CN110723737B - Wool ball type Ti3C2Preparation method and application of (MXene) nano material - Google Patents

Wool ball type Ti3C2Preparation method and application of (MXene) nano material Download PDF

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CN110723737B
CN110723737B CN201911017810.7A CN201911017810A CN110723737B CN 110723737 B CN110723737 B CN 110723737B CN 201911017810 A CN201911017810 A CN 201911017810A CN 110723737 B CN110723737 B CN 110723737B
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mxene
nano material
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CN110723737A (en
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李子炯
刘燕月
朱祥
杨鹏
郭东方
商继敏
孙敏
程学瑞
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Zhengzhou University of Light Industry
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    • 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
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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
    • 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

Abstract

Disclosure of the inventionA hair ball type Ti3C2The preparation method and the application of the (MXene) nano material comprise the following steps: subjecting a precursor Ti3AlC2(MAX) adding the Ti powder into HF, magnetically stirring for 72 hours at room temperature, centrifugally washing to neutrality, collecting precipitate, and drying at 60 ℃ to obtain black powder, namely the two-dimensional Ti3C2(MXene) material; two-dimensional Ti3C2(MXene) material is added to a solution containing a strong base and H2O2The mixed solution is stirred evenly and then is subjected to hydro-thermal treatment, the precipitate is collected by centrifugation and dried at 60 ℃ to obtain a white powdery sample, namely the hair ball type Ti3C2(MXene) nanomaterial. The prepared ball type Ti3C2The (MXene) nano material has excellent electrochemical energy storage performance, and provides a simple and easy-to-operate preparation path for the application of the (MXene) nano material in the aspects of electrode materials such as super capacitors, lithium ion batteries and the like.

Description

Wool ball type Ti3C2Preparation method and application of (MXene) nano material
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a method for preparing a ball-shaped Ti3C2(MXene) nanomaterial preparation method.
Background
Ti3C2(MXene) is a novel graphene-like two-dimensional material, the rich functional groups on the surface of the material endow the material with excellent chemical reaction activity and hydrophilicity, and the unique structure ensures that the material has good conductivity and thermal stability, thereby increasing the energy storage capacity of the material, and the material is widely applied to electrochemical cells such as super capacitors, lithium ion batteries, sodium ion batteries and the likeThe field of energy storage becomes a research hotspot in the fields of chemistry, physics, materials and the like. But the defects of low specific mass capacity, easy agglomeration and the like prevent the wide application of the material. Therefore, how to prepare Ti with different morphologies3C2(MXene) is a prerequisite for its extensive application in the above-mentioned fields.
To date, researchers have dealt with Ti3C2The controllable preparation of (MXene) nano materials is researched greatly, and controllable preparation of nano sheets, nano belts and the like is realized. Yury Gogotsi et al published "Two-Dimensional Nanocrystals Produced by y enhancement of Ti3AlC2Adv. Mater. 2011, 23, 4248-3AlC2Al is etched by adding the material into HF to prepare the sheet layer MXene, the process is simple and easy to realize, but the mass specific capacitance of the material is very low. Zhong-Shuai Wu et al published "Alkalized Ti3C2MXene nanoribons with extended interlayer spacing for high-capacity sodium and potassium ion batteries, Nano Energy 40 (2017) 1-8 ″, which are prepared by continuous shaking in KOH alkaline solution3C2MXene nanobelts achieve high capacitance in sodium and potassium ion batteries. Therefore, the development of a new material morphology has very important practical significance.
Disclosure of Invention
The technical problem to be solved by the invention is to prepare Ti3C2(MXene) new morphology restriction, prevention of Ti3C2The nano sheets are piled and agglomerated again, thereby providing a capillary Ti3C2A preparation method of (MXene) nano material and application thereof as electrode material.
In order to solve the technical problems, the invention adopts the following technical scheme:
wool ball type Ti3C2The preparation method of the (MXene) nano material comprises the following steps:
(1) subjecting a precursor Ti3AlC2(MAX) adding HF, magnetically stirring at room temperature for 72 hours, centrifuging and washing to neutrality, collectingPrecipitating, drying at 60 ℃ to obtain black powder, namely the two-dimensional Ti3C2(MXene) material;
(2) two-dimensional Ti3C2(MXene) material added to the contained strong base and H2O2The mixed solution is stirred evenly and then is subjected to hydro-thermal treatment, the precipitate is collected by centrifugation and dried at 60 ℃ to obtain a white powdery sample, namely the hair ball type Ti3C2(MXene) nanomaterial.
Further, 1g of precursor Ti in the step (1)3AlC2(MAX) HF120mL is required, and HF may be replaced with a LiF-HCl mixed solution.
Further, the strong base in the step (2) is NaOH or KOH.
Further, the mixed solution in the step (2) is composed of a strong alkali aqueous solution and 30% by mass of hydrogen peroxide, wherein the molar concentration of the strong alkali in the strong alkali aqueous solution is 0.5M-1M.
Further, 0.1g of two-dimensional Ti in the step (2)3C2The (MXene) material needs 20-50mL of strong alkali aqueous solution and 0.34-0.68 mL of 30% hydrogen peroxide by mass fraction.
Further, the temperature of the hydrothermal treatment in the step (2) is 80-140 ℃, and the time is 8-12 h.
The hair ball type Ti prepared by the preparation method3C2The (MXene) nano material is used as an electrode material and applied to super capacitors, lithium ion batteries, sodium ion batteries and the like.
The invention has the beneficial effects that: the invention uses HF as an etchant, H2O2As an oxidant, the gross ball type Ti is realized by optimizing parameters such as hydrothermal temperature, alkali solution concentration and the like3C2Controllable preparation of (MXene) nano material. The obtained hair ball type Ti3C2The surface of the nano material is fluffy and the surface area is large. The preparation method has the advantages of simple process, strong operability, environmental friendliness, large-scale preparation and the like, and the prepared hair ball type Ti3C2The (MXene) nano material has good electrochemical performanceAnd a simple and easy-to-operate preparation path is provided for research and application of electrode materials such as super capacitors, lithium ion batteries and the like.
Drawings
FIG. 1 shows a ball-shaped Ti of the present invention3C2(MXene) nanomaterial preparation process flow diagram;
FIG. 2 shows a hair ball type Ti prepared in example 1 of the present invention3C2SEM image of (MXene);
FIG. 3 shows a hair ball type Ti prepared in example 1 of the present invention3C2(MXene) electrochemical performance plot;
FIG. 4 shows a hair ball type Ti prepared in example 2 of the present invention3C2SEM image of (MXene);
FIG. 5 shows a hair ball type Ti prepared in example 3 of the present invention3C2SEM image of (MXene);
FIG. 6 shows a hair ball type Ti prepared in example 4 of the present invention3C2SEM image of (MXene).
Detailed Description
The following examples will further illustrate the invention in conjunction with the accompanying drawings. It is to be understood that the following examples are intended only to illustrate the present invention and are not intended to limit the scope of the invention, the particular experimental conditions and techniques, and that certain insubstantial modifications and adaptations are often made in accordance with conventional procedures.
Example 1
Hair bulb type Ti of the example3C2The preparation method of the (MXene) nano material comprises the following steps:
(1) 1g of precursor Ti3AlC2(MAX) is added into 120ml HF, magnetic stirring is carried out for 72h at room temperature, centrifugal washing is carried out to neutrality, precipitate is collected, and black powder is obtained after drying at 60 ℃, namely two-dimensional Ti3C2(MXene) material;
(2) mixing 100mg of Ti3C2The material was added to a solution containing 30 ml of 1M sodium hydroxide and 0.68 ml of 30% H2O2The mixed solution of (3) is stirred uniformly. Then, the mixture was subjected to hydrothermal treatment at 140 ℃ for 12 hours, and the precipitate was collected by centrifugation to obtain a powderDrying the sample at 60 ℃ for 12h to obtain the ball-shaped Ti3C2(MXene) nanomaterial, denoted NT.
The experimental process is shown in fig. 1, and the SEM image and the electrochemical spectrum of the prepared nanomaterial are shown in fig. 2 and 3.
Example 2
Hair bulb type Ti of the example3C2The preparation method of the (MXene) nano material comprises the following steps:
(1) 1g of precursor Ti3AlC2(MAX) is added into 120ml solution, magnetic stirring is carried out for 72h at room temperature, centrifugal washing is carried out until the solution is neutral, precipitate is collected, and black powder is obtained after drying at 60 ℃, namely the two-dimensional Ti3C2(MXene) material;
(2) mixing 100mg of Ti3C2(MXene) Material was added to a solution containing 30 ml of 1M potassium hydroxide and 0.68 ml of 30% H2O2The mixed solution of (3) is stirred uniformly. Then carrying out hydrothermal treatment at 100 ℃ for 12h, collecting precipitates by centrifugation to obtain a powdery sample, and drying at 60 ℃ for 12h to obtain the ball-shaped Ti3C2(MXene) nanomaterial, denoted KT.
The experimental process is shown in fig. 1, and the SEM image and the electrochemical spectrum of the prepared nanomaterial are shown in fig. 4 and 3.
Example 3
Hair bulb type Ti of the example3C2The preparation method of the (MXene) nano material comprises the following steps:
(1) 1g of precursor Ti3AlC2(MAX) is added into 120ml (LiF-HCl), magnetic stirring is carried out for 72h at room temperature, centrifugal washing is carried out until the solution is neutral, precipitate is collected, and black powder is obtained after drying at 60 ℃, namely the two-dimensional Ti3C2(MXene) material;
(2) mixing 100mg of Ti3C2(MXene) Material was added to a solution containing 30 ml of 0.5M potassium hydroxide and 0.34 ml of 30% H2O2The mixed solution of (3) is stirred uniformly. Then hydrothermally treating at 140 deg.C for 12h, centrifuging, collecting precipitate to obtain powder sample, and heating at 60 deg.CDrying for 12 h.
The experimental process is shown in fig. 1, and the SEM image and the electrochemical spectrum of the prepared nanomaterial are shown in fig. 5 and 3.
Comparative example 1 (without hydrogen peroxide)
The hair bulb type Ti according to the example3C2The preparation method of the (MXene) nano material comprises the following steps:
(1) 1g of precursor Ti3AlC2(MAX) is added into 120ml HF, magnetic stirring is carried out for 72h at room temperature, centrifugal washing is carried out to neutrality, precipitate is collected, and black powder is obtained after drying at 60 ℃, namely two-dimensional Ti3C2(MXene) material;
(2) mixing 100mg of Ti3C2(MXene) material was added to a solution containing 30 ml of 1M strong base and stirred well. Then, the mixture was hydrothermally treated at 140 ℃ for 12 hours, and the precipitate was collected by centrifugation to obtain a powdery sample, which was dried at 60 ℃ for 12 hours.
The experimental process is shown in fig. 1, and the SEM image and the electrochemical spectrum of the prepared nanomaterial are shown in fig. 6 and 3.
As can be seen from fig. 3, in the same voltage interval, the charging and discharging time of the electrode of the MXenes material after alkalifying with the strong alkali solution is increased, which shows that the alkalifying operation increases the capacitance of the MXenes material. We can calculate Ti Δ V at a current of 0.08A according to the formula ∁ = i Δ t ⁄ m3C2Mass specific capacitances of KT and NT were 117.6F g-1、181.8 F g-1、185.2 F g-1The data show that the mass specific capacitance of the electrode made of the MXenes material after alkalization is larger than that of the electrode made of the material without alkalization, which shows that the performance of the electrode is enhanced after alkalization, and the performance of the material is enhanced through oxidation of hydrogen peroxide.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (7)

1. Wool ball type Ti3C2The preparation method of the (MXene) nano material is characterized by comprising the following steps:
(1) subjecting a precursor Ti3AlC2(MAX) adding the Ti powder into HF, magnetically stirring for 72 hours at room temperature, centrifugally washing to neutrality, collecting precipitate, and drying at 60 ℃ to obtain black powder, namely the two-dimensional Ti3C2(MXene) material;
(2) two-dimensional Ti3C2(MXene) material is added to a solution containing a strong base and H2O2The mixed solution is stirred evenly and then is subjected to hydro-thermal treatment, the precipitate is collected by centrifugation and dried at 60 ℃ to obtain a white powdery sample, namely the hair ball type Ti3C2(MXene) nanomaterial.
2. The hair bulb type Ti of claim 13C2The preparation method of the (MXene) nano material is characterized by comprising the following steps: 1g of precursor Ti in the step (1)3AlC2(MAX) requires HF120 mL.
3. The hair bulb type Ti of claim 13C2The preparation method of the (MXene) nano material is characterized by comprising the following steps: the strong base in the step (2) is NaOH or KOH.
4. The hair bulb type Ti of claim 13C2The preparation method of the (MXene) nano material is characterized by comprising the following steps: the mixed solution in the step (2) is composed of a strong alkali aqueous solution and 30% hydrogen peroxide by mass, wherein the molar concentration of the strong alkali in the strong alkali aqueous solution is 0.5-1M.
5. The hair-bulb type Ti of claim 43C2The preparation method of the (MXene) nano material is characterized by comprising the following steps: in the step (2), 0.1g of two-dimensional Ti3C2The (MXene) material needs 20-50mL of strong alkali aqueous solution and 0.34-0.68 mL of 30% hydrogen peroxide.
6. The hair bulb type Ti of claim 13C2The preparation method of the (MXene) nano material is characterized by comprising the following steps: the temperature of the hydrothermal treatment in the step (2) is 80-140 ℃, and the time is 8-12 h.
7. Hair bulb type Ti produced by the production method according to any one of claims 1 to 63C2The (MXene) nano material is used as an electrode material and applied to super capacitors, lithium ion batteries and sodium ion batteries.
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CN111187619B (en) * 2020-02-27 2021-02-26 北京科技大学 MXene quantum dot fluorescence enhancement method
CN111248224B (en) * 2020-03-04 2021-03-16 北京科技大学 Preparation method and antibacterial activity test method of antibacterial agent based on MXene quantum dots
CN111501326A (en) * 2020-05-13 2020-08-07 郑州大学 Multifunctional wearable polymer/MXene composite fabric heater and preparation method thereof
CN112047342B (en) * 2020-08-14 2021-12-07 东南大学 Preparation method of MXene microspheres
CN111969193B (en) * 2020-08-26 2022-09-09 中北大学 Si @ MXene nano composite material and preparation method thereof
CN112768259B (en) * 2020-12-30 2022-06-14 郑州轻工业大学 Preparation method and application of MXene derivative/metal nano composite material
CN113735124B (en) * 2021-07-27 2023-01-24 深圳技术大学 Preparation method and application of MXene two-dimensional material
CN115520870A (en) * 2022-10-14 2022-12-27 山东省科学院能源研究所 MXene-based sodium metal negative electrode deposition framework with two-dimensional/three-dimensional hybrid structure and preparation method thereof

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CN104016345B (en) * 2014-06-03 2016-04-27 河海大学 The preparation method of one kind Graphene two-dimensional layer titanium carbide nanometer sheet
CN107001051B (en) * 2014-09-25 2020-02-07 德雷塞尔大学 Physical form of MXene materials exhibiting novel electrical and optical properties
CN104556221A (en) * 2014-12-05 2015-04-29 常州轻工职业技术学院 TiO2/lamellar graphite nano composite material as well as preparation method thereof
CN105271231B (en) * 2015-10-28 2017-06-20 盐城工学院 A kind of two-dimensional nano Ti3C2The preparation method of piece
CN106025200B (en) * 2016-05-24 2019-07-30 浙江大学 A kind of preparation method and applications of N doping MXene cell negative electrode material
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