Perovskite material, and preparation method therefor and use thereof

Abstract

A perovskite material, and a preparation method therefor and the use thereof. The composition of the perovskite material is Ln0.9-xCexN0.4-yMyTi0.6O3-δ, wherein 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. The perovskite material has CeO2 nano-island-shaped particles and NM alloy nanosphere-shaped particles precipitated on the surface. The perovskite material can be used as an anode material for a solid oxide fuel cell, and has both excellent catalytic activity and long-term operation stability.

Description

Perovskite material and preparation method and application thereof

[0001] Cross-reference information

[0002] The present application claims priority to the Chinese patent application No. 202411079055.6, filed on August 7, 2024, and entitled "Perovskite material and preparation method and application thereof", the content of which is incorporated herein by reference in its entirety. TECHNICAL FIELD

[0003] The present application belongs to the technical field of solid oxide fuel cells, and particularly relates to a perovskite material which can be used as an anode material of a solid oxide fuel cell. BACKGROUND

[0004] Hydrogen energy, as a secondary energy, has many advantages such as zero carbon, high efficiency, can be used as an energy interconnection medium, and can be stored, and can be applied in many fields such as transportation, industry, and construction. Hydrogen energy and renewable energy electric energy form an "electricity-hydrogen-electricity" coupling conversion path, which can promote the solution of the intermittency, volatility and randomness of renewable electricity consumption. Developing efficient hydrogen power generation technology in the "hydrogen-electricity" process and green hydrogen production technology in the "electricity-hydrogen" process is of great significance to promote energy transformation.

[0005] High-temperature solid oxide cells (SOC) with all-solid-state ceramic structure have extremely high energy conversion efficiency, and are one of the current leading clean energy technologies. SOC can operate reversibly and has two working modes: one is a fuel cell power generation mode (SOFC), which uses hydrogen as fuel and has a primary power generation efficiency of 50-65% and a heat and power cogeneration efficiency of more than 90%; the other is an electrolysis cell mode (SOEC), which can produce hydrogen from water with an efficiency of more than 85% and an energy consumption of only 2.6 kWh / Nm 3 Hydrogen. SOC not only effectively consumes surplus renewable energy electric energy and converts it into hydrogen energy, but also converts stored hydrogen energy into electric energy when there is a lack of primary electric power. SOC plays an important role in the field of energy conversion as a green and efficient hydrogen use and production technology.

[0006] At present, the SOC battery which has been commercialized generally uses the traditional nickel / yttrium stabilized zirconia cermet material (Ni / YSZ) as the anode material, and the cermet material has excellent electrocatalytic activity, electrical conductivity and mechanical strength. However, the Ni / YSZ anode material is prone to carbon deposition when using hydrocarbons as fuel (such as natural gas), which leads to a significant decline in electrochemical performance. In addition, the Ni / YSZ anode material is prone to particle coarsening and growth under long-term high-temperature conditions, which causes the electrocatalytic performance to gradually decline. Based on this, the industry is committed to developing materials that can replace the Ni / YSZ anode material, such as titanate perovskite materials with excellent anti-carbon deposition performance and structural stability. However, although the titanate perovskite performs well in stability, its catalytic activity as an anode material is significantly lower than that of the Ni / YSZ anode material.

[0007] Therefore, there is still a need to study new materials that can be used as solid oxide fuel cell anode materials and have excellent catalytic activity and long-term operation stability. SUMMARY

[0008] The purpose of the present application is to provide a solid oxide fuel cell anode material with excellent catalytic activity and long-term operation stability.

[0009] In order to achieve the above-mentioned purpose, the present application provides the following technical solutions.

[0010] In a first aspect, the present application 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 ; wherein 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;

[0011] The perovskite material has CeO2 nano-island particles and NM alloy nano-spherical particles precipitated on the surface.

[0012] The perovskite material provided by the present application is a perovskite material prepared by doping Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δA perovskite material with in-situ constructed multi-element hetero-nanostructure, CeO2-NM@LnCeNMTiO, is prepared by co-precipitating CeO2 nano-island particles and NM alloy nano-spherical particles on the surface of a perovskite material. The perovskite material has excellent catalytic activity and long-term running stability.

[0013] According to a preferred embodiment of the first aspect, preferably, the diameter of the CeO2 nano-island particles is 1-500 nm.

[0014] According to a preferred embodiment of the first aspect, preferably, the diameter of the NM alloy nano-spherical particles is 1-100 nm.

[0015] According to a preferred embodiment of the first aspect, preferably, the perovskite material of the present application has a composition of Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ The perovskite material is prepared by sequentially subjecting a perovskite powder material with a composition of Ln

[0016] More preferably, the annealing temperature of the low-temperature annealing treatment is 800-1300℃.

[0017] More preferably, the annealing time of the low-temperature annealing treatment is 0.1-20 h.

[0018] More preferably, the oxidation atmosphere of the low-temperature annealing treatment is an air atmosphere or an oxygen atmosphere.

[0019] More preferably, the temperature of the reduction treatment is 500-1000℃.

[0020] More preferably, the time of the reduction treatment is 0.1-100 h.

[0021] More preferably, the atmosphere of the reduction treatment is a pure H2 atmosphere or a mixed gas atmosphere of at least one of N2 and an inert gas (e.g., Ar) and H2.

[0022] More preferably, the perovskite powder material has a particle size of 0.1-20 μm. 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ The perovskite material is prepared by sequentially subjecting a perovskite powder material with a composition of Ln

[0023] In the second aspect, the present application provides a preparation method of the perovskite material according to the first aspect, wherein the method comprises:

[0024] a perovskite powder material with a composition of Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ ; wherein 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;

[0025] a perovskite powder material with a composition of Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ is subjected to low-temperature annealing treatment in an oxidizing atmosphere to cause CeO2 nano-island particles to precipitate on the surface of the perovskite powder material, thereby obtaining a powder material after low-temperature annealing treatment;

[0026] The powder material after low-temperature annealing treatment is subjected to reduction treatment to cause NM alloy nano-spherical particles to precipitate on the surface of the perovskite material, thereby obtaining the perovskite material according to the first aspect of the application. The CeO2 nano-island particles and the NM alloy nano-spherical particles precipitated on the surface of the perovskite material prepared in this way have a firm interface with the matrix material.

[0027] According to a preferred embodiment of the second aspect, a perovskite powder material with a composition of Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ comprises the following steps:

[0028] The oxides of Ln, Ce, N, M, and Ti are weighed according to a molar ratio of 0.9-x: x: 0.4-y: y: 0.6, and the oxides of Ln, Ce, N, M, and Ti are mixed with a solvent to prepare an oxide suspension; wherein 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, 0.2 > x > 0, 0.4 > y > 0, 0.1 > δ > 0;

[0029] The oxide suspension is subjected to drying treatment to obtain a powder, and the powder obtained after drying treatment is subjected to two-stage high-temperature calcination to obtain a perovskite powder material with a composition of Ln 0.9-x Ce x N 0.4-y My 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℃;

[0030] 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;

[0031] 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;

[0032] More preferably, the solvent includes at least one of acetone, ethanol, isopropanol and deionized water;

[0033] More preferably, the calcination time of the first stage of high-temperature calcination is 0.1-50 hours;

[0034] More preferably, the calcination time of the second stage high-temperature calcination is 0.1-50 h;

[0035] More preferably, the drying process is achieved by baking;

[0036] More preferably, the pulverization process is achieved by planetary ball milling.

[0037] 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.

[0038] According to the preferred embodiment of the second aspect, the annealing temperature for low-temperature annealing is 800-1300°C.

[0039] According to a preferred embodiment of the second aspect, the annealing time of the low-temperature annealing treatment is 0.1-20h.

[0040] According to a preferred embodiment of the second aspect, the oxidation atmosphere of the low-temperature annealing treatment is an air atmosphere or an oxygen atmosphere.

[0041] According to a preferred embodiment of the second aspect, the temperature of the reduction treatment is 500-1000℃.

[0042] According to a preferred embodiment of the second aspect, the time of the reduction treatment is 0.1-100h.

[0043] According to a preferred embodiment of the second aspect, the atmosphere of the reduction treatment is a pure H2 atmosphere or a mixed gas atmosphere of at least one of N2 and an inert gas (e.g. Ar) and H2.

[0044] In a third aspect, the present application provides the perovskite material provided by the first aspect for use as an anode material of a solid oxide fuel cell.

[0045] The technical scheme of the present application provides a CeO2-NM@LnCeNMTiO perovskite material with in-situ constructed multi-element heterogeneous nanostructure. The perovskite material has excellent catalytic activity and long-term running stability. Compared with the prior art, the technical scheme of the present application has the following beneficial effects:

[0046] (1) The perovskite material provided by the present application precipitates a large number of catalytically active nano cerium oxide island particles and metal alloy nanospheres on the surface of the LnCeNMTiO titanate perovskite, which can significantly improve the electrocatalytic performance and stability. The interface between the nano particles precipitated on the surface of the LnCeNMTiO titanate perovskite and the parent material is firm, and it is not easy to grow and accumulate carbon. When using methane and other hydrocarbons as fuel for SOFC power generation, it can exhibit good catalytic activity and stability.

[0047] (2) The preparation method of the perovskite material provided by the present application is simple and controllable in the process of precipitating nano particles on the surface of the LnCeNMTiO titanate perovskite. The size and quantity of nano cerium oxide island particles and nano alloy spherical particles can be adjusted according to different needs. For example, this can be achieved by changing the proportion and composition of each element of the perovskite material itself, the particle size of the material after ball milling, the annealing time and temperature, and the reduction time and temperature, etc.

[0048] (3) The process method (i.e. annealing and reduction) for co-precipitating nano cerium oxide island particles and nano metal alloy spherical particles adopted by the preparation method of the perovskite material provided by the present application has high coincidence degree with the preparation (high-temperature calcination) and testing process (reduction atmosphere) of SOFC battery, and does not need to increase additional operation steps to achieve co-precipitation, thus having good economic type and operability.

[0049] (4) The perovskite material provided by the application co-precipitates nano cerium oxide island particles and nano metal alloy spherical particles, and the co-precipitation of the nano cerium oxide island particles and the nano metal alloy spherical particles can play a synergistic effect, and can significantly improve the stability and catalytic activity of the electrode material.

[0050] The precipitation of the cerium oxide particles can improve the carbon deposition resistance of the electrode material, but the cerium oxide particles are prone to reduction and volume expansion in a fuel atmosphere; the introduction of the single alloy element can enhance the catalytic activity of the electrode material on small fuel molecules, but the alloy particles are prone to carbon deposition and performance degradation. The perovskite material provided by the application co-precipitates cerium oxide particles and metal alloy particles, the metal alloy particles can regulate the precipitation state of the cerium oxide and enhance the structural stability of the cerium oxide, the precipitation of the cerium oxide can also improve the performance of the metal alloy particles and enhance the stability of the metal alloy particles, and the co-precipitation of the cerium oxide and the metal alloy particles can play a synergistic effect, so that the perovskite material provided by the application has excellent catalytic activity and long-term operation stability. BRIEF DESCRIPTION OF DRAWINGS

[0051] Fig. 1 is a microstructure diagram of the perovskite material provided in Example 1.

[0052] Fig. 2 is a microstructure diagram of the perovskite material provided in Example 2.

[0053] Fig. 3 is a microstructure diagram of the perovskite material provided in Example 3.

[0054] Fig. 4 is a microstructure diagram of the perovskite material provided in Example 4.

[0055] Fig. 5 is a microstructure diagram of the perovskite material provided in Comparative Example 1.

[0056] Fig. 6 is a microstructure diagram of the perovskite material provided in Comparative Example 2.

[0057] Fig. 7 is a microstructure diagram of the perovskite material provided in Comparative Example 3.

[0058] Fig. 8 is a microstructure diagram of the perovskite material provided in Comparative Example 4.

[0059] Fig. 9 is a cell impedance spectrum diagram of the solid oxide fuel cell anode material provided by the perovskite material in Example 1, Example 2, and Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4, respectively.

[0060] Fig. 10 is a button single cell I-V-P curve diagram of the solid oxide fuel cell anode material provided by the perovskite material in Example 1, Example 2, and Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4, respectively. DETAILED DESCRIPTION

[0061] In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are some but not all of the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0062] Embodiment 1

[0063] The present embodiment provides a perovskite material, wherein the material is prepared by the following preparation method:

[0064] (1) La2O3, CeO2, NiO, Fe2O3 and TiO2 are weighed according to the molar ratio of La, Ce, Ni, Fe and Ti being 0.8:0.1:0.1:0.3:0.6; the La2O3, CeO2, NiO, Fe2O3 and TiO2 are added into acetone, stirred uniformly, and then an oxide suspension is prepared by using an ultrasonic oscillator to oscillate at 4 MHz for 30 min.

[0065] (2) The oxide suspension prepared in step (1) is dried, the powder obtained after drying is calcined at 1100℃ for 10 h, and then calcined at 1450℃ for 5 h to obtain a perovskite material with the composition of La 0.8 Ce 0.1 Ni 0.1 Fe 0.3 Ti 0.6 O 3-δ , which is named as LCNFT material.

[0066] (3) The LCNFT material obtained in step (2) is crushed to a particle size of about 4 μm by using a planetary ball mill to obtain a perovskite powder material with the composition of La 0.8 Ce 0.1 Ni 0.1 Fe 0.3 Ti 0.6 O 3-δ , which is named as LCNFT powder material.

[0067] (4) The LCNFT powder material obtained in step (3) is subjected to low-temperature annealing treatment (the temperature of the low-temperature annealing treatment is 1250℃, and the time is 2 h) in an air atmosphere to make CeO2 nano-island particles precipitate on the surface, so as to obtain a powder material after low-temperature annealing treatment, which is named as CeO2@LCNFT material.

[0068] (5) The low-temperature annealed powder material obtained in step (4) is reduced under a 5 Vol% H2 / 95 Vol% N2reducing atmosphere (the reduction temperature is 900°C, and the time is 10 h) to make the surface precipitate NiFe alloy nanospherical particles, thereby obtaining the perovskite material to be prepared in this example, which is named as CeO2-NiFe@LCeNFT material.

[0069] As shown in FIG. 1, the perovskite material prepared in this example has a multi-element heterogeneous nanostructure, and the surface precipitates CeO2nanoparticle island particles (such as the blocky or similar blocky particle structure in FIG. 1) and NiFe alloy nanospherical particles (such as the spherical particle structure in FIG. 1). The particle size of the CeO2nanoparticle island particles is about 450 nm, and the particle size of the NiFe alloy nanospherical particles is about 90 nm.

[0070] Example 2

[0071] This example provides a perovskite material, wherein the material is prepared by the following preparation method:

[0072] (1) La2O3, CeO2, NiO, CoO, and TiO2are weighed according to the molar ratio of La, Ce, Ni, Co, and Ti being 0.8:0.1:0.1:0.3:0.6; the La2O3, CeO2, NiO, CoO, and TiO2are added to acetone, stirred uniformly, and then an ultrasonic oscillator is used to oscillate at 4 MHz for 30 min to prepare an oxide suspension.

[0073] (2) The oxide suspension prepared in step (1) is dried, and the powder obtained after drying is calcined at 1100°C for 10 h, and then calcined at 1450°C for 5 h to obtain a perovskite material with a composition of La 0.8 Ce 0.1 Ni 0.1 Co 0.3 Ti 0.6 O 3-δ , which is named as LCNCT material.

[0074] (3) The LCNCT material obtained in step (2) is ground by a planetary ball mill to a particle size of about 4 μm to obtain a perovskite powder material with a composition of La 0.8 Ce 0.1 Ni 0.1 Co 0.3 Ti 0.6 O 3-δ , which is named as LCNCT powder material.

[0075] (4) The LCeNFT powder material obtained in step (3) is subjected to low-temperature annealing treatment (the temperature of the low-temperature annealing treatment is 1250°C, and the time is 2h) in an air atmosphere, so that CeO2nano-island particles are precipitated on the surface thereof, to obtain a powder material after low-temperature annealing treatment, which is named as a CeO2@LCeNCT material.

[0076] (5) The powder material after low-temperature annealing treatment obtained in step (4) is subjected to reduction treatment (the temperature of the reduction treatment is 900°C, and the time is 10h) in a 5Vol% H2 / 95Vol% N2reducing atmosphere, so that NiCo alloy nano-spherical particles are precipitated on the surface thereof, to obtain the perovskite material to be prepared in the present embodiment, which is named as a CeO2-NiCo@LCeNCT material.

[0077] As shown in FIG. 2, the perovskite material prepared in the present embodiment has a multi-element heterogeneous nanostructure, and CeO2nano-island particles (such as the blocky or blocky-like particle structure in FIG. 2) and NiCo alloy nano-spherical particles (such as the spherical particle structure in FIG. 2) are precipitated on the surface thereof, the particle size of the CeO2nano-island particles is about 220nm, and the particle size of the NiCo alloy nano-spherical particles is about 45nm.

[0078] Example 3

[0079] The present embodiment provides a perovskite material, wherein the material is prepared by the following preparation method:

[0080] (1) La2O3, CeO2, CoO, Fe2O3, and TiO2are weighed according to the molar ratio of La, Ce, Co, Fe, and Ti being 0.85:0.05:0.2:0.2:0.6; the La2O3, CeO2, CoO, Fe2O3, and TiO2are stirred uniformly in acetone, and then an oxide suspension is prepared by using an ultrasonic oscillator to oscillate at 4MHz for 30min.

[0081] (2) The oxide suspension prepared in step (1) is dried, and the powder obtained after drying is calcined at 1100°C for 10h, and then calcined at 1450°C for 5h, to obtain a perovskite material with the composition of La 0.85 Ce 0.05 Co 0.2 Fe 0.2 Ti 0.6 O 3-δ , which is named as an LCeCFT material.

[0082] (3) The LCeCFT material obtained in step (2) is crushed to a particle size of about 4μm by using a planetary ball mill, to obtain a perovskite material with the composition of La 0.85 Ce 0.05 Co 0.2 Fe0.2 Ti 0.6 O 3-δ LCeCFT powder material;

[0083] (4) The LCeCFT powder material obtained in step (3) is subjected to low-temperature annealing treatment (the temperature of the low-temperature annealing treatment is 1250°C, and the time is 2h) in an air atmosphere, so that CeO2 nano-island particles are precipitated on the surface, to obtain a powder material after low-temperature annealing treatment, which is named as CeO2@LCeCFT material.

[0084] (5) The powder material after low-temperature annealing treatment obtained in step (4) is subjected to reduction treatment (the temperature of the reduction treatment is 900°C, and the time is 10h) in a 5Vol% H2 / 95Vol% N2 reducing atmosphere, so that CoFe alloy nano-spherical particles are precipitated on the surface, to obtain the perovskite material to be prepared in this embodiment, which is named as CeO2-CoFe@LCeCFT material.

[0085] As shown in FIG. 3, the perovskite material prepared in this embodiment has a multi-element heterogeneous nanostructure, and CeO2 nano-island particles (such as the blocky or similar blocky particle structure in FIG. 3) and CoFe alloy nano-spherical particles (such as the spherical particle structure in FIG. 3) are precipitated on the surface, the particle size of the CeO2 nano-island particles is about 130nm, and the particle size of the CoFe alloy nano-spherical particles is about 65nm.

[0086] Example 4

[0087] This embodiment provides a perovskite material, wherein the material is prepared by the following preparation method:

[0088] (1) La2O3, CeO2, NiO, Fe2O3 and TiO2 are weighed according to the molar ratio of La, Ce, Ni, Fe and Ti being 0.8:0.1:0.1:0.3:0.6; the La2O3, CeO2, NiO, Fe2O3 and TiO2 are stirred uniformly in acetone, and then an oxide suspension is prepared by using an ultrasonic oscillator to oscillate at 4MHz for 30min.

[0089] (2) The oxide suspension prepared in step (1) is dried, and the powder obtained after drying is calcined at 1100°C for 10h, and then calcined at 1450°C for 5h, to obtain a perovskite material with the composition of La 0.8 Ce 0.1 Ni 0.1 Fe 0.3 Ti 0.6 O 3-δ (named as LCeNFT material).

[0090] (3) The LCeNFT material obtained in step (2) is crushed by a planetary ball mill to a particle size of about 4 pm to obtain a perovskite powder material with a composition of La 0.8 Ce 0.1 Ni 0.1 Fe 0.3 Ti 0.6 O 3-δ ;

[0091] (4) The LCeNFT powder material obtained in step (3) is subjected to low-temperature annealing treatment (the temperature of the low-temperature annealing treatment is 1100°C, and the time is 4h) in an air atmosphere to cause CeO2 nano-island particles to precipitate on the surface, thereby obtaining a powder material after low-temperature annealing treatment, which is named as a CeO2@LCeNFT material.

[0092] (5) The powder material after low-temperature annealing treatment obtained in step (4) is subjected to reduction treatment (the temperature of the reduction treatment is 800°C, and the time is 20h) in a 5Vol% H2 / 95Vol% N2 reducing atmosphere to cause NiFe alloy nano-spherical particles to precipitate on the surface, thereby obtaining the perovskite material to be prepared in the present embodiment, which is named as a CeO2-NiFe@LCeNFT material.

[0093] As shown in FIG. 4, the perovskite material prepared in the present embodiment has a multi-element heterogeneous nanostructure, and CeO2 nano-island particles (such as the blocky or blocky-like particle structure in FIG. 4) and NiFe alloy nano-spherical particles (such as the spherical particle structure in FIG. 4) precipitate on the surface. The particle size of the CeO2 nano-island particles is about 180 nm, and the particle size of the NiFe alloy nano-spherical particles is about 35 nm.

[0094] Comparative Example 1

[0095] The present comparative example provides a perovskite material, wherein the material is prepared by the following preparation method:

[0096] (1) La2O3, CeO2, NiO, Fe2O3, and TiO2 are weighed according to a molar ratio of La:Ce:Ni:Fe:Ti of 0.8:0.1:0.1:0.3:0.6; the La2O3, CeO2, NiO, Fe2O3, and TiO2 are added into acetone, stirred uniformly, and then subjected to ultrasonic oscillation for 30 min at 4 MHz using an ultrasonic oscillator to prepare an oxide suspension.

[0097] (2) The oxide suspension prepared in step (1) is dried, and the powder obtained after drying is calcined at 1100°C for 10h, and then calcined at 1450°C for 5h to obtain a perovskite powder material with a composition of La 0.8 Ce 0.1 Ni 0.1 Fe0.3 Ti 0.6 O 3-δ perovskite material (named as LCeNFT material).

[0098] (3) The LCeNFT material obtained in step (2) is crushed by a planetary ball mill to a particle size of about 4 μm to obtain a perovskite powder material with a composition of La 0.8 Ce 0.1 Ni 0.1 Fe 0.3 Ti 0.6 O 3-δ , i.e. LCeNFT powder material;

[0099] (4) The LCeNFT powder material obtained in step (3) is subjected to low-temperature annealing treatment (the temperature of the low-temperature annealing treatment is 1250 °C, and the time is 2 h) in an air atmosphere to cause CeO2nanoparticle island-shaped particles to precipitate on the surface thereof to obtain a perovskite material to be prepared in the present comparative example, which is named as CeO2@LCeNFT material.

[0100] As shown in FIG. 5, the perovskite material prepared in the present comparative example has CeO2nanoparticles precipitated on the surface thereof, and the particle size of the CeO2nanoparticles is about 200 nm.

[0101] Comparative Example 2

[0102] The present comparative example provides a perovskite material, wherein the material is prepared by the following preparation method:

[0103] (1) La2O3, CeO2, NiO, Fe2O3, and TiO2are weighed according to a molar ratio of La:Ce:Ni:Fe:Ti of 0.8:0.1:0.1:0.3:0.6; the La2O3, CeO2, NiO, Fe2O3, and TiO2are added into acetone, stirred uniformly, and then subjected to ultrasonic oscillation for 30 min at 4 MHz using an ultrasonic oscillator to prepare an oxide suspension.

[0104] (2) The oxide suspension prepared in step (1) is dried, and the powder obtained after drying is calcined at 1100 °C for 10 h, and then calcined at 1450 °C for 5 h to obtain a perovskite material with a composition of La 0.8 Ce 0.1 Ni 0.1 Fe 0.3 Ti 0.6 O 3-δ , i.e. LCeNFT material.

[0105] (3) The LCeNFT material obtained in step (2) is crushed by a planetary ball mill to a particle size of about 4 μm to obtain a perovskite powder material with a composition of La 0.8 Ce0.1 Ni 0.1 Fe 0.3 Ti 0.6 O 3-δ perovskite material, namely LCeNFT powder material;

[0106] (4) The LCeNFT powder material obtained in step (3) is subjected to reduction treatment (the temperature of the reduction treatment is 900°C, and the time is 10h) under a 5Vol% H2 / 95Vol% N2reducing atmosphere, so that NiFe alloy nanospherical particles are precipitated on the surface thereof, to obtain a perovskite material to be prepared in the present comparative example, which is named as NiFe@LCeNFT material.

[0107] As shown in FIG. 6, the perovskite material prepared in the present comparative example has NiFe alloy nanospherical particles precipitated on the surface thereof, and the particle size of the NiFe alloy nanospherical particles is about 58nm.

[0108] Comparative Example 3

[0109] The present comparative example provides a perovskite material, wherein the material is prepared by the following preparation method:

[0110] (1) La2O3, CeO2, NiO, Fe2O3, and TiO2are weighed according to the molar ratio of La, Ce, Ni, Fe, and Ti being 0.8:0.1:0.1:0.3:0.6; the La2O3, CeO2, NiO, Fe2O3, and TiO2are added into acetone, stirred uniformly, and then subjected to ultrasonic oscillation for 30min at 4MHz using an ultrasonic oscillator to prepare an oxide suspension.

[0111] (2) The oxide suspension prepared in step (1) is dried, and the powder obtained after drying is calcined at 1100°C for 10h, and then calcined at 1450°C for 5h, to obtain a perovskite material with the composition of La 0.8 Ce 0.1 Ni 0.1 Fe 0.3 Ti 0.6 O 3-δ , which is named as LCeNFT material.

[0112] (3) The LCeNFT material obtained in step (2) is ground to a particle size of about 4μm using a planetary ball mill, to obtain a perovskite powder material with the composition of La 0.8 Ce 0.1 Ni 0.1 Fe 0.3 Ti 0.6 O 3-δ , which is the perovskite material to be prepared in the present comparative example, and is named as LCeNFT powder material.

[0113] As shown in FIG. 7, the perovskite material prepared in the present comparative example has a smooth surface and does not precipitate any nanoparticles.

[0114] Comparative Example 4

[0115] The present comparative example provides a perovskite material, wherein the material is prepared by the following preparation method:

[0116] (1) La2O3, CeO2, NiO and TiO2 were weighed according to the molar ratio of La, Ce, Ni and Ti of 0.8:0.1:0.4:0.6; the La2O3, CeO2, NiO and TiO2 were added into acetone and stirred uniformly, and then an oxide suspension was prepared by using an ultrasonic oscillator at 4 MHz for 30 min.

[0117] (2) The oxide suspension prepared in step (1) was dried, and the powder obtained after drying was calcined at 1100°C for 10 h, and then calcined at 1450°C for 5 h to obtain a perovskite material with a composition of La 0.8 Ce 0.1 Ni 0.4 Ti 0.6 O 3-δ , which is named as LCeNT material.

[0118] (3) The LCeNT material obtained in step (2) was ground by a planetary ball mill to a particle size of about 4 μm to obtain a perovskite powder material with a composition of La 0.8 Ce 0.1 Ni 0.4 Ti 0.6 O 3-δ , which is named as LCeNT powder material.

[0119] (4) The LCeNT powder material obtained in step (3) was subjected to low-temperature annealing treatment (the temperature of the low-temperature annealing treatment was 1250°C, and the time was 2 h) in an air atmosphere to precipitate CeO2 nanoparticles on the surface, and a powder material after low-temperature annealing treatment was obtained, which is named as CeO2@LCeNT material.

[0120] (5) The powder material after low-temperature annealing treatment obtained in step (4) was subjected to reduction treatment (the temperature of the reduction treatment was 900°C, and the time was 10 h) in a 5 Vol% H2 / 95 Vol% N2 reducing atmosphere to precipitate Ni nanoparticles on the surface, and a perovskite material to be prepared in the present example was obtained, which is named as CeO2-Ni@LCeNFT material.

[0121] As shown in FIG. 8, the perovskite material prepared in the present comparative example grows a large number of nanoparticles with different characteristics on the surface, including CeO2nanoparticles (such as the block-like or similar block-like particle structure in FIG. 8) and Ni metal nanoparticles (such as the spherical particle structure in FIG. 8), the particle size of the CeO2nanoparticles is about 180 nm, and the particle size of the Ni metal nanoparticles is about 56 nm. Notably, cracks appear on the edges of the CeO2nanoparticles, indicating that the structure of the CeO2nanoparticles changes after the reduction treatment, leading to the deterioration of the interface between the CeO2nanoparticles and the substrate.

[0122] Experimental Example 1

[0123] The perovskite materials provided in Example 1, Example 2, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4 were subjected to performance tests. Specifically:

[0124] The perovskite materials provided in Example 1, Example 2, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4 were subjected to performance tests. Specifically: 0.8 Sr 0.2 MnO3-YSZ composite material (purchased from Ningbo Suofu People Energy Technology Co., Ltd.) as the cathode material, and YSZ as the electrolyte to assemble a solid oxide fuel cell-electrolyte supported button single cell.

[0125] The assembled electrolyte supported button single cell was subjected to performance tests, including electrochemical impedance spectroscopy test and current-voltage scanning test, wherein the temperature was 800°C, the gas was pure hydrogen, and the flow rate was 50 mL / min.

[0126] The results are shown in FIGS. 9 and 10.

[0127] FIG. 9 is a battery impedance spectrogram. As can be seen from FIG. 9, the impedance of the battery assembled with the perovskite material provided in Comparative Example 3 (LCeNFT) as the anode material is the largest, about 9.0 Ω·cm 2 , the catalytic activity of the electrode material without any annealing and reduction treatment is poor. When the CeO2@LCeNFT material (Comparative Example 1) obtained by annealing to precipitate cerium oxide particles or the NiFe@LCeNFT material (Comparative Example 2) obtained by reduction treatment to precipitate NiFe nanoparticles is used as the anode, the impedance decreases to 7.7 Ω·cm 2 and 5.1 Ω·cm 2 , respectively, indicating that the precipitation of nanoparticles can improve the electrocatalytic activity of the electrode material to a certain extent. When the CeO2-NiFe@LCeNFT material provided in Example 1, which co-precipitates CeO2nanoparticle islands and NiFe alloy nanoparticle spheres, is used as the anode, the impedance of the battery is extremely low, about 1.8 Ω·cm 2The battery impedance was only 2.5 Ω·cm when the CeO2-NiCo@LCeNCT material provided in Example 2 was used as the anode 2 The battery impedance was 3.7 Ω·cm when the CeO2-Ni@LCeNT material provided in Comparative Example 4 was used as the anode 2 , which was greater than that of Example 1 and Example 2, indicating that alloy particle precipitation was more obvious than single metal particle in improving the performance of the battery.

[0128] Figure 10 is a button single battery I-V-P curve. As can be seen from Figure 10, the maximum power density of the battery assembled with the perovskite material (LCeNFT) provided in Comparative Example 3 as the anode material was the lowest, about 345 mW·cm -2 ; the second was the battery assembled with the perovskite material (CeO2@LCeNFT) provided in Comparative Example 1 as the anode material, and the maximum power density was about 471 mW·cm -2 ; the third was the battery assembled with the perovskite material (NiFe@LCeNFT) provided in Comparative Example 2 as the anode material, and the maximum power density was about 661 mW·cm -2 ; the fourth was the battery assembled with the perovskite material (CeO2-Ni@LCeNT) provided in Comparative Example 4 as the anode material, and the maximum power density was about 784 mW·cm -2 ; the maximum power densities of the batteries assembled with the perovskite materials provided in Example 1 and Example 2 as the anode materials were the highest, about 1022 mW·cm -2 and 917 mW·cm -2 , respectively. The overall regularity was consistent with the regularity of the electrochemical impedance data in Figure 7. By comparing Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4, it can be seen that the precipitation of nano cerium oxide and alloy NiFe (or NiCo) particles significantly improved the performance of the battery, and the maximum power density was increased by 196% compared with Comparative Example 3 (without particle precipitation), 117% compared with Comparative Example 1 (only CeO2 precipitation), 55% compared with Comparative Example 2 (only NiFe alloy precipitation), and 30% compared with Comparative Example 4 (precipitation of CeO2 and Ni). This indicated that the method of precipitating high-activity metal oxide CeO2 and alloy NiFe (or NiCo) nanoparticles on the surface of the anode material, thereby constructing a multi-element heterogeneous nanostructure, could more significantly improve the performance of the corresponding battery.

[0129] The micro-morphology of the perovskite materials provided by Comparative Example 1, Example 2 and Comparative Example 4 is shown in FIG. 1, FIG. 2 and FIG. 6. As can be seen from FIG. 1, FIG. 2 and FIG. 6, the interface between the cerium oxide island particles and the perovskite base material of the perovskite materials provided by Example 1 and Example 2 is good after reduction treatment, while the interface between the cerium oxide particles and the perovskite base material of the perovskite material provided by Comparative Example 4 has obvious cracks after reduction treatment.

[0130] The above results show that the high-activity metal oxide CeO2 and alloy NiFe (or NiCo) nanoparticles are precipitated on the surface of the perovskite material to construct a multi-element heterogeneous nanostructure, which can not only significantly improve the performance of the corresponding battery, but also enhance the structural stability of the nanostructure in a strong reducing atmosphere (for example, H2).

[0131] The above-described embodiments are for better explaining the present application, and it is not difficult for those skilled in the art to make various modifications to these embodiments without departing from the principles and spirits of the present application. Therefore, the present application is not limited to the embodiments herein, and any improvement and change made to the present application by those skilled in the art according to the principles and spirits of the present application should be within the protection scope of the present application.

Claims

1. 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 ; 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, M is one of Ni, Fe, Co, Mn, Cu, and N and M are not the same element; The perovskite material has CeO2 nano-island particles and NM alloy nano-spherical particles precipitated on the surface.

2. The perovskite material of claim 1, wherein, The diameter of the CeO2 nano-island particles is 1-500 nm.

3. The perovskite material of claim 1, wherein, The diameter of the NM alloy nano-spherical particles is 1-100 nm.

4. The perovskite material of claim 1, wherein, The perovskite material of the present application is prepared from a perovskite powder material with the composition of Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ under an oxidizing atmosphere and a reduction treatment in sequence; wherein the annealing temperature of the low-temperature annealing treatment is not more than 1300℃.

5. The perovskite material of claim 4, wherein, The annealing temperature of the low-temperature annealing treatment is 800-1300 °C. The annealing time of the low-temperature annealing treatment is 0.1-20 h. The oxidation atmosphere of the low-temperature annealing treatment is an air atmosphere or an oxygen atmosphere.

6. The perovskite material of claim 4, wherein, The temperature of the reduction treatment is 500-1000 °C. The time of the reduction treatment is 0.1-100 h. The atmosphere of the reduction treatment is a pure H2 atmosphere or a mixed gas atmosphere of at least one of N2 and an inert gas and H2.

7. The perovskite material of claim 4, wherein, The component is Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ The particle size of the perovskite powder material is 0.1-20 μm.

8. A method of producing the perovskite material of any one of claims 1-7, wherein, The method comprises: A perovskite powder material having the composition Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ ; The ingredients are Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ The perovskite powder material is subjected to low-temperature annealing treatment in an oxidizing atmosphere, so that CeO2 nano-island particles are precipitated on the surface, obtaining a powder material after low-temperature annealing treatment. The powder material after the low-temperature annealing treatment is subjected to a reduction treatment, so that NM alloy nano-spherical particles are precipitated on the surface, to obtain the perovskite material of any one of claims 1-7, and the CeO2 nano-island particles and the NM alloy nano-spherical particles precipitated on the surface of the prepared perovskite material have a firm interface with the parent material.

9. The production method according to claim 8, wherein A perovskite powder material having the composition Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ comprising: The oxides of Ln, Ce, N, M and Ti are weighed according to the molar ratio of Ln:Ce:N:M:Ti being 0.9-x:x:0.4-y:y:0.6, and the oxides of Ln, Ce, N, M and Ti are mixed with a solvent to prepare an oxide suspension; The oxide suspension is dried to obtain a powder, and the powder is subjected to two-stage high-temperature calcination to obtain a perovskite material with a composition of Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ ; wherein the calcination temperature of the first-stage high-temperature calcination is 900-1100°C, and the calcination temperature of the second-stage high-temperature calcination is 1300-1700°C. A perovskite material having a composition of Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ is subjected to a pulverization treatment to obtain a perovskite powder material having a composition of Ln 0.9-x Ce x N 0.4-y M y Ti 0.6 O 3-δ .

10. The production method according to claim 9, wherein The oxides of Ln, Ce, N, M and Ti are mixed with a solvent to prepare an oxide suspension, which comprises: after the oxides of Ln, Ce, N, M and Ti are mixed with a solvent, ultrasonic oscillation is performed to obtain an oxide suspension.

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

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

13. The perovskite material of any one of claims 1-7 as an anode material for a solid oxide fuel cell.

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