CN114763265B - Rare earth doped MXene microsphere and preparation method thereof - Google Patents

Rare earth doped MXene microsphere and preparation method thereof Download PDF

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CN114763265B
CN114763265B CN202110042185.2A CN202110042185A CN114763265B CN 114763265 B CN114763265 B CN 114763265B CN 202110042185 A CN202110042185 A CN 202110042185A CN 114763265 B CN114763265 B CN 114763265B
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rare earth
mxene
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complexing agent
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CN114763265A (en
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王钰
任富强
刘静静
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Institute of Process Engineering of CAS
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/921—Titanium carbide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/949—Tungsten or molybdenum carbides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • C01P2006/21—Attrition-index or crushing strength of granulates
    • 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

Abstract

The invention provides a rare earth doped MXene microsphere and a preparation method thereof, wherein the preparation method comprises the following steps: mixing rare earth metal oxide, an ammonia carboxyl complexing agent and water to carry out a complexing reaction to obtain a complex solution; mixing the complex solution with MXene powder, spray drying and forming to obtain the rare earth doped MXene microsphere. According to the method, rare earth is introduced into the complexing agent and then mixed with the MXene powder, so that the dispersibility of the rare earth in the complexing agent and the dispersibility of the rare earth in the MXene powder as a whole are improved, the interfacial bonding property of the rare earth and the MXene powder is improved, and the strength and the conductivity of the material are enhanced; the method has the advantages of simple process, wide raw material sources, low cost, energy conservation, environmental protection and wide industrial application prospect.

Description

Rare earth doped MXene microsphere and preparation method thereof
Technical Field
The invention belongs to the technical field of two-dimensional material preparation, and relates to a rare earth doped MXene microsphere and a preparation method thereof.
Background
MXene is used as a novel transition metal carbide, nitride or carbonitride with a two-dimensional structure, is a graphene-like two-dimensional material discovered in recent years, and has wide application prospect in the field of metal reinforced phase materials due to ultrahigh volume specific capacity, metal-level conductivity, excellent mechanical properties, good hydrophilicity and rich surface chemistry. However, as the micro-morphology of the MXene is assembled into the macro-morphology which can be used practically, the two-dimensional sheets are easy to stack to form a high-density lamellar structure, thereby causing serious attenuation of the mechanical properties of the metal material. In addition, the introduction of a ceramic phase into a metal material inevitably reduces the conductivity of the metal material, and how to improve the strength of the metal material without sacrificing the conductivity of the metal material is a difficulty of current researches.
The rare earth element has a series of characteristics of strong chemical activity, large atomic radius, easy doping with other metal ions and nonmetal ions, and the like, and is often used as a doping element or a composite material component to prepare a high-performance material. CN 111472033a discloses a method for preparing an MXene reinforced aluminum alloy wire with a composite coating, which comprises mixing an MXene nano-sheet with aluminum alloy powder, performing extrusion molding densification treatment to obtain an MXene reinforced aluminum alloy wire matrix, configuring a plasma auxiliary micro-arc induction electrolyte, and forming a super-hydrophobic composite coating on the surface of the MXene reinforced aluminum alloy wire matrix by using the plasma auxiliary micro-arc induction for one step to obtain the MXene reinforced aluminum alloy wire with the composite coating; the obtained material has the defects of complex process, MXene nano sheet stacking, narrow application range and the like although the mechanical property and the conductivity are good.
CN 105536834a discloses a method for preparing ceria/two-dimensional layered titanium carbide composite material by precipitation method, which comprises: high purity ternary layered Ti 3 AlC 2 High-energy ball milling of powder to refine grains; two-dimensional layered nanomaterial MXene-Ti 3 C 2 Is prepared by hydrofluoric acid corrosion; precipitation of MXene-Ti 3 C 2 CeO formation between surfaces and layers 2 Make it carry MXene-Ti 3 C 2 Obtaining CeO 2 /MXene-Ti 3 C 2 A nanocomposite; the method is to compound the MXene two-dimensional material and the rare earth metal oxide to prepare the composite material, the dispersion uniformity is still to be improved, and the doping application of the rare earth metal is not involved.
In summary, for the application of MXene, a suitable method is also needed to modify it and regulate the structure to improve the mechanical and electrical properties thereof, and at the same time, simplify the preparation method thereof, thereby meeting the needs of industrial application.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a rare earth doped MXene microsphere and a preparation method thereof, wherein rare earth elements are introduced into a complexing agent through a complexing reaction, so that high dispersibility of the rare earth doped MXene powder is realized, and interface binding property of the rare earth and the MXene powder is improved, thereby improving strength and conductivity of the MXene microsphere and expanding application range of the MXene microsphere.
To achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a method for preparing rare earth doped MXene microspheres, which comprises the following steps:
(1) Mixing rare earth metal oxide, an ammonia carboxyl complexing agent and water to carry out a complexing reaction to obtain a complex solution;
(2) And (3) mixing the complex solution obtained in the step (1) with MXene powder, spray-drying and forming to obtain the rare earth doped MXene microsphere.
In the invention, the rare earth element of the MXene powder is doped for modification, and in view of the poor dispersibility of the rare earth element and weak bonding effect with the MXene powder in the existing modification mode, the rare earth is firstly subjected to complexation reaction and introduced into an aminocarboxylic complexing agent, so that the dispersibility of the rare earth in the complexing agent and the dispersibility of the rare earth in the MXene powder as a whole can be improved, the reactivity of the rare earth after complexation with the MXene powder is enhanced, the interface bonding property with the MXene powder is improved, the strength, the sphericity and the particle size of the MXene microsphere after rare earth doping are enhanced, the conductivity is improved, the mechanical property and the electrical property are obviously improved, and the application prospect is better.
The following technical scheme is a preferred technical scheme of the invention, but is not a limitation of the technical scheme provided by the invention, and the technical purpose and beneficial effects of the invention can be better achieved and realized through the following technical scheme.
As a preferred embodiment of the present invention, the rare earth metal oxide in step (1) includes any one or a combination of at least two of yttrium oxide, lanthanum oxide, or cerium oxide, and typical but non-limiting examples of the combination are: yttrium oxide and lanthanum oxide, lanthanum oxide and cerium oxide, and yttrium oxide, lanthanum oxide and cerium oxide.
Preferably, the aminocarboxylic complexing agent of step (1) comprises any one or a combination of at least two of ethylenediamine tetraacetic acid, cyclohexanediamine tetraacetic acid or triethylenetetramine hexaacetic acid, typical but non-limiting examples of such combinations being: combinations of ethylenediamine tetraacetic acid and cyclohexanediamine tetraacetic acid, combinations of cyclohexanediamine tetraacetic acid and triethylenetetramine hexaacetic acid, combinations of ethylenediamine tetraacetic acid, cyclohexanediamine tetraacetic acid and triethylenetetramine hexaacetic acid, and the like.
Preferably, the mixing sequence of the rare earth metal oxide, the aminocarboxylic complexing agent and the water in the step (1) is as follows: firstly, the ammonia-carboxyl complexing agent is heated and dispersed in water to obtain an ammonia-carboxyl complexing agent aqueous solution, and then rare earth metal oxide is added.
Preferably, the heating and dispersing time is 20 to 45min, for example, 20min, 25min, 30min, 35min, 40min or 45min, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the concentration of the aqueous solution of the aminocarboxylic complexing agent is 0.1 to 5.0wt%, for example 0.1wt%, 0.5wt%, 1.0wt%, 2.0wt%, 3.0wt%, 4.0wt% or 5.0wt%, etc., but is not limited to the recited values, and other non-recited values within this range are equally applicable.
In the invention, the complexing reaction mainly comprises the complexing reaction of rare earth oxide and an aminocarboxylic complexing agent, and the complexing reaction can generate an organic metal compound; and then mixing and granulating the organic metal compound and the MXene, coating rare earth elements on the surface of the MXene, improving the strength and sphericity of the MXene microsphere after rare earth doping, and improving the conductivity of the material.
In a preferred embodiment of the present invention, the temperature of the complexing reaction in the step (1) is 60 to 90 ℃, for example 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃, but the complexing reaction is not limited to the values listed, and other values not listed in the range of the values are equally applicable.
Preferably, the time of the complexing reaction in step (1) is 1 to 10 hours, for example 1 hour, 2 hours, 4 hours, 6 hours, 8 hours or 10 hours, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the heating mode of the complexing reaction in the step (1) is microwave heating, the heating power is 10 to 90W, for example, 10W, 20W, 30W, 40W, 50W, 60W, 80W or 90W, but the heating mode is not limited to the listed values, and other non-listed values in the range of the values are equally applicable; the frequency of the microwave is 1000 to 4000MHz, for example, 1000MHz, 1500MHz, 2000MHz, 2500MHz, 3000MHz, 3500MHz, 4000MHz, etc., but not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
In the invention, the heat of the complexation reaction is provided by utilizing microwave heating, the accurate control of the complexation reaction is realized by regulating and controlling the frequency and the temperature of the microwaves, and the process is simple.
Preferably, the solids content of the complex solution of step (1) is 0.1 to 5.0wt%, e.g. 0.1wt%, 0.5wt%, 1.0wt%, 2.0wt%, 3.0wt%, 4.0wt% or 5.0wt%, etc., but is not limited to the recited values, other non-recited values within this range of values are equally applicable.
As a preferable technical scheme of the invention, the MXene powder in the step (2) is obtained by acid etching of MAX powder.
Preferably, the acid comprises hydrofluoric acid, the mass fraction of which is 5 to 60wt%, such as 5wt%, 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, or 60wt%, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the MXene powder has a two-dimensional sheet structure, and the number of layers is 1 to 10, for example, 1, 3, 5, 6, 8, or 10 layers, but the present invention is not limited to the listed values, and other values not listed in the range of the values are equally applicable.
Preferably, the MAX powder is prepared by mixing metal and metal carbide and sintering.
Preferably, the metal comprises a transition metal and a main group element.
Preferably, the transition metal comprises any one of titanium, chromium, niobium or molybdenum, and the main group element comprises aluminum or silicon.
Preferably, the metal carbide is a carbide of the corresponding transition metal, preferably titanium carbide.
In the invention, the metal carbide can be replaced by a simple carbon material, such as graphene, and is mixed with the selected metal and sintered to prepare MAX powder.
Preferably, the mixing mode is mechanical mixing, and the mixing time is 10 to 120min, for example, 10min, 30min, 45min, 60min, 75min, 90min, 100min, 120min, etc., but the mixing mode is not limited to the listed values, and other non-listed values in the range of the values are equally applicable.
Preferably, the sintering temperature is 1300 to 1500 ℃, for example 1300 ℃, 1350 ℃, 1400 ℃, 1450 ℃, 1500 ℃, or the like, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the sintering time is 2 to 6 hours, for example, 2 hours, 3 hours, 4 hours, 5 hours, or 6 hours, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the sintering is protected by an inert gas.
As a preferable technical scheme of the invention, the MAX powder is obtained by crushing after the sintering is completed.
The particle size of the MAX powder is preferably 0.1 to 30 μm, for example, 0.1 μm, 0.5 μm, 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, etc., but the MAX powder is not limited to the listed values, and other non-listed values within the range are equally applicable.
As a preferable technical scheme of the invention, the complex solution in the step (2) is mechanically stirred and mixed with MXene powder to obtain mixed slurry.
Preferably, the mechanical stirring and mixing time is 3 to 30min, for example, 3min, 5min, 10min, 15min, 20min, 25min, 30min, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the solids content of the mixed slurry is 0.1 to 10.0wt%, such as 0.1wt%, 0.5wt%, 1.0wt%, 2.0wt%, 4.0wt%, 6.0wt%, 8.0wt%, or 10.0wt%, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the viscosity of the mixed slurry is adjusted to 100 to 300mpa·s, for example, 100mpa·s, 120mpa·s, 150mpa·s, 180mpa·s, 200mpa·s, 240mpa·s, 270mpa·s, or 300mpa·s, etc., before the spray drying in the step (2), but the viscosity is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are similarly applicable.
As a preferred embodiment of the present invention, the gas used in the spray drying in the step (2) is supplied by a fan having a frequency of 5 to 50Hz, for example, 5Hz, 10Hz, 20Hz, 30Hz, 40Hz or 50Hz, etc., but the present invention is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
Preferably, the spray-drying temperature in the step (2) is 60 to 200 ℃, for example 60 ℃, 80 ℃, 100 ℃, 120 ℃, 150 ℃, 180 ℃, 200 ℃, or the like, but is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
Preferably, the gas flow rate of the spray drying in the step (2) is 10 to 100L/min, for example, 10L/min, 20L/min, 40L/min, 50L/min, 60L/min, 80L/min or 100L/min, etc., but the present invention is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
Preferably, the slurry flow rate of the spray drying in the step (2) is 2 to 20mL/min, for example, 2mL/min, 5mL/min, 8mL/min, 10mL/min, 12mL/min, 15mL/min, 18mL/min or 20mL/min, etc., but not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
In the invention, the MXene powder and the complex are mixed and then spray-dried for granulation molding, and the controllable preparation of the rare earth oxide doped MXene powder is realized through the regulation and control of the frequency of a fan, the spray granulation temperature, the gas flow and the liquid flow.
As a preferable technical scheme of the invention, the spray-dried formed particles in the step (2) are naturally cooled to room temperature.
Preferably, after the spray drying in the step (2), the particle diameter of the molded particles is 2 to 20. Mu.m, for example, 2 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 18 μm or 20 μm, etc., but not limited to the values listed, and other values not listed in the range are equally applicable.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Mixing rare earth metal oxide, an aminocarboxylic complexing agent and water in the following mixing sequence: firstly, heating and dispersing an ammonia carboxyl complexing agent in water for 20-45 min to obtain an ammonia carboxyl complexing agent aqueous solution with the concentration of 0.1-5.0 wt%, then adding rare earth metal oxide to carry out a complexing reaction, wherein the temperature of the complexing reaction is 60-90 ℃ and the time is 1-10 h, the heating mode of the complexing reaction is microwave heating, the heating power is 10-90W, the frequency of the microwave is 1000-4000 MHz, and the complex solution with the solid content of 0.1-5.0 wt% is obtained;
(2) Mechanically stirring and mixing the complex solution obtained in the step (1) with MXene powder for 3-30 min to obtain mixed slurry with the solid phase content of 0.1-10.0wt%, regulating the viscosity of the mixed slurry to 100-300 mPa.s, and then performing spray drying, wherein the temperature of the spray drying is 60-200 ℃, the gas is provided by a fan, the frequency of the fan is 5-50 Hz, the gas flow of the spray drying is 10-100L/min, the slurry flow is 2-20 mL/min, and the formed particles after the spray drying are naturally cooled to room temperature to obtain the rare earth doped MXene microspheres with the particle size of 2-20 mu m;
the MXene powder is obtained by etching MAX powder through hydrofluoric acid, the MAX powder is prepared by mixing metal and metal carbide and then sintering and crushing, the sintering temperature is 1300-1500 ℃, the sintering time is 2-6 h, the sintering is protected by inert gas, and the particle size of the MAX powder is 0.1-30 mu m.
On the other hand, the invention provides the rare earth doped MXene microsphere prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the method, rare earth is introduced into the complexing agent and then mixed with the MXene powder, so that the dispersibility of the rare earth in the complexing agent and the dispersibility of the rare earth in the MXene powder in the whole are improved, the interfacial bonding property of the rare earth and the MXene powder is improved, the strength and the conductivity of the material are enhanced, the conductivity can reach more than 37.6mS/m, and the compressive strength can reach more than 3.5 MPa;
(2) The method can also realize the accurate control of the reaction process, the result and the product structure through the operations of microwave heating, spray drying and the like, and the obtained product has high sphericity and uniform particle size;
(3) The method disclosed by the invention is simple in process, wide in raw material source, low in cost, energy-saving and environment-friendly, and wide in industrial application prospect.
Drawings
FIG. 1 is an SEM image of rare earth doped MXene microspheres provided in example 1 of the invention.
Detailed Description
For better illustrating the present invention, the technical scheme of the present invention is convenient to understand, and the present invention is further described in detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
The invention provides a preparation method of rare earth doped MXene microspheres, which comprises the following steps:
(1) Mixing rare earth metal oxide, an ammonia carboxyl complexing agent and water to carry out a complexing reaction to obtain a complex solution;
(2) And (3) mixing the complex solution obtained in the step (1) with MXene powder, spray-drying and forming to obtain the rare earth doped MXene microsphere.
The following are exemplary but non-limiting examples of the invention:
example 1:
the embodiment provides a preparation method of rare earth doped MXene microspheres, which comprises the following steps:
(1) Mixing yttrium oxide, ethylenediamine tetraacetic acid and deionized water in the following mixing sequence: firstly, heating and dispersing ethylenediamine tetraacetic acid in water for 30min to obtain ethylenediamine tetraacetic acid aqueous solution, then adding yttrium oxide, and carrying out a complexation reaction, wherein the temperature of the complexation reaction is 60 ℃, the heating mode is microwave heating, the heating power is 50W, the time is 5h, the microwave frequency is 2500MHz, and the complex solution with the solid content of 1.0wt% is obtained;
(2) Mechanically stirring and mixing the complex solution obtained in the step (1) with MXene powder for 10min to obtain mixed slurry with the solid content of 2.0wt%, regulating the viscosity of the mixed slurry to be 100 mPa.s, then spray-drying at 60 ℃, wherein the used gas is provided by a fan, the frequency of the fan is 10Hz, the flow rate of the spray-dried gas is 10L/min, the flow rate of the slurry is 5mL/min, and naturally cooling to room temperature to obtain rare earth doped MXene microspheres;
the MXene powder is obtained by etching MAX powder by adopting hydrofluoric acid with the mass fraction of 40wt%, the MAX powder is obtained by mechanically mixing titanium powder, aluminum powder and titanium carbide for 30min, sintering for 4h in argon atmosphere at 1300 ℃, and crushing, and the average particle size of the MAX powder is 0.5 mu m.
The rare earth doped MXene microspheres were characterized by Scanning Electron Microscopy (SEM), and their SEM images are shown in FIG. 1, respectively.
In this example, as can be seen from FIG. 1, the rare earth doped MXene microsphere has a particle size of about 5 μm;
through tests, the conductivity of the rare earth doped MXene microsphere is 38mS/m, and the compressive strength is 3.5MPa.
Example 2:
the embodiment provides a preparation method of rare earth doped MXene microspheres, which comprises the following steps:
(1) Mixing lanthanum oxide, cyclohexanediamine tetraacetic acid and deionized water in the following mixing sequence: heating and dispersing cyclohexanediamine tetraacetic acid in water for 45min to obtain cyclohexanediamine tetraacetic acid aqueous solution, then adding lanthanum oxide, and carrying out a complexation reaction, wherein the temperature of the complexation reaction is 75 ℃, the heating mode is microwave heating, the heating power is 90W, the time is 2h, the microwave frequency is 4000MHz, and the complex solution with the solid content of 2.0wt% is obtained;
(2) Mechanically stirring and mixing the complex solution obtained in the step (1) with MXene powder for 30min to obtain mixed slurry with the solid content of 4.0wt%, regulating the viscosity of the mixed slurry to 200 mPa.s, then spray-drying at 100 ℃, wherein the used gas is provided by a fan, the frequency of the fan is 30Hz, the flow rate of the spray-dried gas is 40L/min, the flow rate of the slurry is 10mL/min, and naturally cooling to room temperature to obtain rare earth doped MXene microspheres;
the MXene powder is obtained by etching MAX powder by adopting hydrofluoric acid with the mass fraction of 20wt%, the MAX powder is obtained by mechanically mixing titanium powder, aluminum powder and titanium carbide for 50min, sintering for 6h in argon atmosphere at 1400 ℃, and then crushing, and the average particle size of the MAX powder is 5 mu m.
In this example, the rare earth doped MXene microspheres were tested to have a particle size of about 4 μm; the conductivity of the rare earth doped MXene microsphere is 40mS/m, and the compressive strength is 4.2MPa.
Example 3:
the embodiment provides a preparation method of rare earth doped MXene microspheres, which comprises the following steps:
(1) Mixing cerium oxide, triethylene tetramine hexaacetic acid and deionized water, wherein the mixing sequence is as follows: firstly, heating and dispersing triethylene tetramine hexaacetic acid in water for 20min to obtain a triethylene tetramine hexaacetic acid aqueous solution, then adding cerium oxide, and carrying out a complexing reaction, wherein the temperature of the complexing reaction is 90 ℃, the heating mode is microwave heating, the heating power is 30W, the time is 1h, the microwave frequency is 1000MHz, and the complex solution with the solid content of 5.0wt% is obtained;
(2) Mechanically stirring and mixing the complex solution obtained in the step (1) with MXene powder for 15min to obtain mixed slurry with the solid content of 10.0wt%, regulating the viscosity of the mixed slurry to 300 mPa.s, then spray-drying at 200 ℃, wherein the used gas is provided by a fan, the frequency of the fan is 50Hz, the flow rate of the spray-dried gas is 80L/min, the flow rate of the slurry is 20mL/min, and naturally cooling to room temperature to obtain rare earth doped MXene microspheres;
the MXene powder is obtained by etching MAX powder by adopting hydrofluoric acid with the mass fraction of 50wt%, the MAX powder is obtained by mechanically mixing titanium powder, aluminum powder and titanium carbide for 90min, sintering for 2h in neon atmosphere at 1500 ℃, and then crushing, and the average particle size of the MAX powder is 10 mu m.
In this example, the rare earth doped MXene microspheres were tested to have a conductivity of 41.4mS/m and a compressive strength of 5.2MPa.
Example 4:
the embodiment provides a preparation method of rare earth doped MXene microspheres, which comprises the following steps:
(1) Lanthanum oxide, cerium oxide, ethylenediamine tetraacetic acid and deionized water are mixed in the following mixing sequence: firstly, heating and dispersing ethylenediamine tetraacetic acid in water for 40min to obtain ethylenediamine tetraacetic acid aqueous solution, then adding lanthanum oxide and cerium oxide with the mass ratio of 1:1, and carrying out complexation reaction, wherein the temperature of the complexation reaction is 80 ℃, the heating mode is microwave heating, the heating power is 70W, the time is 4h, the microwave frequency is 3000MHz, and the complex solution with the solid content of 4.0wt% is obtained;
(2) Mechanically stirring and mixing the complex solution obtained in the step (1) with MXene powder for 5min to obtain mixed slurry with the solid content of 6.0wt%, regulating the viscosity of the mixed slurry to 150 mPa.s, then spray-drying at 150 ℃, wherein the used gas is provided by a fan, the frequency of the fan is 20Hz, the flow rate of the spray-dried gas is 60L/min, the flow rate of the slurry is 8mL/min, and naturally cooling to room temperature to obtain rare earth doped MXene microspheres;
the MXene powder is obtained by etching MAX powder by adopting hydrofluoric acid with the mass fraction of 30wt%, the MAX powder is obtained by mechanically mixing molybdenum powder, aluminum powder and graphene for 60min, sintering for 5h in argon atmosphere at 1350 ℃, and crushing, and the average particle size of the MAX powder is 15 mu m.
In this example, the rare earth doped MXene microspheres were tested to have a conductivity of 38.9mS/m and a compressive strength of 4.7MPa.
Example 5:
the embodiment provides a preparation method of rare earth doped MXene microspheres, which comprises the following steps:
(1) Mixing lanthanum oxide, ethylenediamine tetraacetic acid, cyclohexanediamine tetraacetic acid and deionized water in the following mixing sequence: firstly, heating and dispersing ethylenediamine tetraacetic acid and cyclohexanediamine tetraacetic acid with the volume ratio of 1:1 in water for 30min to obtain an organic polymer aqueous solution, then adding lanthanum oxide, and carrying out a complexation reaction, wherein the temperature of the complexation reaction is 70 ℃, the heating mode is microwave heating, the heating power is 40W, the time is 8h, the microwave frequency is 1800MHz, and a complex solution with the solid content of 0.5wt% is obtained;
(2) Mechanically stirring and mixing the complex solution obtained in the step (1) with MXene powder for 15min to obtain mixed slurry with the solid content of 1.0wt%, regulating the viscosity of the mixed slurry to 250 mPa.s, then spray-drying at 120 ℃, wherein the used gas is provided by a fan, the frequency of the fan is 40Hz, the flow rate of the spray-dried gas is 30L/min, the flow rate of the slurry is 3mL/min, and naturally cooling to room temperature to obtain rare earth doped MXene microspheres;
the MXene powder is obtained by etching MAX powder by adopting hydrofluoric acid with the mass fraction of 10wt%, the MAX powder is obtained by mechanically mixing titanium powder, silicon powder and graphene for 10min, then sintering the mixture for 3h in argon atmosphere at 1450 ℃, and then crushing the mixture, and the average particle size of the MAX powder is 2 mu m.
In this example, the rare earth doped MXene microspheres were tested to have a conductivity of 37.6mS/m and a compressive strength of 4.6MPa.
Comparative example 1:
this comparative example provides a method for preparing rare earth doped MXene microspheres, which is different from the method of example 1 only in that: the step (1) is not included, namely, the yttrium oxide does not undergo complexation reaction, and the yttrium oxide is directly dispersed and then mixed with the MXene powder.
In this comparative example, since the rare earth metal doped with the MXene powder was not added with the complexing agent, the dispersibility of the rare earth in the MXene powder was not good, and the bonding effect between the rare earth and the MXene powder was also not facilitated, thereby affecting the strength of the obtained material, and the compressive strength was only 2.8MPa, and the conductivity was also affected by the improvement of the conductivity due to the poor dispersibility of the rare earth metal, which was measured under the same conditions as in example 1, at which time the conductivity of the material was only 33.1mS/m.
It can be seen from the above examples and comparative examples that the method of the invention promotes the improvement of the dispersibility of the rare earth in the complexing agent and the whole of the complexing agent in the MXene powder by introducing the rare earth into the complexing agent and then mixing with the MXene powder, thereby being beneficial to improving the interfacial bonding property of the rare earth and the MXene powder, enhancing the strength and the conductivity of the material, having the conductivity of more than 37.6mS/m and the compressive strength of more than 3.5 MPa; the method has the advantages of simple process, wide raw material sources, low cost, energy conservation, environmental protection and wide industrial application prospect.
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions for the method of the present invention, addition of auxiliary steps, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.

Claims (32)

1. The preparation method of the rare earth doped MXene microsphere is characterized by comprising the following steps of:
(1) Mixing rare earth metal oxide, an ammonia carboxyl complexing agent and water to perform a complexing reaction, wherein the temperature of the complexing reaction is 60-90 ℃, the heating mode of the complexing reaction is microwave heating, the heating power is 10-90W, and the frequency of microwaves is 1000-4000 MHz, so as to obtain a complex solution;
(2) Mixing the complex solution obtained in the step (1) with MXene powder, spray-drying and forming, wherein the spray-drying temperature is 60-200 ℃, and the flow rate of the spray-dried slurry is 2-20 mL/min, so as to obtain the rare earth doped MXene microsphere.
2. The method of claim 1, wherein the rare earth metal oxide of step (1) comprises any one or a combination of at least two of yttria, lanthana, and ceria.
3. The method of claim 1, wherein the aminocarboxylic complexing agent of step (1) comprises any one or a combination of at least two of ethylenediamine tetraacetic acid, cyclohexanediamine tetraacetic acid, or triethylenetetramine hexaacetic acid.
4. The method of claim 1, wherein the mixing sequence of the rare earth metal oxide, the aminocarboxylic complexing agent and the water in step (1) is: firstly, the ammonia-carboxyl complexing agent is heated and dispersed in water to obtain an ammonia-carboxyl complexing agent aqueous solution, and then rare earth metal oxide is added.
5. The method according to claim 4, wherein the time for heat dispersion is 20 to 45 minutes.
6. The method according to claim 4, wherein the concentration of the aqueous solution of the aminocarboxylic complexing agent is 0.1 to 5.0wt%.
7. The method according to claim 1, wherein the time of the complexing reaction in the step (1) is 1 to 10 hours.
8. The process according to claim 1, wherein the complex solution of step (1) has a solids content of 0.1 to 5.0wt%.
9. The method of claim 1, wherein the MXene powder of step (2) is obtained from MAX powder by acid etching.
10. The preparation method according to claim 9, wherein the acid comprises hydrofluoric acid, and the mass fraction of the acid is 5-60 wt%.
11. The preparation method according to claim 1, wherein the MXene powder has a two-dimensional lamellar structure, and the number of layers is 1-10.
12. The method according to claim 9, wherein the MAX powder is prepared by mixing and sintering a metal and a metal carbide.
13. The method of claim 12, wherein the metal comprises a transition metal and a main group element.
14. The method of claim 13, wherein the transition metal comprises any one of titanium, chromium, niobium, or molybdenum, and the main group element comprises aluminum or silicon.
15. The method of claim 14, wherein the metal carbide is a carbide of a corresponding transition metal.
16. The method of claim 15, wherein the metal carbide is titanium carbide.
17. The method according to claim 12, wherein the mixing is mechanical mixing for a period of 10 to 120 minutes.
18. The method of claim 12, wherein the sintering temperature is 1300-1500 ℃.
19. The method of claim 12, wherein the sintering time is 2 to 6 hours.
20. The method of claim 12, wherein the sintering is protected by an inert gas.
21. The method according to claim 12, wherein the MAX powder is obtained by crushing after the sintering.
22. The method according to claim 21, wherein the MAX powder has a particle size of 0.1 to 30 μm.
23. The method according to claim 1, wherein the complex solution of step (2) is mechanically stirred and mixed with MXene powder to obtain a mixed slurry.
24. The method of claim 23, wherein the mechanical agitation is performed for a period of 3 to 30 minutes.
25. The method of claim 23, wherein the mixed slurry has a solids content of 0.1 to 10.0wt%.
26. The method according to claim 23, wherein the viscosity of the mixed slurry is adjusted to 100 to 300 mPa-s before the spray-drying in step (2).
27. The method according to claim 1, wherein the gas used for spray drying in the step (2) is supplied by a fan having a frequency of 5 to 50Hz.
28. The method according to claim 1, wherein the spray-drying gas flow rate in the step (2) is 10 to 100L/min.
29. The method of claim 1, wherein the spray-dried shaped particles of step (2) are naturally cooled to room temperature.
30. The method according to claim 1, wherein the rare earth doped MXene microsphere in step (2) has a particle size of 2 to 20 μm.
31. The preparation method according to claim 1, characterized in that the preparation method comprises the steps of:
(1) Mixing rare earth metal oxide, an aminocarboxylic complexing agent and water in the following mixing sequence: firstly, heating and dispersing an ammonia carboxyl complexing agent in water for 20-45 min to obtain an ammonia carboxyl complexing agent aqueous solution with the concentration of 0.1-5.0 wt%, then adding rare earth metal oxide to carry out a complexing reaction, wherein the temperature of the complexing reaction is 60-90 ℃ and the time is 1-10 h, the heating mode of the complexing reaction is microwave heating, the heating power is 10-90W, the frequency of the microwave is 1000-4000 MHz, and the complex solution with the solid content of 0.1-5.0 wt% is obtained;
(2) Mechanically stirring and mixing the complex solution obtained in the step (1) with MXene powder for 3-30 min to obtain mixed slurry with the solid content of 0.1-10.0wt%, regulating the viscosity of the mixed slurry to 100-300 mPa.s, and then performing spray drying, wherein the temperature of the spray drying is 60-200 ℃, the gas is provided by a fan, the frequency of the fan is 5-50 Hz, the gas flow of the spray drying is 10-100L/min, the slurry flow is 2-20 mL/min, and the molded particles after the spray drying are naturally cooled to room temperature to obtain the rare earth doped MXene microspheres with the particle size of 2-20 mu m;
the MXene powder is obtained by etching MAX powder through hydrofluoric acid, the MAX powder is prepared by mixing metal and metal carbide and then sintering and crushing, the sintering temperature is 1300-1500 ℃, the sintering time is 2-6 h, the sintering is protected by inert gas, and the particle size of the MAX powder is 0.1-30 mu m.
32. A rare earth doped MXene microsphere prepared by the method of any one of claims 1-31.
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CN105536834A (en) * 2015-12-09 2016-05-04 陕西科技大学 Method for preparing cerium dioxide/two-dimensional layered titanium carbide composite material through precipitation process
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