CN113299893A - Molybdenum disulfide @ graphite alkyne composite material, and preparation method and application thereof - Google Patents
Molybdenum disulfide @ graphite alkyne composite material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a molybdenum disulfide @ graphite alkyne composite material. The preparation process has the characteristics of simple method, low cost and environmental friendliness. The invention also discloses a molybdenum disulfide @ graphite alkyne composite material prepared by the method, which has the advantages of good conductivity, large specific surface area and the like, and the sheet graphite alkyne increases the conductivity of the composite material and is MoS2The nucleation and growth of the template are provided, thereby avoiding MoS2And (4) agglomeration. The invention also discloses application of the molybdenum disulfide @ graphite alkyne composite material in a sodium ion battery, wherein the larger interlayer spacing is beneficial to embedding and releasing sodium ions without causing larger volume expansion, the rate capability and the circulation stability of the sodium ion battery are ensured, and the specific capacity of the sodium ion battery is improved.
Description
Technical Field
The invention relates to the field of electrochemical energy storage, and relates to a molybdenum disulfide @ graphite alkyne composite material, a preparation method and application.
Background
With the rapid development of modern socioeconomic, the demand of human beings on energy is increasing. However, the reserves of traditional energy sources such as coal, petroleum and natural gas are continuously reduced, and the problem of environmental pollution caused by the traditional energy supply system is increasingly serious, so that the development of the society and the further improvement of the quality of life of human beings are greatly limited. Therefore, the search for new energy, especially pollution-free clean energy, has become a research hotspot of modern research personnel.
The sodium ion battery is the same as the lithium ion battery, and is also a green energy storage mode. However, the lithium ion battery has the problems of low lithium abundance and uneven resource distribution, about 70 percent of the lithium ion battery is concentrated in south America, and 80 percent of the lithium ion battery in China depends on import. In addition, the potential safety hazard of the lithium ion battery is difficult to meet the application requirement of large-scale energy storage. Compared with lithium ion batteries, sodium ion batteries have the following advantages: (1) the sodium salt raw material has abundant reserves and low price, and compared with the ternary cathode material of the lithium ion battery, the adopted ferro-manganese nickel-based cathode material has half of the raw material cost; (2) due to the characteristics of sodium salt, the low-concentration electrolyte (the electrolyte with the same concentration and the sodium salt conductivity higher than that of the lithium electrolyte by about 20%) is allowed to be used, so that the cost is reduced; (3) sodium ions do not form an alloy with aluminum, and the cathode can adopt aluminum foil as a current collector, so that the cost can be further reduced by about 8 percent, and the weight can be reduced by about 10 percent; (4) the sodium ion battery is allowed to discharge to zero volts due to its no over-discharge characteristics. Compared with a lead-acid battery, the sodium ion battery with the same capacity has smaller volume, lighter weight, higher specific energy by more than 2 times and longer cycle life, and is possible to replace the lead-acid battery and gradually realize lead-free in the fields of low-speed electric vehicles, energy storage and the like in the future. However, the radius of the sodium ions is larger than that of the lithium ions, so that the sodium ions are more prone to be inserted into the space between anion interstitial sites in a larger cation octahedron or triangular prism configuration in the process of being inserted into the crystal structure of the material. Secondly, the relative atomic mass of sodium ions is greater than that of lithium ions, while the electrode potential of sodium ions is about 300mV higher than that of lithium ions, which factors in combination result in a sodium ion battery having a lower mass energy density than a lithium ion battery.
Therefore, in order to improve the energy density of the sodium ion battery, it is important to find a negative electrode material with high conductivity and larger gap so that sodium ions can be smoothly inserted and extracted.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the preparation method of the molybdenum disulfide @ graphite alkyne composite material, which has the characteristics of simple operation, mild reaction condition and high yield.
The second purpose of the invention is to provide the graphite alkyne and molybdenum disulfide @ graphite alkyne composite material obtained by the preparation method, and the graphite alkyne and molybdenum disulfide @ graphite alkyne composite material has the characteristics of high specific capacity, good rate capability, good cycle stability and the like.
The invention also aims to provide the application of the molybdenum disulfide @ graphite alkyne composite material in the sodium-ion battery.
One of the purposes of the invention is realized by adopting the following technical scheme:
a preparation method of a molybdenum disulfide @ graphite alkyne composite material comprises the steps of adding cobalt salt and pyridine into a hexa-ethynylbenzene solution, reacting, washing and drying to obtain graphite alkyne; and adding the prepared graphite alkyne into a sodium molybdate and thiourea solution, uniformly mixing, and carrying out hydrothermal reaction to obtain the molybdenum disulfide @ graphite alkyne composite material.
Further, the method specifically comprises the following steps:
(1) sequentially adding hexa (trimethylsilyl-ethynyl) benzene and tetra-n-butyl ammonium fluoride trihydrate into an organic solvent under the inert gas atmosphere, stirring for 15-30min at the temperature of 0-4 ℃, and washing and drying to obtain a hexaethynyl benzene solution;
(2) mixing the hexaethynylbenzene solution obtained in the step (1) with cobalt salt and pyridine, reacting at 40-50 ℃ for 10-15h, washing and drying to obtain the graphdiyne;
(3) and (3) adding the graphite alkyne obtained in the step (2) into a thiourea solution of sodium molybdate, uniformly mixing, carrying out hydrothermal reaction at the temperature of 160-200 ℃ for 16-20h, washing, and drying to obtain the molybdenum disulfide @ graphite alkyne composite material.
Further, in the step (1), the organic solvent is dichloromethane, and the proportion of the dichloromethane, the hexa (trimethylsilyl-ethynyl) benzene and the tetra-n-butylammonium fluoride is 40-60mL:80-100mg:1 mL; the cobalt salt is cobalt acetate, and the proportion of the hexa-ethynylbenzene solution to the cobalt salt and the pyridine in the step (2) is 1mg/mL to 20-25mg to 10-15 mL.
Further, the molar ratio of the graphyne to the sodium molybdate in the step (3) is 0.05-0.5: 1.
The second purpose of the invention is realized by adopting the following technical scheme:
the molybdenum disulfide @ graphite alkyne composite material is prepared by the preparation method.
The third purpose of the invention is realized by adopting the following technical scheme:
the application of the molybdenum disulfide @ graphite alkyne composite material in a sodium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a preparation method of a molybdenum disulfide @ graphite alkyne composite material, which is characterized in that hexaethynylbenzene solution, cobalt salt and pyridine are mixed and reacted to obtain graphite alkyne. And then mixing the prepared lamellar graphite alkyne with a molybdenum source and a sulfur source, and carrying out one-step solvothermal reaction to obtain the molybdenum disulfide @ graphite alkyne composite material. The preparation process of the graphdiyne has short period, and the lamellar graphdiyne can be obtained without any template, the method is simple, and the conditions are mild. The lamellar graphite alkyne provides abundant nucleation sites for the growth of molybdenum disulfide and effectively avoids the agglomeration of molybdenum disulfide. The preparation process has the characteristics of simple method, low cost and environmental friendliness, and the prepared product has small size and uniform appearance.
2. The invention also provides the graphite alkyne and molybdenum disulfide @ graphite alkyne composite material prepared by the preparation method. The graphdiyne prepared by the method is a thin porous nanosheet which has a folded structure and is communicated, so that the contact area with an electrolyte is increased, the active sites of an electrochemical reaction are increased, and the polarization is reduced. The molybdenum disulfide @ graphite alkyne composite material obtained by the method has the remarkable advantages of good conductivity, large specific surface area and the like, and the lamellar graphite alkyne increases the conductivity of the composite material on one hand and is MoS on the other hand2The nucleation and growth of the template are provided, thereby avoiding MoS2And (4) agglomeration. The molybdenum disulfide @ graphite alkyne composite material prepared by the method has the characteristics of large interlayer spacing, small size, uniform appearance and the like.
3. The invention also provides application of the molybdenum disulfide @ graphite alkyne composite material in a sodium ion battery. The molybdenum disulfide @ graphite alkyne composite material obtained by the invention is applied to a sodium ion battery cathode material, has good rate capability and has the current density of 1000mAh g-1When the specific capacity is up to 300mAh g-1. The molybdenum disulfide @ graphite alkyne composite material obtained by the preparation method disclosed by the invention has larger interlayer spacing, so that the insertion and the separation of sodium ions are facilitated, larger volume expansion is avoided, the rate capability and the circulation stability of a sodium ion battery are ensured, and the specific capacity of the sodium ion battery is improved; the nano lamellar structure has stronger surface activity, and is beneficial to the alloying of sodium ions, thereby improving the sodium storage performance. The lamellar structure is also favorable for the molybdenum disulfide @ graphite alkyne composite material to be fully soaked by the electrolyte, the contact area with the electrolyte is increased, and the polarization phenomenon of sodium ions in the charging and discharging process is weakened.
Drawings
FIG. 1 is an XRD (X-ray diffraction) pattern of a molybdenum disulfide @ graphite alkyne composite material prepared in example 1 of the invention;
fig. 2 is SEM and TEM images of the molybdenum disulfide @ graphite alkyne composite material prepared in example 1 of the present invention, where fig. 2a, 2b, and 2c are SEM images of graphite alkyne, fig. 2d and 2e are TEM images of the molybdenum disulfide @ graphite alkyne composite material, and fig. 2f is an HRTEM image of the molybdenum disulfide @ graphite alkyne composite material;
FIG. 3 is a Raman diagram of graphdiyne prepared in example 1 of the present invention;
fig. 4 is a graph of rate performance of the molybdenum disulfide @ graphite alkyne composite material prepared in example 1 of the present invention as a sodium ion battery negative electrode material at different current densities;
FIG. 5 shows that the molybdenum disulfide @ graphite alkyne composite material prepared in example 1 of the present invention is used as a negative electrode material of a sodium ion battery at a current density of 1000mA g-1Graph of the cycle performance of (a).
Detailed Description
The present invention will be further described with reference to the accompanying drawings and the detailed description, and it should be noted that any combination of the embodiments or technical features described below can be used to form a new embodiment without conflict.
Example 1
Preparing a molybdenum disulfide @ graphite alkyne composite material:
(1) to a reaction flask containing 50mL of Dichloromethane (DCM) were added, in order, 100mg of hexakis (trimethylsilyl-ethynyl) benzene (HEB-TMS) and 1mL of tetra-n-butylammonium fluoride Trihydrate (TBAF) under a nitrogen atmosphere, and stirred at 0 ℃ for 15min to obtain a mixture, and then the above mixture was washed twice with 50mL of deionized water, and then dried over anhydrous magnesium sulfate to obtain a hexaethynylbenzene solution.
(2) Dripping the hexaethynylbenzene solution obtained in the step (1) into a round bottle containing cobalt acetate and pyridine, wherein the addition ratio of the hexaethynylbenzene solution to the cobalt acetate and the pyridine is 1mg/mL:25mg:10mL, and reacting for 12h at 40 ℃. After the reaction is finished, the graphite alkyne (GDY) powder is obtained after the graphite alkyne is washed by pyridine, dimethylformamide, 1M HCl and deionized water in sequence and dried.
(3) Adding the graphyne obtained in the step (2) into 1mol/L thiourea solution of sodium molybdate, wherein the molar ratio of the graphyne to the sodium molybdate is 0.5:1, carrying out ultrasonic treatment for 1h, and then uniformly mixing the solutionTransferred to a 20mL reaction vessel and reacted at 200 ℃ for 20 h. After the reaction is finished, washing and drying the precipitate to obtain molybdenum disulfide @ graphite alkyne (MoS)2@ GDY) composite powder.
Example 2
Preparing a molybdenum disulfide @ graphite alkyne composite material:
(1) to a reaction flask containing 40mL of Dichloromethane (DCM) were added in this order 80mg of hexa (trimethylsilyl-ethynyl) benzene (HEB-TMS) and 1mL of tetra-n-butylammonium fluoride Trihydrate (TBAF) under a nitrogen atmosphere, and stirred at 4 ℃ for 30min to obtain a mixture, and then the above mixture was washed twice with 50mL of deionized water and then dried over anhydrous magnesium sulfate to obtain a hexaethynylbenzene solution.
(2) Dripping the hexaethynylbenzene solution obtained in the step (1) into a round bottle containing cobalt acetate and pyridine, wherein the addition ratio of the hexaethynylbenzene solution to the cobalt acetate and the pyridine is 1mg/mL:20mg:15mL, and reacting for 10h at 40 ℃. After the reaction is finished, the graphite alkyne (GDY) powder is obtained after the graphite alkyne is washed by pyridine, dimethylformamide, 1M HCl and deionized water in sequence and dried.
(3) And (3) adding the graphyne obtained in the step (2) into 1mol/L thiourea solution of sodium molybdate, wherein the molar ratio of the graphyne to the sodium molybdate is 0.05:1, carrying out ultrasonic treatment for 1h, transferring the uniformly mixed solution into a 20mL reaction kettle, and reacting for 16h at 160 ℃. After the reaction is finished, washing and drying the precipitate to obtain molybdenum disulfide @ graphite alkyne (MoS)2@ GDY) composite powder.
Example 3
Preparing a molybdenum disulfide @ graphite alkyne composite material:
(1) to a reaction flask containing 60mL of Dichloromethane (DCM) were added 90mg of hexa (trimethylsilyl-ethynyl) benzene (HEB-TMS) and 1mL of tetra-n-butylammonium fluoride Trihydrate (TBAF) in this order under a nitrogen atmosphere, and stirred at 0 ℃ for 20min to obtain a mixture, and then the above mixture was washed twice with 50mL of deionized water and then dried over anhydrous magnesium sulfate to obtain a hexaethynylbenzene solution.
(2) Dripping the hexaethynylbenzene solution obtained in the step (1) into a round bottle containing cobalt acetate and pyridine, wherein the addition ratio of the hexaethynylbenzene solution to the cobalt acetate and the pyridine is 1mg/mL:20mg:10mL, and reacting for 15h at 50 ℃. After the reaction is finished, the graphite alkyne (GDY) powder is obtained after the graphite alkyne is washed by pyridine, dimethylformamide, 1M HCl and deionized water in sequence and dried.
(3) And (3) adding the graphyne obtained in the step (2) into 1mol/L thiourea solution of sodium molybdate, wherein the molar ratio of the graphyne to the sodium molybdate is 0.1:1, carrying out ultrasonic treatment for 1h, transferring the uniformly mixed solution into a 20mL reaction kettle, and reacting for 18h at 180 ℃. After the reaction is finished, washing and drying the precipitate to obtain molybdenum disulfide @ graphite alkyne (MoS)2@ GDY) composite powder.
Comparative example 1
Comparative example 1 differs from example 1 in that: and (3) dispersing the purchased commercial graphite alkyne blocks in an ethanol solution for ultrasonic dispersion, performing ultrasonic treatment in a water bath at the temperature of 8 ℃ for 4 days, and centrifuging to obtain graphite alkyne nanosheets with different thicknesses, wherein the graphite alkyne synthesized in the step (2) in the embodiment 1 is replaced, and the rest is the same as that in the embodiment 1.
Comparative example 2
Comparative example 2 differs from example 1 in that: firstly, preparing molybdenum disulfide from a sodium molybdate and thiourea solution by a hydrothermal method, and then mixing the molybdenum disulfide and a hexaethynylbenzene solution to prepare the molybdenum disulfide @ graphite alkyne composite material, wherein the rest is the same as that in the embodiment 1.
Comparative example 3
Comparative example 3 differs from example 1 in that: and (3) putting the washed and dried copper sheet into a mixed solvent of acetone, anhydrous pyridine and tetramethylethylenediamine (the volume ratio of the acetone to the anhydrous pyridine to the tetramethylethylenediamine is 100:5:1), adding a hexaethynylbenzene monomer solution dissolved by acetone into the mixed solvent under an argon atmosphere, and reacting the whole system for 20 hours at 60 ℃. And (3) washing the copper sheet by using ethanol and acetone after the reaction is finished, and carrying out ultrasonic treatment on the powder growing on the copper sheet to obtain the graphite alkyne powder. The rest is the same as in example 1.
Comparative example 4
Firstly, graphene is dissolved in N, N-dimethylformamide to obtain a graphene solution through ultrasound, then sodium molybdate and thiourea are added to obtain a mixed solution, wherein the adding proportion of the graphene, the sodium molybdate and the thiourea is the same as that of the grapyne, the sodium molybdate and the thiourea in the embodiment 1. And carrying out solvothermal reaction on the obtained mixed solution at 200 ℃ for 20h to prepare the molybdenum disulfide @ graphene composite material.
Experimental example 1
The molybdenum disulfide @ graphite alkyne obtained in examples 1 to 3 is subjected to systematic study on the morphology, components and microstructure by modern nanometer test analysis technologies such as XRD, SEM, TEM, HRTEM and the like, and the results are as follows:
the XRD characterization of the product obtained in each example was performed first (FIG. 1), and the XRD spectrum and MoS were combined2And the result shows that the molybdenum disulfide @ graphite alkyne compound is successfully obtained. The graphdine and the molybdenum disulfide @ graphdine obtained in example 1 are further characterized by SEM (fig. 2) and TEM (fig. 2), the graphs show that the graphdine is a thin porous nanosheet with a folded structure and is communicated with the graphene, the molybdenum disulfide @ graphdine composite material is further analyzed in microstructure, and fig. 2f can clearly show that the lattice stripes of the nanoparticles have two different orientations, the lattice spacings are 0.365nm and 0.620nm respectively, and the two orientations correspond to the crystal face of the graphdine (002) and MoS respectively2(002) Crystal face, Raman spectrum characterization of the graphdine obtained in example 1, as shown in FIG. 3, 3 shock absorption peaks of the graphdine were observed at 1386cm-1、1571cm-1、 2179cm-1。
Experimental example 2
Application of molybdenum disulfide @ graphite alkyne composite material in sodium ion battery
Mixing the molybdenum disulfide @ graphite alkyne composite material obtained in the example 1 with acetylene black and sodium carboxymethylcellulose according to the mass ratio of 8:1:1, adding a proper amount of deionized water, stirring uniformly to be pasty, uniformly coating on a copper foil with the thickness of 10-20 microns by using an automatic coating dryer, drying at 60 ℃ for 10min, drying at 100 ℃ under a vacuum condition for 24h, punching to prepare a circular electrode plate with the diameter of 16mm, and transferring a weighing mark of the prepared electrode plate into a glove box filled with argon for later use.
The sodium ion battery obtained by the invention takes a sodium sheet as a counter electrode, and the molybdenum disulfide is contained in the sodium sheet obtained by the stepsThe @ graphite alkyne composite material has a circular electrode slice as a working electrode (the load of active substances is 1mg), a microporous polypropylene membrane as a diaphragm and electrolyte concentration of 1mol/L, wherein NaClO4As solute, EC, DMC, FEC with a volume ratio of 1:1:1 are solutes. The battery assembling process is carried out in a glove box filled with high-purity argon, the battery type is a CR 2016 type button battery, and the opening sealing is carried out after the assembling is finished.
And (4) placing the battery assembled in the step for 6-12 h, and then carrying out electrochemical test. The cycle test of the experimental sodium-ion battery is completed on a blue-electricity battery test system CTA (CT2001A blue-electricity electronic products Co., Ltd., Wuhan city) at room temperature, and the voltage range is 0.01-3.0V. The electrochemical AC impedance test was performed at an electrochemical workstation (CHI660D) at a frequency in the range of 0.1-100 KHz.
The test result is shown in fig. 4, and the rate performance of the sodium ion battery using the molybdenum disulfide @ graphite alkyne composite material prepared in example 1 as the working electrode is tested under different current densities, when the current densities are respectively 200mA g-1、500mA g-1、 800mA g-1、1000mA g-1The specific capacity of the sodium ion battery is 400mAh g respectively-1、380mAh g-1、330mAh g-1、300mAh g-1From this, it is understood that the specific capacity of the material decreases in order as the current density increases. But when the current density is restored to 200mA g-1When the specific capacity is recovered to 400mAh g-1. Therefore, the sodium ion battery taking the molybdenum disulfide @ graphite alkyne composite material prepared by the method as the working electrode has good rate capability.
FIG. 5 shows that the current density of the sodium-ion battery using the molybdenum disulfide @ graphite alkyne composite material prepared in example 1 as the working electrode is 1000mAh g-1Graph of the cycle performance of (1), which shows the current density of 1000mAh g-1After the circulation for 100 weeks, the specific capacity of the sodium-ion battery is 230mAh g-1The attenuation rate is small. The coulomb efficiency of the sodium ion battery in the circulating process is kept to be about 100 percent, which shows that the sodium ion battery obtained by the invention has good circulating stability and higher coulomb efficiency.
The performance of the composites obtained in examples 2 to 3 and comparative examples 1 to 4 as the negative electrode material of sodium ion batteries was measured in the same manner as in experimental example 2, and the results are shown in table 1.
TABLE 1
From table 1, the molybdenum disulfide @ graphite alkyne composite material prepared by the method has larger specific capacity under different current densities. Compared with the example 1, the commercial graphite alkyne blocks are layered in an ultrasonic mode, the reaction period is long, and the laminar graphite alkyne obtained by ultrasonic is uneven, thick and incapable of being MoS2The growth of the graphene provides more effective attachment sites, the specific surface area of the graphite alkyne obtained by ultrasonic is small, the graphite alkyne is not in sufficient contact with electrolyte, and sodium ions have larger electrochemical polarization and concentration polarization phenomena in the charging and discharging processes of the battery, so that the specific capacity under different current densities is exerted to be small.
Compared with the example 1, the preparation method of the molybdenum disulfide @ graphite alkyne composite material comprises the steps of firstly preparing the molybdenum disulfide, and then mixing the molybdenum disulfide and the hexaethynylbenzene serving as the precursor of the graphite alkyne. Compared with the embodiment 1, the molybdenum disulfide nano lamellar structure prepared in the comparative example 2 is very easy to agglomerate, the contact between an electrode material and an electrolyte cannot be improved to the greatest extent by firstly synthesizing molybdenum disulfide and then compounding the molybdenum disulfide with graphite alkyne, and the molybdenum disulfide nano lamellar structure serving as a negative electrode material of a sodium ion battery cannot realize the efficient intercalation and deintercalation process of sodium ions, so that the specific capacity under different current densities cannot be effectively exerted.
Comparative example 3 the specific capacity of the resulting composite was slightly lower than that of example 1, but the process for preparing graphyne of comparative example 3 required the use of copper sheets as the template for growing graphyne, which was more complicated than that of example 1. Compared with the embodiment 1, the graphene is used for replacing the graphene, and the obtained molybdenum disulfide @ graphene composite material has a more serious agglomeration phenomenon compared with the molybdenum disulfide @ graphene composite material, is not beneficial to the process of embedding and removing sodium ions, and therefore, the specific capacity is slightly lower under different current densities.
In conclusion, the invention provides a preparation method of the molybdenum disulfide @ graphite alkyne composite material, and the lamellar graphite alkyne is obtained by mixing and reacting hexaethynylbenzene solution, cobalt salt and pyridine. The preparation process is simple to operate, any template is not needed, the prepared graphdiyne is a thin porous nanosheet which has a folded structure and is communicated, the contact area with an electrolyte is increased, the active sites of electrochemical reaction are increased, and polarization is reduced.
The molybdenum disulfide @ graphite alkyne composite material is prepared by a simple one-step solvothermal method, and the conductivity of the composite material is increased on the one hand by the lamellar graphite alkyne, namely MoS on the other hand2The nucleation and growth of the template are provided, thereby avoiding MoS2And (4) agglomeration. The molybdenum disulfide @ graphite alkyne composite material prepared by the method has the advantages of large interlayer spacing, small size, uniform appearance, low cost, no toxicity, no pollution and the like. The molybdenum disulfide @ graphite alkyne composite material obtained by the invention is applied to a sodium ion battery cathode material, has good rate performance and circulation stability, and has a current density of 1000mAh g-1When the specific capacity is up to 300mAh g-1The attenuation is smaller. The molybdenum disulfide @ graphite alkyne composite material obtained by the method has larger interlayer spacing, is more favorable for the embedding and the separation of sodium ions without causing larger volume expansion, and ensures the rate capability and the cycle stability of a sodium ion battery; the nano-sheet structure has stronger surface activity, and is beneficial to the alloying of sodium ions, thereby improving the sodium storage performance. The lamellar structure is also favorable for the molybdenum disulfide @ graphite alkyne composite material to be fully soaked by the electrolyte, the contact area with the electrolyte is increased, and the polarization phenomenon of sodium ions in the charging and discharging process is weakened.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (6)
1. A preparation method of a molybdenum disulfide @ graphite alkyne composite material is characterized in that cobalt salt and pyridine are added into a hexa-ethynylbenzene solution, and after reaction, the graphite alkyne is obtained through washing and drying; and adding the prepared graphite alkyne into a sodium molybdate and thiourea solution, uniformly mixing, and carrying out hydrothermal reaction to obtain the molybdenum disulfide @ graphite alkyne composite material.
2. The preparation method of the molybdenum disulfide @ graphite alkyne composite material as defined in claim 1, comprising the steps of:
(1) sequentially adding hexa (trimethylsilyl-ethynyl) benzene and tetra-n-butylammonium fluoride trihydrate to an organic solvent under an inert gas atmosphere, stirring for 15-30min at 0-4 ℃, and washing and drying to obtain a hexaethynyl benzene solution;
(2) mixing the hexaethynylbenzene solution obtained in the step (1) with cobalt salt and pyridine, reacting at 40-50 ℃ for 10-15h, washing and drying to obtain the graphdiyne;
(3) and (3) adding the graphite alkyne obtained in the step (2) into a thiourea solution of sodium molybdate, uniformly mixing, carrying out hydrothermal reaction at 160-200 ℃ for 16-20h, washing, and drying to obtain the molybdenum disulfide @ graphite alkyne composite material.
3. The preparation method of molybdenum disulfide @ graphite alkyne composite material as claimed in claim 2, wherein the organic solvent in the step (1) is dichloromethane, and the ratio of dichloromethane, hexa (trimethylsilyl-ethynyl) benzene and tetra-n-butylammonium fluoride is 40-60mL:80-100mg:1 mL; the cobalt salt is cobalt acetate, and the proportion of the hexaethynylbenzene solution to the cobalt salt and the pyridine in the step (2) is 1mg/mL to 20-25mg to 10-15 mL.
4. The method for preparing the molybdenum disulfide @ graphite alkyne composite material as defined in claim 2, wherein the molar ratio of graphite alkyne to sodium molybdate in the step (3) is 0.05-0.5: 1.
5. Molybdenum disulfide @ graphite alkyne composite material, characterized in that it is obtained by a process as claimed in any one of claims 1 to 4.
6. The use of molybdenum disulfide @ graphite alkyne composite as in claim 5 in a sodium ion battery.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114050241A (en) * | 2021-11-10 | 2022-02-15 | 南京大学 | Molybdenum disulfide @ carbon-based nanocage composite material with threshold-limiting structure and preparation method and application thereof |
| CN114203952A (en) * | 2021-11-24 | 2022-03-18 | 江苏大学 | Sodium ion battery cathode, preparation method and application |
| CN114570390A (en) * | 2022-04-13 | 2022-06-03 | 新疆大学 | Preparation method of thin-layer oxygen-containing graphite alkyne-coated metal composite catalyst |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102142541A (en) * | 2011-02-25 | 2011-08-03 | 浙江大学 | High capacity and stable cyclic performance lithium ion battery electrode and preparation method thereof |
| CN103943373A (en) * | 2014-03-27 | 2014-07-23 | 中国科学院化学研究所 | Application of graphdiyne in metal ion batteries and super-capacitors |
| CN105161691A (en) * | 2015-10-10 | 2015-12-16 | 岭南师范学院 | Preparation method of less-layer MoS2/phosphorus-doped graphene electrochemical sodium-storage combined electrode |
| CN107352627A (en) * | 2017-06-02 | 2017-11-17 | 深圳大学 | Water warfare composite and its preparation method and application |
| CN108807835A (en) * | 2017-04-28 | 2018-11-13 | 福建新峰二维材料科技有限公司 | The preparation method and battery of one type of metal graphene negative material |
| CN108987750A (en) * | 2018-05-28 | 2018-12-11 | 中国科学院青岛生物能源与过程研究所 | It a kind of preparation of carbon nanomaterial and its is applied on sodium-ion battery |
| CN109082677A (en) * | 2018-09-11 | 2018-12-25 | 太原师范学院 | A kind of application of the Bipolar Membrane of area load graphite alkene in photoelectrocatalysis water decomposition |
| CN109626353A (en) * | 2018-12-27 | 2019-04-16 | 中山大学 | A kind of cm size grade graphite alkene and its preparation method and application using the synthesis of liquid-liquid interface polymerization reaction |
| CN109713258A (en) * | 2018-12-06 | 2019-05-03 | 盐城工学院 | A kind of cobalt doped molybdenum sulfide-graphene-carbon composite and its preparation method and application |
| CN109860536A (en) * | 2018-12-18 | 2019-06-07 | 中科廊坊过程工程研究院 | A kind of lithium-rich manganese base material and its preparation method and application |
| CN110729297A (en) * | 2019-10-24 | 2020-01-24 | 北京科技大学 | Graphite alkyne and molybdenum disulfide combined nonvolatile multilevel photoelectric memory and preparation |
| CN111333061A (en) * | 2018-12-18 | 2020-06-26 | 青岛科技大学 | Preparation method of graphyne film and graphyne film |
-
2021
- 2021-05-22 CN CN202110561484.7A patent/CN113299893B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102142541A (en) * | 2011-02-25 | 2011-08-03 | 浙江大学 | High capacity and stable cyclic performance lithium ion battery electrode and preparation method thereof |
| CN103943373A (en) * | 2014-03-27 | 2014-07-23 | 中国科学院化学研究所 | Application of graphdiyne in metal ion batteries and super-capacitors |
| CN105161691A (en) * | 2015-10-10 | 2015-12-16 | 岭南师范学院 | Preparation method of less-layer MoS2/phosphorus-doped graphene electrochemical sodium-storage combined electrode |
| CN108807835A (en) * | 2017-04-28 | 2018-11-13 | 福建新峰二维材料科技有限公司 | The preparation method and battery of one type of metal graphene negative material |
| CN107352627A (en) * | 2017-06-02 | 2017-11-17 | 深圳大学 | Water warfare composite and its preparation method and application |
| CN108987750A (en) * | 2018-05-28 | 2018-12-11 | 中国科学院青岛生物能源与过程研究所 | It a kind of preparation of carbon nanomaterial and its is applied on sodium-ion battery |
| CN109082677A (en) * | 2018-09-11 | 2018-12-25 | 太原师范学院 | A kind of application of the Bipolar Membrane of area load graphite alkene in photoelectrocatalysis water decomposition |
| CN109713258A (en) * | 2018-12-06 | 2019-05-03 | 盐城工学院 | A kind of cobalt doped molybdenum sulfide-graphene-carbon composite and its preparation method and application |
| CN109860536A (en) * | 2018-12-18 | 2019-06-07 | 中科廊坊过程工程研究院 | A kind of lithium-rich manganese base material and its preparation method and application |
| CN111333061A (en) * | 2018-12-18 | 2020-06-26 | 青岛科技大学 | Preparation method of graphyne film and graphyne film |
| CN109626353A (en) * | 2018-12-27 | 2019-04-16 | 中山大学 | A kind of cm size grade graphite alkene and its preparation method and application using the synthesis of liquid-liquid interface polymerization reaction |
| CN110729297A (en) * | 2019-10-24 | 2020-01-24 | 北京科技大学 | Graphite alkyne and molybdenum disulfide combined nonvolatile multilevel photoelectric memory and preparation |
Non-Patent Citations (5)
| Title |
|---|
| BIN-WEI YAO等: "Non-Volatile Electrolyte-Gated Transistors Based on Graphdiyne/MoS2 with Robust Stability for Low-Power Neuromorphic Computing and Logic-In-Memory", 《ADV. FUNCT. MATER.》, vol. 31, no. 25, 17 April 2021 (2021-04-17), pages 1 - 12 * |
| JUAN GAO等: "Robust C–S bond integrated graphdiyne-MoS2 nanohybrids for enhanced lithium storage capability", 《CHEMICAL ENGINEERING JOURNAL》, vol. 373, 15 May 2019 (2019-05-15), pages 660 - 667 * |
| 周钰皓: "基于碳基二维材料的平面异质结的电子输运性质的研究", 《中国优秀硕士学位论文全文数据库（工程科技I辑）》, vol. 2021, no. 02, 15 February 2021 (2021-02-15), pages 020 - 1184 * |
| 白利忠等: "MoS2/石墨烯复合材料的制备及其电化学性能", 《功能材料》 * |
| 白利忠等: "MoS2/石墨烯复合材料的制备及其电化学性能", 《功能材料》, no. 09, 29 September 2018 (2018-09-29), pages 213 - 217 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114050241A (en) * | 2021-11-10 | 2022-02-15 | 南京大学 | Molybdenum disulfide @ carbon-based nanocage composite material with threshold-limiting structure and preparation method and application thereof |
| CN114203952A (en) * | 2021-11-24 | 2022-03-18 | 江苏大学 | Sodium ion battery cathode, preparation method and application |
| CN114570390A (en) * | 2022-04-13 | 2022-06-03 | 新疆大学 | Preparation method of thin-layer oxygen-containing graphite alkyne-coated metal composite catalyst |
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