High-entropy spinel electrode material, preparation method thereof and solid oxide electrolytic cell
By preparing high-entropy spinel electrode materials, the problem of phase decomposition of traditional spinel materials at high temperatures in solid oxide electrolytic cells was solved, achieving a balance between high-temperature stability and catalytic activity, and ensuring the stable operation of the electrolytic cell.
Patent Information
- Application Number
- CN202511866425.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-11
- Publication Date
- 2026-02-24
AI Technical Summary
Traditional transition metal spinel materials are prone to phase decomposition at high temperatures in solid oxide electrolytic cells, resulting in insufficient phase stability and difficulty in achieving both high catalytic activity and adaptability to high-temperature environments.
High-entropy spinel electrode material with the general chemical formula RO4 is used, in which R is composed of five or more elements selected from Mg, Mo, Sc, Co, Mn, Fe, Ni, Cu, Al, Zn, Cd, Cr and In. It is prepared by solid-state synthesis, sol-gel method, combustion method or hydrothermal method to form a uniform and dense single-phase spinel structure. The high-entropy mixing effect is used to improve thermodynamic stability and increase atomic diffusion energy barrier, thereby inhibiting phase decomposition.
It significantly improves the thermodynamic and kinetic stability of spinel materials at high temperatures, solves the phase decomposition problem, ensures the long-term stable operation of the electrode in the solid oxide electrolytic cell, and also has excellent electrochemical catalytic activity.
Smart Images
Figure CN121556070A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of solid oxide electrolytic cells, and in particular to a high-entropy spinel electrode material and its preparation method, as well as a solid oxide electrolytic cell. Background Technology
[0002] Solid oxide electrolyzers are efficient and clean energy conversion devices. They possess high energy conversion efficiency, directly converting electrical energy into hydrogen energy, enabling the storage of renewable energy. Compared to room-temperature water electrolysis, solid oxide electrolyzers typically operate between 500 and 800°C. This high temperature lowers the theoretical decomposition voltage of the electrolysis reaction and significantly increases the electrode reaction rate and ion conduction rate in the solid electrolyte, reducing overpotential loss. This means less electrical energy input is required at the same voltage. While this high-temperature operating environment helps improve chemical reaction rates and efficiency, it also presents challenges in material selection and thermal management, causing spinel materials, which perform well in room-temperature water electrolysis, to decompose at high temperatures.
[0003] In room-temperature water electrolysis, transition metal spinel materials such as NiFe₂O₄, CoFe₂O₄, NiCo₂O₄, and MnCo₂O₄ exhibit significantly better oxygen evolution reaction catalytic activity than pure nickel, cobalt, or iron oxides in alkaline environments. Their activity is often close to, and under certain conditions even exceeds, that of benchmark noble metal oxides. Transition metal spinel materials are rich in constituent elements (Fe, Co, Ni, and Mn, etc.) and relatively inexpensive. In the AB₂O₄ structure of transition metal spinel materials, the A-site is typically a divalent metal ion, and the B-site is typically a trivalent metal ion. Their elemental composition and chemical structure are highly tunable, providing a vast space for catalyst design. By adjusting the type, ratio, valence state, and defect concentration of the metals at the A / B sites, their electronic structure and surface active sites can be finely optimized, thereby significantly improving catalytic activity. These advantages make them potential applications in solid oxide electrolyzers. However, they also face some challenges, such as electrode activity, long-term stability, and material durability.
[0004] High-entropy materials exhibit a fourfold effect. Introducing a high-entropy strategy into spinel structures is a promising material design approach, expected to significantly improve their thermal stability at high temperatures, thereby partially alleviating the phase decomposition challenges (especially phase decomposition problems) they face in solid oxide electrolyzer applications. The high-entropy effect brought about by the high-entropy strategy can improve the thermodynamic stability of single-phase solid solutions relative to decomposition products and significantly delay decomposition kinetics. This provides strong support and great potential for addressing the high-temperature reduction instability of spinel in solid oxide electrolyzer applications.
[0005] In summary, research on spinel electrode materials is promising. Based on elements that are abundant and inexpensive, introducing a high-entropy strategy into spinel can improve its phase stability. Developing a new stable material system suitable for the harsh high-temperature environment of solid oxide electrolysis cells is of great application potential. Summary of the Invention
[0006] The technical problem to be solved by the present invention is to address the above-mentioned deficiencies in the prior art by providing a high-entropy spinel electrode material and its preparation method, as well as a solid oxide electrolytic cell, to solve the technical problems that traditional transition metal spinel materials are prone to phase decomposition and insufficient phase stability under high-temperature conditions in solid oxide electrolytic cells, and that it is difficult to balance high catalytic activity and high-temperature environmental adaptability.
[0007] In a first aspect, the present invention provides a high-entropy spinel electrode material having a spinel crystal structure and a general chemical formula of RO4; wherein R is composed of five or more elements selected from Mg, Mo, Sc, Co, Mn, Fe, Ni, Cu, Al, Zn, Cd, Cr, and In, and the stoichiometric coefficients x of each element in R are... i All satisfy 0.25≤x i ≤1.
[0008] Preferably, R includes at least one of the following combinations: Fe and Co, Co and Ni, and Fe and Ni.
[0009] Preferably, the high-entropy spinel electrode material is Fe. 0.6 Mn 0.6 Co 0.6 Ni 0.6 Cr 0.6 O4 material or (CoMnFeMg) 0.25 CrO4 material.
[0010] Secondly, the present invention also provides a method for preparing any of the above-mentioned high-entropy spinel electrode materials, wherein the preparation method is any one of solid-state synthesis, sol-gel method, combustion method, hydrothermal method or solvothermal method.
[0011] Preferably, the preparation method is to obtain Fe by combustion. 0.6 Mn 0.6 Co 0.6 Ni 0.6 Cr 0.6 The specific steps for using O4 high-entropy spinel electrode material are as follows: Iron source, manganese source, cobalt source, nickel source, chromium source, glycine and deionized water are mixed evenly and heated in a water bath until the water is completely evaporated to obtain the precursor; The precursor was first held at 300–400℃ for 2–4 hours, and then sintered at 800–1000℃ for 4–6 hours to finally obtain Fe. 0.6 Mn 0.6 Co 0.6 Ni 0.6 Cr 0.6 O4 high-entropy spinel electrode material.
[0012] Preferably, the iron source is ferric nitrate nonahydrate, the manganese source is manganese nitrate hydrate, the cobalt source is cobalt nitrate hexahydrate, the nickel source is nickel nitrate hexahydrate, and the chromium source is chromium nitrate nonahydrate; the molar ratio of the iron source, manganese source, cobalt source, nickel source, and chromium source is 1:1:1:1:1.
[0013] Preferably, the preparation method is to obtain (CoMnFeMg) using the sol-gel method. 0.25 The specific steps for developing CrO4 high-entropy spinel electrode material are as follows: The iron source, manganese source, cobalt source, magnesium source, chromium source, citric acid monohydrate, and deionized water are mixed evenly to obtain the first solution; Mix ethylenediaminetetraacetic acid with an aqueous ammonia solution and stir until the solution becomes clear to obtain a second solution; After mixing the first solution and the second solution, the pH value was adjusted to 7, and the mixture was heated in a water bath at 80-100℃ until a gel was formed to obtain the gel precursor. The gel precursor was first held at 250–300 °C for 7–9 h, and then sintered at 800–1000 °C for 4–6 h to finally obtain (CoMnFeMg). 0.25 CrO4 high-entropy spinel electrode material.
[0014] Preferably, the iron source is ferric nitrate nonahydrate, the manganese source is manganese nitrate hydrate, the cobalt source is cobalt nitrate hexahydrate, the magnesium source is magnesium nitrate hexahydrate, and the chromium source is chromium nitrate nonahydrate; the molar ratio of the iron source, manganese source, cobalt source, magnesium source, and chromium source is 1:1:1:1:4.
[0015] Thirdly, the present invention also provides a solid oxide electrolytic cell, comprising a cathode, an electrolyte layer, and an anode sequentially stacked; wherein the anode comprises a high-entropy spinel electrode material as described in any of the preceding claims; and the electrolyte layer is BaZr. 0.4 Ce 0.4 Y 0.2 O 3-δ Materials, where 0 ≤ δ ≤ 0.4.
[0016] Preferably, the solid oxide electrolytic cell operates at a current density of 500 mA. cm -2 At that time, the corresponding operating voltage is 1.2V; the solid oxide electrolytic cell operates at a current density of 1500mA. cm -2At that time, the corresponding operating voltage is 1.4V.
[0017] The beneficial effects of this invention are as follows: Unlike existing technologies, this invention provides a high-entropy spinel electrode material and its preparation method, as well as a solid oxide electrolytic cell. The aforementioned high-entropy spinel electrode material has a spinel crystal structure and the general chemical formula RO4; wherein R is composed of five or more elements selected from Mg, Mo, Sc, Co, Mn, Fe, Ni, Cu, Al, Zn, Cd, Cr, and In, and the stoichiometric coefficients x of each element in R are... i All satisfy 0.25≤x i ≤1. This invention constructs component R using five or more specific metallic elements, and the stoichiometric coefficients of each element are controlled within 0.25 ≤ x. i Within a reasonable range of ≤1, not only can a uniform and dense single-phase spinel crystal structure be formed, but the high-entropy mixing effect also reduces the Gibbs free energy of the system, significantly improving the thermodynamic stability of the material and giving the spinel structure a greater energy advantage compared to the decomposition products. Simultaneously, the lattice distortion caused by multi-element coherent substitution greatly increases the atomic diffusion barrier, effectively delaying the kinetic processes of elemental segregation and phase separation at high temperatures, thus suppressing phase decomposition from both thermodynamic and kinetic perspectives. Therefore, the aforementioned high-entropy spinel electrode material can eliminate the phase decomposition problem that exists when spinel materials are used in solid oxide electrolytic cells, which is beneficial to the stable operation of solid oxide electrolytic cells. Attached Figure Description
[0018] Figure 1 Fe provided in Example 1 0.6 Mn 0.6 Co 0.6 Ni 0.6 Cr 0.6 XRD pattern of O4 high-entropy spinel electrode material; Figure 2 (CoMnFeMg) provided in Example 2 0.25 XRD pattern of CrO4 high-entropy spinel electrode material; Figure 3 Fe provided in Example 1 0.6 Mn 0.6 Co 0.6 Ni 0.6 Cr 0.6 Performance test diagram of O4 high-entropy spinel electrode material in solid oxide electrolytic cells. Detailed Implementation
[0019] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. 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 of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0020] The technical problem to be solved by the present invention is to address the above-mentioned deficiencies in the prior art by providing a high-entropy spinel electrode material and its preparation method, as well as a solid oxide electrolytic cell. The high-entropy spinel electrode material can significantly enhance the stability of spinel, eliminate the phase decomposition problem that exists when traditional spinel materials are used in solid oxide electrolytic cells, and is beneficial to the stable operation of solid oxide electrolytic cells.
[0021] To achieve the above technical objectives, this application adopts the following technical solution: In a first aspect, the present invention provides a high-entropy spinel electrode material, which is a high-entropy material with a spinel crystal structure and a general chemical formula of RO4; wherein R is composed of five or more elements selected from Mg, Mo, Sc, Co, Mn, Fe, Ni, Cu, Al, Zn, Cd, Cr and In, and the stoichiometric coefficients x of each element in R are... i All satisfy 0.25≤x i ≤1.
[0022] Specifically, the aforementioned high-entropy spinel electrode material can form a stable spinel crystal structure, significantly improve the thermodynamic stability of the material and reduce the Gibbs free energy of the system by means of the high-entropy mixing effect. At the same time, it increases the atomic diffusion energy barrier through lattice distortion caused by multi-element coherent substitution, suppressing the phase decomposition phenomenon at high temperatures from both thermodynamic and kinetic dimensions, effectively solving the problem of easy structural damage of traditional spinel materials under high-temperature conditions in solid oxide electrolytic cells.
[0023] In one embodiment, R comprises at least one of the following: a combination of Fe and Co, a combination of Co and Ni, or a combination of Fe and Ni. The three transition metal elements Fe, Co, and Ni possess excellent electrochemical activity and tunable ionic valence states. On the one hand, they can synergistically enhance the lattice matching degree of high-entropy spinel with other constituent elements, further consolidating the stability of the single-phase structure, strengthening the thermodynamic advantages brought by the high-entropy effect and the inhibitory effect of lattice distortion on atomic diffusion, and more effectively resisting the risk of phase decomposition under high-temperature conditions in solid oxide electrolytic cells. On the other hand, as core active elements in the oxygen evolution reaction (OER), the combination of Fe, Co, and Ni can enrich the active sites on the electrode surface, optimize electron transport efficiency and catalytic kinetics, enabling the material to maintain high-temperature structural stability while possessing excellent electrochemical catalytic activity.
[0024] In one embodiment, the high-entropy spinel electrode material is Fe. 0.6 Mn 0.6 Co 0.6 Ni 0.6 Cr 0.6 O4 material or (CoMnFeMg) 0.25 CrO4 material.
[0025] Secondly, the present invention also provides a method for preparing any of the above-mentioned high-entropy spinel electrode materials, wherein the preparation method is any one of solid-state synthesis, sol-gel method, combustion method, hydrothermal method, or solvothermal method; wherein... The above preparation methods are characterized by mature technology and controllable parameters, which can precisely control the crystal structure and elemental uniformity of the material, ensure the formation of a stable single-phase spinel structure, avoid the formation of impurity phases, and guarantee the high-temperature stability and catalytic performance of the material.
[0026] In one embodiment, the preparation method is to obtain Fe by combustion. 0.6 Mn 0.6 Co 0.6 Ni 0.6 Cr 0.6 The specific steps for using O4 high-entropy spinel electrode material are as follows: Iron source, manganese source, cobalt source, nickel source, chromium source, glycine and deionized water are mixed evenly and heated in a water bath until the water is completely evaporated to obtain the precursor; The precursor was first held at 300–400℃ for 2–4 hours, and then sintered at 800–1000℃ for 4–6 hours to finally obtain Fe. 0.6 Mn 0.6 Co 0.6 Ni 0.6 Cr 0.6 O4 high-entropy spinel electrode material.
[0027] Specifically, this embodiment uses a combustion method to prepare Fe. 0.6 Mn 0.6 Co 0.6 Ni 0.6 Cr 0.6 O4 high-entropy spinel electrode material is produced by uniformly mixing multi-metal sources such as iron and manganese with glycine and deionized water, followed by water bath heating to evaporate the water, thus obtaining a precursor with uniform elemental distribution. Then, a two-step heat treatment is carried out, which involves holding at 300-400℃ to remove impurities and then sintering at 800-1000℃. This process can take advantage of the high efficiency and simple operation of the combustion method to precisely control the crystal growth process, ensuring that all metal elements react fully and dissolve uniformly, forming a dense spinel crystal with good single-phase properties. Furthermore, the controllable sintering parameters can ensure that the material has both excellent high-temperature structural integrity and oxygen evolution reaction catalytic activity.
[0028] Furthermore, the iron source is ferric nitrate nonahydrate, the manganese source is manganese nitrate hydrate, the cobalt source is cobalt nitrate hexahydrate, the nickel source is nickel nitrate hexahydrate, and the chromium source is chromium nitrate nonahydrate; the molar ratio of the iron source, manganese source, cobalt source, nickel source, and chromium source is 1:1:1:1:1.
[0029] In another embodiment, (CoMnFeMg) is prepared by a sol-gel method. 0.25 The specific steps for developing CrO4 high-entropy spinel electrode material are as follows: The iron source, manganese source, cobalt source, magnesium source, chromium source, citric acid monohydrate, and deionized water are mixed evenly to obtain the first solution; Mix ethylenediaminetetraacetic acid with an ammonia solution and stir until the solution becomes clear to obtain a second solution; After mixing the first solution and the second solution, the pH value was adjusted to 7, and the mixture was heated in a water bath at 80-100°C until a gel was formed to obtain the gel precursor. The gel precursor was first held at 250–300 °C for 7–9 h, and then sintered at 800–1000 °C for 4–6 h to finally obtain (CoMnFeMg). 0.25 CrO4 high-entropy spinel electrode material.
[0030] Specifically, the above preparation method utilizes the synergistic chelation of citric acid monohydrate and ethylenediaminetetraacetic acid (EDTA), combined with a process design that precisely adjusts the pH to 7, to ensure that multi-metal ions such as iron, manganese, and cobalt are fully and uniformly dispersed in the solution system. A homogeneous and stable gel precursor is formed by heating in a water bath at 80–100°C. Then, the organic matter is fully decomposed and the precursor purified by holding at 250–300°C for 7–9 hours. Finally, sintering at 800–1000°C completes the densification and growth of the spinel crystal structure. This process leverages the molecular-level mixing advantage of the sol-gel method to ensure uniform solid solution formation of a single-phase spinel structure, enhancing the high-entropy effect and lattice distortion-induced high-temperature stability, effectively resisting the risk of phase decomposition under solid oxide electrolysis (SOEC) conditions. Furthermore, through precise matching of the chelation system and heat treatment parameters, it maximizes the retention of active sites on the material surface and optimizes electron and ion transport efficiency, giving the material both excellent high-temperature structural integrity and oxygen evolution reaction catalytic activity.
[0031] Furthermore, the iron source is ferric nitrate nonahydrate, the manganese source is manganese nitrate hydrate, the cobalt source is cobalt nitrate hexahydrate, the magnesium source is magnesium nitrate hexahydrate, and the chromium source is chromium nitrate nonahydrate; the molar ratio of the iron source, manganese source, cobalt source, magnesium source, and chromium source is 1:1:1:1:4.
[0032] Thirdly, the present invention also provides a solid oxide electrolytic cell, comprising a cathode, an electrolyte layer, and an anode sequentially stacked; wherein the anode comprises a high-entropy spinel electrode material as described in any of the preceding claims; and the electrolyte layer is BaZr. 0.4 Ce 0.4 Y 0.2 O 3-δ Materials, where 0 ≤ δ ≤ 0.4.
[0033] Specifically, the above-mentioned solid oxide electrolytic cell uses the high-entropy spinel electrode material provided by this invention as the anode, which can completely solve the problem of high-temperature phase decomposition of traditional anode materials and ensure the long-term structural integrity and catalytic activity of the electrode; the electrolyte layer is made of BaZr. 0.4 Ce 0.4 Y 0.2 O 3-δ (0≤δ≤0.4) material, which is well compatible with anode materials, can efficiently conduct ions and block gases, further enhancing the structural stability of the battery.
[0034] Furthermore, the solid oxide electrolytic cell achieves a current density of 500 mA. cm -2 At that time, the corresponding operating voltage is 1.2V; the solid oxide electrolytic cell operates at a current density of 1500mA. cm -2 At this time, the corresponding operating voltage is 1.4V; among them, the above performance parameters demonstrate the core advantages of low energy consumption and high conversion efficiency, ultimately enabling the solid oxide electrolytic cell to operate continuously, efficiently, and stably under harsh high-temperature environments.
[0035] The technical solution of the present invention will now be further described with reference to specific embodiments.
[0036] Example 1: This embodiment 1 provides an Fe obtained by combustion method. 0.6 Mn 0.6 Co 0.6 Ni 0.6 Cr 0.6 The preparation method of O4 powder specifically includes: Step (1): Add ferric nitrate nonahydrate (4.85g), manganese nitrate hydrate (2.15g), cobalt nitrate hexahydrate (3.49g), nickel nitrate hexahydrate (3.49g), chromium nitrate nonahydrate (4.81g) and glycine (24.02g) to deionized water in sequence, stir and mix evenly to obtain a mixed solution; Step (2): Place the above mixed solution in a 90°C water bath and heat until the water is completely evaporated to obtain the precursor; Step (3): The above precursor was first held at 350℃ for 3 hours, and then sintered at 900℃ for 5 hours to finally obtain Fe.0.6 Mn 0.6 Co 0.6 Ni 0.6 Cr 0.6 O4 powder. Specifically, regarding the obtained Fe 0.6 Mn 0.6 Co 0.6 Ni 0.6 Cr 0.6 XRD (X-ray Diffraction) analysis was performed on the O4 powder, and the results are as follows: Figure 1 As shown: Figure 1 The XRD pattern shows sharp and high-intensity diffraction peaks, indicating that the material has good crystallinity. At the same time, no impurity phase diffraction peaks appear in the pattern, indicating that the powder has a single spinel crystal structure. All metal elements have been uniformly dissolved to form a single-phase high-entropy spinel without phase separation. This verifies that the combustion method preparation process in Example 1 can efficiently synthesize target high-entropy spinel powder with a pure structure and complete crystallization.
[0037] Example 2: Example 2 provides a (CoMnFeMg) prepared using the sol-gel method. 0.25 The specific preparation methods for CrO4 powder include: Step (1): Weigh out cobalt nitrate hexahydrate (10.91g), manganese nitrate hydrate (6.71g), ferric nitrate nonahydrate (15.15g), magnesium nitrate hexahydrate (9.62g), chromium nitrate nonahydrate (60.02g) and citric acid monohydrate (420.28g), add the above materials to deionized water in sequence, stir and mix until uniformly dispersed to obtain the first solution; Step (2): Weigh 292.24 g of ethylenediaminetetraacetic acid and add it to an ammonia solution. Stir continuously until the solution becomes clear to obtain the second solution. Step (3): Mix the first solution obtained in step (1) with the second solution obtained in step (2) evenly, adjust the pH value of the system to 7, and then heat the mixed solution in a 90°C water bath until a uniform gel state is formed to obtain the gel precursor. Step (4): The gel precursor was first kept at 280℃ for 8 hours, and then sintered at 900℃ for 5 hours to finally obtain (CoMnFeMg). 0.25 CrO4 powder.
[0038] Specifically, regarding the obtained (CoMnFeMg) 0.25 XRD analysis of CrO4 powder yielded the following results: Figure 2 As shown: Figure 2The XRD pattern shows sharp diffraction peaks, indicating that the powder has good crystallinity. At the same time, no impurity phase diffraction peaks are found in the pattern, indicating that the powder has a single spinel crystal structure. Elements such as Co, Mn, Fe, Mg, and Cr have been uniformly dissolved to form a single-phase high-entropy spinel without phase separation. This verifies that the sol-gel method of Example 2 can synthesize a target high-entropy spinel powder with a pure structure and complete crystallization.
[0039] Specifically, with BaZr 0.4 Ce 0.4 Y 0.2 O 3-δ (0≤δ≤0.4) The material is an electrolyte, and the Fe prepared in Example 1 is used. 0.6 Mn 0.6 Co 0.6 Ni 0.6 Cr 0.6 A slurry obtained by mixing and stirring O4 high-entropy spinel electrode material, binder (prepared by mixing fish oil, ethyl cellulose and terpineol), and organic solvent is coated onto the electrolyte to prepare a solid oxide electrolytic cell.
[0040] Full cells were prepared and tested using a co-pressure method. The specific process is as follows: 0.5 g of dry, uniform fuel electrode powder (composed of NiO powder and the aforementioned electrolyte powder, with a NiO to electrolyte mass ratio of 57:43) was placed in a cylindrical mold. A pressure of 10 MPa was applied and held for 1 min to form a fuel electrode preform. The electrolyte powder was then uniformly dispersed on the fuel electrode preform, co-pressed at 12 MPa for 1 min, and co-sintered at 1400°C for 5 h to form an electrolyte-fuel electrode support. 0.6 Mn 0.6 Co 0.6 Ni 0.6 Cr 0.6 The O4 high-entropy spinel electrode material was mixed with a binder and an organic solvent to obtain a slurry, which was then screen-printed onto the electrolyte surface. Subsequently, it was sintered in air at 900°C for 3 hours to obtain a solid oxide electrolytic cell. At an operating temperature of 600°C, the current changes under different voltages were recorded, and the results are as follows: Figure 3 As shown.
[0041] Depend on Figure 3 It can be seen that at an operating temperature of 600℃, the voltage of this solid oxide full cell shows a steady upward trend with increasing current density, which is consistent with the typical IV characteristics of an electrolytic cell: when the current density reaches 500mA... cm -2 At that time, the corresponding operating voltage is approximately 1.2V; when the current density increases to 1500mA cm -2At this point, the corresponding operating voltage is approximately 1.4V. This result indicates that the solid oxide electrolytic cell can maintain a relatively low operating voltage even at high current densities, demonstrating excellent electrochemical performance and energy conversion efficiency. It also confirms the properties of Fe... 0.6 Mn 0.6 Co 0.6 Ni 0.6 Cr 0.6 O4, as an anode material, can balance structural stability and catalytic activity under high-temperature conditions, effectively supporting the battery to achieve efficient and stable operation.
[0042] Compared with existing technologies, this invention has the following core advantages: Through innovative high-entropy component design and adapted preparation process, the high-entropy spinel electrode material provided by this invention can significantly improve the thermodynamic and kinetic stability of the spinel crystal structure compared with existing electrode materials. It fundamentally solves the technical pain point that traditional spinel materials are prone to phase decomposition under high-temperature conditions in solid oxide electrolytic cells, thereby providing key material and process support for the long-term, efficient and stable operation of solid oxide electrolytic cells, and significantly improving the reliability and service life of devices.
[0043] It should be noted that all the above embodiments belong to the same inventive concept, and the descriptions of each embodiment have different focuses. Where the description in a particular embodiment is not detailed, please refer to the description in other embodiments.
[0044] The above embodiments merely illustrate implementation methods of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.
Claims
1. A high-entropy spinel electrode material, characterized in that, The high-entropy spinel electrode material has a spinel crystal structure and the general chemical formula RO4; wherein R is composed of five or more elements selected from Mg, Mo, Sc, Co, Mn, Fe, Ni, Cu, Al, Zn, Cd, Cr and In, and the stoichiometric coefficients x of each element in R are... i All satisfy 0.25≤x i ≤1.
2. The high-entropy spinel electrode material according to claim 1, characterized in that, The R includes at least one of the following combinations: Fe and Co, Co and Ni, and Fe and Ni.
3. The high-entropy spinel electrode material according to claim 2, characterized in that, The high-entropy spinel electrode material is Fe. 0.6 Mn 0.6 Co 0.6 Ni 0.6 Cr 0.6 O4 material or (CoMnFeMg) 0.25 CrO4 material.
4. A method for preparing a high-entropy spinel electrode material according to any one of claims 1 to 3, characterized in that, The preparation method is any one of solid-phase synthesis, sol-gel method, combustion method, hydrothermal method or solvothermal method.
5. The method for preparing the high-entropy spinel electrode material according to claim 4, characterized in that, The preparation method is to obtain Fe by combustion. 0.6 Mn 0.6 Co 0.6 Ni 0.6 Cr 0.6 The specific steps for using O4 high-entropy spinel electrode material are as follows: Iron source, manganese source, cobalt source, nickel source, chromium source, glycine and deionized water are mixed evenly and heated in a water bath until the water is completely evaporated to obtain the precursor; The precursor was first held at 300–400°C for 2–4 hours, and then sintered at 800–1000°C for 4–6 hours to finally obtain Fe. 0.6 Mn 0.6 Co 0.6 Ni 0.6 Cr 0.6 O4 high-entropy spinel electrode material.
6. The method for preparing the high-entropy spinel electrode material according to claim 5, characterized in that, The iron source is ferric nitrate nonahydrate, the manganese source is manganese nitrate hydrate, the cobalt source is cobalt nitrate hexahydrate, the nickel source is nickel nitrate hexahydrate, and the chromium source is chromium nitrate nonahydrate; the molar ratio of the iron source, the manganese source, the cobalt source, the nickel source, and the chromium source is 1:1:1:1:
1.
7. The method for preparing the high-entropy spinel electrode material according to claim 4, characterized in that, The preparation method involves using the sol-gel method to obtain (CoMnFeMg). 0.25 The specific steps for developing CrO4 high-entropy spinel electrode material are as follows: The iron source, manganese source, cobalt source, magnesium source, chromium source, citric acid monohydrate, and deionized water are mixed evenly to obtain the first solution; Mix ethylenediaminetetraacetic acid with an aqueous ammonia solution and stir until the solution becomes clear to obtain a second solution; After mixing the first solution and the second solution, the pH value was adjusted to 7, and the mixture was heated in a water bath at 80-100°C until a gel was formed to obtain the gel precursor. The gel precursor was first held at 250–300 °C for 7–9 h, and then sintered at 800–1000 °C for 4–6 h to finally obtain (CoMnFeMg). 0.25 CrO4 high-entropy spinel electrode material.
8. The method for preparing the high-entropy spinel electrode material according to claim 7, characterized in that, The iron source is ferric nitrate nonahydrate, the manganese source is manganese nitrate hydrate, the cobalt source is cobalt nitrate hexahydrate, the magnesium source is magnesium nitrate hexahydrate, and the chromium source is chromium nitrate nonahydrate; the molar ratio of the iron source, the manganese source, the cobalt source, the magnesium source, and the chromium source is 1:1:1:1:
4.
9. A solid oxide electrolytic cell, characterized in that, The electrode comprises a cathode, an electrolyte layer, and an anode, which are stacked sequentially; wherein the anode comprises the high-entropy spinel electrode material according to any one of claims 1 to 3; and the electrolyte layer is BaZr. 0.4 Ce 0.4 Y 0.2 O 3-δ Materials, where 0 ≤ δ ≤ 0.
4.
10. The solid oxide electrolytic cell according to claim 9, characterized in that, The solid oxide electrolytic cell operates at a current density of 500 mA. cm -2 At this time, the corresponding operating voltage is 1.2V; the solid oxide electrolytic cell operates at a current density of 1500mA. cm -2 At that time, the corresponding operating voltage is 1.4V.