CN107978742B - C-doped flower spherical titanium dioxide/molybdenum disulfide composite material formed by nanosheets and preparation method thereof - Google Patents
C-doped flower spherical titanium dioxide/molybdenum disulfide composite material formed by nanosheets and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a C-doped flower-like spherical TiO formed by nanosheets2/MoS2Composite material and process for preparing the same, wherein TiO2From anatase and monoclinic TiO2(B) And (4) forming. Firstly, preparing flower-ball-shaped C-doped TiO by taking acetic acid as a solvent, polyvinylpyrrolidone (PVP) as a dispersing agent and a carbon source and tetrabutyl titanate (TBT) as a titanium source through a solvothermal method and calcining2(ii) a By synthetic C-doped TiO2Taking ammonium molybdate as a molybdenum source and thiourea as a sulfur source as a framework to obtain C-doped TiO by a hydrothermal method2/MoS2A composite material. The method regulates and controls the TiO in the composite material by regulating and controlling the amount of the molybdenum source and the sulfur source2And MoS2The mass ratio of (A) to (B) is controlled by controlling the calcination temperature to control the TiO content2A crystalline form of (a). In addition, TiO is not changed after compounding2The morphology of (2). In the process of preparing the composite material, the preparation method is simple, the preparation process is safe, the energy consumption is low, and the operability is strong.
Description
Technical Field
The invention relates to a C-doped flower-ball-shaped TiO formed by nanosheets2/MoS2A composite material and a preparation method thereof belong to the field of new energy materials.
Background
Lithium Ion Batteries (LIBs) are considered to be the most promising energy storage devices in portable electronic and electric vehicles. Although conventional graphite anodes have been commercialized, their capacity is very low (372mA h g)-1) The practical application of the method in portable electronic and electric automobiles is limited to a great extent. In addition, since LIBs negative electrode materials are accompanied by severe volume expansion during long-time charge and discharge, the materials are severely crushed, resulting in irreversible capacity loss and reduced cycle stability. Therefore, the cycle performance, rate performance, and safety performance of LIBs need to be further improved.
Titanium dioxide (TiO)2) As one of the most prominent anode materials of LIBs, the lithium ion battery has the advantages of good safety, low cost, wide sources, environmental friendliness and the like. In the lithium ion (Li)+) In the intercalation/deintercalation process of, TiO2Is stable in structure, and does not have electrochemical lithium deposition, which is critical to the safety performance of LIBs. In a cyclic process, TiO2Less volume expansion (<4%) are generally considered as other metal oxide/sulfide frameworks or protective layers. Monoclinic TiO2(B) Belongs to TiO2Compared with anatase, rutile and brookite, the rare crystal form has more open pore channels and is more suitable for Li+Transport, can accommodate more Li+It is more suitable for LIBs. However, TiO2The conductivity is poor, the performance of the cathode material is limited by the electrochemical performance, and when Li is used+Embedded TiO2After the inner layer lattice, in TiO2Surface difficulty in forming effective electric field, Li+It is difficult to completely remove.
Molybdenum disulfide (MoS)2) Is a typical two-dimensional transition metal sulfide having a layered structure similar to graphene, stacked together by van der Waals force interaction, having
(with respect to graphene)
) Larger interlayer spacing, which favors Li+And (4) embedding. However, MoS2Still suffer from large volume expansion and poor conductivity during the lithium intercalation/deintercalation process, resulting in MoS2Poor cycle performance and rate capability in LIBs anode material applications.
TiO2/MoS2The composite material can effectively overcome the defects of two materials and improve the application performance of the materials. For example, chinese patent application publication No. CN 104437555 a (application No. 201410598619.7) discloses a wave MoS2Nanometer sheet inlaid with dandelion TiO2The patent discloses a nanosphere composite heterojunction semiconductor material and a preparation method thereof, wherein the preparation method comprises the following steps: preparation of wavy MoS by a two-step solvothermal method2Nanometer sheet inlaid with dandelion TiO2The nanosphere composite heterojunction semiconductor material is suitable for the field of photocatalysis, and the effect in the field of lithium ion batteries is not obvious. Chinese patent document with application publication No. CN 106058200A (application No. 201610608242.8) discloses a method for simultaneously modifying titanium dioxide lithium ion battery cathode material by using carbon and monolayer molybdenum disulfide, which is to prepare TiO simultaneously modified by carbon and monolayer molybdenum disulfide nanosheet by using a chemical vapor deposition method2The method for preparing the composite material is complex in steps, and requires freeze drying and chemical vapor deposition, so that the requirement on equipment is high.
Disclosure of Invention
Aiming at the prior art, the invention aims to provide a method for preparing C-doped flower-shaped spherical TiO formed by nanosheets by using a two-step method2/MoS2Composite material and preparation method thereof, and C-doped flower-shaped spherical TiO formed by nanosheets prepared by the method2/MoS2The composite material has wider application prospect in the field of lithium ion batteries.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a C-doped flower-like TiO formed from nanosheets2/MoS2The preparation method of the composite material comprises the following steps: firstly, acetic acid is taken as a solvent, polyvinylpyrrolidone (PVP, average molecular weight 40000) is taken as a dispersant and a carbon source, tetrabutyl titanate (TBT) is taken as a titanium source, and anatase and monoclinic TiO are prepared by adopting a solvothermal method and calcining2(B) Composed flower-ball-shaped TiO2Wherein the average molecular weight of PVP is 40000 g/mol; with synthetic flower-ball-shaped TiO2Using ammonium molybdate as a molybdenum source and thiourea as a sulfur source as a framework to obtain the C-doped flower-shaped TiO formed by the nano-sheets by a hydrothermal method2/MoS2A composite material.
In a second aspect of the invention, the C-doped flower-shaped spherical TiO formed by the nanosheets prepared by the method is provided2/MoS2A composite material.
The third aspect of the invention provides the application of the material in preparing a lithium ion negative electrode material.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) the preparation method of the invention adopts TBT as a titanium source, acetic acid as a solvent, PVP with average molecular weight of 40000 as a dispersant, and obtains the flower-ball-shaped TiO through the combined action of acetic acid and PVP by solvothermal and calcination2. The method is simple and convenient to operate, and has low requirements on reaction conditions.
(2) In the present invention, by N2Calcining under the protection of gas to carbonize PVP in the precursor to increase the conductivity of the material.
(3) In the present invention, the optimum molar ratio of ammonium molybdate to thiourea is 1: 2.2, with a slight excess of thiourea to ensure complete reaction of ammonium molybdate while retarding MoS2Reducing the MoS2Providing more active sites for lithium ion insertion.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 shows a flower-ball-shaped C-doped TiO prepared in example 5 of the present invention2Transmission Electron Micrographs (TEM) and Scanning Electron Micrographs (SEM);
FIG. 2 is a C-doped flower-like TiO formed from nanoplates prepared in example 5 of the invention2/MoS2Transmission Electron Micrographs (TEM) and Scanning Electron Micrographs (SEM) of the composite;
FIG. 3 is a C-doped flower-like TiO formed from nanoplates prepared by example 5 of the invention2/MoS2Magnified Transmission Electron Microscopy (TEM) of the composite;
FIG. 4 is a C-doped flower-like TiO formed from nanoplates prepared by example 5 of the invention2/MoS2High power transmission electron micrographs (HRTEM) of the composite;
FIG. 5 is a C-doped flower-like TiO formed from nanoplates prepared by example 5 of the invention2/MoS2X-ray diffraction pattern (XRD) of the composite material.
FIG. 6 is a C-doped flower ball TiO formed from nanoplates prepared by example 5 of the invention2/MoS2Composite material and flower-ball-shaped TiO2And pure MoS2Cycle performance diagrams for lithium ion batteries.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, and/or combinations thereof, unless the context clearly indicates otherwise.
As described in the background, the prior art is concerned with TiO as a negative electrode material for lithium ion batteries2And MoS2The composite material and the preparation method thereof have certain defects, and in order to solve the technical problems, the invention provides a C-doped flower-shaped TiO sphere formed by nanosheets2/MoS2The preparation method of the composite material comprises the following steps: firstly, acetic acid is taken as a solvent, polyvinylpyrrolidone (PVP, average molecular weight 40000) is taken as a dispersant and a carbon source, tetrabutyl titanate (TBT) is taken as a titanium source, and anatase and monoclinic TiO are prepared by adopting a solvothermal method and calcining2(B) Composed of C-doped flower-like TiO2(ii) a With synthetic flower-ball-shaped TiO2Using ammonium molybdate as a molybdenum source and thiourea as a sulfur source as a framework to obtain the C-doped flower-shaped TiO formed by the nano-sheets by a hydrothermal method2/MoS2The composite material has the diameter of 2-3 mu m (preferably 3 mu m) and is prepared by mixing C with flower-ball-shaped TiO2Is formed by polymerizing flaky petals, the thickness of the petals is 8-12 nm, MoS2Is uniformly adhered to TiO2On the surface of the sheet petals.
The flower-ball-shaped C-doped TiO of the invention2Is formed by polymerizing flaky petals. Wherein, the thinner nanometer sheet petal is used for the lithium ion battery to reduce the lithium ion transmission path. Meanwhile, the flaky petals are gathered into a flower ball shape, so that the volume change of the material in the charging and discharging process can be slowed down. TiO formed into flower ball shape by polymerization for preparing thinner nano-sheet petal2In the test process, the inventor of the invention finds that the different PVP causes different morphologies of the prepared material, and the bigger the molecular weight of the PVP is, the bigger the viscosity is, so that the TiO with the specific morphology cannot be prepared2Material, TiO prepared by the invention2The microsphere flaky petals are uniform in size and shape.
In the composite material, MoS2Is 6-7 layers of single-layer MoS2The stacked nano-sheets (scaly, the scale size is about 10 nm) have the interlayer spacing of 0.63 nm.
In a preferred embodiment of the invention, the C-doped flower-like TiO formed by the nanoplatelets2/MoS2The preparation method of the composite material comprises the following steps:
dissolving PVP in acetic acid, and stirring to obtain a transparent solution;
adding TBT into the transparent solution obtained in the step I, and stirring to obtain a suspension;
thirdly, the suspension prepared in the second step is subjected to solvothermal reaction, and is cooled, separated, washed and dried to obtain the catalyst
Precipitating;
fourthly, calcining the precipitate prepared in the third step; then cooling to obtain TiO2Powder;
fifthly, the TiO obtained in the step IV2Adding the powder, ammonium molybdate and thiourea into water, stirring and ultrasonically dispersing to obtain uniform suspension;
sixthly, carrying out hydrothermal reaction on the suspension prepared in the fifth step, cooling after the hydrothermal reaction is finished, separating, washing and drying to obtain a precipitate; wherein, TiO2The mass ratio of the powder, the ammonium molybdate and the thiourea is 2: 1-4.
In the step (i) of the present invention,
in the test process, the inventor of the application finds that the acetic acid solutions with different contents of PVP have great difference on the appearance of the prepared material, and further has great influence on the performance of the material. The PVP acetic acid solution with the mass concentration preferably selected by the invention can obtain TiO with ideal morphology2. In the invention of TiO2Mainly acts as a skeleton, so preparing TiO2Has dispersed petals and is suitable for MoS2Attached to the petals. Proved by experiments, compared with the nano-wire, the flower-ball-shaped TiO formed by the nano-sheet2In the presence of MoS2The composite material has larger contact area during compounding, thereby obtaining the composite material with higher specific capacity, and the specific capacity is 100mA g-1Reaches 621mA h g at the current density of-1The specific capacitance of (c). Through a large number of experiments, the addition ratio of the acetic acid to the polyvinylpyrrolidone is preferably (0.18-0.2) g:40mL, more preferably 0.2g:40 mL.
Preferably, the stirring temperature is 25-30 ℃; more preferably, the stirring temperature is 25 ℃. At this temperature, PVP is sufficiently dissolved in acetic acid, while excessive volatilization of acetic acid is prevented.
Preferably, the stirring and dissolving time is 0.5-1 h; more preferably, stirring is carried out for 0.5 h. The advantages are that: the PVP was stirred well to form a homogeneous solution while minimizing the time for acetic acid to evaporate.
In the second step of the present invention,
preferably, the stirring temperature is 25-30 ℃; more preferably, the stirring temperature is 25 ℃, at which the energy consumption can be reduced while preventing excessive volatilization of acetic acid.
Preferably, TBT is added dropwise to the transparent solution obtained in the step (r) for 10 min. The advantages are that: the slow dropping speed enables the TBT to obtain better dispersion in acetic acid, and the hydrolysis rate of the TBT is reduced.
Preferably, the stirring and dispersing TBT time is 0.5-1 h; more preferably, the stirring time is 1 h. The advantages are that: so that the TBT and the acetic acid solution of the PVP are uniformly mixed and well combined, and conditions are provided for the full solvent thermal reaction in a thermostat.
Preferably, the addition ratio of the acetic acid, the polyvinylpyrrolidone and the tetrabutyl titanate is (0.18-0.2) g:40 mL: (1-2) mL.
In the third step of the invention, the solvothermal reaction conditions are as follows: the temperature is 150 ℃, and the reaction time is 24 h.
The detergent is deionized water and absolute ethyl alcohol, and is washed for 3-6 times; preferably, the washing is performed 3 times with deionized water and 2 times with anhydrous ethanol.
The drying temperature is 50-60 ℃; preferably, the drying temperature is 50 ℃ and the drying time is 12 h.
In the fourth step of the invention, the calcining condition is 400-550 ℃ for 1-3 h; preferably, the calcination condition is 400 ℃, the calcination is carried out for 2h, and the calcination is carried out under N2In gas protection. The advantages are that: the invention has low calcining temperature and can reduce the energy consumption. Meanwhile, monoclinic TiO can be obtained by low-temperature calcination2(B) Polycrystalline mixed with anataseTiO2。
In the fifth step of the invention, TiO2The mass ratio of the powder to the ammonium molybdate to the thiourea is 2: 1-4; preferably, TiO2The mass ratio of the powder, the ammonium molybdate and the thiourea is 1: 1.
The invention adopts specific raw material mass ratio (TiO)2The mass ratio of the powder, the ammonium molybdate and the thiourea is 2: 1-4), and due to less excess of the sulfur source, the MoS2Slow reaction rate during formation, in addition to TiO2Spatial limitation of petals, so MoS2Form nano-sheets with smaller size to be attached on TiO2On the flower petal. In addition, smaller size MoS2Providing more active sites for lithium ion insertion. Simultaneous MoS2Attached to TiO2The petal buffers the volume change in the charging and discharging process and enhances the cycle stability of the material.
Preferably, the stirring time is 1 h; preferably, the ultrasonic dispersion time is 0.5 h.
In step sixthly, the hydrothermal reaction conditions are preferably as follows: the temperature is 200 ℃ and the time is 24 h.
The detergent is deionized water and absolute ethyl alcohol, and is washed for 3-6 times; preferably, the washing is performed 3 times with deionized water and 2 times with anhydrous ethanol.
The drying temperature is 50-60 ℃; preferably, the drying temperature is 50 ℃ and the drying time is 12 h.
In a preferred embodiment of the invention, the C-doped flower-shaped spherical TiO formed by the nanosheets prepared by the method is provided2/MoS2The micro-morphology of the composite material is in a flower ball shape, the diameter of the composite material is 1.8-2.2 mu m, and carbon and MoS are contained in the composite material2TiO doped in flower ball shape2Medium, flower ball shaped TiO2From anatase and monoclinic TiO2(B) Composition of MoS2Is in a hexagonal crystalline phase.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
0.2g of PVP (average molecular weight 40000g/mol) was dissolved in 40mL of acetic acid and stirred well. Stirring for 0.5h, slowly dropwise adding 1mL of TBT into the obtained solution, violently stirring for 1h to obtain uniform milky white suspension, transferring the obtained milky white suspension to a reaction kettle, and placing the reaction kettle in a constant temperature box at 150 ℃ for hydrothermal reaction for 24 h; centrifuging, washing, drying and grinding the milky white suspension after the hydrothermal reaction, and calcining for 2h at 400 ℃ in the air to obtain TiO2And (3) powder.
0.2g of the prepared TiO was taken2Dispersing the powder in 40mL of deionized water to obtain a uniform suspension, adding 0.2g of ammonium molybdate and 0.2g of thiourea into the obtained suspension, stirring for 1h, performing ultrasonic dispersion for 0.5h, transferring the suspension to a reaction kettle, and performing hydrothermal reaction in a thermostat at 200 ℃ for 24 h; centrifuging, washing, drying and grinding the suspension after the hydrothermal reaction to obtain TiO2/MoS2And (3) powder.
Example 2
0.2g of PVP (average molecular weight 40000g/mol) was dissolved in 40mL of acetic acid and stirred well. Stirring for 0.5h, slowly dropwise adding 1mL of TBT into the obtained solution, violently stirring for 1h to obtain uniform milky white suspension, transferring the obtained milky white suspension to a reaction kettle, and placing the reaction kettle in a constant temperature box at 150 ℃ for hydrothermal reaction for 24 h; centrifuging, washing, drying and grinding the milky white suspension after the hydrothermal reaction, and calcining for 2h at 450 ℃ in the air to obtain TiO2And (3) powder.
0.2g of the prepared TiO was taken2Dispersing the powder in 40mL of deionized water to obtain a uniform suspension, adding 0.2g of ammonium molybdate and 0.2g of thiourea into the obtained suspension, stirring for 1h, performing ultrasonic dispersion for 0.5h, transferring the suspension to a reaction kettle, and performing hydrothermal reaction in a thermostat at 200 ℃ for 24 h; centrifuging, washing, drying and grinding the suspension after the hydrothermal reaction to obtain TiO2/MoS2And (3) powder.
Example 3
0.2g of PVP (average molecular weight 40000g/mol) was dissolved in 40mL of acetic acid and stirred well. Stirring for 0.5h, slowly dripping 1mL of TBT into the obtained solution, and vigorously stirring for 1h to obtainUniformly stirring the milky white suspension, transferring the obtained milky white suspension to a reaction kettle, and placing the milky white suspension in a thermostat at 150 ℃ for hydrothermal reaction for 24 hours; centrifuging, washing, drying and grinding the milky white suspension after the hydrothermal reaction, and calcining the milky white suspension in air at 500 ℃ for 2 hours to obtain TiO2And (3) powder.
0.2g of the prepared TiO was taken2Dispersing the powder in 40mL of deionized water to obtain a uniform suspension, adding 0.2g of ammonium molybdate and 0.2g of thiourea into the obtained suspension, stirring for 1h, performing ultrasonic dispersion for 0.5h, transferring the suspension to a reaction kettle, and performing hydrothermal reaction in a thermostat at 200 ℃ for 24 h; centrifuging, washing, drying and grinding the suspension after the hydrothermal reaction to obtain TiO2/MoS2And (3) powder.
Example 4
0.2g of PVP (average molecular weight 40000g/mol) was dissolved in 40mL of acetic acid and stirred well. Stirring for 0.5h, slowly dropwise adding 1mL of TBT into the obtained solution, violently stirring for 1h to obtain uniform milky white suspension, transferring the obtained milky white suspension to a reaction kettle, and placing the reaction kettle in a constant temperature box at 150 ℃ for hydrothermal reaction for 24 h; centrifuging, washing, drying and grinding the milky white suspension after the hydrothermal reaction in N2Calcining for 2h at 400 ℃ in the atmosphere to obtain C-doped TiO2And (3) powder.
0.2g of the prepared C-doped TiO was taken2Dispersing the powder in 40mL of deionized water to obtain a uniform suspension, adding 0.1g of ammonium molybdate and 0.1g of thiourea into the obtained suspension, stirring for 1h, performing ultrasonic dispersion for 0.5h, transferring the suspension to a reaction kettle, and performing hydrothermal reaction in a thermostat at 200 ℃ for 24 h; centrifuging, washing, drying and grinding the suspension after the hydrothermal reaction to obtain the C-doped TiO2/MoS2And (3) powder.
Example 5
0.2g of PVP (average molecular weight 40000g/mol) was dissolved in 40mL of acetic acid and stirred well. Stirring for 0.5h, slowly dropwise adding 1mL of TBT into the obtained solution, violently stirring for 1h to obtain uniform milky white suspension, transferring the obtained milky white suspension to a reaction kettle, and placing the reaction kettle in a constant temperature box at 150 ℃ for hydrothermal reaction for 24 h; the milky white suspension after the hydrothermal reactionCentrifuging, washing, drying, grinding, and purifying in N2Calcining for 2h at 400 ℃ in the atmosphere to obtain C-doped TiO2And (3) powder.
0.2g of the prepared C-doped TiO was taken2Dispersing the powder in 40mL of deionized water to obtain a uniform suspension, adding 0.2g of ammonium molybdate and 0.2g of thiourea into the obtained suspension, stirring for 1h, performing ultrasonic dispersion for 0.5h, transferring the suspension to a reaction kettle, and performing hydrothermal reaction in a thermostat at 200 ℃ for 24 h; centrifuging, washing, drying and grinding the suspension after the hydrothermal reaction to obtain the C-doped TiO2/MoS2And (3) powder.
The TiO prepared by the method is observed by a transmission electron microscope, as shown in figure 1a2The morphology of (a) is flower-ball-shaped with a size of about 3 μm, as shown in FIG. 1b, flower-ball-shaped TiO2Is formed by polymerizing flaky petals, and the thickness of the petals is about 10 nm. As shown in FIG. 2, TiO prepared by the method2/MoS2The morphology of (A) is also flower ball shaped, MoS2Attached to TiO2Above, TiO2The size difference before and after compounding is not large. FIG. 3 shows TiO prepared by the method2/MoS2Enlarged view of the edge of (g), MoS can be seen2Is small in size and is uniformly dispersed in TiO2In the gap (b) of (c). FIG. 4 shows TiO prepared by the method2/MoS2High power TEM of (MoS), MoS can be seen2Is 6-7 layers of single-layer MoS2The stacked nano-sheets (scaly, the scale size is about 10 nm) have the interlayer spacing of 0.63 nm. FIG. 5 is an XRD pattern of the prepared material showing TiO by comparison with a standard card2Is anatase and monoclinic TiO2(B)，MoS2Is in a hexagonal crystalline phase. FIG. 6 is a cycle stability chart of the prepared material applied to a lithium ion battery, and from the chart, TiO with a specific morphology prepared by the invention can be seen2/MoS2The composite material has higher specific capacity and better cycling stability, and the specific capacity is 100mA g-1The current density of the alloy can reach 621mA h g after being circulated for 100 times-1The specific capacitance of the alloy is obviously superior to that of TiO with other morphologies2The related composite material has important significance in the application of the lithium ion battery.
Example 6
0.2g of PVP (average molecular weight 40000g/mol) was dissolved in 40mL of acetic acid and stirred well. Stirring for 0.5h, slowly dropwise adding 1mL of TBT into the obtained solution, violently stirring for 1h to obtain uniform milky white suspension, transferring the obtained milky white suspension to a reaction kettle, and placing the reaction kettle in a constant temperature box at 150 ℃ for hydrothermal reaction for 24 h; centrifuging, washing, drying and grinding the milky white suspension after the hydrothermal reaction in N2Calcining for 2h at 400 ℃ in the atmosphere to obtain C-doped TiO2And (3) powder.
0.2g of the prepared TiO was taken2Dispersing the powder in 40mL of deionized water to obtain a uniform suspension, adding 0.4g of ammonium molybdate and 0.4g of thiourea into the obtained suspension, stirring for 1h, performing ultrasonic dispersion for 0.5h, transferring the suspension to a reaction kettle, and performing hydrothermal reaction in a thermostat at 200 ℃ for 24 h; centrifuging, washing, drying and grinding the suspension after the hydrothermal reaction to obtain the C-doped TiO2/MoS2And (3) powder.
Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications or variations may be made without inventive faculty based on the technical solutions of the present invention.
Claims (15)
1. C-doped flower-ball-shaped TiO2/MoS2The preparation method of the composite material is characterized by comprising the following steps: firstly, acetic acid is taken as a solvent, polyvinylpyrrolidone with the average molecular weight of 40000g/moL is taken as a dispersant and a carbon source, tetrabutyl titanate is taken as a titanium source, and anatase and monoclinic TiO are prepared by adopting a solvothermal method and calcining2(B) Composed flower-ball-shaped TiO2Wherein the addition ratio of polyvinylpyrrolidone to acetic acid is 0.18-0.2 g to 40 mL; with synthetic flower-ball-shaped TiO2Using ammonium molybdate as a molybdenum source and thiourea as a sulfur source as a framework to obtain the C-doped flower-shaped TiO formed by the nano-sheets by a hydrothermal method2/MoS2Composite material of, wherein, TiO2And the mass ratio of ammonium molybdate to thiourea is 1: 1: 1; integral bodyThe diameter of the composite material is 2-3 mu m, and in the composite material, C-doped flower-ball-shaped TiO2Is formed by polymerizing flaky petals, the thickness of the petals is 8-12 nm, MoS2Is uniformly adhered to TiO2On the surface of the sheet petals;
the solvothermal reaction conditions are as follows: the temperature is 150 ℃, and the reaction time is 24 h;
the calcining condition is 400-550 ℃ and 1-3 h;
the hydrothermal reaction condition is 200 ℃, and the hydrothermal reaction lasts 24 hours.
2. The method of claim 1, comprising the steps of:
dissolving polyvinylpyrrolidone in acetic acid, and stirring to obtain a transparent solution;
adding tetrabutyl titanate into the transparent solution obtained in the step one, and stirring to obtain a suspension;
thirdly, carrying out solvothermal reaction on the suspension prepared in the second step, cooling after the solvothermal reaction is finished, separating, washing and drying to obtain a precipitate;
fourthly, calcining the precipitate prepared in the third step; then cooling to obtain TiO2Powder;
fifthly, the TiO obtained in the step IV2Adding the powder, ammonium molybdate and thiourea into water, stirring and ultrasonically dispersing to obtain uniform suspension;
sixthly, the suspension prepared in the fifth step is subjected to hydrothermal reaction, and is cooled after the hydrothermal reaction is finished, and then the solution is separated, washed and dried to obtain precipitate, namely the C-doped flower-ball-shaped TiO formed by the nanosheets2/MoS2A composite material.
3. The method of claim 2, wherein: in the first step, the stirring temperature is 25-30 ℃ when the materials are uniformly mixed; stirring for dissolving for 0.5-1 h.
4. The method of claim 3, wherein: in the first step, the stirring temperature is 25 ℃; the stirring dissolution time is 0.5 h.
5. The method of claim 2, wherein: in the second step, the stirring temperature is 25-30 ℃ when the mixture is uniformly mixed; and (3) dropwise adding tetrabutyl titanate into the transparent solution obtained in the step (i), wherein the dropwise adding time of tetrabutyl titanate is 10 min.
6. The method of claim 5, wherein: in the second step, the stirring temperature is 25 ℃.
7. The method of claim 2, wherein: in the third step, the detergent is deionized water and absolute ethyl alcohol, and is washed for 3-6 times;
the drying temperature is 50-60 ℃; the drying time was 12 h.
8. The method of claim 7, wherein: in the third step, the washing method comprises the following steps: the mixture was washed with deionized water 3 times and then with absolute ethanol 2 times.
9. The method of claim 7, wherein: in the third step, the drying temperature is 50 ℃.
10. The method of claim 2, wherein: in the fourth step, the calcination condition is 400 ℃, the calcination time is 2 hours, and the calcination time is N2Under the protection of gas.
11. The method of claim 2, wherein: in the fifth step, stirring and dispersing for 1 hour; ultrasonic treatment is carried out for 0.5 h.
12. The method of claim 2, wherein: sixthly, washing for 3-6 times by using deionized water and absolute ethyl alcohol as a washing agent; the drying temperature is 50-60 ℃; the drying time was 12 h.
13. The method of claim 12, wherein: in the step sixthly, the washing method comprises the following steps: the mixture was washed with deionized water 3 times and then with absolute ethanol 2 times.
14. The method of claim 12, wherein: in the step, the drying temperature is 50 ℃.
15. The C-doped flower-shaped TiO of any one of claims 1 to 142/MoS2The preparation method of the composite material is applied to the preparation of the lithium ion battery cathode material.
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| CN108878159A (en) * | 2018-05-23 | 2018-11-23 | 江苏大学 | 2D/1D structure molybdenum disulfide/bismuth sulfide nano composite material and preparation method thereof |
| CN109659512A (en) * | 2018-11-20 | 2019-04-19 | 济南大学 | A kind of flower ball-shaped TiO2/ MoO2 composite nano materials, preparation method and application |
| CN109967106B (en) * | 2019-04-23 | 2021-09-21 | 齐鲁工业大学 | Preparation method of two-dimensional structure composite material |
| CN110129112A (en) * | 2019-06-05 | 2019-08-16 | 青岛科技大学 | A kind of flower-shaped molybdenum disulfide/titanium dioxide nanometer composite particles ER fluid and preparation method thereof |
| CN111036190A (en) * | 2019-12-18 | 2020-04-21 | 吉林师范大学 | Preparation method of carbon-doped modified zinc oxide visible-light-driven photocatalyst |
| CN112290003B (en) * | 2020-11-04 | 2021-07-23 | 齐鲁工业大学 | Molybdenum disulfide titanium dioxide cathode material of lithium ion battery and preparation method and application thereof |
| CN113023778B (en) * | 2021-03-04 | 2022-12-02 | 青岛科技大学 | Molybdenum disulfide nanosheet coated titanium-based MOF (Metal organic framework) derived titanium dioxide composite material, and preparation method and application thereof |
| CN113078266B (en) * | 2021-03-18 | 2022-12-27 | 中北大学 | Polyacid-modified titanium dioxide nano material and preparation method and application thereof |
| CN114349054A (en) * | 2021-12-23 | 2022-04-15 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of flower-bud-shaped molybdenum sulfide-titanium dioxide-B composite material, product and application thereof |
| CN115318310B (en) * | 2022-07-18 | 2023-08-22 | 西安交通大学 | Preparation of C-doped MoS 2 @TiO 2 Method for aerogel catalysts |
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