CN109592684B - Petal spherical titanium carbide Ti3C2Mxene and preparation method and application thereof - Google Patents

Petal spherical titanium carbide Ti3C2Mxene and preparation method and application thereof Download PDF

Info

Publication number
CN109592684B
CN109592684B CN201811546933.5A CN201811546933A CN109592684B CN 109592684 B CN109592684 B CN 109592684B CN 201811546933 A CN201811546933 A CN 201811546933A CN 109592684 B CN109592684 B CN 109592684B
Authority
CN
China
Prior art keywords
titanium carbide
petal
spherical titanium
alc
powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811546933.5A
Other languages
Chinese (zh)
Other versions
CN109592684A (en
Inventor
高发明
宋丹丹
栾孙锐
杨兵义
李岩
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yanshan University
Original Assignee
Yanshan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yanshan University filed Critical Yanshan University
Priority to CN201811546933.5A priority Critical patent/CN109592684B/en
Publication of CN109592684A publication Critical patent/CN109592684A/en
Application granted granted Critical
Publication of CN109592684B publication Critical patent/CN109592684B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C01B32/921—Titanium carbide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33—Electric or magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
    • 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
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/45—Aggregated particles or particles with an intergrown morphology
    • 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
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • 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
    • C01P2004/64—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
    • C01P2006/12—Surface area
    • 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
    • C01P2006/16—Pore diameter
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Catalysts (AREA)

Abstract

The invention belongs to the technical field of material preparation, and particularly relates to petal spherical titanium carbide and a preparation method and application thereof. The petal spherical titanium carbide provided by the invention is composed of nanosheets with the thickness of 20-30 nm; the petal spherical titanium carbide is provided with pores, and the pore diameter of the pores is 20-50 nm; the petal spherical titanium carbide has a particle size of 200-300 nm. The titanium carbide provided by the invention has a petal spherical structure formed by ultrathin nanosheets, so that the titanium carbide has an excellent nanometer effect and a larger specific surface area, and the electrochemical performance of the material is improved.

Description

Petal spherical titanium carbide Ti3C2Mxene and preparation method and application thereof
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to petal spherical titanium carbide and a preparation method and application thereof.
Background
Since the successful exfoliation of graphene by Novoselov and geom and co-workers in 2004, the research of two-dimensional materials has entered a period of rapid development. Meanwhile, the graphene-like material greatly enriches two-dimensional material families, such as two-dimensional transition metal carbides or carbonitrides (MXenes), black phosphorus, metal organic framework Materials (MOFs), covalent organic framework materials (COFs), polymers, silylene, antimonene, inorganic perovskite and organic-inorganic mixed perovskite and the like.
MXenes is a two-dimensional layered transition metal carbide or nitride, and the compound is a novel two-dimensional material generated by selectively etching MAX phase in hydrofluoric acid solution to remove intermediate elements, wherein M is transition metal element such as Ti, Mo, Sc, Zr and the like, A is main group element (mostly Al and Si), and X is main group element such as Al and SiCarbon or nitrogen. MXenes materials are widely used in hydrogen storage and electrochemistry fields based on their unique layered structure, excellent metal conductivity, hydrophilicity, electrochemical properties and large specific surface area, for example, Ti3C2The Mxene material has a potential application prospect in the fields of hydrogen storage, lithium ion batteries, electrocatalysis, super capacitors, sensors and the like. Ti commonly used at present3C2Although the Mxene material has the characteristic of layering, when the Mxene material is used as an electrochemical material, the metal conductivity is not ideal, and the application of the material is limited.
Disclosure of Invention
The invention aims to provide petal spherical titanium carbide and a preparation method and application thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides petal spherical titanium carbide, which consists of nanosheets with the thickness of 20-30 nm; the petal spherical titanium carbide is provided with pores, and the pore diameter of the pores is 20-50 nm; the petal spherical titanium carbide has a particle size of 200-300 nm.
Preferably, the specific surface area of the petal-shaped spherical titanium carbide is 28-40 m2·g-1。
The invention provides a preparation method of petal-shaped spherical titanium carbide in the technical scheme, which comprises the following steps:
(1) under the condition of stirring, adding Ti3AlC2Adding the powder into a hydrofluoric acid solution, and etching to obtain titanium carbide;
(2) under the ultrasonic condition, stripping the titanium carbide obtained in the step (1) by using different intercalators to obtain petal-shaped spherical titanium carbide;
the intercalating agent comprises N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide or acetonitrile.
Preferably, Ti in said step (1)3AlC2The particle size of the powder is less than or equal to 300 meshes.
Preferably, the mass concentration of the hydrofluoric acid solution in the step (1) is 10-30%.
Preferably, Ti in said step (1)3AlC2The ratio of the mass of the powder to the volume of the hydrofluoric acid solution is more than or equal to 1g to 10 mL.
Preferably, Ti in said step (1)3AlC2The addition rate of the powder is 0.1-0.5 g/min.
Preferably, the etching time in the step (1) is 24-48 h.
Preferably, the power of the ultrasound in the step (2) is 180-240W; the ultrasonic time is 8-24 h.
The invention also provides application of the petal spherical titanium carbide in the technical scheme or the petal spherical titanium carbide prepared by the preparation method in the technical scheme in the fields of hydrogen storage, lithium ion batteries, electrocatalysis, supercapacitors or sensors.
The petal spherical titanium carbide provided by the invention is composed of nanosheets with the thickness of 20-30 nm; the petal spherical titanium carbide is provided with pores, and the pore diameter of the pores is 20-50 nm; the petal spherical titanium carbide has a particle size of 200-300 nm. The titanium carbide provided by the invention has a petal spherical structure formed by ultrathin nanosheets, so that the titanium carbide has an excellent nanometer effect and a larger specific surface area, and the electrochemical performance of the material is improved.
The petal-shaped spherical titanium carbide provided by the invention is obtained by respectively stripping different intercalation agents under the assistance of ultrasound, and the method is simple and easy to control and has low cost.
The petal-shaped spherical titanium carbide material provided by the invention has excellent conductivity and has application value in the fields of hydrogen storage, lithium ion batteries, electrocatalysis, supercapacitors and sensors.
Drawings
FIG. 1 is a scanning electron micrograph of titanium carbide obtained in example 1 of the present invention;
FIG. 2 is a scanning electron microscope photograph of petal-shaped spherical titanium carbide obtained in example 1 of the present invention;
FIG. 3 is a transmission electron microscope photograph of petal-shaped spherical titanium carbide obtained in example 2 of the present invention;
FIG. 4 is an X-ray diffraction chart of petal-shaped spherical titanium carbide obtained in example 3 of the present invention;
FIG. 5 is an AC impedance test chart of a petal-shaped spherical titanium carbide modified glassy carbon electrode obtained in example 3 of the present invention;
FIG. 6 is a schematic diagram of a petal-shaped spherical titanium carbide dispersion obtained in example 4 of the present invention.
Detailed Description
The invention provides petal spherical titanium carbide, which consists of nanosheets with the thickness of 20-30 nm; the petal spherical titanium carbide is provided with pores, and the pore diameter of the pores is 20-50 nm; the petal spherical titanium carbide has a particle size of 200-300 nm.
The petal spherical titanium carbide provided by the invention is composed of nanosheets with the thickness of 20-30 nm, wherein the thickness of the nanosheets is preferably 20-28 nm, and more preferably 20-25 nm; the petal spherical titanium carbide has pores, and the pore diameter of the pores is 20-50 nm, preferably 30-50 nm; the petal spherical titanium carbide has a particle size of 200-300 nm, preferably 210-280 nm, and more preferably 220-270 nm. In the invention, the nano sheets in the petal-shaped spherical titanium carbide are irregularly arranged to form a pore structure, so that the specific surface area of the petal-shaped spherical titanium carbide is increased. In the invention, the specific surface area of the petal-shaped spherical titanium carbide is preferably 28-40 m2·g-1More preferably 32 to 40m2·g-1。
The invention provides a preparation method of petal-shaped spherical titanium carbide in the technical scheme, which comprises the following steps:
(1) under the condition of stirring, adding Ti3AlC2Adding the powder into a hydrofluoric acid solution, and etching to obtain titanium carbide;
(2) under the ultrasonic condition, stripping the titanium carbide obtained in the step (1) by using different intercalators to obtain petal-shaped spherical titanium carbide;
the intercalating agent comprises N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide or acetonitrile.
The invention mixes Ti under the condition of stirring3AlC2The powder is added into a hydrofluoric acid solution,and obtaining the titanium carbide after etching.
In the present invention, the Ti is3AlC2The particle size of the powder is preferably less than or equal to 300 meshes, and more preferably 350-500 meshes. The invention is directed to the Ti3AlC2The source of the powder is not particularly limited and commercially available products well known to those skilled in the art may be used. The present invention is preferably applied to commercially available Ti3AlC2Ball milling the powder to make Ti3AlC2The particle size of the powder was homogenized. In the present invention, for commercially available Ti3AlC2When the powder is subjected to ball milling, wet milling is preferred, and a reagent used for the wet milling is preferably ethanol; when ball-milled, commercially available Ti3AlC2The volume ratio of the mass of the powder to the volume of the ethanol is preferably (5-10) g, (30-50) mL, more preferably (6-9) g, (35-45) mL; the rotation speed is preferably 300 to 450r/min, and more preferably 320 to 430 r/min; the ball milling time is preferably 2 to 4 hours, and more preferably 2.5 to 3.5 hours. Preferred for Ti in the present invention3AlC2The powder is ball-milled, so that the granularity of the powder can be refined and homogenized, the subsequent preparation time of the titanium carbide is shortened, and the electrical property of the titanium carbide material can be improved to a certain extent.
After ball milling, the slurry after ball milling is preferably washed by ethanol, and the washing frequency is preferably 3-6 times; after washing, the washed solid material is preferably dried, and the drying temperature is preferably 50-80 ℃, and more preferably 55-75 ℃; the drying time is preferably 12-24 hours, and more preferably 14-20 hours. After drying, the invention preferably screens the dried material to obtain the Ti3AlC2And (3) pulverizing. The invention has no special requirement on the mesh number of the screen mesh for sieving, and Ti with the particle size can be obtained3AlC2And (5) pulverizing.
In the present invention, the Ti is3AlC2Adding the powder into a hydrofluoric acid solution under the condition of stirring, wherein the stirring speed is preferably 200-500 r/min, more preferably 250-450 r/min, and further preferably 300-400 r/min; the addition rate is preferably 0.1 to 0.5g/min, more preferably 0.13 to 0.47g/min, and still more preferably 0.15 to 0.45 g/min.
In the present invention, the hydrogenThe mass concentration of the fluoric acid solution is preferably 10-30%, more preferably 12-28%, and still more preferably 15-25%. The source of the hydrofluoric acid is not particularly required in the present invention, and commercially available products well known to those skilled in the art may be used. In the present invention, the Ti is used in etching3AlC2The mass ratio of the powder to the hydrofluoric acid solution is preferably not less than 1 g/10 mL, more preferably (1-5) g:10mL, more preferably (1.5 to 4.5) g:10 mL. In the present invention, the etching time is selected from Ti3AlC2After the powder is added, the etching time is preferably 24-48 h, more preferably 26-45 h, and further preferably 28-42 h; in the invention, the etching process is assisted by stirring, and the stirring speed is preferably 200-500 r/min, more preferably 250-450 r/min, and still more preferably 300-400 r/min.
In the present invention, the etching refers to hydrofluoric acid and Ti3AlC2The Al in the powder reacts to generate titanium carbide. According to the invention, the etching is preferably carried out under the above conditions, so that the dissolution of titanium carbide can be avoided, the yield of the titanium carbide is improved, the defect of the titanium carbide can be eliminated, and the titanium carbide with high conductivity can be obtained.
After etching, the invention preferably washes the black solid material obtained after etching to remove the residual hydrofluoric acid and obtain pure titanium carbide. In the present invention, the washing reagent is preferably ultrapure water. The invention has no special requirement on the washing mode, and the pH value of the cleaning solution is preferably 5-6.
After titanium carbide is obtained, the method utilizes different intercalation agents to strip the titanium carbide under the ultrasonic condition, and the petal-shaped spherical titanium carbide is obtained. In the present invention, the intercalating agent comprises N, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), Dimethylsulfoxide (DMSO) or acetonitrile, more preferably N, N-dimethylformamide, N-methylpyrrolidone or dimethylsulfoxide.
In the present invention, the different intercalating agent preferably comprises two different intercalating agents. When the different intercalants are two different intercalants, the present invention defines the exfoliation process as follows: the stripping is divided into a first stripping and a second stripping which are sequentially carried out, and the intercalation agent for the first stripping is a first intercalation agent; the intercalation agent for the second stripping is a second intercalation agent.
In the invention, when the first intercalation agent is N, N-dimethylformamide, the second intercalation agent is preferably N-methylpyrrolidone, dimethyl sulfoxide or acetonitrile, and more preferably N-methylpyrrolidone or dimethyl sulfoxide;
when the first intercalating agent is N-methylpyrrolidone, the second intercalating agent is preferably N, N-dimethylformamide, dimethyl sulfoxide or acetonitrile, and more preferably N, N-dimethylformamide or dimethyl sulfoxide;
when the first intercalating agent is dimethyl sulfoxide, the second intercalating agent is preferably N, N-dimethylformamide, N-methylpyrrolidone or acetonitrile, and more preferably N, N-dimethylformamide or N-methylpyrrolidone;
when the first intercalating agent is acetonitrile, the second intercalating agent is preferably N, N-dimethylformamide, N-methylpyrrolidone, or dimethyl sulfoxide, and more preferably N, N-dimethylformamide or dimethyl sulfoxide.
In the invention, when the intercalators are two different intercalators, the volume ratio of the first intercalator to the second intercalator is 0.8-1.5: 1, and more preferably 0.9-1.3: 1.
In the invention, the ratio of the mass of the titanium carbide to the volume of the first intercalating agent in the first stripping is preferably (0.5-1.2) g:15mL, more preferably (0.6-1.1) g:15mL, and still more preferably (0.6-1.0) g:15 mL; the power of the ultrasonic wave is preferably 180-240W, and more preferably 200-220W; the ultrasonic time is preferably 8-24 h, more preferably 8-22 h, and further preferably 10-16 h; the time of the ultrasonic treatment is the time of the first stripping.
After the first stripping is completed, the invention preferably centrifuges the upper suspension after the first stripping, and alcohol washes the obtained solid material to perform the second stripping. In the invention, the rotation speed of the centrifugation is preferably 5000-8000 r/min; the alcohol washing detergent is preferably ethanol; the number of times of alcohol washing is preferably 3-6. The present invention has no special requirement on the specific cleaning mode of the alcohol washing, and the method is well known to those skilled in the art. After the alcohol washing, the dispersion liquid in the last alcohol washing is preferably centrifuged to obtain a solid after the first stripping in the present invention.
In the invention, in the second stripping, the volume ratio of the solid mass after the first stripping to the second intercalator is preferably (0.37-0.75) g:15mL, more preferably (0.45-0.75) g:15mL, and still more preferably (0.45-0.6) g:15 mL; the power of the ultrasonic wave is preferably 180-240W, and more preferably 200-220W; the ultrasonic time is preferably 8-24 h, more preferably 8-22 h, and further preferably 10-16 h; the time of the ultrasonic treatment is the time of the second stripping.
In the present invention, in the etching step, the first peeling step, and the second peeling step, the titanium carbide is inevitably lost, and therefore, the mass of the second peeled solid is less than that of the first peeled solid.
After the second stripping is completed, the upper suspension obtained after the second stripping is preferably centrifuged, and then the obtained solid material is subjected to alcohol washing. In the invention, the rotation speed of the centrifugation is preferably 5000-8000 r/min; the alcohol washing detergent is preferably ethanol; the number of times of alcohol washing is preferably 2-4 times, and more preferably 3 times; after the alcohol washing, in the present invention, it is preferable to dry the solid material obtained after the alcohol washing to obtain petal-shaped spherical titanium carbide. The invention has no special requirement on the drying mode, and can remove the washing agent for alcohol washing in the solid material.
The invention also provides application of the petal spherical titanium carbide in the technical scheme or the petal spherical titanium carbide prepared by the preparation method in the technical scheme in the fields of hydrogen storage, lithium ion batteries, electrocatalysis, supercapacitors and sensors. The invention has no special requirements on the specific application mode of the petal spherical titanium carbide in the field, and can adopt a mode which is well known by the technical personnel in the field.
For further illustration of the present invention, the following detailed description of a petal-shaped spherical titanium carbide and its preparation method and application are provided in connection with the accompanying drawings and examples, which should not be construed as limiting the scope of the present invention.
Example 1
First, 5g of Ti was purchased3AlC2The raw materials are dispersed in a ball milling tank filled with 30mL of ethanol reagent, and ball milling is carried out for 2h at the rotating speed of 350r/min, so as to obtain uniform slurry. Then, the slurry is filtered and washed by absolute ethyl alcohol for 3 times, and is dried in a vacuum oven at the temperature of 50 ℃ for 12 hours, and the ball-milled Ti is3AlC2Powder, placing in a 300-mesh screen mesh, and sieving to obtain Ti with particle size less than 300 meshes3AlC2And (3) powder. Pouring 10 percent of hydrofluoric acid solution into a plastic container at room temperature, putting a rotor, adjusting the magnetic stirring speed to 200r/min, and slowly adding 2g of ball-milled Ti within 10min3AlC2Powder of 1g of Ti with stirring3AlC2The powder corresponds to 10mL of hydrofluoric acid etching solution, and magnetic stirring is maintained for 24 h. And then, centrifugally cleaning the mixed solution in ultrapure water until the pH value of the supernatant is 5-6. Finally, washing the obtained black precipitate for 3 times by using a DMF solvent, firstly carrying out ultrasonic treatment on the obtained solid material in 15mL of DMSO for 8 hours at 200W ultrasonic power, taking an upper-layer suspension for centrifugation, carrying out centrifugal washing on the obtained solid material for 3 times by using ethanol, then carrying out ultrasonic treatment on the obtained solid material in DMF for 8 hours at 200W ultrasonic power, wherein the volume ratio of the DMSO to the DMF is 1:1, taking the upper-layer suspension for centrifugation, carrying out centrifugal washing on the obtained solid material for 3 times by using ethanol, and drying to obtain the petal spherical Ti3C2Solid of Mxene material.
Example 2
First, 5g of Ti was purchased3AlC2The raw materials are dispersed in a ball milling tank filled with 50mL of ethanol reagent, and ball milling is carried out for 3h at the rotating speed of 400r/min, so as to obtain uniform slurry. Then, the slurry is filtered and washed by absolute ethyl alcohol for 3 times, and is dried in a vacuum oven at the temperature of 80 ℃ for 12 hours, and the ball-milled Ti is3AlC2Powder, placing in a 300-mesh screen mesh, and sieving to obtain Ti with particle size less than 300 meshes3AlC2And (3) powder. Pouring 20 percent hydrofluoric acid solution into a plastic container at room temperature, putting a rotor, adjusting the magnetic stirring speed to 250r/min, and slowly adding 3g of ball-milled Ti within 15min3AlC2Powder of 1g of Ti with stirring3AlC2The powder corresponds to 10mL of hydrofluoric acid etching solution, and magnetic stirring is maintained for 36 h. And then, centrifugally cleaning the mixed solution in ultrapure water until the pH value of the supernatant is 5-6. Finally, washing the obtained black precipitate for 3 times by using absolute ethyl alcohol, firstly carrying out ultrasonic treatment on the obtained solid material in 15mL of NMP for 10h at 200W ultrasonic power, taking an upper-layer suspension for centrifugation, carrying out centrifugal washing on the obtained solid material for 4 times by using ethyl alcohol, then carrying out ultrasonic treatment on the obtained solid material in 12mL of DMSO for 10h at 200W ultrasonic power, taking an upper-layer suspension for centrifugation, carrying out centrifugal washing on the obtained solid material for 3 times by using ethyl alcohol, and drying to obtain the petal-shaped spherical Ti3C2Solid of Mxene material.
Example 3
First, 8g of Ti was purchased3AlC2And dispersing the powder into a ball milling tank filled with 50mL of ethanol reagent, and carrying out ball milling for 4h at the rotating speed of 450r/min to obtain uniform slurry. Then, the slurry was filtered and washed 5 times with anhydrous ethanol and dried in a vacuum oven at 80 ℃ for 16 hours, and the resulting Ti was obtained3AlC2Powder, placing in a 300-mesh screen mesh, and sieving to obtain Ti with particle size less than 300 meshes3AlC2And (3) powder. Pouring 10 percent of hydrofluoric acid solution into a plastic container at room temperature, putting a rotor, adjusting the magnetic stirring speed to 300r/min, and slowly adding 3g of ball-milled Ti within 10min3AlC2Powder of 1g of Ti with stirring3AlC2The powder corresponds to 10mL of hydrofluoric acid etching solution, and magnetic stirring is maintained for 24 h. And then, centrifugally cleaning the mixed solution in ultrapure water until the pH of the supernatant is 5-6. Finally, washing the obtained black precipitate for 3 times by using an NMP solvent, firstly carrying out ultrasonic treatment on the obtained solid material in 12mL of DMF for 24h at 200W ultrasonic power, taking an upper layer suspension for centrifugation, carrying out centrifugal washing on the obtained solid material for 5 times by using ethanol, then carrying out ultrasonic treatment on the obtained solid material in 15mL of NMP for 24h at 200W ultrasonic power, taking an upper layer suspension for centrifugation, carrying out centrifugal washing on the obtained solid material for 3 times by using ethanol, and drying to obtain the petal-shaped spherical Ti3C2Solid of Mxene material.
Example 4
First, 10g of Ti was purchased3AlC2And dispersing the powder into a ball milling tank filled with 30mL of ethanol reagent, and carrying out ball milling for 4h at the rotating speed of 450r/min to obtain uniform slurry. Then, the slurry was filtered and washed with anhydrous ethanol 3 times, and dried in a vacuum oven at 80 ℃ for 24 hours, and the obtained Ti was obtained3AlC2Powder, placing in a 300-mesh screen mesh, and sieving to obtain Ti with particle size less than 300 meshes3AlC2And (3) powder. At room temperature, 30 percent by mass of hydrofluoric acid solution is poured into a plastic container, a rotor is arranged, the magnetic stirring speed is adjusted to 500r/min, and then 5g of ball-milled Ti is slowly added within 15min3AlC2Powder of 1g of Ti with stirring3AlC2The powder corresponds to 10mL of hydrofluoric acid etching solution, and magnetic stirring is maintained for 48 h. Next, the mixture was centrifuged in ultrapure water and washed until the pH reached about 6. Finally, washing the obtained black precipitate for 3 times by using absolute ethyl alcohol, performing ultrasonic treatment for 16h in 30mL of acetonitrile at 200W ultrasonic power, centrifuging the upper suspension, centrifugally washing the obtained solid material for 6 times by using ethyl alcohol, further performing ultrasonic treatment for 16h in 35mL of DMSO at 200W ultrasonic power, centrifuging the upper suspension, centrifugally washing the obtained solid material for 3 times by using ethyl alcohol, and drying to obtain petal spherical Ti3C2Solid of Mxene material.
Characterization of Performance and results
And (3) characterizing the shapes of the titanium carbide and the petal spherical titanium carbide obtained in the embodiments 1-4 by using a scanning electron microscope. FIG. 1 shows the titanium carbide prepared in example 1, and it can be seen from FIG. 1 that the titanium carbide prepared in example 1 has a layered structure similar to an accordion, and the thickness of the structure is about 200 to 300 nm. FIG. 2 shows petal-shaped spherical titanium carbide prepared in example 1, and as can be seen from FIG. 2, the petal-shaped spherical titanium carbide is composed of nanosheets having a thickness of 20-30 nm, and can provide a large active surface area and abundant active sites. The test results of examples 2 to 4 are similar to those of example 1, and all are petal spherical titanium carbide.
The shapes of the petal-shaped spherical titanium carbide obtained in the embodiments 1 to 4 are characterized by using a transmission electron microscope, and as shown in fig. 3 corresponding to the petal-shaped spherical titanium carbide obtained in the embodiment 2, the material obtained in the embodiment has a flower-shaped shape formed by thin nanosheets, and the thickness of the nanosheets is 20 to 30nm as can be seen from fig. 3. The morphology of the petal spherical titanium carbide obtained in examples 1, 3 and 4 was similar to that of example 2.
Characterizing the pore structure and the specific surface area of the petal-shaped spherical titanium carbide obtained in the examples 1 to 4 by using a BET specific surface area test method/specific surface area and a pore diameter analyzer (AutosorbiQ, Congta, USA), wherein the characterization result shows that the pore diameter distribution of the petal-shaped spherical titanium carbide obtained in the examples 1 to 4 is within a range of 20-50 nm and belongs to a typical mesoporous structure; the specific surface area of each of the petal-shaped spherical titanium carbides obtained in examples 1 to 4 was about 29m2·g-1、36m2·g-1、33m2·g-1And 38m2·g-1。
The structure of the petal-shaped spherical titanium carbide obtained in examples 1 to 4 was characterized by an X-ray diffractometer. FIG. 4 is an XRD pattern of petal-shaped spherical titanium carbide obtained in example 3, in which four main characteristic diffraction peaks and Ti are respectively present in the XRD pattern3C2The (002), (004), (006) and (110) crystal faces of Mxene correspond, which indicates that the material obtained by the invention is Ti3C2Mxene (titanium carbide two-dimensional layered structure). The characterization results of examples 1, 2 and 4 all show that the material obtained by the invention is Ti3C2Mxene structure.
The petal spherical titanium carbide obtained in example 1 to 4 and absolute ethyl alcohol were mixed in the following ratio of 5mg titanium carbide: 10mL of absolute ethyl alcohol is mixed according to the mass ratio to prepare slurry, a glassy carbon electrode is modified by physical adsorption (namely, a dropping coating mode), a three-electrode system is adopted to carry out electrochemical impedance test on the modified electrode, and fig. 5 corresponds to the test result of example 3, and the petal spherical Ti can be seen from fig. 53C2In the Nyquist curve of the Mxene modified glassy carbon electrode, the diameter of a semicircle is far smaller than that of a bare glassy carbon electrode, which shows that the petal spherical Ti prepared by the method is3C2The Mxene material has excellent metal conductivity and electrochemical activity. The test results of examples 1, 2 and 4 are similar to those of example 3, and the invention provides a petal ballThe electrochemical impedance test resistance value of the titanium carbide is lower than 30 omega, and the material has excellent conductivity.
The petal spherical titanium carbide obtained in the examples 1 to 4 is dispersed in ethanol, wherein 20mg of petal spherical titanium carbide is dispersed in 30mL of ethanol in the example 1, 20mg of petal spherical titanium carbide is dispersed in 50mL of ethanol in the example 2, and 20mg of petal spherical titanium carbide is dispersed in 40mL of ethanol in the examples 3 and 4, so as to represent the dispersibility of the petal spherical titanium carbide. FIG. 6 shows the results of the test on petal-shaped spherical titanium carbide obtained in example 4, and it can be seen from FIG. 6 that the alcohol dispersion of petal-shaped spherical titanium carbide is uniformly dispersed without significant precipitation, and the dispersion is light gray; after being placed for two weeks, the petal-shaped spherical titanium carbide still has no obvious change, and the petal-shaped spherical titanium carbide provided by the invention can be massively produced. Examples 1-3 all gave, as in example 4, a light gray dispersion which was uniformly dispersed and had no significant precipitation.
According to the embodiment, the nano sheet in the petal-shaped spherical titanium carbide provided by the invention is thinner and is only 20-30 nm, the specific surface area of the material is increased, and the mesoporous structure is favorable for improving the electrochemical activity of the material, so that the petal-shaped spherical titanium carbide can be applied to the fields of hydrogen storage, lithium ion batteries, electrocatalysis, supercapacitors and sensors.
The invention adopts different organic solvents to intercalate Ti3C2And preparing petal-shaped Ti by using an ultrasonic-assisted method3C2Mxene material, increased Ti3C2The interlayer distance is long, the stripping process is more efficient, the operation steps are simple, and the cost is low; no complex equipment is needed, large-scale production can be carried out, and industrialization is realized.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.

Claims (10)

1. Petal spherical titanium carbide Ti3C2Mxene, which is formed by the thickness of 20-30 nmA nanosheet; the petal spherical titanium carbide is provided with pores, and the pore diameter of the pores is 20-50 nm; the petal spherical titanium carbide has a particle size of 200-300 nm.
2. The petal spherical titanium carbide Ti of claim 13C2Mxene is characterized in that the specific surface area of the petal spherical titanium carbide is 28-40 m2·g-1。
3. Petal spherical titanium carbide Ti as set forth in claim 1 or 23C2A process for the preparation of Mxene comprising the steps of:
(1) under the condition of stirring, adding Ti3AlC2Adding the powder into a hydrofluoric acid solution, and etching to obtain titanium carbide;
(2) under the ultrasonic condition, stripping the titanium carbide obtained in the step (1) by using different intercalators to obtain petal-shaped spherical titanium carbide;
the intercalating agent comprises N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide or acetonitrile.
4. The method according to claim 3, wherein Ti in the step (1) is used3AlC2The particle size of the powder is less than or equal to 300 meshes.
5. The method according to claim 3, wherein the hydrofluoric acid solution used in the step (1) has a concentration of 10 to 30% by mass.
6. The method according to claim 3 or 5, wherein Ti in the step (1) is used3AlC2The ratio of the mass of the powder to the volume of the hydrofluoric acid solution is more than or equal to 1g to 10 mL.
7. The method according to claim 3, 4 or 5, wherein Ti in the step (1) is used3AlC2The addition rate of the powder is 0.1-0.5 g/min.
8. The preparation method according to claim 3, 4 or 5, wherein the etching time in the step (1) is 24-48 h.
9. The preparation method according to claim 3, wherein the power of the ultrasound in the step (2) is 180 to 240W; the ultrasonic time is 8-24 h.
10. The petal spherical titanium carbide Ti as set forth in claim 1 or 23C2Mxene or petal spherical titanium carbide Ti prepared by the preparation method of any one of claims 3 to 93C2The Mxene can be applied to the fields of hydrogen storage, lithium ion batteries, electrocatalysis, supercapacitors or sensors.
CN201811546933.5A 2018-12-18 2018-12-18 Petal spherical titanium carbide Ti3C2Mxene and preparation method and application thereof Active CN109592684B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811546933.5A CN109592684B (en) 2018-12-18 2018-12-18 Petal spherical titanium carbide Ti3C2Mxene and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811546933.5A CN109592684B (en) 2018-12-18 2018-12-18 Petal spherical titanium carbide Ti3C2Mxene and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN109592684A CN109592684A (en) 2019-04-09
CN109592684B true CN109592684B (en) 2020-09-01

Family

ID=65963097

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811546933.5A Active CN109592684B (en) 2018-12-18 2018-12-18 Petal spherical titanium carbide Ti3C2Mxene and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN109592684B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110098326A (en) * 2019-05-28 2019-08-06 湖北大学 A kind of two dimension Ti3C2- MXene thin-film material and preparation method thereof and the application in resistance-variable storing device
CN110735151A (en) * 2019-06-20 2020-01-31 常州大学 Preparation method of titanium carbide composite indium zinc sulfide photo-anode
CN111816868A (en) * 2020-07-24 2020-10-23 杭州肄康新材料有限公司 Tin disulfide cladding two-dimensional lamellar Ti3C2Lithium ion battery
CN115477303B (en) * 2021-06-16 2024-03-29 哈尔滨工业大学 Method for preparing thin-layer dispersed two-dimensional MXees material

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010017127A (en) * 1999-08-09 2001-03-05 황해웅 Manufacturing method of spherical TiC powder
CN104016345A (en) * 2014-06-03 2014-09-03 河海大学 Method for preparing graphene-like two-dimensional laminar titanium carbide nanoplate
CN107324335A (en) * 2017-08-17 2017-11-07 浙江大学 A kind of utilization ultrasonic wave added prepares the Mxene Ti of layering3C2Method
CN107364865A (en) * 2017-07-04 2017-11-21 龙岩紫荆创新研究院 A kind of method for preparing micron order increasing material manufacturing spherical carbide titanium powder
CN108423645A (en) * 2018-04-12 2018-08-21 大连理工大学 A kind of three-dimensional MXene and its universal synthesis method
CN108987126A (en) * 2018-09-28 2018-12-11 大连理工大学 A kind of Ti3C2/ Ni combination electrode material and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010017127A (en) * 1999-08-09 2001-03-05 황해웅 Manufacturing method of spherical TiC powder
CN104016345A (en) * 2014-06-03 2014-09-03 河海大学 Method for preparing graphene-like two-dimensional laminar titanium carbide nanoplate
CN107364865A (en) * 2017-07-04 2017-11-21 龙岩紫荆创新研究院 A kind of method for preparing micron order increasing material manufacturing spherical carbide titanium powder
CN107324335A (en) * 2017-08-17 2017-11-07 浙江大学 A kind of utilization ultrasonic wave added prepares the Mxene Ti of layering3C2Method
CN108423645A (en) * 2018-04-12 2018-08-21 大连理工大学 A kind of three-dimensional MXene and its universal synthesis method
CN108987126A (en) * 2018-09-28 2018-12-11 大连理工大学 A kind of Ti3C2/ Ni combination electrode material and preparation method thereof

Also Published As

Publication number Publication date
CN109592684A (en) 2019-04-09

Similar Documents

Publication Publication Date Title
CN109592684B (en) Petal spherical titanium carbide Ti3C2Mxene and preparation method and application thereof
Luo et al. Critical thickness of phenolic resin-based carbon interfacial layer for improving long cycling stability of silicon nanoparticle anodes
Zhou et al. Polyaniline-encapsulated silicon on three-dimensional carbon nanotubes foam with enhanced electrochemical performance for lithium-ion batteries
Cui et al. High surface area C/SiO2 composites from rice husks as a high-performance anode for lithium ion batteries
CN107204445B (en) A kind of lithium ion battery three-dimensional porous silicon-carbon cathode material and preparation method thereof
Xu et al. In situ construction of carbon nanotubes/nitrogen-doped carbon polyhedra hybrids for supercapacitors
CN109167066A (en) A kind of preparation method of few layer titanium carbide growth in situ nitrogen-doped carbon nanometer pipe three-dimensional composite material
CN105949512B (en) Intercalation assembling boron nitride-graphene composite material, using and preparation method thereof
CN103903879B (en) Porous grapheme/ MnO2 composite film and preparation method and application thereof
Jiang et al. Hollow silica spheres with facile carbon modification as an anode material for lithium-ion batteries
Wang et al. Alginate-based hierarchical porous carbon aerogel for high-performance supercapacitors
CN104973591B (en) High-quality graphene and preparation method thereof
Tao et al. Flexible binder-free reduced graphene oxide wrapped Si/carbon fibers paper anode for high-performance lithium ion batteries
WO2016138802A1 (en) Method for preparing biomass graphene by using cellulose as raw material
Zhao et al. Preparation of hierarchical graphdiyne hollow nanospheres as anode for lithium-ion batteries
CN107915853A (en) A kind of nano-cellulose/graphene composite and flexible film and preparation method and application
CN107946086A (en) It is a kind of using graphene as full carbon resistance rod of ultracapacitor flexible self-supporting of binding agent and preparation method thereof
CN106744841B (en) Preparation method of three-dimensional porous graphene film constructed by single-layer graphene
CN104030280A (en) Preparation method of graphene paper
CN104876213A (en) Graphene material and preparation method of electrode material of graphene material
CN113247887A (en) Preparation method of hierarchical porous graphene and application of hierarchical porous graphene
CN106486295A (en) The preparation method of the Graphene of high specific capacitance/high surface carbon composite
CN106910640A (en) Controllable graphene nanometer sheet electrode material of a kind of form and its preparation method and application
Xia et al. Microwave-assisted facile and rapid synthesis of layered metal hydroxide nanosheet arrays towards high-performance aqueous hybrid supercapacitors
CN104103823B (en) A kind of layering Li 4ti 5o 12the preparation method of graphene complex lithium ion battery cathode material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant