WO2015188726A1 - 氮掺杂石墨烯包覆纳米硫正极复合材料、其制备方法及应用 - Google Patents

氮掺杂石墨烯包覆纳米硫正极复合材料、其制备方法及应用 Download PDF

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WO2015188726A1
WO2015188726A1 PCT/CN2015/080885 CN2015080885W WO2015188726A1 WO 2015188726 A1 WO2015188726 A1 WO 2015188726A1 CN 2015080885 W CN2015080885 W CN 2015080885W WO 2015188726 A1 WO2015188726 A1 WO 2015188726A1
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nitrogen
sulfur
doped graphene
composite material
coated nano
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English (en)
French (fr)
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张跃钢
丘勇才
李宛飞
李桂珠
侯远
刘美男
周莉莎
叶方敏
李洪飞
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中国科学院苏州纳米技术与纳米仿生研究所
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Priority to JP2017512093A priority Critical patent/JP6360252B2/ja
Priority to EP15807123.3A priority patent/EP3157080B1/en
Priority to KR1020167034228A priority patent/KR20170003646A/ko
Priority to US15/317,405 priority patent/US10439213B2/en
Publication of WO2015188726A1 publication Critical patent/WO2015188726A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/08—Simple coacervation, i.e. addition of highly hydrophilic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention particularly relates to a nitrogen-doped graphene-coated nano-sulfur cathode composite material, a preparation method thereof and the application of the composite material in a lithium-sulfur battery, and belongs to the fields of chemical power source and material science.
  • the lithium-sulfur battery device is a chemical conversion battery composed of a sulfur positive electrode, an electrolyte and a lithium negative electrode, and the sulfur positive electrode usually selects an appropriate mixing ratio of the active material, the conductive agent and the binder.
  • the utilization rate is low, irreversible loss and capacity attenuation, resulting in low actual capacity of lithium-sulfur battery, cycle performance and poor rate, which seriously restricts the practical application of the battery.
  • the most researched and effective method is to nano-vulcanize and load active materials into carbon-based materials with good electrical conductivity (carbon nanotubes, porous carbon, In the case of graphene, carbon fiber, graphene oxide, etc., a composite positive electrode material is formed, and the electrochemical activity of the low-conductive active substance sulfur is achieved by the conductivity of the carbon-based material and the contact with the nano-sulfur, and the utilization rate is improved, and the use of these materials is high.
  • the specific surface area limits the dissolution of polysulfide into the electrolyte during electrochemical cycling and the various negative effects caused thereby, thereby increasing the discharge capacity and cycle performance of the battery.
  • graphene is a two-dimensional material of a monoatomic layer carbon film composed of sp2 hybrid carbon atoms in a hexagonal close-packed structure, and has excellent electrical conductivity, good chemical stability, excellent mechanical properties, and high theoretical specific surface area ( 2630m 2 g -1 ), very suitable for conductive carrier materials for battery active materials.
  • RSCAdvances 2013, 3, 2558-2560; Nano Lett., 2011, 11, 2644-2647 shows better battery device performance, but these composite materials are low.
  • the specific capacity at the magnification is only 600-800 mAh.g -1 , and the high-rate performance does not show the advantages of the graphene material, which may be related to the surface area reduction caused by the agglomeration stack of the unfunctionalized graphene itself.
  • Graphene oxide-loaded nano-sulfur as a positive electrode material for lithium-sulfur battery research J. Am. Chem. Soc. 2011, 133, 18522-18525; Nano.
  • the sulfur content of the composite is only 33%, even at such low sulfur content, Its 0.1C first-stage capacity is only 1047mAh.g -1 , and has dropped to 700mAh.g -1 after 50 cycles; moreover, its high-rate discharge capacity is not prominent, such as 0.5C capacity is 450mAhg -1 or so.
  • the 1C capacity is about 400 mAh.g -1
  • the 2C capacity is about 360 mAh.g -1
  • the graphene dispersion used for coating in the method is obtained by reducing the toxic substance hydrazine as a reducing agent.
  • the main object of the present invention is to provide a nitrogen-doped graphene-coated nano-sulfur positive electrode composite material having high capacity, high cycle performance and high magnification.
  • Another object of the present invention is to provide a nitrogen-doped graphene-coated nano-sulfur positive electrode composite material. Preparation method.
  • a third object of the present invention is to provide the use of the aforementioned nitrogen-doped graphene-coated nanosulfur cathode composite material in a lithium-sulfur battery device.
  • a nitrogen-doped graphene-coated nano-sulfur cathode composite material comprising
  • the nitrogen-doped graphene is mainly overlapped to form an effective three-dimensional conductive network.
  • nano-sulfur particles uniformly coated by the nitrogen-doped graphene sheets.
  • the nitrogen-doped graphene has a nitrogen content of 2 to 10% by weight.
  • the conductivity of the nitrogen-doped graphene is 1000 to 30000 S/m.
  • the composite material has a sulfur loading of 40 to 85 wt%.
  • the nano-sulfur particles have a particle diameter of 10 to 50 nm.
  • the discharge capacity at 0.2C rate can reach 1200mAh.g -1 or more, the discharge capacity at 1C rate can reach 1000mAh.g -1 or more, the discharge capacity at 2C rate It can reach 800mAh.g -1 or above, and the discharge capacity can reach 600mAh.g -1 or more at 5C rate.
  • the composite material when used as a cathode material for a lithium sulfur battery, 2000 cycles at a 2C rate has a lower capacity decay rate (0.028% or less per cycle), and high cycle stability is maintained.
  • a preparation method of a nitrogen-doped graphene-coated nano-sulfur cathode composite material comprises: dispersing nitrogen-doped graphene in a liquid phase reaction system containing at least a sulfur source and an acid, and in-situ chemistry through a sulfur source and an acid The nano-sulfur particles are reacted and deposited to prepare the nitrogen-doped graphene-coated nano-sulfur particle composite.
  • the preparation method of the nitrogen-doped graphene-coated nano-sulfur positive electrode composite material comprises:
  • the graphene oxide powder is placed in a protective atmosphere, and a nitrogen source gas is passed through the reaction with the graphene oxide powder to obtain the nitrogen-doped graphene.
  • step b may include:
  • the nitrogen source gas includes ammonia gas or a mixed gas of ammonia gas and a protective gas.
  • the protective gas comprises argon or nitrogen.
  • the sulfur source comprises a sulfur-containing metal salt
  • the sulfur-containing metal salt is at least selected from the group consisting of sodium sulfide, sodium polysulfide, and sodium thiosulfate
  • the acid is at least selected from the group consisting of hydrochloric acid, sulfuric acid, and formic acid. Any of dicarboxylic acid, phosphoric acid, nitric acid and acetic acid.
  • reaction temperature of the in-situ chemical reaction is -10 ° C to 60 ° C.
  • a lithium-sulfur battery comprising a positive electrode, a negative electrode and an electrolyte, the positive electrode comprising any of the aforementioned nitrogen-doped graphene-coated nano-sulfur positive electrode composite materials.
  • the sulfur content of the pole piece may reach 60% by weight or more.
  • the advantages of the present invention include: in the nitrogen-doped graphene-coated nano-sulfur cathode composite material, sulfur can be effectively contacted with highly conductive nitrogen-doped graphene at an electrochemically active level.
  • the composite material has high conductivity, and the nano-sulfur particles can be more effectively contacted with the nitrogen-doped graphene, which not only can greatly improve the utilization and rate performance of the low-conductivity active substance sulfur, and does not require additional addition.
  • a large amount of conductive agent also greatly increases the energy density of the battery, and at the same time, because of the encapsulation function of the nitrogen-doped graphene carrier of the sheet-like pleated structure and the generation of nitrogen in the carrier during the charge-discharge process
  • the mutual attraction of sulfides effectively suppresses the dissolution and shuttle effect in the lithium-sulfur battery, improves the cycle stability of the battery, and thereby improves the overall performance of the lithium-sulfur battery.
  • the lithium-sulfur battery assembled with the nitrogen-doped graphene-coated nano-sulfur positive electrode composite material as a positive electrode material has the characteristics of high capacity, high cycle stability and high rate performance.
  • FIG. 1 is a schematic view showing the structure of a nitrogen-doped graphene-coated nano-sulfur positive electrode composite material according to the present invention
  • Example 2 is a scanning electron micrograph of a nitrogen-doped graphene-coated nano-sulfur positive electrode composite material 1 obtained in Example 1 of the present invention
  • FIG. 3 is a catalytic performance test chart of a nitrogen-doped graphene-coated nano-sulfur positive electrode composite material 1 in Embodiment 4 of the present invention
  • Example 4 is a charge and discharge capacity map of a nitrogen-doped graphene-coated nano-sulfur positive electrode composite material 1 at different magnifications in Example 4 of the present invention
  • FIG. 5 is a catalytic performance test chart of a nitrogen-doped graphene-coated nano-sulfur positive electrode composite material 2 in Embodiment 5 of the present invention.
  • Example 6 is a graph showing the electrochemical performance test of the nitrogen-doped graphene-coated nanosulfur cathode composite material 3 in Example 6 of the present invention.
  • One aspect of the present invention provides a nitrogen-doped graphene-coated nano-sulfur positive electrode composite material, which is mainly composed of nitrogen-doped graphene and nano-sulfur particles, wherein the nano-sulfur is uniformly wrapped by nitrogen-doped graphene,
  • the high conductivity nitrogen-doped graphene forms an effective three-dimensional conductive network by overlapping each other.
  • a typical structure of the nitrogen-doped graphene-coated nano-sulfur particle composite can be as shown in FIG.
  • the nitrogen-doped graphene has a nitrogen content of 2 to 10% by weight and a conductivity of 1000 to 30000 S/m, and the nitrogen content and conductivity can be controlled by the reduction nitridation temperature and time.
  • nano-sulfur particles have a size of 10 to 50 nm.
  • the nitrogen-doped graphene-coated nano-sulfur particle composite material has a sulfur loading of 40 to 85 wt%.
  • the discharge capacity at 0.2C rate can reach 1200mAh.g -1 or more, the discharge capacity at 1C rate can reach 1000mAh.g -1 or more, and discharged at 2C rate The capacity can reach 800mAh.g -1 or above, and the discharge capacity can reach 600mAh.g -1 or more at 5C rate. 2000 cycles at 2C rate have a lower capacity decay rate (less than 0.028% per cycle), maintaining high cycle stability.
  • Another aspect of the present invention provides a method for preparing a nitrogen-doped graphene-coated nano-sulfur cathode composite material, comprising: dispersing nitrogen-doped graphene in a liquid phase reaction system containing at least a sulfur source and an acid; The in-situ chemical reaction of the sulfur source and the acid deposits the nano-sulfur particles, thereby preparing the nitrogen-doped graphene-coated nano-sulfur particle composite.
  • the nitrogen-doped graphene can be prepared by various schemes known in the art.
  • the graphene oxide powder can be placed in a protective atmosphere, and a nitrogen source gas is passed through to react with the graphene oxide powder. Thereby the nitrogen-doped graphene is obtained.
  • the graphene oxide powder can also be obtained by various schemes known in the art, for example, an aqueous dispersion of graphene oxide can be prepared by the Hummer method, and freeze-dried to obtain a graphene oxide powder;
  • the graphene oxide powder may be placed in a closed reaction environment, and a protective gas (for example, an inert gas or the like) is introduced to form a protective atmosphere, and then 1 to 100 ml/ The flow rate of the minute is introduced into the nitrogen source gas, and the temperature of the closed reaction environment is raised to 600 ° C to 950 ° C within 2 h, and the nitrogen source gas is sufficiently reacted with the graphene oxide powder to obtain the nitrogen doping.
  • a protective gas for example, an inert gas or the like
  • the aforementioned nitrogen source gas may be selected from, but not limited to, ammonia gas or a mixture of ammonia gas and a protective gas (for example, argon gas, nitrogen gas, etc.), preferably 100% ammonia gas.
  • a protective gas for example, argon gas, nitrogen gas, etc.
  • the aforementioned nitrogen source gas flow rate is particularly preferably 30 ml/min.
  • the temperature range of the aforementioned nitriding reaction is particularly preferably 750 °C.
  • the temperature of the reaction environment it is particularly preferable to raise the temperature of the reaction environment to 600 ° C to 950 ° C in a time of less than or equal to 25 minutes, and preferably, after the reaction temperature is reached, the temperature is maintained for 0.1 to 24 h. It is especially preferably 30 minutes.
  • the nitrogen content and conductivity of the nitrogen-doped graphene can be controlled by controlling the reaction temperature and time.
  • the size of the nano-sulfur particles can be adjusted by controlling the reaction temperature and the sulfur source concentration.
  • the sulfur loading of the nitrogen-doped graphene-coated nano-sulfur particle composite material may be added Quality control of the sulfur source.
  • the preparation method of the nitrogen-doped graphene-coated nano-sulfur cathode composite material may include: first preparing a graphene oxide water dispersion solution by a Hummer method, and obtaining a graphene oxide powder by freeze-drying. Then weigh the graphene oxide powder in the corundum crucible and transfer it to the tube furnace. First, the air in the tube furnace is replaced with an inert gas, and then replaced with a nitrogen source gas, and the temperature is raised to a set temperature, and the temperature is kept constant.
  • the acid may be selected from, but not limited to, hydrochloric acid, sulfuric acid, formic acid, dicarboxylic acid, phosphoric acid, nitric acid and acetic acid or a mixture of several.
  • the reaction temperature of the in-situ chemical reaction is preferably from -10 ° C to 60 ° C, particularly preferably 0 ° C.
  • Still another aspect of the present invention provides the use of the nitrogen-doped graphene-coated nano-sulfur positive electrode composite in the preparation of a lithium-sulfur battery, for example, as a positive electrode material for fabricating a lithium-sulfur battery device.
  • Still another aspect of the present invention provides a lithium sulfur battery comprising a positive electrode, a negative electrode, and an electrolyte, the positive electrode comprising any of the foregoing nitrogen-doped graphene-coated nanosulfur positive electrode composite materials.
  • the positive electrode may include a current collector and a coating, wherein the coating may be mainly composed of the nitrogen-doped graphene-coated nano-sulfur positive electrode composite material and various binders known in the art, and may of course also include Other common auxiliary ingredients known in the industry.
  • the invention adopts the graphene oxide prepared by the Hummer method which can be mass-produced as a raw material, and obtains a high conductivity nitrogen-doped graphene by further reducing nitrogen at the same time in the presence of a nitrogen gas such as ammonia gas, and further adopting nitrogen.
  • the doped graphene is a conductive substrate, and the nitrogen-doped graphene-coated nano-sulfur positive electrode composite material is prepared by chemical reaction in-situ loading to achieve the purpose of uniform distribution and compounding, and can be exhausted without adding any conductive agent.
  • the invention may increase the utilization of sulfur and inhibit the dissolution of polysulfide ions generated during the electrochemical reaction and shuttle between the two poles, improve the electrochemical stability and cycle performance of the positive electrode material, and achieve 100 cycles of charge and discharge at 2C high rate.
  • the capacity is maintained at 700mAh/g
  • the invention is suitable for preparing a lithium-sulfur battery cathode material with high capacity and high cycle performance and high magnification.
  • Example 1 Preparation of nitrogen-doped graphene-coated nano-sulfur positive electrode composite 1
  • the graphene is prepared by the Hummers method: natural graphite powder (20 g) is added to a concentrated sulfuric acid solution (30 mL) containing potassium persulfate (10 g) and phosphorus pentoxide (10 g), and reacted at 80 ° C for 6 hours. It was cooled to room temperature, filtered, washed with water, and dried to obtain pre-oxidized graphite. Pre-oxidized graphite (0.5g) was added to 12 ml of concentrated sulfuric acid. Under ice bath conditions, potassium permanganate (1.5 g) was added in portions with vigorous stirring. After the addition, the temperature was raised to 35 ° C and the reaction was continued for 2 hours.
  • the reaction system was slowly diluted with 24 ml of deionized water, and the resulting mixture was warmed to 80 ° C for half an hour, then returned to room temperature, then 70 ml of deionized water was added, and the reaction was quenched with 1.25 ml of 30% hydrogen peroxide.
  • the obtained yellow suspension was filtered, washed with 125 ml of 5 wt% diluted hydrochloric acid to remove metal ions, and then washed three times with deionized water.
  • the obtained viscous solid was dispersed in deionized water, and the precipitate was removed by centrifugation, and the residue was dialyzed 2 A dispersion of graphene oxide was obtained over the week, and after freeze-drying, 0.6 g of graphene oxide powder was obtained.
  • the second step is the preparation of nitrogen-doped graphene 1 : 0.6 g of graphene oxide powder is placed in a corundum boat, transferred to a quartz tube of a tube furnace, and replaced by argon gas (purity 99.99%). The air is then converted into pure ammonia gas, the flow rate is controlled at 30 ml/min, the heating rate is set at 30 ° C / min, and the temperature is programmed to 750 ° C for 30 minutes to obtain nitrogen-doped graphene 0.4 g, and the nitrogen doping is tested by the four-electrode method.
  • the heterographene 1 has a conductivity of 27,200 S/m and a nitrogen content of 3.4% by weight.
  • the third step is the preparation of nitrogen-doped graphene-coated nano-sulfur cathode composite material 1:
  • the second step is the preparation of nitrogen-doped graphene 2: 0.6 g of graphene oxide powder is placed in a corundum boat, transferred to a quartz tube of a tube furnace, and replaced by argon gas (purity 99.99%). Air, then control the flow rate of pure ammonia gas is 100 ml / min, the flow rate of argon gas (purity 99.99%) is 1000 ml / min, and the temperature is programmed to 750 °C (the temperature is below °C unless otherwise specified) for 120 minutes.
  • 0.3 g of nitrogen-doped graphene was tested by a four-electrode method for nitrogen-doped graphene 2 with a conductivity of 20000 S/m and a nitrogen content of 3.1 wt%.
  • the third step is the preparation of nitrogen-doped graphene-coated nano-sulfur cathode composite material 2:
  • the second step is the preparation of nitrogen-doped graphene 3: 0.6 g of graphene oxide powder is placed in a corundum boat, transferred to a quartz tube of a tube furnace, and replaced by argon gas (purity 99.99%). The air was then converted to pure ammonia gas, the flow rate was controlled at 30 ml/min, the heating rate was set at 30 ° C / min, and the temperature was programmed to 900 ° C for 30 minutes to obtain nitrogen-doped graphene 0.2 g, and the nitrogen was tested by the four-electrode method.
  • the doped graphene 2 has a conductivity of 26,500 S/m and a nitrogen content of 4.2%.
  • the third step is the preparation of nitrogen-doped graphene-coated nano-sulfur cathode composite material 3:
  • thermogravimetric analysis test results show that the sulfur content of the nitrogen-doped graphene-coated nano-sulfur cathode composite material 3 is 80%.
  • Example 4 Electrochemical performance test of nitrogen-doped graphene-coated nano-sulfur cathode composite 1
  • the nitrogen-doped graphene-coated nano-sulfur cathode composite material 1 is a cathode material of a lithium-sulfur battery device, and the nitrogen-doped graphene-coated nano-sulfur cathode composite material 1 and the binder PVDF are mixed at a mass ratio of 92:8, N -Methylpyrrolidone is a solvent, uniformly coated on aluminum foil, the average sulfur loading of the electrode is 0.8 mg/cm 2 , vacuum drying at 50 ° C for 24 hours, punching the pole piece, argon gas glove box, taking lithium piece as the negative electrode, 1M bis(trifluoromethanesulfonimide lithium) 1,3-dioxolane/ethylene glycol dimethyl ether (1:1 by volume) containing 1% by weight of lithium nitrate and Li 2 S 8 (0.025M) for electrolysis Liquid, 2025 battery case assembled battery.
  • the battery was electrochemically tested by a blue electric device.
  • Example 5 Electrochemical performance test of nitrogen-doped graphene coated nano-sulfur cathode composite 2
  • the nitrogen-doped graphene-coated nano-sulfur cathode composite material 2 is a cathode material of a lithium-sulfur battery device, and the nitrogen-doped graphene-coated nano-sulfur cathode composite material 2 and the binder PVDF are mixed at a mass ratio of 92:8, N -Methylpyrrolidone is a solvent, uniformly coated on aluminum foil, the average sulfur loading of the electrode is 0.8 mg/cm 2 , vacuum drying at 50 ° C for 24 hours, punching the pole piece, argon gas glove box, taking lithium piece as the negative electrode, 1M bis(trifluoromethanesulfonimide lithium) 1,3-dioxolane/ethylene glycol dimethyl ether (1:1 by volume) containing 1% by weight of lithium nitrate and Li 2 S 8 (0.025M) for electrolysis Liquid, 2025 battery case assembled battery.
  • the battery was electrochemically tested by a blue electric device.
  • Example 6 Electrochemical performance test of nitrogen-doped graphene coated nano-sulfur cathode composite 3
  • the nitrogen-doped graphene-coated nano-sulfur cathode composite material 3 is a cathode material of a lithium-sulfur battery device, and the nitrogen-doped graphene-coated nano-sulfur cathode composite material 3 and the binder PVDF are mixed at a mass ratio of 92:8, N -Methylpyrrolidone is a solvent, uniformly coated on aluminum foil, the average sulfur loading of the electrode is 0.8 mg/cm 2 , vacuum drying at 50 ° C for 24 hours, punching the pole piece, argon gas glove box, taking lithium piece as the negative electrode, 1M bis(trifluoromethanesulfonimide lithium) 1,3-dioxolane/ethylene glycol dimethyl ether (1:1 by volume) containing 1% by weight of lithium nitrate and Li 2 S 8 (0.025M) for electrolysis Liquid, 2025 battery case assembled battery.
  • the battery was electrochemically tested by a blue electric device.

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Abstract

本发明公开了一种氮掺杂石墨烯包覆纳米硫正极复合材料、其制备方法及应用。该复合材料包括：主要由氮掺杂石墨烯相互交叠形成有效的三维导电网络，以及被氮掺杂石墨烯片层均匀包裹的纳米硫颗粒。该复合材料的制备方法包括：将氮掺杂石墨烯分散于至少含有硫源及酸的液相反应体系中，通过硫源与酸的原位化学反应沉积纳米硫颗粒，从而制得目标产物。本发明的复合材料具有高导电性，硫的利用率和倍率性能高，可有效地抑制锂硫电池中的溶解和穿梭效应，提高电池的循环稳定性，以该氮掺杂石墨烯包覆纳米硫正极复合材料作为正极材料组装的锂硫电池具有高容量、高循环稳定性、高倍率性能等特点，且该复合材料的制备工艺简单，成本低廉，适于规模化生产。

Description

氮掺杂石墨烯包覆纳米硫正极复合材料、其制备方法及应用 技术领域
本发明具体涉及一种氮掺杂石墨烯包覆纳米硫正极复合材料、其制备方法以及所述复合材料在锂硫电池中的应用，属于化学电源和材料科学领域。
背景技术
基于双电子电化学氧化还原反应
Figure PCTCN2015080885-appb-000001
的锂硫电池，由于其高的理论比容量(1675mAh/g，是基于LiFePO4传统锂电池的理论比容量的几乎10倍)，高的理论比能量(2600Wh/Kg)以及其活性物质硫储量丰富价格低廉低毒等优点，越来越受到学术界、产业界和各国政府的极大关注。
锂硫电池器件是一种化学转换电池，有硫正极、电解液和锂负极构成，其中的硫正极通常选择适当混合比例的活性材料、导电剂和粘结剂。活性材料中的硫以及充放电产物多硫化物(Li2Sx,x＝1～8)的低导电性和绝缘性，另外，充放电中间产物多硫化物(Li2Sx,x＝4～8)易溶解于电解液中进而在两极间的穿梭，以及从活性物质硫电化学反应完全转换成硫化锂所造成的体积膨胀(大约80％)导致的电极结构破坏，这些都会造成活性物质的利用率变低、不可逆损失和容量衰减，从而导致锂硫电池的实际容量低，循环性能以及倍率差，严重制约了电池的实际应用。
为了解决锂硫电池中存在的这些问题，提高器件的性能，目前研究的最多且行之有效的方法是将活性物质纳米硫化并负载到具有良好导电性的碳基材料(碳纳米管、多孔碳、石墨烯、碳纤维、氧化石墨烯等)中，形成复合正极材料，利用碳基材料的导电性以及与纳米硫的接触实现低导电活性物质硫的电化学活性，提高利用率，利用这些材料的高的比表面积限制电化学循环过程中多硫化物溶入电解液和由此引起的各种负面作用，从而提高电池的放电容量和循环性能。例如，石墨烯是由sp2杂化碳原子按照六方密排结构组成的单原子层碳薄膜二维材料，具备优良的导电性能，良好的化学稳定性，优异的力学性能 以及高的理论比表面积(2630m2g-1)，非常适合用于电池活性物质的导电载体材料。目前，石墨烯包覆硫复合材料的研究(RSCAdvances，2013，3，2558-2560；Nano Lett.，2011，11，2644-2647)，表现出比较好的电池器件性能，但是这些复合材料在低倍率下的比容量仅为600～800mAh.g-1，高倍率性能也没能表现出石墨烯材料应有的优势，可能与没有功能化的石墨烯本身易团聚堆叠导致的表面积降低有关。氧化石墨烯负载纳米硫作为正极材料用于锂硫电池的研究(J.Am.Chem.Soc.2011,133,18522-18525；Nano.Lett.,2013,13,5891-5899)，尽管表现出较好的循环稳定性，不过，氧化石墨烯的在低温加热的条件下还原效果不佳，所得复合材料导电性与石墨烯相比较差，需要另外添加20wt％的导电剂，从而导致电极重量增加，大大降低了电池的能量密度。石墨烯包覆的硫/碳纳米纤维复合材料的研究(Nano Lett.，2013，13，2485-2489)，该复合材料中硫的含量仅为33％，即便在这么低的硫含量条件下，其0.1C的首放容量也仅为1047mAh.g-1，50次循环后已下降为700mAh.g-1左右；而且，其高倍率放电容量也不突出，如0.5C容量为450mAhg-1左右，1C容量为400mAh.g-1左右，2C容量为360mAh.g-1左右，并且该方法中用于包覆的石墨烯分散液是由有毒物质肼作为还原剂还原制得的。石墨烯包覆的多壁碳纳米管/硫复合材料的研究(Nano Lett.,2013,13,4642-4649),该复合材料中石墨烯是有氧化石墨烯在95℃下加热还原得到，氧化石墨烯的还原程度有限，所得复合材料导电性较差，影响材料的电化学性能，这一点突出表现在高倍率性能上，尽管其0.2C的首放容量达到了1396mAh.g-1，但其1C容量为743mAh.g-1，2C容量为502mAh.g-1。因此，目前亟需开发工艺简单高效、易规模化生产、环境友好，具有高比容量、长循环寿命和高倍率性能的硫/碳复合正极材料及其制备方法。
发明内容
鉴于现有技术的不足，本发明的主要目的在于提供一种具有高容量、高循环性能、高倍率的氮掺杂石墨烯包覆纳米硫正极复合材料。
本发明的另一目的是提供制备上述氮掺杂石墨烯包覆纳米硫正极复合材料 的制备方法。
本发明的第三个目的是提供前述氮掺杂石墨烯包覆纳米硫正极复合材料在锂硫电池器件中的应用。
为实现前述发明目的，本发明采用的技术方案如下：
一种氮掺杂石墨烯包覆纳米硫正极复合材料，其包括
主要由氮掺杂石墨烯相互交叠形成有效的三维导电网络，
以及被氮掺杂石墨烯片层均匀包裹的纳米硫颗粒。
进一步的，所述氮掺杂石墨烯的含氮量为2～10wt％。
进一步的，所述氮掺杂石墨烯的导电率为1000～30000S/m。
进一步的，所述复合材料的载硫量为40～85wt％。
进一步的，所述纳米硫颗粒的粒径为10～50nm。
进一步的，所述复合材料用作锂硫电池正极材料时，0.2C倍率下放电容量可以达到1200mAh.g-1以上，1C倍率下放电容量可以达到1000mAh.g-1以上，2C倍率下放电容量可以达到800mAh.g-1以上，5C倍率下放电容量可以达到600mAh.g-1以上。
进一步的，所述复合材料用作锂硫电池正极材料时，2C倍率下2000个循环具有较低的容量衰减率(每个循环0.028％以下)，保持高的循环稳定性。
一种氮掺杂石墨烯包覆纳米硫正极复合材料的制备方法，包括：将氮掺杂石墨烯分散于至少含有硫源及酸的液相反应体系中，通过硫源与酸的原位化学反应沉积纳米硫颗粒，从而制得所述氮掺杂石墨烯包覆纳米硫颗粒复合材料。
作为可行实施方案之一，所述氮掺杂石墨烯包覆纳米硫正极复合材料的制备方法包括：
a、通过Hummer法制备氧化石墨烯的水分散液，并冷冻干燥获得氧化石墨烯粉末；
b、将所述氧化石墨烯粉末置于保护性气氛中，并通入氮源气体与所述氧化石墨烯粉末反应，从而获得所述氮掺杂石墨烯。
进一步的，步骤b可以包括：
将所述氧化石墨烯粉末置于封闭反应环境中，并通入保护性气体形成保护性气氛，再以1～100毫升/分钟的流速通入氮源气体，并将该封闭反应环境的温度在2h内升至600℃～950℃，使所述氮源气体与所述氧化石墨烯粉末充分反应，从而获得所述氮掺杂石墨烯。
进一步的，所述氮源气体包括氨气或氨气与保护性气体的混合气体。
进一步的，所述保护性气体包括氩气或氮气。
进一步的，所述硫源包括含硫金属盐，所述含硫金属盐至少选自硫化钠、多硫化钠、硫代硫酸钠中的任一种，所述酸至少选自盐酸、硫酸、甲酸、二甲酸、磷酸、硝酸和乙酸的任一种。
进一步的，所述原位化学反应的反应温度为-10℃～60℃。
前述任一种氮掺杂石墨烯包覆纳米硫正极复合材料在制备锂硫电池中的应用。
一种锂硫电池，包括正极、负极和电解质，所述正极包含前述任一种氮掺杂石墨烯包覆纳米硫正极复合材料。
进一步的，所述正极中不需要添加额外的导电添加剂，极片的含硫量可以达到60wt％以上。
与现有技术相比，本发明的优点包括：该氮掺杂石墨烯包覆纳米硫正极复合材料中，硫在电化学活性层面上与高导电性的氮掺杂石墨烯可以有效地充分接触，使该复合材料具有高导电性，同时纳米硫颗粒可更有效地与氮掺杂石墨烯均匀接触，不但能大幅度提高低导电性活性物质硫的利用率和倍率性能，同时不需要额外添加大量的导电剂(例如20wt％)，也大大提高了电池能量密度，同时因为片状褶皱结构的氮掺杂石墨烯载体的包裹功能以及载体中氮元素孤对电子对充放电过程中生成的多硫化物的相互吸引作用都有效地抑制了锂硫电池中的溶解和穿梭效应，提高电池的循环稳定性，从而实现锂硫电池整体性能的提升。以该氮掺杂石墨烯包覆纳米硫正极复合材料作为正极材料组装的锂硫电池具有高容量、高循环稳定性、高倍率性能等特点。
附图说明
图1是本发明中氮掺杂石墨烯包覆纳米硫正极复合材料的结构示意图；
图2是本发明实施例1所获氮掺杂石墨烯包覆纳米硫正极复合材料1的扫描电镜照片；
图3是本发明实施例4中氮掺杂石墨烯包覆纳米硫正极复合材料1的电化学性能测试图谱；
图4是本发明实施例4中氮掺杂石墨烯包覆纳米硫正极复合材料1在不同倍率下的充放电容量图谱；
图5是本发明实施例5中氮掺杂石墨烯包覆纳米硫正极复合材料2的电化学性能测试图谱；
图6是本发明实施例6中氮掺杂石墨烯包覆纳米硫正极复合材料3的电化学性能测试图谱。
具体实施方式
本发明的一个方面提供了一种氮掺杂石墨烯包覆纳米硫正极复合材料，其主要由氮掺杂石墨烯和纳米硫颗粒构成，其中，纳米硫被氮掺杂石墨烯均匀的包裹，而高导电率的氮掺杂石墨烯通过相互交叠形成有效的三维导电网络。
所述氮掺杂石墨烯包覆纳米硫颗粒复合材料的典型结构可如图1所示。
进一步的，所述氮掺杂石墨烯的含氮量为2～10wt％，导电率为1000～30000S/m，含氮量和导电率可通过还原氮化温度和时间而控制。
进一步的，所述纳米硫颗粒的尺寸大小为10～50nm。
进一步的，所述氮掺杂石墨烯包覆纳米硫颗粒复合材料的载硫量为40～85wt％。
进一步的，所述复合材料在用作锂硫电池正极材料时，0.2C倍率下放电容量可以达到1200mAh.g-1以上，1C倍率下放电容量可以达到1000mAh.g-1以上，2C倍率下放电容量可以达到800mAh.g-1以上，5C倍率下放电容量可以达到600mAh.g-1以上。2C倍率下2000个循环具有较低的容量衰减速率(每个循环在 0.028％以下)，保持高的循环稳定性。
本发明的另一个方面提供了一种氮掺杂石墨烯包覆纳米硫正极复合材料的制备方法，包括：将氮掺杂石墨烯分散于至少含有硫源及酸的液相反应体系中，通过硫源与酸的原位化学反应沉积纳米硫颗粒，从而制得所述氮掺杂石墨烯包覆纳米硫颗粒复合材料。
所述氮掺杂石墨烯可通过业界已知的多种方案制备，例如，可以将所述氧化石墨烯粉末置于保护性气氛中，并通入氮源气体与所述氧化石墨烯粉末反应，从而获得所述氮掺杂石墨烯。
而所述氧化石墨烯粉末同样可通过业界已知的多种方案之类，例如，可以通过Hummer法制备氧化石墨烯的水分散液，并冷冻干燥获得氧化石墨烯粉末；
在一更为具体的实施方案之中，可以将所述氧化石墨烯粉末置于封闭反应环境中，并通入保护性气体(例如惰性气体等)形成保护性气氛，再以1～100毫升/分钟的流速通入氮源气体，并将该封闭反应环境的温度在2h内升至600℃～950℃，使所述氮源气体与所述氧化石墨烯粉末充分反应，从而获得所述氮掺杂石墨烯。
前述的氮源气体可选自但不限于氨气或者氨气与保护性气体(例如，氩气、氮气等)的混合气，优选采用100％氨气。
前述氮源气体流速尤其优选为30毫升/分钟。
前述氮化反应的温度范围尤其优选为750℃。
在对氧化石墨烯进行氮化的过程中，尤其优选在小于或等于25分钟的时间内将反应环境的温度升至600℃～950℃，并且，优选在达到该反应温度后保温0.1～24h，尤其优选为30分钟。
进一步的，在对氧化石墨烯进行氮化的过程中，可以通过控制反应温度和时间而调控所述氮掺杂石墨烯的含氮量和导电率。
进一步的，在硫源与酸原位化学反应的过程中，可以通过控制反应温度和硫源浓度而调整所述纳米硫颗粒的尺寸。
进一步的，所述氮掺杂石墨烯包覆纳米硫颗粒复合材料的载硫量可由加入 的硫源的质量控制。
在一较为典型的实施案例之中，所述氮掺杂石墨烯包覆纳米硫正极复合材料的制备方法可以包括：首先通过Hummer法制备氧化石墨烯水分散溶液，通过冷冻干燥得到氧化石墨烯粉末，然后称量氧化石墨烯粉末放在刚玉坩埚中，转移至管式炉，首先将管式炉中的空气置换成惰性气体，然后再置换为氮源气体，升温至设定温度，保温至一定时间，自然降温至室温，获得氮掺杂石墨烯，将获得的氮掺杂石墨烯通过超声分散在超纯水中，通过原位化学反应沉积硫的方法制备得到氮掺杂石墨烯包覆纳米硫颗粒复合材料。
在本发明中，所述的硫源优选采用含硫金属盐，例如硫化钠、多硫化钠(Na2Sx,x＝2～8)、硫代硫酸钠中的一种或者是几种的混合物，但不限于此。
在本发明中，所述的酸可以选用但不限于盐酸，硫酸，甲酸，二甲酸，磷酸，硝酸和乙酸中的一种或者是几种的混合物。
所述原位化学反应的反应温度优选为-10℃～60℃，尤其优选为0℃。
本发明的又一个方面提供了所述氮掺杂石墨烯包覆纳米硫正极复合材料在制备锂硫电池中的用途，例如，可作为正极材料用于制作锂硫电池器件。
本发明的再一个方面提供了一种锂硫电池，其包括正极、负极和电解质，所述正极包含前述任一种氮掺杂石墨烯包覆纳米硫正极复合材料。
进一步的，所述正极可以包括集流体以及涂层，其中涂层可主要由所述氮掺杂石墨烯包覆纳米硫正极复合材料和业界已知的多种粘结剂组成，当然也可包含其它业界已知的常见辅助成分。
本发明将已经可以规模化生产的Hummer法制备的氧化石墨烯为原料，通过在氨气等含氮气体存在条件下，高温还原同时掺氮得到高导电率的氮掺杂石墨烯，进一步以氮掺杂石墨烯为导电基底，采用化学反应原位负载包裹制备氮掺杂石墨烯包覆纳米硫正极复合材料，以达到均匀分布复合的目的，在不需要添加任何导电剂的基础上，可以尽可能提高硫的利用率以及抑制电化学反应过程中产生的多硫离子溶解及其在两极间的穿梭，改善正极材料的电化学稳定性和循环性能，实现2C高倍率下充放电100次循环放电容量维持在700mAh/g以 上，适于制备高容量高循环性能高倍率的锂硫电池正极材料。
下面结合附图及具体实施例对本发明的技术方案做进一步详细的说明，但本发明的保护范围不限于这些实施例。
实施例1：氮掺杂石墨烯包覆纳米硫正极复合材料1的制备
第一步，Hummers法制备氧化石墨烯：取天然石墨粉(20g)加入到含有过硫酸钾(10g)和五氧化二磷(10g)浓硫酸溶液中(30mL),80℃反应6个小时自然冷却至室温，过滤，水洗，干燥，得到预氧化石墨。取预氧化石墨(0.5g)加入到12毫升浓硫酸中，冰浴条件，剧烈搅拌下分批加入高锰酸钾(1.5g)，加完后升温至35℃继续反应2个小时，随后往反应体系中慢慢加入24毫升去离子水稀释，所得到的混合物升温至80℃反应半个小时，然后恢复至室温，再加入70毫升去离子水，用1.25毫升30％双氧水终止反应。所得到的的黄色悬浊液过滤，用125毫升的5wt％稀盐酸洗涤去除金属离子，然后用去离子水洗三次，所得到的粘稠固体分散到去离子水中，离心去除沉淀，剩余物透析2周以上即得到氧化石墨烯的分散液，冷冻干燥后获得氧化石墨烯粉末0.6g。
第二步，氮掺杂石墨烯1的制备：取0.6g的氧化石墨烯粉末放入刚玉舟中，转移至管式炉的石英管中，通过氩气(纯度99.99％)置换去除体系中的空气，然后转换成纯氨气，控制流速为30毫升/分钟，设置升温速率30℃/分钟，程序升温至750℃氮化30分钟得到氮掺杂石墨烯0.4g，通过四电极法测试氮掺杂石墨烯1导电率为27200S/m，含氮量3.4wt％。
第三步，氮掺杂石墨烯包覆纳米硫正极复合材料1的制备：
基于反应方程式(2Na2S+Na2S2O3+6HCOOH＝4S+6HCOONa+3H2O)，取2.7g的九水硫化钠(Na2S.9H2O)和0.89g的硫代硫酸钠溶于50毫升去离子水中，剧烈搅拌下加入到含有150mg氮掺杂石墨烯1的水分散溶液中，所得到的的混合溶液继续搅拌2个小时，零度下以30～40滴/分钟的速度慢慢滴加50mL甲酸溶液(2M)，反应过夜，过滤，用去离子水充分洗涤，干燥，得到大约0.5g氮掺杂石墨烯包覆纳米硫正极复合材料1，其形貌如图2所示，纳米硫颗粒的尺寸小于50nm。热重分析测试结果表明氮掺杂石墨烯包覆纳米硫正极复 合材料1的含硫量为65.2wt％。
实施例2：氮掺杂石墨烯包覆纳米硫正极复合材料2的制备
第一步，Hummers法制备氧化石墨烯参照实施例1步骤一。
第二步，氮掺杂石墨烯2的制备：取0.6g的氧化石墨烯粉末放入刚玉舟中，转移至管式炉的石英管中，通过氩气(纯度99.99％)置换去除体系中的空气，然后控制纯氨气的流速为100毫升/分钟，氩气(纯度99.99％)的流速为1000毫升/分钟，程序升温至750度(如下若非特别说明，均为℃)氮化120分钟得到氮掺杂石墨烯0.3g，通过四电极法测试氮掺杂石墨烯2导电率为20000S/m，含氮量3.1wt％。
第三步，氮掺杂石墨烯包覆纳米硫正极复合材料2的制备：
取0.89g的硫代硫酸钠溶于50毫升去离子水中，剧烈搅拌下加入到含有150mg氮掺杂石墨烯2的水分散溶液中，所得到的混合溶液继续搅拌2个小时，室温下以30～40滴/分钟的速度慢慢滴加50mL盐酸溶液(2M)，反应过夜，过滤，用去离子水充分洗涤，干燥，得到大约0.3g氮掺杂石墨烯包覆纳米硫正极复合材料2，其形貌与实施例1相近，纳米硫颗粒的尺寸大小为大约在20～50nm范围。热重分析测试结果表明氮掺杂石墨烯包覆纳米硫正极复合材料2的含硫量为45wt％。
实施例3：氮掺杂石墨烯包覆纳米硫正极复合材料3的制备
第一步，Hummers法制备氧化石墨烯参照实施例1步骤一。
第二步，氮掺杂石墨烯3的制备：取0.6g的氧化石墨烯粉末放入刚玉舟中，转移至管式炉的石英管中，通过氩气(纯度99.99％)置换去除体系中的空气，然后转换成纯氨气，控制流速为30毫升/分钟，设置升温速率为30℃/分钟，程序升温至900℃氮化30分钟得到氮掺杂石墨烯0.2g，通过四电极法测试氮掺杂石墨烯2导电率为26500S/m，含氮量4.2％。
第三步，氮掺杂石墨烯包覆纳米硫正极复合材料3的制备：
基于反应方程式(2Na2S+Na2S2O3+6HCOOH＝4S+6HCOONa+3H2O)，取10.8g的九水硫化钠(Na2S.9H2O)和3.56g的硫代硫酸钠溶于50毫升去离 子水中，剧烈搅拌下加入到含有150mg氮掺杂石墨烯3的水分散溶液中，所得到的混合溶液继续搅拌2个小时，零下4度以30～40滴/分钟的速度慢慢滴加50mL甲酸溶液(2M)，反应过夜，过滤，用去离子水充分洗涤，干燥，得到大约0.7g氮掺杂石墨烯包覆纳米硫正极复合材料，其形貌与实施例1相近，纳米硫颗粒的尺寸小于50nm。热重分析测试结果表明氮掺杂石墨烯包覆纳米硫正极复合材料3的含硫量为80％。
实施例4：氮掺杂石墨烯包覆纳米硫正极复合材料1的电化学性能测试
用氮掺杂石墨烯包覆纳米硫正极复合材料1为锂硫电池器件正极材料，通过氮掺杂石墨烯包覆纳米硫正极复合材料1与粘结剂PVDF以质量比92：8混合，N-甲基吡咯烷酮为溶剂，均匀涂布在铝箔上，电极平均硫载量为0.8mg/cm2，50℃真空干燥24个小时，冲极片，氩气手套箱中，以锂片为负极，1M的双三氟甲烷磺酰亚胺锂的1,3-二氧五环/乙二醇二甲醚(体积比1:1)含1wt％硝酸锂以及Li2S8(0.025M)为电解液，2025电池壳组装电池。通过蓝电设备对电池进行电化学测试。正极片硫的含量60wt％，2C倍率，2000个循环充放电后，容量仍然在400mAh/g以上。
实施例5：氮掺杂石墨烯包覆纳米硫正极复合材料2的电化学性能测试
用氮掺杂石墨烯包覆纳米硫正极复合材料2为锂硫电池器件正极材料，通过氮掺杂石墨烯包覆纳米硫正极复合材料2与粘结剂PVDF以质量比92：8混合，N-甲基吡咯烷酮为溶剂，均匀涂布在铝箔上，电极平均硫载量为0.8mg/cm2，50℃真空干燥24个小时，冲极片，氩气手套箱中，以锂片为负极，1M的双三氟甲烷磺酰亚胺锂的1,3-二氧五环/乙二醇二甲醚(体积比1:1)含1wt％硝酸锂以及Li2S8(0.025M)为电解液，2025电池壳组装电池。通过蓝电设备对电池进行电化学测试。正极片硫的含量达到40wt％左右，0.2C倍率，50个循环充放电后，放电容量仍然在1000mAh/g以上。
实施例6：氮掺杂石墨烯包覆纳米硫正极复合材料3的电化学性能测试
用氮掺杂石墨烯包覆纳米硫正极复合材料3为锂硫电池器件正极材料，通过氮掺杂石墨烯包覆纳米硫正极复合材料3与粘结剂PVDF以质量比92：8混 合，N-甲基吡咯烷酮为溶剂，均匀涂布在铝箔上，电极平均硫载量为0.8mg/cm2，50℃真空干燥24个小时，冲极片，氩气手套箱中，以锂片为负极，1M的双三氟甲烷磺酰亚胺锂的1,3-二氧五环/乙二醇二甲醚(体积比1:1)含1wt％硝酸锂以及Li2S8(0.025M)为电解液，2025电池壳组装电池。通过蓝电设备对电池进行电化学测试。正极片硫的含量达到70wt％，0.2C倍率，50个循环充放电后，放电容量仍然在700mAh/g以上。
以上对本发明做了详尽的描述，其目的在于让熟悉此领域技术的人士能够了解本发明的内容并加以实施，并不能以此限制本发明的保护范围，凡根据本发明的精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围内。

Claims (16)

  1. 一种氮掺杂石墨烯包覆纳米硫正极复合材料，其特征在于包括
    主要由氮掺杂石墨烯相互交叠形成有效的三维导电网络，
    以及被氮掺杂石墨烯片层均匀包裹的纳米硫颗粒。
  2. 根据权利要求1所述氮掺杂石墨烯包覆纳米硫正极复合材料，其特征在于所述氮掺杂石墨烯的含氮量为2～10wt％。
  3. 根据权利要求1所述氮掺杂石墨烯包覆纳米硫正极复合材料，其特征在于所述氮掺杂石墨烯的导电率为1000～30000S/m。
  4. 根据权利要求1所述氮掺杂石墨烯包覆纳米硫正极复合材料，其特征在于所述复合材料的载硫量为40～85wt％。
  5. 根据权利要求1所述氮掺杂石墨烯包覆纳米硫正极复合材料，其特征在于所述纳米硫颗粒的粒径为10～50nm。
  6. 根据权利要求1-5中任一项所述氮掺杂石墨烯包覆纳米硫正极复合材料，其特征在于所述复合材料在应用为锂硫电池正极材料时，0.2C倍率下放电容量在1200mAh.g-1以上，1C倍率下放电容量在1000mAh.g-1以上，2C倍率下放电容量在800mAh.g-1以上，5C倍率下放电容量在600mAh.g-1以上。
  7. 根据权利要求1-5中任一项所述氮掺杂石墨烯包覆纳米硫正极复合材料，其特征在于所述复合材料在应用为锂硫电池正极材料时，2C倍率下2000个循环以内，每个循环的容量衰减率在0.028％以下。
  8. 权利要求1-7中任一项所述氮掺杂石墨烯包覆纳米硫正极复合材料的制备方法，其特征在于包括：将氮掺杂石墨烯分散于至少含有硫源及酸的液相反应体系中，通过硫源与酸的原位化学反应沉积纳米硫颗粒，从而制得所述氮掺杂石墨烯包覆纳米硫颗粒复合材料。
  9. 根据权利要求8所述氮掺杂石墨烯包覆纳米硫正极复合材料的制备方法，其特征在于包括：
    a、通过Hummer法制备氧化石墨烯的水分散液，并冷冻干燥获得氧化石墨 烯粉末；
    b、将所述氧化石墨烯粉末置于保护性气氛中，并通入氮源气体与所述氧化石墨烯粉末反应，从而获得所述氮掺杂石墨烯。
  10. 根据权利要求8所述氮掺杂石墨烯包覆纳米硫正极复合材料的制备方法，其特征在于步骤b包括：
    将所述氧化石墨烯粉末置于封闭反应环境中，并通入保护性气体形成保护性气氛，再以1～100毫升/分钟的流速通入氮源气体，并将该封闭反应环境的温度在2h内升至600℃～950℃，使所述氮源气体与所述氧化石墨烯粉末充分反应，从而获得所述氮掺杂石墨烯。
  11. 根据权利要求8所述氮掺杂石墨烯包覆纳米硫正极复合材料的制备方法，其特征在于所述氮源气体包括氨气或氨气与保护性气体的混合气体，所述保护性气体包括氩气或氮气。
  12. 根据权利要求8所述氮掺杂石墨烯包覆纳米硫正极复合材料的制备方法，其特征在于所述硫源包括含硫金属盐，所述含硫金属盐至少选自硫化钠、多硫化钠、硫代硫酸钠中的任一种，所述酸至少选自盐酸，硫酸，甲酸，二甲酸，磷酸，硝酸和乙酸的任一种。
  13. 根据权利要求8或12所述氮掺杂石墨烯包覆纳米硫正极复合材料的制备方法，其特征在于所述原位化学反应的反应温度为-10℃～60℃。
  14. 权利要求1-13中任一项所述氮掺杂石墨烯包覆纳米硫正极复合材料在制备锂硫电池中的应用。
  15. 一种锂硫电池，包括正极、负极和电解质，其特征在于所述正极包含权利要求1-12中任一项所述的氮掺杂石墨烯包覆纳米硫正极复合材料。
  16. 根据权利要求15所述的锂硫电池，其特征在于所述正极不含除所述氮掺杂石墨烯包覆纳米硫正极复合材料之外的导电添加剂。
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CN106784760A (zh) * 2017-04-05 2017-05-31 深圳市佩成科技有限责任公司 一种氮掺杂石墨烯/氢氧化锌/空心硫复合材料的制备方法
CN107359321A (zh) * 2017-06-09 2017-11-17 深圳启辰新能源科技有限公司 球形结构的氮掺杂碳/钛氧化物双壳包覆钛氧化物/硫的锂硫电池正极材料及其制备方法
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