CN116282023A - Heteroatom doped MXene material and preparation method and application thereof - Google Patents
Heteroatom doped MXene material and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
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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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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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
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C01P2006/40—Electric properties
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- 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
Abstract
The application relates to the technical field of material preparation, in particular to a heteroatom doped MXene material, and a preparation method and application thereof. According to the preparation method, the MAX phase ceramic material is used as a precursor, and the MXene solution is prepared through etching, so that the hetero-atom doping of hetero-atoms on the MXene material is realized in a short time, and the electrochemical energy storage performance of the MXene material is enhanced. Meanwhile, the problem of re-stacking of the MXene material in the film forming process is avoided. The adopted microwave irradiation treatment method can realize doping of hetero atoms in a short time, has simple use instrument, does not generate other byproducts in the treatment process, is very efficient, environment-friendly and energy-saving, has high safety coefficient and is favorable for wide use.
Description
Technical Field
The application belongs to the technical field of material preparation, and particularly relates to a heteroatom doped MXene material, and a preparation method and application thereof.
Background
MXene is a two-dimensional transition metal carbide/nitride/carbonitride, and many MXenes have been predicted to have excellent electronic, optical, plasma and thermoelectric properties, have the characteristics of high conductivity, high specific surface area, high bulk density, hydrophilic surface and the like, and exhibit great potential in the energy storage field.
Although the theoretical capacity of the MXene material is high, the potential interlayer energy storage space is not fully utilized, and mainly because the MXene material is a two-dimensional material, the sheets of the MXene material are easily laminated, which is unfavorable for electrolyte transmission, and the electrochemical utilization rate of the MXene material is seriously reduced. In addition, the MXene material has irregular shape, so that the materials are not in smooth contact, and a smooth conductive network is not formed. To overcome the shortcomings of materials, many researchers have used atoms to dope MXene materials.
Hitherto, there are solvothermal method, plasma treatment method, heat treatment method and the like for research on the doping direction of the MXene, and various doping treatment methods currently used are not favorable for ensuring the structure and the property of the MXene material on one hand, and long doping reaction period and complicated steps on the other hand, and are unfavorable for safe production and preparation.
Therefore, the development of a preparation process of the heteroatom doped MXene material, which is safe and reliable and has simple steps, and the research of the application of the heteroatom doped MXene material have important practical significance.
Disclosure of Invention
The invention aims to provide a heteroatom doped MXene material, and a preparation method and application thereof, and aims to solve the problems of long doping reaction period, step redundancy and unsafe preparation flow in the prior art.
In order to achieve the purposes of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for preparing a heteroatom doped MXene material, comprising the steps of:
mixing a precursor MAX phase ceramic material, an acid solution and fluoric acid salt, and then carrying out etching reaction to prepare an MXene solution;
providing a doping agent, and sequentially mixing the doping agent and the MXene solution, and carrying out reduced pressure filtration treatment to obtain a doping agent/MXene film material;
and carrying out microwave irradiation treatment on the dopant/MXene film material, and then carrying out post-treatment to obtain the heteroatom doped MXene material.
In a second aspect, the present application provides a heteroatom-doped MXene material, the heteroatom-doped MXene material being prepared by a method for preparing a heteroatom-doped MXene material, wherein the heteroatom is selected from at least one of a nitrogen atom, a sulfur atom, and a phosphorus atom.
In a third aspect, the present application provides the use of a heteroatom doped MXene material as an electrode material for a supercapacitor.
According to the preparation method of the heteroatom doped MXene material, MAX phase ceramic material is used as a precursor, MXene solution is prepared through etching reaction, and the doping agent is introduced. The method of microwave irradiation treatment realizes the doping of hetero atoms to the MXene material in a short time, introduces hetero atoms into the sheets of the MXene material to strengthen the electrochemical performance of the MXene material, avoids the agglomeration of the MXene material and further improves the material performance, realizes the doping effect of the hetero atoms in a short time, has simple use instrument, does not generate other byproducts in the treatment process, is very simple and efficient, is environment-friendly and energy-saving, has high safety coefficient and is favorable for wide use.
The heteroatom-doped MXene material provided in the second aspect of the application is prepared by a preparation method of the heteroatom-doped MXene material, wherein the heteroatom is at least one selected from nitrogen atoms, sulfur atoms and phosphorus atoms; the heteroatom doped MXene material is doped, so that the agglomeration and re-stacking of the MXene material can be prevented to a certain extent, the wettability, ion transportation property and electron conductivity of the MXene material are improved, and the obtained heteroatom doped MXene material has higher specific capacitance, capacitance retention rate and cycle performance and can be widely applied to the field of capacitors.
The heteroatom doped MXene material provided by the third aspect of the application is used as the electrode material of the super capacitor, and the obtained heteroatom doped MXene material has higher specific capacitance, capacitance retention rate and cycle performance, so that the heteroatom doped MXene material can be used as the electrode material in the field of capacitors, can improve the performance of the capacitors, and is beneficial to large-scale use.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following description will briefly introduce the drawings that are needed in the embodiments or the description of the prior art, it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a nitrogen-doped Ti prepared according to example 1 of the present application 3 C 2 T x XRD and SEM analysis charts are carried out on the materials respectively.
FIG. 2 is a nitrogen-doped Ti prepared according to example 1 of the present application 3 C 2 T x XPS full spectrum analysis is performed on the material.
FIG. 3 is a nitrogen doped Ti prepared according to example 1 of the present application 3 C 2 T x Materials and conventional Ti 3 C 2 T x CV diagrams of the material as electrode material at different scanning speeds of the supercapacitor device.
FIG. 4 is a nitrogen doped Ti prepared as provided in example 1 of the present application 3 C 2 T x Area ratio capacitance analysis chart of materials as electrode materials under different bending angles and current densities in a supercapacitor device.
FIG. 5 is a nitrogen-doped Ti prepared according to example 1 of the present application 3 C 2 T x Materials and conventional Ti 3 C 2 T x Capacitance contribution ratio analysis chart of the material at 5 mV/s.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved by the present application more clear, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of an association object, which means that there may be three relationships, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
It should be understood that, in various embodiments of the present application, the sequence number of each process does not mean that the sequence of execution is sequential, and some or all of the steps may be executed in parallel or sequentially, where the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application in the examples and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weights of the relevant components mentioned in the embodiments of the present application may refer not only to specific contents of the components, but also to the proportional relationship between the weights of the components, and thus, any ratio of the contents of the relevant components according to the embodiments of the present application may be enlarged or reduced within the scope disclosed in the embodiments of the present application. Specifically, the mass in the specification of the embodiment of the present application may be a mass unit well known in the chemical industry field such as μ g, mg, g, kg.
The terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated for distinguishing between objects such as substances from each other. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.
In a first aspect, an embodiment of the present application provides a method for preparing a heteroatom doped MXene material, including the steps of:
s01, mixing a precursor MAX phase ceramic material, an acid solution and fluorite, and then carrying out etching reaction to prepare an MXene solution;
s02, providing a doping agent, and sequentially mixing the doping agent and the MXene solution, and carrying out reduced pressure filtration treatment to obtain a doping agent/MXene film material;
s03, carrying out microwave irradiation treatment on the dopant/MXene film material, and then carrying out post-treatment to obtain the heteroatom doped MXene material.
According to the preparation method of the heteroatom doped MXene material, provided by the embodiment of the application, the MAX phase ceramic material is used as a precursor, the MXene solution is prepared through etching reaction, the MXene solution and the doping agent are mixed and filtered, microwave irradiation treatment is carried out, heteroatoms are introduced into the sheets of the MXene material to enhance the electrochemical performance of the MXene material, the problem of stacking the MXene material again in the film forming process is avoided, the material performance is further improved, the adopted microwave irradiation treatment method can realize heteroatom doping in a short time, the use instrument is simple, no other byproducts are generated in the treatment process, and the method is very simple and efficient, environment-friendly and energy-saving, has high safety coefficient, and is favorable for wide use.
In step S01, the precursor MAX phase ceramic material, the acid solution and the fluorite are mixed and processed, and then an etching reaction is carried out to prepare the MXene solution.
In some embodiments, the precursor MAX phase ceramic material comprises M 2 AX phase ceramic material, M 3 AX 2 Phase ceramic material and M 4 AX 3 Phase ceramic materials, wherein M represents a transition metal element, A represents a main group element, and X represents carbon or nitrogen.
In some embodiments, the precursor MAX phase ceramic material is selected from, but not limited to, V 2 AlC、Ti 3 AlC 2 、Nb 2 AlC、Cr 2 AlC、Ti 3 AlC 2 Any one of the following. In a specific embodiment of the present application, the precursor MAX phase ceramic material is Ti 3 AlC 2 。
In some embodiments, an acid solution is provided to facilitate reaction with the fluorite to form hydrofluoric acid, and the precursor MAX phase ceramic material is etched with the hydrofluoric acid to obtain the MXene solution.
In some embodiments, the acid solution includes, but is not limited to, hydrochloric acid, sulfuric acid, nitric acid solutions.
In some embodiments, the fluoroacid salt is selected from at least one of NaF, caF, liF, KF.
In some embodiments, the volume ratio of the acid solution to the fluorite is 20-25:1, and by controlling the excess acid solution, the whole reaction system is ensured to be an acid system in the reaction process, and the excess hydrogen ions provided by the acid solution can react with the fluoride ions to form hydrofluoric acid, so that the etching treatment of the precursor MAX phase ceramic material is facilitated, and the complete etching of the precursor MAX phase ceramic material is ensured, and the MXene solution is prepared.
And further, mixing the precursor MAX phase ceramic material, an acid solution and fluoric acid salt, and then carrying out etching reaction, thereby preparing the MXene solution.
In some embodiments, the etching reaction is performed at a temperature of 40-60 ℃ for 24-26 hours, and under the reaction condition of heating in the water bath, the precursor MAX phase ceramic material is ensured to be completely reacted. In some embodiments, the water bath is heated to 40 ℃ for 24 hours.
In some embodiments, the mass concentration of the prepared MXene solution is 1-3 mg/mL, and the mass concentration of the MXene solution is controlled to be moderate, so that hetero atoms can be doped better in the subsequent reaction process with the doping agent, and the problem of layered stacking of the MXene material is solved. In some embodiments, the mass concentration of the resulting MXene solution comprises 1mg/mL, 1.5mg/mL, 2mg/mL, 2.5mg/mL, 3mg/mL.
In step S02, a dopant is provided, and the dopant and the MXene solution are sequentially mixed and subjected to reduced pressure filtration treatment, so that the dopant/MXene film material is obtained.
In some embodiments, the dopant is selected from the group consisting of simple substances or compounds of at least one of the nitrogen, sulfur, and phosphorus elements.
In some embodiments, the nitrogen-containing compound is selected from CH 4 N 2 S、CH 4 N 2 O、C 3 H 6 N 6 、C 2 H 4 N 4 At least one of them.
In some embodiments, the sulfur-containing compound is selected from Na 2 S·9H 2 O、ZnS、Li 2 At least one of S.
In some embodiments, the elemental or compound of the phosphorus-containing element is selected from C 6 H 18 O 24 P 6 、NaH 2 PO 2 At least one of red phosphorus.
Further, the doping agent and the MXene solution are sequentially mixed and subjected to reduced pressure filtration treatment, so that the doping agent/MXene film material is obtained.
In some embodiments, the dopant may be dissolved first to enhance the electrochemical performance of the dopant before mixing with the MXene solution, and then mixed with the MXene solution after the dopant solution is obtained.
The doping agent and the MXene solution are stirred at normal temperature, and suction filtration is carried out to obtain the doping agent/MXene film material.
In the step S03, the dopant/MXene film material is subjected to microwave irradiation treatment and then post-treatment to obtain the heteroatom doped MXene material.
In some embodiments, different atmosphere conditions such as air, argon, nitrogen, helium, etc. may be provided during the microwave irradiation treatment.
Further, the dopant/MXene film material is subjected to microwave irradiation treatment.
In some embodiments, the number of microwave irradiation treatments is selected from 1 to 5. In some embodiments, the number of microwave irradiation treatments is selected from 1, 2, 3, 4, 5.
In some embodiments, the microwave irradiation treatment has a microwave power of 500-900W and a microwave time of 5-15 s. In some embodiments, the microwave power of the microwave irradiation process includes, but is not limited to, 500W, 550W, 600W, 650W, 700W, 750W, 800W, 850W, 900W. In some embodiments, the microwave time includes, but is not limited to, 5s, 7s, 9s, 11s, 13s, 15s.
In some embodiments, the dopant is selected from Na 2 S·9H 2 When in O, control Na 2 S 9H 2 Mixing the O and the MXene solution with the mass ratio of 30-180:1 to obtain Na 2 S·9H 2 O/MXene film material, na 2 S·9H 2 And carrying out microwave irradiation treatment on the O/MXene film material, wherein the power of the microwave irradiation treatment is 300-900W, the time is 6-7 seconds, the times are 2-10 times, and the sulfur-doped MXene material is obtained.
Further, the dopant is Na 2 S·9H 2 In the O process, the mass ratio of the doping agent to the MXene solution is controlled to be 120:1, and the Na is obtained through mixing treatment 2 S·9H 2 O/MXene film material, na 2 S·9H 2 And carrying out microwave irradiation treatment on the O/MXene film material, wherein the power of the microwave irradiation treatment is 900W, the time is 6 seconds, and the times are 2 times, so as to obtain the sulfur-doped MXene material.
In some embodiments, the dopant selects CH 4 N 2 S, control CH 4 N 2 Mixing the S and the MXene solution with the mass ratio of 10-25:1 to obtain CH 4 N 2 S/MXene film material, CH 4 N 2 And carrying out microwave irradiation treatment on the S/MXene film material, wherein the power of the microwave irradiation treatment is 300-900W, the time is 6-12 seconds, and the times are 2-10 times, so as to obtain the nitrogen-doped MXene material. Further, the dopant selects CH 4 N 2 S, control CH 4 N 2 Mixing the S and the MXene solution in a mass ratio of 20:1 to obtain CH 4 N 2 S/MXene film material, CH 4 N 2 And carrying out microwave irradiation treatment on the S/MXene film material, wherein the power of the microwave irradiation treatment is 700W, the time is 10 seconds, and the times are 4 times, so as to obtain the nitrogen-doped MXene material.
In some specific embodiments, when the dopant selects red phosphorus, mixing the red phosphorus and the MXene solution in a mass ratio of 1-4:3 to obtain a red phosphorus/MXene thin film material, and performing microwave irradiation treatment on the red phosphorus/MXene thin film material, wherein the power of the microwave irradiation treatment is 400-800W, the time is 10-20 seconds, and the times are 2-4 times to obtain the phosphorus doped MXene material. Further, when the doping agent selects red phosphorus, mixing the red phosphorus and the MXene solution according to the mass ratio of 1:3 to obtain a red phosphorus/MXene film material, and carrying out microwave irradiation treatment on the red phosphorus/MXene film material, wherein the power of the microwave irradiation treatment is 600W, the time is 10 seconds, and the times are 4 times to obtain the phosphorus doped MXene material.
In some embodiments, the post-processing includes: washing and drying.
In a second aspect, the embodiment of the present application provides a heteroatom-doped MXene material, where the heteroatom-doped MXene material is prepared by a method for preparing a heteroatom-doped MXene material, and the heteroatom is at least one selected from a nitrogen atom, a sulfur atom, and a phosphorus atom.
The heteroatom-doped MXene material provided in the second aspect of the embodiment of the application is prepared by a preparation method of the heteroatom-doped MXene material, wherein the heteroatom is at least one selected from nitrogen atoms, sulfur atoms and phosphorus atoms; the heteroatom doped MXene material is doped, so that the agglomeration and stacking of the MXene material can be prevented to a certain extent, the wettability, ion transportation property and electron conductivity of the MXene material are improved, and the obtained heteroatom doped MXene material has higher specific capacitance, capacitance retention rate and cycle performance and can be widely applied to the field of capacitors.
In a third aspect, embodiments of the present application provide an application of a heteroatom doped MXene material as an electrode material of a supercapacitor
The heteroatom doped MXene material provided by the third aspect of the embodiment of the application is used as the electrode material of the super capacitor, and the obtained heteroatom doped MXene material has higher specific capacitance, capacitance retention rate and cycle performance, so that the heteroatom doped MXene material can be used as the electrode material in the field of capacitors, can improve the performance of the capacitors, and is beneficial to large-scale use.
The following description is made with reference to specific embodiments.
Example 1
Heteroatom doped MXene material and preparation method thereof
The heteroatom doped MXene material is nitrogen doped Ti 3 C 2 T x Material
The preparation method comprises the following steps:
precursor MAX phase ceramic material Ti 3 AlC 2 Mixing hydrochloric acid solution and fluorite etching solution, and then reacting for 24 hours under the condition of water bath heating at 40 ℃ to prepare MXene solution with the mass concentration of 1-3 mg/mL;
providing a dopant thiourea, adding thiourea into 15ml L of 0.01M hydrochloric acid aqueous solution, stirring for 30 minutes to prepare a protonated thiourea solution as a dopant solution, and then adding 15M L of Ti with a concentration of 2mg/M L to the dopant solution 3 C 2 T x The MXene colloid solution is decompressed and filtered to obtain a doping agent/MXene film material;
placing a dopant/MXene film material into a glass bottle, filling argon, performing microwave irradiation treatment for 10 seconds under 700W power, washing and drying to obtain nitrogen-doped Ti 3 C 2 T x A material.
Example 2
Heteroatom doped MXene material and preparation method thereof
The heteroatom doped MXene material is sulfur doped Ti 3 C 2 Tx material
The preparation method comprises the following steps:
precursor MAX phase ceramic material Ti 3 AlC 2 Mixing hydrochloric acid solution and fluorite etching solution, and then reacting for 24 hours under the condition of water bath heating at 40 ℃ to prepare MXene solution with the mass concentration of 1-3 mg/mL;
providing a dopant Na 2 S·9H 2 O, na 2 S·9H 2 Mixing O and MXene solution in sequence, and carrying out reduced pressure filtration treatment to obtain a dopant/MXene film material;
placing a dopant/MXene film material into a glass bottle, filling argon, performing microwave irradiation treatment for 6 seconds under 900W power, performing microwave irradiation treatment for 2 times, washing, and drying to obtain sulfur-doped Ti 3 C 2 Tx material.
Example 3
Heteroatom doped MXene material and preparation method thereof
The heteroatom doped MXene material is phosphorus doped Ti 3 C 2 T x Material
The preparation method comprises the following steps:
precursor MAX phase ceramic material Ti 3 AlC 2 Mixing hydrochloric acid solution and fluorite etching solution, and then reacting for 24 hours under the condition of water bath heating at 40 ℃ to prepare MXene solution with the mass concentration of 1-3 mg/mL;
providing red phosphorus as a doping agent, adding red phosphorus powder into 15mL of potassium hydroxide solution with the concentration of 4mol/L, stirring and ultrasonic treatment for 30 minutes, and then adding 15m L of Ti with the concentration of 2mg/m L 3 C 2 T x Adding the MXene colloidal solution into the solution, uniformly mixing, and carrying out reduced pressure filtration treatment to obtain a doping agent/MXene film material;
placing a dopant/MXene film material into a glass bottle, filling argon, performing microwave irradiation treatment for 10 seconds under 600W power, performing microwave irradiation treatment for 4 times, washing and drying to obtain phosphorus doped Ti 3 C 2 T x A material.
Comparative example 1
thiourea/Ti 3 C 2 T x Material and preparation thereof
0.6g of thiourea was added to 15mL of a 0.01M aqueous hydrochloric acid solution and stirred for 20 minutes, and then 15mL of Ti having a concentration of 2mg/mL was added to the above solution 3 C 2 T x MXene colloid solution is mixed and stirred for 2 hours, then vacuum filtration is carried out to form a film, and the film is placed into a vacuum drying oven to be dried for 12 hours, thus obtaining thiourea/Ti 3 C 2 T x A material.
Performance testing
(one) Nitrogen-doped Ti prepared in example 1 3 C 2 T x XRD and SEM analysis were performed on the materials, respectively.
(II) Nitrogen-doped Ti prepared in example 1 3 C 2 T x XPS total spectrum analysis was performed on the material.
(III) Nitrogen-doped Ti prepared in example 1 3 C 2 T x Materials and conventional Ti 3 C 2 T x And the material is used as an electrode material to analyze the capacitance performance of the CV diagram of the supercapacitor device under different scanning speeds.
(IV) Nitrogen-doped Ti prepared in example 1 3 C 2 T x The material is used as an electrode material in a supercapacitor device, and the area specific capacitance of each current density under different bending angles is analyzed.
(fifth) Nitrogen-doped Ti prepared in example 1 3 C 2 T x Materials and conventional Ti 3 C 2 T x The material was calculated for its capacitance contribution at 5 mV/s.
Analysis of results
(one) Nitrogen-doped Ti prepared in example 1 3 C 2 T x As a result of XRD and SEM analysis of the material, respectively, as shown in FIG. 1, it was found that Ti was found by XRD in FIG. 1 (a) 3 C 2 T x The XRD curves of the sample and the nitrogen doped sample are basically consistent, which shows that the microwave assisted nitrogen doping does not cause obvious change to the crystal structure of the material; FIG. 1 (b) (c) canIn order to show that the nitrogen doping shows a more loose stacked structure compared with the pure MXene, the permeation of electrolyte is facilitated when the nitrogen doping is used as an electrode material, and the ion transmission efficiency is improved.
(II) Nitrogen-doped Ti prepared in example 1 3 C 2 T x XPS total spectrum analysis of the material, the results of which are shown in FIG. 2, it can be observed from FIG. 2 that Ti, C, O, F present in the sample should be derived from Ti 3 C 2 T x The MXene bulk and its surface groups, while the presence of the N element indicates successful preparation of nitrogen doped MXene.
(III) Nitrogen-doped Ti prepared in example 1 3 C 2 T x Materials and conventional Ti 3 C 2 T x CV diagrams of the material serving as an electrode material under different scanning speeds of the supercapacitor device are analyzed, and the capacitance performance is analyzed; as a result, as shown in FIG. 3, it can be found that comparative MXene, nitrogen doped with Ti 3 C 2 T x The shape of the material is more similar to a rectangle, and the material is slightly deformed along with the increase of the sweeping speed, which shows that the assembled super capacitor has better capacitance performance.
(IV) Nitrogen-doped Ti prepared in example 1 3 C 2 T x The material is used as an electrode material in a supercapacitor device, and the area specific capacitance of each current density under different bending angles is analyzed; as a result, as shown in fig. 4, it can be found that the specific capacitance of the device can be maintained substantially unchanged at different bending angles, indicating that the material has excellent performance stability.
(fifth) Nitrogen-doped Ti prepared in example 1 3 C 2 T x Materials and conventional Ti 3 C 2 T x The capacitance contribution rate of the material is calculated at 5mV/s, and the result is shown in FIG. 5, wherein FIG. 5 (a) and FIG. 5 (b) are MXene and nitrogen doped Ti prepared in example 1 respectively 3 C 2 T x The capacitance contribution rate of the material at 5mV/s is found to be 13.67% higher than that of the material after nitrogen doping.
In summary, the preparation method of the heteroatom doped MXene material provided by the application prepares the MXene solution by etching reaction by taking the MAX phase ceramic material as a precursor, introduces the doping agent to dope the MXene material in a short time by utilizing a microwave irradiation treatment method, introduces the heteroatom into a sheet layer of the MXene material to enhance the electrochemical performance of the MXene material, avoids the agglomeration of the MXene material and further improves the material performance, realizes the doping effect of the heteroatom in a short time by adopting the microwave irradiation treatment method, has simple instrument, does not generate other byproducts in the treatment process, is very simple and efficient, is environment-friendly and energy-saving, has high safety coefficient, and is favorable for wide use.
The foregoing description of the preferred embodiments of the present application is not intended to be limiting, but is intended to cover any and all modifications, equivalents, and alternatives falling within the spirit and principles of the present application.
Claims (10)
1. The preparation method of the heteroatom doped MXene material is characterized by comprising the following steps of:
mixing a precursor MAX phase ceramic material, an acid solution and fluoric acid salt, and then carrying out etching reaction to prepare an MXene solution;
providing a doping agent, and sequentially mixing the doping agent and the MXene solution, and carrying out reduced pressure filtration treatment to obtain a doping agent/MXene film material;
and carrying out microwave irradiation treatment on the dopant/MXene film material, and then carrying out post-treatment to obtain the heteroatom doped MXene material.
2. The method of claim 1, wherein the dopant is selected from the group consisting of elemental substances and compounds of at least one of nitrogen, sulfur, and phosphorus.
3. The method of preparing a heteroatom doped MXene material according to claim 2, wherein the nitrogen element-containing compound is selected from CH 4 N 2 S、CH 4 N 2 O、C 3 H 6 N 6 、C 2 H 4 N 4 At least one of (a)One of the two; and/or the number of the groups of groups,
the sulfur-containing compound is selected from Na 2 S·9H 2 O、ZnS、Li 2 At least one of S; and/or the number of the groups of groups,
the simple substance or compound containing phosphorus element is selected from C 6 H 18 O 24 P 6 、NaH 2 PO 2 At least one of red phosphorus.
4. The method for preparing a heteroatom doped MXene material according to claim 1, characterized in that the number of microwave irradiation treatments is chosen from 1 to 5.
5. The method for preparing a heteroatom doped MXene material according to claim 1, wherein the microwave power of the microwave irradiation treatment is 500-900W and the microwave time is 5-15 s.
6. The method of preparing a heteroatom doped MXene material according to any of claims 1-5, wherein the precursor MAX phase ceramic material is selected from V 2 AlC、Ti 3 AlC 2 、Nb 2 AlC、Cr 2 AlC、Ti 3 AlC 2 Any one of the following.
7. The method of any one of claims 1 to 5, wherein the fluoric acid salt is at least one selected from NaF, caF, liF, KF.
8. The method for preparing a heteroatom doped MXene material according to any one of claims 1-5, wherein the mass concentration of the MXene solution is 1-3 mg/mL.
9. The heteroatom-doped MXene material is characterized in that the heteroatom-doped MXene material is prepared by the preparation method of the heteroatom-doped MXene material according to any one of claims 1-8, wherein the heteroatom is at least one selected from nitrogen atoms, sulfur atoms and phosphorus atoms.
10. Use of the heteroatom-doped MXene material of claim 9 as an electrode material for a supercapacitor.
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| NISHA GUPTA ET AL.: "Microwave-assisted rapid synthesis of titanium phosphate free phosphorus doped Ti3C2 MXene with boosted pseudocapacitance", 《J.MATER.CHEM. A》, vol. 10, 30 June 2022 (2022-06-30), pages 15794 - 15810 * |
| 邵雅斌 著: "《二维材料的光学非线性吸收及载流子动力学研究》", vol. 1, 28 February 2022, 冶金工业出版社, pages: 109 * |
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