on a dilution layer to obtain a catalyst layer. The nickel-based nanoparticles and the cerium-zirconium composite oxide are mixed with a binder and stirred evenly, then coated on a YSZ-based anode material, dried, and sintered to obtain a catalyst layer.
[0021] In the technical solution defined by the present invention, the catalyst layer adopts a process of casting-isostatic pressing-sintering, and can be prepared in batches.
[0022] In some technical solutions, optionally, mixing nickel nitrate, cerium nitrate, and zirconium nitrate to obtain a mixed metal precipitate includes: mixing nickel nitrate, cerium nitrate, and zirconium nitrate to obtain a first mixed solution; adding a complexing agent to the first mixed solution to obtain a second mixed solution; adjusting the pH value of the second mixed solution to a first pH value; stirring the second mixed solution; allowing the stirred second mixed solution to stand, and obtaining a mixed metal precipitate.
[0023] In this technical solution, the specific steps of obtaining a mixed metal precipitate from nickel, cerium, and zirconium nitrates include:
[0024] Mixing nickel nitrate, cerium nitrate, and zirconium nitrate to obtain a first mixed solution. The nickel, cerium, and zirconium nitrates are mixed in a molar ratio of (1.8 - 2.2):(0.8 - 1.2):(0.8 - 1.2). Optionally, the nickel, cerium, and zirconium nitrates are mixed in a molar ratio of 2:1:1.
[0025] Adding a complexing agent to the first mixed solution to obtain a second mixed solution. Optionally, the complexing agent includes ethylenediaminetetraacetic acid (EDTA). A complexing agent is a compound that can form complex ions with metal ions, effectively removing metal impurities, improving the purity and stability of the solution, enhancing the buffering capacity of the solution, and preventing changes in the pH value.
[0026] Adjusting the pH value of the second mixed solution to a first pH value. Optionally, the first pH value is 8.5 to 9.5. The first pH value is preferably 9.
[0027] Stirring the second mixed solution. After stirring evenly, it is beneficial for various chemical substances to come into full contact and carry out complexation reactions.
[0028] Let the stirred second mixed solution stand to obtain a mixed metal precipitate. The standing time of the second mixed solution is the first time, and the first time is 23 h to 25 h. By controlling the standing time, on the one hand, it can avoid too short a standing time to ensure the full precipitation of the mixed metal precipitate; on the other hand, it can avoid too long a standing time, which is beneficial to improving the preparation efficiency and shortening the preparation cycle.
[0029] In some technical solutions, optionally, nickel-based nanoparticles and cerium-zirconium composite oxide in powder form are obtained from the mixed metal precipitate, including: filtering, washing, and drying the mixed metal precipitate; calcining the treated mixed metal precipitate at the first temperature to obtain nickel-based nanoparticles and cerium-zirconium composite oxide in powder form.
[0030] In this technical solution, the specific steps for obtaining nickel-based nanoparticles and cerium-zirconium composite oxide in powder form from the mixed metal precipitate include:
[0031] Filter, wash, and dry the mixed metal precipitate. A series of steps such as filtering, washing, and drying help to remove some impurities, which is beneficial to improving the purity of the nickel-based nanoparticles and cerium-zirconium composite oxide in powder form.
[0032] Calcine the treated mixed metal precipitate at the first temperature to obtain nickel-based nanoparticles and cerium-zirconium composite oxide in powder form. Optionally, the first temperature is 550 °C to 650 °C. The first temperature is preferably 600 °C. The calcination time of the mixed metal precipitate is the second time, and the second time is 1.5 h to 2.5 h. Optionally, the second time is preferably 2 h.
[0033] In some technical solutions, optionally, the first temperature is 550 °C to 650 °C.
[0034] In this technical solution, by controlling the calcination temperature of the mixed metal precipitate, on the one hand, it can avoid too low a calcination temperature (the first temperature) to ensure sufficient calcination of the mixed metal precipitate; on the other hand, it can avoid too high a calcination temperature, which is beneficial to saving energy and reducing the possibility of other chemical reactions occurring at too high a temperature.
[0035] In some technical solutions, optionally, the calcination time of the mixed metal precipitate is the second time, and the second time is 1.5 h to 2.5 h.
[0036] In this technical solution, by controlling the calcination time of the mixed metal precipitate, on the one hand, it can avoid too short a calcination time (the second time) to ensure sufficient calcination of the mixed metal precipitate; on the other hand, it can avoid too long a calcination time, which is beneficial to improving the preparation efficiency and shortening the preparation cycle.
[0037] In some technical solutions, optionally, nickel-based nanoparticles and cerium-zirconium composite oxides are coated on the dilution layer to obtain a catalyst layer, including: mixing nickel-based nanoparticles, cerium-zirconium composite oxides, polyvinylpyrrolidone and ethanol to obtain a first mixed coating; coating the first mixed coating on the dilution layer, drying and then sintering at a second temperature to obtain the catalyst layer.
[0038] In this technical solution, coating nickel-based nanoparticles and cerium-zirconium composite oxides on the dilution layer to obtain a catalyst layer, the specific steps include:
[0039] Mix nickel-based nanoparticles, cerium-zirconium composite oxides, polyvinylpyrrolidone and ethanol to obtain a first mixed coating. Among them, polyvinylpyrrolidone (PVP) is a non-ionic polymer compound. Ethanol is a kind of alcohol compound with the chemical formula C2H6O. Mix nickel-based nanoparticles, cerium-zirconium composite oxides, polyvinylpyrrolidone and ethanol according to the mass ratio of (2.8 - 3.2):(1.8 - 2.2):(1.8 - 2.2):(0.8 - 1.2). Optionally, mix nickel-based nanoparticles, cerium-zirconium composite oxides, polyvinylpyrrolidone and ethanol according to the mass ratio of 3:2:2:1.
[0040] Coat the first mixed coating on the dilution layer, dry and then sinter at a second temperature to obtain the catalyst layer. Stir the mixed substances evenly and then coat them on the YSZ-based anode material. After the first mixed coating is dried, sinter it at a second temperature to obtain the catalyst layer. Optionally, the second temperature is 750 °C to 850 °C. The second temperature is preferably 800 °C. Optionally, the sintering time of the dried first mixed coating is the third time, and the third time is 1.5 h to 2.5 h. The third time is preferably 2 h.
[0041] In some technical solutions, optionally, the second temperature is 750 °C to 850 °C.
[0042] In this technical solution, by controlling the temperature during the sintering of the dried first mixed coating, on the one hand, it can avoid too low sintering temperature (the second temperature) to ensure sufficient sintering of the dried first mixed coating; on the other hand, it can avoid too high sintering temperature, which is beneficial to saving energy and reducing the possibility of other chemical reactions occurring at too high temperatures.
[0043] In some technical solutions, optionally, the sintering time of the dried first mixed coating is the third time, and the third time is 1.5 h to 2.5 h.
[0044] In this technical solution, by controlling the sintering time of the dried first mixed coating, on the one hand, it is possible to avoid too short a sintering time (the third time) to ensure sufficient sintering of the first mixed coating; on the other hand, it is possible to avoid too long a sintering time, which is beneficial to improving the preparation efficiency and shortening the preparation cycle.
[0045] In some technical solutions, optionally, a dilution layer composed of yttria-stabilized zirconia, nickel-based nanoparticles, and cerium-zirconium composite oxide is prepared, and the dilution layer covers the electrolyte layer, including: mixing yttria-stabilized zirconia in powder form, nickel-based nanoparticles, and cerium-zirconium composite oxide in powder form, adding a binder and stirring to form a slurry; coating the slurry on the electrolyte layer, drying and sintering at a third temperature to obtain the dilution layer.
[0046] In this technical solution, the specific steps for preparing the dilution layer include:
[0047] Mix yttria-stabilized zirconia in powder form, nickel-based nanoparticles, and cerium-zirconium composite oxide in powder form, add a binder and stir to form a slurry. Optionally, the binder includes polyethylene glycol. By adding the binder, it is beneficial to improve the bonding performance of the slurry and have a stronger adsorption capacity.
[0048] Coat the slurry on the electrolyte layer, dry and sinter at a third temperature to obtain the dilution layer. Optionally, the third temperature is 750°C to 850°C. The third temperature is preferably 800°C. Optionally, the sintering time for the dried slurry is the fourth time, and the fourth time is 1.5 h to 2.5 h. The fourth time is preferably 2 h.
[0049] In some technical solutions, optionally, the third temperature is 750°C to 850°C.
[0050] In this technical solution, by controlling the temperature during sintering of the dried slurry, on the one hand, it is possible to avoid too low a sintering temperature (the third temperature) to ensure sufficient sintering of the dried slurry; on the other hand, it is possible to avoid too high a sintering temperature, which is beneficial to saving energy and reducing the possibility of other chemical reactions occurring at too high a temperature.
[0051] In some technical solutions, optionally, the sintering time for the dried slurry is the fourth time, and the fourth time is 1.5 h to 2.5 h.
[0052] In this technical solution, by controlling the sintering time of the dried slurry, on the one hand, it is possible to avoid too short a sintering time (the fourth time) to ensure sufficient sintering of the dried slurry; on the other hand, it is possible to avoid too long a sintering time, which is beneficial to improving the preparation efficiency and shortening the preparation cycle.
[0053] In some technical solutions, optionally, preparing the anode support includes: preparing an anode support composed of yttria-stabilized zirconia and nickel oxide.
[0054] In this technical solution, the chemical formula of yttria (Y2O3)-stabilized zirconia (ZrO2) is YSZ. The chemical formula of nickel oxide is NiO. Optionally, the mass proportion of yttria-stabilized zirconia in the anode support is 35% to 45%. By controlling the mass proportion of yttria-stabilized zirconia in the anode support, the chemical properties of the anode structure can be ensured. Optionally, the mass proportion of nickel oxide in the anode support is 55% to 65%. By controlling the mass proportion of nickel oxide in the anode support, the structural properties of the anode structure can be ensured, making the anode structure have sufficient structural strength. In the anode support, the mass ratio between yttria-stabilized zirconia and nickel oxide is preferably 2:3.
[0055] In some technical solutions, optionally, the mass proportion of yttria-stabilized zirconia in the anode support is 35% to 45%.
[0056] In this technical solution, by controlling the mass proportion of yttria-stabilized zirconia in the anode support, the chemical properties of the anode structure can be ensured.
[0057] In some technical solutions, optionally, the mass proportion of nickel oxide in the anode support is 55% to 65%.
[0058] In this technical solution, by controlling the mass proportion of nickel oxide in the anode support, the structural properties of the anode structure can be ensured, making the anode structure have sufficient structural strength.
[0059] In some technical solutions, optionally, preparing the electrolyte layer, where the electrolyte layer covers the anode support, includes: preparing an electrolyte layer composed of yttria-stabilized zirconia, and the electrolyte layer covers the anode support.
[0060] In this technical solution, by covering the electrolyte layer on the anode support, the chemical properties of the anode structure can be ensured.
[0061] The second aspect of the present invention provides an anode structure, which is prepared by the preparation method of the anode of the solid oxide fuel cell in any of the above technical solutions.
[0062] According to the technical solution of the anode structure provided by the present invention, the anode structure is prepared by the preparation method of the anode of the solid oxide fuel cell in any of the above technical solutions. The anode structure includes an anode support, an electrolyte layer, a dilution layer, and a catalyst layer. Among them, the electrolyte layer covers the anode support. By covering the electrolyte layer on the anode support, the chemical properties of the anode structure can be ensured. Further, the dilution layer covers the electrolyte layer. By adding a dilution layer to the anode structure, the dilution layer serves as a transition layer between the catalyst layer and the electrolyte layer, which can reduce reactions and diffusion and maintain the structural stability of the battery. Further, the catalyst layer covers the dilution layer. By adding an independent catalyst layer to the anode structure, under a carbon-containing fuel atmosphere, biomass gas can be effectively converted into carbon monoxide (CO) and hydrogen (H2) that can be used in a solid oxide fuel cell system. This can avoid direct contact between hydrocarbons and the anode, thereby facilitating the inhibition of the formation of a solid carbon layer and reducing the impact of carbon deposition on the electrode performance. It can also improve the treatment and utilization efficiency of biomass waste in the solid oxide fuel cell system, reduce costs and environmental impacts.
[0063] The third aspect of the present invention provides a solid oxide fuel cell system, including the anode structure in the above technical solution.
[0064] According to the technical solution of the solid oxide fuel cell system provided by the present invention, the solid oxide fuel cell system includes the anode structure in the above technical solution. The solid oxide fuel cell system has the beneficial effects of the above technical solution and will not be elaborated here. Description of the Drawings
[0065] Figure 1 Shows a flowchart of the preparation method of the anode of the solid oxide fuel cell according to an embodiment of the present invention;
[0066] Figure 2 Shows one of the flowcharts of the preparation method of the catalyst layer according to an embodiment of the present invention;
[0067] Figure 3 Shows another flowchart of the preparation method of the catalyst layer according to an embodiment of the present invention;
[0068] Figure 4 Shows a flowchart of the preparation method of the dilution layer according to an embodiment of the present invention;
[0069] Figure 5 Shows a schematic diagram of the anode structure according to an embodiment of the present invention;
[0070] Figure 6 Shows a schematic diagram of the solid oxide fuel cell system according to an embodiment of the present invention.
[0071] Among them, Figure 5 and Figure 6 the corresponding relationship between the reference numerals and the component names in the drawings is as follows:
[0072] 500: Anode structure; 510: Anode support; 520: Electrolyte layer; 530: Dilution layer; 540: Catalyst layer; 600: Solid oxide fuel cell system. Detailed implementation manners
[0073] To make the objectives, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without making creative efforts shall fall within the protection scope of the present invention.
[0074] In an embodiment according to the present invention, as Figure 1 shown, the specific steps of the preparation method of the anode of the solid oxide fuel cell include:
[0075] S102, Prepare the anode support. The anode support is the support structure of the electrode. Optionally, the anode support includes yttria-stabilized zirconia and nickel oxide. Among them, the chemical formula of yttria (Y2O3)-stabilized zirconia (ZrO2) is YSZ. The chemical formula of nickel oxide is NiO. Optionally, the mass ratio of yttria-stabilized zirconia in the anode support is 35% to 45%. By controlling the mass ratio of yttria-stabilized zirconia in the anode support, the chemical properties of the anode structure can be ensured. Optionally, the mass ratio of nickel oxide in the anode support is 55% to 65%. By controlling the mass ratio of nickel oxide in the anode support, the structural properties of the anode structure can be ensured, so that the anode structure has sufficient structural strength. In the anode support, the mass ratio between yttria-stabilized zirconia and nickel oxide is preferably 2:3.
[0076] S104, Prepare the electrolyte layer, and the electrolyte layer covers the anode support. Optionally, the electrolyte layer includes YSZ (yttria-stabilized zirconia). By covering the electrolyte layer on the anode support, the chemical properties of the anode structure can be ensured.
[0077] S106. Prepare a dilution layer composed of yttria-stabilized zirconia, nickel-based nanoparticles, and cerium-zirconium composite oxide, and the dilution layer covers the electrolyte layer. The dilution layer (DL layer) is formed by mixing YSZ, nickel-based nanoparticles, and cerium-zirconium composite oxide. The dilution layer serves as a transition layer between the catalyst layer and the electrolyte layer, which can reduce reactions and diffusion and maintain the structural stability of the battery.
[0078] S108. Prepare a catalyst layer composed of nickel-based nanoparticles and cerium-zirconium composite oxide, and the catalyst layer covers the dilution layer. The catalyst layer (Ni-CZO) includes nickel-based nanoparticles and cerium-zirconium composite oxide, and has a high specific surface area and high catalytic activity. Among them, the specific surface area refers to the total area per unit mass of the material. The catalyst layer exhibits excellent electrochemical performance and durability in a biomass atmosphere containing hydrocarbons such as methane, ethane, and propane. Compared with traditional YSZ-based anode materials, its maximum power density increases from 320.3 mW / cm 2 to 486.2 mW / cm 2 , an increase of 51.8%, and no obvious carbon deposition phenomenon is found after long-term operation. Optionally, the catalyst layer adopts a tape casting-isostatic pressing-sintering process and can be prepared in batches.
[0079] In the technical solutions defined in the present invention, on the one hand, by adding an independent catalyst layer to the anode structure, it is possible to effectively convert biomass gas into carbon monoxide (CO) and hydrogen (H2) that can be used in a solid oxide fuel cell system in a carbonaceous fuel atmosphere. This can avoid direct contact between hydrocarbons and the anode, which is beneficial to suppressing the formation of a solid carbon layer and reducing the impact of carbon deposition on the electrode performance. It can also improve the treatment and utilization efficiency of biomass waste in the solid oxide fuel cell system, reduce costs and environmental impacts; on the other hand, by adding a dilution layer to the anode structure, the dilution layer serves as a transition layer between the catalyst layer and the electrolyte layer, which can reduce reactions and diffusion and maintain the structural stability of the battery.
[0080] In some embodiments, optionally, as Figure 2 shown, the specific steps of the preparation method of the catalyst layer include:
[0081] S202. Mix nickel nitrate, cerium nitrate, and zirconium nitrate to obtain a mixed metal precipitate. Nickel nitrate, cerium nitrate, and zirconium nitrate are mixed in a certain molar ratio. After adding a complex, the pH value of the solution is adjusted, stirred evenly, and then left standing to finally obtain a mixed metal precipitate.
[0082] S204. Nickel-based nanoparticles and cerium-zirconium composite oxide in powder form are obtained from the mixed metal precipitate. The mixed metal precipitate is subjected to a series of treatments such as filtration, washing, and drying to obtain nickel-based nanoparticles and cerium-zirconium composite oxide in powder form.
[0083] S206. The nickel-based nanoparticles and the cerium-zirconium composite oxide are coated on the dilution layer to obtain a catalyst layer. The nickel-based nanoparticles and the cerium-zirconium composite oxide are mixed with a binder and stirred evenly, then coated on the YSZ-based anode material and dried, followed by sintering to obtain the catalyst layer.
[0084] In the technical solution defined by the present invention, the catalyst layer adopts the process of tape casting-isostatic pressing-sintering and can be prepared in batches.
[0085] In some embodiments, optionally, as Figure 3 shown, the specific steps of the preparation method of the catalyst layer include:
[0086] S302. Nickel nitrate, cerium nitrate, and zirconium nitrate are mixed to obtain a first mixed solution. The nitrates of nickel, cerium, and zirconium are mixed at a molar ratio of (1.8 - 2.2):(0.8 - 1.2):(0.8 - 1.2). Optionally, the nitrates of nickel, cerium, and zirconium are mixed at a molar ratio of 2:1:1.
[0087] S304. A complexing agent is added to the first mixed solution to obtain a second mixed solution. Optionally, the complexing agent includes ethylenediaminetetraacetic acid (EDTA). The complexing agent is a compound that can form complex ions with metal ions, effectively removing metal impurities, improving the purity and stability of the solution, enhancing the buffering capacity of the solution, and preventing changes in the pH value.
[0088] S306. The pH value of the second mixed solution is adjusted to a first pH value. Optionally, the first pH value is 8.5 to 9.5. The first pH value is preferably 9.
[0089] S308. The second mixed solution is stirred. After stirring evenly, it is beneficial for various chemical substances to come into full contact and carry out complexation reactions.
[0090] S310. The stirred second mixed solution is allowed to stand, and a mixed metal precipitate is obtained. The standing time of the second mixed solution is a first time, and the first time is 23h to 25h. By controlling the standing time, on the one hand, it can avoid too short a standing time to ensure the full precipitation of the mixed metal precipitate; on the other hand, it can avoid too long a standing time, which is beneficial to improving the preparation efficiency and shortening the preparation cycle.
[0091] S312. Filter, wash, and dry the mixed metal precipitate. A series of steps such as filtering, washing, and drying help remove some impurities, which is beneficial to improving the purity of nickel-based nanoparticles and cerium-zirconium composite oxides in powder form.
[0092] S314. Calcinate the treated mixed metal precipitate at a first temperature to obtain nickel-based nanoparticles and cerium-zirconium composite oxides in powder form. Optionally, the first temperature is 550 °C to 650 °C. The first temperature is preferably 600 °C. The time for calcining the mixed metal precipitate is a second time, and the second time is 1.5 h to 2.5 h. Optionally, the second time is preferably 2 h.
[0093] S316. Mix nickel-based nanoparticles, cerium-zirconium composite oxides, polyvinylpyrrolidone, and ethanol to obtain a first mixed coating. Among them, polyvinylpyrrolidone (PVP) is a non-ionic polymer compound. Ethanol is a kind of alcohol compound with the chemical formula C2H6O. Mix nickel-based nanoparticles, cerium-zirconium composite oxides, polyvinylpyrrolidone, and ethanol according to a mass ratio of (2.8 - 3.2):(1.8 - 2.2):(1.8 - 2.2):(0.8 - 1.2). Optionally, mix nickel-based nanoparticles, cerium-zirconium composite oxides, polyvinylpyrrolidone, and ethanol according to a mass ratio of 3:2:2:1.
[0094] S318. Coat the first mixed coating on the dilution layer, dry it, and then sinter it at a second temperature to obtain a catalyst layer. Stir the mixed substances evenly and then coat them on the YSZ-based anode material. After the first mixed coating is dried, sinter it at a second temperature to obtain the catalyst layer. Optionally, the second temperature is 750 °C to 850 °C. The second temperature is preferably 800 °C. Optionally, the time for sintering the dried first mixed coating is a third time, and the third time is 1.5 h to 2.5 h. The third time is preferably 2 h.
[0095] In some embodiments, optionally, the first temperature is 550 °C to 650 °C. By controlling the calcination temperature of the mixed metal precipitate, on the one hand, it can avoid too low a calcination temperature (the first temperature) to ensure sufficient calcination of the mixed metal precipitate; on the other hand, it can avoid too high a calcination temperature, which is beneficial to saving energy and reducing the possibility of other chemical reactions occurring at too high a temperature.
[0096] In some embodiments, optionally, the calcination time of the mixed metal precipitate is a second time, and the second time is 1.5 h to 2.5 h. By controlling the calcination time of the mixed metal precipitate, on the one hand, it can avoid too short a calcination time (the second time) to ensure sufficient calcination of the mixed metal precipitate; on the other hand, it can avoid too long a calcination time, which is beneficial to improving the preparation efficiency and shortening the preparation cycle.
[0097] In some embodiments, optionally, the second temperature is 750 °C to 850 °C. By controlling the temperature during sintering of the dried first mixed coating, on the one hand, it can avoid too low a sintering temperature (the second temperature) to ensure sufficient sintering of the dried first mixed coating; on the other hand, it can avoid too high a sintering temperature, which is beneficial to saving energy and reducing the possibility of other chemical reactions occurring at too high a temperature.
[0098] In some embodiments, optionally, the sintering time of the dried first mixed coating is a third time, and the third time is 1.5 h to 2.5 h. By controlling the sintering time of the dried first mixed coating, on the one hand, it can avoid too short a sintering time (the third time) to ensure sufficient sintering of the first mixed coating; on the other hand, it can avoid too long a sintering time, which is beneficial to improving the preparation efficiency and shortening the preparation cycle.
[0099] In some embodiments, optionally, as Figure 4 shown, the specific steps of the preparation method of the dilution layer include:
[0100] S402, Mix yttria-stabilized zirconia in powder form, nickel-based nanoparticles, and cerium-zirconium composite oxide in powder form, add a binder and stir to form a slurry. Optionally, the binder includes polyethylene glycol. By adding the binder, it is beneficial to improve the bonding performance of the slurry and have stronger adsorption ability.
[0101] S404, Coat the slurry on the electrolyte layer, dry it and sinter it at a third temperature to obtain a dilution layer. Optionally, the third temperature is 750 °C to 850 °C. The third temperature is preferably 800 °C. Optionally, the sintering time of the dried slurry is a fourth time, and the fourth time is 1.5 h to 2.5 h. The fourth time is preferably 2 h.
[0102] In some embodiments, optionally, the third temperature is 750 °C to 850 °C. By controlling the temperature during sintering of the dried slurry, on the one hand, it can avoid too low a sintering temperature (the third temperature) to ensure sufficient sintering of the dried slurry; on the other hand, it can avoid too high a sintering temperature, which is beneficial to saving energy and reducing the possibility of other chemical reactions occurring at too high a temperature.
[0103] In some embodiments, optionally, the sintering time of the dried slurry is the fourth time, and the fourth time is 1.5 h to 2.5 h. By controlling the sintering time of the dried slurry, on the one hand, it can avoid too short a sintering time (the fourth time) to ensure sufficient sintering of the dried slurry; on the other hand, it can avoid too long a sintering time, which is beneficial to improving the preparation efficiency and shortening the preparation cycle.
[0104] In some embodiments, optionally, preparing the anode support includes: preparing an anode support composed of yttria-stabilized zirconia and nickel oxide. The chemical formula of yttria (Y2O3)-stabilized zirconia (ZrO2) is YSZ. The chemical formula of nickel oxide is NiO. Optionally, the mass proportion of yttria-stabilized zirconia in the anode support is 35% to 45%. By controlling the mass proportion of yttria-stabilized zirconia in the anode support, the chemical properties of the anode structure can be ensured. Optionally, the mass proportion of nickel oxide in the anode support is 55% to 65%. By controlling the mass proportion of nickel oxide in the anode support, the structural properties of the anode structure can be ensured, making the anode structure have sufficient structural strength. In the anode support, the mass ratio between yttria-stabilized zirconia and nickel oxide is preferably 2:3.
[0105] In some embodiments, optionally, the mass proportion of yttria-stabilized zirconia in the anode support is 35% to 45%. By controlling the mass proportion of yttria-stabilized zirconia in the anode support, the chemical properties of the anode structure can be ensured.
[0106] In some embodiments, optionally, the mass proportion of nickel oxide in the anode support is 55% to 65%. By controlling the mass proportion of nickel oxide in the anode support, the structural properties of the anode structure can be ensured, making the anode structure have sufficient structural strength.
[0107] In some embodiments, optionally, preparing the electrolyte layer, where the electrolyte layer covers the anode support, includes: preparing an electrolyte layer composed of yttria-stabilized zirconia, and the electrolyte layer covers the anode support. By covering the electrolyte layer on the anode support, the chemical properties of the anode structure can be ensured.
[0108] In an embodiment according to the present invention, the anode structure 500 is prepared by the preparation method of the anode of the solid oxide fuel cell in any of the above embodiments. As Figure 5As shown, the anode structure 500 includes an anode support 510, an electrolyte layer 520, a dilution layer 530, and a catalyst layer 540. Among them, the electrolyte layer 520 covers the anode support 510. By covering the electrolyte layer 520 on the anode support 510, the chemical properties of the anode structure 500 can be ensured. Further, the dilution layer 530 covers the electrolyte layer 520. By adding a dilution layer 530 in the anode structure 500, the dilution layer 530 serves as a transition layer between the catalyst layer 540 and the electrolyte layer 520, which can reduce reactions and diffusion and maintain the structural stability of the battery. Further, the catalyst layer 540 covers the dilution layer 530. By adding an independent catalyst layer 540 in the anode structure 500, under a carbonaceous fuel atmosphere, biomass gas can be effectively converted into carbon monoxide (CO) and hydrogen (H2) that can be used in the solid oxide fuel cell system 600. This can avoid direct contact between hydrocarbons and the anode, which is beneficial to inhibiting the formation of a solid carbon layer and reducing the impact of carbon deposition on the electrode performance. It can also improve the treatment and utilization efficiency of the solid oxide fuel cell system 600 for biomass waste, reduce costs and environmental impacts.
[0109] In one embodiment according to the present invention, as Figure 6 shown, the solid oxide fuel cell system 600 includes the anode structure 500 in the above embodiment. The solid oxide fuel cell system 600 has the beneficial effects of the above technical solutions and will not be elaborated here.
[0110] The above are the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.
Claims
1. A method for preparing an anode of a solid oxide fuel cell, characterized in that, Including: Preparing an anode support; Preparing an electrolyte layer, which covers the anode support; Preparing a dilution layer composed of yttria-stabilized zirconia, nickel-based nanoparticles, and cerium-zirconium composite oxide, which covers the electrolyte layer; Preparing a catalyst layer composed of the nickel-based nanoparticles and the cerium-zirconium composite oxide, which covers the dilution layer.
2. The method for preparing the anode of a solid oxide fuel cell according to claim 1, wherein The step of preparing the catalyst layer composed of the nickel-based nanoparticles and the cerium-zirconium composite oxide, which covers the dilution layer, includes: Mixing nickel nitrate, cerium nitrate, and zirconium nitrate to obtain a mixed metal precipitate; Obtaining the nickel-based nanoparticles and the cerium-zirconium composite oxide in powder form from the mixed metal precipitate; Covering the nickel-based nanoparticles and the cerium-zirconium composite oxide on the dilution layer to obtain the catalyst layer.
3. The method for preparing the anode of the solid oxide fuel cell according to claim 2, wherein, The step of mixing nickel nitrate, cerium nitrate, and zirconium nitrate to obtain a mixed metal precipitate includes: Mixing the nickel nitrate, the cerium nitrate, and the zirconium nitrate to obtain a first mixed solution; Adding a complexing agent to the first mixed solution to obtain a second mixed solution; Adjusting the pH value of the second mixed solution to a first pH value; Stirring the second mixed solution; Allowing the stirred second mixed solution to stand and obtaining the mixed metal precipitate.
4. The method for preparing the anode of a solid oxide fuel cell according to claim 3, wherein The complexing agent includes ethylenediaminetetraacetic acid.
5. The method for preparing the anode of a solid oxide fuel cell according to claim 3, characterized in that, The first pH value is 8.5 to 9.
5.
6. The method for preparing the anode of a solid oxide fuel cell according to claim 3, wherein, The standing time of the second mixed solution is a first time, and the first time is 23 h to 25 h.
7. The preparation method of the anode of the solid oxide fuel cell according to claim 2, characterized in that, The step of obtaining the nickel-based nanoparticles and the cerium-zirconium composite oxide in powder form from the mixed metal precipitate includes: Filtering, washing, and drying the mixed metal precipitate; Calcining the treated mixed metal precipitate at a first temperature to obtain the nickel-based nanoparticles and the cerium-zirconium composite oxide in powder form.
8. The preparation method of the anode of the solid oxide fuel cell according to claim 7, characterized in that The first temperature is 550 °C to 650 °C.
9. The method for preparing the anode of a solid oxide fuel cell according to claim 7, characterized in that, The calcining time of the mixed metal precipitate is a second time, and the second time is 1.5 h to 2.5 h.
10. The method for preparing the anode of a solid oxide fuel cell according to claim 2, wherein, The step of covering the nickel-based nanoparticles and the cerium-zirconium composite oxide on the dilution layer to obtain the catalyst layer includes: Mixing the nickel-based nanoparticles, the cerium-zirconium composite oxide, polyvinylpyrrolidone, and ethanol to obtain a first mixed coating; Coating the first mixed coating on the dilution layer, drying, and sintering at a second temperature to obtain the catalyst layer.
11. The method for preparing the anode of the solid oxide fuel cell according to claim 10, wherein, The second temperature is 750 °C to 850 °C.
12. The method for preparing the anode of the solid oxide fuel cell according to claim 10, wherein The sintering time of the dried first mixed coating is a third time, and the third time is 1.5 h to 2.5 h.
13. The method for preparing the anode of a solid oxide fuel cell according to any one of claims 1 to 12, characterized in that, The step of preparing a dilution layer composed of yttria-stabilized zirconia, nickel-based nanoparticles, and cerium-zirconium composite oxide, which covers the electrolyte layer, includes: Mixing the yttria-stabilized zirconia in powder form, the nickel-based nanoparticles, and the cerium-zirconium composite oxide in powder form, adding a binder, and stirring to form a slurry; Coat the slurry on the electrolyte layer, and after drying, sinter it at a third temperature to obtain the dilution layer.
14. The method for preparing the anode of a solid oxide fuel cell according to claim 13, wherein, The binder includes polyethylene glycol.
15. The method for preparing the anode of a solid oxide fuel cell according to claim 13, characterized in that, The third temperature is 750 °C to 850 °C.
16. The method for preparing the anode of a solid oxide fuel cell according to claim 13, characterized in that, The sintering time of the dried slurry is a fourth time, and the fourth time is 1.5 h to 2.5 h.
17. The method for preparing the anode of a solid oxide fuel cell according to any one of claims 1 to 12, characterized in that, The preparation of the anode support includes: Prepare the anode support composed of the yttria-stabilized zirconia and nickel oxide.
18. The method for preparing the anode of a solid oxide fuel cell according to claim 17, characterized in that, The mass ratio of the yttria-stabilized zirconia in the anode support is 35% to 45%.
19. The method for preparing the anode of the solid oxide fuel cell according to claim 17, wherein The mass ratio of the nickel oxide in the anode support is 55% to 65%.
20. The method for preparing the anode of a solid oxide fuel cell according to any one of claims 1 to 12, characterized in that, The preparation of the electrolyte layer, which covers the anode support, includes: Prepare the electrolyte layer composed of the yttria-stabilized zirconia, which covers the anode support.
21. An anode structure, characterized in that, Prepared by the method for preparing the anode of the solid oxide fuel cell according to any one of claims 1 to 20.
22. A solid oxide fuel cell system, characterized in that, Includes the anode structure as claimed in claim 21.