CN109817918B - Sulfur-doped MXene composite material and preparation method and application thereof - Google Patents
Sulfur-doped MXene composite material and preparation method and application thereof Download PDFInfo
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- CN109817918B CN109817918B CN201910057080.7A CN201910057080A CN109817918B CN 109817918 B CN109817918 B CN 109817918B CN 201910057080 A CN201910057080 A CN 201910057080A CN 109817918 B CN109817918 B CN 109817918B
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Abstract
The invention discloses a sulfur-doped MXene composite material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) mixing MXene and a sulfur source according to a mass ratio of 1: 1-20, adding the mixture into deionized water, stirring and heating to prepare mixed liquid with the concentration of 5-80 mg/ml; (2) transferring the mixed solution into a reaction kettle, heating to 80-200 ℃, reacting for 4-36h, and then cooling to room temperature; (3) and (3) washing the product obtained in the step (2) with a detergent, centrifuging, and then carrying out vacuum drying to obtain the sulfur-doped MXene composite material. The sulfur-doped MXene composite material prepared by the method has the advantages of high structural stability, stable cycle performance, high charging and discharging coulombic efficiency and the like, and the prepared negative electrode material is moderate in potassium intercalation/deintercalation potential and good in cycle performance and multiplying power performance.
Description
Technical Field
The invention belongs to the field of new energy materials, and particularly relates to a preparation method of a sulfur-doped MXene composite material and application of the sulfur-doped MXene composite material in a potassium ion battery.
Background
With the rapid development of modern society, the traditional energy is exhausted day by day, and the search for new clean energy becomes more urgent. The lithium ion battery is the core direction of the field of chargeable and dischargeable batteries since birth due to good chemical stability and electrochemical performance, but the storage of lithium is limited, the exploitation difficulty is high, and the lithium ion battery is difficult to be widely applied. To find alternatives to lithium ion batteries, potassium, which is chemically similar and has been stored in greater quantities, is beginning to be of interest to researchers. Has important scientific significance for the research of the high-performance potassium ion battery cathode.
The radius of potassium ions is larger than that of lithium ions, the interlayer spacing of the traditional commercial graphite electrode is small and cannot meet the requirement of rapid de-intercalation of potassium ions, and the MXene material is used as a novel two-dimensional layered material and is shaped like a book page. The material has good conductivity and high specific surface area, and is suitable for being used as a negative electrode material of a potassium ion battery. However, the performance of the pure MXene material used as the negative electrode material of the potassium ion battery is still unsatisfactory. By carrying out sulfur doping on MXene, the interlayer spacing can be increased, and a potassium ion diffusion channel is optimized, so that the electrochemical performance of the potassium ion battery is improved.
Disclosure of Invention
In view of the problems in the prior art, an object of the present invention is to provide a sulfur-doped MXene composite material. The invention also aims to provide a preparation method of the sulfur-doped MXene composite material. Further, the invention provides application of the sulfur-doped MXene composite material, and the sulfur-doped MXene composite material is used as a potassium ion battery negative electrode.
The invention adopts the following technical scheme:
a preparation method of a sulfur-doped MXene composite material comprises the following steps:
(1) mixing MXene and a sulfur source according to a mass ratio of 1: 1-20 (such as 1: 2-15, 1: 5-10, 1: 6-8) adding into deionized water, stirring and heating to prepare a mixed solution with a concentration of 5-80mg/ml (such as 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75 mg/ml);
(2) transferring the mixed solution into a reaction kettle, heating to 80-200 deg.C (such as 80 deg.C, 90 deg.C, 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C, 160 deg.C, 170 deg.C, 180 deg.C, 190 deg.C, 200 deg.C), reacting for 4-36h (such as 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36h), and cooling to room temperature;
(3) and (3) washing the product obtained in the step (2) with a detergent, centrifuging, and then carrying out vacuum drying to obtain the sulfur-doped MXene composite material.
Further, the sulfur source is at least one of diphenyl sulfide and 2-phenethyl mercaptan, the diphenyl sulfide is preferred, and the preferred mass ratio is (2-5): 1 thiophenyl ether and 2-phenethyl mercaptan.
Further, MXene is Ti3C2Tx、Mo3C2Tx、V3C2Tx、Ti3N2Tx、Mo3N2Tx、V3N2TxOne or more of (a).
Further, the sulfur doping amount of the sulfur-doped MXene composite material is 1 wt% -20 wt%, preferably 2 wt% -12 wt%.
Further, the sulfur doping amount of the sulfur-doped MXene composite material is 3 wt% to 15 wt% (e.g., 3.5, 4.5, 5.5, 6.5, 7.5, 8.5, 9.5, 10.5, 11.5, 12.5, 13.5, 14.5 wt%).
Further, the detergent is at least one of deionized water and ethanol, for example, the detergent is alternately washed with deionized water and ethanol for 2-6 times, for example, 3 times.
Further, the rotation speed used in the centrifugation in the step (3) is 3000-.
Further, the temperature of vacuum drying in step (3) is 50-70 ℃, preferably 60 ℃, the drying time is 8-24h (e.g. 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24h), and the vacuum degree is not more than 135Pa, e.g. not more than 133Pa, e.g. not more than 125, 115, 105, 95, 85 Pa.
A sulfur-doped MXene composite material prepared by the preparation method.
The application of the sulfur-doped MXene composite material is to apply the sulfur-doped MXene composite material to a potassium ion battery negative electrode.
The invention has the beneficial effects that:
(1) the sulfur-doped MXene composite material prepared by the method has the advantages of high structural stability, stable cycle performance, good rate performance, high charging and discharging coulombic efficiency and the like, and the prepared negative electrode material has moderate potassium intercalation/deintercalation potential and good cycle performance and rate performance;
(2) the preparation method is simple, the doping amount of the sulfur element is controllable, and the preparation method is suitable for large-scale application.
Drawings
Fig. 1 is a scanning electron microscope image of undoped MXene material in comparative example 1;
FIG. 2 is a scanning electron microscope image of the sulfur-doped MXene composite material in example 1;
FIG. 3 is a graph showing the cycle performance of the potassium ion battery cathode made of the sulfur-doped MXene composite material in example 1;
fig. 4 is a graph of cycle performance of the potassium ion battery anode made of the undoped MXene material in comparative example 1.
Detailed Description
For better explanation of the present invention, the following specific examples are further illustrated, but the present invention is not limited to the specific examples.
Example 1
A preparation method of a sulfur-doped MXene composite material comprises the following steps:
(1) weigh 0.1g of Ti3C2TxAdding 0.1g of thiophenyl ether into deionized water, heating to 50 ℃ and magnetically stirring for 1 hour to obtain a mixed solution.
(2) And transferring the mixed solution to a reaction kettle, sealing, placing the reaction kettle in an oven, and adjusting the reaction temperature to 80 ℃ for 4 hours.
(3) And washing the obtained product with deionized water and ethanol for 3 times alternately, centrifuging at a centrifuging speed of 3000r/min for 2min, and finally drying in a vacuum drying oven at 60 ℃ for 8 h.
(4) Preparing a potassium ion battery cathode: mixing the obtained sulfur-doped MXene, a polyvinylidene fluoride binder and carbon black according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, uniformly stirring to form slurry, coating the slurry on a current collector, and performing vacuum drying and slicing to obtain the sulfur-doped MXene battery cathode.
(5) Fig. 1 shows that the undoped MXene has an accordion shape, and after doping, fig. 2 shows the shape of the doped MXene in the embodiment. The specific surface area of MXene after doping is 172m2The thickness of the coating is 0.71nm, the sulfur atom content is 1 percent, and the specific surface area is far larger than that of the undoped MXene (40.8 m)2/g), interlayer spacing (0.64 nm); FIG. 3 shows that the reversible capacity of the doped MXene of the embodiment after 100 cycles is 251mAh/g under the current density of 100mA/g, which is 2.6 times of the reversible capacity (93.8mAh/g) of the negative electrode of the undoped MXene potassium ion battery of FIG. 4.
Example 2
A preparation method of a sulfur-doped MXene composite material comprises the following steps:
(1) weigh 0.2g of Ti3C2TxAdding 2g of thiophenyl ether into deionized water, heating to 60 ℃, and magnetically stirring for 3 hours to obtain a mixed solution.
(2) And transferring the mixed solution to a reaction kettle, sealing, placing the reaction kettle in an oven, and adjusting the reaction temperature to 160 ℃ for 18 hours.
(3) The obtained product is washed by deionized water and ethanol for 3 times alternately, and is centrifuged for 3min at the centrifugation speed of 3250r/min, and finally is put into a vacuum drying oven to be dried for 16h at the temperature of 60 ℃.
(4) Preparing a potassium ion battery cathode: mixing the obtained sulfur-doped MXene, a polyvinylidene fluoride binder and carbon black according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, uniformly stirring to form slurry, coating the slurry on a current collector, and performing vacuum drying and slicing to obtain the sulfur-doped MXene battery cathode.
(5) The specific surface area of MXene after doping in this example is 365m2The specific surface area of the doped MXene is far greater than that of the undoped MXene (40.8 m)2/g), interlayer spacing (0.64 nm); the reversible capacity of the doped MXene in the embodiment after 100 cycles under the current density of 100mA/g is 363mAh/g, which is 3.8 times of that of the cathode (93.8mAh/g) of the undoped MXene potassium ion battery.
Example 3
A preparation method of a sulfur-doped MXene composite material comprises the following steps:
(1) weigh 0.5g of Ti3C2TxAdding 10g of thiophenyl ether into deionized water, heating to 70 ℃, and magnetically stirring for 5 hours to obtain a mixed solution.
(2) And transferring the mixed solution to a reaction kettle, sealing, placing the reaction kettle in an oven, and adjusting the reaction temperature to 200 ℃ for 36 hours.
(3) The obtained product is washed by deionized water and ethanol for 3 times alternately, centrifuged for 4min at the centrifugal speed of 3500r/min, and finally put into a vacuum drying oven to be dried for 24h at the temperature of 60 ℃.
(4) Preparing a potassium ion battery cathode: mixing the obtained sulfur-doped MXene, a polyvinylidene fluoride binder and carbon black according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, uniformly stirring to form slurry, coating the slurry on a current collector, and performing vacuum drying and slicing to obtain the sulfur-doped MXene battery cathode.
(5) The specific surface area of MXene after doping in this example is 291m2The specific surface area of the doped MXene is far greater than that of the undoped MXene (40.8 m)2/g), interlayer spacing (0.64 nm); the doped MXene of the embodiment can be cycled for 100 circles under the current density of 100mA/gThe inverse capacity is 301mAh/g, which is 3.2 times of that of the cathode (93.8mAh/g) of the undoped MXene potassium ion battery.
Example 4
A preparation method of a sulfur-doped MXene composite material comprises the following steps:
(1) weigh 0.1g of Ti3C2Tx0.1g of Mo3C2TxAdding 2g of thiophenyl ether into deionized water, heating to 60 ℃, and magnetically stirring for 3 hours to obtain a mixed solution.
(2) And transferring the mixed solution to a reaction kettle, sealing, placing the reaction kettle in an oven, and adjusting the reaction temperature to 100 ℃ for 6 hours.
(3) The obtained product is washed by deionized water and ethanol for 3 times alternately, centrifuged for 3min at the centrifugation speed of 3250r/min, and finally dried in a vacuum drying oven at 60 ℃ for 10 h.
(4) Preparing a potassium ion battery cathode: mixing the obtained sulfur-doped MXene, a polyvinylidene fluoride binder and carbon black according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, uniformly stirring to form slurry, coating the slurry on a current collector, and performing vacuum drying and slicing to obtain the sulfur-doped MXene battery cathode.
(5) The reversible capacity of the doped MXene in the embodiment after 100 cycles under the current density of 100mA/g is 372mAh/g, which is 4.0 times of that of the cathode (93.8mAh/g) of the undoped MXene potassium ion battery.
Example 5
A preparation method of a sulfur-doped MXene composite material comprises the following steps:
(1) weigh 0.2g of V3C2TxAdding 2g of 2-phenethyl mercaptan into deionized water, heating to 60 ℃, and magnetically stirring for 3 hours to obtain a mixed solution.
(2) And transferring the mixed solution to a reaction kettle, sealing, placing the reaction kettle in an oven, and adjusting the reaction temperature to 120 ℃ for 8 hours.
(3) And washing the obtained product with deionized water and ethanol for 3 times alternately, centrifuging for 3min at a centrifugation speed of 3250r/min, and finally placing the product in a vacuum drying oven to dry for 8h at 60 ℃.
(4) Preparing a potassium ion battery cathode: mixing the obtained sulfur-doped MXene, a polyvinylidene fluoride binder and carbon black according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, uniformly stirring to form slurry, coating the slurry on a current collector, and performing vacuum drying and slicing to obtain the sulfur-doped MXene battery cathode.
(5) The reversible capacity of the doped MXene in the embodiment after 100 cycles under the current density of 100mA/g is 368mAh/g, which is 3.9 times of that of the cathode (93.8mAh/g) of the undoped MXene potassium ion battery.
Comparative example 1: the procedure for preparing the negative electrode of the potassium ion battery without doping MXene is the same as that of example 2.
Table 1: performance testing
The above description is only exemplary of the present invention and is not intended to limit the scope of the present invention, which is defined by the claims appended hereto, as well as the appended claims.
Claims (4)
1. The preparation method of the sulfur-doped MXene potassium ion battery negative electrode composite material is characterized by comprising the following steps of:
(1) mixing MXene and a sulfur source according to a mass ratio of 1: 5-10, adding the mixture into deionized water, stirring and heating the mixture to prepare mixed liquid with the concentration of 5-80 mg/ml;
(2) transferring the mixed solution into a reaction kettle, heating to 80-200 ℃, reacting for 4-36h, and then cooling to room temperature;
(3) washing the product obtained in the step (2) with a detergent, centrifuging, and then carrying out vacuum drying to obtain the sulfur-doped MXene potassium ion battery negative electrode composite material;
the sulfur source is diphenyl sulfide;
the MXene is Ti3C2TxAnd Mo3C2Tx；
The sulfur doping amount of the sulfur-doped MXene potassium ion battery negative electrode composite material is 9 wt%;
the detergent is at least one of deionized water and ethanol;
the rotation speed for centrifugation in the step (3) is 3000-.
2. The preparation method of the sulfur-doped MXene potassium ion battery anode composite material according to claim 1, wherein the temperature of vacuum drying in step (3) is 50-70 ℃, the drying time is 8-24h, and the vacuum degree is not more than 135 Pa.
3. The sulfur-doped MXene potassium ion battery anode composite material prepared according to the preparation method of any one of claims 1-2.
4. The application of the sulfur-doped MXene potassium ion battery anode composite material according to claim 3, wherein the sulfur-doped MXene potassium ion battery anode composite material is used for a potassium ion battery anode.
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| CN109888279B (en) * | 2019-01-15 | 2022-01-04 | 五邑大学 | Selenium-doped MXene material and preparation method and application thereof |
| CN113969171A (en) * | 2020-07-24 | 2022-01-25 | Tcl科技集团股份有限公司 | Preparation method of doped MXene quantum dots, optical film and QLED |
| CN112018347A (en) * | 2020-08-10 | 2020-12-01 | 五邑大学 | NbS2/MXene composite material and preparation method thereof |
| CN112133892A (en) * | 2020-08-10 | 2020-12-25 | 五邑大学 | Sulfur-doped ReSe2Preparation method of/MXene composite material |
| CN112018349B (en) * | 2020-08-12 | 2022-04-08 | 五邑大学 | CoTe2/MXene composite material and preparation method thereof |
| CN112072101A (en) * | 2020-08-14 | 2020-12-11 | 五邑大学 | Boron-doped MXene material and preparation method thereof |
| CN112191244B (en) * | 2020-08-31 | 2023-03-31 | 浙江工业大学 | Activated carbon-supported gold-based catalyst, preparation method thereof and application thereof in acetylene hydrogenation |
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