CN111217402A - Hexahydric spinel type iron-cobalt-chromium-manganese-copper-zinc series high-entropy oxide and powder preparation method thereof - Google Patents

Hexahydric spinel type iron-cobalt-chromium-manganese-copper-zinc series high-entropy oxide and powder preparation method thereof Download PDF

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CN111217402A
CN111217402A CN202010162798.5A CN202010162798A CN111217402A CN 111217402 A CN111217402 A CN 111217402A CN 202010162798 A CN202010162798 A CN 202010162798A CN 111217402 A CN111217402 A CN 111217402A
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entropy oxide
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张建军
夏午阳
梁炳亮
陈卫华
何文
欧阳晟
刘长虹
王义良
刘锦
艾云龙
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Abstract

The invention discloses a hexabasic spinel type Fe-Co-Cr-Mn-Cu-Zn series high-entropy oxide and a powder preparation method thereof, belonging to the field of high-entropy oxide ceramic powder materials. The chemical formula of the high-entropy oxide is (FeCoCrMnCuZn)3O4The crystal structure is a face-centered cubic structure, and the space point group is Fd-3 m. The preparation process comprises the following steps: mixing Fe2O3、Cr2O3、Co2O3、MnO2Mixing CuO and ZnO powder, ball-milling, drying and sieving the ball-milled powder; however, the device is not suitable for use in a kitchenAnd then calcining and heating the mixture in a muffle furnace to 800-1000 ℃, wherein the calcining time is 1-3 hours, and cooling the calcined mixture in the furnace to room temperature to obtain the single-phase high-entropy oxide ceramic powder with the spinel structure. The preparation method has the advantages of low cost, short production period, industrial production, simple operation process, low energy consumption and the like, and the prepared powder has high purity, smaller particle size and uniform distribution, and can be widely applied to the field of novel energy materials such as super capacitor electrodes, lithium ion battery electrodes, hydrogen production by water electrolysis and the like.

Description

Hexahydric spinel type iron-cobalt-chromium-manganese-copper-zinc series high-entropy oxide and powder preparation method thereof
Technical Field
The invention belongs to the field of high-entropy oxide powder materials, and particularly relates to a hexabasic spinel type Fe-Co-Cr-Mn-Cu-Zn series high-entropy oxide and a powder preparation method thereof.
Background
Different from the design concept that one or two principal elements are adopted in the traditional alloy, the high-entropy alloy is an alloy with 5 or more than 5 principal elements, the content of each principal element is between 5 wt% and 35 wt%, and a simple solid solution structure (FCC, BCC, HCP and the like) can be obtained due to the high configuration entropy. The high-entropy alloy has a thermodynamic high-entropy effect, a kinetic slow diffusion effect, a structural lattice distortion effect and a performance cocktail response. In 2015, Rost et al extended this design concept to the study of high entropy oxide ceramics. In recent years, research on spinel-type high-entropy oxides has been attracting attention.
High-purity NiO, MnO and Fe in equimolar ratio by DabrowaJ and the like2O3、Co3O4(99.7 wt.%) and Cr2O3(99 wt%) as raw material, using vibration ball milling method to mix them uniformly, pressing them into round piece with 200MPa pressure, then calcining at 1050 deg.C for 20h, finally putting the sample on aluminium plate and quenching to room temperature to obtain single-phase spinel structure (CoCrFeMnNi)3O4High entropy oxide (
Figure BDA0002406388350000011
J,Stygar M,
Figure BDA0002406388350000012
A,et al.Synthesis and microstructure of the(Co,Cr,Fe,Mn,Ni)3O4high entropy oxide characterized by spinel structure[J].MaterialsLetters,2018,216:32-36.)。
The Chinese patent of Wangyuan application (patent publication No. CN 110190259A) a preparation method of nano high-entropy oxide and lithium ion battery cathode material discloses (FeTiMgZnCu)3O4The preparation method of the high-entropy oxide adopts the raw material powder with the purity of 99.99 wt%, the rotating speed of the high-energy ball milling method is as high as 1000-2000 r/min, the calcining temperature is 1000-1100 ℃, the calcining time is 20-30 hours, and finally (FeTiMgZnCu) is needed3O4Ball milling is carried out in the high-entropy oxide ethanol-isopropanol mixed solvent for 60-70 hours to obtain nanometer (FeTiMgZnCu)3O4High entropy oxide powder.
Stygar M et al as high purity Co3O4、Cr2O3NiO, MgO, MnO (99.97 wt.%) and Fe2O3(99.9 wt%) as raw material, ball milling and mixing (600r/min, 90min) by planetary ball mill, pressing into round piece, sintering at 1000 deg.C for 20 hr, and quenching in air on aluminum plate to room temperature to obtain the final product (CoCrFeMnNi)3O4、(CoCrFeMgMn)3O4And (CrFeMgMnNi)3O4The high entropy oxide (Stygar M,
Figure BDA0002406388350000013
J,
Figure BDA0002406388350000014
M,et al.Formation andproperties of high entropy oxides in Co-Cr-Fe-Mg-Mn-Ni-O system:novel(Cr,Fe,Mg,Mn,Ni)3O4and(Co,Cr,Fe,Mg,Mn)3O4high entropy spinels[J].Journal of theEuropean Ceramic Society,2019.)。
high purity Co of GrzesikZ et al in equimolar ratio3O4、Cr2O3、Fe2O3MnO and NiO (99.7 wt%) as raw materials, ball-milling and mixing uniformly by using a planetary ball mill at a high rotation speed of 600r/min, then pressing into round pieces, then keeping the temperature at 1000 ℃ for 20 hours, and finally putting the sample on an aluminum plate to quench to room temperature to prepare the high-entropy oxide (CoCrFeMnNi) with the single-phase spinel structure3O4(Grzesik Z,
Figure BDA0002406388350000021
G,Miszczak M,et al.Defect structure andtransport properties of(Co,Cr,Fe,Mn,Ni)3O4spinel-structured high entropyoxide[J].Journal of the European Ceramic Society,2019.)。
Chinese invention patent (application publication No. CN 110364717A) of Wangdan, etc. discloses a spinel type high-entropy oxide electrode material and a preparation method thereof, wherein the chemical formula of the high-entropy oxide electrode material is (FeCoNiCrMn)3O4、(FeZnNiCrMn)3O4、(FeCoZnCrMn)3O4、(FeCoNiCrMnCu)3O4In the preparation method, the temperature is raised to 900-1100 ℃ for high-temperature calcination, and the constant-temperature calcination time is 10-20 hours.
Chinese invention patent (application publication No. CN 109052491A) applied by Aiqin and the like discloses a preparation method of a spinel type porous high-entropy oxide material as a lithium ion battery cathode material, which adopts metal nitrate as a metal source and one or a mixture of more of tartaric acid, citric acid, glucose, hexamethyltetramine and ethylenediamine tetraacetic acid as fuel, and regulates the characteristics of the spinel type high-entropy oxide nano-powder such as particle size, morphology and the like by controlling the concentration of a metal salt raw material, the type and the addition of the fuel, the type and the addition of a combustion improver and an ignition mode.
MaoA and the like adopt a solution combustion synthesis method to prepare spinel type (CrFeMnNiZn)3O4And (CrFeMnCoZn)3O4The specific method of the high-entropy oxide is as follows: mixing 5 nitrates with equal molar ratio, dissolving in deionized water, adding a certain amount of glycine, stirring uniformly to obtain a precursor solution, drying the precursor solution to obtain a gel, and finally, burning and synthesizing in a horizontal electric heating semitransparent gold melting furnace to obtain the high-entropy oxide (MaoA, Xiaong H Z, Zhang ZG, et al.A new class of spinel high-entropy oxides with controllable spinel magnetic properties [ J].Journal of Magnetism and Magnetic Materials,2020,497:165884.)。
In summary, the preparation methods of spinel type high-entropy oxides disclosed in the current domestic and foreign literature reports or the domestic patent of invention mainly include two solid-phase reaction methods and wet chemical methods, wherein the solid-phase reaction method adopts a long heat preservation time (10-20 hours, 20-30 hours), and the solid-phase reaction method needs to be placed on an aluminum plate for air quenching, so that the preparation method has the characteristics of complex process and long period; in addition, the spinel-type high-entropy oxide prepared by a wet chemical method (including a solution combustion synthesis method) has the characteristics of high raw material cost, multiple preparation steps, complex and uncontrollable process and the like. And related reports of the high-entropy oxide with a hexabasic spinel structure do not exist at present, and the invention provides a hexabasic spinel type high-entropy oxide of iron, cobalt, chromium, manganese, copper and zinc and a powder preparation method thereof.
Disclosure of Invention
The invention aims to solve the problems that: the invention provides a preparation method of hexabasic spinel type iron-cobalt-chromium-manganese-copper-zinc series high-entropy oxide and powder thereof, which adopts a method combining a mechanical ball milling method and a solid-phase sintering method to prepare a hexabasic high-entropy oxide material.
The technical scheme provided by the invention for solving the problems is as follows: a hexabasic spinel type high-entropy oxide of Fe-Co-Cr-Mn-Cu-Zn series has a chemical formula of (FeCoCrMnCuZn)3O4The crystal structure is a face-centered cubic structure, and the space point group is Fd-3 m.
A six-element spinel type high-entropy oxide of Fe, Co, Cr, Mn, Cu and Zn series and a powder preparation method thereof are disclosed, wherein the method comprises the following steps:
step 1: separately weighing Fe2O3、Co2O3、Cr2O3、MnO2CuO and ZnO powders;
step 2: performing ball milling mixing and drying on the powder weighed in the step 1;
and step 3: calcining the mixed powder obtained in the step 2 in air atmosphere to obtain the single-phase spinel (FeCoCrMnCuZn)3O4High entropy oxide powder.
Preferably, the raw material Fe in the step 12O3、Co2O3、Cr2O3、MnO2The molar ratio of CuO to ZnO is 1: 2: 1.
Preferably, in the step 3, the heating temperature is 800-1000 ℃, the calcining time is 1-3 hours, and the furnace is cooled to room temperature after calcining.
Compared with the prior art, the invention has the advantages that: the preparation method adopts the idea of combining the mechanical ball milling method and the solid-phase sintering method, and the method for preparing the hexabasic spinel type high-entropy oxide powder material has the advantages of simple method, simple operation and the like, and is suitable for industrial production and application. The spinel type high-entropy oxide powder material prepared by the preparation method has the advantages of high purity, small particle size, uniform distribution and the like.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1: example 1 spinel type (FeCoCrMnCuZn)3O4XRD pattern of high entropy oxide powder;
FIG. 2: example 1 spinel type (FeCoCrMnCuZn)3O4SEM images of high entropy oxide powders;
FIG. 3: example 1 spinel type (FeCoCrMnCuZn)3O4EDS spectrogram and element proportion of the high-entropy oxide powder;
FIG. 4: example 1 spinel type (FeCoCrMnCuZn)3O4EDS-Mapping image of high entropy oxide powder;
Detailed Description
The following detailed description of the embodiments of the present invention will be provided with reference to the accompanying drawings and examples, so that how to implement the embodiments of the present invention by using technical means to solve the technical problems and achieve the technical effects can be fully understood and implemented.
Example 1
A six-element spinel type high-entropy oxide of Fe, Co, Cr, Mn, Cu and Zn series and a powder preparation method thereof comprise the following steps:
step 1, mixing:
(1) fe is weighed according to the molar ratio of 1: 2: 1 respectively2O3(49.6g)、Co2O3(51.6g)、Cr2O3(47.2g)、MnO2(58.8g), CuO (24.7g) and ZnO (25.1g) powders, and the mixed powders were charged into a ball mill pot;
(2) ZrO is respectively added according to the mass ratio of the ball, the material and the water of 3: 12Grinding balls and distilled water;
(3) placing the polyurethane ball milling tank on a tank ball milling mill station for ball milling continuously for 12 hours at a rotating speed of 220r/min to obtain mixed powder;
(4) drying and sieving the ball-milled powder.
Step 2, calcining:
sieving the raw materialsCalcining the mixed powder in a muffle furnace to heat to 1000 ℃ for 1 hour, cooling the furnace to room temperature after calcining to obtain the single-phase spinel structure (FeCoCrMnCuZn)3O4High entropy oxide powder material.
FIGS. 1 to 4 show the spinel-type (FeCoCrMnCuZn) obtained in example 13O4The pictures obtained by the characterization of the high-entropy oxide powder are as follows:
FIG. 1 shows the spinel type (FeCoCrMnCuZn)3O4XRD pattern of high entropy oxide powder with 2 theta diffraction angle as abscissa and diffraction intensity as ordinate, and the pattern is compared with Fe with spinel crystal structure in JCPDS database3O4The spectral lines (PDF #19-0629) are very consistent, indicating that the spinel-type (FeCoCrMnCuZn) prepared by the embodiment of the invention3O4The high-entropy oxide powder is a single-phase solid solution with a face-centered cubic crystal structure.
FIG. 2 shows the spinel type (FeCoCrMnCuZn) of example 13O4SEM image of high entropy oxide powder.
FIGS. 3 and 4 are respectively the spinel type (FeCoCrMnCuZn) of example 13O4EDS and EDS-Mapping images of high entropy oxide powders, indicating the spinel type (FeCoCrMnCuZn)3O4The elements of the high-entropy oxide powder are uniformly distributed.
Example 2
A six-element spinel type high-entropy oxide of Fe, Co, Cr, Mn, Cu and Zn series and a powder preparation method thereof comprise the following steps:
step 1, mixing:
(1) fe is weighed according to the molar ratio of 1: 2: 1 respectively2O3(49.6g)、Co2O3(51.6g)、Cr2O3(47.2g)、MnO2(58.8g), CuO (24.7g) and ZnO (25.1g) powders, and the mixed powders were charged into a ball mill pot;
(2) ZrO is respectively added according to the mass ratio of the ball, the material and the water of 3: 12Grinding balls and distilled water;
(3) placing the polyurethane ball milling tank on a tank ball milling mill station for ball milling continuously for 12 hours at a rotating speed of 220r/min to obtain mixed powder;
(4) drying and sieving the ball-milled powder.
Step 2, calcining:
calcining the sieved mixed powder in a muffle furnace to heat to 900 ℃, calcining for 2 hours, cooling the calcined mixed powder to room temperature to obtain the single-phase spinel structure (FeCoCrMnCuZn)3O4High entropy oxide powder material.
Example 3
A six-element spinel type high-entropy oxide of Fe, Co, Cr, Mn, Cu and Zn series and a powder preparation method thereof comprise the following steps:
step 1, mixing:
(1) fe is weighed according to the molar ratio of 1: 2: 1 respectively2O3(49.6g)、Co2O3(51.6g)、Cr2O3(47.2g)、MnO2(58.8g), CuO (24.7g) and ZnO (25.1g) powders, and the mixed powders were charged into a ball mill pot;
(2) ZrO is respectively added according to the mass ratio of the ball, the material and the water of 3: 12Grinding balls and distilled water;
(3) placing the polyurethane ball milling tank on a tank ball milling mill station for ball milling continuously for 12 hours at a rotating speed of 220r/min to obtain mixed powder;
(4) drying and sieving the ball-milled powder.
Step 2, calcining:
calcining the sieved mixed powder in a muffle furnace to 800 ℃ for 3 hours, cooling the calcined mixed powder to room temperature to obtain the single-phase spinel structure (FeCoCrMnCuZn)3O4High entropy oxide powder material.
The foregoing is merely illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the claims. The present invention is not limited to the above embodiments, and the specific structure thereof is allowed to vary. All changes which come within the scope of the invention as defined by the independent claims are intended to be embraced therein.

Claims (4)

1. A hexabasic spinel type high-entropy oxide of Fe, Co, Cr, Mn, Cu and Zn series is characterized in that: the chemical formula of the iron-cobalt-chromium-manganese-copper-zinc series high-entropy oxide is (FeCoCrMnCuZn)3O4The crystal structure is a face-centered cubic structure, and the space point group is Fd-3 m.
2. A six-element spinel type high-entropy oxide of Fe, Co, Cr, Mn, Cu and Zn and a powder preparation method thereof are characterized by comprising the following steps:
step 1: separately weighing Fe2O3、Co2O3、Cr2O3、MnO2CuO and ZnO powders;
step 2: performing ball milling mixing and drying on the powder weighed in the step 1;
and step 3: calcining the mixed powder obtained in the step 2 in air atmosphere to obtain the single-phase spinel (FeCoCrMnCuZn)3O4High entropy oxide powder.
3. The preparation method of the hexabasic spinel type high-entropy oxide of Fe, Co, Cr, Mn, Cu and Zn and the powder material thereof according to claim 2 is characterized in that: the raw material Fe in the step 12O3、Co2O3、Cr2O3、MnO2The molar ratio of CuO to ZnO is 1: 2: 1.
4. The preparation method of the hexabasic spinel type Fe-Co-Cr-Mn-Cu-Zn series high-entropy oxide and the powder material thereof according to claim 2 or 3 is characterized in that: in the step 3, the heating temperature is 800-1000 ℃, the calcining time is 1-3 hours, and the furnace is cooled to the room temperature after calcining.
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CN111892400A (en) * 2020-08-18 2020-11-06 新沂市锡沂高新材料产业技术研究院有限公司 High-transmittance high-entropy transparent ceramic and preparation method thereof
CN112538253A (en) * 2020-12-07 2021-03-23 陕西生益科技有限公司 Magnetic dielectric resin composition, laminated board containing same and printed circuit board containing laminated board
CN112811891A (en) * 2020-12-26 2021-05-18 重庆材料研究院有限公司 Spinel phase high-entropy thermistor material and preparation method thereof
CN113501709A (en) * 2021-07-19 2021-10-15 中国科学院兰州化学物理研究所 Synthesis of spinel-type high-entropy oxide Material (MCoFeCrMn) by hydrothermal method3O4Method (2)
CN113636607A (en) * 2021-08-03 2021-11-12 中国矿业大学 Preparation method of high-entropy oxide of lithium ion battery negative electrode material
CN114369376A (en) * 2022-01-28 2022-04-19 湖南信诺颜料科技有限公司 High-brightness cobalt melanin and preparation method thereof
CN115155611A (en) * 2022-07-20 2022-10-11 中南大学 Single-phase spinel type magnetic high-entropy oxide catalyst and preparation method and application thereof
CN115594496A (en) * 2022-10-31 2023-01-13 安徽大学（Cn） Medium-entropy ceramic with spinel structure and preparation method thereof
CN115595025A (en) * 2021-07-08 2023-01-13 武汉苏泊尔炊具有限公司（Cn） Non-stick material, preparation method thereof, non-stick coating and cooking utensil
CN115594497A (en) * 2022-10-31 2023-01-13 安徽大学（Cn） High-entropy ceramic with spinel structure and preparation method and application thereof
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CN111892400A (en) * 2020-08-18 2020-11-06 新沂市锡沂高新材料产业技术研究院有限公司 High-transmittance high-entropy transparent ceramic and preparation method thereof
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CN112811891A (en) * 2020-12-26 2021-05-18 重庆材料研究院有限公司 Spinel phase high-entropy thermistor material and preparation method thereof
CN112811891B (en) * 2020-12-26 2022-08-02 重庆材料研究院有限公司 Spinel phase high-entropy thermistor material and preparation method thereof
CN115595025B (en) * 2021-07-08 2023-09-08 武汉苏泊尔炊具有限公司 Non-stick material, preparation method thereof, non-stick coating and cooking utensil
CN115595025A (en) * 2021-07-08 2023-01-13 武汉苏泊尔炊具有限公司（Cn） Non-stick material, preparation method thereof, non-stick coating and cooking utensil
CN113501709B (en) * 2021-07-19 2022-11-01 中国科学院兰州化学物理研究所 Synthesis of spinel-type high-entropy oxide Material (MCoFeCrMn) by hydrothermal method3O4Method (2)
CN113501709A (en) * 2021-07-19 2021-10-15 中国科学院兰州化学物理研究所 Synthesis of spinel-type high-entropy oxide Material (MCoFeCrMn) by hydrothermal method3O4Method (2)
CN113636607A (en) * 2021-08-03 2021-11-12 中国矿业大学 Preparation method of high-entropy oxide of lithium ion battery negative electrode material
CN114369376A (en) * 2022-01-28 2022-04-19 湖南信诺颜料科技有限公司 High-brightness cobalt melanin and preparation method thereof
CN115155611A (en) * 2022-07-20 2022-10-11 中南大学 Single-phase spinel type magnetic high-entropy oxide catalyst and preparation method and application thereof
CN115155611B (en) * 2022-07-20 2023-08-11 中南大学 Single-phase spinel type magnetic high-entropy oxide catalyst, and preparation method and application thereof
CN115594496A (en) * 2022-10-31 2023-01-13 安徽大学（Cn） Medium-entropy ceramic with spinel structure and preparation method thereof
CN115594497A (en) * 2022-10-31 2023-01-13 安徽大学（Cn） High-entropy ceramic with spinel structure and preparation method and application thereof
CN115594496B (en) * 2022-10-31 2023-06-27 安徽大学 Intermediate entropy ceramic with spinel structure and preparation method thereof
CN117902890A (en) * 2024-01-26 2024-04-19 中国科学院兰州化学物理研究所 Spinel-corundum dual-phase high-entropy ceramic powder material and preparation method thereof
CN117902890B (en) * 2024-01-26 2024-05-28 中国科学院兰州化学物理研究所 Spinel-corundum dual-phase high-entropy ceramic powder material and preparation method thereof

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