CN111554912A - Tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery cathode composite material and preparation method thereof - Google Patents
Tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery cathode composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of nano composite material synthesis and battery material preparation, and discloses a tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery cathode composite material and a preparation method thereof. The synthesized tin @ carbon @ molybdenum disulfide yolk-shell structure composite material can effectively relieve the volume change of tin and molybdenum disulfide nano materials in the charge-discharge cycle process, and further improve the cycle stability of the material. The method comprises the following steps: firstly, dispersing a silicon dioxide template prepared by tetraethoxysilane under an alkaline condition in an ethanol-water solution of urea and sodium stannate, then carrying out hydrothermal reaction on the suspension, and corroding a product with hydrofluoric acid to obtain the stannic oxide hollow sphere. And secondly, coating polydopamine serving as a carbon source on the tin dioxide hollow spheres. And thirdly, coating molybdenum disulfide nanosheets on the outer layer of the polydopamine through a hydrothermal reaction, and finally sintering at a high temperature in a hydrogen/argon mixed atmosphere to obtain the tin @ carbon @ molybdenum disulfide yolk-shell structure composite material.
Description
Technical Field
The invention belongs to the technical field of composite material synthesis and battery material preparation, and particularly relates to a tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery cathode composite material and a preparation method thereof.
Background
In recent years, with eachThe requirements of electronic products on lithium ion batteries are getting higher and higher, and the research on novel lithium ion battery materials with high specific capacity and good cycle stability is very important and urgent. Compared with the traditional graphite material, the material has lower theoretical capacity of 372mAh g-1It is difficult to meet the ever-increasing demand for higher energy from lithium ion batteries. Tin-based material 994mAh g due to its higher theoretical capacity-1And the material is considered to be an ideal candidate material in the lithium ion battery cathode material. However, during repeated charge and discharge cycles, the tin-based material undergoes large volume changes, resulting in material breakage and pulverization, further resulting in reduced cycle stability and lower coulombic efficiency; moreover, poor conductivity of tin-based materials leads to poor charge-discharge rate performance and the like, hindering further applications thereof.
Researchers effectively relieve the volume change of the material in the charge-discharge cycle process and improve the conductivity of the material by adopting strategies of compounding a nano tin-based material and a carbon material, reasonably designing the structure of the tin-based material, introducing other high-capacity compounds into the tin-based negative electrode material and the like. The first strategy is: the nano tin-based material and the carbon material are compounded, so that the conductivity of the tin-based material can be improved, the volume expansion of the tin-based material can be partially relieved, and the circulation stability of the material can be improved. The second strategy is: the tin-based material is designed into special hollow and core-shell structures such as a cubic box, a hollow nanosphere, a yolk-shell structure and the like, so that the volume change of the material in the charge-discharge cycle process is relieved. The third strategy is: by adding another substance having a high theoretical capacity (e.g. MoS)2) The tin-based material is introduced to form a composite, which can greatly improve the total theoretical capacity of the composite. Of the three strategies described above, however, the first strategy was due to the large amount of low theoretical capacity carbon material (theoretical capacity 372mAh g-1) The introduction of (2) causes the reduction of the total theoretical capacity of the tin-based carbon-containing composite material, influences the improvement of the reversible capacity of the tin-based carbon-containing composite material, and in addition, the effect of the flexible carbon material on relieving the volume change of the material in the charge-discharge cycle process is relatively limited; the second and third strategies, the simple hollow and yolk-shell structures and the relatively poor conductivity of the two-phase composite, affect itFurther improvement of rate capability and cycle capability.
In summary, the conductivity, reversible capacity and cycling stability of the tin-based materials synthesized by the prior art are still not ideal. An effective solution to the above problem is still lacking.
Disclosure of Invention
The invention provides a tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery cathode composite material and a preparation method thereof, wherein tin in the composite material has high theoretical capacity, low cost and easy acquisition; the introduction of a small amount of carbon material can improve the conductivity of the composite material; the molybdenum disulfide has high theoretical capacity and good stability; the preparation method of the composite material combines the strategies of performance optimization such as size, compounding with carbon materials, yolk-shell structure, introduction of high-capacity compounds and the like, improves the conductivity and reversible capacity of the tin-based material, and simultaneously improves the cycling stability of the tin-based material.
The technical scheme of the invention is realized as follows:
a preparation method of a tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery cathode composite material comprises the following steps:
s1, dropwise adding 2mL of concentrated ammonia water into a mixed solution of 80mL of ethanol and 10mL of water, dropwise adding 4mL of ethyl orthosilicate in the stirring process, stirring at normal temperature for 4 hours, centrifuging, and washing to obtain the silicon dioxide nanospheres.
S2, dissolving 9.0g of urea and 1.3g of sodium stannate in a mixed solution of 100mL of ethanol and 240mL of water, and then ultrasonically dispersing 1.2g of silicon dioxide nanosphere template in the solution for 1 hour to obtain a reaction solution. And then transferring the reaction liquid into a hydrothermal reaction kettle with a Teflon lining, reacting at 170 ℃ for 36 hours, cooling, centrifuging, and washing to obtain the silicon dioxide @ tin dioxide nanospheres. And finally, transferring the silicon dioxide @ tin dioxide nanoparticles to 100mL of 5% hydrofluoric acid to corrode for 1 hour to remove the silicon dioxide template, centrifuging, washing with water, and drying to obtain the tin dioxide hollow nanospheres.
S3, weighing the tin dioxide hollow nanospheres with the mass of 0.1g, and dispersing the tin dioxide hollow nanospheres in 0.01 mol.L-1100 (c)And adding 0.05g of dopamine hydrochloride into the mL of trihydroxymethyl aminomethane buffer solution, continuously stirring and reacting for 24 hours at room temperature, and finally centrifuging, washing and drying to obtain the tin dioxide @ poly dopamine hydrochloride hollow nanospheres.
S4, dissolving 0.2g of ammonium tetrathiomolybdate in 40mL of water, adding 0.1g of tin dioxide @ polydopamine hollow nanosphere, and fully stirring to obtain a reaction solution. Transferring the reaction liquid into a hydrothermal reaction kettle with a Teflon lining, reacting for 15 hours at 190 ℃, cooling, centrifuging, washing and drying. And finally calcining the product obtained after the hydrothermal reaction for 2 hours at 600 ℃ in a hydrogen/argon mixed atmosphere to obtain the yolk-shell structure tin @ carbon @ molybdenum disulfide composite material.
As a further technical scheme, in the step S2, in the process of dissolving urea and sodium stannate in the ethanol-water mixed solution, and then ultrasonically dispersing the silica nanosphere template in the mixed solution for 1 hour to obtain a reaction solution, the amounts of urea, sodium stannate, silica nanospheres, ethanol and water are 9g, 1.3g, 1.2g, 100mL and 240mL, respectively.
As a further technical scheme, the reaction temperature of the hydrothermal reaction kettle in the step S2 is 170 ℃, and the reaction time is 36 hours.
As a further technical scheme, the dosage of the tin dioxide hollow nanospheres and the dopamine hydrochloride in the step S3 is 0.1g and 0.05g respectively.
As a further means, the concentration of the 100mL tris solution in step S3 was 0.01 mol. L-1。
As a further technical scheme, in the step S4, the mass ratio of the tin dioxide @ polydopamine hollow nanospheres to the tetrathiomolybdic acid is 0.1:0.1 to 0.4.
As a further technical scheme, the reaction temperature of the hydrothermal reaction in the step S4 is 170-210 ℃, and the reaction time is 12-24 hours.
As a further technical scheme, the calcination temperature of the product after the hydrothermal reaction in the step S4 is 550-650 ℃, and the calcination time is 1-4 hours.
The tin @ carbon @ molybdenum disulfide negative electrode composite material obtained by the preparation method of the yolk-shell structure tin @ carbon @ molybdenum disulfide is characterized in that the particle size of the silicon dioxide nano-sphere template in the step S1 is about 220-320 nm, and the particle size of the tin @ carbon @ molybdenum disulfide negative electrode composite material in the step S4 is about 250-350 nm.
The working principle and the beneficial effects of the invention are as follows:
1. the invention provides a preparation method of a tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery cathode composite material, which is simple in preparation process and easy to operate. The tin in the composite material has high theoretical capacity, low cost and easy acquisition; the introduction of a small amount of carbon material can improve the conductivity of the composite material; the molybdenum disulfide has high theoretical capacity and good stability. The method combines three performance optimization strategies of compounding a nano tin-based material and a carbon material, designing a yolk-shell structure, introducing a high-capacity compound and the like, improves the reversible capacity of the tin-based material, and improves the cycle stability of the tin-based material.
2. In the invention, the synthesized tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery cathode composite material is prepared at 100mA g-1After the current density is cycled for 50 times, the specific capacity of the lithium ion battery still has 806mAh g-1Compared with the specific capacity (372mAh g) of the traditional commercial graphite lithium ion battery cathode material-1) The method has the advantages of remarkable promotion, uniform particle distribution, uniform size and excellent cycling stability, and is suitable for being used as a lithium ion battery cathode composite material and popularized and used.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a Transmission Electron Microscope (TEM) image of a lithium ion battery anode composite material with a tin @ carbon @ molybdenum disulfide yolk-shell structure prepared in example 1 of the present invention;
FIG. 2 is a Transmission Electron Microscope (TEM) image of a lithium ion battery anode composite material with a tin @ carbon @ molybdenum disulfide yolk-shell structure prepared in example 2 of the present invention;
FIG. 3 is a Transmission Electron Microscope (TEM) image of a lithium ion battery anode composite material with a tin @ carbon @ molybdenum disulfide yolk-shell structure prepared in example 3 of the present invention;
FIG. 4 is a Transmission Electron Microscope (TEM) image of a negative electrode composite material of a lithium ion battery with a tin @ carbon @ molybdenum disulfide yolk-shell structure, which is prepared in example 4 of the present invention;
FIG. 5 is a Transmission Electron Microscope (TEM) image of a negative electrode composite material of a lithium ion battery with a yolk-shell structure of tin @ carbon @ molybdenum disulfide, prepared in example 5 of the present invention;
FIG. 6 is a Transmission Electron Microscope (TEM) image of a negative electrode composite material of a lithium ion battery with a yolk-shell structure of tin @ carbon @ molybdenum disulfide, prepared in example 6 of the present invention;
fig. 7 is an X-ray diffraction (XRD) pattern of the tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery anode composite material prepared in example 1 of the present invention.
In the figure: the peak marked with the symbol "#" represents the diffraction peak of tin, and the peak marked with the symbol "+" represents the diffraction peak of molybdenum disulfide;
FIG. 8 shows that the current density of the negative electrode composite material of the lithium ion battery with the yolk-shell structure of tin @ carbon @ molybdenum disulfide prepared in example 1 is 100mA g-1Cycle performance graph below.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery cathode composite material comprises the following steps:
s1, dropwise adding 2mL of concentrated ammonia water into a mixed solution of 80mL of ethanol and 10mL of water, dropwise adding 4mL of ethyl orthosilicate in the stirring process, stirring at normal temperature for 4 hours, centrifuging, and washing to obtain the silicon dioxide nanospheres.
S2, dissolving 9.0g of urea and 1.3g of sodium stannate in a mixed solution of 100mL of ethanol and 240mL of water, and then ultrasonically dispersing 1.2g of silicon dioxide nanosphere template in the solution for 1 hour to obtain a reaction solution. And then transferring the reaction liquid into a hydrothermal reaction kettle with a Teflon lining, reacting at 170 ℃ for 36 hours, cooling, centrifuging, and washing to obtain the silicon dioxide @ tin dioxide nanospheres. And finally, transferring the silicon dioxide @ tin dioxide nanoparticles to 100mL of 5% hydrofluoric acid to corrode for 1 hour to remove the silicon dioxide template, centrifuging, washing with water, and drying to obtain the tin dioxide hollow nanospheres.
S3, weighing the tin dioxide hollow nanospheres with the mass of 0.1g, and dispersing the tin dioxide hollow nanospheres in 0.01 mol.L-1Then 0.05g of dopamine hydrochloride is added into 100mL of trihydroxymethyl aminomethane buffer solution, the mixture is continuously stirred and reacted for 24 hours at room temperature, and finally, the mixture is centrifuged, washed and dried to obtain the stannic oxide @ poly dopamine hydrochloride hollow nanospheres.
S4, dissolving 0.2g of ammonium tetrathiomolybdate in 40mL of water, adding 0.1g of tin dioxide hollow @ polydopamine nanosphere, and fully stirring to obtain a reaction solution. Transferring the reaction liquid into a hydrothermal reaction kettle with a Teflon lining, reacting for 15 hours at 190 ℃, cooling, centrifuging, washing and drying. And finally calcining the product obtained after the hydrothermal reaction for 2 hours at 600 ℃ in a hydrogen/argon mixed atmosphere to obtain the yolk-shell structure tin @ carbon @ molybdenum disulfide composite material.
Example 2
A preparation method of a tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery cathode composite material comprises the following steps:
s1, dropwise adding 2mL of concentrated ammonia water into a mixed solution of 80mL of ethanol and 10mL of water, dropwise adding 4mL of ethyl orthosilicate in the stirring process, stirring at normal temperature for 4 hours, centrifuging, and washing to obtain the silicon dioxide nanospheres.
S2, dissolving 9.0g of urea and 1.3g of sodium stannate in a mixed solution of 100mL of ethanol and 240mL of water, and then ultrasonically dispersing 1.2g of silicon dioxide nanosphere template in the solution for 1 hour to obtain a reaction solution. And then transferring the reaction liquid into a hydrothermal reaction kettle with a Teflon lining, reacting at 170 ℃ for 36 hours, cooling, centrifuging, and washing to obtain the silicon dioxide @ tin dioxide nanospheres. And finally, transferring the silicon dioxide @ tin dioxide nanoparticles to 100mL of 5% hydrofluoric acid to corrode for 1 hour to remove the silicon dioxide template, centrifuging, washing with water, and drying to obtain the tin dioxide hollow nanospheres.
S3, weighing the tin dioxide hollow nanospheres with the mass of 0.1g, and dispersing the tin dioxide hollow nanospheres in 0.01 mol.L-1Then 0.05g of dopamine hydrochloride is added into 100mL of trihydroxymethyl aminomethane buffer solution, the mixture is continuously stirred and reacted for 24 hours at room temperature, and finally, the mixture is centrifuged, washed and dried to obtain the stannic oxide @ poly dopamine hydrochloride hollow nanospheres.
S4, adding 0.1g of ammonium tetrathiomolybdate into 40mL of aqueous solution, stirring and dissolving, adding 0.1g of tin dioxide @ polydopamine hollow nanospheres, and fully stirring until the solution is dissolved to obtain a reaction solution. Transferring the reaction solution into a high-pressure reaction kettle to react for 12 hours at the temperature of 210 ℃, cooling, centrifuging, washing and drying. And finally calcining the product obtained after the hydrothermal reaction for 1 hour at 650 ℃ in a hydrogen/argon mixed atmosphere to obtain the yolk-shell structure tin @ carbon @ molybdenum disulfide composite material.
Example 3
A preparation method of a tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery cathode composite material comprises the following steps:
s1, dropwise adding 2mL of concentrated ammonia water into a mixed solution of 80mL of ethanol and 10mL of water, dropwise adding 4mL of ethyl orthosilicate in the stirring process, stirring at normal temperature for 4 hours, centrifuging, and washing to obtain the silicon dioxide nanospheres.
S2, dissolving 9.0g of urea and 1.3g of sodium stannate in a mixed solution of 100mL of ethanol and 240mL of water, and then ultrasonically dispersing 1.2g of silicon dioxide nanosphere template in the solution for 1 hour to obtain a reaction solution. And then transferring the reaction liquid into a hydrothermal reaction kettle with a Teflon lining, reacting at 170 ℃ for 36 hours, cooling, centrifuging, and washing to obtain the silicon dioxide @ tin dioxide nanospheres. And finally, transferring the silicon dioxide @ tin dioxide nanoparticles to 100mL of 5% hydrofluoric acid to corrode for 1 hour to remove the silicon dioxide template, centrifuging, washing with water, and drying to obtain the tin dioxide hollow nanospheres.
S3, weighing the tin dioxide hollow nanospheres with the mass of 0.1g, and dispersing the tin dioxide hollow nanospheres in 0.01 mol.L-1Then 0.05g of dopamine hydrochloride is added into 100mL of trihydroxymethyl aminomethane buffer solution, the mixture is continuously stirred and reacted for 24 hours at room temperature, and finally, the mixture is centrifuged, washed and dried to obtain the stannic oxide @ poly dopamine hydrochloride hollow nanospheres.
S4, adding 0.4g of ammonium tetrathiomolybdate into 40mL of aqueous solution, stirring and dissolving, adding 0.1g of tin dioxide @ polydopamine hollow nanospheres, and fully stirring until the solution is dissolved to obtain a reaction solution. Transferring the reaction liquid into a high-pressure reaction kettle to react for 24 hours at the temperature of 170 ℃, cooling, centrifuging, washing and drying. And finally calcining the product obtained after the hydrothermal reaction for 4 hours at 550 ℃ in a hydrogen/argon mixed atmosphere to obtain the yolk-shell structure tin @ carbon @ molybdenum disulfide composite material.
Example 4
A preparation method of a tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery cathode composite material comprises the following steps:
s1, dropwise adding 2mL of concentrated ammonia water into a mixed solution of 80mL of ethanol and 10mL of water, dropwise adding 4mL of ethyl orthosilicate in the stirring process, stirring at normal temperature for 4 hours, centrifuging, and washing to obtain the silicon dioxide nanospheres.
S2, dissolving 9.0g of urea and 1.3g of sodium stannate in a mixed solution of 100mL of ethanol and 240mL of water, and then ultrasonically dispersing 1.2g of silicon dioxide nanosphere template in the solution for 1 hour to obtain a reaction solution. And then transferring the reaction liquid into a hydrothermal reaction kettle with a Teflon lining, reacting at 170 ℃ for 36 hours, cooling, centrifuging, and washing to obtain the silicon dioxide @ tin dioxide nanospheres. And finally, transferring the silicon dioxide @ tin dioxide nanoparticles to 100mL of 5% hydrofluoric acid to corrode for 1 hour to remove the silicon dioxide template, centrifuging, washing with water, and drying to obtain the tin dioxide hollow nanospheres.
S3, weighing the tin dioxide hollow nanospheres with the mass of 0.1g, and dispersing the tin dioxide hollow nanospheres in 0.01 mol.L-1Then 0.05g dopamine hydrochloride is added into 100mL trihydroxymethyl aminomethane buffer solution, and the mixture is placed in a chamberAnd continuously stirring and reacting for 24 hours under a warm condition, and finally centrifuging, washing and drying to obtain the stannic oxide @ poly (dopamine hydrochloride) hollow nanospheres.
S4, adding 0.2g of ammonium tetrathiomolybdate into 40mL of aqueous solution, stirring and dissolving, adding 0.1g of tin dioxide @ polydopamine hollow nanospheres, and fully stirring until the solution is dissolved to obtain a reaction solution. Transferring the reaction solution into a high-pressure reaction kettle to react for 12 hours at 190 ℃, cooling, centrifuging, washing and drying. And finally calcining the product obtained after the hydrothermal reaction for 1 hour at 550 ℃ in a hydrogen/argon mixed atmosphere to obtain the yolk-shell structure tin @ carbon @ molybdenum disulfide composite material.
Example 5
A preparation method of a tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery cathode composite material comprises the following steps:
s1, dropwise adding 2mL of concentrated ammonia water into a mixed solution of 80mL of ethanol and 10mL of water, dropwise adding 4mL of ethyl orthosilicate in the stirring process, stirring at normal temperature for 4 hours, centrifuging, and washing to obtain the silicon dioxide nanospheres.
S2, dissolving 9.0g of urea and 1.3g of sodium stannate in a mixed solution of 100mL of ethanol and 240mL of water, and then ultrasonically dispersing 1.2g of silicon dioxide nanosphere template in the solution for 1 hour to obtain a reaction solution. And then transferring the reaction liquid into a hydrothermal reaction kettle with a Teflon lining, reacting at 170 ℃ for 36 hours, cooling, centrifuging, and washing to obtain the silicon dioxide @ tin dioxide nanospheres. And finally, transferring the silicon dioxide @ tin dioxide nanoparticles to 100mL of 5% hydrofluoric acid to corrode for 1 hour to remove the silicon dioxide template, centrifuging, washing with water, and drying to obtain the tin dioxide hollow nanospheres.
S3, weighing the tin dioxide hollow nanospheres with the mass of 0.1g, and dispersing the tin dioxide hollow nanospheres in 0.01 mol.L-1Then 0.05g of dopamine hydrochloride is added into 100mL of trihydroxymethyl aminomethane buffer solution, the mixture is continuously stirred and reacted for 24 hours at room temperature, and finally, the mixture is centrifuged, washed and dried to obtain the stannic oxide @ poly dopamine hydrochloride hollow nanospheres.
S4, adding 0.1g of ammonium tetrathiomolybdate into 40mL of aqueous solution, stirring and dissolving, adding 0.1g of tin dioxide @ polydopamine hollow nanospheres, and fully stirring until the solution is dissolved to obtain a reaction solution. Transferring the reaction liquid into a high-pressure reaction kettle to react for 15 hours at the temperature of 170 ℃, cooling, centrifuging, washing and drying. And finally calcining the product obtained after the hydrothermal reaction for 4 hours at 600 ℃ in a hydrogen/argon mixed atmosphere to obtain the yolk-shell structure tin @ carbon @ molybdenum disulfide composite material.
Example 6
A preparation method of a tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery cathode composite material comprises the following steps:
s1, dropwise adding 2mL of concentrated ammonia water into a mixed solution of 80mL of ethanol and 10mL of water, dropwise adding 4mL of ethyl orthosilicate in the stirring process, stirring at normal temperature for 4 hours, centrifuging, and washing to obtain the silicon dioxide nanospheres.
S2, dissolving 9.0g of urea and 1.3g of sodium stannate in a mixed solution of 100mL of ethanol and 240mL of water, and then ultrasonically dispersing 1.2g of silicon dioxide nanosphere template in the solution for 1 hour to obtain a reaction solution. And then transferring the reaction liquid into a hydrothermal reaction kettle with a Teflon lining, reacting at 170 ℃ for 36 hours, cooling, centrifuging, and washing to obtain the silicon dioxide @ tin dioxide nanospheres. And finally, transferring the silicon dioxide @ tin dioxide nanoparticles to 100mL of 5% hydrofluoric acid to corrode for 1 hour to remove the silicon dioxide template, centrifuging, washing with water, and drying to obtain the tin dioxide hollow nanospheres.
S3, weighing the tin dioxide hollow nanospheres with the mass of 0.1g, and dispersing the tin dioxide hollow nanospheres in 0.01 mol.L-1Then 0.05g of dopamine hydrochloride is added into 100mL of trihydroxymethyl aminomethane buffer solution, the mixture is continuously stirred and reacted for 24 hours at room temperature, and finally, the mixture is centrifuged, washed and dried to obtain the stannic oxide @ poly dopamine hydrochloride hollow nanospheres.
S4, adding 0.4g of ammonium tetrathiomolybdate into 40mL of aqueous solution, stirring and dissolving, adding 0.1g of tin dioxide @ polydopamine hollow nanospheres, and fully stirring until the solution is dissolved to obtain a reaction solution. Transferring the reaction solution into a high-pressure reaction kettle to react for 24 hours at the temperature of 210 ℃, cooling, centrifuging, washing and drying. And finally calcining the product obtained after the hydrothermal reaction for 2 hours at 650 ℃ in a hydrogen/argon mixed atmosphere to obtain the yolk-shell structure tin @ carbon @ molybdenum disulfide composite material.
Transmission Electron Microscope (TEM) images of the tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery negative electrode composite materials prepared in the examples 1-6 are shown in figures 1-6, and it can be seen from the TEM images that the tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery negative electrode composite materials prepared in the examples 1-6 are uniform in particle size distribution and have particle sizes of 250-350 nm.
The invention also discloses a tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery cathode composite material prepared by the method. An X-ray diffraction (XRD) pattern of the lithium ion battery cathode composite material with the tin @ carbon @ molybdenum disulfide yolk-shell structure prepared in example 1 is shown in fig. 7, from which diffraction peaks of tin and molybdenum disulfide can be respectively seen, and X-ray diffraction (XRD) tests were also performed on the lithium ion battery cathode composite materials with the tin @ carbon @ molybdenum disulfide yolk-shell structure prepared in examples 2 to 6, and the test results are the same as those in fig. 7, so that the X-ray diffraction (XRD) patterns are omitted.
The cycle stability test data of the lithium ion battery anode composite material with the tin @ carbon @ molybdenum disulfide yolk-shell structure prepared in example 1 is shown in fig. 8, and it can be seen from the figure that the lithium ion battery anode composite material with the tin @ carbon @ molybdenum disulfide yolk-shell structure prepared in example 1 is 100mA g-1Under the current density, the discharge specific capacity after 50 times of charge-discharge circulation is stabilized at 806mAh g-1The lithium ion battery cathode composite material with the yolk-shell structure of tin @ carbon @ molybdenum disulfide prepared in example 1 of the invention has excellent cycle stability, and the cycle stability test is also performed on the lithium ion battery cathode composite material with the yolk-shell structure of tin @ carbon @ molybdenum disulfide prepared in examples 2 to 6, and the test result is the same as that in fig. 8, so that the test is omitted.
The above-mentioned embodiments are merely exemplary, which should not be construed as limiting the present invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (5)
1. A preparation method of a lithium ion battery cathode composite material with a tin @ carbon @ molybdenum disulfide yolk-shell structure. The method is characterized by comprising the following steps:
s1, dropwise adding ammonia water into a mixed solution of ethanol and water, uniformly stirring, dropwise adding ethyl orthosilicate into the mixed solution, stirring at room temperature, washing, and centrifuging to obtain silicon dioxide nanospheres;
s2, dissolving urea and sodium stannate in a mixed solution of ethanol and water respectively, and then dispersing the silicon dioxide nanosphere template in the solution; then transferring the suspension into a hydrothermal reaction kettle for heating reaction, centrifuging and washing to obtain silicon dioxide @ tin dioxide nanospheres; finally, corroding the silicon dioxide @ tin dioxide nanospheres by using a hydrofluoric acid aqueous solution, and removing the silicon dioxide to obtain tin dioxide hollow spheres;
s3, adding the prepared stannic oxide hollow sphere and dopamine hydrochloride into a buffer solution of tris (hydroxymethyl) aminomethane, stirring for 24 hours, centrifuging, washing and drying to obtain a stannic oxide @ polydopamine hollow nanosphere;
s4, dispersing the tin dioxide @ polydopamine hollow nanospheres in an ammonium tetrathiomolybdate aqueous solution, and fully stirring; then transferring the reaction solution into a hydrothermal reaction kettle for heating reaction; and finally, calcining the product obtained after the hydrothermal reaction at high temperature in a hydrogen/argon mixed atmosphere to obtain the composite material with the yolk-shell structure of tin @ carbon @ molybdenum disulfide.
2. The preparation method of the tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery negative electrode composite material as claimed in claim 1, wherein the mass ratio of the tin dioxide @ polydopamine hollow nanospheres to the ammonium tetrathiomolybdate in the step S4 is 0.1: 0.1-0.4.
3. The preparation method of the tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery cathode composite material as claimed in claim 1, wherein the reaction temperature of the heating reaction in the hydrothermal reaction kettle in the step S4 is 170-210 ℃, and the reaction time is 12-24 hours.
4. The preparation method of the negative electrode composite material of the lithium ion battery with the yolk-shell structure of tin @ carbon @ molybdenum disulfide as claimed in claim 1, wherein the product obtained after the hydrothermal reaction in the step S4 is calcined at 550 ℃ and 650 ℃ for 1-4 hours in a mixed atmosphere of hydrogen and argon.
5. The tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery negative electrode composite material is characterized by being obtained by the preparation method of the tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery negative electrode composite material according to any one of claims 1 to 4, wherein the particle size of the tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery negative electrode composite material is 250-350 nm.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112290018A (en) * | 2020-09-29 | 2021-01-29 | 郑州大学 | SnO (stannic oxide)2Modified MoS2Hollow microsphere sulfur-loaded positive electrode composite material and application thereof in lithium-sulfur battery |
| CN112310366A (en) * | 2020-10-09 | 2021-02-02 | 上海交通大学 | Molybdenum disulfide/metal oxide composite material for energy storage device electrode and preparation thereof |
| CN113675382A (en) * | 2021-07-07 | 2021-11-19 | 扬州大学 | Sn/MoS2@ C composite material and preparation method and application thereof |
| CN113629230A (en) * | 2021-08-05 | 2021-11-09 | 合肥国轩电池材料有限公司 | Lithium ion battery cathode material and preparation method thereof |
| CN113851645A (en) * | 2021-08-30 | 2021-12-28 | 厦门大学 | Zinc sulfide/tin-carbon compound and preparation method and application thereof |
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