WO2019119351A1 - Matériau d'électrode négative de batterie au lithium-ion et son procédé de préparation, et batterie au lithium-ion - Google Patents

Matériau d'électrode négative de batterie au lithium-ion et son procédé de préparation, et batterie au lithium-ion Download PDF

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Publication number
WO2019119351A1
WO2019119351A1 PCT/CN2017/117739 CN2017117739W WO2019119351A1 WO 2019119351 A1 WO2019119351 A1 WO 2019119351A1 CN 2017117739 W CN2017117739 W CN 2017117739W WO 2019119351 A1 WO2019119351 A1 WO 2019119351A1
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WO
WIPO (PCT)
Prior art keywords
molybdenum disulfide
preparation
negative electrode
lithium ion
graphene oxide
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Application number
PCT/CN2017/117739
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English (en)
Chinese (zh)
Inventor
钟卓洪
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惠州拓邦电气技术有限公司
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Priority to PCT/CN2017/117739 priority Critical patent/WO2019119351A1/fr
Publication of WO2019119351A1 publication Critical patent/WO2019119351A1/fr

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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • 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
    • 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

Definitions

  • the invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery anode material and a preparation method thereof.
  • Lithium battery has the characteristics of high energy density, high voltage, light weight, no pollution, no memory effect, and overcomes the shortcomings of poor safety performance of lithium batteries. It is widely used in portable electric appliances (mobile phones, digital cameras, laptop camcorders). , CD machines, etc., energy reserves (wind, water, tidal, solar, etc.), large-scale power equipment (electric vehicles, hybrid vehicles, etc.), and power grid peaking and many other fields. Due to the state's policy support for power battery companies, the demand for lithium-ion batteries in the field of electric vehicles or hybrid electric vehicles has exploded.
  • molybdenum disulfide with a layered structure similar to graphite has attracted great interest due to its high theoretical capacity (up to 670 mAhg -1 ).
  • its electrochemical performance such as cycle stability is poor, mainly due to its poor electron/ion conductivity and volume expansion caused by repeated insertion and removal of lithium ions.
  • the technical problem to be solved by the present invention is to provide a method for preparing a lithium ion battery anode material which is simple and easy to operate, and which can be used for mass production, and a cathode material obtained, and a lithium ion battery using the anode material.
  • the technical solution adopted by the present invention to solve the technical problem thereof is to provide a method for preparing a negative electrode material for a lithium ion battery, wherein the negative electrode material is a three-dimensional porous molybdenum disulfide/nitrogen-doped graphene composite material, and the preparation method comprises the following steps:
  • the obtained three-dimensional solid matter is freeze-dried to obtain a three-dimensional porous molybdenum disulfide/nitrogen-doped graphene composite material.
  • step S1 comprises the following steps:
  • the molybdenum disulfide dispersion is centrifuged at high speed, and the supernatant is taken for filtration and dried to obtain molybdenum disulfide nanosheets.
  • step S1.2 after high-speed centrifugation, the supernatant is treated with a PVDF membrane as a membrane, and the stripped molybdenum disulfide nanosheet is deposited on the PVDF membrane by suction filtration.
  • step S2 comprises the following steps:
  • the molybdenum disulfide nanosheet and the graphene oxide sheet are dispersed in a dimethylformamide solution and ultrasonicated in an ice water bath to obtain a mixed liquid containing the molybdenum disulfide nanosheet and the graphene oxide sheet.
  • the mass ratio of the molybdenum disulfide nanosheet dispersion to the graphene oxide sheet is 1:1 to 5:1.
  • step S3 the mixed liquid is transferred to a stainless steel reaction vessel, and reacted at a constant temperature of 200-300 ° C for 6-16 h; after the reaction is completed, it is naturally cooled to obtain a three-dimensional solid.
  • step S4 the three-dimensional solid is washed with deionized water before being freeze-dried.
  • the invention also provides a negative electrode material for a lithium ion battery, wherein the negative electrode material is a three-dimensional porous molybdenum disulfide/nitrogen-doped graphene composite material, which is obtained by the preparation method according to any one of the above.
  • the present invention also provides a lithium ion battery comprising a negative electrode sheet made of the above negative electrode material.
  • the invention has the beneficial effects that the three-dimensional porous molybdenum disulfide/nitrogen-doped graphene composite material is prepared by the co-assembly method, which is simple and easy to operate, and can be used for mass production.
  • the composite material has a three-dimensional porous structure and is used as a negative electrode material for a lithium ion battery, and has the advantages of high capacity, good cycle stability, and excellent rate performance.
  • FIG. 1 is a flow chart showing a method of preparing a negative electrode material of the present invention
  • Figure 5 is an XPS spectrum of a composite material prepared according to an embodiment of the present invention.
  • Figure 6 is a graph showing charge and discharge curves of a composite material obtained according to an embodiment of the present invention.
  • Fig. 7 is a graph showing the rate discharge performance of a composite material obtained in an embodiment of the present invention.
  • the negative electrode material is a three-dimensional porous molybdenum disulfide/nitrogen-doped graphene composite material, and the preparation method comprises the following steps:
  • the step S1 may include the following steps:
  • the molybdenum disulfide dispersion is centrifuged at 1000-2000 rpm for 0.5-4 hours at high speed; after centrifugation, the supernatant contains small-sized (30-200 nm) molybdenum disulfide nanosheets.
  • the supernatant is taken for filtration and dried to obtain molybdenum disulfide nanosheets; the molybdenum disulfide nanosheet has a size of 30-200 nm.
  • the supernatant was treated with a PVDF membrane as a membrane, and filtered, and the peeled molybdenum disulfide nanosheet was deposited on the PVDF membrane.
  • the molybdenum disulfide nanosheets can be obtained by drying in a vacuum oven at 100-250 °C.
  • step S2 may include the following steps:
  • Steps S2.1 and S2.2 can be performed arbitrarily or sequentially.
  • the temperature of the ice water bath can be 0 ⁇ 5 ° C; the ultrasonic time is 1-4 hours.
  • the mass ratio of the molybdenum disulfide nanosheet dispersion to the graphene oxide sheet is 1:1 to 5:1.
  • step S2 the molybdenum disulfide nanosheet and the graphene oxide sheet are dispersed together in a dimethylformamide solution, and ultrasonically irradiated in an ice water bath to obtain a molybdenum disulfide nanosheet and oxidation.
  • the temperature of the ice water bath can be 0 ⁇ 5 ° C; the ultrasonic time is 1-4 hours.
  • the mass ratio of the molybdenum disulfide nanosheet dispersion to the graphene oxide sheet is 1:1 to 5:1.
  • the mixture is reacted at a high temperature to obtain a three-dimensional solid.
  • step S3 the mixed liquid is transferred to a stainless steel reaction vessel, and reacted at a constant temperature of 200-300 ° C for 6-16 h; after the reaction is completed, it is naturally cooled to obtain a three-dimensional solid.
  • the obtained three-dimensional solid matter is freeze-dried to obtain a three-dimensional porous molybdenum disulfide/nitrogen-doped graphene composite material.
  • the lyophilization temperature can be from -50 ° C to 0 ° C.
  • step S4 the three-dimensional solid matter is repeatedly washed with deionized water before being freeze-dried to remove the residual dimethylformamide solution.
  • the negative electrode material of the lithium ion battery of the present invention is a three-dimensional porous molybdenum disulfide/nitrogen-doped graphene composite material, which is obtained by the above preparation method.
  • the lithium ion battery of the present invention comprises a negative electrode sheet, and the negative electrode sheet is made of the above negative electrode material.
  • the negative electrode material is coated on the substrate and dried.
  • the positive electrode sheet and the negative electrode sheet and the separator are stacked and wound into a core, and the core is placed in an aluminum shell, an electrolyte is injected, and a lithium ion battery is prepared.
  • molybdenum disulfide powder 10 g was added to 100 ml of NMP solution, sonicated for 6 h under ice water bath conditions, and the resulting dispersion was centrifuged at 1500 rpm for 1 h, and the supernatant contained a small size molybdenum disulfide nanosheet; The supernatant is treated with a PVDF membrane as a membrane, filtered, and the stripped molybdenum disulfide nanosheets are deposited on a PVDF membrane, and the molybdenum disulfide nanosheets are obtained after drying in a vacuum oven.
  • FIG. 2 there are TEM images of molybdenum disulfide and molybdenum disulfide nanosheets, wherein (a) is molybdenum disulfide and (b) is molybdenum disulfide nanosheet.
  • the molybdenum disulfide nanosheets were transparent and ultra-thin, confirming that they were successfully peeled off.
  • graphene oxide sheet was dispersed in 7 ml of dimethylformamide solution and ultrasonicated for 2 h in an ice water bath to obtain a uniform graphene oxide sheet dispersion. Three parts of the graphene oxide sheet dispersion were prepared under the same conditions.
  • the prepared molybdenum disulfide nanosheet dispersion is mixed with the graphene oxide sheet dispersion, and ultrasonically treated for 2 h in an ice water bath to obtain a mass ratio of molybdenum disulfide nanosheet to graphene oxide sheet of 1:1 and 3, respectively. : 1, 5: 1 uniform mixture.
  • the mixture was transferred to a 20 ml stainless steel autoclave and kept at a constant temperature of 240 ° C for 12 h. After completion of the reaction, the mixture was naturally cooled, and the obtained cake was taken out, washed repeatedly with deionized water, and lyophilized to obtain a three-dimensional porous molybdenum disulfide/nitrogen-doped graphene composite material.
  • the composite materials with specific gravity of 1:1, 3:1, and 5:1 of molybdenum disulfide and nitrogen-doped graphene are labeled as MoS 2 /GN-I, MoS 2 /GN-II and MoS 2 /GN-III, respectively. .
  • FIG. 3 An SEM image of the obtained composite material is shown in Fig. 3, wherein (a), (b) and (c) are MoS 2 /GN-I, MoS 2 /GN-II and MoS 2 /GN-III, respectively. It can be seen from Fig. 3 that the graphene sheets constitute a three-dimensional porous network structure, and the molybdenum disulfide nanosheets are embedded in the graphene network structure.
  • Figure 5 shows the XPS spectrum of the sample MoS 2 /GN-II, with the horizontal axis of Binding Energy (eV) and the vertical axis of intensity (Intensity, au) showing elements such as Mo, S, C, N and O.
  • the characteristic peak indicates that the sample MoS 2 /GN-II contains a small amount of N element, which confirms the occurrence of nitrogen doping reaction.
  • the O/C atomic ratio was changed to 0.23, and the relative content of the O element was decreased, confirming the occurrence of the reduction reaction.
  • Figures 6 and 7 are graphs showing electrochemical performance tests of the prepared composite materials, respectively.
  • Figure 6 shows the first three charge and discharge curves of the sample MoS 2 /GN-II at a current density of 100 mAg -1 ; the horizontal axis is the current density (mAg -1 ) and the vertical axis is the voltage (Potential, V).
  • the passenger capacity of MoS 2 /GN-II is about 1200 mAhg -1 .
  • Figure 7 is the rate discharge performance curve of sample MoS 2 /GN-III at different current densities.
  • the horizontal axis is the cycle number and the vertical axis is the discharge capacity (mAh). From the curve, it can be seen that MoS 2 / Excellent GN-III rate performance.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne un matériau d'électrode négative de batterie au lithium-ion et son procédé de préparation, et une batterie au lithium-ion, le matériau d'électrode négative étant un matériau composite de graphène dopé au bisulfure de molybdène/azote poreux tridimensionnel, et le procédé de préparation comprenant les étapes suivantes : S1 : préparer des nanofeuilles de bisulfure de molybdène ; S2 : préparer un liquide mixte contenant des nanofeuilles de bisulfure de molybdène et des feuilles d'oxyde de graphène ; S3 : faire réagir le liquide mixte à haute température pour acquérir une substance solide tridimensionnelle ; S4 : lyophiliser la substance solide tridimensionnelle acquise pour acquérir un matériau composite de graphène dopé au bisulfure de molybdène/azote poreux tridimensionnel. La présente invention prépare le matériau composite de graphène dopé au bisulfure de molybdène/azote poreux tridimensionnel au moyen d'un procédé de co-assemblage, est facile à utiliser, et peut être utilisé pour la production de masse. Le matériau composite a une structure poreuse tridimensionnelle, et présente les avantages d'une capacité élevée, d'une bonne stabilité de cycle et d'une excellente capacité de vitesse lorsqu'il est utilisé en tant que matériau d'électrode négative de batterie au lithium-ion.
PCT/CN2017/117739 2017-12-21 2017-12-21 Matériau d'électrode négative de batterie au lithium-ion et son procédé de préparation, et batterie au lithium-ion WO2019119351A1 (fr)

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CN105263858A (zh) * 2013-03-14 2016-01-20 都柏林圣三一学院教务长、研究员、基金会学者及董事会其他成员 可放大的用于大量制备片状剥离的、无缺陷的、非氧化的二维材料的方法
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