CN110534741A - A kind of fast preparation method and application of few layer MXenes - Google Patents

A kind of fast preparation method and application of few layer MXenes Download PDF

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CN110534741A
CN110534741A CN201910840634.0A CN201910840634A CN110534741A CN 110534741 A CN110534741 A CN 110534741A CN 201910840634 A CN201910840634 A CN 201910840634A CN 110534741 A CN110534741 A CN 110534741A
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mxenes
few layer
ammonium
solution
preparation
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CN110534741B (en
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韩伟强
张顺龙
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Zhejiang University ZJU
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Zhejiang University ZJU
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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

Abstract

The invention discloses the fast preparation method and application of a kind of few layer MXenes, the preparation of few layer MXenes material is to obtain few layer of MXenes solution of favorable dispersibility by removing multilayer MXenes liquid phase in this method；By introducing electrolyte solution, the electrostatic equilibrium of few layer MXenes solution is destroyed, by electrostatic coagulation technique (such as NH of cation auxiliary4+), through standing or low-speed centrifugal or suction filtration, gained colloidal sol or precipitating or filter cake are the MXenes material of layer less；Then the magnanimity preparation of few layer MXenes powder may be implemented in freeze-dried and subsequent annealing.Simple with technical process, few layer of MXenes of preparation is thin with the number of plies, piece diameter is big, good dispersion, soilless sticking caking phenomenon, and has good chemical property, large-scale development and application suitable for lithium ion battery or sodium-ion battery.

Description

A kind of fast preparation method and application of few layer MXenes
Technical field
The present invention relates to technical field of nano material more particularly to a kind of fast preparation method of layer MXenes less and answer With.
Background technique
MXenes material is usually that " A " passed through in corrosion MAX phase material is made, metallic bond, ionic bond in MAX phase crystal With covalent bond and deposit, wherein M is transiting group metal elements, and A is mainly third main group and the 4th main group race element, X be carbon and/or Nitrogen, between M and X mainly in the form of covalent bond and ionic bond connect, between bond strength it is very high；Between M and element A and Then mostly it is connected between A and element A with metallic bond, therefore the intensity of chemical bond is relatively weak.As long as method appropriate is therefore selected to select The A layer atom etched to selecting property in MAX phase is obtained with the MXenes material with two-dimensional appearance feature, directly carves MAX Erosion obtains being multilayer MXenes, if removed, by subsequent technique, few layer of MXenes (10 can be prepared Layer or so and hereinafter, be no more than 20 layers), the chemical general formula of MXenes can use Mn+1XnTxIndicate, wherein M be metallic element Sc, Ti, V, Cr, Zr, Nb, Mo, Hf and Ta etc., X C, N or CN, n are generally 1-3, TxRefer to some uncertain groups of adsorption (such as O, OH, F), also can be omitted Tx, directly use Mn+1XnIt indicates, i.e. Mn+1XnTxAnd Mn+1XnRepresentation method have replaceability. Chemical element composition abundant and unique layer structure assign many unexpected performances of MXenes material, Mxenes tool There is excellent electric conductivity (conductivity 105S/m), conductivity reaches part metals rank；Good (the preferable tensile strength of mechanical performance And flexibility), flexibility easily forms a film and directly uses, and avoids the forming process of subsequent preparation；Interlamellar spacing is larger and flexible adjustable, The etching obtained MXeness interlamellar spacing of ultrasound is Van der Waals force between layers in 1nm or so, interlamellar spacing it is flexible it is adjustable without Its layer structure is destroyed, MXenes surface functional group assigns its hydrophily and surface texture adjustability, while not significantly affecting it Electric conductivity rationally utilizes the property and structure of MXenes, can processability excellent energy storage material and device.
Authorization Notice No. is that the Chinese patent of CN106495210B discloses a kind of preparation method of MXenes colloid, is passed through By H2SO4Solution and NH4HF2Mixing, performs etching MAX raw material using the hydrofluoric acid generated in mixed process, the sulfuric acid of generation Ammonium has heat absorptivity, reduces the severe degree of reaction, avoids the risk for directly using HF acid, but be prepared MXenes number of layers is thicker, is 1nm or so in conjunction with interlamellar spacing, thus it is speculated that its number of plies is unable to give full play at 5000 layers or so The advantage of MXenes two-dimensional material.Application No. is 201810359588.8 Chinese patents to disclose the system of three-dimensional MXenes a kind of Preparation Method, by the way that in a solvent, ultrasonic disperse removes multilayer MXenes at few layer, dry subsequently through freezing MXenes dispersion Dry mode prepares MXenes powder, due to containing a large amount of water in solution, so that freeze-drying process relatively slow (conventional freezing Drying machine is lyophilized 5ml water in centrifuge tube and just needs 2 days or so), whole preparation process is time-consuming and laborious.
In addition, also having many document and patent report about MXenes based composites, led playing MXenes material While electrical dominance, by introducing other materials system, the reunion of MXenes is prevented, as application No. is 201810939968.9 Chinese patent discloses a kind of preparation method of nuclear shell structure nano silicon-MXenes composite negative pole material, application No. is 201810088813.9 Chinese patent discloses a kind of preparation method of MXenes-Co composite material, the preparation of composite material, Although having widened the application of MXenes, the other materials introduced also limits MXenes special performance to a certain extent It plays, such as Ti3C2TxMXenes interlamellar spacing is 1nm or so, is far longer than such as graphene, C3N4, MoS2The interlayer of equal other materials Away from, introduce lesser graphene of interlamellar spacing etc., though the reunion of MXenes can be prevented, for MXenes, be not it is a kind of very Good selection, so far, prepare how quickly, in large quantity few layer MXenes material (number of plies at 10 layers or so and hereinafter, No more than 20 layers), it is still the crucial challenge of comparison.
Summary of the invention
To solve the above problems, the MXenes number of layers of i.e. conventional method preparation is blocked up, or when the number of plies is thinned, There are certain difficulties for the collection of MXenes: (1) when suction filtration, film forming densification is easy, so that suction filtration can not continue to carry out； (2) since density is light, in addition the electrostatic repulsion between electronegativity MXenes lamella, MXenes piece is very steady in aqueous solution It is fixed, it can not be collected by conventional centrifugal, even if high speed centrifugation, few layer MXenes material still can not be centrifuged down, also, conventional Suction filtration and ultracentrifugal collection mode, are easy to appear serious reunion caking phenomenon, can not obtain the powder of favorable dispersibility The MXenes lamella of state, just can not play the advantage of two-dimensional layer MXenes material.The present invention provides a kind of few layers The quick preparation of Mxenes and application, the method provided through the invention can effectively solve the agglomeration traits of MXenes, quickly The large batch of MXenes material for preparing few layer.
To achieve the above object, the present invention the following technical schemes are provided:
A kind of fast preparation method of few layer MXenes, includes the following steps:
(1) MAX raw material is taken, is handled in etching liquid, the MXenes material of multilayer is obtained；
(2) the MXenes material that step (1) obtains is handled in organic molecule or surfactant；
(3) the MXenes material that step (2) obtains is centrifuged, washing precipitating, lift-off processing is abandoned and precipitated, in collection Clear liquid obtains the MXenes solution of few layer；
(4) electrolyte solution containing ammonium ion is added in the MXenes solution that step (3) obtains, electrostatic is poly- It is heavy, it stands or low-speed centrifugal or suction filtration, gained colloidal sol or precipitating or filter cake is the MXenes material of layer less；
(5) material for obtaining step (4) is freeze-dried, annealing, obtains the powder of the MXenes material of few layer.
Further, MXenes material is Ti in step (1)4C3、Ti4N3、Ti3C2、Ti2C、Mo2C、Hf3C2、V3C2、V2C、 V2N、Nb4C3、Nb3C2、Nb2C、Cr3C2、Ta2C、Ta4C3、(Ti0.5Nb0.5) one of C or a variety of combinations.
Further, the etching liquid in step (1) is HF, LiF and HCl, NaF and H2SO4, other salt containing F and acid mixing One of liquid or a variety of combinations.
Further, the organic molecule in step (2) is tetramethylammonium hydroxide, tetrabutylammonium hydroxide, hydrazine hydrate, N- One or more combinations of methyl pyrrolidone, dimethyl sulfoxide, N-METHYLFORMAMIDE, ethyl alcohol.
Further, the surfactant in step (2) is ten alkyl trimethyl ammonium bromides, trimethyl bromination Ammonium, tetradecyltrimethylammonium bromide, cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide, octadecyl three One of ammonio methacrylate, polyvinylpyrrolidone, F127 or a variety of combinations.
Further, the lift-off processing in step (3) is that machinery rocks, ultrasound, one of cell pulverization or combinations thereof, The solvent that MXenes solution uses is one of water, ethyl alcohol, acetone or a variety of combinations.
Further, the electrolyte solution in step (4) is the salt containing ammonium ion, is ammonium hydrogen carbonate, ammonium hydroxide, carbonic acid One of ammonium, ammonium nitrate, ammonium sulfate, ammonium bromide, ammonium chloride, ammonium fluoride or a variety of combinations.
Further, the annealing temperature in step (5) is 70 DEG C -700 DEG C.
Few layer MXenes prepared by the present invention, may be used as the negative electrode material of lithium ion battery or sodium-ion battery.
In above-mentioned technical proposal, the low-speed centrifugal is often referred to revolving speed no more than 6000r/min；Especially in step (4) in, after method processing of the invention, sample can be centrifuged down in this step, be not in conventional method In the case where can not carrying out low-speed centrifugal, but revolving speed is unsuitable excessively high, when revolving speed is higher than 10000r/min, then it is existing to will appear reunion As few layer of MXenes powder of favorable dispersibility being unable to get, with specific reference to implementation comparative example 2 and Figure 12.Described filter is general Logical suction filtration mode, the ammonium ion of introducing, MXenes lamella porous during electrostatic coagulation avoid MXenes in routine Densification phenomenon (densification so that filter process can not carry out) in suction filtration method, after MXenes porous, the process of suction filtration can With lasting progress.
The beneficial effects of the present invention are:
It is removed by etching, the aqueous solution material of few layer MXenes is in electronegativity, i.e., MXenes material is inhaled in surfaces externally and internally Attached negatively charged group (OH-,F-Deng), this is the property of MXenes material itself.Method provided by the invention and tradition are made The method of standby MXenes material is compared, and the present invention makes the sun in electrolyte solution by ingenious introducing electrolyte solution, such as ammonium salt Ion (such as NH4+) MXenes material surface is adsorbed on by electrostatic adsorption, the electrostatic for effectively destroying MXenes solution is flat Electrostatic coagulation occurs for weighing apparatus, after static a period of time or low-speed centrifugal or after filtering, by the MXenes colloidal sol of few volume, either MXenes precipitating or the freeze-drying of filtered filter cake after low-speed centrifugal, annealing, it can convert ammonia for ammonium salt and wave Hair falls to arrive few layer MXenes material powder.Whole experiment process, with reaction is mild, safe, at low cost, the time is short, sets The advantages that standby simple, greatly reduces the solution for needing to be lyophilized in freezing dry process, greatly shortens since electrostatic coagulation acts on Experimentation, there is a good application prospect in industrial mass production.Few layer Mxenes lamella prepared by the present invention has fine Three-dimensional netted lamellar structure, when with scanning electron microscopic observation, from amplification factor be 300 times to 70000 times, be lamella knot Structure, it is preliminary to judge without agglomeration, thickness 10nm or less (being 1nm in conjunction with interlamellar spacing, thus it is speculated that the number of plies is at 10 layers or so), Atomic force microscope test shows that the thickness of some lamellas MXenes material is 2-3nm or so (number of plies is in layer 2-3 or so), fills It defends oneself to be illustrated and (such as NH is assisted by cation4+), it is acted on using electrostatic coagulation, magnanimity prepares the feasible of few layer MXenes material Property, the few layer of MXenes material prepared by the method has very wide in the energy storage fields such as lithium battery and electric chemical super capacitor Wealthy application prospect.
Detailed description of the invention
Fig. 1 is Ti in embodiment 13AlC2Multilayer Ti after raw material and etching3C2TxThe XRD spectrum of MXenes；
Fig. 2 is Ti in embodiment 13AlC2Multilayer Ti after raw material and etching3C2TxThe Raman map of MXenes；
Fig. 3 is the multilayer Ti prepared in embodiment 13C2TxThe stereoscan photograph of MXenes；
Fig. 4 is few layer Ti in embodiment 23C2TxAmmonium bicarbonate soln is added in MXenes solution, after mixing evenly, takes out 20ml is placed on inside vial, in quiescing process, the pictorial diagram photo of solution lamination dynamic change；
Fig. 5 is few layer Ti in embodiment 23C2TxAmmonium bicarbonate soln is added in MXenes solution, and after mixing evenly, solution is quiet The only pictorial diagram photo after 30 minutes；
Fig. 6 is few layer Ti in embodiment 23C2TxPictorial diagram photo after the freeze-drying of MXenes solution；
Fig. 7 is few layer Ti in embodiment 23C2TxThe low power number stereoscan photograph of MXenes powder；
Fig. 8 is few layer Ti in embodiment 23C2TxThe high magnification numbe stereoscan photograph of MXenes powder；
Fig. 9 is few layer Ti in embodiment 23C2TxMXenes powder atomic force microscopy and Thickness Analysis data；
Figure 10 is few layer V in embodiment 32CTxLow, the high magnification numbe stereoscan photograph of MXenes powder；
Figure 11 is few layer Ti in embodiment 42CTxThe stereoscan photograph and element distribution analysis of MXenes powder；
Figure 12 is to implement Ti in comparative example 23C2TxMXenes stereoscan photograph；
Figure 13 is few layer Ti in application examples 13C2TxThe pictorial diagram and stereoscan photograph of MXenes electrode film
Figure 14 is few layer Ti in application examples 23C2TxThe electrochemistry cycle performance of MXenes piece；
Figure 15 is multilayer Ti in Comparison study example 13C2TxThe electrochemistry cycle performance of MXenes electrode slice；
Specific embodiment
Combined with specific embodiments below, application examples, the present invention is further explained.It should be understood that these embodiments are only used for The bright present invention but should not be understood as present invention is limited in any form.In addition, it should also be understood that, having read the contents of the present invention Later, those skilled in the art can make various modifications or changes to the present invention, and such equivalent forms equally fall within the application institute Attached claims limited range.
Embodiment 1
(1) 10g purity is greater than to 98% Ti3AlC2Ceramic powder is added in the HF solution of 100ml 40wt%, normal Temperature is lower to stir 48h；Then deionized water centrifuge washing is used, it is until pH value is 7 or so, the pellet frozen after centrifugation is dry, it Followed by vacuum drying further removes the moisture in material, and drying temperature is 70 DEG C, drying time 12h, after drying Material grinding collects to arrive the Ti of multilayered structure3C2TxMXenes material.
(2) by the Ti of 1g multilayer3C2TxIt is 25wt% tetramethylammonium hydroxide that MXenes material, which is added to 10ml concentration, (TMAOH) it in aqueous solution, is stirred under room temperature for 24 hours, organic molecule intercalation is allowed to enter MXenes interlayer, synusia is increased by intercalation Spacing weakens active force between synusia, is then centrifuged for collecting the multilayer Ti after intercalation3C2TxMXenes precipitation of material, and spend from Sub- water washing is primary, and the precipitating of collection is dispersed in the deionized water of 50ml, is ultrasonically treated, ultrasound 30 minutes, later It is centrifuged, centrifugal rotational speed 3500r/min, centrifugation time is 10 minutes, by the supernatant collection after centrifugation, remains subsequent make With, the precipitating after centrifugation is dispersed again in 50ml deionized water, ultrasound 30 minutes after, be centrifuged, centrifugal rotational speed is 3500r/min, centrifugation time is 10 minutes, by the supernatant collection after centrifugation, stay it is for later use, again by the precipitating after centrifugation It is dispersed in 50ml deionized water, repeats the above process, after total ultrasonic time reaches 4 hours, last time is centrifuged Precipitating afterwards is given up, and aforementioned all supernatants is collected collection, the MXenes solution of about 350ml stays for later use.
(3) in the case of stirring, that 10ml is added dropwise in the MXenes solution of the 350ml into above-mentioned steps (2) is dense The ammonium hydroxide that degree is 28%, it is static after stirring 30 minutes, it, can be so obvious that see that the bottom of beaker has since electrostatic coagulation acts on The precipitating of MXenes generates, and apparent layering occurs, upper layer aqueous solution is outwelled, and the precipitating of lower layer is collected, above-mentioned by repeating Process, i.e., static, the aqueous solution after outwelling layering reduces the water inside MXenes solution, and it is dry to help to reduce subsequent freezing The time of dry process.
(4) after the total volume of MXenes solution is 10ml or so, first by it inside refrigerator pre-freeze, after freezing, into Row freeze-drying, after freeze-drying, powder is collected, and is placed on inside crucible, is made annealing treatment in tube furnace, annealing temperature is 150 DEG C, annealing atmosphere is argon atmosphere, annealing time 6h.
(5) after annealing, powder mull is collected, few layer dry of Ti can be obtained3C2TxMXenes material powder Body, for subsequent use.
Fig. 1 shows: the present embodiment is by initial Ti3AlC2Ceramic powder prepares multilayer Ti3C2TxThe process of MXenes product In, raw material and multilayer Ti3C2TxThe XRD spectrum of MXenes has an apparent difference, and 39 ° of raw material of (104) peak disappears, 18.2 ° and 27.6 ° occur 2 and belong to Ti3C2(OH)2Peak, show MXenes adsorption hydroxyl, (002) peak position is to low-angle side To movement, i.e., 8.9 degree are moved to by 9.9 degree.
Fig. 2 shows raw material Ti3AlC2The Raman map of ceramic powder, 122,180,198 and 268cm-1In corresponding MAX phase C-Ti-Al vibration, 580,630 and 660cm-1C-Ti-C vibrates in corresponding MAX phase, after hf etching, only 150, and 393 Hes 605cm-13 characteristic peaks, Ti-C symmetrical stretching vibration in corresponding MXenes.In conjunction with the stereoscan photograph of Fig. 3, discovery is passed through After the processing of HF acid, raw material Ti3AlC2Ceramic powder can generate apparent multilayered structure, illustrate successfully to have prepared multilayer Ti3C2TxMXenes powder.
Embodiment 2
(1) 10g purity is greater than to 98% Ti3AlC2Ceramic powder is added in the HF solution of 100ml 40wt%, 50 DEG C water-bath in, stir 12h；Then use deionized water centrifuge washing, until pH value be 7 or so, the precipitating after centrifugation is cold Be lyophilized it is dry, followed by vacuum drying, further remove material in moisture, drying temperature be 70 DEG C, drying time 12h, Material grinding after drying is collected to get the Ti of multilayered structure is arrived3C2TxMXenes material.
(2) by the Ti of 1g multilayer3C2TxIt is 25wt% tetrabutylammonium hydroxide that MXenes material, which is added to 10ml concentration, (TBAOH) it in aqueous solution, is stirred under room temperature for 24 hours, organic molecule intercalation is allowed to enter MXenes interlayer, synusia is increased by intercalation Spacing weakens active force between synusia, is then centrifuged for collecting the multilayer MXenes precipitation of material after intercalation, and be washed with deionized Once, the precipitating of collection being dispersed in the deionized water of 70ml, is ultrasonically treated, ultrasound is centrifuged after 30 minutes, from Heart revolving speed is 3500r/min, and centrifugation time is 10 minutes, by the supernatant collection after centrifugation, stay it is for later use, after centrifugation Precipitating reinject 70ml deionized water, precipitating is stirred into solution, ultrasound is centrifuged, centrifugal rotational speed is after 30 minutes 3500r/min, centrifugation time is 10 minutes, by the supernatant collection after centrifugation, stay it is for later use, again by the precipitating after centrifugation 50ml deionized water is injected, is repeated the above process, after total ultrasonic time reaches 4 hours, after last time is centrifuged Precipitating is given up, and aforementioned all supernatants are collected collection, the MXenes solution of about 500ml, stay it is for later use,.
(3) it by 3.2g ammonium bicarbonate solubility in the deionized water of 50ml, after stirring 30 minutes, can obtain uniformly , it is transparent, contain NH4+The ammonium bicarbonate aqueous solution of ion.
(4) in the case of stirring, step (3) are added dropwise in the MXenes solution of the 500ml into above-mentioned steps (2) Middle configuration contains NH4+The ammonium bicarbonate aqueous solution of ion continues stirring 30 minutes after being added, then static, by It is acted in electrostatic coagulation, meeting is so obvious that see that the bottom of beaker has the precipitating of MXenes to generate, and apparent layering occurs, by upper layer Aqueous solution is outwelled, and the solution of lower layer is collected, and the volume of MXenes solution has apparent reduction at this time, and correspondingly, MXenes is molten The concentration of liquid MXenes can increased, and repetition is static, this process of upper water be outwelled, until total volume is in 20ml or so.
(5) after the total volume of MXenes solution is 20ml or so, first by it inside refrigerator pre-freeze, after freezing, into Row freeze-drying, after freeze-drying, powder is collected, and is placed on inside crucible, is made annealing treatment in tube furnace, annealing temperature is 180 DEG C, annealing atmosphere is argon atmosphere, annealing time 6h.
(6) after annealing, powder mull is collected, few layer dry of Ti can be obtained3C2TxMXenes powder, can For subsequent applications.
Fig. 4 shows to introduce cation NH4+After ion, since cation can be adsorbed onto few layer of Ti of electronegativity3C2Tx The surface of MXenes, destroy MXenes rely between repulsive force effect maintenance electrostatic equilibrium (be electronegativity, each other Repel), electrostatic coagulation occurs, in conjunction with Fig. 5, it can be clearly seen that, with the extension of quiescent time, MXenes lamella is easy to sink It falls, after static 30 minutes, MXenes lamella is substantially completely settled, and generates significantly layering, at this time can be by supernatant It outwells, reduces the water content of freeze-drying, shorten the experimental period of freeze-drying.Fig. 6 shows few layer Ti3C2TxMXenes is molten Fluffy netted, quality 1.4g is presented in glue after freeze-drying, it is expected that if the amount of increase early period etching MAX, is used simultaneously More centrifuge tubes, utilize NH4+Few layer Ti may be implemented in ion auxiliary, electrostatic coagulation method3C2TxIt is prepared by the magnanimity of MXenes.
Fig. 7 shows few layer Ti3C2TxMXenes powder, under the scanning electron microscope of low power number, from 300 times of amplification factor, To 2000 times of amplification factor, without significantly reunion caking phenomenon, in conjunction with the high magnification numbe scanning electron microscope of Fig. 8, it can be seen that non- Normal apparent lamellar structure, thickness is in 10nm hereinafter, Ti3C2TxThe interlamellar spacing of MXenes is 1nm or so, it is possible to determine that, gained The MXenes number of plies at 10 layers hereinafter, piece diameter is in 5um or so.The atomic force microscopy and Thickness Analysis clear data of Fig. 9 Show that layer Ti is lacked in part3C2TxThe thickness of MXenes lamella is in 2-3nm, thus it is speculated that Ti3C2TxThe number of plies of MXenes layer 2-3 it Between, piece diameter in 3um or so, in conjunction with Fig. 4-9 experimental phenomena and as a result, absolutely prove that the present invention prepares few layer in quick, magnanimity The feasibility of MXenes powder.
Embodiment 3
(1) 10g purity is greater than to 95% V2AlC ceramic powder is added in the HF solution of 100ml 40wt%, at 55 DEG C Water-bath in, stir 40h；Then deionized water centrifuge washing is used, until pH value is 7 or so, by the pellet frozen after centrifugation It is dry, followed by vacuum drying, further remove the moisture in material, drying temperature is 70 DEG C, drying time 12h, will Material grinding after drying is collected to get the V of multilayered structure is arrived2CTxMXenes material.
(2) by the V of 0.5g multilayer2CTxIt is 25wt% tetramethylammonium hydroxide that MXenes material, which is added to 10ml concentration, It in aqueous solution, is stirred under room temperature for 24 hours, organic molecule intercalation is allowed to enter MXenes interlayer, synusia spacing is increased by intercalation, is weakened Active force between synusia is then centrifuged for collecting the multilayer MXenes precipitation of material after intercalation, and is washed with deionized once, will wash The precipitating collected after washing is dispersed in the deionized water of 50ml, is ultrasonically treated, and ultrasound is centrifuged after 30 minutes, is centrifuged Revolving speed is 3500r/min, and centrifugation time is 10 minutes, by the supernatant collection after centrifugation, stay it is for later use, after centrifugation Precipitating reinjects 50ml deionized water, precipitating is stirred into solution, ultrasound is equally centrifuged, centrifugal rotational speed is after 30 minutes 3500r/min, centrifugation time is 10 minutes, by the supernatant collection after centrifugation, stay it is for later use, again by the precipitating after centrifugation 50ml deionized water is injected, is repeated the above process, after total ultrasonic time reaches 4 hours, after last time is centrifuged Precipitating is given up, and aforementioned all supernatants are collected collection, the about V of 350ml2CTxMXenes solution remains subsequent make With,.
(3) 2g ammonium carbonate is dissolved in the deionized water of 50ml, after stirring 30 minutes, can be obtained uniform, saturating It is bright, contain NH4+The ammonium carbonate solution of ion.
(4) in the case of stirring, the V of the 350ml into above-mentioned steps (2)2CTxStep is added dropwise in MXenes solution Suddenly what is configured in (3) contains NH4+The ammonium carbonate solution of ion continues stirring 30 minutes after being added.
(5) the MXenes solution in step (4) is subjected to centrifugal treating, due to using NH4+It is molten to destroy MXenes for ion The electronegativity of liquid, few layer MXenes material can be easy to be centrifuged, centrifugal rotational speed 2000r/min, and centrifugation time is 10 minutes, the MXenes after centrifugation is precipitated and is collected, is freeze-dried, after freeze-drying, powder is collected, is placed in crucible Face is made annealing treatment in tube furnace, and annealing temperature is 120 DEG C, and annealing atmosphere is argon atmosphere, annealing time 12h.
(6) after annealing, powder mull is collected, few layer dry of V can be obtained2CTxMXenes material powder, For subsequent use.
Figure 10 shows: the V that the present embodiment obtains2CTxMXenes is three-dimensional netted lamellar structure, from 400 times of amplification 70000 amplification factor is counted to again, shows apparent lamella, without agglomeration, illustrates method of the invention, for system The MXenes material of standby vanadium system be also it is applicable, further illustrate universality of the invention.
Embodiment 4
(1) H is measured2SO446gNH is added in the case of stirring in solution 50ml, concentration 8mol/L inside4HF2, It stirs evenly, acid containing HF and (NH is prepared4)SO4Etching liquid, inside be added 5g purity be greater than 98% Ti2AlC ceramics Powder stirs 40h at room temperature；Then deionized water centrifuge washing is used, until supernatant pH value > 6, by the pellet frozen after centrifugation It is dry, followed by vacuum drying, further remove the moisture in material, drying temperature is 70 DEG C, drying time 12h, will Material grinding after drying is collected to get the Ti of multilayered structure is arrived2CTxMXenes material.
(2) by the Ti of 0.5g multilayer2CTxMXenes material is added in the dimethyl sulfoxide organic solution of 20ml, room temperature Lower stirring for 24 hours, allows organic molecule intercalation to enter MXenes interlayer, and the multilayer MXenes material after being then centrifuged for collection intercalation is heavy It forms sediment, and is washed with deionized once, the precipitating collected after washing is dispersed in the deionized water of 50ml, carry out at ultrasound Reason, ultrasound are centrifuged, centrifugal rotational speed 3500r/min after 30 minutes, and centrifugation time is 10 minutes, by the supernatant after centrifugation Liquid is collected, and stays for later use, and the precipitating after centrifugation is reinjected 50ml deionized water, stirs into solution, and ultrasound is after 30 minutes, It is equally centrifuged, centrifugal rotational speed 3500r/min, centrifugation time is 10 minutes, by the supernatant collection after centrifugation, after remaining It is continuous to use, the precipitating after centrifugation is reinjected into 50ml deionized water, is repeated the above process, until to reach 4 small for total ultrasonic time Supernatant is collected collection by Shi Hou, the MXenes solution of about 350ml, stay it is for later use, after last time is centrifuged Precipitating is given up.
(3) it by 3.2g ammonium bicarbonate solubility in the deionized water of 50ml, after stirring 30 minutes, can obtain uniformly , it is transparent, contain NH4+The ammonium bicarbonate aqueous solution of ion.
(4) in the case of stirring, step (3) are added dropwise in the MXenes solution of the 350ml into above-mentioned steps (2) Middle configuration contains NH4+The ammonium bicarbonate aqueous solution of ion continues stirring 30 minutes after being added.
(5) the MXenes solution in step (4) is subjected to centrifugal treating, due to using NH4+It is molten to destroy MXenes for ion The electronegativity of liquid, few layer MXenes material can be centrifuged, and centrifugal rotational speed 2000r/min, centrifugation time is 10 minutes, MXenes after centrifugation is precipitated and is collected, is freeze-dried, after freeze-drying, powder is collected, is placed on inside crucible, in tubular type It is made annealing treatment in furnace, annealing temperature is 120 DEG C, and annealing atmosphere is argon atmosphere, annealing time 12h.
(6) after annealing, powder mull is collected, few layer dry of Ti can be obtained2CTxMXenes material powder Body, for subsequent use.
Figure 11 shows: the Ti of preparation2CTxMXenes number of layers is few, and distribution diagram of element shows core element Ti and C Distribution characteristics region and Ti2C lamella is consistent.
Implement comparative example 1
Similar to Example 1, this comparative example is obtaining few layer Ti3C2TxAfter the aqueous solution of MXenes, about 350ml, 50ml therefrom is measured with beaker, after freezing inside refrigerator, starts to be freeze-dried.
It was found that the process of freeze-drying needs 50h or so, and it is very time-consuming, if few layer of all Ti is lyophilized3C2Tx The aqueous solution of MXenes, the time needed are about 400h, and in contrast, the present invention greatly reduces needs by electrostatic coagulation 350ml solution is processed into the solution of 10ml or so by the liquor capacity of freeze-drying, it is only necessary to which 10h can be lyophilized completely, greatly Efficiency is improved greatly.
Implement comparative example 2
Similar to Example 1, this comparative example is obtaining few layer Ti3C2TxAfter the aqueous solution of MXenes, high speed centrifugation, revolving speed 12000r/min, centrifugation time are 10 minutes, are then freeze-dried, and then after vacuum drying, collect Ti3C2TxMXenes powder End.
If Figure 12 is Ti prepared by this implementation comparative example3C2TxThe stereoscan photograph of MXenes, discovery are agglomerated into block, Under the scanning electron microscope of high magnification numbe, apparent lamella can't see, agglomeration is serious, some areas, by the small of many MXenes Lamella forms a big and thick lamella (as shown in the figure part d), and the MXenes of such method preparation, there are serious reunions Phenomenon can not give full play to the advantage of MXenes two-dimensional layer material in subsequent applications.
Application examples 1
The few layer of MXenes material that the application example uses above-described embodiment 1 to prepare is used as lithium ion battery negative material, adopts Negative pole piece of battery is prepared with suction filtration membrane formation process, will be filtered, the film after vacuum drying is cut, and slice assembles in glove box At fastening lithium ionic cell, the dependence test of chemical property is then carried out.Specific step is as follows:
1. prepared by cathode: 350ml Ti prepared by above-described embodiment 13C2TxMXenes solution, using vacuum filtration Mode prepares film, eliminates conductive agent and binder that usual battery pole piece needs, simplifies pole piece preparation process, freezes It is 10 hours dry in 70 DEG C under vacuum conditions after drying, it is cut into the electrode slice that diameter is 14mm after dry, few layer is made Ti3C2TxMXenes material is the battery cathode sheet of negative electrode material.
2. battery assembly and test: in the glove box of argon atmosphere, using electrode slice obtained above as cathode, with metal Lithium piece is used as to electrode, the LiPF of 1M6(DMC:EMC:FEC=1:1:1) solution is as electrolyte, with Celgard 2300 be every Film is assembled into 2032 fastening lithium ionic cells.Battery charging and discharging test uses constant current charge-discharge on Land battery test system Mode carries out, and voltage tester scope is 0.01~3V.
It is obvious lamella, soilless sticking if Figure 13 is prepared by the application example, to filter the pictorial diagram and scanning electron microscope (SEM) photograph of film forming Phenomenon.
Application examples 2
The few layer of Ti that the application example uses above-described embodiment 1 to prepare3C2TxMXenes material is used as negative electrode of lithium ion battery Negative pole piece of battery is made using coating method in material, and fastening lithium ionic cell is assembled into gloves, then carries out electrochemistry The dependence test of energy.Specific step is as follows:
1. prepared by cathode: few layer of Ti prepared by above-described embodiment 13C2TxMXenes material, according to mass ratio 8:1:1's Ratio is uniformly mixed with mass fraction for 5% Kynoar (PVDF) binder and conductive agent Super P, and stirring is equal It forms slurry after even to be coated on copper foil, 10 hours dry in 90 DEG C under vacuum conditions, it is 14mm's that diameter is cut into after dry Few layer Ti is made in electrode slice3C2TxMXenes material is the battery cathode sheet of negative electrode material.
2. battery assembly and test: in the glove box of argon atmosphere, using electrode slice obtained above as cathode, with metal Lithium piece is used as to electrode, the LiPF of 1M6(DMC:EMC:FEC=1:1:1) solution is as electrolyte, with Celgard 2300 be every Film is assembled into 2032 fastening lithium ionic cells.Battery charging and discharging test uses constant current charge-discharge on Land battery test system Mode carries out, and voltage tester scope is 0.01~3V.If the lithium ion battery that Figure 14 is the application example preparation is in current density Cycle performance figure when 500mA/g, 0.01~3V of voltage range, after circulation 200 is enclosed, specific capacity is 380mAh/g or so, no appearance Measure attenuation trend.
Comparison study example 1
This comparative example uses the multilayer Ti of 1 step of above-described embodiment (1) preparation3C2TxMXenes material is used as lithium ion Negative pole piece of battery is made using coating method in cell negative electrode material, and fastening lithium ionic cell is assembled into gloves, then carries out The dependence test of chemical property.Specific step is as follows:
1. prepared by cathode: multilayer Ti prepared by 1 step of above-described embodiment (1)3C2TxMXenes material, according to mass ratio The ratio of 8:1:1 is uniformly mixed with mass fraction for 5% Kynoar (PVDF) binder and conductive agent Super P, Slurry is mixing uniformly to form coated on copper foil, 10 hours dry in 90 DEG C under vacuum conditions, being cut into diameter after dry is Few layer Ti is made in the electrode slice of 14mm3C2TxMXenes material is the battery cathode sheet of negative electrode material.
2. battery assembly and test: in the glove box of argon atmosphere, using electrode slice obtained above as cathode, with metal Lithium piece is used as to electrode, the LiPF of 1M6(DMC:EMC:FEC=1:1:1) solution is as electrolyte, with Celgard 2300 be every Film is assembled into 2032 fastening lithium ionic cells.Battery charging and discharging test uses constant current charge-discharge on Land battery test system Mode carries out, and voltage tester scope is 0.01~3V.If the lithium ion battery that Figure 15 is the preparation of this comparative example is in current density Cycle performance figure when 500mA/g, 0.01~3V of voltage range, after 350 circle of circulation, specific capacity is 150mAh/g or so, and few Layer MXenes in terms of chemical property there are apparent difference (stable state of few layer, specific capacity are 380mAh/g or so), It absolutely proves, a kind of fast preparation method of few layer MXenes provided by the invention has wide answer in electrochemical energy storage field Use prospect.

Claims (9)

1. a kind of fast preparation method of few layer MXenes, which is characterized in that preparation method includes the following steps:
(1) MAX raw material is taken, is handled in etching liquid, the MXenes material of multilayer is obtained；
(2) the MXenes material that step (1) obtains is handled in organic molecule or surfactant；
(3) the MXenes material that step (2) obtains is centrifuged, washs precipitating, lift-off processing, abandon precipitating, collect supernatant, Obtain the MXenes solution of few layer；
(4) electrolyte solution containing ammonium ion is added in the MXenes solution that step (3) obtains, electrostatic coagulation is quiet It sets or low-speed centrifugal or suction filtration, gained colloidal sol or precipitating or filter cake is the MXenes material of layer less；
(5) material for obtaining step (4) is freeze-dried, makes annealing treatment, and obtains the powder of few layer MXenes.
2. the fast preparation method of few layer MXenes as described in claim 1 a kind of, which is characterized in that in step (1) MXenes material is Ti4C3、Ti4N3、Ti3C2、Ti2C、Mo2C、Hf3C2、V3C2、V2C、V2N、Nb4C3、Nb3C2、Nb2C、Cr3C2、 Ta2C、Ta4C3、(Ti0.5Nb0.5) one of C or a variety of combinations.
3. the fast preparation method of few layer MXenes as described in claim 1 a kind of, which is characterized in that the quarter in step (1) Losing liquid is HF, LiF and HCl, NaF and H2SO4, other salt containing F and acid one of mixed liquor or a variety of combinations.
4. the fast preparation method of few layer MXenes as described in claim 1 a kind of, which is characterized in that having in step (2) Machine molecule is tetramethylammonium hydroxide, tetrabutylammonium hydroxide, hydrazine hydrate, N-Methyl pyrrolidone, dimethyl sulfoxide, N- methyl One or more combinations of formamide, ethyl alcohol.
5. the fast preparation method of few layer MXenes as described in claim 1 a kind of, which is characterized in that the table in step (2) Face activating agent is ten alkyl trimethyl ammonium bromides, dodecyl trimethyl ammonium bromide, tetradecyltrimethylammonium bromide, hexadecane Base trimethylammonium bromide, Cetyltrimethylammonium bromide, octadecyltrimethylammonium chloride, polyvinylpyrrolidone, F127 One of or a variety of combinations.
6. the fast preparation method of few layer MXenes as described in claim 1 a kind of, which is characterized in that the stripping in step (3) From processing be it is mechanical rock, one of ultrasound, cell pulverization or a variety of combinations, the solvent that MXenes solution uses be water, One of ethyl alcohol, acetone or a variety of combinations.
7. the fast preparation method of few layer MXenes as described in claim 1 a kind of, which is characterized in that containing in step (4) The electrolyte solution of ammonium ion is ammonium hydrogen carbonate, ammonium hydroxide, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium bromide, ammonium chloride, fluorination One of ammonium salt solution or a variety of combinations.
8. the fast preparation method of few layer MXenes as described in claim 1 a kind of, which is characterized in that moving back in step (5) Fiery temperature is 70 DEG C -700 DEG C.
9. such as the application for the few layer of MXenes that any one of claim 1-8 the method obtains, which is characterized in that few layer MXenes is used as the negative electrode material of lithium ion battery or sodium-ion battery.
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