WO2021042456A1 - Rapid preparation method for few-layer mxenes and application - Google Patents

Rapid preparation method for few-layer mxenes and application Download PDF

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WO2021042456A1
WO2021042456A1 PCT/CN2019/112588 CN2019112588W WO2021042456A1 WO 2021042456 A1 WO2021042456 A1 WO 2021042456A1 CN 2019112588 W CN2019112588 W CN 2019112588W WO 2021042456 A1 WO2021042456 A1 WO 2021042456A1
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mxenes
layer
few
solution
ammonium
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Chinese (zh)
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韩伟强
张顺龙
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浙江大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0422—Cells or battery with cylindrical casing
    • H01M10/0427—Button cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to the technical field of nanomaterials, in particular to a rapid preparation method and application of a few-layer MXenes.
  • MXenes materials are usually made by corroding the "A" in MAX phase materials.
  • Metal bonds, ionic bonds and covalent bonds coexist in MAX phase crystals, where M is a transition metal element, and A is mainly the third main group and the fourth main group.
  • Main group elements, X is carbon and or nitrogen, M and X are mainly connected in the form of covalent bonds and ionic bonds, and the bonding strength between them is very high; between M and A elements and between A and A elements They are mostly connected by metal bonds, so the strength of chemical bonds is relatively weak.
  • MXenes material with two-dimensional morphology characteristics you can obtain the MXenes material with two-dimensional morphology characteristics, and directly etch the MAX to obtain a multilayer MXenes. If it is peeled off, after the follow-up Process, you can prepare a few layers of MXenes (about 10 layers and below, no more than 20 layers).
  • MXenes can be expressed by M n+1 X n T x , where M is the metal element Sc, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, etc., X is C, N or CN, n is generally 1-3, T x refers to some uncertain groups adsorbed on the surface (such as O, OH, F), and You can omit T x and directly express it with M n+1 X n , that is, the expression methods of M n+1 X n T x and M n+1 X n are interchangeable.
  • the rich chemical element composition and unique layered structure give MXenes material many unexpected properties.
  • Mxenes has excellent electrical conductivity (conductivity of 10 5 S/m), electrical conductivity reaches the level of some metals; good mechanical properties (good The tensile strength and flexibility), the flexibility is easy to form a film and used directly, avoiding the subsequent preparation of the molding process; the layer spacing is large and the flexibility is adjustable, the MXeness layer spacing obtained by etching ultrasound is about 1nm, between layers It is van der Waals force, the layer spacing is flexible and adjustable without destroying its layered structure.
  • the surface functional groups of MXenes endow it with hydrophilicity and surface structure tunability without significantly affecting its electrical conductivity. It can be prepared by rationally using the properties and structure of MXenes. Energy storage materials and devices with excellent performance.
  • the Chinese patent with the authorized announcement number CN106495210B discloses a preparation method of MXenes colloid.
  • Ammonium sulfate has endothermic properties, which reduces the severity of the reaction and avoids the danger of directly using HF acid.
  • the prepared MXenes material has a thicker layer, and the bonding layer spacing is about 1nm. It is estimated that the number of layers is 5000.
  • the advantages of MXenes two-dimensional materials cannot be fully utilized.
  • the Chinese patent with application number 201810359588.8 discloses a method for preparing three-dimensional MXenes.
  • MXenes powder is prepared by freeze-drying. It contains a lot of water, which makes the freeze-drying process relatively slow (conventional freeze-drying machine, it takes about 2 days to freeze-dry 5ml of water in a centrifuge tube), and the entire preparation process is time-consuming and laborious.
  • MXenes-based composite materials While taking advantage of the electrical conductivity of MXenes, other material systems are introduced to prevent the agglomeration of MXenes.
  • the Chinese patent application number 201810939968.9 discloses a core-shell The preparation method of structured nano-silicon-MXenes composite anode material
  • the Chinese patent application number 201810088813.9 discloses a preparation method of MXenes-Co composite material. Although the preparation of composite material broadens the application of MXenes, other materials are introduced, To a certain extent, it also limits the unique performance of MXenes.
  • the layer spacing of Ti 3 C 2 T x MXenes is about 1 nm, which is much larger than the layer spacing of other materials such as graphene, C 3 N 4 , MoS 2 and so on.
  • the introduction of graphene with small interlayer spacing can prevent the agglomeration of MXenes, but it is not a good choice for MXenes. So far, how to prepare MXenes materials with a small number of layers quickly and in large quantities (number of layers) At around 10 floors and below, no more than 20 floors), it is still a key and challenging problem.
  • the invention provides a rapid preparation and application of a few-layer Mxenes.
  • the method provided by the invention can effectively solve the problem of agglomeration of MXenes, and rapidly and mass-produce a few-layer MXenes material.
  • a rapid preparation method of low-layer MXenes includes the following steps:
  • step (3) Centrifuging the MXenes material obtained in step (2), washing the precipitate, stripping treatment, discarding the precipitate, and collecting the supernatant to obtain a low-layer MXenes solution;
  • step (4) The material obtained in step (4) is freeze-dried and annealed to obtain a powder of MXenes material with few layers.
  • the MXenes material in step (1) is Ti 4 C 3 , Ti 4 N 3 , Ti 3 C 2 , Ti 2 C, Mo 2 C, Hf 3 C 2 , V 3 C 2 , V 2 C, V 2 One or a combination of N, Nb 4 C 3 , Nb 3 C 2 , Nb 2 C, Cr 3 C 2 , Ta 2 C, Ta 4 C 3 , and (Ti 0.5 Nb 0.5 )C.
  • the etching solution in step (1) is one or a combination of HF, LiF and HCl, NaF and H 2 SO 4 , and other mixed solutions containing F salts and acids.
  • the organic molecule in step (2) is one of tetramethylammonium hydroxide, tetrabutylammonium hydroxide, hydrazine hydrate, N-methylpyrrolidone, dimethylsulfoxide, N-methylformamide, and ethanol Or a combination of multiple.
  • the surfactant in step (2) is decayl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, cetyl trimethyl ammonium bromide, One or more combinations of methyl ammonium bromide, octadecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, polyvinylpyrrolidone, and F127.
  • the peeling treatment in step (3) is one or a combination of mechanical shaking, ultrasound, cell pulverization, and the solvent used in the MXenes solution is one or a combination of water, ethanol, and acetone.
  • the electrolyte solution in step (4) is a salt containing ammonium ion, which is one of ammonium bicarbonate, ammonia water, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium bromide, ammonium chloride, and ammonium fluoride Or a combination of multiple.
  • ammonium ion is one of ammonium bicarbonate, ammonia water, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium bromide, ammonium chloride, and ammonium fluoride Or a combination of multiple.
  • the annealing temperature in step (5) is 70°C-700°C.
  • the few-layer MXenes prepared by the invention can be used as a negative electrode material for lithium ion batteries or sodium ion batteries.
  • the low-speed centrifugation usually means that the rotation speed does not exceed 6000r/min; especially in step (4), after the method of the present invention is used, the sample can be centrifuged in this step, and there will be no Low-speed centrifugation cannot be performed in the traditional method, but the rotation speed should not be too high.
  • the rotation speed is higher than 10000r/min, agglomeration will occur, and a low-layer MXenes powder with good dispersibility cannot be obtained. Refer to the implementation of Comparative Example 2 and Figures for details. 12.
  • the suction filtration is a common suction filtration method, the introduced ammonium ion, the MXenes sheet becomes porous during the electrostatic precipitation process, which avoids the densification phenomenon of MXenes in the conventional suction filtration method (densification makes the suction filtration process impossible ), after MXenes becomes porous, the suction filtration process can continue.
  • the aqueous material was less negative power, i.e. MXenes material adsorbed negatively charged group (OH -, F -, etc.) in the inner and outer surfaces, which are the properties MXenes material itself.
  • the method provided by the present invention is effective in introducing electrolyte solution, such as ammonium salt, so that cations (such as NH 4+ ) in the electrolyte solution are adsorbed on the surface of MXenes material through electrostatic adsorption. The electrostatic balance of the MXenes solution is destroyed, and electrostatic coagulation occurs.
  • the few-layer Mxenes sheet prepared by the present invention has a good three-dimensional network sheet structure.
  • the magnification ranges from 300 times to 70,000 times, all of which have a sheet structure without agglomeration. It is preliminary judged.
  • the layer thickness is below 10nm (the bonding layer spacing is 1nm, and the number of layers is estimated to be about 10).
  • the atomic force microscope test shows that the layer thickness of some MXenes materials is about 2-3nm (the number of layers is about 2-3 layers), This fully illustrates the feasibility of using cation assistance (such as NH 4+ ) and the use of electrostatic coagulation to prepare a small-layer MXenes material.
  • the small-layer MXenes material prepared by this method can be used in lithium batteries and electrochemical supercapacitors. The energy field has very broad application prospects.
  • Example 1 is the XRD pattern of Ti 3 AlC 2 raw material and the multilayer Ti 3 C 2 T x MXenes after etching in Example 1;
  • Example 2 is the Raman spectrum of Ti 3 AlC 2 raw material and the multilayer Ti 3 C 2 T x MXenes after etching in Example 1;
  • Figure 3 is a scanning electron micrograph of the multilayer Ti 3 C 2 T x MXenes prepared in Example 1;
  • Figure 4 is a photo of the small layer Ti 3 C 2 T x MXenes solution in Example 2 added to the ammonium bicarbonate solution, and after stirring it evenly, take out 20ml and place it in a small glass bottle. During the static process, the layering phenomenon of the solution changes dynamically. ;
  • Fig. 5 is a photo of the physical picture of the small-layer Ti 3 C 2 T x MXenes solution in Example 2 after adding the ammonium bicarbonate solution and stirring the solution evenly, after the solution is still for 30 minutes;
  • Figure 6 is a photo of the physical image of the low-layer Ti 3 C 2 T x MXenes solution in Example 2 after freeze-drying;
  • Fig. 7 is a low-magnification scanning electron microscope photo of the few-layer Ti 3 C 2 T x MXenes powder in Example 2;
  • Fig. 8 is a high-magnification scanning electron microscope photo of the few-layer Ti 3 C 2 T x MXenes powder in Example 2;
  • Fig. 9 is an atomic force microscope photograph and thickness analysis data of a few-layer Ti 3 C 2 T x MXenes powder in Example 2;
  • Figure 10 is a low- and high-magnification scanning electron micrograph of the low- layer V 2 CT x MXenes powder in Example 3;
  • Figure 11 is a scanning electron micrograph and element distribution analysis of a few-layer Ti 2 CT x MXenes powder in Example 4.
  • Fig. 12 is a scanning electron microscope photograph of Ti 3 C 2 T x MXenes in the implementation of Comparative Example 2;
  • Figure 13 is the physical image and scanning electron microscope photo of the few-layer Ti 3 C 2 T x MXenes electrode film in Application Example 1.
  • Figure 14 shows the electrochemical cycling performance of the few-layer Ti 3 C 2 T x MXenes sheet in Application Example 2;
  • Figure 15 shows the electrochemical cycling performance of the multilayer Ti 3 C 2 T x MXenes electrode sheet in Comparative Example 1;
  • the annealing temperature is 150°C
  • the annealing atmosphere is an argon atmosphere
  • the annealing time is 6h.
  • Figure 1 shows that in this example, in the process of preparing multilayer Ti 3 C 2 T x MXenes products from the initial Ti 3 AlC 2 ceramic powder, the XRD patterns of the raw materials and the multilayer Ti 3 C 2 T x MXenes are obviously different.
  • Figure 2 shows that the Raman spectrum of the raw material Ti 3 AlC 2 ceramic powder, 122, 180, 198 and 268 cm -1 correspond to the C-Ti-Al vibration in the MAX phase, and 580, 630 and 660 cm -1 correspond to the C-Ti-C vibration in the MAX phase, hydrogen
  • there are only three characteristic peaks at 150, 393 and 605 cm -1 corresponding to the Ti-C symmetric stretching vibration in MXenes.
  • the raw material Ti 3 AlC 2 ceramic powder will produce an obvious multi-layer structure, indicating that the multi-layer Ti 3 C 2 T x MXenes powder has been successfully prepared.
  • the centrifuge speed is 3500r/min
  • the centrifugation time is 10 minutes
  • the supernatant after centrifugation is collected and saved for subsequent use
  • the centrifuged precipitate is then poured into 70ml of deionized water, and the precipitate is stirred into The solution is sonicated for 30 minutes and then centrifuged at a speed of 3500r/min and a centrifuge time of 10 minutes. Collect the supernatant after centrifugation and save it for subsequent use.
  • the annealing temperature is 180°C
  • the annealing atmosphere is an argon atmosphere
  • the annealing time is 6h.
  • the powder is ground and collected to obtain a dry, few-layer Ti 3 C 2 T x MXenes powder, which can be used for subsequent applications.
  • Figure 4 shows that after the introduction of cation NH 4+ ions, the cations will be adsorbed to the surface of the electronegative few Ti 3 C 2 T x MXenes, which destroys the electrostatic balance maintained by the repulsive forces between MXenes (both are Electronegativity, mutual repulsion), electrostatic coagulation occurs.
  • Figure 5 it can be clearly seen that with the extension of the static time, the MXenes lamellae easily settle down. After 30 minutes of static, the MXenes lamella basically settles completely. If the stratification is more obvious, the supernatant can be discarded at this time to reduce the water content of freeze-drying and shorten the experimental period of freeze-drying.
  • Figure 6 shows that the low-layer Ti 3 C 2 T x MXenes sol appears as a fluffy network after freeze-drying, and its mass is 1.4g. It can be predicted that if the amount of etched MAX is increased in the early stage, more centrifuge tubes will be used at the same time. With the aid of NH 4+ ions, the electrostatic coagulation method can realize the macro-preparation of few layers of Ti 3 C 2 T x MXenes.
  • Figure 7 shows that there is no obvious agglomeration and agglomeration of Ti 3 C 2 T x MXenes powder under low magnification scanning electron microscope from 300 times magnification to 2000 times magnification. Multiple scanning electron microscopy, you can see a very obvious layer structure, the thickness is below 10nm, the layer spacing of Ti 3 C 2 T x MXenes is about 1nm, it can be judged that the obtained MXenes layer number is below 10 layers, and the film diameter is 5um. about.
  • the AFM photos and thickness analysis data in Figure 9 clearly show that the thickness of some of the few Ti 3 C 2 T x MXenes layers is 2-3 nm, and it is speculated that the number of Ti 3 C 2 T x MXenes layers is between 2-3 layers. , The film diameter is about 3um, combined with the experimental phenomena and results of Figures 4-9, fully demonstrate the feasibility of the present invention in the rapid and macro-preparation of low-layer MXenes powder.
  • the centrifuge speed is 3500r/min
  • the centrifugation time is 10 minutes
  • the supernatant after centrifugation is collected and saved for subsequent use
  • the centrifuged precipitate is poured into 50ml of deionized water, and the precipitate is stirred into The solution was sonicated for 30 minutes, and then centrifuged at 3500r/min, and the centrifuge time was 10 minutes. Collect the supernatant after centrifugation and save it for subsequent use.
  • step (3) While stirring, add dropwise the ammonium carbonate aqueous solution containing NH 4+ ions configured in step (3) to the 350ml V 2 CT x MXenes solution in step (2) above, until the addition is complete , Continue to stir for 30 minutes.
  • the powder is ground and collected to obtain a dry, small-layered V 2 CT x MXenes material powder, which can be used for subsequent use.
  • Figure 10 shows that the V 2 CT x MXenes obtained in this example has a three-dimensional networked sheet structure, from 400 times magnification to 70,000 magnification, all showing obvious lamella without agglomeration, which illustrates the present invention
  • the method is also applicable to the preparation of vanadium-based MXenes materials, which further illustrates the universality of the present invention.
  • step (3) While stirring, add dropwise the ammonium bicarbonate aqueous solution containing NH 4+ ions configured in step (3) to the 350ml MXenes solution in step (2) above, and continue stirring until the addition is complete 30 minutes.
  • Figure 11 shows that the prepared Ti 2 CT x MXenes material has a small number of layers, and the element distribution diagram shows that the distribution characteristic areas of the core elements Ti and C are consistent with the Ti 2 C lamellae.
  • Example 2 Similar to Example 1, in this comparative example, after obtaining a few layers of Ti 3 C 2 T x MXenes aqueous solution, it is about 350 ml, from which 50 ml is measured with a beaker, frozen in the refrigerator, and then freeze-dried.
  • the freeze-drying process takes about 50h, which is very time-consuming. If all the aqueous solutions of the low-layer Ti 3 C 2 T x MXenes are to be freeze-dried, the required time is about 400 hours. In contrast, the present invention uses electrostatic coagulation. The volume of the solution that needs to be freeze-dried is greatly reduced, and 350ml of the solution is processed into a solution of about 10ml, and it can be completely freeze-dried in only 10h, which greatly improves the efficiency.
  • Example 2 Similar to Example 1, in this comparative example, after obtaining an aqueous solution of a few layers of Ti 3 C 2 T x MXenes, it was centrifuged at a high speed at a speed of 12000 r/min and a centrifugation time of 10 minutes, then freeze-dried, and then vacuum-dried to collect Ti 3 C 2 T x MXenes powder.
  • the scanning electron microscope photo of Ti 3 C 2 T x MXenes prepared by the comparative example of this embodiment it is found that they are agglomerated into blocks. Under the scanning electron microscope of high magnification, no obvious lamellae are seen, and the agglomeration phenomenon is serious. In some places, A large and thick layer is composed of many small MXenes layers (as shown in part d in the figure). The MXenes prepared by this method have serious agglomeration and cannot fully utilize the two-dimensional layer of MXenes in subsequent applications. Advantages of Shaped Materials.
  • the small-layer MXenes material prepared in the above example 1 is used as the negative electrode material of lithium-ion batteries.
  • the negative electrode of the battery is prepared by the suction and film forming method. The film after suction and vacuum drying is cut and sliced. The button-type lithium-ion battery is assembled in the glove box, and then the relevant test of the electrochemical performance is carried out. Specific steps are as follows:
  • 1Negative electrode preparation The 350ml Ti 3 C 2 T x MXenes solution prepared in the above example 1 is used to prepare the film by vacuum filtration, which eliminates the need for conductive agents and binders for battery pole pieces, and simplifies the pole pieces. In the preparation process, after freeze-drying, it was dried under vacuum at 70°C for 10 hours, and after drying, it was cut into an electrode sheet with a diameter of 14mm to produce a battery negative sheet with a few layers of Ti 3 C 2 T x MXenes material as the negative electrode material.
  • the physical image and the scanning electron microscope image of the film formed by the suction filter are obvious lamellas without agglomeration.
  • the small-layer Ti 3 C 2 T x MXenes material prepared in the above-mentioned Example 1 is used as the negative electrode material of the lithium ion battery.
  • the battery negative pole piece is prepared by the slurry method, and the button type lithium ion battery is assembled in the glove. Then carry out the relevant test of electrochemical performance. Specific steps are as follows:
  • the multilayer Ti 3 C 2 T x MXenes material prepared in step (1) of Example 1 was used as the negative electrode material for lithium ion batteries. Lithium-ion batteries are then tested for electrochemical performance. Specific steps are as follows:
  • the multilayer Ti 3 C 2 T x MXenes material prepared in step (1) of the above embodiment 1 was mixed with 5% polyvinylidene fluoride (PVDF) in a mass ratio of 8:1:1.
  • PVDF polyvinylidene fluoride
  • the binder and the conductive agent Super P are mixed uniformly. After stirring, the slurry is formed and coated on the copper foil, and dried under vacuum at 90°C for 10 hours. After drying, it is cut into an electrode sheet with a diameter of 14mm.
  • the layer Ti 3 C 2 T x MXenes material is the battery negative electrode sheet of the negative electrode material.

Abstract

Provided are a rapid preparation method for few-layer MXenes and application, in the method, the preparation of the few-layer MXenes material obtains a few-layer MXenes solution with good dispersibility by stripping multi-layer MXenes liquid phase; the electrostatic balance of the few-layer MXenes solution with is destroyed by introducing the electrolyte solution, the obtained sol, precipitate or filter cake is the few-layer MXenes material by means of cation-assisted electrostatic precipitation process (such as NH 4+) through standing or low-speed centrifugation or pumping filtration; then macro-scale preparation of the few-layer MXenes powder can be realized through freeze drying and subsequent annealing treatment. The prepared few-layer MXenes are suitable for lithium ion batteries or sodium ion batteries.

Description

一种少层MXenes的快速制备方法及应用A rapid preparation method and application of low-layer MXenes 技术领域Technical field
本发明涉及纳米材料技术领域，尤其涉及一种少层MXenes的快速制备方法及应用。The invention relates to the technical field of nanomaterials, in particular to a rapid preparation method and application of a few-layer MXenes.
背景技术Background technique
MXenes材料通常是通过腐蚀MAX相材料中的“A”制得，MAX相晶体中金属键、离子键和共价键并存，其中M为过渡族金属元素，A主要为第三主族和第四主族族元素，X为碳和或氮，M与X之间主要以共价键和离子键的形式连接，之间的结合强度很高；M与A元素之间以及A与A元素之间则多以金属键相连，故化学键的强度相对较弱。因此只要选择适当的方法选择性地刻蚀MAX相中的A层原子就可以获得具有二维形貌特征的MXenes材料，直接将MAX刻蚀得到的为多层MXenes，如果将其剥离，经过后续工艺，便可以制备得到少层的MXenes(10层左右及以下，不超过20层)，MXenes的化学通式可用M n+1X nT x表示，其中M为金属元素Sc、Ti、V、Cr、Zr、Nb、Mo、Hf和Ta等，X为C、N或CN，n一般为1-3，T x指表面吸附的一些不确定的基团(如O、OH、F)，也可以省略T x，直接用M n+1X n表示，即M n+1X nT x和M n+1X n的表示方法具有可替换性。丰富的化学元素组成和独特的层状结构，赋予MXenes材料许多意想不到的性能，Mxenes具有优异的导电性(电导率10 5S/m)、电导率达到部分金属级别；机械性能佳(较好的拉伸强度和柔性)，柔性易成膜而直接使用，避免了后续制备的成型过程；层间距较大并且柔性可调，刻蚀超声得到的MXeness层间距在1nm左右，层与层之间是范德华力，层间距柔性可调而不破坏其层状结构，MXenes表面官能团赋予其亲水性及表面结构可调性，同时不显著影响其导电性，合理利用MXenes的性质和结构，可制备性能优良的储能材料和器件。 MXenes materials are usually made by corroding the "A" in MAX phase materials. Metal bonds, ionic bonds and covalent bonds coexist in MAX phase crystals, where M is a transition metal element, and A is mainly the third main group and the fourth main group. Main group elements, X is carbon and or nitrogen, M and X are mainly connected in the form of covalent bonds and ionic bonds, and the bonding strength between them is very high; between M and A elements and between A and A elements They are mostly connected by metal bonds, so the strength of chemical bonds is relatively weak. Therefore, as long as you choose an appropriate method to selectively etch the atoms of the A layer in the MAX phase, you can obtain the MXenes material with two-dimensional morphology characteristics, and directly etch the MAX to obtain a multilayer MXenes. If it is peeled off, after the follow-up Process, you can prepare a few layers of MXenes (about 10 layers and below, no more than 20 layers). The general chemical formula of MXenes can be expressed by M n+1 X n T x , where M is the metal element Sc, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, etc., X is C, N or CN, n is generally 1-3, T x refers to some uncertain groups adsorbed on the surface (such as O, OH, F), and You can omit T x and directly express it with M n+1 X n , that is, the expression methods of M n+1 X n T x and M n+1 X n are interchangeable. The rich chemical element composition and unique layered structure give MXenes material many unexpected properties. Mxenes has excellent electrical conductivity (conductivity of 10 5 S/m), electrical conductivity reaches the level of some metals; good mechanical properties (good The tensile strength and flexibility), the flexibility is easy to form a film and used directly, avoiding the subsequent preparation of the molding process; the layer spacing is large and the flexibility is adjustable, the MXeness layer spacing obtained by etching ultrasound is about 1nm, between layers It is van der Waals force, the layer spacing is flexible and adjustable without destroying its layered structure. The surface functional groups of MXenes endow it with hydrophilicity and surface structure tunability without significantly affecting its electrical conductivity. It can be prepared by rationally using the properties and structure of MXenes. Energy storage materials and devices with excellent performance.
授权公告号为CN106495210B的中国专利公开了一种MXenes胶体的制备方法，通过将H 2SO 4溶液与NH 4HF 2混合，利用混合过程中产生的氢氟酸对MAX原料进行刻蚀，产生的硫酸铵具有吸热性，减小了反应的剧烈程度，避免了直接使用HF酸的危险性，但制备得到的MXenes材料层数较厚，结合层间距为1nm左右，推测其层数在5000层左右，无法充分发挥MXenes二维材料的优势。申 请号为201810359588.8的中国专利公开了一种三维MXenes的制备方法，通过把MXenes分散在溶剂中，超声分散将多层MXenes剥离成少层，后续通过冷冻干燥的方式来制备MXenes粉体，由于溶液中含有大量的水，使得冻干过程比较缓慢(常规冷冻干燥机，在离心管里冻干5ml水就需要2天左右)，整个制备过程费时费力。 The Chinese patent with the authorized announcement number CN106495210B discloses a preparation method of MXenes colloid. By mixing H 2 SO 4 solution with NH 4 HF 2 and using the hydrofluoric acid produced during the mixing process to etch MAX raw materials, Ammonium sulfate has endothermic properties, which reduces the severity of the reaction and avoids the danger of directly using HF acid. However, the prepared MXenes material has a thicker layer, and the bonding layer spacing is about 1nm. It is estimated that the number of layers is 5000. The advantages of MXenes two-dimensional materials cannot be fully utilized. The Chinese patent with application number 201810359588.8 discloses a method for preparing three-dimensional MXenes. By dispersing MXenes in a solvent and ultrasonically dispersing, the multilayer MXenes are stripped into a few layers, and then MXenes powder is prepared by freeze-drying. It contains a lot of water, which makes the freeze-drying process relatively slow (conventional freeze-drying machine, it takes about 2 days to freeze-dry 5ml of water in a centrifuge tube), and the entire preparation process is time-consuming and laborious.
此外，关于MXenes基复合材料，也有很多的文献和专利报道，在发挥MXenes材料导电优势的同时，通过引入其他材料体系，阻止MXenes的团聚，如申请号为201810939968.9的中国专利公开了一种核壳结构纳米硅-MXenes复合负极材料的制备方法，申请号为201810088813.9的中国专利公开了一种MXenes-Co复合材料的制备方法，复合材料的制备，虽然拓宽了MXenes的应用，但引入的其他材料，在某种程度上，也限制了MXenes独特性能的发挥，如Ti 3C 2T x MXenes层间距为1nm左右，远远大于如石墨烯，C 3N 4，MoS 2等其他材料的层间距，引入层间距较小的石墨烯等，虽能阻止MXenes的团聚，但对MXenes而言，并不是一种很好的选择，目前为止，如何快速、大批量地制备少层的MXenes材料(层数在10层左右及以下，不超过20层)，仍然是一个比较关键的挑战性问题。 In addition, there are many literature and patent reports on MXenes-based composite materials. While taking advantage of the electrical conductivity of MXenes, other material systems are introduced to prevent the agglomeration of MXenes. For example, the Chinese patent application number 201810939968.9 discloses a core-shell The preparation method of structured nano-silicon-MXenes composite anode material, the Chinese patent application number 201810088813.9 discloses a preparation method of MXenes-Co composite material. Although the preparation of composite material broadens the application of MXenes, other materials are introduced, To a certain extent, it also limits the unique performance of MXenes. For example, the layer spacing of Ti 3 C 2 T x MXenes is about 1 nm, which is much larger than the layer spacing of other materials such as graphene, C 3 N 4 , MoS 2 and so on. The introduction of graphene with small interlayer spacing can prevent the agglomeration of MXenes, but it is not a good choice for MXenes. So far, how to prepare MXenes materials with a small number of layers quickly and in large quantities (number of layers) At around 10 floors and below, no more than 20 floors), it is still a key and challenging problem.
发明内容Summary of the invention
为解决上述问题，即常规方法制备的MXenes材料层数过厚，或当把层数减薄时，MXenes的收集存在一定的困难：(1)抽滤的时候，容易成膜致密化，使得抽滤无法持续进行；(2)由于密度轻，加上电负性MXenes片层之间的静电排斥作用，MXenes片在水溶液中非常稳定，无法通过常规离心收集，即使高速离心，少层MXenes材料还是无法离心下去，并且，常规抽滤和高速离心的收集方式，容易出现严重的团聚结块现象，无法获得分散性良好的粉末状态的MXenes片层，便无法发挥二维层状MXenes材料的优势。本发明提供了一种少层Mxenes的快速制备及应用，通过本发明提供的方法，可以有效解决MXenes的团聚问题，快速大批量的制备少层的MXenes材料。In order to solve the above problems, that is, the number of layers of MXenes prepared by conventional methods is too thick, or when the number of layers is reduced, there are certain difficulties in the collection of MXenes: Filtration cannot be continued; (2) Due to the light density and the electrostatic repulsion between the electronegative MXenes sheets, the MXenes sheets are very stable in aqueous solutions and cannot be collected by conventional centrifugation. Even high-speed centrifugation, the few layers of MXenes material are still It cannot be centrifuged down, and the conventional suction filtration and high-speed centrifugation collection methods are prone to serious agglomeration and agglomeration. It is impossible to obtain MXenes sheets in a powder state with good dispersibility, and cannot take advantage of the advantages of two-dimensional layered MXenes materials. The invention provides a rapid preparation and application of a few-layer Mxenes. The method provided by the invention can effectively solve the problem of agglomeration of MXenes, and rapidly and mass-produce a few-layer MXenes material.
为实现上述目的，本发明提供以下技术方案:In order to achieve the above objectives, the present invention provides the following technical solutions:
一种少层MXenes的快速制备方法，包括如下步骤：A rapid preparation method of low-layer MXenes includes the following steps:
(1)取MAX原料，在刻蚀液中处理，得到多层的MXenes材料；(1) Take the MAX raw material and process it in an etching solution to obtain a multilayer MXenes material;
(2)将步骤(1)得到的MXenes材料在有机分子或表面活性剂中处理；(2) Treat the MXenes material obtained in step (1) in organic molecules or surfactants;
(3)将步骤(2)得到的MXenes材料进行离心，洗涤沉淀，剥离处理，弃沉淀，收集上清液，得到少层的MXenes溶液；(3) Centrifuging the MXenes material obtained in step (2), washing the precipitate, stripping treatment, discarding the precipitate, and collecting the supernatant to obtain a low-layer MXenes solution;
(4)将含有铵根离子的电解质溶液加入到步骤(3)得到的MXenes溶液中，静电聚沉，静置或低速离心或抽滤，所得溶胶、或沉淀、或滤饼即为少层的MXenes材料；(4) The electrolyte solution containing ammonium ions is added to the MXenes solution obtained in step (3), electrostatic precipitation, standing or low-speed centrifugation or suction filtration, the resulting sol, or precipitation, or filter cake is less layered MXenes material;
(5)将步骤(4)得到的材料冷冻干燥，退火处理，得到少层的MXenes材料的粉体。(5) The material obtained in step (4) is freeze-dried and annealed to obtain a powder of MXenes material with few layers.
进一步地，步骤(1)中MXenes材料是Ti 4C 3、Ti 4N 3、Ti 3C 2、Ti 2C、Mo 2C、Hf 3C 2、V 3C 2、V 2C、V 2N、Nb 4C 3、Nb 3C 2、Nb 2C、Cr 3C 2、Ta 2C、Ta 4C 3、(Ti 0.5Nb 0.5)C中的一种或多种的组合。 Further, the MXenes material in step (1) is Ti 4 C 3 , Ti 4 N 3 , Ti 3 C 2 , Ti 2 C, Mo 2 C, Hf 3 C 2 , V 3 C 2 , V 2 C, V 2 One or a combination of N, Nb 4 C 3 , Nb 3 C 2 , Nb 2 C, Cr 3 C 2 , Ta 2 C, Ta 4 C 3 , and (Ti 0.5 Nb 0.5 )C.
进一步地，步骤(1)中的刻蚀液为HF、LiF和HCl、NaF和H 2SO 4、其他含F盐和酸的混合液中的一种或多种的组合。 Further, the etching solution in step (1) is one or a combination of HF, LiF and HCl, NaF and H 2 SO 4 , and other mixed solutions containing F salts and acids.
进一步地，步骤(2)中的有机分子是四甲基氢氧化铵、四丁基氢氧化铵、水合肼、N-甲基吡咯烷酮、二甲基亚砜、N-甲基甲酰胺、乙醇的一种或多种的组合。Further, the organic molecule in step (2) is one of tetramethylammonium hydroxide, tetrabutylammonium hydroxide, hydrazine hydrate, N-methylpyrrolidone, dimethylsulfoxide, N-methylformamide, and ethanol Or a combination of multiple.
进一步地，步骤(2)中的表面活性剂是十烷基三甲基溴化铵、十二烷基三甲基溴化铵、十四烷基三甲基溴化铵、十六烷基三甲基溴化铵、十八烷基三甲基溴化铵、十八烷基三甲基氯化铵、聚乙烯吡咯烷酮、F127中的一种或多种的组合。Further, the surfactant in step (2) is decayl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, cetyl trimethyl ammonium bromide, One or more combinations of methyl ammonium bromide, octadecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, polyvinylpyrrolidone, and F127.
进一步地，步骤(3)中的剥离处理是机械摇晃，超声，细胞粉碎中的一种或其组合，MXenes溶液采用的溶剂是水、乙醇、丙酮中的一种或多种的组合。Further, the peeling treatment in step (3) is one or a combination of mechanical shaking, ultrasound, cell pulverization, and the solvent used in the MXenes solution is one or a combination of water, ethanol, and acetone.
进一步地，步骤(4)中的电解质溶液是含有铵根离子的盐，是碳酸氢铵、氨水、碳酸铵、硝酸铵、硫酸铵、溴化铵、氯化铵、氟化铵中的一种或多种的组合。Further, the electrolyte solution in step (4) is a salt containing ammonium ion, which is one of ammonium bicarbonate, ammonia water, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium bromide, ammonium chloride, and ammonium fluoride Or a combination of multiple.
进一步地，步骤(5)中的退火温度为70℃-700℃。Further, the annealing temperature in step (5) is 70°C-700°C.
本发明制备的少层MXenes，可以用作锂离子电池或钠离子电池的负极材料。The few-layer MXenes prepared by the invention can be used as a negative electrode material for lithium ion batteries or sodium ion batteries.
上述技术方案中，所述的低速离心通常指转速不超过6000r/min；尤其是在步骤(4)中，采用本发明的方法处理后，在该步骤中样品是可以离心下去的，不会出现传统方法中无法进行低速离心的情况，但是转速不宜过高，当转速高于10000r/min，则会出现团聚现象，无法得到分散性良好的少层MXenes粉体，具体参考实施对比例2及图12。所述抽滤为普通抽滤方式，引入的铵根离子，静 电聚沉的过程中MXenes片层多孔化，避免了MXenes在常规抽滤方法中的致密化现象(致密化使得抽滤过程无法进行)，MXenes多孔化后，抽滤过程可以持续进行。In the above technical solution, the low-speed centrifugation usually means that the rotation speed does not exceed 6000r/min; especially in step (4), after the method of the present invention is used, the sample can be centrifuged in this step, and there will be no Low-speed centrifugation cannot be performed in the traditional method, but the rotation speed should not be too high. When the rotation speed is higher than 10000r/min, agglomeration will occur, and a low-layer MXenes powder with good dispersibility cannot be obtained. Refer to the implementation of Comparative Example 2 and Figures for details. 12. The suction filtration is a common suction filtration method, the introduced ammonium ion, the MXenes sheet becomes porous during the electrostatic precipitation process, which avoids the densification phenomenon of MXenes in the conventional suction filtration method (densification makes the suction filtration process impossible ), after MXenes becomes porous, the suction filtration process can continue.
本发明的有益效果在于：The beneficial effects of the present invention are:
通过刻蚀剥离，少层MXenes的水溶液材料呈电负性，即MXenes材料在内外表面吸附了带负电荷的集团(OH -,F -等)，这是MXenes材料本身的性质。本发明提供的方法与传统制备MXenes材料的方法相比，本发明通过巧妙引入电解质溶液，如铵盐，使电解质溶液中的阳离子(如NH 4+)通过静电吸附作用吸附在MXenes材料表面，有效破坏了MXenes溶液的静电平衡，发生静电聚沉，静止一段时间或低速离心后或抽滤后，将少体积的MXenes溶胶，或者是低速离心后的MXenes沉淀，或是抽滤后的滤饼冻干，退火处理，即可以将铵盐转化为氨气挥发掉，即得到少层MXenes材料粉体。整个实验过程，具有反应温和、安全、成本低、时间短、设备简单等优点，由于静电聚沉作用，大大减少了冷冻干燥过程中需要冻干的溶液，大大缩短了实验过程，在工业大生产中有很好的应用前景。本发明制备的少层Mxenes片层具有很好的三维网状片层结构，在用扫描电镜观察时，从放大倍数为300倍到70000倍，均为片层结构，没有团聚现象，初步判断，层厚在10nm以下(结合层间距为1nm，推测层数在10层左右)，原子力显微镜测试表明，有些片层MXenes材料的层厚为2-3nm左右(层数在2-3层左右)，充分说明了通过阳离子辅助(如NH 4+)，利用静电聚沉作用，宏量制备少层MXenes材料的可行性，通过此方法制备的少层MXenes材料，在锂电池和电化学超级电容器等储能领域有很广阔的应用前景。 By etching the peeling layer MXenes the aqueous material was less negative power, i.e. MXenes material adsorbed negatively charged group (OH -, F -, etc.) in the inner and outer surfaces, which are the properties MXenes material itself. Compared with the traditional method for preparing MXenes material, the method provided by the present invention is effective in introducing electrolyte solution, such as ammonium salt, so that cations (such as NH 4+ ) in the electrolyte solution are adsorbed on the surface of MXenes material through electrostatic adsorption. The electrostatic balance of the MXenes solution is destroyed, and electrostatic coagulation occurs. After standing for a period of time or after low-speed centrifugation or suction filtration, a small volume of MXenes sol, or MXenes precipitate after low-speed centrifugation, or the filter cake after suction filtration is frozen Drying and annealing treatment can convert the ammonium salt into ammonia gas and volatilize it to obtain a few layers of MXenes material powder. The entire experimental process has the advantages of mild reaction, safety, low cost, short time, simple equipment, etc. Due to the electrostatic coagulation effect, the solution that needs to be freeze-dried during the freeze-drying process is greatly reduced, and the experimental process is greatly shortened. It is used in industrial production. There are very good application prospects in China. The few-layer Mxenes sheet prepared by the present invention has a good three-dimensional network sheet structure. When observed with a scanning electron microscope, the magnification ranges from 300 times to 70,000 times, all of which have a sheet structure without agglomeration. It is preliminary judged. The layer thickness is below 10nm (the bonding layer spacing is 1nm, and the number of layers is estimated to be about 10). The atomic force microscope test shows that the layer thickness of some MXenes materials is about 2-3nm (the number of layers is about 2-3 layers), This fully illustrates the feasibility of using cation assistance (such as NH 4+ ) and the use of electrostatic coagulation to prepare a small-layer MXenes material. The small-layer MXenes material prepared by this method can be used in lithium batteries and electrochemical supercapacitors. The energy field has very broad application prospects.
附图说明Description of the drawings
图1是实施例1中Ti 3AlC 2原料及刻蚀后多层Ti 3C 2T x MXenes的XRD图谱； 1 is the XRD pattern of Ti 3 AlC 2 raw material and the multilayer Ti 3 C 2 T x MXenes after etching in Example 1;
图2是实施例1中Ti 3AlC 2原料及刻蚀后多层Ti 3C 2T x MXenes的拉曼图谱； 2 is the Raman spectrum of Ti 3 AlC 2 raw material and the multilayer Ti 3 C 2 T x MXenes after etching in Example 1;
图3是实施例1中制备的多层Ti 3C 2T x MXenes的扫描电镜照片； Figure 3 is a scanning electron micrograph of the multilayer Ti 3 C 2 T x MXenes prepared in Example 1;
图4是实施例2中少层Ti 3C 2T x MXenes溶液加入碳酸氢铵溶液，搅拌均匀后，取出20ml放在小玻璃瓶里面，静止过程中，溶液分层现象动态变化的实物图照片； Figure 4 is a photo of the small layer Ti 3 C 2 T x MXenes solution in Example 2 added to the ammonium bicarbonate solution, and after stirring it evenly, take out 20ml and place it in a small glass bottle. During the static process, the layering phenomenon of the solution changes dynamically. ；
图5是实施例2中少层Ti 3C 2T x MXenes溶液加入碳酸氢铵溶液，搅拌均匀后， 溶液静止30分钟后的实物图照片； Fig. 5 is a photo of the physical picture of the small-layer Ti 3 C 2 T x MXenes solution in Example 2 after adding the ammonium bicarbonate solution and stirring the solution evenly, after the solution is still for 30 minutes;
图6是实施例2中少层Ti 3C 2T x MXenes溶液冻干后的实物图照片； Figure 6 is a photo of the physical image of the low-layer Ti 3 C 2 T x MXenes solution in Example 2 after freeze-drying;
图7是实施例2中少层Ti 3C 2T x MXenes粉末的低倍数扫描电镜照片； Fig. 7 is a low-magnification scanning electron microscope photo of the few-layer Ti 3 C 2 T x MXenes powder in Example 2;
图8是实施例2中少层Ti 3C 2T x MXenes粉末的高倍数扫描电镜照片； Fig. 8 is a high-magnification scanning electron microscope photo of the few-layer Ti 3 C 2 T x MXenes powder in Example 2;
图9是实施例2中少层Ti 3C 2T x MXenes粉末原子力显微镜照片及厚度分析数据； Fig. 9 is an atomic force microscope photograph and thickness analysis data of a few-layer Ti 3 C 2 T x MXenes powder in Example 2;
图10是实施例3中少层V 2CT x MXenes粉末的低、高倍数扫描电镜照片； Figure 10 is a low- and high-magnification scanning electron micrograph of the low- layer V 2 CT x MXenes powder in Example 3;
图11是实施例4中少层Ti 2CT x MXenes粉末的扫描电镜照片及元素分布分析； Figure 11 is a scanning electron micrograph and element distribution analysis of a few-layer Ti 2 CT x MXenes powder in Example 4;
图12是实施对比例2中Ti 3C 2T x MXenes扫描电镜照片； Fig. 12 is a scanning electron microscope photograph of Ti 3 C 2 T x MXenes in the implementation of Comparative Example 2;
图13是应用例1中少层Ti 3C 2T x MXenes电极薄膜的实物图和扫描电镜照片 Figure 13 is the physical image and scanning electron microscope photo of the few-layer Ti 3 C 2 T x MXenes electrode film in Application Example 1.
图14是应用例2中少层Ti 3C 2T x MXenes片的电化学循环性能； Figure 14 shows the electrochemical cycling performance of the few-layer Ti 3 C 2 T x MXenes sheet in Application Example 2;
图15是应用对比例1中多层Ti 3C 2T x MXenes电极片的电化学循环性能； Figure 15 shows the electrochemical cycling performance of the multilayer Ti 3 C 2 T x MXenes electrode sheet in Comparative Example 1;
具体实施方式detailed description
下面结合具体实施例，应用例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不应理解为用于以任何形式限制本发明。此外应理解，在阅读了本发明的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。The present invention will be further explained below in conjunction with specific embodiments and application examples. It should be understood that these embodiments are only used to illustrate the present invention and should not be construed as limiting the present invention in any form. In addition, it should be understood that after reading the content of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
实施例1Example 1
⑴将10g纯度大于98％的Ti 3AlC 2陶瓷粉体加入到100ml 40wt％的HF溶液中，在常温下搅拌48h；然后用去离子水离心洗涤，直到pH值为7左右，将离心后的沉淀冷冻干燥，之后接着真空烘干，进一步去除材料中的水分，烘干温度为70℃，烘干时间为12h，将烘干后的材料研磨收集，即得到多层结构的Ti 3C 2T x MXenes材料。 ⑴ Add 10g of Ti 3 AlC 2 ceramic powder with a purity of more than 98% to 100ml of 40wt% HF solution and stir for 48h at room temperature; then centrifuge and wash with deionized water until the pH is about 7. The precipitation is freeze-dried, followed by vacuum drying to further remove the moisture in the material. The drying temperature is 70°C and the drying time is 12h. The dried material is ground and collected to obtain a multilayer structure of Ti 3 C 2 T x MXenes materials.
(2)将1g多层的Ti 3C 2T x MXenes材料加入到10ml浓度为25wt％四甲基氢氧化铵(TMAOH)的水溶液中，常温下搅拌24h，让有机分子插层进入MXenes层间，通过插层增加层片间距、减弱层片间作用力，然后离心收集插层后的多层Ti 3C 2T x MXenes材料沉淀，并用去离子水洗涤一次，将收集的沉淀分散在50ml的去离子水中，进行超声处理，超声30分钟，之后进行离心，离心转速为3500r/min，离心时间为10分钟，将离心后的上清液收集，留待后续使用，将离心后的沉淀再次分散在50ml去离子水中，超声30分钟后，进行离心，离心转速为3500r/min， 离心时间为10分钟，将离心后的上清液收集，留待后续使用，将离心后的沉淀再分散在50ml去离子水中，重复上述过程，直到总的超声时间达到4小时后，将最后一次离心后的沉淀舍弃，将前述所有上清液汇集收集，大约是350ml的MXenes溶液，留待后续使用。 (2) Add 1g multilayer Ti 3 C 2 T x MXenes material to 10ml 25wt% tetramethylammonium hydroxide (TMAOH) aqueous solution, stir at room temperature for 24h, let organic molecules intercalate into the MXenes interlayer , Through intercalation to increase the spacing between the layers and weaken the force between the layers, and then centrifuge to collect the intercalated multilayer Ti 3 C 2 T x MXenes material precipitation, and wash it with deionized water once, the collected precipitation is dispersed in 50ml Carry out sonication in deionized water for 30 minutes, then centrifuge at 3500r/min, and centrifuge time for 10 minutes. Collect the supernatant after centrifugation and save it for subsequent use. Disperse the centrifuged precipitate again in After sonicating in 50ml deionized water for 30 minutes, centrifuge at a speed of 3500r/min and a centrifugal time of 10 minutes. Collect the supernatant after centrifugation and save it for subsequent use. Disperse the precipitate after centrifugation in 50ml deionized water. In water, repeat the above process until the total sonication time reaches 4 hours, discard the precipitate after the last centrifugation, and collect all the aforementioned supernatants, which is about 350ml of MXenes solution for subsequent use.
(3)在搅拌的情况下，往上述步骤(2)中的350ml的MXenes溶液中逐滴加入10ml浓度为28％的氨水，搅拌30分钟后，静止，由于静电聚沉作用，会明显得看到烧杯的底部有MXenes的沉淀生成，出现明显的分层，将上层水溶液倒掉，下层的沉淀收集，通过重复上述过程，即静止，倒掉分层后的水溶液，把MXenes溶液里面的水减少，有助于减少后续冷冻干燥过程的时间。(3) Under the condition of stirring, add 10ml of 28% ammonia water dropwise to the 350ml MXenes solution in the above step (2). After stirring for 30 minutes, it will stand still. Due to the effect of electrostatic coagulation, it will be obvious. At the bottom of the beaker, MXenes precipitates are formed, and obvious stratification occurs. Pour out the upper aqueous solution and collect the lower sediments. By repeating the above process, that is, still, discard the layered aqueous solution to reduce the water in the MXenes solution. , Which helps to reduce the time of the subsequent freeze-drying process.
(4)当MXenes溶液的总体积为10ml左右后，先将其在冰箱里面预冻，冻住之后，进行冷冻干燥，冻干之后，将粉末收集，放在坩埚里面，在管式炉中进行退火处理，退火温度为150℃，退火气氛为氩气气氛，退火时间为6h。(4) When the total volume of MXenes solution is about 10ml, pre-freeze it in the refrigerator, freeze-dry it, and then freeze-dry it, collect the powder, put it in a crucible, and perform it in a tube furnace. For annealing treatment, the annealing temperature is 150°C, the annealing atmosphere is an argon atmosphere, and the annealing time is 6h.
(5)退火之后，将粉末研磨收集，便可以得到干燥的少层的Ti 3C 2T x MXenes材料粉体，可供后续使用。 (5) After annealing, the powder is ground and collected, and then a dry, small-layered Ti 3 C 2 T x MXenes material powder can be obtained for subsequent use.
图1表明：本实施例由最初Ti 3AlC 2陶瓷粉体制备多层Ti 3C 2T x MXenes产物的过程中，原料和多层Ti 3C 2T x MXenes的XRD图谱有明显的区别，原料39°的(104)峰消失，18.2°和27.6°出现了2个属于Ti 3C 2(OH) 2的峰，表明MXenes表面吸附了羟基,(002)峰位向小角度方向移动，即由9.9度移动到8.9度。 Figure 1 shows that in this example, in the process of preparing multilayer Ti 3 C 2 T x MXenes products from the initial Ti 3 AlC 2 ceramic powder, the XRD patterns of the raw materials and the multilayer Ti 3 C 2 T x MXenes are obviously different. The (104) peak at 39° of the raw material disappeared, and two peaks belonging to Ti 3 C 2 (OH) 2 appeared at 18.2° and 27.6°, indicating that hydroxyl groups were adsorbed on the surface of MXenes, and the (002) peak position moved to a small angle direction, namely Moved from 9.9 degrees to 8.9 degrees.
图2表明，原料Ti 3AlC 2陶瓷粉体的拉曼图谱，122,180,198和268cm -1对应MAX相中C–Ti–Al振动，580,630和660cm -1对应MAX相中C–Ti–C振动，氢氟酸刻蚀后，只有150,393和605cm -1的3个特征峰，对应MXenes中Ti–C对称伸缩振动。结合图3的扫描电镜照片，发现经过HF酸处理后，原料Ti 3AlC 2陶瓷粉体会产生明显的多层结构，说明成功制备出了多层的Ti 3C 2T x MXenes粉体。 Figure 2 shows that the Raman spectrum of the raw material Ti 3 AlC 2 ceramic powder, 122, 180, 198 and 268 cm -1 correspond to the C-Ti-Al vibration in the MAX phase, and 580, 630 and 660 cm -1 correspond to the C-Ti-C vibration in the MAX phase, hydrogen After fluoric acid etching, there are only three characteristic peaks at 150, 393 and 605 cm -1 , corresponding to the Ti-C symmetric stretching vibration in MXenes. Combined with the scanning electron micrograph of Fig. 3, it is found that after HF acid treatment, the raw material Ti 3 AlC 2 ceramic powder will produce an obvious multi-layer structure, indicating that the multi-layer Ti 3 C 2 T x MXenes powder has been successfully prepared.
实施例2Example 2
⑴将10g纯度大于98％的Ti 3AlC 2陶瓷粉体加入到100ml 40wt％的HF溶液中，在50℃的水浴锅中，搅拌12h；然后用去离子水离心洗涤，直到PH值为7左右，将离心后的沉淀冷冻干燥，之后接着真空烘干，进一步去除材料中的水分， 烘干温度为70℃，烘干时间为12h，将烘干后的材料研磨收集，即得到多层结构的Ti 3C 2T x MXenes材料。 ⑴ Add 10g of Ti 3 AlC 2 ceramic powder with purity greater than 98% to 100ml 40wt% HF solution, stir for 12h in a water bath at 50℃; then centrifuge and wash with deionized water until the pH is about 7 , Freeze-dry the centrifuged precipitate, and then vacuum dry to further remove the moisture in the material, the drying temperature is 70 ℃, the drying time is 12 hours, the dried material is ground and collected to obtain a multilayer structure Ti 3 C 2 T x MXenes material.
(2)将1g多层的Ti 3C 2T x MXenes材料加入到10ml浓度为25wt％四丁基氢氧化铵(TBAOH)的水溶液中，常温下搅拌24h，让有机分子插层进入MXenes层间，通过插层增加层片间距、减弱层片间作用力，然后离心收集插层后的多层MXenes材料沉淀，并用去离子水洗涤一次，将收集的沉淀分散在70ml的去离子水中，进行超声处理，超声30分钟后，进行离心，离心转速为3500r/min，离心时间为10分钟，将离心后的上清液收集，留待后续使用，将离心后的沉淀再注入70ml去离子水，将沉淀搅拌成溶液，超声30分钟后，进行离心，离心转速为3500r/min，离心时间为10分钟，将离心后的上清液收集，留待后续使用，将离心后的沉淀再注入50ml去离子水，重复上述过程，直到总的超声时间达到4小时后，将最后一次离心后的沉淀舍弃，将前述所有上清液汇集收集，大约是500ml的MXenes溶液，留待后续使用，。 (2) Add 1g of multilayer Ti 3 C 2 T x MXenes material to 10ml of 25wt% tetrabutylammonium hydroxide (TBAOH) aqueous solution, stir at room temperature for 24h, let organic molecules intercalate into the MXenes layer, pass Intercalation increases the interlayer spacing and weakens the force between the layers, and then centrifuges to collect the intercalated multilayer MXenes material precipitation, and wash it with deionized water once, disperse the collected precipitation in 70ml of deionized water, and conduct ultrasonic treatment. After 30 minutes of sonication, centrifuge, the centrifuge speed is 3500r/min, the centrifugation time is 10 minutes, the supernatant after centrifugation is collected and saved for subsequent use, the centrifuged precipitate is then poured into 70ml of deionized water, and the precipitate is stirred into The solution is sonicated for 30 minutes and then centrifuged at a speed of 3500r/min and a centrifuge time of 10 minutes. Collect the supernatant after centrifugation and save it for subsequent use. Pour the centrifuged precipitate into 50ml deionized water and repeat the above During the process, until the total sonication time reaches 4 hours, discard the precipitate after the last centrifugation, and collect all the aforementioned supernatants, which is about 500ml of MXenes solution, which is reserved for subsequent use.
(3)将3.2g碳酸氢铵溶解在50ml的去离子水中，搅拌30分钟后，便可以获得均匀的、透明的、含有NH 4+离子的碳酸氢铵水溶液。 (3) Dissolve 3.2 g of ammonium bicarbonate in 50 ml of deionized water, and after stirring for 30 minutes, a uniform, transparent aqueous solution of ammonium bicarbonate containing NH 4+ ions can be obtained.
(4)在搅拌的情况下，往上述步骤(2)中的500ml的MXenes溶液中逐滴加入步骤(3)中配置的含有NH 4+离子的碳酸氢铵水溶液，直到加入完毕后，继续搅拌30分钟，然后静止，由于静电聚沉作用，会明显得看到烧杯的底部有MXenes的沉淀生成，出现明显的分层，将上层水溶液倒掉，下层的溶液收集，此时MXenes溶液的体积会有明显的减少，相应地，MXenes溶液MXenes的浓度会有所增加，重复静止，倒掉上层水这个过程，直到总体积在20ml左右。 (4) While stirring, add dropwise the ammonium bicarbonate aqueous solution containing NH 4+ ions configured in step (3) to the 500 ml MXenes solution in step (2) above, until the addition is complete, continue stirring After 30 minutes, then stand still. Due to the effect of electrostatic coagulation, it is obvious that there is precipitation of MXenes at the bottom of the beaker, and obvious stratification appears. Pour the upper aqueous solution and collect the lower solution. At this time, the volume of the MXenes solution will change. There is a significant decrease. Correspondingly, the concentration of MXenes in the MXenes solution will increase. Repeat the process of standing still and pour the upper layer of water until the total volume is about 20ml.
(5)当MXenes溶液的总体积为20ml左右后，先将其在冰箱里面预冻，冻住之后，进行冷冻干燥，冻干之后，将粉末收集，放在坩埚里面，在管式炉中进行退火处理，退火温度为180℃，退火气氛为氩气气氛，退火时间为6h。(5) When the total volume of the MXenes solution is about 20ml, pre-freeze it in the refrigerator. After freezing, perform freeze-drying. After freeze-drying, collect the powder, put it in a crucible, and perform it in a tube furnace. For the annealing treatment, the annealing temperature is 180°C, the annealing atmosphere is an argon atmosphere, and the annealing time is 6h.
(6)退火之后，将粉末研磨收集，便可以得到干燥的少层的Ti 3C 2T x MXenes粉体，可供后续应用。 (6) After annealing, the powder is ground and collected to obtain a dry, few-layer Ti 3 C 2 T x MXenes powder, which can be used for subsequent applications.
图4表明，引入阳离子NH 4+离子后，由于阳离子会吸附到电负性的少层Ti 3C 2T x MXenes的表面，破坏了MXenes依靠彼此之间排斥力作用维护的静电平衡(均为电负性，彼此排斥)，发生静电聚沉，结合图5，可以明显看出，随 着静止时间的延长，MXenes片层很容易沉降下去，静止30分钟后，MXenes片层基本完全沉降，产生较明显的分层，此时可以将上清液倒掉，减少冷冻干燥的水含量，缩短冷冻干燥的实验周期。图6表明，少层Ti 3C 2T x MXenes溶胶，冻干后呈现蓬松的网状，其质量为1.4g，可以预测，如果前期增大刻蚀MAX的量，同时用更多的离心管，利用NH 4+离子辅助，静电聚沉方法可以实现少层Ti 3C 2T x MXenes的宏量制备。 Figure 4 shows that after the introduction of cation NH 4+ ions, the cations will be adsorbed to the surface of the electronegative few Ti 3 C 2 T x MXenes, which destroys the electrostatic balance maintained by the repulsive forces between MXenes (both are Electronegativity, mutual repulsion), electrostatic coagulation occurs. According to Figure 5, it can be clearly seen that with the extension of the static time, the MXenes lamellae easily settle down. After 30 minutes of static, the MXenes lamella basically settles completely. If the stratification is more obvious, the supernatant can be discarded at this time to reduce the water content of freeze-drying and shorten the experimental period of freeze-drying. Figure 6 shows that the low-layer Ti 3 C 2 T x MXenes sol appears as a fluffy network after freeze-drying, and its mass is 1.4g. It can be predicted that if the amount of etched MAX is increased in the early stage, more centrifuge tubes will be used at the same time. With the aid of NH 4+ ions, the electrostatic coagulation method can realize the macro-preparation of few layers of Ti 3 C 2 T x MXenes.
图7表明，少层Ti 3C 2T x MXenes粉末，在低倍数的扫描电镜下，从300倍的放大倍数，到2000倍的放大倍数，没有明显的团聚结块现象，结合图8的高倍数扫描电镜，可以看到非常明显的片层结构，厚度在10nm以下，Ti 3C 2T x MXenes的层间距为1nm左右，可以判定，所得的MXenes层数在10层以下，片径在5um左右。图9的原子力显微镜照片及厚度分析数据清晰表明，部分少层Ti 3C 2T x MXenes片层的厚度在2-3nm，推测Ti 3C 2T x MXenes的层数在2-3层之间，片径在3um左右，结合图4-9的实验现象及结果，充分说明本发明在快速、宏量制备少层MXenes粉末的可行性。 Figure 7 shows that there is no obvious agglomeration and agglomeration of Ti 3 C 2 T x MXenes powder under low magnification scanning electron microscope from 300 times magnification to 2000 times magnification. Multiple scanning electron microscopy, you can see a very obvious layer structure, the thickness is below 10nm, the layer spacing of Ti 3 C 2 T x MXenes is about 1nm, it can be judged that the obtained MXenes layer number is below 10 layers, and the film diameter is 5um. about. The AFM photos and thickness analysis data in Figure 9 clearly show that the thickness of some of the few Ti 3 C 2 T x MXenes layers is 2-3 nm, and it is speculated that the number of Ti 3 C 2 T x MXenes layers is between 2-3 layers. , The film diameter is about 3um, combined with the experimental phenomena and results of Figures 4-9, fully demonstrate the feasibility of the present invention in the rapid and macro-preparation of low-layer MXenes powder.
实施例3Example 3
⑴将10g纯度大于95％的V 2AlC陶瓷粉体加入到100ml 40wt％的HF溶液中，在55℃的水浴锅中，搅拌40h；然后用去离子水离心洗涤，直到PH值为7左右，将离心后的沉淀冷冻干燥，之后接着真空烘干，进一步去除材料中的水分，烘干温度为70℃，烘干时间为12h，将烘干后的材料研磨收集，即得到多层结构的V 2CT x MXenes材料。 ⑴ Add 10g of V 2 AlC ceramic powder with a purity of more than 95% to 100ml of 40wt% HF solution, stir in a 55℃ water bath for 40h; then centrifuge and wash with deionized water until the pH is about 7. The centrifuged precipitate is freeze-dried, followed by vacuum drying to further remove the moisture in the material. The drying temperature is 70°C and the drying time is 12 hours. The dried material is ground and collected to obtain a multilayer structure of V 2 CT x MXenes material.
(2)将0.5g多层的V 2CT x MXenes材料加入到10ml浓度为25wt％四甲基氢氧化铵的水溶液中，常温下搅拌24h，让有机分子插层进入MXenes层间，通过插层增加层片间距、减弱层片间作用力，然后离心收集插层后的多层MXenes材料沉淀，并用去离子水洗涤一次，将洗涤后收集的沉淀分散在50ml的去离子水中，进行超声处理，超声30分钟后，进行离心，离心转速为3500r/min，离心时间为10分钟，将离心后的上清液收集，留待后续使用，将离心后的沉淀再注入50ml去离子水，将沉淀搅拌成溶液，超声30分钟后，同样进行离心，离心转速为3500r/min，离心时间为10分钟，将离心后的上清液收集，留待后续使用，将离心后的沉淀再注入50ml去离子水，重复上述过程，直到总的超声时间达到4小 时后，将最后一次离心后的沉淀舍弃，将前述所有的上清液汇集收集，大约是350ml的V 2CT x MXenes溶液，留待后续使用，。 (2) Add 0.5g of multilayer V 2 CT x MXenes material to 10ml of 25wt% tetramethylammonium hydroxide aqueous solution, stir for 24h at room temperature, let the organic molecules intercalate into the interlayer of MXenes, and pass through the intercalation. Increase the spacing between the layers and weaken the force between the layers, then collect the intercalated multilayer MXenes material precipitate by centrifugation, and wash it once with deionized water, disperse the collected precipitate in 50ml of deionized water, and conduct ultrasonic treatment. After 30 minutes of sonication, centrifuge, the centrifuge speed is 3500r/min, the centrifugation time is 10 minutes, the supernatant after centrifugation is collected and saved for subsequent use, the centrifuged precipitate is poured into 50ml of deionized water, and the precipitate is stirred into The solution was sonicated for 30 minutes, and then centrifuged at 3500r/min, and the centrifuge time was 10 minutes. Collect the supernatant after centrifugation and save it for subsequent use. Pour the centrifuged precipitate into 50ml deionized water and repeat In the above process, until the total sonication time reaches 4 hours, discard the precipitate after the last centrifugation, and collect all the aforementioned supernatants, which is about 350ml of V 2 CT x MXenes solution, which is reserved for subsequent use.
(3)将2g碳酸铵溶解在50ml的去离子水中，搅拌30分钟后，便可以获得均匀的、透明的、含有NH 4+离子的碳酸铵水溶液。 (3) Dissolve 2 g of ammonium carbonate in 50 ml of deionized water, and stir for 30 minutes to obtain a uniform, transparent aqueous solution of ammonium carbonate containing NH 4+ ions.
(4)在搅拌的情况下，往上述步骤(2)中的350ml的V 2CT x MXenes溶液中逐滴加入步骤(3)中配置的含有NH 4+离子的碳酸铵水溶液，直到加入完毕后，继续搅拌30分钟。 (4) While stirring, add dropwise the ammonium carbonate aqueous solution containing NH 4+ ions configured in step (3) to the 350ml V 2 CT x MXenes solution in step (2) above, until the addition is complete , Continue to stir for 30 minutes.
(5)将步骤(4)中的MXenes溶液进行离心处理，由于使用NH 4+离子，破坏了MXenes溶液的电负性，少层MXenes材料可以很容易得离心下去，离心转速为2000r/min，离心时间为10分钟，将离心后的MXenes沉淀收集，进行冷冻干燥，冻干之后，将粉末收集，放在坩埚里面，在管式炉中进行退火处理，退火温度为120℃，退火气氛为氩气气氛，退火时间为12h。 (5) Centrifuge the MXenes solution in step (4). Because NH 4+ ions are used, the electronegativity of the MXenes solution is destroyed. The small layer of MXenes material can be easily centrifuged. The centrifugal speed is 2000r/min. Centrifugation time is 10 minutes. Collect the centrifuged MXenes precipitate and freeze-dry. After freeze-drying, the powder is collected, placed in a crucible, and annealed in a tube furnace. The annealing temperature is 120°C and the annealing atmosphere is argon. In a gas atmosphere, the annealing time is 12h.
(6)退火之后，将粉末研磨收集，便可以得到干燥的少层的V 2CT x MXenes材料粉体，可供后续使用。 (6) After annealing, the powder is ground and collected to obtain a dry, small-layered V 2 CT x MXenes material powder, which can be used for subsequent use.
图10表明：本实施例得到的V 2CT x MXenes为三维网状的片层结构，从400倍的放大倍数到70000的放大倍数，均展示出明显的片层，没有团聚现象，说明本发明的方法，对于制备钒系的MXenes材料也是适用的，进一步说明了本发明的普适性。 Figure 10 shows that the V 2 CT x MXenes obtained in this example has a three-dimensional networked sheet structure, from 400 times magnification to 70,000 magnification, all showing obvious lamella without agglomeration, which illustrates the present invention The method is also applicable to the preparation of vanadium-based MXenes materials, which further illustrates the universality of the present invention.
实施例4Example 4
⑴量取H 2SO 4溶液50ml，其浓度为8mol/L,在搅拌的情况下，往里面加入46g NH 4HF 2,搅拌均匀，制备得到含HF酸和(NH 4)SO 4的刻蚀液，往里面加入5g纯度大于98％的Ti 2AlC陶瓷粉体，室温下搅拌40h；然后用去离子水离心洗涤，直到上清液PH值>6，将离心后的沉淀冷冻干燥，之后接着真空烘干，进一步去除材料中的水分，烘干温度为70℃，烘干时间为12h，将烘干后的材料研磨收集，即得到多层结构的Ti 2CT x MXenes材料。 ⑴ Measure 50ml of H 2 SO 4 solution, the concentration of which is 8mol/L, add 46g NH 4 HF 2 to it while stirring, and stir evenly to prepare an etching containing HF acid and (NH 4 )SO 4 Add 5g of Ti 2 AlC ceramic powder with a purity greater than 98% to it, stir at room temperature for 40 hours; then centrifuge and wash with deionized water until the PH value of the supernatant is> 6, freeze-dry the centrifuged precipitate, and then Vacuum drying is used to further remove the moisture in the material. The drying temperature is 70°C and the drying time is 12 hours. The dried material is ground and collected to obtain a multilayer structure of Ti 2 CT x MXenes material.
(2)将0.5g多层的Ti 2CT x MXenes材料加入到20ml的二甲基亚砜有机溶液中，常温下搅拌24h，让有机分子插层进入MXenes层间，然后离心收集插层后的多层MXenes材料沉淀，并用去离子水洗涤一次，将洗涤后收集的沉淀分散在50ml的去离子水中，进行超声处理，超声30分钟后，进行离心，离心转速为3500r/min， 离心时间为10分钟，将离心后的上清液收集，留待后续使用，将离心后的沉淀再注入50ml去离子水，搅拌成溶液，超声30分钟后，同样进行离心，离心转速为3500r/min，离心时间为10分钟，将离心后的上清液收集，留待后续使用，将离心后的沉淀再注入50ml去离子水，重复上述过程，直到总的超声时间达到4小时后，将上清液汇集收集，大约是350ml的MXenes溶液，留待后续使用，将最后一次离心后的沉淀舍弃。 (2) Add 0.5g of multilayer Ti 2 CT x MXenes material to 20ml of dimethyl sulfoxide organic solution, stir for 24h at room temperature, let organic molecules intercalate into the MXenes layer, and then centrifuge to collect the intercalated The multi-layer MXenes material is precipitated and washed once with deionized water. The precipitate collected after washing is dispersed in 50ml of deionized water and ultrasonically processed. After 30 minutes of ultrasonication, centrifuge at a speed of 3500r/min and a centrifugal time of 10 After centrifugation, collect the supernatant after centrifugation and save it for subsequent use. Inject the precipitate after centrifugation into 50ml deionized water, stir to form a solution. After sonicating for 30 minutes, perform the same centrifugation. After 10 minutes, collect the supernatant after centrifugation and save it for subsequent use. Inject the precipitate after centrifugation into 50ml deionized water. Repeat the above process until the total ultrasound time reaches 4 hours. Collect the supernatant. It is 350ml of MXenes solution, reserved for subsequent use, and discard the precipitate after the last centrifugation.
(3)将3.2g碳酸氢铵溶解在50ml的去离子水中，搅拌30分钟后，便可以获得均匀的、透明的、含有NH 4+离子的碳酸氢铵水溶液。 (3) Dissolve 3.2 g of ammonium bicarbonate in 50 ml of deionized water, and after stirring for 30 minutes, a uniform, transparent aqueous solution of ammonium bicarbonate containing NH 4+ ions can be obtained.
(4)在搅拌的情况下，往上述步骤(2)中的350ml的MXenes溶液中逐滴加入步骤(3)中配置的含有NH 4+离子的碳酸氢铵水溶液，直到加入完毕后，继续搅拌30分钟。 (4) While stirring, add dropwise the ammonium bicarbonate aqueous solution containing NH 4+ ions configured in step (3) to the 350ml MXenes solution in step (2) above, and continue stirring until the addition is complete 30 minutes.
(5)将步骤(4)中的MXenes溶液进行离心处理，由于使用NH 4+离子，破坏了MXenes溶液的电负性，少层MXenes材料可以离心得下去，离心转速为2000r/min，离心时间为10分钟，将离心后的MXenes沉淀收集，进行冷冻干燥，冻干之后，将粉末收集，放在坩埚里面，在管式炉中进行退火处理，退火温度为120℃，退火气氛为氩气气氛，退火时间为12h。 (5) Centrifuge the MXenes solution in step (4). Because NH 4+ ions are used, the electronegativity of the MXenes solution is destroyed, and a few layers of MXenes material can be centrifuged down. The centrifugal speed is 2000r/min, and the centrifugation time For 10 minutes, collect the centrifuged MXenes precipitate and freeze-dry. After freeze-drying, the powder is collected, placed in a crucible, and annealed in a tube furnace. The annealing temperature is 120°C and the annealing atmosphere is argon. , Annealing time is 12h.
(6)退火之后，将粉末研磨收集，便可以得到干燥的少层的Ti 2CT x MXenes材料粉体，可供后续使用。 (6) After annealing, the powder is ground and collected, and then a dry, small-layer Ti 2 CT x MXene material powder can be obtained for subsequent use.
图11表明：制备的Ti 2CT x MXenes材料层数少，元素分布图表明，核心元素Ti和C的分布特征区域与Ti 2C片层一致。 Figure 11 shows that the prepared Ti 2 CT x MXenes material has a small number of layers, and the element distribution diagram shows that the distribution characteristic areas of the core elements Ti and C are consistent with the Ti 2 C lamellae.
实施对比例1Implementation of Comparative Example 1
与实施例1类似，本对比例在得到少层Ti 3C 2T x MXenes的水溶液后，大约是350ml，从中用烧杯量取50ml，在冰箱里面冻住之后，开始冷冻干燥。 Similar to Example 1, in this comparative example, after obtaining a few layers of Ti 3 C 2 T x MXenes aqueous solution, it is about 350 ml, from which 50 ml is measured with a beaker, frozen in the refrigerator, and then freeze-dried.
发现冷冻干燥的过程需要50h左右，非常费时间，如果要冻干所有的少层Ti 3C 2T x MXenes的水溶液，需要的时间大约是400h，相比之下，本发明通过静电聚沉，大大减少需要冷冻干燥的溶液体积，将350ml溶液处理成10ml左右的溶液，只需要10h就可以完全冻干，大大提高了效率。 It is found that the freeze-drying process takes about 50h, which is very time-consuming. If all the aqueous solutions of the low-layer Ti 3 C 2 T x MXenes are to be freeze-dried, the required time is about 400 hours. In contrast, the present invention uses electrostatic coagulation. The volume of the solution that needs to be freeze-dried is greatly reduced, and 350ml of the solution is processed into a solution of about 10ml, and it can be completely freeze-dried in only 10h, which greatly improves the efficiency.
实施对比例2Implementation of Comparative Example 2
与实施例1类似，本对比例在得到少层Ti 3C 2T x MXenes的水溶液后，高速 离心，转速12000r/min,离心时间为10分钟，然后冷冻干燥，接着真空烘干后，收集Ti 3C 2T x MXenes粉末。 Similar to Example 1, in this comparative example, after obtaining an aqueous solution of a few layers of Ti 3 C 2 T x MXenes, it was centrifuged at a high speed at a speed of 12000 r/min and a centrifugation time of 10 minutes, then freeze-dried, and then vacuum-dried to collect Ti 3 C 2 T x MXenes powder.
如图12为本实施对比例制备的Ti 3C 2T x MXenes的扫描电镜照片，发现团聚成块体，高倍数的扫描电镜下，看不到明显的片层，团聚现象严重，部分地方，由诸多的MXenes的小片层，组成一个大而厚的片层(如图d部分所示)，此种方法制备的MXenes，存在严重的团聚现象，无法在后续应用中，充分发挥MXenes二维层状材料的优势。 As shown in Figure 12, the scanning electron microscope photo of Ti 3 C 2 T x MXenes prepared by the comparative example of this embodiment, it is found that they are agglomerated into blocks. Under the scanning electron microscope of high magnification, no obvious lamellae are seen, and the agglomeration phenomenon is serious. In some places, A large and thick layer is composed of many small MXenes layers (as shown in part d in the figure). The MXenes prepared by this method have serious agglomeration and cannot fully utilize the two-dimensional layer of MXenes in subsequent applications. Advantages of Shaped Materials.
应用例1Application example 1
本应用例采用上述实施例1制备的少层MXenes材料，用作锂离子电池负极材料，采用抽滤成膜法制备电池负极极片，将抽滤，真空烘干后的薄膜裁剪，切片，在手套箱中组装成扣式锂离子电池，然后进行电化学性能的相关测试。具体步骤如下：In this application example, the small-layer MXenes material prepared in the above example 1 is used as the negative electrode material of lithium-ion batteries. The negative electrode of the battery is prepared by the suction and film forming method. The film after suction and vacuum drying is cut and sliced. The button-type lithium-ion battery is assembled in the glove box, and then the relevant test of the electrochemical performance is carried out. Specific steps are as follows:
①负极制备：将上述实施例1制备的350ml Ti 3C 2T x MXenes溶液，采用真空抽滤的方式，制备薄膜，省却了通常电池极片需要的导电剂和粘结剂，简化了极片制备过程，冷冻干燥后，在真空条件下于70℃干燥10小时，干燥后裁成直径为14mm的电极片，制得少层Ti 3C 2T x MXenes材料为负极材料的电池负极片。 ①Negative electrode preparation: The 350ml Ti 3 C 2 T x MXenes solution prepared in the above example 1 is used to prepare the film by vacuum filtration, which eliminates the need for conductive agents and binders for battery pole pieces, and simplifies the pole pieces. In the preparation process, after freeze-drying, it was dried under vacuum at 70°C for 10 hours, and after drying, it was cut into an electrode sheet with a diameter of 14mm to produce a battery negative sheet with a few layers of Ti 3 C 2 T x MXenes material as the negative electrode material.
②电池组装及测试：在氩气气氛的手套箱内，以上述制得的电极片为负极，以金属锂片作为对电极，1M的LiPF 6(DMC：EMC：FEC＝1：1：1)溶液作为电解液，以Celgard 2300为隔膜，装配成2032扣式锂离子电池。电池充放电测试在Land电池测试***上使用恒流充放电模式进行，电压测试范围为0.01～3V。 ②Battery assembly and testing: In a glove box with an argon atmosphere, the electrode sheet prepared above is used as the negative electrode, the metal lithium sheet is used as the counter electrode, and 1M LiPF 6 (DMC:EMC:FEC=1:1:1) The solution is used as an electrolyte, and Celgard 2300 is used as a separator to assemble a 2032 button lithium-ion battery. The battery charge and discharge test is performed on the Land battery test system using constant current charge and discharge mode, and the voltage test range is 0.01 to 3V.
如图13为本应用例制备的，抽滤成膜的实物图和扫描电镜图，为明显片层，无团聚现象。As shown in Figure 13 for this application example, the physical image and the scanning electron microscope image of the film formed by the suction filter are obvious lamellas without agglomeration.
应用例2Application example 2
本应用例采用上述实施例1制备的少层Ti 3C 2T x MXenes材料，用作锂离子电池负极材料，采用涂浆法制得电池负极极片，在手套中组装成扣式锂离子电池，然后进行电化学性能的相关测试。具体步骤如下： In this application example, the small-layer Ti 3 C 2 T x MXenes material prepared in the above-mentioned Example 1 is used as the negative electrode material of the lithium ion battery. The battery negative pole piece is prepared by the slurry method, and the button type lithium ion battery is assembled in the glove. Then carry out the relevant test of electrochemical performance. Specific steps are as follows:
①负极制备：将上述实施例1制备的少层Ti 3C 2T x MXenes材料，按照质量比8:1:1的比例，与质量分数为5％的聚偏氟乙烯(PVDF)粘结剂以及导电剂Super  P混合均匀，搅拌均匀后形成浆料涂覆在铜箔上，在真空条件下于90℃干燥10小时，干燥后裁成直径为14mm的电极片，制得少层Ti 3C 2T x MXenes材料为负极材料的电池负极片。 ①Preparation of negative electrode: The small-layer Ti 3 C 2 T x MXenes material prepared in the above example 1 is combined with a polyvinylidene fluoride (PVDF) binder with a mass fraction of 5% according to a mass ratio of 8:1:1 And the conductive agent Super P is evenly mixed, after stirring, the slurry is formed and coated on the copper foil, and dried at 90°C for 10 hours under vacuum conditions. After drying, it is cut into an electrode sheet with a diameter of 14mm to obtain a small layer of Ti 3 C. 2 T x MXenes material is the negative electrode sheet of the battery.
②电池组装及测试：在氩气气氛的手套箱内，以上述制得的电极片为负极，以金属锂片作为对电极，1M的LiPF 6(DMC：EMC：FEC＝1：1：1)溶液作为电解液，以Celgard 2300为隔膜，装配成2032扣式锂离子电池。电池充放电测试在Land电池测试***上使用恒流充放电模式进行，电压测试范围为0.01～3V。如图14为本应用例制备的锂离子电池在电流密度500mA/g，电压范围0.01～3V时的循环性能图，循环200圈后，比容量为380mAh/g左右，无容量衰减趋势。 ②Battery assembly and testing: In a glove box with an argon atmosphere, the electrode sheet prepared above is used as the negative electrode, the metal lithium sheet is used as the counter electrode, and 1M LiPF 6 (DMC:EMC:FEC=1:1:1) The solution is used as an electrolyte, and Celgard 2300 is used as a separator to assemble a 2032 button lithium-ion battery. The battery charge and discharge test is performed on the Land battery test system using constant current charge and discharge mode, and the voltage test range is 0.01 to 3V. Figure 14 shows the cycle performance diagram of the lithium-ion battery prepared in this application example at a current density of 500mA/g and a voltage range of 0.01-3V. After 200 cycles, the specific capacity is about 380mAh/g, and there is no capacity decay trend.
应用对比例1Application Comparative Example 1
本对比例采用上述实施例1步骤(1)制备的多层Ti 3C 2T x MXenes材料，用作锂离子电池负极材料，采用涂浆法制得电池负极极片，在手套中组装成扣式锂离子电池，然后进行电化学性能的相关测试。具体步骤如下： In this comparative example, the multilayer Ti 3 C 2 T x MXenes material prepared in step (1) of Example 1 was used as the negative electrode material for lithium ion batteries. Lithium-ion batteries are then tested for electrochemical performance. Specific steps are as follows:
①负极制备：将上述实施例1步骤(1)制备的多层Ti 3C 2T x MXenes材料，按照质量比8:1:1的比例，与质量分数为5％的聚偏氟乙烯(PVDF)粘结剂以及导电剂Super P混合均匀，搅拌均匀后形成浆料涂覆在铜箔上，在真空条件下于90℃干燥10小时，干燥后裁成直径为14mm的电极片，制得少层Ti 3C 2T x MXenes材料为负极材料的电池负极片。 ①Preparation of negative electrode: The multilayer Ti 3 C 2 T x MXenes material prepared in step (1) of the above embodiment 1 was mixed with 5% polyvinylidene fluoride (PVDF) in a mass ratio of 8:1:1. ) The binder and the conductive agent Super P are mixed uniformly. After stirring, the slurry is formed and coated on the copper foil, and dried under vacuum at 90°C for 10 hours. After drying, it is cut into an electrode sheet with a diameter of 14mm. The layer Ti 3 C 2 T x MXenes material is the battery negative electrode sheet of the negative electrode material.
②电池组装及测试：在氩气气氛的手套箱内，以上述制得的电极片为负极，以金属锂片作为对电极，1M的LiPF 6(DMC：EMC：FEC＝1：1：1)溶液作为电解液，以Celgard 2300为隔膜，装配成2032扣式锂离子电池。电池充放电测试在Land电池测试***上使用恒流充放电模式进行，电压测试范围为0.01～3V。如图15为本对比例制备的锂离子电池在电流密度500mA/g，电压范围0.01～3V时的循环性能图，循环350圈后，比容量为150mAh/g左右，与少层MXenes在电化学性能方面存在明显的差别(少层的稳定状态，比容量为380mAh/g左右)，充分说明，本发明提供的一种少层MXenes的快速制备方法，在电化学储能领域有广阔的应用前景。 ②Battery assembly and testing: In a glove box with an argon atmosphere, the electrode sheet prepared above is used as the negative electrode, the metal lithium sheet is used as the counter electrode, and 1M LiPF 6 (DMC:EMC:FEC=1:1:1) The solution is used as an electrolyte, and Celgard 2300 is used as a separator to assemble a 2032 button lithium-ion battery. The battery charge and discharge test is performed on the Land battery test system using constant current charge and discharge mode, and the voltage test range is 0.01 to 3V. Figure 15 shows the cycle performance diagram of the lithium ion battery prepared in the comparative example at a current density of 500mA/g and a voltage range of 0.01～3V. After 350 cycles, the specific capacity is about 150mAh/g. There is a significant difference in performance (small-layer stable state, specific capacity is about 380mAh/g), which fully shows that the rapid preparation method of small-layer MXenes provided by the present invention has broad application prospects in the field of electrochemical energy storage .

Claims (9)

  1. 一种少层MXenes的快速制备方法，其特征在于，制备方法包括如下步骤：A rapid preparation method of low-layer MXenes is characterized in that the preparation method includes the following steps:
    (1)取MAX原料，在刻蚀液中处理，得到多层的MXenes材料；(1) Take the MAX raw material and process it in an etching solution to obtain a multilayer MXenes material;
    (2)将步骤(1)得到的MXenes材料在有机分子或表面活性剂中处理；(2) Treat the MXenes material obtained in step (1) in organic molecules or surfactants;
    (3)将步骤(2)得到的MXenes材料进行离心、洗涤沉淀、剥离处理，弃沉淀，收集上清液，得到少层的MXenes溶液；(3) The MXenes material obtained in step (2) is centrifuged, washed and precipitated, and stripped, the precipitate is discarded, and the supernatant is collected to obtain a low-layer MXenes solution;
    (4)将含有铵根离子的电解质溶液加入到步骤(3)得到的MXenes溶液中，静电聚沉，静置或低速离心或抽滤，所得溶胶、或沉淀、或滤饼即为少层的MXenes材料；(4) The electrolyte solution containing ammonium ions is added to the MXenes solution obtained in step (3), electrostatic precipitation, standing or low-speed centrifugation or suction filtration, the resulting sol, or precipitation, or filter cake is less layered MXenes material;
    (5)将步骤(4)得到的材料冷冻干燥、退火处理，得到少层MXenes的粉体。(5) The material obtained in step (4) is freeze-dried and annealed to obtain a powder with few layers of MXenes.
  2. 如权利要求1所述的一种少层MXenes的快速制备方法，其特征在于，步骤(1)中MXenes材料是Ti 4C 3、Ti 4N 3、Ti 3C 2、Ti 2C、Mo 2C、Hf 3C 2、V 3C 2、V 2C、V 2N、Nb 4C 3、Nb 3C 2、Nb 2C、Cr 3C 2、Ta 2C、Ta 4C 3、(Ti 0.5Nb 0.5)C中的一种或多种的组合。 The method for rapid preparation of few-layer MXenes according to claim 1, wherein the MXenes material in step (1) is Ti 4 C 3 , Ti 4 N 3 , Ti 3 C 2 , Ti 2 C, Mo 2 C, Hf 3 C 2 , V 3 C 2 , V 2 C, V 2 N, Nb 4 C 3 , Nb 3 C 2 , Nb 2 C, Cr 3 C 2 , Ta 2 C, Ta 4 C 3 , (Ti 0.5 Nb 0.5 ) A combination of one or more of C.
  3. 如权利要求1所述的一种少层MXenes的快速制备方法，其特征在于，步骤(1)中的刻蚀液为HF、LiF和HCl、NaF和H 2SO 4、其他含F盐和酸的混合液中的一种或多种的组合。 The method for rapid preparation of low-layer MXenes according to claim 1, wherein the etching solution in step (1) is HF, LiF and HCl, NaF and H 2 SO 4 , and other F-containing salts and acids One or more combinations in the mixed liquid.
  4. 如权利要求1所述的一种少层MXenes的快速制备方法，其特征在于，步骤(2)中的有机分子是四甲基氢氧化铵、四丁基氢氧化铵、水合肼、N-甲基吡咯烷酮、二甲基亚砜、N-甲基甲酰胺、乙醇的一种或多种的组合。The method for rapid preparation of low-layer MXenes according to claim 1, wherein the organic molecules in step (2) are tetramethylammonium hydroxide, tetrabutylammonium hydroxide, hydrazine hydrate, and N-methylpyrrolidone , Dimethyl sulfoxide, N-methylformamide, ethanol or a combination of one or more.
  5. 如权利要求1所述的一种少层MXenes的快速制备方法，其特征在于，步骤(2)中的表面活性剂是十烷基三甲基溴化铵、十二烷基三甲基溴化铵、十四烷基三甲基溴化铵、十六烷基三甲基溴化铵、十八烷基三甲基溴化铵、十八烷基三甲基氯化铵、聚乙烯吡咯烷酮、F127中的一种或多种的组合。The rapid preparation method of a few layers of MXenes according to claim 1, wherein the surfactant in step (2) is decayl trimethyl ammonium bromide, dodecyl trimethyl bromide Ammonium, tetradecyl trimethyl ammonium bromide, cetyl trimethyl ammonium bromide, octadecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, polyvinylpyrrolidone, One or more combinations of F127.
  6. 如权利要求1所述的一种少层MXenes的快速制备方法，其特征在于，步骤(3)中的剥离处理是机械摇晃、超声、细胞粉碎中的一种或多种的组合，MXenes溶液采用的溶剂是水、乙醇、丙酮中的一种或多种的组合。The method for rapid preparation of low-layer MXenes according to claim 1, wherein the peeling treatment in step (3) is a combination of one or more of mechanical shaking, ultrasound, and cell pulverization, and the MXenes solution is The solvent is one or a combination of water, ethanol, and acetone.
  7. 如权利要求1所述的一种少层MXenes的快速制备方法，其特征在于，步骤 (4)中的含有铵根离子的电解质溶液是碳酸氢铵、氨水、碳酸铵、硝酸铵、硫酸铵、溴化铵、氯化铵、氟化铵溶液中的一种或多种的组合。A method for rapid preparation of few-layer MXenes according to claim 1, wherein the electrolyte solution containing ammonium ions in step (4) is ammonium bicarbonate, ammonia, ammonium carbonate, ammonium nitrate, ammonium sulfate, A combination of one or more of ammonium bromide, ammonium chloride, and ammonium fluoride solutions.
  8. 如权利要求1所述的一种少层MXenes的快速制备方法，其特征在于，步骤(5)中的退火温度为70℃-700℃。The method for rapid preparation of few-layer MXenes according to claim 1, wherein the annealing temperature in step (5) is 70°C-700°C.
  9. 如权利要求1-8任一项所述方法获得的少层MXenes的应用，其特征在于，所述的少层MXenes用作锂离子电池或钠离子电池的负极材料。The application of the few-layer MXenes obtained by the method of any one of claims 1-8, characterized in that the few-layer MXenes are used as a negative electrode material of a lithium ion battery or a sodium ion battery.
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