CN111106346B - SnS2rGO modified sulfur cathode material and preparation method and application thereof - Google Patents
SnS2rGO modified sulfur cathode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a SnS2the/rGO modified sulfur cathode material and the preparation method and the application thereof comprise the following steps: (1) dissolving a polystyrene template, a tin source and a sulfur source in a solvent, and carrying out solvothermal reaction to obtain a tin disulfide material; (2) mixing a tin disulfide material and graphite oxide, adding the mixture into water, uniformly drying the mixture, and calcining the dried mixture to obtain a tin disulfide/graphene composite material; (3) commercial sulfur and a tin disulfide/graphene composite material are mixed and then placed in a high-temperature furnace for vacuum reaction, and a final product is obtained. SnS prepared by the invention2The rGO modified sulfur anode material effectively combines the advantages of metal sulfides and carbon materials, improves the conductivity of the sulfur anode, improves the active sites of the material, can effectively relieve the volume expansion of the sulfur anode in the charging and discharging process, avoids the problems of reduced charging and discharging efficiency and too fast capacity attenuation caused by the volume expansion, and further improves the electrochemical performance of the material.
Description
Technical Field
Hair brushBelongs to the field of new energy nano material technology and lithium-sulfur batteries, and particularly relates to SnS2A/rGO modified sulfur positive electrode material, a preparation method and an application thereof.
Background
Through decades of development, lithium ion batteries have been successfully applied in the fields of portable electronic products, electric vehicles, and the like. However, conventional positive electrodes (e.g., LiCoO)2、LiFePO4) Negative electrodes (e.g. Graphite, Li)4Ti5O12) The material reaches the energy limit which can be exerted by the material per se, and the requirement of rapid development of the industry cannot be met. Therefore, it is not always easy to develop a high-performance battery material. Elemental sulfur is one of the most abundant elements in the earth crust and can provide 1675 mAh.g in lithium ion battery-1Theoretical specific capacity of 2600Wh kg-1The energy density of (1). In addition, the elemental sulfur also has the advantages of low price, environmental friendliness and the like. However, the problems of dissolution of polysulfide, shuttle effect, and safety of lithium sulfur batteries limit their commercial applications.
A typical lithium-sulfur battery consists of a sulfur positive electrode, a metallic lithium negative electrode, an organic electrolyte and a polymeric separator. In recent years, researchers have attempted various methods to improve the electrochemical performance of lithium sulfur batteries. Among them, there are many reports on modification of a sulfur positive electrode material. Currently, the ideal sulfur positive electrode structure has several characteristics: compact structure for effectively fixing polysulfide, appropriate specific surface area, space capable of accommodating volume expansion of sulfur, and short ion and electron migration paths.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an SnS2rGO modified sulfur positive electrode material, preparation method and application thereof, and SnS prepared by the invention2the/rGO modified sulfur cathode material can effectively improve the expansion problem and improve the cycling stability of the material, and compared with the traditional graphite material, the energy density has obvious advantages.
In order to achieve the purpose, the invention adopts the technical scheme that:
SnS2The preparation method of the/rGO modified sulfur cathode material specifically comprises the following steps:
(1) dissolving a polystyrene template, a tin source and a sulfur source in an ethylene glycol solvent, uniformly stirring and mixing, carrying out a solvothermal reaction, and washing and drying after the reaction to obtain a tin disulfide material;
(2) mixing a tin disulfide material and graphite oxide, adding the mixture into water, ultrasonically mixing the mixture uniformly, drying the mixture, placing the dried mixture in an inert atmosphere, and calcining the dried mixture to obtain a tin disulfide/graphene composite material; the purpose of calcination is to reduce graphite oxide while compounding with tin disulfide;
(3) commercial sulfur and a tin disulfide/graphene composite material are mixed and then placed in a high-temperature furnace for vacuum reaction, and a final product is obtained. In the vacuum reaction process, the sulfur simple substance is changed into a molten state, and the reaction is carried out in a flowing mode, so that the sulfur is uniformly distributed among the graphene sheet layers.
In a further scheme, in the step (1), the tin source is selected from one of stannous chloride dihydrate and anhydrous stannic chloride; the sulfur source is selected from one of sodium thiosulfate, thioacetamide and sodium sulfide; the temperature of the solvothermal reaction is 120-180 ℃, and the time is 12-18 h.
According to a further scheme, in the step (2), the mass ratio of the tin disulfide material to the graphite oxide is 3: 1-5: 1; the drying mode is freeze drying, and the temperature of the freeze drying is minus 30 ℃ to minus 10 ℃; the calcination is carried out in a tube furnace; the calcining temperature is 400-700 ℃, and the time is 3-6 h.
Further, in the step (3), the mass ratio of the commercial sulfur to the product B is 4: 1-7: 1; the heating rate of the high-temperature furnace is 3-5 ℃/min, the temperature of the vacuum reaction is 150-180 ℃, and the time is 12-15 h.
The invention also aims to provide SnS prepared by the preparation method2the/rGO modified sulfur cathode material.
The third purpose of the invention is to provide the SnS2Application of/rGO modified sulfur cathode material in lithium sulfur batteries.
Compared with the prior art, the invention has the following beneficial effects:
(1) the main raw materials required by the preparation method are rich in source, low in price and low in cost; SnS prepared by taking polystyrene as a template2The appearance is better, and presents a spherical appearance.
(2) Graphene (rGO) has higher specific surface area and conductivity, and can provide more active sites; the metal sulfide has good conductivity, and the chemical bond is similar to polysulfide, so that stronger chemical interaction can be generated, and the electrochemical performance of the lithium-sulfur battery is improved. According to the invention, the graphene with large specific surface area and high conductivity is used as a sulfur-fixing matrix, so that the dissolution of polysulfide is effectively inhibited, and the volume expansion is relieved. Since graphene belongs to a non-polar substance and has a weak physical effect with polar polysulfide, the sulfur fixation effect is greatly reduced along with the increase of cycle times. To synthesize SnS2the/rGO material can improve the polarity of the material, form stronger chemical interaction with polysulfide, accelerate the redox reaction of the polysulfide and further improve the electrochemical activity of the lithium-sulfur battery. SnS prepared by the invention2The rGO modified sulfur anode material effectively combines the advantages of metal sulfide and carbon materials, improves the conductivity of the sulfur anode, improves the active sites of the material, has good structural stability, can effectively relieve the volume expansion of the sulfur anode in the charge-discharge process, avoids the problems of reduced charge-discharge efficiency and too fast capacity attenuation caused by the volume expansion, and further improves the electrochemical performance of the material.
(3) SnS prepared by the invention2the/rGO modified sulfur cathode material greatly improves the cycle performance and rate capability of the material, has simple and convenient preparation process, and is beneficial to large-scale production.
Drawings
FIG. 1 shows SnS obtained in example 12a/rGO modified sulfur positive electrode material rate performance diagram;
FIG. 2 shows SnS obtained in example 12a/rGO modified sulfur positive electrode material cycle performance diagram.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the embodiments described are only a few embodiments of the present invention, and 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.
Example 1
Weighing 1g of polystyrene template solid powder by using an electronic balance, adding the polystyrene template solid powder into 50mL of glycol solvent, fully stirring, uniformly mixing, adding 2.25g of stannous chloride dihydrate and 1.58g of sodium thiosulfate solid powder into the mixed solution, fully mixing to form a transparent solution, transferring the solution into a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 12h at 180 ℃, centrifugally cleaning the obtained precipitate by using ethanol, soaking the obtained solid substance in toluene to remove the polystyrene template, then washing by using ethanol, and carrying out vacuum drying (60 ℃, 12 h) to obtain the product. Preparing graphite oxide by using a Hummers method, which comprises the following steps: 70mL of sulfuric acid and 0.5g of sodium nitrate were poured into a 50mL round-bottom flask, and the round-bottom flask was transferred to an ice-water bath and vigorously stirred for 30min until the sodium nitrate was completely dissolved. Then slowly adding the weighed 1g of natural graphite into a round-bottom flask, and stirring for 1 hour with strong force to uniformly mix the graphite; then 3g of potassium permanganate is weighed and slowly added into the round-bottom flask, the temperature is controlled to be not more than 10 ℃, and then the mixed solution is maintained for 2 hours under high-speed stirring, and the color of the solution gradually changes into dark green. The round bottom flask was transferred to a 35 ℃ water bath and stirred for 2h, after stirring was completed 100mL of room temperature deionized water was added, during which the temperature rose sharply, reaching approximately 80 ℃, and then transferred to an 85 ℃ water bath and stirred for 30 min. Pouring the mixed solution into a 1000mL beaker, diluting to 400mL with warm water at 60 ℃, adding 100mL of 5% hydrogen peroxide solution until the solution is bright yellow and no bubbles are generated, and continuing stirring for 30 min. And then, leaching with 500mL of 60 ℃ warm water, washing with 10% hydrochloric acid solution, repeatedly centrifuging and cleaning with deionized water until the supernatant is neutral, pouring the obtained precipitate into a tray, and freeze-drying in a vacuum freeze-drying machine to obtain a product for later use. Mixing the solid powder with graphite oxide prepared by a Hummers method according to a mass ratio of 3:1, dissolving the mixture in 50mL of aqueous solution, ultrasonically mixing the mixture uniformly, freeze-drying the mixture at-30 ℃, placing the mixture in a tubular furnace, heating the mixture to 700 ℃ at a heating rate of 5 ℃/min under the protection of argon atmosphere, preserving the temperature for 3h, cooling the mixture, taking the mixture out, uniformly mixing the mixture with commercial sulfur according to a mass ratio of 1:4, placing the mixture in a high-temperature furnace, heating the mixture to 150 ℃ at a heating rate of 3 ℃/min under a vacuum atmosphere, preserving the temperature for 15h, and cooling the mixture and taking the mixture out to obtain a final product.
Electrochemical performance testing was performed by assembling the materials into button half cells in a glove box. In the assembly of the half cell, a metal lithium foil is used as a negative electrode; the electrolyte is 1mol/L lithium bistrifluoromethanesulfonylimide solution (solvent is the mixture of glycol dimethyl ether and 1, 3-dioxolane in the same volume ratio); the positive electrode takes N-methyl pyrrolidone (NMP) as a solvent, 80 wt% of active substances, 10 wt% of acetylene black and 10 wt% of polyvinylidene fluoride (PVDF) are uniformly mixed, coated on a carbon-coated aluminum foil, placed in a vacuum drying oven for vacuum drying at 70 ℃ for 24 hours, naturally cooled to room temperature, placed on a roller press for rolling, so that the pole piece is tightly attached to the carbon-coated aluminum foil, cut into 12mm round pieces by a cutting machine, weighed, then placed in a vacuum glove box, and assembled into a half-cell. And standing at room temperature for 24h after the assembly is finished, and carrying out electrochemical test after the electrolyte is completely soaked.
FIG. 1 shows SnS2The multiplying power performance diagram of the/rGO modified sulfur cathode material, the test voltage range is 1.8-2.7V, and the cycle multiplying power is increased from 0.2C to 0.5C (918.88 mAh g)-1），1C（799.064 mAh g-1) To 2C (729.288 mAh g)-1) Finally to 5C (688.248 mAh g)-1) And respectively circulating for 5 circles, and finally returning to 0.2C, the reversible specific capacity can be recovered to 1079.02 mAh g-1And Wang et al S/SnS prepared by melt-diffusion reaction2The capacity of the-C material at 4C rate is only 631 mAh g-1Thus, in contrast, this material exhibits superior rate performance.
FIG. 2 shows SnS2Modified sulfur anode material of/rGOThe reversible specific capacity of the ring performance diagram after 1000 cycles under the 2C multiplying power is still maintained at 747.18 mAh g-1The capacity retention ratio was 66.8%, and under the same cycle conditions, S/C-SnS prepared by Qian et al problem group2The specific capacity of the material is 1088 mAh g-1Attenuation to 470 mAh g-1The capacity retention rate is only 43.2%, so that the material prepared by the method has excellent cycle performance.
Example 2
Weighing 1g of polystyrene template solid powder by using an electronic balance, adding the polystyrene template solid powder into 50mL of glycol solvent, fully stirring, uniformly mixing, adding 2.25g of stannous chloride dihydrate and 1.58g of thioacetamide solid powder into the mixed solution, fully mixing to form a transparent solution, transferring the solution into a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting at 120 ℃ for 18h, centrifugally cleaning the obtained precipitate with ethanol, soaking the obtained solid substance in toluene to remove the polystyrene template, then washing with ethanol, vacuum drying (at 60 ℃ and 12 h), mixing the solid powder with graphite oxide prepared by a Hummers method (the preparation method is the same as example 1) in a mass ratio of 4:1, dissolving in 50mL of aqueous solution, uniformly mixing by ultrasonic, freeze-drying at-20 ℃, placing in a tubular furnace, under the protection of argon atmosphere, heating to 400 ℃ at the heating rate of 5 ℃/min, preserving heat for 6 hours, cooling, taking out, uniformly mixing with commercial sulfur at the mass ratio of 1:7, placing in a high-temperature furnace, heating to 180 ℃ at the heating rate of 5 ℃/min under the vacuum atmosphere, preserving heat for 12 hours, cooling, and taking out to obtain the final product.
Example 3
Weighing 1g of polystyrene template solid powder by using an electronic balance, adding the polystyrene template solid powder into 50mL of glycol solvent, fully stirring, uniformly mixing, adding 2.25g of anhydrous tin chloride and 1.58g of sodium sulfide solid powder into the mixed solution, fully mixing to form a transparent solution, transferring the solution into a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 16h at 150 ℃, centrifugally cleaning the obtained precipitate with ethanol, soaking the obtained solid matter in toluene to remove the polystyrene template, then washing with ethanol, vacuum drying (60 ℃, 12 h), mixing the solid powder with graphite oxide (prepared by the Hummers method, the preparation method of which is the same as that of example 1) in a mass ratio of 5:1, dissolving in 50mL of aqueous solution, uniformly mixing by ultrasound, freeze-drying at-10 ℃, placing in a tubular furnace, under the protection of argon atmosphere, heating to 550 ℃ at the heating rate of 5 ℃/min, preserving heat for 4h, cooling, taking out, uniformly mixing with commercial sulfur at the mass ratio of 1:5, placing in a high-temperature furnace, heating to 160 ℃ at the heating rate of 3 ℃/min under the vacuum atmosphere, preserving heat for 12h, cooling, and taking out to obtain the final product.
Claims (10)
1. SnS2The preparation method of the/rGO modified sulfur cathode material is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving a polystyrene template, a tin source and a sulfur source in a solvent, stirring and mixing uniformly, then carrying out a solvothermal reaction, and washing and drying after the reaction to obtain a tin disulfide material; the washing method comprises the following steps: firstly, cleaning with ethanol, then cleaning with toluene, and finally cleaning with ethanol;
(2) mixing a tin disulfide material and graphite oxide, adding the mixture into water, ultrasonically mixing the mixture uniformly, drying the mixture, placing the dried mixture in an inert atmosphere, and calcining the dried mixture to obtain a tin disulfide/graphene composite material;
(3) commercial sulfur and a tin disulfide/graphene composite material are mixed and then placed in a high-temperature furnace for vacuum reaction, and a final product is obtained.
2. The method of claim 1, wherein: in the step (1), the tin source is selected from one of stannous chloride dihydrate and anhydrous stannic chloride; the sulfur source is selected from one of sodium thiosulfate, thioacetamide and sodium sulfide; the solvent is ethylene glycol.
3. The method of claim 1, wherein: in the step (1), the temperature of the solvothermal reaction is 120-180 ℃ and the time is 12-18 h.
4. The method of claim 1, wherein: in the step (2), the mass ratio of the tin disulfide material to the graphite oxide is 3: 1-5: 1.
5. The method of claim 1, wherein: in the step (2), the drying mode is freeze drying, and the temperature of the freeze drying is minus 30 ℃ to minus 10 ℃.
6. The method of claim 1, wherein: in the step (2), the calcination is carried out in a tube furnace; the calcining temperature is 400-700 ℃, and the time is 3-6 h.
7. The method of claim 1, wherein: in the step (3), the mass ratio of the commercial sulfur to the tin disulfide/graphene composite material is 4: 1-7: 1.
8. The method of claim 1, wherein: in the step (3), the temperature rise rate of the high-temperature furnace is 3-5 ℃/min, the temperature of the vacuum reaction is 150-180 ℃, and the time is 12-15 h.
9. SnS prepared by the method of any one of claims 1-82the/rGO modified sulfur cathode material.
10. The SnS of claim 92Application of/rGO modified sulfur cathode material in lithium sulfur batteries.
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| CN112234184A (en) * | 2020-10-14 | 2021-01-15 | 桑顿新能源科技有限公司 | SnS/CNTs/S composite material and preparation method and application thereof |
| CN114420926B (en) * | 2022-01-19 | 2024-03-15 | 湖北亿纬动力有限公司 | Positive electrode host material and preparation method and application thereof |
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