CN111498850A - Two-dimensional transition metal carbonitride and preparation method and application thereof - Google Patents
Two-dimensional transition metal carbonitride and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 47
- 238000005530 etching Methods 0.000 claims abstract description 41
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- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims abstract description 14
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 11
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- 239000002253 acid Substances 0.000 claims description 7
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- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
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- 239000011737 fluorine Substances 0.000 claims description 2
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- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
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- 239000001301 oxygen Substances 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
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- 239000010703 silicon Substances 0.000 claims description 2
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- 239000006185 dispersion Substances 0.000 abstract description 18
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 10
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- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 26
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- 238000002484 cyclic voltammetry Methods 0.000 description 5
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
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- 125000004429 atom Chemical group 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
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- 229910020808 NaBF Inorganic materials 0.000 description 1
- 229910019637 Nb2AlC Inorganic materials 0.000 description 1
- 229910004470 Ta4AlC3 Inorganic materials 0.000 description 1
- 229910009594 Ti2AlN Inorganic materials 0.000 description 1
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- 229910009846 Ti4AlN3 Inorganic materials 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
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- 238000000840 electrochemical analysis Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910021558 transition metal bromide Inorganic materials 0.000 description 1
- 229910021381 transition metal chloride Inorganic materials 0.000 description 1
- 229910021573 transition metal iodide Inorganic materials 0.000 description 1
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- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/921—Titanium carbide
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/076—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with titanium or zirconium or hafnium
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Abstract
The invention discloses a two-dimensional transition metal carbonitride and a preparation method and application thereof, belonging to the technical field of two-dimensional materials. The MAX phase material is added into a fluoroboric acid aqueous solution for normal pressure etching, then is washed and added into a tetraalkylammonium hydroxide aqueous solution for post-treatment, and then is washed to obtain a two-dimensional transition metal carbonitride (MXene) material, and the material can be hand-shaken, vibrated, stirred, dispersed at a high speed or dispersed in water by ultrasonic dispersion to form a stable dispersion liquid. The method avoids the use of hydrofluoric acid, is safer and more environment-friendly compared with hydrofluoric acid etching, and the obtained MXene material has better application in the fields of supercapacitors, lithium ion batteries, electromagnetic shielding and electrocatalysis.
Description
Technical Field
The invention belongs to the technical field of two-dimensional materials, and particularly relates to a two-dimensional transition metal carbonitride and a preparation method and application thereof.
Background
Since the discovery of graphene in 2004, two-dimensional materials have become a research hotspot in academia due to the characteristics of large specific surface area, unique electronic structure, high aspect ratio and the like. The two-dimensional transition metal carbonitride (MXene) is a novel two-dimensional transition metal carbonitride material, has metal conductivity and surface hydrophilicity, is only a plurality of atoms thick, has many surface active sites and excellent conductivity, has excellent application prospects in various fields such as super capacitors, lithium ion batteries, lithium sulfur batteries, electromagnetic shielding, conductive printing, electrocatalysis and adsorption, and is considered to be one of the most potential two-dimensional materials behind graphene.
The currently reported preparation method of MXene mainly adopts a method of etching a MAX phase by HF acid or HF acid generated in situ to remove atoms of a layer A and prepare MXene material; for example, Naguib et al 2011 reported etching Ti with 50% HF3AlC2Preparation of Ti3C2TsPatent CN107001051A discloses a method for preparing MXene material by etching MAX phase with a mixture of alkali metal fluoride such as L iF, NaF, KF, etc. and inorganic strong acid such as HCl or sulfuric acid (MI L D method), however, these methods inevitably involve the use of hydrofluoric acid or the use of a mixture of alkali metal fluoride and strong acid, which upon mixing produces hydrofluoric acid, which is highly corrosive and both its use and post-treatment may produce factors in terms of safety in production and environmental protection, and furthermore, MXene prepared by these methods has a surface with a large amount of F functional groups, which negatively affects the electrochemical properties of the material, besides, patent CN110540236 discloses a method for preparing MXene having surface functional groups of Br or I by etching MAX phase with transition metal bromide or transition metal iodide melt salt, and patent CN109437177 discloses a method for preparing MXene having surface functional groups of Cl by etching MXene with surface functional groups of Cl with transition metal chloride melt salt, both methods requiring 400 degree etchingThe method is carried out at high temperature and under the protection atmosphere of inert gas, and has higher requirements on production equipment and environmental protection safety. Therefore, it is necessary to find a method which avoids the use of hydrofluoric acid and alkali metal fluoride, is simple and energy-saving to operate, and can still effectively etch and prepare MXene.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing MXene based on fluoroboric acid etching and a specific intercalation process. The technical scheme is as follows:
a method for preparing two-dimensional transition metal carbonitride comprises the steps of placing MAX phase materials in a fluoboric acid aqueous solution, and carrying out etching reaction under normal pressure to obtain etching products; then placing the etching product into aqueous solution of tetraalkylammonium hydroxide for post-treatment, and washing to obtain two-dimensional transition metal carbonitride (MXene);
the MAX phase material is Mn+1AXnWherein M is a transition metal, A is aluminum or silicon, X is carbon and/or nitrogen, and n is 1, 2, 3 or 4.
In one embodiment of the invention, the transition metal comprises at least one of Ti, V, Cr, Sc, Zr, Nb, Mo, Hf or Ta.
In one embodiment of the invention, the MAX phase material comprises Ti3AlC2、Ti3SiC2、Ti2AlC、Ti2AlN、Ti4AlN3、V2AlC、Cr2AlC、Sc2AlC、Zr2AlC、Nb2AlC、Nb4AlC3、Mo2AlC、Hf2AlC、Hf2AlN、Ta3AlC2、Ta4AlC3、TiyNb2-yAlC、VyNb2-yC、Mo2Ti2AlC3Wherein 0 is<y<2。
In one embodiment of the invention, the method further comprises: and washing and drying the prepared MXene material to obtain MXene powder.
In one embodiment of the present invention, the mass fraction of the aqueous fluoroboric acid solution is 5 to 70 wt%.
In one embodiment of the present invention, the reaction temperature of the etching reaction is 40 to 110 ℃.
In one embodiment of the present invention, the reaction time of the etching reaction is 4 to 72 hours.
In one embodiment of the invention, the etching reaction is carried out under stirring conditions at a rate of 50 to 1000 rpm.
In one embodiment of the present invention, the removal rate of the a element in the etching product is 90% or more.
In one embodiment of the present invention, the alkyl group of the tetraalkylammonium hydroxide described above can be a methyl group, an ethyl group, a propyl group, a butyl group, or a combination thereof.
In one embodiment of the present invention, the concentration of tetraalkylammonium hydroxide in the aqueous solution of tetraalkylammonium hydroxide is from 5 to 80 wt%. Further preferably 10 to 40%.
In one embodiment of the invention, the tetraalkylammonium hydroxide is used in an amount of 0.5 times or more the mass of the MAX phase material. Further preferably 0.5 times to 10 times.
A two-dimensional transition metal carbonitride prepared by the above method; the molecular formula of the two-dimensional transition metal carbonitride is Mn+1XnTsWherein M is a transition metal, X is carbon and/or nitrogen, TsIs a surface terminal group comprising hydroxyl, fluorine, tetrafluoroborate, oxygen, hydrogen, alkylammonium, or combinations thereof.
The two-dimensional transition metal carbonitride can be dispersed in water to form a stable dispersion liquid; the dispersing mode comprises hand shaking, stirring, high-speed dispersing or ultrasonic.
An MXene film is prepared through dispersing the prepared two-dimensional transition metal carbonitride in water to obtain stable dispersion, and removing water from the dispersion.
The MXene film product is specifically obtained by dispersing two-dimensional transition metal carbonitride in water to form stable dispersion liquid and then carrying out suction filtration.
The two-dimensional transition metal carbonitride (M) according to the present inventionn+1XnTs) The preparation method has good application in the fields of preparing super capacitors, lithium ion batteries, electromagnetic shielding and electrocatalysis.
The invention has the beneficial effects that:
the method effectively prepares the two-dimensional Ti which has a single-layer or few-layer structure and can be stably dispersed in water3C2TsMaterial, two-dimensional Ti3C2TsThe material is easy to form a film, and the removal rate of the element A in the etching process is 90% or more (the removal rate is the mass content of Al after etching is higher than that of Al before etching); the dispersion is dried to obtain two-dimensional Ti3C2TsMaterial powder; the obtained two-dimensional Ti3C2TsThe material has higher specific capacitance under each discharge rate and has better rate performance; wherein the specific capacitance of 1A/g, 2A/g, 5A/g and 10A/g respectively reaches 343.3F/g, 339.2F/g, 338.5F/g and 336F/g, and the preparation method can be applied to the fields of preparation of super capacitors, lithium ion batteries, electromagnetic shielding and electrocatalysis and has wide prospect.
Drawings
FIG. 1 is the XRD pattern of the intermediate etching product obtained in example 1 and the XRD pattern of MXene film obtained after TMAOH treatment is continued.
FIG. 2 is a scanning electron microscope image of the cross section of MXene thin film obtained in example 1.
FIG. 3 shows MXene films prepared in example 1 at 5-100 mV. s-1A CV curve diagram at the sweep speed and a CP curve diagram of 1A/g-10A/g.
FIG. 4 is the XRD pattern of the intermediate etching product obtained in example 2 and the XRD pattern of MXene thin film obtained after TMAOH treatment is continued.
Fig. 5 is a scanning electron microscope image of the MXene film obtained in example 2.
FIG. 6 is a scanning electron micrograph of the material prepared in comparative example 1.
FIG. 7 is a scanning electron micrograph of the material prepared in comparative example 2.
FIG. 8 is a scanning electron micrograph of the material prepared in comparative example 3.
FIG. 9 shows the results of comparative example 4 when the film was formed at 5-100 mV. s-1A CV curve diagram at the sweep speed and a CP curve diagram of 1A/g-10A/g.
Detailed Description
The technical solution of the present invention will be described in detail by specific examples.
Example 1
1g of MAX phase material Ti3AlC240ml of HBF with the mass fraction of 40wt percent is added4Stirring in the aqueous solution at 80 ℃ for 24h at the rotating speed of 400rpm, and then repeatedly centrifuging and washing with water until the pH value of the solution is more than 5 to obtain an etching product;
the etching product was then added to 10m L aqueous tetramethylammonium hydroxide (TMAOH) (25 wt%) solution, stirred at 25 deg.C at 500rpm for 24h, then washed repeatedly with water by centrifugation to a solution pH of less than 9, and after addition of 100g water, by hand shaking, Ti stably dispersed in water was obtained3C2Ts(ii) a Vacuum filtering the black uniform liquid on the upper layer, naturally drying, and separating from the filter membrane to obtain Ti3C2TsA film.
Ti in the course of reaction3AlC2And HBF4Intermediate etching product (80-HBF) obtained by reaction4) XRD spectrum of (1) and Ti prepared by TMAOH post-treatment3C2TsThe XRD spectrum of the material is shown in figure 1. As can be seen from the XRD pattern after TMAOH treatment, Ti3AlC2The disappearance of the characteristic peak corresponds to two-dimensional Ti3C2TsThe characteristics of the material. Ti3C2TsA Scanning Electron Micrograph (SEM) of the film is shown in FIG. 2. At the same time, Ti3C2TsCan be stably dispersed in water without precipitation.
Bound Ti3C2TsThe stability of the dispersion, XRD pattern and scanning electron microscope picture can confirm that the process successfully prepares single-layer or few-layer two-dimensional Ti which can be stably dispersed in water3C2TsA material.
Ti prepared in example 13C2TsThe film is used as a working electrode, the active carbon film through capacitance is used as a counter electrode, Hg/Hg2SO4The electrode was used as a reference electrode, Celgard3501 was used as a separator, and the electrolyte was 3 mol/L H2SO4The battery is assembled into a three-electrode Swagelok battery to carry out Cyclic Voltammetry (CV) and constant current charge and discharge (CP) tests, the CV curve and the CP curve are shown in figure 3, specific capacitances at 1A/g, 2A/g, 5A/g and 10A/g can be calculated from the CP curve to be 343.3F/g, 339.2F/g, 338.5F/g and 336F/g respectively, the battery has higher specific capacitance and rate capability, and the MXene suction filtration film prepared by the conventional MI L D method reported in the prior art (in the same way as the embodiment, the specific capacitance and the rate capability reach or exceed 1mg/cm or more2In the case of the loading amount) is less than or equal to 300F/g when the battery is charged and discharged at the state of 1A/g-10A/g.
Example 2
Same as example 1, but HBF4The temperature of the aqueous solution treatment is changed to 50 ℃, other steps are the same, and the two-dimensional Ti with stable dispersion can be obtained3C2TsThe dispersion is freeze-dried to obtain Ti3C2TsPowder; the dispersion is filtered to obtain Ti3C2TsA film. HBF in this example4After treatment with aqueous solution the material (50-HBF)4) XRD pattern of (A) and freeze-dried Ti3C2TsThe XRD spectrum of the powder is shown in FIG. 4. Ti3C2TsA scanning electron micrograph of the film is shown in FIG. 5. From the obtained XRD spectrum, SEM image and the fact that a black dispersion liquid stably dispersed in water can be obtained, it can be confirmed that two-dimensional Ti is obtained by the preparation3C2TsA material.
Comparative example 1
1g of a MAX material Ti3AlC240ml of HBF with the mass fraction of 40wt percent is added4Stirring the solution in an aqueous solution at 80 ℃ for 24 hours at the rotating speed of 400rpm, and then repeatedly centrifuging and washing the solution by using water until the pH value of the solution is more than 5 to obtain an etching product;
subsequently, it was added to a 2% by mass L iCl aqueous solution of 125m L, stirred at 500rpm for 24 hours, and then washed with water repeatedly by centrifugation until the solution had a high pHAt 5; after 100g of water is added, stably dispersed two-dimensional Ti can not be obtained by hand shaking, high-speed dispersion or ultrasound3C2TsThe dispersion liquid and the black liquid become semitransparent after standing for 24 hours, obvious precipitation occurs, and a product formed by suction filtration is powdery after being dried, so that a film is difficult to form.
The product morphology was examined by scanning electron microscopy, and as shown in fig. 6, the material after L iCl aqueous solution treatment exhibited accordion-like particles, and no effective monolayer exfoliation was achieved.
In connection with example 1, the applicant guesses: HBF4The etching is combined with the post-treatment of the aqueous solution of the alkylammonium hydroxide to obtain the two-dimensional Ti which can be dispersed in the water3C2TsMaterial, preparation of Ti3C2TsThe commonly used method of lithium ion intercalation does not allow HBF4Ti after etching3AlC2Exfoliation to form two-dimensional Ti3C2TsA material.
Furthermore, the applicant found that: ti3AlC2Etching by using L iF and HCl mixed solution, washing, and shaking to obtain flaky two-dimensional Ti3C2TsThe material is directly etched by HF to obtain accordion-shaped particles, which cannot be dispersed in water to form flaky two-dimensional MXene no matter by hand shaking, high-speed dispersion or ultrasound, and can be stripped into flaky two-dimensional Ti by intercalation of L iCl aqueous solution3C2TsHowever, if this post-treatment with a tetraalkylammonium hydroxide aqueous solution is replaced with a conventional L iCl solution treatment as described in the literature, it is not possible to obtain flaky two-dimensional Ti which is easily dispersed in water3C2TsA material. From this, it was also confirmed that: two-dimensional Ti preparation by combination of fluoboric acid etching and tetraalkylammonium hydroxide aqueous solution treatment3C2TsA material; in addition, from XRD of the etching product of the fluoroboric acid of example 2 (FIG. 4), the peak of about 39 degrees is not completely eliminated, and aluminum is not completely etched, but the peak is obtained in material XRD after being treated by TMAOH aqueous solutionDisappearance, indicating that the role of TMAOH here should be a combination of etching and intercalation, allowing the preparation of two-dimensional Ti via fluoroboric acid etching3C2TsThe material was successful.
Comparative example 2
1g of a MAX material Ti3AlC240ml of HBF with the mass fraction of 40wt percent is added4Stirring the solution in an aqueous solution at 80 ℃ for 24 hours at the rotating speed of 400rpm, and then repeatedly centrifuging and washing the solution by using water until the pH value of the solution is more than 5 to obtain an etching product;
then adding 100m of aqueous solution of L mass percent 2.5 percent TMAH into the solution, stirring the solution for 24h at the rotating speed of 500rpm, then repeatedly centrifuging and washing the solution until the pH value of the solution is less than 9, and adding 100g of water, and then obtaining stably dispersed two-dimensional Ti by hand shaking, high-speed dispersion or ultrasound3C2TsThe dispersion liquid and the black liquid become semitransparent after standing for 24 hours, obvious precipitation occurs, and products formed by suction filtration are powdery after being dried and are difficult to form a film.
The product morphology was examined by scanning electron microscopy, as shown in fig. 7, the material treated with 2.5% TMAOH aqueous solution showed accordion-like particles, and no effective single-layer exfoliation was achieved.
In connection with example 1, the applicant guesses: HBF4The etching is combined with the post-treatment of the aqueous solution of the alkylammonium hydroxide with higher concentration to obtain the two-dimensional Ti which can be dispersed in the water3C2TsMaterial, the intercalation method of lower concentration TMAOH solution used for preparing MXene can not lead HBF4Ti after etching3AlC2Exfoliation to form two-dimensional Ti3C2TsA material.
Comparative example 3
0.75g of NaBF was added4Dissolved by adding 15 ml of 37% hydrochloric acid, followed by adding 0.25g of Ti as a MAX material3AlC2Adding into the solution, stirring at 80 deg.C and 400rpm for 24h, repeatedly centrifuging with water to obtain solution pH of above 5, adding into 10 times of tetramethylammonium hydroxide (TMAOH) water solution (25 wt%), stirring at 25 deg.C and 500rpm for 24h,then repeatedly centrifuging and washing with water until the pH of the solution is less than 9, adding 100g of water, and then dispersing by hand shaking, high-speed dispersion or ultrasound, and finding that stably dispersed two-dimensional Ti can not be obtained3C2TsAnd (3) standing the dispersion liquid and the black liquid for 24 hours to form a semitransparent liquid, generating obvious precipitation, and performing suction filtration to form a product which is dried to form powder and difficult to form a film.
The scanning electron micrograph of the dried powder product is shown in FIG. 8, which shows that no accordion-like particles are formed and no exfoliated two-dimensional Ti stably dispersed in water is formed by etching and intercalation3C2Ts。
Comparative example 4
By the method disclosed in patent CN107001051A, 0.8g of L iF is added into 10M of L9M HCl and stirred uniformly, and then 0.5g of Ti is added3AlC2Reacting at room temperature for 24h, washing the product with deionized water until the pH is more than 5, and then adding 100g of deionized water; by hand shaking, Ti stably dispersed in water was obtained3C2Ts(ii) a Vacuum filtering the black uniform liquid on the upper layer, naturally drying, and separating from the filter membrane to obtain Ti3C2TsA film.
Adding the Ti3C2TsThe film is used as a working electrode, the active carbon film through capacitance is used as a counter electrode, Hg/Hg2SO4The electrode was used as a reference electrode, Celgard3501 was used as a separator, and the electrolyte was 3 mol/L H2SO4. CV and CP tests were performed for the assembled three-electrode Swagelok cells, and the test results are shown in FIG. 9, from which the CP curves were calculated to have specific capacitances of 292F/g, 261.8F/g, 245.5F/g, and 198F/g at 1A/g, 2A/g, 5A/g, and 10A/g, respectively.
In connection with example 1, the electrochemical tests of both examples were carried out in the same manner, using an electrode mass of 1mg/cm2On the other hand, MXene prepared by the tetraalkylammonium hydroxide treatment after the fluoroboric acid etching in example 1 has higher specific capacitance at each discharge rate and also has better rate capability.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A method for preparing two-dimensional transition metal carbonitride is characterized in that MAX phase material is placed in fluoboric acid water solution, and etching reaction is carried out under normal pressure to obtain etching product; then placing the etching product into aqueous solution of tetraalkylammonium hydroxide for post-treatment, and washing to obtain two-dimensional transition metal carbonitride;
the MAX phase material is Mn+1AXnWherein M is a transition metal, A is aluminum or silicon, X is carbon and/or nitrogen, and n is 1, 2, 3 or 4.
2. The method of claim 1, wherein the transition metal comprises at least one of Ti, V, Cr, Sc, Zr, Nb, Mo, Hf, or Ta.
3. The method according to claim 1, wherein the mass fraction of the aqueous fluoroboric acid solution is 5 to 70 wt%.
4. The method according to claim 1, wherein the reaction temperature of the etching reaction is 40-110 ℃.
5. The method of claim 1, wherein the etching reaction has a reaction time of 4 to 72 hours.
6. The method according to claim 1, wherein the aqueous solution of tetraalkylammonium hydroxide has a tetraalkylammonium hydroxide concentration of from 5 to 80 wt% based on the mass of the aqueous solution.
7. The method of claim 1, wherein the tetraalkylammonium hydroxide is used in an amount of 0.5 times or more the mass of the MAX phase material.
8. The process of claim 1, wherein the alkyl group of the tetraalkylammonium hydroxide is methyl, ethyl, propyl, butyl, or a combination thereof.
9. A two-dimensional transition metal carbonitride of the formula M prepared by the process of any one of claims 1 to 8 having the formulan+1XnTs(ii) a Wherein M is a transition metal, X is carbon and/or nitrogen, TsIs a surface terminal group comprising hydroxyl, fluorine, tetrafluoroborate, oxygen, hydrogen, alkylammonium, or combinations thereof.
10. Use of the two-dimensional transition metal carbonitride of claim 9 in the preparation of supercapacitors, lithium ion batteries, electromagnetic shielding and electrocatalysis.
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