CN109449002B - Modified Ti3C2TxMaterial, its preparation and use - Google Patents

Modified Ti3C2TxMaterial, its preparation and use Download PDF

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CN109449002B
CN109449002B CN201811434354.1A CN201811434354A CN109449002B CN 109449002 B CN109449002 B CN 109449002B CN 201811434354 A CN201811434354 A CN 201811434354A CN 109449002 B CN109449002 B CN 109449002B
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CN109449002A (en
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李久强
胡杨
林廷睿
赵娜
彭静
翟茂林
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Peking University
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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
    • 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
    • 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
    • H01G11/32—Carbon-based
    • 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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses a modified Ti3C2TxMaterials and their preparation and use. The modified Ti3C2TxThe material has a fold structure and contains amorphous carbon, and gamma rays or electron beams are adopted to irradiate Ti3C2TxPrepared by irradiation in aqueous dispersion. Solvent free radicals and Ti produced during irradiation3C2TxActing not only in Ti3C2TxAmorphous carbon is generated on the surface, and Ti is improved3C2TxElectrical conductivity of the material, but also induces Ti3C2TxThe fragments are assembled into a sheet layer with a fold structure, and Ti is increased3C2TxThe active specific surface area of the material is beneficial to the full contact with the electrolyte. The material is used as a super capacitor electrode material, shows good reversibility and stability in an electrochemical performance test, and has potential application value in the field of energy storage.

Description

Modified Ti3C2TxMaterial, its preparation and use
Technical Field
The invention relates to an MXene material, in particular to a modified Ti containing amorphous carbon and having a fold structure3C2TxMaterials and their preparation and use.
Background
As an electrochemical energy storage device which is currently attracting attention, a super capacitor has the advantages of high power density, fast charge and discharge, and long cycle life, however, the energy density thereof is still to be further improved. MXene is a general term of a series of novel two-dimensional nitrides or carbides, and has the properties of large specific surface area, good conductivity, hydrophilicity and the like. When the material is used as an electrode material, the material also has high mass specific capacitance and volume specific capacitance, high rate performance and excellent cycling stability, and is considered to be an ideal electrode material of a super capacitor.
Researchers have shown through theoretical calculations that MXene without surface groups has metallic conductivity, and the kind and content of surface groups can significantly affect the hydrophilicity and conductivity of materials [ Kurtoglu, m.et al, MRS Communications,2012,2, 133 ]. Researchers have found that the electrochemically active area of MXene materials is often limited by sheet stacking, while the conductivity is often limited by the interlayer resistance, and thus the electrochemical performance can be improved by modifying MXene or preparing MXene-based composites [ Li, l.et al, Journal of Power Sources,2017,364,234; zhao, m.q.et al, Advanced Materials,2014,27(2), 339. Recently, researchers have found that amorphous carbon formed on the surface of MXene during etching and modification can increase the conductivity and improve the capacitance of the material [ Su, X.et al, Journal of Alloys & Compounds, 2018,752,32 ]. Furthermore, the formation of a wrinkled structure also helps to increase the active specific surface area of MXene and thus its capacitive properties [ Bao, W.et al, Advanced Energy Materials,2018,8,1702485 ].
Ti3C2TxIs an MXene material which is the most widely researched at present, has a two-dimensional layered structure and is generally prepared from a precursor Ti3AlC2The etching solution is prepared by selectively etching hydrogen fluoride or hydrogen chloride and lithium fluoride. During liquid phase etching, a large number of terminal groups (-F, -O, -OH) are generally formed on the surface of the material. There are a number of modifications of Ti3C2TxPapers on Materials [ Li, j.et al, Advanced Energy Materials,2018,7, 1602725; hu, m.et al, ACS Nano,2018,12, 3578; wang, H.et al, Journal of Physics&Chemistry of Solids,2018,115,172]And patents [ Chinese patent application publication Nos. CN107633954A and CN106430195A]It has been reported that the methods employed in these studies generally require strict control of conditions so as not to damage the crystal structure, and are difficult to achieve mass production.
Disclosure of Invention
The invention aims to provide a simple and macro-preparation method of modified Ti containing amorphous carbon and having a fold structure3C2TxA material and a preparation method and application thereof.
The invention firstly provides modified Ti3C2TxThe material has a folded structure and is prepared by adopting gamma rays or electron beams on Ti3C2TxPrepared by irradiation in aqueous dispersion, herein referred to as Rad-Ti3C2TxA material, wherein: the Ti atomic layer is in hexagonal close packing; c atoms are filled in octahedral vacant sites; t represents a bond to Ti3C2Surface groups on the surface (mainly Ti atoms) mainly include the following groups: o, OH and F; x represents the T group content. Meanwhile, the material also contains a certain amount of amorphous carbon, and the molar content of the amorphous carbon relative to the total amount of the material is 1-20%.
When T consists of O, OH and F, the modified Ti3C2TxThe material can be specifically expressed as Rad-Ti3C2On(OH)yFzWherein, 0<n<1，0<y<2，0<z<2，y+z+2n＝2。
The invention also provides the Rad-Ti3C2TxThe preparation method of the material comprises the following steps:
1) taking Ti with a certain concentration3C2TxAdding a certain volume of organic solvent and/or a small amount of surfactant into the aqueous dispersion, adjusting the pH value to 1-5, ultrasonically dispersing uniformly, introducing inert gas, and sealing;
2) irradiating the mixed solution obtained in the step 1) by adopting gamma-rays or electron beams;
3) centrifuging the product irradiated in the step 2) to remove supernatant, washing the precipitate, ultrasonically dispersing the precipitate in water, and freeze-drying.
In step 1) of the above method, preferably, the organic solvent is selected from one or more of the following solvents: isopropanol, ethylene glycol, methanol, ethanol, n-propanol and n-butanol. Typically, the pH is adjusted using an acid solution selected from one or more of the following: sulfuric acid, hydrochloric acid, nitric acid and perchloric acid. The inert gas is preferably high purity nitrogen or high purity argon. The surfactant may be selected from one or more of the following: cetyl trimethylammonium bromide (CTAB), n-octyltrimethylammonium bromide (OTAB), tetramethylammonium bromide (TMAB), Sodium Dodecylbenzenesulfonate (SDBS).
In step 1) of the above process, Ti3C2TxThe concentration of the aqueous dispersion can be 1-4 mg/mL. The volume ratio of the organic solvent to the water can be 0-10. The concentration of the surfactant can be 0-4 mg/mL. The ultrasonic dispersion treatment time can be 1-5 min, and the adopted ultrasonic power is 60W for example. The inert gas is introduced for 10-20 min.
In the step 2) of the method, the absorption dose rate of the mixed solution can be 10-100 Gy/min, and the absorption dose can be 1-100 kGy. The gamma-rays may specifically consist of60Co or137Cs, etc. radiation source; the electron beam may be specifically an electron beam (energy of 0.1-10MeV) generated by an electron accelerator.
In the step 3), the rotating speed of the centrifugal treatment can be 2000-5000 rpm, and the centrifugal time can be 5-10 min; removing supernatant, washing the precipitate with deionized water, and repeating the steps for multiple times; then ultrasonically dispersing the mixture in water, and freeze-drying the mixture in a certain concentration, wherein the ultrasonic dispersion treatment time can be 1-5 min, the adopted ultrasonic power is 60W, the concentration of a dispersion solution before freeze-drying can be 1-10 mg/mL, and the freeze-drying treatment time can be 36-96 h.
The invention also provides the Rad-Ti mentioned above3C2TxThe material is applied as an electrode material in a super capacitor.
The invention provides a working electrode which can be used in a super capacitor device of a three-electrode system, and the working electrode comprises an electrode clamp, a bubble film nickel current collector positioned in the electrode clamp and the Rad-Ti3C2TxMaterial, wherein said Rad-Ti3C2TxThe material is located between two pieces of bubble film nickel current collectors.
The working electrode is prepared by the following method: soaking the filmCutting nickel into certain shape, and taking Rad-Ti after freeze-drying3C2TxThe material is placed between two pieces of bubble film nickel for tabletting and then clamped in an electrode clamp to be used as a working electrode.
The invention adopts gamma ray or electron beam radiation method to prepare modified Ti with fold structure for the first time3C2Tx(Rad-Ti3C2Tx) Its advantages are mainly as follows:
(1) the invention adopts gamma-ray or electron beam radiation method to treat Ti at normal temperature3C2TxThe surface is modified, amorphous carbon is generated on the surface of the material, and the conductivity of the material is improved.
(2) Solvent free radicals and Ti produced during irradiation3C2TxAct to make Ti3C2TxThe fragments are assembled into a laminated Ti with a corrugated structure3C2TxThe active specific surface area of the material is increased, and the material is in full contact with the electrolyte.
(3) Compared with the defects that the traditional chemical modification method needs strict control of conditions to avoid damage to a crystal structure, is difficult to realize mass production and the like, the radiation method disclosed by the invention is a modification method which is mild at room temperature, environment-friendly, simple and convenient to operate and controllable in conditions, and the absorbed dose and the dose rate can be adjusted during irradiation, so that the industrial production can be realized.
(4) Rad-Ti prepared by the radiation method as described in advantages (1) and (2)3C2TxBecause the conductivity and the active specific surface area are increased at the same time, the electrochemical performance is obviously improved, and the mass specific capacitance and the area specific capacitance are greatly improved compared with those before modification. Taking the product prepared in example 1 as an example, the specific mass capacitance of the material increased from 108F/g to 148F/g at a current density of 1A/g compared to the sample before radiation modification.
(5)Rad-Ti3C2TxAs a super capacitor electrode material, the material shows good reversibility and stability in an electrochemical performance test, and has potential application value in the field of energy storage.
In summary, the modified Ti prepared by the present invention3C2TxThe method has unique application advantages and wide application prospects in the field of energy storage materials, and has important theoretical and experimental reference values for radiation modification treatment of other MXene materials.
Drawings
FIG. 1 shows the preparation of modified Ti by gamma-ray irradiation3C2TxProcess schematic of materials.
FIG. 2A shows Ti as a starting material used in example 13C2TxA Scanning Electron Microscope (SEM) image of (a);
FIG. 2B shows Rad-Ti prepared in example 13C2TxSEM image of (d).
FIG. 3 shows Ti as a starting material used in example 13C2TxAnd Rad-Ti prepared3C2TxX-ray diffraction (XRD) pattern of (a).
FIG. 4 shows Ti as a starting material used in example 13C2TxAnd Rad-Ti prepared3C2TxRaman spectrum (Raman) map of
FIG. 5A shows Ti as a starting material used in example 13C2TxHigh resolution X-ray photoelectron spectroscopy (XPS) of medium Ti;
FIG. 5B shows Ti as a starting material used in example 13C2TxXPS high resolution of medium C;
FIG. 5C shows Rad-Ti prepared in example 13C2TxXPS high resolution of medium Ti;
FIG. 5D shows Rad-Ti prepared in example 13C2TxXPS high resolution of medium C.
FIG. 6A shows Ti as a starting material used in example 13C2TxCyclic Voltammetry (CV) curves at different sweep rates;
FIG. 6B shows Rad-Ti prepared in example 13C2TxCV curves at different sweep rates.
FIG. 7A shows Ti as a starting material used in example 13C2TxConstant current charge and discharge (GCD) curves at different current densities;
FIG. 7B shows Rad-Ti prepared in example 13C2TxGCD curves at different current densities.
FIG. 8 shows Ti as a starting material used in example 13C2TxAnd Rad-Ti prepared in example 13C2TxThe ac impedance spectrum and the fitted circuit schematic (inset).
Detailed Description
The process of the present invention is illustrated below by means of specific examples, but the present invention is not limited thereto.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1: Rad-Ti3C2TxPreparation and use of
The first step is as follows: preparation of Rad-Ti3C2TxMaterial
Taking 2mg/mL Ti3C2Tx19mL of the aqueous dispersion, 2mL of an isopropyl alcohol solution (V) was addedWater (W)∶VIsopropanol (I-propanol)Adding a small amount of 2mol/L sulfuric acid solution to adjust the pH value of the solution to 2, shaking, performing ultrasonic treatment to uniformly mix the solution (the ultrasonic power is 60W, the ultrasonic treatment time is 5min), and introducing high-purity nitrogen for 10 min; the test tube is sealed and then sent to a cobalt source room of Beijing university for gamma-ray irradiation, the dose rate is 20Gy/min, and the absorbed dose is 20 kGy. The irradiated product was centrifuged (3000rpm, 10min), the supernatant removed, 20mL deionized water was added, sonicated for 5min (60W sonication power), centrifuged again, washed three times and finally lyophilized in a lyophilizer at 2mg/mL for 48 h.
The SEM images of FIGS. 2A and 2B show small, thin Ti after radiation modification3C2TxThe fragments are assembled into a sheet with a larger area and have a corrugated structure. This is because the radicals generated in the solvent during irradiation change the Ti3C2TxSurface radical content and charge amount of the fragmentsAre assembled with each other. And the corrugated structure increases the specific surface area of the material, and is beneficial to the diffusion and contact of electrolyte ions.
The XRD spectrum of fig. 3 further verifies the increased packing and ordering of the lamellae, with a slight right shift of the diffraction peak corresponding to the (002) plane from 2 theta 6.4 ° to 2 theta 6.8 °, demonstrating a slight decrease in interplanar spacing, and in addition, Ti3C2TxThe diffraction peak corresponding to the crystal plane (004) (006) (008), especially the diffraction peak corresponding to the crystal plane (110) (2 theta is 60 degrees), proves that the radiation modification can increase the orderliness of the material to a certain extent.
In the Raman spectrum of FIG. 4, 300cm-1To 700cm-1Three characteristic peaks in the range from non-stoichiometric Ti-C oscillations, 900cm-1To 1800cm-1Two broad peaks in the range are the D and G peaks of graphitic carbon, 1560cm-1The peak at position (D) is G peak and comes from the atomic in-plane vibration of graphite carbon, 1350cm-1The peak at (b) is a D peak and is derived from deformation vibration of the amorphous carbon or hexagonal ring. Comparing the intensity change of the peak before and after modification, it is proved that the radiation modification can be on Ti to some extent3C2TxMore amorphous carbon is formed on the surface.
In the XPS spectra of FIGS. 5A-5D, the radiation modified product and the starting material both contained Ti-C, Ti-OH, Ti-O bonds, and C-C, C-O, C-F bonds, but the modified Rad-Ti3C2TxIn this case, the Ti-O and C-C bonds are significantly increased and the Ti-OH content is reduced, indicating that the radiation modification changes the surface group content and produces more bare C atoms. Based on the XPS results, combined with basic knowledge of theoretical calculations in the literature, the product of example 1 has the formula Rad-Ti3C2On(OH)yFzThe method comprises the following steps: n is 0.64, y is 0.43, z is 0.26, and the content of amorphous carbon is about 10%.
The second step is that: Rad-Ti3C2TxElectrochemical performance test of
A working electrode was prepared by the following method: cutting the nickel foam into 1cm × 1.5cm, and freeze-drying Rad-Ti3C2TxThe material was placed between two pieces of foam nickel, and the sheet was pressed for 30 seconds at a force of 20kN using a tablet press, and sandwiched in an electrode holder as a working electrode, and the mass of the active material contained on the foam nickel was calculated according to the subtraction method.
The working electrode prepared by the method is used as a three-electrode super capacitor electrode for performance test, and the test method and parameters are as follows: the test was carried out using a three-electrode system with 1mol/L NaSO as electrolyte4The solution, counter electrode is platinum sheet electrode, and reference electrode is Ag/AgCl electrode. And (2) performing cyclic voltammetry test on the three-electrode system by using an electrochemical workstation (PGSTAT 302N, Switzerland) at a voltage scanning window of-1V to-0.2V and a scanning rate of 5, 10, 20 and 50 mV/s. A constant-current charging and discharging test is carried out on a three-electrode system by using a battery detection system (CT 2001A, blue-electron corporation, Wuhan city), wherein the voltage range is-1V to-0.2V, and the current density is 1.0, 2.0, 3.0, 5.0 and 10.0A/g.
Comparing fig. 6A and 6B, the CV curve of the product after radiation modification becomes better symmetric and the area increases, demonstrating that the mass specific capacitance of the product increases and has better reversibility. As can be seen from FIG. 6B, the CV curve shape of the modified product is substantially unchanged with the change of the sweep rate and remains symmetrical at a low sweep rate of 5mV/s, which is a typical characteristic of an electrochemical double layer capacitor, whose capacity is derived from the electro-adsorption of ions and no redox reaction occurs. Furthermore, the area of the CV curve varies with sweep rate, and the calculated capacitance value decreases with increasing sweep rate, because electrolyte ions cannot diffuse in time to the active sites of the electrode material at large sweep rates, depending on the structure of the material itself.
Compared with fig. 7A and 7B, the GCD curve of the product after radiation modification has better symmetry and longer charge-discharge time. As can be seen from fig. 7B, the modified product has better GCD curve symmetry at different current densities, which is close to an isosceles triangle, and is typical of capacitor behavior of an electric double layer and has good reversibility. With the increase of the current density, the charging and discharging time is reduced, and the calculated capacitance value is also reduced, which is also a normal phenomenon caused by insufficient diffusion of electrolyte ions when the charging and discharging are too fast. Under the test condition that the current density is 1A/g, the mass specific capacitance of the material is 148F/g, which is 1.4 times that before radiation modification.
As can be seen from fig. 8, the Nyquist curve of the radiation-modified product in the low frequency region is perpendicular to the horizontal axis, and the electric double layer capacitance characteristic of the material is represented. Fitting the result, and calculating to obtain the impedance R of the raw material bodys1.89 omega, charge transfer resistance Rct6.66. omega. and the bulk resistance R of the modified products1.65 omega, charge transfer resistance Rct1.21 omega, which is reduced compared to the value before radiation modification. Bulk resistance reduction results from the generation of amorphous carbon, and material interfacial resistance reduction may result from the generation of a wrinkled structure.
Example 2: Rad-Ti3C2TxPreparation and use of
Will be described in example 160The dose rate of electron beams generated by an electron accelerator was changed to 20kGy/pass for Co gamma-ray, and the absorbed dose was 20kGy, and other preparation and test conditions were the same as in example 1. Rad-Ti prepared under the conditions3C2TxThe material is represented as Rad-Ti3C2On(OH)yFzN is 0.61, y is 0.48, z is 0.3, and the content of amorphous carbon is about 9%. The capacitive properties are comparable to those of the product of example 1.
Example 3: Rad-Ti3C2TxPreparation and use of
The sulfuric acid solution in example 1 was changed to hydrochloric acid solution, and other preparation and test conditions were the same as in example 1. Rad-Ti prepared under the conditions3C2TxThe material is represented as Rad-Ti3C2On(OH)yFzN is 0.58, y is 0.44, z is 0.4, and the content of amorphous carbon is about 9%. The capacitive properties are comparable to those of the product of example 1.
Example 4: Rad-Ti3C2TxPreparation and use of
The isopropyl alcohol in example 1 was changed to ethylene glycol, and other preparation and test conditions were the same as in example 1. At this stripRad-Ti prepared under the part3C2TxThe material is represented as Rad-Ti3C2On(OH)yFzN is 0.65, y is 0.45, z is 0.25, and the content of amorphous carbon is about 8%. The capacitive properties are comparable to those of the product of example 1.
Example 5: Rad-Ti3C2TxPreparation and use of
20mg of cetyltrimethylammonium bromide, a surfactant, was added to the solvent system of example 1. Rad-Ti prepared under the conditions3C2TxThe material is represented as Rad-Ti3C2On(OH)yFzN is 0.52, y is 0.56, z is 0.4, and the content of amorphous carbon is about 10%. The capacitive properties are comparable to those of the product of example 1.
Example 6: Rad-Ti3C2TxPreparation and use of
The dose rate in example 1 was changed to 30Gy/min, and the other preparation and test conditions were the same as in example 1. Rad-Ti prepared under the conditions3C2TxThe material is represented as Rad-Ti3C2On(OH)yFzN is 0.66, y is 0.48, z is 0.2, the content of amorphous carbon is about 6%, and the specific capacitance by mass is 91F/g.
Example 7: Rad-Ti3C2TxPreparation and use of
The volume of isopropanol in example 1 was changed to 0mL, the solvent was water, and other preparation and test conditions were the same as in example 1. Rad-Ti prepared under the conditions3C2TxThe material is represented as Rad-Ti3C2On(OH)yFzN is 0.45, y is 0.68, z is 0.42, the content of amorphous carbon is about 3%, and the specific capacitance by mass is 57F/g.
Example 8: Rad-Ti3C2TxPreparation and use of
The volume of water in example 1 was changed to 0mL, the solvent was isopropanol, and other preparation and test conditions were the same as in example 1. Under the condition ofRad-Ti obtained by the following preparation3C2TxThe material is represented as Rad-Ti3C2On(OH)yFzN is 0.38, y is 0.87, z is 0.37, the content of amorphous carbon is about 4%, and the specific capacitance by mass is 49F/g.
Example 9: Rad-Ti3C2TxPreparation and use of
The absorbed dose in example 1 was changed to 1kGy, and other preparation and test conditions were the same as in example 1. Rad-Ti prepared under the conditions3C2TxThe material is represented as Rad-Ti3C2On(OH)yFzN is 0.56, y is 0.67, z is 0.21, the content of amorphous carbon is about 8%, and the specific capacitance by mass is 100F/g.
Example 10: Rad-Ti3C2TxPreparation and use of
The absorbed dose in example 1 was changed to 2.5kGy, and other preparation and test conditions were the same as in example 1. Rad-Ti prepared under the conditions3C2TxThe material is represented as Rad-Ti3C2On(OH)yFzN is 0.41, y is 0.85, z is 0.33, the content of amorphous carbon is about 8%, and the specific capacitance by mass is 96.7F/g.
Example 11: Rad-Ti3C2TxPreparation and use of
The absorbed dose in example 1 was changed to 5kGy, and other preparation and test conditions were the same as in example 1. Rad-Ti prepared under the conditions3C2TxThe material is represented as Rad-Ti3C2On(OH)yFzN is 0.49, y is 0.62, z is 0.4, the content of amorphous carbon is about 8%, and the specific capacitance by mass is 99.6F/g.
Example 12: Rad-Ti3C2TxPreparation and use of
The absorbed dose in example 1 was changed to 10kGy, and other preparation and test conditions were the same as in example 1. Rad-Ti prepared under the conditions3C2TxMaterial tableShown as Rad-Ti3C2On(OH)yFzN is 0.38, y is 0.77, z is 0.46, the content of amorphous carbon is about 9%, and the specific capacitance by mass is 117F/g.
Example 13: Rad-Ti3C2TxPreparation and use of
The absorbed dose in example 1 was changed to 30kGy, and other preparation and test conditions were the same as in example 1. Rad-Ti prepared under the conditions3C2TxThe material is represented as Rad-Ti3C2On(OH)yFzN is 0.78, y is 0.24, z is 0.2, the content of amorphous carbon is about 11%, and the specific capacitance by mass is 126F/g.
Example 14: Rad-Ti3C2TxPreparation and use of
The absorbed dose in example 1 was changed to 50kGy, and other preparation and test conditions were the same as in example 1. Rad-Ti prepared under the conditions3C2TxThe material is represented as Rad-Ti3C2On(OH)yFzN is 0.81, y is 0.25, z is 0.13, the content of amorphous carbon is about 14%, and the specific capacitance by mass is 124F/g.
Example 15: Rad-Ti3C2TxPreparation and use of
The absorbed dose in example 1 was changed to 100kGy, and other preparation and test conditions were the same as in example 1. Rad-Ti prepared under the conditions3C2TxThe material is represented as Rad-Ti3C2On(OH)yFzN is 0.92, y is 0.09, z is 0.07, the content of amorphous carbon is about 20%, and the specific capacitance by mass is 63F/g.
Example 16: Rad-Ti3C2TxPreparation and use of
The pH was changed to 5 in example 14, and the other preparation and test conditions were the same as in example 14. Rad-Ti prepared under the conditions3C2TxThe material is represented as Rad-Ti3C2On(OH)yFzN is 0.52, y is 0.61, z is 0.35, the content of amorphous carbon is about 5%, and the specific capacitance by mass is 62F/g.
Example 17: Rad-Ti3C2TxPreparation and use of
The pH was changed to 11 in example 14, and the other preparation and test conditions were the same as in example 14. Rad-Ti prepared under the conditions3C2TxThe material is represented as Rad-Ti3C2On(OH)yFzN is 0.52, y is 0.83, z is 0.12, the content of amorphous carbon is about 4%, and the specific capacitance by mass is 54F/g.

Claims (11)

1. Modified Ti3C2TxA material wherein the Ti atomic layers are hexagonally close-packed; c atoms are filled in octahedral vacant sites; t represents a bond to Ti3C2Surface groups on the surface, consisting essentially of: o, OH and F; x represents the T group content; characterized in that the modified Ti3C2TxThe material has a fold structure and is prepared by adopting gamma rays or electron beams on Ti3C2TxIrradiating in water dispersion to obtain; the modified Ti3C2TxThe material also contains an amount of amorphous carbon.
2. The modified Ti as claimed in claim 13C2TxMaterial, characterized in that said T consists of O, OH and F, said modified Ti being3C2TxThe chemical formula of the material is Ti3C2On(OH)yFzWherein, 0<n<1，0<y<2，0<z<2，y+z+2n＝2。
3. The modified Ti as claimed in claim 13C2TxThe material is characterized in that the molar content of the amorphous carbon relative to the total amount of the material is 1-20%.
4. The method according to claim 1 to 3Modified Ti3C2TxThe preparation method of the material comprises the following steps:
1) taking Ti with a certain concentration3C2TxAdding or not adding an organic solvent and/or a surfactant into the aqueous dispersion, adjusting the pH value to 1-5, ultrasonically dispersing uniformly, introducing inert gas, and sealing;
2) irradiating the mixed solution obtained in the step 1) by adopting gamma-rays or electron beams;
3) centrifuging the product irradiated in the step 2) to remove supernatant, washing the precipitate, ultrasonically dispersing the precipitate in water, and freeze-drying.
5. The method according to claim 4, wherein the organic solvent in step 1) is selected from one or more of the following solvents: isopropanol, ethylene glycol, methanol, ethanol, n-propanol and n-butanol.
6. The method according to claim 4, wherein in step 1), no or a small amount of a surfactant is added before the ultrasonic dispersion, wherein the surfactant is selected from one or more of the following substances: cetyl trimethyl ammonium bromide, n-octyl trimethyl ammonium bromide, tetramethyl ammonium bromide and sodium dodecyl benzene sulfonate.
7. The method according to claim 4, wherein the Ti is used in the step 1)3C2TxThe concentration of the aqueous dispersion is 1-4 mg/mL, the volume ratio of the organic solvent to the water is 0-10, and the concentration of the surfactant is 0-4 mg/mL.
8. The method according to claim 4, wherein the absorption dose rate of the mixed solution in the step 2) is 10 to 100Gy/min, and the absorption dose is 1 to 100 kGy.
9. The method of claim 4, wherein the gamma-rays of step 2) are generated from60Co or137Cs radiation sourceRaw; the electron beam is generated by an electron accelerator and has the energy of 0.1-10 MeV.
10. The modified Ti alloy as claimed in any one of claims 1 to 33C2TxThe material is applied to a super capacitor as an electrode material.
11. A working electrode comprising an electrode holder, and a nickel foam current collector and the modified Ti of any one of claims 1 to 3 located in the electrode holder3C2TxMaterial, wherein the modified Ti3C2TxThe material is located between two pieces of bubble film nickel current collectors.
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