CN113745548A - High-entropy ceramic material based on spinel structure and preparation method and application thereof - Google Patents
High-entropy ceramic material based on spinel structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a spinel structure-based high-entropy ceramic material and a preparation method and application thereofx(CayCryFeyNiyZny)O4High-entropy ceramic powder, and x and y satisfy x +5y ═ 2. And coating the calcined high-entropy ceramic powder on the prepared half cell to obtain the novel proton conductor solid oxide fuel cell. The nano-grade novel high-entropy ceramic powder obtained by the method has large specific surface area and good catalytic activity; the method has good repeatability, low cost and easy industrialization, and the product can be used for assembling a battery reactor to efficiently convert gas fuel into electric energy, has good electrochemical stability and is efficiently converted in energyIn the process, cogeneration can still be realized.
Description
Technical Field
The invention relates to the technical field of high-entropy ceramic materials, in particular to a spinel structure-based high-entropy ceramic material and a preparation method and application thereof.
Background
During the last decades, researchers have proposed many cathode materials for H-SOFCs (proton conductor based solid oxide fuel cells), and most of them are based on perovskites or perovskite related structures. Some of these cathode materials may exhibit good performance for proton conductor solid oxide fuel cells. At the same time, spinel oxides have received less attention as cathodes for Solid Oxide Fuel Cells (SOFC) than perovskite cathodes, but they have been widely used as coatings for SOFC contacts.
In recent years, some spinel oxides have been used as cathodes in cation conductor solid oxide fuel cells to achieve good electrochemical performance. These findings indicate that spinel oxides exhibit good catalytic activity for Oxygen Reduction Reaction (ORR) at intermediate temperatures, providing an alternative to the design of SOFCs cathode materials. To our knowledge, however, spinel oxides have not been investigated for use in H-SOFCs, and thus the suitability of spinel oxides as H-SOFCs cathodes is still unknown. Furthermore, high-entropy ceramics which have been proposed in recent years have been put into practical use for many applications, all of which achieve good performance, due to their excellent characteristics and the ability to stabilize equimolar mixtures in the oxide. The high-entropy ceramic generally refers to a single solid solution formed by solid-dissolving five or more metal oxides together in equal molar ratio, and a novel 'high-entropy effect' brought by multi-component cooperation endows the material with rich performance regulation space.
Many researchers have proposed the use of high entropy perovskite oxides as cathodes of conventional oxygen ion conductor solid oxide fuel cells (O-SOFCs), but research on the application of high entropy oxides to proton conductor SOFCs has just begun, and reports on this are rare, and thus many scientific problems in structure-property relationships are unclear. In addition, high entropy ceramic materials have not been used as cathodes for proton conductor solid oxide fuel cells in prior studies. Therefore, the exploration of applying the high-entropy ceramic cathode to the proton conductor solid oxide fuel cell has important practical significance.
In view of the above, there is a need to design an improved high-entropy ceramic material based on spinel structure, and a preparation method and application thereof, so as to solve the above problems.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a spinel structure-based high-entropy ceramic material, a preparation method and application thereof, and MnCo with a nanometer-level high specific surface area is obtained by a sol-gel methodx(CayCryFeyNiyZny)O4The material is applied to proton conductor solid oxide fuel cells, and has good electric energy conversion efficiency and electrochemical stability.
In order to achieve the aim, the invention provides a spinel structure-based high-entropy ceramic material, and the molecular formula of the high-entropy ceramic material is MnCox(CayCryFeyNiyZny)O4Wherein x +5y is 2.
As a further improvement of the invention, x is 1.7-1.9.
The preparation method of the high-entropy ceramic material based on the spinel structure comprises the following steps:
s1, pressing MnCox(CayCryFeyNiyZny)O4Preparing a metal salt aqueous solution according to the stoichiometric ratio of the chemical reaction, adding a complexing agent according to a preset molar ratio, adjusting the pH value to 7-8, heating and gradually evaporating water to obtain a precursor;
s2, calcining the precursor obtained in the step S1 at high temperature to obtain MnCox(CayCryFeyNiyZny)O4。
As a further improvement of the present invention, in step S1, the solute of the aqueous metal salt solution is (CH)3COO)2Mn、Co(NO3)3、CaCO3、Cr(NO3)3、Fe(NO3)3、Ni(NO3)2、Zn(NO3)2(ii) a The complexing agent is citric acid and ethylenediamine tetraacetic acid.
As a further improvement of the invention, the molar ratio of the citric acid to the ethylenediamine tetraacetic acid is 1.5: 1.
As a further improvement of the invention, the ratio of the citric acid to the ethylene diamine tetraacetic acid to the total molar amount of metal ions in the metal salt aqueous solution is 1.5:1: 1.
As a further improvement of the present invention, in step S1, the pH is adjusted by adding ammonia water; the precursor is heated on a magnetic stirrer to evaporate water, and after evaporation, the precursor is continuously heated to be gelatinous and gradually generate the precursor.
As a further improvement of the invention, in step S2, the temperature of the high-temperature calcination is 800-1000 ℃ and the time is 1-4 h.
Use of a high entropy ceramic material based on a spinel structure according to any of the preceding claims for a cathode material of a fuel cell.
As a further improvement of the invention, the high-entropy ceramic material is used for a cathode material of a proton conductor-based solid oxide fuel cell.
As a further improvement of the invention, the application method of the high-entropy ceramic material comprises the following steps: and blending the high-entropy ceramic material and terpineol to prepare cathode slurry, then coating the cathode of the prepared proton conductor-based solid oxide fuel cell, and finally calcining in microwave to assemble the whole cell.
The invention has the beneficial effects that:
1. the spinel structure-based high-entropy ceramic material provided by the invention has a molecular formula of MnCox(CayCryFeyNiyZny)O4The catalyst is prepared by preparing a precursor by a sol-gel method and calcining the precursor at 950 ℃ for 3 h. The preparation method can obtain the nano-grade novel spinel structure-based high-entropy ceramic material, has the characteristics of large specific surface area, high catalytic activity, good chemical stability, good process repeatability, low cost and easiness in industrialization, is applied to the proton conductor solid oxide fuel cell, and long-term stability tests show that the output voltage value of the proton conductor solid oxide fuel cell shows a stable trend, which shows that the stability of the high-entropy ceramic material endows the cell with stable performance.
2. The invention firstly applies the high-entropy ceramic as the cathode material to the research of the proton conductor solid oxide fuel cell, realizes the high-efficiency conversion of gas fuel into electric energy, combines the characteristics of spinel structure materials with excellent catalytic activity and the configuration entropy in the high-entropy ceramic, realizes the high-efficiency energy conversion efficiency, and is expected to realize the cogeneration.
Drawings
FIG. 1 shows MnCo of comparative example 1 of the present invention1.8Ni0.2O4And (3) an X-ray diffraction pattern of the spinel material after calcining at 950 ℃ in air for 3 h.
FIG. 2 shows MnCo prepared at different temperatures in examples 1 to 51.8(Ca0.04Cr0.04Fe0.04Ni0.04Zn0.04)O4X-ray diffraction pattern of high entropy ceramics.
FIG. 3 shows MnCo prepared in example 41.8(Ca0.04Cr0.04Fe0.04Ni0.04Zn0.04)O4High entropy ceramic powder containing CO2Atmosphere (10% CO)2-90% air), the pattern was continuously scanned by high temperature XRD for 12h at 600 ℃.
FIG. 4 shows MnCo prepared in example 61.8(Ca0.04Cr0.04Fe0.04Ni0.04Zn0.04)O4And the power density curve of the high-entropy ceramic powder used as a cathode and assembled into a full battery.
FIG. 5 shows MnCo prepared in example 61.8(Ca0.04Cr0.04Fe0.04Ni0.04Zn0.04)O4Long term stability test pattern of cathode cell.
FIG. 6 shows MnCo prepared in example 61.8(Ca0.04Cr0.04Fe0.04Ni0.04Zn0.04)O4The cathode is applied to a micro-topography before and after performance test of the proton conductor solid oxide fuel cell.
FIG. 7 shows MnCo obtained at different ratiosx(CayCryFeyNiyZny)O4X of high entropy ceramicsRay diffraction pattern.
FIG. 8 shows MnCo obtained at different temperatures1.8(Y0.04Tb0.04Gd0.04Ni0.04Ho0.04)O4X-ray diffraction pattern of high entropy ceramics.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in detail below with reference to specific embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme of the present invention are shown in the specific embodiments, and other details not closely related to the present invention are omitted.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a spinel structure-based high-entropy ceramic material, and the molecular formula of the high-entropy ceramic material is MnCox(CayCryFeyNiyZny)O4Wherein x +5y is 2, and preferably x is 1.7 to 1.9. More preferably, x is 1.8, i.e. the high entropy ceramic material has the formula MnCo1.8(Ca0.04Cr0.04Fe0.04Ni0.04Zn0.04)O4. The ceramic material is AB with a spinel structure2O4(A is Mn, B is other metal elements) cermet as base, B is Cox(CayCryFeyNiyZny) Six elements, thereby obtaining the high-entropy ceramic material with a spinel structure, and the material has excellent catalytic activity and chemical stability.
The preparation method of the high-entropy ceramic material based on the spinel structure comprises the following steps:
s1, pressing MnCox(CayCryFeyNiyZny)O4Preparing a metal salt aqueous solution according to the stoichiometric ratio of the chemical reaction, adding a complexing agent according to a preset molar ratio, adjusting the pH value to 7-8, heating and gradually evaporating water to obtain a precursor;
in particular to (CH)3COO)2Mn、Co(NO3)3、CaCO3(adding a certain amount of nitric acid to dissolve) Cr (NO)3)3、Fe(NO3)3、Ni(NO3)2、Zn(NO3)2According to MnCo1.8(Ca0.04Cr0.04Fe0.04Ni0.04Zn0.04)O4Dissolving the mixture in deionized water according to the stoichiometric ratio, respectively adding citric acid and ethylenediamine tetraacetic acid which are used as complexing agents according to the molar weight of 1.5 times and 1 time of metal ions, adding ammonia water, adjusting the pH value to 7-8, and stirring the clear solution for 6 hours to uniformly mix the clear solution; then heating on a magnetic stirrer to evaporate water, and continuing heating after evaporation to make the gel form and gradually generate a precursor.
S2, calcining the precursor obtained in the step S1 at a high temperature of 800-1000 ℃ for 1-4 h to obtain MnCox(CayCryFeyNiyZny)O4。
The invention adopts a sol-gel method to synthesize MnCox(CayCryFeyNiyZny)O4The material combines the characteristics of a spinel structure material with excellent catalytic activity and the configuration entropy in high-entropy ceramics, the size of the material is in a nanometer level, the specific surface area is larger, the catalytic activity is higher, and the material is used as a cathode material to be applied to a proton conductor solid oxide fuel cell, so that the high-efficiency conversion from fuel to electric energy is realized. The novel material of the invention has good chemical stability. At 600 deg.C under an atmosphere containing carbon dioxide (10% CO)2+ 90% air), no material deterioration was found by high temperature in situ XRD for 12 h. And at a working temperature of 600 ℃ in the presence of 3% waterThe hydrogen wetting gas is used as gas fuel, the long-term stability of the proton conductor solid oxide fuel cell applied by using the material of the invention as a cathode is tested, and the output voltage value shows a stable trend, which also shows that the material has better chemical stability.
The application method of the high-entropy ceramic material comprises the following steps: and blending the high-entropy ceramic material and terpineol to prepare cathode slurry, then coating the cathode of the prepared proton conductor-based solid oxide fuel cell, and finally calcining in microwave to assemble the whole cell. The invention applies the high-entropy ceramic as the cathode material to the research of the proton conductor solid oxide fuel cell for the first time, combines the characteristics of the structures of the high-entropy ceramic and the spinel material, and realizes high-efficiency energy conversion efficiency; the method has good repeatability, low cost and easy industrialization, and the product can be used for assembling a cell reactor, efficiently converts gas fuel into electric energy and is expected to realize cogeneration.
Examples 1 to 5
Examples 1 to 5 provide high entropy ceramic materials based on spinel structure having the chemical formula MnCo1.8(Ca0.04Cr0.04Fe0.04Ni0.04Zn0.04)O4Prepared by the following method:
will (CH)3COO)2Mn、Co(NO3)3、CaCO3、Cr(NO3)3、Fe(NO3)3、Ni(NO3)2、Zn(NO3)2According to MnCo1.8(Ca0.04Cr0.04Fe0.04Ni0.04Zn0.04)O4The stoichiometric ratio of the components is added into the deionized water solution in sequence; and then, adding citric acid according to 1.5 times of the molar weight of the metal ions, adding ethylene diamine tetraacetic acid according to 1 time of the molar weight of the metal ions, adding ammonia water, adjusting the pH value to 7-8, and keeping the aqueous solution clear. Heating the mixture on a magnetic stirrer to evaporate water, and continuously heating the mixture to be gelatinous after evaporation to dryness and gradually generating a precursor; followed by temperatures of 800 ℃ (example 1), 850 ℃ (example 2), 900 ℃ (example 3), 950 ℃ (example 4), 1000 ℃ (real) (example 3)Example 5) was subjected to high temperature calcination for 3 hours.
As shown in FIG. 2, it can be seen that the novel high-entropy material with good stability and high entropy can be obtained after the high-temperature calcination at 800-1000 ℃ for 3 hours. Wherein, the material obtained at 950 ℃ has good power and high energy conversion efficiency.
The novel spinel-structured high-entropy ceramic material MnCo prepared at 950 ℃ in the embodiment1.8(Ca0.04Cr0.04Fe0.4Ni0.04Zn0.04)O4At 600 ℃ CO2The test result is shown in fig. 3, and it can be seen that no other substance is generated in the continuous high-temperature test process, which shows that the novel spinel-structured high-entropy ceramic material prepared by the invention has good chemical stability and does not deteriorate or change the crystal phase under the high-temperature working condition.
Example 6
The novel high-entropy ceramic material of the embodiment has a specific chemical composition of MnCo1.8(Ca0.04Cr0.04Fe0.04Ni0.04Zn0.04)O4And taking the NiO-BCZY as a cathode, taking the NiO-BCZY as an anode support and taking the BCZY as an electrolyte to form a full cell for electrochemical performance test. The assembling method comprises the following steps:
(1) mixing Fe (NO)3)3、(CH3COO)2Mn、Co(NO3)3、CaCO3、Ni(NO3)2、Cr(NO3)3、Zn(NO3)2According to MnCo1.8(Ca0.04Cr0.04Fe0.04Ni0.04Zn0.04)O4The method comprises the following steps of uniformly mixing the components according to the stoichiometric ratio, respectively adding citric acid and ethylenediamine tetraacetic acid which are 1.5 times and 1 time of the molar weight of metal ions as complexing agents, and then adding ammonia water to adjust the pH value to 7-8. Stirring the solution for 5h, heating the solution on a magnetic stirrer to evaporate water, continuing heating after evaporation to make the solution become gel and gradually generate a precursor, and then calcining the gel at 950 ℃ for 3h to obtain pure-phase MnCo1.8(Ca0.04Cr0.04Fe0.04Ni0.04Zn0.04)O4And (3) blending the cathode material with terpineol to prepare cathode slurry.
(2) And (3) putting the pressed half cell into a high-temperature muffle furnace to calcine at 1300 ℃ according to a co-pressing co-firing method by using anode powder and the traditional BCZY electrolyte.
(3) And brushing the mixed cathode slurry on the compact half cell, calcining in microwave, and assembling to obtain the full cell.
The cell output is shown in FIG. 4, and it can be seen from FIG. 4 that when the high-entropy ceramic material is used as the cathode, the temperature is 700 ℃ and H containing 3% of water2The power density reaches 1217mW cm-2The method shows that the novel high-entropy ceramic with the spinel structure has high-efficiency energy conversion capability, namely, the hydrogen fuel can be efficiently converted into electric energy.
MnCo of the present example1.8(Ca0.04Cr0.04Fe0.04Ni0.04Zn0.04)O4Full cell consisting of cathode, at 600 deg.C, containing 3% water in wet H2The long-term stability test was performed under the conditions for 200 hours, as shown in fig. 5. From the figure, it can be seen that, in the process of long-term test, the electric energy output by the battery shows a stable trend as a whole, and no attenuation occurs, which indicates that the novel full battery with the cathode made of high-entropy ceramic disclosed by the invention has good and stable energy conversion efficiency and stable power output performance.
In this example, MnCo is used1.8(Ca0.04Cr0.04Fe0.04Ni0.04Zn0.04)O4The cross section of the full cell with the cathode material is characterized by a scanning electron microscope before and after electrical property tests. The results of the characterization are shown in fig. 6, from which it is clear that the distribution of the assembly layers of the battery and the structural composition of the battery before and after the comparative test did not change.
Example 7
A high-entropy ceramic material based on a spinel structure is different from that of example 4 in thatChemical formula is MnCo1.7(Ca0.06Cr0.06Fe0.06Ni0.06Zn0.06)O4The rest is substantially the same as that of embodiment 4, and will not be described herein.
Example 8
Compared with the example 4, the high-entropy ceramic material based on the spinel structure is different in that the chemical formula is MnCo1.9(Ca0.02Cr0.02Fe0.02Ni0.02Zn0.02)O4The rest is substantially the same as that of embodiment 4, and will not be described herein.
Referring to fig. 7, it can be seen that examples 7 and 8 also successfully produced high entropy ceramic materials based on spinel structure.
Comparative example 1
Will (CH)3COO)2Mn、Co(NO3)3、Ni(NO3)2According to MnCo1.8Ni0.2O4The stoichiometric ratios are added to the aqueous solutions in succession. And then, adding citric acid according to 1.5 times of the molar weight of the metal ions, adding ethylene diamine tetraacetic acid according to 1 time of the molar weight of the metal ions, adding ammonia water, adjusting the pH value to 7-8, and keeping the aqueous solution clear. Heating the mixture on a magnetic stirrer to evaporate water, continuously heating the mixture after evaporation to dryness to enable the mixture to become gel and gradually generate a precursor, and then calcining the precursor at high temperature. The obtained compound is subjected to X-ray diffraction characterization to finally obtain MnCo with a spinel structure1.8Ni0.2O4A cermet.
MnCo prepared in comparative example 1 was assembled using substantially the same battery assembly method as in example 61.8Ni0.2O4The cermet is used as cathode material of proton conductor-based solid oxide fuel cell, and the test result shows that the cermet contains H with 3% of water at 700 DEG C2The power density is 942mW cm-2Thus, it is demonstrated that the novel high entropy ceramic materials disclosed in this invention in combination with spinel structured oxides provide a new material and a new method of designing cathodes for proton conductor solid oxide fuel cells. The present invention provides a new-type high-entropy ceramic materialThe cathode material is applied to a proton conductor solid oxide fuel cell and shows excellent performance. MnCo with spinel structure1.8Ni0.2O4Cathode material of MnCo1.8(Ca0.04Cr0.04Fe0.04Ni0.04Zn0.04)O4The performance of the cathode is obviously improved.
Comparative examples 2 to 6
The chemical formula of the spinel structure-based high-entropy ceramic material provided by comparative examples 2 to 6 is MnCo1.8(Y0.04Tb0.04Gd0.04Ni0.04Ho0.04)O4Prepared by the following method:
will (CH)3COO)2Mn、Co(NO3)3、Y(NO3)3、Tb(NO3)2、Gd(NO3)2、Ni(NO3)2、Ho(NO3)3According to MnCo1.8(Y0.04Tb0.04Gd0.04Ni0.04Ho0.04)O4The stoichiometric ratios are added to the aqueous solutions in succession. And then, adding citric acid according to 1.5 times of the molar weight of the metal ions, adding ethylene diamine tetraacetic acid according to 1 time of the molar weight of the metal ions, adding ammonia water, adjusting the pH value to 7-8, and keeping the aqueous solution clear. Heating the mixture on a magnetic stirrer to evaporate water, continuing heating to gel after evaporation to dryness and gradually generating a precursor, and then respectively carrying out high-temperature calcination for 3 hours at 800 ℃ (comparative example 2), 850 ℃ (comparative example 3), 900 ℃ (comparative example 4), 950 ℃ (comparative example 5) and 1000 ℃ (comparative example 6).
The obtained compound was characterized by X-ray diffraction, and as shown in FIG. 8, it was found that spinel-structured MnCo was not obtained1.8(Y0.04Tb0.04Gd0.04Ni0.04Ho0.04)O4High entropy ceramics. Thus, the MnCo designed by the invention1.8(Ca0.04Cr0.04Fe0.04Ni0.04Zn0.04)O4The high-entropy ceramic material has uniqueness, and the synthesis method of the invention is matched under the composition proportionThe high-entropy ceramic material with stable structure can be obtained, and has excellent electrical property when being used for a proton conductor-based solid oxide fuel cell.
In conclusion, the spinel structure-based high-entropy ceramic material provided by the invention can be used for obtaining nano-grade novel high-entropy ceramic powder MnCo through a sol-gel methodx(CayCryFeyNiyZny)O4. The catalyst has the characteristics of large specific surface area, high catalytic activity, good chemical stability, good process repeatability, low cost and easy industrialization, is used as a cathode material to be applied to the research of proton conductor solid oxide fuel cells, combines the characteristics of spinel structure materials with excellent catalytic activity and the configuration entropy in high-entropy ceramics, realizes high-efficiency energy conversion efficiency, and is expected to realize cogeneration.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (10)
1. A spinel structure-based high-entropy ceramic material is characterized in that the molecular formula of the high-entropy ceramic material is MnCox(CayCryFeyNiyZny)O4Wherein x +5y is 2.
2. A high entropy ceramic material based on spinel structure according to claim 1, characterized in that x is 1.7-1.9.
3. A method for preparing a high-entropy ceramic material based on a spinel structure according to claim 1 or 2, characterized in that it comprises the steps of:
s1, pressing MnCox(CayCryFeyNiyZny)O4Stoichiometric ratio of (A) to (B)Preparing a metal salt aqueous solution, adding a complexing agent according to a preset molar ratio, adjusting the pH value to 7-8, heating and gradually evaporating water to obtain a precursor;
s2, calcining the precursor obtained in the step S1 at high temperature to obtain MnCox(CayCryFeyNiyZny)O4。
4. A method for preparing a high-entropy ceramic material based on a spinel structure according to claim 3, wherein, in step S1, the solute of the aqueous metal salt solution is (CH)3COO)2Mn、Co(NO3)3、CaCO3、Cr(NO3)3、Fe(NO3)3、Ni(NO3)2、Zn(NO3)2(ii) a The complexing agent is citric acid and ethylenediamine tetraacetic acid.
5. A method for preparing a high-entropy ceramic material based on spinel structure according to claim 4, wherein the molar ratio of citric acid to ethylenediamine tetraacetic acid is 1.5:1, and the ratio of citric acid to ethylenediamine tetraacetic acid to the total molar amount of metal ions in the metal salt aqueous solution is 1.5:1: 1.
6. A method for preparing a spinel structure-based high-entropy ceramic material according to claim 3, wherein, in step S1, the pH is adjusted by adding ammonia water; the precursor is heated on a magnetic stirrer to evaporate water, and after evaporation, the precursor is continuously heated to be gelatinous and gradually generate the precursor.
7. A method for preparing a high-entropy ceramic material based on a spinel structure according to claim 3, wherein in step S2, the high-temperature calcination is performed at a temperature of 800-1000 ℃ for 1-4 h.
8. Use of a high-entropy ceramic material based on a spinel structure according to any one of claims 1 to 7, for a cathode material of a fuel cell.
9. Use of a spinel structure-based high entropy ceramic material according to claim 8, wherein said high entropy ceramic material is used as a cathode material for proton conductor based solid oxide fuel cells.
10. The application of the spinel structure-based high-entropy ceramic material of claim 9, which is carried out by the following method: and blending the high-entropy ceramic material and terpineol to prepare cathode slurry, then coating the cathode of the prepared proton conductor-based solid oxide fuel cell, and finally calcining in microwave to assemble the whole cell.
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Cited By (3)
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| CN112624740A (en) * | 2020-12-26 | 2021-04-09 | 重庆材料研究院有限公司 | High-entropy NTC thermistor ceramic material and preparation method thereof |
| CN115010190A (en) * | 2022-06-22 | 2022-09-06 | 北京理工大学重庆创新中心 | High-entropy oxide cathode material and preparation method and application thereof |
| CN116581314A (en) * | 2023-07-07 | 2023-08-11 | 华北电力大学 | High-entropy oxide catalyst for fuel cell and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569786A (en) * | 2012-01-19 | 2012-07-11 | 大连工业大学 | Perovskite Co-based composite negative electrode material as well as preparation and application thereof |
| CN108448125A (en) * | 2018-04-12 | 2018-08-24 | 中国矿业大学 | A kind of cathode material and preparation method of proton conductor solid oxide fuel cell |
| CN108821351A (en) * | 2018-07-25 | 2018-11-16 | 安徽工业大学 | A kind of preparation method of the porous high entropy oxide material of spinel-type |
| CN110526706A (en) * | 2019-09-19 | 2019-12-03 | 安徽工业大学 | A kind of high entropy oxide powder material of eutectic and preparation method |
| CN110600703A (en) * | 2019-09-19 | 2019-12-20 | 安徽工业大学 | Five-element transition metal oxide high-entropy material for lithium ion battery |
| CN113233518A (en) * | 2020-12-25 | 2021-08-10 | 南京工业大学 | Solid oxide fuel cell anode catalytic material with multi-carbon fuel catalytic hydrogen production function and preparation method thereof |
-
2021
- 2021-09-09 CN CN202111056469.3A patent/CN113745548B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569786A (en) * | 2012-01-19 | 2012-07-11 | 大连工业大学 | Perovskite Co-based composite negative electrode material as well as preparation and application thereof |
| CN108448125A (en) * | 2018-04-12 | 2018-08-24 | 中国矿业大学 | A kind of cathode material and preparation method of proton conductor solid oxide fuel cell |
| CN108821351A (en) * | 2018-07-25 | 2018-11-16 | 安徽工业大学 | A kind of preparation method of the porous high entropy oxide material of spinel-type |
| CN110526706A (en) * | 2019-09-19 | 2019-12-03 | 安徽工业大学 | A kind of high entropy oxide powder material of eutectic and preparation method |
| CN110600703A (en) * | 2019-09-19 | 2019-12-20 | 安徽工业大学 | Five-element transition metal oxide high-entropy material for lithium ion battery |
| CN113233518A (en) * | 2020-12-25 | 2021-08-10 | 南京工业大学 | Solid oxide fuel cell anode catalytic material with multi-carbon fuel catalytic hydrogen production function and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112624740A (en) * | 2020-12-26 | 2021-04-09 | 重庆材料研究院有限公司 | High-entropy NTC thermistor ceramic material and preparation method thereof |
| CN112624740B (en) * | 2020-12-26 | 2022-08-02 | 重庆材料研究院有限公司 | High-entropy NTC thermistor ceramic material and preparation method thereof |
| CN115010190A (en) * | 2022-06-22 | 2022-09-06 | 北京理工大学重庆创新中心 | High-entropy oxide cathode material and preparation method and application thereof |
| CN115010190B (en) * | 2022-06-22 | 2023-12-22 | 北京理工大学重庆创新中心 | High-entropy oxide positive electrode material and preparation method and application thereof |
| CN116581314A (en) * | 2023-07-07 | 2023-08-11 | 华北电力大学 | High-entropy oxide catalyst for fuel cell and preparation method thereof |
| CN116581314B (en) * | 2023-07-07 | 2023-09-22 | 华北电力大学 | High-entropy oxide catalyst for fuel cell and preparation method thereof |
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