CN107768643B - Carbon sphere/sulfur/reduced graphene oxide composite material for lithium-sulfur battery and preparation method thereof - Google Patents
Carbon sphere/sulfur/reduced graphene oxide composite material for lithium-sulfur battery and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a carbon sphere/sulfur/reduced graphene oxide composite material for a lithium-sulfur battery and a preparation method thereof. The composite material is prepared by performing heat treatment or solution dipping sulfur precipitation and compounding on sulfur and carbon spheres, mixing and stirring the sulfur/carbon sphere compound with an adhesive to form slurry, coating the slurry on an aluminum foil, drying the slurry, placing the dried slurry in a graphene oxide dispersion liquid, and performing electrochemical reduction deposition to reduce graphene oxide to obtain the reduced graphene oxide-encapsulated sulfur/carbon sphere composite positive electrode material. The carbon spheres prepared by the method have abundant surface folds and internal pore structures, and higher specific surface area (1000 m)2And/g) can load more sulfur, and the solid sulfur content is up to 80%. The reduction oxidation graphene layer has higher conductivity and abundant pore structures, is beneficial to the passing of lithium ions, can effectively inhibit the loss of sulfur and polysulfide, improves the conductivity and the circulation stability of the sulfur/carbon ball composite material, and has higher practical prospect.
Description
Technical Field
The invention relates to a carbon sphere/sulfur/reduced graphene oxide composite material for a lithium-sulfur battery and a preparation method thereof, and belongs to the technical field of lithium-sulfur batteries.
Background
In recent years, the energy and environmental problems are increasingly prominent, and the traditional lithium ion battery cannot meet the market demand due to the rapid development of electronic equipment, especially electric automobiles, so that a brand new high specific energy battery system is sought to become a research hotspot in the field of energy storage. The lithium-sulfur battery is a battery system with sulfur as a positive electrode and metal lithium as a negative electrode, has higher theoretical specific capacity (1675mAh/g), has the theoretical specific energy of 2600Wh/kg, has the advantages of high energy density, low cost, small pollution and the like, and is considered to be one of the next-generation energy storage systems with the most potential.
However, electronic conduction of sulfurThe rate is low (5 × 10)-30S/cm,25 deg.c), poor ion conductivity, large volume change (70%) during charging and discharging, and generation of soluble lithium polysulfide and shuttle effect during charging and discharging, resulting in low utilization rate of active material and short cycle life, and hindering practical process.
The porous carbon material not only has good conductivity, but also has rich pore structures and larger specific surface area, can effectively promote the transmission of electrons and ions, and has better adsorption effect on sulfur and polysulfide, thereby inhibiting the loss of active substances and improving the cycling stability of the electrode material.
Chinese patent CN 106654231A discloses a method for coating a three-dimensional flower-shaped carbon structure with a conductive polymer, flower-shaped zinc oxide and dopamine are compounded, then carbonization and acid treatment are carried out to form the three-dimensional flower-shaped carbon structure, then sulfur filling is carried out, then a layer of conductive polymer is coated on a carbon-sulfur compound, and the conductive polymer layer can inhibit the loss of sulfide and improve the conductivity and the cyclicity. However, the above methods all have the disadvantages of complicated preparation method, difficult regulation of structure, harsh reaction conditions and high raw material cost.
Chinese patent CN 103682280 a discloses a positive electrode material for a lithium-sulfur battery, which is prepared by using graphene oxide, a conductive additive and sulfur particles as raw materials, performing heat treatment on the conductive additive and the sulfur particles, then performing spray drying, mixing the obtained conductive additive/sulfur compound with the graphene oxide, and reducing the graphene oxide with a reducing agent. However, the elemental sulfur prepared by the method is only distributed on the surface of the conductive additive, the elemental sulfur and polysulfide generated in the charging and discharging process cannot be completely bound, the polysulfide lost on the surface of the conductive additive still generates a shuttle effect, and the capacity and energy of the lithium-sulfur battery still quickly decrease.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a carbon sphere/sulfur/reduced graphene oxide composite material for a lithium-sulfur battery and a preparation method thereof. The invention utilizes surface wrinkles and abundant internal pore structures of the carbon spheres to store sulfur and polysulfide, and the surface layer is deposited and reduced with the graphene oxide layer after being coated on the pole piece, thereby inhibiting the loss of the sulfur and the polysulfide. The carbon balls and the reduction graphene oxide layers can effectively improve the conductivity of the electrode material, inhibit the loss of sulfur and polysulfide, and improve the rate capability and the cycle performance of the lithium-sulfur battery.
The invention is realized by the following technical scheme:
the utility model provides a carbon ball/sulphur/reduction oxidation graphite alkene combined material for lithium sulphur battery positive pole, includes carbon ball, elemental sulphur and reduction oxidation graphite alkene, and elemental sulphur stores in the surface fold and the interior pore structure of carbon ball, and reduction oxidation graphite alkene cladding forms reduction oxidation graphite alkene encapsulation layer on sulphur/carbon ball combined material surface.
Preferably, according to the invention, the carbon spheres: elemental sulfur: the mass ratio of the reduced graphene oxide is (0.1-1): 1: (0.1-1).
Preferably, according to the invention, the sulfur content in the sulfur/carbon sphere composite material is 50-90 wt%.
According to the invention, the thickness of the reduced graphene oxide packaging layer is preferably 0.5-100 nm.
The invention provides a preparation method of a carbon sphere/sulfur/reduced graphene oxide composite material for a lithium-sulfur battery anode, which comprises the following steps:
preparing carbon spheres from graphene oxide and a conductive carbon material;
mixing sulfur and carbon spheres to prepare a sulfur/carbon sphere composite material;
and coating the sulfur/carbon sphere composite material on a pole piece, and then depositing and reducing the graphene oxide layer.
According to the present invention, preferably, the step of preparing the carbon spheres by using the graphene oxide and the conductive carbon material is: and mixing the graphene oxide aqueous solution with conductive carbon black, performing ultrasonic treatment to form uniformly dispersed slurry, and performing spray drying to obtain the spherical composite carbon material. The spherical composite carbon material is the carbon sphere.
According to the invention, the concentration of the graphene oxide aqueous solution is 1-10mg/mL, and the mass ratio of the graphene oxide to the conductive carbon black in the graphene oxide aqueous solution is (1-4): (1-4); the ultrasonic frequency is 30-50HZ, the ultrasonic power is 600-1000w, and the ultrasonic time is 2-12 h; the air inlet temperature of spray drying is 120-220 ℃.
According to the invention, the step of preparing the sulfur/carbon sphere composite material by mixing sulfur and carbon spheres is preferably one of the following two methods:
a. mixing sublimed sulfur powder with carbon spheres, ball-milling and uniformly mixing, drying in vacuum, then placing in a hydrothermal reaction kettle, and carrying out closed heat treatment to obtain a sulfur/carbon sphere composite material;
b. dissolving elemental sulfur into an organic solvent, adding carbon spheres, stirring and dipping, removing the organic solvent by rotary evaporation, and drying in vacuum to obtain the sulfur/carbon sphere composite material.
According to the invention, in the preferable method a, the mass ratio of the sublimed sulfur powder to the carbon spheres is 1: (0.1-1), the ball milling time is 1-10h, the vacuum drying temperature is 50-60 ℃, the vacuum drying time is 6-24h, the heat treatment temperature is 150-.
According to a preferable embodiment of the present invention, in the method b, the organic solvent is carbon disulfide, carbon tetrachloride or toluene, and the mass ratio of elemental sulfur dissolved in the organic solvent to the carbon spheres is 1: (0.1-1).
Further preferably, when the organic solvent is carbon disulfide, 5-35g of elemental sulfur is dissolved in every 100ml of the organic solvent; when the organic solvent is carbon tetrachloride, 0.5-1.3g of elemental sulfur is dissolved in each 100ml of the organic solvent; when the organic solvent is toluene, 0.5-2.3g of elemental sulfur is dissolved in each 100ml of the organic solvent.
According to the invention, in the method b, the rotary evaporation temperature is between room temperature and room temperature, the vacuum drying temperature is between 50 and 60 ℃, and the vacuum drying time is between 6 and 24 hours.
According to the invention, the preferable step of coating the sulfur/carbon sphere composite material on the pole piece is as follows: adding a conductive agent and a binder into the sulfur/carbon sphere composite material, wherein the sulfur/carbon sphere composite material comprises the following components in percentage by weight: conductive agent: the mass ratio of the binder is (80-90): (5-10): (5-10), forming uniform slurry, coating on a pole piece, and drying in vacuum.
According to the invention, the binder is preferably one or more of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethylcellulose and styrene butadiene rubber; the pole piece is aluminum foil or aluminum net, the vacuum drying temperature is 80-120 ℃, the vacuum drying time is 2-24h, and the thickness of the coating of the sulfur/carbon ball composite material is 50-200 mu m.
According to a preferred embodiment of the present invention, the method for depositing the reduced graphene oxide layer comprises: and carrying out electrochemical deposition by taking the pole piece coated with the sulfur/carbon sphere composite material as a working electrode, a platinum sheet as a counter electrode, a saturated calomel electrode as a reference electrode and the aqueous dispersion of the graphene oxide as electrolyte to obtain a reduced graphene oxide layer with electrochemical reduction deposited on the surface of the pole piece coated with the sulfur/carbon sphere composite material.
According to the invention, the concentration of the graphene oxide aqueous dispersion is 1-10mg/ml, the working voltage of electrochemical deposition is 0.1-1V, and the deposition time is 1-30 min.
According to the invention, the graphene oxide is preferably prepared by a modified Hummers method, and is carried out according to the prior art.
230ml of 98% concentrated sulfuric acid is added into a dry conical flask, the mixture is cooled to 0-4 ℃ at low temperature, a solid mixture of 10g of natural crystalline flake graphite and 5g of sodium nitrate is added under strong stirring, after the natural crystalline flake graphite and the sodium nitrate are completely dissolved, 30g of potassium permanganate is added in 6 times, the temperature is controlled between 10 ℃ and 15 ℃, the mixture is stirred and reacts for 2.5 hours, and the solution is dark green. Then placing the conical flask in a constant temperature water bath at 35 ℃, and continuously stirring and reacting for 30 min. After the reaction is finished, a certain amount of deionized water is continuously added under stirring, the temperature is controlled to be 80-100 ℃, the stirring is continued for 30min, warm deionized water is used for diluting the reaction solution, 5 percent hydrogen peroxide is added, and the stirring is carried out, so that the solution is golden yellow. Filtering while hot, washing the brown yellow precipitate with 5% hydrochloric acid and deionized water to pH 7, and adding BaCl2Detecting no SO in filtrate by using solution4 2-Are present. Drying the brown yellow precipitate in an oven at 60 ℃ for 48h, grinding and sieving to obtain graphene oxide powder, and ultrasonically dispersing in water to obtain graphene oxide aqueous solutions with different concentrations.
The carbon spheres in the sulfur/carbon sphere composite material have larger specific surface area (900-2/g), and a rich internal pore structure, which can adsorb sulfur and polysulfides; and electrochemically deposited reduced graphene oxideThe conductive carbon sphere has higher conductivity, can inhibit the loss of sulfur and polysulfide on the surface and in the carbon sphere, and enhances the rate capability and the cycle stability of the electrode material. The preparation method is simple, the thickness of the pole piece is easy to regulate and control, customized production can be realized, and the preparation method has a good application prospect.
Drawings
FIG. 1 is a scanning electron microscope image before compounding sulfur with carbon spheres;
FIG. 2 is a scanning electron micrograph of the carbon spheres after sulfur recombination.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to examples, but the present invention is not limited to the following examples.
Example 1:
a preparation method of a reduced graphene oxide/sulfur/carbon sphere composite material for a lithium-sulfur battery comprises the following steps:
1. and (2) taking 200ml of graphene oxide aqueous solution with the concentration of 5mg/ml, adding 0.5g of conductive carbon black, performing ultrasonic dispersion for 2 hours, performing spray drying at the temperature of 150 ℃ to obtain carbon spheres containing graphene oxide, drying, placing in a tubular furnace, performing argon protection, and performing heat treatment at 500 ℃ for 2 hours to obtain the carbon spheres containing reduced graphene oxide.
2. Weighing 1g of the carbon spheres, mixing with 5g of sublimed sulfur, adding a small amount of ethanol for dispersion, ball-milling for 1h, and carrying out vacuum drying treatment at 55 ℃ for 6h to obtain a sulfur/carbon sphere mixture, wherein a scanning electron microscope of the sulfur/carbon sphere mixture is shown in figure 2, and as can be seen from figure 2, sulfur is uniformly stored in surface wrinkles and internal pore structures of the carbon spheres.
3. And (3) taking 5g of the dried sulfur/carbon sphere mixture, placing the mixture in a hydrothermal reaction kettle, and carrying out heat treatment at 150 ℃ for 6h to obtain the sulfur/carbon sphere composite material.
4. 0.90g of sulfur/carbon sphere composite material is taken, mixed with 0.05g of acetylene black and an adhesive containing 0.05g of polytetrafluoroethylene, and added with ethanol and stirred to be uniformly dispersed to form slurry.
5. The slurry is uniformly coated on an aluminum foil with the thickness of 100 mu m, and dried for 12h at 110 ℃ in a vacuum box
6. And (3) immersing the aluminum foil coated with the sulfur/carbon sphere composite material into the aqueous dispersion of graphene oxide with the concentration of 5mg/ml, applying 0.8V voltage, and performing electrochemical precipitation for 1 minute to obtain the sulfur/carbon sphere/reduced graphene oxide composite cathode material deposited with reduced graphene oxide.
The sulfur content of the obtained sulfur/carbon sphere/reduced graphene oxide composite positive electrode material is 75%, and the thickness of the reduced graphene oxide layer is about 15 nm.
Example 2
A preparation method of a reduced graphene oxide/sulfur/carbon sphere composite material for a lithium-sulfur battery comprises the following steps:
1. and (2) adding 1.0g of conductive carbon black into 200ml of graphene oxide aqueous solution with the concentration of 5mg/ml, performing ultrasonic dispersion for 2 hours, performing spray drying at the temperature of 155 ℃ to obtain carbon spheres containing graphene oxide, drying, placing in a tubular furnace, performing argon protection, and performing heat treatment at 500 ℃ for 1 hour to obtain the carbon spheres containing reduced graphene oxide.
2. Weighing 5g of sulfur powder, dissolving the sulfur powder in 500ml of carbon tetrachloride solution, and carrying out ultrasonic treatment for 2h to completely dissolve the sulfur powder.
3. Adding 1g of the prepared carbon spheres into a carbon tetrachloride solution, carrying out rotary evaporation at room temperature, naturally evaporating carbon tetrachloride to dry to obtain a sulfur/carbon sphere compound, and drying for 6 hours in a vacuum drying oven at 55 ℃;
4. 0.90g of sulfur/carbon sphere composite material is taken, mixed with 0.05g of acetylene black and an adhesive containing 0.05g of polytetrafluoroethylene, and added with ethanol and stirred to be uniformly dispersed to form slurry.
5. The slurry was uniformly coated on an aluminum foil with a thickness of 50 μm, and dried in a vacuum oven at 105 ℃ for 12 hours
6. And cutting the aluminum foil coated with the sulfur/carbon sphere composite material into 2 multiplied by 2cm pole pieces, immersing the pole pieces into aqueous dispersion of graphene oxide with the concentration of 5mg/ml, applying 0.5V voltage, and performing electrochemical precipitation for 1 minute to obtain the sulfur/carbon sphere/reduced graphene oxide composite cathode material deposited with the reduced graphene oxide.
The sulfur content of the obtained sulfur/carbon spheres/reduced graphene oxide composite positive electrode material is 80%, and the thickness of the reduced graphene oxide layer is about 12 nm.
Claims (4)
1. A carbon sphere/sulfur/reduced graphene oxide composite material for a lithium-sulfur battery anode comprises a carbon sphere, elemental sulfur and reduced graphene oxide, wherein the elemental sulfur is stored in surface wrinkles and an internal pore structure of the carbon sphere, and the reduced graphene oxide is coated on the surface of the sulfur/carbon sphere composite material to form a reduced graphene oxide packaging layer;
carbon spheres: elemental sulfur: the mass ratio of the reduced graphene oxide is (0.1-1): 1: (0.1-1), the sulfur content in the sulfur/carbon sphere composite material is 50-90 wt%, and the thickness of the reduced graphene oxide packaging layer is 0.5-100 nm;
the preparation method comprises the following steps:
preparing carbon spheres from graphene oxide and a conductive carbon material: mixing the graphene oxide aqueous solution with conductive carbon black, performing ultrasonic treatment to form uniformly dispersed slurry, and performing spray drying to obtain a spherical composite carbon material; the concentration of the graphene oxide aqueous solution is 1-10mg/mL, and the mass ratio of the graphene oxide to the conductive carbon black in the graphene oxide aqueous solution is (1-4): (1-4); the ultrasonic frequency is 30-50Hz, the ultrasonic power is 600-1000w, and the ultrasonic time is 2-12 h; the air inlet temperature of spray drying is 120-220 ℃;
mixing sulfur and carbon spheres to prepare a sulfur/carbon sphere composite material;
coating the sulfur/carbon sphere composite material on a pole piece, and then depositing and reducing a graphene oxide layer;
the step of coating the sulfur/carbon ball composite material on the pole piece is as follows: adding a conductive agent and a binder into the sulfur/carbon sphere composite material, wherein the sulfur/carbon sphere composite material comprises the following components in percentage by weight: conductive agent: the mass ratio of the binder is (80-90): (5-10): (5-10), forming uniform slurry, coating the slurry on a pole piece, and drying in vacuum; the binder is one or more than two of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethylcellulose and styrene butadiene rubber; the pole piece is an aluminum foil or an aluminum net, the vacuum drying temperature is 80-120 ℃, the vacuum drying time is 2-24h, and the thickness of the coating of the sulfur/carbon sphere composite material is 50-200 mu m;
the method for depositing and reducing the graphene oxide layer comprises the following steps: and performing electrochemical deposition by taking the pole piece coated with the sulfur/carbon sphere composite material as a working electrode, a platinum sheet as a counter electrode, a saturated calomel electrode as a reference electrode and aqueous dispersion of graphene oxide as electrolyte to obtain a reduced graphene oxide layer deposited with electrochemical reduction on the surface of the pole piece coated with the sulfur/carbon sphere composite material, wherein the concentration of the aqueous dispersion of graphene oxide is 1-10mg/ml, the working voltage of the electrochemical deposition is 0.1-1V, and the deposition time is 1-30 min.
2. The carbon sphere/sulfur/reduced graphene oxide composite material for a positive electrode of a lithium-sulfur battery according to claim 1, wherein the step of preparing the sulfur/carbon sphere composite material by mixing sulfur with the carbon sphere is performed by one of the following two methods:
a. mixing sublimed sulfur powder with carbon spheres, ball-milling and uniformly mixing, drying in vacuum, then placing in a hydrothermal reaction kettle, and carrying out closed heat treatment to obtain a sulfur/carbon sphere composite material;
b. dissolving elemental sulfur into an organic solvent, adding carbon spheres, stirring and dipping, removing the organic solvent by rotary evaporation, and drying in vacuum to obtain the sulfur/carbon sphere composite material.
3. The carbon sphere/sulfur/reduced graphene oxide composite material for the positive electrode of the lithium-sulfur battery according to claim 2, wherein in the method a, the mass ratio of the sublimed sulfur powder to the carbon spheres is 1: (0.1-1), the ball milling time is 1-10h, the vacuum drying temperature is 50-60 ℃, the vacuum drying time is 6-24h, the heat treatment temperature is 150-.
4. The carbon sphere/sulfur/reduced graphene oxide composite material for the positive electrode of the lithium-sulfur battery according to claim 2, wherein in the method b, the organic solvent is carbon disulfide, carbon tetrachloride or toluene, and the mass ratio of elemental sulfur dissolved in the organic solvent to the carbon spheres is 1: (0.1-1); when the organic solvent is carbon disulfide, 5-35g of elemental sulfur is dissolved in every 100ml of the organic solvent; when the organic solvent is carbon tetrachloride, 0.5-1.3g of elemental sulfur is dissolved in each 100ml of the organic solvent; when the organic solvent is toluene, 0.5-2.3g of elemental sulfur is dissolved in each 100ml of the organic solvent; the rotary evaporation temperature is room temperature, the vacuum drying temperature is 50-60 ℃, and the vacuum drying time is 6-24 h.
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| CN109244393B (en) * | 2018-08-27 | 2020-12-22 | 上海电力学院 | Long-cycle high-rate-performance lithium-sulfur battery positive electrode material and preparation method thereof |
| JP7367059B2 (en) * | 2019-07-02 | 2023-10-23 | エルジー エナジー ソリューション リミテッド | Sulfur-carbon composite, positive electrode for lithium secondary battery and lithium secondary battery containing the same |
| KR20210003691A (en) * | 2019-07-02 | 2021-01-12 | 주식회사 엘지화학 | Sulfur-carbon composite, positive electrode for lithium secondary battery and lithium secondary battery comprising the same |
| KR20210091520A (en) * | 2020-01-14 | 2021-07-22 | 주식회사 엘지에너지솔루션 | Positive active material for lithium secondary battery, manufacturing method and lithium secondary battery comprising the same |
| CN111599986B (en) * | 2020-05-29 | 2021-04-06 | 山东理工大学 | Preparation method and application of self-supporting positive electrode of lithium-sulfur battery with coated structure |
| CN112103484B (en) * | 2020-08-28 | 2021-09-24 | 上海彤程电子材料有限公司 | Positive electrode material for lithium-sulfur battery and lithium-sulfur battery |
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