CN113066673A - Ti3C2Tx-TiO2 nanotube array self-supporting film electrode material and preparation method and application thereof - Google Patents
Ti3C2Tx-TiO2 nanotube array self-supporting film electrode material and preparation method and application thereof Download PDFInfo
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- 239000002071 nanotube Substances 0.000 title claims abstract description 48
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000007772 electrode material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000003990 capacitor Substances 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 238000002242 deionisation method Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 238000001179 sorption measurement Methods 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 238000005530 etching Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 238000009830 intercalation Methods 0.000 claims description 3
- 239000010408 film Substances 0.000 abstract description 32
- 239000010409 thin film Substances 0.000 abstract description 13
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 230000002349 favourable effect Effects 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 238000003491 array Methods 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000012528 membrane Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 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
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Abstract
The invention provides a Ti3C2Tx‑TiO2A nanotube array self-supporting film electrode material and a preparation method and application thereof belong to the field of nano materials. The preparation method comprises the following steps: ti3AlC2Etching, cleaning, stripping and centrifuging to obtain few-layer Ti3C2TxAn aqueous dispersion; ti3C2TxVacuum filtering and drying the aqueous dispersion to obtain Ti3C2TxA self-supporting film; ti3C2TxReacting the self-supporting film in hot alkali liquor and rotating at a certain rotation speed, and cleaning and drying to obtain Ti3C2Tx‑TiO2Nanotube arrays self-supporting films. Ti prepared by the invention3C2Tx‑TiO2Ti in nanotube array self-supporting thin film electrode structure3C2Tx‑TiO2The crystal defects and the array structure with less nanotube structures are favorable for electron transmission, a large number of active sites exposed by the nanotube array are favorable for adsorbing ions or target pollutants, the mechanical property of the material is strong, and the material can be directly used as an electrode material in the fields of super capacitors, capacitor deionization, batteries, electric adsorption and the like.
Description
Technical Field
The invention belongs to the technical field of synthesis of environmental materials, and particularly relates to Ti3C2Tx-TiO2A nanotube array self-supporting film electrode material, a preparation method and application thereof.
Background
Electrode materials are key factors in determining the performance of batteries, capacitors, electrosorption, and the like. The common powdery electrode material is usually required to be mixed and dissolved with a binder and a conductive material, and a film is prepared by processes such as coating, and the added binder and solubilizer can seriously influence the performance of the material; and the coating process is complex, has higher requirements on the operation level of personnel, and does not utilize the popularization of large-scale application, so that the development of the directly applicable self-supporting electrode material with excellent performance is very important.
Disclosure of Invention
Aiming at the defects in the prior art, the primary object of the invention is to provide Ti3C2Tx-TiO2The nanotube array self-supporting thin film electrode material.
It is a second object of the present invention to provide the above Ti3C2Tx-TiO2A method for preparing a nanotube array self-supporting film electrode material.
A third object of the present invention is to provideSupply the above Ti3C2Tx-TiO2The application of the nanotube array self-supporting thin film electrode material.
In order to achieve the above purpose, the solution of the invention is as follows:
ti prepared by the invention3C2Tx-TiO2Ti in nanotube array self-supporting thin film electrode structure3C2Tx-TiO2The crystal defects and the array structure with less nanotube structures are favorable for electron transmission, a large number of active sites exposed by the nanotube array are favorable for adsorbing ions or target pollutants, the mechanical property of the material is strong, and the material can be directly used as an electrode material in the fields of super capacitors, capacitor deionization, batteries, electric adsorption and the like.
Ti3C2Tx-TiO2The preparation method of the nanotube array self-supporting thin film electrode material comprises the following steps:
(1)Ti3AlC2etching, cleaning, intercalation stripping and centrifuging to obtain few-layer Ti3C2TxAn aqueous dispersion;
(2)Ti3C2Txvacuum filtering and drying the aqueous dispersion to obtain Ti3C2TxA self-supporting film;
(3)Ti3C2Txreacting the self-supporting film in hot alkali liquor and rotating at a certain rotation speed, and cleaning and drying to obtain Ti3C2Tx-TiO2Nanotube arrays self-supporting films.
Preferably, in the step (1), one of sodium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide and dimethyl sulfoxide is adopted for Ti3AlC2Intercalation is carried out, and ultrasonic stripping is adopted.
Preferably, in step (1), the power of ultrasonic stripping is more than 600W, and the time is more than 1 h.
Preferably, in step (1), the centrifugal speed is more than 3500rpm, and the supernatant after centrifugation is Ti-poor3C2TxAn aqueous dispersion.
Preferably, in step (2), Ti3C2TxThe concentration of the aqueous dispersion should be 0.5mg/mL to 5mg/mL, Ti in a single film3C2TxThe mass is 12mg-40 mg.
Preferably, in step (2), the temperature at which the film is dried is 20 ℃ to 60 ℃.
Preferably, in the step (3), the alkali liquor is composed of one of sodium hydroxide and potassium hydroxide, the concentration of the alkali liquor is 8-15 mol/L, the heating temperature is 40-80 ℃, and the heating time is 6-12 h.
Preferably, in step (3), the film is protected by a clamp during rotation, and the rotation speed is 300rpm to 600 rpm.
Ti3C2Tx-TiO2The nanotube array self-supporting film electrode material is obtained by the preparation method.
A Ti as described above3C2Tx-TiO2The nanotube array self-supporting film electrode material can be used in the fields of super capacitors, capacitive deionization, batteries, electro-adsorption and the like.
Due to the adoption of the scheme, the invention has the beneficial effects that:
first, Ti prepared by the present invention3C2Tx-TiO2Ti in nanotube array self-supporting thin film electrode structure3C2Tx-TiO2The nanotube structure has fewer crystal defects and the array structure is favorable for electron transmission.
Secondly, the large number of active sites exposed by the nanotube array structure of the present invention is beneficial for adsorbing ions or target pollutants.
Third, Ti prepared by the invention3C2Tx-TiO2The nanotube array self-supporting film electrode has strong mechanical property, and can be directly used for electrode materials without the treatment of size mixing, film scraping and the like.
Fourthly, the preparation method of the invention has simple equipment and simple and easy process, and is suitable for large-scale production.
In summary, the present invention produces a polymer with excellent electrical propertiesTi3C2TxAnd a self-supporting film of (2) and use of Ti3C2TxIs oxidized in hot alkali solution to obtain Ti3C2Tx-TiO2Heterojunction, and forming the nanotube array by applying centripetal force. Ti obtained by the method3C2Tx-TiO2The nanotube array self-supporting thin film electrode has excellent performance, has the characteristics of few crystal defects, fast electron transmission, rich active sites and the like, is simple and easy in process, is suitable for large-scale production, and can be directly applied to electrode materials in the fields of super capacitors, capacitor deionization, batteries, electro-adsorption and the like.
Detailed Description
The invention provides a Ti3C2Tx-TiO2A nanotube array self-supporting film electrode material, a preparation method and application thereof.
Drawings
FIG. 1 shows Ti in example 13C2Tx-TiO2Scanning electron microscope images of the nanotube array self-supporting thin film electrode material;
FIG. 2 is an impedance spectrum of the self-supporting thin film electrode material of Ti3C2Tx-TiO2 nanotube array in example 1;
FIG. 3 is a diagram of the capacitive deionization and desalination performance of the self-supporting thin film electrode material of Ti3C2Tx-TiO2 nanotube array in example 1.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1:
ti of the example3C2Tx-TiO2The preparation method of the nanotube array self-supporting thin film electrode material comprises the following steps:
(1) 2g of lithium fluoride and 9M of 40ml of hydrochloric acid were weighed out and stirred in a polytetrafluoroethylene beaker (volume 100ml) for 30min at a speed of 400 rpm.
(2) 2g of Ti3AlC2Slowly adding into the beaker in the first step, adjusting the reaction temperature to 35 ℃, and continuously stirring24h。
(3) Ti obtained in the step (2)3C2TxThe product was washed by centrifugation (3500rpm, 5min) with deionized water to remove the lower precipitate and the procedure was repeated to pH>5。
(4) Dispersing the product obtained in the step (3) by deionized water, adding proper amount of dimethyl sulfoxide into the mixture, and adding the dimethyl sulfoxide into the mixture in the presence of N2After 2h of sonication under atmosphere, the supernatant was removed by centrifugation (3500rpm, 5 min). 5mL of the supernatant was dried to determine its concentration.
(5) Diluting the supernatant obtained in the step (4) to 2mg/mL, taking 10mL of the supernatant, taking a water system filter membrane as a substrate, and carrying out vacuum filtration to obtain Ti3C2TxA film.
(6) Naturally drying the film obtained in the step (5) at room temperature, and taking down the water system filter membrane to obtain self-supporting Ti3C2TxA film.
(7) Subjecting the self-supporting Ti obtained in (6)3C2TxThe film was placed in a holder and heated at 50 ℃ for 10h with 10mol/L KOH at 400 rpm.
(8) Washing the product of (7) with deionized water to pH<8, drying in an oven at 60 ℃ to obtain Ti3C2Tx-TiO2Nanotube arrays self-supporting films.
FIG. 1 shows Ti in an example of the present invention3C2Tx-TiO2The scanning electron microscope image of the nanotube array self-supporting film electrode material shows that the nanotube array structure uniformly grown on the surface of the film can be seen, and the nanotube array provides more active sites, thereby being beneficial to the adsorption and electron transmission of target pollutants and ions.
FIG. 2 shows Ti in an example of the present invention3C2Tx-TiO2The impedance spectrum of the nanotube array self-supporting thin film electrode material shows that the internal ohmic resistance and the charge transfer resistance of the electrode are respectively 25.33ohm and 1.99ohm, and the lower resistance is favorable for the transmission of electrons.
FIG. 3 shows Ti in an example of the present invention3C2Tx-TiO2Nanotube array self-supporting filmsThe capacitive deionization desalination performance diagram of the membrane electrode material shows that the desalination capacity of the membrane electrode material is as high as 106mg/g under the current density of 30mA/g, and the application potential of the membrane electrode material in the capacitive deionization direction is shown.
Example 2:
ti of the example3C2Tx-TiO2The preparation method of the nanotube array self-supporting thin film electrode material comprises the following steps:
(1) 2g of lithium fluoride and 9M of 40ml of hydrochloric acid were weighed out and stirred in a polytetrafluoroethylene beaker (volume 100ml) for 30min at a speed of 400 rpm.
(2) 2g of Ti3AlC2Slowly adding the mixture into the beaker in the first step, adjusting the reaction temperature to 35 ℃, and continuously stirring for 24 hours.
(3) Ti obtained in the step (2)3C2TxThe product was washed by centrifugation (3500rpm, 5min) with deionized water to remove the lower precipitate and the procedure was repeated to pH>5。
(4) Dispersing the product obtained in the step (3) by deionized water, adding proper amount of dimethyl sulfoxide into the mixture, and adding the dimethyl sulfoxide into the mixture in the presence of N2After 2h of sonication under atmosphere, the supernatant was removed by centrifugation (3500rpm, 5 min). 5mL of the supernatant was dried to determine its concentration.
(5) Diluting the supernatant obtained in the step (4) to 1mg/mL, taking 15mL of the supernatant, taking a water system filter membrane as a substrate, and carrying out vacuum filtration to obtain Ti3C2TxA film.
(6) Naturally drying the film obtained in the step (5) at room temperature, and taking down the water system filter membrane to obtain self-supporting Ti3C2TxA film.
(7) Subjecting the self-supporting Ti obtained in (6)3C2TxThe film was placed in a jig and heated at 50 ℃ for 10 hours at 400rpm with 12mol/L NaOH.
(8) Washing the product of (7) with deionized water to pH<8, drying in an oven at 60 ℃ to obtain Ti3C2Tx-TiO2Nanotube arrays self-supporting films.
Ti3C2Tx-TiO2Nanotube array self-supporting filmsThe membrane electrode material can be used as an electrode material in the fields of super capacitors, capacitive deionization, batteries, electro-adsorption and the like.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments. Those skilled in the art should appreciate that many modifications and variations are possible in light of the above teaching without departing from the scope of the invention.
Claims (10)
1. Ti3C2Tx-TiO2The preparation method of the nanotube array self-supporting film electrode material is characterized by comprising the following steps:
(1)Ti3AlC2etching, cleaning, stripping and centrifuging to obtain few-layer Ti3C2TxAn aqueous dispersion;
(2)Ti3C2Txvacuum filtering and drying the aqueous dispersion to obtain Ti3C2TxA self-supporting film;
(3) reacting the Ti3C2Tx self-supporting film in hot alkali liquor, rotating at a certain rotation speed, cleaning and drying to obtain the Ti3C2Tx-TiO2 nanotube array self-supporting film.
2. The Ti of claim 13C2Tx-TiO2The preparation method of the nanotube array self-supporting film electrode material is characterized by comprising the following steps: in the step (1), one of sodium hydroxide, tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide and dimethyl sulfoxide is adopted to react with Ti3AlC2Intercalation is carried out, and ultrasonic stripping is adopted.
3. The Ti of claim 13C2Tx-TiO2A method for preparing a nanotube array self-supporting film electrode material,the method is characterized in that: in the step (1), the power of ultrasonic stripping is more than 600W, and the time is more than 1 h.
4. The Ti of claim 13C2Tx-TiO2The preparation method of the nanotube array self-supporting film electrode material is characterized by comprising the following steps: in the step (1), the centrifugal speed is more than 3500rpm, and the supernatant after centrifugation is Ti with few layers3C2TxAn aqueous dispersion.
5. The Ti of claim 13C2Tx-TiO2The preparation method of the nanotube array self-supporting film electrode material is characterized by comprising the following steps: in the step (2), Ti3C2TxThe concentration of the aqueous dispersion should be 0.5mg/mL to 5mg/mL, Ti in a single film3C2TxThe mass is 12mg-40 mg.
6. The Ti of claim 13C2Tx-TiO2The preparation method of the nanotube array self-supporting film electrode material is characterized by comprising the following steps: in the step (2), the drying temperature of the film is 20-60 ℃.
7. The Ti of claim 13C2Tx-TiO2The preparation method of the nanotube array self-supporting film electrode material is characterized by comprising the following steps: in the step (3), the alkali liquor is composed of one of sodium hydroxide and potassium hydroxide, the concentration of the alkali liquor is 8-15 mol/L, the heating temperature is 40-80 ℃, and the heating time is 6-12 h.
8. The Ti of claim 13C2Tx-TiO2The preparation method of the nanotube array self-supporting film electrode material is characterized by comprising the following steps: in the step (3), the film is protected by a clamp during rotation, and the rotation speed is 300-600 rpm.
9. Ti3C2Tx-TiO2The nanotube array self-supporting film electrode material is characterized in that: obtained by the process according to any one of claims 1 to 8.
10. Ti according to claim 93C2Tx-TiO2The nanotube array self-supporting film electrode material is applied to the fields of super capacitors, capacitive deionization, batteries and electro-adsorption.
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