CN111799464A - MXene/graphene composite nanosheet, preparation method and application thereof, electrode plate and application thereof - Google Patents

MXene/graphene composite nanosheet, preparation method and application thereof, electrode plate and application thereof Download PDF

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CN111799464A
CN111799464A CN202010649434.XA CN202010649434A CN111799464A CN 111799464 A CN111799464 A CN 111799464A CN 202010649434 A CN202010649434 A CN 202010649434A CN 111799464 A CN111799464 A CN 111799464A
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mxene
nanosheets
graphene
nanosheet
graphene composite
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CN111799464B (en
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张熊
马衍伟
王磊
易莎
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Institute of Electrical Engineering of CAS
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    • 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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J27/24—Nitrogen compounds
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • 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
    • 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
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • 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
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    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
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    • 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

The invention provides an MXene/graphene composite nanosheet, a preparation method and application thereof, an electrode plate and application thereof, and belongs to the technical field of two-dimensional materials. The invention provides a preparation method of MXene/graphene composite nanosheets, which comprises the following steps: mixing MAX and hydrofluoric acid solution, and etching to obtain MXene; mixing the MXene and the tetrabutylammonium hydroxide solution, performing electrostatic adsorption and ultrasonic treatment to obtain a stripped MXene nanosheet; mixing the peeled MXene nanosheets and the graphene oxide suspension, and carrying out self-assembly reaction to obtain MXene nanosheets/graphene oxide nanosheets; and carrying out reduction reaction on the MXene nanosheets/graphene oxide nanosheets under a protective atmosphere to obtain MXene/graphene composite nanosheets. Graphene in the MXene/graphene composite nanosheet prepared by the preparation method provided by the invention cannot be stacked again, the MXene/graphene composite nanosheet has excellent lithium storage performance, and the unique two-dimensional structures of the MXene and the graphene can be maintained.

Description

MXene/graphene composite nanosheet, preparation method and application thereof, electrode plate and application thereof
Technical Field
The invention relates to the technical field of two-dimensional materials, in particular to an MXene/graphene composite nanosheet, a preparation method and application thereof, and an electrode plate and application thereof.
Background
Two-dimensional (2D) transition metal carbide (Ti)3C2、Ti2C、Ta4C3Etc.) and nitrides (Ti)3CN or Ti4N3)Mn+1XnLabeled as MXene, structurally similar to graphene. MXene is derived from the general formula Mn+1AXnWherein M represents a transition metal, a represents a group IIIA or IVA element, X is carbon (C) or nitrogen (N), and N is 1, 2 or 3. With Ti3AlC2For example, to get from Ti3AlC2Extracting Al atomic layer from phase without damaging Ti3AlC2In a layered form of (2), usually Ti3AlC2Soaking the powder in hydrofluoric acid at room temperature, and etching to obtain layered two-dimensional material Ti3C2. MXene has metal conductive characteristics, higher lithium ion storage capacity and good rate performance, is considered to be a potential electrode material of a lithium ion battery or a lithium ion capacitor, and a single-layer or few-layer MXene with more lithium ion storage capacity can be obtained by stripping multiple layers of MXene. However, the peeled MXene nanosheet is unstable in structure and prone to developAnd the re-stacking is carried out, so that the specific surface area of MXene exposed in the electrolyte is greatly reduced, the lithium ion intercalation is hindered, and the performance of MXene as an electrode material is weakened. Currently, an effective method to prevent re-stacking of MXene nanoflakes is to make composites of MXene mixed with other "pillar" materials, where two-dimensional graphene flakes are considered ideal "pillar" materials.
However, the surfaces of Graphene Oxide (GO) and MXene have abundant functional groups, and GO and MXene surfaces are generally negatively charged due to ionization of the functional groups, which makes GO difficult to react with Ti3AlC2Coupled and unstable micro-heterostructure is not beneficial to the exertion of lithium storage performance of the material. Chinese patent CN107633954B discloses a graphene/MXene composite material and application thereof, wherein MXene is only used as conductive particles and added between graphene layers, and MXene is not stripped and has poor lithium storage performance. Chinese patent CN110942921A discloses a preparation method of a novel three-dimensional composite aerogel electrode material, wherein NiCo-LDH is grown on the surface of multilayer layered MXene, graphene oxide is mixed, and freeze drying is carried out to obtain the three-dimensional composite aerogel, however, the re-stacking condition of MXene in the material cannot be solved, and the lithium storage performance is hindered.
Disclosure of Invention
In view of the above, the invention aims to provide an MXene/graphene composite nanosheet, a preparation method and application thereof, and an electrode plate and application thereof. The graphene in the material prepared by the preparation method provided by the invention is not easy to be stacked again, and the lithium storage performance is excellent.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of MXene/graphene composite nanosheets, which comprises the following steps:
mixing MAX and hydrofluoric acid solution, and etching to obtain MXene;
mixing the MXene and the tetrabutylammonium hydroxide solution, performing electrostatic adsorption, and performing ultrasonic treatment and electrostatic adsorption to obtain a peeled MXene nanosheet dispersion liquid;
mixing the peeled MXene nanosheet dispersion liquid and the graphene oxide suspension liquid, and carrying out self-assembly reaction to obtain MXene nanosheets/graphene oxide nanosheets;
and carrying out reduction reaction on the MXene nanosheets/graphene oxide nanosheets under a protective atmosphere to obtain MXene/graphene composite nanosheets.
Preferably, the concentration of the tetrabutylammonium hydroxide solution is 20-25 wt%;
the ratio of the mass of MXene to the volume of the tetrabutylammonium hydroxide solution is 1g: (25-50) mL.
Preferably, the electrostatic adsorption temperature is room temperature, and the time is 10-20 h.
Preferably, the mass ratio of the peeled MXene nanosheets in the peeled MXene nanosheet dispersion liquid to the graphene oxide in the graphene oxide suspension is 1: 10-10: 1.
Preferably, the temperature of the self-assembly reaction is room temperature, and the time is 1-3 h.
Preferably, the temperature of the reduction reaction is 300-500 ℃ and the time is 2-4 h.
The MXene/graphene composite nanosheet prepared by the preparation method provided by the invention has a heterogeneous layered structure and comprises MXene nanosheets and graphene layers which are mutually laminated and peeled.
Preferably, the distance between two adjacent layers in the MXene/graphene composite nanosheet is 1-2 nm.
The invention also provides an electrode plate which comprises a conductive substrate and a conductive layer coated on the surface of the conductive substrate, wherein the conductive layer comprises the MXene/graphene composite nanosheet, conductive carbon black and polyvinylidene fluoride according to the technical scheme.
The invention also provides the MXene/graphene composite nanosheet in the technical scheme, and the electrode piece in the technical scheme is applied to a super capacitor, a lithium ion battery or an electro-catalytic material.
The invention provides a preparation method of MXene/graphene composite nanosheets, which comprises the following steps: mixing MAX and hydrofluoric acid solution, and etching to obtain MXene; mixing the MXene and the tetrabutylammonium hydroxide solution, performing electrostatic adsorption, and performing ultrasonic treatment under a protective atmosphere to obtain a peeled MXene nanosheet dispersion liquid; mixing the peeled MXene nanosheet dispersion liquid and the graphene oxide suspension, carrying out self-assembly reaction, and drying to obtain MXene nanosheets/graphene oxide nanosheets; and carrying out reduction reaction on the MXene nanosheets/graphene oxide nanosheets under a protective atmosphere to obtain MXene/graphene composite nanosheets. According to the invention, after MXene is intercalated and stripped by tetrabutylammonium ions, the surface charge of MXene is modified by the tetrabutylammonium ions and carries positive charges, due to electrostatic action, positively charged stripped MXene nanosheets and negatively charged graphene oxide are self-assembled, MXene interlayer space is further increased, more lithium storage active sites can be exposed, the tetrabutylammonium ions are used as a cation intermediate to assist the two nanosheets to form a unique face-to-face arrangement structure, the unique two-dimensional structures of MXene and graphene are maintained, the two-dimensional structures are stable, the stripped MXene and graphene cannot be stacked again, and the open interlayer space can provide a channel for the rapid transmission of lithium ions; in the reduction reaction process, graphene oxide can be effectively reduced, tetrabutylammonium ions serving as a coupling agent can be removed, the microstructure is maintained, the electron transfer capacity between graphene and MXene is effectively improved, and the conductivity is further optimized. Moreover, the preparation method provided by the invention is simple to operate, low in cost and suitable for industrial production.
Graphene in the MXene/graphene composite nanosheet prepared by the method cannot be stacked again, the MXene/graphene composite nanosheet has excellent lithium storage performance, can keep the unique two-dimensional structure of MXene and graphene, and can be applied to a super capacitor, a lithium ion battery or an electrocatalytic material.
Drawings
Fig. 1 is an X-ray diffraction spectrum of the MXene/graphene composite nanosheet prepared in example 1;
fig. 2 is a scanning electron microscope image of MXene/graphene composite nanosheets prepared in example 1;
fig. 3 is a transmission electron microscope image of MXene/graphene composite nanosheets prepared in example 1;
fig. 4 is an X-ray photoelectron spectrum of the MXene/graphene composite nanosheet prepared in example 1;
FIG. 5 is a graph of rate performance of electrode sheets prepared from MXene/graphene composite nanosheets prepared in examples 1-3.
Detailed Description
The invention provides a preparation method of MXene/graphene composite nanosheets, which comprises the following steps:
mixing MAX and hydrofluoric acid solution, and etching to obtain MXene;
mixing the MXene and the tetrabutylammonium hydroxide solution, performing electrostatic adsorption and ultrasonic treatment to obtain a dispersed solution of peeled MXene nanosheets;
mixing the peeled MXene nanosheet dispersion liquid and the graphene oxide suspension liquid, and carrying out self-assembly reaction to obtain MXene nanosheets/graphene oxide nanosheets;
and carrying out reduction reaction on the MXene nanosheets/graphene oxide nanosheets under a protective atmosphere to obtain MXene/graphene composite nanosheets.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
The MXene is obtained by mixing MAX and hydrofluoric acid solution and etching.
In the invention, the particle size of the MAX is preferably 20-50 μm, and more preferably 35-45 μm; the chemical composition of MAX is preferably Ti3AlC2(ii) a The MAX is preferably purchased from Fossmann technologies (Beijing) Inc. In the present invention, the concentration of the hydrofluoric acid solution is preferably 30 to 50 wt%, more preferably 35 to 45 wt%, and most preferably 40 wt%. In the invention, the mass ratio of the MAX to hydrofluoric acid in the hydrofluoric acid solution is preferably 1 (15-25), more preferably 1 (16.5-22), and most preferably 1 (18-20).
In the present invention, the mixing is preferably stirring mixing, and the speed and time of the stirring mixing are not particularly limited in the present invention, and MAX may be mixed and dispersed in the hydrofluoric acid solution.
In the present invention, the etching is preferably performed under a stirring condition; the etching temperature is preferably room temperature; the time is preferably 12 to 24 hours, more preferably 15 to 21 hours, and most preferably 18 to 20 hours. In the invention, the metal in MAX is removed by hydrofluoric acid during the etching process.
After the etching, the method preferably further comprises the steps of carrying out solid-liquid separation on the etched system, washing the obtained solid component with water, and drying to obtain MXene. The solid-liquid separation mode is not particularly limited, and a solid-liquid separation mode known to those skilled in the art can be adopted, specifically, filtration or centrifugal separation; the conditions for the centrifugation in the present invention are not particularly limited, and the centrifugation conditions known to those skilled in the art may be used. In the invention, the washing with water is preferably deionized water washing, the frequency of the washing with water is not particularly limited, and hydrofluoric acid on the surface of the solid component can be removed completely. In the present invention, the drying is preferably freeze-drying, the temperature of the freeze-drying is preferably-30 to-55 ℃, and more preferably-35 to-45 ℃; the time is preferably 24 to 48 hours, more preferably 30 to 45 hours, and most preferably 35 to 40 hours.
After MXene is obtained, mixing the MXene and the tetrabutylammonium hydroxide solution, and performing ultrasonic treatment after electrostatic adsorption to obtain the peeled MXene nanosheet dispersion.
In the present invention, the concentration of the tetrabutylammonium hydroxide (TBAOH) solution is preferably 20 to 25 wt%, more preferably 21 to 24 wt%, and most preferably 22 to 23 wt%. In the present invention, the ratio of the mass of MXene to the volume of the tetrabutylammonium hydroxide solution is preferably 1g: (25-50) mL, more preferably 1g: (27.5-45) mL, most preferably 1g: (30-40) mL.
In the present invention, the mixing is preferably stirring mixing, and the speed and time of the stirring mixing are not particularly limited in the present invention, and MXene may be mixed and dispersed in the tetrabutylammonium hydroxide solution.
In the present invention, the electrostatic adsorption is preferably performed under stirring conditions; the temperature of the electrostatic adsorption is preferably room temperature; the time is preferably 1020h, more preferably 12-18 h, and most preferably 14-16 h. In the present invention, tetrabutylammonium ion (TBA) is generated during the electrostatic adsorption process+) Intercalated into MXene interlayer, and opened MXene interlayer space to form TBA+Stripping MXene nanosheet.
After the electrostatic adsorption, the invention preferably further comprises the steps of carrying out solid-liquid separation on the system of the electrostatic adsorption reaction, washing the obtained solid component with water, drying, and then placing the dried product in water for ultrasonic dispersion to obtain the peeled MXene nanosheet dispersion liquid.
The solid-liquid separation mode is not particularly limited, and a solid-liquid separation mode known to those skilled in the art can be adopted, specifically, filtration or centrifugal separation; the conditions for the centrifugation in the present invention are not particularly limited, and the centrifugation conditions known to those skilled in the art may be used. In the invention, the washing with water is preferably deionized water washing, and the frequency of the washing with water is not particularly limited, so that hydrofluoric acid can be removed completely. In the present invention, the drying is preferably freeze-drying, the temperature of the freeze-drying is preferably-30 to-55 ℃, and more preferably-35 to-45 ℃; the time is preferably 20-30 h, and more preferably 24 h.
In the invention, the water is preferably deionized water, and the concentration of the peeled MXene nanosheet dispersion is preferably 0.1-10 g/L, more preferably 0.5-8 g/L, and most preferably 1-5 g/L. In the present invention, the ultrasonic dispersion is preferably carried out in a protective atmosphere; the type of the protective atmosphere is not particularly limited in the present invention, and the protective atmosphere known to those skilled in the art may be adopted, specifically, nitrogen or argon; the MXene can be prevented from being oxidized by carrying out ultrasonic dispersion in the protective atmosphere; the ultrasonic power of the ultrasonic treatment is not particularly limited in the invention, and the ultrasonic power well known to those skilled in the art can be adopted; the temperature of the ultrasonic treatment is preferably room temperature; the time of ultrasonic treatment is preferably 90-120 min, and more preferably 100-110 min; the purpose of the sonication was to subject the TBA to+The intercalated MXene is dispersed into a few pieces or a single piece; the number of the small pieces is preferably 2-6, and more preferably 2-3.
After obtaining the peeled MXene nanosheet dispersion liquid, mixing the peeled MXene nanosheet dispersion liquid and the graphene oxide suspension liquid, and carrying out self-assembly reaction to obtain the MXene nanosheet/graphene oxide nanosheet.
In the invention, the concentration of the graphene oxide suspension is preferably 0.1-10 g/L, more preferably 0.5-8 g/L, and most preferably 1-5 g/L. In the invention, the mass ratio of the peeled MXene nanosheets in the peeled MXene nanosheet dispersion liquid to the oxidized graphene in the oxidized graphene suspension liquid is preferably 1: 10-10: 1, more preferably 1: 5-5: 1, and most preferably 1: 3-3: 1.
In the present invention, the peeled MXene nanosheet dispersion liquid and the graphene oxide suspension are preferably mixed by stirring, and the speed and time of the stirring and mixing are not particularly limited, and the peeled MXene nanosheet can be mixed and dispersed in the graphene oxide suspension.
In the present invention, the self-assembly reaction is preferably carried out under stirring conditions; the temperature of the self-assembly reaction is preferably room temperature; the time is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, and most preferably 2 hours. In the present invention, the self-assembly reaction process is positively charged (TBA)+) The peeled MXene nanosheets and negatively charged graphene oxide are subjected to self-assembly through electrostatic adsorption, tetrabutylammonium ions are used as a cation intermediate to assist the two nanosheets to form a unique face-to-face arrangement structure, the unique two-dimensional structures of MXene and graphene are maintained, the graphene cannot be stacked again, more active sites are provided for the insertion of lithium ions, and the expanded MXene interlayer spacing can provide a way for the rapid transmission of the lithium ions.
After the self-assembly reaction, the invention preferably further comprises drying the system of the self-assembly reaction to obtain MXene nanosheets/graphene oxide nanosheets. In the present invention, the drying is preferably freeze-drying, the temperature of the freeze-drying is preferably-30 to-55 ℃, and more preferably-35 to-45 ℃; the time is preferably 15 to 20 hours, more preferably 16 to 19 hours, and most preferably 17 to 18 hours.
After obtaining the MXene nanosheet/graphene oxide nanosheet, carrying out reduction reaction on the MXene nanosheet/graphene oxide nanosheet under a protective atmosphere to obtain the MXene/graphene composite nanosheet.
Before the reduction reaction, the invention preferably further comprises grinding the MXene nanosheets/graphene oxide nanosheets; the grinding is preferably carried out in a mortar, the grinding time is not particularly limited, and the MXene nanosheets/graphene oxide nanosheets can be ground to be uniform and free of large-block agglomeration.
The type of the protective atmosphere is not particularly limited in the present invention, and a protective atmosphere known to those skilled in the art may be used, specifically, nitrogen or argon.
In the invention, the temperature of the reduction reaction is preferably 300-500 ℃, more preferably 350-450 ℃, and most preferably 400 ℃; the heating rate of the temperature from room temperature to the temperature of the reduction reaction is preferably 3-7 ℃/min, and more preferably 5 ℃/min; the time for heat preservation is preferably 2-4 h, more preferably 2.5-3.5 h, and most preferably 3 h. The MXene nanosheet/graphene oxide nanosheet is preferably placed in a corundum crucible to perform reduction reaction in a tubular furnace. In the invention, graphene oxide is effectively reduced into graphene in the reduction reaction process, tetrabutylammonium ions serving as a coupling agent are decomposed at high temperature and removed, and the electron transfer capacity between graphene and MXene is effectively improved while the microstructure is maintained.
The MXene/graphene composite nanosheet prepared by the preparation method provided by the invention has a heterogeneous layered structure and comprises MXene nanosheets and graphene layers which are mutually laminated and peeled.
In the MXene/graphene composite nanosheet, the distance between two adjacent layers is preferably 1-2 nm, and more preferably 1.1-1.5 nm.
Graphene in the MXene/graphene composite nanosheet provided by the invention cannot be stacked again, the MXene/graphene composite nanosheet has excellent lithium storage performance, and the unique two-dimensional structure of MXene and graphene can be maintained.
The invention also provides an electrode plate which comprises a conductive substrate and a conductive layer coated on the surface of the conductive substrate, wherein the conductive layer comprises the MXene/graphene composite nanosheet, conductive carbon black and polyvinylidene fluoride according to the technical scheme.
In the present invention, the method for preparing the electrode sheet preferably comprises the following steps: mixing MXene/graphene composite nanosheets, conductive carbon black, polyvinylidene fluoride and a solvent, and coating the obtained slurry on the surface of a conductive substrate to obtain an electrode plate.
In the invention, the mass ratio of the MXene/graphene composite nanosheet to the conductive carbon black to the polyvinylidene fluoride (PVDF) is preferably (7-9): (0.5-1.5): (0.5 to 1.5), more preferably (7.5 to 8.5): (0.8-1.2): (0.8-1.2), and most preferably 8:1: 1.
In the present invention, the solvent preferably includes a pyrrolidone-type solvent, and the pyrrolidone-type solvent preferably includes N-methylpyrrolidone, 2-pyrrolidone, or N-ethylpyrrolidone. The dosage of the pyrrolidone solvent is not particularly limited, and in the embodiment of the present invention, the ratio of the mass of the MXene/graphene composite nanosheet to the volume of the pyrrolidone solvent is preferably 1g:20 mL.
In the present invention, the mixing is preferably stirring mixing, and the speed and time of the stirring mixing are not particularly limited in the present invention, and the raw materials may be uniformly mixed.
In the present invention, the conductive substrate preferably comprises copper foil or carbon-coated copper foil.
The coating method of the present invention is not particularly limited, and a coating method known to those skilled in the art may be used. In the invention, the coating amount of the slurry is preferably 0.004-0.01 g/cm based on the amount of MXene/graphene composite nanosheets2More preferably 0.005 to 0.007g/cm2。
After the coating, the present invention preferably further comprises drying the coated wet film. In the present invention, the drying is preferably performed by vacuum drying; the drying temperature is preferably 100-150 ℃, and more preferably 110-120 ℃; the time is preferably 5 to 15 hours, and more preferably 6 to 10 hours.
The invention also provides the MXene/graphene composite nanosheet of the technical scheme and application of the electrode plate of the technical scheme in a super capacitor, a lithium ion battery or an electro-catalytic material.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Putting 3g of MAX powder into 60mL of 40 wt% hydrofluoric acid solution, etching for 24h under the stirring condition, carrying out centrifugal separation, washing the obtained solid component with deionized water, and freeze-drying for 24h at-45 ℃ to obtain MXene;
(2) placing 2g of MXene in 70mL of 25 wt% TBAOH solution, performing electrostatic adsorption for 18h at room temperature under the stirring condition, performing centrifugal separation, washing the obtained solid component with deionized water, and performing freeze drying for 24h at-45 ℃ to obtain a stripped MXene nanosheet; placing 0.1g of peeled MXene nanosheet in 100mL of deionized water, and carrying out ultrasonic treatment for 120min in a protective atmosphere to obtain 1g/L peeled MXene nanosheet dispersion liquid;
(3) mixing the 1g/L peeled MXene nanosheet dispersion liquid and 20g/L graphene oxide suspension (the mass ratio of the peeled MXene nanosheets to the graphene oxide is 1:1) at room temperature under the stirring condition, carrying out self-assembly reaction for 2 hours, and then carrying out freeze drying for 20 hours to obtain MXene nanosheets/graphene oxide nanosheets;
(4) grinding the MXene nanosheets/graphene oxide nanosheets uniformly in a mortar, then uniformly paving the ground MXene nanosheets/graphene oxide nanosheets in a corundum crucible, placing the crucible in a tubular furnace, heating to 400 ℃ at the speed of 5 ℃/min under the protection of argon, reducing for 2h, and cooling to room temperature to obtain the MXene/graphene composite nanosheets.
An X-ray diffraction spectrum of the MXene/graphene composite nanosheet prepared in this embodiment is shown in fig. 1, and as can be seen from fig. 1, the MXene/graphene composite nanosheet prepared in the present invention has good crystallinity and high purity. Compared with the MXene obtained in the step (1), the (0002) peak of the MXene/graphene composite nanosheet near 9.1 degrees moves to the left to about 6.2 degrees, which shows that after the MXene and graphene are compounded, the distance between two-dimensional sheets is increased from 0.99nm to 1.28nm, and the increased interlayer distance is favorable for rapid ion transmission and further increases lithium ion storage sites.
Fig. 2 shows a scanning electron microscope image of the MXene/graphene composite nanosheet prepared in this example, and as can be seen from fig. 2, the MXene/graphene composite nanosheet has a sheet-like morphology with heterogeneous layers arranged face to face.
Fig. 3 shows a transmission electron microscope image of the MXene/graphene composite nanosheet prepared in this embodiment, and as can be seen from fig. 3, the graphene flakes and the peeled MXene flakes in the MXene/graphene composite nanosheet are arranged face to face, and the surface of the lamellar layer is smooth, the structure is stable, and the MXene/graphene composite nanosheet has a certain light transmission type, which indicates that the heterostructure of the MXene/graphene composite nanosheet after being compounded can maintain good two-dimensional characteristics.
An X-ray photoelectron energy spectrum of the MXene nanosheet/graphene oxide nanosheet and the MXene/graphene composite nanosheet prepared in this embodiment is shown in fig. 4, wherein C1s is measured photoelectron energy when a 1s orbital electron in a carbon atom is excited. As can be seen from fig. 4, after the MXene/graphene composite nanosheet is subjected to high-temperature reduction, the C-O bond is greatly reduced, and it is proved that the oxygen-containing functional group on the surface of the graphene is reduced at high temperature, so that the conductivity of the material is improved.
Example 2
MXene/graphene composite nanosheets were prepared according to the method of example 1, except that the concentration of the dispersed solution of MXene nanosheets in step (2) was 2 g/L; the mass ratio of the MXene nanosheets to the graphene oxide stripped in the step (3) is 1: 2.
Example 3
MXene/graphene composite nanosheets were prepared according to the method of example 1, except that the concentration of the dispersed solution of MXene nanosheets in step (2) was 0.1 g/L; the mass ratio of the MXene nanosheets to the graphene oxide stripped in the step (3) is 2: 1.
Example 4
MXene/graphene composite nanosheets were prepared according to the method of example 1, except that the volume of the TBAOH solution in step (2) was 55mL, the concentration of the exfoliated MXene nanosheet dispersion was 0.8g/L, and the mass ratio of the exfoliated MXene nanosheets to the graphene oxide in step (3) was 1: 4.
Example 5
Preparing MXene/graphene composite nanosheets according to the method of example 1, except that in step (2), the volume of the TBAOH solution is 55mL, and the concentration of the peeled MXene nanosheet dispersion is 0.8 g/L; the mass ratio of the MXene nanosheets to the graphene oxide stripped in the step (3) is 4: 1.
Example 6
Preparing MXene/graphene composite nanosheets according to the method of example 1, except that in step (2), the volume of the TBAOH solution is 55mL, and the concentration of the peeled MXene nanosheet dispersion is 0.8 g/L; the mass ratio of the MXene nanosheets to the graphene oxide stripped in the step (3) is 1: 6.
Example 7
MXene/graphene composite nanosheets were prepared according to the method of example 1, except that the volume of the TBAOH solution in step (2) was 85mL, the concentration of the exfoliated MXene nanosheet dispersion was 1.2g/L, and the mass ratio of the exfoliated MXene nanosheets to the graphene oxide in step (3) was 6: 1.
Example 8
Preparing MXene/graphene composite nanosheets according to the method of example 1, except that in step (2), the volume of the TBAOH solution is 85mL, and the concentration of the peeled MXene nanosheet dispersion is 1.2 g/L; the mass ratio of the MXene nanosheets to the graphene oxide stripped in the step (3) is 1: 8.
Example 9
Preparing MXene/graphene composite nanosheets according to the method of example 1, except that in step (2), the volume of the TBAOH solution is 85mL, and the concentration of the peeled MXene nanosheet dispersion is 1.2 g/L; the mass ratio of the MXene nanosheets to the graphene oxide stripped in the step (3) is 8: 1.
Example 10
MXene/graphene composite nanosheets were prepared according to the method of example 1, except that the volume of the TBAOH solution in step (2) was 100mL, the concentration of the exfoliated MXene nanosheet dispersion was 1.4g/L, and the mass ratio of the exfoliated MXene nanosheets to the graphene oxide in step (3) was 1: 10.
Example 11
Preparing MXene/graphene composite nanosheets according to the method of example 1, except that in step (2), the volume of the TBAOH solution is 100mL, and the concentration of the peeled MXene nanosheet dispersion is 1.4 g/L; the mass ratio of the MXene nanosheets to the graphene oxide stripped in the step (3) is 10: 1.
Example 12
MXene/graphene composite nanosheets were prepared according to the method of example 1, except that the reduction temperature in step (4) was 300 ℃; the mass ratio of the MXene nanosheets to the graphene oxide stripped in the step (3) is 1: 1.
Example 13
MXene/graphene composite nanosheets were prepared according to the method of example 1, except that the reduction temperature in step (4) was 500 ℃; the mass ratio of the MXene nanosheets to the graphene oxide stripped in the step (3) is 1: 1.
Example 14
Preparing MXene/graphene composite nanosheets according to the method of example 1, except that the temperature rise rate in the step (4) is 3 ℃/min; the mass ratio of the MXene nanosheets to the graphene oxide stripped in the step (3) is 1: 1.
Example 15
MXene/graphene composite nanosheets were prepared according to the method of example 1, except that in step (4), the heating rate was 7 ℃/min; the mass ratio of the MXene nanosheets to the graphene oxide stripped in the step (3) is 1: 1.
Application example
The method comprises the steps of stirring and mixing the MXene/graphene composite nanosheets prepared in examples 1-3, conductive carbon black, polyvinylidene fluoride (PVDF) and N-methyl pyrrolidone respectively, coating the mixture on a copper foil, and carrying out vacuum drying to obtain an electrode piece, wherein the mass ratio of the MXene/graphene composite nanosheets to the conductive carbon black to the PVDF is 8:1:1, and the rate performance graph of the electrode piece is shown in table 1 and fig. 5, wherein the mass ratio of the MXene to the graphene is 1:1 and represents example 1, the mass ratio of the MXene to the graphene is 1:2 and represents example 2, and the mass ratio of the MXene to the graphene is 2:1 and represents example 3.
TABLE 1 Rate Properties of electrode sheets prepared in examples 1-3
Figure BDA0002574335140000121
As can be seen from FIG. 5 and Table 1, when the mass ratio of MXene to graphene is 1:1, the specific capacity of lithium storage at a current density of 50mA/g is about 1394 mAh/g; when the mass ratio of MXene to graphene is 1:2, the lithium storage specific capacity is about 656Ah/g when the current density is 50 mA/g; when the mass ratio of MXene to graphene is 2:1, the lithium storage specific capacity is about 457mAh/g when the current density is 50 mA/g; when the mass ratio of MXene to graphene is 1:1, the specific capacity is 651mAh/g even when the current density is increased to 2A/g. The battery performance is attenuated along with the increase of current density, the damage to the MXene/graphene composite nanosheet structure is irreversible, and therefore the battery performance is slightly attenuated from small to large current to small current. The MXene/graphene composite nanosheet prepared by the method has excellent potential as a lithium storage electrode material.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of MXene/graphene composite nanosheets is characterized by comprising the following steps:
mixing MAX and hydrofluoric acid solution, and etching to obtain MXene;
mixing the MXene and the tetrabutylammonium hydroxide solution, performing electrostatic adsorption and ultrasonic treatment to obtain a dispersed solution of peeled MXene nanosheets;
mixing the peeled MXene nanosheet dispersion liquid and the graphene oxide suspension liquid, and carrying out self-assembly reaction to obtain MXene nanosheets/graphene oxide nanosheets;
and carrying out reduction reaction on the MXene nanosheets/graphene oxide nanosheets under a protective atmosphere to obtain MXene/graphene composite nanosheets.
2. The method according to claim 1, wherein the tetrabutylammonium hydroxide solution has a concentration of 20 to 25 wt%;
the ratio of the mass of MXene to the volume of the tetrabutylammonium hydroxide solution is 1g: (25-50) mL.
3. The preparation method according to claim 1 or 2, wherein the electrostatic adsorption is performed at room temperature for 10-20 h.
4. The preparation method according to claim 1, wherein the mass ratio of the peeled MXene nanosheets in the peeled MXene nanosheet dispersion liquid to the graphene oxide in the graphene oxide suspension liquid is 1: 10-10: 1.
5. The preparation method according to claim 1 or 4, wherein the self-assembly reaction is carried out at room temperature for 1-3 h.
6. The method according to claim 1, wherein the temperature of the reduction reaction is 300 to 500 ℃ and the time is 2 to 4 hours.
7. MXene/graphene composite nanoplatelets prepared by the preparation method of any one of claims 1 to 6, having a heterogeneous layered structure comprising exfoliated MXene nanoplatelets and graphene layers stacked on each other.
8. The MXene/graphene composite nanosheet of claim 7, wherein the distance between two adjacent layers of the MXene/graphene composite nanosheet is 1-2 nm.
9. An electrode plate, comprising a conductive substrate and a conductive layer coated on the surface of the conductive substrate, wherein the conductive layer comprises the MXene/graphene composite nanosheet of any one of claims 7-8, conductive carbon black and polyvinylidene fluoride.
10. The MXene/graphene composite nanosheet of any one of claims 7 to 8 or the electrode sheet of claim 9 for use in a supercapacitor, a lithium ion battery or in electrocatalysis.
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