A Pt nanoparticle-CeO2 embedded composite anode material, its preparation method, and its application.
By embedding Pt nanoparticles into the CeO2 lattice, the problem of easy agglomeration of traditional Ni/YSZ anode materials at high temperatures was solved, achieving efficient charge transfer and catalyst stability, and improving the performance of solid oxide fuel cells.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- XINJIANG UNIVERSITY
- Filing Date
- 2026-03-11
- Publication Date
- 2026-06-19
AI Technical Summary
Traditional Ni/YSZ anode materials are prone to agglomeration and reduced conductivity at high temperatures, leading to a decline in the performance of solid oxide fuel cells.
A Pt nanoparticle-CeO2 embedded composite anode material was prepared by using the MOF template method to embed Pt nanoparticles into the CeO2 lattice, thereby enhancing the metal-support interaction, preventing high-temperature sintering, and improving charge transfer efficiency.
The electrochemical performance and hydrogen hydration activity of CeO2-based anode materials were significantly improved. The prepared solid oxide fuel cell achieved a power density of 1.5 W cm-2 at 800℃, exhibiting good stability and high catalytic performance.
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Figure CN122246156A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of solid oxide fuel cell technology, and particularly relates to a Pt nanoparticle CeO2 embedded composite anode material, its preparation method, and its application. Background Technology
[0002] As human civilization has progressed, energy scarcity and environmental pollution have become two major challenges that humanity must confront in its pursuit of green and rapid development. The dwindling fossil resources and the emissions resulting from their use continue to push the boundaries of sustainable development. Therefore, developing clean, low-carbon, and renewable energy technologies has become a global consensus. Among numerous options, solid oxide fuel cells (SOFCs) demonstrate significant advantages due to their inherent safety and stable operation. This technology directly converts the chemical energy of fuel into electrical energy, a one-step energy conversion method that significantly reduces energy losses from multiple energy conversion stages. Its energy conversion process is not limited by the Carnot cycle, thus possessing inherently high energy conversion efficiency. Based on these outstanding advantages, solid oxide fuel cells have gained considerable favor in the new energy technology field in recent years, with broad application prospects.
[0003] As a crucial component of SOFCs, the anode material significantly impacts the overall performance of the battery. Traditional anodes (Ni / YSZ) exhibit performance degradation after prolonged operation at 800°C in a H2 atmosphere. This is primarily due to the coarsening, aggregation, or oxidation of Ni, leading to a reduction in the three-phase interface and decreased conductivity. Therefore, developing high-performance solid oxide fuel cell anode materials that are less prone to agglomeration is of great importance. Summary of the Invention
[0004] One of the objectives of this invention is to provide a Pt nanoparticle CeO2 embedded composite anode material.
[0005] The second objective of this invention is to provide a method for preparing and applying the above-mentioned Pt nanoparticle CeO2 embedded composite anode material.
[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A method for preparing a Pt nanoparticle-CeO2 embedded composite anode material, the specific steps of which are as follows: (1) MOF-UiO-66(Ce) was prepared using a classical synthesis method; (2) Weigh out UiO-66 (Ce) and Pt-containing compounds according to the stoichiometric ratio of each element in the chemical formula Pt@CeO2-x%. 4+ chlorates, x = 0.4, 0.6, 0.8, 1.0; (3) Weigh the Pt-containing material from step (2)4+ The chlorate was dissolved in methanol to prepare the first solution; (4) Add the UiO-66(Ce) weighed in step (2) to methanol to prepare a second solution; (5) Add the first solution obtained in step (3) to the second solution obtained in step (4) to obtain the third solution; (6) Sonicate the third solution obtained in step (5) until it is completely dispersed; (7) Place the third solution after sonication in step (6) into a water bath at 65-75℃ and heat and stir until the solvent evaporates completely to obtain powder one; (8) Place the powder obtained in step (7) into a forced-air drying oven and dry it at a temperature of about 65-75°C for 5-8 hours to obtain powder (2). (9) After thoroughly grinding the powder obtained in step (8), collect the powder and put it into a muffle furnace, and calcine it at 800-850°C for 4-7 hours in an air atmosphere; (10) Grind the powder after calcination in step (9), add anhydrous ethanol and grind it thoroughly, and dry it to obtain Pt@CeO2-x% solid oxide fuel cell composite anode material, x = 0.4, 0.6, 0.8, 1.0.
[0007] In the preparation method described above, in step (3), the concentration of the first solution is 20-30 mg / mL.
[0008] In the preparation method described above, in step (4), the concentration of the second solution is 60 mg / mL.
[0009] Pt nanoparticle CeO2 embedded composite anode material prepared according to the method described above.
[0010] A method for preparing a solid oxide fuel cell specifically includes the following steps: (1) Weigh the Pt nanoparticle CeO2 embedded composite anode material as described in claim 4, add a certain amount of binder and grind it evenly to make an anode electrode slurry; (2) Weigh out an appropriate amount of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-8 - Gd 0.1 Ce 0.9 O 2-δ Cathode powder is mixed with a certain amount of binder and ground evenly to form a cathode electrode slurry. (3) Weigh out an appropriate amount of La 0.4 Ce 0.6 O 2-δBuffer layer powder is mixed with a certain amount of binder and ground evenly to form a buffer layer slurry. (4) The buffer layer slurry obtained in step (3) above is uniformly coated onto the electrolyte sheet La using screen printing. 0.8 Sr 0.2 Ga 0.8 Mg 0.2 O 3-δ Place one side of the container in a forced-air drying oven at 90℃ and dry for 8-10 minutes; (5) Place the dried electrolyte sheet in a high-temperature tube furnace and calcine it at 1200-1300°C for 1-3 hours in an air atmosphere to obtain the pre-material for making a full battery. (6) The electrode slurries obtained in steps (1) and (2) are uniformly coated onto the electrolyte and buffer layer La, respectively. 0.4 Ce 0.6 O 2-δ Both sides are dried to obtain full battery cells; (7) Place the dried full cell in a high-temperature muffle furnace and calcine it at 800-1100°C for 1-3 hours in an air atmosphere to obtain a solid oxide fuel cell with Pt@CeO2-x% (x = 0.4, 0.6, 0.8, 1.0) material as the anode material.
[0011] In the preparation method described above, the mass ratio of Pt@CeO2-x% (x = 0.4, 0.6, 0.8, 1.0) anode powder to binder used in step (1) is 1:1.5; the binder used is prepared by mixing terpineol and ethyl cellulose in a mass ratio of 9:1.
[0012] The preparation method described above, in step (4) using the electrolyte sheet La 0.8 Sr 0.2 Ga 0.8 Mg 0.2 O 3-δ The thickness is 0.26mm.
[0013] Solid oxide fuel cells prepared according to the preparation method described above.
[0014] This invention provides a Pt nanoparticle-CeO2 embedded composite anode material, its preparation method, and its applications. The MOF template method is used to design Pt nanoparticle structures embedded in CeO2. The Pt nanoparticles are partially embedded in the CeO2 lattice, enhancing the interaction between the metal and the support, promoting efficient charge transfer, and stabilizing the Pt nanoparticles, thus preventing high-temperature sintering. The high specific surface area loaded with small-sized Pt metal nanoparticles allows for efficient dispersion of the noble metal and improves the utilization efficiency of Pt. The partial embedding of Pt nanoparticles in the CeO2 lattice enhances the interaction between the metal and the support. Charge transfer between CeO2 and metal species can precisely regulate the electronic states of the noble metal active sites, thereby optimizing the adsorption strength of reactants and intermediates. This structure effectively prevents metal agglomeration and sintering at high temperatures, enhancing the structural stability of the catalyst.
[0015] The Pt nanoparticle-CeO2 intercalated composite anode material provided by this invention significantly improves the electrochemical performance of CeO2-based anode materials. Furthermore, solid oxide fuel cells prepared using Pt@CeO2-x% (x = 0.4, 0.6, 0.8, 1.0) exhibit good hydroxide activity and stability. Figure 1 Pt@CeO2-0.8% exhibits optimal performance at 800℃, with a power density of 1.5 W / cm³. -2 . Attached Figure Description
[0016] Figure 1 The current-voltage (IV) and current-power density (IP) curves of an 800℃ single cell of Pt@CeO-x% (x = 0, 0.4, 0.6, 0.8, 1.0); Figure 2 XRD patterns of Pt@CeO-x% (x = 0, 0.4, 0.6, 0.8, 1.0); Figure 3 AC-HAADF-STEM image of Pt@CeO-0.8% sample; ac) Pt@CeO-0.8% mapping image, a) Ce element; b) Pt element; c) O element; d and e) (200) crystal plane of cerium oxide; Figure 4 The current-voltage (IV) and current-power density (IP) curves of Pt@CeO-0.8% single cells at 650-800℃ are shown. Detailed Implementation
[0017] The present invention will be described in detail below with reference to specific embodiments. Example 1
[0018] Preparation of UiO-66(Ce): Weigh 1.77g of terephthalic acid and add 60 mL of N,N-dimethylformamide. Place the resulting solution on a heating stirrer, stir and heat to 95℃ for 2 min until the temperature stabilizes to obtain solution one; weigh 5.844g of cerium ammonium nitrate and add 20 mL of water, sonicate to disperse until the solution is clear and transparent to obtain solution two; add solution two to solution one and heat and stir at 95℃ for 15 min to obtain a yellow precipitate. After centrifugation and washing, dry in a vacuum drying oven at 70℃ to obtain UiO-66(Ce) powder. Example 2
[0019] Take 3g of UiO-66(Ce) powder prepared in Example 1, add 50mL of methanol to obtain a second solution; sonicate the second solution for 2 hours; then place it in a 65℃ constant temperature water bath and stir until the methanol evaporates completely. Transfer the obtained sample to a forced-air drying oven and dry at 65℃ for 5 hours. Afterward, grind the obtained powder in a mortar for 30 minutes. Subsequently, place the powder in a muffle furnace and gradually heat it to 800℃ at a rate of 4℃ / min and hold for 4 hours to obtain the target CeO2 anode powder. Example 3
[0020] Take 100 mg of chloroplatinic acid and add it to 5 mL of methanol solution to obtain the first solution; take 3 g of UiO-66(Ce) powder prepared in step (1) and add it to 50 mL of methanol to obtain the second solution; take 800 μm of the first solution and add it to the second solution to obtain the third solution. Sonicate the third solution for 2 hours; then, place it in a 65℃ constant temperature water bath and stir until the methanol evaporates completely. Transfer the obtained sample to a forced-air drying oven and dry it at 65℃ for 5 hours. After that, grind the obtained powder in a mortar for 30 minutes. Then, put the powder into a muffle furnace and gradually heat it to 800℃ at a rate of 4℃ / min and hold it for 4 hours to obtain the target Pt@CeO2-0.4% anode powder. Example 4
[0021] Take 100 mg of chloroplatinic acid and add it to 5 mL of methanol solution to obtain the first solution; take 3 g of UiO-66(Ce) powder prepared in step (1) and add it to 50 mL of methanol to obtain the second solution; take 1200 μm of the first solution and add it to the second solution to obtain the third solution. Sonicate the third solution for 2 hours; then, place it in a 65℃ constant temperature water bath and stir until the methanol evaporates completely. Transfer the obtained sample to a forced-air drying oven and dry it at 65℃ for 5 hours. After that, grind the obtained powder in a mortar for 30 minutes. Then, put the powder into a muffle furnace and gradually heat it to 800℃ at a rate of 4℃ / min and hold it for 4 hours to obtain the target Pt@CeO2-0.6% anode powder. Example 5
[0022] Take 100 mg of chloroplatinic acid and add it to 5 mL of methanol solution to obtain the first solution; take 3 g of UiO-66(Ce) powder prepared in step (1) and add it to 50 mL of methanol to obtain the second solution; take 2000 μm of the first solution and add it to the second solution to obtain the third solution. Sonicate the third solution for 2 hours; then, place it in a 65℃ constant temperature water bath and stir until the methanol evaporates completely. Transfer the obtained sample to a forced-air drying oven and dry it at 65℃ for 5 hours. After that, grind the obtained powder in a mortar for 30 minutes. Then, put the powder into a muffle furnace and gradually heat it to 800℃ at a rate of 4℃ / min and hold it for 4 hours to obtain the target Pt@CeO2-1.0% anode powder. Example 6
[0023] Single cells were prepared using the anode powder prepared in Examples 2-5: Anode powder and cathode powder (LSCF / GDC, commercially available) were mixed with a binder (4 wt% hydroxyethyl cellulose solution) at a mass ratio of 1:1.5 and hand-ground for 30 minutes to obtain a viscous slurry. The resulting slurry was then coated onto both sides of an LSGM electrolyte, dried at 90°C, and subsequently sintered in ambient air to produce a single cell. Silver paste was applied to both sides of the cell for current collection, and the cell was sintered at 650°C for 0.5 hours to obtain a single cell. The prepared button cell was encapsulated at one end of a corundum tube using a high-temperature ceramic component and connected with a silver wire. Example 7
[0024] Battery Testing: To investigate the feasibility of the prepared sample as an anode catalyst, the current-voltage (IV) and current-power density (IP) curves of single cells were tested at 800–650 °C (50 °C intervals) using an Energylab Solartron electrochemical workstation. During testing, current was collected by brushing silver paste onto the anode and cathode surfaces of the single cells, and attaching silver wires to the sides of the anode and cathode. The cells were placed at one end of a corundum tube in the order of silver wire-cell piece-silver wire and sealed with ceramic adhesive. Care was taken to ensure that the cathode side faced upwards in contact with air, and the anode side faced downwards in contact with the fuel gas. The reactor was placed in a vertical furnace and heated to 800 °C (heating rate 3 °C / min), and reduced for 30 min using a 3% wet hydrogen atmosphere (50 ml / min) for electrochemical performance testing. Before testing, the positive and negative electrodes were connected to the Energylab Solartron using a four-electrode method with silver wires as conductors.
[0025] The battery was operated under a humid hydrogen atmosphere (3% H2O) during all electrochemical tests. The peak power densities (Pmax) of the Pt@CeO2-0.8% anode at 800, 750, 700, and 650 °C were 1.50, 1.08, 0.65, and 0.34 W·cm⁻¹, respectively. -2 ,like Figure 4 .
[0026] The results show that the Pt nanoparticle CeO2 embedded composite anode material provided by this invention, characterized by XRD and subjected to phase analysis, is as follows: Figure 2 The final product synthesized under hydrogen atmosphere showed no impurity peaks and exhibited a stable cubic phase structure. The Pt@CeO-0.8% catalyst prepared via an external MOF template dissolution strategy was characterized by ac-HAADF-STEM to investigate the presence and state of Pt species on the CeO2 surface. Figure 2 Pt nanoparticles are anchored to the CeO2 surface in an embedded manner, forming a deeply embedded interface structure.
[0027] Pt nanoparticles are anchored to the CeO2 surface in an embedded manner, forming a deeply embedded interface structure. Figure 3 The solid oxide fuel cell prepared using the preferred anode material provided by this invention has a maximum output power of 1.5 W cm⁻¹ at 800°C under H₂ atmosphere. -2 ， like Figure 4 This shows that Pt nanoparticles partially embedded in CeO2 significantly enhance the metal-support interaction, optimize hydrogen activation, and improve the stability of the catalyst.
[0028] It should be understood that those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.
Claims
1. A method for preparing a Pt nanoparticle CeO2 embedded composite anode material, characterized in that, The specific steps are as follows: (1) Preparation of MOF-UiO-66(Ce); (2) Weigh out UiO-66 (Ce) and Pt-containing compounds according to the stoichiometric ratio of each element in the chemical formula Pt@CeO2-x%. 4+ chlorates, x = 0.4, 0.6, 0.8, 1.0; (3) Weigh the Pt-containing material from step (2) 4+ The chlorate was dissolved in methanol to prepare the first solution; (4) Add the UiO-66(Ce) weighed in step (2) to methanol to prepare a second solution; (5) Add the first solution obtained in step (3) to the second solution obtained in step (4) to obtain the third solution; (6) Sonicate the third solution obtained in step (5) until it is completely dispersed; (7) Place the third solution after sonication in step (6) into a water bath at 65-75℃ and heat and stir until the solvent evaporates completely to obtain powder one; (8) Place the powder obtained in step (7) into a forced-air drying oven and dry it at a temperature of about 65-75°C for 5-8 hours to obtain powder (2). (9) After thoroughly grinding the powder obtained in step (8), collect the powder and put it into a muffle furnace, and calcine it at 800-850°C for 4-7 hours in an air atmosphere; (10) Grind the powder after calcination in step (9), add anhydrous ethanol and grind it thoroughly, and dry it to obtain Pt@CeO2-x% solid oxide fuel cell composite anode material, x = 0.4, 0.6, 0.8, 1.
0.
2. The preparation method according to claim 1, characterized in that, In step (3), the concentration of the first solution is 20-30 mg / mL.
3. The preparation method according to claim 1, characterized in that, In step (4), the concentration of the second solution is 60 mg / mL.
4. Pt nanoparticle CeO2 embedded composite anode material prepared by any one of the methods described in claims 1-3.
5. A method for preparing a solid oxide fuel cell, characterized in that, Specifically, the following steps are included: (1) Take the Pt nanoparticle CeO2 embedded composite anode material as described in claim 4, add a certain amount of binder and grind it evenly to make an anode electrode slurry; (2) Take an appropriate amount of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-8 - Gd 0.1 Ce 0.9 O 2-δ Cathode powder is mixed with a certain amount of binder and ground evenly to form a cathode electrode slurry. (3) Take an appropriate amount of La 0.4 Ce 0.6 O 2-δ Buffer layer powder is mixed with a certain amount of binder and ground evenly to form a buffer layer slurry. (4) The buffer layer slurry obtained in step (3) above is uniformly coated onto the electrolyte sheet La using screen printing. 0.8 Sr 0.2 Ga 0.8 Mg 0.2 O 3-δ Place one side of the container in a forced-air drying oven at 90℃ and dry for 8-10 minutes; (5) Place the dried electrolyte sheet in a high-temperature tube furnace and calcine it at 1200-1300°C for 1-3 hours in an air atmosphere to obtain the pre-material for making a full battery. (6) The electrode slurries obtained in steps (1) and (2) are uniformly coated onto the electrolyte and buffer layer La, respectively. 0.4 Ce 0.6 O 2-δ Both sides are dried to obtain full battery cells; (7) Place the dried full cell from step (6) in a high-temperature muffle furnace and calcine it at 800-1100°C for 1-3 hours in an air atmosphere to obtain a solid oxide fuel cell with Pt@CeO2-x% (x = 0.4, 0.6, 0.8, 1.0) material as the anode material.
6. The preparation method according to claim 5, characterized in that, The mass ratio of Pt@CeO2-x% (x = 0.4, 0.6, 0.8, 1.0) anode powder to binder used in step (1) is 1:1.5; the binder used is prepared by mixing terpineol and ethyl cellulose in a mass ratio of 9:
1.
7. The preparation method according to claim 5, characterized in that, The electrolyte tablet La used in step (4) 0.8 Sr 0.2 Ga 0.8 Mg 0.2 O 3-δ The thickness is 0.26mm.
8. A solid oxide fuel cell prepared according to the preparation method described in claim 5.