CN112047341A - Nb-shaped alloy2C MXene material and preparation method and application thereof - Google Patents

Nb-shaped alloy2C MXene material and preparation method and application thereof Download PDF

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CN112047341A
CN112047341A CN202010894441.6A CN202010894441A CN112047341A CN 112047341 A CN112047341 A CN 112047341A CN 202010894441 A CN202010894441 A CN 202010894441A CN 112047341 A CN112047341 A CN 112047341A
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sodium
mxene
preparation
time
potassium
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CN112047341B (en
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张建新
张文扬
金辉鑫
张友健
杜逸群
王子晗
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Shandong University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • 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
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    • 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
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Abstract

The disclosure relates to the field of battery electrodes, and particularly provides a Nb2C MXene material and its preparation method and application. The material is in an organ shape with lamella separation on the macro scale and in a hexagonal crystal system arrangement on the micro scale. The preparation method of the material comprises the following steps: preparation of Nb2And (3) carrying out selective etching on the AlC MAX phase by using HF, and completely etching off the Al layer to obtain the Al-based material. The problems that metal sodium and potassium ions have large radiuses, dendritic crystals are easily generated in a circulation process, and the lithium battery cannot be replaced in the prior art are solved.

Description

Nb-shaped alloy2C MXene material and preparation method and application thereof
Technical Field
The disclosure relates to the field of battery electrodes, and particularly provides a Nb2C MXene material and its preparation method and application.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
With the successful preparation of graphene, two-dimensional materials have attracted sufficient attention of researchers in recent years. Compared with other materials, the two-dimensional material has large specific surface area, more active sites and ion channels for oxidation-reduction reaction, and better performance in a battery. In recent years, a two-dimensional material attracts attention of researchers, and is an MXene material. The material is prepared by mixing ceramic MAX phase (general formula M)n+1XnTx) Selectively etching away the A layer, wherein M represents transition metal elements such as Ti, Cr, Nb, Mo, V, etc., X represents C or N, and T represents terminal groups such as OH, O, F, Cl, etc. The abundance of terminal groups in this material makes it more compatible with a variety of solvents. In the past, MXene materials have been found to have a low diffusion energy barrier to large diameter ions and a large lamella spacing to facilitate large ion insertion. The MXene material has good metal property, conductivity and mechanical toughness, and can be used as an alternative material of an alkali metal ion battery.
In the prior art, a two-dimensional material Mxene has good performance in a battery and can be used as a next-generation energy storage material. The metal sodium and the metal potassium have low price and excellent performance, and have great potential in replacing metal lithium as a battery cathode material. However, the inventor finds that the ions of the metal sodium and potassium have larger radius, and the circulation process is easy to generate dendrite, so that the commercial application of the metal sodium and potassium is restricted.
Disclosure of Invention
The method aims to solve the problems that metal sodium and potassium ions in the prior art are large in radius, and dendritic crystals are easily generated in a circulation process and cannot replace a lithium battery.
In one or some embodiments of the present disclosure, a Nb is provided2C MXene material in the form of a macroscopically lamellar separated organ and microscopically hexagonal arrangement.
In one or some embodiments of the present disclosure, a Nb is provided2The preparation method of the C MXene material comprises the following steps: preparation of Nb2And (3) carrying out selective etching on the AlC MAX phase by using HF, and completely etching off the Al layer to obtain the Al-based material.
The above Nb2C MXene material or Nb as described above2The product prepared by the preparation method of the C MXene material is applied to batteries.
The above Nb2C MXene material or Nb as described above2The product prepared by the preparation method of the C MXene material is applied to a battery anode.
A button cell, the positive electrode is Nb2C MXene material or Nb as described above2The product prepared by the preparation method of the C MXene material has the negative electrode made of sodium or sodium-potassium alloy material, a diaphragm and an active layer between the negative electrode and the positive electrode, and the active layer is made of an active substance Nb2C MXene, polyvinylidene fluoride, acetylene black and N-methyl pyrrolidone.
One of the above technical solutions has the following advantages or beneficial effects:
the disclosure successfully produces Nb2C MXene material and its use in different alkali metal ion batteries. Accordion shaped Nb2The C MXene material has a laminated stacking structure, and the pores among the laminated layers are larger, so that the reaction area is larger. Moreover, the high-resolution projection electron microscope photograph can show the complete structure. When solid sodium and liquid sodium-potassium alloy are matched as a negative electrode, the lithium-ion battery has good electrochemical performance, such as cycle stability of over 500 weeks and good rate performance. When the liquid sodium-potassium alloy is used as the negative electrode, the growth of dendrites is inhibited. Nb of the present disclosure2The C MXene material is more suitable for being applied to energy storage materials of sodium-potassium ion batteries.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this disclosure, illustrate embodiments of the disclosure and, together with the description, serve to explain the disclosure and not to limit the disclosure.
FIG. 1 shows Nb in example 12Preparation process of C MXene material
FIG. 2 shows Nb in example 12A characterization map of C MXene material, wherein (a) Nb2XRD pattern of C MXene. (b) Nb2Scanning electron microscope of C MXenePhotograph, in which the inset thumbnail is an enlargement of the slice portion. (c-d) Nb2Transmission electron microscope photograph and selected area electron diffraction photograph of C MXene. (e) Nb2High resolution transmission electron micrograph of C MXene, inset is the enlargement of the square box part, and Nb is at the bottom right corner2Crystal structure of C MXene, where black and white parts represent C and Nb, respectively.
FIG. 3 shows the cycling performance of Nb2C MXene in example 3 with metallic sodium, sodium potassium alloy and metallic potassium as the negative electrode, where a is sodium, b is sodium potassium alloy and c is potassium.
FIG. 4 shows Nb in example 32And C MXene respectively takes metal potassium, sodium-potassium alloy and metal sodium as negative electrodes, and the charge-discharge voltage curves of (a-C) cyclic voltammetry Curves (CV) and (d-f) are obtained.
FIG. 5 shows Nb in example 32And (a-C) rate performance and (d-f) Electrochemical Impedance Spectroscopy (EIS) curves of the C MXene when the metal potassium, the sodium-potassium alloy and the metal sodium are respectively used as negative electrodes.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The MXene material disclosed by the disclosure is prepared by mixing ceramic MAX phase (general formula is M)n+1XnTx) Selectively etching away the A layer, wherein M represents transition metal elements such as Ti, Cr, Nb, Mo, V, etc., X represents C or N, and T represents terminal groups such as OH, O, F, Cl, etc.
Nb of the present disclosure2The C MXene material refers to an organ-shaped two-dimensional MXene material Nb formed by selectively etching ceramic MAX phase2C, can also be written as Nb2C，
The method aims to solve the problems that metal sodium and potassium ions in the prior art are large in radius, and dendritic crystals are easily generated in a circulation process and cannot replace a lithium battery.
One or more of the present disclosureIn an embodiment, a Nb is provided2C MXene material in the form of a macroscopically lamellar separated organ and microscopically hexagonal arrangement.
In one or some embodiments of the present disclosure, a Nb is provided2The preparation method of the C MXene material comprises the following steps: preparation of Nb2And (3) carrying out selective etching on the AlC MAX phase by using HF, and completely etching off the Al layer to obtain the Al-based material.
Preferably, Nb is prepared2The AlC MAX phase comprises the following steps: mixing Nb, Al and NbC in certain proportion, ball milling, and heating in inert gas atmosphere for some time to obtain Nb2AlC MAX phase.
Preferably, the mass ratio of Nb to Al to NbC is 1-3:1-3: 1-2;
further preferably, the mass ratio of Nb to Al to NbC is 2:1.2: 1;
preferably, the ball milling time is 20-50 minutes;
further preferably, the ball milling time is 30 minutes;
preferably, the inert gas is argon;
preferably, the heating temperature is 1000-1500 ℃;
further preferably, the heating temperature is 1400 ℃;
preferably, the heating time is 1.5-3.5 h;
more preferably, the heating time is 2 hours.
Preferably, the step of selectively etching is as follows: mixing Nb with2And ball-milling the AlC phase for a period of time, crushing the ball into smaller particles, then selectively etching the particles by using HF (hydrogen fluoride), stirring the particles for the time, centrifuging the particles, collecting precipitates, repeatedly cleaning the precipitates, and drying the precipitates to obtain the nano-crystalline silicon dioxide.
Preferably, the ball milling time is 25-50 minutes;
further preferably, the ball milling time is 30 minutes;
preferably, the mass fraction of HF is 35-50%;
more preferably, the mass fraction of HF is 40%;
preferably, the stirring time is 20-40 h;
further preferably, the stirring time is 24 h;
preferably, the centrifugation speed is 3800-;
further preferably, the centrifugation speed is 4000 rpm;
preferably, the washing is repeated until the pH value is 6-7.
The above Nb2C MXene material or Nb as described above2The product prepared by the preparation method of the C MXene material is applied to batteries.
Preferably, the battery is an alkali metal battery.
The above Nb2C MXene material or Nb as described above2The product prepared by the preparation method of the C MXene material is applied to a battery anode.
Preferably, the battery negative electrode is made of a sodium or sodium-potassium alloy material.
Preferably, the preparation method of the negative electrode made of the sodium-potassium alloy material comprises the following steps: the method comprises the following steps of (1) carrying out physical contact on solid sodium and potassium, applying a certain external force, mutually dissolving the solid sodium and the potassium to obtain a liquid sodium-potassium alloy, placing the liquid sodium-potassium alloy on foamed nickel, heating, and adsorbing the alloy in the foamed nickel to obtain the sodium-potassium alloy;
preferably, the heating temperature is 400-500 ℃;
further preferably, the heating temperature is 420 ℃.
A button cell, the positive electrode is Nb2C MXene material or Nb as described above2According to the product prepared by the preparation method of the C MXene material, the negative electrode is made of a sodium or sodium-potassium alloy material, the diaphragm and the active layer are arranged between the negative electrode and the positive electrode, and the active layer is formed by mixing an active substance, polyvinylidene fluoride, acetylene black and N-methyl pyrrolidone. The electrolyte and the anode and cathode materials required for preparing the battery are fewer, and the laboratory test of the performance of the battery material is convenient
Preferably, the membrane is a glass fiber filter membrane;
preferably, the button cell is 2025 button cell.
Preferably, the preparation method of the active layer comprises the following steps: mixing an active substance, polyvinylidene fluoride and acetylene black in a certain ratio, adding N-methyl pyrrolidone, stirring for a long time, coating the mixed slurry on a copper foil, drying in vacuum at a certain temperature, and cutting the dried pole piece into small wafers to obtain the composite electrode.
Preferably, the mass ratio of the active substance to the polyvinylidene fluoride to the acetylene black is 6-9:0.5-1.5: 0.5-1.5;
further preferably, the mass ratio of the active substance to the polyvinylidene fluoride to the acetylene black is 8:1: 1;
preferably, the stirring time is 20-50 h;
further preferably, the stirring time is 24 h;
preferably, the vacuum drying temperature is 55-80 ℃;
further preferably, the vacuum drying temperature is 60 ℃;
preferably, the vacuum drying time is 8-15 h;
further preferably, the vacuum drying time is 10 h.
Example 1
As shown in FIG. 1, the present embodiment provides a Nb2Preparation method of C MXene material, wherein gray lamella represents Nb2And C, the black sheet layer represents an Al layer, and the small ball represents sodium and potassium ions in the battery. The Nb2C MXene is obtained by selectively etching MAX phase Nb2Al layer in AlC.
The method specifically comprises the following steps: mixing Nb, Al and NbC in the ratio of 2:1.2:1, ball milling for 30 min, and heating at 1400 deg.c for two hr in argon atmosphere to obtain Nb2AlC MAX phase.
Next, 2g of Nb2The AlC was ball milled for 30 minutes to smaller particles and then selectively etched with 40% HF, and the mixture was stirred for 24 hours and centrifuged at 4000 rpm.
Collecting the precipitate and repeatedly cleaning until the pH value of the supernatant is 6-7. After drying, Nb is obtained2C。
The material prepared in this example was characterized by Al and Nb as shown in FIG. 22The C-slices overlap to form a MAX phase. After the MAX is crushed into smaller particles by the nodular graphite, the MAX is selectively etched by HF to formNb with two-dimensional sheet stack2C MXene material. The material has larger specific surface area and a large number of storage sites, and can be used as a battery material with excellent performance.
To Nb2XRD measurement of C MXene showed that three main peaks were marked with squares at 33 °,38 ° and 60 ° in fig. 2 (a). The crystal phase is matched with Nb2C (PDF #75-2169) through analysis, and the crystal planes corresponding to the three main peaks are (201), (211) and (002), respectively.
Nb2The scanning electron micrograph of C MXene is shown in FIG. 2(b), and the inset is an enlargement of the slice portion. It can be seen that Nb2C MXene shows a concertina structure with lamellae separated from each other and at a larger interplanar spacing with more ion channels.
As is more apparent from FIG. 2(c), Nb is shown2C MXene consisting of a flat varying number of lamellae, top left Nb2The side view of C MXene shows that its structure is very loose, with the flakes separated from each other.
The selected area electron diffraction pattern is shown in FIG. 2(d) as a set of symmetric diffraction spots formed around the center spot, illustrating Nb2C MXene is well crystalline. The map is from [010]The crystal planes at other points can be obtained by vector law, observed off-axis and marking the corresponding crystal planes in the graph.
FIG. 2(e) shows an enlarged view of a portion of the sheet. The four lamellae in the figure are separated from each other, illustrating that the Al layer has been completely removed from the MAX phase. Enlarging a portion of the lattice to the right can be seen as Nb on an atomic scale2C MXene exhibits a hexagonal arrangement. Nb2The crystal structure of C MXene is schematically shown in the lower right corner, and the crystal structure also presents a hexagonal system, six atoms around each Nb or C present a regular hexagon and correspond well to a lattice. This indicates that Nb is not damaged during the selective etching of the Al layer2Crystal structure of C.
Example 2
The embodiment provides a preparation method of a 2025 button cell, which includes the following steps:
preparing an active layer: mixing the active substance, polyvinylidene fluoride and acetylene black in a ratio of 8:1:1, adding N-methyl pyrrolidone, and stirring for 24 hours. The mixed slurry was then coated on a copper foil and vacuum dried at 60 ℃ for 10 hours.
And cutting the dried pole piece into small round pieces, and filling the small round pieces into a glove box to form the battery. The glass fiber filter membrane is used as a battery diaphragm. Metallic sodium, potassium and liquid sodium-potassium alloy are respectively used as counter electrodes. All cell assembly was completed in a glove box.
The preparation method of the liquid sodium-potassium alloy comprises the following steps:
solid sodium and solid potassium are in physical contact and are mutually dissolved to form the sodium-potassium alloy after a certain external force is applied. After the alloy is heated to 420 ℃, the alloy is automatically adsorbed on the foamed nickel to obtain the sodium-potassium alloy cathode which can be used for a battery.
Example 3
This example was conducted to examine the performance of the battery prepared in example 2.
Detection means
The crystalline information of the material was obtained by X-ray diffraction (XRD) scanning at a scanning rate of 10 ° per minute. The surface morphology was obtained by a 5kV field emission Scanning Electron Microscope (SEM) and high-resolution projection electron microscope (HR-TEM).
Electrochemical performance test
The voltage interval of the battery is set to be 0.01-3V, the current density used in the cycle performance test is 50mA/g, the current density used in the multiplying power performance test is 50,100,200,500,200,100 and 50mA/g, the sweep speed of a CV curve is 0.5mV/s, and the testing frequency range of an Electrochemical Impedance Spectroscopy (EIS) is 1MHz-0.01 Hz.
Analysis of test data
Nb2The cycling performance of C is shown in fig. 3, which can be cycled for over 500 weeks in all battery systems. When the metallic sodium is used as a negative electrode, the cycle is very stable, and the initial charge-discharge specific capacity is 71.2/62.9 mAh/g. Description of good cycle Performance Nb2The C has stronger capacity of circulating and storing sodium ions. Furthermore, we have found that Nb2The capacity of C rises gradually during cycling, which can be attributed to Nb2C structural adjustment during circulation andand (4) activating. After 500 cycles, the capacity remained 93%, indicating Nb2The C MXene has great potential as an energy storage material of a sodium-ion battery. When liquid sodium-potassium alloy is used as the negative electrode, Nb2The C MXene cycle performance is good, and the initial specific capacity is 89.9/50.4 mAh/g. After short adjustment, the circulation tends to be stable, and the coulombic efficiency is about 100%, which indicates that the reversibility of the material is good. After 500 weeks, the capacity retention was 80%. For Nb with metal potassium as negative electrode2C MXene, the cycle starts somewhat unstably due to dendritic growth and non-smoothness on the surface of the potassium electrode, whereas the ion transport kinetics and charge transfer rate of potassium ions are more easily affected by the electrode surface than sodium ions. Nb2C also shows better electrochemical performance when the liquid sodium-potassium alloy without dendritic generation and with smooth surface is used as the negative electrode than when the metal potassium is used as the negative electrode
Nb2The CV curve of C is shown in FIG. 4. FIG. 4a is Nb2And C, a CV curve with metallic sodium as a negative electrode. An irreversible peak appeared at 2.85V in the first week due to the formation of a solid electrolyte film (SEI film). Moreover, the curves and peaks of this half-cycle are stronger than those of the other cycles, which can be attributed to the further expansion of the lamella spacing during the first sodium modification, making it easier for sodium ions and electrolyte to enter between the lamellae. Over the next few weeks, the curve coincidence is high, indicating that the sodium ions and electrolyte molecules between the lamellae support and fix the lamella spacing. There was a pair of bulges at 1.3/1.7V, caused by the pseudo-adsorption/pseudo-desorption of sodium ions at MXene surface and defects. Next, we can see a strong pair of cathodic/anodic peaks at the 0.01V position, corresponding to the insertion/extraction of sodium ions into/from Nb2C MXene electrode. The peak positions in the CV curves correspond well to the plateau voltages in fig. 4d, and it can also be seen that both the pseudo-adsorption/pseudo-desorption and the insertion/extraction of sodium ions contribute to the capacity increase. Except for the first week, the contact ratio of the charge-discharge voltage curve in the following cycle process is better, which shows that the reversibility of the material is good and the cycle performance is better.
When liquid sodium-potassium alloy and metal potassium are used as negative electrode，Nb2The CV curves of C show some similarities because liquid sodium-potassium alloys can also be used as potassium ion battery negative electrodes. There are two irreversible peaks at 1.5V and 0.4V, corresponding to decomposition of the electrolyte and formation of SEI film. The two peaks in FIG. 4b are offset compared to FIG. 4c because the potassium ions are more reactive in the liquid alloy and are more likely to participate in the redox reaction. In FIGS. 4b-c, a strong peak and a weak bump are shown at the 0.01/0.4V position, corresponding to the insertion/extraction of potassium ions. The charge and discharge voltage curves of fig. 4e-f show similar properties. Except for the first circle, the coincidence of the curve at the back is better, and the coincidence degree is higher when the liquid sodium-potassium alloy is used as the negative electrode, which shows that the cycle performance can be better due to the characteristics of the liquid sodium-potassium alloy for inhibiting the growth of dendrite and smoothing the surface of the electrode.
FIGS. 5a-c show Nb2The rate capability of the C MXene taking metal sodium, liquid sodium-potassium alloy and metal potassium as the negative electrode is tested by using current densities of 50,100,200,500,200,100 and 50 mA/g. The tested battery systems all showed good rate performance. As the current density increases, the capacity decays relatively slowly; as the current density gradually returns to the original level, the capacity level also returns better. When metallic sodium, sodium potassium alloy and metallic potassium were used as the negative electrode, the capacity was recovered to the first 98%, 98% and 90% when the current density was recovered to the first 50 mA/g. It can be seen that Nb2The C MXene can withstand large current impact and keep the functional structure intact without damage. Nb2The electrochemical impedance spectrum curve of the C MXene with the metal sodium, the liquid sodium-potassium alloy and the metal potassium as the negative electrode is shown in FIGS. 5 d-f. The intercept of the Z' axis of the high-frequency part, the size of the semicircle and the slope of the inclined line of the low-frequency part respectively correspond to the ohmic resistance, the interface resistance and the Warburg impedance. Comparing fig. 5e and f, it can be seen that in the potassium ion battery system, when the liquid sodium-potassium alloy is used as the negative electrode, the impedance is low, which is also caused by the characteristics of no dendritic growth and smooth surface of the sodium-potassium alloy.
Example 4
The present embodiment provides an Nb2The preparation method of the C MXene material is different from the embodiment 1In the above-mentioned Nb2The preparation method of the AlC MAX phase adopts a hydrothermal method.
Example 5
This example describes Nb in example 42The C MXene material was prepared into 2025 button cell using only liquid sodium potassium alloy as the counter electrode, and the rest of the preparation method was the same as in example 2.
Example 6
In this embodiment, when the performance of the 2025 button cell described in example 5 is tested, the initial charge-discharge specific capacity is 70.8/40.3mAh/g, the coulombic efficiency is about 80%, and after 500 weeks, the capacity retention rate is 50%. The effect was far inferior to the data measured in example 3, and it is obvious that although example 1 and example 4 use the same etching method to mix Nb2Al in the AlC MAX phase is etched away, however, the obtained Nb is prepared in a different way2The electrochemical performance of AlC MAX material is greatly influenced
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the scope of the present invention, therefore, the present invention is not limited by the appended claims.

Claims (10)

1. Nb-shaped alloy2The C MXene material is characterized in that the material is in a shape of an organ with a layer separated macroscopically and in a hexagonal crystal system arrangement microscopically.
2. Nb-shaped alloy2The preparation method of the C MXene material is characterized by comprising the following steps:
preparation of Nb2And (3) carrying out selective etching on the AlC MAX phase by using HF, and completely etching off the Al layer to obtain the Al-based material.
3. The method of claim 2, wherein Nb is produced2The AlC MAX phase comprises the following steps: mixing Nb, Al and NbC in certain proportion, ball milling, and heating in inert gas atmosphere for some time to obtain Nb2AlC MAX phase;
preferably, the mass ratio of Nb to Al to NbC is 1-3:1-3: 1-2;
further preferably, the mass ratio of Nb to Al to NbC is 2:1.2: 1;
preferably, the ball milling time is 20-50 minutes;
further preferably, the ball milling time is 30 minutes;
preferably, the inert gas is argon;
preferably, the heating temperature is 1000-1500 ℃;
further preferably, the heating temperature is 1400 ℃;
preferably, the heating time is 1.5-3.5 h;
more preferably, the heating time is 2 hours.
4. The method of claim 2, wherein the step of selectively etching comprises:
ball-milling Nb2AlC phase for a period of time, crushing into smaller particles, then selectively etching with HF, stirring for a while, centrifuging, collecting precipitate, repeatedly cleaning, and drying to obtain the final product;
preferably, the ball milling time is 25-50 minutes;
further preferably, the ball milling time is 30 minutes;
preferably, the mass fraction of HF is 35-50%;
more preferably, the mass fraction of HF is 40%;
preferably, the stirring time is 20-40 h;
further preferably, the stirring time is 24 h;
preferably, the centrifugation speed is 3800-;
further preferably, the centrifugation speed is 4000 rpm;
preferably, the washing is repeated until the pH value is 6-7.
5. The Nb of claim 12C MXene material or Nb according to any of claims 2-42The product prepared by the preparation method of the C MXene material is applied to batteries;
preferably, the battery is an alkali metal battery.
6. The Nb of claim 12C MXene material or Nb according to any of claims 2-42The product prepared by the preparation method of the C MXene material is applied to a battery anode.
7. The use of claim 6, wherein the battery negative electrode is made of a sodium or sodium potassium alloy material.
8. The use of claim 7, wherein the preparation method of the negative electrode of the sodium-potassium alloy material comprises the following steps: the method comprises the following steps of (1) carrying out physical contact on solid sodium and potassium, applying a certain external force, mutually dissolving the solid sodium and the potassium to obtain a liquid sodium-potassium alloy, placing the liquid sodium-potassium alloy on foamed nickel, heating, and adsorbing the alloy in the foamed nickel to obtain the sodium-potassium alloy;
preferably, the heating temperature is 400-500 ℃;
further preferably, the heating temperature is 420 ℃.
9. A button cell battery, characterized in that the positive electrode is Nb as described in claim 12C MXene material or Nb according to any of claims 2-42The product prepared by the preparation method of the C MXene material has the negative electrode made of sodium or sodium-potassium alloy material, a diaphragm and an active layer between the negative electrode and the positive electrode, and the active layer is made of an active substance Nb2C MXene, polyvinylidene fluoride, acetylene black and N-methyl pyrrolidone;
preferably, the membrane is a glass fiber filter membrane;
preferably, the button cell is 2025 button cell.
10. The button cell according to claim 9, wherein the active layer is prepared by the following method: adding an active material Nb2Mixing C MXene, polyvinylidene fluoride and acetylene black in a certain proportion, adding N-methyl pyrrolidone, stirring for a long time, coating the mixed slurry on a copper foil, and coatingVacuum drying at a certain temperature, and cutting the dried pole piece into small wafers;
preferably, the mass ratio of the active substance to the polyvinylidene fluoride to the acetylene black is 6-9:0.5-1.5: 0.5-1.5;
further preferably, the mass ratio of the active substance to the polyvinylidene fluoride to the acetylene black is 8:1: 1;
preferably, the stirring time is 20-50 h;
further preferably, the stirring time is 24 h;
preferably, the vacuum drying temperature is 55-80 ℃;
further preferably, the vacuum drying temperature is 60 ℃;
preferably, the vacuum drying time is 8-15 h;
further preferably, the vacuum drying time is 10 h.
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