WO2019119351A1 - Lithium ion battery negative electrode material and preparation method therefor, and lithium ion battery - Google Patents

Lithium ion battery negative electrode material and preparation method therefor, and lithium ion battery Download PDF

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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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molybdenum disulfide
preparation
negative electrode
lithium ion
graphene oxide
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PCT/CN2017/117739
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French (fr)
Chinese (zh)
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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/en
Publication of WO2019119351A1 publication Critical patent/WO2019119351A1/en

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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.

Abstract

Disclosed in the present invention are a lithium ion battery negative electrode material and a preparation method therefor, and a lithium ion battery, the negative electrode material being a three dimensional porous molybdenum disulphide/nitrogen-doped graphene composite material, and the preparation method comprising the following steps: S1: preparing molybdenum disulphide nano sheets; S2: preparing a mixed liquid containing molybdenum disulphide nano sheets and graphene oxide sheets; S3: reacting the mixed liquid at high temperature to acquire a three dimensional solid substance; S4: freeze-drying the acquired three dimensional solid substance to acquire a three dimensional porous molybdenum disulphide/nitrogen-doped graphene composite material. The present invention prepares the three dimensional porous molybdenum disulphide/nitrogen-doped graphene composite material by means of a co-assembly method, is easy to operate, and can be used for mass production. The composite material has a three dimensional porous structure, and has the advantages of high capacity, good cycle stability, and excellent rate capability when used as lithium ion battery negative electrode material.

Description

锂离子电池负极材料及其制备方法、锂离子电池Lithium ion battery anode material and preparation method thereof, lithium ion battery 技术领域Technical field
本发明涉及锂离子电池技术领域，尤其涉及一种锂离子电池负极材料及其制备方法。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.
背景技术Background technique
锂电池能量密度大、电压高、重量轻、无公害、无记忆效应等特点，而且克服了锂电池安全性能差的缺点，被广泛用于便携电器（移动手机、数码相机、笔记本电脑摄录机、CD机等）、能源储备（风能、水能、潮汐能、太阳能等）、大型动力设备（电动车、混合动力汽车等）、以及电网调峰等诸多领域。由于国家对动力电池企业的政策扶持，因此，锂离子电池在电动汽车或混合式电动汽车这个领域的需求已呈***式增长。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.
然而，目前商业化电池所采用的最普遍负极材料为石墨，石墨的较小理论比容量(372 mAhg -1)却限制了锂离子电池在电动汽车领域的进一步应用，因此，开发具有高容量的新型电极材料成为研究的重点。 However, the most common anode material used in commercial batteries is graphite. The smaller theoretical specific capacity of graphite (372 mAhg -1 ) limits the further application of lithium-ion batteries in the field of electric vehicles. Therefore, the development of high-capacity New electrode materials have become the focus of research.
在众多可替代材料中，与石墨具有类似层状结构的二硫化钼因其高理论容量（可高达670 mAhg -1)引起了人们的极大兴趣。然而，二硫化钼在用作锂离子电池负极材料时，其电化学性能如循环稳定性欠佳，主要原因是其差的电子/离子导电性以及锂离子反复嵌入脱出造成的体积膨胀。 Among the many alternative materials, molybdenum disulfide with a layered structure similar to graphite has attracted great interest due to its high theoretical capacity (up to 670 mAhg -1 ). However, when molybdenum disulfide is used as a negative electrode material for lithium ion batteries, 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.
技术问题technical problem
本发明要解决的技术问题在于，提供一种简单易操作，且可用于大批量生产的锂离子电池负极材料的制备方法及制得的负极材料，使用该负极材料的锂离子电池。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.
技术解决方案Technical solution
本发明解决其技术问题所采用的技术方案是：提供一种锂离子电池负极材料的制备方法，负极材料为三维孔状二硫化钼/氮掺杂石墨烯复合材料，该制备方法包括以下步骤：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:
S1、制备二硫化钼纳米片； S1, preparing molybdenum disulfide nanosheets;
S2、制备含二硫化钼纳米片和氧化石墨烯片的混合液； S2, preparing a mixed liquid containing molybdenum disulfide nanosheets and graphene oxide sheets;
S3、将所述混合液在高温下反应，获得三维状固体物；S3, reacting the mixed solution at a high temperature to obtain a three-dimensional solid object;
S4、将获得的三维状固体物进行冷冻干燥，获得三维孔状二硫化钼/氮掺杂石墨烯复合材料。S4. The obtained three-dimensional solid matter is freeze-dried to obtain a three-dimensional porous molybdenum disulfide/nitrogen-doped graphene composite material.
优选地，步骤S1包括以下步骤：Preferably, step S1 comprises the following steps:
S1.1、将二硫化钼粉末加入氮甲基吡咯烷酮溶液中，冰水浴下超声，得到浓度0.1-0.2g/ml的二硫化钼分散液；S1.1, adding molybdenum disulfide powder to a solution of nitromethylpyrrolidone, and ultrasonicating in an ice water bath to obtain a molybdenum disulfide dispersion having a concentration of 0.1-0.2 g/ml;
S1.2、将二硫化钼分散液高速离心，取上清液进行过滤，烘干，获得二硫化钼纳米片。S1.2, the molybdenum disulfide dispersion is centrifuged at high speed, and the supernatant is taken for filtration and dried to obtain molybdenum disulfide nanosheets.
优选地，步骤S1.2中，高速离心后，将上清液以PVDF膜为垫膜，抽滤，剥离好的二硫化钼纳米片沉积在PVDF膜上。Preferably, in 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.
优选地，步骤S2包括以下步骤：Preferably, step S2 comprises the following steps:
S2.1、将二硫化钼纳米片分散于二甲基甲酰胺溶液中，冰水浴下超声，获得浓度为2-8g/ml的二硫化钼纳米片分散液；S2.1, dispersing the molybdenum disulfide nanosheet in a dimethylformamide solution, and ultrasonicating in an ice water bath to obtain a molybdenum disulfide nanosheet dispersion having a concentration of 2-8 g/ml;
S2.2、将氧化石墨烯片分散于二甲基甲酰胺溶液中，冰水浴下超声，获得浓度为2-8g/ml的氧化石墨烯片分散液；S2.2, dispersing the graphene oxide sheet in a dimethylformamide solution, and ultrasonicating in an ice water bath to obtain a graphene oxide sheet dispersion having a concentration of 2-8 g/ml;
S2.3、将二硫化钼纳米片分散液和氧化石墨烯片分散液混合，冰水浴下超声，获得含二硫化钼纳米片和氧化石墨烯片的混合液。 S2.3, mixing the molybdenum disulfide nanosheet dispersion and the graphene oxide sheet dispersion, and ultrasonicating in an ice water bath to obtain a mixed liquid containing the molybdenum disulfide nanosheet and the graphene oxide sheet.
优选地，步骤S2中，将二硫化钼纳米片、氧化石墨烯片分散于二甲基甲酰胺溶液中，冰水浴下超声，获得含二硫化钼纳米片和氧化石墨烯片的混合液。Preferably, in step S2, 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.
优选地，步骤S2获得的混合液中，二硫化钼纳米片分散液和氧化石墨烯片的质量比为1:1-5:1。Preferably, in the mixed solution obtained in the step S2, the mass ratio of the molybdenum disulfide nanosheet dispersion to the graphene oxide sheet is 1:1 to 5:1.
优选地，步骤S3中，将所述混合液转移到不锈钢反应釜中，200-300℃恒温下反应6-16 h；反应结束后，自然冷却，获得三维状固体物。Preferably, in 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.
优选地，步骤S4中，所述三维状固体物进行冷冻干燥前，用去离子水清洗。Preferably, in step S4, the three-dimensional solid is washed with deionized water before being freeze-dried.
本发明还提供一种锂离子电池负极材料，负极材料为三维孔状二硫化钼/氮掺杂石墨烯复合材料，采用上述任一项所述的制备方法制得。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.
本发明还提供一种锂离子电池，包括负极片，所述负极片采用上述的负极材料制成。The present invention also provides a lithium ion battery comprising a negative electrode sheet made of the above negative electrode material.
有益效果Beneficial effect
本发明的有益效果：通过共组装方法制备三维孔状二硫化钼/氮掺杂石墨烯复合材料，简单易操作，可用于大批量生产。该复合材料具有三维多孔结构，用作锂离子电池负极材料具有容量高、循环稳定性好、倍率性能优异等优点。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.
附图说明DRAWINGS
下面将结合附图及实施例对本发明作进一步说明，附图中：The present invention will be further described below in conjunction with the accompanying drawings and embodiments, in which:
图1是本发明的负极材料的制备方法流程图；1 is a flow chart showing a method of preparing a negative electrode material of the present invention;
图2是本发明中二硫化钼和二硫化钼纳米片的TEM图；2 is a TEM image of the molybdenum disulfide and molybdenum disulfide nanosheets of the present invention;
图3是本发明中制得的二硫化钼/氮掺杂石墨烯复合材料的SEM图；3 is an SEM image of a molybdenum disulfide/nitrogen-doped graphene composite material prepared in the present invention;
图4是本发明一实施例制得的复合材料和二硫化钼纳米片的XRD图；4 is an XRD pattern of a composite material and a molybdenum disulfide nanosheet prepared according to an embodiment of the present invention;
图5是本发明一实施例制得的复合材料的XPS谱图；Figure 5 is an XPS spectrum of a composite material prepared according to an embodiment of the present invention;
图6是本发明一实施例制得的复合材料的充放电曲线图；Figure 6 is a graph showing charge and discharge curves of a composite material obtained according to an embodiment of the present invention;
图7是本发明一实施例制得的复合材料的倍率放电性能曲线图。Fig. 7 is a graph showing the rate discharge performance of a composite material obtained in an embodiment of the present invention.
本发明的实施方式Embodiments of the invention
如图1所示，本发明的锂离子电池负极材料的制备方法，负极材料为三维孔状二硫化钼/氮掺杂石墨烯复合材料，该制备方法包括以下步骤：As shown in FIG. 1 , in the method for preparing a negative electrode material for a lithium ion battery 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:
S1、制备二硫化钼纳米片。S1, preparing molybdenum disulfide nanosheets.
具体地，该步骤S1可包括以下步骤：Specifically, the step S1 may include the following steps:
S1.1、将二硫化钼粉末加入氮甲基吡咯烷酮溶液中，冰水浴下超声，得到浓度0.1-0.2g/ml的二硫化钼分散液。冰水浴的温度可为0±5℃；超声时间为4-10小时。S1.1, adding molybdenum disulfide powder to a solution of nitrogen methylpyrrolidone, and ultrasonicating in an ice water bath to obtain a molybdenum disulfide dispersion having a concentration of 0.1-0.2 g/ml. The temperature of the ice water bath can be 0 ± 5 ° C; the ultrasonic time is 4-10 hours.
S1.2、将二硫化钼分散液在1000-2000rpm下高速离心0.5-4小时；离心后上清液中含小尺寸（30-200nm）的二硫化钼纳米片。S1.2, 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.
取上清液进行过滤，烘干，获得二硫化钼纳米片；二硫化钼纳米片尺寸为30-200nm。The supernatant is taken for filtration and dried to obtain molybdenum disulfide nanosheets; the molybdenum disulfide nanosheet has a size of 30-200 nm.
其中，在高速离心后，过滤时，将上清液以PVDF膜为垫膜，抽滤，剥离好的二硫化钼纳米片沉积在PVDF膜上。在真空烘箱中于100-250℃下烘干，即可获得二硫化钼纳米片。Among them, after high-speed centrifugation, when filtering, 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.
S2、制备含二硫化钼纳米片和氧化石墨烯片的混合液。 S2. Preparing a mixture of molybdenum disulfide nanosheets and graphene oxide sheets.
作为一种选择实施方式，步骤S2可包括以下步骤：As an alternative implementation, step S2 may include the following steps:
S2.1、将二硫化钼纳米片分散于二甲基甲酰胺溶液中，冰水浴下超声，获得浓度为2-8g/ml且均一的二硫化钼纳米片分散液；冰水浴的温度可为0±5℃；超声时间为1-4小时。S2.1, dispersing the molybdenum disulfide nanosheet in a dimethylformamide solution, and ultrasonicating in an ice water bath to obtain a uniform dispersion of molybdenum disulfide nanosheets at a concentration of 2-8 g/ml; the temperature of the ice water bath may be 0 ± 5 ° C; ultrasonic time is 1-4 hours.
S2.2、将氧化石墨烯片分散于二甲基甲酰胺溶液中，冰水浴下超声，获得浓度为2-8g/ml且均一的氧化石墨烯片分散液；冰水浴的温度可为0±5℃；超声时间为1-4小时。S2.2, dispersing the graphene oxide sheet in a dimethylformamide solution, and ultrasonicating in an ice water bath to obtain a uniform graphene oxide sheet dispersion having a concentration of 2-8 g/ml; the temperature of the ice water bath may be 0± 5 ° C; ultrasonic time is 1-4 hours.
步骤S2.1、S2.2可任意先后进行，也可同时进行。Steps S2.1 and S2.2 can be performed arbitrarily or sequentially.
S2.3、将二硫化钼纳米片分散液和氧化石墨烯片分散液混合，冰水浴下超声，获得含二硫化钼纳米片和氧化石墨烯片且均一的混合液。S2.3, mixing the molybdenum disulfide nanosheet dispersion and the graphene oxide sheet dispersion, and ultrasonicating in an ice water bath to obtain a uniform mixture containing the molybdenum disulfide nanosheet and the graphene oxide sheet.
冰水浴的温度可为0±5℃；超声时间为1-4小时。The temperature of the ice water bath can be 0 ± 5 ° C; the ultrasonic time is 1-4 hours.
混合液中，二硫化钼纳米片分散液和氧化石墨烯片的质量比为1:1-5:1。In the mixed solution, the mass ratio of the molybdenum disulfide nanosheet dispersion to the graphene oxide sheet is 1:1 to 5:1.
作为另一种选择实施方式，步骤S2中，将二硫化钼纳米片、氧化石墨烯片一起分散于二甲基甲酰胺溶液中，冰水浴下超声，即可获得含二硫化钼纳米片和氧化石墨烯片的混合液。二硫化钼纳米片、氧化石墨烯片和二甲基甲酰胺溶液的用量可参考上述分步进行的实施方式。As another alternative embodiment, in 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. A mixture of graphene sheets. The amount of the molybdenum disulfide nanosheet, the graphene oxide sheet, and the dimethylformamide solution can be referred to the above-described stepwise embodiment.
冰水浴的温度可为0±5℃；超声时间为1-4小时。混合液中，二硫化钼纳米片分散液和氧化石墨烯片的质量比为1:1-5:1。The temperature of the ice water bath can be 0 ± 5 ° C; the ultrasonic time is 1-4 hours. In the mixed solution, the mass ratio of the molybdenum disulfide nanosheet dispersion to the graphene oxide sheet is 1:1 to 5:1.
S3、将混合液在高温下反应，获得三维状固体物。S3. The mixture is reacted at a high temperature to obtain a three-dimensional solid.
具体地，步骤S3中，将混合液转移到不锈钢反应釜中，200-300℃恒温下反应6-16 h；反应结束后，自然冷却，获得三维状固体物。Specifically, in 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.
S4、将获得的三维状固体物进行冷冻干燥，获得三维孔状二硫化钼/氮掺杂石墨烯复合材料。S4. The obtained three-dimensional solid matter is freeze-dried to obtain a three-dimensional porous molybdenum disulfide/nitrogen-doped graphene composite material.
冷冻干燥的温度可为-50℃-0℃。The lyophilization temperature can be from -50 ° C to 0 ° C.
步骤S4中，三维状固体物进行冷冻干燥前，用去离子水反复清洗，去除残留的二甲基甲酰胺溶液。In step S4, the three-dimensional solid matter is repeatedly washed with deionized water before being freeze-dried to remove the residual dimethylformamide solution.
本发明的锂离子电池负极材料，负极材料为三维孔状二硫化钼/氮掺杂石墨烯复合材料，采用上述的制备方法制得。In the negative electrode material of the lithium ion battery of the present invention, the negative electrode material is a three-dimensional porous molybdenum disulfide/nitrogen-doped graphene composite material, which is obtained by the above preparation method.
本发明的锂离子电池，包括负极片，负极片采用上述的负极材料制成。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.
负极片制作时，将负极材料涂覆在基材上，烘干后即得。When the negative electrode sheet is produced, the negative electrode material is coated on the substrate and dried.
将正极片与负极片、隔膜叠置后卷绕成卷芯，将卷芯放入铝壳中，注入电解液，封口，即可制得锂离子电池。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.
下面将以具体实施例来对本发明进行说明。The invention will now be described by way of specific examples.
一、通过液相剥离法制备二硫化钼纳米片1. Preparation of molybdenum disulfide nanosheets by liquid phase stripping method
将10g二硫化钼粉末加入到100ml的NMP溶液中，冰水浴条件下超声处理6h，所得分散液在1500rpm离心速率下离心1h，上清液中所含即为小尺寸的二硫化钼纳米片；将上清液以PVDF膜为垫膜，抽滤，剥离好的二硫化钼纳米片即可沉积在PVDF膜上，真空烘箱中烘干后即可获得二硫化钼纳米片。10 g of molybdenum disulfide powder 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.
如图2所示，为二硫化钼和二硫化钼纳米片的TEM图像，其中（a）为二硫化钼，（b）为二硫化钼纳米片。二硫化钼纳米片呈透明超薄状，证实了其被成功剥离。As shown in 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.
二、制备二硫化钼纳米片分散液Second, the preparation of molybdenum disulfide nanosheet dispersion
取28g二硫化钼纳米片分散于7ml二甲基甲酰胺溶液中，冰水浴条件下超声处理2h，即可获得均一的二硫化钼纳米片分散液。同样方法获得分别含有二硫化钼纳米片84g、140g的分散液。28 g of molybdenum disulfide nanosheets were dispersed in 7 ml of dimethylformamide solution and sonicated for 2 h under ice water bath to obtain a uniform dispersion of molybdenum disulfide nanosheets. In the same manner, a dispersion liquid containing 84 g and 140 g of molybdenum disulfide nanosheets, respectively, was obtained.
三、制备氧化石墨烯片分散液Third, the preparation of graphene oxide sheet dispersion
取28g氧化石墨烯片分散于7ml二甲基甲酰胺溶液中，冰水浴条件下超声2 h，即可获得均一的氧化石墨烯片分散液。同样条件制备3份氧化石墨烯片分散液。A 28 g of 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.
四、制备混合液Fourth, the preparation of the mixture
将制备好的二硫化钼纳米片分散液与氧化石墨烯片分散液混合，冰水浴条件下超声2 h，即可获得二硫化钼纳米片与氧化石墨烯片质量比分别为1:1、3:1、5:1的均一混合液。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.
五、制备三维孔状二硫化钼/氮掺杂石墨烯复合材料V. Preparation of three-dimensional porous molybdenum disulfide/nitrogen-doped graphene composite material
将混合液转移到20 ml的不锈钢反应釜中，240℃恒温保持12 h。反应结束后，自然冷却，将所得块状物取出，用去离子水反复清洗，冷冻干燥，获得含有三维孔状二硫化钼/氮掺杂石墨烯复合材料。将二硫化钼与氮掺杂石墨烯比重分别为1:1、3:1、5:1的复合材料分别标记为MoS 2/GN-I、 MoS 2/GN-II和MoS 2/GN-III。 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. .
获得的复合材料的SEM图像如图3所示，其中（a）、（b）和（c）分别为MoS 2/GN-I、 MoS 2/GN-II和MoS 2/GN-III。从图3中可以看出石墨烯片构成三维多孔网络结构，二硫化钼纳米片被嵌入在石墨烯网络结构之中。 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.
图4为样品MoS 2/GN-II和二硫化钼纳米片的XRD表征图，横轴为2θ（degree,℃）。从图可以看出，相比于纯二硫化钼纳米片的晶面衍射峰（002处），MoS 2/GN-II的晶面衍射峰（002处）强度明显降低，而晶面衍射峰强度代表了二硫化钼纳米片的堆叠程度，进一步验证石墨烯三维网络结构有效抑制了二硫化钼纳米片的堆叠和聚集。 4 is an XRD pattern of samples MoS 2 /GN-II and molybdenum disulfide nanosheets, and the horizontal axis is 2θ (degree, ° C). It can be seen from the figure that the intensity of the crystal plane diffraction peak (002) of MoS 2 /GN-II is significantly lower than that of the pure tungsten disulfide nanosheet. It represents the degree of stacking of molybdenum disulfide nanosheets, further verifying that the graphene three-dimensional network structure effectively inhibits the stacking and aggregation of molybdenum disulfide nanosheets.
图5为样品MoS 2/GN-II的XPS谱图，横轴为结合能（Binding Energy，eV），纵轴为强度（Intensity，a.u.）其中呈现出Mo、S、C、N和O等元素的特征峰，说明该样品MoS 2/GN-II中含有少量的N元素，证实了氮掺杂反应的发生。此外O/C原子比变为0.23，O元素相对含量减少，证实了还原反应的发生。 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. In addition, 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.
图6、7分别为制得的复合材料的电化学性能测试曲线图。其中，图6为样品MoS 2/GN-II在电流密度100 mAg -1下的前三次充放电曲线；横轴为电流密度（mAg -1），纵轴为电压（Potential， V）。从图中可知，MoS 2/GN-II的客容量发挥约为1200mAhg -1。 Figures 6 and 7 are graphs showing electrochemical performance tests of the prepared composite materials, respectively. Among them, 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). As can be seen from the figure, the passenger capacity of MoS 2 /GN-II is about 1200 mAhg -1 .
图7为样品MoS 2/GN-III在不同电流密度下的倍率放电性能曲线，横轴为圈数（Cycle number），纵轴为放电容量（mAh）；从曲线走向可看出，MoS 2/GN-III倍率性能优异。 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.
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。The above is only the embodiment of the present invention, and is not intended to limit the scope of the invention, and the equivalent structure or equivalent process transformation of the present invention and the contents of the drawings may be directly or indirectly applied to other related technologies. The fields are all included in the scope of patent protection of the present invention.

Claims (10)

  1. 一种锂离子电池负极材料的制备方法，其特征在于，负极材料为三维孔状二硫化钼/氮掺杂石墨烯复合材料，该制备方法包括以下步骤：A method for preparing a negative electrode material for a lithium ion battery, characterized in that the negative electrode material is a three-dimensional porous molybdenum disulfide/nitrogen-doped graphene composite material, and the preparation method comprises the following steps:
    S1、制备二硫化钼纳米片； S1, preparing molybdenum disulfide nanosheets;
    S2、制备含二硫化钼纳米片和氧化石墨烯片的混合液； S2, preparing a mixed liquid containing molybdenum disulfide nanosheets and graphene oxide sheets;
    S3、将所述混合液在高温下反应，获得三维状固体物；S3, reacting the mixed solution at a high temperature to obtain a three-dimensional solid object;
    S4、将获得的三维状固体物进行冷冻干燥，获得三维孔状二硫化钼/氮掺杂石墨烯复合材料。S4. The obtained three-dimensional solid matter is freeze-dried to obtain a three-dimensional porous molybdenum disulfide/nitrogen-doped graphene composite material.
  2. 根据权利要求1所述的制备方法，其特征在于，步骤S1包括以下步骤：The preparation method according to claim 1, wherein the step S1 comprises the following steps:
    S1.1、将二硫化钼粉末加入氮甲基吡咯烷酮溶液中，冰水浴下超声，得到浓度0.1-0.2g/ml的二硫化钼分散液；S1.1, adding molybdenum disulfide powder to a solution of nitromethylpyrrolidone, and ultrasonicating in an ice water bath to obtain a molybdenum disulfide dispersion having a concentration of 0.1-0.2 g/ml;
    S1.2、将二硫化钼分散液高速离心，取上清液进行过滤，烘干，获得二硫化钼纳米片。S1.2, the molybdenum disulfide dispersion is centrifuged at high speed, and the supernatant is taken for filtration and dried to obtain molybdenum disulfide nanosheets.
  3. 根据权利要求2所述的制备方法，其特征在于，步骤S1.2中，高速离心后，将上清液以PVDF膜为垫膜，抽滤，剥离好的二硫化钼纳米片沉积在PVDF膜上。The preparation method according to claim 2, wherein in 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. on.
  4. 根据权利要求1所述的制备方法，其特征在于，步骤S2包括以下步骤：The preparation method according to claim 1, wherein the step S2 comprises the following steps:
    S2.1、将二硫化钼纳米片分散于二甲基甲酰胺溶液中，冰水浴下超声，获得浓度为2-8g/ml的二硫化钼纳米片分散液；S2.1, dispersing the molybdenum disulfide nanosheet in a dimethylformamide solution, and ultrasonicating in an ice water bath to obtain a molybdenum disulfide nanosheet dispersion having a concentration of 2-8 g/ml;
    S2.2、将氧化石墨烯片分散于二甲基甲酰胺溶液中，冰水浴下超声，获得浓度为2-8g/ml的氧化石墨烯片分散液；S2.2, dispersing the graphene oxide sheet in a dimethylformamide solution, and ultrasonicating in an ice water bath to obtain a graphene oxide sheet dispersion having a concentration of 2-8 g/ml;
    S2.3、将二硫化钼纳米片分散液和氧化石墨烯片分散液混合，冰水浴下超声，获得含二硫化钼纳米片和氧化石墨烯片的混合液。S2.3, mixing the molybdenum disulfide nanosheet dispersion and the graphene oxide sheet dispersion, and ultrasonicating in an ice water bath to obtain a mixed liquid containing the molybdenum disulfide nanosheet and the graphene oxide sheet.
  5. 根据权利要求1所述的制备方法，其特征在于，步骤S2中，将二硫化钼纳米片、氧化石墨烯片分散于二甲基甲酰胺溶液中，冰水浴下超声，获得含二硫化钼纳米片和氧化石墨烯片的混合液。The preparation method according to claim 1, wherein in step S2, the molybdenum disulfide nanosheet and the graphene oxide sheet are dispersed in a dimethylformamide solution, and ultrasonically irradiated in an ice water bath to obtain a molybdenum disulfide nanometer. A mixture of a sheet and a graphene oxide sheet.
  6. 根据权利要求1所述的制备方法，其特征在于，步骤S2获得的混合液中，二硫化钼纳米片分散液和氧化石墨烯片的质量比为1:1-5:1。The preparation method according to claim 1, wherein the mass ratio of the molybdenum disulfide nanosheet dispersion to the graphene oxide sheet in the mixture obtained in the step S2 is 1:1 to 5:1.
  7. 根据权利要求1所述的制备方法，其特征在于，步骤S3中，将所述混合液转移到不锈钢反应釜中，200-300℃恒温下反应6-16 h；反应结束后，自然冷却，获得三维状固体物。The preparation method according to claim 1, wherein in 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 finished, it is naturally cooled to obtain Three-dimensional solids.
  8. 根据权利要求1所述的制备方法，其特征在于，步骤S4中，所述三维状固体物进行冷冻干燥前，用去离子水清洗。The preparation method according to claim 1, wherein in the step S4, the three-dimensional solid matter is washed with deionized water before being freeze-dried.
  9. 一种锂离子电池负极材料，其特征在于，负极材料为三维孔状二硫化钼/氮掺杂石墨烯复合材料，采用权利要求1-8任一项所述的制备方法制得。A negative electrode material for a lithium ion battery, characterized in that 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 claims 1-8.
  10. 一种锂离子电池，其特征在于，包括负极片，所述负极片采用权利要求9所述的负极材料制成。A lithium ion battery comprising a negative electrode sheet made of the negative electrode material according to claim 9.
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