CN112811473B - Nano bracelet iron sesquioxide/graphene quantum dot/tin dioxide core-shell structure composite material, preparation method thereof and battery application - Google Patents
Nano bracelet iron sesquioxide/graphene quantum dot/tin dioxide core-shell structure composite material, preparation method thereof and battery application Download PDFInfo
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Abstract
The invention provides a nano bracelet iron trioxide/graphene quantum dot/stannic oxide core-shell structure composite material and a preparation method and application thereof. The inside is hollow nanometer bracelet nucleocapsid structure, not only can hold more sulphur active material when the sulphur fumigation to nucleocapsid structure also can effectually alleviate the volume expansion problem of sulphur in the charge-discharge process. Compared with the prior art, the graphene quantum dots are adsorbed in the material, so that the stability and the conductivity are improved; the core-shell structure is beneficial to relieving the volume change of sulfur; the composite material has the capability of adsorbing polysulfide and inhibiting shuttle effect.
Description
Technical Field
The invention belongs to the technical field of new energy materials, and particularly relates to a nano bracelet iron trioxide/graphene quantum dot/tin dioxide core-shell structure composite material, and a preparation method and application thereof.
Background
In the field of energy technology, lithium sulfur batteries are receiving much attention as secondary lithium batteries, and compared with commercially available lithium ion batteries, lithium sulfur batteries have higher specific energy (2600W · h/kg), lower cost of sulfur as an active material, and higher safety in use, and alleviate dendritic crystals generated during charging and discharging of the batteries, thereby increasing the safety of the batteries.
Much research has been done in this direction due to the advantages of lithium-sulfur batteries, but sulfur has poor conductivity, high volume expansion during charge-discharge cycles, and lithium polysulfide (Li) as an intermediate product during the reaction process 2 S n And n is more than or equal to 4 and less than or equal to 8) causes serious shuttling effect and the like, and the problems cause low coulombic efficiency, poor cycle performance and active material loss of the lithium-sulfur battery. Thereby limiting the production and use of the lithium-sulfur battery and being incapable of meeting the requirements in actual life.
Disclosure of Invention
In order to solve the technical problems, the invention provides a nano bracelet iron sesquioxide/graphene quantum dot/tin dioxide core-shell structure composite material and a preparation method thereof. Firstly synthesizing nano bracelet-shaped ferric oxide, then adsorbing graphene quantum dots with good performance, wrapping the outer layers of the graphene quantum dots ferric oxide with silicon dioxide, and finally dissolving the silicon dioxide in a solution through wrapping of tin dioxide to obtain the nano bracelet-shaped ferric oxide/graphene quantum dots/tin dioxide composite material with the core-shell structure. The inside is hollow nanometer bracelet nucleocapsid structure, not only can hold more sulphur active material when the sulphur fumigation to nucleocapsid structure also can effectually alleviate the volume expansion problem of sulphur in the charge-discharge process.
The invention also provides application of the nano bracelet iron trioxide/graphene quantum dot/stannic oxide core-shell structure composite material in manufacturing lithium-sulfur batteries. After the nano-bracelet iron trioxide/graphene quantum dot/stannic oxide core-shell structure composite material prepared by the method is used as a raw material for fumigating sulfur, the prepared lithium-sulfur battery anode is assembled into a lithium-sulfur battery, the battery has good cycling stability, and the battery capacity is still stabilized at 1007mAh g after 100 times of cycling -1 。
The specific technical scheme of the invention is as follows:
the nano bracelet iron sesquioxide/graphene quantum dot/tin dioxide core-shell structure composite material comprises the following steps:
1) adding an iron source into water, continuously adding a pH buffering agent, mixing and stirring uniformly, and carrying out hydrothermal reaction to obtain nano-scale iron sesquioxide;
2) dispersing the nano-bracelet ferric oxide prepared in the step 1) in water, adding a graphene quantum dot solution, uniformly dispersing, and carrying out hydrothermal reaction to obtain graphene quantum dot ferric oxide;
3) dispersing the graphene quantum dot ferric oxide prepared in the step 2) in a solvent, stirring uniformly, adding ammonia water and a silicon source, mixing, stirring and reacting to obtain a nano bracelet graphene quantum dot ferric oxide/silicon dioxide composite nano material composite material;
4) dispersing the nano bracelet graphene quantum dot iron trioxide/silicon dioxide composite nano material composite material prepared in the step 3) in a solvent, adding urea and a tin source, uniformly stirring, and carrying out hydrothermal reaction to obtain the nano bracelet iron trioxide/graphene quantum dot/tin dioxide core-shell structure composite material.
The pH buffering agent in the step 1) consists of sodium sulfate and sodium dihydrogen phosphate;
in the step 1), the dosage ratio of the iron source to the water is 2-12mg/mL, preferably 2.5-10 mg/mL; the iron source in the step 1) is selected from ferric chloride; the dosage ratio of the sodium sulfate to the water in the pH buffering agent is 0.01-0.09mg/mL, preferably 0.02-0.05 mg/mL; the dosage ratio of the sodium dihydrogen phosphate to the super water in the pH buffering agent is 0.01-0.06mg/mL, and preferably 0.02-0.05 mg/mL.
And mixing sodium sulfate and sodium dihydrogen phosphate to obtain a pH buffer solution, and jointly adjusting the acid-base environment to enable the ferric chloride to generate the nano-iron oxide bracelet in a high-temperature weak-alkali environment.
In the step 1), the hydrothermal reaction temperature is 120-230 ℃, preferably 180-220 ℃; the time of the hydrothermal reaction is 12-50h, preferably 24-48 h;
in the step 1), after the hydrothermal reaction is finished, cooling and washing are carried out, and the nano iron sesquioxide of the bracelet is obtained.
In the step 2), the nano-ferric oxide bracelet is dispersed in water, and the dosage ratio is 1-5mg/mL, preferably 2-4 mg/mL;
in the step 2), the concentration of the graphene quantum dot solution is 1mg/ml, and the graphene quantum dot solution is a commercial graphene quantum dot solution. The volume ratio of the graphene quantum dot solution to the water is 1: 3-7;
in the step 2), the temperature of the hydrothermal reaction is 100-200 ℃, preferably 150-200 ℃; the time of the hydrothermal reaction is 5-20h, preferably 8-14 h;
in the step 2), after the hydrothermal reaction, after the solution is cooled, centrifugal drying is carried out, and the graphene quantum dot ferric oxide is obtained.
In the step 3), after the reaction is finished, centrifuging, washing and drying to obtain a nano bracelet graphene quantum dot ferric oxide/silicon dioxide composite nano material composite material;
the solvent in the step 3) is deionized water or a mixed solution of absolute ethyl alcohol and deionized water;
when the mixed solution of absolute ethyl alcohol and deionized water is adopted, the volume ratio of the absolute ethyl alcohol to the deionized water is 3:1-8: 1;
the dosage ratio of the graphene quantum dot ferric oxide to the solvent in the step 3) is 2-6mg/mL, preferably 2-4 mg/mL;
the volume ratio of the ammonia water to the solvent in the step 3) is 1-3.5: 30-50 parts of; preferably 1.5 to 3: 30-50 parts of; the volume ratio of the silicon source to the solvent is 1-3.5: 30-50, preferably 1.5-3: 30-50.
The concentration of the ammonia water in the step 3) is 1.58 mol/L; used for regulating pH value.
In the step 3), the silicon source is tetraethyl orthosilicate.
The stirring time in the step 3) is 1-5h, preferably 2-3 h; the reaction temperature is not required, and is preferably: the reaction was carried out at room temperature. In the reaction process, the silicon dioxide globules are continuously polymerized on the surface of the graphene quantum dot iron oxide.
The solvent in the step 4) is a mixed solution of absolute ethyl alcohol and deionized water, which is helpful for dissolving the solute; the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 1-2: 1.
in the step 4), the dosage ratio of the nano bracelet graphene quantum dot ferric oxide/silicon dioxide composite nano material composite material to the solvent is 2-5mg/mL, preferably 3-4 mg/mL;
the dosage ratio of the urea to the solvent in the step 4) is 0.01-0.05g/mL, preferably 0.03-0.04 g/mL; adding urea to adjust the pH value;
the dosage ratio of the tin source to the solvent in the step 4) is 2-5mg/mL, and preferably 3-4.5 mg/mL;
the tin source in the step 4) is potassium stannate or sodium stannate;
the temperature of the hydrothermal reaction in the step 4) is 120-200 ℃, preferably 150-180 ℃; the time of the hydrothermal reaction is 2-6h, preferably 4-6 h.
And 4) after the hydrothermal reaction is finished, standing, collecting precipitate, washing the precipitate and drying to obtain the nano bracelet iron trioxide/graphene quantum dot/tin dioxide core-shell structure composite material.
The nano bracelet iron trioxide/graphene quantum dot/stannic oxide core-shell structure composite material is prepared by the method, has an overall diameter of 100-200nm, and has a nano bracelet core-shell structure with an internal hollow diameter of 50-60nm, wherein the graphene quantum dot iron trioxide is arranged inside the nano bracelet core-shell structure, and the stannic oxide is arranged outside the nano bracelet core-shell structure.
The battery application of the nano bracelet iron trioxide/graphene quantum dot/tin dioxide core-shell structure composite material provided by the invention is used for manufacturing a lithium-sulfur battery. The specific manufacturing method comprises the following steps: and (3) fumigating sulfur by using the nano bracelet iron trioxide/graphene quantum dot/stannic oxide core-shell structure composite material, and then manufacturing the lithium-sulfur battery anode to further prepare the lithium-sulfur battery.
Firstly, obtaining a nano annular ferric oxide precursor by a hydrothermal method, and then adsorbing graphene quantum dots in the hydrothermal process to enable the graphene quantum dots to be adhered to the surface of the precursor; and finally, compounding a layer of tin dioxide in an alkaline environment regulated by urea, and dissolving the silicon dioxide in the reaction process to obtain the nano bracelet iron trioxide/graphene quantum dot/tin dioxide core-shell structure composite material. If the silicon dioxide layer is not used as a support, tin dioxide grows outside the silicon dioxide, and the silicon dioxide is dissolved, so that a core-shell structure cannot be formed. The graphene quantum dots contained in the composite material are strong in stability, high in acid-base tolerance, excellent in conductivity and environment-friendly, the volume change of sulfur in the charging and discharging process can be effectively relieved by gaps in a core-shell structure of the composite material, the sulfur material is evaporated at high temperature, gap small holes are formed in the outermost tin dioxide layer, gaseous sulfur can volatilize into the core-shell structure, a tin dioxide/S/graphene quantum dot iron oxide structure is formed, the active material sulfur is coated in the tin dioxide layer, the loss of sulfur in the charging and discharging process is reduced, and the performance of a battery is improved. Therefore, the material is used as the anode of the lithium-sulfur battery and has the characteristics of higher capacity and stable cycle performance.
Compared with the prior art, the invention has the following advantages: (1) graphene quantum dots are adsorbed in the material, so that the stability and the conductivity are improved; (2) the core-shell structure is beneficial to relieving the volume change of sulfur; (3) the composite material has the capability of adsorbing polysulfide and inhibiting shuttle effect.
Drawings
FIG. 1 is an SEM image of step 1) of nanometer bracelet iron oxide in example 4;
FIG. 2 is an SEM image (enlarged view) of the nano iron sesquioxide in step 1) of example 4;
fig. 3 is an SEM image of the nano-bracelet graphene quantum dot iron trioxide/silicon dioxide of step 3) of example 4;
fig. 4 is an SEM image of core-shell structure nano bracelet graphene quantum dot iron trioxide/tin dioxide in step 4) of example 4;
fig. 5 is a TEM image of graphene quantum dots;
FIG. 6 is a TEM image of core-shell structure nano-bracelet iron sesquioxide/graphene quantum dots/tin dioxide in step 4) of example 4;
fig. 7 is a TEM image of core-shell structure nano-bracelet iron trioxide/graphene quantum dots/tin dioxide in step 4) of example 5;
fig. 8 is an XRD pattern of the core-shell structure nano bracelet iron sesquioxide/graphene quantum dot/tin dioxide composite material prepared in example 6 after sulfur fumigation;
fig. 9 is a graph illustrating a cycle stability test of the core-shell structure nano bracelet iron trioxide/graphene quantum dot/tin dioxide composite material prepared in example 6 after being subjected to sulfur fumigation as a lithium sulfur battery under a current of 0.4C;
fig. 10 is a charge-discharge curve diagram of the core-shell structure nano bracelet iron trioxide/graphene quantum dot/tin dioxide composite material prepared in example 6 after being subjected to sulfur fumigation, as a lithium sulfur battery, under 0.4C current.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, 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 some embodiments of the present invention, but not all 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.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
The preparation method of the nano bracelet iron trioxide/graphene quantum dot/tin dioxide core-shell structure composite material comprises the following steps:
1) adding 0.35g of ferric chloride into 35ml of deionized water, adding 0.002g of sodium sulfate and 0.001g of sodium dihydrogen phosphate, mixing and stirring uniformly, transferring the solution into a polytetrafluoroethylene inner container for hydrothermal reaction, setting the temperature to be 170 ℃, maintaining for 24 hours, cooling to room temperature, washing and drying to obtain nano-ferric oxide bracelet;
2) dispersing 0.12g of the nano-iron sesquioxide of the bracelet obtained in the step 1) in 28ml of water, adding 6ml of commercial graphene quantum dot solution with the concentration of 1mg/ml, performing ultrasonic treatment until the solution is uniform, transferring the solution to a polytetrafluoroethylene inner container for hydrothermal reaction, setting the temperature to be 160 ℃, maintaining the temperature for 8 hours, cooling the solution, centrifuging and drying to obtain the graphene quantum dot ferric oxide;
3) mixing 0.13g of graphene quantum dot ferric oxide obtained in the step 2) with 35ml of absolute ethyl alcohol and 5ml of deionized water, stirring uniformly, adding 2ml of ammonia water with the concentration of 1.58mol/L and 1.8ml of tetraethyl orthosilicate, mixing, stirring and reacting for 3 hours, and centrifuging, washing and drying after the reaction is finished to obtain the nano bracelet ferric oxide/graphene quantum dot/silicon dioxide composite nanomaterial composite material;
4) and 3) adding 20ml of deionized water and 10ml of ethanol into 0.1g of the nano-bracelet iron sesquioxide/graphene quantum dot/silicon dioxide composite material obtained in the step 3), mixing, adding 0.75g of urea and 0.1g of potassium stannate, uniformly stirring, transferring the solution into a polytetrafluoroethylene inner container, carrying out hydrothermal reaction at 150 ℃ for 5h, dissolving the silicon dioxide in the solution in the reaction process, cooling to room temperature after the reaction is finished, washing, and drying to obtain the nano-bracelet iron sesquioxide/graphene quantum dot/tin dioxide core-shell structure composite material.
Example 2
The preparation method of the nano bracelet iron trioxide/graphene quantum dot/tin dioxide core-shell structure composite material comprises the following steps:
1) adding 0.25g of ferric chloride, 0.0026g of sodium sulfate and 0.00125g of sodium dihydrogen phosphate into 30ml of deionized water, mixing and stirring uniformly, transferring the solution into a polytetrafluoroethylene inner container for hydrothermal reaction, setting the temperature to be 180 ℃, maintaining for 28h, cooling to room temperature, washing and drying to obtain nano ferric oxide of the bracelet;
2) dispersing 0.15g of the nano-iron sesquioxide of the bracelet obtained in the step 1) in 30ml of water, adding 8ml of commercial graphene quantum dot solution with the concentration of 1mg/ml, performing ultrasonic treatment until the solution is uniform, transferring the solution to a polytetrafluoroethylene inner container for hydrothermal reaction, setting the temperature at 180 ℃, maintaining the temperature for 10 hours, cooling the solution, centrifuging and drying to obtain the graphene quantum dot ferric oxide;
3) mixing 0.165g of graphene quantum dot ferric oxide obtained in the step 2) with 32ml of absolute ethyl alcohol and 8ml of deionized water, stirring uniformly, adding 2.3ml of ammonia water with the concentration of 1.58mol/L and 1.4ml of tetraethyl orthosilicate, mixing, stirring, reacting for 2.5 hours, and centrifuging, washing and drying after the reaction is finished to obtain the nano bracelet ferric oxide/graphene quantum dot/silicon dioxide composite nanomaterial composite material;
4) adding 22ml of deionized water and 12ml of ethanol into 0.125g of the nano-bracelet iron trioxide/graphene quantum dot/silicon dioxide composite material obtained in the step 3), mixing, adding 0.655g of urea and 0.12g of potassium stannate, uniformly stirring, transferring the solution into a polytetrafluoroethylene inner container, carrying out hydrothermal reaction at 180 ℃, reacting for 6 hours, and dissolving the silicon dioxide in the solution in the reaction process. And cooling to room temperature, washing and drying to obtain the nano bracelet iron trioxide/graphene quantum dot/tin dioxide core-shell structure composite material.
Example 3
The preparation method of the nano bracelet iron trioxide/graphene quantum dot/stannic oxide core-shell structure composite material comprises the following steps:
1) adding 0.26g of ferric chloride, 0.00345g of sodium sulfate and 0.00125g of sodium dihydrogen phosphate into 40ml of deionized water, mixing and stirring uniformly, transferring the solution into a polytetrafluoroethylene inner container for hydrothermal reaction, setting the temperature to be 180 ℃, maintaining for 36 hours, cooling to room temperature, washing and drying to obtain nano-ferric oxide bracelet;
2) dissolving 0.15g of the nano-iron sesquioxide of the bracelet obtained in the step 1) in 32ml of water, adding 6ml of commercial graphene quantum dot solution with the concentration of 1mg/ml, performing ultrasonic treatment until the solution is uniform, transferring the solution to a polytetrafluoroethylene inner container for hydrothermal reaction, setting the temperature at 180 ℃, maintaining the temperature for 10 hours, cooling the solution, centrifuging and drying to obtain the graphene quantum dot ferric oxide;
3) mixing 0.13g of graphene quantum dot ferric oxide obtained in the step 2) with 28ml of absolute ethyl alcohol and 6ml of deionized water, stirring uniformly, adding 2ml of ammonia water with the concentration of 1.58mol/L and 1.6ml of tetraethyl orthosilicate, mixing, stirring and reacting for 2.5 hours, and centrifuging, washing and drying after the reaction is finished to obtain the nano bracelet ferric oxide/graphene quantum dot/silicon dioxide composite nanomaterial composite material;
4) adding 18ml of deionized water and 10ml of ethanol into 0.125g of the composite material of the nano-bracelet iron sesquioxide/graphene quantum dot/silicon dioxide obtained in the step 3), mixing, adding 0.95g of urea and 0.13g of potassium stannate, uniformly stirring, transferring the solution into a polytetrafluoroethylene inner container, carrying out hydrothermal reaction at 160 ℃, reacting for 5 hours, and dissolving the silicon dioxide in the solution in the reaction process. And after the reaction is finished, cooling to room temperature, washing and drying to obtain the ferric oxide/graphene quantum dot/tin dioxide composite material.
Example 4
The preparation method of the nano bracelet iron trioxide/graphene quantum dot/tin dioxide core-shell structure composite material comprises the following steps:
1) adding 0.245g of ferric chloride, 0.0029g of sodium sulfate and 0.00122g of sodium dihydrogen phosphate into 35ml of deionized water, mixing and stirring uniformly, transferring the solution into a polytetrafluoroethylene inner container for hydrothermal reaction, setting the temperature to be 180 ℃, maintaining for 30h, cooling to room temperature, washing and drying to obtain nano-ferric oxide bracelet; the SEM images are shown in fig. 1 and 2, in fig. 1, the nano bracelet ferric oxide is uniformly distributed, in fig. 2, the nano bracelet ferric oxide is single, the appearance of the nano bracelet is clearly visible, and the diameter is about 200 nm;
2) dispersing 0.135g of the nano-iron sesquioxide of the bracelet obtained in the step 1) in 35ml of water, adding 5ml of commercial graphene quantum dot solution with the concentration of 1mg/ml, performing ultrasonic treatment until the solution is uniform, transferring the solution to a polytetrafluoroethylene inner container for hydrothermal reaction, setting the temperature at 180 ℃, maintaining the temperature for 8 hours, cooling the solution, centrifuging and drying to obtain the graphene quantum dot ferric oxide;
3) mixing 0.1g of graphene quantum dot ferric oxide obtained in the step 2) with 36ml of absolute ethyl alcohol and 5ml of deionized water, stirring uniformly, adding 2ml of ammonia water with the concentration of 1.58mol/L and 1.8ml of tetraethyl orthosilicate, mixing, stirring and reacting for 3.5 hours, and centrifuging, washing and drying after the reaction is finished to obtain the nano bracelet ferric oxide/graphene quantum dot/silicon dioxide composite nanomaterial composite material; the SEM image is shown in fig. 3, which shows that the surface of the originally smooth nano bracelet is covered with a layer of coarse material, and the ferric oxide/graphene quantum dot/silicon dioxide composite material is obtained;
4) adding 18ml of deionized water and 10ml of ethanol into 0.133g of the composite material of the nano-bracelet iron trioxide/graphene quantum dot/silicon dioxide obtained in the step 3), mixing, adding 0.95g of urea and 0.12g of potassium stannate, uniformly stirring, transferring the solution into a polytetrafluoroethylene inner container, carrying out hydrothermal reaction at 180 ℃, reacting for 6 hours, and dissolving the silicon dioxide in the solution in the reaction process. And after the reaction is finished, cooling to room temperature, washing and drying to obtain the ferric oxide/graphene quantum dot/tin dioxide composite material. The SEM image is shown in FIG. 4, which shows the core-shell structure of the ferric oxide/graphene quantum dot/tin dioxide material;
fig. 5 is a TEM image of pure graphene quantum dots, wherein the graphene quantum dots should be small particles of about 1 nm; the TEM image of the step 4) is shown in FIG. 6, the core-shell structure is clearly shown in the image, the morphology of the graphene quantum dots adsorbed in the middle is consistent with the transmission characterization of the graphene quantum dots in FIG. 5, and the final product is proved to obtain the core-shell structure nano bracelet iron trioxide/graphene quantum dots/tin dioxide material.
Example 5
The preparation method of the nano bracelet iron trioxide/graphene quantum dot/tin dioxide core-shell structure composite material comprises the following steps:
1) adding 0.35g of ferric chloride, 0.002g of sodium sulfate and 0.001g of sodium dihydrogen phosphate into 35ml of deionized water, mixing and stirring uniformly, transferring the solution into a polytetrafluoroethylene inner container for hydrothermal reaction, setting the temperature to be 170 ℃, maintaining for 24 hours, cooling to room temperature, washing and drying to obtain the nano ferric oxide bracelet;
2) dispersing 0.12g of the nano-iron sesquioxide of the bracelet obtained in the step 1) in 28ml of water, adding 6ml of commercial graphene quantum dot solution with the concentration of 1mg/ml, performing ultrasonic treatment until the solution is uniform, transferring the solution to a polytetrafluoroethylene inner container for hydrothermal reaction, setting the temperature to be 160 ℃, maintaining the temperature for 8 hours, cooling the solution, centrifuging and drying to obtain the graphene quantum dot ferric oxide;
3) mixing 0.135g of graphene quantum dot ferric oxide obtained in the step 2) with 40ml of absolute ethyl alcohol and 6ml of deionized water, stirring uniformly, adding 2.5ml of ammonia water with the concentration of 1.58mol/L and 1.8ml of tetraethyl orthosilicate, mixing, stirring, reacting for 2.5 hours, and centrifuging, washing and drying after the reaction is finished to obtain the nano bracelet ferric oxide/graphene quantum dot/silicon dioxide composite nanomaterial composite material;
4) adding 15ml of deionized water and 15ml of ethanol into 0.1g of the nano-bracelet iron sesquioxide/graphene quantum dot/silicon dioxide composite material obtained in the step 3), mixing, adding 0.8g of urea and 0.14g of potassium stannate, uniformly stirring, transferring the solution into a polytetrafluoroethylene inner container, carrying out hydrothermal reaction at 180 ℃, reacting for 6 hours, and dissolving the silicon dioxide in the solution in the reaction process. And after the reaction is finished, cooling to room temperature, washing and drying to obtain the ferric oxide/graphene quantum dot/tin dioxide composite material. The transmission characterization in fig. 7 can show the morphology of the graphene quantum dot iron trioxide adsorbed by the graphene quantum dot iron trioxide and then wrapped by a tin dioxide layer, and proves that the final product is a core-shell structure nano bracelet iron trioxide/graphene quantum dot/tin dioxide material;
example 6
The application of the nano bracelet iron trioxide/graphene quantum dot/tin dioxide core-shell structure composite material in the preparation of the lithium-sulfur battery specifically comprises the following steps:
A. and (3) carrying out a sulfur fumigation operation on the final product of the nano-bracelet iron trioxide/graphene quantum dot/tin dioxide core-shell structure composite material obtained in the embodiment 4: mixing sulfur powder and a product in a ratio of 2: 1, pouring the mixture into a polytetrafluoroethylene plastic bottle, exhausting air in an argon environment, sealing, heating in an oven at 155 ℃ for 24 hours, and taking out a sample after cooling to room temperature. An XRD (X-ray diffraction) pattern of the nano bracelet iron trioxide/graphene quantum dot/tin dioxide core-shell structure composite material subjected to sulfur fumigation is shown in figure 8, peaks of sulfur, iron trioxide and tin dioxide are clearly visible, and a high-strength sulfur peak also proves that the material successfully loads a large amount of sulfur active substances.
B. The cured sample was mixed with conductive carbon black, PVDF in a 7: 2: 1, preparing the mixture into uniform slurry by using an N-methylpyrrolidone (NMP) solvent, coating the uniform slurry on an aluminum foil, uniformly coating the uniform slurry into a film by using a scraper, and uniformly adhering the film to the surface of the aluminum foil. Then the prepared coating is placed in a drying oven and dried for 12 hours at the temperature of 60 ℃; after drying, moving the mixture into a vacuum drying oven, and carrying out vacuum drying for 10 hours at the temperature of 60 ℃; then tabletting the dried composite material coating by a roller machine or a tablet press and the like; and cutting an electrode plate by adopting a mechanical cutting machine, taking a lithium plate as a counter electrode, and assembling the lithium sulfur battery by using a commercially available 1mol/L LiTFSI/DME + DOL solution as an electrolyte.
The charge and discharge performance of the lithium-sulfur battery was tested using a battery tester, and the results of the cycling stability test of the obtained product as a positive electrode material of the lithium-sulfur battery at a current of 0.4C are shown in fig. 9 and 10. As can be seen from fig. 9, at a larger current, the capacity and the cycling stability of the battery are still good, and the capacity of the battery is still stabilized at 1007mAh g after 100 cycles -1 It can be seen from fig. 10 that the battery has a stable charging and discharging platform during the charging and discharging process.
The above-mentioned detailed description of the nano bracelet iron trioxide/graphene quantum dot/tin dioxide core-shell structure composite material, the preparation method thereof and the lithium sulfur battery using the composite material in the present invention with reference to the embodiments is illustrative and not restrictive, and several embodiments may be listed according to the limited scope, so that changes and modifications without departing from the general concept of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. The preparation method of the nano bracelet iron trioxide/graphene quantum dot/tin dioxide core-shell structure composite material comprises the following steps:
1) adding an iron source into water, continuously adding a pH buffering agent, mixing and stirring uniformly, and carrying out hydrothermal reaction to obtain nano-scale iron sesquioxide;
2) dispersing the nano-bracelet ferric oxide prepared in the step 1) in water, adding a graphene quantum dot solution, uniformly dispersing, and carrying out hydrothermal reaction to obtain graphene quantum dot ferric oxide;
3) dispersing the graphene quantum dot ferric oxide prepared in the step 2) in a solvent, stirring uniformly, adding ammonia water and a silicon source, mixing, stirring and reacting to obtain a nano bracelet graphene quantum dot ferric oxide/silicon dioxide composite nano material composite material;
4) dispersing the nano bracelet graphene quantum dot ferric oxide/silicon dioxide composite nano material composite material prepared in the step 3) in a solvent, adding urea and a tin source, uniformly stirring, and carrying out hydrothermal reaction to obtain the nano bracelet ferric oxide/graphene quantum dot/tin dioxide core-shell structure composite material.
2. The method of claim 1, wherein the pH buffer in step 1) consists of sodium sulfate and sodium dihydrogen phosphate; the dosage ratio of the iron source to the water is 2-12mg/ml, and the dosage ratio of the sodium sulfate to the water in the pH buffering agent is 0.01-0.09 mg/ml; the dosage ratio of the sodium dihydrogen phosphate to the water in the pH buffering agent is 0.01-0.06 mg/ml.
3. The preparation method as claimed in claim 1 or 2, wherein the hydrothermal reaction temperature in step 1) is 120-230 ℃ and the reaction time is 12-50 h.
4. The preparation method as claimed in claim 1, wherein the temperature of the hydrothermal reaction in step 2) is 100-200 ℃ and the reaction time is 5-20 h.
5. The preparation method according to claim 1, wherein the solvent in step 3) is a mixed solution of absolute ethyl alcohol and deionized water; the volume ratio of the absolute ethyl alcohol to the deionized water is 3:1-8: 1.
6. The preparation method according to claim 1, wherein the solvent in step 4) is a mixed solution of absolute ethyl alcohol and deionized water; the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 1-2: 1.
7. the preparation method as claimed in claim 1 or 6, wherein the hydrothermal reaction in step 4) is carried out at a temperature of 120 ℃ and 200 ℃ for a time of 2-6 h.
8. The preparation method according to claim 1 or 6, wherein the dosage ratio of the nano bracelet graphene quantum dot iron trioxide/silicon dioxide composite nano material composite material to the solvent in the step 4) is 2-5mg/ml, and the dosage ratio of the urea to the solvent is 0.01-0.05 g/ml; the dosage ratio of the tin source to the solvent is 2-5 g/ml.
9. The nano bracelet iron trioxide/graphene quantum dot/tin dioxide core-shell structure composite material prepared by the method of any one of claims 1 to 8.
10. Application of the nano bracelet iron trioxide/graphene quantum dot/tin dioxide core-shell structure composite material prepared by the method according to any one of claims 1 to 8 in manufacturing of lithium-sulfur batteries.
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