A high-entropy ceramic oxygen adsorbent material and a method of making the same

Abstract

The application provides a high-entropy ceramic oxygen adsorbent material and a preparation method thereof, relates to the technical field of ceramic materials, and aims to solve the technical problems of high sintering temperature and working temperature and low adsorption capacity during preparation of an oxygen adsorption medium. 2.5 Al 0.5 Fe 0.5 Ni 0.5 O7, and R is at least five of Yb, La, Pr, Sm, Ce and Gd. The nano high-entropy ceramic oxygen adsorbent material synthesized by the method can realize controllable powder particle size, has the advantages of low working temperature, large oxygen adsorption capacity, fast oxygen adsorption / desorption rate, high cycle stability and the like. The method has the advantages of simplicity, low cost, convenience, rapidness, high purity of prepared samples and the like, and can be mass-produced.

Description

Technical Field

[0001] This invention relates to the technical field of ceramic materials, and in particular to a high-entropy ceramic oxygen adsorbent material and its preparation method. Background Technology

[0002] Currently, the main materials used as oxygen adsorption media include Ba. 0.95 Ca 0.05 Co 0.8 Fe 0.2 O 3-δ La 0.2 Sr 0.8 Co 0.8 Fe 0.2 O 3-δ SrFeCo 0.5 O 3-δ Materials such as RBaCo4O7, while possessing excellent oxygen adsorption and release characteristics, can only effectively adsorb and release oxygen at high temperatures (approximately 800 to 1000°C). High-temperature operation not only increases energy consumption but also damages the material structure, thus affecting the application of oxygen separation materials. Currently, using ceramic-based oxygen adsorbents to separate gas mixtures faces two major challenges: firstly, the required operating temperature leads to increased energy consumption; secondly, the oxygen release rate is slow, reducing oxygen production. Therefore, developing a ceramic oxygen adsorbent material with high-capacity oxygen adsorption, rapid adsorption and release rates, suitable low-temperature operating conditions, and good cycle stability will greatly promote the separation of gas mixtures. Thus, finding new materials that can exhibit highly efficient oxygen adsorption and release activity at lower temperatures has become a key factor in advancing the development of oxygen separation materials.

[0003] In recent years, high-entropy alloys have attracted widespread research interest due to their excellent mechanical and physical properties, unique structure, and broad development prospects. Significant progress has been made in the research of these high-entropy materials, extending beyond traditional high-entropy alloy systems to include high-entropy inorganic non-metallic substances such as metal carbides, diborides, and oxides. When the concept of high entropy is applied to ceramic materials, it often produces some unexpected effects. High-entropy ceramics, as an emerging material, have been developed in recent years. They are composed of a variety of different elements, characterized by their close and uniform distribution within the crystal structure. Compared to traditional ceramic materials, high-entropy ceramics are not only more diverse in chemical composition but also have a more complex crystal structure, thus exhibiting superior mechanical properties, thermal properties, electrical conductivity, and thermal stability. However, the preparation of these materials still faces many challenges. Currently, research on high-entropy oxides mainly focuses on rock-salt structures, while research on high-entropy ceramic oxygen adsorbent material 114 is scarce.

[0004] The fundamental principle behind high-entropy ceramic design is the introduction of local atomic disorder, where multiple elements occupy equivalent lattice sites. Different elements exhibit variations in valence state, ionic radius, electronic configuration, and electronegativity, leading to different properties such as phase stability, lattice-distorted atomic disorder, and slow element diffusion. High-entropy ceramics possess four effects distinct from conventional ceramics: a thermodynamic high-entropy effect, a structural lattice distortion effect, a kinetic hysteresis diffusion effect, and a performance "cocktail" effect. These unique structures and high-entropy effects have attracted widespread attention.

[0005] In the preparation of high-entropy ceramics, sintering temperature and sintering time are undoubtedly the most important and core processes. The sintering process determines the diffusion, mass transfer, and mutual reaction of the raw material powder particles, thereby generating high-entropy single-phase functional ceramics. Solid-state sintering is the simplest and most commonly used method for preparing ceramics. However, traditional sintering techniques suffer from problems such as long sintering times, high sintering temperatures, and coarse grains in sintered samples, hindering the application and research of high-entropy ceramic materials. Furthermore, to obtain single-phase functional ceramics, due to the retarded diffusion effect and impurities in high-entropy materials, prolonged high-temperature holding is often required, which can easily lead to grain coarsening. For example, patent publication number CN104857911A discloses a high-performance oxygen adsorbent and its preparation method, with the structural formula A. 1-x A′ x B 1-y B′ y O 3-δ Where x ranges from 0 to 0.3, y ranges from 0 to 0.3, and 0 < δ < 0.5; A is at least one or more of rare earth metals (La series) and alkaline earth metals (Mg, Ca, Sr, Ba); B is at least one or more of transition metals (Co, Al, Fe, Nb, Cu, Zr, Mn, Cr, Ti). The preparation method is as follows: based on the chemical formula of the target oxygen adsorbent, the raw materials are accurately weighed according to the molar ratio of the metal elements, then ball-milled and mixed evenly. The mixture is then calcined multiple times at high temperatures to prepare perovskite-type oxide powder with larger particles. This powder is then ball-milled again to obtain a multi-metal composite oxide powder, which is the oxygen adsorbent. The calcination temperature of this patent is as high as 900℃-1400℃, while the weight change of the prepared cation adsorbent during temperature fluctuations between 300-925℃ is only 2.6%. Therefore, developing new sintering technologies, shortening sintering time, reducing sintering temperature, obtaining sintered samples with fine grains, and lowering oxygen adsorption temperature to increase adsorption capacity have become the development goals of high-entropy ceramic preparation technology. Summary of the Invention

[0006] To address the technical problems of high sintering and operating temperatures and low adsorption capacity in the preparation of oxygen adsorption media, this invention proposes a high-entropy ceramic oxygen adsorbent material and its preparation method. The method prepares RBaCo... 2.5 Al 0.5 Fe 0.5 Ni 0.5 O7 oxygen adsorbent material has the advantages of low operating temperature, low energy consumption, relatively fast oxygen desorption rate, and high oxygen production efficiency.

[0007] To achieve the above objectives, the technical solution of the present invention is implemented as follows:

[0008] A high-entropy ceramic oxygen adsorbent material, the structural formula of which is: RBaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5 O7, where the R-bit element is at least five of the following: Yb, La, Pr, Sm, Ce, and Gd.

[0009] The structural formula of the high-entropy ceramic oxygen adsorbent material is: Yb 0.2 La 0.2 Pr 0.2 Sm 0.2 Ce 0.2 BaCo 2.5 Al 0.5 Fe 0. 5Ni 0.5 O7, a high-entropy ceramic oxygen adsorbent material, is in the form of spherical powder with a size of 50-500 nm.

[0010] The structural formula of the high-entropy ceramic oxygen adsorbent material is: Yb 1 / 6 La 1 / 6 Pr 1 / 6 Sm 1 / 6 Ce 1 / 6 Gd 1 / 6BaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5 O7.

[0011] A method for preparing a high-entropy ceramic oxygen adsorbent material, comprising the following steps:

[0012] (1) Based on the structural formula of the high-entropy ceramic oxygen adsorbent material, weigh the metal oxides of the R-site elements, BaCO3, Al2O3, Fe2O3 and NiO according to the stoichiometric ratio;

[0013] (2) Disperse and dissolve the powder, alkaline reagent and morphology modifier weighed in step (1) into a solvent, and then carry out a hydrothermal reaction. After the reaction is completed, wash and dry to obtain a porous high-entropy ceramic oxygen adsorbent material.

[0014] (3) The high-entropy ceramic oxygen adsorbent material and chloride salt were mixed and ball-milled, and then the mixed powder was calcined to obtain the high-entropy ceramic oxygen adsorbent material.

[0015] The metal oxide of the R-position element is Yb₂O₃, La₂O₃, or Pr₆O. 11 Sm2O3, Ce2O3 or Gd2O3.

[0016] In step (2), the mass ratio of powder, alkaline reagent, morphology modifier and solvent is 1:(1-1.5):(1-1.5):(0.6-0.8). The alkaline reagent provides an alkaline environment, such as sodium hydroxide. The morphology modifier controls the morphology of the powder, such as sodium citrate, sodium bicarbonate or polyvinyl alcohol.

[0017] The solvent comprises alcohol and water in a mass ratio of 1:(1-1.5).

[0018] The hydrothermal reaction is carried out at a temperature of 150-185℃ for 5-15 hours.

[0019] The mass ratio of the high-entropy ceramic oxygen adsorbent material to chloride salt is 1:(5-10).

[0020] The chloride salt includes NaCl and KCl, with a mass ratio of NaCl to KCl of (40-55):(60-45). The chloride salt is melted at a specific temperature to provide a liquid environment, temperature, and pressure environment for the preparation of the powder.

[0021] The calcination temperature is 700-850℃, and the time is 8-10h.

[0022] The beneficial effects of this invention: This invention utilizes the concept of high-entropy ceramics, by adding oxygen adsorption material RbaCoO 7+δ The number of elements at the R and Co sites in the structure is used to construct a high-entropy structure. A high-pressure, low-temperature sintering process is designed using a combination of hydrothermal and molten salt methods. This process results in a low-temperature, simple sintering method that produces grains with controllable sizes (50nm-500nm) and large specific surface areas (30.07-85.05nm). 2 ·g -1High-entropy ceramic oxygen adsorbent materials were prepared. The prepared nano-high-entropy ceramic oxygen adsorbent material has a 114 structure, uniform size distribution, and a spherical shape with dimensions of 50-500 nm. The lattice constant of the high-entropy ceramic oxygen adsorbent material can be adjusted by regulating the ratio of Yb, La, Pr, Sm, Ce, and Gd, thereby achieving good oxygen adsorption performance and a low operating temperature. It also exhibits advantages such as fast oxygen adsorption / desorption rates and high cycle stability. The prepared high-entropy ceramic oxygen adsorbent material showed a mass change of 3.17% after adsorbing oxygen at 370℃ and 6.49% after adsorbing oxygen at 830℃, solving the problems of high operating temperature, high energy consumption, and slow oxygen adsorption / desorption rates in practical applications of existing oxygen adsorbent materials. Attached Figure Description

[0023] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0024] Figure 1 For Yb 0.2 La 0.2 Pr 0.2 Sm 0.2 Ce 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5 SEM image of O7 nanoparticle high-entropy ceramic oxygen adsorbent material.

[0025] Figure 2 For Yb 0.2 La 0.2 Pr 0.2 Sm 0.2 Ce 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5 Adsorption-desorption curves of O7 nanoparticle high-entropy ceramic oxygen adsorbent material.

[0026] Figure 3 For Yb 0.2 La 0.2 Pr 0.2 Sm 0.2 Ce 0.2 BaCo 2.5 Al 0.5 Fe0.5 Ni 0.5 XRD pattern of O7 nanoparticle high-entropy ceramic oxygen adsorbent material.

[0027] Figure 4 For Yb 0.2 La 0.2 Pr 0.2 Sm 0.2 Ce 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5 Oxygen adsorption performance test chart of O7 nanopowder high-entropy ceramic oxygen adsorbent material. Detailed Implementation

[0028] 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 embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0029] Example 1

[0030] A high-entropy ceramic oxygen adsorbent material, with the structural formula Yb 0.2 La 0.2 Pr 0.2 Sm 0.2 Ce 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0. 5O7, its preparation method includes the following steps:

[0031] (1) Preliminary treatment of oxygen adsorbent materials using hydrothermal method: Weigh Yb2O3, La2O3, and Pr6O according to stoichiometric ratio. 11 Raw materials such as Sm₂O₃, Ce₂O₃, BaCO₃, Al₂O₃, Fe₂O₃, and NiO were weighed and dissolved in a mixed solvent of alcohol and water. The weighed powder was then added to a reaction vessel. The mass ratio of raw materials, sodium hydroxide, and sodium citrate was 1:1:1:0.6, and the ratio of alcohol to water was 1:1. After the reaction, the sample was removed, washed with deionized water and alcohol, and dried to obtain a preliminary high-entropy ceramic oxygen adsorbent material. The reaction time was 15 h at 150℃, and the drying time was 5 h at 50℃.

[0032] (2) Preparation of porous high-entropy ceramic oxygen adsorbent material by mixed alkali method: The high-entropy ceramic oxygen adsorbent material product obtained by hydrothermal method is used as raw material, and NaCl and KCl are mixed at a mass ratio of 40:60, and the two powders mentioned above are mixed at a mass ratio of 1:5; then the mixed powder after roller milling is placed in an alumina crucible and kept at 850℃ for 8 hours, and then washed several times with deionized water to remove excess NaCl and KCl, and dried at 75℃ to finally obtain Yb 0.2 La 0.2 Pr 0.2 Sm 0.2 Ce 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5 O7 nanopowder high-entropy ceramic oxygen adsorbent material.

[0033] Example 2

[0034] A high-entropy ceramic oxygen adsorbent material, with the structural formula Yb 0.2 La 0.2 Pr 0.2 Sm 0.2 Ce 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0. 5O7, its preparation method includes the following steps:

[0035] (1) Preliminary treatment of oxygen adsorbent materials using hydrothermal method: Weigh Yb2O3, La2O3, and Pr6O according to stoichiometric ratio. 11 Raw materials such as Sm₂O₃, Ce₂O₃, BaCO₃, Al₂O₃, Fe₂O₃, and NiO were weighed and dissolved in a mixed solvent of alcohol and water. The weighed powder was then added to a reaction vessel. The mass ratio of raw materials, sodium hydroxide, and sodium citrate was 1:1.5:1.5:0.8, and the ratio of alcohol to water was 1:1.5. After the reaction, the sample was removed, washed with deionized water and alcohol, and dried to initially obtain a high-entropy ceramic oxygen adsorbent material. The reaction temperature was 185℃ for 5 hours, and the drying temperature was 60℃ for 2 hours.

[0036] (2) Preparation of porous high-entropy ceramic oxygen adsorbent material using mixed alkali method: The high-entropy ceramic oxygen adsorbent material product obtained by hydrothermal method was used as raw material, and NaCl and KCl were mixed at a mass ratio of 55:45, and the two powders mentioned above were mixed at a mass ratio of 1:10; then the mixed powder after roller milling was placed in an alumina crucible and kept at 700℃ for 10 hours, and then washed several times with deionized water to remove excess NaCl and KCl, and dried at 80℃ to finally obtain Yb 0.2 La 0.2 Pr 0.2 Sm 0.2 Ce 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5 O7 nanopowder high-entropy ceramic oxygen adsorbent material.

[0037] Example 3

[0038] A high-entropy ceramic oxygen adsorbent material, with the structural formula Yb 0.2 La 0.2 Pr 0.2 Sm 0.2 Ce 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0. 5O7, its preparation method includes the following steps:

[0039] (1) Preliminary treatment of oxygen adsorbent materials using hydrothermal method: Weigh Yb2O3, La2O3, and Pr6O according to stoichiometric ratio. 11 Raw materials such as Sm₂O₃, Ce₂O₃, BaCO₃, Al₂O₃, Fe₂O₃, and NiO were weighed and dissolved in a mixed solvent of alcohol and water. The weighed powder was then added to a reaction vessel. The mass ratio of raw materials, sodium hydroxide, and sodium citrate was 1:1.2:1.3:0.7, and the ratio of alcohol to water was 1:1.3. After the reaction, the sample was removed, washed with deionized water and alcohol, and dried to obtain a preliminary high-entropy ceramic oxygen adsorbent material. The reaction time was 8 hours at 160℃, and the drying time was 4 hours at 55℃.

[0040] (2) Preparation of porous high-entropy ceramic oxygen adsorbent material using mixed alkali method: The high-entropy ceramic oxygen adsorbent material product obtained by hydrothermal method was used as raw material, and NaCl and KCl were mixed at a mass ratio of 50:50, and the two powders mentioned above were mixed at a mass ratio of 1:6; then the mixed powder after roller milling was placed in an alumina crucible and kept at 790℃ for 9 hours, and then washed several times with deionized water to remove excess NaCl and KCl, and dried at 78℃ to finally obtain Yb 0.2 La 0.2 Pr 0.2 Sm 0.2 Ce 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5 O7 nanopowder high-entropy ceramic oxygen adsorbent material.

[0041] Example 4

[0042] A high-entropy ceramic oxygen adsorbent material, with the structural formula Yb 0.2 La 0.2 Pr 0.2 Sm 0.2 Ce 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0. 5O7, its preparation method includes the following steps:

[0043] (1) Preliminary treatment of oxygen adsorbent materials using hydrothermal method: Weigh Yb2O3, La2O3, and Pr6O according to stoichiometric ratio. 11 Raw materials such as Sm₂O₃, Ce₂O₃, BaCO₃, Al₂O₃, Fe₂O₃, and NiO were weighed and dissolved in a mixed solvent of alcohol and water. The weighed powder was then added to a reaction vessel. The mass ratio of raw materials, sodium hydroxide, and sodium citrate was 1:1.4:1.4:0.7, and the ratio of alcohol to water was 1:1.4. After the reaction, the sample was removed, washed with deionized water and alcohol, and dried to obtain a preliminary high-entropy ceramic oxygen adsorbent material. The reaction temperature was 170℃, the reaction time was 11 hours, and the drying temperature was 58℃, the drying time was 4 hours.

[0044] (2) Preparation of porous high-entropy ceramic oxygen adsorbent material using mixed alkali method: The high-entropy ceramic oxygen adsorbent material product obtained by hydrothermal method was used as raw material, and NaCl and KCl were mixed at a mass ratio of 55:45, and the two powders mentioned above were mixed at a mass ratio of 1:8; then the mixed powder after roller milling was placed in an alumina crucible and kept at 830℃ for 9.2 hours, and then washed several times with deionized water to remove excess NaCl and KCl, and dried at 79℃ to finally obtain Yb 0.2 La 0.2 Pr 0.2 Sm 0.2 Ce 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5 O7 nanopowder high-entropy ceramic oxygen adsorbent material.

[0045] Figure 1 Yb was prepared for Example 1 0.2 La 0.2 Pr 0.2 Sm 0.2 Ce 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5 SEM image of O7 nanoparticle high-entropy ceramic oxygen adsorbent material, with powder size between 50-500 nm.

[0046] Figure 2 Yb prepared in Example 1 0.2 La 0.2 Pr 0.2 Sm 0.2 Ce 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5 The adsorption-desorption curves of the O7 nanoparticle high-entropy ceramic oxygen adsorbent material show that its specific surface area is 85.05 m². 2 ·g -1 .

[0047] Figure 3 Yb prepared in Examples 1, 2, and 3 0.2 La 0.2 Pr 0.2 Sm 0.2 Ce 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5XRD pattern of O7 nanoparticle high-entropy ceramic oxygen adsorbent material; test results show that the prepared Yb 0.2 La 0.2 Pr 0.2 Sm 0.2 Ce 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5 The O7 nanoparticle high-entropy ceramic oxygen adsorbent material closely matches the hexagonal close-packed structure represented by the P63mc(186) space group. The XRD pattern of the high-entropy ceramic oxygen adsorbent material was precisely labeled according to the crystal plane index of this space group, verifying that the high-entropy ceramic oxygen adsorbent material has a single 114 structure feature.

[0048] Figure 4 Yb prepared for Examples 1 and 2 0.2 La 0.2 Pr 0.2 Sm 0.2 Ce 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5 The oxygen adsorption performance test chart of the O7 nanoparticle high-entropy ceramic oxygen adsorbent material shows that in the oxygen adsorption-desorption experiment, approximately 30 mg of sample powder was placed in an alumina crucible, and the weight change curve of the sample with increasing temperature was measured in an oxygen atmosphere. The test results indicate that the Yb prepared in Example 1... 0.2 La 0.2 Pr 0.2 Sm 0.2 Ce 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5 The O7 nanoparticle high-entropy ceramic oxygen adsorbent material showed a mass change of 3.17% after adsorbing oxygen at 370℃ and 6.49% after adsorbing oxygen at 830℃. The Yb prepared in Example 2... 0.2 La 0.2 Pr 0.2 Sm 0.2 Ce 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5 The O7 nanoparticle high-entropy ceramic oxygen adsorbent material showed a mass change of 2.71% after adsorbing oxygen at 370℃ and a mass change of 5.72% after adsorbing oxygen at 830℃.

[0049] Example 5

[0050] A high-entropy ceramic oxygen adsorbent material, with the structural formula Yb 0.2 La 0.2 Pr 0.2 Sm 0.2 Gd 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0. 5O7, its preparation method includes the following steps:

[0051] (1) Preliminary treatment of oxygen adsorbent materials using hydrothermal method: Weigh Yb2O3, La2O3, and Pr6O according to stoichiometric ratio. 11 Raw materials such as Sm₂O₃, Gd₂O₃, BaCO₃, Al₂O₃, Fe₂O₃, and NiO were weighed and dissolved in a mixed solvent of alcohol and water. The weighed powder was then added to a reaction vessel. The mass ratio of raw materials, sodium hydroxide, and sodium citrate was 1:1:1:0.6, and the ratio of alcohol to water was 1:1. After the reaction, the sample was removed, washed with deionized water and alcohol, and dried to obtain a preliminary high-entropy ceramic oxygen adsorbent material. The reaction time was 15 h at 150℃, and the drying time was 5 h at 50℃.

[0052] (2) Preparation of porous high-entropy ceramic oxygen adsorbent material by mixed alkali method: The high-entropy ceramic oxygen adsorbent material product obtained by hydrothermal method is used as raw material, and NaCl and KCl are mixed at a mass ratio of 40:60, and the two powders mentioned above are mixed at a mass ratio of 1:5; then the mixed powder after roller milling is placed in an alumina crucible and kept at 850℃ for 8 hours, and then washed several times with deionized water to remove excess NaCl and KCl, and dried at 75℃ to finally obtain Yb 0.2 La 0.2 Pr 0.2 Sm 0.2 Gd 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5 O7 nanopowder high-entropy ceramic oxygen adsorbent material.

[0053] Example 6

[0054] A high-entropy ceramic oxygen adsorbent material, with the structural formula Yb 0.2 La 0.2 Pr 0.2 Ce 0.2 Gd 0.2 BaCo 2.5 Al 0.5Fe 0.5 Ni 0. 5O7, its preparation method includes the following steps:

[0055] (1) Preliminary treatment of oxygen adsorbent materials using hydrothermal method: Yb2O3, La2O3, and Pr6O3 were weighed according to stoichiometric ratio. 11 Raw materials such as Ce₂O₃, Gd₂O₃, BaCO₃, Al₂O₃, Fe₂O₃, and NiO were weighed and dissolved in a mixed solvent of alcohol and water. The weighed powder was then added to a reaction vessel. The mass ratio of raw materials, sodium hydroxide, and sodium citrate was 1:1:1:0.6, and the ratio of alcohol to water was 1:1. After the reaction, the sample was removed, washed with deionized water and alcohol, and dried to obtain a preliminary high-entropy ceramic oxygen adsorbent material. The reaction time was 15 h at 150℃, and the drying time was 5 h at 50℃.

[0056] (2) Preparation of porous high-entropy ceramic oxygen adsorbent material by mixed alkali method: The high-entropy ceramic oxygen adsorbent material product obtained by hydrothermal method is used as raw material, and NaCl and KCl are mixed at a mass ratio of 40:60, and the two powders mentioned above are mixed at a mass ratio of 1:5; then the mixed powder after roller milling is placed in an alumina crucible and kept at 850℃ for 8 hours, and then washed several times with deionized water to remove excess NaCl and KCl, and dried at 75℃ to finally obtain Yb 0.2 La 0.2 Pr 0.2 Ce 0.2 Gd 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5 O7 nanopowder high-entropy ceramic oxygen adsorbent material.

[0057] Example 7

[0058] A high-entropy ceramic oxygen adsorbent material, with the structural formula Yb 0.2 La 0.2 Sm 0.2 Ce 0.2 Gd 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0. 5O7, its preparation method includes the following steps:

[0059] (1) Preliminary treatment of oxygen adsorbent material using hydrothermal method: Yb2O3, La2O3, Sm2O3, Ce2O3, Gd2O3, BaCO3, Al2O3, Fe2O3, NiO and other raw materials were weighed according to stoichiometric ratio. Sodium hydroxide, sodium bicarbonate and other materials were weighed and dissolved in a mixed solvent of alcohol and water. Then the weighed powder was added to the reaction vessel. The mass ratio of raw materials, sodium hydroxide and sodium citrate was 1:1:1:0.6, and the ratio of alcohol to water was 1:1. After the reaction was completed, the sample was taken out, and then washed with deionized water and alcohol and dried to obtain the preliminary high-entropy ceramic oxygen adsorbent material product. The reaction time was 150℃ and the reaction time was 15h. The drying temperature was 50℃ and the drying time was 5h.

[0060] (2) Preparation of porous high-entropy ceramic oxygen adsorbent material by mixed alkali method: The high-entropy ceramic oxygen adsorbent material product obtained by hydrothermal method is used as raw material, and NaCl and KCl are mixed at a mass ratio of 40:60, and the two powders mentioned above are mixed at a mass ratio of 1:5; then the mixed powder after roller milling is placed in an alumina crucible and kept at 850℃ for 8 hours, and then washed several times with deionized water to remove excess NaCl and KCl, and dried at 75℃ to finally obtain Yb 0.2 La 0.2 Sm 0.2 Ce 0.2 Gd 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5 O7 nanopowder high-entropy ceramic oxygen adsorbent material.

[0061] Example 8

[0062] A high-entropy ceramic oxygen adsorbent material, with the structural formula Yb 0.2 Pr 0.2 Sm 0.2 Ce 0.2 Gd 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0. 5O7, its preparation method includes the following steps:

[0063] (1) Preliminary treatment of oxygen adsorbent materials using hydrothermal method: Weigh Yb2O3 and Pr6O according to stoichiometric ratio. 11Raw materials including Sm₂O₃, Ce₂O₃, Gd₂O₃, BaCO₃, Al₂O₃, Fe₂O₃, and NiO were weighed and dissolved in a mixture of alcohol and water. The weighed powder was then added to a reaction vessel. The mass ratio of raw materials, sodium hydroxide, and sodium citrate was 1:1:1:0.6, and the ratio of alcohol to water was 1:1. After the reaction, the sample was removed, washed with deionized water and alcohol, and dried to obtain a preliminary high-entropy ceramic oxygen adsorbent material. The reaction temperature was 150℃ for 15 hours, and the drying temperature was 50℃ for 5 hours.

[0064] (2) Preparation of porous high-entropy ceramic oxygen adsorbent material by mixed alkali method: The high-entropy ceramic oxygen adsorbent material product obtained by hydrothermal method is used as raw material, and NaCl and KCl are mixed at a mass ratio of 40:60, and the two powders mentioned above are mixed at a mass ratio of 1:5; then the mixed powder after roller milling is placed in an alumina crucible and kept at 850℃ for 8 hours, and then washed several times with deionized water to remove excess NaCl and KCl, and dried at 75℃ to finally obtain Yb 0.2 Pr 0.2 Sm 0.2 Ce 0.2 Gd 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5 O7 nanopowder high-entropy ceramic oxygen adsorbent material.

[0065] Example 9

[0066] A high-entropy ceramic oxygen adsorbent material, with the structural formula La 0.2 Sm 0.2 Pr 0.2 Ce 0.2 Gd 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0. 5O7, its preparation method includes the following steps:

[0067] (1) Preliminary treatment of oxygen adsorbent materials using hydrothermal method: weigh La2O3, Sm2O3, and Pr6O according to stoichiometric ratio. 11Raw materials such as Ce₂O₃, Gd₂O₃, BaCO₃, Al₂O₃, Fe₂O₃, and NiO were weighed and dissolved in a mixed solvent of alcohol and water. The weighed powder was then added to a reaction vessel. The mass ratio of raw materials, sodium hydroxide, and sodium citrate was 1:1:1:0.6, and the ratio of alcohol to water was 1:1. After the reaction, the sample was removed, washed with deionized water and alcohol, and dried to obtain a preliminary high-entropy ceramic oxygen adsorbent material. The reaction time was 15 h at 150℃, and the drying time was 5 h at 50℃.

[0068] (2) Preparation of porous high-entropy ceramic oxygen adsorbent material using the mixed alkali method: The high-entropy ceramic oxygen adsorbent material product obtained by the hydrothermal method was used as raw material, and NaCl and KCl were mixed at a mass ratio of 40:60, and the two powders mentioned above were mixed at a mass ratio of 1:5; then the mixed powder after roller milling was placed in an alumina crucible and kept at 850℃ for 8 hours, and then washed several times with deionized water to remove excess NaCl and KCl, and dried at 75℃ to finally obtain La 0.2 Sm 0.2 Pr 0.2 Ce 0.2 Gd 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5 O7 nanopowder high-entropy ceramic oxygen adsorbent material.

[0069] Example 10

[0070] A high-entropy ceramic oxygen adsorbent material, with the structural formula Yb 1 / 6 La 1 / 6 Pr 1 / 6 Sm 1 / 6 Ce 1 / 6 Gd 1 / 6BaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5 O7, its preparation method includes the following steps:

[0071] (1) Preliminary treatment of oxygen adsorbent materials using hydrothermal method: Yb2O3, La2O3, and Pr6O3 were weighed according to stoichiometric ratio. 11Raw materials such as Sm₂O₃, Ce₂O₃, Gd₂O₃, BaCO₃, Al₂O₃, Fe₂O₃, and NiO were weighed and dissolved in a mixture of alcohol and water. The weighed powder was then added to a reaction vessel. The mass ratio of raw materials, sodium hydroxide, and sodium citrate was 1:1:1:0.6, and the ratio of alcohol to water was 1:1. After the reaction, the sample was removed, washed with deionized water and alcohol, and dried to obtain a preliminary high-entropy ceramic oxygen adsorbent material. The reaction time was 15 h at 150℃, and the drying time was 5 h at 50℃.

[0072] (2) Preparation of porous high-entropy ceramic oxygen adsorbent material by mixed alkali method: The high-entropy ceramic oxygen adsorbent material product obtained by hydrothermal method is used as raw material, and NaCl and KCl are mixed at a mass ratio of 40:60, and the two powders mentioned above are mixed at a mass ratio of 1:5; then the mixed powder after roller milling is placed in an alumina crucible and kept at 850℃ for 8 hours, and then washed several times with deionized water to remove excess NaCl and KCl, and dried at 75℃ to finally obtain Yb 1 / 6 La 1 / 6 Pr 1 / 6 Sm 1 / 6 Ce 1 / 6Gd 1 / 6 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5 O7 nanopowder high-entropy ceramic oxygen adsorbent material.

[0073] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A high-entropy ceramic oxygen adsorbent material, characterized in that, The structural formula of the high-entropy ceramic oxygen adsorbent material is: RBaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5 O7, where the R-bit element is at least five of the following: Yb, La, Pr, Sm, Ce, and Gd.

2. The high-entropy ceramic oxygen adsorbent material according to claim 1, characterized in that, The structural formula of the high-entropy ceramic oxygen adsorbent material is: Yb 0.2 La 0.2 Pr 0.2 Sm 0.2 Ce 0.2 BaCo 2.5 Al 0.5 Fe 0.5 Ni 0.5 O7, a high-entropy ceramic oxygen adsorbent material, is in the form of spherical powder with a size of 50-500 nm.

3. The method for preparing the high-entropy ceramic oxygen adsorbent material according to claim 1 or 2, characterized in that, The steps are as follows: (1) Based on the structural formula of the high-entropy ceramic oxygen adsorbent material, weigh the metal oxides of the R-site elements, BaCO3, Al2O3, Fe2O3 and NiO according to the stoichiometric ratio; (2) Disperse and dissolve the powder, alkaline reagent and morphology modifier weighed in step (1) into a solvent, and then carry out a hydrothermal reaction. After the reaction is completed, wash and dry to obtain a porous high-entropy ceramic oxygen adsorbent material. (3) The high-entropy ceramic oxygen adsorbent material prepared in step (2) is mixed and ball-milled with chloride salt, and then the mixed powder is calcined to obtain the high-entropy ceramic oxygen adsorbent material.

4. The preparation method of the high-entropy ceramic oxygen adsorbent material according to claim 3, characterized in that, The metal oxide of the R-position element is Yb₂O₃, La₂O₃, or Pr₆O. 11 Sm2O3, Ce2O3 or Gd2O3.

5. The preparation method of the high-entropy ceramic oxygen adsorbent material according to claim 4, characterized in that, In step (2), the mass ratio of powder, alkaline reagent, morphology modifier and solvent is 1:(1-1.5):(1-1.5):(0.6-0.8), the alkaline reagent is sodium hydroxide; the morphology modifier is sodium citrate, sodium bicarbonate or polyvinyl alcohol.

6. The method for preparing the high-entropy ceramic oxygen adsorbent material according to claim 5, characterized in that, The solvent comprises alcohol and water in a mass ratio of 1:(1-1.5).

7. The method for preparing the high-entropy ceramic oxygen adsorbent material according to any one of claims 3-6, characterized in that, The hydrothermal reaction is carried out at a temperature of 150-185℃ for 5-15 hours.

8. The method for preparing the high-entropy ceramic oxygen adsorbent material according to claim 7, characterized in that, The mass ratio of the high-entropy ceramic oxygen adsorbent material to chloride salt is 1:(5-10).

9. The method for preparing the high-entropy ceramic oxygen adsorbent material according to claim 8, characterized in that, The chloride salt includes NaCl and KCl, with a mass ratio of NaCl to KCl of (40-55):(60-45).

10. The method for preparing the high-entropy ceramic oxygen adsorbent material according to claim 3, characterized in that, The calcination temperature is 700-850℃, and the time is 8-10h.

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