Perovskite material and preparation method and application thereof

Abstract

The invention provides a perovskite material and a preparation method and application thereof. The component of the perovskite material is Ln (0.9-x) CexN (0.4-y) MyTi (0.6) O (3-delta), wherein x is more than 0.2 and more than 0, y is more than 0.4 and more than 0, delta is more than 0.1 and more than 0, Ln is La or Pr, N is one of Ni, Fe and Co, M is one of Ni, Fe, Co, Mn and Cu, and N and M are not the same element; ceO2 nano island-shaped particles and NM alloy nano spherical particles are precipitated on the surface of the perovskite material. The perovskite material can be used as a solid oxide fuel cell anode material, and has excellent catalytic activity and long-term operation stability.

Description

Technical Field

[0001] This invention belongs to the field of solid oxide fuel cell technology, and specifically relates to a perovskite material that can be used as an anode material for solid oxide fuel cells. Background Technology

[0002] Hydrogen energy, as a secondary energy source, possesses numerous advantages such as zero carbon footprint, high efficiency, applicability as an energy interconnection medium, and energy storage capabilities, making it applicable in various fields including transportation, industry, and construction. The combination of hydrogen energy and renewable electricity forms an "electricity-hydrogen-electricity" coupling conversion path, which can help address the intermittent, fluctuating, and random nature of renewable electricity consumption. Developing efficient hydrogen power generation technologies for the "hydrogen to electricity" process and green hydrogen production technologies for the "electricity to hydrogen" process is of great significance for promoting energy transition.

[0003] Solid-state ceramic high-temperature solid oxide cells (SOCs) possess extremely high energy conversion efficiency and are among the most advanced clean energy technologies currently available. SOCs are reversible and operate in two modes: one is a fuel cell power generation mode (Solid Oxide Fuel Cell, SOFC), where hydrogen fuel can achieve a primary power generation efficiency of 50-65% and a combined heat and power efficiency exceeding 90%; the other is an electrolyzer mode (Solid Oxide Electrolysis Cell, SOEC), where water electrolysis can produce hydrogen with an efficiency exceeding 85% and hydrogen production energy consumption of only 2.6 kWh / Nm³. 3 Hydrogen. State-owned hydrogen storage (SOC) can not only effectively absorb surplus renewable energy by converting and storing it as hydrogen, but also convert stored hydrogen into electricity when primary power is unavailable. SOC plays a crucial role in energy conversion as a green and efficient technology for both hydrogen utilization and production.

[0004] Currently, commercially available SOC batteries generally use traditional nickel / yttrium-stabilized zirconium oxide cermet (Ni / YSZ) as the anode material. This cermet material possesses excellent electrocatalytic activity, conductivity, and mechanical strength. However, Ni / YSZ anode materials are prone to carbon deposition when using hydrocarbon fuels (such as natural gas), leading to a significant decrease in electrochemical performance. Furthermore, Ni / YSZ anode materials are prone to particle coarsening under long-term high-temperature conditions, causing a gradual decline in electrocatalytic performance. Based on this, the industry is committed to developing materials that can replace Ni / YSZ anode materials, such as titanate perovskite materials, which have excellent anti-carbon deposition properties and structural stability. However, although titanate perovskites exhibit good stability, their catalytic activity as anode materials is significantly lower than that of Ni / YSZ anode materials.

[0005] Therefore, it is still necessary to study new materials that can be used as anode materials for solid oxide fuel cells and possess both excellent catalytic activity and long-term operational stability. Summary of the Invention

[0006] The purpose of this invention is to provide a solid oxide fuel cell anode material that combines excellent catalytic activity and long-term operational stability.

[0007] To achieve the above objectives, the present invention provides the following technical solution.

[0008] In a first aspect, the present invention provides a perovskite material, wherein the composition of the perovskite material is Ln 0.9- x Ce x N 0.4-y M y Ti 0.6 O 3-δ Among them, 0.2 > x > 0, 0.4 > y > 0, 0.1 > δ > 0, Ln is La or Pr, N is one of Ni, Fe, and Co, M is one of Ni, Fe, Co, Mn, and Cu, and N and M are not the same element;

[0009] CeO2 nano-island particles and NM alloy nanosphere particles are precipitated on the surface of the perovskite material.

[0010] The perovskite material provided by this invention is a type of material produced by using Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ CeO2-NM@LnCeNMTiO, a perovskite material with an in-situ constructed multi-component heterogeneous nanostructure, was obtained by co-precipitating CeO2 nano-islands and NM alloy nanospheres on the surface of the perovskite material. This perovskite material exhibits both excellent catalytic activity and long-term operational stability.

[0011] According to a preferred embodiment of the first aspect, preferably, the diameter of the CeO2 nano-island particles is 1-500 nm.

[0012] According to a preferred embodiment of the first aspect, preferably, the diameter of the NM alloy nanospheres is 1-100 nm.

[0013] According to a preferred embodiment of the first aspect, preferably, the perovskite material of the present invention is composed of a composition of Ln 0.9- x Ce x N 0.4-y M y Ti 0.6 O 3-δThe perovskite powder material was prepared by sequentially performing low-temperature annealing treatment under an oxidizing atmosphere (to precipitate CeO2 nano-island particles on its surface) and reduction treatment (to precipitate NM alloy nano-spherical particles on its surface); wherein the annealing temperature of the low-temperature annealing treatment did not exceed 1300℃.

[0014] More preferably, the annealing temperature for low-temperature annealing is 800-1300℃;

[0015] More preferably, the annealing time for low-temperature annealing is 0.1-20 h;

[0016] More preferably, the oxidizing atmosphere for the low-temperature annealing treatment is an air atmosphere or an oxygen atmosphere;

[0017] More preferably, the reduction treatment temperature is 500-1000℃;

[0018] More preferably, the reduction treatment time is 0.1-100 h;

[0019] More preferably, the atmosphere for the reduction treatment is a pure H2 atmosphere or a mixture of at least one of N2 and an inert gas (e.g., Ar) with H2.

[0020] More preferably, the component is Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ The perovskite powder material has a particle size of 0.1-20 μm.

[0021] In a second aspect, the present invention provides a method for preparing the perovskite material provided in the first aspect, wherein the method includes:

[0022] The preparation component is Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ The perovskite powder material; wherein, 0.2 > x > 0, 0.4 > y > 0, 0.1 > δ > 0, Ln is La or Pr, N is one of Ni, Fe, Co, and M is one of Ni, Fe, Co, Mn, Cu, and N and M are not the same element;

[0023] The component is Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δThe perovskite powder material was subjected to low-temperature annealing under an oxidizing atmosphere to precipitate CeO2 nano-island particles on its surface, resulting in the powder material after low-temperature annealing.

[0024] The powder material after low-temperature annealing is subjected to reduction treatment to precipitate NM alloy nanospheres on its surface, thereby obtaining the perovskite material provided in the first aspect of the invention. The CeO2 nano-island particles and NM alloy nanospheres precipitated on the surface of the prepared perovskite material have a firm interface with the parent material.

[0025] According to the preferred embodiment of the second aspect, the preparation component is Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ Perovskite powder materials include:

[0026] Oxides of Ln, Ce, N, M, and Ti were weighed according to the molar ratio of Ln, Ce, N, M, and Ti of 0.9-x:x:0.4-y:y:0.6. An oxide suspension was prepared by mixing the oxides of Ln, Ce, N, M, and Ti with a solvent. Wherein, Ln is La or Pr, N is one of Ni, Fe, and Co, and M is one of Ni, Fe, Co, Mn, and Cu, and N and M are not the same element. The order of elements is 0.2 > x > 0, 0.4 > y > 0, and 0.1 > δ > 0.

[0027] The oxide suspension was dried to obtain the powder, which was then subjected to two-stage high-temperature calcination to obtain a powder with the composition Ln. 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ The perovskite material; wherein the calcination temperature of the first stage of high-temperature calcination is 900-1100℃, and the calcination temperature of the second stage of high-temperature calcination is 1300-1700℃;

[0028] For component Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ The perovskite material was pulverized to obtain a composition of Ln 0.9- x Ce x N 0.4-y M y Ti 0.6 O 3-δPerovskite powder materials;

[0029] More preferably, the preparation of an oxide suspension by mixing the oxides of Ln, Ce, N, M, and Ti with a solvent comprises: mixing the oxides of Ln, Ce, N, M, and Ti with a solvent and then subjecting the mixture to ultrasonic oscillation to obtain the oxide suspension; further preferably, the oscillation frequency of the ultrasonic oscillation does not exceed 10 MHz; further preferably, the oscillation time of the ultrasonic oscillation is 0.1 to 120 min;

[0030] More preferably, the solvent includes at least one of acetone, ethanol, isopropanol and deionized water;

[0031] More preferably, the calcination time of the first stage of high-temperature calcination is 0.1-50 hours;

[0032] More preferably, the calcination time of the second stage high-temperature calcination is 0.1-50 h;

[0033] More preferably, the drying process is achieved by baking;

[0034] More preferably, the pulverization process is achieved using a planetary ball mill.

[0035] According to a preferred embodiment of the second aspect, the component is Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ The perovskite powder material has a particle size of 0.1-20 μm.

[0036] According to a preferred embodiment of the second aspect, the annealing temperature for low-temperature annealing is 800-1300°C.

[0037] According to the preferred embodiment of the second aspect, the annealing time for the low-temperature annealing treatment is 0.1-20h.

[0038] According to a preferred embodiment of the second aspect, the oxidizing atmosphere for the low-temperature annealing treatment is an air atmosphere or an oxygen atmosphere.

[0039] According to the preferred embodiment of the second aspect, the temperature of the reduction treatment is 500-1000°C.

[0040] According to the preferred embodiment of the second aspect, the reduction process takes 0.1-100 hours.

[0041] According to a preferred embodiment of the second aspect, the atmosphere for the reduction treatment is a pure H2 atmosphere or a mixture of at least one of N2 and an inert gas (e.g., Ar) with H2.

[0042] Thirdly, the present invention provides the application of the perovskite material provided in the first aspect as an anode material for solid oxide fuel cells.

[0043] This invention provides a CeO2-NM@LnCeNMTiO perovskite material with an in-situ constructed multi-component heterogeneous nanostructure. This perovskite material exhibits both excellent catalytic activity and long-term operational stability. Compared with existing technologies, the technical solution provided by this invention has the following beneficial effects:

[0044] (1) The perovskite material provided by this invention precipitates a large number of catalytically active nano-cerium oxide island particles and metal alloy nanosphere particles on the surface of LnCeNMTiO titanate perovskite, which can significantly improve electrocatalytic performance and stability. The nanoparticles precipitated on the surface of LnCeNMTiO titanate perovskite have a strong interface with the parent material, are not easy to grow or deposit carbon, and can exhibit good catalytic activity and stability when using hydrocarbons such as methane as fuel for SOFC power generation.

[0045] (2) The perovskite material preparation method provided by this invention is simple and controllable in that the process of precipitating nanoparticles on the surface of LnCeNMTiO titanate perovskite is simple and controllable. The size and number of nano-cerium oxide island particles and nano-alloy spherical particles can be adjusted according to different needs. For example, it can be achieved by changing the proportion and composition of each element in the perovskite material itself, the particle size of the material after ball milling, the annealing time and temperature, and the reduction time and temperature.

[0046] (3) The process of co-precipitating nano-cerium oxide island particles and nano-metal alloy spherical particles (i.e., annealing and reduction) used in the perovskite material preparation method provided by the present invention has a high degree of overlap with the SOFC battery preparation (high temperature calcination) and testing process (reducing atmosphere). Co-precipitation can be achieved without adding extra operation steps, thus having good economic efficiency and operability.

[0047] (4) The perovskite material provided by the present invention co-precipitates nano-cerium oxide island particles and nano-metal alloy spherical particles. The co-precipitation of nano-cerium oxide island particles and nano-metal alloy spherical particles can play a synergistic role, significantly improving the stability and catalytic activity of the electrode material.

[0048] The precipitation of cerium oxide particles can improve the anti-carbon deposition performance of electrode materials, but they are easily reduced in a fuel atmosphere, leading to volume expansion and performance degradation. The introduction of single alloying elements can enhance the catalytic activity of electrode materials for small fuel molecules, but alloy particles are prone to carbon deposition, resulting in performance degradation. The perovskite material provided by this invention co-precipitates cerium oxide particles and metal alloy particles. The metal alloy particles can regulate the precipitation state of cerium oxide and enhance its structural stability, while the precipitation of cerium oxide can also affect the performance of the metal alloy particles, improving their stability. The co-precipitation of cerium oxide and alloy particles has a synergistic effect, enabling the perovskite material provided by this invention to possess both excellent catalytic activity and long-term operational stability. Attached Figure Description

[0049] Figure 1 This is a microstructure diagram of the perovskite material provided in Example 1.

[0050] Figure 2 This is a microstructure diagram of the perovskite material provided in Example 2.

[0051] Figure 3 This is a microstructure diagram of the perovskite material provided in Example 3.

[0052] Figure 4 This is a microstructure diagram of the perovskite material provided in Example 4.

[0053] Figure 5 The image shows the microstructure of the perovskite material provided in Comparative Example 1.

[0054] Figure 6 The image shows the microstructure of the perovskite material provided in Comparative Example 2.

[0055] Figure 7 The image shows the microstructure of the perovskite material provided in Comparative Example 3.

[0056] Figure 8 The image shows the microstructure of the perovskite material provided in Comparative Example 4.

[0057] Figure 9 The perovskite materials provided in Examples 1, 2, 1, 2, 3, and 4 are shown as battery impedance spectra when they are used as anode materials for solid oxide fuel cells.

[0058] Figure 10 The IVP curves of button cell single cells using the perovskite materials provided in Examples 1, 2, 1, 2, 3, and 4 as anode materials for solid oxide fuel cells are shown. Detailed Implementation

[0059] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the protection scope of the present invention.

[0060] Example 1

[0061] This embodiment provides a perovskite material, which is prepared by the following method:

[0062] (1) Weigh out La2O3, CeO2, NiO, Fe2O3 and TiO2 according to the molar ratio of La, Ce, Ni, Fe and Ti of 0.8:0.1:0.1:0.3:0.6; add La2O3, CeO2, NiO, Fe2O3 and TiO2 to acetone and stir evenly, then use an ultrasonic oscillator to oscillate at 4MHz for 30min to prepare an oxide suspension.

[0063] (2) The oxide suspension prepared in step (1) is dried, and the resulting powder is calcined at 1100℃ for 10 h, and then calcined at 1450℃ for 5 h to obtain a product with the composition La. 0.8 Ce 0.1 Ni 0.1 Fe 0.3 Ti 0.6 O 3-δ The perovskite material (named LCENFT material).

[0064] (3) The LCeNFT material obtained in step (2) was pulverized to a particle size of about 4 μm using a planetary ball mill to obtain a material with the composition La. 0.8 Ce 0.1 Ni 0.1 Fe 0.3 Ti 0.6 O 3-δ The perovskite powder material is LCENFT powder material;

[0065] (4) The LCENFT powder material obtained in step (3) is subjected to low-temperature annealing treatment in air atmosphere (the temperature of low-temperature annealing treatment is 1250℃ and the time is 2h) to precipitate CeO2 nano-island particles on its surface, and the powder material after low-temperature annealing treatment is named CeO2@LCeNFT material.

[0066] (5) The powder material obtained in step (4) after low-temperature annealing is subjected to reduction treatment in a reducing atmosphere of 5 Vol% H2 / 95 Vol% N2 (the temperature of the reduction treatment is 900℃ and the time is 10h) to precipitate NiFe alloy nanospheres on its surface, and the perovskite material to be prepared in this embodiment is obtained and named CeO2-NiFe@LCeNFT material.

[0067] like Figure 1 As shown, the perovskite material prepared in this embodiment has a multi-component heterogeneous nanostructure, with CeO2 nano-island particles precipitated on the surface (such as...). Figure 1 In the blocky or block-like granular structure) and NiFe alloy nanospheres (such as Figure 1 The spherical particle structure of CeO2 nano-island particles has a particle size of approximately 450 nm, while the particle size of NiFe alloy nano-spherical particles is approximately 90 nm.

[0068] Example 2

[0069] This embodiment provides a perovskite material, which is prepared by the following method:

[0070] (1) Weigh La2O3, CeO2, NiO, CoO and TiO2 according to the molar ratio of La, Ce, Ni, Co and Ti of 0.8:0.1:0.1:0.3:0.6; add La2O3, CeO2, NiO, CoO and TiO2 to acetone and stir evenly, then use an ultrasonic oscillator to oscillate at 4MHz for 30min to prepare an oxide suspension.

[0071] (2) The oxide suspension prepared in step (1) is dried, and the resulting powder is calcined at 1100℃ for 10 h, and then calcined at 1450℃ for 5 h to obtain a product with the composition La. 0.8 Ce 0.1 Ni 0.1 Co 0.3 Ti 0.6 O 3-δ The perovskite material (named LCENCT material).

[0072] (3) The LCeNCT material obtained in step (2) was pulverized to a particle size of about 4 μm using a planetary ball mill to obtain a material with the composition La. 0.8 Ce 0.1 Ni 0.1 Co 0.3 Ti 0.6 O 3-δ The perovskite powder material is LCENCT powder material;

[0073] (4) The LCENFT powder material obtained in step (3) is subjected to low-temperature annealing treatment in air atmosphere (the temperature of low-temperature annealing treatment is 1250℃ and the time is 2h) to precipitate CeO2 nano-island particles on its surface, and the powder material after low-temperature annealing treatment is named CeO2@LCeNCT material.

[0074] (5) The powder material obtained in step (4) after low-temperature annealing is subjected to reduction treatment in a reducing atmosphere of 5 Vol% H2 / 95 Vol% N2 (the temperature of the reduction treatment is 900℃ and the time is 10h) to precipitate NiCo alloy nanospheres on its surface, and the perovskite material to be prepared in this embodiment is obtained and named CeO2-NiCo@LCeNCT material.

[0075] like Figure 2 As shown, the perovskite material prepared in this embodiment has a multi-component heterogeneous nanostructure, with CeO2 nano-island particles precipitated on the surface (such as...). Figure 2 (blocky or similar blocky granular structures) and NiCo alloy nanospheres (such as...) Figure 2 The spherical particle structure of CeO2 nano-island particles has a particle size of approximately 220 nm, while the particle size of NiCo alloy nano-spherical particles is approximately 45 nm.

[0076] Example 3

[0077] This embodiment provides a perovskite material, which is prepared by the following method:

[0078] (1) Weigh out La2O3, CeO2, CoO, Fe2O3 and TiO2 according to the molar ratio of La, Ce, Co, Fe and Ti of 0.85:0.05:0.2:0.2:0.6; add La2O3, CeO2, CoO, Fe2O3 and TiO2 to acetone and stir evenly, then use an ultrasonic oscillator to oscillate at 4MHz for 30min to prepare an oxide suspension.

[0079] (2) The oxide suspension prepared in step (1) is dried, and the resulting powder is calcined at 1100℃ for 10 h, and then calcined at 1450℃ for 5 h to obtain a product with the composition La. 0.85 Ce 0.05 Co 0.2 Fe 0.2 Ti 0.6 O 3-δ The perovskite material (named LCECFT material).

[0080] (3) The LCECFT material obtained in step (2) was pulverized to a particle size of about 4 μm using a planetary ball mill to obtain a material with the composition La 0.85 Ce0.05 Co 0.2 Fe 0.2 Ti 0.6 O 3-δ The perovskite powder material is LCECFT powder material;

[0081] (4) The LCECFT powder material obtained in step (3) is subjected to low-temperature annealing treatment in air atmosphere (the temperature of low-temperature annealing treatment is 1250℃ and the time is 2h) to precipitate CeO2 nano-island particles on its surface, and the powder material after low-temperature annealing treatment is named CeO2@LCeCFT material.

[0082] (5) The powder material obtained in step (4) after low-temperature annealing is subjected to reduction treatment in a reducing atmosphere of 5 Vol% H2 / 95 Vol% N2 (the temperature of the reduction treatment is 900℃ and the time is 10h) to precipitate CoFe alloy nanospheres on its surface, and the perovskite material to be prepared in this embodiment is obtained and named CeO2-CoFe@LCeCFT material.

[0083] like Figure 3 As shown, the perovskite material prepared in this embodiment has a multi-component heterogeneous nanostructure, with CeO2 nano-island particles precipitated on the surface (such as...). Figure 3 (blocky or similar blocky particle structures) and CoFe alloy nanospheres (such as...) Figure 3 The CeO2 nano-island particles have a particle size of approximately 130 nm, while the CoFe alloy nano-spherical particles have a particle size of approximately 65 nm.

[0084] Example 4

[0085] This embodiment provides a perovskite material, which is prepared by the following method:

[0086] (1) Weigh out La2O3, CeO2, NiO, Fe2O3 and TiO2 according to the molar ratio of La, Ce, Ni, Fe and Ti of 0.8:0.1:0.1:0.3:0.6; add La2O3, CeO2, NiO, Fe2O3 and TiO2 to acetone and stir evenly, then use an ultrasonic oscillator to oscillate at 4MHz for 30min to prepare an oxide suspension.

[0087] (2) The oxide suspension prepared in step (1) is dried, and the resulting powder is calcined at 1100℃ for 10 h, and then calcined at 1450℃ for 5 h to obtain a product with the composition La. 0.8 Ce 0.1 Ni 0.1 Fe 0.3 Ti 0.6 O3-δ The perovskite material (named LCENFT material).

[0088] (3) The LCeNFT material obtained in step (2) was pulverized to a particle size of about 4 μm using a planetary ball mill to obtain a material with the composition La. 0.8 Ce 0.1 Ni 0.1 Fe 0.3 Ti 0.6 O 3-δ The perovskite powder material is LCENFT powder material;

[0089] (4) The LCENFT powder material obtained in step (3) is subjected to low-temperature annealing treatment in air atmosphere (the temperature of low-temperature annealing treatment is 1100℃ and the time is 4h) to precipitate CeO2 nano-island particles on its surface, and the powder material after low-temperature annealing treatment is named CeO2@LCeNFT material.

[0090] (5) The powder material obtained in step (4) after low-temperature annealing is subjected to reduction treatment in a reducing atmosphere of 5 Vol% H2 / 95 Vol% N2 (the temperature of the reduction treatment is 800℃ and the time is 20h) to precipitate NiFe alloy nanospheres on its surface, and the perovskite material to be prepared in this embodiment is obtained and named CeO2-NiFe@LCeNFT material.

[0091] like Figure 4 As shown, the perovskite material prepared in this embodiment has a multi-component heterogeneous nanostructure, with CeO2 nano-island particles precipitated on the surface (such as...). Figure 4 In the blocky or block-like granular structure) and NiFe alloy nanospheres (such as Figure 4 The CeO2 nano-island particles have a particle size of approximately 180 nm, while the NiFe alloy nano-spherical particles have a particle size of approximately 35 nm.

[0092] Comparative Example 1

[0093] This comparative example provides a perovskite material, which is prepared by the following method:

[0094] (1) Weigh out La2O3, CeO2, NiO, Fe2O3 and TiO2 according to the molar ratio of La, Ce, Ni, Fe and Ti of 0.8:0.1:0.1:0.3:0.6; add La2O3, CeO2, NiO, Fe2O3 and TiO2 to acetone and stir evenly, then use an ultrasonic oscillator to oscillate at 4MHz for 30min to prepare an oxide suspension.

[0095] (2) The oxide suspension prepared in step (1) is dried, and the resulting powder is calcined at 1100℃ for 10 h, and then calcined at 1450℃ for 5 h to obtain a product with the composition La. 0.8 Ce 0.1 Ni 0.1 Fe 0.3 Ti 0.6 O 3-δ The perovskite material (named LCENFT material).

[0096] (3) The LCeNFT material obtained in step (2) was pulverized to a particle size of about 4 μm using a planetary ball mill to obtain a material with the composition La. 0.8 Ce 0.1 Ni 0.1 Fe 0.3 Ti 0.6 O 3-δ The perovskite powder material is LCENFT powder material;

[0097] (4) The LCENFT powder material obtained in step (3) is subjected to low-temperature annealing treatment in air atmosphere (the temperature of low-temperature annealing treatment is 1250℃ and the time is 2h) to precipitate CeO2 nano-island particles on its surface, and the perovskite material to be prepared in this comparative example is obtained and named CeO2@LCeNFT material.

[0098] like Figure 5 As shown, CeO2 nanoparticles are precipitated on the surface of the perovskite material prepared in this comparative example, and the particle size of the CeO2 nanoparticles is about 200 nm.

[0099] Comparative Example 2

[0100] This comparative example provides a perovskite material, which is prepared by the following method:

[0101] (1) Weigh out La2O3, CeO2, NiO, Fe2O3 and TiO2 according to the molar ratio of La, Ce, Ni, Fe and Ti of 0.8:0.1:0.1:0.3:0.6; add La2O3, CeO2, NiO, Fe2O3 and TiO2 to acetone and stir evenly, then use an ultrasonic oscillator to oscillate at 4MHz for 30min to prepare an oxide suspension.

[0102] (2) The oxide suspension prepared in step (1) is dried, and the resulting powder is calcined at 1100℃ for 10 h, and then calcined at 1450℃ for 5 h to obtain a product with the composition La. 0.8 Ce 0.1 Ni 0.1 Fe 0.3 Ti 0.6 O3-δ The perovskite material (named LCENFT material).

[0103] (3) The LCeNFT material obtained in step (2) was pulverized to a particle size of about 4 μm using a planetary ball mill to obtain a material with the composition La. 0.8 Ce 0.1 Ni 0.1 Fe 0.3 Ti 0.6 O 3-δ The perovskite powder material is LCENFT powder material;

[0104] (4) The LCENFT powder material obtained in step (3) is subjected to reduction treatment in a reducing atmosphere of 5 Vol% H2 / 95 Vol% N2 (the temperature of the reduction treatment is 900℃ and the time is 10h) to precipitate NiFe alloy nanospheres on its surface, and the perovskite material to be prepared in this comparative example is obtained and named NiFe@LCeNFT material.

[0105] like Figure 6 As shown, the perovskite material prepared in this comparative example has NiFe alloy nanospheres precipitated on its surface, and the particle size of the NiFe alloy nanospheres is about 58 nm.

[0106] Comparative Example 3

[0107] This comparative example provides a perovskite material, which is prepared by the following method:

[0108] (1) Weigh out La2O3, CeO2, NiO, Fe2O3 and TiO2 according to the molar ratio of La, Ce, Ni, Fe and Ti of 0.8:0.1:0.1:0.3:0.6; add La2O3, CeO2, NiO, Fe2O3 and TiO2 to acetone and stir evenly, then use an ultrasonic oscillator to oscillate at 4MHz for 30min to prepare an oxide suspension.

[0109] (2) The oxide suspension prepared in step (1) is dried, and the resulting powder is calcined at 1100℃ for 10 h, and then calcined at 1450℃ for 5 h to obtain a product with the composition La. 0.8 Ce 0.1 Ni 0.1 Fe 0.3 Ti 0.6 O 3-δ The perovskite material is named LCENFT material.

[0110] (3) The LCeNFT material obtained in step (2) was pulverized to a particle size of about 4 μm using a planetary ball mill to obtain a material with the composition La. 0.8 Ce0.1 Ni 0.1 Fe 0.3 Ti 0.6 O 3-δ The perovskite powder material to be prepared in this comparative example is named LCENFT powder material.

[0111] like Figure 7 As shown, the perovskite material prepared in this comparative example has a smooth and flat surface, with no nanoparticles precipitated.

[0112] Comparative Example 4

[0113] This comparative example provides a perovskite material, which is prepared by the following method:

[0114] (1) Weigh La2O3, CeO2, NiO, and TiO2 according to the molar ratio of La, Ce, Ni, and Ti of 0.8:0.1:0.4:0.6; add La2O3, CeO2, NiO, and TiO2 to acetone and stir evenly. Then, use an ultrasonic oscillator to oscillate at 4MHz for 30 minutes to prepare an oxide suspension.

[0115] (2) The oxide suspension prepared in step (1) is dried, and the resulting powder is calcined at 1100℃ for 10 h, and then calcined at 1450℃ for 5 h to obtain a product with the composition La. 0.8 Ce 0.1 Ni 0.4 Ti 0.6 O 3-δ The perovskite material (named LCENT material).

[0116] (3) The LCeNT material obtained in step (2) was pulverized to a particle size of about 4 μm using a planetary ball mill to obtain a material with the composition La. 0.8 Ce 0.1 Ni 0.4 Ti 0.6 O 3-δ The perovskite powder material is LCENT powder material;

[0117] (4) The LCeNT powder material obtained in step (3) is subjected to low-temperature annealing treatment in air atmosphere (the temperature of low-temperature annealing treatment is 1250℃ and the time is 2h) to precipitate CeO2 nanoparticles on its surface, and the powder material after low-temperature annealing treatment is named CeO2@LCeNT material.

[0118] (5) The powder material obtained in step (4) after low-temperature annealing is subjected to reduction treatment in a reducing atmosphere of 5 Vol% H2 / 95 Vol% N2 (the temperature of the reduction treatment is 900℃ and the time is 10h) to precipitate Ni nanoparticles on its surface, and the perovskite material to be prepared in this embodiment is obtained and named CeO2-Ni@LCeNFT material.

[0119] like Figure 8 As shown, the perovskite material prepared in this comparative example has numerous nanoparticles with different characteristics grown on its surface, including CeO2 nanoparticles (such as...). Figure 8 (blocky or similar blocky granular structures) and Ni metal nanoparticles (such as...) Figure 8 The CeO2 nanoparticles have a particle size of approximately 180 nm, while the Ni metal nanoparticles have a particle size of approximately 56 nm. Notably, cracks appeared at the edges of the CeO2 nanoparticles, indicating that structural changes occurred after the reduction treatment, leading to deterioration of the interface between the nanoparticles and the matrix.

[0120] Experimental Example 1

[0121] The perovskite materials provided in Examples 1, 2, 1, 2, 3, and 4 were subjected to performance tests. Specifically:

[0122] The perovskite materials provided in Examples 1, 2, 1, 2, 3, and 4 were used as anode materials, respectively, and La was used as the anode material. 0.8 Sr 0.2 MnO3-YSZ composite material (purchased from Ningbo Sofor Energy Technology Co., Ltd.) was used as the cathode material, and YSZ was used as the electrolyte to assemble solid oxide fuel cells - electrolyte-supported button cells.

[0123] The assembled electrolyte-supported button cell was subjected to performance tests, including electrochemical impedance spectroscopy and current-voltage scanning tests. The temperature was 800℃, the gas was pure hydrogen, and the flow rate was 50 mL / min.

[0124] The results are as follows Figure 9 , Figure 10 As shown.

[0125] Figure 9 This is the battery impedance spectrum. (From...) Figure 9 As can be seen, the battery assembled using the perovskite material (LCeNFT) provided in Comparative Example 3 as the anode material has the highest impedance, approximately 9.0 Ω·cm. 2Electrode materials that have not undergone any annealing or reduction treatment exhibit poor catalytic activity. When CeO2@LCeNFT material (Comparative Example 1) obtained by annealing cerium oxide particles to precipitate (Comparative Example 2) is used as the anode, or NiFe@LCeNFT material (Comparative Example 2) obtained by reduction treatment to precipitate NiFe nanoparticles is used as the anode, the impedance drop decreases to 7.7 Ω·cm, respectively. 2 and 5.1Ω·cm 2 This indicates that the precipitation of nanoparticles enhances the electrocatalytic activity of the electrode material. When the CeO2-NiFe@LCeNFT material with co-precipitated CeO2 nano-islands and NiFe alloy nanospheres provided in Example 1 is used as the anode, the battery impedance reaches an extremely low level of approximately 1.8 Ω·cm. 2 When the CeO2-NiCo@LCeNCT material with co-precipitated CeO2 nano-islands and NiCo alloy nanospheres provided in Example 2 is used as the anode, the battery impedance is only 2.5 Ω·cm. 2 When the CeO2-Ni@LCeNT material provided in Comparative Example 4 is used as the anode, the cell impedance is 3.7 Ω·cm. 2 The values ​​were greater than those in Examples 1 and 2, indicating that the precipitation of alloy particles has a more significant effect on battery performance than that of single metal particles.

[0126] Figure 10 The IVP curve for a single button cell. Figure 10 As can be seen, the battery assembled using the perovskite material (LCeNFT) provided in Comparative Example 3 as the anode material has the lowest maximum power density, approximately 345 mW·cm⁻¹. -2 Secondly, a battery assembled using the perovskite material (CeO2@LCeNFT) provided in Comparative Example 1 as the anode material had a maximum power density of approximately 471 mW·cm⁻¹. -2 Secondly, a battery assembled using the perovskite material (NiFe@LCeNFT) provided in Comparative Example 2 as the anode material had a maximum power density of approximately 661 mW·cm⁻¹. -2 Subsequently, a battery assembled using the perovskite material (CeO2-Ni@LCeNT) provided in Comparative Example 4 as the anode material was constructed, achieving a maximum power density of approximately 784 mW·cm⁻¹. -2 The batteries assembled using the perovskite materials provided in Examples 1 and 2 as anode materials had the highest maximum power density, at 1022 mW·cm⁻¹, respectively. -2 and 917mW·cm -2 General patterns and Figure 7The electrochemical impedance data showed consistent trends. Comparisons of Comparative Examples 1, 2, 3, and 4 revealed that the precipitation of nano-cerium oxide and alloy NiFe (or NiCo) particles significantly improved battery performance. The maximum power density increased by 196% compared to Comparative Example 3 (no particle precipitation), 117% compared to Comparative Example 1 (only CeO2 precipitation), 55% compared to Comparative Example 2 (only NiFe alloy precipitation), and 30% compared to Comparative Example 4 (CeO2 and Ni precipitation). This indicates that the method of precipitating highly active metal oxide CeO2 and alloy NiFe (or NiCo) nanoparticles on the anode material surface to construct a multi-component heterogeneous nanostructure can significantly improve the performance of the corresponding battery.

[0127] The microstructures of the perovskite materials provided in Comparative Examples 1, 2, and 4 are compared. Figure 1 , Figure 2 , Figure 6 As can be seen, after reduction treatment, the perovskite materials provided in Examples 1 and 2 showed good interfaces between the cerium oxide island particles and the perovskite matrix material, while the perovskite material provided in Comparative Example 4 showed obvious cracks at the interface between the cerium oxide particles and the perovskite matrix material after reduction treatment.

[0128] The above results indicate that the precipitation of highly active metal oxide CeO2 and alloy NiFe (or NiCo) nanoparticles on the surface of perovskite materials to construct multi-component heterogeneous nanostructures can significantly improve the performance of the corresponding batteries and enhance the structural stability of the nanostructures under strong reducing atmospheres (such as H2).

[0129] The embodiments described above are for the purpose of better explaining the present invention. For those skilled in the art, it is not difficult to make various modifications to these embodiments without departing from the principles and spirit of the present invention. Therefore, the present invention is not limited to the embodiments described herein, and any improvements and variations made to the present invention by those skilled in the art based on the principles and spirit of the present invention should be within the scope of protection of the present invention.

Claims

1. A perovskite material, wherein, The composition of this perovskite material is Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ Among them, 0.2 > x > 0, 0.4 > y > 0, 0.1 > δ > 0, Ln is La or Pr, N is one of Ni, Fe, and Co, M is one of Ni, Fe, Co, Mn, and Cu, and N and M are not the same element; CeO2 nano-island particles and NM alloy nanosphere particles are precipitated on the surface of the perovskite material.

2. The perovskite material according to claim 1, wherein, CeO2 nano-island particles have a diameter of 1-500 nm.

3. The perovskite material according to claim 1, wherein, The diameter of NM alloy nanospheres ranges from 1 to 100 nm.

4. The perovskite material according to claim 1, wherein, The perovskite material of the present invention is composed of Ln 0.9- x Ce x N 0.4-y M y Ti 0.6 O 3-δ The perovskite powder material was prepared by sequentially performing low-temperature annealing and reduction treatment under an oxidizing atmosphere; wherein the annealing temperature of the low-temperature annealing treatment did not exceed 1300℃.

5. The perovskite material according to claim 3, wherein, The annealing temperature for low-temperature annealing is 800-1300℃; The annealing time for low-temperature annealing is 0.1-20 hours; The oxidizing atmosphere for low-temperature annealing is either air or oxygen.

6. The perovskite material according to claim 3, wherein, The reduction treatment temperature is 500-1000℃; The reduction process takes 0.1-100 hours. The atmosphere for the reduction treatment is a pure H2 atmosphere or a mixture of at least one of N2 and an inert gas with H2.

7. The perovskite material according to claim 3, wherein, The component is Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ The perovskite powder material has a particle size of 0.1-20 μm.

8. A method for preparing a perovskite material according to any one of claims 1-7, wherein, The method includes: The preparation component is Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ Perovskite powder materials; The component is Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ The perovskite powder material was subjected to low-temperature annealing under an oxidizing atmosphere to precipitate CeO2 nano-island particles on its surface, resulting in the powder material after low-temperature annealing. The powder material after low-temperature annealing is subjected to reduction treatment to precipitate NM alloy nanospheres on its surface, thereby obtaining the perovskite material as described in any one of claims 1-6. The CeO2 nano-island particles and NM alloy nanospheres precipitated on the surface of the prepared perovskite material have a firm interface with the parent material.

9. The preparation method according to claim 8, wherein, The preparation component is Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ Perovskite powder materials include: According to the molar ratio of Ln, Ce, N, M, and Ti of 0.9-x:x:0.4-y:y:0.6, the oxides of Ln, Ce, N, M, and Ti were weighed, and the oxides of Ln, Ce, N, M, and Ti were mixed with a solvent to prepare an oxide suspension. The oxide suspension was dried to obtain the powder, which was then subjected to two-stage high-temperature calcination to obtain a powder with the composition Ln. 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ The perovskite material; wherein the calcination temperature of the first stage of high-temperature calcination is 900-1100℃, and the calcination temperature of the second stage of high-temperature calcination is 1300-1700℃; For component Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ The perovskite material was pulverized to obtain a composition of Ln 0.9- x Ce x N 0.4-y M y Ti 0.6 O 3-δ Perovskite powder materials.

10. The preparation method according to claim 9, wherein, The preparation of oxide suspensions by mixing oxides of Ln, Ce, N, M, and Ti with a solvent includes: mixing oxides of Ln, Ce, N, M, and Ti with a solvent and then subjecting the mixture to ultrasonic vibration to obtain an oxide suspension.

11. The preparation method according to claim 9 or 10, wherein, The solvent includes at least one of acetone, ethanol, isopropanol, and deionized water.

12. The preparation method according to claim 9 or 10, wherein, The calcination time for the first stage of high-temperature calcination is 0.1-50 hours; The calcination time for the second stage of high-temperature calcination is 0.1-50 hours.

13. The use of the perovskite material according to any one of claims 1-7 as an anode material for solid oxide fuel cells.

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