CN116553548A - Five-transition metal high-entropy MXene material and preparation method and application thereof - Google Patents
Five-transition metal high-entropy MXene material and preparation method and application thereof Download PDFInfo
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/5607—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3817—Carbides
Abstract
The invention discloses a preparation method of a pentatransition metal high-entropy MXene material, which comprises the following steps of constructing 514-phase high-entropy MAX material (TiVCrNbMo) 5 AlC 4 Subsequent reaction with an etchant gives high entropy MXene (TiVCrNbMo) 5 C 4 T x By combining high entropy MXene (TiVCrNbMo) 5 C 4 T x Prepared into high entropy MXene (TiVCrNbMo) 5 C 4 T x Aerogel to obtain the five transition metal high-entropy MXene material. The five transition metal high-entropy MXene material prepared by the invention has five kinds of goldThe porous material belongs to the elements, is uniformly distributed and not aggregated, has a three-dimensional macroporous structure formed by overlapping single-layer or few-layer MXene sheets to form an irregular shape, has a thin pore wall structure, has a larger working voltage range, more excellent rate performance and more excellent ionic and electronic conductivity, and further has higher conductivity and charge storage capacity. And the high-entropy MXene electrode material prepared from the five-transition metal high-entropy MXene material has excellent capacitance and excellent cycling stability.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a five-transition metal high-entropy MXene material for a super capacitor, and a preparation method and application thereof.
Background
Since 2011, two-dimensional layered transition metal carbides (MXnes) have been found to have wide application prospects in the fields of supercapacitors, batteries, electrocatalysis and the like due to the characteristics of large interlayer spacing, good conductivity, good chemical stability and hydrophilicity, adjustable interlayer spacing and the like. MXene has the general chemical formula M n+1 X n T x It is M obtained by selectively etching an A atomic layer through the reaction of a precursor MAX material and a proper etchant n+1 X n T x . In the formula, M represents an early transition metal element; a is a group 13-14 element; x is mainly C; t (T) x Representing rich functional groups on the surface of the MXene. Due to the multiple selectivities of early transition metals, the diversity of etching methods, and the wide range of n values, the composition and atomic structure of MXene are tailored to have different physical and chemical properties to meet the needs of multiple fields, becoming a hot topic. Abundant components, excellent conductivity and stability, and easy-to-adjust surface chemistry, make MXnes have very promising applications in energy storage, catalysts, electromagnetic shielding, and the like. After adjustment of the M site element, atomic layers with two or more transition metals exhibit unique electronic structures (semiconductor or metallic features) with accompanying unique surface terminations. Based on the double transition metal structure, can be changedThe bimetallic MXenes have better conductivity, charge storage capacity and catalytic activity by changing the electronic state of the transition metal and the properties of the outer transition metal layer.
Similar to high-entropy alloys, high-entropy MXenes are multi-element materials comprising at least five metallic elements. Due to its novel "high entropy effect" and excellent properties, it has become one of the research hotspots in the material field in recent years. The mixing mode of various main elements of the high-entropy alloy leads to the maximum mixing entropy of the material, the high mixing entropy inhibits the formation of intermetallic compounds, and the formation of saturated solid solution with simple crystal structure is promoted. Under the coupling action of various mechanisms, the high-entropy alloy has excellent properties which are incomparable with those of the traditional materials, such as outstanding in the aspects of mechanics, electromagnetism, high temperature resistance, corrosion resistance and the like, so the high-entropy alloy is regarded as one of key materials which are expected to solve the problem of material performance bottleneck in the current engineering field. However, the existing MXene-based super capacitor has the problems of poor electrode performance, narrow working voltage range, short cycle life and the like. And currently there is a lack of examples of the application of high entropy MXene to the field of supercapacitors.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, the main purpose of the invention is to provide a pentatransition metal high-entropy MXene material and a preparation method thereof, which aims to solve the problems of single preparation method, low purity and easy aggregation of the existing high-entropy MXene material and widen the variety of the high-entropy MXene.
The invention aims at realizing the following technical scheme:
in a first aspect, a method for preparing a hardware transition high-entropy MXene material includes the following steps:
1) High entropy MAX material (TiVCrNbMo) 5 AlC 4 Synthesis of powders
Uniformly mixing Ti, V, cr, nb, mo, al and graphite powder according to a molar ratio of 1:1:1:1:1.3:3.5; spreading the uniformly mixed powder in an alumina crucible, transferring to a tube furnace, and sintering at 1400-1600 ℃ to ensure constant sintering processThe argon flow was set to prevent the sample from being oxidized. After cooling, the surface of the sintered blank is polished by sand paper and ground to obtain a high-entropy MAX material (TiVCrNbMo) 5 AlC 4 A powder;
2) High entropy MXene (TiVCrNbMo) 5 C 4 T x Is synthesized by (a)
MAX material (TiVCrNbMo) 5 AlC 4 Slowly adding the powder into polytetrafluoroethylene reactor containing 40-50% hydrofluoric acid, and maintaining the whole process for 60 seconds to obtain high entropy MAX material (TiVCrNbMo) 5 AlC 4 The ratio of the powder to the hydrofluoric acid solution is 1:10-20g/mL; reacting in a water bath kettle at 45-50 ℃ and continuously stirring for 60-80 hours; centrifuging, dispersing and decanting the suspension after reaction for several times until the pH of the supernatant is equal to>6, collecting the MXenes by vacuum filtration on cellulose filter paper, and vacuum drying at 60 ℃ for 24 hours to obtain the high entropy MXene (TiVCrNbMo) 5 C 4 T x ；
3) High entropy MXene (TiVCrNbMo) 5 C 4 T x Synthesis of aerogel
Taking the high entropy MXene (TiVCrNbMo) obtained in the step 2) 5 C 4 T x Adding into intercalation agent with mass concentration of 10-15wt%, high entropy MXene (TiVCrNbMo) 5 C 4 T x The ratio of the intercalation agent to the intercalation agent is 1:10-40g/mL, and stirring is carried out to obtain a mixture; centrifuging the mixture for the first time to obtain precipitate, and measuring the pH value of the supernatant; dispersing the precipitate with deionized water, centrifuging for the second time to obtain precipitate again, and measuring the pH value of the supernatant again; repeating for several times, when the pH value of the supernatant is 6.0-8.0, dispersing the precipitate again by deionized water, performing ultrasonic treatment for 1-2h under the bubbling action of inert gas, and centrifuging for the third time to obtain the supernatant, namely a few-layer MXene solution; lyophilizing the low-layer MXene solution for 40-60 hr to obtain high entropy MXene (TiVCrNbMo) 5 C 4 T x Aerogel, namely the hardware transition high-entropy MXene material.
Preferably, in the step 1), a temperature programming method is adopted during sintering, wherein the temperature programming speed from room temperature to 1200 ℃ is 10 ℃/min, and the temperature programming speed from 1200 ℃ to sintering temperature is 2 ℃/min.
Preferably, in step 1), the high entropy MAX material (TiVCrNbMo) 5 AlC 4 The particle size of the powder is 50-100 μm.
Preferably, in the step 2), the stirring speed is 300-500r/min, the centrifugal rotating speed is 3000-4000r/min, and the centrifugal time is 3-8min.
Preferably, in the step 3), the rotating speeds of the first centrifugation and the second centrifugation are 4000-6000r/min, and the centrifugation time is 4-6min; the rotation speed of the third centrifugation is 3000-4000r/min, and the centrifugation time is 50-70min.
Preferably, in the step 3), the intercalation agent is any one or more of tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and dimethyl sulfoxide.
Preferably, in step 2), the high entropy MXene (TiVCrNbMo) 5 C 4 T x The multi-layer accordion structure is formed by five transition metal layers and four carbon layers; in step 3), the high entropy MXene (TiVCrNbMo) 5 C 4 T x The aerogel is formed by superposing a plurality of layers of MXene sheets and has a three-dimensional macroporous structure with an irregular shape, and the average thickness of the pore wall is 20 mu m.
In a second aspect, a metal transition high-entropy MXene material prepared according to the preparation method has a molecular formula of M 5 X 4 T x Wherein M is Ti, V, cr, nb and Mo; x represents at least one of carbon, nitrogen or boron; tx represents a surface functional group, said Tx comprising one or more of O, F, cl, br, I or OH.
Preferably, the mass percentage of Ti, V, cr, nb and Mo elements in the hardware transition high-entropy MXene material is 5-30%, and further, the mass percentage of Ti, V, cr, nb and Mo elements is 20%;
in a third aspect, a preparation method of the five-transition metal high-entropy MXene supercapacitor electrode material includes the following steps:
high entropy MXene (TiVCrNbMo) as described above 5 C 4 T x Aerogel and polymerTetrafluoroethylene (PTFE) binder and acetylene black are mixed, the acetylene black is added between MXene sheets to form a conductive network, the mass ratio is 80:10:10, and the acetylene black is dispersed in 0.5-2mL of n-methyl-2-pyrrolidone (NMP) solvent; and homogenizing the obtained mixture by using ultrasonic waves, coating the homogenized mixture on a conductive carbon cloth substrate, and then drying the homogenized mixture in a vacuum freeze drying box for 20-30 hours to obtain the five-transition metal high-entropy MXene super capacitor electrode material.
Compared with the prior art, the invention has at least the following advantages:
1) The five-transition metal high-entropy MXene material provided by the invention has five different early transition metals, and the addition of five metal elements increases the entropy value of the material, so that the crystal structure of the material is more stable; the prepared high-entropy MXene aerogel has a three-dimensional macroporous structure formed by overlapping single-layer or few-layer MXene sheets, and the thin pore wall structure greatly shortens the diffusion distance of electrolyte ions, remarkably optimizes the diffusion kinetics of the electrolyte, increases the contact area with the electrolyte and improves the electrochemical performance; at the same time, the electronic state of the metal and the specific characteristics of the outer transition metal layer are changed, and the stability of the crystal structure is improved, so that the high entropy MXene (TiVCrNbMo) 5 C 4 T x The base super capacitor electrode shows a more stable working state in electrolyte, namely, has a larger working voltage range, more excellent rate performance and more excellent ionic and electronic conductivity, and further has higher conductivity and charge storage capacity.
2) The preparation method of the five transition metal high-entropy MXene material constructs 514-phase high-entropy MAX material (TiVCrNbMo) by directly increasing the atomic layer number 5 AlC 4 Then the high entropy MXene (TiVCrNbMo) is obtained through the reaction with the etchant 5 C 4 T x By combining high entropy MXene (TiVCrNbMo) 5 C 4 T x Prepared into high entropy MXene (TiVCrNbMo) 5 C 4 T x An aerogel; the method increases the configurational entropy by adding element types, thereby reducing the free energy of Gibbs and stabilizing the crystal structure. Thereby leading the high-entropy MXene to have longer cycle lifeAnd can operate over a larger voltage range without polarization; meanwhile, ti, V, cr, nb, mo, al, C elements in the high-entropy MXene material prepared by the method are uniformly distributed in the layered and stacked high-entropy MAX powder, the contents of Ti, V, cr, nb and Mo are close to 20at%, the distribution of five metal elements is very uniform within the range of 5-35%, and no obvious aggregation effect is generated; and is composed of the high entropy MXene (TiVCrNbMo) 5 C 4 T x The high-entropy MXene electrode material prepared from the aerogel has excellent capacitance and excellent cycling stability.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings that are used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is an XRD pattern of high entropy MXene according to example 1 of the invention
FIG. 2 is a photograph of the morphology of example 1 of the present invention; wherein: (a) High entropy MAX, (b) multilayer high entropy MXene, (c, d) high entropy MXene aerogel, (e) scanning electron microscope images of high entropy MXene films; (e) The inset in (a) shows photographs of high entropy MXene thin films obtained by vacuum filtration; (f) a transmission electron microscope image of high entropy MXene; the inset shows 10nm -1 SAED pattern of (C); (g) HAADF-STEM image with high entropy MAX and corresponding element distribution diagram.
FIG. 3 is a photograph of the morphology of example 1 of the present invention; wherein: (a) And (b) top and side views, respectively, of an aberration corrected STEM image of high entropy MXene; (c) High entropy MXene's atomic resolution HAADF and corresponding Super-EDS images.
Fig. 4 is a photograph of the morphology of the present invention in example 2, example 3 and example 4: wherein (a) Ti 3 AlC 2 ，(b)Nb 2 AlC，(c)V 2 AlC，(d)Ti 3 C 2 T x ，(e)Nb 2 CT x And (f) V 2 CT x Is a scanning electron microscope image of (1).
FIG. 5 is a graph showing the performance of the super capacitor according to the embodiment of the present invention and the comparison example; wherein (a) high entropy MXene (denoted HE-MXene in the figure) is scanned at different scan rates (2-100 mV s -1 ) Cyclic voltammogram under); (b) High entropyMXene at different current densities (1-10 Ag -1 ) A constant current charge-discharge curve; (c) High entropy MXene and Ti 3 C 2 T x ，Nb 2 CT x And V 2 CT x Comparison of CV curves of isotransition metals MXnes; (d) High entropy MXene and Ti 3 C 2 T x ，Nb 2 CT x And V 2 CT x Mass capacitance of isomonoscopic transition metals MXenes at different current densities; (e) High entropy MXene and Ti 3 C 2 T x ，Nb 2 CT x And V 2 CT x Impedance diagrams of isotransition metals Mxenes; (f) HE-MXene vs. other kinds of electrode performance.
Detailed Description
The invention will now be described in further detail with reference to the accompanying drawings and examples which are given by way of illustration only and not by way of limitation, and are not intended to limit the scope of the invention. Aspects of the invention are described in this disclosure with reference to the drawings, in which are shown a number of illustrative embodiments. The embodiments of the present disclosure are not necessarily intended to include all aspects of the invention. It should be understood that the various concepts and embodiments described above, as well as those described in more detail below, may be implemented in any of a number of ways, as the disclosed concepts and embodiments are not limited to any implementation. Additionally, some aspects of the disclosure may be used alone or in any suitable combination with other aspects of the disclosure.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1:
1. preparation of hardware transition high-entropy MXene material
A preparation method of a pentatransition metal high-entropy MXene material comprises the following steps:
1) High entropy MAX material (TiVCrNbMo) 5 AlC 4 Synthesis of powders
Uniformly mixing Ti, V, cr, nb, mo, al and graphite powder according to a molar ratio of 1:1:1:1:1.3:3.5; spreading the uniformly mixed powder in an alumina crucible, transferring the alumina crucible into a tube furnace, and sintering at 1500 ℃ to ensure constant argon flow in the whole sintering process so as to prevent the sample from being oxidized; after cooling, the surface of the sintered blank is polished by sand paper and ground to obtain a high-entropy MAX material (TiVCrNbMo) 5 AlC 4 A powder;
2) High entropy MXene (TiVCrNbMo) 5 C 4 T x Is synthesized by (a)
MAX material (TiVCrNbMo) 5 AlC 4 The powder is slowly added into a polytetrafluoroethylene reactor containing 45% hydrofluoric acid by mass, the whole process lasts for 60 seconds, and the high entropy MAX material (TiVCrNbMo) 5 AlC 4 The ratio of the powder to the hydrofluoric acid solution is 1:15g/mL; reacting in a water bath kettle at 45 ℃ and continuously stirring for 70 hours; centrifuging, dispersing and decanting the suspension after reaction for several times until the pH of the supernatant is equal to>6, collecting the MXenes by vacuum filtration on cellulose filter paper, and vacuum drying at 60 ℃ for 24 hours to obtain the high entropy MXene (TiVCrNbMo) 5 C 4 T x
3) High entropy MXene (TiVCrNbMo) 5 C 4 T x Synthesis of aerogel
Taking the high entropy MXene (TiVCrNbMo) obtained in the step 2) 5 C 4 T x Adding into intercalation agent with mass concentration of 10wt% and high entropy MXene (TiVCrNbMo) 5 C 4 T x Mixing the mixture with an intercalating agent at a ratio of 1:30g/mL, and stirring to obtain a mixture; centrifuging the mixture for the first time to obtain precipitate, and measuring the pH value of the supernatant; dispersing the precipitate with deionized water, centrifuging for the second time to obtain precipitate again, and measuring the pH value of the supernatant again; repeating for several times, when the pH value of the supernatant is 7.0, dispersing the precipitate again by adopting deionized water, carrying out ultrasonic treatment for 1.5h under the bubbling action of inert gas, and centrifuging for the third time to obtain the supernatant, namely a few-layer MXene solution; lyophilizing the low-layer MXene solution for 50h to obtain high entropy MXene (TiVCrNbMo) 5 C 4 T x Aerogel, namely the five transition metal high-entropy MXene material.
Wherein in the step 1), a temperature programming method is adopted in sintering, the temperature rising speed from room temperature to 1200 ℃ is 10 ℃/min, the temperature rising speed from 1200 ℃ to sintering temperature is 2 ℃/min, and the prepared high-entropy MAX material (TiVCrNbMo) 5 AlC 4 The particle size of the powder is 50-100 μm.
In the step 2), the stirring speed is 450r/min, the centrifugal rotating speed is 3500r/min, and the centrifugal time is 5min. In the step 3), the rotation speeds of the first centrifugation and the second centrifugation are 5000r/min, and the centrifugation time is 5min; the rotation speed of the third centrifugation is 3500r/min, and the centrifugation time is 60min; the intercalating agent used in this example was tetrabutylammonium hydroxide.
2. Performance test of five transition metal high entropy MXene material:
the performance of the substance obtained by the preparation method provided in the example 1 is detected; the method comprises the following steps:
1) Material identification
The application prepares the high entropy MXene (TiVCrNbMo) from the example 1 5 C 4 T x As a result of XRD measurement of the aerogel material, as shown in FIG. 1, there is a distinct (002) peak at 5℃as shown in FIG. 1, indicating the high entropy MXene (TiVCrNbMo) produced by the present invention 5 C 4 T x Aerogel materials are extremely high in purity and successful synthesis of novel pentatransition metal high-entropy MXene.
2) Topography determination of materials
The morphology and microstructure of the product obtained in steps 1) -3 of example 1 were studied by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM), and the results are shown in FIG. 2, wherein FIG. 2a is a high entropy MAX material (TiVCrNbMo) of example 1 5 AlC 4 Exhibits a typical dense layered structure; after selective etching of the aluminum atomic layer in the high entropy MAX by hydrofluoric acid, the originally compact layered structure is opened, and after washing and vacuum drying, a multi-layer high entropy MXene powder can be obtained, which presents a typical accordion-like microstructure (FIG. 2 b); layering multiple layers of high-entropy MXene powder to obtain a few-layer or single-layer high-entropy MXene solution, and coolingAnd (3) freeze-drying to obtain the high-entropy MXene aerogel, wherein the high-entropy MXene aerogel is in an irregularly-shaped three-dimensional macroporous structure Kong Bibao in a side view, and is formed by stacking few layers or single layers of MXene sheets in a top view, as shown in fig. 2c and 2 d. The three-dimensional hole and thin hole wall structures can greatly shorten the diffusion distance of electrolyte ions and increase the contact area with the electrolyte, thereby being beneficial to improving the electrochemical performance.
3) Film structure of material
The application prepares a low-layer or single-layer high-entropy MXene solution into a HE-MXene film by a vacuum suction filtration method (figure 2 e); the thickness of the resulting high entropy MXene film was about 20. Mu.m. After suction filtration, the two-dimensional material has typical lamellar close-packed appearance of the nano-sheets on the section. This is because the two-dimensional nanoplatelets in the high entropy MXene wet film tend to assemble layer by layer under the force of gravity; the high resolution TEM and corresponding selected area electron diffraction patterns (SAED) clearly demonstrate the lattice and hexagonal structure of the prepared multilayer high entropy MXene, demonstrating that good crystallinity can be well maintained after long-term hydrofluoric acid reaction (fig. 2 f). FIG. 2g shows a high-angle annular dark field scanning transmission electron microscope (HAADF-STEM) image with high entropy MAX and its corresponding element distribution; it can be clearly seen that the Ti, V, cr, nb, mo, al, C element is uniformly distributed in the high entropy MAX powder layer-by-layer stack.
4) Elemental ratio of high entropy material
The present application uses SEM-EDS to analyze the elemental ratios of high entropy MAX and high entropy MXene. EDS point scan results are shown in Table 1:
TABLE 1EDS Point scan results
As can be seen from Table 1, after HF etching, the multi-layer HE-MXene still maintains a transition metal stoichiometry close to its MAX precursor, and a Ti, V, cr, nb, mo ratio of about 1:1:1:1:1. Because Cr-C bonds in the multi-layer high-entropy MXene are weaker than other M-C bonds, the proportion of Cr in the multi-layer HE-MXene is slightly lower than that in the precursor, and the reactivity of the Cr-containing MXene in the selective etching process is stronger. Furthermore, we analyzed the elemental ratios of the single layer MXene using ICP-OES as shown in table 2:
table 2: elemental ratio of MXene
As can be seen from table 2, the contents of Ti, V, cr, nb and Mo are close to 20at.% and are in the range of 5 to 35 at.%.
5) Atomic arrangement of high entropy materials
The application further researches the atomic arrangement of high entropy MXenes by an atomic resolution aberration correcting mirror, and the result is shown in FIG. 3: wherein fig. 3a directly shows some regular arrangements of atoms of different brightness intensities. It is well known that the brightness of an atom is proportional to the square of its atomic number. Following this principle, in the enlarged view of fig. 3a, the brightest atoms are Mo atoms, the darkest atoms are Ti atoms, and the unevenness of the luminance distribution indicates that the m-site element atoms in the high entropy MXene are arranged in a solid solution arrangement. As shown in fig. 3b, there is a distinct dark portion between adjacent layers, which is caused by the reaction of Al atoms with hydrofluoric acid, indicating that the high entropy MAX is successfully converted to high entropy MXene. Importantly, the super-EDS results (fig. 3 c) show that the distribution of the five elements is very uniform, even in the nanometer range, with no significant aggregation effects.
Example 2: preparation of supercapacitor electrode material
A preparation method of a hardware transition high-entropy MXene supercapacitor electrode material comprises the following steps:
high entropy MXene (TiVCrNbMo) prepared in example 1 5 C 4 T x Mixing aerogel, polytetrafluoroethylene (PTFE) adhesive and acetylene black, wherein the acetylene black is added between MXene sheets to form a conductive network, the mass ratio is 80:10:10, and the conductive network is dispersed in 0.5-2mL of n-methyl-2-pyrrolidone (NMP) solvent; homogenizing the obtained mixture with ultrasonic wave, coating on conductive carbon cloth substrate, and drying in vacuum freeze drying oven for 20-30 hr to obtain hardware transition high entropy MXAnd (5) an ene super capacitor electrode material.
Performance test:
1) Electrochemical testing
The application adopts Cyclic Voltammetry (CV), constant current charge-discharge (GCD) and Electrochemical Impedance Spectroscopy (EIS) in 1M KOH electrolyte for testing, and the results are shown in figure 5, specifically, the application selects the range of-1.0 to-0.3V (vs. Hg/HgO) to test the cyclic voltammetry curve of the high-entropy MXene electrode, and the scanning rate is 2-100mV s -1 . As shown in FIG. 5a, the temperature is between 2 and 100mV s -1 At the scanning rate of (2), the CV curve of the high entropy MXene electrode is approximately symmetric and regular rectangle, and no obvious oxidation-reduction peak and polarization phenomenon are observed (namely, no upwarp at the two ends of the CV curve); with the increase of the scanning speed, the CV curve is not obvious in bending, and good reversibility is shown; the GCD test can record a voltage curve changing along with time, and can reflect the charge and discharge performance of the electrode like a CV curve; as shown in fig. 5b, as the current density decreases, the charge-discharge time of the electrode increases, because ions in the electrolyte can be more fully intercalated between the MXene layers with lower current densities; meanwhile, it can be observed that there is an insignificant pressure drop process at the top of the charge-discharge curve; this small voltage drop may reflect the magnitude of the internal resistance of the electrode. The voltage drop is not obvious in the present application, and the internal resistance of the electrode is considered to be low. When the current density is 1Ag -1 The mass capacitance of the high entropy MXene electrode is 284.6F g -1 。
2) Capacitive performance testing
The method tests the capacitance performance of the metal transition high-entropy MXene super capacitor electrode material, and simultaneously introduces single transition metal MXenes, nb 2 CT x ,V 2 CT x And Ti is 3 C 2 T x Supercapacitor electrode materials were prepared as comparative examples, the preparation method of which was the same as that of example 2 described above; wherein Nb is 2 CT x ,V 2 CT x And Ti is 3 C 2 T x The preparation method of (1) is as followsTechniques, not described in detail herein; of course Nb 2 CT x ,V 2 CT x And Ti is 3 C 2 T x Materials are also commercially available; nb thereof 2 CT x ,V 2 CT x And Ti is 3 C 2 T x The morphology diagram of the material is shown in fig. 4; wherein (a) Ti 3 AlC 2 ，(b)Nb 2 AlC，(c)V 2 AlC，(d)Ti 3 C 2 T x ，(e)Nb 2 CT x And (f) V 2 CT x Is a scanning electron microscope image of (1). FIG. 5c shows a scan rate of 100mV s in a 1M KOH electrolyte -1 Different suitable voltage window CV curves for the high entropy MXene electrode and the single transition metal MXene electrode materials in the three-electrode system. It can be seen that the high entropy MXene electrode possesses a high entropy relative to the single transition metal Nb 2 CT x ,V 2 CT x And Ti is 3 C 2 T x The electrodes have a wider operating voltage window. In the same electrolyte, V 2 CT x The electrode material starts to appear slightly polarized at-0.5V (i.e., the two ends of the curve are obviously upwarped), which is more obvious at low scanning rate, while the high entropy MXene electrode working voltage window is 0.7V, and no polarization occurs at both low and high scanning rates. In addition, as can be seen in conjunction with FIGS. 5a, 5c, with Nb 2 CT x ,V 2 CT x And Ti is 3 C 2 T x Compared with the MXene electrode, the cyclic voltammogram of the high-entropy MXene electrode has the largest integral area under the low scanning rate and the high scanning rate, which means that the crystal stability improved by increasing the transition metal species in the MXene can obviously optimize the working state of the MXene electrode in electrolyte, namely the electrochemical performance and the working voltage window of the MXene electrode are improved. Comparing GCD curves, the high-entropy MXene electrode always has longer discharge time than single transition metal MXnes under the conditions of low current density and high current density; the gravimetric capacitance of different MXnes at different current densities is shown in FIG. 5d, and the gravimetric capacitance of the high entropy MXene electrode is still 170Fg when the current density is increased 10 times -1 Exhibits excellent rate performance.
FIG. 5e shows noLike the Nyquist plot of mxnes, the inset is an enlarged plot of the high frequency region. The Nyquist plot consists of a semicircle in the high frequency region and a straight line in the low frequency region. In the high frequency region, the intersection of the semicircle and the real axis is the internal resistance (R s The internal resistance of the material consists of the internal resistance of the active material and the collector, and the contact resistance between the electrode and the electrolyte. The radius of the semicircle is the charge transfer resistance (R ct ) The smaller the radius, the smaller the charge transfer resistance of the electrode; the straight portion of the low frequency region is related to the diffusion of ions in the electrolyte. As can be seen, the high entropy MXene electrode has smaller intercept value and radius in the high frequency region, indicating R s And R is ct Are all lower than single transition metal MXene electrodes. The conductivity of the high entropy MXene was shown to be better. This also reveals the reason why the high entropy MXene electrode has superior capacitive performance. Furthermore, the near vertical lines in the low frequency region demonstrate the capacitive properties of the electrode, indicating that the electrode exhibits rapid diffusion kinetics. By comparing our work with other works (FIG. 5 f), it can be found that (TiVCrNbMo) is prepared by the preparation method of the present application 5 C 4 T x The high-entropy MXene electrode prepared from the aerogel has good capacitance. These excellent preliminary results indicate that (TiVCrNbMo) 5 C 4 T x Aerogel is a promising candidate electrode material for energy storage applications, potentially exceeding the charge storage performance of conventional MXenes. Furthermore, the adjustability of the M-bit in MAX materials provides an infinite opportunity to tailor the composition of the resulting MXenes, which is a desirable choice for energy storage and catalytic applications.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention, and are intended to be included within the scope of the appended claims and description.
Claims (10)
1. The preparation method of the hardware transition high-entropy MXene material is characterized by comprising the following steps of:
1) High entropy MAX material (TiVCrNbMo) 5 AlC 4 Synthesis of powders
Uniformly mixing Ti, V, cr, nb, mo, al and graphite powder according to a molar ratio of 1:1:1:1:1.3:3.5; spreading the uniformly mixed powder in an alumina crucible, transferring to a tube furnace, sintering at 1400-1600 ℃, and ensuring constant argon flow in the whole sintering process to prevent the sample from being oxidized; after cooling, the surface of the sintered blank is polished by sand paper and ground to obtain a high-entropy MAX material (TiVCrNbMo) 5 AlC 4 A powder;
2) High entropy MXene (TiVCrNbMo) 5 C 4 T x Is synthesized by (a)
MAX material (TiVCrNbMo) 5 AlC 4 Slowly adding the powder into polytetrafluoroethylene reactor containing 40-50% hydrofluoric acid, and maintaining the whole process for 60 seconds to obtain high entropy MAX material (TiVCrNbMo) 5 AlC 4 The ratio of the powder to the hydrofluoric acid solution is 1:10-20g/mL; reacting in a water bath kettle at 45-50 ℃ and continuously stirring for 60-80 hours; centrifuging, dispersing and decanting the suspension after reaction for several times until the pH of the supernatant is equal to>6, collecting the MXenes by vacuum filtration on cellulose filter paper, and vacuum drying at 60 ℃ for 24 hours to obtain the high entropy MXene (TiVCrNbMo) 5 C 4 T x ；
3) High entropy MXene (TiVCrNbMo) 5 C 4 T x Synthesis of aerogel
Taking the high entropy MXene (TiVCrNbMo) obtained in the step 2) 5 C 4 T x Adding into intercalation agent with mass concentration of 10-15wt%, high entropy MXene (TiVCrNbMo) 5 C 4 T x The ratio of the intercalation agent to the intercalation agent is 1:10-40g/mL, and stirring is carried out to obtain a mixture; centrifuging the mixture for the first time to obtain precipitate, and measuring the pH value of the supernatant; dispersing the precipitate with deionized water, centrifuging for the second time to obtain precipitate again, and measuring the pH value of the supernatant again; repeating for several times, when the pH value of the supernatant is 6.0-8.0, adopting deionized water to disperse the precipitate again,under the bubbling action of inert gas, carrying out ultrasonic treatment for 1-2h, and carrying out third centrifugation to obtain a supernatant, namely a few-layer MXene solution; lyophilizing the low-layer MXene solution for 40-60 hr to obtain high entropy MXene (TiVCrNbMo) 5 C 4 T x Aerogel, namely the hardware transition high-entropy MXene material.
2. The method for preparing the metal transition high-entropy MXene material according to claim 1, wherein in the step 1), a temperature programming method is adopted in sintering, the temperature programming speed from room temperature to 1200 ℃ is 10 ℃/min, and the temperature programming speed from 1200 ℃ to sintering temperature is 2 ℃/min.
3. The method for preparing a metal transition high-entropy MXene material according to claim 1, wherein in the step 1), the high-entropy MAX material (TiVCrNbMo) 5 AlC 4 The particle size of the powder is 50-100 μm.
4. The method for preparing the metal transition high-entropy MXene material according to claim 1, wherein in the step 2), the stirring speed is 300-500r/min, the centrifugal rotating speed is 3000-4000r/min, and the centrifugal time is 3-8min.
5. The method for preparing the metal transition high-entropy MXene material according to claim 1, wherein in the step 3), the rotation speeds of the first centrifugation and the second centrifugation are 4000-6000r/min, and the centrifugation time is 4-6min; the rotation speed of the third centrifugation is 3000-4000r/min, and the centrifugation time is 50-70min.
6. The method for preparing the metal transition high-entropy MXene material according to claim 1, wherein in the step 3), the intercalating agent is any one or more of tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and dimethyl sulfoxide.
7. The method for preparing the metal transition high-entropy MXene material according to claim 1, wherein in the step 2)The obtained high entropy MXene (TiVCrNbMo) 5 C 4 T x The multi-layer accordion structure is presented, and under the atomic scale, the multi-layer accordion structure is formed by five transition metal layers and four carbon layers alternately; high entropy MXene (TiVCrNbMo) obtained in step 3) 5 C 4 T x The aerogel is formed by stacking few layers and/or single layers of MXene sheets, and has an irregularly-shaped three-dimensional macroporous structure, and the average thickness of the pore wall is 20 mu m.
8. A metal transition high-entropy MXene material prepared by the preparation method according to any one of claims 1-7, wherein the molecular formula of the metal transition high-entropy MXene material is M 5 X 4 T x Wherein M is Ti, V, cr, nb and Mo; x represents at least one of carbon, nitrogen or boron; tx represents a surface functional group, said Tx comprising one or more of O, F, cl, br, I or OH.
9. The hardware transition high-entropy MXene material of claim 8, characterized in that the mass percentage of Ti, V, cr, nb and Mo elements in the hardware transition high-entropy MXene material is 5% -30%.
10. The preparation method of the five-transition metal high-entropy MXene supercapacitor electrode material is characterized by comprising the following steps of:
high entropy MXene (TiVCrNbMo) based on the metal transition high entropy MXene material of claim 8 or 9 5 C 4 T x Mixing aerogel, polytetrafluoroethylene (PTFE) adhesive and acetylene black, wherein the acetylene black is added between MXene sheets to form a conductive network, the mass ratio is 80:10:10, and the conductive network is dispersed in 0.5-2mL of n-methyl-2-pyrrolidone (NMP) solvent; and homogenizing the obtained mixture by using ultrasonic waves, coating the homogenized mixture on a conductive carbon cloth substrate, and then drying the homogenized mixture in a vacuum freeze drying box for 20-30 hours to obtain the five-transition metal high-entropy MXene super capacitor electrode material.
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