WO2022160474A1 - 一种高导电a位高熵纳米金属氧化物及其制备方法 - Google Patents

一种高导电a位高熵纳米金属氧化物及其制备方法 Download PDF

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WO2022160474A1
WO2022160474A1 PCT/CN2021/087934 CN2021087934W WO2022160474A1 WO 2022160474 A1 WO2022160474 A1 WO 2022160474A1 CN 2021087934 W CN2021087934 W CN 2021087934W WO 2022160474 A1 WO2022160474 A1 WO 2022160474A1
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mixed solution
powder
metal oxide
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张玲洁
蔡伟炜
暴宁钟
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Zhejiang University
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    • C01G31/00—Compounds of vanadium
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    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/38—Particle morphology extending in three dimensions cube-like
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    • C01—INORGANIC CHEMISTRY
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    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties

Definitions

  • the invention relates to the field of new materials, in particular to a high-conductivity A-position high-entropy nano-metal oxide (Gd 0.4 Er 0.3 La 0.4 Nd 0.5 Y 0.4 ) (Zr 0.7 , Sn 0.8 , V 0.5 )O 7 and a preparation method thereof.
  • conductive composites are often prepared by adding metal oxide reinforcement phases to improve the ability of the metal matrix to resist arc erosion, such as adding SnO2 to the Ag matrix or Cu matrix to prepare Conductive metal composite material with excellent resistance to arc erosion and fusion welding.
  • metal oxide reinforcement phases such as adding SnO2 to the Ag matrix or Cu matrix to prepare Conductive metal composite material with excellent resistance to arc erosion and fusion welding.
  • the addition of metal oxides also leads to a decrease in the conductivity of the composite material due to the insufficient conductivity of the metal oxide itself, so that it cannot meet the application requirements in the field of electrical conductivity.
  • Multi-element rare earth metal oxides have good electrical conductivity in theory, and their good electrical conductivity mainly comes from two aspects: First, there are a large number of oxygen vacancies due to the distortion of the crystal structure, which makes them in a wide temperature range. It has good electrical transport properties (the resistivity can be as low as 10 3 ⁇ cm); secondly, the synergistic effect of multiple elements makes the material have a higher density of states at the Fermi level and thus have better electronic conductivity.
  • High-entropy oxide is a new type of material, which is composed of 4 or more than 5 kinds of main heterometallic elements.
  • the introduction of various metal elements brings higher conformational entropy to the material, and the increase of conformational entropy can give the material a higher conformational entropy.
  • Introducing the concept of high entropy into the preparation of metal oxides can further improve the performance of metal oxides.
  • the existing high-entropy oxides have low electrical conductivity due to the influence of microstructure design, preparation method, etc., and their electrical conductivity needs to be further improved, so as to make them suitable for more applications in fields requiring high electrical conductivity, including for preparation Conductive alloys, electrical contact composites, conductive composites, multifunctional bio-based composites, conductive/antistatic functional composite coatings, etc.
  • the technical problem to be solved by the present invention is to provide a high-conductivity A-site high-entropy nanometer metal oxide and a preparation method thereof.
  • the solution of the present invention is:
  • a high-conductivity A-position high-entropy nanometer metal oxide the molecular formula of the metal oxide is Gd 0.4 Er 0.3 La 0.4 Nd 0.5 Y 0.4 )(Zr 0.7 , Sn 0.8 , V 0.5 )O 7 ; its appearance is powder
  • the microstructure is shown as square nanosheets with a side length of 4-12 nm and a thickness of 1-3 nm.
  • the present invention further provides a preparation method of the high-conductivity A-position high-entropy nano-metal oxide, comprising the following steps:
  • Gd( NO3 ) 3 , Er( NO3 ) 3 , La( NO3 ) 3 , Nd( NO3 ) 3 , Y(NO 3 ) 3 , ZrOSO 4 , SnCl 4 and NH 4 VO 3 were used as solutes, and deionized water, absolute ethanol and tetrahydrofuran were taken in a mass ratio of 0.3:3:0.5 and mixed to make a solvent; the solute was added to the solvent, The mass ratio of the total mass of the solute to the solvent is 12.6%; stirring for 5-15 minutes to obtain a mixed solution 1, which is for later use;
  • mixed solution 1 and mixed solution 2 by mass ratio of 10 ⁇ 8: 4 ⁇ 6;
  • mixed solution 1 is heated to 50 ⁇ 70 °C, under stirring and ultrasonic conditions, mixed solution 2 is added dropwise to mixed solution 1 after the dropwise addition is completed, further heat up to 85 ⁇ 95°C; stop stirring and keep the temperature for 3 ⁇ 7 hours, then cool down to room temperature to obtain mixed solution 3;
  • mixed solution four is heated to 55 ⁇ 65 °C, and another part of mixed solution two is taken and added dropwise to mixed solution four, and the mass ratio of mixed solution two to mixed solution four is 1.05: 1.25; After the dropwise addition is completed, the temperature is lowered to room temperature under stirring conditions to obtain mixed solution five;
  • the dripping speed is controlled at 1 drop/second.
  • the rotating speed of the shearing emulsifier is 20000-40000 rpm, and the shearing treatment time is 1-3 hours.
  • the heating rate is 3°C/min.
  • the high entropy mentioned in the present invention is a scientific definition, and generally refers to a compound with 4 or more than 5 kinds of elements located in the same chemical structural position.
  • High-entropy materials have better structural stability.
  • the materials can have better designability. Through the adjustment of element types, the desired materials can be obtained. characteristic.
  • the high-entropy oxide described in the present invention is composed of two octahedrons in different positions, namely A-position octahedron and B-position octahedron, and the molecular formula is (Gd 0.4 Er 0.3 La 0.4 Nd 0.5 Y 0.4 ) (Zr 0.7 , Sn 0.8 , V 0.5 )O 7 , wherein the octahedral elements at the A site include Gd, Er, La, Nd, and Y, and the elements at the B site include Zr, Sn, and V.
  • the invention adopts five kinds of rare earth metal element ions to form the A position, and adopts three kinds of metal elements to occupy the B position at the same time, so as to prepare a multi-element metal oxide system.
  • the uniformity of the initial precursor is improved by combining various processes (including step-by-step deposition reconstitution, electrochemical reconstitution, and high-speed shear reconstitution).
  • a structure in which the elements of the A site are uniformly distributed is formed.
  • the introduction of three metal elements at the B site is to adjust the B site, thereby reducing the homogenization energy of the A site elements, which is beneficial to the further homogenization of the metal element ions at the A site.
  • the invention improves the uniformity of the multi-component metal composite system, so that the system can obtain sufficient entropy increase, thereby realizing the preparation of high-entropy materials.
  • the introduction of these five rare earth metal elements greatly increases the density of states of the material at the Fermi level, so that the electrons in the system have higher mobility.
  • the introduction of A-site multi-element rare earth metals and B-site ternary metals the material forms more structural distortions, which in turn brings higher ionic conductance. Therefore, the combined increase in electronic and ionic conductance brings about a great increase in the conductivity of the material.
  • the present invention has the following beneficial effects:
  • the present invention provides a composite process preparation process with strictly controlled parameters, combined with the methods of step-by-step deposition re-reconstruction, electrochemical re-reconstruction and high-speed shear re-reconstruction, to achieve uniform distribution of metal element ions at A and B positions. And the controllable microscopic morphology (square nanosheets); and the greatly increased density of states and large structural distortion at the Fermi level brought about by multi-element homogenization to jointly improve the electronic and ionic conductance of the material, Thereby, a high-conductivity non-metallic material is obtained, and the prepared A-position high-entropy nano-metal oxide has high conductivity.
  • the products prepared by the present invention have the characteristics of high conductivity, and can be used in conductive alloys, electrical contact composite materials, conductive composite materials, multifunctional bio-based composite materials, and conductive/antistatic functions. Composite coatings and other aspects have been better applied.
  • Gd(NO 3 ) 3 , Er(NO 3 ) 3 , La(NO 3 ) 3 , Nd(NO 3 ) 3 , Y(NO 3 ) 3 , ZrOSO 4 , SnCl 4 and NH 4 VO 3 are powdery solids.
  • Anhydrous ethanol, tetrahydrofuran, n-propanol, as well as phenylenediamine, hydrogenated tallow-based primary amine, sorbitol and ethyl carbamate are all commercial reagents.
  • a method for preparing a highly conductive A-site high-entropy nanometer (Gd 0.4 Er 0.3 La 0.4 Nd 0.5 Y 0.4 ) (Zr 0.7 , Sn 0.8 , V 0.5 )O 7 metal oxide, comprising the following steps:
  • Gd(NO 3 ) 3 , Er(NO 3 ) 3 , La(NO 3 ) 3 , Nd(NO 3 ) 3 in a molar ratio of 0.4:0.3:0.4:0.5:0.4:0.7:0.8:0.5, Y(NO 3 ) 3 , ZrOSO 4 , SnCl 4 , NH 4 VO 3 were added to a mixed solution with a mass ratio of deionized water/absolute ethanol/tetrahydrofuran of 0.3:3:0.5, and stirred for 5 minutes to obtain a mixed solution 1 ;
  • the mass ratio of the mixed solution of ionized water/absolute ethanol/tetrahydrofuran (0.3:3:0.5) was 12.6%
  • the mixed solution 1 obtained in step (1) is heated to 50 ° C, and the mixed solution 2 obtained in step (2) is added dropwise to the mixed solution 1 obtained in step (1) at a speed of 1 drop/second while ultrasonically stirring, After the dropwise addition was completed, the temperature was further increased to 85° C. and the stirring was stopped, and after the temperature was maintained for 3 hours, the temperature was further lowered to room temperature to obtain a mixed solution III.
  • the mass ratio of mixed solution 1 and mixed solution 2 is 10:4.
  • step (4) the mixed solution 4 obtained in step (4) is heated to 55° C. while stirring, and another part of mixed solution 2 is added dropwise to the obtained mixed solution 4 in step (4) at a speed of one drop/sec.
  • the mass ratio of the mixed solution 4 is 1.05:1.25; after the dropwise addition is completed, the temperature is lowered to room temperature under the stirring conditions to obtain the mixed solution 5.
  • step (8) Mix the mixture obtained in step (7) with absolute ethanol at a mass ratio of 1:2 and stir evenly, and seal it at 210° C. for solvent heat treatment for 18 hours. After cooling to room temperature, the obtained powder was collected by centrifugation, washed with deionized water and absolute ethanol for 8 times each, and dried to obtain powder 1.
  • step (9) After uniformly mixing the powder 1 obtained in step (8) with ammonium persulfate in a mass ratio of 10:1, seal it, and heat it up to 165° C. and keep the temperature for 13 hours. After cooling to room temperature, the obtained mixed powder was washed 10 times with deionized water, and dried to obtain powder II.
  • step (4) Put the powder 2 obtained in step (4) into a crucible , heat up to 1500°C at a heating rate of 3°C/min, and keep the temperature for 7 hours; 0.3 La 0.4 Nd 0.5 Y 0.4 )(Zr 0.7 , Sn 0.8 , V 0.5 )O 7 metal oxide.
  • A-site high-entropy nano-metal oxide is in the form of powder, and its microstructure is a square nano-sheet with a side length of about 4 nm and a thickness of about 1 nm.
  • the electrical conductivity of the product is 2.1 ⁇ 10 8 S/m.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • a method for preparing a highly conductive A-site high-entropy nanometer (Gd 0.4 Er 0.3 La 0.4 Nd 0.5 Y 0.4 ) (Zr 0.7 , Sn 0.8 , V 0.5 )O 7 metal oxide, comprising the following steps:
  • the mixed solution 1 obtained in step (1) is heated to 70 ° C, and the mixed solution 2 obtained in step (2) is added dropwise to the mixed solution 1 obtained in step (1) at a speed of one drop/second while ultrasonically stirring, After the dropwise addition was completed, the temperature was further raised to 95° C. and the stirring was stopped, and after the temperature was maintained for 7 hours, the temperature was lowered to room temperature to obtain a mixed solution III.
  • the mass ratio of mixed solution 1 and mixed solution 2 is 8:6.
  • step (4) The mixed solution 4 obtained in step (4) is heated to 65° C. while stirring, and the mixed solution 2 obtained in step (2) is added dropwise to the mixed solution 4 obtained in step (4) at a speed of one drop/second, and the mixed solution
  • the mass ratio of 2 to mixed solution 4 is 1.05:1.25; after the dropwise addition is completed, the temperature is lowered to room temperature under stirring conditions to obtain mixed solution 5.
  • step (8) Mix the mixture obtained in step (7) with absolute ethanol at a mass ratio of 1:2 and stir evenly, seal it at 230° C. for solvent heat treatment, and the treatment time is 24 hours. After cooling to room temperature, the obtained powder was collected by centrifugation, washed with deionized water and absolute ethanol for 8 times each, and dried to obtain powder 1.
  • step (9) After uniformly mixing the powder 1 obtained in step (8) with ammonium persulfate in a mass ratio of 10:1, seal it, and heat it up to 175° C. and keep the temperature for 15 hours. After cooling to room temperature, the obtained mixed powder was washed 10 times with deionized water, and dried to obtain powder II.
  • step (4) Put the powder 2 obtained in step (4) into a crucible, heat up to 1700 °C at a heating rate of 3°C/min, and keep the temperature for 9 hours; 0.3 La 0.4 Nd 0.5 Y 0.4 )(Zr 0.7 , Sn 0.8 , V 0.5 )O 7 metal oxide.
  • the electron microscope observation shows that the obtained high-conductivity A-site high-entropy nano-metal oxide is in the form of powder, and its microstructure is a square nano-sheet with a side length of about 12 nm and a thickness of about 3 nm.
  • the electrical conductivity of the product is 7.3 ⁇ 10 8 S/m.
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • a method for preparing a highly conductive A-site high-entropy nanometer (Gd 0.4 Er 0.3 La 0.4 Nd 0.5 Y 0.4 ) (Zr 0.7 , Sn 0.8 , V 0.5 )O 7 metal oxide, comprising the following steps:
  • the mixed solution 1 obtained in step (1) is heated to 60 ° C, and the mixed solution 2 obtained in step (2) is added dropwise to the mixed solution 1 obtained in step (1) at a speed of 1 drop/second while ultrasonically stirring, After the dropwise addition was completed, the temperature was further raised to 90° C. and the stirring was stopped, and after the temperature was maintained for 5 hours, the temperature was further lowered to room temperature to obtain mixed solution III.
  • the mass ratio of mixed solution 1 and mixed solution 2 is 9:7.
  • step (4) The mixed solution 4 obtained in step (4) is heated to 60° C. while stirring, and the mixed solution 2 obtained in step (2) is added dropwise to the mixed solution 4 obtained in step (4) at a speed of one drop/second, and the mixed solution
  • the mass ratio of 2 to mixed solution 4 is 1.05:1.25; after the dropwise addition is completed, the temperature is lowered to room temperature under stirring conditions to obtain mixed solution 5.
  • step (6) using a high-speed shearing emulsifier, carry out high-speed shearing treatment to the mixed solution 5 obtained in step (5) at a speed of 30,000 rev/min, and the shearing time is 2 hours to obtain the mixed solution 6.
  • step (8) Mix the mixture obtained in step (7) with absolute ethanol at a mass ratio of 1:2 and stir evenly, and seal it at 220° C. for solvent heat treatment for 21 hours. After cooling to room temperature, the obtained powder was collected by centrifugation, washed with deionized water and absolute ethanol for 8 times each, and dried to obtain powder 1.
  • step (9) After uniformly mixing the powder 1 obtained in step (8) with ammonium persulfate in a mass ratio of 10:1, seal it, heat it up to 170° C., and keep the temperature for 14 hours. After cooling to room temperature, the obtained mixed powder was washed 10 times with deionized water, and dried to obtain powder II.
  • step (4) Put the powder 2 obtained in step (4) into a crucible, heat up to 1600° C. at a heating rate of 3° C./min , and keep the temperature for 8 hours; 0.3 La 0.4 Nd 0.5 Y 0.4 )(Zr 0.7 , Sn 0.8 , V 0.5 )O 7 metal oxide.
  • the electron microscope observation shows that the obtained high-conductivity A-site high-entropy nano-metal oxide is in the form of powder, and its microstructure is a square nano-sheet with a side length of about 8 nm and a thickness of about 2 nm.
  • the electrical conductivity of the product is 4.1 ⁇ 10 8 S/m.
  • ITO indium tin oxide
  • the electrical conductivity of commercially available ITO is 1.6 ⁇ 10 6 S/m.
  • the electrical conductivity of the commercially available (CoCrFeMnZn) 3 O 4 high-entropy oxide is 1.6 ⁇ 10 3 S/m.

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Abstract

提供一种高导电A位高熵纳米金属氧化物及其制备方法。该金属氧化物的分子式为Gd 0.4Er 0.3La 0.4Nd 0.5Y 0.4)(Zr 0.7,Sn 0.8,V 0.5)O 7；其外观呈粉体状，微观结构显示为边长4～12nm、厚度1～3nm的正方形纳米片。相对于现有的高熵氧化物，具有高导电的特点，能够在导电合金、电接触复合材料、导电复合材料、多功能生物基复合材料、导电/抗静电功能复合涂层等方面得到更好的应用。

Description

一种高导电A位高熵纳米金属氧化物及其制备方法 技术领域
本发明涉及新材料领域，具体涉及一种高导电A位高熵纳米金属氧化物(Gd 0.4Er 0.3La 0.4Nd 0.5Y 0.4)(Zr 0.7,Sn 0.8,V 0.5)O 7及其制备方法。
背景技术
当金属材料应用于高压可通断连接件时，常常通过添加金属氧化物增强相制备导电复合材料，以提高金属基体的抵御电弧侵蚀的能力，如在Ag基体或Cu基体中添加SnO 2以制备具有优良抗电弧侵蚀性及抗熔焊性的导电金属复合材料。但金属氧化物的添加也存在因金属氧化物自身导电性不足而导致的复合材料导电性的下降，从而无法满足在导电领域的应用要求。
多元稀土金属氧化物理论上具有较好的导电性能，其较好的导电性主要来源于两个方面：其一，由于晶体结构畸变导致存在大量的氧空位，使其在很宽的温度范围内具有良好的电输运性能(电阻率可低至10 3μΩ·cm)；其二，多元素协同效应使得在材料费米能级处具有更高的态密度从而具有更好的电子导电性能。
高熵氧化物是一种新型材料，由4种或5种以上的主要异质金属元素构成，多种金属元素的引入为材料带来更高的构象熵，而构象熵的增加，可赋予材料将高熵概念引入金属氧化物的制备可以进一步提高金属氧化物的性能。高熵金属氧化物中的不同元素达到5种以上，可赋予材料更大的结构畸变，从而有利于氧空位的生成；同时多种元素的引入也有利于提高材料费米面处的态密度从而实现更好的电子导电性。
但是，现有高熵氧化物受微观结构设计、制备方法等的影响，导电性较低，需要进一步提高其导电性，从而使其适应于更多需要高导电性领域的应用，包括用于制备导电合金、电接触复合材料、导电复合材料、多功能生物基复合材料、导电/抗静电功能复合涂层等。
发明内容
本发明要解决的技术问题是，提供一种高导电A位高熵纳米金属氧化物及其制备方法。
为解决技术问题，本发明的解决方案是：
提供一种高导电A位高熵纳米金属氧化物，该金属氧化物的分子式为Gd 0.4Er 0.3La 0.4Nd 0.5Y 0.4)(Zr 0.7,Sn 0.8,V 0.5)O 7；其外观呈粉体状，微观结构显示为边长4～12nm、厚度1～3nm的正方形纳米片。
本发明进一步提供了所述高导电A位高熵纳米金属氧化物的制备方法，包括以下步骤：
(1)按摩尔比0.4∶0.3∶0.4∶0.5∶0.4∶0.7∶0.8∶0.5取Gd(NO 3) 3、Er(NO 3) 3、La(NO 3) 3、Nd(NO 3) 3、Y(NO 3) 3、ZrOSO 4、SnCl 4和NH 4VO 3作为溶质，按质量比0.3∶3∶0.5取去离子水、无水乙醇和四氢呋喃混匀制成溶剂；将溶质加入溶剂中，溶质的总质量与溶剂的质量比为12.6％；搅拌5～15分钟，得到混合液一，备用；
(2)按质量比1～3∶0.2～0.4∶7～9∶0.01～0.03取对苯二胺、氢化牛脂基伯胺、山梨醇和氨基甲酰乙酸乙酯作为溶质，加至正丙醇中；溶质的总质量与正丙醇的质量之比为7.5％；搅拌1～3小时，得到混合液二，备用；
(3)按质量比10～8∶4～6取混合液一和混合液二；将混合液一升温至50～70℃，在搅拌和超声条件下，将混合液二滴加至混合液一中；滴加完成后，进一步升温至85～95℃；停止搅拌并保温3～7小时，然后降温至室温，得到混合液三；
(4)将混合液三加入电解池中，采用铂电极为电极，电极两端加3～7V电压，反应13～17分钟后，得到混合液四；
(5)在搅拌条件下将混合液四升温至55～65℃，另取一份混合液二将其滴加至混合液四中，混合液二与混合液四的质量比为1.05∶1.25；滴加完成后，在搅拌条件下降温至室温，得到混合液五；
(6)以剪切乳化机对混合液五进行剪切处理，得到混合液六；
(7)将混合液六进行冷冻干燥处理，得到混合物一；
(8)按质量比1∶2将混合物一与无水乙醇混合，搅拌均匀后，在密闭条件和210～230℃下进行溶剂热处理，处理时间18～24小时；冷却至室温后，离心收集所得粉体，并用去离子水与无水乙醇各清洗8次，烘干后得到粉体一；
(9)按质量比10∶1取粉体一与过硫酸铵，混合均匀后，在密闭条件下升温至165℃～175℃，保温13～15小时；冷却至室温后，将所得混合粉体用去离子水清洗10次，烘干后得到粉体二；
(10)将粉体二放入坩埚，升温至1500℃～1700℃，保温7～9小时；冷却至室温后，得到高导电A位高熵纳米金属氧化物。
本发明所述步骤(3)、(5)中，滴加速度控制在1滴/秒。
本发明所述步骤(6)中，剪切乳化机的转速为20000～40000转/分钟，剪切处理时间1～3小时。
本发明所述步骤(10)中，升温速率为3℃/分钟。
发明原理描述：
本发明所述高熵是科学上的一种定义，一般指位于同一化学结构位的元素种类4种或5种以上的化合物。高熵材料具有更好的结构稳定性，同时由于高熵带来的多种异质元素与结构畸变，可以使得材料具有更好的可设计性，通过元素种类的调整，可以获得希望得到的材料特性。
本发明所述高熵氧化物由两种不同位置的八面体构成，即A位八面体与B位八面体，分子式为(Gd 0.4Er 0.3La 0.4Nd 0.5Y 0.4)(Zr 0.7,Sn 0.8,V 0.5)O 7，其中，位于A位八面体的元素包括Gd、Er、La、Nd、Y，位于B位的元素包括Zr、Sn、V。高熵金属氧化物中的不同元素达到5种以上，可赋予材料更大的结构畸变，从而有利于氧空位的生成；同时通过多种元素的引入也有利于提高材料费米面处的态密度，并且通过本发明所述A位元素的引入，使得各金属元素间的d轨道实现更大程度的重叠，从而极大扩展了金属d轨道的态密度分布，从而使得导电性大大提高。
本发明采用五种稀土金属元素离子构成A位，同时采用三种金属元素占据B位，制备多元金属氧化物体系。为进一步实现A位元素的均匀分布，通过复合多种工艺(包括分步沉积再重构，电化学再重构，高速剪切再重构)的方法，提高初始前驱体均匀性，从而在高温热处理时形成A位各元素均匀分布的结构。而在B位引入三种金属元素，是为了调节B位，从而降低A位元素均匀化能量，有利于A位各金属元素离子的进一步均匀化。本发明提升多元金属复合体系的均匀性，从而使得该体系获得充分的熵增，进而实现高熵材料的制备。
本发明中在A位引入五种稀土金属元素，经过理论计算设计，这五种稀土金属元素的引入使得材料在费米能级处的态密度大大增加，从而使得体系内的电子具有更高的迁移率。另一方面，由于A位多元稀土金属及B位三元金属的引入，从而使得材料形成较多的结构畸变，进而带来了更高的离子电导。因此，电子电导和离子电导的共同提高带来了材料导电性的极大增加。
与现有技术相比，本发明具有以下有益效果：
1、本发明提供通过严格控制参数的复合工艺制备过程，结合分步沉积再重构，电化学再重构以及高速剪切再重构的方法，实现A位及B位金属元素离子分布均匀化及微观形貌的可控化(正方形纳米片)；并利用多元素均匀化带来的费米能级处极大增加的态密度和较大的结构畸变，共同提高材料电子电导和离子电导，从而获得高导电性非金属材料，制得的A位高熵纳米金属氧化物具有高导电性。
2、相对于现有的高熵氧化物，本发明制得的产品具有高导电的特点，能够在导电合金、电接触复合材料、导电复合材料、多功能生物基复合材料、导电/抗静电功能复合涂层等方面得到更好的应用。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
下述实施例中，Gd(NO 3) 3、Er(NO 3) 3、La(NO 3) 3、Nd(NO 3) 3、Y(NO 3) 3、ZrOSO 4、SnCl 4和NH 4VO 3均为粉末状固体。无水乙醇、四氢呋喃、正丙醇，以及苯二胺、氢化牛脂基伯胺、山梨醇和氨基甲酰乙酸乙酯均为商品试剂。
实施例1：
提供的一种高导电A位高熵纳米(Gd 0.4Er 0.3La 0.4Nd 0.5Y 0.4)(Zr 0.7,Sn 0.8,V 0.5)O 7金属氧化物的制备方法，包括如下步骤：
(1)按摩尔比0.4∶0.3∶0.4：0.5：0.4：0.7：0.8：0.5取Gd(NO 3) 3，Er(NO 3) 3，La(NO 3) 3，Nd(NO 3) 3，Y(NO 3) 3，ZrOSO 4，SnCl 4，NH 4VO 3加至去离子水/无水乙醇/四氢呋喃质量比为0.3：3：0.5的混合溶液中，并搅拌5分钟，得到混合液一；Gd(NO 3) 3，Er(NO 3) 3，La(NO 3) 3，Nd(NO 3) 3，Y(NO 3) 3，ZrOSO 4，SnCl 4，NH 4VO 3总质量与去离子水/无水乙醇/四氢呋喃(0.3：3：0.5)混合溶液质量比为12.6％。
(2)按质量比1∶0.2∶7∶0.01取对苯二胺、氢化牛脂基伯胺、山梨醇和氨基甲酰乙酸乙酯，加至正丙醇中，并搅拌1小时，得到混合液二；对苯二胺、氢化牛脂基伯胺、山梨醇和氨基甲酰乙酸乙酯的总质量与正丙醇的质量之比为7.5％；
(3)将步骤(1)所得混合液一，升温至50℃，边搅拌边超声边将步骤(2)所得混合液二以一滴/秒的速度滴加入步骤(1)所得混合液一中，滴加完成后，进一步升温至85℃并停止搅拌，保温3小时后，再降温至室温，得到混合液三。混合液一与混合液二的质量比为10：4。
(4)将混合液三加入电解池中，采用铂电极为电极，电极两端加3V电压，反应13分钟后，得到混合液四；
(5)将步骤(4)所得混合液四，边搅拌边升温至55℃，另取一份混合液二以一滴/秒的速度滴加入步骤(4)所得混合液四中，混合液二与混合液四的质量比为1.05∶1.25；滴加完成后，搅拌条件下降温至室温，得到混合液五。
(6)采用高速剪切乳化机，以20000转/分钟速度对步骤(5)所得混合液五进行高速剪切处理，剪切时间1小时，得到混合液六。
(7)将混合液六进行冷冻干燥处理，得到混合物一。
(8)将步骤(7)所得混合物一以质量比1：2与无水乙醇混合并搅拌均匀，密封于210℃下进行溶剂热处理，处理时间18小时。冷却至室温后，离心收集所得粉体，并用去离子水与无水乙醇各清洗8次，烘干后得到粉体一。
(9)将步骤(8)所得粉体一与过硫酸铵以质量比10：1均匀混合后，密封，并升温至165℃，保温13小时。冷却至室温后，将所得混合粉体用去离子水清洗10次，烘干后得到粉体二。
(10)将步骤(4)所得粉体二放入坩埚，以3℃/分钟的升温速率升温至1500℃，保温7小时；冷却至室温后，得到高导电A位高熵纳米(Gd 0.4Er 0.3La 0.4Nd 0.5Y 0.4)(Zr 0.7,Sn 0.8,V 0.5)O 7金属氧化物。
经电镜观测，所得高导电A位高熵纳米金属氧化物呈粉体状，其微观结构为边长4nm左右，厚度1nm左右的正方形纳米片。
取产品粉体，用粉末压片机以550MPa的压强将粉体压成片，采用四探针法对其进行电导率测试，该产品的电导率为2.1×10 8S/m。
实施例2:
提供的一种高导电A位高熵纳米(Gd 0.4Er 0.3La 0.4Nd 0.5Y 0.4)(Zr 0.7,Sn 0.8,V 0.5)O 7金属氧化物的制备方法，包括如下步骤：
(1)按摩尔比0.4∶0.3∶0.4：0.5：0.4：0.7：0.8：0.5取Gd(NO 3) 3，Er(NO 3) 3，La(NO 3) 3，Nd(NO 3) 3，Y(NO 3) 3，ZrOSO 4，SnCl 4，NH 4VO 3加至去离子水/无水乙醇/四氢呋喃质量比为0.3：3：0.5的混合溶液中，并搅拌10分钟，得到混合液一；Gd(NO 3) 3，Er(NO 3) 3，La(NO 3) 3，Nd(NO 3) 3，Y(NO 3) 3，ZrOSO 4，SnCl 4，NH 4VO 3总质量与去离子水/无水乙醇/四氢呋喃(0.3：3：0.5)混合溶液质量比为12.6％。
(2)按质量比3∶0.4∶9∶0.03取对苯二胺、氢化牛脂基伯胺、山梨醇和氨基甲酰乙酸乙酯，加至正丙醇中，并搅拌3小时，得到混合液二；对苯二胺、氢化牛脂基伯胺、山梨醇和氨基甲酰乙酸乙酯的总质量与正丙醇的质量之比为7.5％；
(3)将步骤(1)所得混合液一，升温至70℃，边搅拌边超声边将步骤(2)所得混合液二以一滴/秒的速度滴加入步骤(1)所得混合液一中，滴加完成后，进一步升温至95℃并停止搅拌，保温7小时后，再降温至室温，得到混合液三。混合液一与混合液二的质量比为8：6。
(4)将混合液三加入电解池中，采用铂电极为电极，电极两端加5V电压，反应17分钟后，得到混合液四；
(5)将步骤(4)所得混合液四，边搅拌边升温至65℃，将步骤(2)所得混合液二以一滴/秒的速度滴加入步骤(4)所得混合液四中，混合液二与混合液四的质量比为1.05∶1.25；滴加完成后，搅拌条件下降温至室温，得到混合液五。
(6)采用高速剪切乳化机，以40000转/分钟速度对步骤(5)所得混合液五进行高速剪切处理，剪切时间3小时，得到混合液六。
(7)将混合液六进行冷冻干燥处理，得到混合物一。
(8)将步骤(7)所得混合物一以质量比1：2与无水乙醇混合并搅拌均匀，密封于230℃下进行溶剂热处理，处理时间24小时。冷却至室温后，离心收集所得粉体，并用去离子水与无水乙醇各清洗8次，烘干后得到粉体一。
(9)将步骤(8)所得粉体一与过硫酸铵以质量比10：1均匀混合后，密封，并升温至175℃，保温15小时。冷却至室温后，将所得混合粉体用去离子水清洗10次，烘干后得到粉体二。
(10)将步骤(4)所得粉体二放入坩埚，以3℃/分钟的升温速率升温至1700℃，保温9小时；冷却至室温后，得到高导电A位高熵纳米(Gd 0.4Er 0.3La 0.4Nd 0.5Y 0.4)(Zr 0.7,Sn 0.8,V 0.5)O 7金属氧化物。
经电镜观测，所得高导电A位高熵纳米金属氧化物呈粉体状，其微观结构为边长12nm左右，厚度3nm左右的正方形纳米片。
取产品粉体，用粉末压片机以550MPa的压强将粉体压成片，采用四探针法对其进行电导率测试，该产品的电导率为7.3×10 8S/m。
实施例3:
提供的一种高导电A位高熵纳米(Gd 0.4Er 0.3La 0.4Nd 0.5Y 0.4)(Zr 0.7,Sn 0.8,V 0.5)O 7金属氧化物的制备方法，包括如下步骤：
(1)按摩尔比0.4∶0.3∶0.4：0.5：0.4：0.7：0.8：0.5取Gd(NO 3) 3，Er(NO 3) 3，La(NO 3) 3，Nd(NO 3) 3，Y(NO 3) 3，ZrOSO 4，SnCl 4，NH 4VO 3加至去离子水/无水乙醇/四氢呋喃质量比为0.3：3：0.5的混合溶液中，并搅拌15分钟，得到混合液一；Gd(NO 3) 3，Er(NO 3) 3，La(NO 3) 3，Nd(NO 3) 3，Y(NO 3) 3，ZrOSO 4，SnCl 4，NH 4VO 3总质量与去离子水/无水乙醇/四氢呋喃(0.3：3：0.5)混合溶液质量比为12.6％。
(2)按质量比2∶0.3∶8∶0.02取对苯二胺、氢化牛脂基伯胺、山梨醇和氨基甲酰乙酸乙酯，加至正丙醇中，并搅拌2小时，得到混合液二；对苯二胺、氢化牛脂基伯胺、山梨醇和氨基甲酰乙酸乙酯的总质量与正丙醇的质量之比为7.5％；
(3)将步骤(1)所得混合液一，升温至60℃，边搅拌边超声边将步骤(2)所得混合液二以一滴/秒的速度滴加入步骤(1)所得混合液一中，滴加完成后，进一步升温至90℃并停止搅拌，保温5小时后，再降温至室温，得到混合液三。混合液一与混合液二的质量比为9：7。
(4)将混合液三加入电解池中，采用铂电极为电极，电极两端加7V电压，反应15分钟后，得到混合液四；
(5)将步骤(4)所得混合液四，边搅拌边升温至60℃，将步骤(2)所得混合液二以一滴/秒的速度滴加入步骤(4)所得混合液四中，混合液二与混合液四的质量比为1.05∶1.25；滴加完成后，搅拌条件下降温至室温，得到混合液五。
(6)采用高速剪切乳化机，以30000转/分钟速度对步骤(5)所得混合液五进行高速剪切处理，剪切时间2小时，得到混合液六。
(7)将混合液六进行冷冻干燥处理，得到混合物一。
(8)将步骤(7)所得混合物一以质量比1：2与无水乙醇混合并搅拌均匀，密封于220℃下进行溶剂热处理，处理时间21小时。冷却至室温后，离心收集所得粉体，并用去离子水与无水乙醇各清洗8次，烘干后得到粉体一。
(9)将步骤(8)所得粉体一与过硫酸铵以质量比10：1均匀混合后，密封，并升温至170℃，保温14小时。冷却至室温后，将所得混合粉体用去离子水清洗10次，烘干后得到粉体二。
(10)将步骤(4)所得粉体二放入坩埚，以3℃/分钟的升温速率升温至1600℃，保温8小时；冷却至室温后，得到高导电A位高熵纳米(Gd 0.4Er 0.3La 0.4Nd 0.5Y 0.4)(Zr 0.7,Sn 0.8,V 0.5)O 7金属氧化物。
经电镜观测，所得高导电A位高熵纳米金属氧化物呈粉体状，其微观结构为边长8nm左右，厚度2nm左右的正方形纳米片。
取产品粉体，用粉末压片机以550MPa的压强将粉体压成片，采用四探针法对其进行电导率测试，该产品的电导率为4.1×10 8S/m。
对比例1
取市售ITO(氧化铟锡)粉体，用粉末压片机以550MPa的压强将粉体压成片，采用四探针法对其进行电导率测试。
经测试，市售ITO(氧化铟锡)的电导率为1.6×10 6S/m。
对比例2
取市售(CoCrFeMnZn) 3O 4高熵氧化物粉体，用粉末压片机以550MPa的压强将粉体压成片，采用四探针法对其进行电导率测试。
经测试，市售(CoCrFeMnZn) 3O 4高熵氧化物的电导率为1.6×10 3S/m。
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。

Claims (5)

  1. 一种高导电A位高熵纳米金属氧化物，其特征在于，该金属氧化物的分子式为Gd 0.4Er 0.3La 0.4Nd 0.5Y 0.4)(Zr 0.7,Sn 0.8,V 0.5)O 7；其外观呈粉体状，微观结构显示为边长4～12nm、厚度1～3nm的正方形纳米片。
  2. 权利要求1所述高导电A位高熵纳米金属氧化物的制备方法，其特征在于，包括以下步骤：
    (1)按摩尔比0.4∶0.3∶0.4∶0.5∶0.4∶0.7∶0.8∶0.5取Gd(NO 3) 3、Er(NO 3) 3、La(NO 3) 3、Nd(NO 3) 3、Y(NO 3) 3、ZrOSO 4、SnCl 4和NH 4VO 3作为溶质，按质量比0.3∶3∶0.5取去离子水、无水乙醇和四氢呋喃混匀制成溶剂；将溶质加入溶剂中，溶质的总质量与溶剂的质量比为12.6％；搅拌5～15分钟，得到混合液一，备用；
    (2)按质量比1～3∶0.2～0.4∶7～9∶0.01～0.03取对苯二胺、氢化牛脂基伯胺、山梨醇和氨基甲酰乙酸乙酯作为溶质，加至正丙醇中；溶质的总质量与正丙醇的质量之比为7.5％；搅拌1～3小时，得到混合液二，备用；
    (3)按质量比10～8∶4～6取混合液一和混合液二；将混合液一升温至50～70℃，在搅拌和超声条件下，将混合液二滴加至混合液一中；滴加完成后，进一步升温至85～95℃；停止搅拌并保温3～7小时，然后降温至室温，得到混合液三；
    (4)将混合液三加入电解池中，采用铂电极为电极，电极两端加3～7V电压，反应13～17分钟后，得到混合液四；
    (5)在搅拌条件下将混合液四升温至55～65℃，另取一份混合液二将其滴加至混合液四中，混合液二与混合液四的质量比为1.05∶1.25；滴加完成后，在搅拌条件下降温至室温，得到混合液五；
    (6)以剪切乳化机对混合液五进行剪切处理，得到混合液六；
    (7)将混合液六进行冷冻干燥处理，得到混合物一；
    (8)按质量比1∶2将混合物一与无水乙醇混合，搅拌均匀后，在密闭条件和210～230℃下进行溶剂热处理，处理时间18～24小时；冷却至室温后，离心收集所得粉体，并用去离子水与无水乙醇各清洗8次，烘干后得到粉体一；
    (9)按质量比10∶1取粉体一与过硫酸铵，混合均匀后，在密闭条件下升温至165℃～175℃，保温13～15小时；冷却至室温后，将所得混合粉体用去离子水清洗10次，烘干后得到粉体二；
    (10)将粉体二放入坩埚，升温至1500℃～1700℃，保温7～9小时；冷却至室温后，得到高导电A位高熵纳米金属氧化物。
  3. 根据权利要求1所述的方法，其特征在于，所述步骤(3)、(5)中，滴加速度控制在1滴/秒。
  4. 根据权利要求1所述的方法，其特征在于，所述步骤(6)中，剪切乳化机的转速为20000～40000转/分钟，剪切处理时间1～3小时。
  5. 根据权利要求1所述的方法，其特征在于，所述步骤(10)中，升温速率为3℃/分钟。
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115432740A (zh) * 2022-08-31 2022-12-06 上海旦元新材料科技有限公司 一种高熵氧化物纳米颗粒单层超晶格的制备方法
CN116023140A (zh) * 2023-01-03 2023-04-28 中国科学院新疆理化技术研究所 基于高熵稀土锡酸盐的氧不敏感型负温度系数热敏材料
CN116143173A (zh) * 2023-01-04 2023-05-23 浙江大学 一种面内零空位缺陷高熵纳米片及其制备方法
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Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160201169A1 (en) * 2015-01-09 2016-07-14 Scoperta, Inc. High entropy alloys with non-high entropy second phases
CN109762519A (zh) * 2019-03-06 2019-05-17 武汉理工大学 高熵合金/氧化物复合纳米吸波材料的制备方法
CN110190259A (zh) * 2019-06-12 2019-08-30 四川大学 一种纳米高熵氧化物的制备方法及锂离子电池负极材料
CN111533557A (zh) * 2020-03-27 2020-08-14 东华大学 一种焦绿石型高熵氧化物固化体及其制备方法
CN111763087A (zh) * 2020-06-29 2020-10-13 西安交通大学 一系列立方萤石型高熵铈氧化物纳米粉体及其制备方法
CN111807418A (zh) * 2020-06-24 2020-10-23 浙江大学 一种非晶态高电导四元金属氮化物及其制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109607615B (zh) * 2019-01-25 2023-06-06 东北大学秦皇岛分校 一种b位高熵钙钛矿氧化物及其制备方法
CN110373596B (zh) * 2019-07-08 2021-05-25 南京工程学院 一种岛状磁晶结构的软磁高熵合金材料及其制备方法
CN112941396B (zh) * 2019-07-29 2022-05-17 南京工业大学 高熵合金纳米框架及其制备方法
CN110592411B (zh) * 2019-09-30 2020-11-24 广东省智能制造研究所 合金构件及其制备方法
CN111441026A (zh) * 2020-05-14 2020-07-24 南京工业大学 一种双相结构高熵合金的制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160201169A1 (en) * 2015-01-09 2016-07-14 Scoperta, Inc. High entropy alloys with non-high entropy second phases
CN109762519A (zh) * 2019-03-06 2019-05-17 武汉理工大学 高熵合金/氧化物复合纳米吸波材料的制备方法
CN110190259A (zh) * 2019-06-12 2019-08-30 四川大学 一种纳米高熵氧化物的制备方法及锂离子电池负极材料
CN111533557A (zh) * 2020-03-27 2020-08-14 东华大学 一种焦绿石型高熵氧化物固化体及其制备方法
CN111807418A (zh) * 2020-06-24 2020-10-23 浙江大学 一种非晶态高电导四元金属氮化物及其制备方法
CN111763087A (zh) * 2020-06-29 2020-10-13 西安交通大学 一系列立方萤石型高熵铈氧化物纳米粉体及其制备方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115432740A (zh) * 2022-08-31 2022-12-06 上海旦元新材料科技有限公司 一种高熵氧化物纳米颗粒单层超晶格的制备方法
CN115432740B (zh) * 2022-08-31 2024-03-01 上海旦元新材料科技有限公司 一种高熵氧化物纳米颗粒单层超晶格的制备方法
CN116023140A (zh) * 2023-01-03 2023-04-28 中国科学院新疆理化技术研究所 基于高熵稀土锡酸盐的氧不敏感型负温度系数热敏材料
CN116023140B (zh) * 2023-01-03 2023-08-22 中国科学院新疆理化技术研究所 基于高熵稀土锡酸盐的氧不敏感型负温度系数热敏材料
CN116143173A (zh) * 2023-01-04 2023-05-23 浙江大学 一种面内零空位缺陷高熵纳米片及其制备方法
CN117105288A (zh) * 2023-10-25 2023-11-24 河南师范大学 一种高熵钒基氧化物材料的制备方法及应用

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