CN113690066B - Graphene quantum dot/few-layer Ti 3 C 2 T x Preparation method and application of composite material - Google Patents

Graphene quantum dot/few-layer Ti 3 C 2 T x Preparation method and application of composite material Download PDF

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CN113690066B
CN113690066B CN202110914474.7A CN202110914474A CN113690066B CN 113690066 B CN113690066 B CN 113690066B CN 202110914474 A CN202110914474 A CN 202110914474A CN 113690066 B CN113690066 B CN 113690066B
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晏泓
张猛
丰宇
郭睿劼
赵晶
王慧芳
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Taiyuan University of Technology
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
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    • H—ELECTRICITY
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses a graphene quantum dot/few-layer Ti 3 C 2 T x A preparation method and application of the composite material. Firstly, preparing few or single-layer Ti by microwave controllable stripping 3 C 2 T x Then, 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 invention can reduce the damage to the transverse dimension of the lamella layer in the stripping process as much as possible by controlling the microwave parameters, thereby obtaining a uniform large-size lamella layer; 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 electricity 3 C 2 T x Assembling 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 Ti 3 C 2 T x Preparation method and application of composite material
Technical Field
The invention relates to a graphene quantum dotA few layers of Ti 3 C 2 T x A 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 M n+1 X n T x . Wherein M represents an early transition metal, X represents a C or N element, T x Representing functional groups (-OH, -F, -O, etc.) attached to the surface of MXene 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. The MXene is of various types, and the invention researches the mature Ti 3 C 2 T x . The work selects an environment-friendly etching agent NaHF 2 Etching of the resulting Ti 3 C 2 T x The 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 MXene transverse dimension is more easily damaged by the ultrasonic oscillation method, and the centrifugal treatment method is lower in efficiency and is 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 insertion of Cr between graphene layers 3+ 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 Ti 3 C 2 T x A process for preparing composite material includes such steps as controllable stripping by microwave method to prepare Ti layer or Ti layer 3 C 2 T x Then, 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 Ti 3 C 2 T x The interlayer water of (2) breaks the layered structure under the expansion work of the steam to form a few or single-sheet layer Ti 3 C 2 T x Greatly increase Ti 3 C 2 T x Specific 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 electricity 3 C 2 T x And the composite material is assembled to form a composite material with few lamella, uniform and stable lamellar channels, high specific surface area and higher capacitance, 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 Ti 3 C 2 T x The preparation method of the composite material comprises the following steps:
(1) Weighing 0.2 to 0.3g of Ti 3 C 2 T x Putting 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 processed in the step (1) in a large crucible, and processing the crucible for 30 to 120s in a microwave oven with the power of 800 to 1000W;
(3) Collecting stepThe powder obtained in the step (2) is Ti with few layers or a single layer 3 C 2 T x ；
Stripped Ti 3 C 2 T x The ultra-thick layer structure of (a) is destroyed; post-exfoliation Ti with reduced lamellae 3 C 2 T x The thickness of the sheet layer is 3 to 5nm.
(4) Modifying the graphene quantum dots to make the graphene quantum dots have positive charges; stirring the Ti and the stripped Ti at normal temperature 3 C 2 T x And carrying out electrostatic self-assembly to form the composite material.
Step (4) preparing graphene quantum dots/few-layer Ti through electrostatic self-assembly 3 C 2 T x A 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 carry positive charges; and obtaining a modified solution dispersed with the modified quantum dots.
(2) Weighing the prepared Ti/single layer according to the filler ratio of the composite material of 5-25 percent 3 C 2 T x Slowly 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 in a vacuum oven at 60 ℃ for 8-10 h for drying; and collecting the powder to obtain the composite material.
The transverse dimension 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 Ti layer/Ti layer under the action of static electricity 3 C 2 T x Between 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 30-120s.
In the above method, the stripped Ti 3 C 2 T x The 2 theta angle is cancelled on the XRD pattern due to the opening of the bulk of the original layered structureIn the SEM image, the distribution is loosely and uniformly distributed and small/monolithic. Ti prepared by the above method 3 C 2 T x The 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 method 3 C 2 T x Cutting square foam nickel with the size of 2 multiplied by 2cm from the composite material; compounding the composite material with polyvinylidene fluoride (PVDF) and acetylene black according to the mass ratio of 8 2 (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 Ti 3 C 2 T x The composite material electrode shows a high-quality capacitance of 262-343F/g under the 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 invention 3 C 2 T x Few/single chip layers have larger grain diameter, complete lamellar structure, fewer layers, stability and controllability and increased specific surface area. And Ti after exfoliation 3 C 2 T x The 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 also 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 1 3 C 2 T x (FIG. a) with few/single Ti layers 3 C 2 T x (FIG. b) comparative SEM image.
FIG. 2 shows the single/few-lamellar Ti after microwave successful exfoliation in example 1 3 C 2 T x AFM images (2 b, 2 c) and XRD (2 a) patterns of (a).
Fig. 3 is an SEM image of the composite material in example 7.
FIG. 4 is a graph of electrochemical properties of the composite material of example 8, the charge-discharge curve of the electrode prepared from 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 protecting mode 2 Etching to obtain Ti 3 C 2 T x Powder; 0.3g of Ti was weighed 3 C 2 T x Adding the powder into a crucible with the volume of 5 mL; preparing a 20mL large crucible, fully spreading copper oxide powder, 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 90s under the power of 800W, and collecting the treated powder.
Etched Ti 3 C 2 T x And Ti after microwave stripping 3 C 2 T x An SEM image of (a) is shown in figure 1. Ti after etching can be seen 3 C 2 T x The Ti is in an accordion shape and has obvious multilayer laminated structure, and the Ti is stripped by microwave 3 C 2 T x Are 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 stripping, the layered structure is significantly destroyed and stripped into few or a single layerThe 2 theta angle disappears in the XRD pattern. Meanwhile, AFM images in FIG. 2 show that less Ti sheets are obtained after stripping 3 C 2 T x The thickness is 3-5nm, thus proving the results of SEM and XRD.
Example 2
Selection of NaHF 2 Etching to obtain Ti 3 C 2 T x Powder; 0.3g of Ti was weighed 3 C 2 T x Adding 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 NaHF 2 Etching to obtain Ti 3 C 2 T x Powder; 0.3g of Ti was weighed 3 C 2 T x Adding 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 NaHF 2 Etching to obtain Ti 3 C 2 T x Powder; 0.3g of Ti was weighed 3 C 2 T x Adding 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 NaHF 2 Etching to obtain Ti 3 C 2 T x Powder; 0.3g of Ti was weighed 3 C 2 T x Adding 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; placing the combined large and small crucibles in a household microwave oven, treating for 60s under 1000W, and collecting the treated powderCan be prepared.
Example 6
Selection of NaHF 2 Etching to obtain Ti 3 C 2 T x Powder; 0.3g of Ti was weighed 3 C 2 T x The powder was added to a 5mL crucible; 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 Ti 3 C 2 T x And 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 Ti 3 C 2 T x And 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 Ti 3 C 2 T x After stirring for 24h, the liquid is filtered by a sand core funnelAnd obtaining 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 positively charged. Selecting 25mg of modified graphene quantum dot solution, and adding 140mg of stripped Ti 3 C 2 T x And 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 (8)

1. Graphene quantum dot/few-layer Ti 3 C 2 T x The preparation method of the composite material is characterized by comprising the following steps:
(1) Weighing 0.2 to 0.3g of Ti 3 C 2 T x Putting the powder into a small crucible 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;
performing microwave treatment for 30 to 120s, wherein the microwave power is 800 to 1000W;
(3) Collecting the powder obtained in the step (2), namely Ti with few layers or single layer 3 C 2 T x ；
(4) Modifying the graphene quantum dots to make the graphene quantum dots have positive charges; stirring the Ti and the stripped Ti at normal temperature 3 C 2 T x And carrying out electrostatic self-assembly to form the composite material.
2. The graphene quantum dot/few-layer Ti of claim 1 3 C 2 T x The preparation method of the composite material is characterized by comprising the following steps: few-layer or single-layer Ti obtained in step (3) 3 C 2 T x The thickness of the sheet layer is 3 to 5nm.
3. The graphene quantum dot/few-layer Ti of claim 1 3 C 2 T x Preparation of composite materialsThe method is characterized by comprising the following steps:
step (4) preparing graphene quantum dots/few-layer Ti through electrostatic self-assembly 3 C 2 T x A 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 few-layer or single-layer Ti prepared in the step (3) according to the filler ratio of the composite material of 5-25% 3 C 2 T x Slowly 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 in a vacuum oven at 60 ℃ for 8-10 h for drying; and collecting the powder to obtain the composite material.
4. The graphene quantum dot/few-layer Ti of claim 3 3 C 2 T x The preparation method of the composite material is characterized by comprising the following steps: the transverse dimension of the composite material sheet layer is uniform and is 4~6 mu m; the graphene quantum dots are uniformly distributed on few layers or single layer of Ti under the action of static electricity 3 C 2 T x Between the surface and the layers.
5. Graphene quantum dot/few-layer Ti prepared by the method of any one of claims 1~4 3 C 2 T x A composite material.
6. The graphene quantum dot/few-layer Ti of claim 5 3 C 2 T x The composite material is applied to a super capacitor or a lithium sodium ion battery.
7. Use according to claim 6, characterized in that: cutting square foam nickel with the size of 2 multiplied by 2 cm; compounding the composite material with polyvinylidene fluoride (PVDF) and acetylene black according to the mass ratio of 8 2 (ii) a Selecting mercury/mercury oxideThe performance of the composite was tested in an electrolytic cell of a three-electrode system with a reference electrode, a platinum electrode as the counter electrode.
8. Use according to claim 7, characterized in that: graphene quantum dot/few-layer Ti 3 C 2 T x The composite material electrode can show a high-quality capacitance of 262 to 343F/g under the current density of 1A/g; the electrode prepared from the composite material still maintains 100% of capacitance retention rate after 10000 charge-discharge cycles.
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