CN114520327A - Preparation method and application of mesoporous molybdenum disulfide/carbon composite material - Google Patents

Preparation method and application of mesoporous molybdenum disulfide/carbon composite material Download PDF

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CN114520327A
CN114520327A CN202011311948.0A CN202011311948A CN114520327A CN 114520327 A CN114520327 A CN 114520327A CN 202011311948 A CN202011311948 A CN 202011311948A CN 114520327 A CN114520327 A CN 114520327A
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molybdenum disulfide
carbon composite
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carbon
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CN114520327B (en
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邓德会
魏泽宇
涂云川
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Dalian Institute of Chemical Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H01M4/624—Electric conductive fillers
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Abstract

The invention discloses a preparation method of a mesoporous molybdenum disulfide/carbon composite material and application of the mesoporous molybdenum disulfide/carbon composite material as a negative active material in a sodium ion battery system. Based on a coprecipitation and high-temperature solid-phase reaction method, molybdenum salt, a sulfur source and a carbon source are simultaneously deposited on the surface of the SBA-15, and a target product is obtained by high-temperature treatment and removal of the SBA-15 template by using a hydrofluoric acid solution. The method is a universal method for preparing the molybdenum disulfide/carbon composite material, and has the characteristics of simple operation and large-scale preparation. The prepared molybdenum disulfide/carbon composite material keeps the original pore structure of SBA-15, the structures of molybdenum disulfide and carbon are excellently compounded together, and the molybdenum disulfide/carbon composite material shows excellent performance and wide application prospect when being used as a cathode material of a sodium ion battery.

Description

Preparation method and application of mesoporous molybdenum disulfide/carbon composite material
Technical Field
The invention relates to the technical field of electrochemical materials, in particular to a preparation method and application of a mesoporous molybdenum disulfide/carbon composite material.
Background
Since the introduction of the first commercial lithium ion battery by the company sony of japan in 1991, the development of lithium batteries has been rapidly progressing (Journal of Power sources.100.101 (2001)). With the continuous development of society, the living standard of people is increasingly improved, and the demand of people on lithium ion batteries is also increasingly greater. Especially in recent years, expansion and development of lithium batteries from portable electronic devices (cell phones, watches, computers, etc.) to large-scale energy storage fields represented by electric vehicles have made a serious examination on the supply of lithium batteries (ionics.20.1651 (2014)). However, the shortage of natural lithium resources and the non-uniformity of the global lithium source distribution cannot meet the requirement of large-scale development of lithium batteries in the future (Nature chemistry.2.510 (2010)). Sodium in the same period as lithium in the periodic table has very similar physicochemical properties to lithium, while sodium is abundant in earth and widely distributed, and the two battery systems also have high similarity in working principle (Advanced Energy materials.2.710 (2012)). As one of the most potential secondary battery replacement systems of the lithium ion battery, the development of a high-performance sodium ion battery is of great significance for meeting the requirement of large-scale energy storage in the future.
The electrode material plays an important role in determining the performance of the battery as an important component of the sodium-ion battery. The electrode material comprises a positive electrode material and a negative electrode material. In terms of positive electrode materials, many of the positive electrode materials in sodium ion battery systems can be derived from lithium battery systems, which tend to exhibit electrochemical properties similar to those of the positive electrode materials in lithium battery systems. In the aspect of the negative electrode material, since the ionic radius of sodium is larger than that of lithium, many negative electrode materials for lithium battery systems cannot be directly used in sodium battery systems, which seriously hinders the progress of commercialization of sodium ion battery systems (Journal of Power sources.243.585 (2013)). Molybdenum disulfide is one of the most promising negative electrode materials in a sodium ion battery system, and the specific S-Mo-S two-dimensional layered structure and the interlayer spacing of 0.62nm ensure the effective transmission of sodium ions in the charge and discharge processes when the molybdenum disulfide is used as a sodium ion negative electrode material (Nano energy.20.1 (2016)). The molybdenum disulfide stores sodium by an intercalation-conversion mechanism and has the concentration of 670mAh g-1The theoretical specific capacity of (a). However, molybdenum disulfide has poor conductivity and is accompanied by a huge volume expansion effect in the charge and discharge processes, so that the molybdenum disulfide has short cycle life and poor rate capability when used as a sodium electricity negative electrode material (Nano energy.41.66 (2017)). One possible solution is to compound molybdenum disulfide with carbon materials to enhance the properties of the material, and related studies have also shown that the introduction of carbon can indeed enhance the conductivity and stability of the material (Advanced Functional materials.27.1702116 (2017)). However, these composites are often prepared by growing a carbon skeleton as a templateMolybdenum sulfide, still fails to meet the practical requirements in terms of capacity and cycle performance, and methods for in situ preparation of carbon and molybdenum disulfide composites remain difficult to study. Thus, molybdenum disulfide/carbon composites with higher capacity and long cycle stability need to be further explored.
Disclosure of Invention
According to the invention, precursors of molybdenum disulfide and carbon are co-deposited on the surface of SBA-15, and after high-temperature solid-phase reaction, a hydrofluoric acid solution is used for removing an SBA-15 template to obtain the molybdenum disulfide/carbon composite material. The prepared molybdenum disulfide/carbon composite material keeps the original pore structure of SBA-15, and the structures of molybdenum disulfide and carbon are excellently compounded together to show excellent electrochemical performance as a cathode material of a sodium ion battery.
The technical means adopted by the invention are as follows:
a preparation method of a molybdenum disulfide/carbon composite material comprises the following steps:
(1) depositing a molybdenum salt, a sulfur source and a carbon source on the surface of the SBA-15 by using a coprecipitation method to obtain a precursor mixture;
(2) carrying out programmed heating treatment on the precursor mixture under an inert atmosphere to reach the end point temperature, and keeping the temperature; molybdenum salt reacts with a sulfur source to generate molybdenum disulfide, and a carbon source is carbonized into carbon;
(3) carrying out temperature programming treatment on the product obtained in the step (2) in a reducing atmosphere to reach the end temperature, and keeping the temperature; the end temperature is higher than the end temperature of the step (2);
(4) and (4) carrying out acid treatment on the product obtained in the step (3), and carrying out acid etching to remove SBA-15 so as to obtain the molybdenum disulfide/carbon composite material.
Further, in the step (1), the mass ratio of the molybdenum salt, the sulfur source and the carbon source is 1:1-3: 0.1-2.
Further, the molybdenum salt is one of ammonium tetrathiomolybdate, ammonium molybdate, ammonium phosphomolybdate, sodium phosphomolybdate or sodium molybdate; the sulfur source is one of thiourea, sodium sulfide, potassium sulfide, ammonium sulfide or thioacetamide; the carbon source is one of soluble starch, sucrose, anhydrous glucose, dopamine hydrochloride, melamine or dicyandiamide.
Further, the codeposition temperature is 60-100 ℃, and the time is 12-24 h.
Further, in the step (2), the inert atmosphere is one of argon, nitrogen or helium; the temperature programming treatment is to heat the temperature to the end point temperature of 400-550 ℃ at the heating rate of 1-10 ℃/min and then preserve the temperature for 2-5 h.
Further, in the step (3), the reducing atmosphere is a mixed atmosphere of hydrogen and an inert atmosphere, and the percentage of hydrogen in the mixed atmosphere is 5% -20%; the temperature programming treatment is to heat the material at a heating rate of 5-15 ℃/min to a final temperature of 700-900 ℃ and to preserve the heat for 0.5-2.5 h.
Further, in the step (4), the acid in the acid treatment is a hydrofluoric acid solution with the concentration of 5% -20%, and the acid treatment time is 6-12 hours; and after washing, drying at the temperature of 60-80 ℃ for 12-24 h.
The invention also provides the molybdenum disulfide/carbon composite material prepared by the preparation method.
Further, the molybdenum disulfide/carbon composite material has mesoporous structure characteristics similar to SBA-15.
The invention also provides an application of the molybdenum disulfide/carbon composite material as a negative electrode material in a sodium ion battery system.
Compared with the prior art, the invention has the following advantages:
1. the reaction process of the invention can synchronously generate molybdenum disulfide and carbon, and compared with a molybdenum disulfide/carbon compound prepared by a simple carbon coating method, the molybdenum disulfide/carbon compound material prepared by the invention has more stable structure.
2. The mesoporous molybdenum disulfide/carbon composite material prepared by the method well keeps the mesoporous characteristics of the original template SBA-15. When the porous structures are used as the negative electrode material of the sodium-ion battery, the porous structures not only increase the contact area of the material and electrolyte, are beneficial to the rapid transmission of sodium ions in the charge and discharge process, but also enhance the structural stability of the material in the long-time charge and discharge process, and show excellent electrochemical performance when the porous structures are used as the negative electrode material of the sodium-ion battery.
3. The preparation method is simple, the application range is wide, and the obtained mesoporous molybdenum disulfide/carbon composite material has potential application prospects in the field of energy storage.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a scanning electron micrograph of the molybdenum disulfide/carbon composite of example 1.
FIG. 2 is a transmission electron micrograph of the molybdenum disulfide/carbon composite of example 1.
FIG. 3 shows that the voltage range of the molybdenum disulfide/carbon composite material in example 1 is 0.4-3V, and the current density is 100 mA-g-1Performance graph of time.
FIG. 4 shows that the voltage range of the molybdenum disulfide/carbon composite material in example 2 is 0.01-3V, and the current density is 500 mA-g-1Performance graph of time.
FIG. 5 shows that the voltage range of the molybdenum disulfide/carbon composite material in example 2 is 0.01-3V, and the current density is 1 A.g-1Performance graph of time.
FIG. 6 is a high resolution SEM image of the Mo disulfide/C composite material of example 3.
FIG. 7 shows that the voltage range of the molybdenum disulfide/carbon composite material in example 3 is 0.01-3V, and the current density is 200 mA-g-1Performance graph of time.
FIG. 8 is a graph of the rate capability of the molybdenum disulfide/carbon composite material of example 3 at a test voltage of 0.01-3V.
FIG. 9 shows that the voltage range of the molybdenum disulfide/carbon composite material in example 3 is 0.01-3V, and the current density is 1 A.g-1Performance graph of time.
FIG. 10 shows the voltage range of 0.01-3V and the current density of 2 A.g for the molybdenum disulfide/carbon composite material of example 3-1Performance graph of time.
FIG. 11 is a graph comparing the performance of the molybdenum disulfide/carbon composite materials in examples 3, 4 and 5 in the voltage measurement range of 0.01-3V and the current density of 1 A.g-1.
FIG. 12 shows that the voltage range of the molybdenum disulfide/carbon composite material in comparative example 1 is 0.01-3V, and the current density is 500 mA-g-1Performance graph of time.
Detailed Description
The whole process of preparing the materials is illustrated in detail by the following examples, which are all conventional products commercially available as raw materials.
(1) Sequentially adding a molybdenum salt, a sulfur source and a carbon source into deionized water, stirring and dissolving completely, adding SBA-15, and performing ultrasonic dispersion to form uniform dispersion liquid.
(2) And (3) placing the dispersion liquid in the step (1) on a magnetic stirrer, stirring at room temperature until the solvent is fully evaporated, and then placing the obtained sample in an air-blast drying oven for further drying.
(3) And (3) placing the dried sample in the step (2) into a tube furnace, carrying out programmed temperature rise to 400-550 ℃ under the protection of argon atmosphere, and keeping the temperature for 2-5 hours.
(4) And (4) after the constant temperature in the step (3) is finished, replacing the argon atmosphere with hydrogen-argon mixed gas, further heating to 700-900 ℃ by a program, and keeping the temperature for 0.5-2.5 h.
(5) Treating the sample obtained in the step (4) by using a hydrofluoric acid solution for 6-12 hours to remove SBA-15, then carrying out suction filtration, and washing with water and ethanol for multiple times until the filtrate is neutral.
(6) And (5) drying the sample to obtain the mesoporous molybdenum disulfide/carbon composite material.
The ultrasonic dispersion time after adding the SBA-15 in the step (1) is preferably 30-60 min.
The drying temperature in the step (2) is preferably 80-100 ℃.
The flow rate of the argon atmosphere in the step (3) is preferably 50-80 mL/min; the temperature programming rate is preferably 2-6 ℃/min.
The volume percentage of the hydrogen in the hydrogen-argon mixed atmosphere in the step (4) is preferably 5-10%; the temperature programming rate is preferably 10-15 ℃/min.
The concentration of the hydrofluoric acid solution used in the step (5) is preferably 10% to 15%.
The drying temperature in the step (6) is preferably 60-80 ℃; the drying time is 12-24 h.
The products of examples 1-5 of the invention were tested by the following instruments and methods:
the morphology of the product in example 1 was characterized by Scanning Electron Microscopy (SEM);
the morphology of the product in example 1 was characterized by Transmission Electron Microscopy (TEM);
the morphology of the product in example 3 was characterized by High Resolution Scanning Electron Microscopy (HRSEM);
the electrochemical performance of the products of examples 1-5 was determined in a sodium ion battery system.
Example 1
The molybdenum disulfide/carbon composite was prepared as follows.
(1) And sequentially stirring and dissolving 300mg of sodium molybdate, 600mg of thiourea and 600mg of cane sugar in 20mL of deionized water, adding 400mg of template SBA-15, and performing ultrasonic dispersion uniformly.
(2) And (3) placing the ultrasonic dispersion liquid in the step (1) on a magnetic stirrer for stirring, and transferring the ultrasonic dispersion liquid into an air-blowing drying oven for drying at 60 ℃ for 24 hours after the solvent is completely volatilized.
(3) And (3) placing the sample completely dried in the step (2) into a tube furnace, and carrying out temperature programming to 400 ℃ at a temperature-raising rate of 5 ℃/min under an argon atmosphere and keeping the temperature for 4 hours.
(4) And (4) after the constant temperature in the step (3) is finished, replacing the argon atmosphere with a hydrogen-argon mixed atmosphere containing 10% of hydrogen, heating from 400 ℃ to 900 ℃ at a programmed heating rate of 10 ℃/min, and keeping the temperature for 2 h.
(5) The sample obtained in (4) was treated with a 10% hydrofluoric acid solution for 6 h. After the treatment, the solution is filtered, and washed with water and ethanol for a plurality of times until the filtrate is neutral.
(6) And (5) drying the sample washed in the step (5) in a blast drying oven for 12 hours to obtain the molybdenum disulfide/carbon composite material.
The scanning electron microscope image of the material shows that the material well maintains the structure of the template SBA-15, and the mesoporous structure existing in the material can be observed through the cross section of the material (see figure 1). The transmission electron microscope image of the material shows that obvious molybdenum disulfide crystal lattice stripes exist in the mesoporous molybdenum disulfide/carbon composite material (see figure 2).
Example 2
The molybdenum disulfide/carbon composite was prepared as follows.
(1) 300mg of sodium molybdate, 600mg of thiourea and 200mg of sucrose are sequentially stirred and dissolved in 20mL of deionized water, 1g of template SBA-15 is added, and the mixture is uniformly dispersed by ultrasonic.
(2) And (3) placing the ultrasonic dispersion liquid in the step (1) on a magnetic stirrer for stirring, and transferring the ultrasonic dispersion liquid into an air-blowing drying oven for drying at 60 ℃ for 24 hours after the solvent is completely volatilized.
(3) And (3) placing the sample completely dried in the step (2) into a tube furnace, and carrying out temperature programming to 400 ℃ at a temperature rising rate of 5 ℃/min under an argon atmosphere and keeping the temperature for 4 hours.
(4) And (4) after the constant temperature in the step (3) is finished, replacing the argon atmosphere with a hydrogen-argon mixed atmosphere containing 10% of hydrogen, heating from 400 ℃ to 900 ℃ at a programmed heating rate of 10 ℃/min, and keeping the temperature for 2 h.
(5) The sample obtained in (4) was treated with a 10% hydrofluoric acid solution for 6 h. After the treatment, the solution is filtered, and washed with water and ethanol for a plurality of times until the filtrate is neutral.
(6) And (5) drying the sample washed in the step (5) in a blast drying oven for 12 hours to obtain the molybdenum disulfide/carbon composite material.
Example 3
The molybdenum disulfide/carbon composite was prepared as follows.
(1) 250mg of sodium molybdate, 350mg of thiourea and 125mg of dopamine hydrochloride are sequentially stirred and dissolved in 20mL of deionized water, 1.5g of template SBA-15 is added, and the mixture is uniformly dispersed by ultrasonic.
(2) And (3) placing the ultrasonic dispersion liquid in the step (1) on a magnetic stirrer for stirring, and transferring the ultrasonic dispersion liquid into an air-blowing drying oven for drying at 60 ℃ for 24 hours after the solvent is completely volatilized.
(3) And (3) placing the sample completely dried in the step (2) into a tube furnace, and carrying out programmed temperature rise to 500 ℃ at a temperature rise rate of 5 ℃/min under an argon atmosphere and keeping the temperature for 2 hours.
(4) And (4) after the constant temperature in the step (3) is finished, replacing the argon atmosphere with a hydrogen-argon mixed atmosphere containing 10% of hydrogen, heating from 500 ℃ to 800 ℃ at a programmed heating rate of 10 ℃/min, and keeping the temperature for 2 hours.
(5) The sample obtained in (4) was treated with a 10% hydrofluoric acid solution for 6 h. After the treatment, the solution is filtered, and washed with water and ethanol for a plurality of times until the filtrate is neutral.
(6) And (6) drying the sample washed in the step (5) in a forced air drying oven for 12 hours to obtain the molybdenum disulfide/carbon composite material.
High resolution scanning electron microscopy images of this material show that the material well replicates the pore structure of SBA-15 (see FIG. 6).
Example 4
The molybdenum disulfide/carbon composite was prepared as follows.
(1) 250mg of sodium molybdate, 350mg of thiourea and 250mg of dopamine hydrochloride are sequentially stirred and dissolved in 20mL of deionized water, 1.5g of template SBA-15 is added, and the mixture is uniformly dispersed by ultrasonic.
(2) And (3) placing the ultrasonic dispersion liquid in the step (1) on a magnetic stirrer for stirring, and transferring the ultrasonic dispersion liquid into an air-blowing drying oven for drying at 60 ℃ for 24 hours after the solvent is completely volatilized.
(3) And (3) placing the sample completely dried in the step (2) into a tube furnace, and carrying out temperature programming to 500 ℃ at a temperature rising rate of 5 ℃ min under an argon atmosphere and keeping the temperature for 2 hours.
(4) And (4) after the constant temperature in the step (3) is finished, replacing the argon atmosphere with a hydrogen-argon mixed atmosphere containing 10% of hydrogen, heating from 500 ℃ to 800 ℃ at a programmed heating rate of 10 ℃/min, and keeping the temperature for 2 hours.
(5) The sample obtained in (4) was treated with a 10% hydrofluoric acid solution for 6 h. After the treatment, the mixture is filtered, and washed by water and ethanol for many times until the filtrate is neutral.
(6) And (5) drying the sample washed in the step (5) in a blast drying oven for 12 hours to obtain the molybdenum disulfide/carbon composite material.
Example 5
The molybdenum disulfide/carbon composite was prepared as follows.
(1) 250mg of sodium molybdate, 350mg of thiourea and 375mg of dopamine hydrochloride are sequentially stirred and dissolved in 20mL of deionized water, 1.5g of template SBA-15 is added, and the mixture is uniformly dispersed by ultrasonic.
(2) And (2) placing the ultrasonic dispersion liquid in the step (1) on a magnetic stirrer for stirring, and transferring the ultrasonic dispersion liquid into an air-blowing drying oven for drying at 60 ℃ for 24 hours after the solvent is completely volatilized.
(3) And (3) placing the sample completely dried in the step (2) into a tube furnace, and carrying out programmed temperature rise to 500 ℃ at a temperature rise rate of 5 ℃/min under an argon atmosphere and keeping the temperature for 2 hours.
(4) And (4) after the constant temperature in the step (3) is finished, replacing the argon atmosphere with a hydrogen-argon mixed atmosphere containing 10% of hydrogen, heating from 500 ℃ to 800 ℃ at a programmed heating rate of 10 ℃/min, and keeping the temperature for 2 hours.
(5) The sample obtained in (4) was treated with a 10% hydrofluoric acid solution for 6 h. After the treatment, the solution is filtered, and washed with water and ethanol for a plurality of times until the filtrate is neutral.
(6) And (6) drying the sample washed in the step (5) in a forced air drying oven for 12 hours to obtain the molybdenum disulfide/carbon composite material.
Comparative example 1
The molybdenum disulfide/carbon composite was prepared as follows.
(1) Stirring 600mg of sucrose, dissolving in 20mL of water, adding 375 mu L of concentrated sulfuric acid, stirring uniformly, adding 400mg of SBA-15 into the solution, stirring to form uniform paste, placing the paste in an oven, heating to 100 ℃ at a programmed heating rate of 10 ℃/min, keeping the temperature for 6h, continuing to heat to 160 ℃ at the programmed heating rate after the constant temperature is over, keeping the temperature for 2h, and obtaining a precursor mixture.
(2) Under the protection of inert atmosphere, heating the precursor mixture in the step (1) to 400 ℃ at a programmed heating rate of 5 ℃/min, keeping the temperature for 4h, further heating to 900 ℃ and keeping the temperature for 2h to obtain the SBA-15 and carbon compound.
(3) 1.1g of ammonium molybdate tetrahydrate was dissolved in 20mL of water with stirring, and then 600mg of the complex in (2) was added to the solution and uniformly dispersed by sonication. Finally, the homogeneous dispersion is stirred dry at room temperature and is dried further in an oven.
(4) Mixing the sample in (3) with 10mL of CS2Transferring the mixture into a reaction kettle, heating to 400 ℃ at the programmed heating rate of 5 ℃/min, and keeping the temperature for 4 hours.
(5) And (3) treating the sample in the step (4) by using 10% hydrofluoric acid solution for 6h, after the treatment is finished, performing suction filtration, washing the filtrate to be neutral by using water and ethanol, and drying the filtrate for 12h at 80 ℃ to obtain a final product.
This comparative example prepared a molybdenum disulfide/carbon composite by first synthesizing a carbon skeleton and then growing molybdenum disulfide on the carbon surface. The performance test data (see fig. 12) indicates that the composite material not only has a low reversible capacity but also exhibits poor cycle stability under long-term cycling tests. This comparative example illustrates that the preparation of a composite by simple molybdenum disulphide growth on a carbon skeleton does not improve the properties of the material very well, and also illustrates the importance of excellent in situ recombination of molybdenum disulphide and carbon.
Application example 1
The molybdenum disulfide/carbon composite material obtained in example 1 was used in a sodium ion battery system, and the electrochemical properties of the molybdenum disulfide/carbon composite material as a battery negative electrode material were examined.
1. Preparation of the battery:
the active material, acetylene black and a bonding agent (PVDF) are sequentially weighed in a mass ratio of 7:2:1 into 1-methyl-2-pyrrolidone with a proper dosage to form uniform active material slurry, the active material slurry is coated on a copper foil by using a coating machine, and then the copper foil is placed in an oven to be dried for 24 hours at 60 ℃. In a glove box filled with argon (ensuring a water oxygen value below 0.1ppm), sodium metal was used as counter electrode, Whatman glass fibre as membrane, 1.0M NaCF3SO3The CR2016 cell was assembled by dissolving the electrolyte in diglyme.
2. Evaluation of electrochemical properties:
the new power battery test system is used for testing the constant-current charging and discharging performance of the battery, the test voltage range is 0.4-3V, and the current density is 100 mA.g-1The cycling stability of the material. All cells were tested in a 30 ℃ incubator。
3. Discussion of the results:
the molybdenum disulfide/carbon composite material of example 1 had a voltage range of 0.4 to 3V and a current density of 100mA g-1The composite material still has 200mAh g even after 120 times of cyclic charge and discharge-1The reversible specific capacity of (see fig. 3).
Application example 2
The molybdenum disulfide/carbon composite material obtained in example 2 is applied to a sodium ion battery system, and the electrochemical performance of the molybdenum disulfide/carbon composite material as a battery cathode material is examined.
1. Preparation of the battery:
the method comprises the steps of weighing an active material, acetylene black and a bonding agent (PVDF) in a proper amount of 1-methyl-2-pyrrolidone in a mass ratio of 7:2:1 to form uniform active material slurry, coating the active material slurry on a copper foil by using a coating machine, and then placing the copper foil in an oven to be dried for 24 hours at 60 ℃. In a glove box filled with argon (ensuring a water oxygen value below 0.1ppm), using metallic sodium as counter electrode, Whatman glass fibre as membrane, 1.0M NaClO4A mixed solution of ethylene carbonate and dimethyl carbonate dissolved in a volume ratio of 1:1 was used as an electrolyte to assemble a CR2016 cell.
2. Evaluation of electrochemical properties:
the new power battery test system is used for testing the constant-current charging and discharging performance of the battery, the test voltage range is 0.01-3V, and the current density is 500 mA.g-1And 1A. g-1Cycling stability of the electrode material. All cells were tested in a 30 ℃ incubator.
3. Discussion of the results:
the molybdenum disulfide/carbon composite material in example 2 had a current density of 500mA · g in a voltage range of 0.01 to 3V-1325mAh g still remains after the charge and discharge of 140 times-1The reversible specific capacity of (see fig. 4). Even at higher current densities of 1A g-1The material still has 295mAh g-1Average reversible specific capacity (see fig. 5).
Application example 3
The molybdenum disulfide/carbon composite material obtained in example 3 was used in a sodium ion battery system, and the electrochemical properties of the molybdenum disulfide/carbon composite material as a battery negative electrode material were examined.
1. Preparation of the battery:
the active material, acetylene black and a bonding agent (PVDF) are sequentially weighed in a mass ratio of 7:2:1 into 1-methyl-2-pyrrolidone with a proper dosage to form uniform active material slurry, the active material slurry is coated on a copper foil by using a coating machine, and then the copper foil is placed in an oven to be dried for 24 hours at 60 ℃. In an argon-filled glove box (ensuring water oxygen values below 0.1ppm), sodium metal was used as counter electrode, Whatman glass fibre as membrane, 1.0M NaPF6CR2016 cells were assembled by dissolving in propylene carbonate and adding 5% fluoroethylene carbonate as electrolyte.
2. Evaluation of electrochemical properties:
the new power battery test system is used for testing the constant-current charging and discharging performance of the battery, the test voltage range is 0.01-3V, and the current density is 200 mA.g-1，1A·g-1And 2A. g-1Cycling stability of the electrode material. And testing the rate capability of the electrode material under the same voltage range. All cells were tested in a 30 ℃ incubator.
3. Discussion of the results:
the molybdenum disulfide/carbon composite of example 3 was at 200 mA-g-1Has a current density as high as 875 mAh.g-1The discharge specific capacity and the first-turn coulombic efficiency of 48 percent show good cycle stability along with the increase of the cycle times, and the material still has nearly 480mAh g even after 100 cycles of charge and discharge-1The reversible specific capacity of (see fig. 7). The material also shows excellent rate capability when the ratio is 100 mA-g respectively-1、200mA·g-1、500mA·g-1、1000mA·g-1And 2000mA · g-1After circulating for 10 cycles at the current density of (1), the current density returns to 100mA · g-1In time, the material still has a high level of 500mAh g-1And maintains good cycling stability (see figure 8). At a high current density of 1A g-1TestingThe material still maintains up to 324mAh g after being charged and discharged for 1000 times-1The reversible specific capacity of (see fig. 9). The material has a higher current density of 2 A.g-1Still maintains good circulation stability, and maintains 262mAh g after the circulation test of 1000 circles-1The reversible specific capacity of (see fig. 10).
Application example 4
The molybdenum disulfide/carbon composite materials obtained in example 4 and example 5 were used in sodium ion battery systems, and the electrochemical properties of the molybdenum disulfide/carbon composite materials as battery negative electrode materials were examined.
1. Preparing a battery:
the active material, acetylene black and a bonding agent (PVDF) are sequentially weighed in a mass ratio of 7:2:1 into 1-methyl-2-pyrrolidone with a proper dosage to form uniform active material slurry, the active material slurry is coated on a copper foil by using a coating machine, and then the copper foil is placed in an oven to be dried for 24 hours at 60 ℃. In an argon-filled glove box (ensuring water oxygen values below 0.1ppm), sodium metal was used as counter electrode, Whatman glass fibre as membrane, 1.0M NaPF6The CR2016 cell was assembled by dissolving in propylene carbonate and adding 5% fluoroethylene carbonate as electrolyte.
2. Evaluation of electrochemical properties:
the new power cell test system is used for testing the constant-current charging and discharging performance of the cell, the test voltage range is 0.01-3V, and the current density is 1 A.g-1Cycling stability of the electrode material. All cells were tested in a 30 ℃ incubator.
3. Discussion of the results:
the materials prepared in examples 4 and 5 were at 1A g-1Shows good cycling stability at all current densities. Wherein the material of example 4 had a composition of about 245mAh g-1The material of example 5 has a reversible specific capacity of about 150mAh g-1The reversible specific capacity of (a). Comparing the performance of the materials of example 3, example 4 and example 5 under the same test conditions, it can be seen that the specific capacity of the material shows regular change along with the change of the dopamine hydrochloride content in the precursor (see fig. 11). Therefore, the change of the carbon content in the molybdenum disulfide/carbon composite material has important influence on the performance of the material, and the improvement of the performance of the material is significant by introducing proper carbon content into the composite material.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.

Claims (9)

1. A preparation method of a molybdenum disulfide/carbon composite material is characterized by comprising the following steps:
(1) co-depositing molybdenum salt, a sulfur source and a carbon source on the surface of SBA-15 by using a co-precipitation method to obtain a precursor mixture;
(2) carrying out temperature programming treatment on the precursor mixture obtained in the step (1) under an inert atmosphere to reach an end point temperature, and keeping the temperature;
(3) carrying out temperature programming treatment on the product obtained in the step (2) in a reducing atmosphere to reach the end temperature, and keeping the temperature; the end temperature is higher than the end temperature of the step (2);
(4) and (4) carrying out acid treatment on the product obtained in the step (3), and washing and drying to obtain the molybdenum disulfide/carbon composite material.
2. The method of claim 1, wherein: in the step (1), the mass ratio of the molybdenum salt to the sulfur source to the carbon source is 1:1-3: 0.1-2.
3. The method of claim 1, wherein: in the step (1), the molybdenum salt is one of ammonium tetrathiomolybdate, ammonium molybdate, ammonium phosphomolybdate, sodium phosphomolybdate or sodium molybdate; the sulfur source is one of thiourea, sodium sulfide, potassium sulfide, ammonium sulfide or thioacetamide; the carbon source is one of soluble starch, sucrose, anhydrous glucose, dopamine hydrochloride, melamine or dicyandiamide.
4. The method of claim 1, wherein: in the step (1), the codeposition temperature is 60-100 ℃, and the time is 12-24 h.
5. The production method according to claim 1, characterized in that: in the step (2), the inert atmosphere is one of argon, nitrogen or helium, and the flow rate is 50-80 mL/min; the temperature programming treatment is that the temperature is raised at the rate of 1-10 ℃/min until the end temperature is 400-550 ℃, and the constant temperature time is 2-5 h.
6. The production method according to claim 1, characterized in that: in the step (3), the reducing atmosphere is a mixed atmosphere of hydrogen and inert atmosphere, and the hydrogen accounts for 5-20% of the mixed atmosphere; the temperature programming treatment is to heat the substrate at a heating rate of 5-15 ℃/min until the end temperature is 700-900 ℃, and then the temperature is kept for 0.5-2.5 h.
7. The production method according to claim 1, characterized in that: in the step (4), the acid in the acid treatment is a hydrofluoric acid solution with the concentration of 5-20%, and the acid treatment time is 6-12 hours; the drying temperature is 60-80 ℃, and the drying time is 12-24 h.
8. A molybdenum disulfide/carbon composite material obtained by the preparation method according to any one of claims 1 to 7, wherein the molybdenum disulfide/carbon composite material has a mesoporous structure.
9. Use of the molybdenum disulfide/carbon composite of claim 8 as a negative electrode material in a sodium ion battery system.
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