CN113690066A - Graphene quantum dot/few-layer Ti3C2TxPreparation method and application of composite material - Google Patents

Graphene quantum dot/few-layer Ti3C2TxPreparation method and application of composite material Download PDF

Info

Publication number
CN113690066A
CN113690066A CN202110914474.7A CN202110914474A CN113690066A CN 113690066 A CN113690066 A CN 113690066A CN 202110914474 A CN202110914474 A CN 202110914474A CN 113690066 A CN113690066 A CN 113690066A
Authority
CN
China
Prior art keywords
composite material
graphene quantum
layer
few
quantum dots
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.)
Granted
Application number
CN202110914474.7A
Other languages
Chinese (zh)
Other versions
CN113690066B (en
Inventor
晏泓
张猛
丰宇
郭睿劼
赵晶
王慧芳
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.)
Taiyuan University of Technology
Original Assignee
Taiyuan University of Technology
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 Taiyuan University of Technology filed Critical Taiyuan University of Technology
Priority to CN202110914474.7A priority Critical patent/CN113690066B/en
Publication of CN113690066A publication Critical patent/CN113690066A/en
Application granted granted Critical
Publication of CN113690066B publication Critical patent/CN113690066B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
    • 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
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • 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
    • H01M4/362—Composites
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/582—Halogenides
    • 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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nanotechnology (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a graphene quantum dot/few-layer Ti3C2TxA preparation method and application of the composite material. Firstly, preparing few or single-layer Ti by microwave controllable stripping3C2TxThen the graphene quantum dots are compounded to form the stable lamellar graphene quantum dotsThe structure is made of a composite material without stacking and with a high capacitance value; the composite material has very wide prospect in the fields of super capacitors, lithium sodium ion batteries and the like. According to the invention, by controlling microwave parameters, the damage to the transverse size of the lamella in the stripping process can be reduced as much as possible, so that a uniform large-size lamella is obtained; in the aspect of synthesizing the composite material, the traditional method of compounding the graphene sheet layer and MXene is abandoned, the graphene quantum dots with changed electric property are selected, and the characteristics of high capacitance value and nano-scale particle size of the quantum dots are utilized to be combined with Ti under the action of static electricity3C2TxAssembling again to form few sheets; the preparation process is controllable, the product structure is stable, and the industrial production is facilitated.

Description

Graphene quantum dot/few-layer Ti3C2TxPreparation method and application of composite material
Technical Field
The invention relates to graphene quantum dot/few-layer Ti3C2TxA preparation method and application of a composite material belong to the technical field of 2D nano material preparation.
Background
Two-dimensional nano material MXene, a novel transition metal carbide and nitride with a layered structure, and the general formula is Mn+1XnTx. Wherein M represents an early transition metal, X represents a C or N element, TxRepresenting functional groups (-OH, -F, -O, etc.) attached to MXene's surface resulting from chemical etching of the precursor MAX phase. With the increasing energy crisis, MXene is considered to be a promising material in the field of energy storage, and can be used in many directions, such as supercapacitors, lithium/sodium ion batteries, transparent conductive coatings, semiconductors, and the like. Of these, MXene is of a wide variety, and the more mature Ti was studied3C2Tx. The work selects an environment-friendly etching agent NaHF2Etched Ti3C2TxThe lamellae are in the order of tens or even hundreds. The method of ultrasonic oscillation or centrifugal peeling is adopted to peel off the multiple layers of MXene, and the method is a mechanical method, so that the sheets with similar sizes and uniform thickness cannot be obtained controllably. The transverse dimension of MXene is more easily damaged by the ultrasonic oscillation method, and the efficiency of the centrifugal treatment method is higherLow and less controllable. In addition to ultrasonic centrifugation, there is also a technique of shaking and centrifugal stripping after microwave heat preservation, but up to now, there is no technique of completely adopting microwave stripping. In the aspect of application, self-weight stacking caused by the structure of MXene always limits that MXene cannot achieve the theoretically-achievable optimal performance. The invention is based on the interpositioned Cr of graphene layers3+The oxidation and reduction of (a) to generate oxygen, and promote the increase of the graphene layer spacing to generate a thought [ reference: from-Temperature interaction and 1000-Fold Chemical Expansion for Scalable Preparation of High-Quality graphics; interlayer water vaporization is utilized to push interlayer spacing to increase, controllable stripping is completed under the action of microwaves, and meanwhile, graphene quantum dots are introduced to form a composite material, so that a uniform stable channel is formed and a large capacitance value is provided.
Disclosure of Invention
The invention aims to provide graphene quantum dot/few-layer Ti3C2TxA process for preparing composite material includes such steps as controllable stripping by microwave method to prepare Ti layer or Ti layer3C2TxThen, the graphene quantum dots are compounded to form a composite material which has a stable layered channel, no stacking structure and a high capacitance value; the composite material has very wide prospect in the fields of super capacitors, lithium sodium ion batteries and the like.
The stripping process of the invention mainly depends on the energy of microwave to instantaneously vaporize Ti3C2TxThe interlayer water of (2) breaks the layered structure under the expansion work of the steam to form a few or single-sheet layer Ti3C2TxGreatly increase Ti3C2TxSpecific surface area of (2). By controlling the microwave parameters, the damage to the transverse dimension of the sheet layer in the stripping process can be reduced as much as possible, so that a uniform large-size sheet layer is obtained. In the aspect of synthesizing composite materials, the method abandons the traditional method of compounding graphene sheet layers and MXene, selects graphene quantum dots capable of changing electric property, utilizes the characteristics of high capacitance value and nano-scale particle size of the quantum dots, and combines the quantum dots with Ti under the action of static electricity3C2TxThen the assembly is carried out again, and the assembly,the composite material with few lamella, uniform and stable lamellar channels, high specific surface area and higher capacitance is formed, the preparation process is controllable, the product structure is stable, and the industrial production is facilitated.
The invention provides a graphene quantum dot/few-layer Ti3C2TxThe preparation method of the composite material comprises the following steps:
(1) weighing 0.2-0.3 g of Ti3C2TxPutting the powder into a crucible with the volume of 5 mL;
(2) preparing a 20mL large crucible, and uniformly and fully spreading copper oxide powder in the crucible so as to quickly heat and absorb redundant energy; placing the small crucible treated in the step (1) in a large crucible, and treating the small crucible for 30-120 s by using a microwave oven with the power of 800-1000W;
(3) collecting the powder obtained in the step (2), namely Ti with few layers or single layer3C2Tx；
Stripped Ti3C2TxThe ultra-thick layer structure of (a) is destroyed; post-exfoliation Ti with reduced lamellae3C2TxThe thickness of the lamella is 3-5 nm.
(4) Modifying the graphene quantum dots to make the graphene quantum dots have positive charges; stirring the Ti and the stripped Ti at normal temperature3C2TxAnd carrying out electrostatic self-assembly to form the composite material.
Step (4) preparing graphene quantum dots/few-layer Ti through electrostatic self-assembly3C2TxA composite material comprising the steps of:
(1) weighing graphene quantum dots, modifying with polydimethyl diene ammonium chloride (PDDA), and stirring for 24h to make the graphene quantum dots have positive charges; and obtaining a modified solution dispersed with the modified quantum dots.
(2) Weighing the prepared Ti-less/single-layer according to the filler ratio of the composite material of 5-25%3C2TxSlowly adding the powder into the modified solution obtained in the step (1) and stirring for 24 hours again;
(3) carrying out suction filtration on the solution after secondary stirring by using a sand core funnel to obtain a filter cake; placing the mixture in a vacuum oven for 8-10 h at 60 ℃ for drying; and collecting the powder to obtain the composite material.
The transverse size of the composite material sheet layer is still uniform and is about 4-5 mu m, and the graphene quantum dots are uniformly distributed on the few/single Ti layer under the action of static electricity3C2TxBetween the surface and the layers.
In the method, the microwave method utilizes interlayer water vaporization to push the lamella to realize stripping, and adds trace water outside and controls microwave parameters to avoid great damage of transverse dimension as much as possible.
In the method, the requirement can be met by using a household microwave oven, the microwave working parameter is 800-1000W, and the processing time is 30-120 s.
In the above method, the stripped Ti3C2TxSince the original bulk of the layered structure is opened up, the 2 θ angle disappears on the XRD pattern, in a loose and uniform distribution of few/monolithic distributions in the SEM image. Ti prepared by the above method3C2TxThe graphene quantum dot composite material can be seen to be evenly paved with quantum dot particles on MXene sheet layers under SEM and TEM.
The invention provides the graphene quantum dot/few-layer Ti prepared by the method3C2TxCutting square foam nickel with the size of 2 multiplied by 2cm from the composite material; compounding the composite material with PVDF and acetylene black in a mass ratio of 8:1:1 to form slurry, and coating the slurry on foamed nickel with a coating amount of 3.8-4.2mg/cm2(ii) a The performance of the composite material is tested in an electrolytic cell of a three-electrode system by taking mercury/mercury oxide as a reference electrode and a platinum electrode as a counter electrode. Graphene quantum dot/few-layer Ti3C2TxThe composite material electrode shows a high-quality capacitance of 262-343F/g under a current density of 1A/g. The electrode prepared from the composite material still maintains 100% of capacitance retention rate after 10000 charge-discharge cycles.
The invention has the beneficial effects that:
compared with the prior art, the stripped Ti of the invention3C2TxThe few/single layer has larger grain diameter, complete lamellar structure, fewer layers, stability and controllability and increased specific surface area. And stripped Ti3C2TxThe few/single-layer structure and the graphene quantum dots are assembled to form the composite material, so that a larger specific surface area can be provided, and the structure of few layers is favorable for directional transmission of ions. The modified graphene quantum dots can be uniformly distributed between layers and on the surface of MXene due to the characteristics of positive charge and small particle size, the advantages of high capacitance value of the graphene quantum dots and the advantages of MXene layered structure are integrated, the self-weight stacking of MXene is avoided due to the composite structure of the material, the long cycle life can be ensured on the premise of providing a high capacitance value, and the material has a very wide prospect in the fields of supercapacitors and lithium sodium batteries.
Drawings
FIG. 1 is a schematic view of a multilayer Ti film before and after microwave stripping in example 13C2Tx(FIG. a) with few/single Ti layers3C2Tx(FIG. b) comparative SEM image.
FIG. 2 shows the single/few-lamellar Ti after microwave successful exfoliation in example 13C2TxAFM images (2b, 2c) and XRD (2a) patterns of (a).
Fig. 3 is an SEM image of the composite material in example 7.
FIG. 4 is a graph of the electrochemical performance of the composite material of example 8, the charge-discharge curve of the electrode prepared from the three materials (FIG. a) and the capacity retention rate after 10000 charge-discharge cycles (FIG. b).
Detailed Description
The technical solution of the present invention is further described below with specific examples, but the scope of the present invention is not limited thereto.
The examples do not show the specific experimental steps or conditions, and the operation or conditions of the conventional experimental steps described in the literature in the field can be followed. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
Selecting NaHF in environment-friendly mode2Etching to obtain Ti3C2TxPowder; 0.3g of Ti was weighed3C2TxAdding the powder into a crucible with the volume of 5 mL; prepare a 20mL of large crucible is filled with copper oxide powder, and the small crucible is placed in the large crucible; and (3) placing the combined large crucible and the combined small crucible in a household microwave oven, treating for 90s under the power of 800W, and collecting the treated powder.
Etched Ti3C2TxAnd Ti after microwave stripping3C2TxAn SEM image of (a) is shown in figure 1. Ti after etching can be seen3C2TxThe Ti is in an accordion shape and has obvious multilayer laminated structure, and the Ti is stripped by microwave3C2TxAre small/monolithic scattered on the substrate and are almost uniform in size. As shown in fig. 2, MXene after etching has an XRD pattern of 2 θ =7.1 °. However, after microwave exfoliation, the layered structure is significantly destroyed, exfoliated to a few or single layers, and the 2 θ angle in the XRD pattern disappears. Meanwhile, AFM images in FIG. 2 show that less Ti sheets are obtained after stripping3C2TxThe thickness is 3-5nm, thus proving the results of SEM and XRD.
Example 2
Selection of NaHF2Etching to obtain Ti3C2TxPowder; 0.3g of Ti was weighed3C2TxAdding the powder into a crucible with the volume of 5 mL; preparing a 20mL large crucible, fully spreading copper oxide powder in the large crucible, and placing a small crucible in the large crucible; and (3) placing the combined large crucible and the combined small crucible in a household microwave oven, treating for 60s under the power of 800W, and collecting the treated powder.
Example 3
Selection of NaHF2Etching to obtain Ti3C2TxPowder; 0.3g of Ti was weighed3C2TxAdding the powder into a crucible with the volume of 5 mL; preparing a 20mL large crucible, fully spreading copper oxide powder in the large crucible, and placing a small crucible in the large crucible; and (3) placing the combined large crucible and the combined small crucible in a household microwave oven, treating for 120s under the power of 800W, and collecting the treated powder.
Example 4
Selection of NaHF2Etching to obtain Ti3C2TxPowder; weighing 0.3gTi3C2TxAdding the powder into a crucible with the volume of 5 mL; preparing a 20mL large crucible, fully spreading copper oxide powder in the large crucible, and placing a small crucible in the large crucible; and (3) placing the combined large crucible and the combined small crucible in a household microwave oven, treating for 50s under the power of 1000W, and collecting the treated powder.
Example 5
Selection of NaHF2Etching to obtain Ti3C2TxPowder; 0.3g of Ti was weighed3C2TxAdding the powder into a crucible with the volume of 5 mL; preparing a 20mL large crucible, fully spreading copper oxide powder in the large crucible, and placing a small crucible in the large crucible; and (3) placing the combined large crucible and the combined small crucible in a household microwave oven, treating for 60s under the power of 1000W, and collecting the treated powder.
Example 6
Selection of NaHF2Etching to obtain Ti3C2TxPowder; 0.3g of Ti was weighed3C2TxAdding the powder into a crucible with the volume of 5 mL; preparing a 20mL large crucible, fully spreading copper oxide powder in the large crucible, and placing a small crucible in the large crucible; and (3) placing the combined large crucible and the combined small crucible in a household microwave oven, processing the combined large crucible and the combined small crucible under the power of 1000W for 80, and collecting the processed powder.
Example 7
PDDA modified graphene quantum dots are selected by the existing method and are provided with positive charges. Selecting 25mg of modified graphene quantum dot solution, and adding 0.32g of stripped Ti3C2TxAnd after stirring for 24 hours, carrying out suction filtration on the liquid by using a sand core funnel to obtain a filter cake. Drying the filter cake in a vacuum oven for 8h at the temperature of 60 ℃; and collecting the powder to obtain the composite material.
Fig. 3 is an SEM image of the composite material in example 7, wherein the large layer in the field of view is MXene, and the spherical particles attached to the surface are graphene quantum dots.
Example 8
PDDA modified graphene quantum dots are selected by the existing method and are provided with positive charges. Selecting 25mg of modified graphene quantum dot solution, and adding 0.23g of stripped Ti3C2TxAnd after stirring for 24 hours, carrying out suction filtration on the liquid by using a sand core funnel to obtain a filter cake. Drying the filter cake in a vacuum oven for 8h at the temperature of 60 ℃; and collecting the powder to obtain the composite material. FIG. 4 is a graph of the electrochemical performance of the composite material obtained in this example, and the capacitance of the composite material is 343F/g, which is much higher than that of MXene electrode, at a current density of 1A/g; and the capacity retention rate is still 100% after 10000 charge-discharge cycles.
Example 9
PDDA modified graphene quantum dots are selected by the existing method and are provided with positive charges. Selecting 25mg of modified graphene quantum dot solution, and adding 0.17g of stripped Ti3C2TxAnd after stirring for 24 hours, carrying out suction filtration on the liquid by using a sand core funnel to obtain a filter cake. Drying the filter cake in a vacuum oven for 8h at the temperature of 60 ℃; and collecting the powder to obtain the composite material.
Example 10
PDDA modified graphene quantum dots are selected by the existing method and are provided with positive charges. Selecting 25mg of modified graphene quantum dot solution, and adding 140mg of stripped Ti3C2TxAnd after stirring for 24 hours, carrying out suction filtration on the liquid by using a sand core funnel to obtain a filter cake. Drying the filter cake in a vacuum oven for 8h at the temperature of 60 ℃; and collecting the powder to obtain the composite material.

Claims (9)

1. Graphene quantum dot/few-layer Ti3C2TxThe preparation method of the composite material is characterized by comprising the following steps:
(1) weighing 0.2-0.3 g of Ti3C2TxPutting the powder into a crucible with the volume of 5 mL;
(2) preparing a 20mL large crucible, uniformly and fully spreading copper oxide powder in the large crucible, placing the small crucible treated in the step (1) in the large crucible, and treating the small crucible by using a microwave oven;
(3) collecting the powder obtained in the step (2), namely Ti with few layers or single layer3C2Tx；
(4) Modifying the graphene quantum dots to make the graphene quantum dots have positive charges; stirring at normal temperatureWith stripped Ti in an atmosphere of3C2TxAnd carrying out electrostatic self-assembly to form the composite material.
2. The graphene quantum dot/few-layer Ti of claim 13C2TxThe preparation method of the composite material is characterized by comprising the following steps: in the step (2), the microwave treatment is carried out for 30-120 s, and the microwave power is 800-1000W.
3. The graphene quantum dot/few-layer Ti of claim 13C2TxThe preparation method of the composite material is characterized by comprising the following steps: few-layer or single-layer Ti obtained in step (3)3C2TxThe thickness of the lamella is 3-5 nm.
4. The graphene quantum dot/few-layer Ti of claim 13C2TxThe preparation method of the composite material is characterized by comprising the following steps:
step (4) preparing graphene quantum dots/few-layer Ti through electrostatic self-assembly3C2TxA composite material comprising the steps of:
(1) weighing graphene quantum dots, modifying the graphene quantum dots by using PDDA (poly dimethyl diene ammonium chloride), and stirring for 24 hours to enable the graphene quantum dots to carry positive charges, so as to obtain a modified solution in which the modified quantum dots are dispersed;
(2) weighing the Ti-less/single-layer composite material prepared in the first step according to the filler ratio of the composite material of 5-25%3C2TxSlowly adding the powder into the modified solution obtained in the step (1) and stirring for 24 hours again;
(3) carrying out suction filtration on the solution after secondary stirring by using a sand core funnel to obtain a filter cake; placing the mixture in a vacuum oven for 8-10 h at 60 ℃ for drying; and collecting the powder to obtain the composite material.
5. The graphene quantum dot/few-layer Ti of claim 43C2TxThe preparation method of the composite material is characterized by comprising the following steps: the transverse size of the composite material sheet layer is uniform and is 4-6 mu m; the graphene quantum dots are electrostaticUniformly distributed in a few/single layer of Ti under the action of3C2TxBetween the surface and the layers.
6. Graphene quantum dot/few-layer Ti prepared by the method of any one of claims 1 to 53C2TxA composite material.
7. The graphene quantum dot/few-layer Ti of claim 63C2TxThe composite material is applied to a super capacitor or a lithium sodium ion battery.
8. Use according to claim 7, characterized in that: cutting square foam nickel with the size of 2 multiplied by 2 cm; compounding the composite material with PVDF and acetylene black in a mass ratio of 8:1:1 to form slurry, and coating the slurry on foamed nickel with a coating amount of 3.8-4.2mg/cm2(ii) a The performance of the composite material is tested in an electrolytic cell of a three-electrode system by taking mercury/mercury oxide as a reference electrode and a platinum electrode as a counter electrode.
9. Use according to claim 8, characterized in that: graphene quantum dot/few-layer Ti3C2TxThe composite material electrode shows a high-quality capacitance of 262-343F/g under a current density of 1A/g; the electrode prepared from the composite material still maintains 100% of capacitance retention rate after 10000 charge-discharge cycles.
CN202110914474.7A 2021-08-10 2021-08-10 Graphene quantum dot/few-layer Ti 3 C 2 T x Preparation method and application of composite material Active CN113690066B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110914474.7A CN113690066B (en) 2021-08-10 2021-08-10 Graphene quantum dot/few-layer Ti 3 C 2 T x Preparation method and application of composite material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110914474.7A CN113690066B (en) 2021-08-10 2021-08-10 Graphene quantum dot/few-layer Ti 3 C 2 T x Preparation method and application of composite material

Publications (2)

Publication Number Publication Date
CN113690066A true CN113690066A (en) 2021-11-23
CN113690066B CN113690066B (en) 2022-11-25

Family

ID=78579293

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110914474.7A Active CN113690066B (en) 2021-08-10 2021-08-10 Graphene quantum dot/few-layer Ti 3 C 2 T x Preparation method and application of composite material

Country Status (1)

Country Link
CN (1) CN113690066B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024061102A1 (en) * 2022-09-21 2024-03-28 Tcl科技集团股份有限公司 Composite material, composition and light-emitting diode

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105084360A (en) * 2015-09-14 2015-11-25 哈尔滨工业大学 Method for stripping two-dimensional nano Ti3C2 lamella by adopting microwave heating assisted ultrasonic method
CN106654189A (en) * 2016-10-26 2017-05-10 东南大学 Method for rapidly preparing carbon nanotube-two-dimensional titanium carbide composite material
CN107230560A (en) * 2017-07-12 2017-10-03 西北师范大学 A kind of method that microwave radiation prepares titanium dioxide/stratiform carbon composite
CN110105087A (en) * 2018-10-10 2019-08-09 西南交通大学 A kind of Ti3C2The regulation method of film surface functional group

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105084360A (en) * 2015-09-14 2015-11-25 哈尔滨工业大学 Method for stripping two-dimensional nano Ti3C2 lamella by adopting microwave heating assisted ultrasonic method
CN106654189A (en) * 2016-10-26 2017-05-10 东南大学 Method for rapidly preparing carbon nanotube-two-dimensional titanium carbide composite material
CN107230560A (en) * 2017-07-12 2017-10-03 西北师范大学 A kind of method that microwave radiation prepares titanium dioxide/stratiform carbon composite
CN110105087A (en) * 2018-10-10 2019-08-09 西南交通大学 A kind of Ti3C2The regulation method of film surface functional group

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ELIAS E. ELEMIKE: ""New perspectives 2Ds to 3Ds MXenes and graphene functionalized systems as high performance energy storage materials "", 《JOURNAL OF ENERGY STORAGE》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024061102A1 (en) * 2022-09-21 2024-03-28 Tcl科技集团股份有限公司 Composite material, composition and light-emitting diode

Also Published As

Publication number Publication date
CN113690066B (en) 2022-11-25

Similar Documents

Publication Publication Date Title
Wang et al. One-step synthesis of spherical Si/C composites with onion-like buffer structure as high-performance anodes for lithium-ion batteries
Ren et al. Ultrathin Si nanosheets dispersed in graphene matrix enable stable interface and high rate capability of anode for lithium‐ion batteries
Wang et al. Approaching the downsizing limit of silicon for surface‐controlled lithium storage
Subalakshmi et al. CuO nano hexagons, an efficient energy storage material for Li-ion battery application
Iwamura et al. Fast and reversible lithium storage in a wrinkled structure formed from Si nanoparticles during lithiation/delithiation cycling
Xu et al. In situ synthesis of porous Si dispersed in carbon nanotube intertwined expanded graphite for high-energy lithium-ion batteries
Han et al. Growth of flexible and porous surface layers of vertical graphene sheets for accommodating huge volume change of silicon in lithium-ion battery anodes
Ma et al. The hollow mesoporous silicon nanobox dually encapsulated by SnO2/C as anode material of lithium ion battery
Lu et al. Facile preparation of a three-dimensional Fe 3 O 4/macroporous graphene composite for high-performance Li storage
WO2012133396A1 (en) Positive electrode active material for magnesium secondary battery, magnesium secondary battery, method for manufacturing positive electrode active material for magnesium secondary battery, and method for manufacturing magnesium secondary battery
Su et al. Silicon@ graphene composite prepared by spray–drying method as anode for lithium ion batteries
Jia et al. Synthesis of porous Co3O4/Reduced graphene oxide by a two-step method for supercapacitors with excellent electrochemical performance
Liu et al. Enhanced electrochemical performance of sandwich-structured polyaniline-wrapped silicon oxide/carbon nanotubes for lithium-ion batteries
CN111200123A (en) Negative electrode material, negative electrode plate and preparation method thereof
Adpakpang et al. Effective chemical route to 2D nanostructured silicon electrode material: phase transition from exfoliated clay nanosheet to porous Si nanoplate
Zhu et al. Yolk-void-shell Si–C nano-particles with tunable void size for high-performance anode of lithium ion batteries
Zhang et al. Engineering of a bowl-like Si@ rGO architecture for an improved lithium ion battery via a synergistic effect
He et al. Microwave-assisted synthesis of nano petal-like α-Ni (OH) 2/RGO and its electrochemical performance
Li et al. Simple synthesis of rice husk hollow carbon-coated flower ZnO for the anode in a high performance lithium-ion battery
Lu et al. Recent development of graphene-based materials for cathode application in lithium batteries: a review and outlook
Zhang et al. Synthesis of N-doped multi-cavity Sn/C composite and utilization to anode in lithium ion batteries
Guo et al. Reduced graphene oxide-coated 3D interconnected SiO2 nanoparticles with enhanced lithium storage performance
CN113690066B (en) Graphene quantum dot/few-layer Ti 3 C 2 T x Preparation method and application of composite material
Fan et al. Li 4 Ti 5 O 12/hollow graphitized nano-carbon composites as anode materials for lithium ion battery
CN113410459A (en) Embedded MoSxThree-dimensional ordered macroporous graphene carbon material of nanosheet, preparation and application

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