CN110304632A - Sheet MXene material and preparation method thereof and energy storage material - Google Patents

Sheet MXene material and preparation method thereof and energy storage material Download PDF

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Publication number
CN110304632A
CN110304632A CN201810228897.1A CN201810228897A CN110304632A CN 110304632 A CN110304632 A CN 110304632A CN 201810228897 A CN201810228897 A CN 201810228897A CN 110304632 A CN110304632 A CN 110304632A
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preparation
mxene
polynary
sheet
fused salt
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刘会军
杨凌旭
曾潮流
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Institute of Metal Research of CAS
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Institute of Metal Research of CAS
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Abstract

The present invention provides the preparation methods and its battery material of a kind of MXene material of sheet.The described method includes: directly formation raw mixture, the structural formula of polynary conducting ceramic material are (M according to stoichiometric ratio1‑xYx)n+1ACn, wherein n=1,2 or 3,0≤x≤1, M and Y are transition metal element, and A is IIIA the or IVA element that atomic number is 13 or more, and C is carbon；Under an inert atmosphere, raw mixture is reacted in melting fused salt, is cooled down after reaction；The fused salt in product mixtures is removed, polynary conducting ceramic material is obtained；A atom in conducting ceramic material is corroded, the MXene material of sheet is obtained.The present invention be able to solve high existing MXene materials synthesis temperature, preparation process and the device is complicated and it is at high cost the problems such as at least one of, and have many advantages, such as quickly, it is efficient, energy-saving and environmental protection, low in cost and be easily achieved large-scale production.

Description

Sheet MXene material and preparation method thereof and energy storage material
Technical field
The present invention relates to conducting ceramic material preparation technical fields, it relates in particular to which one kind being capable of low energy consumption, low cost The method that ground prepares the MXene material of sheet, and the energy storage material comprising sheet MXene material.
Background technique
In general, the field that material is related to is extremely wide, national industrial or agricultural construction and national defense construction, people's lives water such as Flat raising, it is invariably closely related with material, therefore people are described as material on one of the three big pillars of modern civilization.
In recent years, a kind of ternary ceramics with layer structure were received due to having the excellent performance of ceramics and metal concurrently The attention of domestic and international material science researcher.This processable conductivity ceramics is the carbide or nitride of a kind of close-packed hexagonal, And there is obvious anisotropy.Ternary layered ceramic combines the excellent properties of metal and ceramics: ternary layered ceramic is as metal Equally there is good conductive and thermal conductivity, lower Vickers hardness and higher elasticity modulus and modulus of shearing, be easy to machine Tool processing, and there is plasticity at high temperature；There is high-yield strength, high-melting-point, good thermal shock resistance again as ceramics And antioxygenic property.Thus it is expected that ternary layered ceramic makes pottery the high-performance for becoming important collection structure and function integration Porcelain is widely used in the fields such as electromechanics, instrument, metallurgy, chemical industry, automobile, ship, aerospace.
Currently, the method for preparing ternary layered ceramic mainly has self-propagating high-temperature reaction method (SHS), pressure sintering (HP), heat Isostatic pressing method (HIP), discharge plasma sintering method (SPS), pressureless sintering method, vaccum sintering process, mechanical-assisted alloying, with And pulsed discharge sintering process (PDS) etc..But in these methods all have disadvantages such as the device is complicated, high energy consumption and efficiency is low extremely One item missing.In addition, the ternary layered ceramic material of preparation is mostly micron-sized powder since high temperature sintering acts on, and rolled into a ball between particle It is poly- serious.
Two-dimentional transition metal carbide or carbonitride (MXene) are a kind of two-dimension nano materials having recently been developed, It is made by chemical reagent, such as hydrofluoric acid corrosion MAX phase interlayer A atom.The material has a wide range of applications in energy storage field Prospect.However, preparing presoma MAX used in MXene at present is all made of above method preparation.It is required since its particle is larger Etch period is long, and is difficult that the MXene for two-dimensional slice stratiform is completely exfoliated.
Summary of the invention
It is an object of the invention to solve at least one in deficiencies of the prior art.For example, of the invention The first purpose is to solve high existing MXene materials synthesis temperature, preparation process and the device is complicated and it is at high cost the problems such as At least one of in.
To achieve the goals above, one aspect of the present invention provides a kind of preparation method of the MXene material of sheet, institute Preparation method is stated the following steps are included: according to the stoichiometric ratio of polynary conducting ceramic material, directly by the first raw material powder with Second raw material is mixed to form raw mixture, wherein first raw material is carbon material, the knot of the polynary conducting ceramic material Structure formula is (M1-xYx)n+1ACn, wherein n=1,2 or 3, for x in the range of being not less than 0 and being not more than 1, M and Y are respectively transition gold Belong to element, A is IIIA the or IVA element that atomic number is 13 or more (including 13), and C is carbon；Under an inert atmosphere, by institute It states raw mixture to react in melting fused salt, to cool down after reaction, obtain mixed containing reaction product and solid-state fused salt Close object；The fused salt in the product mixtures is removed, the polynary conducting ceramic material with layer structure is obtained；To described polynary A atom in conducting ceramic material is corroded, to obtain the MXene material of sheet.
Another aspect of the present invention provides a kind of preparation method of the MXene material of sheet, and the preparation method includes Following steps: according to the stoichiometric ratio of polynary conducting ceramic material, the first raw material powder is directly mixed into shape with the second raw material At raw mixture, wherein first raw material is carbon material, and the structural formula of the polynary conducting ceramic material is (M1- xYx)n+1ACn, wherein n=1,2 or 3, for x in the range of being not less than 0 and being not more than 1, M and Y are respectively transition metal element, A IIIA the or IVA element for being 13 or more for atomic number, C are carbon；Under an inert atmosphere, by the raw mixture molten Reacted in melting salt, with generate have layer structure polynary conducting ceramic material, to it is described after reaction, to the melting The fluoride of predetermined amount is added in fused salt, it is then cooling to corrode to the A atom in the polynary conducting ceramic material, Obtain the product mixtures of solid-state fused salt and the MXene material containing sheet；Remove fused salt in the product mixtures and Impurity obtains the MXene material of sheet.
In an exemplary embodiment of the present invention, first raw material can be nanoscale carbon material, micron meter Spend at least one of carbon material and the carbon material of mm-scale.For example, first raw material can be graphene, carbon nanotubes At least one of with nanoscale carbon particle.
In an exemplary embodiment of the present invention, size and shape that the preparation method passes through the control carbon material Looks obtain the polynary conducting ceramic material with desired size and pattern, to obtain the lamella with desired size and pattern The MXene material of shape.In addition, the preparation method can also be mm-scale, micron meter by controlling the size of the carbon material Degree or nanoscale obtain the polynary conducting ceramic material with corresponding size respectively, so that obtaining has desired size and shape The MXene material of the sheet of looks.
In an exemplary embodiment of the present invention, second raw material can for from by element M, Y and A simple substance or Compound, the compound of M and C, Y and C compound, Mm+1ACm、Ym+1ACmOr (M1-xYx)m+1ACmIt is selected in the group of composition It is at least one, wherein m=1,2 or 3, and m is less than or equal to n.
In an exemplary embodiment of the present invention, the temperature of the reaction can be 750 DEG C or more.For example, described The temperature of reaction can be 800 DEG C~1000 DEG C.
In an exemplary embodiment of the present invention, the weight of the raw mixture can be molten state fused salt weight 2.5~60%.
Another aspect provides a kind of battery materials.The battery material includes conductive additive and electrode material One of material is a variety of, MXene of the conductive additive containing sheet obtained by preparation method as described above Material, MXene material of the electrode material containing sheet obtained by preparation method as described above.Here, it prepares First raw material used in the MXene material of the sheet can be nanoscale carbon material or micro-meter scale carbon material.Example Such as, the MXene material of the sheet can be nanometer powder, nanofiber, nanometer film or nano block.
Compared with prior art, beneficial effects of the present invention include at least one of the following: cost of material and technique at This is cheap, process flow is simple, safe and reliable, green non-pollution, convenient for large-scale production etc..
Detailed description of the invention
By the description carried out with reference to the accompanying drawing, above-mentioned and/or other purposes of the invention and feature will become more Add clear, in which:
The process that Fig. 1 shows an exemplary embodiment of the preparation method of the MXene material of sheet of the present invention is shown It is intended to；
Fig. 2 shows the processes of another exemplary embodiment of the preparation method of the MXene material of sheet of the present invention Schematic diagram；
Fig. 3 shows Ti made from an exemplary embodiment of preparation method according to the present invention3AlC2Nano-powder XRD spectrum；
Fig. 4 shows the Ti in Fig. 33AlC2The SEM of nano-powder schemes；
Fig. 5 shows the Ti in Fig. 33AlC2The TEM of nano-powder schemes；
Fig. 6 shows Ti made from another exemplary embodiment according to the method for the present invention2The XRD of AlC nano-powder Map；
Fig. 7 shows the Ti in Fig. 62The SEM of AlC nano-powder schemes；
Fig. 8 shows the Ti in Fig. 62The TEM of AlC nano-powder schemes.
Specific embodiment
Hereinafter, the preparation of the MXene material for the sheet that the present invention will be described in detail will be carried out in conjunction with exemplary embodiment The battery material of method and the MXene material using the sheet.
The process that Fig. 1 shows an exemplary embodiment of the preparation method of the MXene material of sheet of the present invention is shown It is intended to.
As shown in Figure 1, in an exemplary embodiment of the present invention, the preparation side of the MXene material with sheet Method can be realized by following steps:
(1) raw mixture is formed
According to the stoichiometric ratio of polynary conducting ceramic material, directly the first raw material powder and the second raw material are mixed to form Raw mixture, and the first raw material is carbon material.Wherein, the structural formula of polynary conducting ceramic material is (M1-xYx)n+1ACn, In, n=1,2 or 3, x are selected in the range of being not less than 0 and being not more than 1.M and Y is respectively a kind of transition metal element and M and Y It is not same element.For example, M and Y respectively can for such as scandium (Sc), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), The transition metal elements such as tantalum (Ta), chromium (Cr), molybdenum (Mo) or tungsten (W).A is IIIA the or IVA element that atomic number is 13 or more, For example, aluminium (Al) and silicon (Si).C is carbon.
In one exemplary embodiment, the second raw material can be according to the stoichiometric ratio of polynary conducting ceramic material come really Its fixed type and the proportion in raw mixture, the second raw material may include a kind of substance or two or more substances.It is worth It is noted that directly the first raw material powder and the second raw material are mixed during forming raw mixture, and Without being pre-processed (for example, being pre-sintered, compression moulding) to raw material and its mixture, without formation presoma.This is advantageous In improving production efficiency, production cost is reduced.In one exemplary embodiment, in the case where x is equal to 0, polynary conductive pottery The structural formula of ceramic material can be Mn+1ACn, for example, Ti3AlC2、Ti2AlC or Nb2AlC etc..It is greater than 0 in x and the case where less than 1 Under, the structural formula of polynary conducting ceramic material can be (Nb1-xTix)2AlC、(Nb1-xTix)3AlC2、(V1-xCrx)3AlC2、(V1- xCrx)2AlC、(Zr1-xTix)3AlC2Or (Zr1-xTix)2AlC etc..
Specifically, raw mixture can be obtained by directly mixing the powder of the first raw material and the second raw material.The One raw material powder can be the carbon material powder of the nanoscales such as graphene, carbon nanotubes, nanoscale carbon particle, can also Think the carbon material powder of micro-meter scale, or the carbon material particles of mm-scale.For example, the first raw material powder can be In conductive carbon black, acetylene black, mesoporous carbon, micropore carbon ball, level hole carbon, activated carbon, hollow carbon sphere, amorphous carbon or carbon fiber It is one or more.Second raw material can for from by the simple substance or compound of element M, Y and A, the compound of M and C, Y and C chemical combination Object, Mm+1ACm、Ym+1ACmOr (M1-xYx)m+1ACmWhat is selected in the group of composition is one or more, wherein m=1,2 or 3, and m Less than or equal to n.That is, the second raw material can be from the simple substance or alloy, Al by transition metal (for example, M and/or Y) Or the simple substance of Si, transition elements (for example, M and/or Y) and Al or Si constitute binary compound, transition elements (for example, M and/ Or Y) with carbon constitute binary compound and Mm+1ACmOr Ym+1ACmTernary compound or (M1-xYx)m+1ACM'sQuaternary It is selected in the group that compound is constituted at least one.For example, the second raw material can be Ti powder and Al powder, or for TiAl alloy powder and Ti powder is perhaps TiC powder and Al powder and Ti powder or is Ti2AlC powder and Ti powder and Al powder.For example, the second raw material can also Think Ti powder, Zr powder and Al powder, is perhaps TiZr alloyed powder and Al powder or is TiZrAl alloyed powder and Ti powder etc..It needs Bright, the second raw material is preferably powder, so as to further increase the reaction speed in fused salt, however, the present invention is unlimited In this, the second raw material can not also be powder, for example, can be block or particle etc..
In an exemplary embodiment of the present invention, directly the first raw material powder is mixed with the second raw material, without carrying out High temperature sintering or the operation such as be pressed into presoma reduce energy consumption and cost so as to improve production efficiency.In addition, inventor After study, it was found that the size and shape by controlling carbon material can obtain the polynary conduction with desired size and pattern Ceramic material, to obtain the MXene material with the sheet of desired size and pattern.For example, by raw mixture Carbon material control is graphene, then can obtain the nanometer film of the polynary conducting ceramic material with layer structure.Raw material is mixed The carbon material control closed in object is carbon nanotubes, then can obtain the Nanowire of the polynary conducting ceramic material with layer structure Dimension.Carbon material in raw mixture is controlled as nanoscale carbon particle, then can obtain with layer structure polynary leads The nano particle of electroceramics material, and then obtain the nano particle of MXene material.In addition, if the first raw material powder is selected For the carbon material powder of micro-meter scale, then the polynary conductivity ceramics material with layer structure in micro-meter scale can be obtained Material.For example, can be mm-scale, micro-meter scale or nanometer by controlling the size of carbon material in one exemplary embodiment Scale obtains the polynary conducting ceramic material with corresponding scale rank respectively.Certainly, in exemplary embodiment of the present invention In, the size of the polynary conducting ceramic material obtained with layer structure can be equivalent to or slightly larger than the first raw material powder Size, this is mainly due in fused salt reaction process such as grow and weak degrees agglomeration caused by.
(2) it is reacted in fuse salt
Under an inert atmosphere, the raw mixture is reacted in melting fused salt, to cool down after reaction, is contained There is the mixture of reaction product Yu solid-state fused salt.Specifically, the shapes such as argon gas can be used in reacting furnace (for example, shaft furnace) At inert atmosphere, and the fused salt of molten state can be formed in reaction to fire container (for example, corundum crucible).Here, fused salt can Think the metal compound fused salt of binary or ternary or more.For example, binary or multi-element metal molten chloride, for example, CaCl2- NaCl、NaCl-KCl、LiCl-KCl-CaCl2Deng.However, the invention is not limited thereto above-mentioned molten chloride, for other gold Belong to compound fused salt, as long as the fused salt environment of melting can be provided for reaction of the invention.
Specifically, the temperature that raw mixture reacts in melting fused salt may be controlled to 750 DEG C or more.However, this Invent it is without being limited thereto, as long as can make reaction occur and continue progress.For example, the temperature of reaction may be 800 DEG C~ 1000℃.Method of the invention has lower reaction temperature, this advantageously reduces energy consumption, is also beneficial to reduce equipment to resistance to height The requirement of temperature, so as to substantially reduce production cost.In addition, in an exemplary embodiment of the present invention, raw mixture Weight can be the 2.5%~60% of melting fused salt weight.Further, the weight of raw mixture can be melting fused salt weight The 5%~40% of amount.
(3) it separates and obtains target product
The fused salt in above-mentioned product mixtures is removed, the polynary conducting ceramic material with layer structure is obtained.It is specific next It says, the fused salt in product mixtures can be removed by cleaning ways such as deionized water immersion, flushings, it is pure to obtain Reaction product.Certainly, also can to by cleaning remove fused salt after residue be dried or low temperature drying handle, with obtain Polynary conducting ceramic material powder with layer structure.
(4) A atom is corroded
A atom in polynary conducting ceramic material with layer structure is corroded, to obtain the MXene of sheet Material.Specifically, the step of corroding to A atom can etch (for example, hydrofluoric acid corrosion etc.) or electrification by strong acid The mode for learning etching is realized.There is good layer in view of the preparation-obtained polynary conducting ceramic material powder of method of the invention Shape structure and nanoscale, therefore, the step of corroding in method of the invention to A atom are carved compared to conventional hydrofluoric acid It loses MAX to be formed for MXene, etching time greatly shortens, and process efficiency is improved.In exemplary implementation of the invention In example, the MXene material of sheet can also become two-dimentional or close two dimension MXene material.
Fig. 2 shows the processes of another exemplary embodiment of the preparation method of the MXene material of sheet of the present invention Schematic diagram.
As shown in Fig. 2, in another exemplary embodiment of the invention, the preparation method of the MXene material of sheet It can be realized by following steps:
(1) raw mixture is formed
The step can be essentially identical with the description as described in step (1) in the above exemplary embodiments.
(2) it is reacted in fuse salt
Under an inert atmosphere, the raw mixture is reacted in melting fused salt, there are the more of layer structure to generate First (for example, ternary or quaternary) conducting ceramic material, to previous reaction after, predetermined amount is added into the melting fused salt Fluoride, it is then cooling to corrode to the A atom in the polynary conducting ceramic material with layer structure, it obtains The product mixtures of solid-state fused salt and the MXene material containing sheet.It specifically, can be in reacting furnace (for example, well formula Furnace) it is interior using the formation inert atmosphere such as argon gas, and molten state can be formed in reaction to fire container (for example, corundum crucible) Fused salt.Here, fused salt can be metal compound fused salt more than binary or ternary.For example, binary or multi-element metal chloride are molten Salt, for example, CaCl2-NaCl、NaCl-KCl、LiCl-KCl-CaCl2Deng.However, the invention is not limited thereto, above-mentioned chloride is molten Salt, for other metal compound fused salts, as long as the fused salt environment of melting can be provided for reaction of the invention.To fused salt The fluoride of middle addition can be one of sodium fluoride, potassium fluoride, lithium fluoride, calcirm-fluoride etc. or a variety of.The addition of fluoride Amount can accordingly be determined according to the amount of A atom.
Specifically, the temperature that raw mixture reacts in melting fused salt may be controlled to 750 DEG C or more.However, this Invent it is without being limited thereto, as long as can make reaction occur and continue progress.For example, the temperature of reaction may be 800 DEG C~ 1000℃.Method of the invention has lower reaction temperature, this advantageously reduces energy consumption, is also beneficial to reduce equipment to resistance to height The requirement of temperature, so as to substantially reduce production cost.In addition, in an exemplary embodiment of the present invention, raw mixture Weight can be the 2.5%~60% of melting fused salt weight.Further, the weight of raw mixture can be melting fused salt weight The 5%~40% of amount.
(3) it separates and obtains target product
The fused salt and impurity (for example, fluoride) in above-mentioned product mixtures are removed, the MXene material of sheet is obtained. Specifically, the fused salt in product mixtures can be removed by cleaning ways such as deionized water immersion, flushings, to obtain Obtain pure reaction product.Certainly, also can to by cleaning remove fused salt after residue be dried or low temperature drying handle, To obtain the MXene material powder of sheet.In an exemplary embodiment of the present invention, the MXene material of sheet can also be with As two-dimentional or close two dimension MXene material.The method of the present exemplary embodiment can further increase reaction efficiency, reduce reaction Cost and energy consumption.
Exemplary embodiment of the present invention is further illustrated below with reference to specific example.
Example 1
Weigh the NaCl-KCl eutectic salts of 20 Unit Weights (for example, kilogram), and with 1.2 Unit Weight Ti powder, 0.23 single Position weight Al powder, 0.2 Unit Weight nanometer C powder (average grain diameter 50nm) mixed, mixture is placed in corundum crucible. Above-mentioned crucible is placed in stainless steel reactor, sealing, logical Ar gas shielded.Temperature controller is used to be warming up to the speed of 5 DEG C/min 900 DEG C, 2h is kept the temperature at this temperature, and then power-off cools to room temperature with the furnace.Products therefrom is taken out, is impregnated and is rushed with deionized water It washes away except residual fused salt, then low temperature drying is up to intermediate product.Hf etching is carried out to obtained intermediate product, obtains piece The MXene material of stratiform.
Obtained intermediate product is tested, XRD spectrum, SEM and TEM photo are respectively as shown in Fig. 3,4 and 5. As seen from Figure 3, resulting nano-powder is Ti3AlC2, by further detecting, Ti in obtained product3AlC2Nanometer The granularity of powder is 80~120nm, purity 99.2wt%.
Example 2
Weigh 20 Unit Weight LiCl-KCl eutectic salts, and with 1.2 Unit Weight Ti powder, 0.25 Unit Weight Al powder, 0.2 Unit Weight nanoscale acetylene black powder (average grain diameter 40nm) is mixed, and mixture is placed in corundum crucible.It will be above-mentioned Crucible is placed in stainless steel reactor, sealing, logical Ar gas shielded.Temperature controller is used to be warming up to 850 DEG C with the speed of 8 DEG C/min, 5h is kept the temperature at this temperature, generates the Ti with layer structure2AlC nano-powder.Then, 0.54 list is added into melting fused salt The fluoride of position weight, to Ti2Al atom in AlC nano-powder is corroded.Then, power-off cools to room temperature with the furnace, Obtain the product mixtures of solid-state fused salt and the MXene nano material containing sheet.Products therefrom is taken out, deionized water is used Soaking flushing removal residual fused salt, then low temperature drying up to sheet MXene nano material.
Example 3
Weigh 40 Unit Weight CaCl2- NaCl eutectic salts, and with 0.8 Unit Weight Ti powder, 0.293 Unit Weight Al powder, 0.09 Unit Weight nanoscale acetylene black powder (average grain diameter 40nm) is mixed, and mixture is placed in corundum crucible.It will Above-mentioned crucible is placed in stainless steel reactor, sealing, logical Ar gas shielded.Temperature controller is used to be warming up to the speed of 10 DEG C/min 950 DEG C, 3h is kept the temperature at this temperature, and then power-off cools to room temperature with the furnace.Products therefrom is taken out, is impregnated and is rushed with deionized water It washes away except residual fused salt, then low temperature drying is up to intermediate product.Hf etching is carried out to obtained intermediate product, obtains piece The MXene nano material of stratiform.
Obtained intermediate product is tested, XRD spectrum, SEM and TEM photo are respectively as shown in Fig. 6,7 and 8. As seen from Figure 6, resulting nano-powder is Ti2AlC, by further detecting, Ti in obtained product2AlC nano powder The granularity of body is 90~120nm, purity 99.5wt%.
Example 4
Weigh 20 Unit Weight NaCl-KCl eutectic salts, and with 1.55 Unit Weight Nb powder, 0.25 Unit Weight Al powder, 0.1 Unit Weight nanometer C powder (average grain diameter 50nm) is mixed, and mixture is placed in corundum crucible.Above-mentioned crucible is put In stainless steel reactor, sealing, logical Ar gas shielded.Temperature controller is used to be warming up to 900 DEG C with the speed of 8 DEG C/min, it is warm herein Degree is lower to keep the temperature 3h, and then power-off cools to room temperature with the furnace.Products therefrom is taken out, it is molten with deionized water soaking flushing removal residual Salt, then low temperature drying is up to Nb2AlC nano-powder.Then, to Nb2AlC nano-powder progress hydrochloric acid mixes molten with sodium fluoride Liquid etching, obtains the MXene nano material of sheet.
Example 5
Weigh 30 Unit Weight NaCl-KCl eutectic salts, and with 0.6 Unit Weight Ti powder, 1.14 Unit Weight Zr powder, 0.27 Unit Weight Al powder, 0.2 Unit Weight acetylene black (average grain diameter 40nm) are mixed, and mixture is placed in corundum crucible In.Above-mentioned crucible is placed in stainless steel reactor, sealing, logical Ar gas shielded.Temperature controller is used to heat up with the speed of 5 DEG C/min To 900 DEG C, 4h is kept the temperature at this temperature, and then power-off cools to room temperature with the furnace.Products therefrom is taken out, is impregnated with deionized water Wash and remove residual fused salt, then low temperature drying is up to (Zr0.5Ti0.5)3AlC2Nano-powder.Then, to (Zr0.5Ti0.5)3AlC2Nano-powder carries out electrochemical etching, obtains the MXene nano material of sheet.
Example 6
Weigh 30 Unit Weight NaCl-KCl eutectic salts, and with 0.4 Unit Weight Ti powder, 0.775 Unit Weight Nb powder, 0.27 Unit Weight Al powder, 0.1 Unit Weight nanoscale graphite powder (average grain diameter 50nm) are mixed, and mixture is placed in just In beautiful crucible.Above-mentioned crucible is placed in stainless steel reactor, sealing, logical Ar gas shielded.Use temperature controller with the speed of 8 DEG C/min Degree is warming up to 850 DEG C, keeps the temperature 5h at this temperature, and then power-off cools to room temperature with the furnace.Products therefrom is taken out, deionization is used Water impregnates wash and remove residual fused salt, and then low temperature drying is up to (Nb0.5Ti0.5)2AlC nano-powder.Then, hydrofluoric acid is carried out Etching, obtains the MXene nano material of sheet.
Example 7
Weigh 30 Unit Weight CaCl2- NaCl eutectic salts, and with 0.638 Unit Weight V powder, 0.65 Unit Weight Cr powder, 0.25 Unit Weight Al powder, 0.2 Unit Weight carbon black (average grain diameter 40nm) are mixed, and mixture is placed in corundum crucible In.Above-mentioned crucible is placed in stainless steel reactor, sealing, logical Ar gas shielded.Temperature controller is used to heat up with the speed of 5 DEG C/min To 900 DEG C, 3h is kept the temperature at this temperature, and then power-off cools to room temperature with the furnace.Products therefrom is taken out, is impregnated with deionized water Wash and remove residual fused salt, then low temperature drying is up to (V0.5Cr0.5)3AlC2Nano-powder.Then, hf etching is carried out, is obtained To the MXene nano material of sheet.
Example 8
Weigh 20 Unit Weight NaCl-KCl eutectic salts, and with 0.8 Unit Weight Ti powder, 0.27 Unit Weight Al powder, 0.1 Unit Weight graphite powder (300 mesh) is mixed, and mixture is placed in corundum crucible.Above-mentioned crucible is placed on stainless steel reaction In device, sealing, logical Ar gas shielded.It uses temperature controller to be warming up to 950 DEG C with the speed of 8 DEG C/min, keeps the temperature 5h at this temperature, so Power-off cools to room temperature with the furnace afterwards.Products therefrom is taken out, removes residual fused salt with deionized water soaking flushing, then low temperature dries Dry Ti to obtain the final product3AlC2Micro-powder.Then, electrochemical etching is carried out, the MXene micro materials of sheet are obtained.
In addition, through detecting, obtained such as Ti3AlC2Nano-powder, Ti2AlC nano-powder, Nb2AlC nano-powder, (V0.5Cr0.5)3AlC2The ternary or quaternary conducting ceramic material, Yi Jina with layer structure of the nanoscales such as nano-powder The MXene material of metrical scale has excellent hydrophily and dispersibility.For example, not settled for 24 hours after ultrasonic disperse in water. In view of Ti of the invention3AlC2、Ti2AlC、Nb2AlC、(V0.5Cr0.5)3AlC2The polynary conductive pottery of the nanoscales such as nano-powder Ceramic material and MXene nano material have excellent hydrophily and dispersibility and good electric conductivity, so of the invention MXene material can be widely applied to energy storage material field.For example, it is contemplated that the electric conductivity excellent to MXene material of the invention And corrosion resistance, therefore the electrode and (or) bipolar plates of battery can be applied to as coating.In addition, method of the invention can also be made It is standby to obtain purity is high, nanometer powder, nanofiber, nanometer film, the nano block of MXene phase with unique layer structure etc..
In addition, although Ti is presented above3AlC2Nano-powder, Ti2AlC nano-powder and Nb2AlC nano-powder, Ti3AlC2Nanotube, Nb2AlC two-dimensional nano lamella, (Zr0.5Ti0.5)3AlC2Nano-powder, (Nb0.5Ti0.5)2AlC nano powder Body, (V0.5Cr0.5)3AlC2The preparation example of nano-powder and its corresponding MXene material, it should be understood that, it is polynary to lead Electroceramics material (M1-xYx)n+1ACnOr Mn+1ACnOther types and its corresponding MXene material can also pass through preparation above Method is realized.For example, ternary or quaternary conducting ceramic material M for Ta, Mo etc.n+1ACnOr (M1-xYx)n+1ACnAnd its it is right The MXene answered can also be prepared by the method for above example, but the reaction temperature of its preparation process and time are opposite Appropriate adjustment may be needed in the reaction temperature of above-mentioned example and time.
In addition, battery material may include conductive additive and electrode material in another exemplary embodiment of the invention One or both of material.Also, the conductive additive contains sheet obtained by preparation method as described above MXene material, MXene material of the electrode material containing sheet obtained by preparation method as described above.For example, The MXene material of the sheet has nanoscale or micro-meter scale.Preferably, the MXene material of the sheet can be Nanometer powder, nanofiber, nanometer film or nano block.
Shown in sum up, the present invention is able to solve high existing MXene materials synthesis temperature, preparation process and the device is complicated and It is one or more in the problems such as at high cost, and have quickly, efficiently, it is energy-saving and environmental protection, low in cost and be easily achieved big rule The advantages that mould produces, detailed impression is described as follows:
1, the conventional preparation for etching the stratiform ternary conducting ceramic material for forming MXene material is mostly using high pressure Or the modes such as sintering, preparation temperature is high, at high cost；The present invention is then directly to mix the first raw material and the second raw material, without It carries out high temperature sintering or the operation such as be pressed into presoma is so as to improve production efficiency reduces energy consumption and cost.
2, the raw material that the present invention mixes is placed in melting fused salt and is reacted, and reaction temperature can be not higher than 1000 DEG C, very As for can be down to 750 DEG C.The process has lower reaction temperature, this advantageously reduces energy consumption, is also beneficial to reduce equipment pair Requirement resistant to high temperature, so as to substantially reduce production cost.Whole technological process is safe and reliable, green non-pollution, is convenient for greatly Large-scale production.
3, method of the invention can prepare the polynary conducting ceramic material with layer structure of nanoscale and its right The MXene nano material answered is (for example, scale can be 100nm or so even smaller polynary conductivity ceramics material of nanoscale stratiform Material or scale can be 100nm or so even the MXene material of smaller nanometer level), compared to conventional micron order material With broader practice range.
4, the present invention prepared by sheet MXene material can be applied to such as battery material conductive additive and (or) numerous areas such as electrode material, catalysis, lubricator additive and antifriction material.
Although having been combined exemplary embodiment above and attached drawing describing the present invention, those of ordinary skill in the art It will be apparent to the skilled artisan that can be carry out various modifications to above-described embodiment in the case where not departing from spirit and scope of the claims.

Claims (18)

1. a kind of preparation method of the MXene material of sheet, which is characterized in that the preparation method comprises the following steps:
According to the stoichiometric ratio of polynary conducting ceramic material, the first raw material powder and the second raw material are directly mixed to form raw material Mixture, wherein first raw material is carbon material, and the structural formula of the polynary conducting ceramic material is (M1-xYx)n+1ACn, In, n=1,2 or 3, for x in the range of being not less than 0 and being not more than 1, M and Y are respectively transition metal element, and A is that atomic number is 13 or more IIIA or IVA element, C are carbon；
Under an inert atmosphere, the raw mixture is reacted in melting fused salt, to cool down after reaction, is obtained containing anti- Answer the mixture of product Yu solid-state fused salt；
The fused salt in the product mixtures is removed, the polynary conducting ceramic material with layer structure is obtained；
A atom in the polynary conducting ceramic material is corroded, to obtain the MXene material of sheet.
2. the preparation method of the MXene material of sheet according to claim 1, which is characterized in that the preparation method The polynary conducting ceramic material with desired size and pattern is obtained by controlling the size and shape of the carbon material.
3. the preparation method of the MXene material of sheet according to claim 1, which is characterized in that the preparation method Size by controlling the carbon material is mm-scale, micro-meter scale or nanoscale obtained respectively with corresponding size Polynary conducting ceramic material.
4. the preparation method of the MXene material of sheet according to claim 1, which is characterized in that first raw material One of carbon material for nanoscale carbon material, micro-meter scale carbon material and mm-scale is a variety of.
5. the preparation method of the MXene material of sheet according to claim 1, which is characterized in that second raw material For from compound, the M by the simple substance or compound of element M, Y and A, the compound of M and C, Y and Cm+1ACm、Ym+1ACmOr (M1- xYx)m+1ACmWhat is selected in the group of composition is one or more, wherein m=1,2 or 3, and m is less than or equal to n.
6. the preparation method of the MXene material of sheet according to claim 1, which is characterized in that the temperature of the reaction Degree is 750 DEG C or more.
7. the preparation method of the MXene material of sheet according to claim 6, which is characterized in that the temperature of the reaction Degree is 800 DEG C~1000 DEG C.
8. the preparation method of the MXene material of sheet according to claim 1, which is characterized in that the raw material mixing The weight of object is the 2.5~60% of molten state fused salt weight.
9. the preparation method of the MXene material of sheet according to claim 1, which is characterized in that it is described to A atom into The step of row corrosion, is realized by way of strong acid etching or electrochemical etching.
10. a kind of preparation method of the MXene material of sheet, which is characterized in that the preparation method comprises the following steps:
According to the stoichiometric ratio of polynary conducting ceramic material, the first raw material powder and the second raw material are directly mixed to form raw material Mixture, wherein first raw material is carbon material, and the structural formula of the polynary conducting ceramic material is (M1-xYx)n+1ACn, In, n=1,2 or 3, for x in the range of being not less than 0 and being not more than 1, M and Y are respectively transition metal element, and A is that atomic number is 13 or more IIIA or IVA element, C are carbon；
Under an inert atmosphere, the raw mixture is reacted in melting fused salt, to generate there is the polynary of layer structure to lead Electroceramics material, to it is described after reaction, the fluoride of predetermined amount is added, into the melting fused salt polynary to lead to described A atom in electroceramics material is corroded, then cooling, obtains the production of solid-state fused salt and the MXene material containing sheet Object mixture；
The fused salt and impurity in the product mixtures are removed, the MXene material of sheet is obtained.
11. the preparation method of the MXene material of sheet according to claim 10, which is characterized in that the preparation side Method obtains the polynary conducting ceramic material with desired size and pattern by controlling the size and shape of the carbon material.
12. the preparation method of the MXene material of sheet according to claim 10, which is characterized in that the preparation side Method is that mm-scale, micro-meter scale or nanoscale are obtained respectively with corresponding size by controlling the size of the carbon material Polynary conducting ceramic material.
13. the preparation method of the MXene material of sheet according to claim 10, which is characterized in that described first is former Material is one of carbon material of nanoscale carbon material, micro-meter scale carbon material and mm-scale or a variety of.
14. the preparation method of the MXene material of sheet according to claim 10, which is characterized in that described second is former Material is from compound, the M by the simple substance or compound of element M, Y and A, the compound of M and C, Y and Cm+1ACm、Ym+1ACmOr (M1- xYx)m+1ACmWhat is selected in the group of composition is one or more, wherein m=1,2 or 3, and m is less than or equal to n.
15. the preparation method of the MXene material of sheet according to claim 10, which is characterized in that the reaction Temperature is 750 DEG C or more.
16. the preparation method of the MXene material of sheet according to claim 15, which is characterized in that the reaction Temperature is 800 DEG C~1000 DEG C.
17. the preparation method of the MXene material of sheet according to claim 10, which is characterized in that the raw material is mixed The weight for closing object is the 2.5~60% of molten state fused salt weight.
18. a kind of battery material, which is characterized in that the battery material includes conductive additive and/or electrode material, described to lead Electric additive and the electrode material contain the MXene of sheet obtained by preparation method as described in claim 1 respectively Material.
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CN111549248A (en) * 2020-06-12 2020-08-18 陕西科技大学 Preparation method of M-site ternary solid solution type MAX phase material
CN112221892A (en) * 2020-08-26 2021-01-15 惠州市海龙模具塑料制品有限公司 Novel metal bipolar plate surface modification method
CN112499601A (en) * 2020-12-15 2021-03-16 江苏师范大学 Method for efficiently preparing thin-layer MXene
CN112853369A (en) * 2020-12-31 2021-05-28 中国科学院上海应用物理研究所 Mike alkene, preparation method thereof, lithium ion battery and application
CN113121236A (en) * 2021-03-02 2021-07-16 西安交通大学 Micron-sized three-dimensional lamellar Ti2AlC ceramic powder and preparation method thereof
CN113248260A (en) * 2021-05-21 2021-08-13 北京航空航天大学 Preparation method and application of novel nitrogen-containing MAX phase material and two-dimensional material
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CN113461010A (en) * 2021-07-07 2021-10-01 南京林业大学 Method for preparing fluorine-free MXene by adopting electrochemical etching method
CN113564546A (en) * 2020-04-28 2021-10-29 安泰科技股份有限公司 Preparation method and system of precoating metal strip for metal bipolar plate
CN116477951A (en) * 2023-04-25 2023-07-25 中南大学 Ta preparation by molten salt method 1/3 Nb 1/3 Ti 1/3 Method for preparing C ceramic nano powder

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WO2021167747A3 (en) * 2020-01-24 2021-09-30 Drexel University Synthesis of mxene suspensions with improved stability
CN115515913A (en) * 2020-01-24 2022-12-23 德雷塞尔大学 Synthesis of MXENE suspensions with improved stability
CN113564546A (en) * 2020-04-28 2021-10-29 安泰科技股份有限公司 Preparation method and system of precoating metal strip for metal bipolar plate
CN113564546B (en) * 2020-04-28 2023-09-19 安泰科技股份有限公司 Preparation method and system of precoated metal strip for metal bipolar plate
CN111549248B (en) * 2020-06-12 2021-04-06 陕西科技大学 Preparation method of M-site ternary solid solution type MAX phase material
CN111549248A (en) * 2020-06-12 2020-08-18 陕西科技大学 Preparation method of M-site ternary solid solution type MAX phase material
CN112221892A (en) * 2020-08-26 2021-01-15 惠州市海龙模具塑料制品有限公司 Novel metal bipolar plate surface modification method
CN112499601A (en) * 2020-12-15 2021-03-16 江苏师范大学 Method for efficiently preparing thin-layer MXene
CN112499601B (en) * 2020-12-15 2023-09-19 江苏师范大学 Method for efficiently preparing thin layer MXene
CN112853369A (en) * 2020-12-31 2021-05-28 中国科学院上海应用物理研究所 Mike alkene, preparation method thereof, lithium ion battery and application
CN113121236A (en) * 2021-03-02 2021-07-16 西安交通大学 Micron-sized three-dimensional lamellar Ti2AlC ceramic powder and preparation method thereof
CN113121236B (en) * 2021-03-02 2022-04-05 西安交通大学 Micron-sized three-dimensional lamellar Ti2AlC ceramic powder and preparation method thereof
CN113248260A (en) * 2021-05-21 2021-08-13 北京航空航天大学 Preparation method and application of novel nitrogen-containing MAX phase material and two-dimensional material
CN113461010A (en) * 2021-07-07 2021-10-01 南京林业大学 Method for preparing fluorine-free MXene by adopting electrochemical etching method
CN113461010B (en) * 2021-07-07 2023-06-09 南京林业大学 Method for preparing fluorine-free MXene by adopting electrochemical etching method
CN116477951A (en) * 2023-04-25 2023-07-25 中南大学 Ta preparation by molten salt method 1/3 Nb 1/3 Ti 1/3 Method for preparing C ceramic nano powder
CN116477951B (en) * 2023-04-25 2024-04-09 中南大学 Ta preparation by molten salt method 1/3 Nb 1/3 Ti 1/3 Method for preparing C ceramic nano powder

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