CN109192940B - Titanium dioxide/graphene multi-element modified Mxene composite material and preparation method thereof - Google Patents
Titanium dioxide/graphene multi-element modified Mxene composite material and preparation method thereof Download PDFInfo
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Abstract
A titanium dioxide/graphene multi-element modified Mxene composite material is prepared by the following steps: (1) adding the Mxene precursor into an HF acid solution, heating, stirring and etching; (2) centrifuging, washing, ultrasonically treating and drying the etched material to obtain an Mxene material; (3) adding the Mxene material into water, performing ultrasonic dispersion, adding a surface charge modifier, and stirring; (4) respectively adding nanoscale titanium dioxide and graphene oxide into water, and performing ultrasonic dispersion to respectively obtain titanium dioxide dispersion liquid and graphene oxide dispersion liquid; (5) sequentially adding titanium dioxide and graphene oxide dispersion liquid into the Mxene dispersion liquid, stirring, carrying out suction filtration, and drying; (6) the heat treatment is carried out in an inert atmosphere. Part of the nano-scale titanium dioxide is inserted between the Mxene layers to improve the longitudinal conductivity of the Mxene, and part of the nano-scale titanium dioxide is adsorbed on the surface of the Mxene material to improve the surface conductivity of the Mxene material; the graphene is coated on the Mxene surface to improve the conductivity of the Mxene surface; the assembled lithium ion battery has high specific capacity, high rate capability and good cycling stability.
Description
Technical Field
The invention relates to a composite material and a preparation method thereof, in particular to a titanium dioxide/graphene multi-element modified Mxene composite material as a lithium ion battery cathode material and a preparation method thereof.
Background
Lithium ion batteries have become ideal energy storage devices due to their advantages of high energy density, high power density, environmental friendliness, long service life, superior safety performance, and the like.
Since the advent of graphene two-dimensional materials, two-dimensional materials have become popular in scientific research. The two-dimensional material has a special layered structure in mechanics, optics, electrochemistry. The information shows excellent performance. At present, two-dimensional materials have been intensively studied in the fields of catalysts, energy storage devices, sensors, biomaterials, and the like.
Graphene is a typical representative of two-dimensional materials. In addition, the discovery of a new two-dimensional material, Mxene, has added a new member to the two-dimensional family of materials in recent years. Among a plurality of two-dimensional materials, Mxene is an ideal cathode material of a super capacitor and a lithium ion battery because of cheap raw materials, excellent electronic conductivity, stable structure, good cycling stability and no precious metal. However, the intrinsic Mxene material has poor surface and longitudinal conductivity, which limits the application of the intrinsic Mxene material in the field of energy storage to a certain extent.
CN107633954A discloses a graphene/Mxene composite electrode material and application thereof, and although the conductivity of the Mxene material is effectively improved by the obtained graphene/Mxene composite material, the longitudinal conductivity of the Mxene material is not improved by the obtained graphene/Mxene composite material through modification.
CN107170587A discloses a sulfur-doped Mxene material, a preparation method and an application thereof, and although the Mxene material is doped and modified by sulfur atoms, the conductivity and the electrochemical performance of the Mxene material are effectively improved, but the specific discharge capacity of the Mxene material is relatively low.
CN104496461 discloses a Ti-based alloy2The preparation method of the CMxene battery electrode material is characterized in that after intercalation stripping, the Mxene material layer spacing is enlarged. However, the Mxene material layer spacing obtained by the preparation method is still relatively small, and other materials cannot be embedded in the Mxene material layer spacing for improving the longitudinal conductivity of the Mxene material.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provide a titanium dioxide/graphene multi-element modified Mxene composite material which has high specific capacity, good rate capability and good cycling stability and is suitable for industrial production and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: a titanium dioxide/graphene multi-element modified Mxene composite material is prepared by the following steps:
(1) adding the Mxene precursor into an HF acid solution, heating, stirring, etching and removing an Al layer;
(2) centrifuging, washing, ultrasonically dispersing and drying the Mxene precursor etched in the step (1) to obtain an Mxene material;
(3) adding the Mxene material obtained in the step (2) into water, performing ultrasonic dispersion, adding a surface charge modifier, and stirring to obtain an Mxene dispersion liquid with positive charges on the surface;
(4) respectively adding nanoscale titanium dioxide and graphene oxide into water, and performing ultrasonic dispersion to respectively obtain a titanium dioxide dispersion solution and a graphene oxide dispersion solution;
(5) sequentially adding the titanium dioxide dispersion liquid and the graphene oxide dispersion liquid into the Mxene dispersion liquid with positive charges on the surface obtained in the step (3), stirring, carrying out suction filtration, and drying to obtain black powder;
(6) and (5) placing the black powder obtained in the step (5) in an inert atmosphere, and carrying out heat treatment to obtain the titanium dioxide/graphene multi-element modified Mxene composite material.
Preferably, in the step (1), the mass fraction of the HF acid solution is 25-65%; the mass ratio of the Mxene precursor to the HF acid is 1: 25-65. The concentration of the HF acid solution is too low or too high, and Mxene with a complete layered structure is difficult to obtain.
Preferably, in the step (1), the etching time is 4-10 h, and more preferably 6-10 h. Too long or too short of the etch time can result in over-etching or under-etching of the Mxene precursor.
Preferably, in the step (1), the heating and stirring speed is 200-600 r/min, and more preferably 300-400 r/min; the heating and stirring temperature is 40-100 ℃, and more preferably 80-90 ℃; the heating and stirring time is 4-10 hours, and more preferably 6-10 hours. The etching temperature is too low or too high, which can result in insufficient etching of the Mxene precursor or damage to the structure.
Preferably, in the step (2), the centrifugal rotating speed is 3000-12000 r/min; the washing is washing with deionized water and ethanol, preferably respectively and alternately washing, and the washing times are more than or equal to 10 times; the ultrasonic dispersion power is 200-400W, and the ultrasonic time is 0.5-2 h; the drying temperature is 60-100 ℃, and the drying time is 6-12 h.
Preferably, in the step (3), the mass of the water is 400-800 times of the mass of the Mxene; the power of the ultrasonic dispersion is 200-400W, and the time is 0.5-2 h; the mass ratio of the surface charge modifier to the Mxene is 5-15 times; the stirring speed is 200-400 r/min, and the time is 1-4 h.
Preferably, in the step (3), the charge surface modifier is one or more of ammonia water, ammonium bicarbonate or cetyl trimethyl ammonium bromide. The surface charge modifier can ionize ammonium cations in water and adsorb the ammonium cations on the surface of the Mxene material with negative charges on the surface to obtain the Mxene with positive charges on the surface, and is more favorable for adsorbing titanium dioxide and graphene oxide. If the amount of the surface charge modifier used is too small, the negative charge Mxene cannot be sufficiently charge-modified, and if the amount of the surface charge modifier used is too large, resources of the surface charge modifier are wasted.
Preferably, in the step (4), the mass ratio of the nano-scale titanium dioxide to the graphene oxide to the Mxene is 5-10: 100. The mass of the water is 500-1500 times of that of the titanium dioxide and the graphene oxide; the ultrasonic dispersion frequency is 200-400W, and the time is 0.5-2 h.
Preferably, in the step (5), the titanium dioxide dispersion liquid and the graphene oxide dispersion liquid are sequentially added into the titanium dioxide dispersion liquid and the graphene oxide dispersion liquid; the stirring speed is 200-400 r/min, and the time is 6-12 h; the drying temperature is 60-100 ℃, and the drying time is 6-12 h.
Preferably, in the step (6), the heat treatment temperature is 300-600 ℃, and the time is 6-12 h; the inert atmosphere is one or more of argon, argon/hydrogen mixed gas or nitrogen.
The invention has the following beneficial effects:
(1) according to the titanium dioxide/graphene multi-element modified Mxene composite material, titanium dioxide is embedded in/adsorbed on the Mxene layer spacing and the surface, and graphene is coated on the Mxene surface, so that the longitudinal and surface conductivity of the Mxene material is effectively improved, and the electrochemical performance of the Mxene material is improved;
(2) the lithium ion battery assembled by the titanium dioxide/graphene multi-element modified Mxene lithium ion battery cathode composite material obtained by the invention has higher specific capacity, excellent cycle performance and capacity reversibility.
Drawings
Fig. 1 is an XRD chart of the titanium dioxide/graphene multi-element modified Mxene of the lithium ion battery negative electrode composite material obtained in example 1 of the present invention;
FIG. 2 is an SEM image of a titanium dioxide/graphene multi-modified Mxene serving as a negative electrode composite material of a lithium ion battery obtained in example 1 of the invention;
fig. 3 is a discharge rate performance curve diagram of a lithium ion battery assembled by the lithium ion battery negative electrode composite material titanium dioxide/graphene multi-element modified Mxene obtained in example 1 of the present invention;
FIG. 4 is a discharge cycle performance diagram of a lithium ion battery assembled by the lithium ion battery negative electrode composite material titanium dioxide/graphene multi-element modified Mxene obtained in example 1 of the invention;
fig. 5 is an impedance spectrum of a lithium ion battery assembled by the lithium ion battery negative electrode composite material titanium dioxide/graphene multi-element modified Mxene obtained in example 1 of the present invention.
Detailed Description
The invention is further illustrated by the following examples and figures.
Graphene oxide used in the embodiments of the present invention is purchased in the age of china nanometer; the chemical reagents used in the examples of the present invention, unless otherwise specified, are commercially available in a conventional manner.
Example 1
(1) Adding 30 g of HF acid (the mass fraction is 40%) into a polytetrafluoroethylene tank, adding 1.0 g of Mxene precursor into the polytetrafluoroethylene tank, stirring the mixture at the constant temperature of 90 ℃ for 6 hours at 400 r/min, and etching the Mxene precursor;
(2) adding the Mxene obtained in the step (1) into water, centrifuging at 10000 r/min, respectively and alternately washing the precipitate for 10 times by using deionized water and absolute ethyl alcohol, carrying out ultrasonic treatment for 1 h at 400W, and drying for 10h at 80 ℃ to obtain an Mxene material;
(3) adding 0.1 g of the Mxene material obtained in the step (2) into 60 mL of deionized water, performing ultrasonic dispersion for 1 h at 400W, adding 0.8 g of ammonium bicarbonate, and stirring for 2 h at 400 r/min to obtain a surface charge modified Mxene material dispersion liquid;
(4) respectively adding 0.005 g of nano-scale titanium dioxide and graphene oxide into 5 mL of deionized water, and ultrasonically dispersing for 2 h under 400W to respectively obtain a titanium dioxide dispersion liquid and a graphene oxide dispersion liquid;
(5) sequentially adding the titanium dioxide dispersion liquid and the graphene oxide dispersion liquid obtained in the step (4) into the Mxene dispersion liquid with the modified surface charge obtained in the step (3), stirring for 8 hours at 400 r/min, performing suction filtration, washing, and drying for 10 hours at 80 ℃ to obtain black powder;
(6) and (3) carrying out heat treatment on the black powder obtained in the step (5) in an inert atmosphere of argon/hydrogen mixed gas (the volume fraction of hydrogen is 5%) at 400 ℃ for 10h to obtain the titanium dioxide/graphene multi-element modified Mxene lithium ion battery cathode composite material.
As shown in FIG. 1, XRD diffraction peaks of the titanium dioxide/graphene multi-element modified Mxene of the lithium ion battery negative electrode composite material obtained in the embodiment of the invention are consistent with those of standard cards (PDF #52-0875 and PDF # 71-1166), which indicates that the obtained titanium dioxide and graphene multi-element modified Mxene are pure phases.
As shown in fig. 2, in an SEM image of the lithium ion battery negative electrode composite material titanium dioxide/graphene multi-element modified Mxene obtained in the embodiment of the present invention, titanium dioxide is uniformly adsorbed/embedded on the surface and layer of Mxene, and graphene is coated on the surface.
Assembling the battery: respectively weighing 0.08 g of the titanium dioxide/graphene multi-element modified Mxene composite material obtained in the embodiment as a negative electrode material, adding 0.01 g of acetylene black (SP) as a conductive agent and 0.01 g of PVDF (HSV-900) as a binder, fully grinding, adding 1.5 mL of NMP for dispersing and mixing, uniformly mixing, pulling slurry on a copper foil with the thickness of 20 mu m to prepare a negative electrode piece, taking metal lithium as a positive electrode, taking polypropylene as a diaphragm and 1mol/L LiPF in an anaerobic glove box6A 2025 button cell is assembled by using a mixed solution of ethylene carbonate, dimethyl carbonate and dimethyl carbonate (volume ratio =1:1: 1) as an electrolyte; and testing the constant current charge and discharge performance of the assembled lithium ion battery under the voltage range of 0.01-3V.
As shown in fig. 3, at a rate of 0.1C (1C =300 mA h/g), the first discharge specific capacity of the assembled lithium ion battery reaches 749.4 mAh/g, and at rates of 0.2C, 0.5C, 1C, 2C, and 5C, the first discharge specific capacities thereof are 318.8 mAh/g, 270.0 mAh/g, 239.7 mAh/g, 212.6 mAh/g, and 150.9 mAh/g, respectively; under the high multiplying power of 10C and 15C, the first discharge specific capacity of the composite material respectively reaches 117.5 mAh/g and 101.3 mAh/g, and then under the multiplying power of 0.1C, the discharge specific capacity of the composite material still can reach 286 mAh/g, which shows that the prepared titanium dioxide/graphene multi-modified Mxene composite material has excellent capacity reversibility.
As shown in fig. 4, at 0.1C rate, the first specific discharge capacity of the assembled lithium ion battery can reach 739.7 mAh/g, and after 100 cycles, the specific discharge capacity is still 300 mAh/g. The lithium ion battery assembled by the titanium dioxide/graphene multi-element modified Mxene serving as the lithium ion battery cathode composite material obtained in the embodiment of the invention has excellent cycle performance.
As shown in fig. 5, the assembled lithium ion battery has a smaller internal resistance, which indicates that the conductivity of the titanium dioxide/graphene multi-element modified Mxene of the lithium ion battery negative electrode composite material obtained in the embodiment of the present invention is greatly improved.
From the above, the lithium ion battery assembled by the titanium dioxide/graphene multi-modified Mxene composite material obtained in the embodiment of the invention has higher specific discharge capacity and good rate performance and cycle performance, and the introduction of the titanium dioxide and the graphene effectively improves the conductivity of the Mxene material.
Example 2
(1) Adding 30 g of HF acid (the mass fraction is 25%) into a polytetrafluoroethylene tank, adding 1.0 g of Mxene precursor into the polytetrafluoroethylene tank, stirring the mixture for 10 hours at the constant temperature of 85 ℃ at 300 r/min, and etching the Mxene precursor;
(2) adding the Mxene obtained in the step (1) into water, centrifuging at 5000 r/min, respectively and alternately washing the precipitate for 10 times by using deionized water and absolute ethyl alcohol, carrying out ultrasonic treatment for 1 h at 400W, and drying for 10h at 80 ℃ to obtain an Mxene material;
(3) adding 0.1 g of the Mxene material obtained in the step (2) into 60 mL of deionized water, performing ultrasonic dispersion for 1 h at 400W, adding 1.5 g of ammonia water, and stirring for 1 h at 400 rpm to obtain a surface charge modified Mxene material dispersion liquid;
(4) respectively adding 0.01 g of nano-scale titanium dioxide and graphene oxide into 5 mL of deionized water, and ultrasonically dispersing for 2 h under 400W to respectively obtain a titanium dioxide dispersion liquid and a graphene oxide dispersion liquid;
(5) adding the titanium dioxide dispersion liquid and the graphene oxide dispersion liquid obtained in the step (4) into the surface charge modified Mxene dispersion liquid obtained in the step (3), stirring for 8 hours at 400 r/min, performing suction filtration, washing, and drying for 12 hours at 80 ℃ to obtain black powder;
(6) and (4) placing the black powder obtained in the step (5) in argon, and performing heat treatment for 6 hours at 600 ℃ to obtain the titanium dioxide/graphene multi-element modified Mxene lithium ion battery cathode composite material.
Through detection, the position of the characteristic peak of the titanium dioxide/graphene multi-element modified Mxene of the lithium ion battery cathode composite material obtained in the embodiment of the invention on XRD is consistent with that of a standard card, and the obtained titanium dioxide/graphene multi-element modified Mxene is a pure phase.
Through detection, titanium dioxide and graphene multi-element modified Mxene of the lithium ion battery cathode composite material obtained in the embodiment of the invention are uniformly adsorbed/embedded on the surface and in the layer of the Mxene, and graphene is coated on the surface of the Mxene.
Assembling the battery: the same as example 1; and testing the constant current charge and discharge performance of the assembled lithium ion battery under the voltage range of 0.01-3V.
Through detection, under the multiplying power of 0.1C (1C =300 mA h/g), the first discharge specific capacity of the assembled lithium ion battery reaches 682.6 mAh/g, and under the multiplying powers of 0.2C, 0.5C, 1C, 2C and 5C, the first discharge specific capacities are 285.5 mAh/g, 228.0 mAh/g, 195.9 mAh/g, 178.2 mAh/g and 141.6 mAh/g respectively; under the high multiplying power of 10C and 15C, the first discharge specific capacity of the composite material respectively reaches 106.5 mAh/g and 89.1 mAh/g, and then under the multiplying power of 0.1C, the discharge specific capacity of the composite material still can reach 278.9 mAh/g, which shows that the prepared titanium dioxide/graphene multi-modified Mxene composite material has excellent capacity reversibility.
Through detection, under the multiplying power of 0.1C, the first discharge specific capacity of the assembled lithium ion battery can reach 682.6 mAh/g, and after 100 cycles, the discharge specific capacity is still 281.8 mAh/g. The lithium ion battery assembled by the titanium dioxide/graphene multi-element modified Mxene serving as the lithium ion battery cathode composite material obtained in the embodiment of the invention has excellent cycle performance.
Through detection, the internal resistance of the assembled lithium ion battery is 31.4 omega, which indicates that the conductivity of the titanium dioxide/graphene multi-element modified Mxene of the lithium ion battery negative electrode composite material obtained by the embodiment of the invention is greatly improved.
From the above, the lithium ion battery assembled by the titanium dioxide/graphene multi-modified Mxene composite material obtained in the embodiment of the invention has higher specific discharge capacity and good rate performance and cycle performance, and the introduction of the titanium dioxide and the graphene effectively improves the conductivity of the Mxene material.
Comparative example 1
(1) Adding 30 g of HF acid (the mass fraction is 40%) into a polytetrafluoroethylene tank, adding 1.0 g of Mxene precursor into the polytetrafluoroethylene tank, stirring the mixture for 6 hours at the constant temperature of 90 ℃ at 300 revolutions per minute, and etching the Mxene precursor;
(2) adding the Mxene obtained in the step (1) into water, centrifuging at 10000 r/min, respectively and alternately washing the precipitate for 10 times by using deionized water and absolute ethyl alcohol, carrying out ultrasonic treatment for 1 h at 400W, and drying for 10h at 80 ℃ to obtain an Mxene material;
(3) adding 0.1 g of the Mxene material obtained in the step (2) into 80 mL of deionized water, performing ultrasonic dispersion for 2 h at 400W, adding 0.8 g of ammonium bicarbonate, and stirring for 2 h at 400 r/min to obtain a surface charge modified Mxene material dispersion liquid;
(4) adding 0.005 g of graphene oxide into 5 mL of deionized water, and performing ultrasonic dispersion for 2 hours at 400W to obtain a graphene oxide dispersion liquid;
(5) adding the graphene oxide dispersion liquid obtained in the step (4) into the surface charge modified Mxene dispersion liquid obtained in the step (3), stirring for 8 hours at 400 r/min, performing suction filtration, washing, and drying for 8 hours at 80 ℃ to obtain black powder;
(6) and (4) placing the black powder obtained in the step (5) in nitrogen, and performing heat treatment for 10 hours at 400 ℃ to obtain the graphene modified Mxene lithium ion battery cathode composite material.
Through detection, the position of the characteristic peak of the graphene modified Mxene of the lithium ion battery cathode composite material obtained in the embodiment of the invention on XRD is consistent with that of a standard card, and the obtained graphene modified Mxene is a pure phase.
Through detection, the graphene modified Mxene of the lithium ion battery negative electrode composite material obtained in the embodiment of the invention is coated on the surface of the graphene.
Assembling the battery: the same as example 1; and testing the constant current charge and discharge performance of the assembled lithium ion battery under the voltage range of 0.01-3V.
Through detection, under the multiplying power of 0.1C (1C =300 mA h/g), the first discharge specific capacity of the assembled lithium ion battery reaches 495.1mAh/g, and under the multiplying powers of 0.2C, 0.5C, 1C, 2C and 5C, the first discharge specific capacities are 220.3 mAh/g, 187.5 mAh/g, 162.0 mAh/g, 137.8 mAh/g and 107.9 mAh/g respectively; under the high multiplying power of 10C and 15C, the first discharge specific capacity respectively reaches 84.2 mAh/g and 81.5 mAh/g, and then under the multiplying power of 0.1C, the discharge specific capacity still can reach 216.5 mAh/g, which shows that the prepared graphene modified Mxene composite material has excellent capacity reversibility.
Through detection, under the multiplying power of 0.1C, the first discharge specific capacity of the assembled lithium ion battery can reach 495.1mAh/g, and after 100 cycles, the discharge specific capacity is still 201.3 mAh/g.
Through detection, the internal resistance of the assembled lithium ion battery is 68.9 omega, the internal resistance is high, and the conductivity is slightly poor.
From the above, the conductivity of the graphene modified Mxene of the lithium ion battery negative electrode composite material obtained by the comparative example cannot be sufficiently improved, so that the prepared composite material has low discharge specific capacity at high rate.
Comparative example 2
(1) Adding 30 g of HF acid (the mass fraction is 40%) into a polytetrafluoroethylene tank, adding 1.0 g of Mxene precursor into the polytetrafluoroethylene tank, stirring the mixture for 6 hours at the constant temperature of 90 ℃ at 300 revolutions per minute, and etching the Mxene precursor;
(2) adding the Mxene obtained in the step (1) into water, centrifuging at 10000 r/min, respectively and alternately washing the precipitate for 10 times by using deionized water and absolute ethyl alcohol, carrying out ultrasonic treatment for 1 h at 400W, and drying for 10h at 80 ℃ to obtain the Mxene material.
Through detection, the position of a characteristic peak of the lithium ion battery cathode material Mxene obtained in the embodiment of the invention on XRD is consistent with that of a standard card, which indicates that the obtained Mxene is a pure phase.
Through detection, the lithium ion battery cathode material Mxene obtained by the embodiment of the invention is of a multilayer sheet structure, and the interlayer spacing is obvious.
Assembling the battery: the same as example 1; and testing the constant current charge and discharge performance of the assembled lithium ion battery under the voltage range of 0.01-3V.
Through detection, under the multiplying power of 0.1C (1C =300 mA h/g), the first discharge specific capacity of the assembled lithium ion battery reaches 494.4mAh/g, and under the multiplying powers of 0.2C, 0.5C, 1C, 2C and 5C, the first discharge specific capacities are 109.9 mAh/g, 80.1 mAh/g, 61.0 mAh/g, 43.7 mAh/g and 12.5 mAh/g respectively; under the high multiplying power of 10C and 15C, the first discharge specific capacity respectively reaches 12.5 mAh/g and 6.7 mAh/g, and then under the multiplying power of 0.1C, the discharge specific capacity still can reach 96.5 mAh/g.
Through detection, under the multiplying power of 0.1C, the first discharge specific capacity of the assembled lithium ion battery can reach 494.4mAh/g, and after 100 cycles, the discharge specific capacity is still 91.3 mAh/g.
Through detection, the internal resistance of the assembled lithium ion battery is 123.6 omega, the internal resistance is high, and the conductivity is poor.
From the above, the Mxene material obtained by the comparative example needs to have improved conductivity, and the Mxene material prepared by the comparative example has low specific discharge capacity at high rate.
In summary, compared with the graphene modified Mxene obtained by a comparative example and the battery assembled by the Mxene, the lithium ion battery assembled by the titanium dioxide/graphene multi-modified Mxene composite material obtained by the embodiments 1-2 of the invention has higher discharge specific capacity and cycle performance, and shows excellent electrochemical performance under large multiplying power; it can be seen that the lithium ion battery assembled by the titanium dioxide/graphene multi-modified Mxene composite material obtained in the embodiments 1-2 of the invention is more stable in a long cycle process, because the introduction of the titanium dioxide and the graphene effectively improves the defects of longitudinal and surface conductivity of the Mxene material, and improves the discharge specific capacity, rate capability and cycle performance of the material.
Claims (24)
1. The titanium dioxide/graphene multi-element modified Mxene composite material is characterized by being prepared by the following method:
(1) adding the Mxene precursor into an HF acid solution, heating, stirring, etching and removing an Al layer;
(2) centrifuging, washing, ultrasonically dispersing and drying the Mxene precursor etched in the step (1) to obtain an Mxene material;
(3) adding the Mxene material obtained in the step (2) into water, performing ultrasonic dispersion, adding a surface charge modifier, and stirring to obtain an Mxene dispersion liquid with positive charges on the surface; the mass of the surface charge modifier is 5-15 times of that of the Mxene material;
(4) respectively adding nanoscale titanium dioxide and graphene oxide into water, and performing ultrasonic dispersion to respectively obtain a titanium dioxide dispersion solution and a graphene oxide dispersion solution; the mass ratio of the nano-scale titanium dioxide to the graphene oxide to the Mxene is 5-10: 100;
(5) sequentially adding the titanium dioxide dispersion liquid and the graphene oxide dispersion liquid into the Mxene dispersion liquid with positive charges on the surface obtained in the step (3), stirring, carrying out suction filtration, and drying to obtain black powder;
(6) and (5) placing the black powder obtained in the step (5) in an inert atmosphere, and carrying out heat treatment to obtain the titanium dioxide/graphene multi-element modified Mxene composite material.
2. The titanium dioxide/graphene multi-element modified Mxene composite material according to claim 1, characterized in that: in the step (1), the mass fraction of the HF acid solution is 25-65%, and the mass ratio of the Mxene precursor to the HF acid is 1: 25-65; the heating and stirring speed is 200-600 revolutions per minute, the heating and stirring temperature is 40-100 ℃, and the heating and stirring time is 4-10 hours; the etching time is 4-10 h.
3. The titanium dioxide/graphene multi-element modified Mxene composite material according to claim 1 or 2, characterized in that: in the step (2), the rotating speed of the centrifugation is 3000-12000 r/min; the washing is washing with deionized water and ethanol, and the washing times are more than or equal to 10 times; the power of ultrasonic dispersion is 200-400W, and the time of ultrasonic dispersion is 0.5-2 h; the drying temperature is 60-100 ℃, and the drying time is 6-12 h.
4. The titanium dioxide/graphene multi-element modified Mxene composite material according to claim 1 or 2, characterized in that: in the step (3), the mass of the water is 400-800 times of that of the Mxene material; the power of ultrasonic dispersion is 200-400W, and the time of ultrasonic dispersion is 0.5-2 h; the stirring speed is 200-400 r/min, and the stirring time is 1-4 h.
5. The titanium dioxide/graphene multi-element modified Mxene composite material according to claim 3, characterized in that: in the step (3), the mass of the water is 400-800 times of that of the Mxene material; the power of ultrasonic dispersion is 200-400W, and the time of ultrasonic dispersion is 0.5-2 h; the stirring speed is 200-400 r/min, and the stirring time is 1-4 h.
6. The titanium dioxide/graphene multi-element modified Mxene composite material according to claim 1 or 2, characterized in that: in the step (3), the surface charge modifier is one or more of ammonia water, ammonium bicarbonate or hexadecyl trimethyl ammonium bromide.
7. The titanium dioxide/graphene multi-element modified Mxene composite material according to claim 3, characterized in that: in the step (3), the surface charge modifier is one or more of ammonia water, ammonium bicarbonate or hexadecyl trimethyl ammonium bromide.
8. The titanium dioxide/graphene multi-element modified Mxene composite material according to claim 4, characterized in that: in the step (3), the surface charge modifier is one or more of ammonia water, ammonium bicarbonate or hexadecyl trimethyl ammonium bromide.
9. The titanium dioxide/graphene multi-element modified Mxene composite material according to claim 1 or 2, characterized in that: in the step (4), the mass of the water is 500-1500 times of that of the titanium dioxide and the graphene oxide; the power of ultrasonic dispersion is 200-400W, and the time of ultrasonic dispersion is 0.5-2 h.
10. The titanium dioxide/graphene multi-element modified Mxene composite material according to claim 3, characterized in that: in the step (4), the mass of the water is 500-1500 times of that of the titanium dioxide and the graphene oxide; the power of ultrasonic dispersion is 200-400W, and the time of ultrasonic dispersion is 0.5-2 h.
11. The titanium dioxide/graphene multi-element modified Mxene composite material according to claim 4, characterized in that: in the step (4), the mass of the water is 500-1500 times of that of the titanium dioxide and the graphene oxide; the power of ultrasonic dispersion is 200-400W, and the time of ultrasonic dispersion is 0.5-2 h.
12. The titanium dioxide/graphene multi-element modified Mxene composite material according to claim 6, characterized in that: in the step (4), the mass of the water is 500-1500 times of that of the titanium dioxide and the graphene oxide; the power of ultrasonic dispersion is 200-400W, and the time of ultrasonic dispersion is 0.5-2 h.
13. The titanium dioxide/graphene multi-element modified Mxene composite material according to claim 1 or 2, characterized in that: in the step (5), the titanium dioxide dispersion liquid and the graphene oxide dispersion liquid are sequentially added into the titanium dioxide dispersion liquid and the graphene oxide dispersion liquid; the stirring speed is 200-400 r/min, and the stirring time is 6-12 h; the drying temperature is 60-100 ℃, and the drying time is 6-12 h.
14. The titanium dioxide/graphene multi-element modified Mxene composite material according to claim 3, characterized in that: in the step (5), the titanium dioxide dispersion liquid and the graphene oxide dispersion liquid are sequentially added into the titanium dioxide dispersion liquid and the graphene oxide dispersion liquid; the stirring speed is 200-400 r/min, and the stirring time is 6-12 h; the drying temperature is 60-100 ℃, and the drying time is 6-12 h.
15. The titanium dioxide/graphene multi-element modified Mxene composite material according to claim 4, characterized in that: in the step (5), the titanium dioxide dispersion liquid and the graphene oxide dispersion liquid are sequentially added into the titanium dioxide dispersion liquid and the graphene oxide dispersion liquid; the stirring speed is 200-400 r/min, and the stirring time is 6-12 h; the drying temperature is 60-100 ℃, and the drying time is 6-12 h.
16. The titanium dioxide/graphene multi-element modified Mxene composite material according to claim 6, characterized in that: in the step (5), the titanium dioxide dispersion liquid and the graphene oxide dispersion liquid are sequentially added into the titanium dioxide dispersion liquid and the graphene oxide dispersion liquid; the stirring speed is 200-400 r/min, and the stirring time is 6-12 h; the drying temperature is 60-100 ℃, and the drying time is 6-12 h.
17. A titanium dioxide/graphene multi-element modified Mxene composite material according to claim 9, wherein: in the step (5), the titanium dioxide dispersion liquid and the graphene oxide dispersion liquid are sequentially added into the titanium dioxide dispersion liquid and the graphene oxide dispersion liquid; the stirring speed is 200-400 r/min, and the stirring time is 6-12 h; the drying temperature is 60-100 ℃, and the drying time is 6-12 h.
18. The titanium dioxide/graphene multi-element modified Mxene composite material according to claim 1 or 2, characterized in that: in the step (6), the heat treatment temperature is 300-600 ℃, and the heat treatment time is 6-12 h; the inert atmosphere is one or more of argon, argon/hydrogen mixed gas or nitrogen.
19. The titanium dioxide/graphene multi-element modified Mxene composite material according to claim 3, characterized in that: in the step (6), the heat treatment temperature is 300-600 ℃, and the heat treatment time is 6-12 h; the inert atmosphere is one or more of argon, argon/hydrogen mixed gas or nitrogen.
20. The titanium dioxide/graphene multi-element modified Mxene composite material according to claim 4, characterized in that: in the step (6), the heat treatment temperature is 300-600 ℃, and the heat treatment time is 6-12 h; the inert atmosphere is one or more of argon, argon/hydrogen mixed gas or nitrogen.
21. The titanium dioxide/graphene multi-element modified Mxene composite material according to claim 6, characterized in that: in the step (6), the heat treatment temperature is 300-600 ℃, and the heat treatment time is 6-12 h; the inert atmosphere is one or more of argon, argon/hydrogen mixed gas or nitrogen.
22. A titanium dioxide/graphene multi-element modified Mxene composite material according to claim 9, wherein: in the step (6), the heat treatment temperature is 300-600 ℃, and the heat treatment time is 6-12 h; the inert atmosphere is one or more of argon, argon/hydrogen mixed gas or nitrogen.
23. A titanium dioxide/graphene multi-element modified Mxene composite material according to claim 13, wherein: in the step (6), the heat treatment temperature is 300-600 ℃, and the heat treatment time is 6-12 h; the inert atmosphere is one or more of argon, argon/hydrogen mixed gas or nitrogen.
24. The titanium dioxide/graphene multi-element modified Mxene composite material of claim 17, wherein: in the step (6), the heat treatment temperature is 300-600 ℃, and the heat treatment time is 6-12 h; the inert atmosphere is one or more of argon, argon/hydrogen mixed gas or nitrogen.
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